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Sample records for carbonate minerals

  1. Microbially mediated mineral carbonation

    NASA Astrophysics Data System (ADS)

    Power, I. M.; Wilson, S. A.; Dipple, G. M.; Southam, G.

    2010-12-01

    Mineral carbonation involves silicate dissolution and carbonate precipitation, which are both natural processes that microorganisms are able to mediate in near surface environments (Ferris et al., 1994; Eq. 1). (Ca,Mg)SiO3 + 2H2CO3 + H2O → (Ca,Mg)CO3 + H2O + H4SiO4 + O2 (1) Cyanobacteria are photoautotrophs with cell surface characteristics and metabolic processes involving inorganic carbon that can induce carbonate precipitation. This occurs partly by concentrating cations within their net-negative cell envelope and through the alkalinization of their microenvironment (Thompson & Ferris, 1990). Regions with mafic and ultramafic bedrock, such as near Atlin, British Columbia, Canada, represent the best potential sources of feedstocks for mineral carbonation. The hydromagnesite playas near Atlin are a natural biogeochemical model for the carbonation of magnesium silicate minerals (Power et al., 2009). Field-based studies at Atlin and corroborating laboratory experiments demonstrate the ability of a microbial consortium dominated by filamentous cyanobacteria to induce the precipitation of carbonate minerals. Phototrophic microbes, such as cyanobacteria, have been proposed as a means for producing biodiesel and other value added products because of their efficiency as solar collectors and low requirement for valuable, cultivable land in comparison to crops (Dismukes et al., 2008). Carbonate precipitation and biomass production could be facilitated using specifically designed ponds to collect waters rich in dissolved cations (e.g., Mg2+ and Ca2+), which would allow for evapoconcentration and provide an appropriate environment for growth of cyanobacteria. Microbially mediated carbonate precipitation does not require large quantities of energy or chemicals needed for industrial systems that have been proposed for rapid carbon capture and storage via mineral carbonation (e.g., Lackner et al., 1995). Therefore, this biogeochemical approach may represent a readily

  2. Accelerating Mineral Carbonation Using Carbonic Anhydrase.

    PubMed

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

    2016-03-01

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

  3. Carbon dioxide sequestration by mineral carbonation

    SciTech Connect

    Gerdemann, Stephen J.; Dahlin David C.; O'Connor William K.; Penner Larry R.

    2003-11-01

    Concerns about global warming caused by the increasing concentration of carbon dioxide and other greenhouse gases in the earth’s atmosphere have resulted in the need for research to reduce or eliminate emissions of these gases. Carbonation of magnesium and calcium silicate minerals is one possible method to achieve this reduction. It is possible to carry out these reactions either in situ (storage underground and subsequent reaction with the host rock to trap CO2 as carbonate minerals) or ex situ (above ground in a more traditional chemical processing plant). Research at the Department of Energy’s Albany Research Center has explored both of these routes. This paper will explore parameters that affect the direct carbonation of magnesium silicate minerals serpentine (Mg3Si2O5(OH)4) and olivine (Mg2SiO4) to produce magnesite (MgCO3), as well as the calcium silicate mineral, wollastonite (CaSiO3), to form calcite (CaCO3). The Columbia River Basalt Group is a multi-layered basaltic lava plateau that has favorable mineralogy and structure for storage of CO2. Up to 25% combined concentration of Ca, Fe2+, and Mg cations could react to form carbonates and thus sequester large quantities of CO2. Core samples from the Columbia River Basalt Group were reacted in an autoclave for up to 2000 hours at temperatures and pressures to simulate in situ conditions. Changes in core porosity, secondary minerals, and solution chemistry were measured.

  4. Mineralization of Carbon Dioxide: Literature Review

    SciTech Connect

    Romanov, V; Soong, Y; Carney, C; Rush, G; Nielsen, B; O'Connor, W

    2015-01-01

    CCS research has been focused on CO2 storage in geologic formations, with many potential risks. An alternative to conventional geologic storage is carbon mineralization, where CO2 is reacted with metal cations to form carbonate minerals. Mineralization methods can be broadly divided into two categories: in situ and ex situ. In situ mineralization, or mineral trapping, is a component of underground geologic sequestration, in which a portion of the injected CO2 reacts with alkaline rock present in the target formation to form solid carbonate species. In ex situ mineralization, the carbonation reaction occurs above ground, within a separate reactor or industrial process. This literature review is meant to provide an update on the current status of research on CO2 mineralization. 2

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  6. Mineralization strategies for carbon dioxide sequestration

    SciTech Connect

    Penner, Larry R.; O'Connor, William K.; Gerdemann, Stephen J.; Dahlin, David C.

    2003-01-01

    Progress is reported in three primary research areas--each concerned with sequestering carbon dioxide into mineral matrices. Direct mineral carbonation was pioneered at Albany Research Center. The method treats the reactant, olivine or serpentine in aqueous media with carbon dioxide at high temperature and pressure to form stable mineral carbonates. Recent results are introduced for pretreatment by high-intensity grinding to improve carbonation efficiency. To prove feasibility of the carbonation process, a new reactor was designed and operated to progress from batch tests to continuous operation. The new reactor is a prototype high-temperature, high-pressure flow loop reactor that will furnish information on flow, energy consumption, and wear and corrosion resulting from slurry flow and the carbonation reaction. A promising alternative mineralization approach is also described. New data are presented for long-term exposure of carbon dioxide to Colombia River Basalt to determine the extent of conversion of carbon dioxide to permanent mineral carbonates. Batch autoclave tests were conducted using drill-core samples of basalt and reacted under conditions that simulate in situ injection into basalt-containing geological formations.

  7. Multiphase Sequestration Geochemistry: Model for Mineral Carbonation

    SciTech Connect

    White, Mark D.; McGrail, B. Peter; Schaef, Herbert T.; Hu, Jian Z.; Hoyt, David W.; Felmy, Andrew R.; Rosso, Kevin M.; Wurstner, Signe K.

    2011-04-01

    Carbonation of formation minerals converts low viscosity supercritical CO2 injected into deep saline reservoirs for geologic sequestration into an immobile form. Until recently the scientific focus of mineralization reactions with reservoir rocks has been those that follow an aqueous-mediated dissolution/precipitation mechanism, driven by the sharp reduction in pH that occurs with CO2 partitioning into the aqueous phase. For sedimentary basin formations the kinetics of aqueous-mediated dissolution/precipitation reactions are sufficiently slow to make the role of mineralization trapping insignificant over a century period. For basaltic saline formations aqueous-phase mineralization progresses at a substantially higher rate, making the role of mineralization trapping significant, if not dominant, over a century period. The overlooked mineralization reactions for both sedimentary and basaltic saline formations, however, are those that occur in liquid or supercritical CO2 phase; where, dissolved water appears to play a catalyst role in the formation of carbonate minerals. A model is proposed in this paper that describes mineral carbonation over sequestration reservoir conditions ranging from dissolved CO2 in aqueous brine to dissolved water in supercritical CO2. The model theory is based on a review of recent experiments directed at understanding the role of water in mineral carbonation reactions of interest in geologic sequestration systems occurring under low water contents.

  8. Impacts of Nickel Nanoparticles on Mineral Carbonation

    PubMed Central

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

    2014-01-01

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

  9. Impacts of nickel nanoparticles on mineral carbonation.

    PubMed

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

    2014-01-01

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

  10. Carbon K-edge Spectra of Carbonate Minerals

    SciTech Connect

    Brandes, J.; Wirick, S; Jacobsen, C

    2010-01-01

    Carbon K-edge X-ray spectroscopy has been applied to the study of a wide range of organic samples, from polymers and coals to interstellar dust particles. Identification of carbonaceous materials within these samples is accomplished by the pattern of resonances in the 280-320 eV energy region. Carbonate minerals are often encountered in the study of natural samples, and have been identified by a distinctive resonance at 290.3 eV. Here C K-edge and Ca L-edge spectra from a range of carbonate minerals are presented. Although all carbonates exhibit a sharp 290 eV resonance, both the precise position of this resonance and the positions of other resonances vary among minerals. The relative strengths of the different carbonate resonances also vary with crystal orientation to the linearly polarized X-ray beam. Intriguingly, several carbonate minerals also exhibit a strong 288.6 eV resonance, consistent with the position of a carbonyl resonance rather than carbonate. Calcite and aragonite, although indistinguishable spectrally at the C K-edge, exhibited significantly different spectra at the Ca L-edge. The distinctive spectral fingerprints of carbonates provide an identification tool, allowing for the examination of such processes as carbon sequestration in minerals, Mn substitution in marine calcium carbonates (dolomitization) and serpentinization of basalts.

  11. Defining reactive sites on hydrated mineral surfaces: Rhombohedral carbonate minerals

    NASA Astrophysics Data System (ADS)

    Villegas-Jiménez, Adrián; Mucci, Alfonso; Pokrovsky, Oleg S.; Schott, Jacques

    2009-08-01

    Despite the success of surface complexation models (SCMs) to interpret the adsorptive properties of mineral surfaces, their construct is sometimes incompatible with fundamental chemical and/or physical constraints, and thus, casts doubts on the physical-chemical significance of the derived model parameters. In this paper, we address the definition of primary surface sites (i.e., adsorption units) at hydrated carbonate mineral surfaces and discuss its implications to the formulation and calibration of surface equilibria for these minerals. Given the abundance of experimental and theoretical information on the structural properties of the hydrated (10.4) cleavage calcite surface, this mineral was chosen for a detailed theoretical analysis of critical issues relevant to the definition of primary surface sites. Accordingly, a single, generic charge-neutral surface site ( tbnd CaCO 3·H 2O 0) is defined for this mineral whereupon mass-action expressions describing adsorption equilibria were formulated. The one-site scheme, analogous to previously postulated descriptions of metal oxide surfaces, allows for a simple, yet realistic, molecular representation of surface reactions and provides a generalized reference state suitable for the calculation of sorption equilibria for rhombohedral carbonate minerals via Law of Mass Action (LMA) and Gibbs Energy Minimization (GEM) approaches. The one-site scheme is extended to other rhombohedral carbonate minerals and tested against published experimental data for magnesite and dolomite in aqueous solutions. A simplified SCM based on this scheme can successfully reproduce surface charge, reasonably simulate the electrokinetic behavior of these minerals, and predict surface speciation agreeing with available spectroscopic data. According to this model, a truly amphoteric behavior is displayed by these surfaces across the pH scale but at circum-neutral pH (5.8-8.2) and relatively high ΣCO 2 (⩾1 mM), proton/bicarbonate co

  12. Modeling flow of mineralized carbon dioxide slurry

    SciTech Connect

    Penner, Larry R.; Dahlin, David C.; Gerdemann, Stephen J.; Saha, K.K.

    2005-04-01

    Direct mineral carbonation was investigated at Albany Research Center (US DOE) as a means to sequester carbon dioxide into stable mineral matrices. Although previous work focused on treating Mg-containing minerals in conventional autoclaves, recent work has been done using pipeline-reactor technology for the high-temperature, high-pressure (HTHP) reaction of the minerals in aqueous/CO2 media. Sequestration of CO2 using above-ground reactors may be uneconomical, but the technology may also be applicable in geological sequestration of CO2. Progress is described in using a prototype HTHP flow-loop reactor to model flow in the dynamic three-phase system to help determine the pumping-energy requirements to optimize reactivity.

  13. [Organic carbon and carbon mineralization characteristics in nature forestry soil].

    PubMed

    Yang, Tian; Dai, Wei; An, Xiao-Juan; Pang, Huan; Zou, Jian-Mei; Zhang, Rui

    2014-03-01

    Through field investigation and indoor analysis, the organic carbon content and organic carbon mineralization characteristics of six kinds of natural forest soil were studied, including the pine forests, evergreen broad-leaved forest, deciduous broad-leaved forest, mixed needle leaf and Korean pine and Chinese pine forest. The results showed that the organic carbon content in the forest soil showed trends of gradual decrease with the increase of soil depth; Double exponential equation fitted well with the organic carbon mineralization process in natural forest soil, accurately reflecting the mineralization reaction characteristics of the natural forest soil. Natural forest soil in each layer had the same mineralization reaction trend, but different intensity. Among them, the reaction intensity in the 0-10 cm soil of the Korean pine forest was the highest, and the intensities of mineralization reaction in its lower layers were also significantly higher than those in the same layers of other natural forest soil; comparison of soil mineralization characteristics of the deciduous broad-leaved forest and coniferous and broad-leaved mixed forest found that the differences of litter species had a relatively strong impact on the active organic carbon content in soil, leading to different characteristics of mineralization reaction.

  14. Estimation of palaeohydrochemical conditions using carbonate minerals

    NASA Astrophysics Data System (ADS)

    Amamiya, H.; Mizuno, T.; Iwatsuki, T.; Yuguchi, T.; Murakami, H.; Saito-Kokubu, Y.

    2014-12-01

    The long-term evolution of geochemical environment in deep underground is indispensable research subject for geological disposal of high-level radioactive waste, because the evolution of geochemical environment would impact migration behavior of radionuclides in deep underground. Many researchers have made efforts previously to elucidate the geochemical environment within the groundwater residence time based on the analysis of the actual groundwater. However, it is impossible to estimate the geochemical environment for the longer time scale than the groundwater residence time in this method. In this case, analysis of the chemical properties of secondary minerals are one of useful method to estimate the paleohydrochemical conditions (temperature, salinity, pH and redox potential). In particular, carbonate minerals would be available to infer the long-term evolution of hydrochemical for the following reasons; -it easily reaches chemical equilibrium with groundwater and precipitates in open space of water flowing path -it reflects the chemical and isotopic composition of groundwater at the time of crystallization We reviewed the previous studies on carbonate minerals and geochemical conditions in deep underground and estimated the hydrochemical characteristics of past groundwater by using carbonate minerals. As a result, it was found that temperature and salinity of the groundwater during crystallization of carbonate minerals were evaluated quantitatively. On the other hand, pH and redox potential can only be understood qualitatively. However, it is suggested that the content of heavy metal elements such as manganese, iron and uranium, and rare earth elements in the carbonate minerals are useful indicators for estimating redox potential. This study was carried out under a contract with METI (Ministry of Economy, Trade and Industry) as part of its R&D supporting program for developing geological disposal technology.

  15. Carbon dioxide sequestration by direct aqueous mineral carbonation

    SciTech Connect

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

    2000-01-01

    Carbon dioxide sequestration by an ex-situ, direct aqueous mineral carbonation process has been investigated over the past two years. This process was conceived to minimize the steps in the conversion of gaseous CO2 to a stable solid. This meant combining two separate reactions, mineral dissolution and carbonate precipitation, into a single unit operation. It was recognized that the conditions favorable for one of these reactions could be detrimental to the other. However, the benefits for a combined aqueous process, in process efficiency and ultimately economics, justified the investigation. The process utilizes a slurry of water, dissolved CO2, and a magnesium silicate mineral, such as olivine [forsterite end member (Mg2SiO4)], or serpentine [Mg3Si2O5(OH)4]. These minerals were selected as the reactants of choice for two reasons: (1) significant abundance in nature; and (2) high molar ratio of the alkaline earth oxides (CaO, MgO) within the minerals. Because it is the alkaline earth oxide that combines with CO2 to form the solid carbonate, those minerals with the highest ratio of these oxides are most favored. Optimum results have been achieved using heat pretreated serpentine feed material, sodium bicarbonate and sodium chloride additions to the solution, and high partial pressure of CO2 (PCO2). Specific conditions include: 155?C; PCO2=185 atm; 15% solids. Under these conditions, 78% conversion of the silicate to the carbonate was achieved in 30 minutes. Future studies are intended to investigate various mineral pretreatment options, the carbonation solution characteristics, alternative reactants, scale-up to a continuous process, geochemical modeling, and process economics.

  16. Mineral Carbonation Employing Ultramafic Mine Waste

    NASA Astrophysics Data System (ADS)

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

    2014-12-01

    Carbonate minerals are an important, stable carbon sink being investigated as a strategy to sequester CO2 produced by human activity. A natural playa (Atlin, BC, CAN) that has demonstrated the ability to microbially-accelerate hydromagnesite formation was used as an experimental model. Growth of microbial mats from Atlin, in a 10 m long flow-through bioreactor catalysed hydromagnesite precipitation under 'natural' conditions. To enhance mineral carbonation, chrysotile from the Clinton Creek Asbestos Mine (YT, CAN) was used as a target substrate for sulphuric acid leaching, releasing as much as 94% of the magnesium into solution via chemical weathering. This magnesium-rich 'feedstock' was used to examine the ability of the microbialites to enhance carbonate mineral precipitation using only atmospheric CO2 as the carbon source. The phototrophic consortium catalysed the precipitation of platy hydromagnesite [Mg5(CO3)4(OH)2·4H2O] accompanied by magnesite [MgCO3], aragonite [CaCO3], and minor dypingite [Mg5(CO3)4(OH)2·5H2O]. Scanning Electron Microscopy-Energy Dispersive Spectroscopy indicated that cell exteriors and extracellular polymeric substances (EPS) served as nucleation sites for carbonate precipitation. In many cases, entire cyanobacteria filaments were entombed in magnesium carbonate coatings, which appeared to contain a framework of EPS. Cell coatings were composed of small crystals, which intuitively resulted from rapid crystal nucleation. Excess nutrient addition generated eutrophic conditions in the bioreactor, resulting in the growth of a pellicle that sealed the bioreactor contents from the atmosphere. The resulting anaerobic conditions induced fermentation and subsequent acid generation, which in turn caused a drop in pH to circumneutral values and a reduction in carbonate precipitation. Monitoring of the water chemistry conditions indicated that a high pH (> 9.4), and relatively high concentrations of magnesium (> 3000 ppm), compared with the natural

  17. Carbon dioxide sequestration by aqueous mineral carbonation of magnesium silicate minerals

    SciTech Connect

    Gerdemann, Stephen J.; Dahlin, David C.; O'Connor, William K.; Penner, Larry R.

    2003-01-01

    The dramatic increase in atmospheric carbon dioxide since the Industrial Revolution has caused concerns about global warming. Fossil-fuel-fired power plants contribute approximately one third of the total human-caused emissions of carbon dioxide. Increased efficiency of these power plants will have a large impact on carbon dioxide emissions, but additional measures will be needed to slow or stop the projected increase in the concentration of atmospheric carbon dioxide. By accelerating the naturally occurring carbonation of magnesium silicate minerals it is possible to sequester carbon dioxide in the geologically stable mineral magnesite (MgCO3). The carbonation of two classes of magnesium silicate minerals, olivine (Mg2SiO4) and serpentine (Mg3Si2O5(OH)4), was investigated in an aqueous process. The slow natural geologic process that converts both of these minerals to magnesite can be accelerated by increasing the surface area, increasing the activity of carbon dioxide in the solution, introducing imperfections into the crystal lattice by high-energy attrition grinding, and in the case of serpentine, by thermally activating the mineral by removing the chemically bound water. The effect of temperature is complex because it affects both the solubility of carbon dioxide and the rate of mineral dissolution in opposing fashions. Thus an optimum temperature for carbonation of olivine is approximately 185 degrees C and 155 degrees C for serpentine. This paper will elucidate the interaction of these variables and use kinetic studies to propose a process for the sequestration of the carbon dioxide.

  18. Novel biological approaches to carbon mineralization

    NASA Astrophysics Data System (ADS)

    Power, Ian; Kenward, Paul; Harrison, Anna; Dipple, Gregory; Raudsepp, Mati; Wilson, Siobhan; Southam, Gordon

    2015-04-01

    Innovative approaches for accelerating and manipulating fundamental geochemical processes are necessary to develop carbon mineralization as a viable strategy for the mitigation of greenhouse gas emissions. Mg-carbonate formation is of interest for both ex situ and in situ CO2 sequestration strategies1. Accordingly, we have investigated approaches to accelerate these water-rock reactions that produce Mg-carbonate minerals using biological approaches. For instance, CO2-limited conditions are encountered in many systems relevant to CO2 sequestration and represent a severe limitation on carbon mineralization. In carbonation experiments, the supply of CO2 was increased with the use of carbonic anhydrase, an enzyme that catalyzes the hydration of aqueous CO2. The presence of carbonic anhydrase had a dramatic impact on carbonation rates of brucite [Mg(OH)2]2, a mineral of interest for carbon sequestration3. In a CO2-rich aqueous environment, cyanobacteria were able to induce hydrated Mg-carbonate precipitation in microcosm experiments through the alkalinization of their microenvironment and concentration of cations on their cell membranes, which also provide regularly spaced, chemically identical sites for mineral nucleation4. In both lines of investigation, the resulting precipitates were metastable hydrated Mg-carbonate minerals rather then magnesite [MgCO3], the most stable Mg-carbonate and therefore the preferred product forsequestering CO2. Consequently, we have investigated approaches to improve magnesite precipitation rate in these low temperature environments. Inopportunely, rates of magnesite precipitation are severely limited at temperatures below 60 ° C due to the strong hydration of Mg2+ ions in solution5. Yet, carboxyl functional groups (R-COOH) are able to cause desolvation of Mg2+ ions6,7. In microcosm experiments using polystyrene microspheres with a high density of carboxyl groups, we were able to precipitate magnesite at room temperature from slightly

  19. Carbon dioxide sequestration in cement kiln dust through mineral carbonation.

    PubMed

    Huntzinger, Deborah N; Gierke, John S; Kawatra, S Komar; Eisele, Timothy C; Sutter, Lawrence L

    2009-03-15

    Carbon sequestration through the formation of carbonates is a potential means to reduce CO2 emissions. Alkaline industrial solid wastes typically have high mass fractions of reactive oxides that may not require preprocessing, making them an attractive source material for mineral carbonation The degree of mineral carbonation achievable in cement kiln dust (CKD) underambienttemperatures and pressures was examined through a series of batch and column experiments. The overall extent and potential mechanisms and rate behavior of the carbonation process were assessed through a complementary set of analytical and empirical methods, including mass change, thermal analysis, and X-ray diffraction. The carbonation reactions were carried out primarily through the reaction of CO2 with Ca(OH)2, and CaCO3 was observed as the predominant carbonation product. A sequestration extent of over 60% was observed within 8 h of reaction without any modifications to the waste. Sequestration appears to follow unreacted core model theory where reaction kinetics are controlled by a first-order rate constant at early times; however, as carbonation progresses, the kinetics of the reaction are attenuated by the extent of the reaction due to diffusion control, with the extent of conversion never reaching completion.

  20. Carbon dioxide sequestration in cement kiln dust through mineral carbonation

    SciTech Connect

    Deborah N. Huntzinger; John S. Gierke; S. Komar Kawatra; Timothy C. Eisele; Lawrence L. Sutter

    2009-03-15

    Carbon sequestration through the formation of carbonates is a potential means to reduce CO{sub 2} emissions. Alkaline industrial solid wastes typically have high mass fractions of reactive oxides that may not require preprocessing, making them an attractive source material for mineral carbonation. The degree of mineral carbonation achievable in cement kiln dust (CKD) under ambient temperatures and pressures was examined through a series of batch and column experiments. The overall extent and potential mechanisms and rate behavior of the carbonation process were assessed through a complementary set of analytical and empirical methods, including mass change, thermal analysis, and X-ray diffraction. The carbonation reactions were carried out primarily through the reaction of CO{sub 2} with Ca(OH){sub 2}, and CaCO{sub 3} was observed as the predominant carbonation product. A sequestration extent of over 60% was observed within 8 h of reaction without any modifications to the waste. Sequestration appears to follow unreacted core model theory where reaction kinetics are controlled by a first-order rate constant at early times; however, as carbonation progresses, the kinetics of the reaction are attenuated by the extent of the reaction due to diffusion control, with the extent of conversion never reaching completion. 35 refs., 3 figs., 1 tab.

  1. SkyMine Carbon Mineralization Pilot Project

    SciTech Connect

    Christenson, Norm; Walters, Jerel

    2014-12-31

    This Topical Report addresses accomplishments achieved during Phase 2b of the SkyMine® Carbon Mineralization Pilot Project. The primary objectives of this project are to design, construct, and operate a system to capture CO2 from a slipstream of flue gas from a commercial coal-fired cement kiln, convert that CO2 to products having commercial value (i.e., beneficial use), show the economic viability of the CO2 capture and conversion process, and thereby advance the technology to the point of readiness for commercial scale demonstration and deployment. The overall process is carbon negative, resulting in mineralization of CO2 that would otherwise be released into the atmosphere. The project will also substantiate market opportunities for the technology by sales of chemicals into existing markets, and identify opportunities to improve technology performance and reduce costs at the commercial scale. The project is being conducted in two phases. The primary objectives of Phase 1 were to evaluate proven SkyMine® process chemistry for commercial pilot-scale operation and complete the preliminary design for the pilot plant to be built and operated in Phase 2, complete a NEPA evaluation, and develop a comprehensive carbon life cycle analysis. The objective of Phase 2b was to build the pilot plant to be operated and tested in Phase 2c.

  2. Mineral Carbonation Feasibility, an Economic Approach.

    NASA Astrophysics Data System (ADS)

    Pasquier, L. C.; Kemache, N.; Cecchi, E.; Mercier, G.; Blais, J. F.; Kentish, S.

    2016-12-01

    Mineral Carbonation (MC) is one of the ways proposed to mitigate Carbon dioxide (CO2) emissions. Although it intends to transform CO2 into a stable and inert carbonate by reacting it with any divalent containing material, MC is still globally seen as an unrealistic methodology to reduce CO2, mostly because carbonation was seen as a sequestration technique only (after CO2 capture). Nevertheless, recent studies considered and showed the feasibility of an integrated capture/storage approach. Thus, MC can be adapted to flue gas or other industrial gas streams more or less concentrated in CO2. Furthermore, carbonation can be applied to various problematics and offers the advantage to be feasible with a broad range of feedstock such as alkaline industrial or mining residues. Using an economic approach where by-product valorization is favored, interesting approaches were identified. More specifically, the particular case of the Québec province shows that different synergies between wastes and industries can be elaborated. The results indicate that MC can be seen as a practical approach to both reduce CO2 emissions and enhance waste remediation. For instance, the feasibility to export significant amounts of serpentinite mining residue to distant industrial sites using the St Lawrence maritime route was demonstrated. Here the applicability stands on the high value of the generated by-products. On the other hand, steel slags or waste concrete need more local applications due to their limited reaction efficiencies and the lower price of calcium carbonates. While transportation is a major factor for the OPEX cost, the profitability relies on the by-products potential sale. Indeed, the production of low carbon footprint materials from the reaction product will also expand the offer of CO2 utilization avenues. The presentation highlights the results of research made in the lab and using economic modeling to draw a portrait of the opportunities and challenges identified with

  3. Relationship between carbon and nitrogen mineralization in a subtropical soil

    NASA Astrophysics Data System (ADS)

    Li, Qianru; Sun, Yue; Zhang, Xinyu; Xu, Xingliang; Kuzyakov, Yakov

    2014-05-01

    In most soils, more than 90% nitrogen is bonded with carbon in organic forms. This indicates that carbon mineralization should be closely coupled with nitrogen mineralization, showing a positive correlation between carbon and nitrogen mineralization. To test this hypothesis above, we conducted an incubation using a subtropical soil for 10 days at 15 °C and 25 °C. 13C-labeled glucose and 15N-labeled ammonium or nitrate was used to separate CO2 and mineral N released from mineralization of soil organic matter and added glucose or inorganic nitrogen. Phospholipid fatty acid (PLFA) and four exoenzymes (i.e. β-1,4- Glucosaminidase, chitinase, acid phosphatase, β-1,4-N- acetyl glucosamine glycosidase) were also analyzed to detect change in microbial activities during the incubation. Our results showed that CO2 release decreased with increasing nitrogen mineralization rates. Temperature did not change this relationship between carbon and nitrogen mineralization. Although some changes in PLFA and the four exoenzymes were observed, these changes did not contribute to changes in carbon and nitrogen mineralization. These findings indicates that carbon and nitrogen mineralization in soil are more complicated than as previously expected. Future investigation should focus on why carbon and nitrogen mineralization are coupled in a negative correlation not in a positive correlation in many soils for a better understanding of carbon and nitrogen transformation during their mineralization.

  4. CARBON DIOXIDE SEQUESTRATION BY MECHANOCHEMICAL CARBONATION OF MINERAL SILICATES

    SciTech Connect

    Michael G. Nelson

    2004-04-01

    The University of Utah and the University of Idaho investigated the carbonation of silicate minerals by mechanochemical processing. This method uses intense grinding, and has the potential of being much less expensive than other methods of mineral sequestration. Tests were conducted in three types of grinding devices. In these tests, natural and synthetic silicate compounds were ground for varying times in the presence of gaseous CO{sub 2}. A significant change takes place in the lizardite variety of serpentine after 15 to 20 minutes of intense grinding in the presence of gaseous CO{sub 2}. The X-ray diffraction spectrum of lizardite thus treated was much different than that of the untreated mineral. This spectrum could not be identified as that of any natural or synthetic material. Laboratory analyses showed that small amounts of carbon are fixed by grinding lizardite, forsterite, and wollastonite (all naturally-occurring minerals), and synthetic magnesium silicate, in the presence of gaseous CO{sub 2}. It was thus concluded that further investigation was warranted, and a follow-up proposal was submitted to the Department of Energy under solicitation number.

  5. Carbon mineralization in the southern Sonoran Desert

    NASA Astrophysics Data System (ADS)

    Núñez, Silvia; Martínez-Yrízar, Angelina; Búrquez, Alberto; García-Oliva, Felipe

    2001-12-01

    We measured carbon mineralization in four different desert habitats (Arroyos, Hillsides, Canopies-Plains and Open-Plains) and the separate effect of litter addition from annual and perennial plants on soil microbial respiration using two laboratory soil incubation experiments. The differences in total aboveground phytomass among habitats correlates with soil nutrient content, soil particulate organic matter (POM) and consequently, C mineralization. The Arroyos habitat with the highest perennial plant phytomass and litter production, had the highest soil nutrient content, soil POM and C mineralization. Litter from annual plants had twice the P concentration than litter from the perennials, but only half the N concentration. Soil microbial respiration was higher with annual plant litter than with perennial plant litter in the Hillsides and Canopies-Plains, suggesting that microbial activity in both habitats was improved by litter with a higher C quality. In contrast, in the poorest habitat, the Open-Plains, the better response to the addition of perennial plant litter suggests that microbial activity may have been constrained by N input.

  6. Integrating Steel Production with Mineral Carbon Sequestration

    SciTech Connect

    Klaus Lackner; Paul Doby; Tuncel Yegulalp; Samuel Krevor; Christopher Graves

    2008-05-01

    The objectives of the project were (i) to develop a combination iron oxide production and carbon sequestration plant that will use serpentine ores as the source of iron and the extraction tailings as the storage element for CO2 disposal, (ii) the identification of locations within the US where this process may be implemented and (iii) to create a standardized process to characterize the serpentine deposits in terms of carbon disposal capacity and iron and steel production capacity. The first objective was not accomplished. The research failed to identify a technique to accelerate direct aqueous mineral carbonation, the limiting step in the integration of steel production and carbon sequestration. Objective (ii) was accomplished. It was found that the sequestration potential of the ultramafic resource surfaces in the US and Puerto Rico is approximately 4,647 Gt of CO2 or over 500 years of current US production of CO2. Lastly, a computer model was developed to investigate the impact of various system parameters (recoveries and efficiencies and capacities of different system components) and serpentinite quality as well as incorporation of CO2 from sources outside the steel industry.

  7. A NOVEL APPROACH TO MINERAL CARBONATION: ENHANCING CARBONATION WHILE AVOIDING MINERAL PRETREATMENT PROCESS COST

    SciTech Connect

    Michael J. McKelvy; Andrew V.G. Chizmeshya; Kyle Squires; Ray W. Carpenter; Hamadallah Bearat

    2005-10-01

    Known fossil fuel reserves, especially coal, can support global energy demands for centuries to come, if the environmental problems associated with CO{sub 2} emissions can be overcome. Unlike other CO{sub 2} sequestration candidate technologies that propose long-term storage, mineral sequestration provides permanent disposal by forming geologically stable mineral carbonates. Carbonation of the widely occurring mineral olivine (e.g., forsterite, Mg{sub 2}SiO{sub 4}) is a large-scale sequestration process candidate for regional implementation, which converts CO{sub 2} into the environmentally benign mineral magnesite (MgCO{sub 3}). The primary goal is cost-competitive process development. As the process is exothermic, it inherently offers low-cost potential. Enhancing carbonation reactivity is key to economic viability. Recent studies at the U.S. DOE Albany Research Center have established that aqueous-solution carbonation using supercritical CO{sub 2} is a promising process; even without olivine activation, 30-50% carbonation has been achieved in an hour. Mechanical activation (e.g., attrition) has accelerated the carbonation process to an industrial timescale (i.e., near completion in less than an hour), at reduced pressure and temperature. However, the activation cost is too high to be economical and lower cost pretreatment options are needed. Herein, we report our first year progress in exploring a novel approach that offers the potential to substantially enhance carbonation reactivity while bypassing pretreatment activation. We have discovered that robust silica-rich passivating layers form on the olivine surface during carbonation. As carbonation proceeds, these passivating layers thicken, fracture and eventually exfoliate, exposing fresh olivine surfaces during rapidly-stirred/circulating carbonation. We are exploring the mechanisms that govern carbonation reactivity and the impact that (1) modeling/controlling the slurry fluid-flow conditions, (2) varying the

  8. Mineral Availability as a Key Regulator of Soil Carbon Storage.

    PubMed

    Yu, Guanghui; Xiao, Jian; Hu, Shuijin; Polizzotto, Matthew L; Zhao, Fangjie; McGrath, Steve P; Li, Huan; Ran, Wei; Shen, Qirong

    2017-05-02

    Mineral binding is a major mechanism for soil carbon (C) stabilization, and mineral availability for C binding critically affects C storage. Yet, the mechanisms regulating mineral availability are poorly understood. Here, we showed that organic amendments in three long-term (23, 154, and 170 yrs, respectively) field experiments significantly increased mineral availability, particularly of short-range-ordered (SRO) phases. Two microcosm studies demonstrated that the presence of roots significantly increased mineral availability and promoted the formation of SRO phases. Mineral transformation experiments and isotopic labeling experiments provided direct evidence that citric acid, a major component of root exudates, promoted the formation of SRO minerals, and that SRO minerals acted as "nuclei" for C retention. Together, these findings indicate that soil organic amendments initialize a positive feedback loop by increasing mineral availability and promoting the formation of SRO minerals for further C binding, thereby possibly serving as a management tool for enhancing carbon storage in soils.

  9. Reactor design considerations in mineral sequestration of carbon dioxide

    SciTech Connect

    Ityokumbul, M.T.; Chander, S.; O'Connor, William K.; Dahlin, David C.; Gerdemann, Stephen J.

    2001-01-01

    One of the promising approaches to lowering the anthropogenic carbon dioxide levels in the atmosphere is mineral sequestration. In this approach, the carbon dioxide reacts with alkaline earth containing silicate minerals forming magnesium and/or calcium carbonates. Mineral carbonation is a multiphase reaction process involving gas, liquid and solid phases. The effective design and scale-up of the slurry reactor for mineral carbonation will require careful delineation of the rate determining step and how it changes with the scale of the reactor. The shrinking core model was used to describe the mineral carbonation reaction. Analysis of laboratory data indicates that the transformations of olivine and serpentine are controlled by chemical reaction and diffusion through an ash layer respectively. Rate parameters for olivine and serpentine carbonation are estimated from the laboratory data.

  10. Energy and economic evaluation of ex situ aqueous mineral carbonation

    SciTech Connect

    O'Connor, William K.; Dahlin, David C.; Rush, Gilbert E.; Gerdemann, Stephen J.; Penner, Larry R.

    2004-09-01

    Aqueous mineral carbonation has been studied at the Albany Research Center as a potential option for CO2 sequestration. Studies have focused on the reaction of Ca-, Fe-, and Mg-silicate minerals with gaseous CO2 to form geologically stable, naturally occurring solid carbonate minerals. Process development has progressed in parallel with a process evaluation study, which was conducted for a mineral carbonation unit scaled to sequester 100% of the CO2 emissions from a 1.3 GW coal-fired power plant. The carbonation plant would require roughly 55 kt/day of mineral reactant to carbonate about 24 kt/day of CO2. The overall cost estimate was approximately $54(US)/ton CO2 sequestered. The power requirement determined for the mineral carbonation unit was about 352 MW, which represents 27% of the net power plant output. Improved mineral pretreatment and reactor design indicate that costs could be reduced by improvements to the reaction efficiency. However, because the material balance is dependent on the stoichiometry of the reaction, the chemistry of the silicate ore reactants, as well as the rection efficiency, the silicate ore demand cannot be reduced beyond a theoretical ratio of about 2:1, silicate ore to CO2. Based on these factors, mineral carbonation may be best suited as a niche option for sequestration, where CO2 point sources coincide with sources of the desired mineral reactants, and may also favor an in situ methodology. Laboratory studies of in situ carbonation have shown promise.

  11. A Novel Approach To Mineral Carbonation: Enhancing Carbonation While Avoiding Mineral Pretreatment Process Cost

    SciTech Connect

    Michael J. McKelvy; Andrew V. G. Chizmeshya; Kyle Squires; Ray W. Carpenter; Hamdallah Bearat

    2006-06-21

    Known fossil fuel reserves, especially coal, can support global energy demands for centuries to come, if the environmental problems associated with CO{sub 2} emissions can be overcome. Unlike other CO{sub 2} sequestration candidate technologies that propose long-term storage, mineral sequestration provides permanent disposal by forming geologically stable mineral carbonates. Carbonation of the widely occurring mineral olivine (e.g., forsterite, Mg{sub 2}SiO{sub 4}) is a large-scale sequestration process candidate for regional implementation, which converts CO{sub 2} into the environmentally benign mineral magnesite (MgCO{sub 3}). The primary goal is cost-competitive process development. As the process is exothermic, it inherently offers low-cost potential. Enhancing carbonation reactivity is key to economic viability. Recent studies at the U.S. DOE Albany Research Center have established that aqueous-solution carbonation using supercritical CO{sub 2} is a promising process; even without olivine activation, 30-50% carbonation has been achieved in an hour. Mechanical activation (e.g., attrition) has accelerated the carbonation process to an industrial timescale (i.e., near completion in less than an hour), at reduced pressure and temperature. However, the activation cost is too high to be economical and lower cost pretreatment options are needed. Herein, we report our second year progress in exploring a novel approach that offers the potential to substantially enhance carbonation reactivity while bypassing pretreatment activation. As our second year progress is intimately related to our earlier work, the report is presented in that context to provide better overall understanding of the progress made. We have discovered that robust silica-rich passivating layers form on the olivine surface during carbonation. As carbonation proceeds, these passivating layers thicken, fracture and eventually exfoliate, exposing fresh olivine surfaces during rapidly

  12. Mars Life? - Orange-colored Carbonate Mineral Globules

    NASA Technical Reports Server (NTRS)

    1996-01-01

    This photograph shows orange-colored carbonate mineral globules found in a meteorite, called ALH84001, believed to have once been a part of Mars. These carbonate minerals in the meteorite are believed to have been formed on Mars more than 3.6 billion years ago. Their structure and chemistry suggest that they may have been formed with the assistance of primitive, bacteria-like living organisms. A two-year investigation by a NASA research team found organic molecules, mineral features characteristic of biological activity and possible microscopic fossils inside of carbonate minerals such as these in the meteorite.

  13. SkyMine Carbon Mineralization Pilot Project

    SciTech Connect

    Joe Jones; Clive Barton; Mark Clayton; Al Yablonsky; David Legere

    2010-09-30

    This Topical Report addresses accomplishments achieved during Phase 1 of the SkyMine{reg_sign} Carbon Mineralization Pilot Project. The primary objectives of this project are to design, construct, and operate a system to capture CO{sub 2} from a slipstream of flue gas from a commercial coal-fired cement kiln, convert that CO{sub 2} to products having commercial value (i.e., beneficial use), show the economic viability of the CO{sub 2} capture and conversion process, and thereby advance the technology to a point of readiness for commercial scale demonstration and proliferation. The project will also substantiate market opportunities for the technology by sales of chemicals into existing markets, and identify opportunities to improve technology performance and reduce costs at commercial scale. The primary objectives of Phase 1 of the project were to elaborate proven SkyMine{reg_sign} process chemistry to commercial pilot-scale operation and complete the preliminary design ('Reference Plant Design') for the pilot plant to be built and operated in Phase 2. Additionally, during Phase 1, information necessary to inform a DOE determination regarding NEPA requirements for the project was developed, and a comprehensive carbon lifecycle analysis was completed. These items were included in the formal application for funding under Phase 2. All Phase 1 objectives were successfully met on schedule and within budget.

  14. Factors affecting ex-situ aqueous mineral carbonation using calcium and magnesium silicate minerals

    SciTech Connect

    Gerdemann, Stephen J.; Dahlin, David C.; O'Connor, William K.; Penner, Larry R.; Rush, G.E.

    2004-01-01

    Carbonation of magnesium- and calcium-silicate minerals to form their respective carbonates is one method to sequester carbon dioxide. Process development studies have identified reactor design as a key component affecting both the capital and operating costs of ex-situ mineral sequestration. Results from mineral carbonation studies conducted in a batch autoclave were utilized to design and construct a unique continuous pipe reactor with 100% recycle (flow-loop reactor). Results from the flow-loop reactor are consistent with batch autoclave tests, and are being used to derive engineering data necessary to design a bench-scale continuous pipeline reactor.

  15. Carbonate Mineralization of Volcanic Province Basalts

    SciTech Connect

    Schaef, Herbert T.; McGrail, B. Peter; Owen, Antionette T.

    2010-03-31

    Flood basalts are receiving increasing attention as possible host formations for geologic sequestration of anthropogenic CO2, with studies underway in the United States, India, Iceland, and Canada. As an extension of our previous experiments with Columbia River basalt, basalts from the eastern United States, India, and South Africa were reacted with aqueous dissolved CO2 and aqueous dissolved CO2-H2S mixtures under supercritical CO2 (scCO2) conditions to study the geochemical reactions resulting from injection of CO2 in such formations. The results of these studies are consistent with cation release behavior measured in our previous experiments (in press) for basalt samples tested in single pass flow through dissolution experiments under dilute solution and mildly acidic conditions. Despite the basalt samples having similar bulk chemistry, mineralogy and apparent dissolution kinetics, long-term static experiments show significant differences in rates of mineralization as well as compositions and morphologies of precipitates that form when the basalts are reacted with CO2-saturated water. For example, basalt from the Newark Basin in the United States was by far the most reactive of any basalt tested to date. Carbonate reaction products for the Newark Basin basalt were globular in form and contained significantly more Fe than the secondary carbonates that precipitated on the other basalt samples. In comparison, the post-reacted samples associated with the Columbia River basalts from the United States contained calcite grains with classic dogtooth spar morphology and trace cation substitution (Mg and Mn). Carbonation of the other basalts produced precipitates with compositions that varied chemically throughout the entire testing period. Examination of polished cross sections of the reacted grains by scanning electron microscopy and energy dispersive x-ray spectroscopy show precipitate overgrowths with varying chemical compositions. Compositional differences in the

  16. A Novel Approach to Mineral Carbonation: Enhancing Carbonation While Avoiding Mineral Pretreatment Process Cost

    SciTech Connect

    Andrew V. G. Chizmeshya; Michael J. McKelvy; Kyle Squires; Ray W. Carpenter; Hamdallah Bearat

    2007-06-21

    Known fossil fuel reserves, especially coal, can support global energy demands for centuries to come, if the environmental problems associated with CO{sub 2} emissions can be overcome. Unlike other CO{sub 2} sequestration candidate technologies that propose long-term storage, mineral sequestration provides permanent disposal by forming geologically stable mineral carbonates. Carbonation of the widely occurring mineral olivine (e.g., forsterite, Mg{sub 2}SiO{sub 4}) is a large-scale sequestration process candidate for regional implementation, which converts CO{sub 2} into the environmentally benign mineral magnesite (MgCO{sub 3}). The primary goal is cost-competitive process development. As the process is exothermic, it inherently offers low-cost potential. Enhancing carbonation reactivity is key to economic viability. Recent studies at the U.S. DOE Albany Research Center have established that aqueous-solution carbonation using supercritical CO{sub 2} is a promising process; even without olivine activation, 30-50% carbonation has been achieved in an hour. Mechanical activation (e.g., attrition) has accelerated the carbonation process to an industrial timescale (i.e., near completion in less than an hour), at reduced pressure and temperature. However, the activation cost is too high to be economical and lower cost pretreatment options are needed. We have discovered that robust silica-rich passivating layers form on the olivine surface during carbonation. As carbonation proceeds, these passivating layers thicken, fracture and eventually exfoliate, exposing fresh olivine surfaces during rapidly-stirred/circulating carbonation. We are exploring the mechanisms that govern carbonation reactivity and the impact that (1) modeling/controlling the slurry fluid-flow conditions, (2) varying the aqueous ion species/size and concentration (e.g., Li+, Na+, K+, Rb+, Cl-, HCO{sub 3}{sup -}), and (3) incorporating select sonication offer to enhance exfoliation and carbonation. Thus

  17. Mapping the Mineral Resource Base for Mineral Carbon-Dioxide Sequestration in the Conterminous United States

    USGS Publications Warehouse

    Krevor, S.C.; Graves, C.R.; Van Gosen, B. S.; McCafferty, A.E.

    2009-01-01

    This database provides information on the occurrence of ultramafic rocks in the conterminous United States that are suitable for sequestering captured carbon dioxide in mineral form, also known as mineral carbon-dioxide sequestration. Mineral carbon-dioxide sequestration is a proposed greenhouse gas mitigation technology whereby carbon dioxide (CO2) is disposed of by reacting it with calcium or magnesium silicate minerals to form a solid magnesium or calcium carbonate product. The technology offers a large capacity to permanently store CO2 in an environmentally benign form via a process that takes little effort to verify or monitor after disposal. These characteristics are unique among its peers in greenhouse gas disposal technologies. The 2005 Intergovernmental Panel on Climate Change report on Carbon Dioxide Capture and Storage suggested that a major gap in mineral CO2 sequestration is locating the magnesium-silicate bedrock available to sequester the carbon dioxide. It is generally known that silicate minerals with high concentrations of magnesium are suitable for mineral carbonation. However, no assessment has been made in the United States that details their geographical distribution and extent, nor has anyone evaluated their potential for use in mineral carbonation. Researchers at Columbia University and the U.S. Geological Survey have developed a digital geologic database of ultramafic rocks in the conterminous United States. Data were compiled from varied-scale geologic maps of magnesium-silicate ultramafic rocks. The focus of our national-scale map is entirely on ultramafic rock types, which typically consist primarily of olivine- and serpentine-rich rocks. These rock types are potentially suitable as source material for mineral CO2 sequestration.

  18. Carbon storage at defect sites in mantle mineral analogues

    NASA Astrophysics Data System (ADS)

    Wu, Jun; Buseck, Peter R.

    2013-10-01

    A significant fraction of Earth's carbon resides in the mantle, but the mode of carbon storage presents a long-standing problem. The mantle contains fluids rich in carbon dioxide and methane, carbonate-bearing melts, carbonate minerals, graphite, diamond and carbides, as well as dissolved carbon atoms in metals. However, it is uncertain whether these can sufficiently account for the total amount of carbon thought to be stored in the mantle and the volume of carbon degassed from the mantle at volcanoes. Moreover, such carbon hosts should significantly affect the physical and chemical behaviour of the mantle, including its melting temperature, electrical conductivity and oxidation state. Here we use in situ transmission electron microscopy to measure the storage of carbon within common mantle mineral analogues--nickel-doped lanthanum chromate perovskite and titanium dioxide--in laboratory experiments at high pressure and temperature. We detect elevated carbon concentrations at defect sites in the nanocrystals, maintained at high pressures within annealed carbon nanocages. Specifically, our experiments show that small stacking faults within the mantle analogue materials are effective carbon sinks at mantle conditions, potentially providing an efficient mechanism for carbon storage in the mantle. Furthermore, this carbon can be readily released under lower pressure conditions, and may therefore help to explain carbon release in volcanic eruptions.

  19. Tuning Electrical Conductivity of Inorganic Minerals with Carbon Nanomaterials.

    PubMed

    Kovalchuk, Anton A; Tour, James M

    2015-12-02

    Conductive powders based on Barite or calcium carbonate with chemically converted graphene (CCG) were successfully synthesized by adsorption of graphene oxide (GO) or graphene oxide nanoribbons (GONRs) onto the mineral surfaces and subsequent chemical reduction with hydrazine. The efficient adsorption of GO or GONRs on the surface of Barite and calcium carbonate-based mineral particles results in graphene-wrapped hybrid materials that demonstrate a concentration dependent electrical conductivity that increases with the GO or GONR loading.

  20. Carbon and nitrogen mineralization are decoupled in organo-mineral fractions

    NASA Astrophysics Data System (ADS)

    Bimüller, Carolin; Mueller, Carsten W.; von Lützow, Margit; Kreyling, Olivia; Kölbl, Angelika; Haug, Stephan; Schloter, Michael; Kögel-Knabner, Ingrid

    2015-04-01

    To improve our comprehension how carbon and nitrogen mineralization are linked in soils, we used a controlled laboratory mineralization approach and compared carbon and nitrogen dynamics in the bulk soil and in soil fractions. Topsoil of a Rendzic Leptosol from a beech forest site near Tuttlingen, Germany, was fractionated into three particle size classes: sand (2000 to 20 µm), silt (20 to 2 µm), and clay (< 2 µm). Bulk soil and particle size fractions were incubated for 40 weeks allowing periodic destructive sampling. We monitored carbon and nitrogen mineralization dynamics, and assessed carbon respiration as well as nitrogen mineralization and microbial biomass carbon and nitrogen contents. Soil organic matter in the incubated fractions was considered by a subsequent density fractionation. The chemical composition of selected samples was qualitatively evaluated by 13C-NMR spectroscopy. When summing up the mineralization rates of the single fractions, the values for respired carbon equaled the bulk soil, whereas the mathematical recombination of mineral nitrogen in all fractions was significantly less than in bulk soil. Hence, carbon mineralization was not affected by the damage of the aggregated soil structure via fractionation, whereas nitrogen mineralization was reduced. Fractionation increased the surface area providing accessory mineral surfaces, which allowed new binding of especially nitrogen-rich compounds, besides ammonium fixation via cation exchange. Density fractionation revealed that organic matter in the sand fraction contained mainly particulate organic matter present as light material comprising partly decomposed plant remnants. The organic matter in the clay fraction was mostly adsorbed on mineral surfaces. Organic matter in the sand and in the clay fraction was dominated by O/N-alkyl C indicating low recalcitrance, but the C/N ratio of organic matter narrowed with decreasing particle size. These results also imply that the C/N ratio as well as

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

    SciTech Connect

    2010-07-01

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

  2. Mineral control of soil organic carbon storage and turnover

    NASA Astrophysics Data System (ADS)

    Torn, Margaret S.; Trumbore, Susan E.; Chadwick, Oliver A.; Vitousek, Peter M.; Hendricks, David M.

    1997-09-01

    A large source of uncertainty in present understanding of the global carbon cycle is the distribution and dynamics of the soil organic carbon reservoir. Most of the organic carbon in soils is degraded to inorganic forms slowly, on timescales from centuries to millennia. Soil minerals are known to play a stabilizing role, but how spatial and temporal variation in soil mineralogy controls the quantity and turnover of long-residence-time organic carbon is not well known. Here we use radiocarbon analyses to explore interactions between soil mineralogy and soil organic carbon along two natural gradients-of soil-age and of climate-in volcanic soil environments. During the first ~150,000 years of soil development, the volcanic parent material weathered to metastable, non-crystalline minerals. Thereafter, the amount of non-crystalline minerals declined, and more stable crystalline minerals accumulated. Soil organic carbon content followed a similar trend, accumulating to a maximum after 150,000 years, and then decreasing by 50% over the next four million years. A positive relationship between non-crystalline minerals and organic carbon was also observed in soils through the climate gradient, indicating that the accumulation and subsequent loss of organic matter were largely driven by changes in the millennial scale cycling of mineral-stabilized carbon, rather than by changes in the amount of fast-cycling organic matter or in net primary productivity. Soil mineralogy is therefore important in determining the quantity of organic carbon stored in soil, its turnover time, and atmosphere-ecosystem carbon fluxes during long-term soil development; this conclusion should be generalizable at least to other humid environments.

  3. Carbon Mineralization Using Phosphate and Silicate Ions

    NASA Astrophysics Data System (ADS)

    Gokturk, H.

    2013-12-01

    ions would enhance the absorption of CO2 into the aerosol even more than the singly or doubly charged ions. Ion containing aerosols also help to catalyze reactions between water and CO2. Hydrated phosphate and silicate ions tend to attract hydrogen atoms from neighboring water molecules to reduce the charged state. When there is CO2 in the vicinity of the ion, the remainder of the water molecule which loses the hydrogen(s) reacts with CO2 to form carbonates. (PO4---) + H2O + CO2 -> (HPO3--) + (HCO3-) (SiO4----) + H2O + CO2 -> (HSiO4---) + (HCO3-) (SiO4----) + H2O + CO2 -> (H2SiO4--) + (CO3--) In conclusion, highly charged phosphate and silicate ions dissolved in water and aerosolized into small droplets can facilitate both the capture and the mineralization of CO2. This method would be especially effective in a CO2 rich environment such as the exhaust gas of a combustion process. [1] H. Gokturk, "Geoengineering with Charged Droplets," AGU Fall Meeting, San Francisco 2011 [2] H. Gokturk, "Atomistic Simulation of Sea Spray Particles," AGU Fall Meeting, San Francisco 2012

  4. Carbonate and sulfate minerals in the Chassigny meteorite

    NASA Technical Reports Server (NTRS)

    Wentworth, Susan J.; Gooding, James L.

    1991-01-01

    SO2 and CO2 from pyrolysis and combustion of bulk Chassigny and infrared traces of sulfate and carbonate minerals have been previously reported. Using scanning electron microscopy (SEM) and energy-dispersive x ray spectrometry (EDS), portions of these samples are searched, and a Ca-sulfate/carbonate association is confirmed.

  5. A literature review of actinide-carbonate mineral interactions

    SciTech Connect

    Stout, D.L.; Carroll, S.A.

    1993-10-01

    Chemical retardation of actinides in groundwater systems is a potentially important mechanism for assessing the performance of the Waste Isolation Pilot Plant (WIPP), a facility intended to demonstrate safe disposal of transuranic waste. Rigorous estimation of chemical retardation during transport through the Culebra Dolomite, a water-bearing unit overlying the WIPP, requires a mechanistic understanding of chemical reactions between dissolved elements and mineral surfaces. This report represents a first step toward this goal by examining the literature for pertinent experimental studies of actinide-carbonate interactions. A summary of existing models is given, along with the types of experiments on which these models are based. Articles pertaining to research into actinide interactions with carbonate minerals are summarized. Select articles involving trace element-carbonate mineral interactions are also reviewed and may serve as templates for future research. A bibliography of related articles is included. Americium(III), and its nonradioactive analog neodymium(III), partition strongly from aqueous solutions into carbonate minerals. Recent thermodynamic, kinetic, and surface studies show that Nd is preferentially removed from solution, forming a Nd-Ca carbonate solid solution. Neptunium(V) is rapidly removed from solution by carbonates. Plutonium incorporation into carbonates is complicated by multiple oxidation states. Little research has been done on the radium(H) and thorium(IV) carbonate systems. Removal of uranyl ion from solution by calcite is limited to monolayer surface coverage.

  6. Sequestration of Martian CO2 by mineral carbonation.

    PubMed

    Tomkinson, Tim; Lee, Martin R; Mark, Darren F; Smith, Caroline L

    2013-01-01

    Carbonation is the water-mediated replacement of silicate minerals, such as olivine, by carbonate, and is commonplace in the Earth's crust. This reaction can remove significant quantities of CO2 from the atmosphere and store it over geological timescales. Here we present the first direct evidence for CO2 sequestration and storage on Mars by mineral carbonation. Electron beam imaging and analysis show that olivine and a plagioclase feldspar-rich mesostasis in the Lafayette meteorite have been replaced by carbonate. The susceptibility of olivine to replacement was enhanced by the presence of smectite veins along which CO2-rich fluids gained access to grain interiors. Lafayette was partially carbonated during the Amazonian, when liquid water was available intermittently and atmospheric CO2 concentrations were close to their present-day values. Earlier in Mars' history, when the planet had a much thicker atmosphere and an active hydrosphere, carbonation is likely to have been an effective mechanism for sequestration of CO2.

  7. Microbially mediated mineral carbonation: roles of phototrophy and heterotrophy.

    PubMed

    Power, Ian M; Wilson, Siobhan A; Small, Darcy P; Dipple, Gregory M; Wan, Wankei; Southam, Gordon

    2011-10-15

    Ultramafic mine tailings from the Diavik Diamond Mine, Canada and the Mount Keith Nickel Mine, Western Australia are valuable feedstocks for sequestering CO₂ via mineral carbonation. In microcosm experiments, tailings were leached using various dilute acids to produce subsaline solutions at circumneutral pH that were inoculated with a phototrophic consortium that is able to induce carbonate precipitation. Geochemical modeling of the experimental solutions indicates that up to 2.5% and 16.7% of the annual emissions for Diavik and Mount Keith mines, respectively, could be sequestered as carbonate minerals and phototrophic biomass. CO₂ sequestration rates are mainly limited by cation availability and the uptake of CO₂. Abundant carbonate mineral precipitation occurred when heterotrophic oxidation of acetate acted as an alternative pathway for CO₂ delivery. These experiments highlight the importance of heterotrophy in producing sufficient DIC concentrations while phototrophy causes alkalinization of waters and produces biomass (fatty acids = 7.6 wt.%), a potential feedstock for biofuel production. Tailings storage facilities could be redesigned to promote CO₂ sequestration by directing leachate waters from tailings piles into specially designed ponds where carbonate precipitation would be mediated by both chemical and biological processes, thereby storing carbon in stable carbonate minerals and potentially valuable biomass.

  8. Earthworms facilitate carbon sequestration through unequal amplification of carbon stabilization compared with mineralization.

    PubMed

    Zhang, Weixin; Hendrix, Paul F; Dame, Lauren E; Burke, Roger A; Wu, Jianping; Neher, Deborah A; Li, Jianxiong; Shao, Yuanhu; Fu, Shenglei

    2013-01-01

    A recent review concluded that earthworm presence increases CO₂ emissions by 33% but does not affect soil organic carbon stocks. However, the findings are controversial and raise new questions. Here we hypothesize that neither an increase in CO₂ emission nor in stabilized carbon would entirely reflect the earthworms' contribution to net carbon sequestration. We show how two widespread earthworm invaders affect net carbon sequestration through impacts on the balance of carbon mineralization and carbon stabilization. Earthworms accelerate carbon activation and induce unequal amplification of carbon stabilization compared with carbon mineralization, which generates an earthworm-mediated 'carbon trap'. We introduce the new concept of sequestration quotient to quantify the unequal processes. The patterns of CO₂ emission and net carbon sequestration are predictable by comparing sequestration quotient values between treatments with and without earthworms. This study clarifies an ecological mechanism by which earthworms may regulate the terrestrial carbon sink.

  9. Carbon mineralization pathways and bioturbation in coastal Brazilian sediments

    PubMed Central

    Quintana, Cintia O.; Shimabukuro, Maurício; Pereira, Camila O.; Alves, Betina G. R.; Moraes, Paula C.; Valdemarsen, Thomas; Kristensen, Erik; Sumida, Paulo Y. G.

    2015-01-01

    Carbon mineralization processes and their dependence on environmental conditions (e.g. through macrobenthic bioturbation) have been widely studied in temperate coastal sediments, but almost nothing is known about these processes in subtropical coastal sediments. This study investigated pathways of organic carbon mineralization and associated effects of macrobenthic bioturbation in winter and summer (September 2012 and February 2014) at the SE Brazilian coast. Iron reduction (FeR) was responsible for 73–81% of total microbial carbon mineralization in September 2012 and 32–61% in February 2014. Similar high rates of FeR have only been documented a few times in coastal sediments and can be sustained by the presence of large bioturbators. Denitrification accounted for 5–27% of total microbial carbon mineralization while no SO42− reduction was detected in any season. Redox profiles suggested that conditions were less reduced in February 2014 than in September 2012, probably associated with low reactivity of the organic matter, higher rates of aerobic respiration and bioirrigation by the higher density of small-macrofauna. Bioturbation by small macrofauna may maintain the sediment oxidized in summer, while large-sized species stimulate the reoxidation of reduced compounds throughout the year. Therefore, bioturbation seems to have an important role modulating the pathways of carbon mineralization in the area. PMID:26525137

  10. Experimental study of pattern formation during carbon dioxide mineralization

    NASA Astrophysics Data System (ADS)

    Schuszter, Gabor; Brau, Fabian; de Wit, Anne

    2015-11-01

    Injection of supercritical carbon dioxide in deep porous aquifers, where mineral carbonation takes place via chemical reactions, is one of the possible long-term storage of this greenhouse gas. This mineralization process is investigated experimentally under controlled conditions in a confined horizontal Hele-Shaw geometry where an aqueous solution of sodium carbonate is injected radially into a solution of calcium chloride. Precipitation of calcium carbonate in various finger, flower or tube-like patterns is observed in the mixing zone between the two solutions. These precipitation structures and their growth dynamics are studied quantitatively as a function of the parameters of the problem, which are the injection rate and the reactant concentrations. In particular, we show the existence of critical concentrations of reactants above which the amount of the calcium carbonate precipitate produced drops significantly.

  11. Catalysis of carbon monoxide methanation by deep sea manganate minerals

    NASA Technical Reports Server (NTRS)

    Cabrera, A. L.; Maple, M. B.; Arrhenius, G.

    1990-01-01

    The catalytic activity of deep sea manganese nodule minerals for the methanation of carbon monoxide was measured with a microcatalytic technique between 200 and 460 degrees C. The manganate minerals were activated at 248 degrees C by immersion into a stream of hydrogen in which pulses of carbon monoxide were injected. Activation energies for the methanation reaction and hydrogen desorption from the manganate minerals were obtained and compared with those of pure nickel. Similar energy values indicate that the activity of the nodule materials for the reaction appears to be related to the amount of reducible transition metals present in the samples (ca. 11 wt.-%). Since the activity of the nodule minerals per gram is comparable to that of pure nickel, most of the transition metal ions located between manganese oxide layers appear to be exposed and available to catalyze the reaction.

  12. Catalysis of carbon monoxide methanation by deep sea manganate minerals

    NASA Technical Reports Server (NTRS)

    Cabrera, A. L.; Maple, M. B.; Arrhenius, G.

    1990-01-01

    The catalytic activity of deep sea manganese nodule minerals for the methanation of carbon monoxide was measured with a microcatalytic technique between 200 and 460 degrees C. The manganate minerals were activated at 248 degrees C by immersion into a stream of hydrogen in which pulses of carbon monoxide were injected. Activation energies for the methanation reaction and hydrogen desorption from the manganate minerals were obtained and compared with those of pure nickel. Similar energy values indicate that the activity of the nodule materials for the reaction appears to be related to the amount of reducible transition metals present in the samples (ca. 11 wt.-%). Since the activity of the nodule minerals per gram is comparable to that of pure nickel, most of the transition metal ions located between manganese oxide layers appear to be exposed and available to catalyze the reaction.

  13. Mineral protection of soil carbon counteracted by root exudates [Root exudates counteract mineral control on soil carbon turnover

    SciTech Connect

    Keiluweit, Marco; Bougoure, Jeremy J.; Nico, Peter S.; Pett-Ridge, Jennifer; Weber, Peter K.; Kleber, Markus

    2015-03-30

    Multiple lines of existing evidence suggest that climate change enhances root exudation of organic compounds into soils. Recent experimental studies show that increased exudate inputs may cause a net loss of soil carbon. This stimulation of microbial carbon mineralization (‘priming’) is commonly rationalized by the assumption that exudates provide a readily bioavailable supply of energy for the decomposition of native soil carbon (co-metabolism). Here we show that an alternate mechanism can cause carbon loss of equal or greater magnitude. We find that a common root exudate, oxalic acid, promotes carbon loss by liberating organic compounds from protective associations with minerals. By enhancing microbial access to previously mineral-protected compounds, this indirect mechanism accelerated carbon loss more than simply increasing the supply of energetically more favourable substrates. Lastly, our results provide insights into the coupled biotic–abiotic mechanisms underlying the ‘priming’ phenomenon and challenge the assumption that mineral-associated carbon is protected from microbial cycling over millennial timescales.

  14. Mineral protection of soil carbon counteracted by root exudates [Root exudates counteract mineral control on soil carbon turnover

    DOE PAGES

    Keiluweit, Marco; Bougoure, Jeremy J.; Nico, Peter S.; ...

    2015-03-30

    Multiple lines of existing evidence suggest that climate change enhances root exudation of organic compounds into soils. Recent experimental studies show that increased exudate inputs may cause a net loss of soil carbon. This stimulation of microbial carbon mineralization (‘priming’) is commonly rationalized by the assumption that exudates provide a readily bioavailable supply of energy for the decomposition of native soil carbon (co-metabolism). Here we show that an alternate mechanism can cause carbon loss of equal or greater magnitude. We find that a common root exudate, oxalic acid, promotes carbon loss by liberating organic compounds from protective associations with minerals.more » By enhancing microbial access to previously mineral-protected compounds, this indirect mechanism accelerated carbon loss more than simply increasing the supply of energetically more favourable substrates. Lastly, our results provide insights into the coupled biotic–abiotic mechanisms underlying the ‘priming’ phenomenon and challenge the assumption that mineral-associated carbon is protected from microbial cycling over millennial timescales.« less

  15. Bioleaching of serpentine group mineral by fungus Talaromyces flavus: application for mineral carbonation

    NASA Astrophysics Data System (ADS)

    Li, Z.; Lianwen, L.; Zhao, L.; Teng, H.

    2011-12-01

    Many studies of serpentine group mineral dissolution for mineral carbonation have been published in recent years. However, most of them focus mainly on either physical and chemical processes or on bacterial function, rather than fungal involvement in the bioleaching of serpentine group mineral. Due to the excessive costs of the magnesium dissolution process, finding a lower energy consumption method will be meaningful. A fungal strain Talaromyces flavus was isolated from serpentinic rock of Donghai (China). No study of its bioleaching ability is currently available. It is thus of great significance to explore the impact of T. flavus on the dissolution of serpentine group mineral. Serpentine rock-inhabiting fungi belonging to Acremonium, Alternaria, Aspergillus, Botryotinia, Cladosporium, Clavicipitaceae, Cosmospora, Fusarium, Monascus, Paecilomyces, Penicillium, Talaromyces, Trichoderma were isolated. These strains were chosen on the basis of resistance to magnesium and nickel characterized in terms of minimum inhibiting concentration (MIC). Specifically, the strain Talaromyces flavus has a high tolerance to both magnesium (1 mol/L) and nickel (10 mM/L), and we examine its bioleaching ability on serpentine group mineral. Contact and separation experiments (cut-off 8 000-14 000 Da), as well as three control experiments, were set up for 30 days. At least three repeated tests were performed for each individual experiment. The results of our experiments demonstrate that the bioleaching ability of T. flavus towards serpentine group mineral is evident. 39.39 wt% of magnesium was extracted from lizardite during the bioleaching period in the contact experiment, which showed a dissolution rate at about a constant 0.126 mM/d before reaching equilibrium in 13 days. The amount of solubilized Mg from chrysotile and antigorite were respectively 37.79 wt% and 29.78 wt% in the contact experiment. These results make clear the influence of mineral structure on mineral bioleaching

  16. Applications of mineral carbonation to geological sequestration of CO2

    SciTech Connect

    O'Connor, William K.; Rush, G.E.

    2005-01-01

    Geological sequestration of CO2 is a promising near-term sequestration methodology. However, migration of the CO2 beyond the natural reservoir seals could become problematic, thus the identification of means to enhance the natural seals could prove beneficial. Injection of a mineral reactant slurry could provide a means to enhance the natural reservoir seals by supplying the necessary cations for precipitation of mineral carbonates. The subject study evaluates the merit of several mineral slurry injection strategies by conduct of a series of laboratory-scale CO2 flood tests on whole core samples of the Mt. Simon sandstone from the Illinois Basin.

  17. Stochastic Modeling of Carbon Photo-mineralization along Arctic Rivers

    NASA Astrophysics Data System (ADS)

    Li, A.; Aubeneau, A. F.; King, T.; Cory, R. M.; Neilson, B. T.; Kling, G. W.; Bolster, D.; Packman, A. I.

    2014-12-01

    Permafrost soil stores twice the amount of carbon found in current atmosphere, leading to increasing concern about climate feedbacks due to thawing of organic carbon stored in arctic permafrost. Current climate models assume that CO2 outgassing occurs only at the site of thawing, overlooking the flushing of dissolved organic carbon (DOC) from soils into surface waters, downstream transport, and the associated opportunities for photochemical transformations. To better understand the mechanisms producing CO2 and the effect of water flow on riverine photo-mineralization of DOC, we developed a stochastic particle-tracking model that characterizes the migration of DOC in arctic rivers and the concurrent photo-mineralization during downstream transport. We calibrated the model against field tracer measurements, and then applied the model to analyze the effects of river geometry and flow on rates of photo-mineralization of DOC to CO2 in the Kuparuk River, Alaska. We found that rates of photo-mineralization were dependent on vertical mixing in the water column and average residence times. When flow paths are restricted to areas near and beneath the river bed, where both flow velocity and light availability are low, the overall photo-mineralization of DOC is reduced. Using this model will improve our understanding of the interactions between hydrological and photochemical controls on CO2 production in surface waters, and provide tools that can be used more generally to assess redistribution and transformation of carbon in arctic and global climate models.

  18. Review of Distribution Coefficients for Radionuclides in Carbonate Minerals

    SciTech Connect

    Sutton, M

    2009-08-14

    An understanding of the transport of radionuclides in carbonate minerals is necessary to be able to predict the fate of (and potentially remediate) radionuclides in the environment. In some environments, carbonate minerals such as calciate, aragonite, dolomite and limestone are present and an understanding of the sorption of radionuclides in these carbonate minerals is therefore advantageous. A list of the radionuclides of interest is given in Table 1. The distribution coefficient, K{sub d} is defined as the ratio of the contaminant concentration bound on the solid phase to the contaminant concentration remaining in the liquid phase at equilibrium. Some authors report distribution coefficients and other report partition coefficients, the data presented in this work assumes equality between these two terms, and data are presented and summarized in this work as logarithmic distribution coefficient (log K{sub D}). Published literature was searched using two methods. Firstly, the JNC Sorption Database, namely Shubutani et al (1999), and Suyama and Sasamoto (2004) was used to select elements of interest and a number of carbonate minerals. Secondly, on-line literature search tools were used to locate relevant published articles from 1900 to 2009. Over 300 data points covering 16 elements (hydrogen, carbon, calcium, nickel, strontium, technetium, palladium, iodine, cesium, samarium, europium, holmium, uranium, neptunium, plutonium and americium) were used to calculate an average and range of log K{sub d} values for each element. Unfortunately, no data could be found for chlorine, argon, krypton, zirconium, niobium, tin, thorium and curium. A description of the data is given below, together with the average, standard deviation, minimum, maximum and number of inputs for radionuclide K{sub d} values for calcite, aragonate, limestone, dolomite and unidentified carbonate rocks in Table 2. Finally, the data are condensed into one group (carbonate minerals) of data for each

  19. Rapid carbon mineralization for permanent disposal of anthropogenic carbon dioxide emissions

    NASA Astrophysics Data System (ADS)

    Matter, Juerg M.; Stute, Martin; Snæbjörnsdottir, Sandra Ó.; Oelkers, Eric H.; Gislason, Sigurdur R.; Aradottir, Edda S.; Sigfusson, Bergur; Gunnarsson, Ingvi; Sigurdardottir, Holmfridur; Gunnlaugsson, Einar; Axelsson, Gudni; Alfredsson, Helgi A.; Wolff-Boenisch, Domenik; Mesfin, Kiflom; Taya, Diana Fernandez de la Reguera; Hall, Jennifer; Dideriksen, Knud; Broecker, Wallace S.

    2016-06-01

    Carbon capture and storage (CCS) provides a solution toward decarbonization of the global economy. The success of this solution depends on the ability to safely and permanently store CO2. This study demonstrates for the first time the permanent disposal of CO2 as environmentally benign carbonate minerals in basaltic rocks. We find that over 95% of the CO2 injected into the CarbFix site in Iceland was mineralized to carbonate minerals in less than 2 years. This result contrasts with the common view that the immobilization of CO2 as carbonate minerals within geologic reservoirs takes several hundreds to thousands of years. Our results, therefore, demonstrate that the safe long-term storage of anthropogenic CO2 emissions through mineralization can be far faster than previously postulated.

  20. Rapid carbon mineralization for permanent disposal of anthropogenic carbon dioxide emissions.

    PubMed

    Matter, Juerg M; Stute, Martin; Snæbjörnsdottir, Sandra Ó; Oelkers, Eric H; Gislason, Sigurdur R; Aradottir, Edda S; Sigfusson, Bergur; Gunnarsson, Ingvi; Sigurdardottir, Holmfridur; Gunnlaugsson, Einar; Axelsson, Gudni; Alfredsson, Helgi A; Wolff-Boenisch, Domenik; Mesfin, Kiflom; Fernandez de la Reguera Taya, Diana; Hall, Jennifer; Dideriksen, Knud; Broecker, Wallace S

    2016-06-10

    Carbon capture and storage (CCS) provides a solution toward decarbonization of the global economy. The success of this solution depends on the ability to safely and permanently store CO2 This study demonstrates for the first time the permanent disposal of CO2 as environmentally benign carbonate minerals in basaltic rocks. We find that over 95% of the CO2 injected into the CarbFix site in Iceland was mineralized to carbonate minerals in less than 2 years. This result contrasts with the common view that the immobilization of CO2 as carbonate minerals within geologic reservoirs takes several hundreds to thousands of years. Our results, therefore, demonstrate that the safe long-term storage of anthropogenic CO2 emissions through mineralization can be far faster than previously postulated.

  1. Carbon dioxide sequestration by direct mineral carbonation: process mineralogy of feed and products

    SciTech Connect

    O'Connor, William K.; Dahlin, David C.; Rush, G.E.; Dahlin, Cheryl L.; Collins, W. Keith

    2001-01-01

    Direct mineral carbonation has been investigated as a process to convert gaseous CO2 into a geologically stable final form. The process utilizes a slurry of water, with bicarbonate and salt additions, mixed with a mineral reactant, such as olivine (Mg2SiO4) or serpentine [Mg3Si2O5(OH)4]. Carbon dioxide is dissolved into this slurry, resulting in dissolution of the mineral and precipitation of magnesium carbonate (MgCO3). Optimum results have been achieved using heat pretreated serpentine feed material and high partial pressure of CO2 (PCO2). Specific conditions include: 155?C; PCO2=185 atm; 15% solids. Under these conditions, 78% conversion of the silicate to the carbonate was achieved in 30 minutes. Process mineralogy has been utilized to characterize the feed and process products, and interpret the mineral dissolution and carbonate precipitation reaction paths.

  2. Mineral Carbonation Using Asbestos-Containing Cement Board Waste

    NASA Astrophysics Data System (ADS)

    Yoon, S.; Roh, Y.

    2012-12-01

    Mineral carbonation appears to be one of the plausible methods for the practical fixation of CO2. Carbon consumption and sequestration by carbonation reactions involving alkaline elements such as Ca and Mg have been developed. Suitable feedstocks for CO2 sequestration are mineral carbonation using Ca/Mg-silicates. Asbestos-containing cement board waste consists of chrysotile asbestos which is one of the Mg-silicate and cement. Chrysotile is one of the raw materials to form carbonate mineral for CO2 fixation in previous studies and cement contains a quantity of calcium which is able to react with CO2. Generally, asbestos-containing cement board waste is dumped in controlled waste sites in South Korea. However, this cannot be regarded as an ultimate solution because dispersion of asbestos fibers in the air is an intrinsic risk during dumping operations and in the long-term management. An alternative solution is thermal transformation of asbestos-containing material into non-hazardous phase. Therefore, the aims of the study were to sequester CO2 using asbestos-containing cement board waste via mineral carbonation and to detoxify chrysotile asbestos in cement board waste via heat treatment. Two steps of experiments were designed: (1) synthesis of a carbonate mineral (i.e., calcite and magnesite), via the physicochemical reactions of fragmented cement board with CO2 and (2) transformation of fibrous asbestos into non-fibrous material through heat treatment. Physicochemical and mineralogical properties of cement board waste were investigated by TG-DTA , XRF, XRD, SEM, and EDS analyses. XRD analysis showed that the calcite (CaCO3) was formed after reaction of fragmented cement board with CO2. Mineralogical characteristics showed minerals such as chrysotile [Mg3Si2O5(OH)4] and calcite (CaCO3) in the reactions of fragmented cement board with CO2 were transformed into calcite (CaCO3), calcium oxide (CaO), and quartz (SiO2) by heat treatment. SEM-EDS analyses showed that

  3. Mineralization of Calcium Carbonate on Multifunctional Peptide Assembly Acting as Mineral Source Supplier and Template.

    PubMed

    Murai, Kazuki; Kinoshita, Takatoshi; Nagata, Kenji; Higuchi, Masahiro

    2016-09-13

    Crystal phase and morphology of biominerals may be precisely regulated by controlled nucleation and selective crystal growth through biomineralization on organic templates such as a protein. We herein propose new control factors of selective crystal growth by the biomineralization process. In this study, a designed β-sheet Ac-VHVEVS-CONH2 peptide was used as a multifunctional template that acted as mineral source supplier and having crystal phase control ability of calcium carbonate (CaCO3) during a self-supplied mineralization. The peptides formed three-dimensional nanofiber networks composed of assembled bilayer β-sheets. The assembly hydrolyzed urea molecules to one carbonate anion and two ammonium cations owing to a charge relay effect between His and Ser residues under mild conditions. CaCO3 was selectively mineralized on the peptide assembly using the generated carbonate anions on the template. Morphology of the obtained CaCO3 was fiber-like structure, similar to that of the peptide template. The mineralized CaCO3 on the peptide template had aragonite phase. This implies that CaCO3 nuclei, generated using the carbonate anions produced by the hydrolysis of urea on the surface of the peptide assembly, preferentially grew into aragonite phase, the growth axis of which aligned parallel to the direction of the β-sheet fiber axis.

  4. Coupled Serpentinsation and Carbonation Reaction in Ultrabasic Minerals

    NASA Astrophysics Data System (ADS)

    Dufaud, F.; Martinez, I.; Shilobreeva, S.; Fiquet, G.

    2006-12-01

    Because of its significant atmospheric abundance compared with the other greenhouse gases, CO2 is by far the most important. One of the options to reduce the anthropogenic CO2 emission into the atmosphere is the mineral storage: the process that converts gaseous CO2 into a geologically stable phase, such as a carbonate. Such reactions, however, are characterized by slow kinetics, which have to be measured since it could be the most limiting factor of geochemical storage of CO2. We have carried out carbonation experiments on olivine, serpentine and orthopyroxene under various conditions in an hydraulic press (1-1.7kbar and 400-500°C). Powders (100-200μm grain size) of these minerals were kept in contact with oxalic acid used as a source of CO2 in platinum capsules and reacted at high pressure and temperature. Experiments conducted under such conditions provide large carbonation rates. The amounts of carbonate formed were measured by decarbonation of the reacted material. Chemical and carbon isotopic mass balance calculations were also done in order to provide precise monitoring of carbonation rates. Mineralogical study of the reacted samples using both SEM (Scanning Electron Microscopy) and TEM (Transmission Electron Microscopy) allowed the identification of the dissolution/precipitation carbonation mechanisms and the observation of nanometer sized magnesite crystals, systematically associated to protoserpentine phases. Strong differences in carbonate textures and carbonation rates were measured as a function of the initial mineral, water fugacity and NaCl concentrations. Similarities and differences of these results with experiments carried out under usual CO2 storage conditions in basic and ultrabasic rock will be discussed.

  5. Probing carbonate in bone forming minerals on the nanometre scale.

    PubMed

    Kłosowski, Michał M; Friederichs, Robert J; Nichol, Robert; Antolin, Nikolas; Carzaniga, Raffaella; Windl, Wolfgang; Best, Serena M; Shefelbine, Sandra J; McComb, David W; Porter, Alexandra E

    2015-07-01

    To devise new strategies to treat bone disease in an ageing society, a more detailed characterisation of the process by which bone mineralises is needed. In vitro studies have suggested that carbonated mineral might be a precursor for deposition of bone apatite. Increased carbonate content in bone may also have significant implications in altering the mechanical properties, for example in diseased bone. However, information about the chemistry and coordination environment of bone mineral, and their spatial distribution within healthy and diseased tissues, is lacking. Spatially resolved analytical transmission electron microscopy is the only method available to probe this information at the length scale of the collagen fibrils in bone. In this study, scanning transmission electron microscopy combined with electron energy-loss spectroscopy (STEM-EELS) was used to differentiate between calcium-containing biominerals (hydroxyapatite, carbonated hydroxyapatite, beta-tricalcium phosphate and calcite). A carbon K-edge peak at 290 eV is a direct marker of the presence of carbonate. We found that the oxygen K-edge structure changed most significantly between minerals allowing discrimination between calcium phosphates and calcium carbonates. The presence of carbonate in carbonated HA (CHA) was confirmed by the formation of peak at 533 eV in the oxygen K-edge. These observations were confirmed by simulations using density functional theory. Finally, we show that this method can be utilised to map carbonate from the crystallites in bone. We propose that our calibration library of EELS spectra could be extended to provide spatially resolved information about the coordination environment within bioceramic implants to stimulate the development of structural biomaterials.

  6. Carbonation of Rock Minerals by Supercritical Carbon Dioxide at 250 degrees C.

    SciTech Connect

    Sugama, T.; Ecker, L.; Butcher, T.

    2010-06-01

    Wet powder-samples of five rock minerals, granite, albite, hornblende, diorite, and biotite mica, were exposed in supercritical carbon dioxide (scCO2) for 3 days at 250 C under 17.23 MPa pressure, and then the susceptibility of the various crystalline phases present in these mineral structures to reactions with hot scCO2 was investigated by XRD and FT-IR. The anorthite present in diorite was identified as the most vulnerable phase to carbonation. In contrast, biotite displayed a great resistance, although its phase was transformed hydrothermally to sanidine and quartz. Granite comprised of two phases, anorthoclase-type albite and quartz. The carbonation of former phase led to the formation of amorphous sodium and potassium carbonates coexisting with the clay-like by-products of the carbonation reaction. The reactivity of quartz to scCO2 was minimal, if any. Among these rock minerals, only hornblende formed crystalline carbonation products, such as calcite and magnesite after exposure, reflecting the likelihood of an increase in its volume. Based upon the feldspar ternary diagram, the carbonation rate of various different minerals in the plagioclase feldspar family depended primarily on the amount of anorthite. On the other hand, alkali feldspar minerals involving anorthoclase-type albite and sanidine had a lower reactivity with scCO2, compared with that of plagioclase feldspar minerals.

  7. Direct Use of Mineral Carbonate for Autotrophy Among Euendolithic Cyanobacteria

    NASA Astrophysics Data System (ADS)

    Guida, B. S.

    2015-12-01

    Cyanobacteria are oxygenic photoautotrophs, and arguably the most important primary producers on the planet, fixing carbon from dissolved inorganic carbon (DIC) in the aquatic environment, and directly from atmospheric CO2 in terrestrial systems. Euendolithic cyanobacteria occupy a very specific niche, inside rocks, which can potentially preclude them from easily accessing those carbon pools, and yet, natural euendolithic communities can support food webs in habitats where they are prominent, such as in marine carbonate platforms and desert carbonate outcrops. In a recently proposed model describing the mechanism of cyanobacterial carbonate boring, we postulated that as the organism dissolves the mineral, liberated CO32- anions will be quickly converted to HCO3- and assimilated directly, making the cyanobacterium independent of external DIC pools for autotrophy. We used natural abundance and tracer stable carbon (13C) isotope analyses accompanied by nanoSIMS imaging in model laboratory systems of cultivated cyanobacteria and in natural mixed communities of marine euendoliths to study the ultimate source of carbon in their biomass. Our results clearly demonstrate that endolithic biomass of these cyanobacteria is significantly derived from mineral carbonate, as opposed to free-living or epilithic biomass, where the source is mixed or coming from the dissolved pool, this holds for model cultures as well as natural communities. In fact, we can increase the lifestyle preference of cultures for endolithic growth versus planktonic or benthic growth, by simply imposing an external DIC limitation in the presence of a carbonate substrate. Our results predict that benthic communities (extant or fossil) that rely heavily on primary production by euendolithic primary producers may show 13C signatures that mimic those of the surrounding carbonate substrate rather than from those of the local seawater.

  8. Carbon dioxide sequestration by direct mineral carbonation: process mineralogy of feed and products

    SciTech Connect

    O'Connor, William K.; Dahlin, David C.; Rush, G.E.; Dahlin, Cheryl L.; Collins, W. Keith

    2002-05-01

    Direct mineral carbonation was investigated as a process to convert gaseous CO[2] into a geologically stable final form. The process utilizes a slurry of water, with bicarbonate and salt additions, mixed with a mineral reactant, such as olivine (Mg[2]SiO[4]) or serpentine [Mg[3]Si[2]O[5](OH)[4

  9. Microbial Surfaces and their Effects on Carbonate Mineralization

    NASA Astrophysics Data System (ADS)

    Cappuccio, J. A.; Pillar, V. D.; Lui, G. V.; Ajo-Franklin, C.

    2011-12-01

    Geologic carbon dioxide sequestration, the underground storage of carbon dioxide (CO2), will be an essential component of climate change mitigation. Carbonate minerals are a promising form of stable CO2 storage, but their geologic formation is slow. Many microbes can increase the rate of carbonate mineral formation; however the mechanisms of such mineralization are largely unknown. Hypothesized mechanisms include metabolic processes that alter pH and supersaturation, as well as cell surface properties that induce mineral nucleation. This work systematically investigates these mechanisms by allowing calcium carbonate (CaCO3) to form in the presence or absence of microbes with various surfaces features included Escherichia coli, Synechocystis sp. PCC 6803, Caulobacter vibrioides, and Lysinibacilllus sphaericus. Surprisingly, formation of stable crystalline CaCO3 was accelerated by the presence of all microbes relative to abiotic solutions. This rate acceleration also occurred for metabolically inactive bacteria, indicating that metabolic activity was not the operating mechanism. Rather, since the CaCO3 crystals increased in number as the cell density increased, these results indicate that many bacterial species accelerate the nucleation of CaCO3 crystals. To understand the role of specific biomolecules on nucleation, we used genetic mutants with altered lipopolysaccharides (LPS) and crystalline surface layer proteins (S-layers). Bacterial surface charge and cation binding was assessed using zeta potential measurements and correlated to the bacterial surface chemistry and biomineralization experiments with varying Ca2+ concentrations. From these results, we postulate that the S-layer surfaces can selectively attract Ca2+ ions, serving as nucleation sites for CaCO3, thereby accelerating crystal formation. These observations provide substantive evidence for a non-specific nucleation mechanism, and stress the importance of microbes, even dead ones, on the rate of

  10. CO₂ sequestration through mineral carbonation of iron oxyhydroxides.

    PubMed

    Lammers, Kristin; Murphy, Riley; Riendeau, Amber; Smirnov, Alexander; Schoonen, Martin A A; Strongin, Daniel R

    2011-12-15

    Carbon dioxide sequestration via the use of sulfide reductants and mineral carbonation of the iron oxyhydroxide polymorphs lepidocrocite, goethite, and akaganeite with supercritical CO(2) (scCO(2)) was investigated using in situ attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), X-ray diffraction (XRD), and transmission electron microscopy (TEM). The exposure of the different iron oxyhydroxides to aqueous sulfide in contact with scCO(2) at ∼70-100 °C resulted in the partial transformation of the minerals to siderite (FeCO(3)) and sulfide phases such as pyrite (FeS(2)). The relative yield of siderite to iron sulfide bearing mineral product was a strong function of the initial sulfide concentration. The order of mineral reactivity with regard to the amount of siderite formation in the scCO(2)/sulfide environment for a specific reaction time was goethite < lepidocrocite ≤ akaganeite. Given the presence of goethite in sedimentary formations, this conversion reaction may have relevance to the subsurface sequestration and geologic storage of carbon dioxide.

  11. Sequestration of Martian CO2 by mineral carbonation

    NASA Astrophysics Data System (ADS)

    Tomkinson, Tim; Lee, Martin R.; Mark, Darren F.; Smith, Caroline L.

    2013-10-01

    Carbonation is the water-mediated replacement of silicate minerals, such as olivine, by carbonate, and is commonplace in the Earth’s crust. This reaction can remove significant quantities of CO2 from the atmosphere and store it over geological timescales. Here we present the first direct evidence for CO2 sequestration and storage on Mars by mineral carbonation. Electron beam imaging and analysis show that olivine and a plagioclase feldspar-rich mesostasis in the Lafayette meteorite have been replaced by carbonate. The susceptibility of olivine to replacement was enhanced by the presence of smectite veins along which CO2-rich fluids gained access to grain interiors. Lafayette was partially carbonated during the Amazonian, when liquid water was available intermittently and atmospheric CO2 concentrations were close to their present-day values. Earlier in Mars’ history, when the planet had a much thicker atmosphere and an active hydrosphere, carbonation is likely to have been an effective mechanism for sequestration of CO2.

  12. Sequestration of Martian CO2 by mineral carbonation

    PubMed Central

    Tomkinson, Tim; Lee, Martin R.; Mark, Darren F.; Smith, Caroline L.

    2013-01-01

    Carbonation is the water-mediated replacement of silicate minerals, such as olivine, by carbonate, and is commonplace in the Earth’s crust. This reaction can remove significant quantities of CO2 from the atmosphere and store it over geological timescales. Here we present the first direct evidence for CO2 sequestration and storage on Mars by mineral carbonation. Electron beam imaging and analysis show that olivine and a plagioclase feldspar-rich mesostasis in the Lafayette meteorite have been replaced by carbonate. The susceptibility of olivine to replacement was enhanced by the presence of smectite veins along which CO2-rich fluids gained access to grain interiors. Lafayette was partially carbonated during the Amazonian, when liquid water was available intermittently and atmospheric CO2 concentrations were close to their present-day values. Earlier in Mars’ history, when the planet had a much thicker atmosphere and an active hydrosphere, carbonation is likely to have been an effective mechanism for sequestration of CO2. PMID:24149494

  13. Elemental composition of extant microbialites: mineral and microbial carbon

    NASA Astrophysics Data System (ADS)

    Valdespino-Castillo, P. M.; Falcón, L. I.; Holman, H. Y. N.; Merino-Ibarra, M.; García-Guzmán, M.; López-Gómez, L. M. D. R.; Martínez, J.; Alcantara-Hernandez, R. J.; Beltran, Y.; Centeno, C.; Cerqueda-Garcia, D.; Pi-Puig, T.; Castillo, F. S.

    2015-12-01

    Microbialites are the modern analogues of ancient microbial consortia. Their existence extends from the Archaean (~3500 mya) until present and their lithified structure evidences the capacity of microbial communities to mediate mineral precipitation. Living microbialites are a useful study model to test the mechanisms involved in carbonates and other minerals precipitation. Here, we studied the chemical composition, the biomass and the microbial structure of extant microbialites. All of these were found in Mexico, in water systems of different and characteristic ionic firms. An elemental analysis (C:N) of microbial biomass was performed and total P was determined. To explore the chemical composition of microbialites as a whole, X-ray diffraction analyses were performed over dry microbialites. While overall inorganic carbon content (carbonates) represented >70% of the living layer, a protocol of inorganic carbon elimination was performed for each sample resulting in organic matter contents between 8 and 16% among microbialites. Stoichiometric ratios of C:N:P in microbialite biomass were different among samples, and the possibility of P limitation was suggested mainly for karstic microbialites, N limitation was suggested for all samples and, more intensively, for soda system microbialites. A differential capacity for biomass allocation among microbialites was observed. Microbialites showed, along the biogeographic gradient, a diverse arrangement of microbial assemblages within the mineral matrix. While environmental factors such as pH and nitrate concentration were the factors that defined the general structure and diversity of these assemblages, we intend to test if the abundance of major ions and trace metals are also defining microbialite characteristics (such as microbial structure and biomass). This work contributes to define a baseline of the chemical nature of extant microbial consortia actively participating in mineral precipitation processes.

  14. Modeling CO2-Water-Mineral Wettability and Mineralization for Carbon Geosequestration.

    PubMed

    Liang, Yunfeng; Tsuji, Shinya; Jia, Jihui; Tsuji, Takeshi; Matsuoka, Toshifumi

    2017-07-18

    Carbon dioxide (CO2) capture and storage (CCS) is an important climate change mitigation option along with improved energy efficiency, renewable energy, and nuclear energy. CO2 geosequestration, that is, to store CO2 under the subsurface of Earth, is feasible because the world's sedimentary basins have high capacity and are often located in the same region of the world as emission sources. How CO2 interacts with the connate water and minerals is the focus of this Account. There are four trapping mechanisms that keep CO2 in the pores of subsurface rocks: (1) structural trapping, (2) residual trapping, (3) dissolution trapping, and (4) mineral trapping. The first two are dominated by capillary action, where wettability controls CO2 and water two-phase flow in porous media. We review state-of-the-art studies on CO2/water/mineral wettability, which was found to depend on pressure and temperature conditions, salt concentration in aqueous solutions, mineral surface chemistry, and geometry. We then review some recent advances in mineral trapping. First, we show that it is possible to reproduce the CO2/water/mineral wettability at a wide range of pressures using molecular dynamics (MD) simulations. As the pressure increases, CO2 gas transforms into a supercritical fluid or liquid at ∼7.4 MPa depending on the environmental temperature. This transition leads to a substantial decrease of the interfacial tension between CO2 and reservoir brine (or pure water). However, the wettability of CO2/water/rock systems depends on the type of rock surface. Recently, we investigated the contact angle of CO2/water/silica systems with two different silica surfaces using MD simulations. We found that contact angle increased with pressure for the hydrophobic (siloxane) surface while it was almost constant for the hydrophilic (silanol) surface, in excellent agreement with experimental observations. Furthermore, we found that the CO2 thin films at the CO2-hydrophilic silica and CO2-H2O

  15. Microbiological quality of carbonated and non-carbonated mineral water stored at different temperatures.

    PubMed

    Korzeniewska, Ewa; Filipkowska, Zofia; Domeradzka, Sylwia; Włodkowski, Kamil

    2005-01-01

    The microbiological quality of five brands of carbonated and non-carbonated mineral water sold in Poland was studied. The study was carried out on the survival of heterotrophic bacteria at 22 and 37 degrees C (pour plate technique) in the samples of mineral waters stored at 4 and 22 degrees C. The one hundred ten bottles (twenty two bottles of each of the five brands) of carbonated and uncarbonated mineral waters with different levels of dissolved solids and organic content were chosen to microorganisms study. Ten bottles of mineral water were studied initially. Fifty bottles were stored at 4 degrees C, the other fifty were kept at 22 degrees C. The haemolysing bacteria in 1 cm3; E. coli, P. aeruginosa and A. hydrophila in 250 cm3 of mineral water were unidentifiable. Total viable count of heterotrophic bacteria at 22 and 37 degrees C in 1 cm3 of mineral water was the highest respectively for brand T and for brands T and M; the lowest for brand Z. Initially, approximately 29% of 110 water samples (respectively 4% of carbonated and 55% of uncarbonated) had bacterial counts greater than Ministry of Health's standards, notwithstanding the number of water samples which doesn't perform requirements grew up to 47% (respectively 36% of carbonated and 58% of uncarbonated) when the time of TVC 37 and 22 degrees C incubation was elongated from 1 and 3 days to 3 and 14 days respectively. The temperature of storage was inessential for the numbers of studied microorganisms. The most important factors were the brand, time of storage and the carbonating or non-carbonating of water. The highest numbers of the bacteria analysed were detected in non-carbonating water, irrespective of the water brand and temperature of storage.

  16. A review of mineral carbonation technologies to sequester CO2.

    PubMed

    Sanna, A; Uibu, M; Caramanna, G; Kuusik, R; Maroto-Valer, M M

    2014-12-07

    Carbon dioxide (CO2) capture and sequestration includes a portfolio of technologies that can potentially sequester billions of tonnes of CO2 per year. Mineral carbonation (MC) is emerging as a potential CCS technology solution to sequester CO2 from smaller/medium emitters, where geological sequestration is not a viable option. In MC processes, CO2 is chemically reacted with calcium- and/or magnesium-containing materials to form stable carbonates. This work investigates the current advancement in the proposed MC technologies and the role they can play in decreasing the overall cost of this CO2 sequestration route. In situ mineral carbonation is a very promising option in terms of resources available and enhanced security, but the technology is still in its infancy and transport and storage costs are still higher than geological storage in sedimentary basins ($17 instead of $8 per tCO2). Ex situ mineral carbonation has been demonstrated on pilot and demonstration scales. However, its application is currently limited by its high costs, which range from $50 to $300 per tCO2 sequestered. Energy use, the reaction rate and material handling are the key factors hindering the success of this technology. The value of the products seems central to render MC economically viable in the same way as conventional CCS seems profitable only when combined with EOR. Large scale projects such as the Skyonic process can help in reducing the knowledge gaps on MC fundamentals and provide accurate costing and data on processes integration and comparison. The literature to date indicates that in the coming decades MC can play an important role in decarbonising the power and industrial sector.

  17. Effects of carbon substrate lability on carbon mineralization dynamics of tropical peat

    NASA Astrophysics Data System (ADS)

    Jauhiainen, Jyrki; Silvennoinen, Hanna; Könönen, Mari; Limin, Suwido; Vasander, Harri

    2016-04-01

    Extensive draining at tropical ombrotrophic peatlands in Southeast Asia has made them global 'hot spots' for greenhouse gas emissions. Management practises and fires have led to changed substrate status, which affects microbial processes. Here, we present the first data on how management practises affect carbon (C) mineralization processes at these soils. We compared the carbon mineralization potentials of pristine forest soils to those of drained fire affected soils at various depths, with and without additional labile substrates (glucose, glutamate and NO3-N) and in oxic and anoxic conditions by dedicated ex situ experiments. Carbon mineralization (CO2 and CH4 production) rates were higher in the pristine site peat, which contains more labile carbon due to higher input via vegetation. Production rates decreased with depth together with decreasing availability of labile carbon. Consequently, the increase in production rates after labile substrate addition was relatively modest from pristine site as compared to the managed site and from the top layers as compared to deeper layers. Methanogenesis had little importance in total carbon mineralization. Adding labile C and N enhanced heterotrophic CO2 production more than the sole addition of N. Surprisingly, oxygen availability was not an ultimate requirement for substantial CO2 production rates, but anoxic respiration yielded comparable rates, especially at the pristine soils. Flooding of these sites will therefore reduce, but not completely cease, peat carbon loss. Reintroduced substantial vegetation and fertilization in degraded peatlands can enrich recalcitrant peat with simple C and N compounds and thus increase microbiological activity.

  18. Numerically Simulating Carbonate Mineralization of Basalt with Injection of Carbon Dioxide into Deep Saline Formations

    SciTech Connect

    White, Mark D.; McGrail, B. Peter; Schaef, Herbert T.; Bacon, Diana H.

    2006-07-08

    The principal mechanisms for the geologic sequestration of carbon dioxide in deep saline formations include geological structural trapping, hydrological entrapment of nonwetting fluids, aqueous phase dissolution and ionization, and geochemical sorption and mineralization. In sedimentary saline formations the dominant mechanisms are structural and dissolution trapping, with moderate to weak contributions from hydrological and geochemical trapping; where, hydrological trapping occurs during the imbibition of aqueous solution into pore spaces occupied by gaseous carbon dioxide, and geochemical trapping is controlled by generally slow reaction kinetics. In addition to being globally abundant and vast, deep basaltic lava formations offer mineralization kinetics that make geochemical trapping a dominate mechanism for trapping carbon dioxide in these formations. For several decades the United States Department of Energy has been investigating Columbia River basalt in the Pacific Northwest as part of its environmental programs and options for natural gas storage. Recently this nonpotable and extensively characterized basalt formation is being reconsidered as a potential reservoir for geologic sequestration of carbon dioxide. The reservoir has an estimated storage capacity of 100 giga tonnes of carbon dioxide and comprises layered basalt flows with sublayering that generally alternates between low permeability massive and high permeability breccia. Chemical analysis of the formation shows 10 wt% Fe, primarily in the +2 valence. The mineralization reaction that makes basalt formations attractive for carbon dioxide sequestration is that of calcium, magnesium, and iron silicates reacting with dissolved carbon dioxide, producing carbonate minerals and amorphous quartz. Preliminary estimates of the kinetics of the silicate-to-carbonate reactions have been determined experimentally and this research is continuing to determine effects of temperature, pressure, rock composition and

  19. Aerobic microbial mineralization of dichloroethene as sole carbon substrate

    USGS Publications Warehouse

    Bradley, P.M.; Chapelle, F.H.

    2000-01-01

    Microorganisms indigenous to the bed sediments of a black- water stream utilized 1,2-dichloroethene (1,2-DCE) as a sole carbon substrate for aerobic metabolism. Although no evidence of growth was observed in the minimal salts culture media used in this study, efficient aerobic microbial mineralization of 1,2-DCE as sole carbon substrate was maintained through three sequential transfers (107 final dilution) of the original environmental innoculum. These results indicate that 1,2-DCE can be utilized as a primary substrate to support microbial metabolism under aerobic conditions.Microorganisms indigenous to the bed sediments of a black-water stream utilized 1,2-dichloroethene (1,2-DCE) as a sole carbon substrate for aerobic metabolism. Although no evidence of growth was observed in the minimal salts culture media used in this study, efficient aerobic microbial mineralization of 1,2-DCE as sole carbon substrate was maintained through three sequential transfers (107 final dilution) of the original environmental innoculum. These results indicate that 1,2-DCE can be utilized as a primary substrate to support microbial metabolism under aerobic conditions.

  20. Mineral carbon storage in peridotite bodies: insights from natural carbonation of peridotite in Oman

    NASA Astrophysics Data System (ADS)

    Streit, E.; Kelemen, P. B.; Matter, J. M.; Spiegelman, M. W.

    2009-12-01

    The formation of solid carbonate minerals offers a safe and permanent storage solution for the disposal of CO2, and injection of CO2 into peridotite bodies may provide an effective and economical method of mineral carbon sequestration. The natural formation of carbonate minerals is quite common in weathering and alteration of tectonically exposed peridotite bodies. In the Oman ophiolite, we observe extensive and rapid formation of carbonate minerals in peridotite: ongoing reaction between peridotite and ground water forms carbonate veins and drives up the pH of the water, leading to the precipitation of extensive travertine terraces where this groundwater emerges at the surface in alkaline springs. These carbonate veins are surprisingly young, and suggest that 10,000 to 100,000 tons CO2/year are consumed by these weathering reactions in Oman. Additionally, large outcrops of listwanite—peridotite in which the peridotite has been completely carbonated—are common in the Oman ophiolite, highlighting that it is possible for the natural system to access a regime of highly efficient conversion to carbonate minerals. The natural carbonation rate could be enhanced and the system pushed to more efficient carbonation of peridotite in several ways. Drilling and hydraulic fracture will increase the volume of peridotite available for reaction, and field observations suggest that the solid volume expansion of the reaction may drive further fracture. Increasing the pCO2 will also yield higher reaction rates and higher carbonation efficiency by stabilizing magnesite and quartz, instead of talc or serpentine as the silicate phase which is usually the case in the observed carbonate veins. Finally, the carbonation of olivine has a maximum reaction rate at a temperature of 185C. 'Clumped isotope' thermometry in the carbonates suggests that the carbonate veins formed at near ambient temperatures while the completely carbonated listwanites formed at temperatures closer to the

  1. Thermodynamic constraints on mineral carbonation of serpentinized peridotite

    NASA Astrophysics Data System (ADS)

    Klein, Frieder; Garrido, Carlos J.

    2011-10-01

    Carbonation of serpentinite appears to be a promising process to mitigate rising concentrations of atmospheric CO 2. However, given that chemical affinities of mineral carbonation reactions in serpentinized peridotite change drastically with temperature, protolith and the activities of dissolved constituents, this process is incompletely understood. In this report numerical models are used to investigate the heterogeneous phase equilibria and the speciation of intergranular fluids during mineral carbonation of serpentinite/dunite at 100, 200, 300 and 400 °C. The results suggest that temperature-dependent activity gradients of both aqueous carbon dioxide (aCO 2,aq) and aqueous silica (aSiO 2,aq) determine the carbonation potential of serpentinite. At low to moderate temperatures there is ample thermodynamic driving force for the carbonation of serpentinite, as the gradients in aSiO 2,aq and aCO 2,aq set between talc-quartz-magnesite and serpentine-brucite equilibria are steepest. With increasing temperature these activity gradients become smaller because the stability fields of brucite, serpentine and talc expand toward higher aCO 2,aq and aSiO 2,aq while the stability field of magnesite contracts. In addition, the enhanced solubility of quartz toward higher temperatures shifts the talc-quartz-magnesite equilibrium to very high aCO 2,aq. Field observations of carbonated serpentinite reveal a rather simple sequence of arrested carbonation reactions, which is typically fossilized as spatially distinct metasomatic zones. A zone of serpentinized peridotite is followed by a zone of serpentine + carbonate, then talc + carbonate and finally quartz + carbonate. Our modeling results not only reproduce these observations, they also suggest that complete carbonation is favored at low to moderate temperatures. Since complete carbonation of serpentinite is achieved at relatively small fluid to rock ratios at temperatures ≤ 200 °C, prolonged fluid influx at low temperatures

  2. Soil Organic Carbon Loss: An Overlooked Factor in the Carbon Sequestration Potential of Enhanced Mineral Weathering

    NASA Astrophysics Data System (ADS)

    Dietzen, Christiana; Harrison, Robert

    2016-04-01

    Weathering of silicate minerals regulates the global carbon cycle on geologic timescales. Several authors have proposed that applying finely ground silicate minerals to soils, where organic acids would enhance the rate of weathering, could increase carbon uptake and mitigate anthropogenic CO2 emissions. Silicate minerals such as olivine could replace lime, which is commonly used to remediate soil acidification, thereby sequestering CO2 while achieving the same increase in soil pH. However, the effect of adding this material on soil organic matter, the largest terrestrial pool of carbon, has yet to be considered. Microbial biomass and respiration have been observed to increase with decreasing acidity, but it is unclear how long the effect lasts. If the addition of silicate minerals promotes the loss of soil organic carbon through decomposition, it could significantly reduce the efficiency of this process or even create a net carbon source. However, it is possible that this initial flush of microbial activity may be compensated for by additional organic matter inputs to soil pools due to increases in plant productivity under less acidic conditions. This study aimed to examine the effects of olivine amendments on soil CO2 flux. A liming treatment representative of typical agricultural practices was also included for comparison. Samples from two highly acidic soils were split into groups amended with olivine or lime and a control group. These samples were incubated at 22°C and constant soil moisture in jars with airtight septa lids. Gas samples were extracted periodically over the course of 2 months and change in headspace CO2 concentration was determined. The effects of enhanced mineral weathering on soil organic matter have yet to be addressed by those promoting this method of carbon sequestration. This project provides the first data on the potential effects of enhanced mineral weathering in the soil environment on soil organic carbon pools.

  3. Manganese carbonate mineralization in the Molango district, Mexico

    USGS Publications Warehouse

    Okita, P.M.

    1992-01-01

    Mn carbonate mineralization is hosted by a finely laminated Upper Jurassic marine sedimentary sequence that forms the base of the Chipoco facies of the Taman Formation (Kimmeridgian). The carbonate ore bed consists of fine-grained rhodochrosite and dispersed organic matter, magnetite, and maghemite but generally only trace quantities of pyrite. Fine laminations and clotted textures suggest deposition in a restricted marine environment. Several geologic and geochemical processes resulted in the formation of Mn carbonate by the early diagenetic reduction of Mn oxides through the oxidation of organic matter and iron sulfide. The ultimate source of the manganese is uncertain but may have been fluvial-sediment loads or hydrothermal activity associated with the rifting of the Gulf of Mexico. -from Author

  4. Drug resistant bacteria in non carbonated mineral waters.

    PubMed

    Massa, S; Petruccioli, M; Fanelli, M; Gori, L

    1995-11-01

    The presence of antibiotic resistant bacteria was revealed among bacteria isolated from non carbonated mineral waters bottled in plastic (PVC) and in glass containers. Heterotrophic plate count values ranged between < 10 and 4.3 x 10(3) and between < 10 and 1.2 x 10(4) colony forming units/ml for the waters bottled in PVC and glass, respectively. The greatest resistance to a single antibiotic, 39.1% of 320 isolates from mineral waters, was found for nalidixic acid. Resistance to the other antibiotics was as follows: ampicillin (26.2%), bacitracin (19.7%), cotrimoxazole (18.7%), streptomycin (15.0%), tetracycline (14.4%), gentamycin (11.6%), chloramphenicol and rifampin (9.7%). The strains resistant to two or more antibiotics (multiple antibiotic resistant, MAR) provided 51% of the total isolates. Identification of 127 MAR strains showed that in the mineral waters gram-positive cocci dominated. The second, third and fourth group of identified MAR phenotypes were, in order to importance, gram-negative non-fermentative rods, gram-positive rods and gram-negative fermentative rods. The importance of the antibiotic resistant bacteria in mineral water is discussed.

  5. Rates of mineral dissolution and carbonation in peridotite and basalt

    NASA Astrophysics Data System (ADS)

    Kelemen, P. B.; Matter, J. M.

    2009-12-01

    We study natural rates and processes of mineral carbonation in peridotite (olivine-rich rock) in mantle rocks exposed to weathering in northern Oman to learn effective mechanisms from natural processes, and seek ways to accelerate them to achieve significant CO2 capture and storage via mineral carbonation at the lowest possible cost. In our first paper (1), we fit data on mantle olivine carbonation from the DOE Albany Research Center (2,3, ARC). These data, and data from Arizona State University (4, ASU) suggest that a peridotite rock volume heated to 185°C and infused with H2O+CO2 at PCO2 > 75 bars could consume ~ 1 ton CO2 per cubic meter of rock per year. Because it is more abundant than peridotite, other workers focus on carbonation of the most common type of lava on Earth, basalt, whose main mineral constituent is generally labradorite, part of the plagioclase feldspar solid solution series. Our intuition is that labradorite carbonation is much slower than mantle olivine carbonation. To quantify this, we compiled data on dissolution of mantle olivine, labradorite, crystalline basalt, and basaltic glass in aqueous fluids, as well as data on mantle olivine carbonation. The dissolution data are calibrated as a function of surface area (i.e., grain size and shape) and pH, as well as temperature, whereas most of the ARC and ASU experiments were done at a single pH and grain size. Thus, for comparison, we calculated dissolution rates for 70 micron spheres at pH 8, close to the ARC and ASU experimental conditions. At these conditions, olivine carbonation observed by ARC and ASU is 100 to 1000 times faster than labradorite and crystalline basalt, and faster than conventionally measured olivine dissolution rates. The ARC and ASU experiments were different from conventional dissolution experiments in several ways that could lead to an enhancement in olivine reaction rates: (a) they may have lower a(Mg) in fluid due to solid MgCO3 (magnesite) precipitation, (b) they

  6. Research status on the sequestration of carbon dioxide by direct aqueous mineral carbonation

    SciTech Connect

    O'Connor, William K.; Dahlin, David C.; Nilsen, David N.; Gerdemann, Stephen J.; Rush, Gilbert E.; Walters, Richard P.; Turner, Paul C.

    2001-01-01

    Direct aqueous mineral carbonation has been investigated as a process to convert gaseous CO2 into a geologically stable, solid final form. The process utilizes a solution of distilled water, or sodium bicarbonate (NaHCO3), sodium chloride (NaCl), and water, mixed with a mineral reactant, such as olivine (Mg2SiO4) or serpentine [Mg3Si2O5(OH)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 magnesium carbonate (MgCO3) in a single unit operation. Mineral reactivity has been increased by pretreatment of the minerals. Thermal activation of serpentine can be achieved by heat pretreatment at 630 C. Carbonation of the thermally activated serpentine, using the bicarbonate-bearing solution, at T=155 C, PCO2=185 atm, and 15% solids, achieved 78% stoichiometric conversion of the silicate to the carbonate in 30 minutes. Recent studies have investigated mechanical activation as an alternative to thermal treatment. The addition of a high intensity attrition grinding step to the size reduction circuit successfully activated both serpentine and olivine. Over 80% stoichiometric conversion of the mechanically activated olivine was achieved in 60 minutes, using the bicarbonate solution at T=185 C, PCO2=150 atm, and 15% solids. Significant carbonation of the mechanically activated minerals, at up to 66% stoichiometric conversion, has also been achieved at ambient temperature (25 C) and PCO2 ={approx}10 atm.

  7. Real Time Pore Structure Evolution during Olivine Mineral Carbonation

    NASA Astrophysics Data System (ADS)

    Zhu, W.; Fusseis, F.; Lisabeth, H. P.; Xiao, X.

    2014-12-01

    Aqueous carbonation of ultramafic rocks has been proposed as a promising method for long-term, secure sequestration of carbon dioxide. While chemical kinetics data indicate that carbonation reaction in olivine is one of the fastest among the mg-bearing minerals, in practice, the factors that limit the extent and rate of carbonation in ultramafic rocks are fluid supply and flux. On the one hand, reaction products could produce passivating layer that prohibits further reactions. On the other hand, the increases in solid volume during carbonation could lead to cracking and create new fluid paths. Whether carbonation in ultramafic rocks is self-limiting or self-sustaining has been hotly debated. Experimental evidence of precipitation of reaction products during olivine carbonation was reported. To date, reaction-driven cracking has not been observed. In this paper, we present the first real-time pore structure evolution data using the x-ray synchrotron microtomography. Sodium bicarbonate (NaHCO3) solution was injected into porous olivine aggregates and in-situ pore structure change during olivine carbonation at a constant confining pressure (12 MPa) and a temperature of 200oC was captured at 30 min. interval for ~160 hours. Shortly after the experiment started, filling-in of the existing pores by precipitation of reaction products was visible. The size of the in-fills kept increasing as reactions continued. After ~48 hours, cracking around the in-fill materials became visible. After ~60 hours, these cracks started to show a clear polygonal pattern, similar to the crack patterns usually seen on the surface of drying mud. After ~72 hours, some of the cracks coalesced into large fractures that cut-through the olivine aggregates. New fractures continued to develop and at the end of the experiment, the sample was completely disintegrated by these fractures. We also conducted nanotomography experiments on a sub-volume of the reacted olivine aggregate. Orthogonal sets of

  8. Active Layer Soil Carbon and Nutrient Mineralization, Barrow, Alaska, 2012

    DOE Data Explorer

    Stan D. Wullschleger; Holly M. Vander Stel; Colleen Iversen; Victoria L. Sloan; Richard J. Norby; Mallory P. Ladd; Jason K. Keller; Ariane Jong; Joanne Childs; Deanne J. Brice

    2015-10-29

    This data set consists of bulk soil characteristics as well as carbon and nutrient mineralization rates of active layer soils manually collected from the field in August, 2012, frozen, and then thawed and incubated across a range of temperatures in the laboratory for 28 day periods in 2013-2015. The soils were collected from four replicate polygons in each of the four Areas (A, B, C, and D) of Intensive Site 1 at the Next-Generation Ecosystem Experiments (NGEE) Arctic site near Barrow, Alaska. Soil samples were coincident with the established Vegetation Plots that are located in center, edge, and trough microtopography in each polygon. Data included are 1) bulk soil characteristics including carbon, nitrogen, gravimetric water content, bulk density, and pH in 5-cm depth increments and also by soil horizon, 2) carbon, nitrogen, and phosphorus mineralization rates for soil horizons incubated aerobically (and in one case both aerobically and anaerobically) for 28 days at temperatures that included 2, 4, 8, and 12 degrees C. Additional soil and incubation data are forthcoming. They will be available when published as part of another paper that includes additional replicate analyses.

  9. Carbon Dioxide Sequestration by Direct Mineral Carbonation: Results from Recent Studies and Current Status

    SciTech Connect

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

    2001-01-01

    Direct mineral carbonation has been investigated as a process to convert gaseous CO2 into a geologically stable, solid final form. The process utilizes a solution of sodium bicarbonate (NaHCO3), sodium chloride (NaCl), and water, mixed with a mineral reactant, such as olivine (Mg2SiO4) or serpentine [Mg3Si2O5(OH)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 magnesium carbonate (MgCO3) in a single unit operation. Optimum results have been achieved using heat pretreated serpentine feed material, with a surface area of roughly 19 m2 per gram, and high partial pressure of CO2 (PCO2). Specific conditions include: 155?C; PCO2=185 atm; 15% solids. Under these conditions, 78% stoichiometric conversion of the silicate to the carbonate was achieved in 30 minutes. Studies suggest that the mineral dissolution rate is primarily surface controlled, while the carbonate precipitation rate is primarily dependent on the bicarbonate concentration of the slurry. Current studies include further examination of the reaction pathways, and an evaluation of the resource potential for the magnesium silicate reactant, particularly olivine. Additional studies include the examination of various pretreatment options, the development of a continuous flow reactor, and an evaluation of the economic feasibility of the process.

  10. Mineral carbonation for carbon sequestration in cement kiln dust from waste piles.

    PubMed

    Huntzinger, Deborah N; Gierke, John S; Sutter, Lawrence L; Kawatra, S Komar; Eisele, Timothy C

    2009-08-30

    Alkaline earth metals, such as calcium and magnesium oxides, readily react with carbon dioxide (CO(2)) to produce stable carbonate minerals. Carbon sequestration through the formation of carbonate minerals is a potential means to reduce CO(2) emissions. Calcium-rich, industrial solid wastes and residues provide a potential source of highly reactive oxides, without the need for pre-processing. This paper presents the first study examining the feasibility of carbon sequestration in cement kiln dust (CKD), a byproduct generated during the manufacturing of cement. A series of column experiments were conducted on segments of intact core taken from landfilled CKD. Based on stoichiometry and measured consumption of CO(2) during the experiments, degrees of carbonation greater than 70% of the material's potential theoretical extent were achieved under ambient temperature and pressure conditions. The overall extent of carbonation/sequestration was greater in columns with lower water contents. The major sequestration product appears to be calcite; however, more detailed material characterization is need on pre- and post-carbonated samples to better elucidate carbonation pathways and products.

  11. Mineral Influence on Microbial Survival During Carbon Sequestration

    NASA Astrophysics Data System (ADS)

    Santillan, E. U.; Shanahan, T. M.; Wolfe, W. W.; Bennett, P.

    2012-12-01

    CO2 sequestered in a deep saline aquifer will perturb subsurface biogeochemistry by acidifying the groundwater and accelerating mineral diagenesis. Subsurface microbial communities heavily influence geochemistry through their metabolic processes, such as with dissimilatory iron reducing bacteria (DIRB). However, CO2 also acts as a sterilant and will perturb these communities. We investigated the role of mineralogy and its effect on the survival of microbes at high PCO2 conditions using the model DIRB Shewanella oneidensis MR-1. Batch cultures of Shewanella were grown to stationary phase and exposed to high PCO2 using modified Parr reactors. Cell viability was then determined by plating cultures after exposure. Results indicate that at low PCO2 (2 bar), growth and iron reduction are decreased and cell death occurs within 1 hour when exposed to CO2 pressures of 10 bar or greater. Further, fatty acid analysis indicates microbial lipid degradation with C18 fatty acids being the slowest lipids to degrade. When cultures were grown in the presence of rocks or minerals representative of the deep subsurface such as carbonates and silicates and exposed to 25 bar CO2, survival lasted beyond 2 hours. The most effective protecting substratum was quartz sandstone, with cultures surviving beyond 8 hours of CO2 exposure. Scanning electron microscope images reveal biofilm formation on the mineral surfaces with copious amounts of extracellular polymeric substances (EPS) present. EPS from these biofilms acts as a reactive barrier to the CO2, slowing the penetration of CO2 into cells and resulting in increased survival. When biofilm cultures were grown with Al and As to simulate the release of toxic metals from minerals such as feldspars and clays, survival time decreased, indicating mineralogy may also enhance microbial death. Biofilms were then grown on iron-coated quartz sand to determine conversely what influence biofilms may have on mineral dissolution during CO2 perturbation

  12. Co-precipitation of phosphate and carbonate minerals: geological and ecological implications

    NASA Astrophysics Data System (ADS)

    Sanchez-Román, Monica; McKenzie, Judith; Vasconcelos, Crisogono

    2015-04-01

    Microorganisms play an important role in natural environments by controlling the metal cations (e.g., Ca2+, Mg2+, Fe2+) and the anions (CO32-, NH4+, PO43-) that precipitate as biominerals (e.g., carbonates, phosphates). In contrast to phosphate minerals, precipitation of carbonate minerals by bacteria has been widely studied in culture experiments and in natural environments. Moreover, studies of sedimentary phosphate minerals and their geological and ecological implications are rare. Nevertheless, phosphate minerals frequently co-precipitate with carbonates in culture experiments and in natural systems. In the present work, we investigate how microorganisms control the mineralogy and geochemistry of phosphate and carbonate minerals. For this, culture experiments were performed to study the co-precipitation of phosphate and carbonate minerals using aerobic heterotrophic bacteria at sedimentary Earth's surface conditions. Ca-Mg carbonate (dolomite, Mg-calcite) and/or Mg-carbonate (hydromagnesite) precipitated with Mg-phosphate (struvite). In most of the cultures, phosphate was the dominant mineral phase found in the bacterial precipitates and carbonates precipitated after phosphate phases. Notably, in all the cultures, we found a mixture of phosphate and carbonate minerals. This study shines new light into the microbial diagenetic processes involved in the co-precipitation of phosphate and carbonate minerals and links the P and C cycles.

  13. Optimized carbonation of magnesium silicate mineral for CO2 storage.

    PubMed

    Eikeland, Espen; Blichfeld, Anders Bank; Tyrsted, Christoffer; Jensen, Anca; Iversen, Bo Brummerstedt

    2015-03-11

    The global ambition of reducing the carbon dioxide emission makes sequestration reactions attractive as an option of storing CO2. One promising environmentally benign technology is based on forming thermodynamically stable carbonated minerals, with the drawback that these reactions usually have low conversion rates. In this work, the carbonation reaction of Mg rich olivine, Mg2SiO4, under supercritical conditions has been studied. The reaction produces MgCO3 at elevated temperature and pressure, with the addition of NaHCO3 and NaCl to improve the reaction rates. A sequestration rate of 70% was achieved within 2 h, using olivine particles of sub-10 μm, whereas 100% conversion was achieved in 4 h. This is one of the fastest complete conversions for this reaction reported to date. The CO2 sequestration rate is found to be highly dependent on the applied temperature and pressure, as well as the addition of NaHCO3. In contrast, adding NaCl was found to have limited effect on the reaction rate. The roles of NaHCO3 and NaCl as catalysts are discussed and especially how their effect changes with increased olivine particle size. The products have been characterized by Rietveld refinement of powder X-ray diffraction, scanning electron microscopy (SEM), and energy-dispersive X-ray (EDX) spectroscopy revealing the formation of amorphous silica and micrometer-sized magnesium carbonate crystals.

  14. Rates of mineral fluid interaction in a carbon storage environment

    NASA Astrophysics Data System (ADS)

    Yardley, B.; Kilpatrick, A.; Rosenqvist, J.

    2013-12-01

    The design of geological carbon storage projects will seek to maximise rapid trapping in more stable forms than simple stratigraphic or structural trapping, and minimise damage to caprocks. In order to do this, the mineral-fluid interactions that arise through CO2 injection must be understood in the context of the injection environment, rather than simply extrapolated from classic mineral dissolution studies. For example, pore waters are unlikely to dissolve additional Si as a consequence of acidification, but will increase their load of metal cations. We have investigated rates of mineral reaction in response to the introduction of CO2 at a range of conditions relevant to undersaturated pore waters close to a CO2 plume. Addition of CO2 to water results in a drop in pH, but where calcite is present, pH rises again rapidly. At room temperature and 3.3 MPa, pH in CO2-saturated water rises from c. 3.4 to 4.5 in 20 hours. Once pore water has been displaced by CO2 and the remaining, residually-trapped water has 'dried out' by evaporation into the flowing CO2, reactions effectively cease, even at 70 degrees C with water-saturated CO2. Dolomite reacts less rapidly than calcite, and continues to dissolve extensively after pH has almost stabilised. Silicate reactivity is slower than for carbonates and leads to progressive transformation of one silicate phase to another via the medium of the pore fluid over an extended period if PCO2 remains high. The cation imbalance generated by rapid carbonate dissolution can be corrected by ion-exchange with clay minerals, if present, thereby accommodating further conversion of silicates. Permeability contrasts between beds mean that injected CO2 advances along the most permeable layers, rapidly displacing water ahead of it but retaining more stable contacts with water in less permeable layers above and below. While calcite dissolution may still be significant ahead of the advancing plume within permeable beds, silicate reactions will be

  15. Mineral carbonation in water-unsaturated porous media

    NASA Astrophysics Data System (ADS)

    Harrison, A. L.; Dipple, G. M.; Mayer, K. U.; Power, I. M.

    2014-12-01

    Ultramafic mine tailings have an untapped capacity to sequester CO2 directly from air or CO2-rich gas streams via carbonation of tailings minerals [1]. The CO2 sequestration capacity of these sites could be exploited simply by increasing the supply of CO2 into tailings, such as through circulation of air or flue gas from mine site power plants [1,2]. Mine tailings storage facilities typically have heterogeneously distributed pore water [1], affecting both the reactive capacity of the porous medium and the exposure of reactive phases to CO2 [3]. We examine the physical reaction processes that govern carbonation efficiency in variably saturated porous media using meter-scale column experiments containing the tailings mineral, brucite [Mg(OH)2], that were supplied with 10% CO2 gas streams. The experiments were instrumented with water content and gas phase CO2 sensors to track changes in water saturation and CO2concentration with time. The precipitation of hydrated Mg-carbonates as rinds encasing brucite particles resulted in passivation of brucite surfaces and an abrupt shut down of the reaction prior to completion. Moreover, the extent of reaction was further limited at low water saturation due to the lack of water available to form hydrated Mg-carbonates, which incorporate water into their crystal structures. Reactive transport modeling using MIN3P-DUSTY [4] revealed that the instantaneous reaction rate was not strongly affected by water saturation, but the reactive capacity was reduced significantly. Surface passivation and water-limited reaction resulted in a highly non-geometric evolution of reactive surface area. The extent of reaction was also limited at high water content because viscous fingering of the gas streams injected at the base of the columns resulted in narrow zones of highly carbonated material, but left a large proportion of brucite unreacted. The implication is that carbonation efficiency in mine tailings could be maximized by targeting an

  16. Carbonate Mineral Assemblages as Inclusions in Yakutian Diamonds: TEM Verifications

    NASA Astrophysics Data System (ADS)

    Logvinova, A. M.; Wirth, R.; Sobolev, N. V.; Taylor, L. A.

    2014-12-01

    Carbonate mineral inclusions are quite rare in diamonds from the upper mantle, but are evidence for a carbonate abundance in the mantle. It is believed that such carbonatitic inclusions originated from high-density fluids (HDFs) that were enclosed in diamond during its growth. Using TEM and EPMA, several kinds of carbonate inclusions have been identified in Yakutian diamonds : aragonite, dolomite, magnesite, Ba-, Sr-, and Fe-rich carbonates. Most of them are represented by multi-phase inclusions of various chemically distinct carbonates, rich in Ca, Mg, and K and associated with minor amounts of silicate, oxide, saline, and volatile phases. Volatiles, leaving some porosity, played a significant role in the diamond growth. A single crystal of aragonite (60μm) is herein reported for the first time. This inclusion is located in the center of a diamond from the Komsomolskaya pipe. Careful CL imaging reveals the total absence of cracks around the aragonite inclusion - i.e., closed system. This inclusion has been identified by X-ray diffraction and microprobe analysis. At temperatures above 1000 0C, aragonite is only stable at high pressures of 5-6 GPa. Inside this aragonite, we observed nanocrystalline inclusions of titanite, Ni-rich sulfide, magnetite, water-bearing Mg-silicate, and fluid bubbles. Dolomite is common in carbonate multi-phase inclusions in diamonds from the Internatsionalnaya, Yubileinaya, and Udachnaya kimberlite pipes. Alluvial diamonds of the northeastern Siberian Platform are divided into two groups based on the composition of HDFs: 1) Mg-rich multi-phase inclusions (60% magnesite + dolomite + Fe-spinel + Ti-silicate + fluid bubbles); and 2) Ca-rich multi-phase inclusions (Ca,Ba-, Ca,Sr-, Ca,Fe-carbonates + Ti-silicate + Ba-apatite + fluid bubbles). High-density fluids also contain K. Volatiles in the fluid bubbles are represented by water, Cl, F, S, CO2, CH4, and heavy hydrocarbons. Origin of the second group of HDFs may be related to the non

  17. Carbonated beverage consumption and bone mineral density among older women: the Rancho Bernardo Study.

    PubMed Central

    Kim, S H; Morton, D J; Barrett-Connor, E L

    1997-01-01

    OBJECTIVES: The association between carbonated beverage consumption and bone mineral density was examined in a community-based cohort of older White women. METHODS: One thousand women 44 to 98 years of age had bone mineral density measured at four sites and provided medical and behavioral histories, including type and quantity of carbonated beverages consumed. RESULTS: Bone mineral density levels were not associated with intake of any type of carbonated beverage after adjustment for age, obesity, calcium intake, exercise, and current use of tobacco and alcohol, thiazides, estrogen, or thyroid hormone. CONCLUSIONS: Modest intake of carbonated beverages does not appear to have adverse effects on bone mineral density in older women. PMID:9103110

  18. Organic carbon production, mineralization and preservation on the Peruvian margin

    NASA Astrophysics Data System (ADS)

    Dale, A. W.; Sommer, S.; Lomnitz, U.; Montes, I.; Treude, T.; Gier, J.; Hensen, C.; Dengler, M.; Stolpovsky, K.; Bryant, L. D.; Wallmann, K.

    2014-09-01

    Carbon cycling in Peruvian margin sediments (11° S and 12° S) was examined at 16 stations from 74 m on the inner shelf down to 1024 m water depth by means of in situ flux measurements, sedimentary geochemistry and modeling. Bottom water oxygen was below detection limit down to ca. 400 m and increased to 53 μM at the deepest station. Sediment accumulation rates and benthic dissolved inorganic carbon fluxes decreased rapidly with water depth. Particulate organic carbon (POC) content was lowest on the inner shelf and at the deep oxygenated stations (< 5%) and highest between 200 and 400 m in the oxygen minimum zone (OMZ, 15-20%). The organic carbon burial efficiency (CBE) was unexpectedly low on the inner shelf (< 20%) when compared to a global database, for reasons which may be linked to the frequent ventilation of the shelf by oceanographic anomalies. CBE at the deeper oxygenated sites was much higher than expected (max. 81%). Elsewhere, CBEs were mostly above the range expected for sediments underlying normal oxic bottom waters, with an average of 51 and 58% for the 11° S and 12° S transects, respectively. Organic carbon rain rates calculated from the benthic fluxes alluded to a very efficient mineralization of organic matter in the water column, with a Martin curve exponent typical of normal oxic waters (0.88 ± 0.09). Yet, mean POC burial rates were 2-5 times higher than the global average for continental margins. The observations at the Peruvian margin suggest that a lack of oxygen does not affect the degradation of organic matter in the water column but promotes the preservation of organic matter in marine sediments.

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

    SciTech Connect

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

    2000-08-01

    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 cost optimization of any lamellar-hydroxide-based mineral carbonation sequestration process.

  20. Impact of exotic earthworms on organic carbon sorption on mineral surfaces and soil carbon inventories in a northern hardwood forest

    Treesearch

    Amy Lyttle; Kyungsoo Yoo; Cindy Hale; Anthony Aufdenkampe; Stephen D. Sebestyen; Kathryn Resner; Alex. Blum

    2015-01-01

    Exotic earthworms are invading forests in North America where native earthworms have been absent since the last glaciation. These earthworms bioturbate soils and may enhance physical interactions between minerals and organic matter (OM), thus affecting mineral sorption of carbon (C) which may affect C cycling. We quantitatively show how OM-mineral sorption and soil C...

  1. Ex-situ and in-situ mineral carbonation as a means to sequester carbon dioxide

    SciTech Connect

    Gerdemann, Stephen J.; Dahlin, David C.; O'Connor, William K.; Penner, Larry R.; Rush, G.E.

    2004-01-01

    The U. S. Department of Energy's Albany Research Center is investigating mineral carbonation as a method of sequestering CO2 from coal-fired-power plants. Magnesium-silicate minerals such as serpentine [Mg3Si2O5(OH)4] and olivine (Mg2SiO4) react with CO2 to produce magnesite (MgCO3), and the calcium-silicate mineral, wollastonite (CaSiO3), reacts to form calcite (CaCO3). It is possible to carry out these reactions either ex situ (above ground in a traditional chemical processing plant) or in situ (storage underground and subsequent reaction with the host rock to trap CO2 as carbonate minerals). For ex situ mineral carbonation to be economically attractive, the reaction must proceed quickly to near completion. The reaction rate is accelerated by raising the activity of CO2 in solution, heat (but not too much), reducing the particle size, high-intensity grinding to disrupt the crystal structure, and, in the case of serpentine, heat-treatment to remove the chemically bound water. All of these carry energy/economic penalties. An economic study illustrates the impact of mineral availability and process parameters on the cost of ex situ carbon sequestration. In situ carbonation offers economic advantages over ex situ processes, because no chemical plant is required. Knowledge gained from the ex situ work was applied to long-term experiments designed to simulate in situ CO2 storage conditions. The Columbia River Basalt Group (CRBG), a multi-layered basaltic lava formation, has potentially favorable mineralogy (up to 25% combined concentration of Ca, Fe2+, and Mg cations) for storage of CO2. However, more information about the interaction of CO2 with aquifers and the host rock is needed. Core samples from the CRBG, as well as samples of olivine, serpentine, and sandstone, were reacted in an autoclave for up to 2000 hours at elevated temperatures and pressures. Changes in core porosity, secondary mineralizations, and both solution and solid chemistry were measured.

  2. Carbon Mineralizability Determines Interactive Effects on Mineralization of Pyrogenic Organic Matter and Soil Organic Carbon

    SciTech Connect

    Whitman, Thea L.; Zhu, Zihua; Lehmann, Johannes C.

    2014-10-31

    Soil organic carbon (SOC) is a critical and active pool in the global C cycle, and the addition of pyrogenic organic matter (PyOM) has been shown to change SOC cycling, increasing or decreasing mineralization rates (often referred to as priming). We adjusted the amount of easily mineralizable C in the soil, through 1-day and 6-month pre-incubations, and in PyOM made from maple wood at 350°C, through extraction. We investigated the impact of these adjustments on C mineralization interactions, excluding pH and nutrient effects and minimizing physical effects. We found short-term increases (+20-30%) in SOC mineralization with PyOM additions in the soil pre-incubated for 6 months. Over the longer term, both the 6-month and 1-day pre-incubated soils experienced net ~10% decreases in SOC mineralization with PyOM additions. This was possibly due to stabilization of SOC on PyOM surfaces, suggested by nanoscale secondary ion mass spectrometry. Additionally, the duration of pre-incubation affected priming interactions, indicating that there may be no optimal pre-incubation time for SOC mineralization studies. We show conclusively that relative mineralizability of SOC in relation to PyOM-24 C is an important determinant of the effect of PyOM additions on SOC mineralization.

  3. Shungites: origin and classification of a new carbon mineral resource

    SciTech Connect

    Ivankin, P.F.; Galdobina, L.P.; Kalinin, Yu.K.

    1987-10-01

    The discovery of a new mineral resource in Karelia-shungite- and the confirmation of the finding in the geological literature have a long history. In 1876, local peasants found black stones near the village of Shun'ga, which were taken to be coal and called Olenets anthracite. A discussion began on the nature of this strange anthracite, which did not burn in furnaces. The found of the Karelian geological school, A.A. Inostrantsev, was the first to doubt that Olenets anthracite was really coal, and he named it shungite. Shungites, very unusual, barely combustible high-carbon rocks, have a variety of potential uses. Although details remain obscure, the authors propose a metasomatic origin involving migration and reduction of carbonaceous compounds driven by igneous intrusions. 10 references.

  4. CO2 Sequestraion by Mineral Carbonation of Cement Material

    NASA Astrophysics Data System (ADS)

    Jo, H.; Jang, Y.

    2010-12-01

    CO2 sequestration by mineral carbonation with cement materials was investigated in this study. Ca extraction and CO2 injection tests were conducted on three different materials (lime, Portland cement, waste concrete) using different extract reagents (NH4Cl, CH3COOH, HCl, and Deionized water) under ambient temperature and pressure conditions. CO2 gas (99.9%) was injected to either supernatant without solids or suspension with solids obtained from extraction tests at 4 ml/min of flow rate. Ca concentrations were measured from filtered solutions before and after CO2 injection. The chemical and mineralogical composition of raw materials and precipitates were determined using X-ray fluorescence and X-ray diffraction, respectively. The morphology and chemical composition of precipitates were analyzed with Field Emission Scanning Electron Microscopy equipped with the Energy Dispersive X-ray analysis. For the extraction tests, Ca concentrations of the extracts were related with the CaO content and type of CaO bearing minerals of the materials, regardless of the extraction solutions. Lime had a higher Ca concentration ranging between 942.7 and 39945.0 mg/L in the extracts than waste concrete (188.4 ~ 2978.1 mg/L) in the extracts due to its higher content of CaO (CaO : 24.5% and waste concrete : 20.3%). In contrast, the Portland cement (6346.0 and 28903.5 mg/L) had lower Ca concentrations than lime (94.27 ~ 39945.0 mg/L), even though the Portland cement (56.3%) had a higher CaO content than lime (24.5%). For a given extraction solution, lime had the highest CO2 carbonation efficiency. In addition, for a given material, the CO2 carbonation efficiency was the highest when NH4Cl solution was used as an extraction solution. Results of material analyses indicate that precipitates from the CO2 injection tests consisted of mostly CaCO3, regardless of types of materials and extraction solutions.

  5. [Clostridium sp. MH18 strain induces the formation of carbonate minerals].

    PubMed

    Guo, Wenwen; Ma, Heng; Li, Fuchun; Wang, Jinping; Su, Ning

    2012-02-04

    We studied the formation of carbonate minerals by bacteria to understand the mechanism of microbial mineralization. Cultures of carbonate precipitation using Lagoa Vermelha medium with 6:1 molar ratio of Mg/Ca within 35 days were made under the mediation of Clostridium sp. (MH18 strain) isolated from soil. At the same time, aseptic experiments without the inoculation were done as the control. Mineral species were determined by X-ray diffraction, and the morphologies of precipitated carbonates were observed using optical microscopy and scanning electron microscopy. In the LV medium, MH18 strain mediated the formation of carbonate mineral, in which high-magnesium calcite was dominant. In the initial stage, the minerals had shapes with dumbbell-like morphology, and finally transformed to spheres. Only a small amount of precipitation appeared in the control, but X-ray diffraction patterns showed that these precipitations were amorphous substance. MH18 strain could induce crystallization of carbonate.

  6. Preparation of pure calcium carbonate by mineral carbonation using industrial byproduct FGD gypsum

    NASA Astrophysics Data System (ADS)

    Song, K.; Kim, W.; Bang, J. H.; Park, S.; Jeon, C. W.

    2015-12-01

    Mineral carbonation is one of the geological approaches for the sequestration of anthropogenic CO2 gas. Its concept is based on the natural weathering processes in which silicate minerals containing divalent cations such as Ca or Mg are carbonated to CaCO3 or MgCO3 in the reaction with CO2gas. Raw materials for the mineral carbonation have been extended to various industrial solid wastes such as steel slag, ashes, or FGD (flue gas desulfurization) gypsum which are rich in divalent cations. These materials have economic advantages when they are produced in CO2 emission sites. Flue gas desulfurization (FGD) gypsum is such a byproduct obtained in at coal-fired power plants. Recently, we carried out a research on the direct mineral carbonation of FGD gypsum for CO2sequestration. It showed high carbonation reactivity under ambient conditions and the process can be described as follows: CaSO4·2H2O + CO2(g) + 2NH4OH(aq) → CaCO3(s) + (NH4)2SO4(aq) (1) At the early stage of the process, calcium carbonate (CaCO3) exists as a dissolved ion pair during the induction period. High-purity CaCO3 could be precipitated from dissolved calcium carbonate solution extracted during the induction period. The effect of experimental parameters on pure CaCO3 was evaluated: CO2 flow rate (1-3 L/min), ammonia content (4-12%), and solid-to-liquid (S/L) ratio (5-300 g/L). FE-SEM (field-emission scanning electron microscopy) and XRD (X-ray diffraction) study revealed that the precipitated CaCO3 was round-shaped vaterite crystals. The induction time was inversely proportional to the CO2 flow rate and the yield for pure CaCO3 increased with the ammonia content. The formation efficiency for pure CaCO3 decreased with S/L (solid/liquid) ratio. It was 90% (mol/mol) when the S/L ratio was 5 g/L. However, S/L ratio didn't affect the maximum solubility limit of dissolved CaCO3.

  7. Factors Affecting the Clumped Isotope Signature of Dissolved Inorganic Carbon and Carbonate Minerals

    NASA Astrophysics Data System (ADS)

    Hill, P. S.; Tripati, A. K.; Schauble, E. A.

    2011-12-01

    18O/16O ratios[a] and 13C-18O bond ordering[b] in many natural and synthetic carbonate minerals may reflect the extent of isotopic equilibration of dissolved inorganic carbon (DIC) species, rather than the crystalline equilibrium. In the simplest case where transport and surface-reaction steps do not impart their own fractionations, the clumped isotope signature (Δ47: the enrichment in per mil of 13C18O16O above the amount expected for a random distribution of isotopes among all CO2 isotopologues) of a carbonate mineral precipitating from solution would preserve the temperature of DIC equilibration at the time of precipitation. We examine the consequences of (1) the time scale of DIC equilibration and (2) precipitation rate on Δ47 values of carbonate minerals, using electronic structure models of molecular clusters that approximate aqueous and crystalline chemical environments. Our use of cluster models for both the aqueous and the mineral phases of the clumped isotope system has the advantage of enabling us to compare aqueous and mineral systems with the same electronic structure methods, partially canceling systematic model errors. Fluid cluster models containing 21-32 water molecules are generated from periodic-boundary-condition molecular dynamics simulations. Mineral clusters are derived from measured crystal structures, with boundaries terminated by link atoms so as to retain Pauling bond strengths with severed distal lattice bonds[c]. Different combinations of density functional theory (DFT) methods and basis sets are compared. These studies, combined with concurrent controlled precipitation experiments, will add to our understanding of the extent of disequilibrium effects on clumping while providing a framework to include previous studies (such as the work of Guo et al. on the kinetic effects of CO2 dehydration and dehydroxyation and acid digestion[e]). [a] Zeebe, R.E. (2007) G3, 8, Q09002,; Zeebe, R.E. (1999) GCA 63, 2001-2007 [b] Tripati, A.K. et al

  8. Minerals

    MedlinePlus

    Minerals are important for your body to stay healthy. Your body uses minerals for many different jobs, including keeping your bones, muscles, heart, and brain working properly. Minerals are also important for making enzymes and hormones. ...

  9. Factors for Microbial Carbon Sources in Organic and Mineral Soils from Eastern United States Deciduous Forests

    SciTech Connect

    Stitt, Caroline R.

    2013-09-16

    Forest soils represent a large portion of global terrestrial carbon; however, which soil carbon sources are used by soil microbes and respired as carbon dioxide (CO2) is not well known. This study will focus on characterizing microbial carbon sources from organic and mineral soils from four eastern United States deciduous forests using a unique radiocarbon (14C) tracer. Results from the dark incubation of organic and mineral soils are heavily influenced by site characteristics when incubated at optimal microbial activity temperature. Sites with considerable differences in temperature, texture, and location differ in carbon source attribution, indicating that site characteristics play a role in soil respiration.

  10. Energy and economic considerations for ex-situ and aqueous mineral carbonation

    SciTech Connect

    O'Connor, William K.; Dahlin, David C.; Rush, G.E.; Gerdemann, Stephen J.; Penner, L.R.

    2004-01-01

    Due to the scale and breadth of carbon dioxide emissions, and speculation regarding their impact on global climate, sequestration of some portion of these emissions has been under increased study. A practical approach to carbon sequestration will likely include several options, which will be driven largely by the energy demand and economics of operation. Aqueous mineral carbonation of calcium and magnesium silicate minerals has been studied as one potential method to sequester carbon dioxide. Although these carbonation reactions are all thermodynamically favored, they occur at geologic rates of reaction. Laboratory studies have demonstrated that these rates of reaction are accelerated with increasing temperature, pressure, and particle surface area. Mineral-specific activation methods were identified, however, each of these techniques incurs energy as well as economic costs. An overview of the mineral availability, pretreatment options and energy demands, and process economics is provided.

  11. A disconnect between O horizon and mineral soil carbon - Implications for soil C sequestration

    SciTech Connect

    Garten Jr, Charles T

    2009-01-01

    Changing inputs of carbon to soil is one means of potentially increasing carbon sequestration in soils for the purpose of mitigating projected increases in atmospheric CO{sub 2} concentrations. The effect of manipulations of aboveground carbon input on soil carbon storage was tested in a temperate, deciduous forest in east Tennessee, USA. A 4.5-year experiment included exclusion of aboveground litterfall and supplemental litter additions (three times ambient) in an upland and a valley that differed in soil nitrogen availability. The estimated decomposition rate of the carbon stock in the O horizon was greater in the valley than in the upland due to higher litter quality (i.e., lower C/N ratios). Short-term litter exclusion or addition had no effect on carbon stock in the mineral soil, measured to a depth of 30 cm, or the partitioning of carbon in the mineral soil between particulate- and mineral-associated organic matter. A two-compartment model was used to interpret results from the field experiments. Field data and a sensitivity analysis of the model were consistent with little carbon transfer between the O horizon and the mineral soil. Increasing aboveground carbon input does not appear to be an effective means of promoting carbon sequestration in forest soil at the location of the present study because a disconnect exists in carbon dynamics between O horizon and mineral soil. Factors that directly increase inputs to belowground soil carbon, via roots, or reduce decomposition rates of organic matter are more likely to benefit efforts to increase carbon sequestration in forests where carbon dynamics in the O horizon are uncoupled from the mineral soil.

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

    SciTech Connect

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

    2001-10-01

    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.

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

    SciTech Connect

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

    2002-11-01

    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 (1) its structural and chemical simplicity, (2) interest in Mg(OH){sub 2} gas-solid carbonation as a potentially cost-effective CO{sub 2} mineral sequestration process component, and (3) 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 final report covers the overall progress of this grant.

  14. Carbon sequestration via aqueous olivine mineral carbonation: role of passivating layer formation.

    PubMed

    Béarat, Hamdallah; McKelvy, Michael J; Chizmeshya, Andrew V G; Gormley, Deirdre; Nunez, Ryan; Carpenter, R W; Squires, Kyle; Wolf, George H

    2006-08-01

    CO2 sequestration via carbonation of widely available low-cost minerals, such as olivine, can permanently dispose of CO2 in an environmentally benign and a geologically stable form. We report the results of studies of the mechanisms that limit aqueous olivine carbonation reactivity under the optimum sequestration reaction conditions observed to date: 1 M NaCl + 0.64 M NaHCO3 at Te 185 degrees C and P(CO2) approximately equal to 135 bar. A reaction limiting silica-rich passivating layer (PL) forms on the feedstock grains, slowing carbonate formation and raising process cost. The morphology and composition of the passivating layers are investigated using scanning and transmission electron microscopy and atomic level modeling. Postreaction analysis of feedstock particles, recovered from stirred autoclave experiments at 1500 rpm, provides unequivocal evidence of local mechanical removal (chipping) of PL material, suggesting particle abrasion. This is corroborated by our observation that carbonation increases dramatically with solid particle concentration in stirred experiments. Multiphase hydrodynamic calculations are combined with experimentto better understand the associated slurry-flow effects. Large-scale atomic-level simulations of the reaction zone suggest that the PL possesses a "glassy" but highly defective SiO2 structure that can permit diffusion of key reactants. Mitigating passivating layer effectiveness is critical to enhancing carbonation and lowering sequestration process cost.

  15. Carbon sequestration via aqueous olivine mineral carbonation: role of passivating layer formation

    SciTech Connect

    Hamdallah Bearat; Michael J. McKelvy; Andrew V.G. Chizmeshya; Deirdre Gormley; Ryan Nunez; R.W. Carpenter; Kyle Squires; George H. Wolf

    2006-08-01

    CO{sub 2} sequestration via carbonation of widely available low-cost minerals, such as olivine, can permanently dispose of CO{sub 2} in an environmentally benign and a geologically stable form. The paper reports the results of studies of the mechanisms that limit aqueous olivine carbonation reactivity under the optimum sequestration reaction conditions observed to date: 1 M NaCl + 0.64 M NaHCO{sub 3} at T {approx} 185{sup o}C and P{sub CO{sub 2}} {approx} 135 bar. A reaction limiting silica-rich passivating layer (PL) forms on the feedstock grains, slowing carbonate formation and raising process cost. The morphology and composition of the passivating layers are investigated using scanning and transmission electron microscopy and atomic level modeling. Postreaction analysis of feedstock particles, recovered from stirred autoclave experiments at 1500 rpm, provides unequivocal evidence of local mechanical removal (chipping) of PL material, suggesting particle abrasion. This is corroborated by the observation that carbonation increases dramatically with solid particle concentration in stirred experiments. Multiphase hydrodynamic calculations are combined with experiment to better understand the associated slurry-flow effects. Large-scale atomic-level simulations of the reaction zone suggest that the PL possesses a 'glassy' but highly defective SiO{sub 2} structure that can permit diffusion of key reactants. Mitigating passivating layer effectiveness is critical to enhancing carbonation and lowering sequestration process cost. 30 refs., 7 figs.

  16. Delineation of Magnesium-rich Ultramafic Rocks Available for Mineral Carbon Sequestration in the United States

    USGS Publications Warehouse

    Krevor, S.C.; Graves, C.R.; Van Gosen, B. S.; McCafferty, A.E.

    2009-01-01

    The 2005 Intergovernmental Panel on Climate Change report on Carbon Dioxide Capture and Storage suggested that a major gap in mineral carbon sequestration is locating the magnesium-silicate bedrock available to sequester CO2. It is generally known that silicate minerals with high concentrations of magnesium are suitable for mineral carbonation. However, no assessment has been made covering the entire United States detailing their geographical distribution and extent, or evaluating their potential for use in mineral carbonation. Researchers at Columbia University and the U.S. Geological Survey have developed a digital geologic database of ultramafic rocks in the continental United States. Data were compiled from varied-scale geologic maps of magnesium-silicate ultramafic rocks. These rock types are potentially suitable as source material for mineral carbon-dioxide sequestration. The focus of the national-scale map is entirely on suitable ultramafic rock types, which typically consist primarily of olivine and serpentine minerals. By combining the map with digital datasets that show non-mineable lands (such as urban areas and National Parks), estimates on potential depth of a surface mine, and the predicted reactivities of the mineral deposits, one can begin to estimate the capacity for CO2 mineral sequestration within the United States. ?? 2009 Elsevier Ltd. All rights reserved.

  17. Mineral Dissolution and Precipitation due to Carbon Dioxide-Water-Rock Interactions: The Significance of Accessory Minerals in Carbonate Reservoirs (Invited)

    NASA Astrophysics Data System (ADS)

    Kaszuba, J. P.; Marcon, V.; Chopping, C.

    2013-12-01

    Accessory minerals in carbonate reservoirs, and in the caprocks that seal these reservoirs, can provide insight into multiphase fluid (CO2 + H2O)-rock interactions and the behavior of CO2 that resides in these water-rock systems. Our program integrates field data, hydrothermal experiments, and geochemical modeling to evaluate CO2-water-rock reactions and processes in a variety of carbonate reservoirs in the Rocky Mountain region of the US. These studies provide insights into a wide range of geologic environments, including natural CO2 reservoirs, geologic carbon sequestration, engineered geothermal systems, enhanced oil and gas recovery, and unconventional hydrocarbon resources. One suite of experiments evaluates the Madison Limestone on the Moxa Arch, Southwest Wyoming, a sulfur-rich natural CO2 reservoir. Mineral textures and geochemical features developed in the experiments suggest that carbonate minerals which constitute the natural reservoir will initially dissolve in response to emplacement of CO2. Euhedral, bladed anhydrite concomitantly precipitates in response to injected CO2. Analogous anhydrite is observed in drill core, suggesting that secondary anhydrite in the natural reservoir may be related to emplacement of CO2 into the Madison Limestone. Carbonate minerals ultimately re-precipitate, and anhydrite dissolves, as the rock buffers the acidity and reasserts geochemical control. Another suite of experiments emulates injection of CO2 for enhanced oil recovery in the Desert Creek Limestone (Paradox Formation), Paradox Basin, Southeast Utah. Euhedral iron oxyhydroxides (hematite) precipitate at pH 4.5 to 5 and low Eh (approximately -0.1 V) as a consequence of water-rock reaction. Injection of CO2 decreases pH to approximately 3.5 and increases Eh by approximately 0.1 V, yielding secondary mineralization of euhedral pyrite instead of iron oxyhydroxides. Carbonate minerals also dissolve and ultimately re-precipitate, as determined by experiments in the

  18. Roles of Transport Limitations and Mineral Heterogeneity in Carbonation of Fractured Basalts.

    PubMed

    Menefee, Anne H; Li, Peiyuan; Giammar, Daniel E; Ellis, Brian R

    2017-08-15

    Basalt formations could enable secure long-term carbon storage by trapping injected CO2 as stable carbonates. Here, a predictive modeling framework was designed to evaluate the roles of transport limitations and mineral spatial distributions on mineral dissolution and carbonation reactions in fractured basalts exposed to CO2-acidified fluids. Reactive transport models were developed in CrunchTope based on data from high-temperature, high-pressure flow-through experiments. Models isolating the effect of transport compared nine flow conditions under the same mineralogy. Heterogeneities were incorporated by segmenting an actual reacted basalt sample, and these results were compared to equivalent flow conditions through randomly generated mineral distributions with the same bulk composition. While pure advective flow with shorter retention times promotes rapid initial carbonation, pure diffusion sustains mineral reactions for longer time frames and generates greater net carbonate volumes. For the same transport conditions and bulk composition, exact mineral spatial distributions do not impact the amount of carbonation but could determine the location by controlling local solution saturation with respect to secondary carbonates. In combination, the results indicate that bulk mineralogy will be more significant than small-scale heterogeneities in controlling the rate and extent of CO2 mineralization, which will likely occur in diffusive zones adjacent to flow paths or in dead-end fractures.

  19. DEVELOPMENT OF A CO2 SEQUESTRATION MODULE BY INTEGRATING MINERAL ACTIVATION AND AQUEOUS CARBONATION

    SciTech Connect

    George Alexander; M. Mercedes Maroto-Valer; Parvana Aksoy; Harold Schobert

    2006-03-25

    Mineral carbonation provides a potential option for the long-term storage of carbon dioxide. Serpentine has been chosen as the feedstock mineral, due to its abundance and availability. However, the relatively low reactivity of serpentine has warranted research into physical and chemical treatments that have been shown to greatly increase its reactivity. The use of sulfuric acid as an accelerating medium for the removal of magnesium from serpentine has recently been investigated. In addition to the challenges presented by the dissolution of serpentine, another challenge is the subsequent carbonation of the magnesium ions. A stable hydration sphere for the magnesium ion reduces the carbonation kinetics by obstructing the formation of the carbonation products. Accordingly, this research has evaluated the solubility of carbon dioxide in aqueous solution, the interaction between the dissociation products of carbon dioxide, and the carbonation potential of the magnesium ion.

  20. Diet influences rates of carbon and nitrogen mineralization from decomposing grasshopper frass and cadavers

    USDA-ARS?s Scientific Manuscript database

    Insect herbivory can produce a pulse of mineral nitrogen (N) in soil from the decomposition of frass and cadavers. In this study we examined how diet quality affects rates of N and carbon (C) mineralization from grasshopper frass and cadavers. Frass was collected from grasshoppers fed natural or mer...

  1. Changes in mineral-associated soil organic carbon pools across a harvested temperate forest chronosequence

    NASA Astrophysics Data System (ADS)

    MacIntyre, S.; Kellman, L. M.; Gabriel, C. E.; Diochon, A.

    2016-12-01

    Due to their substantial pool size, changes in mineral soil carbon (C) stores have the potential to generate significant changes in forest soil C budgets. Harvesting represents a significant land use disturbance that can alter soil organic carbon (SOC) stores, with a number of field studies documenting large losses of SOC following clearcut harvesting. However, little is known about how the distribution of SOC changes amongst mineral-associated pools of differing crystallinity following this disturbance. The objective of this study was to quantify changes in mineral-associated SOC pool sizes through depth and time for podzol soils (mineral soil depths of 0-5, 5-10, 10-15, 15-20, 20-35, and 35-50 cm) of a temperate red spruce harvest chronosequence (representing stand ages of 1yr, 15yr, 45yr, 80yr, and 125+yr) in Nova Scotia, Canada. Samples were subjected to a 4-step sequential chemical dissolution to selectively extract C from mineral pools of increasing crystallinity: soluble minerals (deionized water), organo-metal complexes (Na-pyrophosphate), poorly crystalline minerals (hydroxylamine), and crystalline minerals (Na-dithionite HCl). Carbon concentrations were calculated for the solutions acquired during each stage of the selective dissolution process, providing a time series of changes in mineral-associated C through depth and time following harvesting. A loss of SOC from the organo-metal complexed pool following harvesting was observed, particularly in the deeper mineral soil (20-50cm), with this pool dominating the results. In the soluble and poorly crystalline pools, losses of C were also observed from the deeper mineral soil. Of the 5 sites, the 125+yr age class had the highest concentration of SOC associated with crystalline minerals, with the 0-5cm depth stratum holding a large portion of this C. This study may be useful as a model system for understanding how harvesting disturbance alters mineral pool SOM dynamics in humid temperate forest ecosystems.

  2. Carbonate mineral dissolution kinetics in high pressure experiments

    NASA Astrophysics Data System (ADS)

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

    2012-04-01

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

  3. Integrated Experimental and Modeling Studies of Mineral Carbonation as a Mechanism for Permanent Carbon Sequestration in Mafic/Ultramafic Rocks

    SciTech Connect

    Wang, Zhengrong; Qiu, Lin; Zhang, Shuang; Bolton, Edward; Bercovici, David; Ague, Jay; Karato, Shun-Ichiro; Oristaglio, Michael; Zhu, Wen-Iu; Lisabeth, Harry; Johnson, Kevin

    2014-09-30

    A program of laboratory experiments, modeling and fieldwork was carried out at Yale University, University of Maryland, and University of Hawai‘i, under a DOE Award (DE-FE0004375) to study mineral carbonation as a practical method of geologic carbon sequestration. Mineral carbonation, also called carbon mineralization, is the conversion of (fluid) carbon dioxide into (solid) carbonate minerals in rocks, by way of naturally occurring chemical reactions. Mafic and ultramafic rocks, such as volcanic basalt, are natural candidates for carbonation, because the magnesium and iron silicate minerals in these rocks react with brines of dissolved carbon dioxide to form carbonate minerals. By trapping carbon dioxide (CO2) underground as a constituent of solid rock, carbonation of natural basalt formations would be a secure method of sequestering CO2 captured at power plants in efforts to mitigate climate change. Geochemical laboratory experiments at Yale, carried out in a batch reactor at 200°C and 150 bar (15 MPa), studied carbonation of the olivine mineral forsterite (Mg2SiO4) reacting with CO2 brines in the form of sodium bicarbonate (NaHCO3) solutions. The main carbonation product in these reactions is the carbonate mineral magnesite (MgCO3). A series of 32 runs varied the reaction time, the reactive surface area of olivine grains and powders, the concentration of the reacting fluid, and the starting ratio of fluid to olivine mass. These experiments were the first to study the rate of olivine carbonation under passive conditions approaching equilibrium. The results show that, in a simple batch reaction, olivine carbonation is fastest during the first 24 hours and then slows significantly and even reverses. A natural measure of the extent of carbonation is a quantity called the carbonation fraction, which compares the amount of carbon removed from solution, during a run, to the maximum amount

  4. A New Route for Unburned Carbon Concentration Measurements Eliminating Mineral Content and Coal Rank Effects

    PubMed Central

    Liu, Dong; Duan, Yuan-Yuan; Yang, Zhen; Yu, Hai-Tong

    2014-01-01

    500 million tons of coal fly ash are produced worldwide every year with only 16% of the total amount utilized. Therefore, potential applications using fly ash have both environmental and industrial interests. Unburned carbon concentration measurements are fundamental to effective fly ash applications. Current on-line measurement accuracies are strongly affected by the mineral content and coal rank. This paper describes a char/ash particle cluster spectral emittance method for unburned carbon concentration measurements. The char/ash particle cluster spectral emittance is predicted theoretically here for various unburned carbon concentrations to show that the measurements are sensitive to unburned carbon concentration but insensitive to the mineral content and coal rank at short wavelengths. The results show that the char/ash particle cluster spectral emittance method is a novel and promising route for unburned carbon concentration on-line measurements without being influenced by mineral content or coal rank effects. PMID:24691496

  5. Carbon-mineral adsorbents prepared by pyrolysis of waste materials in the presence of tetrachloromethane.

    PubMed

    Leboda, Roman; Charmas, Barbara; Skubiszewska-Zieba, Jadwiga; Chodorowski, Stanislaw; Oleszczuk, Patryk; Gun'ko, Vladimir M; Pokrovskiy, Valery A

    2005-04-01

    Natural bentonite spent in the process of plant oil bleaching was used as an initial material for preparation of carbon-mineral adsorbents. The spent bleaching earth was treated using four procedures: T (thermal treatment); H (hydrothermal treatment); C (thermal treatment with addition of CCl4 vapor); M (modification of porous structure). Raw bentonite, RB (raw bleaching earth), and carbon materials prepared using plant oil were compared. The physicochemical characteristics of the adsorbents were determined using different methods: nitrogen adsorption/desorption, XRD, TEM, and MS-TPD. Carbon-mineral adsorbents contain from 5.23 to 19.92% C (w/w) and carbon adsorbents include from 84.2 to 91.18% C (w/w). Parallel processes of organic substance carbonization, porous structure modification, sublimation or evaporation of metal chlorides, and removal of hydrogen chloride take place during pyrolysis of waste mineral materials in the CCl4 atmosphere.

  6. Sequestering CO(2) by mineral carbonation: stability against acid rain exposure.

    PubMed

    Allen, Daniel J; Brent, Geoff F

    2010-04-01

    Mineral carbonation is a potentially attractive alternative to storage of compressed CO(2) in underground repositories, known as geosequestration. Processes for the conversion of basic ores, such as magnesium silicates, to carbonates have been proposed by various researchers, with storage of the carbonate as backfill in the original mine representing a solid carbon sink. The stability of such carbon sinks against acid rain and other sources of strong acids is examined here. It is acknowledged that in the presence of strong acid, carbonates will dissolve and release carbon dioxide. A sensitivity analysis covering annual average rainfall and pH that may be encountered in industrialized areas of the United States, China, Europe, and Australia was conducted to determine maximum CO(2) rerelease rates from mineral carbonation carbon sinks. This analysis is based on a worst-case premise that is equivalent to assuming infinitely rapid kinetics of dissolution of the carbonate. The analysis shows that under any likely conditions of pH and rainfall, leakage rates of stored CO(2) are negligible. This is illustrated in a hypothetical case study under Australian conditions. It is thus proposed that sequestration by mineral carbonation can be considered to be permanent on practical human time scales. Other possible sources of acid have also been considered.

  7. Short-Range-Order Mineral Physical Protection On Black Carbon Stabilization

    NASA Astrophysics Data System (ADS)

    Liang, B.; Weng, Y. T.; Wang, C. C.; Song, Y. F.; Lehmann, J.; Wang, C. H.

    2015-12-01

    Soil organic matter is one of the largest reservoirs in global carbon cycle, and black carbon (BC) represents a chemical resistant component. Black C plays an important role in global climate change. Generally considered recalcitrant due to high aromaticity, the reactive surface and functional groups of BC are crucial for carbon sequestration in soils. Mineral sorption and physical protection is an important mechanism for BC long term stabilization and sequestration in environments. Previous studies on mineral protection of BC were limited to analysis techniques in two-dimensions, for example, by SEM, TEM, and NanoSIMS. Little is known about the scope of organo-mineral association, the in-situ distribution and forms of minerals, and the ultimate interplay of BC and minerals. The aim of this study is to investigate the three-dimensional interaction of organic C and minerals in submicron scale using synchrotron-based Transmission X-ray Microcopy (TXM) and Fourier-Transform Infrared Spectroscopy (FTIR). Abundant poorly-crystallined nano-minerals particles were observed. These short-range-order (SRO) minerals also aggregate into clusters and sheets, and form envelops-like structures on the surface of BC. On top of large surface contact area, the intimate interplay between BC and minerals reinforces the stability of both organic C and minerals, resulting from chemical bonding through cation bridging and ligand exchange. The mineral protection enhances BC stabilization and sequestration and lowers its bioavailability in environment. The results suggest that mineral physical protection for BC sequestration may be more important than previous understanding.

  8. Harnessing mineral carbonation reactions to seal fractured shales and sequester carbon

    NASA Astrophysics Data System (ADS)

    Clarens, A. F.; Tao, Z.

    2014-12-01

    Shale oil and gas are being developed widely in the United States despite the potential for long-term climate impacts driven by burning these new hydrocarbon resources and by fugitive emissions from fractured formations. Here the carbonation of calcium-based silicates is studied as a method to re-seal fractured shale formations and to store significant amounts of CO2 after hydrocarbon extraction. Ex situ mineral carbonation has been studied extensively for trapping CO2 from power plants but the application of these reactions directly within shale matrix under in situ conditions to seal shales and sequester carbon has not been studied. The reaction requires the solid calcium-based silicates being present within the shale fracture matrix and flooded with high-pressure CO2. The pressure and temperature within most shale formations would enable this carbonation reaction to precipitate solid calcium carbonate, which would clog fractures. Silicates could be injected in the same way that proppants are injected into shale gas wells. Wollastonite was tested here but other silicate minerals such as olivine could also be used in much the same way. To prove this concept, batch experiments were carried out under reservoir conditions representative of the Marcellus Shale in the presence of ground shale particles (39-177μm) and CaSiO3 powder. X-ray diffraction (XRD) patterns revealed the conversion of CaSiO3 into CaCO3 after 24 hours. Quantitative XRD analysis was used to determine that the conversion ratio of CaSiO3 was ~55% at 3100 Psi and 75oC. The reaction was sensitive to both temperature and pressure with ~58% conversion at an increased temperature of 95oC and only ~50% at lower pressure (2200psi). The morphology observed by Scanning Electron Microscopy (SEM) reveals that the shale particle surfaces are covered with precipitated calcite crystals ranging in size from 1 to 5 μm. Using energy-dispersive X-ray spectroscopy (EDS), the locations of residual CaSiO3and

  9. Experimental evidence for chemo-mechanical coupling during carbon mineralization in ultramafic rocks

    NASA Astrophysics Data System (ADS)

    Lisabeth, H. P.; Zhu, W.; Kelemen, P. B.; Ilgen, A.

    2017-09-01

    Storing carbon dioxide in the subsurface as carbonate minerals has the benefit of long-term stability and immobility. Ultramafic rock formations have been suggested as a potential reservoir for this type of storage due to the availability of cations to react with dissolved carbon dioxide and the fast reaction rates associated with minerals common in ultramafic formations; however, the rapid reactions have the potential to couple with the mechanical and hydraulic behavior of the rocks and little is known about the extent and mechanisms of this coupling. In this study, we argue that the dissolution of primary minerals and the precipitation of secondary minerals along pre-existing fractures in samples lead to reductions in both the apparent Young's modulus and shear strength of aggregates, accompanied by reduction in permeability. Hydrostatic and triaxial deformation experiments were run on dunite samples saturated with de-ionized water and carbon dioxide-rich solutions while stress, strain, permeability and pore fluid chemistry were monitored. Sample microstructures were examined after reaction and deformation using scanning electron microscopy (SEM). The results show that channelized dissolution and carbonate mineral precipitation in the samples saturated with carbon dioxide-rich solutions modify the structure of grain boundaries, leading to the observed reductions in stiffness, strength and permeability. A geochemical model was run to help interpret fluid chemical data, and we find that the apparent reaction rates in our experiments are faster than rates calculated from powder reactors, suggesting mechanically enhanced reaction rates. In conclusion, we find that chemo-mechanical coupling during carbon mineralization in dunites leads to substantial modification of mechanical and hydraulic behavior that needs to be accounted for in future modeling efforts of in situ carbon mineralization projects.

  10. Abiotic transformation of carbon tetrachloride at mineral surfaces. Final report, September 1990-September 1993

    SciTech Connect

    Kriegman-King, M.; Reinhard, M.

    1994-02-01

    The report addresses the ability of natural mineral surfaces to abiotically transform halogenated organic compounds in subsurface environments. The research focuses on carbon tetrachloride (CC14) as the halogenated organic and biotite, vermiculite, and pyrite as the mineral surfaces. The CCl4 transformation rates and products were quantified under different environmental conditions. The disappearance of CCl4 was significantly faster in the presence of mineral surfaces than in homogeneous solution. In systems containing the sheet silicates and HS-, the rate of reaction was dependent on the temperature, hydrogen sulfide ion concentration, surface concentration, and Fe(II) content in the minerals.

  11. Carbon, nitrogen, and phosphorus mineralization in northern wetlands

    SciTech Connect

    Bridgham, S.D.; Updegraff, K.; Pastor, J.

    1998-07-01

    The authors examined rates of C, N, and P mineralization in soils from 16 northern Minnesota wetlands that occur across an ombrotrophic-minerotrophic gradient. Soils were incubated at 30 C under aerobic and anaerobic conditions for 59 wk, and the results were fit with a two-pool kinetic model. Additionally, 39 different soil quality variables were used in a principal components analysis (PCA) to predict mineralization rates. Mineralization of C, N, and P differed significantly among wetland types, aeration status (aerobic vs. anaerobic), and their interaction term. Despite low total soil N and P, there was a rapid turnover of the nutrient pools in ombrotrophic sites, particularly under aerobic conditions. On a volumetric basis, C and N mineralization increased in a predictable manner across the ombrotrophic-minerotrophic gradient, largely due to increasing soil bulk density. However, P mineralization per cubic centimeter remained relatively high in the bogs. The higher total P content of more minerotrophic soils appears to be offset by greater P immobilization due to geochemical sorption, yielding overall lower availability. Large differences in mineralization rates in northern wetland communities demonstrate that climate change models should not consider these areas as homogeneous entities.

  12. Effects of mineral additives on biochar formation: carbon retention, stability, and properties.

    PubMed

    Li, Feiyue; Cao, Xinde; Zhao, Ling; Wang, Jianfei; Ding, Zhenliang

    2014-10-07

    Biochar is being recognized as a promising tool for long-term carbon sequestration, and biochar with high carbon retention and strong stability is supposed to be explored for that purpose. In this study, three minerals, including kaolin, calcite (CaCO3), and calcium dihydrogen phosphate [Ca(H2PO4)2], were added to rice straw feedstock at the ratio of 20% (w/w) for biochar formation through pyrolysis treatment, aiming to improve carbon retention and stabilization in biochar. Kaolin and CaCO3 had little effect on the carbon retention, whereas Ca(H2PO4)2 increased the carbon retention by up to 29% compared to untreated biochar. Although the carbon loss from the kaolin-modified biochar with hydrogen peroxide oxidation was enhanced, CaCO3 and Ca(H2PO4)2 modification reduced the carbon loss by 18.6 and 58.5%, respectively. Moreover, all three minerals reduced carbon loss of biochar with potassium dichromate oxidation from 0.3 to 38.8%. The microbial mineralization as CO2 emission in all three modified biochars was reduced by 22.2-88.7% under aerobic incubation and 5-61% under anaerobic incubation. Enhanced carbon retention and stability of biochar with mineral treatment might be caused by the enhanced formation of aromatic C, which was evidenced by cross-polarization magic angle spinning (13)C nuclear magnetic resonance spectra and Fourier transform infrared spectroscopy analysis. Our results indicated that the three minerals, especially Ca(H2PO4)2, were effective in increasing carbon retention and strengthening biochar stabilization, which provided a novel idea that people could explore and produce the designated biochar with high carbon sequestration capacity and stability.

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

    NASA Astrophysics Data System (ADS)

    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

  14. Amorphous calcium carbonate controls avian eggshell mineralization: A new paradigm for understanding rapid eggshell calcification.

    PubMed

    Rodríguez-Navarro, Alejandro B; Marie, Pauline; Nys, Yves; Hincke, Maxwell T; Gautron, Joel

    2015-06-01

    Avian eggshell mineralization is the fastest biogenic calcification process known in nature. How this is achieved while producing a highly crystalline material composed of large calcite columnar single crystals remains largely unknown. Here we report that eggshell mineral originates from the accumulation of flat disk-shaped amorphous calcium carbonate (ACC) particles on specific organic sites on the eggshell membrane, which are rich in proteins and sulfated proteoglycans. These structures known as mammillary cores promote the nucleation and stabilization of a amorphous calcium carbonate with calcitic short range order which predetermine the calcite composition of the mature eggshell. The amorphous nature of the precursor phase was confirmed by the diffuse scattering of X-rays and electrons. The nascent calcitic short-range order of this transient mineral phase was revealed by infrared spectroscopy and HRTEM. The ACC mineral deposited around the mammillary core sites progressively transforms directly into calcite crystals without the occurrence of any intermediate phase. Ionic speciation data suggest that the uterine fluid is equilibrated with amorphous calcium carbonate, throughout the duration of eggshell mineralization process, supporting that this mineral phase is constantly forming at the shell mineralization front. On the other hand, the transient amorphous calcium carbonate mineral deposits, as well as the calcite crystals into which they are converted, form by the ordered aggregation of nanoparticles that support the rapid mineralization of the eggshell. The results of this study alter our current understanding of avian eggshell calcification and provide new insights into the genesis and formation of calcium carbonate biominerals in vertebrates. Copyright © 2015 Elsevier Inc. All rights reserved.

  15. The extent of carbon mineralization in boreal soils controls compositional changes

    NASA Astrophysics Data System (ADS)

    Mercier Quideau, S.; Oh, S.; Paré, D.

    2013-12-01

    Almost twenty percent of global carbon stocks in vegetation and soil are found in boreal soils, making them the largest terrestrial carbon storehouse in the world. Yet, despite their importance in the global carbon budget, very little is known about the exact nature and decomposition pathways of organic matter in these soils. The overall objective of this study was to examine the effects of vegetation and disturbance (fire and harvest) on: 1) soil organic matter composition, and 2) decomposition-induced changes in composition from a range of representative boreal forest and peatland ecosystems. Forest floor and peat samples (0-10 cm) were obtained from 17 sites along an east-west transect from New Brunswick to British Columbia, Canada. Carbon mineralization rates were measured during a 1-year laboratory incubation at 10 °C. Carbon chemistry in pre- and post-incubation samples was characterized by solid-state ramped-cross-polarization (RAMP-CP) 13C nuclear magnetic resonance (NMR). The percentage of carbon mineralized during incubation ranged from 1 to 24%, and corresponded to significant increases in aromatic, phenolic, and carbonyl carbons. As expected, significant differences in carbon composition pre-incubation were found among vegetation types regardless of disturbance and sampling location. May be more interestingly, comparable differences among samples persisted post-incubation. In addition, decomposition-induced changes in carbon chemistry significantly differed among vegetation types. Samples from Jack pine and Douglas fir stands, which experienced the highest carbon mineralization, also showed the greatest increase in aromatic, phenolic, and carbonyl carbons. Overall, changes in carbon chemistry were significantly correlated to the percentage of carbon mineralized; i.e., the extent of decomposition that the samples underwent.

  16. Development of models for predicting carbon mineralization and associated phytotoxicity in compost-amended soil.

    PubMed

    Aslam, Danielle N; Vandergheynst, Jean S; Rumsey, Thomas R

    2008-12-01

    Phytotoxicity of compost-amended soil is related to carbon mineralization associated with compost decomposition. The objective of this research was to determine if compost carbon mineralization potential, estimated using compost respiration rate measurements, could be combined with carbon mineralization kinetic models to predict phytotoxicity of compost-amended soil. First-order, second-order, and Monod kinetic models that include compost carbon mineralization potential, compost amendment rate, incubation time, and temperature were developed and compared for their ability to predict carbon mineralization kinetics. Experiments utilized two soil types amended with 0%, 5%, and 50% (v/v) food waste and green waste composts, incubated at 20 degrees C, 25 degrees C, 30 degrees C, 35 degrees C, and 45 degrees C for model development and under a diurnal temperature cycle from 20 degrees C to 30 degrees C for model validation. For most cases, a first-order model had an equivalent or better fit to the data than the other models. Mineralizable carbon estimated using the first-order model was significantly correlated to the probability of phytotoxicity in compost-amended soil.

  17. [A NIR qualitative and quantitative model of 8 kinds of carbonate-containing mineral Chinese medicines].

    PubMed

    Yuan, Ming-Yang; Huang, Bi-Sheng; Yu, Chi; Liu, Yi-Mei; Chen, Ke-Li

    2014-01-01

    The aim of this paper is to apply near infrared spectroscopy techniques to construct a rapid identification method for 8 kinds of mineral Chinese Medicines containing carbonates. The qualitative model using clustering analysis method in OPUS software can identify accurately 8 kinds of carbonate-containing mineral Chinese medicines. The near-infrared quantitative model was established by using partial least squares method (PLS) for 7 mineral Chinese Medicines in which main component is calcium carbonate. Compared with the results by EDTA titration, the established quantitative analysis model for calcium carbonate content showed a good prediction result that when the content is between 47.61% -99.17%, the average relative deviation of the prediction result is 0.24% and the average recovery rate was 100.3%. The results also showed that the model using near infrared spectroscopy can get not only a rapid identification of the 8 mineral Chinese medicines containing carbonates, but also an accurate and reliabe content determination of calcium carbonate for the 7 mineral Chinese medicines which contain the component.

  18. Recent developments and perspectives on the treatment of industrial wastes by mineral carbonation — a review

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

    Besides producing a substantial portion of anthropogenic CO2 emissions, the industrial sector also generates significant quantities of solid residues. Mineral carbonation of alkaline wastes enables the combination of these two by-products, increasing the sustainability of industrial activities. On top of sequestering CO2 in geochemically stable form, mineral carbonation of waste materials also brings benefits such as stabilization of leaching, basicity and structural integrity, enabling further valorization of the residues, either via reduced waste treatment or landfilling costs, or via the production of marketable products. This paper reviews the current state-of-the-art of this technology and the latest developments in this field. Focus is given to the beneficial effects of mineral carbonation when applied to metallurgical slags, incineration ashes, mining tailings, asbestos containing materials, red mud, and oil shale processing residues. Efforts to intensify the carbonation reaction rate and improve the mineral conversion via process intensification routes, such as the application of ultrasound, hot-stage processing and integrated reactor technologies, are described. Valorization opportunities closest to making the transition from laboratory research to commercial reality, particularly in the form of shaped construction materials and precipitated calcium carbonate, are highlighted. Lastly, the context of mineral carbonation among the range of CCS options is discussed.

  19. Recent developments and perspectives on the treatment of industrial wastes by mineral carbonation — a review

    NASA Astrophysics Data System (ADS)

    Bodor, Marius; Santos, Rafael; Gerven, Tom; Vlad, Maria

    2013-12-01

    Besides producing a substantial portion of anthropogenic CO2 emissions, the industrial sector also generates significant quantities of solid residues. Mineral carbonation of alkaline wastes enables the combination of these two by-products, increasing the sustainability of industrial activities. On top of sequestering CO2 in geochemically stable form, mineral carbonation of waste materials also brings benefits such as stabilization of leaching, basicity and structural integrity, enabling further valorization of the residues, either via reduced waste treatment or landfilling costs, or via the production of marketable products. This paper reviews the current state-of-the-art of this technology and the latest developments in this field. Focus is given to the beneficial effects of mineral carbonation when applied to metallurgical slags, incineration ashes, mining tailings, asbestos containing materials, red mud, and oil shale processing residues. Efforts to intensify the carbonation reaction rate and improve the mineral conversion via process intensification routes, such as the application of ultrasound, hot-stage processing and integrated reactor technologies, are described. Valorization opportunities closest to making the transition from laboratory research to commercial reality, particularly in the form of shaped construction materials and precipitated calcium carbonate, are highlighted. Lastly, the context of mineral carbonation among the range of CCS options is discussed.

  20. Interface Induced Carbonate Mineralization: A Fundamental Geochemical Process Relevant to Carbon Sequestration

    SciTech Connect

    Teng, H. Henry; Xu, Huifang

    2013-07-17

    We have approached the long-standing geochemical question why anhydrous high-Mg carbonate minerals (i.e., magnesite and dolomite) cannot be formed at ambient conditions from a new perspective by exploring the formation of MgCO{sub 3} and Mg{sub x}Ca{sub (1-x)}CO{sub 3} in non-aqueous solutions. Data collected from our experiments in this funding period suggest that a fundamental barrier, other than cation hydration, exists that prevents Mg{sup 2+} and CO{sub 3}{sup 2-} ions from forming long-range ordered structures. We propose that this barrier mainly stems from the lattice limitation on the spatial configuration of CO{sub 3} groups in magnesite crystals. On the other hand, the measured higher distribution coefficients of Mg between magnesian calcites formed in the absence and presence of water give us a first direct proof to support and quantify the cation hydration effect.

  1. Is the exchangeable fraction determining the activity of mineral associated carbon?

    NASA Astrophysics Data System (ADS)

    Schrumpf, Marion; Mayer, Allegra; Kaiser, Klaus; Trumbore, Susan

    2017-04-01

    Sorption of organic molecules to mineral surfaces is assumed to be playing an important role for the long-term persistence of organic carbon (OC) in soils. Possibly due to the different mechanisms by which organic matter can be associated with minerals, not all carbon is equally strong bound to mineral surfaces. Therefore, it was observed that despite old average ages of mineral associated carbon, a portion is typically active. Assuming that active carbon has to be desorbed from mineral surfaces before mineralization, we hypothesize that (1) exchangeable OC will be younger than the residue, and that the portion of exchangeable carbon will (2) depend on the amount of pedogenic oxides and (3) decline with soil depth due to increasing ages of mineral associated OC with depth. To test these hypotheses, we treated the heavy fraction (d > 1.6 g cm-3) of five different soils and from three soil depths (0-5 cm, 10-20 cm, 30-40 cm) with NaF as a strong anion exchanger. Carbon and radiocarbon (14C) content were determined in both, extracts and residues. In order to test, if the extraction was able to remove all active carbon from mineral surfaces, and to get an idea about maximum ages of mineral associated carbon, we additionally treated the heavy fraction with heated (60°C) H2O2, and analyzed OC and 14C content in the residue. The NaF treatment removed on average 60±10% of total carbon from mineral surfaces. Following our expectation, the age of removed carbon was younger, and the residue older than the bulk HF fraction across soils and soil depths with an average 14C difference of 91‰. There was, however, no detectable influence of soil mineralogy or soil depth on the portion of exchangeable OC. Exchangeable OC was rather correlated to total OC in mineral associated fractions across sites and depths and proportional to OC in the residue. Only at the agricultural site studied with overall smallest OC contents, exchangeable OC was 25% less than at the other sites

  2. Soil mineral surfaces of paddy soils are accessible for organic carbon accumulation after decalcification

    NASA Astrophysics Data System (ADS)

    Wissing, Livia

    2013-04-01

    We studied organic carbon (OC) accumulation due to organo-mineral associations during soil development on calcareous parent material. Two chronosequences in Zhejiang Province, PR China, were investigated; one under paddy cultivation with a maximum soil age of 2000 years, and the other under upland crops where the oldest soil was 700 years old. Bulk soils and soil fractions of the uppermost A horizons were analyzed for OC concentrations and radio carbon contents. Total pedogenic iron (Fed) concentration was determined by dithionite extraction and the proportion of oxalate extractable iron (Feox) was extracted by using the method of Schwertmann (1964). The specific surface area (SSA) of soil minerals was measured by the BET-N2 method (Brunauer et al., 1938) under four conditions: untreated, after organic matter removal, after iron removal and after removal of both. Within 700/2000 years of pedogenesis, we observed no change in clay mineral composition and no additional formation of the SSA of soil minerals. But the soils differed in the degree of decalcification, OC accumulation and in the formation of iron. Paddy soil management led to an enhanced decalcification and larger OC accumulation. Management-induced redox cycles caused larger proportions of Feox in paddy soils. Their large SSA, added to the surface area of clay minerals, provided additional options for OC covering. Unexpectedly, there was no evidence of formation of secondary minerals during soil development, which could provide new surfaces for OC accumulation. However, the study revealed higher OC coverings of mineral surfaces after decalcification in paddy soils. As carbonate and Ca2+ ions seemed to interconnect clay minerals, making their surface accessible to OC, the faster dissolution of carbonate and leaching of Ca2+ ions in paddy soils made additional clay mineral surfaces available to OC. In contrast, the surface area of minerals in non-paddy soils, in which decalcification was much lower, seemed

  3. How relevant is chemical recalcitrance for predicting climatic effects on mineral soil carbon stocks?

    NASA Astrophysics Data System (ADS)

    Hopkins, F. M.; Torn, M. S.; Trumbore, S.

    2011-12-01

    The role of chemical recalcitrance in mediating the effect of warming on soil carbon stocks has been a focus of research efforts aimed toward the larger goal of prediction of carbon loss from soils in the 21st century. Arrhenius kinetics provides a theoretical basis for the prediction that reaction of chemically recalcitrant carbon compounds (those with higher activation energy) should be more temperature sensitive than compounds with faster turnover rates (lower activation energy). This relationship has even been integrated into models of soil carbon dynamics. However, since chemically recalcitrant compounds have, by definition, slower turnover rates, their response to warming should ultimately be far smaller than those of faster turnover compounds in terms of overall respiratory loss (Sierra 2011). Regardless of the relative temperature sensitivity of recalcitrant soil carbon, it remains an open question how important enhanced decomposition of chemically recalcitrant carbon in mineral soils is for potential feedbacks between warming and soil carbon stocks. To lend insight to this question, we present a series of incubation warming experiments with soils from two forest Free Air CO2 Enrichment (FACE) sites. Because of the distinct carbon isotope (radiocarbon free) signature of the CO2 fumigation gas, soil carbon in elevated CO2 plots has incorporated a decade of labeled carbon. By measuring the radiocarbon signature of flux, which reflects FACE label carbon in CO2 elevated plots, and the atmospheric history of radiocarbon in CO2 control plots, we attributed warming-induced increases in flux rates to soil carbon pools of different ages. Much of our knowledge about decomposition of recalcitrant compounds comes from litter decomposition, where chemical recalcitrance is the presumed control on decomposition rates. By comparing the response of litter and mineral soils to warming, we infer the role of chemical recalcitrance in mineral soils. Flux rates from both organic

  4. Mineral sequestration of carbon dioxide in peridotitic and basaltic rocks using seawater for carbonation

    NASA Astrophysics Data System (ADS)

    Wolff-Boenisch, Domenik; Wenau, Stefan; Gislason, Sigurdur

    2010-05-01

    In-situ mineral sequestration requires huge volumes of water for carbonation of CO2 which is injected as one fluid phase into the appropriate reactive subsurface for subsequent mineralization. The amount of water needed to dissolve one ton of CO2 is about 27 tons at 25 bar partial pressure and 25 ° C (Gislason et al., 2010). The CarbFix pilot injection project at the Hellisheidi geothermal power plant in SW Iceland taps a shallow aquifer to overcome this critical issue of water demand. Fresh water sources in Iceland are plenty and often replenished. However, areas of basaltic rock suitable for CO2 mineral sequestration are often situated in more arid climate zones or in areas of high population density with high drinking water demand, e.g. the Indian Deccan Trapps. To overcome this problem, CO2 can alternatively be dissolved in seawater prior to injection, as the amount of available seawater is practically unlimited. Furthermore, the ocean floor has been discussed as potential CO2 storage site (Goldberg et al., 2008) conferring seawater a key role in the viability of this trapping technique of carbon dioxide, irrespective of additional technical challenges and costs. Based on its much higher amount of total dissolved solids seawater displays some different properties from fresh water that may be harnessed to increase the efficiency of fluid-rock interaction and the precipitation of carbonates. Especially some of the seawater anions, e.g., fluoride, sulfate, and organic compounds have been shown to accelerate the dissolution kinetics of basaltic glass (Oelkers and Gislason, 2001; Wolff-Boenisch et al., 2004; Flaathen et al., 2009) and may also potentially enhance dissolution reactions of peridotite or crystalline basalt. Such increased dissolution kinetics would cause a faster rise in pH due to enhanced proton consumption in the dissolution reaction and also increase the amount of solute divalent cations, both crucial processes to successful carbonatization, a p

  5. Effects of switching from calcium carbonate to lanthanum carbonate on bone mineral metabolism in hemodialysis patients.

    PubMed

    Manabe, Rie; Fukami, Kei; Ando, Ryotaro; Sakai, Kazuko; Kusumoto, Takuo; Hazama, Takuma; Adachi, Takeki; Kaida, Yusuke; Nakayama, Yosuke; Ueda, Seiji; Kohno, Keisuke; Wada, Yoshifumi; Yamagishi, Sho-ichi; Okuda, Seiya

    2013-04-01

    Phosphate binders are useful for the treatment of hyperphosphatemia in hemodialysis (HD) patients. This study was performed to examine the effects of switching from calcium carbonate (CC) to lanthanum carbonate (LC) on bone mineral metabolism and inflammatory markers in HD patients. We conducted 29 stable HD patients receiving CC, which was replaced by LC and followed-up for 12 weeks. Patients underwent determinants of blood chemistries such as serum calcium (Ca), phosphorus, parathyroid hormone (PTH) and vitamin D status, and interleukin-6 (IL-6) mRNA levels in whole blood cells were evaluated by real-time PCR just before and after the treatment with LC. Corrected Ca [corrected] levels were significantly reduced, but serum phosphorus levels (P levels) were unchanged after LC treatment. Switching to LC increased whole-PTH, osteocalcin, 1,25(OH)(2) D(3) levels and 1,25(OH)(2) D(3)/25(OH)D(3) ratio. 1,25(OH)(2) D(3)/25(OH)D(3) ratio was negatively correlated with HD duration. Furthermore, whole blood cell IL-6 mRNA levels were significantly reduced by LC treatment. We provided that the switching from CC to LC improved Ca overload and ameliorated vitamin D and inflammatory status in HD patients. These observations suggest that LC may play a protective role for the progression of atherosclerosis and vascular calcification in these patients. © 2013 The Authors. Therapeutic Apheresis and Dialysis © 2013 International Society for Apheresis.

  6. The Black Lake (Quebec, Canada) mineral carbonation experimental station: CO2 capture in mine waste

    NASA Astrophysics Data System (ADS)

    Beaudoin, G.; Constantin, M.; Duchesne, J.; Dupuis, C.; Entrazi, A.; Gras, A.; Huot, F.; Fortier, R.; Hebert, R.; Larachi, F.; Lechat, K.; Lemieux, J. M.; Molson, J. W. H.; Maldague, X.; Therrien, R.; Assima, G. P.

    2014-12-01

    Passive mineral carbonation of chrysotile mining and milling waste was discovered at the Black Lake mine, southern Québec, 10 years ago. Indurated crusts were found at the surface and within waste piles where mineral and rock fragments are cemented by hydrated magnesium carbonates. A long-term research program has yielded significant insight into the process of CO2 capture from the atmosphere, and how it can be implemented during mining operations. Laboratory experiments show that the waste mineralogy is crucial, brucite being more reactive than serpentine. Partial water saturation, circa 40%, is also critical to dissolve magnesium from minerals, and transport aqueous CO2 to precipitation sites. Grain armoring by iron oxidation induced by dissolved oxygen prevents further reaction. Two experimental cells constructed with milling waste and fitted with various monitoring probes (T, H2O content, leachate) and gas sampling ports, have been monitored for more than 3 years, along with environmental conditions. The interstitial gas in the cells remains depleted in CO2 indicating continuous capture of ambient atmospheric CO2 at rates faster than advection to reaction sites. The energy released by the exothermic mineral carbonation reactions has been observed both in laboratory experiments (up to 4 °C) and in the field. Warm air, depleted to 10 ppmv CO2, vents at the surface of the waste piles, indicating reaction with atmospheric CO2 deep inside the piles. A thermal anomaly, detected by airborne infrared and coincident with a known venting area, was selected for locating a 100 m deep borehole fitted with sensor arrays to monitor active mineral carbonation within the pile. The borehole has intersected areas where mineral carbonation has indurated the milling waste. The borehole will be monitored for the next 3 years to better understand the mineral carbonation process, and its potential to yield recoverable geothermal energy in mining environments.

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

    SciTech Connect

    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.

  8. Clay mineral continental amplifier for marine carbon sequestration in a greenhouse ocean.

    PubMed

    Kennedy, Martin J; Wagner, Thomas

    2011-06-14

    The majority of carbon sequestration at the Earth's surface occurs in marine continental margin settings within fine-grained sediments whose mineral properties are a function of continental climatic conditions. We report very high mineral surface area (MSA) values of 300 and 570 m(2) g in Late Cretaceous black shales from Ocean Drilling Program site 959 of the Deep Ivorian Basin that vary on subcentennial time scales corresponding with abrupt increases from approximately 3 to approximately 18% total organic carbon (TOC). The observed MSA changes with TOC across multiple scales of variability and on a sample-by-sample basis (centimeter scale), provides a rigorous test of a hypothesized influence on organic carbon burial by detrital clay mineral controlled MSA. Changes in TOC also correspond with geochemical and sedimentological evidence for water column anoxia. Bioturbated intervals show a lower organic carbon loading on mineral surface area of 0.1 mg-OC m(-2) when compared to 0.4 mg-OC m(-2) for laminated and sulfidic sediments. Although either anoxia or mineral surface protection may be capable of producing TOC of < 5%, when brought together they produced the very high TOC (10-18%) apparent in these sediments. This nonlinear response in carbon burial resulted from minor precession-driven changes of continental climate influencing clay mineral properties and runoff from the African continent. This study identifies a previously unrecognized land-sea connection among continental weathering, clay mineral production, and anoxia and a nonlinear effect on marine carbon sequestration during the Coniacian-Santonian Oceanic Anoxic Event 3 in the tropical eastern Atlantic.

  9. Mineral bioavailability and bone mineral contents in pigs given calcium carbonate postprandially.

    PubMed

    Pointillart, A; Colin, C; Lacroix, H C; Guéguen, L

    1995-10-01

    We have further investigated the "meal effect" on mineral bioavailability in pigs by mineral balance studies and measurements of bone ash contents and bending moment. A group of seven pigs (CAA) was given all its dietary Ca as CaCO3 5 h after the first daily meal for 8 weeks. The control group of seven pigs received CaCO3 in the meal. Both groups were given normal P within the meals. Ca and P absorption and retention were evaluated by a 10-day balance trial. Several bones were collected at slaughter to determine bone ash, Ca, and P contents and bending moment (three-point bending test). Ingesting Ca after the meal did not affect Ca bioavailability or phosphorus absorption, but did reduce P retention, which in turn decreased the bone scores. Osteopenia, indicated by decreased total mineral contents of bones (and decreased ash:bone volume ratio), was associated with elevated plasma osteocalcin in the CAA group. Thus, CaCO3 need not be incorporated into a meal for high Ca absorption, provided that Ca is given after a meal, but simultaneous intakes of Ca and P are required for the best mineral retention.

  10. Effect of sulfate and carbonate minerals on particle-size distributions in arid soils

    USGS Publications Warehouse

    Goossens, Dirk; Buck, Brenda J.; Teng, Yuazxin; Robins, Colin; Goldstein, Harland L.

    2014-01-01

    Arid soils pose unique problems during measurement and interpretation of particle-size distributions (PSDs) because they often contain high concentrations of water-soluble salts. This study investigates the effects of sulfate and carbonate minerals on grain-size analysis by comparing analyses in water, in which the minerals dissolve, and isopropanol (IPA), in which they do not. The presence of gypsum, in particular, substantially affects particle-size analysis once the concentration of gypsum in the sample exceeds the mineral’s solubility threshold. For smaller concentrations particle-size results are unaffected. This is because at concentrations above the solubility threshold fine particles cement together or bind to coarser particles or aggregates already present in the sample, or soluble mineral coatings enlarge grains. Formation of discrete crystallites exacerbates the problem. When soluble minerals are dissolved the original, insoluble grains will become partly or entirely liberated. Thus, removing soluble minerals will result in an increase in measured fine particles. Distortion of particle-size analysis is larger for sulfate minerals than for carbonate minerals because of the much higher solubility in water of the former. When possible, arid soils should be analyzed using a liquid in which the mineral grains do not dissolve, such as IPA, because the results will more accurately reflect the PSD under most arid soil field conditions. This is especially important when interpreting soil and environmental processes affected by particle size.

  11. Mineral formation in stellar winds. V. Formation of calcium carbonate

    NASA Astrophysics Data System (ADS)

    Ferrarotti, A. S.; Gail, H.-P.

    2005-02-01

    An emission band around 92 μm found in a few IR spectra from highly evolved stars was proposed to be due to the presence of carbonate dust grains in the circumstellar material (Kemper et al. \\cite{Kem02a}, Nature, 415, 295). This contribution presents the results of a model calculation for the condensation of calcite (CaCO_3) in the stellar wind of AGB stars. It is shown that the quantities of carbonate dust formed relative to the quantities of silicate dust are negligibly small. This results from the fact that carbonates form at a much lower temperature than the silicate dust components. Carbonate dust formation then is suppressed by the strong acceleration of the wind material by radiation pressure on the silicate dust and the subsequent rapid dilution of the wind material. This makes it highly improbable that carbonate dust can be formed in stellar outflows.

  12. Mineral-Based Coating of Plasma-Treated Carbon Fibre Rovings for Carbon Concrete Composites with Enhanced Mechanical Performance

    PubMed Central

    Schneider, Kai; Lieboldt, Matthias; Liebscher, Marco; Fröhlich, Maik; Hempel, Simone; Butler, Marko; Schröfl, Christof; Mechtcherine, Viktor

    2017-01-01

    Surfaces of carbon fibre roving were modified by means of a low temperature plasma treatment to improve their bonding with mineral fines; the latter serving as an inorganic fibre coating for the improved mechanical performance of carbon reinforcement in concrete matrices. Variation of the plasma conditions, such as gas composition and treatment time, was accomplished to establish polar groups on the carbon fibres prior to contact with the suspension of mineral particles in water. Subsequently, the rovings were implemented in a fine concrete matrix and their pull-out performance was assessed. Every plasma treatment resulted in increased pull-out forces in comparison to the reference samples without plasma treatment, indicating a better bonding between the mineral coating material and the carbon fibres. Significant differences were found, depending on gas composition and treatment time. Microscopic investigations showed that the samples with the highest pull-out force exhibited carbon fibre surfaces with the largest areas of hydration products grown on them. Additionally, the coating material ingresses into the multifilament roving in these specimens, leading to better force transfer between individual carbon filaments and between the entire roving and surrounding matrix, thus explaining the superior mechanical performance of the specimens containing appropriately plasma-treated carbon roving. PMID:28772719

  13. Mineral-Based Coating of Plasma-Treated Carbon Fibre Rovings for Carbon Concrete Composites with Enhanced Mechanical Performance.

    PubMed

    Schneider, Kai; Lieboldt, Matthias; Liebscher, Marco; Fröhlich, Maik; Hempel, Simone; Butler, Marko; Schröfl, Christof; Mechtcherine, Viktor

    2017-03-29

    Surfaces of carbon fibre roving were modified by means of a low temperature plasma treatment to improve their bonding with mineral fines; the latter serving as an inorganic fibre coating for the improved mechanical performance of carbon reinforcement in concrete matrices. Variation of the plasma conditions, such as gas composition and treatment time, was accomplished to establish polar groups on the carbon fibres prior to contact with the suspension of mineral particles in water. Subsequently, the rovings were implemented in a fine concrete matrix and their pull-out performance was assessed. Every plasma treatment resulted in increased pull-out forces in comparison to the reference samples without plasma treatment, indicating a better bonding between the mineral coating material and the carbon fibres. Significant differences were found, depending on gas composition and treatment time. Microscopic investigations showed that the samples with the highest pull-out force exhibited carbon fibre surfaces with the largest areas of hydration products grown on them. Additionally, the coating material ingresses into the multifilament roving in these specimens, leading to better force transfer between individual carbon filaments and between the entire roving and surrounding matrix, thus explaining the superior mechanical performance of the specimens containing appropriately plasma-treated carbon roving.

  14. Organo-mineral complexation alters carbon and nitrogen cycling in stream microbial assemblages

    NASA Astrophysics Data System (ADS)

    Hunter, William Ross; Wanek, Wolfgang; Prommer, Judith; Mooshammer, Maria; Battin, Tom

    2014-05-01

    Inland waters are of global biogeochemical importance receiving carbon inputs of ~ 4.8 Pg C y-1. Of this 12 % is buried, 18 % transported to the oceans, and 70 % supports aquatic secondary production. However, the mechanisms that determine the fate of organic matter (OM) in these systems are poorly defined. One important aspect is the formation of organo-mineral complexes in aquatic systems and their potential as a route for OM transport and burial vs. microbial utilization as organic carbon (C) and nitrogen (N) sources. Organo-mineral particles form by sorption of dissolved OM to freshly eroded mineral surfaces and may contribute to ecosystem-scale particulate OM fluxes. We tested the availability of mineral-sorbed OM as a C & N source for streamwater microbial assemblages and streambed biofilms. Organo-mineral particles were constructed in vitro by sorption of 13C:15N-labelled amino acids to hydrated kaolin particles, and microbial degradation of these particles compared with equivalent doses of 13C:15N-labelled free amino acids. Experiments were conducted in 120 ml mesocosms over 7 days using biofilms and streamwater sampled from the Oberer Seebach stream (Austria), tracing assimilation and mineralization of 13C and 15N labels from mineral-sorbed and dissolved amino acids. Here we present data on the effects of organo-mineral sorption upon amino acid mineralization and its C:N stoichiometry. Organo-mineral sorption had a significant effect upon microbial activity, restricting C and N mineralization by both the biofilm and streamwater treatments. Distinct differences in community response were observed, with both dissolved and mineral-stabilized amino acids playing an enhanced role in the metabolism of the streamwater microbial community. Mineral-sorption of amino acids differentially affected C & N mineralization and reduced the C:N ratio of the dissolved amino acid pool. The present study demonstrates that organo-mineral complexes restrict microbial degradation

  15. Static Adsorption of an Ethoxylated Nonionic Surfactant on Carbonate Minerals.

    PubMed

    Jian, Guoqing; Puerto, Maura C; Wehowsky, Anna; Dong, Pengfei; Johnston, Keith P; Hirasaki, George J; Biswal, Sibani Lisa

    2016-10-11

    The static adsorption of C12-14E22, which is a highly ethoxylated nonionic surfactant, was studied on different minerals using high-performance liquid chromatography (HPLC) combined with an evaporative light scattering detector (ELSD). Of particular interest is the surfactant adsorption in the presence of CO2 because it can be used for foam flooding in enhanced oil recovery applications. The effects of the mineral type, impurities, salinity, and temperature were investigated. The adsorption of C12-14E22 on pure calcite was as low as 0.01 mg/m(2) but higher on dolomite depending on the silica and clay content in the mineral. The adsorption remained unchanged when the experiments were performed using a brine solution or 0.101 MPa (1 atm) CO2, which indicates that electrostatic force is not the governing factor that drives the adsorption. The adsorption of C12-14E22 on silica may be due to hydrogen bonding between the oxygen in the ethoxy groups of the surfactant and the hydroxyl groups on the mineral surface. Additionally, thermal decomposition of the surfactant was severe at 80 °C but can be inhibited by operating in a reducing environment. Under reducing conditions, adsorption of C12-14E22 increased at higher temperatures.

  16. Limiting factors for carbon-mineral complexation: Responses to land use types and the implications for carbon sequestration

    NASA Astrophysics Data System (ADS)

    Chen, C.; Yoo, K.; Aufdenkampe, A. K.

    2009-12-01

    The cycles of carbon (C) and minerals are largely considered independently. However, there is a growing consensus that C complexation onto mineral surface is critical in protecting C from decomposition and thus lengthening C turnover time. To create C-mineral complexes, physical contact must occur between organic matter and minerals, yet production of C is spatially separated from mineral surface production. We hypothesized that (1) C-mineral complexation is typically limited by either availability of C or mineral surface, (2) land use type and depth strongly affect which one of the two limits the complexation, and (3) accelerated erosion and fluvial sedimentation, by mixing C with minerals, results in creating additional C-mineral complexes within watersheds. We targeted a mixed-land use watershed in the Piedmont region of southeast Pennsylvania. In the uplands, plowed agricultural soils, compared to the neighboring forest soils, had low C contents. Accelerated soil erosion from uplands and subsequent sedimentation behind mill dams during the colonial time has been suggested as responsible for the fluvial deposits within the watershed. In the uplands, soil samples were collected to the depth of soil-saprolite boundary in a second-growth forest (~100 years old) and an adjacent agricultural field. A soil at the floodplain was also sampled to the depth of a first buried A horizon. In the forest A-horizon soil, as C contents increased, mineral-complexed C pool was saturated and C-mineral complexation was limited by the availability of mineral surface. In contrast, in the agricultural A horizon, C availability limited the complexation. In the A horizon of floodplain soil, as in the forest soil, further C-mineral complexation requires greater availability of mineral surface. Therefore, while minerals eroded from the forest may not complex further C, agricultural erosion may contribute to creating C-mineral complexes during the sediment transit through fluvial networks

  17. Carbon and nitrogen mineralization in vineyard acid soils amended with a bentonitic winery waste

    NASA Astrophysics Data System (ADS)

    Fernández-Calviño, David; Rodríguez-Salgado, Isabel; Pérez-Rodríguez, Paula; Díaz-Raviña, Montserrat; Nóvoa-Muñoz, Juan Carlos; Arias-Estévez, Manuel

    2015-04-01

    Carbon mineralization and nitrogen ammonification processes were determined in different vineyard soils. The measurements were performed in samples non-amended and amended with different bentonitic winery waste concentrations. Carbon mineralization was measured as CO2 released by the soil under laboratory conditions, whereas NH4+ was determined after its extraction with KCl 2M. The time evolution of both, carbon mineralization and nitrogen ammonification, was followed during 42 days. The released CO2 was low in the analyzed vineyard soils, and hence the metabolic activity in these soils was low. The addition of the bentonitic winery waste to the studied soils increased highly the carbon mineralization (2-5 fold), showing that the organic matter added together the bentonitic waste to the soil have low stability. In both cases, amended and non-amended samples, the maximum carbon mineralization was measured during the first days (2-4 days), decreasing as the incubation time increased. The NH4+ results showed an important effect of bentonitic winery waste on the ammonification behavior in the studied soils. In the non-amended samples the ammonification was no detected in none of the soils, whereas in the amended soils important NH4+ concentrations were detected. In these cases, the ammonification was fast, reaching the maximum values of NH4 between 7 and 14 days after the bentonitic waste additions. Also, the percentages of ammonification respect to the total nitrogen in the soil were high, showing that the nitrogen provided by the bentonitic waste to the soil is non-stable. The fast carbon mineralization found in the soils amended with bentonitic winery wastes shows low possibilities of the use of this waste for the increasing the organic carbon pools in the soil.On the other hand, the use of this waste as N-fertilizer can be possible. However, due its fast ammonification, the waste should be added to the soils during active plant growth periods.

  18. Raman microspectroscopy for in situ examination of carbon-microbe-mineral interactions

    NASA Astrophysics Data System (ADS)

    Creamer, C.; Foster, A. L.; Lawrence, C. R.; Mcfarland, J. W.; Waldrop, M. P.

    2016-12-01

    The changing paradigm of soil organic matter formation and turnover is focused at the nexus of microbe-carbon-mineral interactions. However, visualizing biotic and abiotic stabilization of C on mineral surfaces is difficult given our current techniques. Therefore we investigated Raman microspectroscopy as a potential tool to examine microbially mediated organo-mineral associations. Raman microspectroscopy is a non-destructive technique that has been used to identify microorganisms and minerals, and to quantify microbial assimilation of 13C labeled substrates in culture. We developed a partial least squares regression (PLSR) model to accurately quantify (within 5%) adsorption of four model 12C substrates (glucose, glutamic acid, oxalic acid, p-hydroxybenzoic acid) on a range of soil minerals. We also developed a PLSR model to quantify the incorporation of 13C into E. coli cells. Using these two models, along with measures of the 13C content of respired CO2, we determined the allocation of glucose-derived C into mineral-associated microbial biomass and respired CO2 in situ and through time. We observed progressive 13C enrichment of microbial biomass with incubation time, as well as 13C enrichment of CO2 indicating preferential decomposition of glucose-derived C. We will also present results on the application of our in situ chamber to quantify the formation of organo-mineral associations under both abiotic and biotic conditions with a variety of C and mineral substrates, as well as the rate of turnover and stabilization of microbial residues. Application of Raman microspectroscopy to microbial-mineral interactions represents a novel method to quantify microbial transformation of C substrates and subsequent mineral stabilization without destructive sampling, and has the potential to provide new insights to our conceptual understanding of carbon-microbe-mineral interactions.

  19. Carbonate-mineral/water interactions in sulfide-rich mine tailings

    NASA Astrophysics Data System (ADS)

    Al, Tom A.; Martin, Chris J.; Blowes, David W.

    2000-12-01

    The chemical composition and mineralogy of coatings on carbonate minerals from mine tailings have been studied using aqueous geochemical methods, Time-of-Flight Laser-Ionization Mass Spectrometry (TOF-LIMS) and Transmission Electron Microscopy (TEM). The goal is to study major and trace element partitioning between the aqueous and solid phase, and to infer mechanisms that control the concentrations of elements in the pore water of sulfide-rich mine tailings. Pore-water samples and carbonate-mineral grains were collected from four geochemically distinct zones within the tailings. Oxidation of sulfide minerals near the surface results in a large range in pore-water pH (3.85 to 6.98) and aqueous concentrations of metals and sulfate. With increasing depth in the tailings, mineral-water interactions lead to increasing pH, and decreasing concentrations of metals and sulfate. Calculated mineral saturation indices, trends in the abundance of Ca, Fe, Mg and Mn in TOF-LIMS profiles through the secondary coatings, and electron diffraction patterns obtained from the coatings, suggest that precipitation/dissolution of jarosite-group minerals, gypsum, goethite, akaganéite, amorphous Fe oxyhydroxides and siderite control the aqueous Ca, Fe, Na, K and SO 4 concentrations. The occurrence of secondary coatings on primary minerals is widespread, and reactions with the secondary minerals, rather than the primary mineral substrate, probably represent the principal controls on trace-element distributions in the pore water. The data indicate that adsorption, surface-complexation and co-precipitation reactions are important controls on the concentrations of trace elements in the pore water. The occurrence of siderite coatings on the surface of ankerite grains suggests that Fe-bearing dolomite-structure carbonate minerals dissolve incongruently. This corroborates inferences made by previous workers that solubility differences between calcite and siderite lead to calcite dissolution and

  20. Reaction kinetics of CO2 carbonation with Mg-rich minerals.

    PubMed

    Kwon, Soonchul; Fan, Maohong; Dacosta, Herbert F M; Russell, Armistead G; Tsouris, Costas

    2011-07-07

    Due to their low price, wide availability, and stability of the resulting carbonates, Mg-rich minerals are promising materials for carbonating CO(2). Direct carbonation of CO(2) with Mg-rich minerals reported in this research for the first time could be considerably superior to conventional liquid extraction processes from an energy consumption perspective due to its avoidance of the use of a large amount of water with high specific heat capacity and latent heat of vaporization. Kinetic models of the reactions of the direct CO(2) carbonation with Mg-rich minerals and within simulated flue gas environments are important to the scale-up of reactor designs. Unfortunately, such models have not been made available thus far. This research was initiated to fill that gap. Magnesium silicate (Mg(2)SiO(4)), a representative compound in Mg-rich minerals, was used to study CO(2) carbonation reaction kinetics under given simulated flue gas conditions. It was found that the chosen sorbent deactivation model fits well the experimental data collected under given conditions. A reaction order of 1 with respect to CO(2) is obtained from experimental data. The Arrhenius form of CO(2) carbonation with Mg(2)SiO(4) is established based on changes in the rate constants of the chosen deactivation model as a function of temperature.

  1. The influence of 10 years reduced tillage on the potential carbon mineralization of silt loam soils under a temperate climate.

    PubMed

    D'haene, Karoline; Van den Bossche, Annemie; De Neve, Stefaan; Gabriels, Donald; Hofman, Georges

    2006-01-01

    The influence of 10 years reduced tillage (RT) on the potential carbon mineralization of the 0-5 cm layer of silt loam soils in Belgium under a temperate climate was investigated. Therefore, four fields at three locations under 10 years of RT and fields under conventional tillage (CT) with comparable crop rotation were selected. The higher % soil organic carbon in the upper layer resulted in a higher potential carbon mineralization of the RT fields. The small increase in % soil organic carbon and potential carbon mineralization of RT fields was contributed to the high soil disturbance due to incorporation of manure in the upper layer and the production of sugar beets and potatoes. Simulating ploughing by emptying and refilling the soil cores resulted mostly in a higher potential carbon mineralization. However, the differences were not significant due to the high variability in potential carbon mineralization.

  2. Carbonate turbidites in volcaniclastic metasedimentary rocks of the Mineral Bluff, Fm, Murphy, NC

    SciTech Connect

    Fritz, W.J.; La Tour, T.E.; Stakes, D.S.

    1985-01-01

    Outcrops of the metasedimentary Mineral Bluff Fm near Murphy, North Carolina contain thin lenses to discontinuous layers of calc-silicate in volcaniclastic mudstone. Despite the metamorphism, sedimentary structures preserved in the mudstones include: ripple cross laminations, scour surfaces, crossbedding and graded beds. The calc-silicate layers vary from 2-25cm thick and are zoned from carbonate-rich center to silicate-rich margins. May layers have no carbonate center preserved. Major calc-silicate minerals are carbonate, plagioclase, hornblende, Ca-garnet, and quartz; accessory minerals are clinozoisite, apatite, Fe-Ti oxides, and pyrite. Siltstone immediately adjacent to calc-silicate layers contains much biotite whose abundance decreases away from the calc-silicate layers. Greater original carbonate in siltstone nearest carbonate layers would have facilitated biotite growth. Within calc-silicate layers, hornblende is concentrated near both margins, but in greater concentration near stratigraphic tops. The authors also interpret this as grading within original muddy carbonate turbidites. The calc-silicate turbidite layers may have been derived from the nearby Murphy Marble, a large time-equivalent late Proterozoic or early Paleozoic carbonate unit. The Murphy Marble was a large shallow water carbonate reef associated with an island arc. Other time-equivalent, nearshore rock units in the area are the beach sandstone of the Nottely Quartzite and the locally carbonate-rich volcaniclastic Brasstown Formation. The authors envisage the depositional environment for the Mineral Bluff Fm as a deep basin, distal from the island arc, that received fine-grained volcaniclastic debris from the arc, episodically interrupted by a carbonate turbidity flow.

  3. Mineralogy and Geochemical Processes of Carbonate Mineral-rich Sulfide Mine Tailings, Zimapan, Mexico

    NASA Astrophysics Data System (ADS)

    McClure, R. J.; Deng, Y.; Loeppert, R.; Herbert, B. E.; Carrillo, R.; Gonzalez, C.

    2009-12-01

    Mining for silver, lead, zinc, and copper in Zimapan, Hidalgo State, Mexico has been ongoing since 1576. High concentrations of heavy metals have been found in several mine tailing heaps in the Zimapan area, with concentrations of arsenic observed as high as 28,690 mg/kg and levels of Pb as high as 2772 mg/kg. Unsecured tailings heaps and associated acid mine drainage has presented tremendous problems to revegetation, water quality, and dust emission control in the Zimapan area. Although acid mine drainage problems related to weathering of sulfide minerals have been extensively studied and are well known, the weathering products of sulfides in areas with a significant presence of carbonate minerals and their effect on the mobility of heavy metals warrant further study. Carbonate minerals are expected to neutralize sulfuric acid produced from weathering of sulfide minerals, however, in the Zimapan area localized areas of pH as low as 1.8 were observed within carbonate mineral-rich tailing heaps. The objectives of this study are to characterize (1) the heavy metal-containing sulfide minerals in the initial tailing materials, (2) the intermediate oxidation products of sulfide minerals within the carbonate-rich tailings, (3) chemical species of heavy metals within pH gradients between 1.8 and 8.2, the approximate natural pH of limestone, and (4) the mobility of soluble and colloidal heavy metals and arsenic within the carbonate-rich tailings. Representative mine tailings and their intermediate oxidation products have been sampled from the Zimapan area. Mineralogical characterization will be conducted with X-ray diffraction, infrared spectroscopy, electron microscopes and microprobes, and chemical methods. Chemical species will be extracted by selective dissolution methods. Preliminary results have identified calcite as the dominant mineral in the tailing heaps with a pH of 7, suggesting non-equilibrium with the acidic weathering products. Other minerals identified in

  4. [Effects of variable temperature on organic carbon mineralization in typical limestone soils].

    PubMed

    Wang, Lian-Ge; Gao, Yan-Hong; Ding, Chang-Huan; Ci, En; Xie, De-Ti

    2014-11-01

    Soil sampling in the field and incubation experiment in the laboratory were conducted to investigate the responses of soil organic carbon (SOC) mineralization to variable temperature regimes in the topsoil of limestone soils from forest land and dry land. Two incubated limestone soils were sampled from the 0-10 cm layers of typical forest land and dry land respectively, which were distributed in Tianlong Mountain area of Puding county, Guizhou province. The soils were incubated for 56 d under two different temperature regimes including variable temperature (range: 15-25 degrees C, interval: 12 h) and constant temperature (20 degrees C), and the cumulative temperature was the same in the two temperature treatments. In the entire incubation period (56 d), the SOC cumulative mineralization (63.32 mg x kg(-1)) in the limestone soil from dry land (SH) under the variable temperature was lower than that (63.96 mg x kg(-1)) at constant 20 degrees C, and there was no significant difference in the SOC cumulative mineralization between the variable and constant temperature treatments (P < 0.05). While the cumulative mineralization (169.46 mg x kg(-1)) of organic carbon in the limestone soil from forest land (SL) under the variable temperature was significantly lower than that (209.52 mg x kg(-1)) at constant 20 degrees C. The results indicated that the responses of SOC mineralization to the variable temperature were obviously different between SL and SH soils. The SOC content and composition were significantly different between SL and SH soils affected by vegetation and land use type, which suggested that SOC content and composition were important factors causing the different responses of SOC mineralization to variable temperature between SL and SH soils. In addition, the dissolved organic carbon (DOC) content of two limestone soils were highly (P < 0.01) positively correlated with daily mineralization of soil organic carbon in both temperature treatments, which implied that

  5. Mineral Depositions of Calcifying Skin Disorders are Predominantly Composed of Carbonate Apatite.

    PubMed

    Franzen, Michael; Müller-More, Elena; Cadamuro, Janne; Koller, Josef; Salmhofer, Wolfgang; Wohlmuth-Wieser, Iris; Kronberger, Cornelia; Salmhofer, Hermann

    2017-06-29

    Subcutaneous calcifications can lead to complications, including pain, inflammation, ulceration and immobilization. Studies on the pathophysiology of mineral compositions and effective treatment modalities are limited. We therefore studied 14 patients with subcutaneous calcifications. Mineral material was collected and analysed by Fourier transform infrared spectrometry. Blood analyses were run to evaluate systemic alterations of mineral metabolism. Carbonate apatite (CAP) was found to be the single constituent in the majority of patients (n = 9, 64.3%), 3 cases (21.4%) had a composition of CAP and calcium oxalate dihydrate and one case had a combination of CAP and magnesium ammonium phosphate, whereas CAP was the major component in all 4 cases. Only one case showed predominantly calcium oxalate. CAP was found to be the only or predominant component in subcutaneous calcifications. Chemical analyses of the mineral compositions may aid in the development of new treatment regimes to improve the solubility of mineral components and to decrease extraosseous calcifications.

  6. Monitoring CO2 Sequestration by Mineral Carbonation in Mine Tailings at Thetford Mines, Quebec, Canada

    NASA Astrophysics Data System (ADS)

    Lechat, K.; Lemieux, J. M.; Molson, J. W. H.; Beaudoin, G.; Hebert, R.

    2014-12-01

    Mineral carbonation is considered a permanent option to capture and store atmospheric CO2. This reaction occurs naturally under ambient conditions in ultramafic mining and milling waste. In the region of Thetford Mines, Quebec, chrysotile mining has produced approximately 0.8 Gt of magnesium-rich milling waste, which mainly consists of poorly sorted ultramafic rock fragments (< 10 cm) and chrysotile fibers. To quantify the amount of CO2 that can be captured in the mine wastes of Thetford Mines, two experimental pilot-scale tailings cells were constructed and instrumented for measuring soil temperature, volumetric water content, gas pressure and gas composition, with ambient conditions recorded by an autonomous meteorological station. The cells were monitored for water geochemistry, carbon content and mineralogy, with the objective to better understand the mineral carbonation processes under natural conditions and to propose a conceptual model for mineral carbonation at the pilot scale. To validate this model, numerical simulations with the MIN3P reactive transport code have been carried out. The chemical composition of the cell leachate (pH > 10, Mg from 85 to 140 mg.L-1, and high total alkalinity from 260 to 300 mg.L-1 CaCO3) is consistent with active CO2 mineralization reactions within the cell. SEM analyses show precipitation of dypingite with a lamellar texture and cemented grain surfaces. The milling waste contains up to 1.2% C, which indicates CO2 sequestration by mineral carbonation. Measured CO2 concentrations in the interstitial air are also ten times lower than in the atmosphere. Analysis of seasonal variations in fluid flow and heat transfer (essentially by thermal conduction) shows that molecular diffusion is the main process for CO2 supply within the experimental cells. These observations have helped develop a conceptual model for mineral carbonation in the wastes and were used to calibrate the reactive transport model.

  7. Ab initio studies of methane and carbon dioxide affinity to carbon compounds and minerals

    NASA Astrophysics Data System (ADS)

    Wlazlo, Mateusz; Siklitskaya, Alexandra; Majewski, Jacek

    2017-04-01

    Understanding of physico-chemistry of capture and storage of carbon dioxide and methane might be crucial for development of the novel technologies meant: (i) to deal with the global warming process through the reduction of the CO2 atmospheric concentration by sequestration, and (ii) to enhance oil recovery, on the other hand. The accurate description of CO2 and CH4 adsorption to minerals and carbonaceous systems (which constitute the main component of sedimentary rocks) is essential to reach this goal. We have employed the ab initio molecular dynamics AIMD) based on the density functional theory (DFT) to study the affinity of CO2 and CH4 from gaseous phase, also at elevated temperatures and hydrostatic pressure, to pristine and defected graphene, spiral carbon nanoparticles (spiroids), calcite rocks (represented by the most stable (10-14) surface of CaCoO3), CaO, MgO, illite, and kaolonite. In the case of kaolonite that exhibits layered crystallographic structure, we have also studied the intercalation of CO2. These studies provide valuable quantitative predictions and shed light on physical mechanisms governing the processes of chemisorption and physisorption of the CO2 and CH4 molecules, revealing also the essential role of Van der Waals interaction. In particular, we find out that CO2 molecules in supercritical gaseous phase (i.e. at temperature of order 60oC and moderate hydrostatic pressure of 20-30 MPa) change their shape from linear one to the water like bended V-shape with angle between C-O chemical bonds smaller than 180 degrees. This shape change of CO2 molecules facilitates the CO2 adsorption. Therefore, in the temperature-pressure conditions of shale deposits, the adsorption probability of CO2 can be enhanced in comparison to the ambient conditions. It turns out that the carbon atoms in the surrounding of characteristic Stone-Wales (or 5-7) defects in graphene are more reactive towards adsorption of CO2 and CH4 molecules. In the case of CO2 adsorption

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

    PubMed

    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 CO2-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 CO2-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 CO2-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 CO2-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 CO2-injection into carbonate-mineral saline aquifers.

  9. Surface materials map of Afghanistan: carbonates, phyllosilicates, sulfates, altered minerals, and other materials

    USGS Publications Warehouse

    Kokaly, Raymond F.; King, Trude V.V.; Hoefen, Todd M.; Dudek, Kathleen B.; Livo, Keith E.

    2012-01-01

    This map shows the distribution of selected carbonates, phyllosilicates, sulfates, altered minerals, and other materials derived from analysis of HyMap imaging spectrometer data of Afghanistan. Using a NASA (National Aeronautics and Space Administration) WB-57 aircraft flown at an altitude of ~15,240 meters or ~50,000 feet, 218 flight lines of data were collected over Afghanistan between August 22 and October 2, 2007. The HyMap data were converted to apparent surface reflectance, then further empirically adjusted using ground-based reflectance measurements. The reflectance spectrum of each pixel of HyMap data was compared to the spectral features of reference entries in a spectral library of minerals, vegetation, water, ice, and snow. This map shows the spatial distribution of minerals that have diagnostic absorption features in the shortwave infrared wavelengths. These absorption features result primarily from characteristic chemical bonds and mineralogical vibrations. Several criteria, including (1) the reliability of detection and discrimination of minerals using the HyMap spectrometer data, (2) the relative abundance of minerals, and (3) the importance of particular minerals to studies of Afghanistan's natural resources, guided the selection of entries in the reference spectral library and, therefore, guided the selection of mineral classes shown on this map. Minerals occurring abundantly at the surface and those having unique spectral features were easily detected and discriminated. Minerals having similar spectral features were less easily discriminated, especially where the minerals were not particularly abundant and (or) where vegetation cover reduced the absorption strength of mineral features. Complications in reflectance calibration also affected the detection and identification of minerals.

  10. Morphological changes during enhanced carbonation of asbestos containing material and its comparison to magnesium silicate minerals.

    PubMed

    Gadikota, Greeshma; Natali, Claudio; Boschi, Chiara; Park, Ah-Hyung Alissa

    2014-01-15

    The disintegration of asbestos containing materials (ACM) over time can result in the mobilization of toxic chrysotile ((Mg, Fe)3Si2O5(OH)4)) fibers. Therefore, carbonation of these materials can be used to alter the fibrous morphology of asbestos and help mitigate anthropogenic CO2 emissions, depending on the amount of available alkaline metal in the materials. A series of high pressure carbonation experiments were performed in a batch reactor at PCO2 of 139atm using solvents containing different ligands (i.e., oxalate and acetate). The results of ACM carbonation were compared to those of magnesium silicate minerals which have been proposed to permanently store CO2 via mineral carbonation. The study revealed that oxalate even at a low concentration of 0.1M was effective in enhancing the extent of ACM carbonation and higher reaction temperatures also resulted in increased ACM carbonation. Formation of phases such as dolomite ((Ca, Mg)(CO3)2), whewellite (CaC2O4·H2O) and glushinskite (MgC2O4·2H2O) and a reduction in the chrysotile content was noted. Significant changes in the particle size and surface morphologies of ACM and magnesium silicate minerals toward non-fibrous structures were observed after their carbonation.

  11. Mineral replacements during carbonation of peridotite: implications for carbon dioxide sequestration in ultramafic rocks

    NASA Astrophysics Data System (ADS)

    Beinlich, Andreas; Hövelmann, Jörn; Plümper, Oliver; Austrheim, Hâkon

    2010-05-01

    , together with poorly crystalline serpentine and extremely fine grained talc. Hydrothermal batch experiments (130-160 bar PCO2; 200° C; 1-3 weeks reaction time) show that the alteration product after olivine is the favorable site of reaction presumably due to the large reactive surface area. In contrast, the olivine relicts have reacted to a significantly lesser extend, whereas the serpentine veins remain virtually unreacted. The dissolution of the compartment fillings is followed by nucleation and growth of calcite crystals also revealing that precipitation of calcite is strongly favored over magnesite as soon as the system contains Ca. The preferred precipitation of calcite is also supported by geochemical modeling (using Phreeqc), which shows that the Mg-bearing carbonates (dolomite, magnesite) only form if the fluid is sufficiently depleted in Ca. The compositional and textural differences between different samples as well as different run products from experiments indicate that the described clasts evolved from peridotite due to extreme mobilization of Mg, development of secondary porosity, and infill of carbonates. Mg removed from the clasts is partly consumed by replacement reactions in the vicinity of the clasts where Fe-minerals (almandine) are altered to Mg-minerals (talc). For basins containing abundant peridotite clasts, the outlined process will influence the CO2 and MgO budget. References: IPCC Special report: Carbon Dioxide Capture and Storage, Summary for Policymakers, 2005.

  12. Mineral carbonation: energy costs of pretreatment options and insights gained from flow loop reaction studies

    SciTech Connect

    Penner, Larry R.; O'Connor, William K.; Dahlin, David C.; Gerdemann, Stephen J.; Rush, Gilbert E.

    2004-01-01

    Sequestration of carbon as a stable mineral carbonate has been proposed to mitigate environmental concerns that carbon dioxide may with time escape from its sequestered matrix using alternative sequestration technologies. A method has been developed to prepare stable carbonate products by reacting CO2 with magnesium silicate minerals in aqueous bicarbonate/chloride media at high temperature and pressure. Because this approach is inherently expensive due to slow reaction rates and high capital costs, studies were conducted to improve the reaction rates through mineral pretreatment steps and to cut expenses through improved reactor technology. An overview is given for the estimated cost of the process including sensitivity to grinding and heating as pretreatment options for several mineral feedstocks. The energy costs are evaluated for each pretreatment in terms of net carbon avoided. New studies with a high-temperature, high-pressure flow-loop reactor have yielded information on overcoming kinetic barriers experienced with processing in stirred autoclave reactors. Repeated tests with the flow-loop reactor have yielded insights on wear and failure of system components, on challenges to maintain and measure flow, and for better understanding of the reaction mechanism.

  13. Carbon mineralization and carbonate preservation in modern cold-water coral reef sediments on the Norwegian shelf

    NASA Astrophysics Data System (ADS)

    Wehrmann, L. M.; Knab, N. J.; Pirlet, H.; Unnithan, V.; Wild, C.; Ferdelman, T. G.

    2009-04-01

    Cold-water coral ecosystems are considered hot-spots of biodiversity and biomass production and may be a regionally important contributor to carbonate production. The impact of these ecosystems on biogeochemical processes and carbonate preservation in associated sediments were studied at Røst Reef and Traenadjupet Reef, two modern (post-glacial) cold-water coral reefs on the Mid-Norwegian shelf. Sulfate and iron reduction as well as carbonate dissolution and precipitation were investigated by combining pore-water geochemical profiles, steady state modeling, as well as solid phase analyses and sulfate reduction rate measurements on gravity cores of up to 3.25 m length. Low extents of sulfate depletion and dissolved inorganic carbon (DIC) production, combined with sulfate reduction rates not exceeding 3 nmol S cm-3 d-1, suggested that overall anaerobic carbon mineralization in the sediments was low. These data showed that the coral fragment-bearing siliciclastic sediments were effectively decoupled from the productive pelagic ecosystem by the complex reef surface framework. Organic matter being mineralized by sulfate reduction was calculated to consist of 57% carbon bound in CH2O groups and 43% carbon in -CH2- groups. Methane concentrations were below 1 μM, and failed to support the hypothesis of a linkage between the distribution of cold-water coral reefs and the presence of hydrocarbon seepage. Reductive iron oxide dissolution linked to microbial sulfate reduction buffered the pore-water carbonate system and inhibited acid-driven coral skeleton dissolution. A large pool of reactive iron was available leading to the formation of iron sulfide minerals. Constant pore-water Ca2+, Mg2+ and Sr2+ concentrations in most cores and decreasing Ca2+ and Sr2+ concentrations with depth in core 23-18 GC indicated diagenetic carbonate precipitation. This was consistent with the excellent preservation of buried coral fragments.

  14. Carbon mineralization and carbonate preservation in modern cold-water coral reef sediments on the Norwegian shelf

    NASA Astrophysics Data System (ADS)

    Wehrmann, L. M.; Knab, N. J.; Pirlet, H.; Unnithan, V.; Wild, C.; Ferdelman, T. G.

    2008-12-01

    Cold-water coral ecosystems are considered hot-spots of biodiversity and biomass production and may be a regionally important contributor to carbonate production. The impact of these ecosystems on biogeochemical processes and carbonate preservation in associated sediments were studied at Røst Reef and Traenadjupet Reef, two modern (post-glacial) cold-water coral reefs on the Mid-Norwegian shelf. Sulfate and iron reduction as well as carbonate dissolution and precipitation were investigated by combining pore-water geochemical profiles, steady state modeling, as well as solid phase analyses and sulfate reduction rate measurements on gravity cores of up to 3.2 m length. Low extents of sulfate depletion and dissolved inorganic carbon (DIC) production, combined with sulfate reduction rates not exceeding 3 nmolS cm-3 d-1, suggested that overall anaerobic carbon mineralization in the sediments was low. These data showed that the coral fragment-bearing siliciclastic sediments were effectively decoupled from the productive pelagic ecosystem by the complex reef surface framework. Organic matter being mineralized by sulfate reduction was calculated to consist of 57% carbon bound in -CH2O- groups and 43% carbon in -CH2- groups. Methane concentrations were below 1 μM, and failed to support the hypothesis of a linkage between the distribution of cold-water coral reefs and the presence of hydrocarbon seepage. Iron reduction linked to microbial sulfate reduction buffered the pore-water carbonate system and inhibited acid driven coral skeleton dissolution. A large pool of reactive iron was available leading to the formation of iron sulfide minerals. Constant pore-water Ca2+, Mg2+ and Sr2+ concentrations in most cores and decreasing Ca2+ and Sr2+ concentrations with depth in core 23-18 GC indicated diagenetic carbonate precipitation. This was consistent with the excellent preservation of buried coral fragments.

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

    SciTech Connect

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

    1991-03-01

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

  16. Microbial Contribution to Organic Carbon Sequestration in Mineral Soil

    USDA-ARS?s Scientific Manuscript database

    Soil productivity and sustainability are dependent on soil organic matter (SOM). Our understanding on how organic inputs to soil from microbial processes become converted to SOM is still limited. This study aims to understand how microbes affect carbon (C) sequestration and the formation of recalcit...

  17. Beyond temperature: Clumped isotope signatures in dissolved inorganic carbon species and the influence of solution chemistry on carbonate mineral composition

    NASA Astrophysics Data System (ADS)

    Tripati, Aradhna K.; Hill, Pamela S.; Eagle, Robert A.; Mosenfelder, Jed L.; Tang, Jianwu; Schauble, Edwin A.; Eiler, John M.; Zeebe, Richard E.; Uchikawa, Joji; Coplen, Tyler B.; Ries, Justin B.; Henry, Drew

    2015-10-01

    "Clumped-isotope" thermometry is an emerging tool to probe the temperature history of surface and subsurface environments based on measurements of the proportion of 13C and 18O isotopes bound to each other within carbonate minerals in 13C18O16O22- groups (heavy isotope "clumps"). Although most clumped isotope geothermometry implicitly presumes carbonate crystals have attained lattice equilibrium (i.e., thermodynamic equilibrium for a mineral, which is independent of solution chemistry), several factors other than temperature, including dissolved inorganic carbon (DIC) speciation may influence mineral isotopic signatures. Therefore we used a combination of approaches to understand the potential influence of different variables on the clumped isotope (and oxygen isotope) composition of minerals. We conducted witherite precipitation experiments at a single temperature and at varied pH to empirically determine 13C-18O bond ordering (Δ47) and δ18O of CO32- and HCO3- molecules at a 25 °C equilibrium. Ab initio cluster models based on density functional theory were used to predict equilibrium 13C-18O bond abundances and δ18O of different DIC species and minerals as a function of temperature. Experiments and theory indicate Δ47 and δ18O compositions of CO32- and HCO3- ions are significantly different from each other. Experiments constrain the Δ47-δ18O slope for a pH effect (0.011 ± 0.001; 12 ⩾ pH ⩾ 7). Rapidly-growing temperate corals exhibit disequilibrium mineral isotopic signatures with a Δ47-δ18O slope of 0.011 ± 0.003, consistent with a pH effect. Our theoretical calculations for carbonate minerals indicate equilibrium lattice calcite values for Δ47 and δ18O are intermediate between HCO3- and CO32-. We analyzed synthetic calcites grown at temperatures ranging from 0.5 to 50 °C with and without the enzyme carbonic anhydrase present. This enzyme catalyzes oxygen isotopic exchange between DIC species and is present in many natural systems. The two

  18. DEVELOPMENT OF A CO2 SEQUESTRATION MODULE BY INTEGRATING MINERAL ACTIVATION AND AQUEOUS CARBONATION

    SciTech Connect

    M. Mercedes Maroto-Valer; John M. Andresen; George Alexander

    2004-11-15

    Mineral carbonation is a promising concept for permanent CO{sub 2} sequestration due to the vast natural abundance of the raw minerals, the permanent storage of CO{sub 2} in solid form as carbonates, and the overall reaction being exothermic. However, the primary drawback to mineral carbonation is the reaction kinetics. To accelerate the reaction, aqueous carbonation processes are preferred, where the minerals are firstly dissolved in solution. In aqueous carbonation, the key step is the dissolution rate of the mineral, where the mineral dissolution reaction is likely to be surface controlled. In order to accelerate the dissolution process, the serpentine can be ground to very fine particle size (<37 {micro}m), but this is a very energy intensive process. Alternatively, magnesium could be chemically extracted in aqueous solution. Phase I showed that chemical surface activation helps to dissolve the magnesium from the serpentine minerals (particle size {approx}100 {micro}m), and furthermore, the carbonation reaction can be conducted under mild conditions (20 C and 650 psig) compared to previous studies that required >185 C, >1850 psig and <37 {micro}m particle size. Phase I also showed that over 70% of the magnesium can be extracted at ambient temperature leaving amorphous SiO{sub 2} with surface areas {approx} 330m{sup 2}/g. The overall objective of Phase 2 of this research program is to optimize the active carbonation process developed in Phase I in order to design an integrated CO{sub 2} sequestration module. During the current reporting period, Task 1 ''Mineral activation'' was initiated and focused on a parametric study to optimize the operation conditions for the mineral activation, where serpentine and sulfuric acid were reacted, as following the results from Phase 1. Several experimental factors were outlined as having a potential influence on the mineral activation. This study has focused to date on the effects of varying the acid concentration, particle

  19. Microbially enhanced carbon capture and storage by mineral-trapping and solubility-trapping.

    PubMed

    Mitchell, Andrew C; Dideriksen, Knud; Spangler, Lee H; Cunningham, Alfred B; Gerlach, Robin

    2010-07-01

    The potential of microorganisms for enhancing carbon capture and storage (CCS) via mineral-trapping (where dissolved CO(2) is precipitated in carbonate minerals) and solubility trapping (as dissolved carbonate species in solution) was investigated. The bacterial hydrolysis of urea (ureolysis) was investigated in microcosms including synthetic brine (SB) mimicking a prospective deep subsurface CCS site with variable headspace pressures [p(CO(2))] of (13)C-CO(2). Dissolved Ca(2+) in the SB was completely precipitated as calcite during microbially induced hydrolysis of 5-20 g L(-1) urea. The incorporation of carbonate ions from (13)C-CO(2) ((13)C-CO(3)(2-)) into calcite increased with increasing p((13)CO(2)) and increasing urea concentrations: from 8.3% of total carbon in CaCO(3) at 1 g L(-1) to 31% at 5 g L(-1), and 37% at 20 g L(-1). This demonstrated that ureolysis was effective at precipitating initially gaseous [CO(2)(g)] originating from the headspace over the brine. Modeling the change in brine chemistry and carbonate precipitation after equilibration with the initial p(CO(2)) demonstrated that no net precipitation of CO(2)(g) via mineral-trapping occurred, since urea hydrolysis results in the production of dissolved inorganic carbon. However, the pH increase induced by bacterial ureolysis generated a net flux of CO(2)(g) into the brine. This reduced the headspace concentration of CO(2) by up to 32 mM per 100 mM urea hydrolyzed because the capacity of the brine for carbonate ions was increased, thus enhancing the solubility-trapping capacity of the brine. Together with the previously demonstrated permeability reduction of rock cores at high pressure by microbial biofilms and resilience of biofilms to supercritical CO(2), this suggests that engineered biomineralizing biofilms may enhance CCS via solubility-trapping, mineral formation, and CO(2)(g) leakage reduction.

  20. Direct nano-scale observations of carbon mineralization during brucite dissolution (Invited)

    NASA Astrophysics Data System (ADS)

    Hoevelmann, J.; Putnis, C. V.; Ruiz Agudo, E.; Austrheim, H.

    2013-12-01

    Aqueous mineral carbonation for ex situ CO2 sequestration involves coupled dissolution and precipitation processes occurring at the mineral-fluid interface. Critical insight into the reaction mechanisms is therefore gained from direct nano-scale observations of carbonation reactions using advanced analytical techniques such as Atomic Force Microscopy (AFM). Here we present a series of in situ an ex situ AFM experiments on the dissolution and carbonation of brucite [Mg(OH)2] at varying pH (2-12), temperature (23-40°C), aqueous NaHCO3 concentration (10-5-1 M), and PCO2 (0-1 atm). In all experiments, brucite dissolution proceeded by the formation and spreading of etch pits with equilateral triangular shapes. Dissolution rates increased with decreasing pH and increasing NaHCO3 concentration. Simultaneously with dissolution of brucite, the growth of a Mg-carbonate phase (probably dypingite) was directly observed. In NaHCO3 solutions (pH 7.2 - 9.3,), precipitation of Mg-carbonates was limited. Enhanced precipitation was, however, observed in acidified NaHCO3 solutions (pH 5, DIC ≈ 25.5 mM) and in solutions that were equilibrated under a CO2 atmosphere (pH 4, DIC ≈ 25.2 mM). Nucleation predominantly occurred in areas of high dissolution, such as deep step edges, suggesting that the carbonation reaction is locally diffusion-transport controlled within a fluid-mineral boundary layer and is the result of interface-coupled dissolution-precipitation. More extensive particle growth was also observed after ex situ experiments lasting for several hours. This AFM study contributes to an improved understanding of the mechanism of aqueous brucite carbonation at low temperature and PCO2 conditions and has implications for the development of mineral carbonation schemes involving brucite as well as silicates (e.g., serpentines) that contain 'brucite-layers' as structural components.

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

    PubMed

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

    2016-02-02

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

  2. CO2 storage in solid form: a study of direct mineral carbonation

    SciTech Connect

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

    2000-01-01

    Direct mineral carbonation by an ex-situ process in an aqueous system has been investigated over the past two years. The process utilizes a slurry of water mixed with a magnesium silicate mineral, such as olivine [forsterite end member (Mg2SiO4)], or serpentine [Mg3Si2O5(OH)4]. This slurry is reacted with sub- or 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+ ion hydrolyzes the mineral, liberating Mg2+ cations which react with the bicarbonate to form the solid carbonate. Results of the baseline tests, conducted on ground products of the natural minerals, have demonstrated that the kinetics of the reaction are slow at ambient temperature (22 C) and subcritical CO2 pressures (below 73 atm). However, at elevated temperature and pressure, coupled with continuous stirring of the slurry and gas dispersion within the water column, significant conversion to the carbonate occurs. Extent of reaction is roughly 90% within 24 hours, at 185 C and partial pressure of CO2 (PCO2) of 115 atm. Heat pretreatment of the serpentine, coupled with bicarbonate and salt additions to the solution, improve reaction kinetics, resulting in an extent of reaction of roughly 80% within 0.5 hours, at 155 C and PCO2 of 185 atm. Subsequent tests are intended to examine various pretreatment options, the carbonation solution characteristics, as well as other mineral groups.

  3. Impacts of diffusive transport on carbonate mineral formation from magnesium silicate-CO2-water reactions.

    PubMed

    Giammar, Daniel E; Wang, Fei; Guo, Bin; Surface, J Andrew; Peters, Catherine A; Conradi, Mark S; Hayes, Sophia E

    2014-12-16

    Reactions of CO2 with magnesium silicate minerals to precipitate magnesium carbonates can result in stable carbon sequestration. This process can be employed in ex situ reactors or during geologic carbon sequestration in magnesium-rich formations. The reaction of aqueous CO2 with the magnesium silicate mineral forsterite was studied in systems with transport controlled by diffusion. The approach integrated bench-scale experiments, an in situ spectroscopic technique, and reactive transport modeling. Experiments were performed using a tube packed with forsterite and open at one end to a CO2-rich solution. The location and amounts of carbonate minerals that formed were determined by postexperiment characterization of the solids. Complementing this ex situ characterization, (13)C NMR spectroscopy tracked the inorganic carbon transport and speciation in situ. The data were compared with the output of reactive transport simulations that accounted for diffusive transport processes, aqueous speciation, and the forsterite dissolution rate. All three approaches found that the onset of magnesium carbonate precipitation was spatially localized about 1 cm from the opening of the forsterite bed. Magnesite was the dominant reaction product. Geochemical gradients that developed in the diffusion-limited zones led to locally supersaturated conditions at specific locations even while the volume-averaged properties of the system remained undersaturated.

  4. A cryogenic fluorescence spectroscopic study of uranyl carbonate, phosphate, and oxyhydroxide minerals

    SciTech Connect

    Wang, Zheming; Zachara, John M.; Liu, Chongxuan; Gassman, Paul L.; Felmy, Andrew R.; Clark, Sue B.

    2008-11-03

    In this work we have applied liquid-helium temperature (LHeT) time-resolved laser-induced fluorescence spectroscopy (TRLIF) to characterize a series of natural and synthetic minerals of uranium carbonate, phosphate and oxyhydroxides including rutherfordine, zellerite, liebigite, phosphuranylite, meta-autunite, meta-torbernite, uranyl phosphate, sodium-uranyl-phosphate, bequerelite, clarkeite, curite, schoepite and compregnacite, and compared their spectral characteristics among these minerals as well as our previously published data on uranyl silicates. For the carbonate minerals, the fluorescence spectra depend on the stoichiometry of the mineral. For the phosphate minerals the fluorescence spectra closely resemble each other despite the differences in their composition and structure. For all uranium oxyhydroxides, the fluorescence spectra are largely red-shifted as compared with those of the uranium carbonates and phosphates and their vibronic bands are broadened and less resolved. The much enhanced spectra resolution at LHeT allows more accurate calculation of the O=U=O symmetrical stretch frequency, ν1, corresponding to the average spacing of the vibronic peaks of the fluorescence spectra and the spectral origin as reflected by the position of the first vibronic band. It was found that both the average ν1 and λ1 values correlate well with the average basicity of the inorganic anion.

  5. Mineral Sequestration of Carbon Dixoide in a Sandstone-Shale System

    SciTech Connect

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

    2004-07-09

    A conceptual model of CO2 injection in bedded sandstone-shale sequences has been developed using hydrogeologic properties and mineral compositions commonly encountered in Gulf Coast sediments. Numerical simulations were performed with the reactive fluid flow and geochemical transport code TOUGHREACT to analyze mass transfer between sandstone and shale layers and CO2 immobilization through carbonate precipitation. Results indicate that most CO2 sequestration occurs in the sandstone. The major CO2 trapping minerals are dawsonite and ankerite. The CO2 mineral-trapping capacity after 100,000 years reaches about 90 kg per cubic meter of the medium. The CO2 trapping capacity depends on primary mineral composition. Precipitation of siderite and ankerite requires Fe+2 supplied mainly by chlorite and some by hematite dissolution and reduction. Precipitation of dawsonite requires Na+ provided by oligoclase dissolution. The initial abundance of chlorite and oligoclase therefore affects the CO2 mineral trapping capacity. The sequestration time required depends on the kinetic rate of mineral dissolution and precipitation. Dawsonite reaction kinetics is not well understood, and sensitivity regarding the precipitation rate was examined. The addition of CO2 as secondary carbonates results in decreased porosity. The leaching of chemical constituents from the interior of the shale causes slightly increased porosity. The limited information currently available for the mineralogy of natural high-pressure CO2 gas reservoirs is also generally consistent with our simulation. The ''numerical experiments'' give a detailed understanding of the dynamic evolution of a sandstone-shale geochemical system.

  6. Dissolution and secondary mineral precipitation in basalts due to reactions with carbonic acid

    NASA Astrophysics Data System (ADS)

    Kanakiya, Shreya; Adam, Ludmila; Esteban, Lionel; Rowe, Michael C.; Shane, Phil

    2017-06-01

    One of the leading hydrothermal alteration processes in volcanic environments is when rock-forming minerals with high concentrations of iron, magnesium, and calcium react with CO2 and water to form carbonate minerals. This is used to the advantage of geologic sequestration of anthropogenic CO2. Here we experimentally investigate how mineral carbonation processes alter the rock microstructure due to CO2-water-rock interactions. In order to characterize these changes, CO2-water-rock alteration in Auckland Volcanic Field young basalts (less than 0.3 Ma) is studied before and after a 140 day reaction period. We investigate how whole core basalts with similar geochemistry but different porosity, permeability, pore geometry, and volcanic glass content alter due to CO2-water-rock reactions. Ankerite and aluminosilicate minerals precipitate as secondary phases in the pore space. However, rock dissolution mechanisms are found to dominate this secondary mineral precipitation resulting in an increase in porosity and decrease in rigidity of all samples. The basalt with the highest initial porosity and volcanic glass volume shows the most secondary mineral precipitation. At the same time, this sample exhibits the greatest increase in porosity and permeability, and a decrease in rock rigidity post reaction. For the measured samples, we observe a correlation between volcanic glass volume and rock porosity increase due to rock-fluid reactions. We believe this study can help understand the dynamic rock-fluid interactions when monitoring field scale CO2 sequestration projects in basalts.

  7. [Exogenous nitrogen enrichment impact on the carbon mineralization and DOC of the freshwater marsh soil].

    PubMed

    Liu, De-yan; Song, Chang-chun; Wang, Li; Wang, Li-li; Li, Ying-chen

    2008-12-01

    By laboratory incubation experiment, under aerobic and submerged soil moisture conditions, we investigated the mineralization of soil organic carbon (SOC) and contents of dissolved organic carbon (DOC) with different nitrogen inputs in a freshwater marsh soil. The results showed that under aerobic condition, there were no significant effects on the mineralization of SOC and contents of DOC as the net nitrogen input was 1 mg x g(-1) (N1), however, they were significantly higher than control and N1 treatments when nitrogen input increased to 2 and 5 mg x g(-1) (N2, N3), and the amount of DOC was respectively 187.22% and 203.25% higher than control (250.62 mg x kg(-1)). Under submerged condition, all N treatments restrained the mineralization of SOC, and the content of DOC was respectively 88.34% (N1), 82.69% (N2) and 80.04% (N3) lower than control (642.52 mg x kg(-1)). There were significant positive correlations between the contents of DOC and the amounts of cumulative C by mineralization (R2 was 0.939 and 0.843, respectively), which suggested that the changes of DOC affected by N input might be one of the important reasons that arose the differences of SOC mineralization. The results also indicate that as the waterlogged environment disappeared in wetland, the supply of exogenous nitrogen might bring large loss of SOC through enhancing the mineralization of SOC and leaching of DOC.

  8. Where is mineral ballast important for surface export of particulate organic carbon in the ocean?

    PubMed Central

    Le Moigne, Frédéric A C; Pabortsava, Katsiaryna; Marcinko, Charlotte L J; Martin, Patrick; Sanders, Richard J

    2014-01-01

    Correlations between particulate organic carbon (POC) and mineral fluxes in the deep ocean have inspired the inclusion of “ballast effect” parameterizations in carbon cycle models. A recent study demonstrated regional variability in the effect of ballast minerals on the flux of POC in the deep ocean. We have undertaken a similar analysis of shallow export data from the Arctic, Atlantic, and Southern Oceans. Mineral ballasting is of greatest importance in the high-latitude North Atlantic, where 60% of the POC flux is associated with ballast minerals. This fraction drops to around 40% in the Southern Ocean. The remainder of the export flux is not associated with minerals, and this unballasted fraction thus often dominates the export flux. The proportion of mineral-associated POC flux often scales with regional variation in export efficiency (the proportion of primary production that is exported). However, local discrepancies suggest that regional differences in ecology also impact the magnitude of surface export. We propose that POC export will not respond equally across all high-latitude regions to possible future changes in ballast availability. PMID:26074644

  9. Beyond temperature: Clumped isotope signatures in dissolved inorganic carbon species and the influence of solution chemistry on carbonate mineral composition

    USGS Publications Warehouse

    Tripati, Aradhna K.; Hill, Pamela S.; Eagle, Robert A.; Mosenfelder, Jed L.; Tang, Jianwu; Schauble, Edwin A.; Eiler, John M.; Zeebe, Richard E.; Uchikawa, Joji; Coplen, Tyler B.; Ries, Justin B.; Henry, Drew

    2015-01-01

    “Clumped-isotope” thermometry is an emerging tool to probe the temperature history of surface and subsurface environments based on measurements of the proportion of 13C and 18O isotopes bound to each other within carbonate minerals in 13C18O16O22- groups (heavy isotope “clumps”). Although most clumped isotope geothermometry implicitly presumes carbonate crystals have attained lattice equilibrium (i.e., thermodynamic equilibrium for a mineral, which is independent of solution chemistry), several factors other than temperature, including dissolved inorganic carbon (DIC) speciation may influence mineral isotopic signatures. Therefore we used a combination of approaches to understand the potential influence of different variables on the clumped isotope (and oxygen isotope) composition of minerals.We conducted witherite precipitation experiments at a single temperature and at varied pH to empirically determine 13C-18O bond ordering (Δ47) and δ18O of CO32- and HCO3- molecules at a 25 °C equilibrium. Ab initio cluster models based on density functional theory were used to predict equilibrium 13C-18O bond abundances and δ18O of different DIC species and minerals as a function of temperature. Experiments and theory indicate Δ47 and δ18O compositions of CO32- and HCO3- ions are significantly different from each other. Experiments constrain the Δ47-δ18O slope for a pH effect (0.011 ± 0.001; 12 ⩾ pH ⩾ 7). Rapidly-growing temperate corals exhibit disequilibrium mineral isotopic signatures with a Δ47-δ18O slope of 0.011 ± 0.003, consistent with a pH effect.Our theoretical calculations for carbonate minerals indicate equilibrium lattice calcite values for Δ47 and δ18O are intermediate between HCO3− and CO32−. We analyzed synthetic calcites grown at temperatures ranging from 0.5 to 50 °C with and without the enzyme carbonic anhydrase present. This enzyme catalyzes oxygen isotopic exchange between DIC species and is present in many

  10. Quantitative identification of metastable magnesium carbonate minerals by solid-state 13C NMR spectroscopy.

    PubMed

    Moore, Jeremy K; Surface, J Andrew; Brenner, Allison; Wang, Louis S; Skemer, Philip; Conradi, Mark S; Hayes, Sophia E

    2015-01-06

    In the conversion of CO2 to mineral carbonates for the permanent geosequestration of CO2, there are multiple magnesium carbonate phases that are potential reaction products. Solid-state (13)C NMR is demonstrated as an effective tool for distinguishing magnesium carbonate phases and quantitatively characterizing magnesium carbonate mixtures. Several of these mineral phases include magnesite, hydromagnesite, dypingite, and nesquehonite, which differ in composition by the number of waters of hydration or the number of crystallographic hydroxyl groups. These carbonates often form in mixtures with nearly overlapping (13)C NMR resonances which makes their identification and analysis difficult. In this study, these phases have been investigated with solid-state (13)C NMR spectroscopy, including both static and magic-angle spinning (MAS) experiments. Static spectra yield chemical shift anisotropy (CSA) lineshapes that are indicative of the site-symmetry variations of the carbon environments. MAS spectra yield isotropic chemical shifts for each crystallographically inequivalent carbon and spin-lattice relaxation times, T1, yield characteristic information that assist in species discrimination. These detailed parameters, and the combination of static and MAS analyses, can aid investigations of mixed carbonates by (13)C NMR.

  11. A rapid and cost effective method for soil carbon mineralization under static incubations

    USDA-ARS?s Scientific Manuscript database

    Soil incubations with subsequent measurement of carbon dioxide (CO2) evolved are common soil assays to estimate C mineralization rates and active organic C. Two common methods used to detect CO2 in laboratory incubations are gas chromatography (GC) and alkali absorption followed by titration (NaOH)...

  12. A rapid and cost effective method for soil carbon mineralization under static incubations

    USDA-ARS?s Scientific Manuscript database

    Soil incubations with subsequent determination of carbon dioxide (CO2) are common soil assays used to estimate C mineralization rates and active organic C pools. Two common methods used to detect CO2 in laboratory incubations are gas chromatography (GC) and alkali absorption followed by titration (...

  13. CO2 mitigation potential of mineral carbonation with industrial alkalinity sources in the United States.

    PubMed

    Kirchofer, Abby; Becker, Austin; Brandt, Adam; Wilcox, Jennifer

    2013-07-02

    The availability of industrial alkalinity sources is investigated to determine their potential for the simultaneous capture and sequestration of CO2 from point-source emissions in the United States. Industrial alkalinity sources investigated include fly ash, cement kiln dust, and iron and steel slag. Their feasibility for mineral carbonation is determined by their relative abundance for CO2 reactivity and their proximity to point-source CO2 emissions. In addition, the available aggregate markets are investigated as possible sinks for mineral carbonation products. We show that in the U.S., industrial alkaline byproducts have the potential to mitigate approximately 7.6 Mt CO2/yr, of which 7.0 Mt CO2/yr are CO2 captured through mineral carbonation and 0.6 Mt CO2/yr are CO2 emissions avoided through reuse as synthetic aggregate (replacing sand and gravel). The emission reductions represent a small share (i.e., 0.1%) of total U.S. CO2 emissions; however, industrial byproducts may represent comparatively low-cost methods for the advancement of mineral carbonation technologies, which may be extended to more abundant yet expensive natural alkalinity sources.

  14. Fast and slow adsorption of carbamazepine on biochar as affected by carbon structure and mineral composition.

    PubMed

    Chen, Jian; Zhang, Di; Zhang, Huang; Ghosh, Saikat; Pan, Bo

    2017-02-01

    The influence of carbon structure and mineral composition of biochar on fast adsorption and slow adsorption of ionic organic contaminants (IOCs) is still unclear. This study used carbamazepine (CBZ) as adsorbate, peanut-shell-derived biochars produced at different charred temperatures, and the corresponding acid-washed biochars as adsorbents, to investigate the adsorption kinetics as affected by carbon structure and mineral composition of biochar. The adsorption of CBZ on amorphous (loose) carbon was lower than aromatic (condensed) carbon, but the former mainly contributed to the fast adsorption of CBZ. The hydrophobic and π-π interactions were likely the predominant adsorption mechanisms of CBZ on biochar. The ratio of CBZ fast and slow adsorption fractions (ffast/fslow) significantly reduced after acid-wash treatment of the biochars. The X-ray diffraction and Fourier transform infrared spectra indicated that minerals, including CaCO3, KAlO2, and quartz, were likely responsible for the fast adsorption of CBZ by the hydrogen bonds between CBZ and -OH on the surface of minerals. These results are useful for better understanding of the environmental behavior and prediction of the environmental risks of IOCs in biochar-amended soils. Copyright © 2016 Elsevier B.V. All rights reserved.

  15. Carbon Mineralization in Two Ultisols Amended with Different Sources and Particle Sizes of Pyrolyzed Biochar

    EPA Science Inventory

    Biochar produced during pyrolysis has the potential to enhance soil fertility and reduce greenhouse gas emissions. The influence of biochar properties (e.g., particle size) on both short- and long-term carbon (C) mineralization of biochar remains unclear. There is minimal informa...

  16. Carbon Mineralization in Two Ultisols Amended with Different Sources and Particle Sizes of Pyrolyzed Biochar

    EPA Science Inventory

    Biochar produced during pyrolysis has the potential to enhance soil fertility and reduce greenhouse gas emissions. The influence of biochar properties (e.g., particle size) on both short- and long-term carbon (C) mineralization of biochar remains unclear. There is minimal informa...

  17. 16 CFR 802.3 - Acquisitions of carbon-based mineral reserves.

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... exemption in § 802.3 for transfers of associated exploration or production assets. 3. “A,” an oil company... reserves. 802.3 Section 802.3 Commercial Practices FEDERAL TRADE COMMISSION RULES, REGULATIONS, STATEMENTS... § 802.3 Acquisitions of carbon-based mineral reserves. (a) An acquisition of reserves of oil,...

  18. 16 CFR 802.3 - Acquisitions of carbon-based mineral reserves.

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... exemption in § 802.3 for transfers of associated exploration or production assets. 3. “A,” an oil company... reserves. 802.3 Section 802.3 Commercial Practices FEDERAL TRADE COMMISSION RULES, REGULATIONS, STATEMENTS... § 802.3 Acquisitions of carbon-based mineral reserves. (a) An acquisition of reserves of oil,...

  19. 16 CFR 802.3 - Acquisitions of carbon-based mineral reserves.

    Code of Federal Regulations, 2014 CFR

    2014-01-01

    ... exemption in § 802.3 for transfers of associated exploration or production assets. 3. “A,” an oil company... reserves. 802.3 Section 802.3 Commercial Practices FEDERAL TRADE COMMISSION RULES, REGULATIONS, STATEMENTS... § 802.3 Acquisitions of carbon-based mineral reserves. (a) An acquisition of reserves of oil,...

  20. 16 CFR 802.3 - Acquisitions of carbon-based mineral reserves.

    Code of Federal Regulations, 2013 CFR

    2013-01-01

    ... exemption in § 802.3 for transfers of associated exploration or production assets. 3. “A,” an oil company... reserves. 802.3 Section 802.3 Commercial Practices FEDERAL TRADE COMMISSION RULES, REGULATIONS, STATEMENTS... § 802.3 Acquisitions of carbon-based mineral reserves. (a) An acquisition of reserves of oil,...

  1. 16 CFR 802.3 - Acquisitions of carbon-based mineral reserves.

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... exemption in § 802.3 for transfers of associated exploration or production assets. 3. “A,” an oil company... reserves. 802.3 Section 802.3 Commercial Practices FEDERAL TRADE COMMISSION RULES, REGULATIONS, STATEMENTS... § 802.3 Acquisitions of carbon-based mineral reserves. (a) An acquisition of reserves of oil,...

  2. Soil organic carbon quality in forested mineral wetlands at different mean annual temperature.

    Treesearch

    Cinzia Fissore; Christian P. Giardina; Randall K. Kolka; Carl C. Trettin

    2009-01-01

    Forested mineral soil wetlands (FMSW) store large stocks of soil organic carbon (SOC), but little is known on: (i) whether the quality of SOC stored in these soils (proportion of active versus more resistant SOC compounds) differs from SOC in upland soils; (ii) how the quality of SOC in FMSW varies with mean annual temperature (MAT); and (iii) whether SOC decomposition...

  3. Carbon mineralization in two ultisols amended with different sources and particle sizes of pyrolyzed biochar

    USDA-ARS?s Scientific Manuscript database

    Biochar produced during pyrolysis has the potential to enhance soil fertility and reduce greenhouse gas emissions. The influence of biochar properties (e.g. particle size) on both short- and long-term carbon (C) mineralization of biochar remains unclear. There is minimal information on the potential...

  4. Mineralization of organic carbon on and in the sediment of Lake Grevelingen

    NASA Astrophysics Data System (ADS)

    Lindeboom, H. J.; De Klerk, H. A. J.; Sandee, A. J. J.

    Within the framework of a research project on the carbon cycle in saline Lake Grevelingen a study of the mineralization on and in the sediment was made. The oxygen uptake by the sediment was measured using the bell jar method at 6 sampling stations. Applying a C over O 2 conversion factor of 0.29, it was calculated that 330 g·m -2 is mineralized in the sediment of the lake annually. By means of biomass estimates of the macroflora and fauna inside the bell jars and regression analysis, the contribution of these organisms to the carbon mineralization rate was calculated to be 70 and 95 g·m -2·a -1, respectively. The effect of oxygen gradients and apparent diffusion coefficients upon the oxygen uptake rate was studied with microelectrodes. This indicated that bioturbation is a major factor influencing the oxygen uptake rate. A good correlation between this rate and temperature was found.

  5. Geophysical Delination of Mg-Rich Ultramafic Rocksfor Mineral Carbon Sequestration

    USGS Publications Warehouse

    McCafferty, Anne E.; Van Gosen, Brad S.; Krevor, Sam C.; Graves, Chris R.

    2009-01-01

    A similar version of this slide presentation was given at the 2009 Society for Mining, Metallurgy, and Exploration (SME) annual meeting in Denver, Colorado, in February 2009. This presentation was part of the 'Industrial Minerals: Reducing Carbon Footprint in Industrial Minerals' session. Two other related talks were presented in the same session by Sam Krevor of Columbia University. The first talk provided a status report on mineral CO2 sequestration as an industrial process. The second talk presented a national-scale geologic compilation of rocks favorable for mineral CO2 sequestration in the United States. This presentation, an extension of the latter talk, shows how airborne geophysical data can be used to further refine the geologic mapping of ultramafic rocks.

  6. Development of a CO2 Sequestration Module by Integrating Mineral Activation and Aqueous Carbonation

    SciTech Connect

    George Alexander; Parvana Aksoy; John Andresen; Mercedes Maroto-Valer; Harold Schobert

    2006-08-14

    Mineral carbonation is a promising concept for permanent CO{sub 2} sequestration due to the vast natural abundance of the raw materials and the permanent storage of CO{sub 2} in solid form as carbonates. The sequestration of CO{sub 2} through the employment of magnesium silicates--olivine and serpentine--is beyond the proof of concept stage. For the work done in this project, serpentine was chosen as the feedstock mineral due to its abundance and availability. Although the reactivity of olivine is greater than that of serpentine, physical and chemical treatments have been shown to increase greatly the reactivity of serpentine. The primary drawback to mineral carbonation is reaction kinetics. To accelerate the carbonation, aqueous processes are preferred, where the minerals are first dissolved in solution. In aqueous carbonation, the key step is the dissolution rate of the mineral, where the mineral dissolution reaction is likely to be surface-controlled. The relatively low reactivity of serpentine has warranted research into physical and chemical treatments that have been shown to greatly increase its reactivity. The use of sulfuric acid as an accelerating medium for the removal of magnesium from serpentine has been investigated. To accelerate the dissolution process, the mineral can be ground to very fine particle size, <37 {micro}m, but this is a very energy-intensive process. Previous work in our laboratory showed that chemical surface activation helps to dissolve magnesium from the serpentine (of particle size {approx} 100 {micro}m) and that the carbonation reaction can be conducted under mild conditions (20 C and 4.6 MPa) compared to previous studies that required >185 C, >13 MPa, and <37 {micro}m particle size. This work also showed that over 70% of the magnesium can be extracted at ambient temperature, leaving an amorphous silica with surface area of about 330 m{sup 2}/g. The overall objective of this research program is to optimize the active carbonation

  7. Predicting long-term carbon mineralization and trace gas production from thawing permafrost of Northeast Siberia.

    PubMed

    Knoblauch, Christian; Beer, Christian; Sosnin, Alexander; Wagner, Dirk; Pfeiffer, Eva-Maria

    2013-04-01

    The currently observed Arctic warming will increase permafrost degradation followed by mineralization of formerly frozen organic matter to carbon dioxide (CO2 ) and methane (CH4 ). Despite increasing awareness of permafrost carbon vulnerability, the potential long-term formation of trace gases from thawing permafrost remains unclear. The objective of the current study is to quantify the potential long-term release of trace gases from permafrost organic matter. Therefore, Holocene and Pleistocene permafrost deposits were sampled in the Lena River Delta, Northeast Siberia. The sampled permafrost contained between 0.6% and 12.4% organic carbon. CO2 and CH4 production was measured for 1200 days in aerobic and anaerobic incubations at 4 °C. The derived fluxes were used to estimate parameters of a two pool carbon degradation model. Total CO2 production was similar in Holocene permafrost (1.3 ± 0.8 mg CO2 -C gdw(-1) aerobically, 0.25 ± 0.13 mg CO2 -C gdw(-1) anaerobically) as in 34 000-42 000-year-old Pleistocene permafrost (1.6 ± 1.2 mg CO2 -C gdw(-1) aerobically, 0.26 ± 0.10 mg CO2 -C gdw(-1) anaerobically). The main predictor for carbon mineralization was the content of organic matter. Anaerobic conditions strongly reduced carbon mineralization since only 25% of aerobically mineralized carbon was released as CO2 and CH4 in the absence of oxygen. CH4 production was low or absent in most of the Pleistocene permafrost and always started after a significant delay. After 1200 days on average 3.1% of initial carbon was mineralized to CO2 under aerobic conditions while without oxygen 0.55% were released as CO2 and 0.28% as CH4 . The calibrated carbon degradation model predicted cumulative CO2 production over a period of 100 years accounting for 15.1% (aerobic) and 1.8% (anaerobic) of initial organic carbon, which is significantly less than recent estimates. The multiyear time series from the incubation experiments helps to more reliably constrain projections of future

  8. Limitations and opportunities for Permian-Triassic carbonate-carbon isotope stratigraphy posed by microbial-controlled diagenetic mineral additions

    NASA Astrophysics Data System (ADS)

    Schobben, Martin; van de Velde, Sebastiaan; Suchocka, Jana; Leda, Lucyna; Korn, Dieter; Struck, Ulrich; Vinzenz Ullmann, Clemens; Hairapetian, Vachik; Ghaderi, Abbas; Korte, Christoph; Newton, Robert J.; Poulton, Simon W.; Wignall, Paul B.

    2017-04-01

    Bulk-carbonate stable carbon isotope records are used to proxy the ancient biogeochemical carbon cycle as well as aid in determining the age of sedimentary deposits. However, the multicomponent nature and the component-specific diagenetic potential of bulk-rock pose limits on the applicability of this proxy in recording ancient seawater chemistry and its usability as a stratigraphic aid. The aim of this study is to disentangle primary trends from diagenetic signals in carbonate-carbon isotope records traversing the Permian-Triassic boundary in marine carbonate-bearing sequences of Iran and South China. We observe, 1) a global first-order trend towards depleted carbon isotope values across the Permian-Triassic transition, 2) second-order carbon isotope variability superimposed on the first-order trend, and 3) a temporal trend in the amplitude of the second-order carbon isotope fluctuations. By application of a diagenetic model, we show that microbial-steered carbonate additions can introduce diagenetic carbon isotope signals to the carbonate archive. Organic carbon sedimentation has the potential to fuel this (sub)seafloor microbial pathway of carbonate stabilization and determines trajectories of diagenetic bulk-rock carbon isotope alteration. Moreover, we identified through this numerical exercise that lowered marine sulfate levels makes the sedimentary system vulnerable to diagenetic modulations of the primary carbon isotope signal, by modest changes of organic carbon supply. This approach suggests that latest Permian reduced bioturbation, consequential heterogeneous organic matter accumulation and authigenic mineralization can explain the temporal trend of increased second-order carbon isotope scatter, whilst retaining the first-order trend. In conclusion, the combined dataset and calculations suggest that the application of carbon isotope chemostratigraphy of the Permian-Triassic boundary is at present limited to the recognition of broad temporal patterns

  9. Developments in CO2 mineral carbonation of oil shale ash.

    PubMed

    Uibu, M; Velts, O; Kuusik, R

    2010-02-15

    Solid waste and atmospheric emissions originating from power production are serious problems worldwide. In the Republic of Estonia, the energy sector is predominantly based on combustion of a low-grade carbonaceous fossil fuel: Estonian oil shale. Depending on the combustion technology, oil shale ash contains 10-25% free lime. To transport the ash to wet open-air deposits, a hydraulic system is used in which 10(7)-10(8) cubic meters of Ca(2+)-ion-saturated alkaline water (pH level 12-13) is recycled between the plant and sedimentation ponds. The goals of the current work were to design an ash-water suspension carbonation process in a continuous mode laboratory-scale plant and to search for potential means of intensifying the water neutralization process. The carbonation process was optimized by cascading reactor columns in which the pH progressed from alkaline to almost neutral. The amount of CO(2) captured from flue gases can reach 1-1.2 million ton at the 2007 production level of the SC Narva Power Plants. Laboratory-scale neutralization experiments were carried out to compare two reactor designs. Sedimentation of PCC particles of rhombohedral crystalline structure was demonstrated and their main characteristics were determined. A new method providing 50x greater specific intensity is also discussed.

  10. Band gap-tunable potassium doped graphitic carbon nitride with enhanced mineralization ability.

    PubMed

    Hu, Shaozheng; Li, Fayun; Fan, Zhiping; Wang, Fei; Zhao, Yanfeng; Lv, Zhenbo

    2015-01-21

    Band gap-tunable potassium doped graphitic carbon nitride with enhanced mineralization ability was prepared using dicyandiamide monomer and potassium hydrate as precursors. X-ray diffraction (XRD), N2 adsorption, UV-Vis spectroscopy, Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), photoluminescence (PL) and X-ray photoelectron spectroscopy (XPS) were used to characterize the prepared catalysts. The CB and VB potentials of graphitic carbon nitride could be tuned from -1.09 and +1.56 eV to -0.31 and +2.21 eV by controlling the K concentration. Besides, the addition of potassium inhibited the crystal growth of graphitic carbon nitride, enhanced the surface area and increased the separation rate for photogenerated electrons and holes. The visible-light-driven Rhodamine B (RhB) photodegradation and mineralization performances were significantly improved after potassium doping. A possible influence mechanism of the potassium concentration on the photocatalytic performance was proposed.

  11. Characterizing the Influence of Plant Growth on Carbon Association with Fresh Soil Minerals

    NASA Astrophysics Data System (ADS)

    Neurath, R.; Jacoby, I. X.; Whitman, T.; Nico, P. S.; Pett-Ridge, J.; Weber, P. K.; Lipton, A.; Firestone, M. K.

    2016-12-01

    The zone of root influence (rhizosphere) is a dynamic soil environment with active carbon release, highly active and phylogentically distinct microbial communities, and unique edaphic properties (i.e. redox, pH). We hypothesize that mineral-SOM associations in the rhizosphere differ from those in bulk soil, possibly altering the persistance and fluxes of this carbon. We investigated how SOM first associates with soil minerals during growth of Avena barbata, a Mediterranean annual grass. We grew A. barbata with 99 atom% 13CO2 and tracked 13C-labeled photosynthate into soil where three minerals types were incubated: quartz, kaolinite, and ferrihydrite. Our work suggests these different mineral types recruit different amounts of mineral-associated carbon and microbial community composition (16S and ITS with Illumina MiSeq). Here, we have focused on the micron scale to characterize the composition and source of mineral-associated SOM. Using scanning transmission X-ray microscopy (STXM), we defined major classes of C compounds, and overlaid those data with characterization of Fe mineral speciation. In the same regions of interest, we used correlated nano-scale secondary ion mass-spectrometry (NanoSIMS) analyses to assess the isotopic enrichment of these C compounds. Based on the degree of 13C-labeling in each feature, we can determine whether the initial source of the OM was plant-derived, bulk soil, or mixed. For a more bulk-scale perspective, we also conducted sequential extractions of SOM associated with Fe and Al phases to look at the bonding chemistry of these compounds. We found that minerals in the rhizosphere had unique SOM compositions, notably, rhizosphere-incubated minerals were more enriched in aromatic compounds. The source of these aromatics is likely from the bulk soil and not from the plants, suggesting re-mobilization of SOM during plant growth. Our work also shows the importance of considering the microbial communities that associate with soil minerals

  12. Fundamental Science Tools for Geologic Carbon Sequestration and Mineral Carbonation Chemistry: In Situ Magic Angle Spinning (MAS) Nuclear Magnetic Resonance

    NASA Astrophysics Data System (ADS)

    Hoyt, D. W.; Turcu, R. V.; Sears, J. A.; Rosso, K. M.; Burton, S. D.; Kwak, J.; Felmy, A. R.; Hu, J.

    2010-12-01

    GCS is one of the most promising ways of mitigating atmospheric greenhouse gases. Mineral carbonation reactions are potentially important to the long-term sealing effectiveness of caprock but remain poorly predictable, particularly reactions occurring in low-water supercritical CO2(scCO2)-dominated environments where the chemistry has not been adequately explored. In situ probes that provide molecular-level information is desirable for investigating mechanisms and rates of GCS mineral carbonation reactions. MAS-NMR is a powerful tool for obtaining detailed molecular structure and dynamics information of a system regardless whether the system is in a solid, a liquid, a gaseous, or a supercritical state, or a mixture thereof. However, MAS NMR under scCO2 conditions has never been realized due to the tremendous technical difficulties of achieving and maintaining high pressure within a fast spinning MAS rotor. In this work, we report development of a unique high pressure MAS NMR capability, and its application to mineral carbonation chemistry in scCO2 under geologically relevant temperatures and pressures. Our high pressure MAS rotor has successfully maintained scCO2 conditions with minimal leakage over a period of 72 hours. Mineral carbonation reactions of a model magnesium silicate (forsterite) reacted with 96 bars scCO2 containing varying amounts of H2O (both below and above saturation of the scCO2) were investigated at 50○C. Figure 1 shows typical in situ 13C MAS NMR spectra demonstrating that the peaks corresponding to the reactants, intermediates, and the magnesium carbonation products are all observed in a single spectrum. For example, the scCO2 peak is located at 126.1 ppm. Reaction intermediates include the aqueous species HCO3-(160 ppm), partially hydrated/hydroxylated magnesium carbonates(166-168 ppm), and can easily be distinguished from final product magnesite(170 ppm). The new capability and this model mineral carbonation process will be overviewed in

  13. High-temperature carbonate minerals in the Stillwater Complex, Montana, USA

    NASA Astrophysics Data System (ADS)

    Aird, Hannah M.; Boudreau, Alan E.

    2013-10-01

    High-temperature carbonate minerals have been observed in association with sulfide minerals below the platiniferous Johns-Manville (J-M) reef of the Stillwater Complex in a stratigraphic section that has been previously shown to be characterized by unusually Cl-rich apatite. The carbonate assemblage consists of dolomite with exsolved calcite in contact with sulfide minerals: chalcopyrite and pyrrhotite in the Peridotite Zone; and pyrrhotite with pentlandite, pyrite and chalcopyrite in Gabbronorite Zone I of the Lower Banded Series. A reaction rim surrounds the carbonate-sulfide assemblages, showing an alteration of the host orthopyroxene to a more calcium-enriched, Fe-depleted pyroxene. The calcite-dolomite geothermometer yields a minimum formation temperature as high as 950 °C for the unmixed assemblages. Iron and manganese concentrations exceed the range seen in carbonatite and mantle xenolith carbonates and are distinctly different from the nearly pure end-member carbonates associated with greenschist-grade (and lower) assemblages (e.g., carbonate veins in serpentinite) that occur locally throughout the complex. The association of high-temperature carbonates with sulfides beneath the J-M reef supports the hydromagmatic theory which involves a late-stage chloride-carbonate fluid percolating upwards, dissolving PGE and sulfides and redepositing them at a higher stratigraphic level. Characterization of the processes which form strategically important metal deposits, such as the J-M reef of the Stillwater Complex and the analogous Merensky reef of the Bushveld Complex in South Africa, could potentially lead to better exploration models and, more broadly, a deeper understanding of the cooling and compositional evolution of large bodies of ultramafic and mafic magma and of carbonatites, on both a local and a regional scale.

  14. Minerals

    NASA Astrophysics Data System (ADS)

    Wenk, Hans-Rudolf; Bulakh, Andrei

    2004-06-01

    This introduction to mineralogy for undergraduate and graduate students in geology and materials science has been designed for a semester course. Covering all aspects of mineralogy in an integrated way, it links mineral properties with broader geological processes, and conveys their economic importance throughout the text. Handy reference tables and a glossary of terms make this study an indispensable guide for the next generation of mineralogy students.

  15. Carbonate Mineral Formation on Mars: Clues from Stable Isotope Variation Seen in Cryogenic Laboratory Studies of Carbonate Salts

    NASA Technical Reports Server (NTRS)

    Socki, Richard; Niles, Paul B.; Sun, Tao; Fu, Qi; Romanek, Christopher S.; Gibson, Everett K.

    2013-01-01

    The geologic history of water on the planet Mars is intimately connected to the formation of carbonate minerals through atmospheric CO2 and its control of the climate history of Mars. Carbonate mineral formation under modern martian atmospheric conditions could be a critical factor in controlling the martian climate in a means similar to the rock weathering cycle on Earth. The combination of evidence for liquid water on the martian surface and cold surface conditions suggest fluid freezing could be very common on the surface of Mars. Cryogenic calcite forms readily when a rise in pH occurs as a result of carbon dioxide degassing quickly from freezing Ca-bicarbonate-rich water solutions. This is a process that has been observed in some terrestrial settings such as arctic permafrost cave deposits, lakebeds of the Dry Valleys of Antarctica, and in aufeis (river icings) from rivers of N.E. Alaska. We report here the results of a series of laboratory experiments that were conducted to simulate potential cryogenic carbonate formation on the planet Mars. These results indicate that carbonates grown under martian conditions (controlled atmospheric pressure and temperature) show enrichments from starting bicarbonate fluids in both carbon and oxygen isotopes beyond equilibrium values with average delta13C(DIC-CARB) values of 20.5%0 which exceed the expected equilibrium fractionation factor of [10(sup 3) ln alpha = 13%0] at 0 degC. Oxygen isotopes showed a smaller enrichment with delta18O(H2O-CARB) values of 35.5%0, slightly exceeding the equilibrium fractionation factor of [10(sup 3) ln alpha = 34%0 ] at 0degC. Large kinetic carbon isotope effects during carbonate precipitation could substantially affect the carbon isotope evolution of CO2 on Mars allowing for more efficient removal of 13C from the Noachian atmosphere enriched by atmospheric loss. This mechanism would be consistent with the observations of large carbon isotope variations in martian materials despite the

  16. Carbonate Mineral Formation on Mars: Clues from Stable Isotope Variation Seen in Cryogenic Laboratory Studies of Carbonate Salts

    NASA Technical Reports Server (NTRS)

    Socki, Richard; Niles, Paul B.; Sun, Tao; Fu, Qi; Romanek, Christopher S.; Gibson, Everett K.

    2013-01-01

    The geologic history of water on the planet Mars is intimately connected to the formation of carbonate minerals through atmospheric CO2 and its control of the climate history of Mars. Carbonate mineral formation under modern martian atmospheric conditions could be a critical factor in controlling the martian climate in a means similar to the rock weathering cycle on Earth. The combination of evidence for liquid water on the martian surface and cold surface conditions suggest fluid freezing could be very common on the surface of Mars. Cryogenic calcite forms readily when a rise in pH occurs as a result of carbon dioxide degassing quickly from freezing Ca-bicarbonate-rich water solutions. This is a process that has been observed in some terrestrial settings such as arctic permafrost cave deposits, lakebeds of the Dry Valleys of Antarctica, and in aufeis (river icings) from rivers of N.E. Alaska. We report here the results of a series of laboratory experiments that were conducted to simulate potential cryogenic carbonate formation on the planet Mars. These results indicate that carbonates grown under martian conditions (controlled atmospheric pressure and temperature) show enrichments from starting bicarbonate fluids in both carbon and oxygen isotopes beyond equilibrium values with average delta13C(DIC-CARB) values of 20.5%0 which exceed the expected equilibrium fractionation factor of [10(sup 3) ln alpha = 13%0] at 0 degC. Oxygen isotopes showed a smaller enrichment with delta18O(H2O-CARB) values of 35.5%0, slightly exceeding the equilibrium fractionation factor of [10(sup 3) ln alpha = 34%0 ] at 0degC. Large kinetic carbon isotope effects during carbonate precipitation could substantially affect the carbon isotope evolution of CO2 on Mars allowing for more efficient removal of 13C from the Noachian atmosphere enriched by atmospheric loss. This mechanism would be consistent with the observations of large carbon isotope variations in martian materials despite the

  17. Carbonate Mineral Formation on Mars: Clues from Stable Isotope Variations Seen in Cryogenic Laboratory Studies of Carbonate Salts

    NASA Astrophysics Data System (ADS)

    Socki, R.; Niles, P. B.; Sun, T.; Fu, Q.; Romanek, C. S.; Gibson, E. K.

    2013-12-01

    The geologic history of water on the planet Mars is intimately connected to the formation of carbonate minerals through atmospheric CO2 and its control of the climate history of Mars. Carbonate mineral formation under modern martian atmospheric conditions could be a critical factor in controlling the martian climate in a means similar to the rock weathering cycle on Earth. The combination of evidence for liquid water on the martian surface and cold surface conditions suggest fluid freezing could be very common on the surface of Mars. Cryogenic calcite forms readily when a rise in pH occurs as a result of carbon dioxide degassing quickly from freezing Ca-bicarbonate-rich water solutions. This is a process that has been observed in some terrestrial settings such as arctic permafrost cave deposits, lakebeds of the Dry Valleys of Antarctica, and in aufeis (river icings) from rivers of N.E. Alaska. We report here the results of a series of laboratory experiments that were conducted to simulate potential cryogenic carbonate formation on the planet Mars. These results indicate that carbonates grown under martian conditions (controlled atmospheric pressure and temperature) show enrichments from starting bicarbonate fluids in both carbon and oxygen isotopes beyond equilibrium values with average Δ13C(DIC-CARB) values of ~20.5‰ which exceed the expected equilibrium fractionation factor of [103 ln α = ~13‰] at 0°C. Oxygen isotopes showed a smaller enrichment with Δ18O(H2O-CARB) values of ~35.5‰, slightly exceeding the equilibrium fractionation factor of [103 ln α = ~34‰] at 0°C. Large kinetic carbon isotope effects during carbonate precipitation could substantially affect the carbon isotope evolution of CO2 on Mars allowing for more efficient removal of 13C from the Noachian atmosphere enriched by atmospheric loss. This mechanism would be consistent with the observations of large carbon isotope variations in martian materials despite the relative paucity of

  18. [Transformation of carbonate minerals in a cyano-bacterial mat in the course of laboratory modeling].

    PubMed

    Zaĭtseva, L V; Orleanskiĭ, V K; Alekseev, A O; Ushatinskaia, G T; Gerasimenko, L M

    2007-01-01

    A laboratory model of a cyano-bacterial mat with mineral layers of carbonates was used to examine the dynamics of the transformation of calcium-magnesium carbonate under the conditions of a soda lake. The activity of various organisms of the cyanobacterial community results in conditions under which the Ca-Mg carbonate precipitate undergoes changes. The crystal lattice of the initial carbonate is restructured; its mineralogical composition changes depending on the conditions of the mat. In magnesium calcites, which are formed under such low-temperature conditions, a rudimentary cation adjustment can occur with the formation of dolomite domains. These experiments confirm the hypothesis that the dolomite found in stromatolites is of a secondary origin and can be formed in the course of transformation of Ca-Mg carbonates under alkaline conditions in an alkaliphilic cyanobacterial community.

  19. Adsorption of bisphenol-A from aqueous solution onto minerals and carbon adsorbents.

    PubMed

    Tsai, Wen-Tien; Lai, Chi-Wei; Su, Ting-Yi

    2006-06-30

    The adsorption behaviors of bisphenol-A, which has been listed as one of endocrine disrupting chemicals, from aqueous solution onto four minerals including andesite, diatomaceous earth, titanium dioxide, and activated bleaching earth, and two activated carbons with coconut-based and coal-based virgins were examined in this work. Based on the adsorption results at the specified conditions, the adsorption capacities of activated carbons are significantly larger than those of mineral adsorbents, implying that the former is effective for removal of the highly hydrophobic adsorbate from the aqueous solution because of its high surface area and low surface polarity. The adsorption capacities of bisphenol-A onto these mineral adsorbents with different pore properties are almost similar in magnitude mainly due to the weakly electrostatic interaction between the mineral surface with negative charge and the target adsorbate with hydrophobic nature. Further, a simplified kinetic model, pseudo-second-order, was tested to investigate the adsorption behaviors of bisphenol-A onto the two common activated carbons at different solution conditions. It was found that the adsorption process could be well described with the pseudo-second-order model. The kinetic parameters of the model obtained in the present work are in line with the pore properties of the two adsorbents.

  20. Prevalence and Contribution of Anaerobic Microsites to Carbon Mineralization in Upland Soils

    NASA Astrophysics Data System (ADS)

    Fendorf, S. E.; Keiluweit, M.; Gee, K. E.; Kleber, M.; Wanzek, T.; Nico, P. S.

    2015-12-01

    Soil organic matter (SOM) storage, or residence time, is dominantly controlled by the mineralization (oxidation) rate, which is affected by climatic factors (particularly temperature and rainfall) influencing microbial metabolic rates as well as SOM chemistry, mineral-organic associations, and physical protection. Variation in anaerobic respiratory pathways can further, and dramatically, impact carbon oxidation rates. Within the aggregated structure of soils, steep chemical gradients arise from the supply of oxygen and nutrients along macropores that are rapidly consumed (relative to supply) within the micropore domains of aggregate interiors. As a consequence of demand exceeding oxygen supply within soil aggregates and peds, an appreciable fraction of the soil volume may persist in an anaerobic state within upland, agriculturally productive system. Factors limiting oxygen diffusion and availability such as soil texture, soil moisture content, organic matter input, and aggregate size (soil structure) provide central controls on microbial carbon mineralization rates. Here, we combine laboratory studies with manipulations of field samples and in-field measurements to illustrate how soil structure and carbon availability interact to impose anaerobic conditions and associated respiratory constraints on organic matter mineralization rates and thus storage within soils.

  1. Carbon uptake, microbial community structure, and mineralization of layered mats from Imperial Geyser, Yellowstone National Park

    NASA Astrophysics Data System (ADS)

    Woycheese, K. M.; Grabenstatter, J.; Haddad, A.; Ricci, J. N.; Johnson, H.; Berelson, W.; Spear, J. R.; Caporaso, J. G.; International Geobiology Course 2011

    2011-12-01

    Layered microbial mats provide an analog for early microbial communities, and remain one of the few microbiological structures consistently preserved in the geologic record. Despite this, growth rates, metabolic capabilities, and methods of mineralization in modern communities are poorly understood. Imperial Geyser, an alkaline siliceous hot spring in Yellowstone National Park, provides a useful setting to study these parameters. Mat and water samples (T = 64-40 °C) were collected for 13C analysis and 13C-spiked bicarbonate and acetate incubation experiments. Carbon isotopes were measured for the stream water, pore water and biomass. We experimentally determined rates of bicarbonate uptake, acetate uptake and mineral content. Bicarbonate uptake rates ranged from 0 - 0.4% per day, while acetate uptake rates ranged from 0 - 2.0% per day. These results indicate that the mat biomass is capable of turnover in about 300 days resulting in potential growth rates of 1-2 cm/year. Organic carbon content (% dry weight) ranged from 2 to 16%, and decreased with depth in the mat. The mineral content of these mats is predominantly amorphous SiO2. An inverse correlation between mineral percent and bicarbonate uptake rate was observed, suggesting that there may be a link between metabolism and the prevention of mineralization. Comparing the 13C and carbon uptake rates with 16S rDNA pyrosequencing data we were able to hypothesize the carbon fixation pathways and heterotrophic interactions occurring in this environment. In general, two patterns of 13C values were observed. The first pattern was characterized by increased heterotrophy with depth. In the other, preliminary evidence supporting a photoheterotrophic lifestyle for Roseiflexus spp. was found.

  2. Infrared and Raman spectroscopic characterization of the carbonate mineral huanghoite - And in comparison with selected rare earth carbonates

    NASA Astrophysics Data System (ADS)

    Frost, Ray L.; López, Andrés; Scholz, Ricardo; Xi, Yunfei; Belotti, Fernanda Maria

    2013-11-01

    Raman spectroscopy complimented with infrared spectroscopy has been used to study the rare earth based mineral huanghoite with possible formula given as BaCe(CO3)2F and compared with the Raman spectra of a series of selected natural halogenated carbonates from different origins including bastnasite, parisite and northupite. The Raman spectrum of huanghoite displays three bands are at 1072, 1084 and 1091 cm-1 attributed to the CO32- symmetric stretching vibration. The observation of three symmetric stretching vibrations is very unusual. The position of CO32- symmetric stretching vibration varies with mineral composition. Infrared spectroscopy of huanghoite show bands at 1319, 1382, 1422 and 1470 cm-1. No Raman bands of huanghoite were observed in these positions. Raman spectra of bastnasite, parisite and northupite show a single band at 1433, 1420 and 1554 cm-1 assigned to the ν3 (CO3)2- antisymmetric stretching mode. The observation of additional Raman bands for the ν3 modes for some halogenated carbonates is significant in that it shows distortion of the carbonate anion in the mineral structure. Four Raman bands for huanghoite are observed at 687, 704, 718 and 730 cm-1and assigned to the (CO3)2- ν2 bending modes. Raman bands are observed for huanghoite at around 627 cm-1 and are assigned to the (CO3)2- ν4 bending modes. Raman bands are observed for the carbonate ν4 in phase bending modes at 722 cm-1 for bastnasite, 736 and 684 cm-1 for parisite, 714 cm-1 for northupite. Raman bands for huanghoite observed at 3259, 3484 and 3589 cm-1 are attributed to water stretching bands. Multiple bands are observed in the OH stretching region for bastnasite and parisite indicating the presence of water and OH units in their mineral structure. Vibrational spectroscopy enables new information on the structure of huanghoite to be assessed.

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

    PubMed

    Rahmani, Omeid; Highfield, James; Junin, Radzuan; Tyrer, Mark; Pour, Amin Beiranvand

    2016-03-16

    In this work, the potential of CO₂ mineral carbonation of brucite (Mg(OH)2) derived from the Mount Tawai peridotite (forsterite based (Mg)₂SiO4) 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.

  4. The efficiency of CO2 sequestration via carbonate mineralization with simulated wastewaters of high salinity.

    PubMed

    Mignardi, S; De Vito, C; Ferrini, V; Martin, R F

    2011-07-15

    Salinity generally strongly affects the solubility of carbon dioxide in aqueous solution. This would seem to involve a reduction of the efficiency of the carbonate mineralization process with the objective to sequester this greenhouse gas. On the contrary, we demonstrate here that with a more concentrated solution of magnesium chloride, the residence time of CO(2) is enhanced in the aqueous medium because of a reduced tendency to produce CO(2(g)). Experiments intended to simulate more closely the Mg-rich wastewaters that are industrially available have been carried out using solutions differing in Mg concentration (7, 16, 32 g L(-1) Mg). A comparison of the efficiency of the CO(2) mineralization process among sets of experiments shows that the reduction of the efficiency, to about 65%, was lower than that expected, as the low degree of CO(2) degassing results in the enhanced availability of carbonic ions to react with Mg ions to form stable carbonate minerals over a longer time. Copyright © 2011 Elsevier B.V. All rights reserved.

  5. Integration of CO2 capture and mineral carbonation by using recyclable ammonium salts.

    PubMed

    Wang, Xiaolong; Maroto-Valer, M Mercedes

    2011-09-19

    A new approach to capture and store CO(2) by mineral carbonation using recyclable ammonium salts was studied. This process integrates CO(2) capture with mineral carbonation by employing NH(3), NH(4)HSO(4), and NH(4)HCO(3) in the capture, mineral dissolution, and carbonation steps, respectively. NH(4)HSO(4) and NH(3) can then be regenerated by thermal decomposition of (NH(4))(2)SO(4). The use of NH(4)HCO(3) as the source of CO(2) can avoid desorption and compression of CO(2). The mass ratio of Mg/NH(4)HCO(3)/NH(3) is the key factor controlling carbonation and the optimum ratio of 1:4:2 gives a conversion of Mg ions to hydromagnesite of 95.5%. Thermogravimetric analysis studies indicated that the regeneration efficiency of NH(4)HSO(4) and NH(3) in this process is 95%. The mass balance of the process shows that about 2.63 tonnes of serpentine, 0.12 tonnes of NH(4)HSO(4), 7.48 tonnes of NH(4)HCO(3), and 0.04 tonnes of NH(3) are required to sequester 1 tonne of CO(2) as hydromagnesite. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Integration of CO2 Capture and Mineral Carbonation by Using Recyclable Ammonium Salts

    PubMed Central

    Wang, Xiaolong; Maroto-Valer, M Mercedes

    2011-01-01

    A new approach to capture and store CO2 by mineral carbonation using recyclable ammonium salts was studied. This process integrates CO2 capture with mineral carbonation by employing NH3, NH4HSO4, and NH4HCO3 in the capture, mineral dissolution, and carbonation steps, respectively. NH4HSO4 and NH3 can then be regenerated by thermal decomposition of (NH4)2SO4. The use of NH4HCO3 as the source of CO2 can avoid desorption and compression of CO2. The mass ratio of Mg/NH4HCO3/NH3 is the key factor controlling carbonation and the optimum ratio of 1:4:2 gives a conversion of Mg ions to hydromagnesite of 95.5 %. Thermogravimetric analysis studies indicated that the regeneration efficiency of NH4HSO4 and NH3 in this process is 95 %. The mass balance of the process shows that about 2.63 tonnes of serpentine, 0.12 tonnes of NH4HSO4, 7.48 tonnes of NH4HCO3, and 0.04 tonnes of NH3 are required to sequester 1 tonne of CO2 as hydromagnesite. PMID:21732542

  7. [Effects of temperature on organic carbon mineralization in paddy soils with different clay content].

    PubMed

    Ren, Xiu-E; Tong, Cheng-Li; Sun, Zhong-Lin; Tang, Guo-Yong; Xiao, He-Ai; Wu, Jin-Shui

    2007-10-01

    An incubation test with three kinds of paddy soil (sandy loam, clay loam, and silty clay soils) in subtropical region was conducted at 10, 15, 20, 25 and 30 degrees C to examine the response of the mineralization of soil organic carbon (SOC) to temperature change. The results showed that during the period of 160 d incubation, the accumulative mineralized amount of SOC in sandy loam, clay loam, and silty clay soils at 30 degrees C was 3.5, 5.2 and 4.7 times as much as that at 10 degrees C, respectively. The mineralization rate was lower and relatively stable at lower temperatures (< or = 20 C), but was higher at the beginning of incubation and decreased and became stable as the time prolonged at higher temperatures (> or = 25 degrees C). During incubation, the temperature coefficient (Q10) of SOC mineralization in test soils fluctuated, with an average Q10 in sandy loam, clay loam, and silty clay soils being 1.92, 2.37 and 2.32, respectively. There was a positive exponential correlation between SOC mineralization constant k and temperature (P < 0.01), and the response of SOC mineralization to temperature change was in the order of clay loam soil > silty clay soil > sandy loam soil.

  8. Extracellular enzymes and soil carbon dynamics: exploring the effects of soil clay minerals

    NASA Astrophysics Data System (ADS)

    Olagoke, Folasade; Kalbitz, Karsten; Vogel, Cordula

    2017-04-01

    The importance of extracellular enzymes (EEs) in soil biogeochemical processes is well established. EEs are particularly decisive for carbon cycling through decomposition of organic matter (OM). The effectiveness of EEs in the soil depends on a number of factors including the amount and composition of clay minerals. However, the impact of interactions between clay minerals and EEs on the turnover rate of soil OM vis-a-vis carbon cycling in the soil is still poorly understood. Effects of clay minerals on activities of EEs have been mostly studied using clay minerals isolated from the soil matrix. Thus, it is not well elucidated how representative these results are for in-situ conditions. In this study, we analyzed the effect of different amounts of clay minerals added to soil on the activities of EEs towards understanding the role of interaction between clay minerals and EEs in soil carbon dynamics. We investigated three enzymes, α-glucosidase (AG), β-glucosidase (BG) and cellobiohydrolase (CB), which are important for soil carbon cycling. All assay preparations and measurements were carried out using fluorometric methods (MUF based substrates). A clay mineral (montmorillonite) was added to soil materials at four levels increasing the clay content in a logarithmic scale: +0% (control); +0.1%; +1% and +10%. The effects of clay minerals on EEs were analysed in two phases: firstly, the effects on the enzymes present in the soil were determined, and secondly the effect on a commercial enzyme (AG) added to the soil was tested. First results revealed that increasing the clay content in the soil led to a reduction in the activity of EEs. For AG and BG, significant reduction in activity was noted (P < 0.05) when the soil enriched with clay minerals was compared to the control (no clay addition). The CB, on the other hand, showed no statistical differences between the control and all treatments with addition of clay minerals. Similarly, in the second experiment with the

  9. Impact of activated carbon, biochar and compost on the desorption and mineralization of phenanthrene in soil.

    PubMed

    Marchal, Geoffrey; Smith, Kilian E C; Rein, Arno; Winding, Anne; Wollensen de Jonge, Lis; Trapp, Stefan; Karlson, Ulrich G

    2013-10-01

    Sorption of PAHs to carbonaceous soil amendments reduces their dissolved concentrations, limiting toxicity but also potentially biodegradation. Therefore, the maximum abiotic desorption of freshly sorbed phenanthrene (≤5 mg kg(-1)) was measured in three soils amended with activated carbon (AC), biochar or compost. Total amounts of phenanthrene desorbed were similar between the different soils, but the amendment type had a large influence. Complete desorption was observed in the unamended and compost amended soils, but this reduced for biochar (41% desorbed) and AC (8% desorbed). Cumulative amounts mineralized were 28% for the unamended control, 19% for compost, 13% for biochar and 4% for AC. Therefore, the effects of the amendments in soil in reducing desorption were also reflected in the extents of mineralization. Modeling was used to analyze key processes, indicating that for the AC and charcoal treatments bacterial activity did not limit mineralization, but rather desorption into the dissolved phase. Copyright © 2013 Elsevier Ltd. All rights reserved.

  10. Effects of fungicides mancozeb and dinocap on carbon and nitrogen mineralization in soils.

    PubMed

    Cernohlávková, Jitka; Jarkovský, Jirí; Hofman, Jakub

    2009-01-01

    In our study, effects of fungicides mancozeb and dinocap on C and N mineralization were measured in arable and grassland soil. The soils were treated with these fungicides at the application and 10 times lower doses and then incubated at 20 degrees C for 2 weeks. Carbon mineralization (basal and substrate-induced respiration) and nitrogen mineralization (potential ammonification and nitrification) were evaluated 1 and 14 days after the treatment. After 14 days, ammonification was decreased to 48% and 83% at dinocap application dose in arable and grassland soil, respectively. Application dose of mancozeb caused significant decrease of nitrification to 11.2% and 5.6% in arable and grassland soil, respectively. Basal respiration and substrate-induced growth were rather stimulated by fungicides, especially at lower application doses. To conclude, potential risk may exist to soil microorganisms and their activities in soils treated routinely by mancozeb or dinocap.

  11. Carbon Mineralization Pathways and Early Diagenesis in Lake Erie Sediments

    NASA Astrophysics Data System (ADS)

    O Neill, A. H.; Crowe, S. A.; Song, Z.; Mucci, A.; Sundby, B.; Fryer, B. J.; Fowle, D. A.

    2004-12-01

    to render solid phase Fe (III) bioavailable. Mn2+ voltammetric peaks were shifted to potentials more negative than the -1.53 to -1.55 mV commonly observed in marine pore waters. This shift is consistent with previous studies in freshwaters and has been ascribed to Mn2+ complexation by organic ligands (e.g. Luther et al, 2003). However, this shift may be due to analytical artifacts associated with using a solid state Ag/AgCl reference electrode in low ionic strength solutions. Measurable sulphide in the first 5 cm below the sediment-water interface is sporadic which suggests that sulphate reduction occurs in micro-environments locally enriched in organic carbon. Preliminary cultivation-independent, microbiological analyses have revealed 16s rDNA clones that are closely related to known species capable of enzymatic reduction of Fe(III) and the dechlorination of organic compounds (e.g. Anaeromyxobacter dehalogenans). These organisms were vertically dispersed within several different core sections suggestive of an intriguing tie between diagenetic reactions and anthropogenic organic compound degradation in these sediments. Coupling high-resolution voltammetry and spatially resolved genomic tools to investigate the controls on sediment pore water chemistry holds a promising future for elucidating the controls on early diagenesis in freshwater ecosystems.

  12. Carbonate Geochemistry of Marine Authigenic Carbonates and Host Sediments: Exploring Mineral Formation Pathways and Organic Preservation Potential in Modern Sediments

    NASA Astrophysics Data System (ADS)

    Smirnoff, M. N.; Loyd, S. J.

    2016-12-01

    Ancient authigenic dolomites (e.g., concretions) have been long studied in order to determine formation conditions and provide insight into shallow diagenetic environments. The formation of these dolomites is commonly attributed to the anaerobic microbial degradation of organic matter (a process that can increase the local pore water alkalinity), based on carbon isotope as well as other geochemical data. Authigenic dolomites also occur in modern, "still soft" sediments rich in organic matter. However, a comprehensive carbon isotopic characterization of these precipitates has yet to be conducted. Preliminary data show a wide range of δ13C values (about -11 to +12‰). Positive values that typify dolomites of the Gulf of California and the southwestern African margin indicate methanogenesis. Dolomites of the Peru margin and Cariaco Basin yield negative values that may represent a variety of organic matter degradation mechanisms. Regardless of specific mechanisms, organic matter degradation can promote authigenesis. Ultimately, mineralization encases primary sedimentary components and may act to preserve organic matter from subsequent degradation due to permeability reduction resulting from cementation. Concretionary carbonates have been found to preserve macro and micro fossils, metastable sedimentary grains, magnetic minerals, sedimentary structures, various specific organic compounds, and overmature organic matter exposed in outcrop. However, a similar protective relationship has not been demonstrated for disseminated, bulk organic matter in still-soft sediments. The study of these sediments 1) reveal the relationship between organic carbon degradation and authigenesis and 2) may provide insight into the potential of cementation to preserve organic matter during subsequent burial.

  13. Prediction of soil organic carbon concentration and soil bulk density of mineral soils for soil organic carbon stock estimation

    NASA Astrophysics Data System (ADS)

    Putku, Elsa; Astover, Alar; Ritz, Christian

    2016-04-01

    Soil monitoring networks provide a powerful base for estimating and predicting nation's soil status in many aspects. The datasets of soil monitoring are often hierarchically structured demanding sophisticated data analyzing methods. The National Soil Monitoring of Estonia was based on a hierarchical data sampling scheme as each of the monitoring site was divided into four transects with 10 sampling points on each transect. We hypothesized that the hierarchical structure in Estonian Soil Monitoring network data requires a multi-level mixed model approach to achieve good prediction accuracy of soil properties. We used this database to predict soil bulk density and soil organic carbon concentration of mineral soils in arable land using different statistical methods: median approach, linear regression and mixed model; additionally, random forests for SOC concentration. We compared the prediction results and selected the model with the best prediction accuracy to estimate soil organic carbon stock. The mixed model approach achieved the best prediction accuracy in both soil organic carbon (RMSE 0.22%) and bulk density (RMSE 0.09 g cm-3) prediction. Other considered methods under- or overestimated higher and lower values of soil parameters. Thus, using these predictions we calculated the soil organic carbon stock of mineral arable soils and applied the model to a specific case of Tartu County in Estonia. Average estimated SOC stock of Tartu County is 54.8 t C ha-1 and total topsoil SOC stock 1.8 Tg in humus horizon.

  14. Effect of peroxide on neutralization-potential values of siderite and other carbonate minerals.

    PubMed

    Jambor, J L; Dutrizac, J E; Raudsepp, M; Groat, L A

    2003-01-01

    To assess quantitatively the effect of peroxide addition to standard static tests of the neutralization potential (NP) of mine wastes, 10 specimens of carbonate minerals, including five of siderite (FeCO3) and two of rhodochrosite (MnCO3), were analyzed by electron microprobe. The compositions of the siderite span a range from 60 to 86 mol % Fe. Tests of NP for the siderite diluted with 80% (w/w) kaolinite gave values of 647 to 737 kg CaCO3 equivalent per Mg for determinations by the standard Sobek method. However, if it is assumed that the ferrous carbonate component of the mineral does not contribute to NP in field situations because oxidation of Fe(II) to Fe(III) and the subsequent hydrolysis of Fe(III) leads to the release of an equivalent amount of acid, then the calculated NP for the samples ranges from 110 to 390 kg CaCO3 equivalent per Mg. Two different methods involving the addition of peroxide to the test solutions were successful in bringing the measured NP values closer to the theoretical ones. By contrast, the tests with rhodochrosite indicated the Mn(II) to be stable. For long-term environmental planning, especially for wastes from metalliferous sulfide-poor deposits in which gradual dissolution of silicate and aluminosilicate minerals may be involved in attenuating the acidity, consideration in the overall NP budget needs to be given to the ferrous iron content of those minerals. The presence of Fe2+-bearing minerals, especially carbonates, in tested mine-waste materials may lead to overestimated Sobek NP values, thus increasing the risk of poor-quality drainage and the need for costly remediation.

  15. Calcium carbonate mineralization mediated by in vitro cultured mantle cells from Pinctada fucata.

    PubMed

    Kong, Wei; Li, Shiguo; Xiang, Liang; Xie, Liping; Zhang, Rongqing

    2015-08-07

    Formation of the molluscan shell is believed to be an extracellular event mediated by matrix proteins. We report calcium carbonate mineralization mediated by Pinctada fucata mantle cells. Crystals only appeared when mantle cells were present in the crystallization solution. These crystals were piled up in highly ordered units and showed the typical characteristics of biomineralization products. A thin organic framework was observed after dissolving the crystals in EDTA. Some crystals had etched surfaces with a much smoother appearance than other parts. Mantle cells were observed to be attached to some of these smooth surfaces. These results suggest that mantle cells may be directly involved in the nucleation and remodeling process of calcium carbonate mineralization. Our result demonstrate the practicability of studying the mantle cell mechanism of biomineralization and contribute to the overall understanding of the shell formation process. Copyright © 2015 Elsevier Inc. All rights reserved.

  16. The effect of SO2 on mineral carbonation in batch tests

    SciTech Connect

    Summers, Cathy A.; Dahlin, David C.; Ochs, Thomas L.

    2004-01-01

    CO2 sequestration is a key element of future emission-free fossil-fueled power plants. Other constituents of flue gas must also be captured and rendered innocuous. Contemporary power plants remove SOx from exit gases, but next-generation plants may simultaneously treat CO2, SOx, and other pollutants. Pioneering tests at the U.S. Department of Energy's Albany Research Center investigated the combined treatment of CO2 and SO2 in a mineral-carbonation process. SO2 was removed from the gas stream, and as a small fraction of the total volume of mineralizing gas, it did not inhibit the carbonation reaction. The results indicate that this approach to CO2 sequestration could be used to treat multiple pollutants.

  17. Calibrating the ChemCam LIBS for carbonate minerals on Mars

    SciTech Connect

    Wiens, Roger C; Clegg, Samuel M; Ollila, Ann M; Barefield, James E; Lanza, Nina; Newsom, Horton E

    2009-01-01

    The ChemCam instrument suite on board the NASA Mars Science Laboratory (MSL) rover includes the first LIBS instrument for extraterrestrial applications. Here we examine carbonate minerals in a simulated martian environment using the LIDS technique in order to better understand the in situ signature of these materials on Mars. Both chemical composition and rock type are determined using multivariate analysis (MVA) techniques. Composition is confirmed using scanning electron microscopy (SEM) techniques. Our initial results suggest that ChemCam can recognize and differentiate between carbonate materials on Mars.

  18. Calibrating the ChemCam laser-induced breakdown spectroscopy instrument for carbonate minerals on Mars

    SciTech Connect

    Lanza, Nina L.; Wiens, Roger C.; Clegg, Samuel M.; Ollila, Ann M.; Humphries, Seth D.; Newsom, Horton E.; Barefield, James E.

    2010-05-01

    The ChemCam instrument suite onboard the NASA Mars Science Laboratory rover includes the first laser-induced breakdown spectroscopy (LIBS) instrument for extraterrestrial applications. Here we examine carbonate minerals in a simulated martian environment to better understand the LIBS signature of these materials on Mars. Both chemical composition and rock type are determined using multivariate analysis techniques. Composition is confirmed using scanning electron microscopy. Our results show that ChemCam can recognize and differentiate between different types of carbonate materials on Mars.

  19. Calibrating the ChemCam LIBS for Carbonate Minerals on Mars

    DOE R&D Accomplishments Database

    Wiens, Roger C.; Clegg, Samuel M.; Ollila, Ann M.; Barefield, James E.; Lanza, Nina; Newsom, Horton E.

    2009-01-01

    The ChemCam instrument suite on board the NASA Mars Science Laboratory (MSL) rover includes the first LIBS instrument for extraterrestrial applications. Here we examine carbonate minerals in a simulated martian environment using the LIDS technique in order to better understand the in situ signature of these materials on Mars. Both chemical composition and rock type are determined using multivariate analysis (MVA) techniques. Composition is confirmed using scanning electron microscopy (SEM) techniques. Our initial results suggest that ChemCam can recognize and differentiate between carbonate materials on Mars.

  20. Modeling of the Dynamics of Burning a Granule of Carbonate Mineral

    NASA Astrophysics Data System (ADS)

    Savin, A. V.; Moiseev, A. A.; Smirnov, P. G.

    2017-01-01

    Thermophysical processes occurring during the thermal decarbonization of natural carbonate minerals (limestones, magnesites) have been investigated. A new model of the working process of burning a single spherical carbonate granule in the form of a system of ordinary differential equations has been proposed. This system makes it possible to generalize, in a natural manner, the model to the multidimensional and nonstationary cases where a moving mass of loose material is described. A comparison of the numerical calculations of the decarbonization dynamics and the measurement results obtained under totally controlled laboratory conditions has proved the high accuracy of the proposed model.

  1. Ocular injuries caused by metal caps of carbonated mineral water bottles.

    PubMed

    Erdurman, Fazıl Cüneyt; Ceylan, Osman Melih; Hürmeriç, Volkan; Pellumbi, Alfrida; Durukan, Ali Hakan; Sobacı, Güngör

    2013-05-01

    Bottles containing carbonated drinks are potentially hazardous to the eye. In this study, we aimed to document the clinical characteristics and visual outcomes in a series of patients with ocular injury from flying metal caps of carbonated mineral water bottles. Retrospective review of ocular injuries due to metal caps of carbonated mineral water bottles. Sixteen eyes of sixteen patients were included in the study. All of the patients were male, with a mean age of 24 years. Ten of the patients had a history of using improper tools for bottle cap removal. The left eye was involved in twelve cases and the right eye in four cases. All patients had contusion-type closed-globe injury. Varying degrees of hyphema were observed in all patients, and vitreous hemorrhage was present in four. The visual acuity at the last follow-up was 20/20 in 15 of the patients. The use of a bottle cap opener is essential for preventing ocular damage from pressed metal caps of carbonated drinks. In addition to popularising the use of screw cap bottles, warning labels that alert consumers about the possibility of eye injury should be placed on carbonated drinks with pressed metal caps.

  2. Mineral resources of the Prospect Mountain Wilderness Study Area, Carbon County, Wyoming

    SciTech Connect

    du Bray, E.A.; Bankey, V.; Hill, R.H.; Ryan, G.S.

    1989-01-01

    The Prospect Mountain Wilderness Study Area is about 20 mi east-southeast of Encampment in Carbon County, Wyoming. This study area is underlain by middle Proterozoic gabbro, granite, and hornblende gneiss, which is locally cut by pegmatite dikes. There are no identified resources and no potential for undiscovered energy resources in this study area. Resource potential for all undiscovered metallic commodities and for industrial mineral is low.

  3. Carbon availability controls the growth of detritivores (Lumbricidae) and their effect on nitrogen mineralization.

    PubMed

    Tiunov, Alexei V; Scheu, Stefan

    2004-01-01

    Activity of soil decomposer microorganisms is generally limited by carbon availability, but factors controlling saprophagous soil animals remain largely unknown. In contrast to microorganisms, animals are unable to exploit mineral nutrient pools. Therefore, it has been suggested that soil animals, and earthworms in particular, are limited by the availability of nitrogen. In contrast to this view, a strong increase in density and biomass of endogeic earthworms in response to labile organic carbon addition has been documented in field experiments. The hypothesis that the growth of endogeic earthworms is primarily limited by carbon availability was tested in a laboratory experiment lasting for 10 weeks. In addition, it was investigated whether the effects of earthworms on microbial activity and nutrient mineralization depend on the availability of carbon resources. We manipulated food availability to the endogeic earthworm species Octolasion tyrtaeum by using two soils with different organic matter content, providing access to different amounts of soil, and adding labile organic carbon (glucose) enriched in (13)C. Glucose addition strongly increased the growth of O. tyrtaeum. From 8 to 17% of the total C in earthworm tissue was assimilated from the glucose added. Soil microbial biomass was not strongly affected by the addition of glucose, though basal respiration was significantly increased and up to 50% of the carbon added as glucose was incorporated into soil organic matter. The impact of earthworms on the mineralization and leaching of nitrogen depended on C availability. As expected, in C-limited soil, the presence of earthworms strongly increased nitrogen leaching. However, when C availability was increased by the addition of glucose, this pattern was reversed, i.e. the presence of O. tyrtaeum decreased nitrogen leaching and its availability to soil microflora. We conclude that irrespective of the total carbon content of soils, O. tyrtaeum was primarily limited

  4. Carbon dioxide mineralization process design and evaluation: concepts, case studies, and considerations.

    PubMed

    Yuen, Yeo Tze; Sharratt, Paul N; Jie, Bu

    2016-11-01

    Numerous carbon dioxide mineralization (CM) processes have been proposed to overcome the slow rate of natural weathering of silicate minerals. Ten of these proposals are mentioned in this article. The proposals are described in terms of the four major areas relating to CM process design: pre-treatment, purification, carbonation, and reagent recycling operations. Any known specifics based on probable or representative operating and reaction conditions are listed, and basic analysis of the strengths and shortcomings associated with the individual process designs are given in this article. The processes typically employ physical or chemical pseudo-catalytic methods to enhance the rate of carbon dioxide mineralization; however, both methods have its own associated advantages and problems. To examine the feasibility of a CM process, three key aspects should be included in the evaluation criteria: energy use, operational considerations as well as product value and economics. Recommendations regarding the optimal level of emphasis and implementation of measures to control these aspects are given, and these will depend very much on the desired process objectives. Ultimately, a mix-and-match approach to process design might be required to provide viable and economic proposals for CM processes.

  5. Carbonation of Artificial Silicate Minerals in Soils: Passive Removal of Atmospheric CO2

    NASA Astrophysics Data System (ADS)

    Washbourne, C.; Renforth, P.; Manning, D. A.

    2010-12-01

    Sequestration of CO2 in global soils is a widely recognised phenomenon, which is amenable to an environmental engineering approach. It is proposed that the use of direct soil engineering, promoting CO2 sequestration by accelerating the activity of reactive mineral substrates, has the potential to harness the significant carbon turnover of the global pedologic system (75 x 10^15 gC/yr [1]) [2][3][4]. Estimates of C capture potential through this process are 100-1000 MTa-1. This study focuses on the ambient carbonation of high-Ca residues as agents of mineral CCS. A synergy of contemporary field observations is presented, alongside data acquired from laboratory testing (acid digestion, optical petrography, SEM, IRMS) of carbonated material recovered from urban brown-field and former industrial sites in north east England. It is demonstrated that urban soils may accumulate ~30 kg/m2 (300 T/ha) of carbon over 10 years as inorganic calcium carbonate, approximately twice the typical organic C content of rural soils, ~17.5 kg/m2 in the UK. Stable isotope data (δ13C and δ18O) confirm that over 90% of the carbon is derived from the atmosphere. Economic and mechanical constraints on experimental performance in industrial batch reactor settings have strongly influenced the contemporary view on the efficacy of mineral CCS for large-scale environmental application [5][6][7]. Effective, low-energy field-scale implementation of mineral CCS through soil engineering would counter many of these concerns. Proof of principle for carbon capture efficacy of artificial silicates in soil engineering has been demonstrated [4]; proof of field scale feasibility will be demonstrated though continuing empirical field observation, engineered field cell construction and laboratory investigation. [1] Schlesinger, W. H., et al. (2000), Biogeochemistry, Vol. 48: 7-20. [2] Lal, R. (2003), Critical Reviews in Plant Sciences, 22, pp. 151-184. [3] Manning, D. A. C., (2008), Mineralogical Magazine

  6. Exploring biotic vs. abiotic controls on syngenetic carbonate and clay mineral precipitation

    NASA Astrophysics Data System (ADS)

    Nascimento, Gabriela S.; McKenzie, Judith A.; Martinez Ruiz, Francisca; Bontognali, Tomaso R. R.; Vasconcelos, Crisogono

    2016-04-01

    A possible syngenetic relationship between carbonate and clay mineral precipitation has been reported for sedimentary rocks deposited in both lacustrine and marine sedimentary environments throughout the geological record. In particular, the mineral dolomite is often found associated with Mg-rich clays, such as stevensite. It is notable that this carbonate/clay association has been recorded in numerous samples taken from modern dolomite precipitating environments; for example, the Coorong lakes, South Australia, coastal sabkhas, Abu Dhabi, UAE and coastal hypersaline lagoons (Lagoa Vermelha and Brejo do Espinho) east of Rio de Janeiro, Brazil. An HRTEM study of samples from these three locations indicates a possible physical/chemical association between the Ca-dolomite and Mg-rich clays, demonstrating a probable co-precipitation. To test this hypothesis, we have conducted a series of biotic and abiotic laboratory experiments. If this syngenesis actually occurs in nature, what, if any, are the biogeochemical processes controlling these precipitation reactions? Our experiments were designed to determine the extent of the biotic versus abiotic component influencing the mineral precipitation and, in the case of a biotic influence, to understand the mechanism through which microorganisms might mediate the formation of clay minerals. The experiments were carried out in the Geomicrobiology Laboratory of ETH Zürich using cultures of living microbes and artificial organic compounds that simulate functional groups present in natural biofilms formed under both aerobic and anaerobic conditions. In addition, pure inorganic experiments were designed to understand possible physico-chemical conditions for diagenetic processes that could induce dissolution of Mg-carbonates and precipitation of Mg-rich clays. Our results show a remarkable biotic influence during the formation of clay minerals. Specifically, extracellular polymeric substances (EPS), released by microbes in their

  7. How much CO2 is trapped in carbonate minerals of a natural CO2 occurrence?

    NASA Astrophysics Data System (ADS)

    Király, Csilla; Szabó, Zsuzsanna; Szamosfalvi, Ágnes; Cseresznyés, Dóra; Király, Edit; Szabó, Csaba; Falus, György

    2017-04-01

    Carbon Capture and Storage (CCS) is a transitional technology to decrease CO2 emissions from human fossil fuel usage and, therefore, to mitigate climate change. The most important criteria of a CO2 geological storage reservoir is that it must hold the injected CO2 for geological time scales without its significant seepage. The injected CO2 undergoes physical and chemical reactions in the reservoir rocks such as structural-stratigraphic, residual, dissolution or mineral trapping mechanisms. Among these, the safest is the mineral trapping, when carbonate minerals such as calcite, ankerite, siderite, dolomite and dawsonite build the CO2 into their crystal structures. The study of natural CO2 occurrences may help to understand the processes in CO2 reservoirs on geological time scales. This is the reason why the selected, the Mihályi-Répcelak natural CO2 occurrence as our research area, which is able to provide particular and highly significant information for the future of CO2 storage. The area is one of the best known CO2 fields in Central Europe. The main aim of this study is to estimate the amount of CO2 trapped in the mineral phase at Mihályi-Répcelak CO2 reservoirs. For gaining the suitable data, we apply petrographic, major and trace element (microprobe and LA-ICP-MS) and stable isotope analysis (mass spectrometry) and thermodynamic and kinetic geochemical models coded in PHREEQC. Rock and pore water compositions of the same formation, representing the pre-CO2 flooding stages of the Mihályi-Répcelak natural CO2 reservoirs are used in the models. Kinetic rate parameters are derived from the USGS report of Palandri and Kharaka (2004). The results of petrographic analysis show that a significant amount of dawsonite (NaAlCO3(OH)2, max. 16 m/m%) precipitated in the rock due to its reactions with CO2 which flooded the reservoir. This carbonate mineral alone traps about 10-30 kg/m3 of the reservoir rock from the CO2 at Mihályi-Répcelak area, which is an

  8. Microbial and Chemical Enhancement of In-Situ Carbon Mineralization in Geological Formation

    SciTech Connect

    Matter, J.; Chandran, K.

    2013-05-31

    Predictions of global energy usage suggest a continued increase in carbon emissions and rising concentrations of CO{sub 2} in the atmosphere unless major changes are made to the way energy is produced and used. Various carbon capture and storage (CCS) technologies are currently being developed, but unfortunately little is known regarding the fundamental characteristics of CO{sub 2}-mineral reactions to allow a viable in-situ carbon mineralization that would provide the most permanent and safe storage of geologically-injected CO{sub 2}. The ultimate goal of this research project was to develop a microbial and chemical enhancement scheme for in-situ carbon mineralization in geologic formations in order to achieve long-term stability of injected CO{sub 2}. Thermodynamic and kinetic studies of CO{sub 2}-mineral-brine systems were systematically performed to develop the in-situ mineral carbonation process that utilizes organic acids produced by a microbial reactor. The major participants in the project are three faculty members and their graduate and undergraduate students at the School of Engineering and Applied Science and at the Lamont-Doherty Earth Observatory at Columbia University: Alissa Park in Earth and Environmental Engineering & Chemical Engineering (PI), Juerg Matter in Earth and Environmental Science (Co-PI), and Kartik Chandran in Earth and Environmental Engineering (Co-PI). Two graduate students, Huangjing Zhao and Edris Taher, were trained as a part of this project as well as a number of graduate students and undergraduate students who participated part-time. Edris Taher received his MS degree in 2012 and Huangjing Zhao will defend his PhD on Jan. 15th, 2014. The interdisciplinary training provided by this project was valuable to those students who are entering into the workforce in the United States. Furthermore, the findings from this study were and will be published in referred journals to disseminate the results. The list of the papers is given at

  9. Effect of the concentration of inherent mineral elements on the adsorption capacity of coconut shell-based activated carbons.

    PubMed

    Afrane, G; Achaw, Osei-Wusu

    2008-09-01

    Coconut shells of West Africa Tall, a local variety of the coconut species Cocos nucifera L., were taken from five different geographical locations in Ghana and examined for the presence and concentration levels of some selected mineral elements using atomic absorption spectrometer. Activated carbons were subsequently made from the shells by the physical method. The iodine adsorption characteristics of the activated carbons measured showed a definite relationship to the concentration levels of potassium and other mineral elements in the precursor shell. Samples with lower total minerals content recorded higher iodine numbers. It was observed that the origin of the shells was related to the concentration levels of the analyzed mineral elements in the shells, which in turn affected the adsorption capacity of the activated carbons. The results of this study have important implications for the sourcing of coconuts whose shells are used in the manufacture of activated carbons.

  10. Do Forest Age and Soil Depth Affect Carbon and Nitrogen Adsorption in Mineral Horizons?

    NASA Astrophysics Data System (ADS)

    Spina, P. G.; Lovett, G. M.; Fuss, C. B.; Goodale, C. L.; Lang, A.; Fahey, T.

    2015-12-01

    Mineral soils retain large amounts of organic matter through sorption on the surfaces of mineral soils, the largest pools of carbon (C) and nitrogen (N) in the forests of the northeastern U.S. In addition to determining organic matter storage, adsorption and desorption processes are important controllers of runoff chemistry. We are studying adsorption dynamics of mineral soils collected from a chronosequence of hardwood forest sites in the White Mountains, NH to determine how soils vary in their DOM adsorption capacities as a function of effective C and N saturation. We hypothesize that forest age determines proximity to saturation because young forests may need to mine soil organic matter (SOM) in mineral soils to obtain nitrogen to meet growth demands, while the soils of older forests have had time to reaccumulate SOM, eventually reaching C and N saturation. Consequently, we expect adsorption capacities to first increase with forest age in young forests, as the trees mine C and N from mineral surfaces. They will then decrease with forest age in older forests as mining slows and C and N begin to re-accumulate. Batch experiments were conducted with mineral soil samples and dilutions of forest floor leachate. However, preliminary results from a mature forest site (about 100 years old), which we predicted to be a low point of C and N saturation from decades of mining, contradict expectations. Dissolved organic carbon (DOC) adsorption in its shallow mineral soil layers (0-3 cm below E or A horizons) are lower than younger sites ranging from 20 to about 40 years old. In addition to forest age, soil depths also affect N retention dynamics in forest soils. We hypothesized that deeper mineral soils might have greater adsorption capacities due to the fact that they are exposed to less DOC and DON leaching from organic layers and therefore less saturated. Results from the same mature forest site confirm this. Soils from 3-10 cm depth have more potential to adsorb DOC and

  11. Earthworms facilitate carbon sequestration through unequal amplification of carbon stabilization compared with mineralization

    EPA Science Inventory

    A recent review concluded that earthworm presence increases CO2 emissions by 33% but does not affect soil organic carbon stocks. However, the findings are controversial and raise new questions. Here we hypothesize that neither an increase in CO2 emission nor in stabilized carbon...

  12. Earthworms facilitate carbon sequestration through unequal amplification of carbon stabilization compared with mineralization

    EPA Science Inventory

    A recent review concluded that earthworm presence increases CO2 emissions by 33% but does not affect soil organic carbon stocks. However, the findings are controversial and raise new questions. Here we hypothesize that neither an increase in CO2 emission nor in stabilized carbon...

  13. Bulk and Stable Isotopic Compositions of Carbonate Minerals in Martian Meteorite Allan Hills 84001: No Proof of High Formation Temperature

    NASA Technical Reports Server (NTRS)

    Treiman, Allan H.; Romanek, Christopher S.

    1998-01-01

    Understanding the origin of carbonate minerals in the Martian meteorite Allan Hills (ALH) 84001 is crucial to evaluating the hypothesis that they contain traces of ancient Martian life. Using arguments based on chemical equilibria among carbonates and fluids, an origin at greater than 650 C (inimical to life) has been proposed. However, the bulk and stable isotopic compositions of the carbonate minerals are open to multiple interpretations and so lend no particular support to a high-temperature origin. Other methods (possibly less direct) will have to be used to determine the formation temperature of the carbonates in ALH 84001.

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

    SciTech Connect

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

    1999-09-01

    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(OH){sub 2} carbonation is a leading process candidate, which generates the stable naturally occurring mineral magnesite (MgCO{sub 3}) and water. Key to process cost and viability are the carbonation reaction rate and its degree of completion. This process, which involves simultaneous dehydroxylation and carbonation is very promising, but far from optimized. In order to optimize the dehydroxylation/carbonation process, an atomic-level understanding of the mechanisms involved is needed. Since Mg(OH){sub 2} dehydroxylation is intimately associated with the carbonation process, its mechanisms are also of direct interest in understanding and optimizing the process. In the first project year, our investigations have focused on developing an atomic-level understanding of the dehydroxylation/carbonation reaction mechanisms that govern the overall carbonation reaction process in well crystallized material. In years two and three, we will also explore the roles of crystalline defects and impurities. Environmental-cell, dynamic high-resolution transmission electron microscopy has been used to directly observe the dehydroxylation process at the atomic-level for the first time. These observations were combined with advanced computational modeling studies to better elucidate the atomic-level process. These studies were combined with direct carbonation studies to better elucidate dehydroxylation/carbonation reaction mechanisms. Dehydroxylation follows a lamellar nucleation and growth process involving oxide layer formation. These layers form lamellar oxyhydroxide regions, which can

  15. Sequestration of carbon dioxide by indirect mineralization using Victorian brown coal fly ash.

    PubMed

    Sun, Yong; Parikh, Vinay; Zhang, Lian

    2012-03-30

    The use of an industry waste, brown coal fly ash collected from the Latrobe Valley, Victoria, Australia, has been tested for the post-combustion CO(2) capture through indirect minersalization in acetic acid leachate. Upon the initial leaching, the majority of calcium and magnesium in fly ash were dissolved into solution, the carbonation potential of which was investigated subsequently through the use of a continuously stirred high-pressure autoclave reactor and the characterization of carbonation precipitates by various facilities. A large CO(2) capture capacity of fly ash under mild conditions has been confirmed. The CO(2) was fixed in both carbonate precipitates and water-soluble bicarbonate, and the conversion between these two species was achievable at approximately 60°C and a CO(2) partial pressure above 3 bar. The kinetic analysis confirmed a fast reaction rate for the carbonation of the brown coal ash-derived leachate at a global activation energy of 12.7 kJ/mol. It is much lower than that for natural minerals and is also very close to the potassium carbonate/piperazine system. The CO(2) capture capacity of this system has also proven to reach maximum 264 kg CO(2)/ton fly ash which is comparable to the natural minerals tested in the literature. As the fly ash is a valueless waste and requires no comminution prior to use, the technology developed here is highly efficient and energy-saving, the resulting carbonate products of which are invaluable for the use as additive to cement and in the paper and pulp industry.

  16. Application of calcium carbonate slows down organic amendments mineralization in reclaimed soils

    NASA Astrophysics Data System (ADS)

    Zornoza, Raúl; Faz, Ángel; Acosta, José A.; Martínez-Martínez, Silvia; Ángeles Muñoz, M.

    2014-05-01

    A field experiment was set up in Cartagena-La Unión Mining District, SE Spain, aimed at evaluating the short-term effects of pig slurry (PS) amendment alone and together with marble waste (MW) on organic matter mineralization, microbial activity and stabilization of heavy metals in two tailing ponds. These structures pose environmental risk owing to high metals contents, low organic matter and nutrients, and null vegetation. Carbon mineralization, exchangeable metals and microbiological properties were monitored during 67 days. The application of amendments led to a rapid decrease of exchangeable metals concentrations, except for Cu, with decreases up to 98%, 75% and 97% for Cd, Pb and Zn, respectively. The combined addition of MW+PS was the treatment with greater reduction in metals concentrations. The addition of PS caused a significant increase in respiration rates, although in MW+PS plots respiration was lower than in PS plots. The mineralised C from the pig slurry was low, approximately 25-30% and 4-12% for PS and MW+PS treatments, respectively. Soluble carbon (Csol), microbial biomass carbon (MBC) and β-galactosidase and β-glucosidase activities increased after the application of the organic amendment. However, after 3 days these parameters started a decreasing trend reaching similar values than control from approximately day 25 for Csol and MBC. The PS treatment promoted highest values in enzyme activities, which remained high upon time. Arylesterase activity increased in the MW+PS treatment. Thus, the remediation techniques used improved soil microbiological status and reduced metal availability. The combined application of PS+MW reduced the degradability of the organic compounds. Keywords: organic wastes, mine soils stabilization, carbon mineralization, microbial activity.

  17. Geochemical modeling of the influence of silicate mineral alteration on alkalinity production and carbonate precipitation

    NASA Astrophysics Data System (ADS)

    Herda, Gerhard; Kraemer, Stephan M.; Gier, Susanne; Meister, Patrick

    2016-04-01

    High CO2 partial pressure (pCO2) in deep rock reservoirs causes acidification of the porefluid. Such conditions occur during injection and subsurface storage of CO2 (to prevent the release of greenhouse gas) but also naturally in zones of strong methanogenic microbial activity in organic matter-rich ocean margin sediments. The acidic fluids are corrosive to carbonates and bear the risk of leakage of CO2 gas to the surface. Porefluid acidification may be moderated by processes that increase the alkalinity, i.e. that produce weak acid anions capable of buffering the acidification imposed by the CO2. Often, alkalinity increases as a result of anaerobic microbial activity, such as anaerobic oxidation of methane. However, on a long term the alteration of silicates, in particular, clay minerals, may be a more efficient mechanism of alkalinity production. Under altered temperature, pressure and porefluid composition at depth, clay minerals may change to thermodynamically more stable states, thereby increasing the alkalinity of the porefluid by partial leaching of Mg-(OH)2 and Ca-(OH)2 (e.g. Wallmann et al., 2008; Mavromatis et al., 2014). This alteration may even be enhanced by a high pCO2. Thus, silicate alteration can be essential for a long-term stabilization of volatile CO2 in the form of bicarbonate or may even induce precipitation of carbonate minerals, but these processes are not fully understood yet. The goal of this study is to simulate the alkalinity effect of silicate alteration under diagenetic conditions and high pCO2 by geochemical modeling. We are using the program PHREEQC (Parkhurst and Appelo, 2013) to generate high rock/fluid ratio characteristics for deep subsurface rock reservoirs. Since we are interested in the long-term evolution of diagenetic processes, over millions of years, we do not consider kinetics but calculate the theoretically possible equilibrium conditions. In a first step we are calculating the saturation state of different clay minerals

  18. Mineral sequestration of CO(2) by aqueous carbonation of coal combustion fly-ash.

    PubMed

    Montes-Hernandez, G; Pérez-López, R; Renard, F; Nieto, J M; Charlet, L

    2009-01-30

    The increasing CO(2) concentration in the Earth's atmosphere, mainly caused by fossil fuel combustion, has led to concerns about global warming. A technology that could possibly contribute to reducing carbon dioxide emissions is the in-situ mineral sequestration (long term geological storage) or the ex-situ mineral sequestration (controlled industrial reactors) of CO(2). In the present study, we propose to use coal combustion fly-ash, an industrial waste that contains about 4.1 wt.% of lime (CaO), to sequester carbon dioxide by aqueous carbonation. The carbonation reaction was carried out in two successive chemical reactions, first, the irreversible hydration of lime. second, the spontaneous carbonation of calcium hydroxide suspension. A significant CaO-CaCO(3) chemical transformation (approximately 82% of carbonation efficiency) was estimated by pressure-mass balance after 2h of reaction at 30 degrees C. In addition, the qualitative comparison of X-ray diffraction spectra for reactants and products revealed a complete CaO-CaCO(3) conversion. The carbonation efficiency of CaO was independent on the initial pressure of CO(2) (10, 20, 30 and 40 bar) and it was not significantly affected by reaction temperature (room temperature "20-25", 30 and 60 degrees C) and by fly-ash dose (50, 100, 150 g). The kinetic data demonstrated that the initial rate of CO(2) transfer was enhanced by carbonation process for our experiments. The precipitate calcium carbonate was characterized by isolated micrometric particles and micrometric agglomerates of calcite (SEM observations). Finally, the geochemical modelling using PHREEQC software indicated that the final solutions (i.e. after reaction) are supersaturated with respect to calcium carbonate (0.7 < or = saturation index < or = 1.1). This experimental study demonstrates that 1 ton of fly-ash could sequester up to 26 kg of CO(2), i.e. 38.18 ton of fly-ash per ton of CO(2) sequestered. This confirms the possibility to use this

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

    NASA Astrophysics Data System (ADS)

    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.

  20. Impact of Permeability and Mineralization on an Injected Carbon Dioxide Plume in the South Georgia Rift Basin.

    NASA Astrophysics Data System (ADS)

    Alshammari, A.; Brantley, D.; Knapp, C. C.; Lakshmi, V.

    2016-12-01

    We will study the injection of one million tons per year of super critical phase carbon dioxide in the South Georgia Rift Basin for a 30-year period followed by a 100-year shut-in. We will determine the fault leakage coefficient corresponding to a logarithmic range of subsurface permeability and the mineralization of the injected carbon dioxide. This will help to predict the migration patterns of the sequestered carbon dioxide in the subsurface. These simulations for carbon dioxide flow and mineralization rate and the volume of mineral trapping will use the Computer Modeling Group™ (CMG) software. The simulations will extend to several decades to determine the end products of the system. The South Georgia Rift Basin is located in the Southeastern portion of United States and has been the location for recent studies of carbon dioxide sequestration.

  1. CarbFix I: Rapid CO2 mineralization in basalt for permanent carbon storage

    NASA Astrophysics Data System (ADS)

    Matter, J. M.; Stute, M.; Snæbjörnsdóttir, S.; Gíslason, S. R.; Oelkers, E. H.; Sigfússon, B.; Gunnarsson, I.; Aradottir, E. S.; Gunnlaugsson, E.; Broecker, W. S.

    2015-12-01

    Carbon dioxide mineralization via CO2-fluid-rock reactions provides the most permanent solution for geologic CO2 storage. Basalts, onshore or offshore, have the potential to store million metric tons of CO2 as (Ca, Mg, Fe) carbonates [1, 2]. However, as of today it was unclear how fast CO2 is converted to carbonate minerals in-situ in a basalt storage reservoir. The CarbFix I project in Iceland was designed to verify in-situ CO2 mineralization in basaltic rocks. Two injection tests were performed at the CarbFix I pilot injection site near the Hellisheidi geothermal power plant in 2012. 175 tons of pure CO2 and 73 tons of a CO2+H2S mixture were injection from January to March 2012 and in June 2013, respectively. The gases were injected fully dissolved in groundwater into a permeable basalt formation between 400 and 800 m depth using a novel CO2 injection system. Using conservative (SF6, SF5CF3) and reactive (14C) tracers, we quantitatively monitor and detect dissolved and chemically transformed CO2. Tracer breakthrough curves obtained from the first monitoring well indicate that the injected solution arrived in a fast short pulse and a late broad peak. Ratios of 14C/SF6, 14C/SF5CF3 or DIC/SF6 and DIC/SF5CF3 are significantly lower in the monitoring well compared to the injection well, indicating that the injected dissolved CO2 reacted. Mass balance calculations using the tracer data reveal that >95% of the injected CO2 has been mineralized over a period of two years. Evidence of carbonate precipitation has been found in core samples that were collected from the storage reservoir using wireline core drilling as well as in and on the submersible pump in the monitoring well. Results from the core analysis will be presented with emphasis on the CO2 mineralization. [1] McGrail et al. (2006) JGR 111, B12201; [2] Goldberg et al. (2008) PNAS 105(29), 9920-9925.

  2. Carbon Isotope Systematics in Mineral-Catalyzed Hydrothermal Organic Synthesis Processes at High Temperature and Pressures

    NASA Technical Reports Server (NTRS)

    Fu, Qi; Socki, R. A.; Niles, Paul B.

    2011-01-01

    Observation of methane in the Martian atmosphere has been reported by different detection techniques. Reduction of CO2 and/or CO during serpentization by mineral surface catalyzed Fischer-Tropsch Type (FTT) synthesis may be one possible process responsible for methane generation on Mars. With the evidence a recent study has discovered for serpentinization in deeply buried carbon rich sediments, and more showing extensive water-rock interaction in Martian history, it seems likely that abiotic methane generation via serpentinization reactions may have been common on Mars. Experiments involving mineral-catalyzed hydrothermal organic synthesis processes were conducted at 750 C and 5.5 Kbars. Alkanes, alcohols and carboxylic acids were identified as organic compounds. No "isotopic reversal" of delta C-13 values was observed for alkanes or carboxylic acids, suggesting a different reaction pathway than polymerization. Alcohols were proposed as intermediaries formed on mineral surfaces at experimental conditions. Carbon isotope data were used in this study to unravel the reaction pathways of abiotic formation of organic compounds in hydrothermal systems at high temperatures and pressures. They are instrumental in constraining the origin and evolution history of organic compounds on Mars and other planets.

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

    SciTech Connect

    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.

  4. Bauxite residue neutralization with simultaneous mineral carbonation using atmospheric CO2.

    PubMed

    Han, Young-Soo; Ji, Sangwoo; Lee, Pyeong-Koo; Oh, Chamteut

    2017-03-15

    Simultaneous carbon mineralization during neutralization of bauxite residue, a caustic alkaline by-product of alumina refining, was tested using laboratory batch and a field pilot study in contact with atmospheric CO2. Since CO2 sequestration is limited by the Ca concentration in the bauxite residue, extra Ca sources were added in a semi-soluble mineral and salt form (flue gas desulfurization gypsum or CaCl2) to verify whether this Ca addition accelerated and enlarged the CO2 sequestration obtained as a consequence of neutralization. The results of 55 days of batch and longer-term field tests were in good agreement, and the neutralization rate was accelerated through the addition of both Ca sources. Without the addition of the extra Ca source, atmospheric CO2 contributed to neutralization of pore water alkalinity alone, while Ca addition induced further neutralization through mineral carbonation of atmospheric CO2 to CaCO3. This simple addition of environmentally benign Ca to bauxite residue may provide a feasible bauxite residue management practice that is cost-effective and easy to apply in the field.

  5. Quantitative assessment of elemental carbon in the lungs of never smokers, cigarette smokers, and coal miners.

    PubMed

    Saxena, Rajiv K; McClure, Michael E; Hays, Michael D; Green, Francis H Y; McPhee, Laura J; Vallyathan, V; Gilmour, M Ian

    2011-01-01

    Inhalation exposure to particulates such as cigarette smoke and coal dust is known to contribute to the development of chronic lung disease. The purpose of this study was to estimate the amount of elemental carbon (EC) deposits from autopsied lung samples from cigarette smokers, miners, and control subjects and explore the relationship between EC level, exposure history, and the extent of chronic lung disease. The samples comprised three subgroups representing never smokers (8), chronic cigarette smokers (26), and coal miners (6). Following the dissolution of lung tissue, the extracted EC residue was quantified using a thermal-optical transmission (TOT) carbon analyzer. Mean EC levels in the lungs of the control group were 56.68 ± 24.86 (SD) μg/g dry lung weight. Respective mean EC values in lung samples from the smokers and coal miners were 449.56 ± 320.3 μg/g and 6678.2 ± 6162 μg/g. These values were significantly higher than those obtained from the never-smoker group. EC levels in the lung and pack-years of cigarette smoking correlated significantly, as did EC levels and the severity of small airway disease. This study provides one of the first quantitative assessments of EC in human lungs from populations at high relative risk for the development of chronic lung disease.

  6. Carbon Footprint of Biofuel Sugarcane Produced in Mineral and Organic Soils in Florida

    SciTech Connect

    Izursa, Jose-Luis; Hanlon, Edward; Amponsah, Nana; Capece, John

    2013-02-06

    Ethanol produced from sugarcane is an existing and accessible form of renewable energy. In this study, we applied the Life Cycle Assessment (LCA) approach to estimate the Carbon Footprint (CFP) of biofuel sugarcane produced on mineral (sandy) and organic (muck) soils in Florida. CFP was estimated from greenhouse gas (GHG) emissions (CO2, CH4, and N2O) during the biofuel sugarcane cultivation. The data for the energy (fossil fuels and electricity), equipment, and chemical fertilizers were taken from enterprise budgets prepared by the University of Florida based on surveys and interviews obtained from local growers during the cropping years 2007/2008 and 2009/2010 for mineral soils and 2008/2009 for organic soils. Emissions from biomass burning and organic land use were calculated based on the IPCC guidelines. The results show that the CFP for biofuel sugarcane production is 0.04 kg CO2e kg-1y-1 when produced in mineral soils and 0.46 kg CO2e kg-1y-1 when produced in organic soils. Most of the GHG emissions from production of biofuel sugarcane in mineral soils come from equipment (33%), fertilizers (28%), and biomass burning (27%); whereas GHG emissions from production in organic soils come predominantly from the soil (93%). This difference should be considered to adopt new practices for a more sustainable farming system if biofuel feedstocks are to be considered.

  7. Mineral elements of subtropical tree seedlings in response to elevated carbon dioxide and nitrogen addition.

    PubMed

    Huang, Wenjuan; Zhou, Guoyi; Liu, Juxiu; Zhang, Deqiang; Liu, Shizhong; Chu, Guowei; Fang, Xiong

    2015-01-01

    Mineral elements in plants have been strongly affected by increased atmospheric carbon dioxide (CO2) concentrations and nitrogen (N) deposition due to human activities. However, such understanding is largely limited to N and phosphorus in grassland. Using open-top chambers, we examined the concentrations of potassium (K), calcium (Ca), magnesium (Mg), aluminum (Al), copper (Cu) and manganese (Mn) in the leaves and roots of the seedlings of five subtropical tree species in response to elevated CO2 (ca. 700 μmol CO2 mol(-1)) and N addition (100 kg N ha(-1) yr(-1)) from 2005 to 2009. These mineral elements in the roots responded more strongly to elevated CO2 and N addition than those in the leaves. Elevated CO2 did not consistently decrease the concentrations of plant mineral elements, with increases in K, Al, Cu and Mn in some tree species. N addition decreased K and had no influence on Cu in the five tree species. Given the shifts in plant mineral elements, Schima superba and Castanopsis hystrix were less responsive to elevated CO2 and N addition alone, respectively. Our results indicate that plant stoichiometry would be altered by increasing CO2 and N deposition, and K would likely become a limiting nutrient under increasing N deposition in subtropics.

  8. Monitoring crude oil mineralization in salt marshes: Use of stable carbon isotope ratios

    SciTech Connect

    Jackson, A.W.; Pardue, J.H.; Araujo, R.

    1996-04-01

    In laboratory microcosms using salt marsh soils and in field trials, it was possible to monitor and quantify crude oil mineralization by measuring changes in CO{sub 2} {delta}{sup 13}C signatures and the rate of CO{sub 2} production. These values are easy to obtain and can be combined with simple isotope mass balance equations to determine the rate of mineralization from both the crude oil and indigenous carbon pool. Hydrocarbon degradation was confirmed by simultaneous decreases in alkane-, isoprenoid-, and PAH-hopane ratios. Additionally, the pseudo-first-order rate constants of alkane degradation (0.087 day{sup -1}) and CO{sub 2} production (0.082 day{sup -1}) from oil predicted by the {delta}{sup 13}C signatures were statistically indistinguishable. The addition of inorganic nitrogen and phosphate increased the rate of mineralization of crude oil in aerated microcosms but had no clear effect on in situ studies. This procedure appears to offer a means of definitively quantifying crude oil mineralization in a sensitive, inexpensive, and simple manner in environments with appropriate background {delta}{sup 13}C signatures. 23 refs., 5 figs., 1 tab.

  9. [Effects of water content on redox potential and carbon mineralization of wetland sediments].

    PubMed

    Yang, Gai-ren; Tong, Cheng-li; Xiao, He-ai; Wu, Jin-shui

    2009-08-15

    To better understand the effect of soil water contents on redox potential (Eh), and their impacts on C mineralization in natural wetland, sediment samples from 3 types of wetlands (fen, humus marsh and marshy meadow) in the San-jiang Plate region of North China were incubated (25 degrees C) for 155 d under a range of reducing and oxidizing conditions by controlling water contents (varied from 24% to 232% of water holding capacity) (WHC). CO2-C evolved during incubation was measured at different time intervals. Results showed that Eh of sediments decreased significantly as water content increased from 24% WHC (lighted moisturized) to about 100% WHC, then decreased slightly as water content increased further to a level of submersed (about 2 cm water-depths). The accumulative amount of CO2-C evolved from the sediments indicated that the optimum water contents for mineralization of organic C are 32%, 48% and 76%-100% WHC for sediments of fen, humus marsh, and marshy meadow, respectively. The relationship between mineralization rates and redox potentials (Eh) were well fitted with second order parabola equations (p < 0.05). Mineralization rates and accumulative amount of organic C displayed a positive correlation with Eh up to 300 mV. However, a significant negative correlation was observed when Eh increased above 300 mV. Results demonstrated that low redox potential is the controlling factor of carbon accumulation of wetland in San-jiang Plate region.

  10. Reflectance spectroscopy of oxalate minerals and relevance to Solar System carbon inventories

    NASA Astrophysics Data System (ADS)

    Applin, Daniel M.; Izawa, Matthew R. M.; Cloutis, Edward A.

    2016-11-01

    The diversity of oxalate formation mechanisms suggests that significant concentrations of oxalic acid and oxalate minerals could be widely distributed in the Solar System. We have carried out a systematic study of the reflectance spectra of oxalate minerals and oxalic acid, covering the 0.2-16 μm wavelength region. Our analyses show that oxalates exhibit unique spectral features that enable discrimination between oxalate phases and from other commonly occurring compounds, including carbonates, in all regions of the spectrum except for the visible. Using these spectral data, we consider the possible contribution of oxalate minerals to previously observed reflectance spectra of many objects throughout the Solar System, including satellites, comets, and asteroids. We find that polycarboxylic acid dimers and their salts may explain the reflectance spectra of many carbonaceous asteroids in the 3 μm spectral region. We suggest surface concentration of these compounds may be a type of space weathering from the photochemical and oxidative decomposition of the organic macromolecular material found in carbonaceous chondrites. The stability and ubiquity of these minerals on Earth, in extraterrestrial materials, and in association with biological processes make them useful for many applications in Earth and planetary sciences.

  11. Infrared and infrared emission spectroscopic study of selected magnesium carbonate minerals containing ferric iron--implications for the geosequestration of greenhouse gases.

    PubMed

    Frost, Ray L; Bahfenne, Silmarilly; Graham, Jessica

    2008-12-15

    The proposal to remove greenhouse gases by pumping liquid carbon dioxide several kilometres below ground level implies that many carbonate containing minerals will be formed. Among these minerals, the formation of two hydrotalcite-like minerals coalingite and brugnatellite is possible, thus necessitating a study of such minerals and their thermal stability. The two such carbonate-bearing minerals brugnatellite and coalingite have been characterised by a combination of infrared and infrared emission spectroscopy. Infrared emission spectroscopy is most useful to determine the stability of these minerals. The infrared spectra of the OH stretching region are characterised by OH and water stretching vibrations. Intense (CO3)(2-) symmetric and antisymmetric stretching vibrations support the concept that the carbonate ion is distorted in these minerals. The position of the water bending vibration indicates that the water is strongly hydrogen bonded in the mineral structure. IES spectra show the temperature range of the thermal stability of these minerals.

  12. Carbon- and Sulfur-bearing Minerals in the Martian Meteorite ALH 84001

    NASA Astrophysics Data System (ADS)

    Romanek, C. S.; Thomas, K. L.; Gibson, E. K., Jr.; McKay, D. S.; Socki, R. A.

    1995-09-01

    Unusual carbonate minerals in ALH 84001 [1] provide insights into surficial processes that may have occurred on Mars, but despite detailed geochemical studies [2-4] carbonate petrogenesis has yet to be fully-characterized. High-resolution TEM and SEM analyses were performed on C- and S-bearing mineral grains to better constrain the nature and timing of carbonate mineralization events. Morphological elements: C- and S-bearing minerals in ALH 84001 commonly occur as spheroidal aggregates or fine-grained vug-filling structures. Spheroids are either orange or black, ~150 micrometers (+/- 50 micrometers) in diameter and highly-flattened (10-30 micrometers thick). Orange spheroids have limpid amber-colored cores and white to translucent mantles which are sometimes bound by thin black rims (< 10 micrometers). When viewed under cathodoluminescence, cores are non-luminescent while mantles luminesce a uniform bright-orange color. Black spheroids are less frequently observed; while they are similar in dimension to the orange spheroids they are chemically more heterogeneous. Black irregular aggregates fill residual pore-space between mineral grains. These structures are comprised of extremely fine-grained (< 2 micrometers) material that occasionally forms lenticular stringers up to 50 micrometers in length. Chemistry and Mineralogy: Small grains (30 micrometers dia.) were removed from C- and S-bearing aggregates, microtomed (~100 nm thick) and examined by TEM for imaging, electron diffraction, and elemental analysis. The orange spheroids have cores composed of Fe-Mg-Ca carbonate, with the centers having the highest concentration of Fe (45 mol%) and Ca (15 mol%). The concentration of Mg increases outward to almost pure MgCO3. TEM results support previous analyses of carbonate chemistry [1-4] and clearly indicate that a wide range of Mg-Fe-Ca solid solution exists in carbonate at a scale of ~10 nm. White mantles of the orange spheroids are composed of nearly pure MgCO3 (<5 mol

  13. Earthworm impacts on organo-mineral interactions and soil carbon inventories in Fennoscandian boreal and sub-arctic landscapes

    NASA Astrophysics Data System (ADS)

    Wackett, Adrian; Yoo, Kyungsoo; Cameron, Erin; Klaminder, Jonatan

    2017-04-01

    Boreal and sub-arctic environments sustain some of the most pristine and fragile ecosystems in the world and house a disproportionate amount of the global soil carbon pool. Although the historical view of soil carbon turnover has focused on the intrinsic molecular structure of organic matter, recent work has highlighted the importance of stabilizing soil carbon on reactive mineral surfaces. However, the rates and mechanisms controlling these processes at high latitudes are poorly understood. Here we explored the biogeochemical impacts of deep-burrowing earthworm species on a range of Fennoscandian forest soils to investigate how earthworms impact soil carbon inventories and organo-mineral associations across boreal and sub-arctic landscapes. We sampled soils and earthworms at six sites spanning almost ten degrees latitude and encompassing a wide range of soil types and textures, permitting simultaneous consideration of how climate and mineralogy affect earthworm-mediated shifts in soil carbon dynamics. Across all sites, earthworms significantly decreased the carbon and nitrogen contents of the upper 10 cm, presumably through consumption of the humus layer and subsequent incorporation of the underlying mineral soil into upper organic horizons. Their mixing of humus and underlying soil also generally increased the proportion of mineral surface area occluded by organic matter, although the extent to which earthworms facilitate such organo-mineral interactions appears to be controlled by soil texture and mineralogy. This work indicates that quantitative measurements of mineral surface area and its extent of coverage by soil organic matter facilitate scaling up of molecular interactions between organic matter and minerals to the level of soil profiles and landscapes. Our preliminary data also strongly suggests that earthworms have profound effects on the fate of soil carbon and nitrogen in boreal and sub-arctic environments, highlighting the need for a better

  14. A genetic model for Na-carbonate mineral precipitation in the Miocene Beypazarı trona deposit, Ankara province, Turkey

    NASA Astrophysics Data System (ADS)

    García-Veigas, Javier; Gündoğan, İbrahim; Helvacı, Cahit; Prats, Eva

    2013-08-01

    The Miocene Beypazarı trona deposit in Central Anatolia (Turkey), with estimated reserves of 250 million of tons of soda ash (sodium carbonate), is the second largest Na-carbonate deposit in the world. Petrographic observations of sodium-carbonate evaporites from basin-center cores show that the evaporites and associated minerals underwent significant early diagenetic mineral transformations in the Beypazarı Basin. Trona, pirssonite and nahcolite are the major evaporite minerals, with subordinate bradleyite, shortite and thenardite. Pirssonite occurs in organic-rich muds (oil shales). Pirssonite is not a primary mineral but rather appears to have formed diagenetically from displacive gaylussite. Trona precipitated subaqueously (in lake waters) and as interstitial phase in playa muds. Nahcolite is a later diagenetic mineral replacing both trona and pirssonite beds. Evaporite minerals are closely related to pyrite in oil shales and are also associated with diagenetic silicates (Mg-rich smectites, zeolites, K-feldspar, searlesite, and idiomorphic quartz) formed by reaction of alkaline brines with pyroclastic deposits. The proposed sedimentary model involves an alkaline lake in which water depth fluctuated from deep, perennial, meromictic (stratified) stages to shallow, ephemeral, playa lake stages. Lake margin clastic deposits are absent in the center of the basin wherein Na-carbonate minerals were formed, suggesting the prevalence of a groundwater regime during drawdown events.

  15. Comparison of Caprock Mineral Characteristics at Field Demonstration Sites for Saline Aquifer Sequestration of Carbon Dioxide

    SciTech Connect

    Griffith, C.A.; Lowry, G.; Dzombak, D.; Soong, Yee; Hedges, S.W.

    2008-10-01

    In 2003 the U.S Department of Energy initiated regional partnership programs to address the concern for rising atmospheric CO2. These partnerships were formed to explore regional and economical means for geologically sequestering CO2 across the United States and to set the stage for future commercial applications. Several options exist for geological sequestration and among these sequestering CO2 into deep saline aquifers is one of the most promising. This is due, in part, to the possibility of stabilized permanent storage through mineral precipitation from chemical interactions of the injected carbon dioxide with the brine and reservoir rock. There are nine field demonstration sites for saline sequestration among the regional partnerships in Phase II development to validate the overall commercial feasibility for CO2 geological sequestration. Of the nine sites considered for Phase II saline sequestration demonstration, seven are profiled in this study for their caprock lithologic and mineral characteristics.

  16. Utility of Biofilms and Biologically-Induced Mineralization in Geologic Carbon Sequestration

    NASA Astrophysics Data System (ADS)

    Gerlach, R.; Mitchell, A. C.; Cunningham, A. B.; Spangler, L.

    2010-12-01

    Geologic carbon sequestration involves the injection of CO2 into underground formations including oil beds, deep un-minable coal seams, basaltic rocks, and deep saline aquifers with temperature and pressure conditions such that CO2 will often be in the supercritical state. Four trapping mechanisms are proposed to play significant roles in the deep geologic sequestration of CO2: formation trapping, capillary trapping, solubility trapping, and mineral trapping. Our research has shown that, independent of the host rock, microbial biofilms are capable of enhancing formation trapping, solubility trapping, and mineral trapping. i) We have demonstrated that engineered microbial biofilms are capable of reducing the permeability of rock cores at pressures and temperatures, which would be found in the presence of supercritical CO2. ii) The biofilms have been demonstrated to be resistant to supercritical CO2. iii) Biofilms precipitate CO2 in the form of calcium carbonate (CaCO3), which resists dissolution by brine and scCO2. iv) Microbial activity can increase CO2 solubilization thus improving solubility trapping. Recent activities have begun to focus on practical aspects related to the implementation of biofilm-enhanced geologic carbon sequestration technologies in field situations.

  17. Carbonate Mineral Formation under the Influence of Limestone-Colonizing Actinobacteria: Morphology and Polymorphism

    PubMed Central

    Cao, Chengliang; Jiang, Jihong; Sun, Henry; Huang, Ying; Tao, Faxiang; Lian, Bin

    2016-01-01

    Microorganisms and their biomineralization processes are widespread in almost every environment on earth. In this work, Streptomyces luteogriseus DHS C014, a dominant lithophilous actinobacteria isolated from microbial mats on limestone rocks, was used to investigate its potential biomineralization to allow a better understanding of bacterial contributions to carbonate mineralization in nature. The ammonium carbonate free-drift method was used with mycelium pellets, culture supernatant, and spent culture of the strain. Mineralogical analyses showed that hexagonal prism calcite was only observed in the sub-surfaces of the mycelium pellets, which is a novel morphology mediated by microbes. Hemispheroidal vaterite appeared in the presence of spent culture, mainly because of the effects of soluble microbial products (SMP) during mineralization. When using the culture supernatant, doughnut-like vaterite was favored by actinobacterial mycelia, which has not yet been captured in previous studies. Our analyses suggested that the effects of mycelium pellets as a molecular template almost gained an advantage over SMP both in crystal nucleation and growth, having nothing to do with biological activity. It is thereby convinced that lithophilous actinobacteria, S. luteogriseus DHS C014, owing to its advantageous genetic metabolism and filamentous structure, showed good biomineralization abilities, maybe it would have geoactive potential for biogenic carbonate in local microenvironments. PMID:27148166

  18. Carbonate Mineral Formation under the Influence of Limestone-Colonizing Actinobacteria: Morphology and Polymorphism.

    PubMed

    Cao, Chengliang; Jiang, Jihong; Sun, Henry; Huang, Ying; Tao, Faxiang; Lian, Bin

    2016-01-01

    Microorganisms and their biomineralization processes are widespread in almost every environment on earth. In this work, Streptomyces luteogriseus DHS C014, a dominant lithophilous actinobacteria isolated from microbial mats on limestone rocks, was used to investigate its potential biomineralization to allow a better understanding of bacterial contributions to carbonate mineralization in nature. The ammonium carbonate free-drift method was used with mycelium pellets, culture supernatant, and spent culture of the strain. Mineralogical analyses showed that hexagonal prism calcite was only observed in the sub-surfaces of the mycelium pellets, which is a novel morphology mediated by microbes. Hemispheroidal vaterite appeared in the presence of spent culture, mainly because of the effects of soluble microbial products (SMP) during mineralization. When using the culture supernatant, doughnut-like vaterite was favored by actinobacterial mycelia, which has not yet been captured in previous studies. Our analyses suggested that the effects of mycelium pellets as a molecular template almost gained an advantage over SMP both in crystal nucleation and growth, having nothing to do with biological activity. It is thereby convinced that lithophilous actinobacteria, S. luteogriseus DHS C014, owing to its advantageous genetic metabolism and filamentous structure, showed good biomineralization abilities, maybe it would have geoactive potential for biogenic carbonate in local microenvironments.

  19. Calculation of site-specific carbon-isotope fractionation in pedogenic oxide minerals.

    PubMed

    Rustad, James R; Zarzycki, Piotr

    2008-07-29

    Ab initio molecular dynamics and quantum chemistry techniques are used to calculate the structure, vibrational frequencies, and carbon-isotope fractionation factors of the carbon dioxide component [CO(2)(m)] of soil (oxy)hydroxide minerals goethite, diaspore, and gibbsite. We have identified two possible pathways of incorporation of CO(2)(m) into (oxy)hydroxide crystal structures: one in which the C(4+) substitutes for four H(+) [CO(2)(m)(A)] and another in which C(4+) substitutes for (Al(3+),Fe(3+)) + H(+) [CO(2)(m)(B)]. Calculations of isotope fractionation factors give large differences between the two structures, with the CO(2)(m)(A) being isotopically lighter than CO(2)(m)(B) by approximately 10 per mil in the case of gibbsite and nearly 20 per mil in the case of goethite. The reduced partition function ratio of CO(2)(m)(B) structure in goethite differs from CO(2)(g) by <1 per mil. The predicted fractionation for gibbsite is >10 per mil higher, close to those measured for calcite and aragonite. The surprisingly large difference in the carbon-isotope fractionation factor between the CO(2)(m)(A) and CO(2)(m)(B) structures within a given mineral suggests that the isotopic signatures of soil (oxy)hydroxide could be heterogeneous.

  20. Calculation of site-specific carbon-isotope fractionation in pedogenic oxide minerals

    PubMed Central

    Rustad, James R.; Zarzycki, Piotr

    2008-01-01

    Ab initio molecular dynamics and quantum chemistry techniques are used to calculate the structure, vibrational frequencies, and carbon-isotope fractionation factors of the carbon dioxide component [CO2(m)] of soil (oxy)hydroxide minerals goethite, diaspore, and gibbsite. We have identified two possible pathways of incorporation of CO2(m) into (oxy)hydroxide crystal structures: one in which the C4+ substitutes for four H+ [CO2(m)A] and another in which C4+ substitutes for (Al3+,Fe3+) + H+ [CO2(m)B]. Calculations of isotope fractionation factors give large differences between the two structures, with the CO2(m)A being isotopically lighter than CO2(m)B by ≈10 per mil in the case of gibbsite and nearly 20 per mil in the case of goethite. The reduced partition function ratio of CO2(m)B structure in goethite differs from CO2(g) by <1 per mil. The predicted fractionation for gibbsite is >10 per mil higher, close to those measured for calcite and aragonite. The surprisingly large difference in the carbon-isotope fractionation factor between the CO2(m)A and CO2(m)B structures within a given mineral suggests that the isotopic signatures of soil (oxy)hydroxide could be heterogeneous. PMID:18641124

  1. Influence of carbon structure and mineral association of coals on their combustion characteristics for pulverized coal injection (PCI) application

    SciTech Connect

    Gupta, S.; Al-Omari, Y.; Sahajwalla, V.; French, D.

    2006-06-15

    The influence of carbon structure and mineral matter of three pulverized coals on their char characteristics including reactivity was studied under a range of combustion conditions in a drop tube furnace (DTF) and thermogravimetric (TGA) furnace for PCI application. Physical and chemical properties of coals and their combustion derivatives were characterized by automated reflectogram. X-ray diffraction, scanning electron microscope, and BET N{sub 2} adsorption. The QEMSCAN{asterisk} technique was used to characterize the heterogeneous nature of minerals of discrete coal particles. The TGA char reactivity was related to the proportion of coal particles displaying strong association of calcium/sulfur phases with carbon matrix to highlight the catalytic influence of minerals on char reactivity at low temperatures. The study suggested that during DTF combustion tests at 1200{sup o}C, char reaction rates might have been catalyzed by coal minerals, particularly due to illite and its association with carbon. Under the same combustion conditions, most of the coal minerals did not transform significantly to slag phases. Coal burnout was found to improve significantly in a combustion temperature range of 1200 to 1500{sup o}C. The improvement of coal burnout with temperature appeared to be influenced by coal properties, particularly as a function of the chemical nature of minerals, as well as the degree of associations with other minerals. The study implies that coals with similar mineral compositions might not necessarily reflect similar combustion behavior due to the differences in their associations with other phases.

  2. Effect of pCO2 on direct flue gas mineral carbonation at pilot scale.

    PubMed

    Mouedhen, Ikbel; Kemache, Nassima; Pasquier, Louis-César; Cecchi, Emmanuelle; Blais, Jean-François; Mercier, Guy

    2017-08-01

    Concerns about global warming phenomena induced the development of research about the control of anthropogenic greenhouse gases emissions. The current work studies on the scaling up of aqueous mineral carbonation route to reduce the CO2 emissions at the chimney of industrial emitters. The reactivity of serpentinite in a stirred tank reactor was studied for several partial pressures of CO2 (pCO2) (0.4, 0.7, 1.3 and 1.6 bar). Prior to carbonation, the feedstock was finely grinded and dehydroxyled at 650 °C by a thermal treatment. The major content of magnetite was removed (7.5 wt% · total weight(-1)). Experiments were carried out under batch mode at room temperature using real cement plant flue gas (14-18 vol% CO2) and open pit drainage water. The effect of the raw water and the pCO2 on the carbonation efficiency was measured. First, the main results showed a positive effect of the quarry water as a slight enhancement of the Mg leaching in comparison with distilled water. Secondly, a pCO2 of 1.3 bar was the optimal working pressure which provided the highest efficiency of the carbonation reaction (0.8 gCO2 · g residue(-1)). Precipitation rates of dissolved CO2 ranged from 7% to 33%. Pure precipitate was obtained and essentially composed of Nesquehonite. At a pCO2 of 1.3 bar, additional physical retreatment of the solid material after being contacted with 6 batches of gas enhanced considerably mineral carbonation efficiency (0.17 gCO2 · g residue(-1).). Copyright © 2017 Elsevier Ltd. All rights reserved.

  3. [Characteristics of soil organic carbon mineralization at different temperatures in paddy soils under long-term fertilization].

    PubMed

    Lin, Shan; Chen, Tao; Zhao, Jin-Song; Xiang, Rong-Biao; Hu, Rong-Gui; Zhang, Shui-Qing; Wang, Mi-Lan; Lu, Zhao-Qi

    2014-05-01

    Dynamics of soil organic carbon mineralization affected by long-term fertilizations and temperature in relation to different soil carbon fractions were investigated in paddy soils. Soil samples were collected from the plough layer of 3 long-term national experimental sites in Xinhua, Ningxiang and Taojiang counties of Hunan Province. Mineralization of soil organic C was estimated by 33-day aerobic incubation at different temperatures of 10, 20 and 30 degrees C. The results showed that the rates of CO2 production were higher during the earlier phase (0-13 d) in all treatments, and then decreased according to a logarithm function. Higher incubation temperature strengthened C mineralization in the different treatments. The quantities of cumulative CO2 production in NPK with manure or straw treatments were greater than in inorganic fertilizers treatments. The Q10 values in the different soil treatments ranged from 1.01-1.53. There were significantly positive correlations between the Q10 values and soil total organic carbon (TOC), easy oxidation organic carbon (EOOC), humic acid carbon (C(HA)), fulvic acid carbon (CFA). The cumulative amount of mineralized C was significantly positively correlated with microbial biomass carbon (MBC) at 10 and 20 degrees C, but not significantly at 30 degrees C. Significant correlations were found between the cumulative amount of mineralized C and different soil carbon fractions and C(HA)/C(FA). The correlations of differ- ent soil carbon fractions with the ratio of cumulative mineralized C to TOC were negatively correlated at 10 degrees C, but not significantly at 20 and 30 degrees C. These results suggested that the application of NPK with manure or straw would be helpful to increase the sequestration of C in paddy soils and reduce its contribution of CO2 release in the atmosphere.

  4. [Soil organic carbon and nitrogen mineralization along a forest successional gradient in Southern China].

    PubMed

    Ouyang, Xue-Jun; Zhou, Guo-Yi; Wei, Shi-Guang; Huang, Zhong-Liang; Li, Jiong; Zhang, De-Qiang

    2007-08-01

    With incubation test, this paper studied the characteristics of organic C and N mineralization in 0-10 cm soil layer under three forest types, i. e., pine (Pinus massoniana) forest (PMF), pine and broad-leaved mixed forest (PBMF) and monsoon evergreen broad-leaved forest (MEBF), which were in a successional series in Dinghushan Mountain of Southern China. The results showed that after incubation for 52 weeks, the cumulative emission of CO2-C from PMF, PBMF and MEBF soil was 30.66 +/- 3.36, 58.17 +/- 7.25 and 59.31 +/- 13.58 mg x kg(-1), respectively, and 64.12%, 64.41% and 65.12% of which were released in the first 9 weeks. The cumulative emission of CO2-C was always significantly smaller from PMF soil than from PBMF and MEBF soils, and its change pattern over time fitted well with a two-pool kinetic model. The parameters based on the model implicated that the mineralization rates of soil labile and recalcitrant organic carbon tended to decrease with the forest type changing from PMF to PBMF and MEBF. The cumulative amount of CH4 after 52 weeks incubation and the net production of available N and nitrate after 20 weeks incubation were significantly higher in MEBF soil than in PBMF soil, and also, in PBMF soil than in PMF soil. NO3(-) -N was the dominant form in net available N production. The change in soil organic carbon mineralization rate caused by forest type change was an inherent way to affect soil organic carbon content.

  5. Crystallinity of chitin and carbonate mineral components independently record crustacean biomineralization

    NASA Astrophysics Data System (ADS)

    Mergelsberg, S. T.; Michel, F. M.; Mukhopadhyay, B.; Dove, P. M.

    2016-02-01

    Some of the earliest evidence for crustacean organisms is attributed to the discovery of Peytoia nathorsti, a predatory arthropod from 500 Ma (Cong, P. et al., 2014). These animals presumably began with a soft exoskeleton and evolved to fill diverse ecological niches while adopting a mineralized skeleton that is rarely preserved in its entirety (Klompmaker, A.A. et al., 2015). That is, one or more of the primary skeleton components (calcium carbonate minerals, the polysaccharide chitin, and minor proteins) were subject to decomposition during fossilization and preservation. These missing pieces present a significant obstacle to reconstructing ecosystem variability over long time periods. Our recent study of the exoskeletons from ten Malacostraca species suggests the physical and chemical structure of chitin holds promise as a secondary proxy for reconstructing skeleton reinforcement. Using high-energy X-ray diffraction and a novel Raman spectroscopy technique to enhance resolution, we determined the detailed nanostructures of chitin and the associated calcium carbonate minerals that comprise the cuticles of multiple body parts. Crab cuticles from the order Brachyura (Dungeness and Rock crabs) exhibit elevated crystallinities of the chitin and calcite in the more reinforced structures (such as the claw). In contrast, the cuticle of lobster body parts show a much greater variability of calcium carbonate crystallinity and a very consistent crystallinity of chitin. Calcite and chitin crystallinity exhibit a dependency within a species (body part to body part), but these dependencies can be different between taxa. Insights from this study suggest high resolution structural analyses hold promise for developing new proxies for the paleo-environment and paleo-ecology of specific Malacostraca animals, regardless of how well the specimen is preserved.

  6. Carbon and nitrogen mineralization rates after application of organic amendments to soil.

    PubMed

    Flavel, Tamara C; Murphy, Daniel V

    2006-01-01

    The objective of this study was to quantify C and N mineralization rates from a range of organic amendments that differed in their total C and N contents and C quality, to gain a better understanding of their influence on the soil N cycle. A pelletized poultry manure (PP), two green waste-based composts (GWCa, GWCb), a straw-based compost (SBC), and a vermi-cast (VER) were incubated in a coarse-textured soil at 15 degrees C for 142 d. The C quality of each amendment was determined by chemical analysis and by 13C nuclear magnetic resonance (NMR). Carbon dioxide (CO2-C) evolution was determined using alkali traps. Gross N mineralization rates were calculated by 15N isotopic pool dilution. The CO2-C evolution rates and gross N mineralization rates were generally higher in amended soils than in the control soil. With the exception of GWCb all amendments released inorganic N at concentrations that would be high enough to warrant a reduction in inorganic N fertilizer application rates. The amount of N released from PP was high indicating that application rates should be reduced, or alternative amendments used, to minimize leaching losses in regions where ground water quality is of concern. There was a highly significant relationship between CO2-C evolution and gross N mineralization (R2= 0.95). Some of the chemically determined C quality parameters had significant relationships (p < 0.05) with both the cumulative amounts of C and N evolved. However, we found no significant relationships between 13C NMR spectral groupings, or their ratios, and either the CO2-C evolved or gross N mineralized from the amendments.

  7. Oxygen and carbon isotope ratios of hydrothermal minerals from Yellowstone drill cores

    USGS Publications Warehouse

    Sturchio, N.C.; Keith, T.E.C.; Muehlenbachs, K.

    1990-01-01

    Oxygen and carbon isotope ratios were measured for hydrothermal minerals (silica, clay and calcite) from fractures and vugs in altered rhyolite, located between 28 and 129 m below surface (in situ temperatures ranging from 81 to 199??C) in Yellowstone drill holes. The purpose of this study was to investigate the mechanism of formation of these minerals. The ??18O values of the thirty-two analyzed silica samples (quartz, chalcedony, ??-cristobalite, and ??-cristobalite) range from -7.5 to +2.8???. About one third of the silica 7samples have ??18O values that are consistent with isotopic equilibrium with present thermal waters; most of the other silica samples appear to have precipitated from water enriched in 18O (up to 4.7???) relative to present thermal water, assuming precipitation at present in situ temperatures. Available data on fluid-inclusion homogenization temperatures in hydrothermal quartz indicate that silica precipitation occurred mostly at temperatures above those measured during drilling and imply that 15O enrichments in water during silica precipitation were generally larger than those estimated from present conditions. Similarly, clay minerals (celadonite and smectite) have ??18O values higher (by 3.5 to 7.9???) than equilibrium values under present conditions. In contrast, all eight analyzed calcite samples are close to isotopic equilibrium with present thermal waters. The frequent incidence of apparent 18O enrichment in thermal water from which the hydrothermal minerals precipitated may indicate that a higher proportion of strongly 18O-enriched deep hydrothermal fluid once circulated through shallow portions of the Yellowstone system, or that a recurring transient 18O-enrichment effect occurs at shallow depths and is caused either by sudden decompressional boiling or by isotopic exchange at low water/rock ratios in new fractures. The mineralogy and apparent 18O enrichments of hydrothermal fracture-filling minerals are consistent with deposition

  8. Topsoil organic carbon mineralization and CO2 evolution of three paddy soils from South China and the temperature dependence.

    PubMed

    Zhang, Xu-Hui; Li, Lian-Qing; Pan, Gen-Xing

    2007-01-01

    Carbon mineralization and its response to climatic warming have been receiving global attention for the last decade. Although the virtual influence of temperature effect is still in great debate, little is known on the mineralization of organic carbon (SOC) of paddy soils of China under warming. SOC mineralization of three major types of China's paddy soils is studied through laboratory incubation for 114 d under soil moisture regime of 70% water holding capacity at 20 degrees C and 25 degrees C respectively. The carbon that mineralized as CO2 evolved was measured every day in the first 32 d and every two days in the following days. Carbon mineralized during the 114 d incubation ranged from 3.51 to 9.22 mg CO2-C/gC at 20 degrees C and from 4.24 to 11.35 mg CO2-C/gC at 25 degrees C respectively; and a mineralizable C pool in the range of 0.24 to 0.59 gC/kg, varying with different soils. The whole course of C mineralization in the 114 d incubation could be divided into three stages of varying rates, representing the three subpools of the total mineralizable C: very actively mineralized C at 1-23 d, actively mineralized C at 24-74 d and a slowly mineralized pool with low and more or less stabilized C mineralization rate at 75-114 d. The calculated Q10 values ranged from 1.0 to 2.4, varying with the soil types and N status. Neither the total SOC pool nor the labile C pool could account for the total mineralization potential of the soils studied, despite a well correlation of labile C with the shortly and actively mineralized C, which were shown in sensitive response to soil warming. However, the portion of microbial C pool and the soil C/N ratio controlled the C mineralization and the temperature dependence. Therefore, C sequestration may not result in an increase of C mineralization proportionally. The relative control of C bioavailability and microbial metabolic activity on C mineralization with respect to stabilization of sequestered C in the paddy soils of China is

  9. Sequestered carbon on clay mineral probed by electron paramagnetic resonance and X-ray photoelectron spectroscopy.

    PubMed

    Lombardi, Kátia Cylene; Mangrich, Antonio Salvio; Wypych, Fernando; Rodrigues-Filho, Ubirajara Pereira; Guimarães, José L; Schreiner, Wido H

    2006-03-01

    This paper describes the interaction among soil organic matter components with kaolinite, an important clay mineral present in tropical soils, especially in Brazil. XPS data show that the soil organic matter adsorbed on kaolinite has aromatic and aliphatic structures, with phenolic and/or alcoholic functions and carbonyl carbons (CO) of amide and/or carboxylic groups. The N1s spectrum of the kaolinite shows an asymmetric peak that is assigned to amide and protonated ammines probably from humin. The interaction between them is strong enough to resist chemical oxidative or reductive attack besides loose amide functionalities. EPR data show that reductive treatment reduces some Fe3+ of the kaolinite structure, loosing organic components. A schematic representation of the reduction of structural Fe3+ in the concentrated domains and consequently increased concentration of Fe3+ ions in diluted domains of the spectrum is presented. This reinforces the hypothesis that humin is a stable carbon sink in soils when adsorbed to clays.

  10. Microbial biomass and carbon mineralization in agricultural soils as affected by pesticide addition.

    PubMed

    Kumar, Anjani; Nayak, A K; Shukla, Arvind K; Panda, B B; Raja, R; Shahid, Mohammad; Tripathi, Rahul; Mohanty, Sangita; Rath, P C

    2012-04-01

    A laboratory study was conducted with four pesticides, viz. a fungicide (carbendazim), two insecticides (chlorpyrifos and cartap hydrochloride) and an herbicide (pretilachlor) applied to a sandy clay loam soil at a field rate to determine their effect on microbial biomass carbon (MBC) and carbon mineralization (C(min)). The MBC content of soil increased with time up to 30 days in cartap hydrochloride as well as chlorpyrifos treated soil. Thereafter, it decreased and reached close to the initial level by 90th day. However, in carbendazim treated soil, the MBC showed a decreasing trend up to 45 days and subsequently increased up to 90 days. In pretilachlor treated soil, MBC increased through the first 15 days, and thereafter decreased to the initial level. Application of carbendazim, chlorpyrifos and cartap hydrochloride decreased C(min) for the first 30 days and then increased afterwards, while pretilachlor treated soil showed an increasing trend.

  11. Effect of Additives and pH on the Formation of Carbonate Mineral by CO2 Sequestration of Cement Paste

    NASA Astrophysics Data System (ADS)

    Lee, J. H.; Hwang, J.; Lee, H.; Son, B. S.; Oh, J.

    2015-12-01

    CO2 in the atmosphere causes a global warming that is a big issue nowadays. Many studies of CO2 capture and storage (CCS) technologies have been studied all over the world. Waste cement is a good source for aqueous carbonation because it is rich in calcium. Therefore, this study was performed to develop the aqueous carbonation method for waste cement powder. Cement paste was made with water/cement ratio of 6:4 and cured for 28 days in water bath. The cement paste was pulverized into a fine powder sizing less than 0.15 mm. To study effect of additives and pH on the formation of carbonate minerals, aqueous carbonation experiments were conducted. The mineral compositions and morphology of carbonate mineral were identified by XRD and SEM/EDS analysis. 1.0 M NaCl and 0.25 M MgCl2 were applied as additives. Aqueous carbonation experiment was conducted with injecting pure CO2 gas (99.9%) to a reactor containing 200 ㎖ of reacting solution. The pH of reacting solution was controled to determine formational condition of carbonate minerals. In 0.25 M MgCl2 solution, calcite was dominant mineral at high pH. More aragonite, however, formed as decreasing pH of solution with injection of CO2. The presence of Mg2+ in solution makes aragonite more dominant than calcite. Aragonite was mainly formed at the high pH of solution with 1.0 M NaCl additive, whereas calcite was more preponderant mineral than aragonite as falling pH. It show that unstable aragonite transformed to calcite as decreasing pH. In no additive solution, vaterite was dominantly formed at the initial stage of experiement, but unstable vaterite transformed to well crystallized calcite with further carbonation.

  12. Mineral dissolution and precipitation in carbonate dominated terranes assessed using Mg isotopes

    NASA Astrophysics Data System (ADS)

    Tipper, E.; Calmels, D.; Gaillardet, J.; Galy, A.

    2013-12-01

    Carbonate weathering by carbonic acid consumes atmospheric CO2 during mineral dissolution, fixing it as aqueous bicarbonate over millennial time-scales. Ocean acidification has increased the solubility of CO2 in seawater by changing the balance of pH to alkalinity (the oceanic reservoir of carbon). This has lengthened the time-scale for CO2 sequestration by carbonate weathering to tens of thousands of years. At a global scale, the net consumption of CO2 is at least equal to that from silicate weathering, but there is far less work on carbonate weathering compared to silicate weathering because it has generally been assumed to be CO2 neutral on geological time-scales. Carbonate rocks are more readily dissolved than silicate rocks, meaning that their dissolution will likely respond much more rapidly to global environmental change when compared with the dissolution of silicate minerals. Although far less concentrated than Ca in many carbonates, Mg substitutes for Ca and is more concentrated than any other metal ion. Tracing the behavior of Mg in river waters, using Mg stable isotopes (26Mg/24Mg ratio expressed as delta26Mg in per mil units) is therefore a novel way to understand the complex series of dissolution/precipitation reactions that govern solute concentrations of Ca and Mg, and hence CO2 transfer by carbonate weathering. We present new Mg isotope data on a series of river and spring waters from the Jura mountains in North-East France. The stratigraphic column is relatively uniform throughout the Jura mountains and is dominated by limestones. As the limestone of the Jura Mountains were deposited in high-energy shallow water environments (shore line, lagoon and coral reefs), they are usually clay and organic poor. The delta26Mg of the local rocks is very constant at circa -4permil. The delta26Mg of the river waters is also fairly constant, but offset from the rock at -2.5permil. This is an intriguing observation because the dissolution of limestones is expected

  13. Direct mineral carbonation of steelmaking slag for CO2 sequestration at room temperature.

    PubMed

    Rushendra Revathy, T D; Palanivelu, K; Ramachandran, A

    2016-04-01

    Rapid increase of CO2 concentration in the atmosphere has forced the international community towards adopting actions to restrain from the impacts of climate change. Moreover, in India, the dependence on fossil fuels is projected to increase in the future, implying the necessity of capturing CO2 in a safe manner. Alkaline solid wastes can be utilized for CO2 sequestration by which its disposal issues in the country could also be met. The present work focuses to study direct mineral carbonation of steelmaking slag (SS) at room temperature and low-pressure conditions (<10 bar). Direct mineral carbonation of SS was carried out in a batch reactor with pure CO2 gas. The process parameters that may influence the carbonation of SS, namely, CO2 gas pressure, liquid to solid ratio (L/S) and reaction time were also studied. The results showed that maximum sequestration of SS was attained in the aqueous route with a capacity of 82 g of CO2/kg (6 bar, L/S ratio of 10 and 3 h). In the gas-solid route, maximum sequestration capacity of about 11.1 g of CO2/kg of SS (3 bar and 3 h) was achieved indicating that aqueous route is the better one under the conditions studied. These findings demonstrate that SS is a promising resource and this approach could be further developed and used for CO2 sequestration in the country. The carbonation process was evidenced using FT-IR, XRD, SEM and TG analysis.

  14. From atoms to minerals: how calcium carbonates form and why we should care.

    NASA Astrophysics Data System (ADS)

    Diego Rodriguez-Blanco, Juan

    2017-04-01

    Calcium carbonate minerals are ubiquitous on Earth where they play a key role in many marine and terrestrial biomineralization processes, controlling the evolution of past and future ocean chemistry and a large part of the global carbon cycle. However, the mechanisms by which biominerals form and transform are not well understood because these processes frequently involve the formation of poorly-ordered and crystalline metastable phases (e.g., amorphous calcium carbonate, vaterite, monohydrocalcite). Furthermore, the degree of ordering, hydration and particle size of these phases and their crystallisation pathways are largely controlled by their origin and conditions of formation. These include a number of factors like temperature, pH, and concentration of foreign ions in solution (e.g., Mg2+, Sr2+, SO42-, organics, etc.). Over the last few years, new experimental and characterization approaches have been developed, combining classical characterization techniques with synchrotron-based methods that allow in situ and real-time monitoring of the reactions (e.g., time-resolved synchrotron-based scattering and diffraction, pair distribution function). These techniques have provided very useful data to attain the mechanisms and quantify the kinetics of crystallization in abiotic systems. I will present a series of results obtained from synchrotron- and lab-based experiments that shed light on the mechanisms of formation of a number of biominerals (e.g., vaterite, calcite, aragonite, monohydrocalcite, dolomite). These results provide a detailed understanding of how calcium carbonate phases form during biomineralization processes, the effects of seawater ions and organics during the formation and transformation of biominerals, and the implications for past and future ocean chemistry, CO2 capture and storage and industrial mineral synthesis.

  15. Differential controls on soil carbon density and mineralization among contrasting forest types in a temperate forest ecosystem

    PubMed Central

    You, Ye-Ming; Wang, Juan; Sun, Xiao-Lu; Tang, Zuo-Xin; Zhou, Zhi-Yong; Sun, Osbert Jianxin

    2016-01-01

    Understanding the controls on soil carbon dynamics is crucial for modeling responses of ecosystem carbon balance to global change, yet few studies provide explicit knowledge on the direct and indirect effects of forest stands on soil carbon via microbial processes. We investigated tree species, soil, and site factors in relation to soil carbon density and mineralization in a temperate forest of central China. We found that soil microbial biomass and community structure, extracellular enzyme activities, and most of the site factors studied varied significantly across contrasting forest types, and that the associations between activities of soil extracellular enzymes and microbial community structure appeared to be weak and inconsistent across forest types, implicating complex mechanisms in the microbial regulation of soil carbon metabolism in relation to tree species. Overall, variations in soil carbon density and mineralization are predominantly accounted for by shared effects of tree species, soil, microclimate, and microbial traits rather than the individual effects of the four categories of factors. Our findings point to differential controls on soil carbon density and mineralization among contrasting forest types and highlight the challenge to incorporate microbial processes for constraining soil carbon dynamics in global carbon cycle models. PMID:26925871

  16. From Carbonatite to Ikaite: How high-T carbonates are transformed into low-T carbonate minerals in SW Greenland

    NASA Astrophysics Data System (ADS)

    Stockmann, G. J.; Tollefsen, E.; Ranta, E.; Skelton, A.; Sturkell, E.; Lundqvist, L.

    2015-12-01

    The 1300 Ma Grønnedal-Íka igneous complex in southwest Greenland comprises nepheline syenites and carbonatites. It belongs to a suite of intrusions formed 1300-1100 Ma ago referred to as the Gardar period. In modern time (the last ca. 8000 years), fluid-rock interactions involving the nepheline syenites and carbonatites gives rise to about one thousand submarine columns made of the rare low-T mineral ikaite (CaCO3x6H2O). The columns are found in a shallow, narrow fjord named Ikka Fjord and their distribution clearly follows the outcrop of the Grønnedal-Íka complex. When meteoric water percolates through the highly fractured complex, a sodium carbonate solution of pH 10 is formed through hitherto unknown fluid-rock reactions. This basic solution seeps up through fractures at the bottom of Ikka Fjord and when mixed with seawater, the mineral ikaite is formed. As the seepage water has a lower density than seawater, there is an upwards flow that creates columns. What is peculiar about ikaite is its limited stability making it unstable above +6 °C. Isotopic studies of ikaite reveal a seawater origin for the Ca2+ ions, and the carbonatite being the most likely source for the CO32- ions. The carbonatite is mainly of søvite composition (CaCO3) with high contents of siderite and ankerite in certain areas. The nepheline syenites contain Na,K-rich minerals like nepheline, alkali-feldspar, aegirine-augite, katophorite and biotite. Nepheline is mainly replaced by muscovite, and aegirine-augite partly by chlorite, which could release sodium into solution. A dolerite dyke of unknown age prompted extensive mineralization of magnetite by activating hydrothermal fluid convection. The fluid interacted with the carbonatite, replacing siderite and ankerite by magnetite and later hematite. In a newly launched project at Stockholm University, we are trying to unravel the chemical reactions taking place inside the Grønnedal-Íka igneous complex leading to the formation of the

  17. Distinct temperature sensitivity of soil carbon decomposition in forest organic layer and mineral soil.

    PubMed

    Xu, Wenhua; Li, Wei; Jiang, Ping; Wang, Hui; Bai, Edith

    2014-10-01

    The roles of substrate availability and quality in determining temperature sensitivity (Q10) of soil carbon (C) decomposition are still unclear, which limits our ability to predict how soil C storage and cycling would respond to climate change. Here we determined Q10 in surface organic layer and subsurface mineral soil along an elevation gradient in a temperate forest ecosystem. Q10 was calculated by comparing the times required to respire a given amount of soil C at 15 and 25°C in a 350-day incubation. Results indicated that Q10 of the organic layer was 0.22-0.71 (absolute difference) higher than Q10 of the mineral soil. Q10 in both the organic layer (2.5-3.4) and the mineral soil (2.1-2.8) increased with decreasing substrate quality during the incubation. This enhancement of Q10 over incubation time in both layers suggested that Q10 of more labile C was lower than that of more recalcitrant C, consistent with the Arrhenius kinetics. No clear trend of Q10 was found along the elevation gradient. Because the soil organic C pool of the organic layer in temperate forests is large, its higher temperature sensitivity highlights its importance in C cycling under global warming.

  18. Distinct temperature sensitivity of soil carbon decomposition in forest organic layer and mineral soil

    NASA Astrophysics Data System (ADS)

    Xu, Wenhua; Li, Wei; Jiang, Ping; Wang, Hui; Bai, Edith

    2014-10-01

    The roles of substrate availability and quality in determining temperature sensitivity (Q10) of soil carbon (C) decomposition are still unclear, which limits our ability to predict how soil C storage and cycling would respond to climate change. Here we determined Q10 in surface organic layer and subsurface mineral soil along an elevation gradient in a temperate forest ecosystem. Q10 was calculated by comparing the times required to respire a given amount of soil C at 15 and 25°C in a 350-day incubation. Results indicated that Q10 of the organic layer was 0.22-0.71 (absolute difference) higher than Q10 of the mineral soil. Q10 in both the organic layer (2.5-3.4) and the mineral soil (2.1-2.8) increased with decreasing substrate quality during the incubation. This enhancement of Q10 over incubation time in both layers suggested that Q10 of more labile C was lower than that of more recalcitrant C, consistent with the Arrhenius kinetics. No clear trend of Q10 was found along the elevation gradient. Because the soil organic C pool of the organic layer in temperate forests is large, its higher temperature sensitivity highlights its importance in C cycling under global warming.

  19. Survival of Escherichia coli and Aeromonas hydrophila in non-carbonated mineral water.

    PubMed

    Korzeniewska, Ewa; Filipkowska, Zofia; Zarnoch, Dagny; Tworus, Katarzyna

    2005-01-01

    The study was carried out on the survival of Escherichia coli and Aeromonas hydrophila in samples of mineral waters. Enumeration of the bacteria was performed by spread inoculation of samples (0.1 cm3) over the surface of selected media in Petri plates. Twenty bottles (four bottles of each of the five brands) of non-carbonated mineral waters with different levels of dissolved solids and organic content were chosen to study every strain. Ten bottles were stored at 4 degrees C, the other ten were kept at 22 degrees C. Half of the samples of mineral water was filtered, the remaining water was unfiltered. The resulting growth curves depended on the time of storage. The number of E. coli increased during the first two weeks (except the seventh day) and decreased during the next days. E. coli was detected in 70% of samples of water after 182 days. The number of A. hydrophila decreased during the first three days, increased on the seventh day and decreased during the next days. A. hydrophila was detected in 15% of the samples of water after 182 days. The temperature of storage was inessential for growth. The most important factors were the brand and the filtering or unfiltering of water. The highest numbers of the bacteria analysed were detected in filtered water, irrespective of the water brand and temperature of storage.

  20. Distinct temperature sensitivity of soil carbon decomposition in forest organic layer and mineral soil

    PubMed Central

    Xu, Wenhua; Li, Wei; Jiang, Ping; Wang, Hui; Bai, Edith

    2014-01-01

    The roles of substrate availability and quality in determining temperature sensitivity (Q10) of soil carbon (C) decomposition are still unclear, which limits our ability to predict how soil C storage and cycling would respond to climate change. Here we determined Q10 in surface organic layer and subsurface mineral soil along an elevation gradient in a temperate forest ecosystem. Q10 was calculated by comparing the times required to respire a given amount of soil C at 15 and 25°C in a 350-day incubation. Results indicated that Q10 of the organic layer was 0.22–0.71 (absolute difference) higher than Q10 of the mineral soil. Q10 in both the organic layer (2.5–3.4) and the mineral soil (2.1–2.8) increased with decreasing substrate quality during the incubation. This enhancement of Q10 over incubation time in both layers suggested that Q10 of more labile C was lower than that of more recalcitrant C, consistent with the Arrhenius kinetics. No clear trend of Q10 was found along the elevation gradient. Because the soil organic C pool of the organic layer in temperate forests is large, its higher temperature sensitivity highlights its importance in C cycling under global warming. PMID:25270905

  1. Factors driving carbon mineralization priming effect in a soil amended with different types of biochar

    NASA Astrophysics Data System (ADS)

    Cely, P.; Tarquis, A. M.; Paz-Ferreiro, J.; Méndez, A.; Gascó, G.

    2014-03-01

    The effect of biochar on soil carbon mineralization priming effect depends on the characteristics of the raw materials, production method and pyrolysis conditions. The goal of the present study is to evaluate the impact of three different types of biochar on soil CO2 emissions and in different physicochemical properties. For this purpose, a sandy-loam soil was amended with the three biochars (BI, BII and BIII) at a rate of 8 wt % and soil CO2 emissions were measured for 45 days. BI is produced from a mixed wood sieving's from wood chip production, BII from a mixture of paper sludge and wheat husks and BIII from sewage sludge. Cumulative CO2 emissions of biochars, soil and amended soil were well fit to a simple first-order kinetic model with correlation coefficients (r2) greater than 0.97. Results shown a negative priming effect in the soil after addition of BI and a positive priming effect in the case of soil amended with BII and BIII. These results can be related with different biochar properties such as ash content, volatile matter, fixed carbon, organic carbon oxidised with dichromate, soluble carbon and metal and phenolic substances content in addition to surface biochar properties. Three biochars increased the values of soil field capacity and wilting point, while effects over pH and cation exchange capacity were not observed.

  2. Oxic and anoxic mineralization of simple carbon substrates in peat at low temperatures

    NASA Astrophysics Data System (ADS)

    Segura, Javier; Sparrman, Tobias; Nilsson, Mats; Schleucher, Jürgen; Öquist, Mats

    2016-04-01

    Northern peatlands store approximately one-quarter of the world's soil carbon and typically act as net carbon sinks. However a large fraction of the carbon fixed during the growing season can be emitted back to the atmosphere during winter as CO2 and CH4, despite low temperatures and frozen conditions, making low temperature biogeochemical processes crucial for the long-term net ecosystem carbon balance. However, the metabolic processes driving carbon mineralization under winter conditions are poorly understood and whether or not peat microbial communities can maintain metabolic activity at temperatures below freezing is uncertain. Here we present results from an incubation study aimed at elucidating the potential of peat microbial communities to mineralize simple carbon substrates to CO2 and CH4 at low temperatures. Peat samples from the acrotelm were amended with [13C]- glucose and incubated at -5 °C, -3 °C, +4 °C, and +9 °C under both oxic and anoxic conditions, and rates of CO2 and CH4 production were determined. In addition, incorporation of the labelled substrate into phospholipid fatty acids (PLFAs) were determined to account for microbial growth during mineralization and the metabolic partitioning between catabolic and anabolic activity. Biogenic [13C]-CO2 was produced from the added substrate in peat samples incubated both under oxic and anoxic conditions. Under oxic conditions the production rates were 3.5, 2.3, 0.3 and 0.07 mg CO2 g SOM-1day-1 at +9 °C, +4 °C, -3 °C and -5 °C, respectively, and corresponding rates for anoxic conditions were 1.1, 1.0, 0.03 and 0.01 mg CO2 g SOM-1day-1. Consequently the observed Q10 values of the temperature sensitivity under both oxic and anoxic conditions increased dramatically upon soil freezing. However, anoxic mineralization appears less sensitive to temperature as compared to when oxygen is present. Methane was also produced and detected across the range of the incubation temperatures in the anoxic

  3. Sodium-rich carbonated natural mineral water ingestion and blood pressure.

    PubMed

    Santos, Alejandro; Martins, Maria João; Guimarães, João Tiago; Severo, Milton; Azevedo, Isabel

    2010-02-01

    There is a strong positive correlation between sodium chloride intake and hypertension. In industrialized countries the ingestion of carbonated and non-carbonated mineral water is an important source of calorie-free fluids. The mineral content of these waters varies greatly, with many brands containing high levels of sodium. However, some mineral waters contain greater amounts of bicarbonate instead of chloride as the anion associated with the sodium cation. This is relevant because it is well established that the effect of sodium on blood pressure depends on the corresponding anion. Additionally the pressor effect of sodium bicarbonate is much lower than that of equivalent amounts of sodium chloride. The aim of our work was to evaluate the effect of ingesting a sodium-rich carbonated mineral water (Agua das Pedras) on blood pressure values in normotensive individuals. This crossover, non-blinded study evaluated 17 individuals (9 female and 8 male), aged 24-53 years, median body mass index (BMI) < 23, randomly allocated in two groups, ingesting 500 ml/day of Agua das Pedras or Agua Vitalis. Each arm of the study lasted 7 weeks, with 6 weeks of washout between them. Twenty-four hour urinary samples were collected at the beginning and end of each arm to determine pH and sodium and potassium excretion. Blood pressure and body weight were measured weekly throughout the study. A mixed-effects model was used to compare groups (p < 0.05). The Wilcoxon test was used to analyze electrolyte excretion. No differences were observed in blood pressure values between treatments or from baseline values. We found a positive correlation between BMI and blood pressure. The daily ingestion of 500 ml of Agua das Pedras had no effect on blood pressure. A study by Schorr and co-workers found that the ingestion of bicarbonate-rich water (1.5 l/day) had hypotensive effects in an elderly population. However, these results should be verified in hypertensive subjects, who are more likely to

  4. Iron and carbon metabolism by a mineral-oxidizing Alicyclobacillus-like bacterium.

    PubMed

    Yahya, Adibah; Hallberg, Kevin B; Johnson, D Barrie

    2008-04-01

    A novel iron-oxidizing, moderately thermophilic, acidophilic bacterium (strain "GSM") was isolated from mineral spoil taken from a gold mine in Montana. Biomolecular analysis showed that it was most closely related to Alicyclobacillus tolerans, although the two bacteria differed in some key respects, including the absence (in strain GSM) of varpi-alicyclic fatty acids and in their chromosomal base compositions. Isolate GSM was able to grow in oxygen-free media using ferric iron as terminal electron acceptor confirming that it was a facultative anaerobe, a trait not previously described in Alicyclobacillus spp.. The acidophile used both organic and inorganic sources of energy and carbon, although growth and iron oxidation by isolate GSM was uncoupled in media that contained both fructose and ferrous iron. Fructose utilization suppressed iron oxidation, and oxidation of ferrous iron occurred only when fructose was depleted. In contrast, fructose catabolism was suppressed when bacteria were harvested while actively oxidizing iron, suggesting that both ferrous iron- and fructose-oxidation are inducible in this acidophile. Isolate GSM accelerated the oxidative dissolution of pyrite in liquid media either free of, or amended with, organic carbon, although redox potentials were significantly different in these media. The potential of this isolate for commercial mineral processing is discussed.

  5. Carbon dioxide exchange of a perennial bioenergy crop cultivation on a mineral soil

    NASA Astrophysics Data System (ADS)

    Lind, S. E.; Shurpali, N. J.; Peltola, O.; Mammarella, I.; Hyvönen, N.; Maljanen, M.; Räty, M.; Virkajärvi, P.; Martikainen, P. J.

    2015-10-01

    One of the strategies to reduce carbon dioxide (CO2) emissions from the energy sector is to increase the use of renewable energy sources such as bioenergy crops. Bioenergy is not necessarily carbon neutral because of greenhouse gas (GHG) emissions during biomass production, field management and transportation. The present study focuses on the cultivation of reed canary grass (RCG, Phalaris arundinaceae L.), a perennial bioenergy crop, on a mineral soil. To quantify the CO2 exchange of this RCG cultivation system, and to understand the key factors controlling its CO2 exchange, the net ecosystem CO2 exchange (NEE) was measured during three years using the eddy covariance (EC) method. The RCG cultivation thrived well producing yields of 6200 and 6700 kg DW ha-1 in 2010 and 2011, respectively. Gross photosynthesis (GPP) was controlled mainly by radiation from June to September. Vapour pressure deficit (VPD), air temperature or soil moisture did not limit photosynthesis during the growing season. Total ecosystem respiration (TER) increased with soil temperature, green area index and GPP. Annual NEE was -262 and -256 g C m-2 in 2010 and 2011, respectively. Throughout the studied period, cumulative NEE was -575 g C m-2. When compared to the published data for RCG on an organic soil, the cultivation of this crop on a mineral soil had higher capacity to take up CO2 from the atmosphere.

  6. Solution chemistry of carbonate minerals and its effects on the flotation of hematite with sodium oleate

    NASA Astrophysics Data System (ADS)

    Li, Dong; Yin, Wan-zhong; Xue, Ji-wei; Yao, Jin; Fu, Ya-feng; Liu, Qi

    2017-07-01

    The effects of carbonate minerals (dolomite and siderite) on the flotation of hematite using sodium oleate as a collector were investigated through flotation tests, supplemented by dissolution measurements, solution chemistry calculations, zeta-potential measurements, Fourier transform infrared (FTIR) spectroscopic studies, and X-ray photoelectron spectroscopy (XPS) analyses. The results of flotation tests show that the presence of siderite or dolomite reduced the recovery of hematite and that the inhibiting effects of dolomite were stronger. Dissolution measurements, solution chemistry calculations, and flotation tests confirmed that both the cations (Ca2+ and Mg2+) and CO3 2- ions dissolved from dolomite depressed hematite flotation, whereas only the CO3 2- ions dissolved from siderite were responsible for hematite depression. The zeta-potential, FTIR spectroscopic, and XPS analyses indicated that Ca2+, Mg2+, and CO3 2- (HCO3 -) could adsorb onto the hematite surface, thereby hindering the adsorption of sodium oleate, which was the main reason for the inhibiting effects of carbonate minerals on hematite flotation.

  7. Influence of Substrate Mineralogy on Bacterial Mineralization of Calcium Carbonate: Implications for Stone Conservation

    PubMed Central

    Jroundi, Fadwa; Schiro, Mara; Ruiz-Agudo, Encarnación; González-Muñoz, María Teresa

    2012-01-01

    The influence of mineral substrate composition and structure on bacterial calcium carbonate productivity and polymorph selection was studied. Bacterial calcium carbonate precipitation occurred on calcitic (Iceland spar single crystals, marble, and porous limestone) and silicate (glass coverslips, porous sintered glass, and quartz sandstone) substrates following culturing in liquid medium (M-3P) inoculated with different types of bacteria (Myxococcus xanthus, Brevundimonas diminuta, and a carbonatogenic bacterial community isolated from porous calcarenite stone in a historical building) and direct application of sterile M-3P medium to limestone and sandstone with their own bacterial communities. Field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), powder X-ray diffraction (XRD), and 2-dimensional XRD (2D-XRD) analyses revealed that abundant highly oriented calcite crystals formed homoepitaxially on the calcitic substrates, irrespective of the bacterial type. Conversely, scattered spheroidal vaterite entombing bacterial cells formed on the silicate substrates. These results show that carbonate phase selection is not strain specific and that under equal culture conditions, the substrate type is the overruling factor for calcium carbonate polymorph selection. Furthermore, carbonate productivity is strongly dependent on the mineralogy of the substrate. Calcitic substrates offer a higher affinity for bacterial attachment than silicate substrates, thereby fostering bacterial growth and metabolic activity, resulting in higher production of calcium carbonate cement. Bacterial calcite grows coherently over the calcitic substrate and is therefore more chemically and mechanically stable than metastable vaterite, which formed incoherently on the silicate substrates. The implications of these results for technological applications of bacterial carbonatogenesis, including building stone conservation, are discussed. PMID:22447589

  8. Influence of substrate mineralogy on bacterial mineralization of calcium carbonate: implications for stone conservation.

    PubMed

    Rodriguez-Navarro, Carlos; Jroundi, Fadwa; Schiro, Mara; Ruiz-Agudo, Encarnación; González-Muñoz, María Teresa

    2012-06-01

    The influence of mineral substrate composition and structure on bacterial calcium carbonate productivity and polymorph selection was studied. Bacterial calcium carbonate precipitation occurred on calcitic (Iceland spar single crystals, marble, and porous limestone) and silicate (glass coverslips, porous sintered glass, and quartz sandstone) substrates following culturing in liquid medium (M-3P) inoculated with different types of bacteria (Myxococcus xanthus, Brevundimonas diminuta, and a carbonatogenic bacterial community isolated from porous calcarenite stone in a historical building) and direct application of sterile M-3P medium to limestone and sandstone with their own bacterial communities. Field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), powder X-ray diffraction (XRD), and 2-dimensional XRD (2D-XRD) analyses revealed that abundant highly oriented calcite crystals formed homoepitaxially on the calcitic substrates, irrespective of the bacterial type. Conversely, scattered spheroidal vaterite entombing bacterial cells formed on the silicate substrates. These results show that carbonate phase selection is not strain specific and that under equal culture conditions, the substrate type is the overruling factor for calcium carbonate polymorph selection. Furthermore, carbonate productivity is strongly dependent on the mineralogy of the substrate. Calcitic substrates offer a higher affinity for bacterial attachment than silicate substrates, thereby fostering bacterial growth and metabolic activity, resulting in higher production of calcium carbonate cement. Bacterial calcite grows coherently over the calcitic substrate and is therefore more chemically and mechanically stable than metastable vaterite, which formed incoherently on the silicate substrates. The implications of these results for technological applications of bacterial carbonatogenesis, including building stone conservation, are discussed.

  9. Conventional intensive logging promotes loss of organic carbon from the mineral soil.

    PubMed

    Dean, Christopher; Kirkpatrick, James B; Friedland, Andrew J

    2017-01-01

    There are few data, but diametrically opposed opinions, about the impacts of forest logging on soil organic carbon (SOC). Reviews and research articles conclude either that there is no effect, or show contradictory effects. Given that SOC is a substantial store of potential greenhouse gasses and forest logging and harvesting is routine, resolution is important. We review forest logging SOC studies and provide an overarching conceptual explanation for their findings. The literature can be separated into short-term empirical studies, longer-term empirical studies and long-term modelling. All modelling that includes major aboveground and belowground biomass pools shows a long-term (i.e. ≥300 years) decrease in SOC when a primary forest is logged and then subjected to harvesting cycles. The empirical longer-term studies indicate likewise. With successive harvests the net emission accumulates but is only statistically perceptible after centuries. Short-term SOC flux varies around zero. The long-term drop in SOC in the mineral soil is driven by the biomass drop from the primary forest level but takes time to adjust to the new temporal average biomass. We show agreement between secondary forest SOC stocks derived purely from biomass information and stocks derived from complex forest harvest modelling. Thus, conclusions that conventional harvests do not deplete SOC in the mineral soil have been a function of their short time frames. Forest managers, climate change modellers and environmental policymakers need to assume a long-term net transfer of SOC from the mineral soil to the atmosphere when primary forests are logged and then undergo harvest cycles. However, from a greenhouse accounting perspective, forest SOC is not the entire story. Forest wood products that ultimately reach landfill, and some portion of which produces some soil-like material there rather than in the forest, could possibly help attenuate the forest SOC emission by adding to a carbon pool in

  10. Carbonate minerals, oxygen and carbon isotopes in modern temperate bryozoa, eastern Tasmania, Australia

    NASA Astrophysics Data System (ADS)

    Prasada Rao, C.

    1993-12-01

    X-ray analysis of cool temperate bryozoa from eastern shelf carbonates indicates the occurrence of a spectrum of low-Mg calcite to high-Mg calcite with variable amounts of aragonite. Bryozoa contain variable amounts of CaCO 3 cements. In bryozoa δ18O values increase and δ13C values decrease with increasing aragonite content probably due to the occurrence of vaterite. Aragonite contents decrease with decreasing water temperatures as established by oxygen isotope thermometry. Tasmanian bryozoa may be enriched in δ18O up to 0.7‰ due to aragonite and high Mg-calcite contents. δ13C values of bryozoa composed of pure calcite are similar to those of associated brachiopods. δ18O and δ13C values of bryozoa are unaffected by kinetic and metabolic effects. The isotopic field of temperate bryozoa differs from tropical carbonates by having heavier δ18O ( 1.3‰ ± 0.5) and lighter δ13C ( 1.8‰ ± 0.8) values than bulk tropical carbonates. The bryozoa are in equilibrium with upwelling deep seawater and surface subantarctic water and therefore intersect seafloor diagenesis and upwelling water trend lines. Mol% MgCO 3 content ranges from 2 to 11 in calcite and corresponds to 5-14°C water temperatures. The δ18O values of bryozoa give a range of temperatures from 7° to 13°C, slightly less than the 4-15°C obtained from δ18O of Tasmanian brachiopods. This discrepancy is probably due to either minor biochemical fractionation or to bryozoa being in equilibrium with warmer waters.

  11. AMBIENT CARBONATION of MINING RESIDUES: Understanding the Mechanisms and Optimization of Direct Carbon Dioxide Mineral Sequestration

    NASA Astrophysics Data System (ADS)

    Assima, G. P.; Larachi, F.; Molson, J. W.; Beaudoin, G.

    2013-12-01

    The huge amounts (GTs) of ultramafic mining residues (UMRs) produced by mining activities around the world and accumulated in multi-square-kilometer stockpiles are stimulating a vivid interest regarding their possible use as a stable and permanent sink for CO2. Virtually costless and often found crushed and / or ground, UMRs are being considered as ideal candidates for atmospheric CO2 mitigation. The present work, therefore, explores the potential of several UMRs available in Quebec (Thetford Mines, Asbestos, Nunavik, Amos, Otish Mountains), for carbonation under ambient conditions, as a cost-effective alternative to remove low-concentration CO2 from the atmosphere and alleviate global warming. Several experimental reactors have been built to specifically simulate various climatic changes at the laboratory scale. The impact of various environmental conditions to which the residues are subjected to in their storage location, including temperature variations, precipitation, flooding, drought, changing water saturation, oxygen gradient and CO2 diffusion have been thoroughly studied. Dry and heavy-rain periods are unsuitable for efficient CO2 sequestration. Low liquid saturation within UMRs pores favors carbonation by combining fast percolation of gaseous CO2, rapid dissemination of CO2 dissolved species and creation of highly reactive sites throughout the mining residue pile. Partly saturated samples were also found to exhibit lower gaseous CO2 breakthrough times across the mining residues. Warm periods significantly accelerate the rate of CO2 uptake as compared to cold periods, which, in contrast are characterized by heat generation levels that could possibly be exploited by low temperature geothermal systems. A temperature rise from 10 to 40 °C was accompanied by a ten-fold increase in initial reaction rate. The carbonation reaction caused a rise in UMRs temperature up to 4.9°C during experiments at a 10°C. The presence of oxygen in the reaction medium induces

  12. Basalt-CO2-H2O Interactions and Variability in Carbonate Mineralization Rates

    SciTech Connect

    Schaef, Herbert T.; McGrail, B. Peter; Owen, Antionette T.

    2009-02-01

    Flood basalts are receiving increasing attention as possible host formations for geologic sequestration of anthropogenic CO2, with studies underway in the U.S., India, Iceland, and Canada. Our previous laboratory studies with Columbia River basalts showed relative quick precipitation of carbonate minerals compared to other siliclastic rocks when batch reacted with water and supercritical CO2. In this study, our prior work with Columbia River basalt was extended to tests with basalts from the eastern U.S., India, and Africa. The basalts are all similar in bulk chemistry and share common minerals such as plagioclase, augite, and a glassy mesostasis. Single pass flow through dissolution experiments under dilute solution and mildly acidic conditions indicate similar cation release behavior among the basalt samples tested. Despite similar bulk chemistry and apparent dissolution kinetics, long-term static experiments with CO2 saturated water show significant differences in rates of mineralization as well as precipitate chemistry and morphology. For example, basalt from the Newark Basin in the U.S. is by far the most reactive of any basalt tested to date. Carbonate reaction products for the Newark Basin basalt were globular in form and contained significantly more Fe than the secondary carbonates that precipitated on the other basalt samples. Calcite grains with classic “dogtooth spar” morphology and trace cation substitution (Mg and Mn) were observed in post-reacted samples associated with the Columbia River basalts. Other basalts produced solid precipitates with compositions that varied chemically throughout the entire testing period. Polished cross sections of the reacted grains show precipitate overgrowths with irregular regions outlined by dark and bright layers indicative of zonations of different compositions. For example, SEM-EDX analysis across carbonate precipitates, which resulted from 854 days of reaction of the Central Atlantic Mafic Province (CAMP

  13. The Impact of Mineral Dissolution on Multiphase Flow in Permeable Carbonates

    NASA Astrophysics Data System (ADS)

    Krevor, S. C.; Niu, B.

    2015-12-01

    Carbon dioxide injection into deep saline aquifers is governed by a number of physicochemical processes at a broad range of spatial scales including mineral dissolution and precipitation, fluid flow, and capillary trapping. Past efforts have mostly focused on measuring the multiphase flow properties, capillarity, relative permeability, and residual trapping. However, the impact of fluid-rock interaction on these properties is less well understood. In this work we have made a series of measurements characterizing the impact of rock mineral dissolution on multiphase flow in three carbonate rocks. We used core flooding techniques to mimic reactive conditions representative of the near the well bore and far field regions of a carbonate reservoir CO2 injection project. Tests sequentially induced mineral dissolution and characterized the impacts on multiphase flow properties. Temperature retarded acid was used to uniformly dissolve calcite in Ketton, Estaillades, and Edward Brown rock cores. A single dissolution stages removed approximately 0.5% of the mass of the rocks and measurements of relative permeability and residual trapping were made after each stage along with mercury injection capillary pressure (MICP) to quantify the variation of in the pore size distribution. Three Stages were performed on each of carbonates rocks. Imaging with x-ray micro-CT and medical CT were used to quantify the porosity variation and observe the changes in pore structure and multiphase flow properties at scales from the um to the cm. The pore size distribution of the rocks was observed to both increase and become less uniform with progressive dissolution, as shown in Figure 1. For Ketton, the micro-pores, with size range from 0.01 um to 0.1um, have less been involved in the reaction than the macro-pores (10 um to 100 um). A larger spread in capillary trapping was seen around a characteristic initial-residual curve. Relative permeability changes with progressive dissolution was not well

  14. Negative CO2 emissions via subsurface mineral carbonation in fractured peridotite

    NASA Astrophysics Data System (ADS)

    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 < 10 to 100 per ton CO2. As for other CCS methods, upscaling requires infrastructure resembling the 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

  15. Snow Impurities on Central Asian Glaciers: Mineral Dust, Organic & Elemental Carbon

    NASA Astrophysics Data System (ADS)

    Schmale, J.; Kang, S.; Peltier, R.; Sprenger, M.; Guo, J.; Li, Y.; Zhang, Q.

    2014-12-01

    In Central Asia, 90 % of the population depend on water stored in glaciers and mountain snow cover. Accelerated melting can be induced by the deposition of e.g., mineral dust and black carbon that reduce the surface albedo. Data on source regions and chemical characteristics of snow impurities are however scarce in Central Asia. We studied aerosol deposited between summers of 2012 and 2013on three different glaciers in the Kyrgyz Republic. Samples were taken from two snow pits on the glacier Abramov in the northern Pamir and from one snow pit on Ak-Shiirak and Suek in the central Tien Shan. The snow was analyzed for elemental and total organic carbon, major ions and mineral dust. In addition, dissolved organic carbon was speciated by using the Aerodyne high-resolution time-of-flight aerosol spectrometer. Elevated mineral dust concentrations were found on all glaciers during summer and winter with lower annual average concentrations (20 mg l-1)in the northern Pamir (factor 5 to 6). Correlations between dust tracers varied, indicating different source regions. Average EC concentrations showed seasonal variation in the northern Pamir (> 100 μg l-1 in summer, < 30 μg l-1 in winter) while there was little variation throughout the year in the central Tien Shan (~ 200 μg l-1). Similarly, OC:EC ratios showed no seasonal cycle in that region averaging around 3. On Abramov, the ratio was significantly higher in winter (> 12) than in summer (< 4). The average O:C ratios across all glaciers ranged between 0.65 and 1.09, indicating a high degree of oxygenation which suggests long-range transport of the organic snow impurities. Marker substances such as potassium and mercury and their correlations suggest contribution from biomass burning emissions. Atmospheric measurements in August 2013 were conducted to obtain information on background aerosol characteristics in the remote high mountain areas. The average black carbon concentration was 0.26 μg/m³ (± 0.24 μg/m³).

  16. Carbon and nitrogen pools and mineralization rates in boreal forest soil after stump harvesting

    NASA Astrophysics Data System (ADS)

    Kaarakka, Lilli; Hyvönen, Riitta; Strömgren, Monika; Palviainen, Marjo; Persson, Tryggve; Olsson, Bengt A.; Helmisaari, Heljä-Sisko

    2016-04-01

    The use of forest-derived biomass has steadily increased in the Finland and Sweden during the past decades. Thus, more intensive forest management practices are becoming more common in the region, such as whole-tree harvesting, both above- and belowground. Stump harvesting causes a direct removal of carbon (C) in the form of biomass from the stand and can cause extensive soil disturbance, which in turn can result in increased C mineralization. In this study, the effects of stump harvesting on soil C and nitrogen (N) mineralization, and soil surface disturbance were studied at two different clear-felled Norway spruce (Picea abies) stands in Central Finland. The treatments were conventional stem-only harvesting combined with mounding (WTH) and stump harvesting (i.e. complete tree harvesting) combined with mounding (WTH+S). Logging residues were removed from all study sites. Soil samples down to a depth of 20 cm were systematically collected from the different soil disturbance surfaces (undisturbed soil, the mounds and the pits) 12-13 years after final harvest. Soil samples were incubated in the laboratory to determine the C and N mineralization rates. In addition, total C and N pools were estimated for each disturbance class and soil layer. Soil C and N pools were lower following stump harvesting, however, no statistically significant treatment effect was detected. Instead, C mineralization responses to treatment intensity was site-specific. C/N-ratio and organic matter content were significantly affected by harvest intensity. The observed changes in C and N pools appear to be related to the intrinsic variation of the surface disturbance and soil characteristics, and harvesting per se, rather than treatment intensity. Long-term studies are however needed to draw long-term conclusions whether stump harvesting significantly changes soil C and nutrient dynamics.

  17. Low dissolved organic carbon input from fresh litter to deep mineral soils

    SciTech Connect

    Froeberg, Mats J; Jardine, Philip M; Hanson, Paul J; Swanston, Christopher; Todd Jr, Donald E; Phillips, Jana Randolph; Garten Jr, Charles T

    2007-01-01

    Dissolved organic carbon (DOC) leached from recent litter in the forest floor has been suggested to be an important source of C to the mineral soil of forest ecosystems. In order to determine the rate at which this flux of C occurs we have taken advantage of a local release of 14C at Oak Ridge National Laboratory Reservation, USA (latitude N 35 58'; longitude W 84 16'). Eight replicate 7x7 m plots were estab lished at four field sites on the reservation in an upland oak forest setting. Half of the plots were provided with 14C-enriched litter (∆14C ≈1000 ), and the other half with near-background litter (∆14C ≈220 ) over multiple years. Differences in the labeled leaf litter were used to quantify the movement of litter derived DOC through the soil profile. Soil solutions were collected over several years with tension lysimeters at 15 and 70 cm depth and measured for DOC concentration and 14C abundance. The net amount of DOC retained between 15 and 70 cm was 1.5-6 g m-2 y-1. There were significant effects of the litter additions on the 14C abundance in the DOC, but the net transport of 14C from the added litter was small. The difference in ∆14C between the treatments with enriched and near-background litter was only about 130 at both depths, which is small compared with the difference in Δ14C in the added litter. The primary source of DOC within the mineral soil must therefore have been either the Oe/Oa horizon or the organic matter in the mineral soil. Over a 2-year time frame, leaching of DOC from recent litter did not have a major impact on the C stock in the mineral soil below 15 cm in this ecosystem.

  18. Isotopic fractionation of Mg 2+(aq), Ca 2+(aq), and Fe 2+(aq) with carbonate minerals

    NASA Astrophysics Data System (ADS)

    Rustad, James R.; Casey, William H.; Yin, Qing-Zhu; Bylaska, Eric J.; Felmy, Andrew R.; Bogatko, Stuart A.; Jackson, Virgil E.; Dixon, David A.

    2010-11-01

    Density-functional electronic structure calculations are used to compute the equilibrium constants for 26Mg/ 24Mg and 44Ca/ 40Ca isotope exchange between carbonate minerals and uncomplexed divalent aquo ions. The most reliable calculations at the B3LYP/6-311++G(2d,2p) level predict equilibrium constants K, reported as 10 3ln ( K) at 25 °C, of -5.3, -1.1, and +1.2 for 26Mg/ 24Mg exchange between calcite (CaCO 3), magnesite (MgCO 3), and dolomite (Ca 0.5Mg 0.5CO 3), respectively, and Mg 2+(aq), with positive values indicating enrichment of the heavy isotope in the mineral phase. For 44Ca/ 40Ca exchange between calcite and Ca 2+(aq) at 25 °C, the calculations predict values of +1.5 for Ca 2+(aq) in 6-fold coordination and +4.1 for Ca 2+(aq) in 7-fold coordination. We find that the reduced partition function ratios can be reliably computed from systems as small as M(CO)610- and M(HO)62+ embedded in a set of fixed atoms representing the second-shell (and greater) coordination environment. We find that the aqueous cluster representing the aquo ion is much more sensitive to improvements in the basis set than the calculations on the mineral systems, and that fractionation factors should be computed using the best possible basis set for the aquo complex, even if the reduced partition function ratio calculated with the same basis set is not available for the mineral system. The new calculations show that the previous discrepancies between theory and experiment for Fe 3+-hematite and Fe 2+-siderite fractionations arise from an insufficiently accurate reduced partition function ratio for the Fe 3+(aq) and Fe 2+(aq) species.

  19. Isotopic Fractionation of Mg2+(aq), Ca2+(aq), and Fe2+(aq) with Carbonate Minerals

    SciTech Connect

    Rustad, James R.; Casey, William H.; Yin, Qing-Zhu; Bylaska, Eric J.; Felmy, Andrew R.; Bogatko, Stuart A.; Jackson, Virgil E.; Dixon, David A.

    2010-11-15

    Density functional electronic structure calculations are used to compute the equilibrium constant (the isotope fractionation factor) for 26Mg/24Mg and 44Ca/40Ca isotope exchange between carbonate minerals and uncomplexed divalent aquo ions. The most reliable calculations at the B3LYP/6-311++G(2d,2p) level predict equilibrium constants K, reported as 103ln(K) at 25 °C, of -5.3, -1.1, and +1.1 for 26Mg/24Mg exchange between calcite (CaCO3), magnesite (MgCO3), and dolomite (Ca0.5Mg0.5CO3), respectively, and Mg2+(aq), with positive values indicating enrichment in the mineral phase. For 44Ca/40Ca exchange between calcite and Ca2+(aq), the calculations predict values of +1.5 for Ca2+(aq) in six-fold coordination and +4.1 for Ca2+(aq) in seven-fold coordination. We find that the reduced partition function ratios can be reliably computed from systems as small as M(CO3)610- and M2+(H2O)6 embedded in a set of fixed atoms representing the 2nd shell (and greater) coordination environment. We find that the aqueous cluster representing the aquo ion is much more sensitive to improvements in the basis set than the calculations on the mineral systems, and that fractionation factors should be computed using 2 the best possible basis set for the aquo complex, even if the reduced partition function ratio calculated with the same basis set is not available for the mineral system. The new calculations show that the previous discrepancies between theory and experiment for Fe3+-hematite and Fe2+-siderite fractionations arise from an insufficiently accurate reduced partition function ratio for the Fe3+(aq) and Fe2+(aq) species.

  20. Earthworm species influence on carbon-mineral association in a sugar maple forest in northern Minnesota

    NASA Astrophysics Data System (ADS)

    Lyttle, A.; Yoo, K.; Aufdenkampe, A. K.; Hale, C. M.; Sebestyen, S. D.

    2011-12-01

    Non-native European earthworms are invading previously earthworm-free hardwood forests in the northern Great Lakes Region. Whereas earthworms' impacts on soil morphology and geochemical properties have been well documented in agricultural settings, the role of earthworms in biogeochemical cycles of undisturbed forests remains poorly understood. The forest soils that were recently invaded by exotic earthworms, therefore, provide a unique opportunity to understand how and how much earthworms contribute to biogeochemistry of non-agricultural environments. Increased degree and extent of soil mixing is one of the better known consequences of the earthworm invasion. Our hypothesis is that invasive earthworms positively affect carbon (C) stabilization by enhancing contacts between organic matter and minerals. We are studying C-mineral complexation along a well-established earthworm chronosequence in a sugar maple forest in northern Minnesota. We have observed changes in total earthworm biomass, A horizon C storage, and total specific surface area (SSA) of minerals as the invasion progresses. Because each earthworm species has different feeding and dwelling habits, biogeochemical imprints of the invasion reflect not only earthworms' biomass but also their species composition. All earthworm species show an increase in their biomass with greater time length since the invasion, though epigeic earthworms tend to be the pioneer species. As the total earthworm biomass increases, we find greater incorporation of organic C into the A horizon; the O horizon thickness decreases from 8 to 0 cm as the A horizon thickens from ~5 cm to ~12 cm. While leaf litter biomass is negatively correlated with total earthworm biomass, dramatic decreases in litter biomass are coupled with considerable increases in the biomass of epi-endogeic species. Despite the general decrease in C storage in the A horizon with greater degree of invasion, the storages fluctuate along the transect because

  1. Carbonation of Clay Minerals Exposed to scCO2/Water at 200 degrees and 250 degrees C

    SciTech Connect

    Sugama, T.; Ecker, L.; Gill, S.; Butcher, T.; Bour, D.

    2010-11-01

    To clarify the mechanisms of carbonation of clay minerals, such as bentonite, kaolinite, and soft clay, we exposed them to supercritical carbon dioxide (scCO2)/water at temperatures of 200 and 250 C and pressures of 1500 and 2000 psi for 72- and 107-hours. Bentonite, comprising three crystalline phases, montmorillonite (MMT), anorthoclase-type albite, and quartz was susceptible to reactions with ionic carbonic acid yielded by the interactions between scCO2 and water, particularly MMT and anorthoclase-type albite phases. For MMT, the cation-exchangeable ions, such as Na+ and Ca2+, present in its basal interplanar space, were replaced by proton, H+, from ionic carbonic acid; thereafter, the cations leaching from MMT directly reacted with CO32- as a counter ion of H+ to form carbonate compounds. Such in-situ carbonation process in basal space caused the shrinkage and breakage of the spacing structure within MMT. In contrast, the wet carbonation of anorthoclase-type albite, categorized as rock minerals, entailed the formation of three amorphous by-products, such as carbonates, kaolinite-like compounds, and silicon dioxide. Together, these two different carbonations caused the disintegration and corruption of bentonite. Kaolinite clay containing the amorphous carbonates and silicon dioxide was inert to wet carbonation. We noted only a gain in weight due to its water uptake, suggesting that kaolinite-like by-products generated by the wet carbonation of rock minerals might remain unchanged even during extended exposure. Soft clay consisting of two crystalline phases, dolomite and silicon dioxide, also was unaltered by wet carbonation, despite the uptake of water.

  2. Diffusion of helium in carbonates: Effects of mineral structure and composition

    NASA Astrophysics Data System (ADS)

    Cherniak, D. J.; Amidon, W.; Hobbs, D.; Watson, E. B.

    2015-09-01

    Diffusion of helium has been characterized in four carbonates: calcite, dolomite, magnesite, and aragonite. Cleaved or oriented and polished slabs of carbonate minerals were implanted with 100 keV or 3 MeV 3He at doses of 5 × 10153He/cm2 and 1 × 10163He/cm2, respectively, and annealed in 1-atm furnaces. 3He distributions following diffusion experiments were measured with nuclear reaction analysis using the reaction 3He(d,p)4He. Our results show that He diffusion in calcite is the fastest among the carbonates studied, with diffusivities progressively slower in magnesite, dolomite and aragonite. In the case of the isomorphic trigonal carbonates (calcite, dolomite, magnesite), these observations are broadly consistent with predictions based on lattice characteristics such as unit cell size and inter-atomic apertures, with diffusivities faster in more open carbonate structures. Dolomite is an exception to this trend, suggesting that its unique ordered R3 crystal structure may play a role in slowing helium diffusion. Diffusion is anisotropic in all of the trigonal carbonates, and is typically slowest for diffusion along the c direction, and faster for diffusion normal to c and in directions normal to cleavage surfaces. The patterns of diffusional anisotropy are predicted to first order by the size of limiting inter-atomic apertures along any given crystallographic direction, providing additional support to the concept of modeling crystal lattices as "molecular sieves" with regard to diffusion of helium. When the effects of anisotropy and diffusion domain size are considered, our results are in reasonable agreement with previous results from bulk degassing of natural samples. Modeling of helium diffusive loss shows that calcite and magnesite are unlikely to be retentive of helium on the Earth's surface for typical grain sizes and time/temperature conditions. Dolomite and aragonite may be retentive under cooler conditions, but because helium retention is strongly

  3. Mineral formation and organo-mineral controls on the bioavailability of carbon at the terrestrial-aquatic interface

    NASA Astrophysics Data System (ADS)

    Rod, K. A.; Smith, A. P.; Renslow, R.

    2016-12-01

    Recent evidence highlights the importance of organo-mineral interactions in regulating the source or sink capacity of soil. High surface area soils, such as allophane-rich or clay-rich soils, retain organic matter (OM) via sorption to mineral surfaces which can also contribute physical isolation in interlayer spaces. Despite the direct correlation between mineral surfaces and OM accumulation, the pedogenic processes controlling the abundance of reactive surface areas and their distribution in the mineral matrix remains unclear. As global soil temperatures rise, the dissolution of primary minerals and formation of new secondary minerals may be thermodynamically favored as part of soil weathering process. Newly formed minerals can supply surfaces for organo-metallic bonding and may, therefore, stabilize OM by surface bonding and physical exclusion. This is especially relevant in environments that intersect terrestrial and aquatic systems, such as the capillary fringe zone in riparian ecosystems. To test the mechanisms of mineral surface area protection of OM, we facilitated secondary precipitation of alumino-silicates in the presence of OM held at two different temperatures in natural Nisqually River sediments (Mt Rainier, WA). This was a three month reaction intended to simulate early pedogenesis. To tease out the influence of mineral surface area increase during pedogenesis, we incubated the sediments at two different soil moisture contents to induce biodegradation. We measured OM desorption, biodegradation, and the molecular composition of mineral-associated OM both prior to and following the temperature manipulation. To simulate the saturation of capillary fringe sediment and associated transport and reaction of OM, column experiments were conducted using the reacted sediments. More co-precipitation was observed in the 20°C solution compared to the 4°C reacted solution suggesting that warming trends alter mineral development and may remove more OM from solution

  4. Carbonate minerals in porous media decrease mobility of polyacrylic acid modified zero-valent iron nanoparticles used for groundwater remediation.

    PubMed

    Laumann, Susanne; Micić, Vesna; Lowry, Gregory V; Hofmann, Thilo

    2013-08-01

    The limited transport of nanoscale zero-valent iron (nZVI) in porous media is a major obstacle to its widespread application for in situ groundwater remediation. Previous studies on nZVI transport have mainly been carried out in quartz porous media. The effect of carbonate minerals, which often predominate in aquifers, has not been evaluated to date. This study assessed the influence of the carbonate minerals in porous media on the transport of polyacrylic acid modified nZVI (PAA-nZVI). Increasing the proportion of carbonate sand in the porous media resulted in less transport of PAA-nZVI. Predicted travel distances were reduced to a few centimeters in pure carbonate sand compared to approximately 1.6 m in quartz sand. Transport modeling showed that the attachment efficiency and deposition rate coefficient increased linearly with increasing proportion of carbonate sand. Copyright © 2013 Elsevier Ltd. All rights reserved.

  5. Carbon dioxide exchange of a perennial bioenergy crop cultivation on a mineral soil

    NASA Astrophysics Data System (ADS)

    Lind, Saara E.; Shurpali, Narasinha J.; Peltola, Olli; Mammarella, Ivan; Hyvönen, Niina; Maljanen, Marja; Räty, Mari; Virkajärvi, Perttu; Martikainen, Pertti J.

    2016-03-01

    One of the strategies to reduce carbon dioxide (CO2) emissions from the energy sector is to increase the use of renewable energy sources such as bioenergy crops. Bioenergy is not necessarily carbon neutral because of greenhouse gas (GHG) emissions during biomass production, field management and transportation. The present study focuses on the cultivation of reed canary grass (RCG, Phalaris arundinacea L.), a perennial bioenergy crop, on a mineral soil. To quantify the CO2 exchange of this RCG cultivation system, and to understand the key factors controlling its CO2 exchange, the net ecosystem CO2 exchange (NEE) was measured from July 2009 until the end of 2011 using the eddy covariance (EC) method. The RCG cultivation thrived well producing yields of 6200 and 6700 kg DW ha-1 in 2010 and 2011, respectively. Gross photosynthesis (GPP) was controlled mainly by radiation from June to September. Vapour pressure deficit (VPD), air temperature or soil moisture did not limit photosynthesis during the growing season. Total ecosystem respiration (TER) increased with soil temperature, green area index and GPP. Annual NEE was -262 and -256 g C m-2 in 2010 and 2011, respectively. Throughout the study period from July 2009 until the end of 2011, cumulative NEE was -575 g C m-2. Carbon balance and its regulatory factors were compared to the published results of a comparison site on drained organic soil cultivated with RCG in the same climate. On this mineral soil site, the RCG had higher capacity to take up CO2 from the atmosphere than on the comparison site.

  6. Mineral inclusions in sublithospheric diamonds from Juina, Brazil: Subducted protoliths, carbonated melts and protokimberlite magmatism

    NASA Astrophysics Data System (ADS)

    Walter, Michael; Bulanova, Galina; Smith, Chris; Armstrong, Lora; Kohn, Simon; Blundy, Jon; Gobbo, Luiz

    2010-05-01

    A suite of Type II Diamonds from the Cretaceous Collier 4 kimberlite pipe, Juina Kimberlite Field, Brazil, include syngenetic mineral inclusions comprising a remarkable range of compositions that include calcium- and titanium-rich perovskite, Ca-rich majoritic garnet, olivine, TAPP phase, CAS phase, K-hollandite phase, SiO2, FeO, native iron, low-Ni sulphides, and Ca-Mg carbonate. The diamonds also exhibit a range in carbon isotopic composition (δ13C ) that effectively spans that observed in the global diamond population. Diamonds with heavy, mantle-like δ13C (-5 to -10) contain mineral inclusions indicating a transition zone origin from mafic protoliths. Diamonds with intermediate δ13C (-12 to -15) contain inclusions with chemistry indicating crystallization from near-primary and differentiated carbonated melts derived from oceanic crust in the deep upper mantle or transition zone. Diamonds with extremely light δ13C (~ -25) host inclusions with chemistry akin to high pressure-temperature phases expected to form in the transition zone from subducted pelagic sediments. Collectively, the Collier 4 diamonds and their inclusions indicate multi-stage growth histories in dynamically changing chemical environments. A 206Pb/238U age of 101±7 Ma on a CaTiSi-perovskite inclusion is close to the kimberlite emplacement time (93.1 ±1.5 Ma). This young inclusion age, together with the chemical and isotopic characteristics indicating the role of subducted materials, suggest a model in which the generation of sublithospheric diamonds and their inclusions, and the proto-kimberlite magmas, are related genetically to the interaction of subducted lithosphere and a Cretaceous plume.

  7. Calculating carbon mass balance from unsaturated soil columns treated with CaSO₄₋minerals: test of soil carbon sequestration.

    PubMed

    Han, Young-Soo; Tokunaga, Tetsu K

    2014-12-01

    Renewed interest in managing C balance in soils is motivated by increasing atmospheric concentrations of CO2 and consequent climate change. Here, experiments were conducted in soil columns to determine C mass balances with and without addition of CaSO4-minerals (anhydrite and gypsum), which were hypothesized to promote soil organic carbon (SOC) retention and soil inorganic carbon (SIC) precipitation as calcite under slightly alkaline conditions. Changes in C contents in three phases (gas, liquid and solid) were measured in unsaturated soil columns tested for one year and comprehensive C mass balances were determined. The tested soil columns had no C inputs, and only C utilization by microbial activity and C transformations were assumed in the C chemistry. The measurements showed that changes in C inventories occurred through two processes, SOC loss and SIC gain. However, the measured SOC losses in the treated columns were lower than their corresponding control columns, indicating that the amendments promoted SOC retention. The SOC losses resulted mostly from microbial respiration and loss of CO2 to the atmosphere rather than from chemical leaching. Microbial oxidation of SOC appears to have been suppressed by increased Ca(2+) and SO4(2)(-) from dissolution of CaSO4 minerals. For the conditions tested, SIC accumulation per m(2) soil area under CaSO4-treatment ranged from 130 to 260 g C m(-1) infiltrated water (20-120 g C m(-1) infiltrated water as net C benefit). These results demonstrate the potential for increasing C sequestration in slightly alkaline soils via CaSO4-treatment. Copyright © 2014 Elsevier Ltd. All rights reserved.

  8. CO2-mineral Wettability and Implications for Understanding Leakage Processes from Geologic Carbon Sequestration Sites

    NASA Astrophysics Data System (ADS)

    Clarens, A. F.; Edwards, I.; Wang, S.

    2011-12-01

    In geological carbon sequestration (GCS), leakage events will be difficult to predict because parcels of CO2 will travel over long length scales and encounter a number of heterogeneous formations and endogenous brine in their rise to the surface. A constitutive model of a rising parcel of CO2 includes at least three main forces: 1) buoyant forces, 2) surface tension forces, and 3) shear drag forces. Of these, surface tension forces are of great significance, especially for predicting capillary and mineral trapping, and are affected by surface tension and the three-phase contact angle between CO2, brine, and the solid host mineral surfaces. Very limited experimental data on contact angles in GCS relevant systems has been reported in the academic literature. Here, the contact angle of several of the rock and clay species prevailing near GCS sites, e.g. quartz, feldspar, calcite, kaolinite, smectite and illite, were measured under a range of relevant temperature, pressure and ionic strength conditions. The measurements were made in a custom-built high-pressure view cell by introducing precisely controlled pendant CO2 droplets of constant volume to smooth and clean mineral surfaces after saturating the surrounding brine with CO2 and images were recorded using a high resolution digital camera. Images were processed and the contact angle measured using ImageJ software with a plug-in designed for this purpose. To measure the contact angle of CO2 on clay surfaces, ultra-pure microscope glass slides were coated with cleaned and particle-size-separated clay particles using hydrolyzed polyvinyl alcohol to ensure adhesion and a continuous coating on the surface. The uniform morphology of the surface was confirmed using electron microscopy. Preliminary results demonstrate differences in contact angle between the tested minerals, with calcite > quartz > feldspar. The absolute differences between the minerals were on the order of 3-7%. The

  9. Spectral reflectance of carbonate minerals and rocks in the visible and near infrared (0.35 - 2.55 microns) and its applications in carbonate petrology

    NASA Technical Reports Server (NTRS)

    Gaffey, S. J.

    1984-01-01

    Reflection spectroscopy in the visible and near infrared (0.35 to 2.55 micron) offers a rapid, inexpensive, nondestructive tool for determining the mineralogy and investigating the minor element chemistry of the hard-to-discriminate carbonate minerals, and can, in one step, provide information previously obtainable only by the combined application of two or more analytical techniques. When light interacts with a mineral certain wavelengths are preferentially absorbed. The number, positions, widths and relative intensities of these absorptions are diagnostic of the mineralogy and chemical composition of the sample. At least seven bands due to vibrations of the carbonate radical occur between 1.60 and 2.55 micron. Positions of these bands vary from one carbonae mineral to another and can be used for mineral identification. Cation mass is the primary factor controlling band position; cation radius plays a secondary role.

  10. Infrared and Raman spectroscopic characterization of the carbonate bearing silicate mineral aerinite - Implications for the molecular structure

    NASA Astrophysics Data System (ADS)

    Frost, Ray L.; Scholz, Ricardo; López, Andrés

    2015-10-01

    The mineral aerinite is an interesting mineral because it contains both silicate and carbonate units which is unusual. It is also a highly colored mineral being bright blue/purple. We have studied aerinite using a combination of techniques which included scanning electron microscopy, energy dispersive X-ray analysis, Raman and infrared spectroscopy. Raman bands at 1049 and 1072 cm-1 are assigned to the carbonate symmetric stretching mode. This observation supports the concept of the non-equivalence of the carbonate units in the structure of aerinite. Multiple infrared bands at 1354, 1390 and 1450 cm-1 supports this concept. Raman bands at 933 and 974 cm-1 are assigned to silicon-oxygen stretching vibrations. Multiple hydroxyl stretching and bending vibrations show that water is in different molecular environments in the aerinite structure.

  11. Carbon mineralization and soil fertility at high altitude grasslands in the Bolivian Andean

    NASA Astrophysics Data System (ADS)

    Zornoza, R.; Muñoz, M. A.; Faz, A.

    2012-04-01

    The high grasslands of Apolobamba provide a natural habitat for a high number of wild and domestic camelids such as vicuna (Vicugna vicugna) and alpaca (Lama pacos) in Bolivia. Because of the importance of the camelid raising for the Apolobambás inhabitant economy, it is fundamental to determine the natural resources condition and their availability for the camelid support. The soil organic matter plays a crucial role in the maintenance of the soil fertility at high grasslands. On the other hand, soil respiration is the primary pathway for CO2 fixed by plants returning to the atmosphere and its study is essential to evaluate the soil organic matter mineralization and the global C cycle. Based on this, the objectives of this research were to: (i) evaluate the soil fertility and (ii) determine soil organic matter mineralization on the basis of CO2 releases in Apolobamba. Regarding the lastly vicuna censuses carried out in the studied area, eight representative zones with dissimilar vicuna densities were selected. Other characteristics were also considered to select the study zones: (1) alpaca densities, (2) vegetation communities (3) plant cover and (4) landscape and geo-morphological description. Soil samples from different samplings were collected. Soil respiration was determined at two temperatures: 15 °C (based on the highest atmosphere temperature that was registered in the area) and 25 °C, in order to monitor the increase in soil respiration (Q10). The physico-chemical soil results pointed out the good soil fertility. However, erosive processes could be taken place likely caused by the alpaca grazing. High total organic carbon contents were observed corresponding to the highest soil respiration at 15 °C. This observation was supported by the relationship found between the total organic carbon and the soil respiration. A noticeable increase of the soil respiration when the temperature increased 10 °C was reported (from 1083 ± 47 g C m-2 yr-1 at 15 °C to

  12. [Impacts of Biochar Input on Mineralization of Native Soil Organic Carbon].

    PubMed

    Chen, Wei; Hu, Xue-yu; Lu, Hai-nan

    2015-06-01

    Since the biochar was applied in soil, its function in carbon sink had become a research hotspot recently. However, the present studies showed that its function in carbon sink remained controversial and the interaction between biochar and soil organic carbon remained to be investigated. So our study used paddy soil (C3 soil) as the experimental soil, and added washed (CS) or unwashed (CN) corn stalk (C4 crop). Biochar was mixed with soil uniformity by two kinds of weight, each treatment was 1% and 3% of the soil (CS1%, CS3% and CN1%, CN3%). Soil without biochar was used as the control treatment (CK), every treatments repeated three times. Then indoor culturing experiments was carried out to study the effect of biochar on the mineralization of organic carbon. The results showed as follows: (1) During the 180 days' experiment, the accumulated amount of released CO2 in CS1%, CS3% and CN1% groups were 1865.7, 1864.4 and 1856.2 mL x kg(-1) respectively, all were higher than the CK (1779.0 mL x kg(-1)). But the differences were not significant. However, the accumulated amount of released CO2 in the CN3% group was the highest (2289.1 mL x kg(-1)), which was significantly higher than those of all other groups. This showed that high addition of CS biochar significantly reduced the soil CO2 release. (2) The accumulated amount of released CO2 of native soil from the CK treatment, CS treatment and CN treatment were 1534.2, 1000.4 and 1153.7 mL x kg(-1) respectively, among which the CK group is significantly higher than the others. It showed that additions of two kinds of biochar both could inhibit the mineralization of organic carbon in the soil. The result of priming effect also proved that: the PE value of CS 3% group was -34.8%, and the PE value of CN 3% group was -24.8%. This showed that the negative priming effect significantly induced by washed (CS) biochar.

  13. Carbonate-hosted nonsulphide Zn-Pb mineralization of southern British Columbia, Canada

    NASA Astrophysics Data System (ADS)

    Paradis, Suzanne; Keevil, Halley; Simandl, George J.; Raudsepp, Mati

    2015-12-01

    Many carbonate-hosted sulphide deposits in the Salmo district of southern British Columbia have near-surface Zn- and Pb-bearing iron oxide-rich gossans. The gossans formed when carbonate-hosted, base metal sulphides were subjected to intense supergene weathering processes and metals were liberated by the oxidation of sulphide minerals. Two types of supergene carbonate-hosted nonsulphide deposits, direct replacement (`red ore') and wallrock replacement (`white ore'), are present in the Salmo district. The direct replacement deposits formed by the oxidation of primary sulphides; the base metals passed into solution and were redistributed and trapped within the space occupied by the oxidized portion of the sulphide protore. Depending on the extent of replacement of the sulphides by Zn-, Pb- and Fe-bearing oxides, silicates, carbonates and phosphates, the resulting ore can be called `mixed' (sulphides and nonsulphides) or simply `nonsulphide'. The wallrock replacement deposits formed when base metals liberated by the oxidation of sulphides were transported by circulating supergene solutions down and/or away from the sulphides to form wallrock replacement deposits. The direct replacement nonsulphide zones of the Salmo district overlay the sulphide bodies in which they replaced the sulphides and carbonates, forming large irregular replacement masses, encrustations and open-space fillings. They consist predominantly of hematite, goethite, hemimorphite [Zn4Si2O7(OH)2·H2O], minor hydrozincite [Zn5(CO3)2(OH)6], cerussite [PbCO3] and traces of willemite [Zn2SiO4]. The wallrock replacement zones consist mainly of hemimorphite with local occurrences of iron oxides, hopeite [Zn3(PO4)2·4H2O] and tarbuttite [Zn2(PO4)(OH)]. No remnants of sulphides were observed in the replacement zones. The Salmo nonsulphide deposits were formed by prolonged weathering of Mississippi Valley-type (MVT) mineralization that underwent dissolution and oxidation of the pyrite, sphalerite and galena

  14. Carbon mineralization in two ultisols amended with different sources and particle sizes of pyrolyzed biochar.

    PubMed

    Sigua, G C; Novak, J M; Watts, D W; Cantrell, K B; Shumaker, P D; Szögi, A A; Johnson, M G

    2014-05-01

    Biochar produced during pyrolysis has the potential to enhance soil fertility and reduce greenhouse gas emissions. The influence of biochar properties (e.g., particle size) on both short- and long-term carbon (C) mineralization of biochar remains unclear. There is minimal information on the potential effects of biochar particle sizes on their breakdowns by soil microorganism, so it is unknown if the particle size of biochar influences C mineralization rate and/or stability in soils. In order to evaluate the effect of different sources (BS) and particle sizes (BF) of biochar on C loss and/or stability in soils, an incubation study on C mineralization of different biochar sources and particle sizes was established using two soils (ST): Norfolk soil (fine loamy, kaolinitic, thermic, typic Kandiudults) and Coxville soil (fine loamy kaolinitic, thermic, Paleaquults). In separate incubation vessels, these soils were amended with one of two manure-based biochars (poultry litters, PL; swine solids, SS) or one of two lignocellulosic-based biochars (switchgrass, SG; pine chips, PC) which were processed into two particle sizes (dust, <0.42 mm; pellet, >2 mm). The amount of CO2 evolved varied significantly between soils (p≤0.0001); particle sizes (p≤0.0001) and the interactions of biochar source (p≤0.001) and forms of biochars (p≤0.0001) with soil types. Averaged across soils and sources of biochar, CO2-C evolved from dust-sized biochar (281 mg kg(-1)) was significantly higher than pellet-sized biochar (226 mg kg(-1)). Coxville soils with SS biochar produced the greatest average CO2-C of 428 mg kg(-1) and Norfolk soils with PC had the lowest CO2-C production (93 mg kg(-1)). Measured rates of carbon mineralization also varied with soils and sources of biochar (Norfolk: PL>SS>SG≥PC; Coxville: PC>SG>SS>PL). The average net CO2-C evolved from the Coxville soils (385 mg kg(-1)) was about threefold more than the CO2-C evolved from the Norfolk soils (123 mg kg(-1)). Our

  15. Single minerals, carbon- and ice-coated single minerals for calibration of GIADA onboard ROSETTA to comet 67P/Churyumov-Gerasimenko

    NASA Astrophysics Data System (ADS)

    Ferrari, Marco; Della Corte, Vincenzo; Rotundi, Alessandra; Rietmeijer, Frans J. M.

    2014-10-01

    In preparation of the rendezvous of the European Space Agency Rosetta spacecraft with short period Jupiter Family comet 67P/Churyumov-Gerasimenko we undertook the selection and characterization of mineral grains to serve as analogs of dust from the comet. Specifically, these dust analogs are used to calibrate the performance of the onboard Grain Impact Analyser and Dust Accumulator (GIADA) instrument at the comet. Our selection of suitable natural analog minerals was guided by the finding of an asteroid-like mineralogy in Jupiter Family comet Wild 2. We selected (1) anhydrous silicate minerals [forsterite and fayalite (end-members of the olivine solid solution series), enstatite, melilite, alkali-feldspar and anorthite], (2) hydrated layer silicates (kaolinite, serpentine, and talc), (3) pyrrhotite, and (4) corundum. Four size fractions, viz. 500-250 μm, 250-100 μm, 100-50 μm and 50-20 μm, were prepared for each analog mineral. In addition, each selected analog mineral, from each size bin, was coated with carbon layer. Similarly another set of analog grains were coated with a layer of sodium hexafluorosilicate (Na2SiF6) crystals representing comet water-ice, for what concerns their optical properties. Laboratory experiments to calibrate the GIADA performance using these analogs are currently underway. We report the availability of analogs that will enable the calibration of various instruments onboard Rosetta.

  16. Heterocystous Cyanobacteria in Microbialites Play an Important Role in N2 Fixation and Carbonate Mineral Precipitation

    NASA Astrophysics Data System (ADS)

    Alcantara-Hernandez, R. J.

    2015-12-01

    Lake Alchichica is a maars type crater-lake located in Central Mexico (pH > 8.9, EC ~13.39 mS cm-1). This limnological system harbors two types of microbialites that can be found around the entire perimeter of the lake (Fig. 1). These structures are representative examples of complex and diverse microbiological assemblages, where microbial activity promotes lithification by trapping, binding and/or precipitating detrital or chemical sediments. Previous studies determined that the microbialites of Lake Alchichica fix N2 to thrive under the N-limiting conditions of the lake, and that these nitrogenase activity peaks are related to heterocystous cyanobacteria that couple photosynthesis to N2 fixation during daylight periods. Heterocystous cyanobacteria (Nostocales) together with Oscillatoriales (non-heterocystous filamentous cyanobacteria) and other cyanobacterial groups have been described as the most abundant cyanobacteria in Alchichica microbialites, and in lithifying mats. Our results suggest that heterocystous cyanobacteria play an important role not only by fixing N2 for biomass construction, but also because their heterocysts host in their external cell membranes main sites for carbonate mineral precipitation including calcium carbonates and siderite. Previous research has shown that the heterocyst is the specialized site for cellular respiration associated to the pH decrease of vegetative/photosynthetic cells, contributing thus to the precipitation of carbonates and the accretion of the organosedimentary structure

  17. Minerals and clay minerals assemblages in organic-rich facies: the case study of the Sinemurian-Pliensbachian carbonate deposits of the western Lusitanian Basin (Portugal)

    NASA Astrophysics Data System (ADS)

    Caniço, Ana; Duarte, Luís V.; Silva, Ricardo L.; Rocha, Fernando; Graciano Mendonça Filho, João

    2015-04-01

    The uppermost Sinemurian-Pliensbachian series of the western part of the Lusitanian Basin is composed by hemipelagic carbonates particularly enriched in organic matter. Great part of this succession, considered to be one of the most important potential source rock intervals of Portugal, crops out in the S. Pedro de Moel and Peniche sectors, belonging to the Água de Madeiros and Vale das Fontes formations. In this study, supported by a detailed and integrated stratigraphic framework, we analyzed 98 marly samples (whole-rock mineralogy and clay minerals assemblages) from the aforementioned formations in the S. Pedro de Moel and Peniche sectors. X-ray Diffraction analysis followed the standard procedures and the semi-quantification of the different mineral phases was calculated using MacDiff 4.2.6. The goals of this work are to demonstrate the vertical variability of the mineral composition of these two units and investigate the relationship between the clay minerals assemblages and the content in organic matter (Total organic carbon: TOC). Besides the abundance of calcite and phyllosilicates, whole-rock mineralogy revealed the presence of quartz, potassium feldspar, dolomite, and pyrite (trace amounts). Other minerals like anhydrite, barite and gypsum occur sporadically. The clay minerals assemblages are dominated by illite+illite/smectite mixed-layers (minimum of 59%), always associated with kaolinite (maximum of 37%) and chlorite (maximum of 25%); sporadically smectite occurs in trace amounts. Generally, high TOC levels (i.e., black shale facies with TOC reaching up to 22 wt.% in both units, see Duarte et al., 2010), show a major increase in chlorite and kaolinite (lower values of illite+illite/smectite mixed layers). A kaolinite enrichment is also observed just above the Sinemurian-Pliensbachian boundary (base of Praia da Pedra Lisa Member of Água de Madeiros Formation; values varying between 30 and 37%). This event is associated with a second-order regressive

  18. Oxygen and carbon isotope ratios of hydrothermal minerals from Yellowstone drill cores

    NASA Astrophysics Data System (ADS)

    Sturchio, N. C.; Keith, T. E. C.; Muehlenbachs, K.

    1990-01-01

    Oxygen and carbon isotope ratios were measured for hydrothermal minerals (silica, clay and calcite) from fractures and vugs in altered rhyolite, located between 28 and 129 m below surface ( in situ temperatures ranging from 81 to 199°C) in Yellowstone drill holes. The purpose of this study was to investigate the mechanism of formation of these minerals. The δ 18O values of the thirty-two analyzed silica samples (quartz, chalcedony, α-cristobalite, and β-cristobalite) range from -7.5 to +2.8‰ . About one third of the silica 7samples have δ 18O values that are consistent with isotopic equilibrium with present thermal waters; most of the other silica samples appear to have precipitated from water enriched in 18O (up to 4.7‰) relative to present thermal water, assuming precipitation at present in situ temperatures. Available data on fluid-inclusion homogenization temperatures in hydrothermal quartz indicate that silica precipitation occurred mostly at temperatures above those measured during drilling and imply that 15O enrichments in water during silica precipitation were generally larger than those estimated from present conditions. Similarly, clay minerals (celadonite and smectite) have δ 18O values higher (by 3.5 to 7.9‰) than equilibrium values under present conditions. In contrast, all eight analyzed calcite samples are close to isotopic equilibrium with present thermal waters. The frequent incidence of apparent 18O enrichment in thermal water from which the hydrothermal minerals precipitated may indicate that a higher proportion of strongly 18O-enriched deep hydrothermal fluid once circulated through shallow portions of the Yellowstone system, or that a recurring transient 18O-enrichment effect occurs at shallow depths and is caused either by sudden decompressional boiling or by isotopic exchange at low water/rock ratios in new fractures. The mineralogy and apparent 18O enrichments of hydrothermal fracture-filling minerals are consistent with

  19. Zinc oxide nanoparticles affect carbon and nitrogen mineralization of Phoenix dactylifera leaf litter in a sandy soil.

    PubMed

    Rashid, Muhammad Imtiaz; Shahzad, Tanvir; Shahid, Muhammad; Ismail, Iqbal M I; Shah, Ghulam Mustafa; Almeelbi, Talal

    2017-02-15

    We investigated the impact of zinc oxide nanoparticles (ZnO NPs; 1000mgkg(-1) soil) on soil microbes and their associated soil functions such as date palm (Phoenix dactylifera) leaf litter (5gkg(-1) soil) carbon and nitrogen mineralization in mesocosms containing sandy soil. Nanoparticles application in litter-amended soil significantly decreased the cultivable heterotrophic bacterial and fungal colony forming units (cfu) compared to only litter-amended soil. The decrease in cfu could be related to lower microbial biomass carbon in nanoparticles-litter amended soil. Likewise, ZnO NPs also reduced CO2 emission by 10% in aforementioned treatment but this was higher than control (soil only). Labile Zn was only detected in the microbial biomass of nanoparticles-litter applied soil indicating that microorganisms consumed this element from freely available nutrients in the soil. In this treatment, dissolved organic carbon and mineral nitrogen were 25 and 34% lower respectively compared to litter-amended soil. Such toxic effects of nanoparticles on litter decomposition resulted in 130 and 122% lower carbon and nitrogen mineralization efficiency respectively. Hence, our results entail that ZnO NPs are toxic to soil microbes and affect their function i.e., carbon and nitrogen mineralization of applied litter thus confirming their toxicity to microbial associated soil functions. Copyright © 2016 Elsevier B.V. All rights reserved.

  20. Modulation of the initial mineralization process of SaOS-2 cells by carbonic anhydrase activators and polyphosphate.

    PubMed

    Wang, Xiaohong; Schröder, Heinz C; Schlossmacher, Ute; Neufurth, Meik; Feng, Qingling; Diehl-Seifert, Bärbel; Müller, Werner E G

    2014-05-01

    Ca-phosphate/hydroxyapatite (HA) crystals constitute the mineral matrix of vertebrate bones, while Ca-carbonate is the predominant mineral of many invertebrates, like mollusks. Recent results suggest that CaCO₃ is also synthesized during early bone formation. We demonstrate that carbonic anhydrase-driven CaCO₃ formation in vitro is activated by organic extracts from the demosponge Suberites domuncula as well as by quinolinic acid, one component isolated from these extracts. Further results revealed that the stimulatory effect of bicarbonate (HCO₃ (-)) ions on mineralization of osteoblast-like SaOS-2 cells is strongly enhanced if the cells are exposed to inorganic polyphosphate (polyP), a linear polymer of phosphate linked by energy-rich phosphodiester bonds. The effect of polyP, administered as polyP (Ca²⁺ salt), on HA formation was found to be amplified by addition of the carbonic anhydrase-activating sponge extract or quinolinic acid. Our results support the assumption that CaCO₃ deposits, acting as bio-seeds for Ca-carbonated phosphate formation, are formed as an intermediate during HA mineralization and that the carbonic anhydrase-mediated formation of those deposits is under a positive-negative feedback control by bone alkaline phosphatase-dependent polyP metabolism, offering new targets for therapy of bone diseases/defects.

  1. Biocompatibility and mineralization activity of fresh or set white mineral trioxide aggregate, biomimetic carbonated apatite, and synthetic hydroxyapatite.

    PubMed

    Danesh, Farzad; Tootian, Zahra; Jahanbani, Jahanfar; Rabiee, Mahmood; Fazelipour, Simin; Taghva, Orod; Shabaninia, Shahryar

    2010-06-01

    The purpose of this study was to evaluate the effect of apatite formation on tissue contact with white mineral trioxide aggregate (WMTA) and compare this apatite with a synthetic hydroxyapatite (SHAp) in subcutaneous connective tissue of rats. Thirty-three Wistar rats were used in this study. Polyethylene tubes filled with WMTA, apatite formed by WMTA (BCAp), and an SHAp along with empty tubes were implanted into dorsal connective tissue of rats for 15, 30, and 60 days. Set MTA covered with BCAp (set MTA/BCAp) was implanted as well. The specimens were stained with hematoxylin and eosin and von Kossa and evaluated for inflammatory reactions and mineralization through a light microscope. All groups evoked a moderate chronic inflammatory reaction at 15 days, which subsided with time. No statistically significant difference was found among the groups (p >.05). BCAp did not stimulate mineralization. WMTA, SHAp, and set MTA/BCAp induced significantly more dystrophic calcification than BCAp (p < .05). WMTA and set MTA/BCAp stimulated the same amount of calcification (p >.05). Our results suggested a possible role of apatite formation on the mineralization induction characteristics of WMTA, which indicated a definite effect on biocompatibility. BCAp produced by WMTA differed from SHAp in mineralization activity. Copyright 2010 American Association of Endodontists. Published by Elsevier Inc. All rights reserved.

  2. Early stages of carbonate mineralization revealed from molecular simulations: Implications for biomineral formation

    NASA Astrophysics Data System (ADS)

    Wallace, A. F.; DeYoreo, J.; Banfield, J. F.

    2011-12-01

    The carbonate mineral constituents of many biomineralized products, formed both in and ex vivo, grow by a multi-stage crystallization process that involves the nucleation and structural reorganization of transient amorphous phases. The existence of transient phases and cluster species has significant implications for carbonate nucleation and growth in natural and engineered environments, both modern and ancient. The structure of these intermediate phases remains elusive, as does the nature of the disorder to order transition, however, these process details may strongly influence the interpretation of elemental and isotopic climate proxy data obtained from authigenic and biogenic carbonates. While molecular simulations have been applied to certain aspects of crystal growth, studies of metal carbonate nucleation are strongly inhibited by the presence of kinetic traps that prevent adequate sampling of the potential landscape upon which the growing clusters reside within timescales accessible by simulation. This research addresses this challenge by marrying the recent Kawska-Zahn (KZ) approach to simulation of crystal nucleation and growth from solution with replica-exchange molecular dynamics (REMD) techniques. REMD has been used previously to enhance sampling of protein conformations that occupy energy wells that are separated by sizable thermodynamic and kinetic barriers, and is used here to probe the initial formation and onset of order within hydrated calcium and iron carbonate cluster species during nucleation. Results to date suggest that growing clusters initiate as short linear ion chains that evolve into two- and three-dimensional structures with continued growth. The planar structures exhibit an obvious 2d lattice, while establishment of a 3d lattice is hindered by incomplete ion desolvation. The formation of a dehydrated core consisting of a single carbonate ion is observed when the clusters are ~0.75 nm. At the same size a distorted, but discernible

  3. Vibrational spectra of the hydrated carbonate minerals ikaite, monohydrocalcite, lansfordite and nesquehonite.

    PubMed

    Coleyshaw, Esther E; Crump, Gregory; Griffith, William P

    2003-08-01

    The Raman (200-4000 cm(-1)) and infrared (600-4000 cm(-1)) spectra of four rare carbonate hydrate minerals are reported. These are naturally occurring and synthetic ikaite CaCO3.6H2O, and nesquehonite MgCO3.3H2O; natural monohydrocalcite CaCO3.H2O, and synthetic lansfordite MgCO3.5H2O. The spectra of synthetic ikaite partially substituted with 2H2O and also with 13C were measured, as were those of synthetic deuteriated nesquehonite. Spectra of ikaite and lansfordite, both of which decompose at room temperatures, were measured below 0 degrees C. Assignments of fundamental modes are proposed.

  4. Impact of black carbon in the extraction and mineralization of phenanthrene in soil.

    PubMed

    Rhodes, Angela H; Carlin, Alisdair; Semple, Kirk T

    2008-02-01

    During the past century, increased biomass burning and fossil fuel consumption have drastically increased the input of black carbon (BC) into the environment, and that has been shown to influence the behavior of organic contaminants in soil. A study was conducted to investigate the effects of BC on the relationship between aqueous hydroxypropyl-beta-cyclodextrin (HPCD) extraction and microbial mineralization (bioaccessibility) of 14C-phenanthrene (10 mg kg(-1)) in four soils amended with 0, 0.1, 0.5, 1, 2.5, and 5% (% dry wt soil) activated charcoal, a type of BC. Mineralisation was monitored over 20 d incubation, within respirometric assays, using an inoculum containing a phenanthrene-degrading pseudomonad and compared to HPCD extraction (24 h) using 50 mM aqueous solution; analyses were conducted after 1, 25, 50, and 100 d soil-phenanthrene contact time. Statistical analyses revealed that for each soil the addition of BC led to significant (P < 0.001) reductions in both HPCD extractability and microbial mineralization. Linear correlations for BC concentrations of 0% (r2 = 0.95; slope = 0.89) and 0.1% (r2 = 0.67; slope = 0.95) revealed a highly significant (P < 0.01) relationship between HPCD extractability and total mineralization (20 d), indicating a direct prediction of phenanthrene bioaccessibility by HPCD. However, in soils amended with 0.5, 1, 2.5, and 5% BC exhibited r2 values ranging 0.51-0.13 and slopes of 2.19-12.73. This study has shown that BC strongly sorbs phenanthrene causing reductions in extractability and, to a lesser extent, bioaccessibility to degrading microorganisms.

  5. Microbial carbon mineralization in tropical lowland and montane forest soils of Peru.

    PubMed

    Whitaker, Jeanette; Ostle, Nicholas; McNamara, Niall P; Nottingham, Andrew T; Stott, Andrew W; Bardgett, Richard D; Salinas, Norma; Ccahuana, Adan J Q; Meir, Patrick

    2014-01-01

    Climate change is affecting the amount and complexity of plant inputs to tropical forest soils. This is likely to influence the carbon (C) balance of these ecosystems by altering decomposition processes e.g., "positive priming effects" that accelerate soil organic matter mineralization. However, the mechanisms determining the magnitude of priming effects are poorly understood. We investigated potential mechanisms by adding (13)C labeled substrates, as surrogates of plant inputs, to soils from an elevation gradient of tropical lowland and montane forests. We hypothesized that priming effects would increase with elevation due to increasing microbial nitrogen limitation, and that microbial community composition would strongly influence the magnitude of priming effects. Quantifying the sources of respired C (substrate or soil organic matter) in response to substrate addition revealed no consistent patterns in priming effects with elevation. Instead we found that substrate quality (complexity and nitrogen content) was the dominant factor controlling priming effects. For example a nitrogenous substrate induced a large increase in soil organic matter mineralization whilst a complex C substrate caused negligible change. Differences in the functional capacity of specific microbial groups, rather than microbial community composition per se, were responsible for these substrate-driven differences in priming effects. Our findings suggest that the microbial pathways by which plant inputs and soil organic matter are mineralized are determined primarily by the quality of plant inputs and the functional capacity of microbial taxa, rather than the abiotic properties of the soil. Changes in the complexity and stoichiometry of plant inputs to soil in response to climate change may therefore be important in regulating soil C dynamics in tropical forest soils.

  6. Impact-Induced Shock-Stress Effects in Cometary Analogue Olivine, Pyroxene, Carbonate and Serpentine Minerals

    NASA Astrophysics Data System (ADS)

    Lederer, Susan M.; Jensen, Elizabeth A.; Fane, Michael; Strojia, Cierra; Smith, Douglas C.; Keller, Lindsay P.; Lindsay, Sean S.; Wooden, Diane H.; Cintala, Mark J.; Zolensky, Michael E.

    2014-11-01

    The primary goal of the Stardust mission was to collect dust particles as the spacecraft flew past Comet 81P/Wild 2. The morphologies of several returned grains of forsterite and enstatite suggest that they have experienced shock effects due to collisions (Jacobs et al. MAPS 44, 2009; Keller et al., GCA 72, 2008; Tomeoka et al, MAPS 43, 2008). Because the particles were collected at an encounter speed of ~6 km/s, it was natural to question whether the collection process itself generated those microstructural shock features or if they were sustained prior to their capture in the aerogel. Analyses of the grains suggest the latter, namely, that the particles had undergone high-velocity impacts sometime before their capture.With this in mind, unshocked minerals were impacted with the vertical gun in the NASA Johnson Space Center Experimental Impact Laboratory at 2.0 - 2.8 km/s, speeds that a typical comet might experience during its tenure in the Kuiper Belt (Stern 2002). Targets included minerals found in cometary dust and asteroids, including magnesium-rich pyroxenes (enstatite and diopside), magnesium-rich olivine (forsterite), carbonates (magnesite and siderite), and serpentine. Projectiles were Al2O3 spheres. Transmission electron microscope (TEM) imaging of experimentally shocked forsterite and enstatite samples reveal morphologies and densities of planar dislocations similar to those of the Stardust samples. Comparisons between TEM images of the Stardust grains and those of the experimentally shocked minerals will be presented.Funding was provided by the NASA PG&G grant 09-PGG09-0115, NSF grant AST-1010012, and a Cottrell College Scholarship through the Research Corporation. Special thanks to the NASA EIL staff, F. Cardenas and R. Montes.

  7. Microbial carbon mineralization in tropical lowland and montane forest soils of Peru

    PubMed Central

    Whitaker, Jeanette; Ostle, Nicholas; McNamara, Niall P.; Nottingham, Andrew T.; Stott, Andrew W.; Bardgett, Richard D.; Salinas, Norma; Ccahuana, Adan J. Q.; Meir, Patrick

    2014-01-01

    Climate change is affecting the amount and complexity of plant inputs to tropical forest soils. This is likely to influence the carbon (C) balance of these ecosystems by altering decomposition processes e.g., “positive priming effects” that accelerate soil organic matter mineralization. However, the mechanisms determining the magnitude of priming effects are poorly understood. We investigated potential mechanisms by adding 13C labeled substrates, as surrogates of plant inputs, to soils from an elevation gradient of tropical lowland and montane forests. We hypothesized that priming effects would increase with elevation due to increasing microbial nitrogen limitation, and that microbial community composition would strongly influence the magnitude of priming effects. Quantifying the sources of respired C (substrate or soil organic matter) in response to substrate addition revealed no consistent patterns in priming effects with elevation. Instead we found that substrate quality (complexity and nitrogen content) was the dominant factor controlling priming effects. For example a nitrogenous substrate induced a large increase in soil organic matter mineralization whilst a complex C substrate caused negligible change. Differences in the functional capacity of specific microbial groups, rather than microbial community composition per se, were responsible for these substrate-driven differences in priming effects. Our findings suggest that the microbial pathways by which plant inputs and soil organic matter are mineralized are determined primarily by the quality of plant inputs and the functional capacity of microbial taxa, rather than the abiotic properties of the soil. Changes in the complexity and stoichiometry of plant inputs to soil in response to climate change may therefore be important in regulating soil C dynamics in tropical forest soils. PMID:25566230

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

    SciTech Connect

    Brent Constantz; Randy Seeker; Martin Devenney

    2010-06-30

    Calera's innovative Mineralization via Aqueous Precipitation (MAP) technology for the capture and conversion of CO{sub 2} to useful materials for use in the built environment was further developed and proven in the Phase 1 Department of Energy Grant. The process was scaled to 300 gallon batch reactors and subsequently to Pilot Plant scale for the continuous production of product with the production of reactive calcium carbonate material that was evaluated as a supplementary cementitious material (SCM). The Calera SCM{trademark} was evaluated as a 20% replacement for ordinary portland cement and demonstrated to meet the industry specification ASTM 1157 which is a standard performance specification for hydraulic cement. The performance of the 20% replacement material was comparable to the 100% ordinary portland cement control in terms of compressive strength and workability as measured by a variety of ASTM standard tests. In addition to the performance metrics, detailed characterization of the Calera SCM was performed using advanced analytical techniques to better understand the material interaction with the phases of ordinary portland cement. X-ray synchrotron diffraction studies at the Advanced Photon Source in Argonne National Lab confirmed the presence of an amorphous phase(s) in addition to the crystalline calcium carbonate phases in the reactive carbonate material. The presence of carboaluminate phases as a result of the interaction of the reactive carbonate materials with ordinary portland cement was also confirmed. A Life Cycle Assessment was completed for several cases based on different Calera process configurations and compared against the life cycle of ordinary portland cement. In addition to the materials development efforts, the Calera technology for the production of product using an innovative building materials demonstration plant was developed beyond conceptual engineering to a detailed design with a construction schedule and cost estimate.

  9. Single-walled carbon nanotubes functionalized with sodium hyaluronate enhance bone mineralization

    PubMed Central

    Sá, M.A.; Ribeiro, H.J.; Valverde, T.M.; Sousa, B.R.; Martins-Júnior, P.A.; Mendes, R.M.; Ladeira, L.O.; Resende, R.R.; Kitten, G.T.; Ferreira, A.J.

    2015-01-01

    The aim of this study was to evaluate the effects of sodium hyaluronate (HY), single-walled carbon nanotubes (SWCNTs) and HY-functionalized SWCNTs (HY-SWCNTs) on the behavior of primary osteoblasts, as well as to investigate the deposition of inorganic crystals on titanium surfaces coated with these biocomposites. Primary osteoblasts were obtained from the calvarial bones of male newborn Wistar rats (5 rats for each cell extraction). We assessed cell viability using the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl-2H-tetrazolium bromide assay and by double-staining with propidium iodide and Hoechst. We also assessed the formation of mineralized bone nodules by von Kossa staining, the mRNA expression of bone repair proteins, and the deposition of inorganic crystals on titanium surfaces coated with HY, SWCNTs, or HY-SWCNTs. The results showed that treatment with these biocomposites did not alter the viability of primary osteoblasts. Furthermore, deposition of mineralized bone nodules was significantly increased by cells treated with HY and HY-SWCNTs. This can be partly explained by an increase in the mRNA expression of type I and III collagen, osteocalcin, and bone morphogenetic proteins 2 and 4. Additionally, the titanium surface treated with HY-SWCNTs showed a significant increase in the deposition of inorganic crystals. Thus, our data indicate that HY, SWCNTs, and HY-SWCNTs are potentially useful for the development of new strategies for bone tissue engineering. PMID:26648087

  10. Redistribution of soil water by a saprotrophic fungus enhances carbon mineralization.

    PubMed

    Guhr, Alexander; Borken, Werner; Spohn, Marie; Matzner, Egbert

    2015-11-24

    The desiccation of upper soil horizons is a common phenomenon, leading to a decrease in soil microbial activity and mineralization. Recent studies have shown that fungal communities and fungal-based food webs are less sensitive and better adapted to soil desiccation than bacterial-based food webs. One reason for a better fungal adaptation to soil desiccation may be hydraulic redistribution of water by mycelia networks. Here we show that a saprotrophic fungus (Agaricus bisporus) redistributes water from moist (-0.03 MPa) into dry (-9.5 MPa) soil at about 0.3 cm ⋅ min(-1) in single hyphae, resulting in an increase in soil water potential after 72 h. The increase in soil moisture by hydraulic redistribution significantly enhanced carbon mineralization by 2,800% and enzymatic activity by 250-350% in the previously dry soil compartment within 168 h. Our results demonstrate that hydraulic redistribution can partly compensate water deficiency if water is available in other zones of the mycelia network. Hydraulic redistribution is likely one of the mechanisms behind higher drought resistance of soil fungi compared with bacteria. Moreover, hydraulic redistribution by saprotrophic fungi is an underrated pathway of water transport in soils and may lead to a transfer of water to zones of high fungal activity.

  11. The role of ocean acidification in systemic carbonate mineral suppression in the Bering Sea

    NASA Astrophysics Data System (ADS)

    Mathis, Jeremy T.; Cross, Jessica N.; Bates, Nicholas R.

    2011-10-01

    Ocean acidification driven by absorption of anthropogenic carbon dioxide (CO2) from the atmosphere is now recognized as a systemic, global process that could threaten diverse marine ecosystems and a number of commercially important species. The change in calcium carbonate (CaCO3) mineral saturation states (Ω) brought on by the reduction of seawater pH is most pronounced in high latitude regions where unique biogeochemical processes create an environment more susceptible to the suppression of Ω values for aragonite and calcite, which are critical to shell building organisms. New observations from the eastern Bering Sea shelf show that remineralization of organic matter exported from surface waters rapidly increases bottom water CO2 concentrations over the shelf in summer and fall, suppressing Ω values. The removal of CO2 from surface waters by high rates of phytoplankton primary production increases Ω values between spring and summer, but these increases are partly counteracted by mixing with sea ice melt water and terrestrial river runoff that have low Ω values. While these environmental processes play an important role in creating seasonally low saturation states, ocean uptake of anthropogenic CO2 has shifted Ω values for aragonite to below the saturation horizon in broad regions across the shelf for at least several months each year. Furthermore, we also report that calcite became undersaturated in September of 2009 in the bottom waters over the shelf. The reduction in CaCO3 mineral saturation states could have profound implications for several keystone calcifying species in the Bering Sea, particularly the commercially important crab fisheries.

  12. Metal immobilization by sludge-derived biochar: roles of mineral oxides and carbonized organic compartment.

    PubMed

    Zhang, Weihua; Huang, Xinchen; Jia, Yanming; Rees, Frederic; Tsang, Daniel C W; Qiu, Rongliang; Wang, Hong

    2017-04-01

    Pyrolyzing sludge into biochar is a potentially promising recycling/disposal solution for municipal wastewater sludge, and the sludge-derived biochar (SDBC) presents an excellent sorbent for metal immobilization. As SDBC is composed of both mineral oxides and carbonized organic compartment, this study therefore compared the sorption behaviour of Pb and Zn on SDBC to those of individual and mixture of activated carbon (AC) and amorphous aluminium oxide (Al2O3). Batch experiments were conducted at 25 and 45 °C, and the metal-loaded sorbents were artificially aged in the atmosphere for 1-60 days followed by additional sorption experiments. The Pb sorption was generally higher than Zn sorption, and the co-presence of Pb reduced Zn sorption on each studied sorbent. Higher sorption capacities were observed at 45 °C than 25 °C for SDBC and AC, while the opposite was shown for Al2O3, indicating the significance of temperature-dependent diffusion processes in SDBC and AC. Nevertheless, metal sorption was more selective on Al2O3 that showed a greater affinity towards Pb over Zn under competition, correlating with the reducible fraction of sequential extraction. Furthermore, significant amounts of Pb and Zn were additionally sorbed on SDBC following 30-day ageing. The X-ray diffraction revealed the formation of metal-phosphate precipitates, while the X-ray photoelectron spectroscopy showed a larger quantity of metal-oxygen bonding after 30-day ageing of metal-loaded SDBC. The results may imply favourable long-term transformation and additional sorption capacity of SDBC. In conclusion, SDBC resembles the sorption characteristics of both organic and mineral sorbents in different aspects, presenting an appropriate material for metal immobilization during soil amendment.

  13. Concentration effect on equilibrium fractionation of Mg-Ca isotopes in carbonate minerals: Insights from first-principles calculations

    NASA Astrophysics Data System (ADS)

    Wang, Wenzhong; Qin, Tian; Zhou, Chen; Huang, Shichun; Wu, Zhongqing; Huang, Fang

    2017-07-01

    Naturally occurring carbonates have a wide variation in Mg and Ca contents. Using the density-functional-theory calculations, this study examines the effect of Mg and Ca concentrations on bond lengths and equilibrium fractionation factors of Mg-Ca isotopes among calcite-type carbonate minerals (MgxCa1-xCO3). Mg content x and Ca content (1-x) of the investigated carbonate minerals range from 1/12 to 1 and from 1/36 to 1, respectively. Concentration of Ca and Mg in carbonates have significant effects on Ca-O and Mg-O bond lengths when x is close to 0, 0.5 or 1. Because equilibrium isotope fractionation factors (103lnα) are mainly controlled by their relevant bond strengths, which can be measured using their average bond lengths, 103lnα of 26Mg/24Mg and 44Ca/40Ca between calcite-type carbonate minerals and dolomite also vary dramatically with Mg content, especially when x is close to 0 and 1. For instance, at 300 K, 103lnα of 26Mg/24Mg between Mg1/12Ca11/12CO3 and dolomite (x = 0.5) is ∼-4.3‰, while 103lnα of 44Ca/40Ca between Mg23/24Ca1/24CO3 and dolomite is ∼6‰. Dolomite is enriched in 26Mg but depleted in 44Ca relative to all other carbonate minerals, which is consistent with it having the shortest Mg-O bond length and the longest Ca-O bond lengths among all carbonates. At 300 K, a small change of x from 0.5 to 0.6 in dolomite could result in 1‰ variation in 103lnβ of 26Mg/24Mg. Therefore, the concentration effect in carbonate minerals should be taken into account when applying the isotope fractionation factors of carbonate minerals to understand geochemical processes.

  14. Mesocosm-Scale Experimental Quantification of Plant-Fungi Associations on Carbon Fluxes and Mineral Weathering

    NASA Astrophysics Data System (ADS)

    Andrews, M. Y.; Palmer, B.; Leake, J. R.; Banwart, S. A.; Beerling, D. J.

    2009-12-01

    The rise of land plants in the Paleozoic is classically implicated as driving lower atmospheric CO2 levels through enhanced weathering of Ca and Mg bearing silicate minerals. However, this view overlooks the fact that plants coevolved with associated mycorrhizal fungi over this time, with many of the weathering processes usually ascribed to plants actually being driven by the combined activities of roots and mycorrhizal fungi. Here we present initial results from a novel mesocosm-scale laboratory experiment designed to allow investigation of plant-driven carbon flux and mineral weathering at different soil depths under ambient (400 ppm) and elevated (1500 ppm) atmospheric CO2. Four species of plants were chosen to address evolutionary trends in symbiotic mycorrhizal association and rooting depth on biologically driven silicate weathering under the different CO2 regimes. Gymnosperms were used to investigate potential differences in weathering capabilities of two fungal symbioses: Sequoia sempervirens and Metasequoia glyptostroboides (arbuscular mycorrhizal, AM) and Pinus sylvestris (ectomycorrhizal, EM), and the shallow rooted ancient fern, Osmunda regalis, used to provide a contrast to the three more deeply rooted trees. Plants were grown in a cylindrical mesocosm with four horizontal inserts at each depth. These inserts are a mesh-covered dual-core unit whereby an inner core containing silicate minerals can be rotated within an outer core. The mesh excludes roots from the cylinders allowing fungal-rock pairings to be examined at each depth. Each core contains either basalt or granite, each with severed (rotated cores) or intact (static cores) mycorrhizae. This system provides a unique opportunity to examine the ability of a plant to weather minerals with and without its symbiotic fungi. Preliminary results indicate marked differences in nutritional and water requirements, and response to elevated CO2 between the species. The bulk solution chemistries (p

  15. Reducing conditions can alter the source of respired carbon and stimulate decomposition in mineral soils

    NASA Astrophysics Data System (ADS)

    Huang, W.; Hall, S. J.

    2016-12-01

    Soil organic matter decomposition is widely thought to be constrained by reducing conditions in flooded wetland ecosystems. However, the potential impact of periodic reducing conditions on carbon (C) mineralization in terrestrial mineral soils that experience transient moisture saturation has received less attention. Here we incubated three Mollisols amended with C4 leaf litter at three different soil moisture levels (field capacity for the control, intermediate, and saturation) over three months in the laboratory. Soil CO2 and CH4 production and isotope ratios of CO2 (δ13CO2) were measured daily using a tunable diode laser for the first two weeks and weekly thereafter. Soil Eh dropped from 516 mV to -184 mV in the intermediate and saturated soils during the first seventeen days; iron (Fe) reduction occurred in both intermediate and saturated soils after the seventh day. Total CO2 production rate in the intermediate and saturated soils was initially lower than the control, but exceeded the control after the eleventh day. After three months, mean cumulative CO2 production was significantly higher in the intermediate soil moisture treatment (152 μmol CO2 g-1 soil, P < 0.01) and equivalent between the saturated and control soils (128 and 141 μmol CO2 g-1 soil, P = 0.11). The intermediate and saturated soils also induced substantial CH4 production. Differences in mean δ13CO2 (-14.0‰ for the control and -22.7‰ for the saturated soils) over the first two weeks (before CH4 production began) showed that CO2 production from the saturated soils was derived from different C source(s) compared to the control. These findings challenge traditional paradigms by showing that reducing conditions can enhance C mineralization, perhaps by facilitating microbial access to alternative or occluded C sources. We suggest that Fe reduction could be an important mechanism of C loss in mineral soils due to the release of adsorbed or co-precipitated organic matter during Fe

  16. CO2-brine-mineral Reactions in Geological Carbon Storage: Results from an EOR Experiment

    NASA Astrophysics Data System (ADS)

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

    2012-04-01

    Dissolution of CO2 in brines and reactions of the acid brines ultimately dissolving silicate minerals and precipitating carbonate minerals are the prime long-term mechanisms for stabilising the light supercritical CO2 in geological carbon storage. However the rates of dissolution are very uncertain as they are likely to depend on the heterogeneity of the flow of CO2, the possibility of convective instability of the denser CO2-saturated brines and on fluid-mineral reactions which buffer brine acidity. We report the results of sampling brines and gases during a phase of CO2 injection for enhanced oil recovery in a small oil field. Brines and gases were sampled at production wells daily for 3 months after initiation of CO2 injection and again for two weeks after 5 months. Noble gas isotopic spikes were detected at producing wells within days of initial CO2 injection but signals continued for weeks, and at some producers for the duration of the sampling period, attesting to the complexity of gas-species pathways. Interpretations are complicated by the previous history of the oil field and re-injection of produced water prior to injection of CO2. However water sampled from some producing wells during the phase of CO2 injection showed monotonic increases in alkalinity and in concentrations of major cations to levels in excess of those in the injected water. The marked increase in Na, and smaller increases in Ca, Mg, Si, K and Sr are interpreted primarily to result from silicate dissolution as the lack of increase in S and Cl concentrations preclude additions of more saline waters. Early calcite dissolution was followed by re-precipitation. 87Sr/86Sr ratios in the waters apparently exceed the 87Sr/86Sr ratios of acetic and hydrochloric acid leaches of carbonate fractions of the reservoir rocks and the silicate residues from the leaching. This may indicate incongruent dissolution of Sr or larger scale isotopic heterogeneity of the reservoir. This is being investigated

  17. Metagenomes from Thawing Low-Soil-Organic-Carbon Mineral Cryosols and Permafrost of the Canadian High Arctic

    PubMed Central

    Chauhan, Archana; Layton, Alice C.; Vishnivetskaya, Tatiana A.; Williams, Daniel; Pfiffner, Susan M.; Rekepalli, Bhanu; Stackhouse, Brandon; Lau, Maggie C. Y.; Phelps, Tommy J.; Mykytczuk, Nadia; Ronholm, Jennifer; Whyte, Lyle; Onstott, Tullis C.

    2014-01-01

    Microbial release of greenhouse gases from thawing permafrost is a global concern. Seventy-six metagenomes were generated from low-soil-organic-carbon mineral cryosols from Axel Heiberg Island, Nunavut, Canada, during a controlled thawing experiment. Permafrost thawing resulted in an increase in anaerobic fermenters and sulfate-reducing bacteria but not methanogens. PMID:25414511

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

    SciTech Connect

    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.

  19. Geochemistry of metastable carbonate minerals from the Brush Creek marine interval (Missourian), Indiana County, Pennsylvania

    SciTech Connect

    Cercone, K.R.; Kime, A.; Mutchler, S.; Rittle, K. )

    1991-08-01

    Many marine fossils from the Missourian Brush Creek interval of western Pennsylvania display partial preservation of metastable aragonite and high-magnesium calcite shell material. Bivalve mollusks have been shown by x-ray diffraction to contain as much as 96% aragonite, with lesser amounts of both high-magnesium and low-magnesium calcite. Stable carbon and oxygen isotopic ratios from these bivalves suggest they precipitated in equilibrium with Pennsylvanian ocean water. The bellerophontid Pharkidonotus, which exhibits partial recrystallization textures under scanning electron microscopy, consists of 45% aragonite and 55% low-magnesium calcite, and has slightly more depleted isotopic values than bivalves. Crinoids also appear to have been partially recrystallized, resulting in a mixture of primary high-magnesium calcite and secondary low-magnesium calcite and microdolomite, with much of the original shell structure still preserved. The degree of preservation of metastable carbonate minerals varies both stratigraphically and spatially within the Brush Creek interval. Maximum preservation occurs in organic-rich shales deposited in low-lying areas of the Brush Creek sea floor. The preservation of aragonite and high-magnesium calcite in such units may have resulted from a lack of circulating porewater during early diagenesis.

  20. Effects of platinum from vehicle exhaust catalyst on carbon and nitrogen mineralization in soils.

    PubMed

    Kalbitz, Karsten; Schwesig, David; Wang, Wenxia

    2008-11-01

    There is strong evidence of continuously increasing contamination of soils with platinum group elements (PGE), in particular with platinum (Pt) from vehicle exhaust catalysts in roadside soils. However, knowledge about the effects of Pt contamination on soil processes is very limited. The objective of this study was to investigate whether the contamination of soils with Pt at realistic environmental levels leads to observable adverse effects on selected indicator parameters of the carbon and nitrogen turnover in soils. Incubation experiments with artificially contaminated soils and solutions containing dissolved organic matter (DOM) were carried out by the use of milled material from a Pt-containing vehicle exhaust catalyst. Interaction of the catalyst material with the soil resulted in a mobilization of Pt into the dissolved phase reaching up to 0.1% of the added Pt. The amount of Pt mobilization seemed to be mainly driven by the pH of the soil. Mineralization of carbon and nitrogen did not reveal any significant adverse effect of the Pt addition as compared to the control samples. Future studies dealing with Pt effects on soil processes should focus on environmental conditions favoring Pt mobilization, e.g. such as very low pH values or large concentrations of DOM.

  1. In vitro formation of Ca-oxalates and the mineral glushinskite by fungal interaction with carbonate substrates and seawater

    NASA Astrophysics Data System (ADS)

    Kolo, K.; Claeys, Ph.

    2005-04-01

    This study investigates the in vitro formation of Ca-oxalates and glushinskite through fungal interaction with carbonate substrates and seawater. In the first experiment, thin-sections prepared from dolomitic rock samples of Terwagne Formation (Carboniferous, Viséan, northern France) served as substrates. The thin sections placed in Petri dishes were exposed to fungi grown from naturally existing airborne spores. In the second experiment, fungal growth and mineral formation was monitored using only standard seawater (SSW) as substrate. Fungal growth media consisted of a high protein/carbohydrates and sugar diet with demineralised water for irrigation. Fungal growth process reached completion under uncontrolled laboratory conditions. The fungal interaction and attack on the carbonate substrates resulted in the formation of Ca-oxalates (weddellite CaC2O4·2(H2O), whewellite (CaC2O4·(H2O)) and glushinskite MgC2O4·2(H2O) associated with the destruction of the original substrate and its replacement by the new minerals. The seawater substrate resulted also in the formation of glushinskite and Ca-oxalates. Both of Ca and Mg were mobilized from the experimental substrates by fungi. The newly formed minerals and textural changes caused by fungal attack on the carbonate substrate were investigated using light and scanning electron microscopy (SEM-EDX), x-ray diffraction (XRD) and Raman spectroscopy. The results document the role of microorganisms in biomineralization, neo-mineral formation and sediment diagenesis. They also reveal the capacity of living fungi to interact with liquid substrates and precipitate new minerals. This work is the first report on the in vitro formation of the mineral glushinskite through fungal-carbonate and sea water substrates interactions processes.

  2. Incorporation of Np(V) and U(VI) in Carbonate and Sulfate Minerals Crystallized from Aqueous Solution

    SciTech Connect

    Balboni, Enrica; Morrison, Jessica M.; Wang, Zheming; Engelhard, Mark H.; Burns, Peter C.

    2015-02-15

    The neptunyl Np(V)O2 + and uranyl U(VI)O2 2+ ions are soluble in groundwater, although their interaction with minerals in the subsurface may impact their mobility. One mechanism for the immobilization of actinyl ions in the subsurface is coprecipitation in low-temperature minerals that form naturally, or that are induced to form as part of a remediation strategy. Important differences in the crystal-chemical behavior of the Np(V) neptunyl and U(VI) uranyl ions suggest their behavior towards incorporation into growing crystals may differ significantly. Using a selection of low temperature minerals synthesized in aqueous systems under ambient conditions, this study examines the factors that impact the structural incorporation of the Np(V) neptunyl and U(VI) uranyl ions in carbonate and sulfate minerals.

  3. Toward a parameterization of global-scale organic carbon mineralization kinetics in surface marine sediments

    NASA Astrophysics Data System (ADS)

    Stolpovsky, K.; Dale, A. W.; Wallmann, K.

    2015-06-01

    An empirical function is derived for predicting the rate-depth profile of particulate organic carbon (POC) degradation in surface marine sediments including the bioturbated layer. The rate takes the form of a power law analogous to the Middelburg function. The functional parameters were optimized by simulating measured benthic O2 and NO3- fluxes at 185 stations worldwide using a diagenetic model. The novelty of this work rests with the finding that the vertically resolved POC degradation rate in the bioturbated zone can be determined using a simple function where the POC rain rate is the governing variable. Although imperfect, the model is able to fit 71% of paired O2 and NO3- fluxes to within 50% of measured values. It further provides realistic geochemical concentration-depth profiles, NO3- penetration depths, and apparent first-order POC mineralization rate constants. The model performs less well on the continental shelf due to the high sediment heterogeneity there. When applied to globally resolved maps of rain rate, the model predicts a global denitrification rate of 182 ± 88 Tg yr-1 of N and a POC burial rate of 107 ± 52 Tg yr-1 of C with a mean carbon burial efficiency of 6.1%. These results are in very good agreement with published values. Our proposed function is conceptually simple, requires less parameterization than multi-G-type models, and is suitable for nonsteady state applications. It provides a basis for more accurately simulating benthic nutrient fluxes and carbonate dissolution rates in Earth system models.

  4. Stable isotopes of carbon dioxide in soil gas over massive sulfide mineralization at Crandon, Wisconsin

    USGS Publications Warehouse

    Alpers, C.N.; Dettman, D.L.; Lohmann, K.C.; Brabec, D.

    1990-01-01

    rule out the possible mechanism of carbonate dissolution driven by pyrite oxidation, as proposed by Lovell et al. (1983) and McCarthy et al. (1986). Further work is needed on seasonal and daily variations of CO2 concentrations and stable isotope ratios in various hydrogeologic and ecologic settings so that more effective sampling strategies can be developed for mineral exploration using soil gases. ?? 1990.

  5. Chemical Interaction of Mg-CARBONATE and the Earth's Lower Mantle Minerals

    NASA Astrophysics Data System (ADS)

    Spivak, Anna; Solopova, Natalia; Litvin, Yuriy; Dubrovinsky, Leonid

    2013-04-01

    Diamonds of lower mantle origin are rare but important guests at Earth surface currying crucial information about deep interiors. Apart minerals expected to be similar in Earth lower mantle (particularly Mg-Fe-Al silicates and MgO-FeO oxides) ultra-deep diamonds contain primary inclusions of carbonates indicating that they are presented in the Earth lower mantle. Carbonates of magnesium, calcium, iron and sodium are stable at wide pressure-temperature conditions close to the geotherm. We studied interaction of Mg-carbonates with ferropericlase, perovskite employing laser-heated diamond anvil cell (DAC) at pressures up to 60 GPa and temperatures over 3000 K. Melting of Mg-carbonate is determined as congruent under PT-conditions of the lower mantle. The MgCO3 melts are stable in an expanded high-pressure high-temperature field. We observed formation of diamond at 18 and 40 GPa as a result of decomposition of MgCO3 melt at temperatures above 3500 K on the high-temperature boundary of the field. Melting reactions of the MgCO3-(Mg,Fe)O system were studied in the 30-63 GPa range at high temperatures up to 3600 K. It was found that decomposition boundary of MgCO3-(Mg,Fe)O melt is close to the pure MgCO3 decomposition one within ± 150 K (accuracy of DAC experiment). Preliminary data shows that perovskite -(Mg,Fe)(Si,Al)O3reacts with MgCO3 at PT-conditions of 24GPa/2000K and 60GPa/2500K, that is close to the boundary of congruent MgCO3 melting. The reaction is accompanied with formation of diamond and MgO. The experimental data on melting phase relations MgCO3, MgCO3 - (Mg,Fe)O and MgCO3-(Mg,Fe)(Si,Al)O3 systems combined with diamond crystallization are applied to the problem of ultra-deep diamond formation in carbonate-bearing parental media of the Earth's lower mantle. This work was funded by the Ministry of education and science of Russian Federation, project 8317, 16.740.11.0621, grants RFBR 12-05-33044 and 11-05-000401.

  6. Relationship of serum elastin peptide level to single breath transfer factor for carbon monoxide in French coal miners

    PubMed Central

    Frette, C.; Jacob, M. P.; Wei, S. M.; Bertrand, J. P.; Laurent, P.; Kauffmann, F.; Pham, Q. T.

    1997-01-01

    BACKGROUND: Clinical and epidemiological studies have given discordant results on the usefulness of the level of circulating elastin peptide (EP), a potential marker of both elastin destruction (a key phenomenon in pulmonary emphysema) and neosynthesis, for assessing structural changes in the lung extracellular matrix. The aim of the present study was to explore the relationship between levels of EP and forced expiratory volume in one second (FEV1) and single breath transfer factor for carbon monoxide (TLCO and KCO) in coal miners. METHODS: The study population comprised 227 working coal miners aged 34-50 years consisting of 75 miners heavily exposed to underground coal dust with pulmonary radiographs classified as 0/1 or 1/0 by the International Labour Office classification, 75 exposed miners with radiographs classified as normal (0/0), and 77 miners slightly exposed to coal dust with normal radiographs. The subjects answered a standardised questionnaire and performed spirometric tests and a carbon monoxide (CO) transfer test. RESULTS: No association was observed between EP levels and % predicted FEV1 (or FEV1/FVC). The level of EP increased significantly with decreased % predicted TLCO (r = -0.20). Miners in the lowest % predicted KCO quintile had higher EP levels than the rest (3.28 (1.37) vs 2.47 (1.16)). A significantly lower EP level was observed in miners with radiographs classified as 1/0 or 0/1, especially in those with round opacities, compared with miners with a normal radiograph, and in current smokers compared with the rest. CONCLUSIONS: The results of this study suggest that the level of EP may reflect some remodelling activity in emphysema and lung fibrosis. 


 PMID:9516897

  7. In vitro formation of Ca-oxalates and the mineral glushinskite by fungal interaction with carbonate substrates and seawater

    NASA Astrophysics Data System (ADS)

    Kolo, K.; Claeys, Ph.

    2005-10-01

    This study investigates the in vitro formation of Ca-oxalates and glushinskite through fungal interaction with carbonate substrates and seawater as a process of biologically induced metal recycling and neo-mineral formation. The study also emphasizes the role of the substrates as metal donors. In the first experiment, thin sections prepared from dolomitic rock samples of Terwagne Formation (Carboniferous, Viséan, northern France) served as substrates. The thin sections placed in Petri dishes were exposed to fungi grown from naturally existing airborne spores. In the second experiment, fungal growth and mineral formation was monitored using only standard seawater (SSW) as a substrate. Fungal growth media consisted of a high protein/carbohydrates and sugar diet with demineralized water for irrigation. Fungal growth process reached completion under uncontrolled laboratory conditions. The newly formed minerals and textural changes caused by fungal attack on the carbonate substrates were investigated using light and scanning electron microscopy (SEM-EDX), x-ray diffraction (XRD) and Raman spectroscopy. The fungal interaction and attack on the dolomitic and seawater substrates resulted in the formation of Ca-oxalates (weddellite CaC2O4·2(H2O), whewellite (CaC2O4·(H2O)) and glushinskite MgC2O4·2(H2O) associated with the destruction of the original hard substrates and their replacement by the new minerals. Both of Ca and Mg were mobilized from the experimental substrates by fungi. This metal mobilization involved a recycling of substrate metals into newly formed minerals. The biochemical and diagenetic results of the interaction strongly marked the attacked substrates with a biological fingerprint. Such fingerprints are biomarkers of primitive life. The formation of glushinskite is of specific importance that is related, besides its importance as a biomineral bearing a recycled Mg, to the possibility of its transformation through diagenetic pathway into an Mg carbonate

  8. Interactions Between Mineral Surfaces, Substrates, Enzymes, and Microbes Result in Hysteretic Temperature Sensitivities and Microbial Carbon Use Efficiencies and Weaker Predicted Carbon-Climate Feedbacks

    NASA Astrophysics Data System (ADS)

    Riley, W. J.; Tang, J.

    2014-12-01

    We hypothesize that the large observed variability in decomposition temperature sensitivity and carbon use efficiency arises from interactions between temperature, microbial biogeochemistry, and mineral surface sorptive reactions. To test this hypothesis, we developed a numerical model that integrates the Dynamic Energy Budget concept for microbial physiology, microbial trait-based community structure and competition, process-specific thermodynamically ­­based temperature sensitivity, a non-linear mineral sorption isotherm, and enzyme dynamics. We show, because mineral surfaces interact with substrates, enzymes, and microbes, both temperature sensitivity and microbial carbon use efficiency are hysteretic and highly variable. Further, by mimicking the traditional approach to interpreting soil incubation observations, we demonstrate that the conventional labile and recalcitrant substrate characterization for temperature sensitivity is flawed. In a 4 K temperature perturbation experiment, our fully dynamic model predicted more variable but weaker carbon-climate feedbacks than did the static temperature sensitivity and carbon use efficiency model when forced with yearly, daily, and hourly variable temperatures. These results imply that current earth system models likely over-estimate the response of soil carbon stocks to global warming.

  9. The distribution of secondary mineral phases along an eroding hillslope and its effect on carbon stabilization mechanisms and the fate of soil carbon fractions

    NASA Astrophysics Data System (ADS)

    Doetterl, Sebastian; Cornelis, Jean-Thomas; Opfergelt, Sophie; Boeckx, Pascal; Bodé, Samuel; Six, Johan; Van Oost, Kristof

    2014-05-01

    Soil redistribution processes can change soil carbon (C) dynamics drastically by moving carbon from high decomposition and re-sequestration environments at the eroding hillslope to low decomposition and burial at the depositional footslope and valley basin. This leads to not only spatially diverse soil carbon storage throughout the landscape, but also to qualitative changes of the transported carbon and the mineral phase. The interaction between those parameters and the effect on stabilization mechanisms for soil C are still a matter of debate. Here, we present an analysis that aims to clarify the bio/geo-chemical and mineralogical components involved in stabilizing C at various depths along an eroding cropped slope and how this affects the abundance of microbial derived carbon. We use the results of an incubation experiment combined with the abundance of amino sugars in different isolated soil C fractions as a tracer for the stability of the respective fraction. We applied further (i) a sequential extraction of the reactive soil phase using pyrophosphate, oxalate and dithionite-citrate-bicarbonate, and (ii) a qualitative analysis of the clay mineralogy, to analyze the changes in the mineral phase for the different isolated fractions along the slope transect. Our results emphasize the importance of physical protection within microaggregates to stabilize buried, chemically labile C. Our data further indicates that the stability of these aggregates is related to the presence of organo-mineral associations and poorly crystalline minerals. However, decreasing contents of these minerals with depth indicate a temporal limitation of this stabilization mechanism. Non-expandable clay minerals experience a relative enrichment at the depositional site while expandable clay minerals experience the same at the eroding site. These changes in clay mineralogy along the slope are partly responsible for the abundance of silt and clay associated C and the effectiveness of the clay

  10. Carbon Nanofiber/Polycaprolactone/Mineralized Hydroxyapatite Nanofibrous Scaffolds for Potential Orthopedic Applications.

    PubMed

    Elangomannan, Shinyjoy; Louis, Kavitha; Dharmaraj, Bhagya Mathi; Kandasamy, Venkata Saravanan; Soundarapandian, Kannan; Gopi, Dhanaraj

    2017-02-22

    Hydroxyapatite (Ca10 (PO4)6(OH)2, HAP), a multimineral substituted calcium phosphate is one of the most substantial bone mineral component that has been widely used as bone replacement materials because of its bioactive and biocompatible properties. However, the use of HAP as bone implants is restricted due to its brittle nature and poor mechanical properties. To overcome this defect and to generate suitable bone implant material, HAP is combined with biodegradable polymer (polycaprolactone, PCL). To enhance the mechanical property of the composite, carbon nanofibers (CNF) is incorporated to the composite, which has long been considered for hard and soft tissue implant due to its exceptional mechanical and structural properties. It is well-known that nanofibrous scaffold are the most-prominent material for the bone reconstruction. We have developed a new remarkable CNF/PCL/mineralized hydroxyapatite (M-HAP) nanofibrous scaffolds on titanium (Ti). The as-developed coatings were characterized by various techniques. The results indicate the formation and homogeneous distribution of components in the nanofibrous scaffolds. Incorporation of CNF into the PCL/M-HAP composite significantly improves the adhesion strength and elastic modulus of the scaffolds. Furthermore, the responses of human osteosarcoma (HOS MG63) cells cultured onto the scaffolds demonstrate that the viability of cells were considerably high for CNF-incorporated PCL/M-HAP than for PCL/M-HAP. In vivo analysis show the presence of soft fibrous tissue growth without any significant inflammatory signs, which suggests that incorporated CNF did not counteract the favorable biological roles of HAP. For load-bearing applications, research in various bone models is needed to substantiate the clinical availability. Thus, from the obtained results, we suggest that CNF/PCL/M-HAP nanofibrous scaffolds can be considered as potential candidates for orthopedic applications.

  11. The accumulation of organic carbon in mineral soils by afforestation of abandoned farmland.

    PubMed

    Wei, Xiaorong; Qiu, Liping; Shao, Mingan; Zhang, Xingchang; Gale, William J

    2012-01-01

    The afforestation of abandoned farmland significantly influences soil organic carbon (OC). However, the dynamics between OC inputs after afforestation and the original OC are not well understood. To learn more about soil OC dynamics after afforestation of farmland, we measured the soil OC content in paired forest and farmland plots in Shaanxi Province, China. The forest plots had been established on farmland 18, 24, 48, 100, and 200 yr previously. The natural (13)C abundance of soil organic matter was also analyzed to distinguish between crop- and forest-derived C in the afforested soils. We observed a nonlinear accumulation of total OC in the 0-80 cm depth of the mineral soil across time. Total soil OC accumulated more rapidly under forest stands aged 18 to 48 yr than under forest stands aged 100 or 200 yrs. The rate of OC accumulation was also greater in the 0-10 cm depth than in the 10-80 cm depth. Forest-derived OC in afforested soils also accumulated nonlinearly across time, with the greatest increase in the 0-20 cm depth. Forest-derived OC in afforest soils accounted for 52-86% of the total OC in the 0-10 cm depth, 36-61% of the total OC in the 10-20 cm depth, and 11-50% of the total OC in the 20-80 cm depth. Crop-derived OC concentrations in the 0-20 cm depth decreased slightly after afforestation, but there was no change in crop-derived OC concentrations in the 20-80 cm depth. The results of our study support the claim that afforestation of farmland can sequester atmospheric CO(2) by increasing soil OC stocks. Changes in the OC stocks of mineral soils after afforestation appear to be influenced mainly by the input of forest-derived C rather than by the loss of original OC.

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

  13. Synthetic iron (hydr)oxide-glucose associations in subsurface soil: Effects on decomposability of mineral associated carbon.

    PubMed

    Porras, R C; Hicks Pries, C E; Torn, M S; Nico, P S

    2017-09-13

    Soils are a globally important reservoir of organic carbon. There is a growing understanding that interactions with soil mineral phases contribute to the accumulation and retention of otherwise degradable organic matter (OM) in soils and sediments. However, the bioavailability of organic compounds in mineral-organic-associations (MOAs), especially under varying environmental conditions is not well known. To assess the impact of mineral association and warming on the decomposition of an easily respirable organic substrate (glucose), we conducted a series of laboratory incubations at different temperatures with field-collected soils from 10 to 20cm, 50-60cm, and 80-90cm depth. We added (13)C-labeled glucose either directly to native soil or sorbed to one of two synthetic iron (hydr)oxide phases (goethite and ferrihydrite) that differ in crystallinity and affinity for sorbing glucose. We found that: (1) association with the Fe (hydr)oxide minerals reduced the decomposition rate of glucose by >99.5% relative to rate of decomposition for free glucose in soil; (2) the respiration rate per gram carbon did not differ appreciably with depth, suggesting a similar degree of decomposability for native C across depths and that under the incubation conditions total carbon availability represents the principal limitation on respiration under these conditions as opposed to reduced abundance of decomposers or moisture and oxygen limitations; (3) addition of free glucose enhanced native carbon respiration at all soil depths with the largest effect at 50-60cm; (4) in general respiration of the organo-mineral complex (glucose and iron-(hydr)oxide) was less temperature sensitive than was respiration of native carbon; (5) the addition of organic free mineral decreased the rate of soil respiration in the intermediate 50-60cm depth soil. The results emphasize the key role of MOAs in regulating the fluxes of carbon from soils to the atmosphere and in turn the stocks of soil carbon

  14. [Effects of Chinese prickly ash orchard on soil organic carbon mineralization and labile organic carbon in karst rocky desertification region of Guizhou province].

    PubMed

    Zhang, Wen-Juan; Liao, Hong-Kai; Long, Jian; Li, Juan; Liu, Ling-Fei

    2015-03-01

    Taking 5-year-old Chinese prickly ash orchard (PO-5), 17-year-old Chinese prickly ash orchard (PO- 17), 30-year-old Chinese prickly ash orchard (PO-30) and the forest land (FL, about 60 years) in typical demonstration area of desertification control test in southwestern Guizhou as our research objects, the aim of this study using a batch incubation experiment was to research the mineralization characteristics of soil organic carbon and changes of the labile soil organic carbon contents at different depths (0-15 cm, 15-30 cm, and 30-50 cm). The results showed that: the cumulative mineralization amounts of soil organic carbon were in the order of 30-year-old Chinese prickly ash orchard, the forest land, 5-year-old Chinese prickly ash orchard and 17-year-old Chinese prickly ash orchard at corresponding depth. Distribution ratios of CO2-C cumulative mineralization amount to SOC contents were higher in Chinese prickly ash orchards than in forest land at each depth. Cultivation of Chinese prickly ash in long-term enhanced the mineralization of soil organic carbon, and decreased the stability of soil organic carbon. Readily oxidized carbon and particulate organic carbon in forest land soils were significantly more than those in Chinese prickly ash orchards at each depth (P < 0.05). With the increasing times of cultivation of Chinese prickly ash, the contents of readily oxidized carbon and particulate organic carbon first increased and then declined at 0-15 cm and 15-30 cm depth, respectively, but an opposite trend was found at 30-50 cm depth. At 0-15 cm and 15-30 cm, cultivation of Chinese prickly ash could be good for improving the contents of labile soil organic carbon in short term, but it was not conducive in long-term. In this study, we found that cultivation of Chinese prickly ash was beneficial for the accumulation of labile organic carbon at the 30-50 cm depth.

  15. Tufa in Northern England: depositional facies, carbonate mineral fabrics, and role of biomineralization

    NASA Astrophysics Data System (ADS)

    Manzo, E.; Mawson, M.; Perri, E.; Tucker, M. E.

    2009-04-01

    soil hereabouts, and are gradually being washed down slope. Pisoids vary in size and shape, ranging from rods to sub-spherical forms, up to several cm long or a cm or more in diameter. The external surface is a smooth dull surface of a pale grey-buff colour; the nucleus may be a plant fragment, tufa intraclast or rock fragment. Microfacies Teesdale tufa is characterized by three microfacies all contributing to a basic stromatolitic or laminated microfabric: dendrolite, dense micrite and palisades of sparite. Laminae consist of an irregular alternation of the three microfacies, which vary in abundance within the main depositional facies. Dendrolitic layers are characterized of mineralized, upward-branching cyanobacterial filaments, forming bush-like fans. Coarse sparitic layers consist of palisades of bladed calcite spar characterized by rhombohedral terminations. Micritic layers consist of dark-brown dense laminae with some clotted fabric, composed of dark micritic crystals. In thin-section molds of moss stems are often preserved by a sparitic layer that formed a coating before decay of the moss organic tissues. Cavities are abundant in moss tufa and crusts. They are often empty or in some case filled by detrital particles. Pisoids under the microscope show a cortex characterized by a concentric structure consisting mainly dense micritic layers alternating with sporadic sparitic and/or dendrolitic layers. Calcified cyanobacterial filaments or their molds are very evident in the dendrolitic laminae, but also occur in the other microfacies, being incorporated in both the sparite macro-crystals and the micritic layers. Nanofacies of minerals The mineral composition of the autochthonous carbonate forming tufa is calcite with a few mole% Mg. Sub-hedral crystals of calcite, several tens of microns in size, form sparite crystals. Sub-polygonal micro-crystals and elongate fibres a few microns in size compose dense micrite and calcified filaments. Under extra-high SEM

  16. Assessing the use of composts from multiple sources based on the characteristics of carbon mineralization in soil.

    PubMed

    Zhang, Xu; Zhao, Yue; Zhu, Longji; Cui, Hongyang; Jia, Liming; Xie, Xinyu; Li, Jiming; Wei, Zimin

    2017-09-08

    In order to improve soil quality, reduce wastes and mitigate climate change, it is necessary to understand the balance between soil organic carbon (SOC) accumulation and depletion under different organic waste compost amended soils. The effects of proportion (5%, 15%, 30%), compost type (sewage sludge (SS), tomato stem waste (TSW), municipal solid waste (MSW), kitchen waste (KW), cabbage waste (CW), peat (P), chicken manure (CM), dairy cattle manure (DCM)) and the black soil (CK). Their initial biochemical composition (carbon, nitrogen, C:N ratio) on carbon (C) mineralization in soil amended compost have been investigated. The CO2-C production of different treatments were measured to indicate the levels of carbon (C) mineralization during 50d of laboratory incubation. And the one order E model (M1E) was used to quantify C mineralization kinetics. The results demonstrated that the respiration and C mineralization of soil were promoted by amending composts. The C mineralization ability increased when the percentage of compost added to the soil also increased and affected by compost type in the order CM>KW, CW>SS, DCM, TSW>MSW, P>CK at the same amended level. Based on the values of C0 and k1 from M1E model, a management method in agronomic application of compost products to the precise fertilization was proposed. The SS, DCM and TSW composts were more suitable in supplying fertilizer to the plant. Otherwise, The P and MSW composts can serve the purpose of long-term nutrient retention, whereas the CW and KW composts could be used as soil remediation agent. Copyright © 2017 Elsevier Ltd. All rights reserved.

  17. [Seasonal dynamics of soil organic carbon mineralization for two forest types in Xiaoxing'an Mountains, China].

    PubMed

    Gao, Fei; Lin, Wei; Cui, Xiao-yang

    2016-01-01

    To investigate the seasonal dynamics of soil organic carbon (SOC) mineralization in Xiaoxing'an Mountain, we incubated soil samples collected from virgin Korean pine forest and broad-leaved secondary forest in different seasons in the laboratory and measured the SOC mineralization rate and cumulative SOC mineralization (Cm). We employed simultaneous reaction model to describe C mineralization kinetics and estimated SOC mineralization parameters including soil easily mineralizable C (C1), potentially mineralizable C (C₀). We also analyzed the relations between Cm, C₁and their influencing factors. Results showed that the incubated SOC mineralization rate and Cm for 0-5 cm soil layer decreased from early spring to late autumn, while for 5-10 cm soil layer the seasonal variation was not statistically significant for both forest types. The C₁ in 0-5 and 5-10 cm soil layers varied from 42.92-92.18 and 19.23-32.95 mg kg⁻¹, respectively, while the C₀ in 0-5 and 5-10 cm soil layers varied from 863.92-3957.15 and 434.15-865.79 mg · kg⁻¹, respec- tively. Both C₁ and C₀ decreased from early spring to late autumn. The proportions of C₀ in SOC for two forest types were 0.74%-2.78% and 1.11%-1.84% in 0-5 and 5-10 cm soil layers, respectively, and decreased from early spring to late autumn, indicating that SOC tended to become more stable as a whole from spring to autumn. The Cm and C₀ were significantly positively correlated to in situ soil water content and hot water-extractable carbohydrate content, but were not correlated to in situ soil temperature and cool water-extractable carbohydrate content. We concluded that soil labile organic carbon, soil physical and chemical properties contributed to the seasonal dynamics of SOC mineralization in the forests.

  18. Ocean acidification and biologically induced seasonality of carbonate mineral saturation states in the western Arctic Ocean

    NASA Astrophysics Data System (ADS)

    Bates, Nicholas R.; Mathis, Jeremy T.; Cooper, Lee W.

    2009-11-01

    Calcium carbonate (CaCO3) mineral saturation states for aragonite (Ωaragonite) and calcite (Ωcalcite) are calculated for waters of the Chukchi Sea shelf and Canada Basin of the western Arctic Ocean during the Shelf-Basin Interactions project from 2002 to 2004. On the Chukchi Sea shelf, a strong seasonality and vertical differentiation of aragonite and calcite saturation states was observed. During the summertime sea ice retreat period, high rates of phytoplankton primary production and net community production act to increase the Ωaragonite and Ωcalcite of surface waters, while subsurface waters become undersaturated with respect to aragonite due primarily to remineralization of organic matter to CO2. This seasonal "phytoplankton-carbonate saturation state" interaction induces strong undersaturation of aragonite (Ωaragonite = <0.7-1) at ˜40-150 m depth in the northern Chukchi Sea and in the Canada Basin within upper halocline waters at ˜100-200 m depth. Patches of aragonite undersaturated surface water were also found in the Canada Basin resulting from significant sea ice melt contributions (>10%). The seasonal aragonite undersaturation of waters observed on the Chukchi Sea shelf is likely a recent phenomenon that results from the uptake of anthropogenic CO2 and subsequent ocean acidification, with seasonality of saturation states superimposed by biological processes. These undersaturated waters are potentially highly corrosive to calcifying benthic fauna (e.g., bivalves and echinoderms) found on the shelf, with implications for the food sources of large benthic feeding mammals (e.g., walrus, gray whales, and bearded seals). The benthic ecosystem of the Chukchi Sea (and other Arctic Ocean shelves) is thus potentially vulnerable to future ocean acidification and suppression of CaCO3 saturation states.

  19. Synthesis of iron-based chemical looping sorbents integrated with pH swing carbon mineral sequestration.

    PubMed

    Kim, Hyung Ray; Lee, Dong Hyun; Fan, Liang-Shih; Park, Ah-Hyung Alissa

    2009-12-01

    The previously developed pH swing carbon mineral sequestration immobilizes the gaseous CO2 into a thermodynamically stable solid, MgCO3, using Mg-bearing minerals such as serpentine. This mineral carbonation technology is particularly promising since it generates value-added solid products: high surface area silica, iron oxide, and magnesium carbonate, while providing a safe and permanent storage option for CO2. By carefully controlling the pH of the system, these solids products can be produced with high purity. This study focuses on the synthesis of iron oxide particles as a chemical looping sorbent in order to achieve the integration between carbon capture and storage technologies. Since the solubility of Fe in aqueous phase is relatively low at neutral pH, the effect of the weak acid and chelating agents on the extraction of Fe from serpentine was investigated. The synthesized iron-based chemical looping sorbent was found to be as effective as commercially available iron oxide nanoparticles at converting syngas into high purity H2, while producing a sequestration-ready CO2 stream.

  20. Mineral Carbonation in Wet Supercritical CO2: An in situ High-Pressure Magic Angle Spinning Nuclear Magnetic Resonance Study

    NASA Astrophysics Data System (ADS)

    Turcu, R. V.; Hoyt, D. H.; Sears, J. A.; Rosso, K. M.; Felmy, A. R.; Hu, J. Z.

    2011-12-01

    Understanding the mechanisms and kinetics of mineral carbonation reactions relevant to sequestering carbon dioxide as a supercritical fluid (scCO2) in geologic formations is crucial for accurately predicting long-term storage risks. In situ probes that provide molecular-level information at geologically relevant temperatures and pressures are highly desirable and challenging to develop. Magic angle spinning nuclear magnetic resonance (MAS NMR) is a powerful tool for obtaining detailed molecular structure and dynamics information of a system regardless whether the system is in a solid, a liquid, a gaseous, a supercritical state, or a mixture thereof. However, MAS NMR under scCO2 conditions has never been realized due to the tremendous technical difficulties of achieving and maintaining high pressure within a fast spinning MAS sample rotor. In this work, we report development of a unique high pressure MAS NMR capability capable of handling fluid pressure exceeding 170 bars and temperatures up to 80°C, and its application to mineral carbonation in scCO2 under geologically relevant temperatures and pressures. Mineral carbonation reactions of the magnesium silicate mineral forsterite and the magnesium hydroxide brucite reacted with scCO2 (up to 170 bar) and containing variable content of H2O (at, below, and above saturation in scCO2) were investigated at 50 to 70°C. In situ 13C MAS NMR spectra show peaks corresponding to the reactants, intermediates, and the magnesium carbonation products in a single spectrum. For example, Figure 1 shows the reaction dynamics, i.e., the formation and conversion of reaction intermediates, i.e., HCO3- and nesquehonite, to magnesite as a function of time at 70°C. This capability offers a significant advantage over traditional ex situ 13C MAS experiments on similar systems, where, for example, CO2 and HCO3- are not directly observable.

  1. Electrochemical mineral scale prevention and removal on electrically conducting carbon nanotube--polyamide reverse osmosis membranes.

    PubMed

    Duan, Wenyan; Dudchenko, Alexander; Mende, Elizabeth; Flyer, Celeste; Zhu, Xiaobo; Jassby, David

    2014-05-01

    The electrochemical prevention and removal of CaSO4 and CaCO3 mineral scales on electrically conducting carbon nanotube - polyamide reverse osmosis membrane was investigated. Different electrical potentials were applied to the membrane surface while filtering model scaling solutions with high saturation indices. Scaling progression was monitored through flux measurements. CaCO3 scale was efficiently removed from the membrane surface through the intermittent application of a 2.5 V potential to the membrane surface, when the membrane acted as an anode. Water oxidation at the anode, which led to proton formation, resulted in the dissolution of deposited CaCO3 crystals. CaSO4 scale formation was significantly retarded through the continuous application of 1.5 V DC to the membrane surface, when the membrane was operated as an anode. The continuous application of a sufficient electrical potential to the membrane surface leads to the formation of a thick layer of counter-ions along the membrane surface that pushed CaSO4 crystal formation away from the membrane surface, allowing the formed crystals to be carried away by the cross-flow. We developed a simple model, based on a modified Poisson-Boltzmann equation, which qualitatively explained our observed experimental results.

  2. Temperature and moisture responses to carbon mineralization in the biochar-amended saline soil.

    PubMed

    Sun, Junna; He, Fuhong; Zhang, Zhenhua; Shao, Hongbo; Xu, Gang

    2016-11-01

    This study assessed the effects of temperature and moisture on carbon mineralization (Cmin) in a saline soil system with biochar amendment. The dynamics of Cmin were monitored in a biochar-amended saline soil for 220days by incubation experiments under different conditions of temperature (15°C, 25°C and 35°C) and moisture (30%, 70% and 105% of the water-holding capacity). Results showed that as the incubation temperature rose, cumulative Cmin consistently increased in soil added with 0-4% biochar. The two-compartment model could well describe the dynamics of Cmin. The temperature rise increased the concentration of labile C in soil, but reduced the turnover time of labile and recalcitrant C pools and the value of temperature coefficient Q10. The response of Cmin to moisture was varying in soil amended with different levels of biochar. In the control treatment (soil alone), cumulative Cmin increased only when soil moisture was >105%. In the biochar treatments, however, 70% of water-holding capacity was optimal for Cmin, except for 2%-biochar treatment at 35°C. The findings highlight the necessity to consider the combined effects of soil moisture, temperature and the amount of biochar added for assessing Cmin in biochar-amended saline soils.

  3. Formation of carbon dioxide hydrate in soil and soil mineral suspensions with electrolytes.

    PubMed

    Lamorena, Rheo B; Lee, Woojin

    2008-04-15

    We have identified the effects of solid surface (soil, bentonite, kaolinite, nontronite, and pyrite) and electrolyte (NaCl, KCl, CaCl2, and MgCl2) types on the formation and dissociation of CO2 hydrate in this study. The hydrate formation experiments were conducted by injecting CO2 gas into the soil suspensions with and without electrolytes in a 50 mL pressurized vessel. The formation of CO2 hydrate in deionized water was faster than that in aqueous electrolyte solutions. The addition of soil suspensions accelerated the formation of CO2 hydrate in the electrolyte solutions. The hydrate formation times in the solid suspensions without electrolytes were very similar to that in the deionized water. We did not observe any significant differences between the hydrate dissociation in the solid suspension and that in the deionized water. The pHs of clay mineral suspensions decreased significantly after CO2 hydrate formation and dissociation experiments, while the pH of the soil suspension slightly decreased by less than pH 1 and that of pyrite slightly increased due to the dissolution of CO2 forming carbonic acid. The results obtained from this research could be indirectly applied to the fate of CO2 sequestered into geological formations as well as its storage as a form of CO2 hydrate.

  4. Predicting bi-decadal organic carbon mineralization in northwestern European soils with Rock-Eval pyrolysis

    NASA Astrophysics Data System (ADS)

    Soucemarianadin, Laure; Barré, Pierre; Baudin, François; Chenu, Claire; Houot, Sabine; Kätterer, Thomas; Macdonald, Andy; van Oort, Folkert; Plante, Alain F.; Cécillon, Lauric

    2017-04-01

    The organic carbon reservoir of soils is a key component of climate change, calling for an accurate knowledge of the residence time of soil organic carbon (SOC). Existing proxies of the size of SOC labile pool such as SOC fractionation or respiration tests are time consuming and unable to consistently predict SOC mineralization over years to decades. Similarly, models of SOC dynamics often yield unrealistic values of the size of SOC kinetic pools. Thermal analysis of bulk soil samples has recently been shown to provide useful and cost-effective information regarding the long-term in-situ decomposition of SOC. Barré et al. (2016) analyzed soil samples from long-term bare fallow sites in northwestern Europe using Rock-Eval 6 pyrolysis (RE6), and demonstrated that persistent SOC is thermally more stable and has less hydrogen-rich compounds (low RE6 HI parameter) than labile SOC. The objective of this study was to predict SOC loss over a 20-year period (i.e. the size of the SOC pool with a residence time lower than 20 years) using RE6 indicators. Thirty-six archive soil samples coming from 4 long-term bare fallow chronosequences (Grignon, France; Rothamsted, Great Britain; Ultuna, Sweden; Versailles, France) were used in this study. For each sample, the value of bi-decadal SOC mineralization was obtained from the observed SOC dynamics of its long-term bare fallow plot (approximated by a spline function). Those values ranged from 0.8 to 14.3 gC·kg-1 (concentration data), representing 8.6 to 50.6% of total SOC (proportion data). All samples were analyzed using RE6 and simple linear regression models were used to predict bi-decadal SOC loss (concentration and proportion data) from 4 RE6 parameters: HI, OI, PC/SOC and T50 CO2 oxidation. HI (the amount of hydrogen-rich effluents formed during the pyrolysis phase of RE6; mgCH.g-1SOC) and OI (the CO2 yield during the pyrolysis phase of RE6; mgCO2.g-1SOC) parameters describe SOC bulk chemistry. PC/SOC (the amount of organic

  5. Soil Incubations Synthesis Study to Identify and Constrain Relations of Soil Properties and Carbon Mineralization

    NASA Astrophysics Data System (ADS)

    Moyano, F. E.; Chenu, C.

    2010-12-01

    Soil carbon models use temperature and moisture relations commonly derived from one or a few representative experimental studies on the topic. These relations are then applied to a more or less wide range of soils, depending on the model type and use. Despite the number of studies looking at such relations, models are yet incapable of successfully simulating carbon dynamics in a wide range of soils. Relations between soil moisture and carbon mineralization are particularly difficult to predict, something which is necessarily related to complicated and yet unexplained aspects of soil and organic matter properties. Soil incubations under controlled conditions are well suited for studying the effect of different factors and their interactions. However, since most incubation studies use one or only a few soil types, extrapolating the results of single studies to a range of soils, as is done in most models, leads to inexact predictions. A problem in analyzing and comparing results from multiple studies lies in the use of different units, especially in the case of soil moisture measurements where, without the required soil characteristics, different units cannot be inter-converted. A comparison is further complicated by most studies giving functions fitted and parameterized for a particular dataset, but since the data is usually not available, alternative functions cannot be derived to effectively compare with other measurements. The project presented here shows the first steps in building a database from soil incubation studies serving as the basis for a statistically significant comparison of datasets. First results are likewise given. Our initial aim is to collect and make comparable datasets from different sources, by directly converting units or using pedotransfer functions, and by including as much data on soil properties and treatments as available. We then analyze the data to find relations between moisture, temperature, soil properties and microbial activity

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

    SciTech Connect

    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

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

    PubMed

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

    2013-06-18

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

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

    PubMed Central

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

    2013-01-01

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

  9. Residence time, mineralization processes and groundwater origin within a carbonate coastal aquifer with a thick unsaturated zone

    NASA Astrophysics Data System (ADS)

    Santoni, S.; Huneau, F.; Garel, E.; Vergnaud-Ayraud, V.; Labasque, T.; Aquilina, L.; Jaunat, J.; Celle-Jeanton, H.

    2016-09-01

    This study aims at establishing groundwater residence times, identifying mineralization processes and determining groundwater origins within a carbonate coastal aquifer with thick unsaturated zone and lying on a granitic depression. A multi-tracer approach (major ions, SiO2, Br-, Ba+, Sr2+, 18O, 2H, 13C, 3H, Ne, Ar) combined with a groundwater residence time determination using CFCs and SF6 allows defining the global setting of the study site. A typical mineralization conditioned by the sea sprays and the carbonate matrix helped to validate the groundwater weighted residence times from using a binary mixing model. Terrigenic SF6 excesses have been detected and quantified, which permits to identify a groundwater flow from the surrounding fractured granites towards the lower aquifer principally. The use of CFCs and SF6 as a first hydrogeological investigation tool is possible and very relevant despite the thick unsaturated zone and the hydraulic connexion with a granitic environment.

  10. Cobalt-molybdenum catalysts based on carbon-mineral materials from sapropel for the large organic molecules transformation

    NASA Astrophysics Data System (ADS)

    Terekhova, E. N.; Belskaya, O. B.

    2017-08-01

    The investigations results of cobalt-molybdenum catalysts obtained using carbon-mineral materials from sapropel as support are presented. The effect of the support modification method (acidic, alkaline treatment, activation by water vapor) on the catalysts properties in the model transformation reactions of 1-methylnaphthalene and dibenzothiophene is shown. It was found that acidic treatment resulted in increased specific surface of carbon-mineral materials (with the preservation of a large-pored structure), supported metals dispersion, and to the formation of acidic centers on the surface. The use of a catalyst prepared with acidic treatment led to an increase in the conversion of methylnaphthalene and dibenzothiophene by about 4 and 3 times, respectively, compared to the initial sample without modification.

  11. Use of Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy To Identify Microbial Metabolic Products on Carbonate Mineral Surfaces▿ †

    PubMed Central

    Bullen, Heather A.; Oehrle, Stuart A.; Bennett, Ariel F.; Taylor, Nicholas M.; Barton, Hazel A.

    2008-01-01

    This paper demonstrates the use of attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy to detect microbial metabolic products on carbonate mineral surfaces. By creating an ATR-FTIR spectral database for specific organic acids using ATR-FTIR spectroscopy we were able to distinguish metabolic acids on calcite surfaces following Escherichia coli growth. The production of these acids by E. coli was verified using high-performance liquid chromatography with refractive index detection. The development of this technique has allowed us to identify microbial metabolic products on carbonate surfaces in nutrient-limited cave environments. PMID:18502924

  12. Electro-Fenton oxidation of para-aminosalicylic acid: degradation kinetics and mineralization pathway using Pt/carbon-felt and BDD/carbon-felt cells.

    PubMed

    Oturan, Nihal; Aravindakumar, Charuvila T; Olvera-Vargas, Hugo; Sunil Paul, Mathew M; Oturan, Mehmet A

    2017-05-31

    Degradation of a widely used antibiotic, the para-aminosalicylic acid (PAS), and mineralization of its aqueous solution was investigated by electro-Fenton process using Pt/carbon-felt and boron-doped diamond (BDD)/carbon-felt cells with applied currents in the range of 50-1000 mA. This process produces the highly oxidizing species, the hydroxyl radical ((•)OH), which is mainly responsible for the oxidative degradation of PAS. An absolute rate constant of 4.17 × 10(9) M(-1) s(-1) for the oxidation of PAS by (●)OH was determined from the competition kinetics method. Degradation rate of PAS increased with current reaching an optimal value of 500 mA with complete disappearance of 0.1 mM PAS at 7 min using Pt/carbon-felt cell. The optimum degradation rate was reached at 300 mA for BDD/carbon-felt. The latter cell was found more efficient in total organic carbon (TOC) removal where a complete mineralization was achieved within 240 min. A multi-step mineralization process was observed with the formation of a number of aromatic intermediates, short-chain carboxylic acids, and inorganic ions. Eight aromatic intermediate products were identified using both LC-Q-ToF-MS and GC-MS techniques. These products were the result of hydroxylation of PAS followed by multiple additions of hydroxyl radicals to form polyhydroxylated derivatives. HPLC and GC/MS analyses demonstrated that extended oxidation of these intermediate products conducted to the formation of various short-chain carboxylic acids. Prolonged electrolysis resulted in a complete mineralization of PAS with the evolution of inorganic ions such as NO3(-) and NH4(+). Based on the identified intermediates, carboxylic acids and inorganic ions, a plausible mineralization pathway is also deduced. The remarkably high degree of mineralization (100%) achieved by the present EF process highlights the potential application of this technique to the complete removal of salicylic acid-based pharmaceuticals from

  13. Inventario mundial de la calidad del carbon mineral (WoCQI) [The world coal quality inventory (WoCQI)

    USGS Publications Warehouse

    Finkelman, R.B.; Lovern, V.S.

    2001-01-01

    Los oficiales encargados de la politica comercial de cada pais requieren informacion clara y precisa sobre el recurso del carbon mineral, particularmente sobre sus propiedades y caracteristicas, para tomar decisiones bien fundamentadas con respecto al mejor uso de los recursos naturales, necesidades de importacion y oportunidades de exportacion, objetivos de politica interna y externa, oportunidades de transferencia tecnologica, posibilidades de inversion externa, estudios ambientales y de salud, y asuntos relacionados con el uso de productos secundarios y su disposicion.

  14. New strategies for submicron characterization the carbon binding of reactive minerals in long-term contrasting fertilized soils: implications for soil carbon storage

    NASA Astrophysics Data System (ADS)

    Xiao, Jian; He, Xinhua; Hao, Jialong; Zhou, Ying; Zheng, Lirong; Ran, Wei; Shen, Qirong; Yu, Guanghui

    2016-06-01

    Mineral binding is a major mechanism for soil carbon (C) stabilization. However, the submicron information about the in situ mechanisms of different fertilization practices affecting organo-mineral complexes and associated C preservation remains unclear. Here, we applied nano-scale secondary ion mass spectrometry (NanoSIMS), X-ray photoelectron spectroscopy (XPS), and X-ray absorption fine structure spectroscopy (XAFS) to examine differentiating effects of inorganic versus organic fertilization on interactions between highly reactive minerals and soil C preservation. To examine such interactions, soils and their extracted colloids were collected during a 24-year long-term fertilization period (1990-2014) (no fertilization, control; chemical nitrogen (N), phosphorus (P), and potassium (K) fertilization, NPK; and NPK plus swine manure fertilization, NPKM). The results for different fertilization conditions showed a ranked soil organic matter concentration with NPKM > NPK > control. Meanwhile, oxalate-extracted Al (Alo), Fe (Feo), short-range ordered Al (Alxps), Fe (Fexps), and dissolved organic carbon (DOC) ranked with NPKM > control > NPK, but the ratios of DOC / Alxps and DOC / Fexps ranked with NPKM > NPK > control. Compared with the NPK treatment, the NPKM treatment enhanced the C-binding loadings of Al and Fe minerals in soil colloids at the submicron scale. Furthermore, a greater concentration of highly reactive Al and Fe minerals was presented under NPKM than under NPK. Together, these submicron-scale findings suggest that both the reactive mineral species and their associations with C are differentially affected by 24-year long-term inorganic and organic fertilization.

  15. Incorporation of Np(V) and U(VI) in carbonate and sulfate minerals crystallized from aqueous solution

    NASA Astrophysics Data System (ADS)

    Balboni, Enrica; Morrison, Jessica M.; Wang, Zheming; Engelhard, Mark H.; Burns, Peter C.

    2015-02-01

    The neptunyl Np(V)O2+ and uranyl U(VI)O22+ ions are soluble in groundwater, although their interaction with minerals in the subsurface may impact their mobility. One mechanism for the immobilization of actinyl ions in the subsurface is co-precipitation in low-temperature minerals that form naturally, or that are induced to form as part of a remediation strategy. Important differences in the crystal-chemical behavior of the Np(V) neptunyl and U(VI) uranyl ions suggest their behavior towards incorporation into growing crystals may differ significantly. Using a selection of low-temperature minerals synthesized in aqueous systems under ambient conditions, this study examines the factors that impact the structural incorporation of the Np(V) neptunyl and U(VI) uranyl ions in carbonate and sulfate minerals. Calcite (CaCO3), aragonite (CaCO3), gypsum (CaSO4·2H2O), strontianite (SrCO3), cerussite (PbCO3), celestine (SrSO4), and anglesite (PbSO4) were synthesized from aqueous solutions containing either 400-1000 ppm of U(VI) or Np(V) relative to the divalent cation present in the system. The synthetic products were investigated by inductively coupled plasma mass spectrometry, luminescence and time resolved luminescence spectroscopy, X-ray photoelectron spectroscopy, and transmission electron microscopy. Amongst the carbonate minerals, calcite significantly favors Np(V) incorporation over U(VI). U(VI) and Np(V) are incorporated in aragonite and strontianite in similar amounts, whereas cerussite did not incorporate either U(VI) or Np(V) under the synthesis conditions. The sulfate minerals weakly interact with the actinyl ions, relative to the carbonate minerals. Incorporation of U(VI) and Np(V) in celestine was observed at the level of a few tens of ppm; anglesite and gypsum did not incorporate detectable U(VI) or Np(V). Luminescence spectra of the uranyl incorporated in aragonite and strontianite are consistent with a uranyl unit coordinated by three bidentate CO32- groups

  16. [Response of mineralization of dissolved organic carbon to soil moisture in paddy and upland soils in hilly red soil region].

    PubMed

    Chen, Xiang-Bi; Wang, Ai-Hua; Hu, Le-Ning; Huang, Yuan; Li, Yang; He, Xun-Yang; Su, Yi-Rong

    2014-03-01

    Typical paddy and upland soils were collected from a hilly subtropical red-soil region. 14C-labeled dissolved organic carbon (14C-DOC) was extracted from the paddy and upland soils incorporated with 14C-labeled straw after a 30-day (d) incubation period under simulated field conditions. A 100-d incubation experiment (25 degrees C) with the addition of 14C-DOC to paddy and upland soils was conducted to monitor the dynamics of 14C-DOC mineralization under different soil moisture conditions [45%, 60%, 75%, 90%, and 105% of the field water holding capacity (WHC)]. The results showed that after 100 days, 28.7%-61.4% of the labeled DOC in the two types of soils was mineralized to CO2. The mineralization rates of DOC in the paddy soils were significantly higher than in the upland soils under all soil moisture conditions, owing to the less complex composition of DOC in the paddy soils. The aerobic condition was beneficial for DOC mineralization in both soils, and the anaerobic condition was beneficial for DOC accumulation. The biodegradability and the proportion of the labile fraction of the added DOC increased with the increase of soil moisture (45% -90% WHC). Within 100 days, the labile DOC fraction accounted for 80.5%-91.1% (paddy soil) and 66.3%-72.4% (upland soil) of the cumulative mineralization of DOC, implying that the biodegradation rate of DOC was controlled by the percentage of labile DOC fraction.

  17. Persistence of Mineral-Associated Soil Organic Carbon in European Soil Profiles

    NASA Astrophysics Data System (ADS)

    Mayer, A.; Schrumpf, M.; Trumbore, S.

    2014-12-01

    Soil Organic Carbon (SOC) is a heterogeneous mixture of components that are not equally biologically available, including light, plant derived material, dissolved organic carbon, and mineral-associated organic matter (MOM). Radiocarbon ages of bulk SOC average across this heterogeneity. Of particular interest is whether there are small amounts of very old OC (the so-called 'passive' pool) that can mask the fact that much of the OM is much younger. MOM has been shown to be older than the light fraction and DOC, but MOM is also a mixture of old and young material. This study seeks to clarify the quantity of C persisting on millennial time scales at different depths in the soil profile, and what factors allow this fraction to be more persistent than other fractions. We studied the fraction and age of C of the most chemically and physically stable fraction we could isolate from five European soils with differing land use, parent material, and soil type. First we isolated the MOM fraction by density, and then oxidized the MOM fraction with H2O2 to remove the labile C. The oxidation resistant residue was analyzed for C content and radiocarbon signature. The oxidation procedure removed 70-95% of the MOM fraction; the residue had a consistently older radiocarbon signature than the initial MOM, indicating that the C removed was younger than the bulk average. This stable fraction ranged from 100 radiocarbon years Before Present (BP) in the top 5 cm, to 10,000 years BP at the 30-40 cm depth. Non-crystalline iron concentrations were correlated with the absolute amount of SOC protected from oxidation, but not its proportion or age. With the exception of a tilled cropland site, all examined profiles exhibited a nearly linear depletion in radiocarbon signature with depth in both the protected and oxidizable MOM, confirming that the most chemically and physically stable C is oldest at the deepest point in a 50 cm profile. Ongoing work on this study will further elucidate how the

  18. Effect of Mineral Dissolution/Precipitation and CO2 Exsolution on CO2 transport in Geological Carbon Storage.

    PubMed

    Xu, Ruina; Li, Rong; Ma, Jin; He, Di; Jiang, Peixue

    2017-09-19

    Geological carbon sequestration (GCS) in deep saline aquifers is an effective means for storing carbon dioxide to address global climate change. As the time after injection increases, the safety of storage increases as the CO2 transforms from a separate phase to CO2(aq) and HCO3(-) by dissolution and then to carbonates by mineral dissolution. However, subsequent depressurization could lead to dissolved CO2(aq) escaping from the formation water and creating a new separate phase which may reduce the GCS system safety. The mineral dissolution and the CO2 exsolution and mineral precipitation during depressurization change the morphology, porosity, and permeability of the porous rock medium, which then affects the two-phase flow of the CO2 and formation water. A better understanding of these effects on the CO2-water two-phase flow will improve predictions of the long-term CO2 storage reliability, especially the impact of depressurization on the long-term stability. In this Account, we summarize our recent work on the effect of CO2 exsolution and mineral dissolution/precipitation on CO2 transport in GCS reservoirs. We place emphasis on understanding the behavior and transformation of the carbon components in the reservoir, including CO2(sc/g), CO2(aq), HCO3(-), and carbonate minerals (calcite and dolomite), highlight their transport and mobility by coupled geochemical and two-phase flow processes, and consider the implications of these transport mechanisms on estimates of the long-term safety of GCS. We describe experimental and numerical pore- and core-scale methods used in our lab in conjunction with industrial and international partners to investigate these effects. Experimental results show how mineral dissolution affects permeability, capillary pressure, and relative permeability, which are important phenomena affecting the input parameters for reservoir flow modeling. The porosity and the absolute permeability increase when CO2 dissolved water is continuously

  19. Large uraniferous springs and associated uranium minerals, Shirley Mountains, Carbon County, Wyoming -- A preliminary report

    USGS Publications Warehouse

    Love, J.D.

    1963-01-01

    Ten springs along the southeast flank of the Shirley Mountains, Carbon County, Wyoming, have water containing from 12 to 27 parts per billion uranium, have a total estimated flow of 3 million gallons of clear fresh water per day, and have a combined annual output that may be as much as 166 pounds of uranium. These springs emerge from Pennsylvanian, Permian, and Triassic rocks on the east flank of a faulted anticlinal fold. In the vicinity of several springs, metatyuyamunite occurs locally in crystalline calcite veins averaging 3 feet in width but reaching a maximum of 24 feet. The veins are as much as several hundred feet long-and cut vertically through sandstones of Pennsylvanian age overlying the Madison Limestone (Mississippian). This limestone is believed to be the source of the calcite. A 3-foot channel sample cross one calcite vein contains 0.089 percent uranium. Lesser amounts of uranium were obtained from other channel samples. Selected samples contain from 0.39 to 2.2 percent uranium and from 0.25 to 0.86 percent vanadium. Three possible sources of the uranium are: (1) Precambrian rocks, (2) Paleozoic rocks, (3) Pliocene(?) tuffaceous strata that were deposited unconformably across older .rocks in both the graphically high and low parts of the area, but were subsequently removed by erosion except for a few small remnants, one of which contains carnotite. There is apparently a close genetic relation between the uraniferous springs and uranium mineralization in the calcite veins. Data from this locality illustrate how uraniferous ground water can be used as a guide in the exploration for areas where uranium deposits may occur. Also demonstrated is the fact that significant quantities of uranium are present in water of some large flowing springs.

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

    NASA Astrophysics Data System (ADS)

    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

  1. Mineral Occurrence, Translocation, and Weathering in Soils Developed on Four Types of Carbonate and Non-carbonate Alluvial Fan Deposits in Mojave Desert, Southeastern California

    NASA Astrophysics Data System (ADS)

    Deng, Y.; McDonald, E. V.

    2007-12-01

    Soil geomorphology and mineralogy can reveal important clues about Quaternary climate change and geochemical process occurring in desert soils. We investigated (1) the mineral transformation in desert soils developed on four types of alluvial fans (carbonate and non-carbonate) under the same conditions of climate and landscape evolution; and (2) the effects of age, parent materials, and eolian processes on the transformation and translocation of the minerals. Four types of alluvial-fan deposits along the Providence Mountains piedmonts, Mojave Desert, southeastern California, USA were studied: (1) carbonate rocks, primarily limestone and marble (LS), (2) fine-grained rhyodacite and rhyolitic tuff mixed with plutonic and carbonate rocks (VX), (3) fine- to coarse- grained mixed plutonic (PM) rocks, and (4) coarse-grained quartz monzonite (QM). These juxtaposed fan deposits are physically correlated in a small area (about 20 km by 15 km) and experienced the same climatic changes in the late Pleistocene and Holocene. The soils show characteristic mineral compositions of arid/semiarid soils: calcite is present in nearly all of the samples, and a few of the oldest soils contain gypsum and soluble salts. Parent material has profound influence on clay mineral composition of the soils: (1) talc were observed only in soils developed on the volcanic mixture fan deposits, and talc occurs in all horizons; (2) palygorskite occur mainly in the petrocalcic (Bkm) of old soils developed on the LS and VX fan deposits, indicating pedogenic origin; (3) chlorite was observed mainly in soils developed on VX fan deposits (all ages) and on some LS deposits, but it is absent in soils developed on PM and QM fan deposits; and (4) vermiculite was common throughout soils developed on plutonic rock fan deposits. These mineralogical differences suggest that minerals in the soils are primarily inherited from their parent materials and that mineral weathering in this area was weak. Except the

  2. Short-term dynamics of carbon and nitrogen using compost, compost-biochar mixture and organo-mineral biochar.

    PubMed

    Darby, Ian; Xu, Cheng-Yuan; Wallace, Helen M; Joseph, Stephen; Pace, Ben; Bai, Shahla Hosseini

    2016-06-01

    This study aims to examine the effects of different organic treatments including compost (generated from cattle hide waste and plant material), compost mixed with biochar (compost + biochar) and a new formulation of organo-mineral biochar (produced by mixing biochar with clay, minerals and chicken manure) on carbon (C) nitrogen (N) cycling. We used compost at the rate of 20 t ha(-1), compost 20 t ha(-1) mixed with 10 t ha(-1) biochar (compost + biochar) and organo-mineral biochar which also contained 10 t ha(-1) biochar. Control samples received neither of the treatments. Compost and compost + biochar increased NH4 (+) -N concentrations for a short time, mainly due to the release of their NH4 (+) -N content. Compost + biochar did not alter N cycling of the compost significantly but did significantly increase CO2 emission compared to control. Compost significantly increased N2O emission compared to control. Compost + biochar did not significantly change N supply and also did not decrease CO2 and N2O emissions compared to compost, suggesting probably higher rates of biochar may be required to be added to the compost to significantly affect compost-induced C and N alteration. The organo-mineral biochar had no effect on N cycling and did not stimulate CO2 and N2O emission compared to the control. However, organo-mineral biochar maintained significantly higher dissolved organic carbon (DOC) than compost and compost + biochar from after day 14 to the end of the incubation. Biochar used in organo-mineral biochar had increased organic C adsorption which may become available eventually. However, increased DOC in organo-mineral biochar probably originated from both biochar and chicken manure which was not differentiated in this experiment. Hence, in our experiment, compost, compost + biochar and organo-mineral biochar affected C and N cycling differently mainly due to their different content.

  3. Binding carbon dioxide in mineral form: A critical step towards a zero-emission coal power plant

    SciTech Connect

    Lackner, K.S.; Butt, D.P.; Wendt, C.H.

    1998-11-01

    This is the final report of a three-year, Laboratory Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). The authors have successfully developed the foundation for sequestration of carbon dioxide in mineral form. The purpose of this technology is to maintain the competitiveness of coal energy, even when in the future environmental and political pressures will require a drastic reduction in carbon dioxide emissions. In contrast to most other sequestration methods, this is not aiming at a partial solution of the problem, or at buying time for phasing out fossil energy. Instead, the goal is to obtain a complete and economic solution of the problem, and thus maintain access to the vast fossil energy reservoir. Such a technology will guarantee energy availability for many centuries even if world economic growth exceeds the most optimistic estimates. The approach differs from all others in that the authors are developing an industrial process that chemically binds the carbon dioxide in an exothermic reaction into a mineral carbonate that is thermodynamically stable and environmentally benign.

  4. A composite reactor with wetted-wall column for mineral carbonation study in three-phase systems.

    PubMed

    Zhu, Chen; Yao, Xizhi; Zhao, Liang; Teng, H Henry

    2016-11-01

    Despite the availability of various reactors designed to study gas-liquid reactions, no appropriate devices are available to accurately investigate triple-phased mineral carbonation reactions involving CO2 gas, aqueous solutions (containing divalent cations), and carbonate minerals. This report presents a composite reactor that combines a modified conventional wetted-wall column, a pH control module, and an attachment to monitor precipitation reactions. Our test and calibration experiments show that the absorption column behaved largely in agreement with theoretical predictions and previous observations. Experimental confirmation of CO2 absorption in NaOH and ethanolamine supported the effectiveness of the column for gas-liquid interaction. A test run in the CO2-NH3-MgCl2 system carried out for real time investigation of the relevant carbonation reactions shows that the reactor's performance closely followed the expected reaction path reflected in pH change, the occurrence of precipitation, and the rate of NH3 addition, indicating the appropriateness of the composite device in studying triple-phase carbonation process.

  5. Hydrochemistry and origin of CO2 gas and noble gas of carbonated mineral water in the Gyeongbuk-Gangwon Province, South Korea

    NASA Astrophysics Data System (ADS)

    Jeong, C. H.; Yoo, S. W.

    2012-04-01

    Hydrochemical, carbon isotopic (δ13CDIC) analyses of 11 samples, and noble gas isotopic analyses of 8 samples collected in the Gangwon and the Gyeongbuk area of South Korea were carried out to elucidate hydrochemical characteristics and to interpret the source of noble gases and CO2 gas. The carbonated mineral waters show a weak acidic pH between 5.59 and 6.04. An electrical conductivity of carbonated mineral waters ranges from 302 to 864 μS/cm. The chemical composition of all carbonated mineral waters can be grouped into only one type such as Ca-HCO3. A high content of Fe and Mn in carbonated mineral waters exceeds a regulation limit of drinking water. The δ13CDIC values of carbonated mineral waters show the range of -5.30~-2.84 ‰. This range indicates that the carbon of carbonated mineral waters is mainly supplied from a deep-seated source and partly from an inorganic carbonate source. The 3He/4He ratios of the carbonated mineral waters show the range of 1.51×10-6 to 6.45×10-6. The carbonated mineral waters on the 3He/4He and 4He/20Ne diagram are plotted into three groups: deep seated area such as mantle source, atmospheric area, and air-mantle mixing area. A wide range of 4He/20Ne ratios is observed (0.036×10-6 to 1.76×10-6), showing evidence that while radiogenic 4He is dominant in these water samples, He of mantle-origin is also supplied to these waters. It is estimated that supply of CO2 gas and noble gas of a deep-seated source into carbonated waters is closely related to geologic structures such as fault and geologic boundary. Key words: carbonated mineral waters, hydrochemical composition, carbon isotope, 3He/4He, deep-seated origin

  6. Interactive control of minerals, wildfire, and erosion on soil carbon stabilization in conifer ecosystems of the western U.S.

    NASA Astrophysics Data System (ADS)

    Rasmussen, C.

    2014-12-01

    Answering the question of what controls the fate and stabilization of organic carbon in forest soils is central to understanding the role of western US ecosystems in mitigating climate change, optimizing forest management, and quantifying local and regional terrestrial carbon budgets. Over half of forest soil C is stored belowground, stabilized by a number of separate, but interacting physical, chemical and biological mechanisms. Here we synthesize data from a series of field and laboratory studies focused on identifying mineral, physical, and landscape position controls on belowground C stabilization mechanisms in western U.S. conifer ecosystems. Results from these studies demonstrate an important for role for short-range-order Fe- and Al-oxyhydroxides and Al-humus complexes in C stabilization, and that the soil mineral assemblage moderates C cycling via control on partitioning of C into physical fractions ("free", "occluded", "mineral") with varying MRT and chemistry. Measures of occluded fraction chemical composition by 13C-NMR indicate this fraction is 2-5 times more enriched in pyrogenic C than the bulk soil and that this fraction is on the order of ~25 to 65% charred materials. Radiocarbon analyses of a large set of conifer soil samples from California and Arizona further indicate the occluded fraction is generally older than either the free light or mineral fraction. In particular, soil C in convergent, water and sediment gathering portions of the landscape are enriched in long MRT charred materials. These results indicate an important role for the interaction of soil mineral assemblage, wildfire, and erosion in controlling belowground C storage and stabilization in western conifer forests. Drought and wildfire are expected to increase with climate change and thus may exert significant control on belowground C storage directly through biochemical and physical changes in aboveground biomass, production of charred materials, and indirectly via post

  7. Equilibrium magnesium isotope fractionation between aqueous Mg2+ and carbonate minerals: Insights from path integral molecular dynamics

    NASA Astrophysics Data System (ADS)

    Pinilla, Carlos; Blanchard, Marc; Balan, Etienne; Natarajan, Suresh K.; Vuilleumier, Rodolphe; Mauri, Francesco

    2015-08-01

    The theoretical determination of the isotopic fractionation between an aqueous solution and a mineral is of utmost importance in Earth sciences. While for crystals, it is well established that equilibrium isotopic fractionation factors can be calculated using a statistical thermodynamic approach based on the vibrational properties, several theoretical methods are currently used to model ions in aqueous solution. In this work, we present a systematic study to determine the reduced partition function ratio (β-factor) of aqueous Mg2+ using several levels of theory within the simulations. In particular, using an empirical force field, we compare and discuss the performance of the exact results obtained from path integral molecular dynamics (PIMD) simulations, with respect to the more traditional methods based on vibrational properties and the cluster approximation. The results show the importance of including configurational disorder for the estimation of the equilibrium isotope fractionation factor. We also show that using the vibrational frequencies computed from snapshots taken from equilibrated classical molecular dynamics represents a good approximation for the study of aqueous ions. Based on these conclusions, the β-factor of aqueous Mg2+ have been estimated from a Car-Parrinello molecular dynamics (CPMD) simulation with an ab initio force field, and combined with the β-factors of carbonate minerals (magnesite, dolomite, calcite and aragonite). Mg β-factor of Mg-bearing aragonite, calculated here for the first time, displays a lower value than the three other carbonate minerals. This is explained by a strong distortion of the cationic site leading to a decrease of the coordination number during Ca-Mg substitution. Overall, the equilibrium magnesium isotope fractionation factors between aqueous Mg2+ and carbonate minerals that derive from this methodological study support the previous theoretical results obtained from embedded cluster models.

  8. Thermodynamic Control of the Isotope Composition of Divalent Metal Cations in Aqueous Solutions and in Carbonate Minerals

    NASA Astrophysics Data System (ADS)

    Schott, J.; Mavromatis, V.; Pearce, C. R.; Fujii, T.; Oelkers, E. H.

    2014-12-01

    The very contrasting steric and electronic properties of divalent metals dramatically affect the reactivity and composition of their aqueous species and their partitioning between fluids and minerals. These contrasting properties result also in very distinct kinetic and thermodynamic trends of their isotopic composition in aqueous fluids and carbonate minerals. For example, if alkaline earths in calcite are all enriched in light isotopes, only Mg exhibits a decrease of its isotope fractionation with increasing calcite growth rate. Moreover, the Mg2+ aquo ion is the only alkaline earth ion whose isotopic composition is markedly affected by the presence in solution of inorganic ligands like bicarbonate, carbonate or sulfate. The distinct behavior of Mg stems from the reduced lability of water molecules in its coordination sphere and from the reduction of its aquo ion coordination sphere when it coordinates to HCO3- and CO32-. Ab initio calculations show that the preferred four hydration number of Mg in stable Mg bicarbonate and Mg carbonate monomers results in a strong enrichment in 26Mg of these species compared to Mg(H2O)62+ (i.e. 1000lnβ26/24MgCO3°-1000lnβ26/24Mg2+ = 5.16 ‰; Fujii, personal communication). The analysis of recent experiments on Mg isotope fractionation between carbonate crystals and solution using density functionnal theory estimation of lnβ values from Fujii i) confirm the marked impact of carbonate and bicarbonate ligands on the isotope composition of Mg in calcite and magnesite and ii) allow to reconcile First-principles and experimental estimates of equilibrium Mg isotope fractionation in carbonate crystals. Recent experiments also confirm that the strong affinity of Zn2+ or Cu2+ for RO- ligands results in a marked impact of fluid pH, ΣCO2(aq) and/or carboxylic ligands concentrations on the isotope composition of these metals in carbonate minerals. These observations provide new insights into the parameters controlling the isotope

  9. Formation of Carbonate Minerals in Martian Meteorite ALH 84001 from Cool Water Near the Surface of Mars

    NASA Astrophysics Data System (ADS)

    Taylor, G. J.

    2011-12-01

    Carbonate minerals in the Allan Hills 84001 meteorite are important because they ought to contain information about the chemistry and temperature of the water they formed in. They are also an important part of testing the idea that the meteorite contains evidence of past life on Mars. Hypotheses for the origin of the carbonates are impressively varied. A key test of the ideas is to determine the temperature at which the carbonates formed. Estimates up to now range from a bit below freezing to 700 oC, too big a range to test anything! To address the problem Itay Halevy, Woodward Fischer, and John Eiler (Caltech) used an approach that involves "clumped" isotope thermometry, which makes comparisons among different isotopic compositions of extracted CO2. This allowed the investigators to use the isotopic abundances of both carbon and oxygen. The results indicate that the carbonates formed at 18 ± 4 oC from a shallow subsurface (upper few meters to tens of meters) pool of water that was gradually evaporating. The wet episode did not last long, leading Halevy and his colleagues to conclude that the environment may have been too transient for life to have emerged here from scratch. On the other hand, if life already existed on the Martian surface this wet near-surface environment would have provided a happy home. An impact blasted the Martian home of ALH 84001, causing a transient heating event, perhaps disturbing the isotopic record...or perhaps not because the event was so short. In any case, the clumped isotope thermometry approach seems to have given a good measurement of the temperature at which the carbonate minerals formed.

  10. Ultra-fine grinding and mechanical activation of mine waste rock using a high-speed stirred mill for mineral carbonation

    NASA Astrophysics Data System (ADS)

    Li, Jia-jie; Hitch, Michael

    2015-10-01

    CO2 sequestration by mineral carbonation can permanently store CO2 and mitigate climate change. However, the cost and reaction rate of mineral carbonation must be balanced to be viable for industrial applications. In this study, it was attempted to reduce the carbonation costs by using mine waste rock as a feed stock and to enhance the reaction rate using wet mechanical activation as a pre-treatment method. Slurry rheological properties, particle size distribution, specific surface area, crystallinity, and CO2 sequestration reaction efficiency of the initial and mechanically activated mine waste rock and olivine were characterized. The results show that serpentine acts as a catalyst, increasing the slurry yield stress, assisting new surface formation, and hindering the size reduction and structure amorphization. Mechanically activated mine waste rock exhibits a higher carbonation conversion than olivine with equal specific milling energy input. The use of a high-speed stirred mill may render the mineral carbonation suitable for mining industrial practice.

  11. Environmental benefits of using magnesium carbonate minerals as new wildfire retardants instead of commercially available, phosphate-based compounds.

    PubMed

    Liodakis, S; Tsoukala, M

    2010-10-01

    A serial batch leaching experiment has been carried out to evaluate the release of elements from the ash of Pinus halepensis needles burned under two test conditions-with and without treatment of the forest species with the carbonate minerals (huntite and hydromagnesite) in aqueous solution (pH 6). The ash (before and after leaching) and leachates were analyzed using atomic absorption spectroscopy and X-ray diffraction. Compared with data from samples treated with the commercially available, phosphate-based fire retardant diammonium phosphate (DAP), we found that use of huntite or hydromagnesite was much more successful in obstructing the release of the toxic elements present in the ash, probably because of the alkaline conditions resulting from decomposition of the minerals during burning. In contrast, DAP tended to be more able to facilitate the extraction of some toxic metals (e.g., Zn, Cu, Mn), probably because of the acidic conditions resulting from its decomposition to phosphoric acid. Data from this study thus lend strong support to the use of magnesium carbonate minerals as new wildfire retardants, because they were shown to be more friendly to the environment (e.g., soil, ground, and underground water streams) than those currently in use (e.g., phosphate or sulfate salt type).

  12. Geochemical modeling of scale formation, and formation damage during production from sulfate and carbonate mineral-bearing reservoirs

    SciTech Connect

    Macgowan, D.B.; Dunn, T.L.; Surdam, R.C. )

    1991-03-01

    The physical and chemical processes that affect reservoir fluids during production can be modeled by methodologies similar to those used for modeling clastic diagenesis. That these processes may result in formation damage and scale formation make them of interest to production geologists and engineers. Pathway modeling, based upon a series of critical divides, predicts which reactions are likely to occur between formation, production tubing, and reservoir fluids. Thermodynamic equilibria modeling calculates direction and magnitude of possible reactions. Integration of these approaches with observations of patterns of scale formation, production line, and formation damage yield a model capable of predicting the magnitude and direction of reactions that may produce negative impacts on reservoir production. Critical divides characterizing these processes in carbonate and sulfate mineral-bearing reservoirs include: (1) presence or absence of sulfate-bearing minerals within the production volume; (2) presence of iron within production line or formation; (3) ratio of concentration of bicarbonate to hydrogen sulfide; (4) capacity of aqueous and solid phases to buffer formation fluid pH; and (5) magnitude of pressure and temperature drops during production. The model qualitatively predicts: (1) likelihood of sulfide, sulfate, or carbonate mineral precipitation during production; (2) souring of the reservoir; and (3) corrosion of production tubing. The model has been developed from production histories for Weber Sandstone reservoirs, Colorado and Wyoming, and has been applied to examples of reservoir production from Tensleep and Minnelusa reservoirs in Wyoming.

  13. Mineral associated and aggregate-occluded soil carbon decreased with increasing nitrogen and residue input for three decades

    NASA Astrophysics Data System (ADS)

    Shahbaz, Muhammad; Kuzyakov, Yakov; Heitkamp, Felix

    2016-04-01

    Cropland soils may be a source or sink for atmospheric CO2. Therefore, effects of cropland management and fertilization on soil organic carbon (SOC) can be assessed best in long-term experiments. Generally, it is assumed that change in SOC is linearly related to C-input into the soil. However, recently it has been shown that residue incorporation resulted to only small extents in the increase of SOC levels. This gives rise to environmental concerns regarding the efficient use of crop residue. Such concerns are also applicable for the well designed and documented long-term experiment of Puch, Germany, in a silt-loam soil. The crop rotation is winter barley - winter wheat - silage maize. Five organic amendments were combined with N-fertiliser rates. The levels of organic amendments are unamended control (CON), straw was removed; farmyard manure (FYM), straw was removed; straw incorporation (STR); slurry application (SLU), straw was removed; and straw incorporation combined with slurry application (STSL). Three levels of mineral fertilizer application were selected: no nitrogen (N0); medium, 100 kg N ha-1year-1 (N2); and high, 200 kg N ha-1 year-1 (N4). These treatments resulted in a wide range of mean annual carbon input (1 - 5 t C ha-1 year-1). We hypothesize that the amount of soil carbon stored in different fractions will increase with C-input, but the effect will decrease in the order free light fraction (f-LF), occluded light fraction (o-LF) and heavy mineral-associated fraction (