Science.gov

Sample records for co2 chemical upgrading

  1. A review on optimization production and upgrading biogas through CO2 removal using various techniques.

    PubMed

    Andriani, Dian; Wresta, Arini; Atmaja, Tinton Dwi; Saepudin, Aep

    2014-02-01

    Biogas from anaerobic digestion of organic materials is a renewable energy resource that consists mainly of CH4 and CO2. Trace components that are often present in biogas are water vapor, hydrogen sulfide, siloxanes, hydrocarbons, ammonia, oxygen, carbon monoxide, and nitrogen. Considering the biogas is a clean and renewable form of energy that could well substitute the conventional source of energy (fossil fuels), the optimization of this type of energy becomes substantial. Various optimization techniques in biogas production process had been developed, including pretreatment, biotechnological approaches, co-digestion as well as the use of serial digester. For some application, the certain purity degree of biogas is needed. The presence of CO2 and other trace components in biogas could affect engine performance adversely. Reducing CO2 content will significantly upgrade the quality of biogas and enhancing the calorific value. Upgrading is generally performed in order to meet the standards for use as vehicle fuel or for injection in the natural gas grid. Different methods for biogas upgrading are used. They differ in functioning, the necessary quality conditions of the incoming gas, and the efficiency. Biogas can be purified from CO2 using pressure swing adsorption, membrane separation, physical or chemical CO2 absorption. This paper reviews the various techniques, which could be used to optimize the biogas production as well as to upgrade the biogas quality.

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

    PubMed

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

    2014-12-01

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

  3. Metal-organic frameworks for upgrading biogas via CO2 adsorption to biogas green energy.

    PubMed

    Chaemchuen, Somboon; Kabir, Nawsad Alam; Zhou, Kui; Verpoort, Francis

    2013-12-21

    In the midst of the global climate change phenomenon, mainly caused by fossil fuel burning to provide energy for our daily life and discharge of CO2 into the atmosphere, biogas is one of the important renewable energy sources that can be upgraded and applied as a fuel source for energy in daily life. The advantages of the production of hybrid materials, metal-organic framework (MOF) adsorbents, expected for the biogas upgrading, rely on the bulk separation of CO2 under near-ambient conditions. This review highlights the challenges for MOF adsorbents, which have the greatest upgrading abilities for biogas via selective passage of methane. The key factors improving the ideal MOF materials for these high CO2 capture and selectivity uses for biogas upgrading to produce bio-methane and reduce fossil-fuel CO2 emission will be discussed.

  4. Remote sensing of chemical warfare agent by CO2 -lidar

    NASA Astrophysics Data System (ADS)

    Geiko, Pavel P.; Smirnov, Sergey S.

    2014-11-01

    The possibilities of remote sensing of chemical warfare agent by differential absorption method were analyzed. The CO2 - laser emission lines suitable for sounding of chemical warfare agent with provision for disturbing absorptions by water vapor were choose. The detection range of chemical warfare agents was estimated for a lidar based on CO2 - laser The other factors influencing upon echolocation range were analyzed.

  5. Interpenetrating Metal-Metalloporphyrin Framework for Selective CO2 Uptake and Chemical Transformation of CO2.

    PubMed

    Gao, Wen-Yang; Tsai, Chen-Yen; Wojtas, Lukasz; Thiounn, Timmy; Lin, Chu-Chieh; Ma, Shengqian

    2016-08-01

    Herein we report a robust primitive cubic (pcu)-topology metal-metalloporphyrin framework (MMPF), MMPF-18, which was constructed from a ubiquitous secondary building unit of a tetranuclear zinc cluster, Zn4(μ4-O)(-COO)6, and a linear organic linker of 5,15-bis(4-carboxyphenyl)porphyrin (H2bcpp). The strong π-π stacking from porphyrins and the lengthy H2bcpp ligand affords a 4-fold-interpenetrating network along with reduced void spaces and confined narrow channels. Thereby, MMPF-18 presents segmented pores and high-density metalloporphyrin centers for selective CO2 uptake over CH4 and size-selective chemical transformation of CO2 with epoxides forming cyclic carbonates under ambient conditions. PMID:27337152

  6. Evaporative CO2 microchannel cooling for the LHCb VELO pixel upgrade

    NASA Astrophysics Data System (ADS)

    de Aguiar Francisco, O. A.; Buytaert, J.; Collins, P.; Dumps, R.; John, M.; Mapelli, A.; Romagnoli, G.

    2015-05-01

    The LHCb Vertex Detector (VELO) will be upgraded in 2018 to a lightweight pixel detector capable of 40 MHz readout and operation in very close proximity to the LHC beams. The thermal management of the system will be provided by evaporative CO2 circulating in microchannels embedded within thin silicon plates. This solution has been selected due to the excellent thermal efficiency, the absence of thermal expansion mismatch with silicon ASICs and sensors, the radiation hardness of CO2, and very low contribution to the material budget. Although microchannel cooling is gaining considerable attention for applications related to microelectronics, it is still a novel technology for particle physics experiments, in particular when combined with evaporative CO2 cooling. The R&D effort for LHCb is focused on the design and layout of the channels together with a fluidic connector and its attachment which must withstand pressures up to 170 bar. Even distribution of the coolant is ensured by means of the use of restrictions implemented before the entrance to a race track like layout of the main cooling channels. The coolant flow and pressure drop have been simulated as well as the thermal performance of the device. This proceeding describes the design and optimization of the cooling system for LHCb and the latest prototyping results.

  7. Utilization of CO2 fixating bacterium Actinobacillus succinogenes 130Z for simultaneous biogas upgrading and biosuccinic acid production.

    PubMed

    Gunnarsson, Ingólfur B; Alvarado-Morales, Merlin; Angelidaki, Irini

    2014-10-21

    Biogas is an attractive renewable energy carrier. However, it contains CO2 which limits its use for certain applications. Here we report a novel approach for removing CO2 from biogas and capturing it as a biochemical through a biological process. This approach entails converting CO2 into biosuccinic acid using the bacterial strain Actinobacillus succinogenes 130 Z, and simultaneously producing high-purity CH4 (> 95%). Results showed that when pressure during fermentation was increased from 101.325 to 140 kPa, higher CO2 solubility was achieved, thereby positively affecting final succinic acid yield and titer, CO2 consumption rate, and CH4 purity. When using biogas as the only CO2 source at 140 kPa, the CO2 consumption rate corresponded to 2.59 L CO2 L(-1) d(-1) with a final succinic acid titer of 14.4 g L(-1). Under this pressure condition, the highest succinic acid yield and biogas quality reached corresponded to 0.635 g g(-1) and 95.4% (v v(-1)) CH4 content, respectively, after 24 h fermentation. This work represents the first successful attempt to develop a system capable of upgrading biogas to vehicle fuel/gas grid quality and simultaneously produce biosuccinic acid, a valuable building block with large market potential in the near term.

  8. Hydroquinone and Quinone-Grafted Porous Carbons for Highly Selective CO2 Capture from Flue Gases and Natural Gas Upgrading.

    PubMed

    Wang, Jun; Krishna, Rajamani; Yang, Jiangfeng; Deng, Shuguang

    2015-08-01

    Hydroquinone and quinone functional groups were grafted onto a hierarchical porous carbon framework via the Friedel-Crafts reaction to develop more efficient adsorbents for the selective capture and removal of carbon dioxide from flue gases and natural gas. The oxygen-doped porous carbons were characterized with scanning electron microscopy, transmission electron microscopy, X-ray powder diffraction, Fourier transform infrared spectroscopy, and Raman spectroscopy. CO2, CH4, and N2 adsorption isotherms were measured and correlated with the Langmuir model. An ideal adsorbed solution theory (IAST) selectivity for the CO2/N2 separation of 26.5 (298 K, 1 atm) was obtained on the hydroquinone-grafted carbon, which is 58.7% higher than that of the pristine porous carbon, and a CO2/CH4 selectivity value of 4.6 (298 K, 1 atm) was obtained on the quinone-grafted carbon (OAC-2), which represents a 28.4% improvement over the pristine porous carbon. The highest CO2 adsorption capacity on the oxygen-doped carbon adsorbents is 3.46 mmol g(-1) at 298 K and 1 atm. In addition, transient breakthrough simulations for CO2/CH4/N2 mixture separation were conducted to demonstrate the good separation performance of the oxygen-doped carbons in fixed bed adsorbers. Combining excellent adsorption separation properties and low heats of adsorption, the oxygen-doped carbons developed in this work appear to be very promising for flue gas treatment and natural gas upgrading.

  9. Will chemical defenses become more effective against specialist herbivores under elevated CO2?

    PubMed

    Landosky, John M; Karowe, David N

    2014-10-01

    Elevated atmospheric CO2 is known to affect plant-insect herbivore interactions. Elevated CO2 causes leaf nitrogen to decrease, the ostensible cause of herbivore compensatory feeding. CO2 may also affect herbivore consumption by altering chemical defenses via changes in plant hormones. We considered the effects of elevated CO2, in conjunction with soil fertility and damage (simulated herbivory), on glucosinolate concentrations of mustard (Brassica nigra) and collard (B. oleracea var. acephala) and the effects of leaf nitrogen and glucosinolate groups on specialist Pieris rapae consumption. Elevated CO2 affected B. oleracea but not B. nigra glucosinolates; responses to soil fertility and damage were also species-specific. Soil fertility and damage also affected B. oleracea glucosinolates differently under elevated CO2. Glucosinolates did not affect P. rapae consumption at either CO2 concentration in B. nigra, but had CO2-specific effects on consumption in B. oleracea. At ambient CO2, leaf nitrogen had strong effects on glucosinolate concentrations and P. rapae consumption but only gluconasturtiin was a feeding stimulant. At elevated CO2, direct effects of leaf nitrogen were weaker, but glucosinolates had stronger effects on consumption. Gluconasturtiin and aliphatic glucosinolates were feeding stimulants and indole glucosinolates were feeding deterrents. These results do not support the compensatory feeding hypothesis as the sole driver of changes in P. rapae consumption under elevated CO2. Support for hormone-mediated CO2 response (HMCR) was mixed; it explained few treatment effects on constitutive or induced glucosinolates, but did explain patterns in SEMs. Further, the novel feeding deterrent effect of indole glucosinolates under elevated CO2 in B. oleracae underscores the importance of defensive chemistry in CO2 response. We speculate that P. rapae indole glucosinolate detoxification mechanisms may have been overwhelmed under elevated CO2 forcing slowed

  10. Will chemical defenses become more effective against specialist herbivores under elevated CO2?

    PubMed

    Landosky, John M; Karowe, David N

    2014-10-01

    Elevated atmospheric CO2 is known to affect plant-insect herbivore interactions. Elevated CO2 causes leaf nitrogen to decrease, the ostensible cause of herbivore compensatory feeding. CO2 may also affect herbivore consumption by altering chemical defenses via changes in plant hormones. We considered the effects of elevated CO2, in conjunction with soil fertility and damage (simulated herbivory), on glucosinolate concentrations of mustard (Brassica nigra) and collard (B. oleracea var. acephala) and the effects of leaf nitrogen and glucosinolate groups on specialist Pieris rapae consumption. Elevated CO2 affected B. oleracea but not B. nigra glucosinolates; responses to soil fertility and damage were also species-specific. Soil fertility and damage also affected B. oleracea glucosinolates differently under elevated CO2. Glucosinolates did not affect P. rapae consumption at either CO2 concentration in B. nigra, but had CO2-specific effects on consumption in B. oleracea. At ambient CO2, leaf nitrogen had strong effects on glucosinolate concentrations and P. rapae consumption but only gluconasturtiin was a feeding stimulant. At elevated CO2, direct effects of leaf nitrogen were weaker, but glucosinolates had stronger effects on consumption. Gluconasturtiin and aliphatic glucosinolates were feeding stimulants and indole glucosinolates were feeding deterrents. These results do not support the compensatory feeding hypothesis as the sole driver of changes in P. rapae consumption under elevated CO2. Support for hormone-mediated CO2 response (HMCR) was mixed; it explained few treatment effects on constitutive or induced glucosinolates, but did explain patterns in SEMs. Further, the novel feeding deterrent effect of indole glucosinolates under elevated CO2 in B. oleracae underscores the importance of defensive chemistry in CO2 response. We speculate that P. rapae indole glucosinolate detoxification mechanisms may have been overwhelmed under elevated CO2 forcing slowed

  11. Low-temperature upgrading of low-calorific biogas for CO2 mitigation using DBD-catalyst hybrid reactor

    NASA Astrophysics Data System (ADS)

    Nozaki, Tomohiro; Tsukijihara, Hiroyuki; Fukui, Wataru; Okazaki, Ken

    2006-10-01

    Although huge amounts of biogas, which consists of 20-60% of CH4 in CO2/N2, can be obtained from landfills, coal mines, and agricultural residues, most of them are simply flared and wasted: because global warming potential of biogas is 5-15 times as potent as CO2. Poor combustibility of such biogas makes it difficult to utilize in conventional energy system. The purpose of this project is to promote the profitable recovery of methane from poor biogas via non-thermal plasma technology. We propose low-temperature steam reforming of biogas using DBD generated in catalyst beds. Methane is partially converted into hydrogen, and then fed into internal combustion engines for improved ignition stability as well as efficient operation. Low-temperature steam reforming is beneficial because exhaust gas from an engine can be used to activate catalyst beds. Space velocity (3600-15000 hr-1), reaction temperature (300-650^oC), and energy cost (30-150 kJ per mol CH4) have been investigated with simulated biogas (20-60% CH4 in mixtures of CO2/N2). The DBD enhances reaction rate of CH4 by a factor of ten at given catalyst temperatures, which is a rate-determining step of methane steam reforming, while species concentration of upgraded biogas was governed by thermodynamic equilibrium in the presence of catalyst.

  12. CO2 utilization: an enabling element to move to a resource- and energy-efficient chemical and fuel production.

    PubMed

    Ampelli, Claudio; Perathoner, Siglinda; Centi, Gabriele

    2015-03-13

    CO(2) conversion will be at the core of the future of low-carbon chemical and energy industry. This review gives a glimpse into the possibilities in this field by discussing (i) CO(2) circular economy and its impact on the chemical and energy value chain, (ii) the role of CO(2) in a future scenario of chemical industry, (iii) new routes for CO(2) utilization, including emerging biotechnology routes, (iv) the technology roadmap for CO(2) chemical utilization, (v) the introduction of renewable energy in the chemical production chain through CO(2) utilization, and (vi) CO(2) as a suitable C-source to move to a low-carbon chemical industry, discussing in particular syngas and light olefin production from CO(2). There are thus many stimulating possibilities offered by using CO(2) and this review shows this new perspective on CO(2) at the industrial, societal and scientific levels.

  13. CO2 utilization: an enabling element to move to a resource- and energy-efficient chemical and fuel production.

    PubMed

    Ampelli, Claudio; Perathoner, Siglinda; Centi, Gabriele

    2015-03-13

    CO(2) conversion will be at the core of the future of low-carbon chemical and energy industry. This review gives a glimpse into the possibilities in this field by discussing (i) CO(2) circular economy and its impact on the chemical and energy value chain, (ii) the role of CO(2) in a future scenario of chemical industry, (iii) new routes for CO(2) utilization, including emerging biotechnology routes, (iv) the technology roadmap for CO(2) chemical utilization, (v) the introduction of renewable energy in the chemical production chain through CO(2) utilization, and (vi) CO(2) as a suitable C-source to move to a low-carbon chemical industry, discussing in particular syngas and light olefin production from CO(2). There are thus many stimulating possibilities offered by using CO(2) and this review shows this new perspective on CO(2) at the industrial, societal and scientific levels. PMID:25666059

  14. Organic reactions for the electrochemical and photochemical production of chemical fuels from CO2--The reduction chemistry of carboxylic acids and derivatives as bent CO2 surrogates.

    PubMed

    Luca, Oana R; Fenwick, Aidan Q

    2015-11-01

    The present review covers organic transformations involved in the reduction of CO2 to chemical fuels. In particular, we focus on reactions of CO2 with organic molecules to yield carboxylic acid derivatives as a first step in CO2 reduction reaction sequences. These biomimetic initial steps create opportunities for tandem electrochemical/chemical reductions. We draw parallels between long-standing knowledge of CO2 reactivity from organic chemistry, organocatalysis, surface science and electrocatalysis. We point out some possible non-faradaic chemical reactions that may contribute to product distributions in the production of solar fuels from CO2. These reactions may be accelerated by thermal effects such as resistive heating and illumination.

  15. Early opportunities of CO2 geological storage deployment in coal chemical industry in China

    SciTech Connect

    Wei, Ning; Li, Xiaochun; Liu, Shengnan; Dahowski, Robert T.; Davidson, Casie L.

    2014-11-12

    Abstract: Carbon dioxide capture and geological storage (CCS) is regarded as a promising option for climate change mitigation; however, the high capture cost is the major barrier to large-scale deployment of CCS technologies. High-purity CO2 emission sources can reduce or even avoid the capture requirements and costs. Among these high-purity CO2 sources, certain coal chemical industry processes are very important, especially in China. In this paper, the basic characteristics of coal chemical industries in China is investigated and analyzed. As of 2013 there were more than 100 coal chemical plants in operation or in late planning stages. These emission sources together emit 430 million tons CO2 per year, of which about 30% are emit high-purity and pure CO2 (CO2 concentration >80% and >99% respectively).Four typical source-sink pairs are studied by a techno-economic evaluation, including site screening and selection, source-sink matching, concept design, and experienced economic evaluation. The technical-economic evaluation shows that the levelized cost of a CO2 capture and aquifer storage project in the coal chemistry industry ranges from 14 USD/t to 17 USD/t CO2. When a 15USD/t CO2 tax and 15USD/t for CO2 sold to EOR are considered, the levelized cost of CCS project are negative, which suggests a net economic benefit from some of these CCS projects. This might provide China early opportunities to deploy and scale-up CCS projects in the near future.

  16. Thermo-chemical process with sewage sludge by using CO2.

    PubMed

    Kwon, Eilhann E; Yi, Haakrho; Kwon, Hyun-Han

    2013-10-15

    This work proposed a novel methodology for energy recovery from sewage sludge via the thermo-chemical process. The impact of CO2 co-feed on the thermo-chemical process (pyrolysis and gasification) of sewage sludge was mainly investigated to enhance thermal efficiency and to modify the end products from the pyrolysis and gasification process. The CO2 injected into the pyrolysis and gasification process enhance the generation of CO. As compared to the thermo-chemical process in an inert atmosphere (i.e., N2), the generation of CO in the presence of CO2 was enhanced approximately 200% at the temperature regime from 600 to 900 °C. The introduction of CO2 into the pyrolysis and gasification process enabled the condensable hydrocarbons (tar) to be reduced considerably by expediting thermal cracking (i.e., approximately 30-40%); thus, exploiting CO2 as chemical feedstock and/or reaction medium for the pyrolysis and gasification process leads to higher thermal efficiency, which leads to environmental benefits. This work also showed that sewage sludge could be a very strong candidate for energy recovery and a raw material for chemical feedstock. PMID:23792821

  17. Biocatalysis for the application of CO2 as a chemical feedstock

    PubMed Central

    Easton, Christopher J

    2015-01-01

    Summary Biocatalysts, capable of efficiently transforming CO2 into other more reduced forms of carbon, offer sustainable alternatives to current oxidative technologies that rely on diminishing natural fossil-fuel deposits. Enzymes that catalyse CO2 fixation steps in carbon assimilation pathways are promising catalysts for the sustainable transformation of this safe and renewable feedstock into central metabolites. These may be further converted into a wide range of fuels and commodity chemicals, through the multitude of known enzymatic reactions. The required reducing equivalents for the net carbon reductions may be drawn from solar energy, electricity or chemical oxidation, and delivered in vitro or through cellular mechanisms, while enzyme catalysis lowers the activation barriers of the CO2 transformations to make them more energy efficient. The development of technologies that treat CO2-transforming enzymes and other cellular components as modules that may be assembled into synthetic reaction circuits will facilitate the use of CO2 as a renewable chemical feedstock, greatly enabling a sustainable carbon bio-economy. PMID:26734087

  18. Sigmoid Correlations for Gas Solubility and Enthalpy Change of Chemical Absorption of CO2

    DOE PAGES

    Huang, Kuan; Wu, You-Ting; Dai, Sheng

    2015-10-01

    Knowledge of the relationship between gas solubility and enthalpy change of chemical absorption of CO2 is very important for exploring energy-efficient absorbents for CO2 capture. To this end, equations that can directly correlate gas solubility with absorption enthalpy were derived through combining the van’t Hoff equation with the reaction equilibrium thermodynamic model (RETM). In this study, two typical reaction mechanisms for chemical absorption of CO2 (1:1 and 1:2) were considered for RETM. The variations of gas solubility with enthalpy change were found to be distinctively sigmoid functions, regardless of the investigated temperature and pressure or assumed reaction forms between CO2more » and the absorbent molecule. Theoretically calculated variation curves of gas solubility vs enthalpy change agreed well with experimental results reported in literature. Also, on the basis of the trade-off relationship between gas solubility and enthalpy change, criterions for evaluating energy-efficient chemical absorbents for CO2 capture were proposed.« less

  19. Biocatalysis for the application of CO2 as a chemical feedstock.

    PubMed

    Alissandratos, Apostolos; Easton, Christopher J

    2015-01-01

    Biocatalysts, capable of efficiently transforming CO2 into other more reduced forms of carbon, offer sustainable alternatives to current oxidative technologies that rely on diminishing natural fossil-fuel deposits. Enzymes that catalyse CO2 fixation steps in carbon assimilation pathways are promising catalysts for the sustainable transformation of this safe and renewable feedstock into central metabolites. These may be further converted into a wide range of fuels and commodity chemicals, through the multitude of known enzymatic reactions. The required reducing equivalents for the net carbon reductions may be drawn from solar energy, electricity or chemical oxidation, and delivered in vitro or through cellular mechanisms, while enzyme catalysis lowers the activation barriers of the CO2 transformations to make them more energy efficient. The development of technologies that treat CO2-transforming enzymes and other cellular components as modules that may be assembled into synthetic reaction circuits will facilitate the use of CO2 as a renewable chemical feedstock, greatly enabling a sustainable carbon bio-economy. PMID:26734087

  20. Global CO2-consumption by chemical weathering: What is the contribution of highly active weathering regions?

    NASA Astrophysics Data System (ADS)

    Hartmann, Jens; Jansen, Nils; Dürr, Hans H.; Kempe, Stephan; Köhler, Peter

    2010-05-01

    CO2-consumption by chemical weathering of silicates and resulting silicate/carbonate weathering ratios influences the terrestrial lateral inorganic carbon flux to the ocean and long-term climate changes. However, little is known of the spatial extension of highly active weathering regions and their proportion of global CO2-consumption. As those regions may be of significant importance for global climate change, global CO2-consumption is calculated here at high resolution, to adequately represent them. In previous studies global CO2-consumption is estimated using two different approaches: i) a reverse approach based on hydrochemical fluxes from large rivers and ii) a forward approach applying spatially explicit a function for CO2-consumption. The first approach results in an estimate without providing a spatial resolution for highly active regions and the second approach applied six lithological classes while including three sediment classes (shale, sandstone and carbonate rock) based at a 1° or 2° grid resolution. It remained uncertain, if the applied lithological classification schemes represent adequately CO2-consumption from sediments on a global scale (as well as liberation of other elements like phosphorus or silicon by chemical weatheirng). This is due to the large variability of sediment properties, their diagenetic history and the contribution from carbonates apparent in silicate dominated lithological classes. To address these issues, a CO2-consumption model, trained at high-resolution data, is applied here to a global vector based lithological map with 15 lithological classes. The calibration data were obtained from areas representing a wide range of weathering rates. Resulting global CO2-consumption by chemical weathering is similar to earlier estimates (237 Mt C a-1) but the proportion of silicate weathering is 63%, and thus larger than previous estimates (49 to 60%). The application of the enhanced lithological classification scheme reveals that it

  1. O3, CO2 and chemical fractionation in ponderosa pine saplings

    EPA Science Inventory

    Environmental factors can affect plant tissue quality which is important for quality of organic matter inputs into soil food webs and decomposition of soil organic matter. Thus the effects of increases in CO2 and O3 and their interactions were determined for various chemical fra...

  2. CO2 injection induced chemical composition and mechanical property change of shaly caprock

    NASA Astrophysics Data System (ADS)

    Liu, M.; Chalaturnyk, R. J.

    2012-04-01

    A suite of tests designed to assess the hydro-geomechanical properties of Cardium Zone Member shale, Lea Park Formation shale, Middle and Lower Cardium Formation sandstone specimens recovered from Pembina Cardium CO2 Monitoring Pilot Project at the Pembina Field, Alberta was completed in 2011. The testing program was designed to generate results for use in reservoir geomechanical simulations to assess the response of formation overlying the Upper Cretaceous Cardium Formation under carbon dioxide injection operation. To supplement these reservoir geomechanical tests, a systematic set of experiments have been conducted on Lea Park Formation shale samples to investigate the impact of exposure to CO2 saturated brine. Shale samples were mounted in plastic holders with epoxy resin to avoid collapse and then put in cell filled with 3g/L NaCl brine for saturation at 2MPa. Afterward, rock chips were exposed to CO2-rich 3g/L NaCl brine at 50°C, 2MPa for different period of time. Surface chemical compositions for both intact and CO2 treated samples were indentified using X-ray Photoelectron Spectroscopy (XPS). X-ray Diffraction (XRD) tests were also carried out as a reference to XPS scanning results. Current results from XPS scanning showed slight decreases in potassium and moderate decreases in aluminum that indicates rock/brine/CO2 interactions have indeed resulted in mineralogy changes within the rock. Perhaps as significant is the increase in carbon within the shale specimens providing some evidence for the potential of CO2 sorption in these shales that could increase the storage capacity of the CO2 storage complex. To further complement these geochemical tests, multiple scCO2 capillary breakthrough tests are being conducted to assess the shale's longer term sealing efficiency. These tests are being carried out with supercritical state CO2 on NaCl brine saturated rock plugs. Both before and after each test, permeability measurements are conducted to detect fluid

  3. Microbial, Physical and Chemical Drivers of COS and 18O-CO2 Exchange in Soils

    NASA Astrophysics Data System (ADS)

    Meredith, L. K.; Boye, K.; Whelan, M.; Pang, E.; von Sperber, C.; Brueggemann, N.; Berry, J. A.; Welander, P. V.

    2015-12-01

    Carbonyl sulfide (COS) and the oxygen isotope composition (δ18O) of CO2 are potential tools for differentiating the contributions of photosynthesis and respiration to the balance of global carbon cycling. These processes are coupled at the leaf level via the enzyme carbonic anhydrase (CA), which hydrolyzes CO2 in the first biochemical step of the photosynthetic pathway (CO2 + H2O ⇌ HCO3- + H+) and correspondingly structural analogue COS (COS + H2O → CO2 + H2S). CA also accelerates the exchange of oxygen isotopes between CO2 and H2O leading to a distinct isotopic imprint [1]. The biogeochemical cycles of these tracers include significant, yet poorly characterized soil processes that challenge their utility for probing the carbon cycle. In soils, microbial CA also hydrolyze COS and accelerate O isotope exchange between CO2 and soil water. Soils have been observed to emit COS by undetermined processes. To account for these soil processes, measurements are needed to identify the key microbial, chemical, and physical factors. In this study, we survey COS and δ18O exchange in twenty different soils spanning a variety of biomes and soil properties. By comparing COS fluxes and δ18O-CO2 values emitted from moist soils we investigate whether the same types of CA catalyze these two processes. Additionally, we seek to identify the potential chemical drivers of COS emissions by measuring COS fluxes in dry soils. These data are compared with soil physical (bulk density, volumetric water content, texture), chemical (pH, elemental analysis, sulfate, sulfur K-edge XANES), and microbial measurements (biomass and phylogeny). Furthermore, we determine the abundance and diversity of CA-encoding genes to directly link CA with measured soil function. This work will define the best predictors for COS fluxes and δ18O-CO2 values from our suite of biogeochemical measurements. The suitability of identified predictor variables can be tested in follow-up studies and applied for modeling

  4. CO2 recycling: a key strategy to introduce green energy in the chemical production chain.

    PubMed

    Perathoner, Siglinda; Centi, Gabriele

    2014-05-01

    The introduction of renewable energy in the chemical production chain is a key strategic factor both to realize a sustainable, resource-efficient, low-carbon economy and society and to drive innovation and competiveness in the chemical production. This Concept discusses this concept in terms of motivations, perspectives, and impact as well as technical barriers to achieve this goal. It is shown how an important element to realize this scenario is to foster the paths converting carbon dioxide (CO2) into feedstock for the chemical/process industry, which is one of the most efficient methods to rapidly introduce renewable energy into the chemical production chain. Some of the possible options to proceed in this direction are discussed, with focus on the technical barriers and enabling factors such as catalysis. The tight interconnection between CO2 management and the use of renewable energy is evidenced. PMID:24599714

  5. CO2 recycling: a key strategy to introduce green energy in the chemical production chain.

    PubMed

    Perathoner, Siglinda; Centi, Gabriele

    2014-05-01

    The introduction of renewable energy in the chemical production chain is a key strategic factor both to realize a sustainable, resource-efficient, low-carbon economy and society and to drive innovation and competiveness in the chemical production. This Concept discusses this concept in terms of motivations, perspectives, and impact as well as technical barriers to achieve this goal. It is shown how an important element to realize this scenario is to foster the paths converting carbon dioxide (CO2) into feedstock for the chemical/process industry, which is one of the most efficient methods to rapidly introduce renewable energy into the chemical production chain. Some of the possible options to proceed in this direction are discussed, with focus on the technical barriers and enabling factors such as catalysis. The tight interconnection between CO2 management and the use of renewable energy is evidenced.

  6. Laboratory Investigations of the Hydro-Mechanical-Chemical Coupling Behaviour of Sandstone in CO2 Storage in Aquifers

    NASA Astrophysics Data System (ADS)

    Zhou, Hui; Hu, Dawei; Zhang, Fan; Shao, Jianfu; Feng, Xiating

    2016-02-01

    This paper is devoted to experimental investigations of the hydro-mechanical-chemical coupling behaviour of sandstone in the context of CO2 storage in aquifers. We focused on the evolution of creep strain, the transport properties and the elastic modulus of sandstone under the effect of CO2-brine or CO2 alone. A summary of previous laboratory results is first presented, including mechanical, poromechanical and hydro-mechanical-chemical coupling properties. Tests were then performed to investigate the evolution of the creep strain and permeability during the injection of CO2-brine or CO2 alone. After the injection of CO2-brine or CO2 alone, an instantaneous volumetric dilatancy was observed due to the decrease in the effective confining stress. However, CO2 alone had a significant influence on the creep strain and permeability compared to the small influence of CO2-brine. This phenomenon can be attributed to the acceleration of the CO2-brine-rock reaction by the generation of carbonic acid induced by the dissolution of CO2 into the brine. The original indentation tests on samples after the CO2-brine-rock reaction were also performed and indicated that the elastic modulus decreased with an increasing reaction time. The present laboratory results can advance our knowledge of the hydro-mechanical-chemical coupling behaviour of sandstone in CO2 storage in aquifers.

  7. CO2 laser scribe of chemically strengthened glass with high surface compressive stress

    NASA Astrophysics Data System (ADS)

    Li, Xinghua; Vaddi, Butchi R.

    2011-03-01

    Chemically strengthened glass is finding increasing use in handheld, IT and TV cover glass applications. Chemically strengthened glass, particularly with high (>600MPa) compressive stress (CS) and deeper depth of layer (DOL), enable to retain higher strength after damage than non-strengthened glass when its surface is abraded. Corning Gorilla® Glass has particularly proven to be advantageous over competition in this attribute. However, due to high compressive stress (CS) and Central Tension (CT) cutting ion-exchanged glass is extremely difficult and often unmanageable where ever the applications require dicing the chemically strengthened mother glass into smaller parts. We at Corning have developed a CO2 laser scribe and break method (LSB) to separate a single chemically strengthened glass sheet into plurality of devices. Furthermore, CO2 laser scribe and break method enables debris-free separation of glass with high edge strength due to its mirror-like edge finish. We have investigated laser scribe and break of chemically strengthened glass with surface compressive stress greater than 600 MPa. In this paper we present the results of CO2 scribe and break method and underlying laser scribing mechanisms. We demonstrated cross-scribe repetitively on GEN 2 size chemically strengthened glass substrates. Specimens for edge strength measurements of different thickness and CS/DOL glass were prepared using the laser scribe and break technique. The specimens were tested using the standard 4-point bend method and the results are presented.

  8. Impact of atmospheric CO2 rise on chemical weathering of the continental surfaces

    NASA Astrophysics Data System (ADS)

    Godderis, Y.; Roelandt, C.; Beaulieu, E.; Kaplan, J. O.; Schott, J.

    2009-04-01

    Continental weathering consumes atmospheric CO2. Recent analysis of field data has shown that this flux is rapidly reacting to ongoing climate (ref 1) and land use changes (ref 2), displaying an increase of up to 40 % over a few decades. Weathering processes are thus a potentially important component of the present day global carbon cycle. We developed numerical model describing continental weathering reactions based on laboratory kinetic laws and coupled to numerical model of the productivity of the biosphere (B-WITCH)(ref 3,4). This model is able to simulate the chemical composition of streams for both small and large continental watersheds. In this model, we emphasized the role of land plants in controlling belowground hydrological fluxes and decreasing the pH of percolating water through root respiration, both of which heavily impact weathering rates. Both climate change and increasing atmospheric CO2 concentrations affect the productivity and biogeography of the terrestrial biosphere through direct climate effects and CO2 fertilization. With our weathering model coupled to a dynamic global vegetation model, we have the capability to explore the impact of CO2 and climate change on rock weathering. With regards to CO2 fertilization, we calculate that the overall weathering rate may potentially rise by 20 % when CO2 increases up to 8 times the present day pressure for a large tropical watershed (Orinoco). This change is driven by a decrease in evapotranspiration when CO2 rises, and thus by an increase in the weathering profile drainage. We extend our sensitivity tests to the fertilization effect to 20 sites all over the world under various climatic, biospheric and lithologic conditions, and the results will be discussed. ref 1: Gislason et al., EPSL, 277, 213-222, 2008 ref 2: Raymond et al.,Nature, 451, 449-452, 2008 ref 3: Godd

  9. Bio-electrochemical synthesis of commodity chemicals by autotrophic acetogens utilizing CO2 for environmental remediation.

    PubMed

    Jabeen, Gugan; Farooq, Robina

    2016-09-01

    Bio-electrochemical synthesis (BES) is a technique in which electro-autotrophic bacteria such as Clostridium ljungdahlii utilize electric currents as an electron source from the cathode to reduce CO2 to extracellular, multicarbon, exquisite products through autotrophic conversion. The BES of volatile fatty acids and alcohols directly from CO2 is a sustainable alternative for non-renewable, petroleum-based polymer production. This conversion of CO2 implies reduction of greenhouse gas emissions. The synthesis of heptanoic acid, heptanol, hexanoic acid and hexanol, for the first time, by Clostridium ljungdahlii was a remarkable achievement of BES. In our study, these microorganisms were cultivated on the cathode of a bio-electrochemical cell at -400 mV by a DC power supply at 37 degree Centrigrade, pH 6.8, and was studied for both batch and continuous systems. Pre-enrichment of bio-cathode enhanced the electroactivity of cells and resulted in maximizing extracellular products in less time. The main aim of the research was to investigate the impact of low-cost substrate CO2, and the longer cathode recovery range was due to bacterial reduction of CO2 to multicarbon chemical commodities with electrons driven from the cathode. Reactor design was simplified for cost-effectiveness and to enhance energy efficiencies. The Columbic recovery of ethanoic acid, ethanol, ethyl butyrate, hexanoic acid, heptanoic acid and hexanol being in excess of 80 percent proved that BES was a remarkable technology. PMID:27581929

  10. Bio-electrochemical synthesis of commodity chemicals by autotrophic acetogens utilizing CO2 for environmental remediation.

    PubMed

    Jabeen, Gugan; Farooq, Robina

    2016-09-01

    Bio-electrochemical synthesis (BES) is a technique in which electro-autotrophic bacteria such as Clostridium ljungdahlii utilize electric currents as an electron source from the cathode to reduce CO2 to extracellular, multicarbon, exquisite products through autotrophic conversion. The BES of volatile fatty acids and alcohols directly from CO2 is a sustainable alternative for non-renewable, petroleum-based polymer production. This conversion of CO2 implies reduction of greenhouse gas emissions. The synthesis of heptanoic acid, heptanol, hexanoic acid and hexanol, for the first time, by Clostridium ljungdahlii was a remarkable achievement of BES. In our study, these microorganisms were cultivated on the cathode of a bio-electrochemical cell at -400 mV by a DC power supply at 37 degree Centrigrade, pH 6.8, and was studied for both batch and continuous systems. Pre-enrichment of bio-cathode enhanced the electroactivity of cells and resulted in maximizing extracellular products in less time. The main aim of the research was to investigate the impact of low-cost substrate CO2, and the longer cathode recovery range was due to bacterial reduction of CO2 to multicarbon chemical commodities with electrons driven from the cathode. Reactor design was simplified for cost-effectiveness and to enhance energy efficiencies. The Columbic recovery of ethanoic acid, ethanol, ethyl butyrate, hexanoic acid, heptanoic acid and hexanol being in excess of 80 percent proved that BES was a remarkable technology.

  11. Microbial electrolysis desalination and chemical-production cell for CO2 sequestration.

    PubMed

    Zhu, Xiuping; Logan, Bruce E

    2014-05-01

    Mineral carbonation can be used for CO2 sequestration, but the reaction rate is slow. In order to accelerate mineral carbonation, acid generated in a microbial electrolysis desalination and chemical-production cell (MEDCC) was examined to dissolve natural minerals rich in magnesium/calcium silicates (serpentine), and the alkali generated by the same process was used to absorb CO2 and precipitate magnesium/calcium carbonates. The concentrations of Mg(2+) and Ca(2+) dissolved from serpentine increased 20 and 145 times by using the acid solution. Under optimal conditions, 24 mg of CO2 was absorbed into the alkaline solution and 13 mg of CO2 was precipitated as magnesium/calcium carbonates over a fed-batch cycle (24h). Additionally, the MEDCC removed 94% of the COD (initially 822 mg/L) and achieved 22% desalination (initially 35 g/L NaCl). These results demonstrate the viability of this process for effective CO2 sequestration using renewable organic matter and natural minerals.

  12. Frontiers, Opportunities, and Challenges in Biochemical and Chemical Catalysis of CO2

    SciTech Connect

    Appel, Aaron M.; Bercaw, John E.; Bocarsly, Andrew B.; Dobbek, Holger; DuBois, Daniel L.; Dupuis, Michel; Ferry, James G.; Fujita, Etsuko; Hille, Russ; Kenis, Paul; Kerfeld, Cheryl A.; Morris, Robert H.; Peden, Charles HF; Portis, Archie; Ragsdale, Steve; Rauchfuss, Thomas B.; Reek, Joost; Seefeldt, Lance C.; Thauer, Rudolf K.; Waldrop, Grover L.

    2013-08-14

    Our central premise is that catalytic scientists can learn by studying how these important metabolic processes occur in nature. Complementarily, biochemists can learn by studying how catalytic scientists view these same chemical transformations promoted by synthetic catalysts. From these studies, hypotheses can be developed and tested through manipulation of enzyme structure and by synthesizing simple molecular catalysts to incorporate different structural features of the enzymes. It is hoped that these studies will lead to new and useful concepts in catalyst design for fuel production and utilization. This paper describes the results of a workshop held to explore these concepts in regard to the development of new and more efficient catalytic processes for the conversion of CO2 to a variety of carbon-based fuels. The organization of this overview/review is as follows: 1) The first section briefly explores how interactions between the catalysis and biological communities have been fruitful in developing new catalysts for the reduction of protons to hydrogen, the simplest fuel generation reaction. 2) The second section assesses the state of the art in both biological and chemical reduction of CO2 by two electrons to form either carbon monoxide (CO) or formate (HCOO-). It also attempts to identify common principles between biological and synthetic catalysts and productive areas for future research. 3) The third section explores both biological and chemical processes that result in the reduction of CO2 beyond the level of CO and formate, again seeking to identify common principles and productive areas of future research. 4) The fourth section explores the formation of carbon-carbon bonds in biological and chemical systems in the same vein as the other sections. 5) A fifth section addresses the role of non-redox reactions of CO2 in biological systems and their role in carbon metabolism, with a parallel discussion of chemical systems. 6) In section 6, the topics of

  13. Stochastic Modeling of CO2 Migrations and Chemical Reactions in Deep Saline Formations

    NASA Astrophysics Data System (ADS)

    Ni, C.; Lee, I.; Lin, C.

    2013-12-01

    correlation lengths in a Gaussian covariance model are varied in the MCS and the uncertainty of the CO2 and other chemical concentrations are evaluated based on 144 random realizations. In this study a constant injection rate of100Mt/year supercritical CO2 is applied in the bottom of CF. The continuous injection time is 20 years and the uncertainty results are evaluated at 100 years. By comparing with the case without small-scale variability simulation results show that the CO2 plume sizes in the horizontal direction increase from tens of meters to hundreds of meters when the variances of small-scale variability are varied from 1.0 to 4.0. The changes of correlation lengths (i.e., from 100m, 200m, to 400m) show small contribution on the size increases of CO2 plumes. Other uncertainties of chemical concentrations show behaviors similar to the CO2 plume patterns.

  14. Chemical and Physical Reactions of Wellbore Cement under CO2 Storage Conditions: Effects of Cement Additives

    NASA Astrophysics Data System (ADS)

    Kutchko, B. G.; Strazisar, B. R.; Huerta, N.; Lowry, G. V.; Dzombak, D. A.; Thaulow, N.

    2008-12-01

    Sequestration of CO2 into geologic formations requires long-term storage and low leakage rates to be effective. Active and abandoned wells in candidate storage formations must be evaluated as potential leakage points. Wellbore integrity is an important part of an overall integrated assessment program being developed at NETL to assess potential risks at CO2 storage sites. Such a program is needed for ongoing policy and regulatory decisions for geologic carbon sequestration. The permeability and integrity of the cement in the well is a primary factor affecting its ability to prevent leakage. Cement must be able to maintain low permeability over lengthy exposure to reservoir conditions in a CO2 injection and storage scenario. Although it is known that cement may be altered by exposure to CO2, the results of ongoing research indicate that cement curing conditions, fluid properties, and cement additives play a significant role in the rate of alteration and reaction. The objective of this study is to improve understanding of the factors affecting wellbore cement integrity for large-scale geologic carbon sequestration projects. Due to the high frequency use of additives (pozzolan) in wellbore cement, it is also essential to understand the reaction of these cement-pozzolan systems upon exposure to CO2 under sequestration conditions (15.5 MPa and 50°C). Laboratory experiments were performed to determine the physical and chemical changes, as well as the rate of alteration of commonly used pozzolan-cement systems under simulated sequestration reservoir conditions, including both supercritical CO2 and CO2-saturated brine. The rate of alteration of the cement-pozzolan systems is considerably faster than with neat cement. However, the alteration of physical properties is much less significant with the pozzolanic blends. Permeability of a carbonated pozzolanic cement paste remains sufficiently small to block significant vertical migration of CO2 in a wellbore. All of the

  15. A method for incorporating equilibrium chemical reactions into multiphase flow models for CO2 storage

    NASA Astrophysics Data System (ADS)

    Saaltink, Maarten W.; Vilarrasa, Victor; De Gaspari, Francesca; Silva, Orlando; Carrera, Jesús; Rötting, Tobias S.

    2013-12-01

    CO2 injection and storage in deep saline aquifers involves many coupled processes, including multiphase flow, heat and mass transport, rock deformation and mineral precipitation and dissolution. Coupling is especially critical in carbonate aquifers, where minerals will tend to dissolve in response to the dissolution of CO2 into the brine. The resulting neutralization will drive further dissolution of both CO2 and calcite. This suggests that large cavities may be formed and that proper simulation may require full coupling of reactive transport and multiphase flow. We show that solving the latter may suffice whenever two requirements are met: (1) all reactions can be assumed to occur in equilibrium and (2) the chemical system can be calculated as a function of the state variables of the multiphase flow model (i.e., liquid and gas pressure, and temperature). We redefine the components of multiphase flow codes (traditionally, water and CO2), so that they are conservative for all reactions of the chemical system. This requires modifying the traditional constitutive relationships of the multiphase flow codes, but yields the concentrations of all species and all reaction rates by simply performing speciation and mass balance calculations at the end of each time step. We applied this method to the H2O-CO2-Na-Cl-CaCO3 system, so as to model CO2 injection into a carbonate aquifer containing brine. Results were very similar to those obtained with traditional formulations, which implies that full coupling of reactive transport and multi-phase flow is not really needed for this kind of systems, but the resulting simplifications may make it advisable even for cases where the above requirements are not met. Regarding the behavior of carbonate rocks, we find that porosity development near the injection well is small because of the low solubility of calcite. Moreover, dissolution concentrates at the front of the advancing CO2 plume because the brine below the plume tends to reach

  16. Chemicals loading in acetylated bamboo assisted by supercritical CO2 based on phase equilibrium data

    NASA Astrophysics Data System (ADS)

    Silviana, Petermann, M.

    2015-12-01

    Indonesia has a large tropical forest. However, the deforestation still appears annually and vastly. This reason drives a use of bamboo as wood alternative. Recently, there are many modifications of bamboo in order to prolong the shelf life. Unfortunately, the processes need more chemicals and time. Based on wood modification, esterifying of bamboo was undertaken in present of a dense gas, i.e. supercritical CO2. Calculation of chemicals loading referred to ASTM D1413-99 by using the phase equilibrium data at optimum condition by a statistical design. The results showed that the acetylation of bamboo assisted by supercritical CO2 required 14.73 kg acetic anhydride/m3 of bamboo for a treatment of one hour.

  17. Chemical Reactions of Portland Cement with Aqueous CO2 and Their Impacts on Cement's Mechanical Properties under Geologic CO2 Sequestration Conditions.

    PubMed

    Li, Qingyun; Lim, Yun Mook; Flores, Katharine M; Kranjc, Kelly; Jun, Young-Shin

    2015-05-19

    To provide information on wellbore cement integrity in the application of geologic CO2 sequestration (GCS), chemical and mechanical alterations were analyzed for cement paste samples reacted for 10 days under GCS conditions. The reactions were at 95 °C and had 100 bar of either N2 (control condition) or CO2 contacting the reaction brine solution with an ionic strength of 0.5 M adjusted by NaCl. Chemical analyses showed that the 3.0 cm × 1.1 cm × 0.3 cm samples were significantly attacked by aqueous CO2 and developed layer structures with a total attacked depth of 1220 μm. Microscale mechanical property analyses showed that the hardness and indentation modulus of the carbonated layer were 2-3 times greater than for the intact cement, but those in the portlandite-dissolved region decreased by ∼50%. The strength and elastic modulus of the bulk cement samples were reduced by 93% and 84%, respectively. The properties of the microscale regions, layer structure, microcracks, and swelling of the outer layers combined to affect the overall mechanical properties. These findings improve understanding of wellbore integrity from both chemical and mechanical viewpoints and can be utilized to improve the safety and efficiency of CO2 storage.

  18. Chemical Reactions of Portland Cement with Aqueous CO2 and Their Impacts on Cement's Mechanical Properties under Geologic CO2 Sequestration Conditions.

    PubMed

    Li, Qingyun; Lim, Yun Mook; Flores, Katharine M; Kranjc, Kelly; Jun, Young-Shin

    2015-05-19

    To provide information on wellbore cement integrity in the application of geologic CO2 sequestration (GCS), chemical and mechanical alterations were analyzed for cement paste samples reacted for 10 days under GCS conditions. The reactions were at 95 °C and had 100 bar of either N2 (control condition) or CO2 contacting the reaction brine solution with an ionic strength of 0.5 M adjusted by NaCl. Chemical analyses showed that the 3.0 cm × 1.1 cm × 0.3 cm samples were significantly attacked by aqueous CO2 and developed layer structures with a total attacked depth of 1220 μm. Microscale mechanical property analyses showed that the hardness and indentation modulus of the carbonated layer were 2-3 times greater than for the intact cement, but those in the portlandite-dissolved region decreased by ∼50%. The strength and elastic modulus of the bulk cement samples were reduced by 93% and 84%, respectively. The properties of the microscale regions, layer structure, microcracks, and swelling of the outer layers combined to affect the overall mechanical properties. These findings improve understanding of wellbore integrity from both chemical and mechanical viewpoints and can be utilized to improve the safety and efficiency of CO2 storage. PMID:25893278

  19. Graphene Coating of Silicon Nanoparticles with CO2 -Enhanced Chemical Vapor Deposition.

    PubMed

    Son, In Hyuk; Park, Jong Hwan; Kwon, Soonchul; Choi, Jang Wook; Rümmeli, Mark H

    2016-02-01

    Understanding the growth of graphene over Si species is becoming ever more important as the huge potential for the combination of these two materials becomes more apparent, not only for device fabrication but also in energy applications, particularly in Li-ion batteries. Thus, the drive for the direct fabrication of graphene over Si is crucial because indirect approaches, by their very nature, require processing steps that, in general, contaminate, damage, and are costly. In this work, the direct chemical vapor deposition growth of few-layer graphene over Si nanoparticles is systematically explored through experiment and theory with the use of a reducer, H2 or the use of a mild oxidant, CO2 combined with CH4 . Unlike the case of CH4 , with the use of CO2 as a mild oxidant in the reaction, the graphene layers form neatly over the surface and encapsulate the Si particles. SiC formation is also prevented. These structures show exceptionally good electrochemical performance as high capacity anodes for lithium-ion batteries. Density functional theory studies show the presence of CO2 not only prevents SiC formation but helps enhance the catalytic activity of the particles by maintaining an SiOx surface. In addition, CO2 can enhance graphitization. PMID:26662621

  20. Chemical and anatomical changes in Liquidambar styraciflua L. xylem after long term exposure to elevated CO2.

    PubMed

    Kim, Keonhee; Labbé, Nicole; Warren, Jeffrey M; Elder, Thomas; Rials, Timothy G

    2015-03-01

    The anatomical and chemical characteristics of sweetgum were studied after 11 years of elevated CO2 (544 ppm, ambient at 391 ppm) exposure. Anatomically, branch xylem cells were larger for elevated CO2 trees, and the cell wall thickness was thinner. Chemically, elevated CO2 exposure did not impact the structural components of the stem wood, but non-structural components were significantly affected. Principal component analysis (PCA) was employed to detect differences between the CO2 treatments by considering numerous structural and chemical variables, as well as tree size, and data from previously published sources (i.e., root biomass, production and turnover). The PCA results indicated a clear separation between trees exposed to ambient and elevated CO2 conditions. Correlation loadings plots of the PCA revealed that stem structural components, ash, Ca, Mg, total phenolics, root biomass, production and turnover were the major responses that contribute to the separation between the elevated and ambient CO2 treated trees. PMID:25603157

  1. Chemical and anatomical changes in Liquidambar styraciflua L. xylem after long term exposure to elevated CO2.

    PubMed

    Kim, Keonhee; Labbé, Nicole; Warren, Jeffrey M; Elder, Thomas; Rials, Timothy G

    2015-03-01

    The anatomical and chemical characteristics of sweetgum were studied after 11 years of elevated CO2 (544 ppm, ambient at 391 ppm) exposure. Anatomically, branch xylem cells were larger for elevated CO2 trees, and the cell wall thickness was thinner. Chemically, elevated CO2 exposure did not impact the structural components of the stem wood, but non-structural components were significantly affected. Principal component analysis (PCA) was employed to detect differences between the CO2 treatments by considering numerous structural and chemical variables, as well as tree size, and data from previously published sources (i.e., root biomass, production and turnover). The PCA results indicated a clear separation between trees exposed to ambient and elevated CO2 conditions. Correlation loadings plots of the PCA revealed that stem structural components, ash, Ca, Mg, total phenolics, root biomass, production and turnover were the major responses that contribute to the separation between the elevated and ambient CO2 treated trees.

  2. STREAM GEOCHEMISTRY, CHEMICAL WEATHERING AND CO2 CONSUMPTION POTENTIAL OF ANDESITIC TERRAINS, DOMINICA, LESSER ANTILLES

    NASA Astrophysics Data System (ADS)

    Goldsmith, S. T.; Carey, A. E.; Johnson, B. M.; Welch, S. A.; Lyons, W.; McDowell, W. H.; Pigott, J. S.

    2009-12-01

    Recent studies of chemical weathering of andesitic-dacitic material on high standing islands (HSIs) have shown these terrains have some of the highest observed rates of chemical weathering and associated CO2 consumption yet reported. However, the paucity of stream gauge data in many of these terrains has limited determination of chemical weathering product fluxes. In July 2006 and March 2008, stream water samples were collected and manual stream gauging was performed in watersheds throughout the volcanic island of Dominica in the Lesser Antilles. Distinct wet and dry season solute concentrations reveals the importance of seasonal variations on the weathering signal. A cluster analysis of the stream geochemical data shows the importance of parent material age on the overall delivery of solutes. Observed Ca:Na, HCO3:Na and Mg:Na ratios suggest crystallinity of the parent material may also play an important role in determining weathering fluxes. From total dissolved solids concentrations and mean annual discharge calculations chemical weathering yields were calculated and found to be similar to those previously determined for basaltic terrains. Silicate fluxes and associated CO2 consumption determined from this study are amongst the highest determined to date. The calculated chemical fluxes from this study confirm the weathering potential of andesitic-dacitic terrains and that additional studies of these terrains are warranted.

  3. Stream geochemistry, chemical weathering and CO 2 consumption potential of andesitic terrains, Dominica, Lesser Antilles

    NASA Astrophysics Data System (ADS)

    Goldsmith, Steven T.; Carey, Anne E.; Johnson, Brent M.; Welch, Susan A.; Lyons, W. Berry; McDowell, William H.; Pigott, Jeffrey S.

    2010-01-01

    Recent studies of chemical weathering of andesitic-dacitic material on high-standing islands (HSIs) have shown these terrains have some of the highest observed rates of chemical weathering and associated CO 2 consumption yet reported. However, the paucity of stream gauge data in many of these terrains has limited determination of chemical weathering product fluxes. In July 2006 and March 2008, stream water samples were collected and manual stream gauging was performed in watersheds throughout the volcanic island of Dominica in the Lesser Antilles. Distinct wet and dry season solute concentrations reveal the importance of seasonal variations on the weathering signal. A cluster analysis of the stream geochemical data shows the importance of parent material age on the overall delivery of solutes. Observed Ca:Na, HCO 3:Na and Mg:Na ratios suggest crystallinity of the parent material may also play an important role in determining weathering fluxes. From total dissolved solids concentrations and mean annual discharge calculations we calculate chemical weathering yields of (6-106 t km -2 a -1), which are similar to those previously determined for basalt terrains. Silicate fluxes (3.1-55.4 t km -2 a -1) and associated CO 2 consumption (190-1575 × 10 3 mol km -2 a -1) determined from our study are among the highest determined to date. The calculated chemical fluxes from our study confirm the weathering potential of andesitic-dacitic terrains and that additional studies of these terrains are warranted.

  4. Catalytic upgrading of butyric acid towards fine chemicals and biofuels

    PubMed Central

    Sjöblom, Magnus; Matsakas, Leonidas; Christakopoulos, Paul; Rova, Ulrika

    2016-01-01

    Fermentation-based production of butyric acid is robust and efficient. Modern catalytic technologies make it possible to convert butyric acid to important fine chemicals and biofuels. Here, current chemocatalytic and biocatalytic conversion methods are reviewed with a focus on upgrading butyric acid to 1-butanol or butyl-butyrate. Supported Ruthenium- and Platinum-based catalyst and lipase exhibit important activities which can pave the way for more sustainable process concepts for the production of green fuels and chemicals. PMID:26994015

  5. Chemical absorption and CO2 biofixation via the cultivation of Spirulina in semicontinuous mode with nutrient recycle.

    PubMed

    da Rosa, Gabriel Martins; Moraes, Luiza; Cardias, Bruna Barcelos; de Souza, Michele da Rosa Andrade Zimmermann; Costa, Jorge Alberto Vieira

    2015-09-01

    The chemical absorption of carbon dioxide (CO2) is a technique used for the mitigation of the greenhouse effect. However, this process consumes high amounts of energy to regenerate the absorbent and to separate the CO2. CO2 removal by microalgae can be obtained via the photosynthesis process. The objective of this study was to investigate the cultivation and the macromolecules production by Spirulina sp. LEB 18 with the addition of monoethanolamine (MEA) and CO2. In the cultivation with MEA, were obtained higher results of specific growth rate, biomass productivity, CO2 biofixation, CO2 use efficiency, and lower generation time. Besides this, the carbohydrate concentration obtained at the end of this assay was approximately 96.0% higher than the control assay. Therefore, Spirulina can be produced using medium recycle and the addition of MEA, thereby promoting the reduction of CO2 emissions and showing potential for areas that require higher concentrations of carbohydrates, such as in bioethanol production.

  6. Chemical Processes with Supercritical CO2 in Engineered Geologic Systems: Significance, Previous Study, and Path Forward (Invited)

    NASA Astrophysics Data System (ADS)

    Xu, T.; Pruess, K.

    2009-12-01

    Chemical reactions with dissolved CO2 in the aqueous phase have long been considered in fundamental geosciences and practical applications. Recently, studies on geologic carbon sequestration and enhanced geothermal systems using CO2 as heat transmission fluid have brought new interests in chemical reaction processes directly with supercritical CO2 (scCO2, or gas phase). In the vicinity of a CO2 injection well, the aqueous fluid initially present in a geological formation would be quickly removed by dissolution (evaporation) into the flowing gas stream and by immiscible displacement by the scCO2, creating a gas phase dominant zone. In this zone, the water evaporation could cause formation dry-out and precipitation of salt near the injection well, reducing formation porosity, permeability, and injectivity. The scCO2 may directly attack well construction materials such as cement. Over time, the gas phase will tend to migrate upwards towards the caprock because the density of the scCO2 is lower than that of the aqueous phase. In the upper portions of the reservoir, the scCO2 will directly react with caprock minerals and alter the hydrological properties and mechanical strength. On the other hand, the scCO2 phase will maintain the dissolution into the aqueous phase, lowering pH, inducing mineral dissolution, complexing with dissolved cations, increasing CO2 solubility, increasing the density of the aqueous phase, and promoting “convective mixing”. Chemical processes are quite different in the scCO2 dominant geologic systems. The absence of an aqueous phase poses unique questions, as little is presently known about the chemistry of non-aqueous systems. Additional issues arise from the reactivity of water that is dissolved in the ScCO2 phase. In this presentation, the author will discuss the importance, state of the studies performed, and future research directions.

  7. Controlled noxious chemical stimulation: responses of rat trigeminal brainstem neurones to CO2 pulses applied to the nasal mucosa.

    PubMed

    Anton, F; Peppel, P; Euchner, I; Handwerker, H O

    1991-02-25

    The nasal mucosa of halothane-anesthetized rats was stimulated with defined CO2 pulses. Recordings were performed from single trigeminal brainstem neurons to characterize their responses to this controlled chemical irritation. All cells examined with this stimulus displayed graded discharges to increasing concentrations of CO2. Enhanced responses were obtained in a group of neurons when the duration of the interstimulus interval was increased. The application of chemical irritants, notably mustard oil or acetic acid induced vigorous ongoing discharges in all cells tested. The CO2 stimulation method described here thus provides an ideal model for the quantitative physiological and pharmacological examination of chemically induced nociception.

  8. FMC Chemicals: Burner Management System Upgrade Improves Performance and Saves Energy at a Chemical Plant

    SciTech Connect

    2004-07-01

    FMC Chemicals Corporation increased the efficiency of two large coal-fired boilers at its soda ash mine in Green River, Wyoming, by upgrading the burner management system. The project yields annual energy savings of 250,000 MMBtu.

  9. A Single-Culture Bioprocess of Methanothermobacter thermautotrophicus to Upgrade Digester Biogas by CO2-to-CH4 Conversion with H2

    PubMed Central

    Martin, Matthew R.; Fornero, Jeffrey J.; Angenent, Largus T.

    2013-01-01

    We optimized and tested a postbioprocessing step with a single-culture archaeon to upgrade biogas (i.e., increase methane content) from anaerobic digesters via conversion of CO2 into CH4 by feeding H2 gas. We optimized a culture of the thermophilic methanogen Methanothermobacter thermautotrophicus using: (1) a synthetic H2/CO2 mixture; (2) the same mixture with pressurization; (3) a synthetic biogas with different CH4 contents and H2; and (4) an industrial, untreated biogas and H2. A laboratory culture with a robust growth (dry weight of 6.4–7.4 g/L; OD600 of 13.6–15.4), a volumetric methane production rate of 21 L/L culture-day, and a H2 conversion efficiency of 89% was moved to an industrial anaerobic digester facility, where it was restarted and fed untreated biogas with a methane content of ~70% at a rate such that CO2 was in excess of the stoichiometric requirements in relation to H2. Over an 8-day operating period, the dry weight of the culture initially decreased slightly before stabilizing at an elevated level of ~8 g/L to achieve a volumetric methane production rate of 21 L/L culture-day and a H2 conversion efficiency of 62%. While some microbial contamination of the culture was observed via microscopy, it did not affect the methane production rate of the culture. PMID:24194675

  10. CO2 sequestration in a radial Hele-Shaw cell via an interfacial chemical reaction

    NASA Astrophysics Data System (ADS)

    White, Andrew R.; Ward, Thomas

    2012-09-01

    In this manuscript, experimental data for the displacement of a finite volume of aqueous Ca(OH)2 using CO2 gas in a radial Hele-Shaw cell will be presented. This chemical reaction is known to generate CaCO3 precipitate along the gas-liquid interface and we seek to understand the influence of the reactive process on fluid displacement. The reactive experiment is compared with the non-reactive case to determine if there are any measurable differences between the two in the range of parameters: CO2 pressures (1%-10% of an atmosphere measured in gage pressure), liquid volumes (either 50 or 70 μl), and Ca(OH)2 concentrations (0, 10, or 20 mM) studied. Analysis is performed by measuring the displacing fluid area Agas and total fluid area Atot to determine several quantities (gas expansion rate, quasi-equilibrium film rate and value, and presence of fingering instability) used to distinguish the experiments. In general there appears to be little effect of the chemical reaction on most of the measured quantities.

  11. Biogas upgrading by chemical absorption using ammonia rich absorbents derived from wastewater.

    PubMed

    McLeod, Andrew; Jefferson, Bruce; McAdam, Ewan J

    2014-12-15

    The use of ammonia (NH3) rich wastewaters as an ecological chemical absorption solvent for the selective extraction of carbon dioxide (CO2) during biogas upgrading to 'biomethane' has been studied. Aqueous ammonia absorbents of up to 10,000 gNH3 m(-3) demonstrated CO2 absorption rates higher than recorded in the literature for packed columns using 20,000-80,000 g NH3 m(-3) which can be ascribed to the process intensification provided by the hollow fibre membrane contactor used in this study to support absorption. Centrifuge return liquors (2325 g m(-3) ionised ammonium, NH4(+)) and a regenerant (477 gNH4(+) m(-3)) produced from a cationic ion exchanger used to harvest NH4(+) from crude wastewater were also tested. Carbon dioxide fluxes measured for both wastewaters compared reasonably with analogue ammonia absorption solvents of equivalent NH3 concentration. Importantly, this demonstrates that ammonia rich wastewaters can facilitate chemically enhanced CO2 separation which eliminates the need for costly exogenic chemicals or complex chemical handling which are critical barriers to implementation of chemical absorption. When testing NH3 analogues, the potential to recover the reaction product ammonium bicarbonate (NH4HCO3) in crystalline form was also illustrated. This is significant as it suggests a new pathway for ammonia separation which avoids biological nitrification and produces ammonia stabilised into a commercially viable fertiliser (NH4HCO3). However, in real ammonia rich wastewaters, sodium bicarbonate and calcium carbonate were preferentially formed over NH4HCO3 although it is proposed that NH4HCO3 can be preferentially formed by manipulating both ion exchange and absorbent chemistry. PMID:25277752

  12. Electrocatalytic upgrading of biomass pyrolysis oils to chemical and fuel

    NASA Astrophysics Data System (ADS)

    Lam, Chun Ho

    The present project's aim is to liquefy biomass through fast pyrolysis and then upgrade the resulting "bio-oil" to renewable fuels and chemicals by intensifying its energy content using electricity. This choice reflects three points: (a) Liquid hydrocarbons are and will long be the most practical fuels and chemical feedstocks because of their energy density (both mass and volume basis), their stability and relative ease of handling, and the well-established infrastructure for their processing, distribution and use; (b) In the U.S., the total carbon content of annually harvestable, non-food biomass is significantly less than that in a year's petroleum usage, so retention of plant-captured carbon is a priority; and (c) Modern technologies for conversion of sunlight into usable energy forms---specifically, electrical power---are already an order of magnitude more efficient than plants are at storing solar energy in chemical form. Biomass fast pyrolysis (BFP) generates flammable gases, char, and "bio-oil", a viscous, corrosive, and highly oxygenated liquid consisting of large amounts of acetic acid and water together with hundreds of other organic compounds. With essentially the same energy density as biomass and a tendency to polymerize, this material cannot practically be stored or transported long distances. It must be upgraded by dehydration, deoxygenation, and hydrogenation to make it both chemically and energetically compatible with modern vehicles and fuels. Thus, this project seeks to develop low cost, general, scalable, robust electrocatalytic methods for reduction of bio-oil into fuels and chemicals.

  13. Colour and chemical changes of the lime wood surface due to CO2 laser thermal modification

    NASA Astrophysics Data System (ADS)

    Kubovský, Ivan; Kačík, František

    2014-12-01

    We studied colour and main wood components changes of lime wood caused by CO2 laser beam irradiation. The dry surface of lime wood (Tilia vulgaris L.) was irradiated with the CO2 laser beam (wavelength of 10.6 μm) at different exposures (expressed as the irradiation dose). Colour changes were monitored by the spectrophotometer, chemical changes were observed by the ATR-FTIR spectroscopy and carbohydrates were analysed by the HPLC method. With the growth of the irradiation dose (from 8.1 to 28.7 J cm-2) lightness (ΔL*) decrease and increase of the total colour difference (ΔE*) were observed. Higher values of the input energy lead to accelerating the mutual reaction of the functional groups resulting in the subsequent condensation of lignin. The total decrease in saccharides at the highest irradiation dose reaches 27.39% of the initial amount of saccharides in the reference sample. We have observed degradation and loss of hemicelluloses.

  14. Investigation of chemical-free nutrient removal and recovery from CO2-rich wastewater.

    PubMed

    Jordaan, Elsie M; Rezania, Babak; Ciçek, Nazim

    2013-01-01

    The feasibility of a bench-scale system for removal and recovery of phosphorus (P) as struvite from CO2-rich wastewater was tested. A continuous 12 L reactor system combining a fluidized seedbed and aeration for pH increase was developed and tested using synthetic feed. For a 100 mL min(-1) influent rate, an aeration and recycle rate combination of 7 L min(-1) and 700 mL min(-1) was sufficient for increasing and maintaining the reactor pH from 6.7 to between 7.6 and 8.0. Significant P removal was achieved in 6 h runs without a seedbed (91-92%), while neither the struvite nor sand seedbeds improved P removal (91-96%). Struvite was recovered in all runs, with additional calcium (Ca) precipitation in the seedbed runs. Reactor operation was possible for an extended period of time, up to 46 h without any major adjustment during long-term run. The average P removal was 88%, and precipitate collected after 24 h was found to be mainly struvite, while the final precipitate had a Ca: total phosphorus molar ratio of 0.56 and also contained calcite. This study has demonstrated the technical feasibility of an aerated crystallization reactor system for chemical-free struvite removal and recovery from CO2-rich wastewater such as stored livestock manure.

  15. Supercritical CO2 extract of Cinnamomum zeylanicum: chemical characterization and antityrosinase activity.

    PubMed

    Marongiu, Bruno; Piras, Alessandra; Porcedda, Silvia; Tuveri, Enrica; Sanjust, Enrico; Meli, Massimo; Sollai, Francesca; Zucca, Paolo; Rescigno, Antonio

    2007-11-28

    The volatile oil of the bark of Cinnamomum zeylanicum was extracted by means of supercritical CO2 fluid extraction in different conditions of pressure and temperature. Its chemical composition was characterized by GC-MS analysis. Nineteen compounds, which in the supercritical extract represented >95% of the oil, were identified. (E)-Cinnamaldehyde (77.1%), (E)-beta-caryophyllene (6.0%), alpha-terpineol (4.4%), and eugenol (3.0%) were found to be the major constituents. The SFE oil of cinnamon was screened for its biological activity about the formation of melanin in vitro. The extract showed antityrosinase activity and was able to reduce the formation of insoluble flakes of melanin from tyrosine. The oil also delayed the browning effect in apple homogenate. (E)-Cinnamaldehyde and eugenol were found to be mainly responsible of this inhibition effect.

  16. Photocatalytic Reduction of CO2 over Heterostructure Semiconductors into Value-Added Chemicals.

    PubMed

    Guo, Ling-Ju; Wang, Yan-Jie; He, Tao

    2016-08-01

    Photoreduction of CO2 , which utilizes solar energy to convert CO2 into hydrocarbons, can be an effective means to overcome the increasing energy crisis and mitigate the rising emissions of greenhouse gas. This article covers recent advances in the CO2 photoreduction over heterostructure-based photocatalysts. The fundamentals of CO2 photoreduction and classification of the heterostructured photocatalysts are discussed first, followed by the latest work on the CO2 photoreduction over heterostructured photocatalysts in terms of the classification of the coupling semiconductors. Finally, a brief summary and a perspective on the challenges in this area are presented. PMID:27276171

  17. Upgraded biogas from municipal solid waste for natural gas substitution and CO2 reduction--a case study of Austria, Italy, and Spain.

    PubMed

    Starr, Katherine; Villalba, Gara; Gabarrell, Xavier

    2015-04-01

    Biogas is rich in methane and can be further purified through biogas upgrading technologies, presenting a viable alternative to natural gas. Landfills and anaerobic digestors treating municipal solid waste are a large source of such biogas. They therefore offer an attractive opportunity to tap into this potential source of natural gas while at the same time minimizing the global warming impact resulting from methane emissions in waste management schemes (WMS) and fossil fuel consumption reduction. This study looks at the current municipal solid waste flows of Spain, Italy, and Austria over one year (2009), in order to determine how much biogas is generated. Then it examines how much natural gas could be substituted by using four different biogas upgrading technologies. Based on current waste generation rates, exploratory but realistic WMS were created for each country in order to maximize biogas production and potential for natural gas substitution. It was found that the potential substitution of natural gas by biogas resulting from the current WMS seems rather insignificant: 0.2% for Austria, 0.6% for Italy and 0.3% for Spain. However, if the WMS is redesigned to maximize biogas production, these figures can increase to 0.7% for Austria, 1% for Italy and 2% for Spain. Furthermore, the potential CO2 reduction as a consequence of capturing the biogas and replacing fossil fuel can result in up to a 93% reduction of the annual national waste greenhouse gas emissions of Spain and Italy.

  18. Chemical and anatomical changes in Liquidambar styraciflua L. xylem after long term exposure to elevated CO2

    DOE PAGES

    Kim, Keonhee; Labbé, Nicole; Warren, Jeffrey M.; Elder, Thomas; Rials, Timothy G.

    2015-01-17

    The anatomical and chemical characteristics of sweetgum were studied after 11 years of elevated CO2 (544 ppm, ambient at 391 ppm) exposure. Anatomically, branch xylem cells were larger for elevated CO2 trees, and the cell wall thickness was thinner. Chemically, elevated CO2 exposure did not impact the structural components of the stem wood, but non-structural components were significantly affected. Principal component analysis (PCA) was employed to detect differences between the CO2 treatments by considering numerous structural and chemical variables, as well as tree size, and data from previously published sources (for example, root biomass, production and turnover). The PCA resultsmore » indicated a clear separation between trees exposed to ambient and elevated CO2 conditions. Lastly, correlation loadings plots of the PCA revealed that stem structural components, ash, Ca, Mg, total phenolics, root biomass, production and turnover were the major responses that contribute to the separation between the elevated and ambient CO2 treated trees.« less

  19. Chemical absorption and CO2 biofixation via the cultivation of Spirulina in semicontinuous mode with nutrient recycle.

    PubMed

    da Rosa, Gabriel Martins; Moraes, Luiza; Cardias, Bruna Barcelos; de Souza, Michele da Rosa Andrade Zimmermann; Costa, Jorge Alberto Vieira

    2015-09-01

    The chemical absorption of carbon dioxide (CO2) is a technique used for the mitigation of the greenhouse effect. However, this process consumes high amounts of energy to regenerate the absorbent and to separate the CO2. CO2 removal by microalgae can be obtained via the photosynthesis process. The objective of this study was to investigate the cultivation and the macromolecules production by Spirulina sp. LEB 18 with the addition of monoethanolamine (MEA) and CO2. In the cultivation with MEA, were obtained higher results of specific growth rate, biomass productivity, CO2 biofixation, CO2 use efficiency, and lower generation time. Besides this, the carbohydrate concentration obtained at the end of this assay was approximately 96.0% higher than the control assay. Therefore, Spirulina can be produced using medium recycle and the addition of MEA, thereby promoting the reduction of CO2 emissions and showing potential for areas that require higher concentrations of carbohydrates, such as in bioethanol production. PMID:26051496

  20. Effect of chemical environment and rock composition on fracture mechanics properties of reservoir lithologies in context of CO2 sequestration

    NASA Astrophysics Data System (ADS)

    Major, J. R.; Eichhubl, P.; Callahan, O. A.

    2015-12-01

    The coupled chemical and mechanical response of reservoir and seal rocks to injection of CO2 have major implications on the short and long term security of sequestered carbon. Many current numerical models evaluating behavior of reservoirs and seals during and after CO2 injection in the subsurface consider chemistry and mechanics separately and use only simple mechanical stability criteria while ignoring time-dependent failure parameters. CO2 injection irreversibly alters the subsurface chemical environment which can then affect geomechanical properties on a range of time scales by altering rock mineralogy and cements through dissolution, remobilization, and precipitation. It has also been documented that geomechanical parameters such as fracture toughness (KIC) and subcritical index (SCI) are sensitive to chemical environment. Double torsion fracture mechanics testing of reservoir lithologies under controlled environmental conditions relevant to CO2 sequestration show that chemical environment can measurably affect KIC and SCI. This coupled chemical-mechanical behavior is also influenced by rock composition, grains, amount and types of cement, and fabric. Fracture mechanics testing of the Aztec Sandstone, a largely silica-cemented, subarkose sandstone demonstrate it is less sensitive to chemical environment than Entrada Sandstone, a silty, clay-rich sandstone. The presence of de-ionized water lowers KIC by approximately 20% and SCI 30% in the Aztec Sandstone relative to tests performed in air, whereas the Entrada Sandstone shows reductions on the order of 70% and 90%, respectively. These results indicate that rock composition influences the chemical-mechanical response to deformation, and that the relative chemical reactivity of target reservoirs should be recognized in context of CO2 sequestration. In general, inert grains and cements such as quartz will be less sensitive to the changing subsurface environment than carbonates and clays.

  1. Bimetallic catalysts for upgrading of biomass to fuels and chemicals.

    PubMed

    Alonso, David Martin; Wettstein, Stephanie G; Dumesic, James A

    2012-12-21

    Research interest in biomass conversion to fuels and chemicals has increased significantly in the last decade as the necessity for a renewable source of carbon has become more evident. Accordingly, many different reactions and processes to convert biomass into high-value products and fuels have been proposed in the literature. Special attention has been given to the conversion of lignocellulosic biomass, which does not compete with food sources and is widely available as a low cost feedstock. In this review, we start with a brief introduction on lignocellulose and the different chemical structures of its components: cellulose, hemicellulose, and lignin. These three components allow for the production of different chemicals after fractionation. After a brief overview of the main reactions involved in biomass conversion, we focus on those where bimetallic catalysts are playing an important role. Although the reactions are similar for cellulose and hemicellulose, which contain C(6) and C(5) sugars, respectively, different products are obtained, and therefore, they have been reviewed separately. The third major fraction of lignocellulose that we address is lignin, which has significant challenges to overcome, as its structure makes catalytic processing more challenging. Bimetallic catalysts offer the possibility of enabling lignocellulosic processing to become a larger part of the biofuels and renewable chemical industry. This review summarizes recent results published in the literature for biomass upgrading reactions using bimetallic catalysts. PMID:22872312

  2. Effects of Steam and CO2 in the Fluidizing Gas when Using Bituminous Coal in Chemical-Looping Combustion

    NASA Astrophysics Data System (ADS)

    Leion, H.; Lyngfelt, A.; Mattisson, T.

    Chemical-looping combustion (CLC) is a combustion technology where an oxygen carrier is used to transfer oxygen from the combustion air to the fuel in order to avoid direct contact between air and fuel. Thus, the CO2 is inherently separated from the flue gases with a potential for considerably lower energy penalty and cost compared to other techniques for CO2 separation. The oxygen carrier is circulated between two reactors, a fuel and an air reactor, where the flue gas from the air reactor contains oxygen depleted air and the flue gas from the fuel reactor contains mainly CO2 and H2O. The water can easily be condensed and the remaining CO2 can be transported for underground storage. Most of the prior work with CLC has focused on using natural gas and syngas as fuel and oxygen carrying material normally produced from pure chemicals. However, recent work on adapting the CLC process for solid fuels with ores and natural minerals as oxygen carrier shows promising results. This paper will present results from reactivity investigations in a laboratory fluidized-bed reactor system using previously investigated natural mineral ilmenite as oxygen carrier and a bituminous Colombian coal as fuel. Experiments were conducted at a temperature of 970°C with N2, steam, and/or CO2 in the fluidizing gas. Synergy effects between steam and CO2 on fuel conversion was noted. The results show that the fuel conversion was a roughly a factor 5 faster with steam as compared to CO2 in the fluidizing gas.

  3. Calculating chemical equilibria in the heparin-Co2+ ion-glycine system

    NASA Astrophysics Data System (ADS)

    Feofanova, M. A.; Frantseva, Yu. V.; Zhuravlev, E. V.; Ryasensky, S. S.; Baranova, N. V.

    2013-08-01

    Results from investigating interactions in the heparin-Co2+ ion-glycine system are presented. The stoichiometry of cobalt complexes with heparin and glycine compositions CoOHHtpGly4- and CoHepGly3- is established.

  4. Development of a Method for Measuring Carbon Balance in Chemical Sequestration of CO2

    SciTech Connect

    Cheng, Zhongxian; Pan, Wei-Ping; Riley, John T.

    2006-09-09

    Anthropogenic CO2 released from fossil fuel combustion is a primary greenhouse gas which contributes to “global warming.” It is estimated that stationary power generation contributes over one-third of total CO2 emissions. Reducing CO2 in the atmosphere can be accomplished either by decreasing the rate at which CO2 is emitted into the atmosphere or by increasing the rate at which it is removed from it. Extensive research has been conducted on determining a fast and inexpensive method to sequester carbon dioxide. These methods can be classified into two categories, CO2 fixation by natural sink process for CO2, or direct CO2 sequestration by artificial processes. In direct sequestration, CO2 produced from sources such as coal-fired power plants, would be captured from the exhausted gases. CO2 from a combustion exhaust gas is absorbed with an aqueous ammonia solution through scrubbing. The captured CO2 is then used to synthesize ammonium bicarbonate (ABC or NH4HCO3), an economical source of nitrogen fertilizer. In this work, we studied the carbon distribution after fertilizer is synthesized from CO2. The synthesized fertilizer in laboratory is used as a “CO2 carrier” to “transport” CO2 from the atmosphere to crops. After biological assimilation and metabolism in crops treated with ABC, a considerable amount of the carbon source is absorbed by the plants with increased biomass production. The majority of the unused carbon source percolates into the soil as carbonates, such as calcium carbonate (CaCO3) and magnesium carbonate (MgCO3). These carbonates are environmentally benign. As insoluble salts, they are found in normal rocks and can be stored safely and permanently in soil. This investigation mainly focuses on the carbon distribution after the synthesized fertilizer is applied to soil. Quantitative examination of carbon distribution in an ecosystem is a challenging task since the carbon in the soil may come from various sources. Therefore synthesized 14C

  5. Numerical Simulation of Thermal-Hydrological-Mechanical-Chemical Processes during CO2 Geo-sequestration in Saline Aquifer

    NASA Astrophysics Data System (ADS)

    zhang, R.; Winterfeld, P.; Yin, X.; Wu, Y.

    2013-12-01

    The significance of thermal-hydrologic-mechanical-chemical (THMC) processes is well recognized in the operation of CO2 geo-sequestration. Geomechanical and geochemical effects may significantly change aqueous phase composition, porosity and permeability of the formation, and in turn flow and transport. The TOUGHREACT simulator (Xu et al., 2004) has the capability to quantitatively simulate multiphase fluid flow, solute transport and geochemical reactions during CO2 sequestration in saline aquifers using a sequential coupling. Using a mean stress formulation, stresses, displacements, and rock deformations due to fluid injection have been simulated by the recently developed TOUGH2-CSM (Winterfeld and Wu, 2011) to account for the geomechanical effects in CO2 sequestration in saline aquifers. Based on these previously developed numerical simulators: TOUGH-ECO2N (Pruess, 2005), TOUGHREACT, and TOUGH2-CSM, we present general mathematical formulations of the THMC processes. Two coupled computational frameworks (sequentially coupled procedure and fully coupled procedure) are developed to simulate reactive, multiphase transport of CO2 in saline aquifer with thermal and geomechanical effects; both of them model (1) fluid and heat flow, and solute transport in the aqueous phase within a three-phase mixture, (2) stresses and displacements related to the mean stress, (3) non-isothermal effects on fluid properties and reaction processes, and (4) chemical equilibrium and kinetics of fluid-rock and gas-rock interactions. A set of partial differential equations is formulated to represent the physical, mechanical and chemical processes. The accuracy of the THMC models is demonstrated using four examples with analytical solutions: (1) 1D reactive transport under chemical equilibrium conditions, (2) 1D reactive transport with chemical kinetics, (3) 1D heat conduction, and (4) 1D consolidation. Finally, the developed reactive transport models with general chemical compositions are

  6. Chemical-mechanical coupling observed for depleted oil reservoirs subjected to long-term CO2-exposure - A case study of the Werkendam natural CO2 analogue field

    NASA Astrophysics Data System (ADS)

    Hangx, Suzanne; Bakker, Elisenda; Bertier, Pieter; Nover, Georg; Busch, Andreas

    2015-10-01

    Geological storage of CO2 is one of the most promising technologies to rapidly reduce anthropogenic emissions of carbon dioxide. In order to ensure storage integrity, it is important to understand the effect of long-term CO2/brine/rock interactions on the mechanical behaviour of a storage complex. As most of these reactions are too slow to reproduce on laboratory timescales, we studied a natural CO2 analogue reservoir (the Röt Fringe Sandstone, Werkendam field, the Netherlands; 125-135 Ma of CO2-exposure) and its unreacted counterpart. We focused on CO2-induced mineralogical and porosity-permeability changes, and their effect on mechanical behaviour of both intact rock and simulated fault gouge. Overall, CO2-exposure did not lead to drastic mineralogical changes. The CO2-exposed material shows a stronger dependence of permeability on porosity, which is attributed to differences in diagenesis (closed-system diagenesis and hydrocarbon emplacement) taking place before CO2 charging. The limited extent of reaction was in part the result of bitumen coatings protecting specific mineral phases from reaction. In local, mm-sized zones displaying significant anhydrite cement dissolution, enhanced porosity was observed. For most of the reservoir the long-term mechanical behaviour after CO2-exposure could be described by the behaviour of the unreacted sandstone, while these more 'porous' zones had a lower rock strength. In addition, CO2-exposure did not affect the fault friction behaviour, and slip is expected to result in stable sliding. Simple stress path calculations predict that reservoir failure due to depletion and injection is unlikely, even for the 'porous' zones, nor will fault reactivation occur for realistic injection scenarios.

  7. Microbial Reverse-Electrodialysis Electrolysis and Chemical-Production Cell for H2 Production and CO2 Sequestration

    PubMed Central

    2014-01-01

    Natural mineral carbonation can be accelerated using acid and alkali solutions to enhance atmospheric CO2 sequestration, but the production of these solutions needs to be carbon-neutral. A microbial reverse-electrodialysis electrolysis and chemical-production cell (MRECC) was developed to produce these solutions and H2 gas using only renewable energy sources (organic matter and salinity gradient). Using acetate (0.82 g/L) as a fuel for microorganisms to generate electricity in the anode chamber (liquid volume of 28 mL), 0.45 mmol of acid and 1.09 mmol of alkali were produced at production efficiencies of 35% and 86%, respectively, along with 10 mL of H2 gas. Serpentine dissolution was enhanced 17–87-fold using the acid solution, with approximately 9 mL of CO2 absorbed and 4 mg of CO2 fixed as magnesium or calcium carbonates. The operational costs, based on mineral digging and grinding, and water pumping, were estimated to be only $25/metric ton of CO2 fixed as insoluble carbonates. Considering the additional economic benefits of H2 generation and possible wastewater treatment, this method may be a cost-effective and environmentally friendly method for CO2 sequestration. PMID:24741666

  8. High temperature chemical kinetic study of the H2-CO-CO2-NO reaction system

    NASA Technical Reports Server (NTRS)

    Jachimowski, C. J.

    1975-01-01

    An experimental study of the kinetics of the H2-CO-CO2-NO reaction system was made behind incident shock waves at temperatures of 2460 and 2950 K. The overall rate of the reaction was measured by monitoring radiation from the CO + O yields CO2 + h upoilon reaction. Correlation of these data with a detailed reaction mechanism showed that the high-temperature rate of the reaction N + OH yields NO + H can be described by the low-temperature (320 K) rate coefficient. Catalytic dissociation of molecular hydrogen was an important reaction under the tests conditions.

  9. A Review of Hazardous Chemical Species Associated with CO2 Capturefrom Coal-Fired Power Plants and Their Potential Fate in CO2 GeologicStorage

    SciTech Connect

    Apps, J.A.

    2006-02-23

    Conventional coal-burning power plants are major contributors of excess CO2 to the atmospheric inventory. Because such plants are stationary, they are particularly amenable to CO2 capture and disposal by deep injection into confined geologic formations. However, the energy penalty for CO2 separation and compression is steep, and could lead to a 30-40 percent reduction in useable power output. Integrated gas combined cycle (IGCC) plants are thermodynamically more efficient, i.e.,produce less CO2 for a given power output, and are more suitable for CO2 capture. Therefore, if CO2 capture and deep subsurface disposal were to be considered seriously, the preferred approach would be to build replacement IGCC plants with integrated CO2 capture, rather than retrofit existing conventional plants. Coal contains minor quantities of sulfur and nitrogen compounds, which are of concern, as their release into the atmosphere leads to the formation of urban ozone and acid rain, the destruction of stratospheric ozone, and global warming. Coal also contains many trace elements that are potentially hazardous to human health and the environment. During CO2 separation and capture, these constituents could inadvertently contaminate the separated CO2 and be co-injected. The concentrations and speciation of the co-injected contaminants would differ markedly, depending on whether CO2 is captured during the operation of a conventional or an IGCC plant, and the specific nature of the plant design and CO2 separation technology. However, regardless of plant design or separation procedures, most of the hazardous constituents effectively partition into the solid waste residue. This would lead to an approximately two order of magnitude reduction in contaminant concentration compared with that present in the coal. Potential exceptions are Hg in conventional plants, and Hg and possibly Cd, Mo and Pb in IGCC plants. CO2 capture and injection disposal could afford an opportunity to deliberately capture

  10. Chemical ordering and large tunnel magnetoresistance in Co2FeAl/MgAl2O4/Co2FeAl(001) junctions

    NASA Astrophysics Data System (ADS)

    Scheike, Thomas; Sukegawa, Hiroaki; Inomata, Koichiro; Ohkubo, Tadakatsu; Hono, Kazuhiro; Mitani, Seiji

    2016-05-01

    Epitaxial magnetic tunnel junctions (MTJs) with a Co2FeAl/CoFe (0.5 nm)/MgAl2O4/Co2FeAl(001) structure were fabricated by magnetron sputtering. High-temperature in situ annealing led to a high degree of B2-order in the Co2FeAl layers and cation order of the MgAl2O4 barrier. Large tunnel magnetoresistance (TMR) of up to 342% was obtained at room temperature (616% at 4 K), in contrast to the TMR ratio ( ≲ 160%) suppressed by the band-folding effect in Fe/cation-ordered MgAl2O4/Fe MTJs. The present study reveals that the high degree of B2-order and the resulting high spin polarization in the Co2FeAl electrodes enable us to bypass the band-folding problem in spinel barriers.

  11. Fate of injected CO2 in the Wilcox Group, Louisiana, Gulf Coast Basin: Chemical and isotopic tracers of microbial-brine-rock-CO2 interactions

    USGS Publications Warehouse

    Shelton, Jenna L.; McIntosh, Jennifer C.; Warwick, Peter D.; Lee Zhi Yi, Amelia

    2016-01-01

    The “2800’ sandstone” of the Olla oil field is an oil and gas-producing reservoir in a coal-bearing interval of the Paleocene–Eocene Wilcox Group in north-central Louisiana, USA. In the 1980s, this producing unit was flooded with CO2 in an enhanced oil recovery (EOR) project, leaving ∼30% of the injected CO2 in the 2800’ sandstone post-injection. This study utilizes isotopic and geochemical tracers from co-produced natural gas, oil and brine to determine the fate of the injected CO2, including the possibility of enhanced microbial conversion of CO2 to CH4 via methanogenesis. Stable carbon isotopes of CO2, CH4 and DIC, together with mol% CO2 show that 4 out of 17 wells sampled in the 2800’ sandstone are still producing injected CO2. The dominant fate of the injected CO2appears to be dissolution in formation fluids and gas-phase trapping. There is some isotopic and geochemical evidence for enhanced microbial methanogenesis in 2 samples; however, the CO2 spread unevenly throughout the reservoir, and thus cannot explain the elevated indicators for methanogenesis observed across the entire field. Vertical migration out of the target 2800’ sandstone reservoir is also apparent in 3 samples located stratigraphically above the target sand. Reservoirs comparable to the 2800’ sandstone, located along a 90-km transect, were also sampled to investigate regional trends in gas composition, brine chemistry and microbial activity. Microbial methane, likely sourced from biodegradation of organic substrates within the formation, was found in all oil fields sampled, while indicators of methanogenesis (e.g. high alkalinity, δ13C-CO2 and δ13C-DIC values) and oxidation of propane were greatest in the Olla Field, likely due to its more ideal environmental conditions (i.e. suitable range of pH, temperature, salinity, sulfate and iron concentrations).

  12. A Lumped, Macroscopic Approach to Modeling Soil Moisture, CO2 Transport, and Chemical Weathering in the Critical Zone

    NASA Astrophysics Data System (ADS)

    Porporato, A. M.; Parolari, A.

    2015-12-01

    Ecohydrological processes in the root zone act as a dynamic interface between the atmosphere and the deeper soil layers, modulating the conditions that drive chemical weathering along the soil profile. Among these processes, soil moisture dynamics respond to intermittent rainfall pulses and to runoff and evapotranspiration losses. In addition, carbon dioxide (CO2) and its associated acidity are introduced into the soil moisture via root and microbial respiration. The coupling of soil moisture and CO2 dynamics in the root zone acts as an important controller of the critical zone development through the chemical weathering and water chemistry exported through runoff and percolation. Due to spatial and temporal variability and non-linearity, modeling these coupled root zone soil moisture and CO2 dynamics presents a number of challenges. In this talk, a lumped, macroscopic approach to modeling soil moisture, CO2 transport, and chemical weathering in the critical zone is introduced. The model considers a homogeneous soil column, therefore simplifying known spatial heterogeneities, and focuses on temporal variability resulting from non-linear processes and stochastic rainfall forcing. First, at short time-scales, the deterministic temporal evolution of soil moisture, dissolved inorganic carbon, pH, and alkalinity is analyzed using a dynamical system approach. Second, at longer inter-annual time-scales where rainfall stochasticity becomes an important driver of the system behavior, the system is analyzed probabilistically and its average behavior described using a novel macroscopic approach. This averaging of the nonlinear stochastic dynamics results in a closure problem that is addressed through a first-order approximation of non-linear fluxes, including the correlation between soil moisture and solutes. The model provides a method to assess how changes in external forcing or system properties propagate into and alter critical zone structure and function, and to isolate

  13. CHEMICAL FIXATION OF CO2 IN COAL COMBUSTION PRODUCTS AND RECYCLING THROUGH BIOSYSTEMS

    SciTech Connect

    C. Henry Copeland; Paul Pier; Samantha Whitehead; Paul Enlow; Richard Strickland; David Behel

    2003-12-15

    This Annual Technical Progress Report presents the principle results in enhanced growth of algae using coal combustion products as a catalyst to increase bicarbonate levels in solution. A co-current reactor is present that increases the gas phase to bicarbonate transfer rate by a factor of five to nine. The bicarbonate concentration at a given pH is approximately double that obtained using a control column of similar construction. Algae growth experiments were performed under laboratory conditions to obtain baseline production rates and to perfect experimental methods. The final product of this initial phase in algae production is presented. Algal growth can be limited by several factors, including the level of bicarbonate available for photosynthesis, the pH of the growth solution, nutrient levels, and the size of the cell population, which determines the available space for additional growth. In order to supply additional CO2 to increase photosynthesis and algal biomass production, fly ash reactor has been demonstrated to increase the available CO2 in solution above the limits that are achievable with dissolved gas alone. The amount of dissolved CO2 can be used to control pH for optimum growth. Periodic harvesting of algae can be used to maintain algae in the exponential, rapid growth phase. An 800 liter scale up demonstrated that larger scale production is possible. The larger experiment demonstrated that indirect addition of CO2 is feasible and produces significantly less stress on the algal system. With better harvesting methods, nutrient management, and carbon dioxide management, an annual biomass harvest of about 9,000 metric tons per square kilometer (36 MT per acre) appears to be feasible. To sequester carbon, the algal biomass needs to be placed in a permanent location. If drying is undesirable, the biomass will eventually begin to aerobically decompose. It was demonstrated that algal biomass is a suitable feed to an anaerobic digester to produce methane

  14. Enhanced stability and chemical resistance of a new nanoscale biocatalyst for accelerating CO2 absorption into a carbonate solution.

    PubMed

    Zhang, Shihan; Lu, Hong; Lu, Yongqi

    2013-12-01

    A novel potassium-carbonate-based absorption process is currently being developed to reduce the energy consumption when capturing CO2 from coal combustion flue gas. The process employs the enzyme carbonic anhydrase (CA) as a catalyst to accelerate the rate of CO2 absorption. This study focused on the immobilization of a new variant of the CA enzyme onto a new group of nonporous nanoparticles to improve the enzyme's thermal stability and its chemical resistance to major impurities from the flue gas. The CA enzyme was manufactured at the pilot scale by a leading enzyme company. As carrier materials, two different batches of SiO2-ZrO2 composite nanoparticles and one batch of silica nanoparticle were synthesized using a flame spray pyrolysis method. Classic Danckwerts absorption theory with reaction was applied to determine the kinetics of the immobilized enzymes for CO2 absorption. The immobilized enzymes retained 56-88% of their original activity in a K2CO3/KHCO3 solution over a 60-day test period at 50 °C, compared with a 30% activity retention for their free CA enzyme counterpart. The immobilized CA enzymes also revealed improved chemical stability. The inactivation kinetics of the free and immobilized CA enzymes in the K2CO3/KHCO3 solution were experimentally quantified. PMID:24187930

  15. Magnetic and chemical order-disorder transformations in Co2Fe(Ga1-xSix) and Co2Fe(Al1-ySiy) Heusler alloys

    NASA Astrophysics Data System (ADS)

    Umetsu, Rie Y.; Okubo, Akinari; Kainuma, Ryosuke

    2012-04-01

    The concentration dependence of the order-disorder phase transformation temperature from the L21 to the B2 phase (TtL21/B2) and magnetic properties of Co2Fe(Ga1-xSix) and Co2Fe(Al1-ySiy) Heusler alloys were investigated. In the phase diagrams, a crossover of the Curie temperature (TC) and TtL21/B2 was confirmed at around y = 0.45 in Co2Fe(Al1-ySiy), whereas the TC and TtL21/B2 monotonically changed with x in Co2Fe (Ga1-xSix). The slopes of the linear concentration dependence of TtL21/B2 for Co2Fe(Al1-ySiy) drastically changed at about y = 0.45, suggesting that the chemical interchange energy between Fe and Al in Co2FeAl alloy is affected by the magnetic ordering.

  16. Towards understanding the variability in biospheric CO2 fluxes: using FTIR spectrometry and a chemical transport model to investigate the sources and sinks of carbonyl sulfide and its link to CO2

    NASA Astrophysics Data System (ADS)

    Wang, Yuting; Deutscher, Nicholas M.; Palm, Mathias; Warneke, Thorsten; Notholt, Justus; Baker, Ian; Berry, Joe; Suntharalingam, Parvadha; Jones, Nicholas; Mahieu, Emmanuel; Lejeune, Bernard; Hannigan, James; Conway, Stephanie; Mendonca, Joseph; Strong, Kimberly; Campbell, J. Elliott; Wolf, Adam; Kremser, Stefanie

    2016-02-01

    Understanding carbon dioxide (CO2) biospheric processes is of great importance because the terrestrial exchange drives the seasonal and interannual variability of CO2 in the atmosphere. Atmospheric inversions based on CO2 concentration measurements alone can only determine net biosphere fluxes, but not differentiate between photosynthesis (uptake) and respiration (production). Carbonyl sulfide (OCS) could provide an important additional constraint: it is also taken up by plants during photosynthesis but not emitted during respiration, and therefore is a potential means to differentiate between these processes. Solar absorption Fourier Transform InfraRed (FTIR) spectrometry allows for the retrievals of the atmospheric concentrations of both CO2 and OCS from measured solar absorption spectra. Here, we investigate co-located and quasi-simultaneous FTIR measurements of OCS and CO2 performed at five selected sites located in the Northern Hemisphere. These measurements are compared to simulations of OCS and CO2 using a chemical transport model (GEOS-Chem). The coupled biospheric fluxes of OCS and CO2 from the simple biosphere model (SiB) are used in the study. The CO2 simulation with SiB fluxes agrees with the measurements well, while the OCS simulation reproduced a weaker drawdown than FTIR measurements at selected sites, and a smaller latitudinal gradient in the Northern Hemisphere during growing season when comparing with HIPPO (HIAPER Pole-to-Pole Observations) data spanning both hemispheres. An offset in the timing of the seasonal cycle minimum between SiB simulation and measurements is also seen. Using OCS as a photosynthesis proxy can help to understand how the biospheric processes are reproduced in models and to further understand the carbon cycle in the real world.

  17. Crystal engineering of an nbo topology metal-organic framework for chemical fixation of CO2 under ambient conditions.

    PubMed

    Gao, Wen-Yang; Chen, Yao; Niu, Youhong; Williams, Kia; Cash, Lindsay; Perez, Pastor J; Wojtas, Lukasz; Cai, Jianfeng; Chen, Yu-Sheng; Ma, Shengqian

    2014-03-01

    Crystal engineering of the nbo metal-organic framework (MOF) platform MOF-505 with a custom-designed azamacrocycle ligand (1,4,7,10-tetrazazcyclododecane-N,N',N'',N'''-tetra-p-methylbenzoic acid) leads to a high density of well-oriented Lewis active sites within the cuboctahedral cage in MMCF-2, [Cu2(Cu-tactmb)(H2O)3(NO3)2]. This MOF demonstrates high catalytic activity for the chemical fixation of CO2 into cyclic carbonates at room temperature under 1 atm pressure.

  18. Highly Efficient Oxygen-Storage Material with Intrinsic Coke Resistance for Chemical Looping Combustion-Based CO2 Capture.

    PubMed

    Imtiaz, Qasim; Kurlov, Alexey; Rupp, Jennifer Lilia Marguerite; Müller, Christoph Rüdiger

    2015-06-22

    Chemical looping combustion (CLC) and chemical looping with oxygen uncoupling (CLOU) are emerging thermochemical CO2 capture cycles that allow the capture of CO2 with a small energy penalty. Here, the development of suitable oxygen carrier materials is a key aspect to transfer these promising concepts to practical installations. CuO is an attractive material for CLC and CLOU because of its high oxygen-storage capacity (20 wt %), fast reaction kinetics, and high equilibrium partial pressure of oxygen at typical operating temperatures (850-1000 °C). However, despite its promising characteristics, its low Tammann temperature requires the development of new strategies to phase-stabilize CuO-based oxygen carriers. In this work, we report a strategy based on stabilization by co-precipitated ceria (CeO2-x ), which allowed us to increase the oxygen capacity, coke resistance, and redox stability of CuO-based oxygen carriers substantially. The performance of the new oxygen carriers was evaluated in detail and compared to the current state-of-the-art materials, that is, Al2 O3 -stabilized CuO with similar CuO loadings. We also demonstrate that the higher intrinsic oxygen uptake, release, and mobility in CeO2-x -stabilized CuO leads to a three times higher carbon deposition resistance compared to that of Al2 O3 -stabilized CuO. Moreover, we report a high cyclic stability without phase intermixing for CeO2-x -supported CuO. This was accompanied by a lower reduction temperature compared to state-of-the-art Al2 O3 -supported CuO. As a result of its high resistance towards carbon deposition and fast oxygen uncoupling kinetics, CeO2-x -stabilized CuO is identified as a very promising material for CLC- and CLOU-based CO2 capture architectures.

  19. Control of convective dissolution by chemical reactions: general classification and application to CO(2) dissolution in reactive aqueous solutions.

    PubMed

    Loodts, V; Thomas, C; Rongy, L; De Wit, A

    2014-09-12

    In partially miscible two-layer systems within a gravity field, buoyancy-driven convective motions can appear when one phase dissolves with a finite solubility into the other one. We investigate the influence of chemical reactions on such convective dissolution by a linear stability analysis of a reaction-diffusion-convection model. We show theoretically that a chemical reaction can either enhance or decrease the onset time of the convection, depending on the type of density profile building up in time in the reactive solution. We classify the stabilizing and destabilizing scenarios in a parameter space spanned by the solutal Rayleigh numbers. As an example, we experimentally demonstrate the possibility to enhance the convective dissolution of gaseous CO_{2} in aqueous solutions by a classical acid-base reaction.

  20. Control of Convective Dissolution by Chemical Reactions: General Classification and Application to CO2 Dissolution in Reactive Aqueous Solutions

    NASA Astrophysics Data System (ADS)

    Loodts, V.; Thomas, C.; Rongy, L.; De Wit, A.

    2014-09-01

    In partially miscible two-layer systems within a gravity field, buoyancy-driven convective motions can appear when one phase dissolves with a finite solubility into the other one. We investigate the influence of chemical reactions on such convective dissolution by a linear stability analysis of a reaction-diffusion-convection model. We show theoretically that a chemical reaction can either enhance or decrease the onset time of the convection, depending on the type of density profile building up in time in the reactive solution. We classify the stabilizing and destabilizing scenarios in a parameter space spanned by the solutal Rayleigh numbers. As an example, we experimentally demonstrate the possibility to enhance the convective dissolution of gaseous CO2 in aqueous solutions by a classical acid-base reaction.

  1. Chemical Reaction CO+OH(•) → CO2+H(•) Autocatalyzed by Carbon Dioxide: Quantum Chemical Study of the Potential Energy Surfaces.

    PubMed

    Masunov, Artëm E; Wait, Elizabeth; Vasu, Subith S

    2016-08-01

    The supercritical carbon dioxide medium, used to increase efficiency in oxy combustion fossil energy technology, may drastically alter both rates and mechanisms of chemical reactions. Here we investigate potential energy surface of the second most important combustion reaction with quantum chemistry methods. Two types of effects are reported: formation of the covalent intermediates and formation of van der Waals complexes by spectator CO2 molecule. While spectator molecule alter the activation barrier only slightly, the covalent bonding opens a new reaction pathway. The mechanism includes sequential covalent binding of CO2 to OH radical and CO molecule, hydrogen transfer from oxygen to carbon atoms, and CH bond dissociation. This reduces the activation barrier by 11 kcal/mol at the rate-determining step and is expected to accelerate the reaction rate. The finding of predicted catalytic effect is expected to play an important role not only in combustion but also in a broad array of chemical processes taking place in supercritical CO2 medium. It may open a new venue for controlling reaction rates for chemical manufacturing. PMID:27351778

  2. Chemical Reaction CO+OH(•) → CO2+H(•) Autocatalyzed by Carbon Dioxide: Quantum Chemical Study of the Potential Energy Surfaces.

    PubMed

    Masunov, Artëm E; Wait, Elizabeth; Vasu, Subith S

    2016-08-01

    The supercritical carbon dioxide medium, used to increase efficiency in oxy combustion fossil energy technology, may drastically alter both rates and mechanisms of chemical reactions. Here we investigate potential energy surface of the second most important combustion reaction with quantum chemistry methods. Two types of effects are reported: formation of the covalent intermediates and formation of van der Waals complexes by spectator CO2 molecule. While spectator molecule alter the activation barrier only slightly, the covalent bonding opens a new reaction pathway. The mechanism includes sequential covalent binding of CO2 to OH radical and CO molecule, hydrogen transfer from oxygen to carbon atoms, and CH bond dissociation. This reduces the activation barrier by 11 kcal/mol at the rate-determining step and is expected to accelerate the reaction rate. The finding of predicted catalytic effect is expected to play an important role not only in combustion but also in a broad array of chemical processes taking place in supercritical CO2 medium. It may open a new venue for controlling reaction rates for chemical manufacturing.

  3. The contribution of changes in P release and CO2 consumption by chemical weathering to the historical trend in land carbon uptake

    NASA Astrophysics Data System (ADS)

    Goodale, C. L.; Fredriksen, G.; McCalley, C. K.; Sparks, J. P.; Thomas, S. A.

    2011-12-01

    The atmospheric carbon dioxide (CO2) concentration has increased to a level unprecedented in the last 2 million years, and the concentration is projected to increase further with a rate unseen in geological past. The increase in CO2 cause a rise in surface temperatures and changes in the hydrological cycle through the redistribution of rainfall patterns. All of these changes will impact the weathering of rocks, which in turn affect atmospheric CO2 concentrations via two different pathways. On the one hand, CO2 is consumed by the dissolution reaction of the exposed minerals. And on the other hand, biological CO2 fixation is affected due to changes in phosphorus release from minerals, as biological activity is constrained by phosphorus availability at large scales. The traditional view is that both effects are negligible on a centennial time scale, but recent work on catchment scale challenge this view in favor of a potential high sensitivity of weathering to ongoing climate and land use changes. To globally quantify the contribution of CO2 fixation associated with weathering on the historical trend in terrestrial CO2 uptake, we applied a model of chemical weathering and phosphorus release under climate reconstructions from four Earth System Models. The simulations indicate that changes in weathering could have contributed considerably to the trend in terrestrial CO2 uptake since the pre-industrial revolution, with warming being the main driver of change. The increase in biological CO2 fixation is of comparable magnitude as the increase in CO2 consumption by chemical weathering. Our simulations support the previous findings on catchment scale that weathering can change significantly on a centennial time scale. This finding has implications for 21st century climate projections, which ignore changes in weathering, as well as for long-term airborne fraction of CO2 emissions, whose calculation usually neglects changes in phosphorus availability.

  4. Direct PEM fuel cell using "organic chemical hydrides" with zero-CO2 emission and low-crossover.

    PubMed

    Kariya, Nobuko; Fukuoka, Atsushi; Ichikawa, Masaru

    2006-04-14

    A series of "organic chemical hydrides" such as cyclohexane, methylcyclohexane, cyclohexene, 2-propanol, and cyclohexanol were applied to the direct PEM fuel cell. High performances of the PEM fuel cell were achieved by using cyclohexane (OCV = 920 mV, PD(max) = 15 mW cm(-2)) and 2-propanol (OCV = 790 mV, PD(max) = 78 mW cm(-2)) as fuels without CO(2) emissions. The rates of fuel crossover for cyclohexane, 2-propanol, and methanol were estimated, and the rates of fuel permeation of cyclohexane and 2-propanol were lower than that of methanol. Water electrolysis and electro-reductive hydrogenation of acetone mediated by PEM were carried out and formation of 2-propanol in cathode side was observed. This system is the first example of a "rechargeable" direct fuel cell.

  5. Percolation of CO2-rich fluids in a limestone sample: Evolution of hydraulic, electrical, chemical, and structural properties

    NASA Astrophysics Data System (ADS)

    Vialle, Stéphanie; Contraires, Simon; Zinzsner, Bernard; Clavaud, Jean-Baptiste; Mahiouz, Karim; Zuddas, Pierpaolo; Zamora, Maria

    2014-04-01

    Percolation of CO2-rich fluids in limestones causes the dissolution (and eventual reprecipitation) of calcium carbonate minerals, which affect the rock microstructure and change the rock petrophysical properties (i.e., hydraulic, electrical, and elastic properties). In addition, microstructural changes further feed back to affect the chemical reactions. To better understand this coupled problem and to assess the possibility of geophysical monitoring, we performed reactive percolation laboratory experiments on a well-characterized carbonate sample 35 cm in length and 10 cm in diameter. In a comprehensive study, we present integrated measurements of aqueous chemistry (pH, calcium concentration, and total alkalinity), petrophysical properties (permeability, electrical formation factor, and acoustic velocities), and X-ray tomography imaging. The measured chemical and electrical parameters allowed rapid detection of the dissolution of calcite in the downstream fluid. After circulating fluids of various salinities at 5mL min-1 for 32 days (about 290 pore sample volumes) at a pCO2 of 1 atm (pH = 4), porosity increased by 7% (from 0.29 to 0.31), permeability increased by 1 order of magnitude (from 0.12 D to 0.97 D), and the electrical formation factor decreased by 15% (from 15.7 to 13.3). X-ray microtomography revealed the creation of wormholes; these, along with the convex curvature of the permeability-porosity relationship, are consistent with a transport-controlled dissolution regime for which advection processes are greater than diffusion processes, confirming results from previous numerical studies. This study shows that nonseismic geophysical techniques (i.e., electrical measurements) are promising for monitoring geochemical changes within the subsurface due to fluid-rock interactions.

  6. Novel process and catalytic materials for converting CO2 and H2 containing mixtures to liquid fuels and chemicals.

    PubMed

    Meiri, Nora; Dinburg, Yakov; Amoyal, Meital; Koukouliev, Viatcheslav; Nehemya, Roxana Vidruk; Landau, Miron V; Herskowitz, Moti

    2015-01-01

    Carbon dioxide and water are renewable and the most abundant feedstocks for the production of chemicals and fungible fuels. However, the current technologies for production of hydrogen from water are not competitive. Therefore, reacting carbon dioxide with hydrogen is not economically viable in the near future. Other alternatives include natural gas, biogas or biomass for the production of carbon dioxide, hydrogen and carbon monoxide mixtures that react to yield chemicals and fungible fuels. The latter process requires a high performance catalyst that enhances the reverse water-gas-shift (RWGS) reaction and Fischer-Tropsch synthesis (FTS) to higher hydrocarbons combined with an optimal reactor system. Important aspects of a novel catalyst, based on a Fe spinel and three-reactor system developed for this purpose published in our recent paper and patent, were investigated in this study. Potassium was found to be a key promoter that improves the reaction rates of the RWGS and FTS and increases the selectivity of higher hydrocarbons while producing mostly olefins. It changed the texture of the catalyst, stabilized the Fe-Al-O spinel, thus preventing decomposition into Fe3O4 and Al2O3. Potassium also increased the content of Fe5C2 while shifting Fe in the oxide and carbide phases to a more reduced state. In addition, it increased the relative exposure of carbide iron on the catalysts surface, the CO2 adsorption and the adsorption strength. A detailed kinetic model of the RWGS, FTS and methanation reactions was developed for the Fe spinel catalyst based on extensive experimental data measured over a range of operating conditions. Significant oligomerization activity of the catalyst was found. Testing the pelletized catalyst with CO2, CO and H2 mixtures over a range of operating conditions demonstrated its high productivity to higher hydrocarbons. The composition of the liquid (C5+) was found to be a function of the potassium content and the composition of the feedstock

  7. Novel process and catalytic materials for converting CO2 and H2 containing mixtures to liquid fuels and chemicals.

    PubMed

    Meiri, Nora; Dinburg, Yakov; Amoyal, Meital; Koukouliev, Viatcheslav; Nehemya, Roxana Vidruk; Landau, Miron V; Herskowitz, Moti

    2015-01-01

    Carbon dioxide and water are renewable and the most abundant feedstocks for the production of chemicals and fungible fuels. However, the current technologies for production of hydrogen from water are not competitive. Therefore, reacting carbon dioxide with hydrogen is not economically viable in the near future. Other alternatives include natural gas, biogas or biomass for the production of carbon dioxide, hydrogen and carbon monoxide mixtures that react to yield chemicals and fungible fuels. The latter process requires a high performance catalyst that enhances the reverse water-gas-shift (RWGS) reaction and Fischer-Tropsch synthesis (FTS) to higher hydrocarbons combined with an optimal reactor system. Important aspects of a novel catalyst, based on a Fe spinel and three-reactor system developed for this purpose published in our recent paper and patent, were investigated in this study. Potassium was found to be a key promoter that improves the reaction rates of the RWGS and FTS and increases the selectivity of higher hydrocarbons while producing mostly olefins. It changed the texture of the catalyst, stabilized the Fe-Al-O spinel, thus preventing decomposition into Fe3O4 and Al2O3. Potassium also increased the content of Fe5C2 while shifting Fe in the oxide and carbide phases to a more reduced state. In addition, it increased the relative exposure of carbide iron on the catalysts surface, the CO2 adsorption and the adsorption strength. A detailed kinetic model of the RWGS, FTS and methanation reactions was developed for the Fe spinel catalyst based on extensive experimental data measured over a range of operating conditions. Significant oligomerization activity of the catalyst was found. Testing the pelletized catalyst with CO2, CO and H2 mixtures over a range of operating conditions demonstrated its high productivity to higher hydrocarbons. The composition of the liquid (C5+) was found to be a function of the potassium content and the composition of the feedstock.

  8. Flow paths and chemical reactivity of CO2 in carbonates using Mercury-Intrusion Capillary Pressure data and dimensionless numbers

    NASA Astrophysics Data System (ADS)

    Vialle, S.; Dvorkin, J. P.; Mavko, G. M.

    2012-12-01

    Experiments performed earlier by Vialle and Vanorio (2011) [1] have showed that the injection of CO2-rich water (pH=3.2) in various calcite limestones lead to heterogeneous dissolution of the pore structure, inducing secondary porosity and changing the rock stiffness. The presence of oil in the pore space affects the magnitude of these changes by lowering the reactive surface area. We present here a semi-quantitative analysis at the mesoscale to investigate how different initial pore microgeometries and heterogeneities in pore microgeometry affect the fluid-rock interactions. In particular, we aim at quantitatively explaining (1) why, in clean samples, higher-porosity micrite with rounded grains appears to be more affected by dissolution than tight micrite and spar cement and (2) why, for the same number of pore volumes of fluid injected, the magnitude of the changes in porosity (and subsequently elastic properties) differs among the studied rock samples. Rock microgeometry is studied by classical rock-physics methods, He-pycnometry and Mercury-Intrusion Capillary Pressure (MICP) tests, as well as by Scanning Electron Microscopy (SEM) imaging. Experiments were performed on subsamples (~0.5cm3) extracted from core plugs (~12cm3): two Fontainebleau sandstones, to serve as benchmarks, and two calcite carbonates from two different geological formations. In order to relate pore microgeometry to flow paths and chemical reactivity of CO2 in carbonate rocks, we chose to work at a scale that lies between the pore scale and the core scale. The method consists of physically subdividing the core plugs under examination into subsets based on the pore-throat sizes; these subsets correspond to three types of microstructure: "macropores", "microporous rounded micrite", and "spar cement"/"tight micrite". The dimensionless Péclet (Pe) and Damkhöler (Da) numbers, defined as the ratio between the advection rate and the diffusion rate, and as the ratio between the reaction rate and

  9. Mass Conservation in a Chemical Transport Model and its Effect on CO2 and SF6 Simulations

    NASA Technical Reports Server (NTRS)

    Zhu, Z.; Weaver, C.; Kawa, S. R.; Douglass, A. R.; Bhartia, P. K. (Technical Monitor)

    2002-01-01

    Chemical transport models (CTMs) must conserve mass to be useful for applications involving assessment of the effect of various pollutants on the troposphere and stratosphere. Furthermore, calculations of the evolution of constituents such as SF6 are used to evaluate overall model transport, and interpretation of such simulations is clouded if mass conservation is not assured. For realistic simulations or predictions, it is crucial that constituents are not produced or lost by transport or other processes in the CTMs. Analysis of CO2 and SF6 experiments using a CTM shows that problems with mass conservation can seriously degrade the simulations. Failure to conserve mass results from inconsistency of the surface pressure tendency and the divergence of horizontal mass flux when the model is forced by assimilated meteorological data. We have developed an effective method to eliminate the inconsistency by modifying the divergent part of the wind field. The changes in the wind fields are quite small but the impact on mass conservation is large. Parameterizations of physical processes such as convection or turbulent transport can also affect mass conservation. The lack of conservation is small but accumulates when integrations are lengthy such as required for SF6. This lack of conservation is found using winds from either a GCM or from an assimilation system. A simple adjustment removes much of the inaccuracy in the convective parameterization. A CO2 simulation using assimilated winds from the most recent version of the Goddard Earth Observing System Data Assimilation System will be used to illustrate the impact of these transport improvements.

  10. Chemical and morphological changes during olivine carbonation for CO2 storage in the presence of NaCl and NaHCO3.

    PubMed

    Gadikota, Greeshma; Matter, Juerg; Kelemen, Peter; Park, Ah-Hhyung Alissa

    2014-03-14

    The increasing concentrations of CO2 in the atmosphere are attributed to the rising consumption of fossil fuels for energy generation around the world. One of the most stable and environmentally benign methods of reducing atmospheric CO2 is by storing it as thermodynamically stable carbonate minerals. Olivine ((Mg,Fe)2SiO4) is an abundant mineral that reacts with CO2 to form Mg-carbonate. The carbonation of olivine can be enhanced by injecting solutions containing CO2 at high partial pressure into olivine-rich formations at high temperatures, or by performing ex situ mineral carbonation in a reactor system with temperature and pressure control. In this study, the effects of NaHCO3 and NaCl, whose roles in enhanced mineral carbonation have been debated, were investigated in detail along with the effects of temperature, CO2 partial pressure and reaction time for determining the extent of olivine carbonation and its associated chemical and morphological changes. At high temperature and high CO2 pressure conditions, more than 70% olivine carbonation was achieved in 3 hours in the presence of 0.64 M NaHCO3. In contrast, NaCl did not significantly affect olivine carbonation. As olivine was dissolved and carbonated, its pore volume, surface area and particle size were significantly changed and these changes influenced subsequent reactivity of olivine. Thus, for both long-term simulation of olivine carbonation in geologic formations and the ex situ reactor design, the morphological changes of olivine during its reaction with CO2 should be carefully considered in order to accurately estimate the CO2 storage capacity and understand the mechanisms for CO2 trapping by olivine.

  11. CO2 enhanced chemical vapor deposition growth of few-layer graphene over NiO(x).

    PubMed

    Son, In Hyuk; Song, Hyun Jae; Kwon, Soonchul; Bachmatiuk, Alicja; Lee, Seung Jae; Benayad, Anass; Park, Jong Hwan; Choi, Jae-Young; Chang, Hyuk; Rümmeli, Mark H

    2014-09-23

    The use of mild oxidants in chemical vapor deposition (CVD) reactions has proven enormously useful. This was also true for the CVD growth of carbon nanotubes. As yet though, the use of mild oxidants in the CVD of graphene has remained unexplored. Here we explore the use of CO2 as a mild oxidant during the growth of graphene over Ni with CH4 as the feedstock. Both our experimental and theoretical findings provide in-depth insight into the growth mechanisms and point to the mild oxidants playing multiple roles. Mild oxidants lead to the formation of a suboxide in the Ni, which suppresses the bulk diffusion of C species suggesting a surface growth mechanism. Moreover, the formation of a suboxide leads to enhanced catalytic activity at the substrate surface, which allows reduced synthesis temperatures, even as low as 700 °C. Even at these low temperatures, the quality of the graphene is exceedingly high as indicated by a negligible D mode in the Raman spectra. These findings suggest the use of mild oxidants in the CVD fabrication as a whole could have a positive impact. PMID:25171048

  12. OPERATIONAL EXPERIENCE: UPGRADED MPC AND A SYSTEMS FOR THE RADIOCHEMICAL PLANT OF THE SIBERIAN CHEMICAL COMBINE

    SciTech Connect

    RODRIGUEZ,C.GOLOSKOKOV,I.FISHBONE,L.GOODEY,K.LOOMIS,M.CRAIN,B.JR.LARSEN,R.

    2003-07-18

    The success of reducing the risk of nuclear proliferation through physical protection and material control/accounting systems depends upon the development of an effective design that includes consideration of the objectives of the systems and the resources available to implement the design. Included among the objectives of the design are facility characterization, definition of threat, and identification of targets. When considering resources, the designer must consider funds available, rapid low-cost elements, technology elements, human resources, and the availability of resources to sustain operation of the end system. The Siberian Chemical Combine (SCC) is a multi-function nuclear facility located in the Tomsk region of Siberia, Russia. Beginning in 1996, SCC joined with the United States Department of Energy (US/DOE) Material Protection, Control, and Accounting (MPC&A) Program to develop and implement MPC&A upgrades for the Radiochemical, Chemical Metallurgical, Conversion, Uranium Enrichment, and Reactor Plants of the SCC. At the Radiochemical Plant the MPC&A design and implementation process has been largely completed for the Plutonium Storage Facility and related areas of the Radiochemical Plant. Design and implementation of upgrades for the Radiochemical Plant include rapid physical protection upgrades such as bricking up of doors and windows, and installation of security-hardened doors. Rapid material control and accounting upgrades include installation of modern balances and bar code equipment. Comprehensive MPC&A upgrades include the installation of access controls to sensitive areas of the Plant, alarm communication and display (AC&D) systems to detect and annunciate alarm conditions, closed circuit (CCTV) systems to assess alarm conditions, central and secondary alarm station upgrades that enable security forces to assess and respond to alarm conditions, material control and accounting upgrades that include upgraded physical inventory procedures, and

  13. Using Carbonyl Sulfide Column Measurements and a Chemical Transport Model to Investigate Variability in Biospheric CO2 Fluxes

    NASA Astrophysics Data System (ADS)

    Wang, Y.; Palm, M.; Deutscher, N. M.; Warneke, T.; Notholt, J.; Baker, I. T.; Berry, J. A.; Suntharalingam, P.; Campbell, J. E.; Wolf, A.

    2014-12-01

    Understanding the CO2 processes on land is of great importance, because the terrestrial exchange drives the seasonal and interannual variability of CO2 in the atmosphere. Atmospheric inversions based on CO2 concentration measurements alone can only determine net biosphere fluxes, but not differentiate between photosynthesis (uptake) and respiration (production). Carbonyl sulfide (OCS) could provide an important additional constraint: it is also taken up by plants during photosynthesis but not emitted during respiration, and therefore is a potential means to differentiate between these processes. Solar absorption Fourier Transform InfraRed (FTIR) spectrometry allows for the retrieval of the atmospheric concentrations of both CO2 and OCS. Here, we investigate co-located and nearly simultaneous measurements of OCS and CO2 measured at 3 sites via FTIR spectrometers. These northern-hemispheric sites span a wide range of latitudes and all have multiple year time-series. The sites include Ny-Alesund (79°N), Bremen (53°N) and Paramaribo (6°N). We compare these measurements to simulations of OCS and CO2 using the GEOS-Chem model. The simulations are driven by different land biospheric fluxes of OCS and CO2 to match the seasonality of the measurements. The simple biosphere model (SiB-COS) are used in the study because it simultaneously calculates the biospheric fluxes of both OCS and CO2. The CO2 simulation with SiB fluxes agrees with the measurements better than a simulation using CASA. Comparison of the OCS simulations with different fluxes indicates that the latitudinal distribution of the OCS fluxes within SiB needs to be adjusted.

  14. Using Carbonyl Sulfide column measurements and a Chemical Transport Model to investigate variability in biospheric CO2 fluxes

    NASA Astrophysics Data System (ADS)

    Wang, Yuting; Petri, Christof; Palm, Mathias; Warneke, Thorsten; Baker, Ian; Berry, Joe; Suntharalingam, Parvadha; Campbell, Elliott; Wolf, Adam; Deutscher, Nick; Notholt, Justus

    2015-04-01

    Understanding the CO2 processes on land is of great importance, because the terrestrial exchange drives the seasonal and interannual variability of CO2 in the atmosphere. Atmospheric inversions based on CO2 concentration measurements alone can only determine net biosphere fluxes, but not differentiate between photosynthesis (uptake) and respiration (production). Carbonyl sulfide (OCS) could provide an important additional constraint: it is also taken up by plants during photosynthesis but not emitted during respiration, and therefore is a potential means to differentiate between these processes. Solar absorption Fourier Transform InfraRed (FTIR) spectrometry allows for the retrieval of the atmospheric concentrations of both CO2 and OCS. Here, we investigate co-located and nearly simultaneous measurements of OCS and CO2 measured at 3 sites via FTIR spectrometers. These northern-hemispheric sites span a wide range of latitudes and all have multiple year time-series. The sites include Ny-Alesund (79°N), Bremen (53°N) and Paramaribo (6°N). We compare these measurements to simulations of OCS and CO2 using the GEOS-Chem model. The simulations are driven by different land biospheric fluxes of OCS and CO2 to match the seasonality of the measurements. The simple biosphere model (SiB-COS) are used in the study because it simultaneously calculates the biospheric fluxes of both OCS and CO2. The CO2 simulation with SiB fluxes agrees with the measurements better than a simulation using CASA. Comparison of the OCS simulations with different fluxes indicates that the latitudinal distribution of the OCS fluxes within SiB needs to be adjusted.

  15. Application of Chemical Doping and Architectural Design Principles To Fabricate Nanowire Co2Ni3ZnO8 Arrays for Aqueous Asymmetric Supercapacitors.

    PubMed

    Liu, Qi; Yang, Bin; Liu, Jingyuan; Yuan, Yi; Zhang, Hongsen; Liu, Lianhe; Wang, Jun; Li, Rumin

    2016-08-10

    Electrode materials derived from transition metal oxides have a serious problem of low electron transfer rate, which restricts their practical application. However, chemically doped graphene transforms the chemical bonding configuration to enhance electron transfer rate and, therefore, facilitates the successful fabrication of Co2Ni3ZnO8 nanowire arrays. In addition, the Co2Ni3ZnO8 electrode materials, considered as Ni and Zn ions doped into Co3O4, have a high electron transfer rate and electrochemical response capability, because the doping increases the degree of crystal defect and reaction of Co/Ni ions with the electrolyte. Hence, the Co2Ni3ZnO8 electrode exhibits a high rate property and excellent electrochemical cycle stability, as determined by electrochemical analysis of the relationship between specific capacitance, IR drop, Coulomb efficiency, and different current densities. From the results of a three-electrode system of electrochemical measurement, the Co2Ni3ZnO8 electrode demonstrates a specific capacitance of 1115 F g(-1) and retains 89.9% capacitance after 2000 cycles at a current density of 4 A g(-1). The energy density of the asymmetric supercapacitor (AC//Co2Ni3ZnO8) is 54.04 W h kg(-1) at the power density of 3200 W kg(-1). PMID:27428712

  16. Application of Chemical Doping and Architectural Design Principles To Fabricate Nanowire Co2Ni3ZnO8 Arrays for Aqueous Asymmetric Supercapacitors.

    PubMed

    Liu, Qi; Yang, Bin; Liu, Jingyuan; Yuan, Yi; Zhang, Hongsen; Liu, Lianhe; Wang, Jun; Li, Rumin

    2016-08-10

    Electrode materials derived from transition metal oxides have a serious problem of low electron transfer rate, which restricts their practical application. However, chemically doped graphene transforms the chemical bonding configuration to enhance electron transfer rate and, therefore, facilitates the successful fabrication of Co2Ni3ZnO8 nanowire arrays. In addition, the Co2Ni3ZnO8 electrode materials, considered as Ni and Zn ions doped into Co3O4, have a high electron transfer rate and electrochemical response capability, because the doping increases the degree of crystal defect and reaction of Co/Ni ions with the electrolyte. Hence, the Co2Ni3ZnO8 electrode exhibits a high rate property and excellent electrochemical cycle stability, as determined by electrochemical analysis of the relationship between specific capacitance, IR drop, Coulomb efficiency, and different current densities. From the results of a three-electrode system of electrochemical measurement, the Co2Ni3ZnO8 electrode demonstrates a specific capacitance of 1115 F g(-1) and retains 89.9% capacitance after 2000 cycles at a current density of 4 A g(-1). The energy density of the asymmetric supercapacitor (AC//Co2Ni3ZnO8) is 54.04 W h kg(-1) at the power density of 3200 W kg(-1).

  17. A microporous Cu-MOF with optimized open metal sites and pore spaces for high gas storage and active chemical fixation of CO2.

    PubMed

    Gao, Chao-Ying; Tian, Hong-Rui; Ai, Jing; Li, Lei-Jiao; Dang, Song; Lan, Ya-Qian; Sun, Zhong-Ming

    2016-09-25

    A microporous Cu-MOF with optimized open metal sites and pore space was constructed based on a designed bent ligand; it exhibits high-capacity multiple gas storage under atmospheric pressure and efficient catalytic activity for chemical fixation of CO2 under mild conditions.

  18. A microporous Cu-MOF with optimized open metal sites and pore spaces for high gas storage and active chemical fixation of CO2.

    PubMed

    Gao, Chao-Ying; Tian, Hong-Rui; Ai, Jing; Li, Lei-Jiao; Dang, Song; Lan, Ya-Qian; Sun, Zhong-Ming

    2016-09-25

    A microporous Cu-MOF with optimized open metal sites and pore space was constructed based on a designed bent ligand; it exhibits high-capacity multiple gas storage under atmospheric pressure and efficient catalytic activity for chemical fixation of CO2 under mild conditions. PMID:27550833

  19. A coupling alternative to reactive transport simulations for long-term prediction of chemical reactions in heterogeneous CO2 storage systems

    NASA Astrophysics Data System (ADS)

    De Lucia, M.; Kempka, T.; Kühn, M.

    2015-02-01

    Fully coupled, multi-phase reactive transport simulations of CO2 storage systems can be approximated by a simplified one-way coupling of hydrodynamics and reactive chemistry. The main characteristics of such systems, and hypotheses underlying the proposed alternative coupling, are (i) that the presence of CO2 is the only driving force for chemical reactions and (ii) that its migration in the reservoir is only marginally affected by immobilisation due to chemical reactions. In the simplified coupling, the exposure time to CO2 of each element of the hydrodynamic grid is estimated by non-reactive simulations and the reaction path of one single batch geochemical model is applied to each grid element during its exposure time. In heterogeneous settings, analytical scaling relationships provide the dependency of velocity and amount of reactions to porosity and gas saturation. The analysis of TOUGHREACT fully coupled reactive transport simulations of CO2 injection in saline aquifer, inspired to the Ketzin pilot site (Germany), both in homogeneous and heterogeneous settings, confirms that the reaction paths predicted by fully coupled simulations in every element of the grid show a high degree of self-similarity. A threshold value for the minimum concentration of dissolved CO2 considered chemically active is shown to mitigate the effects of the discrepancy between dissolved CO2 migration in non-reactive and fully coupled simulations. In real life, the optimal threshold value is unknown and has to be estimated, e.g. by means of 1-D or 2-D simulations, resulting in an uncertainty ultimately due to the process de-coupling. However, such uncertainty is more than acceptable given that the alternative coupling enables using grids of the order of millions of elements, profiting from much better description of heterogeneous reservoirs at a fraction of the calculation time of fully coupled models.

  20. A coupling alternative to reactive transport simulations for long-term prediction of chemical reactions in heterogeneous CO2 storage systems

    NASA Astrophysics Data System (ADS)

    De Lucia, M.; Kempka, T.; Kühn, M.

    2014-09-01

    Fully-coupled, multi-phase reactive transport simulations of CO2 storage systems can be approximated by a simplified one-way coupling of hydrodynamics and reactive chemistry. The main characteristics of such systems, and hypotheses underlying the proposed alternative coupling, are (i) that the presence of CO2 is the only driving force for chemical reactions and (ii) that its migration in the reservoir is only marginally affected by immobilization due to chemical reactions. In the simplified coupling, the exposure time to CO2 of each element of the hydrodynamic grid is estimated by non-reactive simulations and the reaction path of one single batch geochemical model is applied to each grid element during its exposure time. In heterogeneous settings, analytical scaling relationships provide the dependency of velocity and amount of reactions to porosity and gas saturation. The analysis of TOUGHREACT fully coupled reactive transport simulations of CO2 injection in saline aquifer, inspired to the Ketzin pilot site (Germany), both in homogeneous and heterogeneous settings, confirms that the reaction paths predicted by fully coupled simulations in every element of the grid show a high degree of self-similarity. A threshold value for the minimum concentration of dissolved CO2 considered chemically active is showed to mitigate the effects of the discrepancy between dissolved CO2 migration in non-reactive and fully coupled simulations. In real life, the optimal threshold value is unknown and has to be estimated, e.g., by means of 1-D or 2-D simulations, resulting in an uncertainty ultimately due to the process de-coupling. However, such uncertainty is more than acceptable given that the alternative coupling enables using grids in the order of million elements, profiting from much better description of heterogeneous reservoirs at a fraction of the calculation time of fully coupled models.

  1. Coal Direct Chemical Looping Retrofit to Pulverized Coal Power Plants for In-Situ CO2 Capture

    SciTech Connect

    Zeng, Liang; Li, Fanxing; Kim, Ray; Bayham, Samuel; McGiveron, Omar; Tong, Andrew; Connell, Daniel; Luo, Siwei; Sridhar, Deepak; Wang, Fei; Sun, Zhenchao; Fan, Liang-Shih

    2013-09-30

    A novel Coal Direct Chemical Looping (CDCL) system is proposed to effectively capture CO2 from existing PC power plants. The work during the past three years has led to an oxygen carrier particle with satisfactory performance. Moreover, successful laboratory, bench scale, and integrated demonstrations have been performed. The proposed project further advanced the novel CDCL technology to sub-pilot scale (25 kWth). To be more specific, the following objectives attained in the proposed project are: 1. to further improve the oxygen carrying capacity as well as the sulfur/ash tolerance of the current (working) particle; 2. to demonstrate continuous CDCL operations in an integrated mode with > 99% coal (bituminous, subbituminous, and lignite) conversion as well as the production of high temperature exhaust gas stream that is suitable for steam generation in existing PC boilers; 3. to identify, via demonstrations, the fate of sulfur and NOx; 4. to conduct thorough techno-economic analysis that validates the technical and economical attractiveness of the CDCL system. The objectives outlined above were achieved through collaborative efforts among all the participants. CONSOL Energy Inc. performed the techno-economic analysis of the CDCL process. Shell/CRI was able to perform feasibility and economic studies on the large scale particle synthesis and provide composite particles for the sub-pilot scale testing. The experience of B&W (with boilers) and Air Products (with handling gases) assisted the retrofit system design as well as the demonstration unit operations. The experience gained from the sub-pilot scale demonstration of the Syngas Chemical Looping (SCL) process at OSU was able to ensure the successful handling of the solids. Phase 1 focused on studies to improve the current particle to better suit the CDCL operations. The optimum operating conditions for the reducer reactor such as the temperature, char gasification enhancer type, and flow rate were identified. The

  2. Climate Extreme Effects on the Chemical Composition of Temperate Grassland Species under Ambient and Elevated CO2: A Comparison of Fructan and Non-Fructan Accumulators

    PubMed Central

    Zinta, Gaurav; Van den Ende, Wim; Janssens, Ivan A.; Asard, Han

    2014-01-01

    Elevated CO2 concentrations and extreme climate events, are two increasing components of the ongoing global climatic change factors, may alter plant chemical composition and thereby their economic and ecological characteristics, e.g. nutritional quality and decomposition rates. To investigate the impact of climate extremes on tissue quality, four temperate grassland species: the fructan accumulating grasses Lolium perenne, Poa pratensis, and the nitrogen (N) fixing legumes Medicago lupulina and Lotus corniculatus were subjected to water deficit at elevated temperature (+3°C), under ambient CO2 (392 ppm) and elevated CO2 (620 ppm). As a general observation, the effects of the climate extreme were larger and more ubiquitous in combination with elevated CO2. The imposed climate extreme increased non-structural carbohydrate and phenolics in all species, whereas it increased lignin in legumes and decreased tannins in grasses. However, there was no significant effect of climate extreme on structural carbohydrates, proteins, lipids and mineral contents and stoichiometric ratios. In combination with elevated CO2, climate extreme elicited larger increases in fructan and sucrose content in the grasses without affecting the total carbohydrate content, while it significantly increased total carbohydrates in legumes. The accumulation of carbohydrates in legumes was accompanied by higher activity of sucrose phosphate synthase, sucrose synthase and ADP-Glc pyrophosphorylase. In the legumes, elevated CO2 in combination with climate extreme reduced protein, phosphorus (P) and magnesium (Mg) contents and the total element:N ratio and it increased phenol, lignin, tannin, carbon (C), nitrogen (N) contents and C:N, C:P and N:P ratios. On the other hand, the tissue composition of the fructan accumulating grasses was not affected at this level, in line with recent views that fructans contribute to cellular homeostasis under stress. It is speculated that quality losses will be less

  3. Climate extreme effects on the chemical composition of temperate grassland species under ambient and elevated CO2: a comparison of fructan and non-fructan accumulators.

    PubMed

    AbdElgawad, Hamada; Peshev, Darin; Zinta, Gaurav; Van den Ende, Wim; Janssens, Ivan A; Asard, Han

    2014-01-01

    Elevated CO2 concentrations and extreme climate events, are two increasing components of the ongoing global climatic change factors, may alter plant chemical composition and thereby their economic and ecological characteristics, e.g. nutritional quality and decomposition rates. To investigate the impact of climate extremes on tissue quality, four temperate grassland species: the fructan accumulating grasses Lolium perenne, Poa pratensis, and the nitrogen (N) fixing legumes Medicago lupulina and Lotus corniculatus were subjected to water deficit at elevated temperature (+3°C), under ambient CO2 (392 ppm) and elevated CO2 (620 ppm). As a general observation, the effects of the climate extreme were larger and more ubiquitous in combination with elevated CO2. The imposed climate extreme increased non-structural carbohydrate and phenolics in all species, whereas it increased lignin in legumes and decreased tannins in grasses. However, there was no significant effect of climate extreme on structural carbohydrates, proteins, lipids and mineral contents and stoichiometric ratios. In combination with elevated CO2, climate extreme elicited larger increases in fructan and sucrose content in the grasses without affecting the total carbohydrate content, while it significantly increased total carbohydrates in legumes. The accumulation of carbohydrates in legumes was accompanied by higher activity of sucrose phosphate synthase, sucrose synthase and ADP-Glc pyrophosphorylase. In the legumes, elevated CO2 in combination with climate extreme reduced protein, phosphorus (P) and magnesium (Mg) contents and the total element:N ratio and it increased phenol, lignin, tannin, carbon (C), nitrogen (N) contents and C:N, C:P and N:P ratios. On the other hand, the tissue composition of the fructan accumulating grasses was not affected at this level, in line with recent views that fructans contribute to cellular homeostasis under stress. It is speculated that quality losses will be less

  4. Chemical structures of coal lithotypes before and after CO2 adsorption as investigated by advanced solid-state 13C nuclear magnetic resonance spectroscopy

    USGS Publications Warehouse

    Cao, X.; Mastalerz, Maria; Chappell, M.A.; Miller, L.F.; Li, Y.; Mao, J.

    2011-01-01

    Four lithotypes (vitrain, bright clarain, clarain, and fusain) of a high volatile bituminous Springfield Coal from the Illinois Basin were characterized using advanced solid-state 13C nuclear magnetic resonance (NMR) spectroscopy. The NMR techniques included quantitative direct polarization/magic angle spinning (DP/MAS), cross polarization/total sideband suppression (CP/TOSS), dipolar dephasing, CHn selection, and recoupled C-H long-range dipolar dephasing techniques. The lithotypes that experienced high-pressure CO2 adsorption isotherm analysis were also analyzed to determine possible changes in coal structure as a result of CO2 saturation at high pressure and subsequent evacuation. The main carbon functionalities present in original vitrain, bright clarain, clarain and fusain were aromatic carbons (65.9%-86.1%), nonpolar alkyl groups (9.0%-28.9%), and aromatic C-O carbons (4.1%-9.5%). Among these lithotypes, aromaticity increased in the order of clarain, bright clarain, vitrain, and fusain, whereas the fraction of alkyl carbons decreased in the same order. Fusain was distinct from other three lithotypes in respect to its highest aromatic composition (86.1%) and remarkably small fraction of alkyl carbons (11.0%). The aromatic cluster size in fusain was larger than that in bright clarain. The lithotypes studied responded differently to high pressure CO2 saturation. After exposure to high pressure CO2, vitrain and fusain showed a decrease in aromaticity but an increase in the fraction of alkyl carbons, whereas bright clarain and clarain displayed an increase in aromaticity but a decrease in the fraction of alkyl carbons. Aromatic fused-rings were larger for bright clarain but smaller for fusain in the post-CO2 adsorption samples compared to the original lithotypes. These observations suggested chemical CO2-coal interactions at high pressure and the selectivity of lithotypes in response to CO2 adsorption. ?? 2011 Elsevier B.V.

  5. Climate extreme effects on the chemical composition of temperate grassland species under ambient and elevated CO2: a comparison of fructan and non-fructan accumulators.

    PubMed

    AbdElgawad, Hamada; Peshev, Darin; Zinta, Gaurav; Van den Ende, Wim; Janssens, Ivan A; Asard, Han

    2014-01-01

    Elevated CO2 concentrations and extreme climate events, are two increasing components of the ongoing global climatic change factors, may alter plant chemical composition and thereby their economic and ecological characteristics, e.g. nutritional quality and decomposition rates. To investigate the impact of climate extremes on tissue quality, four temperate grassland species: the fructan accumulating grasses Lolium perenne, Poa pratensis, and the nitrogen (N) fixing legumes Medicago lupulina and Lotus corniculatus were subjected to water deficit at elevated temperature (+3°C), under ambient CO2 (392 ppm) and elevated CO2 (620 ppm). As a general observation, the effects of the climate extreme were larger and more ubiquitous in combination with elevated CO2. The imposed climate extreme increased non-structural carbohydrate and phenolics in all species, whereas it increased lignin in legumes and decreased tannins in grasses. However, there was no significant effect of climate extreme on structural carbohydrates, proteins, lipids and mineral contents and stoichiometric ratios. In combination with elevated CO2, climate extreme elicited larger increases in fructan and sucrose content in the grasses without affecting the total carbohydrate content, while it significantly increased total carbohydrates in legumes. The accumulation of carbohydrates in legumes was accompanied by higher activity of sucrose phosphate synthase, sucrose synthase and ADP-Glc pyrophosphorylase. In the legumes, elevated CO2 in combination with climate extreme reduced protein, phosphorus (P) and magnesium (Mg) contents and the total element:N ratio and it increased phenol, lignin, tannin, carbon (C), nitrogen (N) contents and C:N, C:P and N:P ratios. On the other hand, the tissue composition of the fructan accumulating grasses was not affected at this level, in line with recent views that fructans contribute to cellular homeostasis under stress. It is speculated that quality losses will be less

  6. DIC dynamics in stream water of volcanic settings: climatic and lithology impact on the CO2 chemical weathering (Lesser Antilles, Reunion, French Massif Central and Iceland)

    NASA Astrophysics Data System (ADS)

    Rive, K.; Agrinier, P.; Gaillardet, J.

    2006-12-01

    The chemical weathering of the volcanic rocks plays a key role in the regulation of atmospheric CO2. Indeed, CO2 is one of the main proton suppliers (e.g. Louvat, 1997; Dessert et al., 2003) via the acid-base system of the dissolved inorganic carbon (DIC = H2CO3 + HCO3- + CO32-). Consequently, riverine DIC fluxes can help to constrain chemical erosion fluxes. However the behavior of DIC in rivers must be first understood because it can be affected by many geochemical processes (e.g. CO2 degassing, carbonate precipitation/dissolution, photosynthesis, organic matter decay). In order to investigate these processes, we have used the δ13C of the DIC. Four volcanic sites have been studied. They have different climates (tropical, temperate and sub-polar), different lithologies and different histories of formation: basaltic-andesitic islands (subduction arc of the Lesser Antilles: Guadeloupe, Dominica and Martinique) and basaltic islands (Reunion hot spot and Iceland hot spot-MOR system). The main differences between these sites are 1) the thickness of soils, and 2) the type and the abundance of vegetation (both are controlled by climatic factors: the mean annual temperature and the mean annual rainfall) and 3) the absence of sedimentary carbonate rocks. The common points among these sites are the high relieves and the magmatic CO2 degassing which controls the DIC of the hydrothermal springs. In such active volcanism settings, magmatic CO2 contribution is seen only in few streams, generally located close to the volcano heights and in the proximity of the hydrothermal springs. These streams show high δ13CDIC, generally around -3 ‰, and high DIC. The rivers in all sampling sites show an endmember with a δ13CDIC of about -15 ‰, characteristic of the organic matter. Therefore, like in large rivers(e.g. Aucour et al., 1999 or Telmer and Veizer, 1999), organic matters are the main sources of DIC in these streams, even on sites with few vegetation (limited to grasslands or

  7. Chemical modification of nanometric TiO2 particles by anchoring functional silane molecules in supercritical CO2

    NASA Astrophysics Data System (ADS)

    López-Periago, Ana M.; Sandoval, Wendy; Domingo, Concepción

    2014-03-01

    Supercritical carbon dioxide (scCO2) was used as a green solvent for the grafting of complex functional organosilanes containing nitrogen moieties on titanium dioxide (TiO2) nanoparticles using two strategies. The first strategy involved the preparation of two functional silanes, 4-nitrophenyl-(3-(trimethoxysilyl)-propyl)methanimine (NPTMS) and 4-(((3-(trimethoxysilyl)propyl)imino)methyl)-benzaldehyde (FPTMS) and further deposited under anhydrous conditions and scCO2 onto the TiO2 surface. The second strategy involved the scCO2 anhydrous deposition of bifunctional commercial silanes on the TiO2 surface. Two structures were synthesized. The first consisted in grafted TiO2 nanoparticles prepared by addition of the ligand, ((1R,2R)-N-(pyridin-2-ylmethyl)-2-(((E)-pyridin-2-ylmethylene) amino)-cyclohexan-1-amine (LPy-red), and designated as Ti-Cl-LPy-red. The second structure was synthesized by the reaction of (1,2)-diaminocylohexane (Dac), through the reactive site of 3-(Trimethoxysilyl)propyl methacrylate (MPTMS) previously deposited on the TiO2 surface and designated as Ti-MP-Dac. The synthesized silanes were characterized by ATR-FT and NMR spectroscopies and mass spectrometry. ATR-FT spectroscopy confirmed the presence of the silanes on the surface of the hybrid nanoparticles. Thermogravimetic analysis was used to estimate the loading of the silane grafted through both hydrogen and covalent bonding on the TiO2 surface. Further characterization of the solid samples was done by N2 adsorption-desorption and UV-vis diffuse reflectance.

  8. CO2-neutral fuels

    NASA Astrophysics Data System (ADS)

    Goede, A. P. H.

    2015-08-01

    The need for storage of renewable energy (RE) generated by photovoltaic, concentrated solar and wind arises from the fact that supply and demand are ill-matched both geographically and temporarily. This already causes problems of overcapacity and grid congestion in countries where the fraction of RE exceeds the 20% level. A system approach is needed, which focusses not only on the energy source, but includes conversion, storage, transport, distribution, use and, last but not least, the recycling of waste. Furthermore, there is a need for more flexibility in the energy system, rather than relying on electrification, integration with other energy systems, for example the gas network, would yield a system less vulnerable to failure and better adapted to requirements. For example, long-term large-scale storage of electrical energy is limited by capacity, yet needed to cover weekly to seasonal demand. This limitation can be overcome by coupling the electricity net to the gas system, considering the fact that the Dutch gas network alone has a storage capacity of 552 TWh, sufficient to cover the entire EU energy demand for over a month. This lecture explores energy storage in chemicals bonds. The focus is on chemicals other than hydrogen, taking advantage of the higher volumetric energy density of hydrocarbons, in this case methane, which has an approximate 3.5 times higher volumetric energy density. More importantly, it allows the ready use of existing gas infrastructure for energy storage, transport and distribution. Intermittent wind electricity generated is converted into synthetic methane, the Power to Gas (P2G) scheme, by splitting feedstock CO2 and H2O into synthesis gas, a mixture of CO and H2. Syngas plays a central role in the synthesis of a range of hydrocarbon products, including methane, diesel and dimethyl ether. The splitting is accomplished by innovative means; plasmolysis and high-temperature solid oxygen electrolysis. A CO2-neutral fuel cycle is

  9. Photoelectrocatalytic reduction of CO2 into chemicals using Pt-modified reduced graphene oxide combined with Pt-modified TiO2 nanotubes.

    PubMed

    Cheng, Jun; Zhang, Meng; Wu, Gai; Wang, Xin; Zhou, Junhu; Cen, Kefa

    2014-06-17

    The photoelectrocatalytic (PEC) reduction of CO2 into high-value chemicals is beneficial in alleviating global warming and advancing a low-carbon economy. In this work, Pt-modified reduced graphene oxide (Pt-RGO) and Pt-modified TiO2 nanotubes (Pt-TNT) were combined as cathode and photoanode catalysts, respectively, to form a PEC reactor for converting CO2 into valuable chemicals. XRD, XPS, TEM, AFM, and SEM were employed to characterize the microstructures of the Pt-RGO and Pt-TNT catalysts. Reduction products, such as C2H5OH and CH3COOH, were obtained from CO2 under band gap illumination and biased voltage. A combined liquid product generation rate (CH3OH, C2H5OH, HCOOH, and CH3COOH) of approximately 600 nmol/(h·cm(2)) was observed. Carbon atom conversion rate reached 1,130 nmol/(h·cm(2)), which were much higher than those achieved using Pt-modified carbon nanotubes and platinum carbon as cathode catalysts. PMID:24846604

  10. Major ion chemistry in the headwaters of the Yamuna river system:. Chemical weathering, its temperature dependence and CO 2 consumption in the Himalaya

    NASA Astrophysics Data System (ADS)

    Dalai, T. K.; Krishnaswami, S.; Sarin, M. M.

    2002-10-01

    The Yamuna river and its tributaries in the Himalaya constitute the Yamuna River System (YRS). The YRS basin has a drainage area and discharge comparable in magnitude to those of the Bhagirathi and the Alaknanda rivers, which merge to form the Ganga at the foothills of the Himalaya. A detailed geochemical study of the YRS was carried out to determine: (i) the relative significance of silicate, carbonate and evaporite weathering in contributing to its major ion composition; (ii) CO 2 consumption via silicate weathering; and (iii) the factors regulating chemical weathering of silicates in the basin. The results show that the YRS waters are mildly alkaline, with a wide range of TDS, ˜32 to ˜620 mg l-1. In these waters, the abundances of Ca, Mg and alkalinity, which account for most of TDS, are derived mainly from carbonates. Many of the tributaries in the lower reaches of the Yamuna basin are supersaturated with calcite. In addition to carbonic acid, sulphuric acid generated by oxidation of pyrites also seems to be supplying protons for chemical weathering. Silicate weathering in YRS basin contributes, on average, ˜25% (molar basis) of total cations on a basin wide scale. Silicate weathering, however, does not seem to be intense in the basin as evident from low Si/(Na*+K) in the waters, ˜1.2 and low values of chemical index of alteration (CIA) in bed sediments, ˜60. CO 2 drawdown resulting from silicate weathering in the YRS basin in the Himalaya during monsoon ranges between (4 to 7) × 10 5 moles km -2 y -1. This is higher than that estimated for the Ganga at Rishikesh for the same season. The CO 2 consumption rates in the Yamuna and the Ganga basins in the Himalaya are higher than the global average value, suggesting enhanced CO 2 drawdown in the southern slopes of the Himalaya. The impact of this enhanced drawdown on the global CO 2 budget may not be pronounced, as the drainage area of the YRS and the Ganga in the Himalaya is small. The CO 2 drawdown by

  11. Spring carbonate chemistry dynamics of surface waters in the northern East China Sea: Water mixing, biological uptake of CO2, and chemical buffering capacity

    NASA Astrophysics Data System (ADS)

    Zhai, Wei-Dong; Chen, Jian-Fang; Jin, Hai-Yan; Li, Hong-Liang; Liu, Jin-Wen; He, Xian-Qiang; Bai, Yan

    2014-09-01

    We investigated sea surface total alkalinity (TAlk), dissolved inorganic carbon (DIC), dissolved oxygen (DO), and satellite-derived chlorophyll-a in the connection between the Yellow Sea and the East China Sea (ECS) during April to early May 2007. In spring, Changjiang dilution water (CDW), ECS offshore water, and together with Yellow Sea water (YSW) occupied the northern ECS. Using 16 day composite satellite-derived chlorophyll-a images, several algal blooms were identified in the CDW and ECS offshore water. Correspondingly, biological DIC drawdown of 73 ± 20 μmol kg-1, oversaturated DO of 10-110 μmol O2 kg-1, and low fugacity of CO2 of 181-304 μatm were revealed in these two waters. YSW also showed CO2 uptake in spring, due to the very low temperature. However, its intrusion virtually counteracted CO2 uptake in the northern ECS. In the CDW and the ECS offshore water, Revelle factor was 9.3-11.7 and 8.9-10.6, respectively, while relatively high Revelle factor values of 11.4-13.0 were revealed in YSW. In the ECS offshore water, the observed relationship between DIC drawdown and oversaturated DO departed from the Redfield ratio, indicating an effect of chemical buffering capacity on the carbonate system during air-sea reequilibration. Given the fact that the chemical buffering capacity slows down the air-sea reequilibration of CO2, the early spring DIC drawdown may have durative effects on the sea surface carbonate system until early summer. Although our study is subject to limited temporal and spatial coverage of sampling, these insights are fundamental to understanding sea surface carbonate chemistry dynamics in this important ocean margin.

  12. Towards Ideal NOx and CO2 Emission Control Technology for Bio-Oils Combustion Energy System Using a Plasma-Chemical Hybrid Process

    NASA Astrophysics Data System (ADS)

    Okubo, M.; Fujishima, H.; Yamato, Y.; Kuroki, T.; Tanaka, A.; Otsuka, K.

    2013-03-01

    A pilot-scale low-emission boiler system consisting of a bio-fuel boiler and plasma-chemical hybrid NOx removal system is investigated. This system can achieve carbon neutrality because the bio-fuel boiler uses waste vegetable oil as one of the fuels. The plasma-chemical hybrid NOx removal system has two processes: NO oxidation by ozone produced from plasma ozonizers and NO2 removal using a Na2SO3 chemical scrubber. Test demonstrations of the system are carried out for mixed oils (mixture of A-heavy oil and waste vegetable oil). Stable combustion is achieved for the mixed oil (20 - 50% waste vegetable oil). Properties of flue gas—e.g., O2, CO2 and NOx—when firing mixed oils are nearly the same as those when firing heavy oil for an average flue gas flow rate of 1000 Nm3/h. NOx concentrations at the boiler outlet are 90 - 95 ppm. Furthermore, during a 300-min continuous operation when firing 20% mixed oil, NOx removal efficiency of more than 90% (less than 10 ppm NOx emission) is confirmed. In addition, the CO2 reduction when heavy oil is replaced with waste vegetable oil is estimated. The system comparison is described between the plasma-chemical hybrid NOx removal and the conventional technology.

  13. Water geochemistry of the Qiantangjiang River, East China: Chemical weathering and CO2 consumption in a basin affected by severe acid deposition

    NASA Astrophysics Data System (ADS)

    Liu, Wenjing; Shi, Chao; Xu, Zhifang; Zhao, Tong; Jiang, Hao; Liang, Chongshan; Zhang, Xuan; Zhou, Li; Yu, Chong

    2016-09-01

    The chemical composition of the Qiantangjiang River, the largest river in Zhejiang province in eastern China, was measured to understand the chemical weathering of rocks and the associated CO2 consumption and anthropogenic influences within a silicate-dominated river basin. The average total dissolved solids (TDS, 113 mg l-1) and total cation concentration (TZ+, 1357 μeq l-1) of the river waters are comparable with those of global major rivers. Ca2+ and HCO3- followed by Na2+ and SO42-, dominate the ionic composition of the river water. There are four major reservoirs (carbonates, silicates, atmospheric and anthropogenic inputs) contributing to the total dissolved load of the investigated rivers. The dissolved loads of the rivers are dominated by both carbonate and silicate weathering, which together account for about 76.3% of the total cationic load origin. The cationic chemical weathering rates of silicate and carbonate for the Qiantangjiang basin are estimated to be approximately 4.9 ton km-2 a-1 and 13.9 ton km-2 a-1, respectively. The calculated CO2 consumption rates with the assumption that all the protons involved in the weathering reaction are provided by carbonic acid are 369 × 103 mol km-2 a-1 and 273 × 103 mol km-2 a-1 by carbonate and silicate weathering, respectively. As one of the most severe impacted area by acid rain in China, H2SO4 from acid precipitation is also an important proton donor in weathering reactions. When H2SO4 is considered, the CO2 consumption rates for the river basin are estimated at 286 × 103 mol km-2 a-1 for carbonate weathering and 211 × 103 mol km-2 a-1 for silicate weathering, respectively. The results highlight that the drawdown effect of CO2 consumption by carbonate and silicate weathering can be largely overestimated if the role of sulfuric acid is ignored, especially in the area heavily impacted by acid deposition like Qiantangjiang basin. The actual CO2 consumption rates (after sulfuric acid weathering effect

  14. Final Report: Development of a Chemical Model to Predict the Interactions between Supercritical CO2, Fluid and Rock in EGS Reservoirs

    SciTech Connect

    McPherson, Brian J.; Pan, Feng

    2014-09-24

    This report summarizes development of a coupled-process reservoir model for simulating enhanced geothermal systems (EGS) that utilize supercritical carbon dioxide as a working fluid. Specifically, the project team developed an advanced chemical kinetic model for evaluating important processes in EGS reservoirs, such as mineral precipitation and dissolution at elevated temperature and pressure, and for evaluating potential impacts on EGS surface facilities by related chemical processes. We assembled a new database for better-calibrated simulation of water/brine/ rock/CO2 interactions in EGS reservoirs. This database utilizes existing kinetic and other chemical data, and we updated those data to reflect corrections for elevated temperature and pressure conditions of EGS reservoirs.

  15. Chemical Changes in Pore Water Composition due to CO2 Injection Under In-Situ P-T Condition of the Altmark Gas Reservoir, Germany

    NASA Astrophysics Data System (ADS)

    Huq, F.; Nowak, M.; Haderlein, S.; Grathwohl, P.

    2012-12-01

    CO2 storage in depleted gas reservoir combined with enhanced gas recovery may be an economically feasible option to mitigate global warming. The Altmark gas field, located in the western part of the Northeast German Basin, is being considered as a potential candidate for this purpose. Under reservoir conditions (50 bars and 125°C), the CO2 saturated water causes dissolution and subsequent precipitation of minerals of the surrounding rock matrix. Therefore, the main objective of the current study was to investigate the chemical changes in fluid composition due to dissolution/precipitation of minerals under controlled laboratory conditions. A dry sandstone plug from the Altmark reservoir was mounted in a newly designed autoclave system and flushed by a pre-equilibrated mixture of water saturated with CO2 at a constant flow rate of 0.25 cm/h for 12 days at reservoir conditions. Fluid samples were taken at regular intervals for major and trace element analysis and pH was measured simultaneously in the partially de-gassed samples. Fluid analysis showed an increased concentration of Na, K and Cl ions at the beginning indicating early leaching of halite and sylvite which initially inhibited the dissolution of alkali feldspars. Feldspar dissolution occurred later and slower indicated by lower concentrations of Na and K reflecting the lower solubility and slow dissolution kinetics of feldspar. Dissolution of anhydrite was predominantly observed from the increased concentration of Ca and SO4 at earlier time periods. However, the Ca/SO4 molar ratio (>1) indicated the concurrent dissolution of both calcite and anhydrite. The presence of carbonates buffered the pH until day 6. Moreover, the mobilization of Mn, Mg, Ba and Fe might be derived from carbonate impurities. Thermodynamic calculations of mineral saturation indices enabled an evaluation of the CO2-water-rock interactions during the experiment and highlighted the dissolution of the Ca-bearing minerals in the studied

  16. Spatial variability structure of soil CO2 emission and soil physical and chemical properties characterized by fractal dimension in sugarcane areas

    NASA Astrophysics Data System (ADS)

    Bicalho, E. S.; Teixeira, D. B.; Panosso, A. R.; Perillo, L. I.; Iamaguti, J. L.; Pereira, G. T.; La Scala, N., Jr.

    2012-04-01

    Soil CO2 emission (FCO2) is influenced by chemical, physical and biological factors that affect the production of CO2 in the soil and its transport to the atmosphere, varying in time and space depending on environmental conditions, including the management of agricultural area. The aim of this study was to investigate the structure of spatial variability of FCO2 and soil properties by using fractal dimension (DF), derived from isotropic variograms at different scales, and construction of fractograms. The experimental area consisted of a regular grid of 60 × 60 m on sugarcane area under green management, containing 141 points spaced at minimum distances ranging from 0.5 to 10 m. Soil CO2 emission, soil temperature and soil moisture were evaluated over a period of 7 days, and soil chemical and physical properties were determined by sampling at a depth of 0.0 to 0.1 m. FCO2 showed an overall average of 1.51 µmol m-2 s-1, correlated significantly (p < 0.05) with soil physical factors such as soil bulk density, air-filled pore space, macroporosity and microporosity. Significant DF values were obtained in the characterization of FCO2 in medium and large scales (from 20 m). Variations in DF with the scale, which is the fractogram, indicate that the structure of FCO2 variability is similar to that observed for the soil temperature and total pore volume, and reverse for the other soil properties, except for macroporosity, sand content, soil organic matter, carbon stock, C/N ratio and CEC, which fractograms were not significantly correlated to the FCO2 fractogram. Thus, the structure of spatial variability for most soil properties, characterized by fractogram, presents a significant relationship with the structure of spatial variability of FCO2, generally with similar or dissimilar behavior, indicating the possibility of using the fractogram as tool to better observe the behavior of the spatial dependence of the variables along the scale.

  17. Catalysis for biomass and CO2 use through solar energy: opening new scenarios for a sustainable and low-carbon chemical production.

    PubMed

    Lanzafame, Paola; Centi, Gabriele; Perathoner, Siglinda

    2014-11-21

    The use of biomass, bio-waste and CO2 derived raw materials, the latter synthesized using H2 produced using renewable energy sources, opens new scenarios to develop a sustainable and low carbon chemical production, particularly in regions such as Europe lacking in other resources. This tutorial review discusses first this new scenario with the aim to point out, between the different possible options, those more relevant to enable this new future scenario for the chemical production, commenting in particular the different drivers (economic, technological and strategic, environmental and sustainability and socio-political) which guide the selection. The case of the use of non-fossil fuel based raw materials for the sustainable production of light olefins is discussed in more detail, but the production of other olefins and polyolefins, of drop-in intermediates and other platform molecules are also analysed. The final part discusses the role of catalysis in establishing this new scenario, summarizing the development of catalysts with respect to industrial targets, for (i) the production of light olefins by catalytic dehydration of ethanol and by CO2 conversion via FTO process, (ii) the catalytic synthesis of butadiene from ethanol, butanol and butanediols, and (iii) the catalytic synthesis of HMF and its conversion to 2,5-FDCA, adipic acid, caprolactam and 1,6-hexanediol. PMID:24577063

  18. Catalysis for biomass and CO2 use through solar energy: opening new scenarios for a sustainable and low-carbon chemical production.

    PubMed

    Lanzafame, Paola; Centi, Gabriele; Perathoner, Siglinda

    2014-11-21

    The use of biomass, bio-waste and CO2 derived raw materials, the latter synthesized using H2 produced using renewable energy sources, opens new scenarios to develop a sustainable and low carbon chemical production, particularly in regions such as Europe lacking in other resources. This tutorial review discusses first this new scenario with the aim to point out, between the different possible options, those more relevant to enable this new future scenario for the chemical production, commenting in particular the different drivers (economic, technological and strategic, environmental and sustainability and socio-political) which guide the selection. The case of the use of non-fossil fuel based raw materials for the sustainable production of light olefins is discussed in more detail, but the production of other olefins and polyolefins, of drop-in intermediates and other platform molecules are also analysed. The final part discusses the role of catalysis in establishing this new scenario, summarizing the development of catalysts with respect to industrial targets, for (i) the production of light olefins by catalytic dehydration of ethanol and by CO2 conversion via FTO process, (ii) the catalytic synthesis of butadiene from ethanol, butanol and butanediols, and (iii) the catalytic synthesis of HMF and its conversion to 2,5-FDCA, adipic acid, caprolactam and 1,6-hexanediol.

  19. CO2-Neutral Fuels

    NASA Astrophysics Data System (ADS)

    Goede, Adelbert; van de Sanden, Richard

    2016-06-01

    Mimicking the biogeochemical cycle of System Earth, synthetic hydrocarbon fuels are produced from recycled CO2 and H2O powered by renewable energy. Recapturing CO2 after use closes the carbon cycle, rendering the fuel cycle CO2 neutral. Non-equilibrium molecular CO2 vibrations are key to high energy efficiency.

  20. Selecting CO2 Sources for CO2 Utilization by Environmental-Merit-Order Curves.

    PubMed

    von der Assen, Niklas; Müller, Leonard J; Steingrube, Annette; Voll, Philip; Bardow, André

    2016-02-01

    Capture and utilization of CO2 as alternative carbon feedstock for fuels, chemicals, and materials aims at reducing greenhouse gas emissions and fossil resource use. For capture of CO2, a large variety of CO2 sources exists. Since they emit much more CO2 than the expected demand for CO2 utilization, the environmentally most favorable CO2 sources should be selected. For this purpose, we introduce the environmental-merit-order (EMO) curve to rank CO2 sources according to their environmental impacts over the available CO2 supply. To determine the environmental impacts of CO2 capture, compression and transport, we conducted a comprehensive literature study for the energy demands of CO2 supply, and constructed a database for CO2 sources in Europe. Mapping these CO2 sources reveals that CO2 transport distances are usually small. Thus, neglecting transport in a first step, we find that environmental impacts are minimized by capturing CO2 first from chemical plants and natural gas processing, then from paper mills, power plants, and iron and steel plants. In a second step, we computed regional EMO curves considering transport and country-specific impacts for energy supply. Building upon regional EMO curves, we identify favorable locations for CO2 utilization with lowest environmental impacts of CO2 supply, so-called CO2 oases.

  1. Selecting CO2 Sources for CO2 Utilization by Environmental-Merit-Order Curves.

    PubMed

    von der Assen, Niklas; Müller, Leonard J; Steingrube, Annette; Voll, Philip; Bardow, André

    2016-02-01

    Capture and utilization of CO2 as alternative carbon feedstock for fuels, chemicals, and materials aims at reducing greenhouse gas emissions and fossil resource use. For capture of CO2, a large variety of CO2 sources exists. Since they emit much more CO2 than the expected demand for CO2 utilization, the environmentally most favorable CO2 sources should be selected. For this purpose, we introduce the environmental-merit-order (EMO) curve to rank CO2 sources according to their environmental impacts over the available CO2 supply. To determine the environmental impacts of CO2 capture, compression and transport, we conducted a comprehensive literature study for the energy demands of CO2 supply, and constructed a database for CO2 sources in Europe. Mapping these CO2 sources reveals that CO2 transport distances are usually small. Thus, neglecting transport in a first step, we find that environmental impacts are minimized by capturing CO2 first from chemical plants and natural gas processing, then from paper mills, power plants, and iron and steel plants. In a second step, we computed regional EMO curves considering transport and country-specific impacts for energy supply. Building upon regional EMO curves, we identify favorable locations for CO2 utilization with lowest environmental impacts of CO2 supply, so-called CO2 oases. PMID:26752014

  2. Chemical weathering rate, denudation rate, and atmospheric and soil CO2 consumption of Paraná flood basalts in São Paulo State, Brazil

    NASA Astrophysics Data System (ADS)

    da Conceição, Fabiano Tomazini; dos Santos, Carolina Mathias; de Souza Sardinha, Diego; Navarro, Guillermo Rafael Beltran; Godoy, Letícia Hirata

    2015-03-01

    The chemical weathering rate and atmospheric/soil CO2 consumption of Paraná flood basalts in the Preto Stream basin, São Paulo State, Brazil, were evaluated using major elements as natural tracers. Surface and rain water samples were collected in 2006, and analyses were performed to assess pH, temperature, dissolved oxygen (DO), electrical conductivity (EC) and total dissolved solids (TDS), including SO42-, NO3-, PO43 -, HCO3-, Cl-, SiO2, Ca2 +, Mg2 +, Na+ and K+. Fresh rocks and C horizon samples were also collected, taking into account their geological context, abundance and spatial distribution, to analyze major elements and mineralogy. The Preto Stream, downstream from the city of Ribeirão Preto, receives several elements/compounds as a result of anthropogenic activities, with only sulfate yielding negative flux values. The negative flux of SO42 - can be attributed to atmospheric loading that is mainly related to anthropogenic inputs. After corrections were made for atmospheric inputs, the riverine transport of dissolved material was found to be 30 t km- 2 y- 1, with the majority of the dissolved material transported during the summer (wet) months. The chemical weathering rate and atmospheric/soil CO2 consumption were 6 m/Ma and 0.4 · 106 mol km- 2 y- 1, respectively. The chemical weathering rate falls within the lower range of Paraná flood basalt denudation rates between 135 and 35 Ma previously inferred from chronological studies. This comparison suggests that rates of basalt weathering in Brazil's present-day tropical climate differ by at most one order of magnitude from those prevalent at the time of hothouse Earth. The main weathering process is the monosiallitization of anorthoclase, augite, anorthite and microcline. Magnetite is not weathered and thus remains in the soil profile.

  3. A PCP Pincer Ligand for Coordination Polymers with Versatile Chemical Reactivity: Selective Activation of CO2 Gas over CO Gas in the Solid State.

    PubMed

    He, Junpeng; Waggoner, Nolan W; Dunning, Samuel G; Steiner, Alexander; Lynch, Vincent M; Humphrey, Simon M

    2016-09-26

    A tetra(carboxylated) PCP pincer ligand has been synthesized as a building block for porous coordination polymers (PCPs). The air- and moisture-stable PCP metalloligands are rigid tetratopic linkers that are geometrically akin to ligands used in the synthesis of robust metal-organic frameworks (MOFs). Here, the design principle is demonstrated by cyclometalation with Pd(II) Cl and subsequent use of the metalloligand to prepare a crystalline 3D MOF by direct reaction with Co(II) ions and structural resolution by single crystal X-ray diffraction. The Pd-Cl groups inside the pores are accessible to post-synthetic modifications that facilitate chemical reactions previously unobserved in MOFs: a Pd-CH3 activated material undergoes rapid insertion of CO2 gas to give Pd-OC(O)CH3 at 1 atm and 298 K. However, since the material is highly selective for the adsorption of CO2 over CO, a Pd-N3 modified version resists CO insertion under the same conditions. PMID:27532740

  4. A PCP Pincer Ligand for Coordination Polymers with Versatile Chemical Reactivity: Selective Activation of CO2 Gas over CO Gas in the Solid State.

    PubMed

    He, Junpeng; Waggoner, Nolan W; Dunning, Samuel G; Steiner, Alexander; Lynch, Vincent M; Humphrey, Simon M

    2016-09-26

    A tetra(carboxylated) PCP pincer ligand has been synthesized as a building block for porous coordination polymers (PCPs). The air- and moisture-stable PCP metalloligands are rigid tetratopic linkers that are geometrically akin to ligands used in the synthesis of robust metal-organic frameworks (MOFs). Here, the design principle is demonstrated by cyclometalation with Pd(II) Cl and subsequent use of the metalloligand to prepare a crystalline 3D MOF by direct reaction with Co(II) ions and structural resolution by single crystal X-ray diffraction. The Pd-Cl groups inside the pores are accessible to post-synthetic modifications that facilitate chemical reactions previously unobserved in MOFs: a Pd-CH3 activated material undergoes rapid insertion of CO2 gas to give Pd-OC(O)CH3 at 1 atm and 298 K. However, since the material is highly selective for the adsorption of CO2 over CO, a Pd-N3 modified version resists CO insertion under the same conditions.

  5. Assessment of the biospheric contribution to surface atmospheric CO2 concentrations over East Asia with a regional chemical transport model

    NASA Astrophysics Data System (ADS)

    Kou, Xingxia; Zhang, Meigen; Peng, Zhen; Wang, Yinghong

    2015-03-01

    A regional chemical transport model, RAMS-CMAQ, was employed to assess the impacts of biosphere-atmosphere C2 exchange on seasonal variations in atmospheric C2 concentrations over East Asia. Simulated C2 concentrations were compared with observations at 12 surface stations and the comparison showed they were generally in good agreement. Both observations and simulations suggested that surface C2 over East Asia features a summertime trough due to biospheric absorption, while in some urban areas surface C2 has a distinct summer peak, which could be attributed to the strong impact from anthropogenic emissions. Analysis of the model results indicated that biospheric fluxes and fossil-fuel emissions are comparably important in shaping spatial distributions of C2 near the surface over East Asia. Biospheric flux plays an important role in the prevailing spatial pattern of C2 enhancement and reduction on the synoptic scale due to the strong seasonality of biospheric C2 flux. The elevation of C2 levels by the biosphere during winter was found to be larger than 5 ppm in North China and Southeast China, and during summertime a significant depletion (⩾ 7 ppm) occurred in most areas, except for the Indo-China Peninsula where positive bioflux values were found.

  6. CO2 -Responsive polymers.

    PubMed

    Lin, Shaojian; Theato, Patrick

    2013-07-25

    This Review focuses on the recent progress in the area of CO2 -responsive polymers and provides detailed descriptions of these existing examples. CO2 -responsive polymers can be categorized into three types based on their CO2 -responsive groups: amidine, amine, and carboxyl groups. Compared with traditional temperature, pH, or light stimuli-responsive polymers, CO2 -responsive polymers provide the advantage to use CO2 as a "green" trigger as well as to capture CO2 directly from air. In addition, the current challenges of CO2 -responsive polymers are discussed and the different solution methods are compared. Noteworthy, CO2 -responsive polymers are considered to have a prosperous future in various scientific areas.

  7. Bosch CO2 Reduction System Development

    NASA Technical Reports Server (NTRS)

    Holmes, R. F.; King, C. D.; Keller, E. E.

    1976-01-01

    Development of a Bosch process CO2 reduction unit was continued, and, by means of hardware modifications, the performance was substantially improved. Benefits of the hardware upgrading were demonstrated by extensive unit operation and data acquisition in the laboratory. This work was accomplished on a cold seal configuration of the Bosch unit.

  8. CO2 laser modeling

    NASA Technical Reports Server (NTRS)

    Johnson, Barry

    1992-01-01

    The topics covered include the following: (1) CO2 laser kinetics modeling; (2) gas lifetimes in pulsed CO2 lasers; (3) frequency chirp and laser pulse spectral analysis; (4) LAWS A' Design Study; and (5) discharge circuit components for LAWS. The appendices include LAWS Memos, computer modeling of pulsed CO2 lasers for lidar applications, discharge circuit considerations for pulsed CO2 lidars, and presentation made at the Code RC Review.

  9. Novel bifunctional catalysts based on crystalline multi-oxide matrices containing iron ions for CO2 hydrogenation to liquid fuels and chemicals.

    PubMed

    Utsis, N; Vidruk-Nehemya, R; Landau, M V; Herskowitz, M

    2016-07-01

    Seven solid mono-, bi- and tri-metallic oxide matrices where Fe(2+,3+) ions are distributed in different chemical/spatial environments were synthesized and characterized by XRD, N2-adsorption and EDAX methods. After basification with potassium, all matrices were activated by carburization or reduction-carburization under conditions selected based on the TPC/TPR spectra, tailoring the carburization extent of iron. The performances of the activated Fe-based catalysts with respect to CO2 conversion and C5+ selectivity were measured in a fixed-bed reactor under standard conditions in transient and continuous operation modes in units containing one or three reactors in series with water separations between the reactors. The catalysts were characterized by XRD, N2-adsorption, HRTEM-EELS and XPS before and after steady-state operation in the reactors. It was found that the rate of CO2 conversion is not limited by thermodynamic equilibrium but is strongly restricted by water inhibition and it depends on the nature of the Fe-oxide precursor. The ratio between the FTS and RWGS rates, which determines the C5+ hydrocarbons productivity, is strongly affected by the nature of the Fe-oxide matrix. The catalysts derived from the Fe-Al-O spinel and Fe-Ba-hexaaluminate precursors displayed the best balance of the two functions RFTS/RRWGS = 0.77-0.78. They were followed by magnetite, CuFe-delafossite, K-ferrite, Fe-La-hexaaluminate and LaFe-perovskite with a gradual lowering of RFTS/RRWGS from 0.60 to 0.15 and a gradual decrease in the C5+ productivity. The active sites that enhance the RWGS reaction are located on the surface of the Fe-oxide phases, while the FTS and methanation reactions occur on the surface of the Fe-carbide phases.

  10. Novel bifunctional catalysts based on crystalline multi-oxide matrices containing iron ions for CO2 hydrogenation to liquid fuels and chemicals.

    PubMed

    Utsis, N; Vidruk-Nehemya, R; Landau, M V; Herskowitz, M

    2016-07-01

    Seven solid mono-, bi- and tri-metallic oxide matrices where Fe(2+,3+) ions are distributed in different chemical/spatial environments were synthesized and characterized by XRD, N2-adsorption and EDAX methods. After basification with potassium, all matrices were activated by carburization or reduction-carburization under conditions selected based on the TPC/TPR spectra, tailoring the carburization extent of iron. The performances of the activated Fe-based catalysts with respect to CO2 conversion and C5+ selectivity were measured in a fixed-bed reactor under standard conditions in transient and continuous operation modes in units containing one or three reactors in series with water separations between the reactors. The catalysts were characterized by XRD, N2-adsorption, HRTEM-EELS and XPS before and after steady-state operation in the reactors. It was found that the rate of CO2 conversion is not limited by thermodynamic equilibrium but is strongly restricted by water inhibition and it depends on the nature of the Fe-oxide precursor. The ratio between the FTS and RWGS rates, which determines the C5+ hydrocarbons productivity, is strongly affected by the nature of the Fe-oxide matrix. The catalysts derived from the Fe-Al-O spinel and Fe-Ba-hexaaluminate precursors displayed the best balance of the two functions RFTS/RRWGS = 0.77-0.78. They were followed by magnetite, CuFe-delafossite, K-ferrite, Fe-La-hexaaluminate and LaFe-perovskite with a gradual lowering of RFTS/RRWGS from 0.60 to 0.15 and a gradual decrease in the C5+ productivity. The active sites that enhance the RWGS reaction are located on the surface of the Fe-oxide phases, while the FTS and methanation reactions occur on the surface of the Fe-carbide phases. PMID:27075823

  11. Adsorption of carbon dioxide (CO2) at S functionalized boron nitride (BN) and aluminum nitride (AlN) nanotubes (9, 0): A quantum chemical investigation

    NASA Astrophysics Data System (ADS)

    Najafi, Meysam

    2016-10-01

    We employed density functional theory to characterize CO2 adsorption on BNNT and AlNNT surfaces. The effects of S functionalization on the adsorption of CO2 gas on BNNT and AlNNT surfaces were investigated. Results reveal that adsorptions of CO2 on studied nanotubes were exothermic and experimentally possible from the energetic viewpoint. Results show that, Ead values of CO2 on AlNNT surface were more negative than corresponding values of BNNT. Results reveal that, S functionalization of studied nanotubes causes an increase in the absolute values of Ead of CO2 on surface of studied nanotubes. These results show that, there are good linearity dependencies between Ead and orbital energy values of studied nanotubes. Therefore we can conclude the Ead and orbital energy values are highly sensitive to the adsorption process which these may be used for the selection the suitable nanotubes with enhanced CO2 adsorption potential.

  12. Effects of xenon insertion into hydrogen bromide. Comparison of the electronic structure of the HBr···CO2 and HXeBr···CO2 complexes using quantum chemical topology methods: electron localization function, atoms in molecules and symmetry adapted perturbation theory.

    PubMed

    Makarewicz, Emilia; Gordon, Agnieszka J; Mierzwicki, Krzysztof; Latajka, Zdzislaw; Berski, Slawomir

    2014-06-01

    Quantum chemistry methods have been applied to study the influence of the Xe atom inserted into the hydrogen-bromine bond (HBr → HXeBr), particularly on the nature of atomic interactions in the HBr···CO2 and HXeBr···CO2 complexes. Detailed analysis of the nature of chemical bonds has been carried out using topological analysis of the electron localization function, while topological analysis of electron density was used to gain insight into the nature of weak nonbonding interactions. Symmetry-adapted perturbation theory within the orbital approach was applied for greater understanding of the physical contributions to the total interaction energy.

  13. Advanced Technologies for Monitoring CO2 Saturation and Pore Pressure in Geologic Formations: Linking the Chemical and Physical Effects to Elastic and Transport Properties

    SciTech Connect

    Mavko, G.; Vanorio, T.; Vialle, S.; Saxena, N.

    2014-03-31

    Ultrasonic P- and S-wave velocities were measured over a range of confining pressures while injecting CO2 and brine into the samples. Pore fluid pressure was also varied and monitored together with porosity during injection. Effective medium models were developed to understand the mechanisms and impact of observed changes and to provide the means for implementation of the interpretation methodologies in the field. Ultrasonic P- and S-wave velocities in carbonate rocks show as much as 20-50% decrease after injection of the reactive CO2-brine mixture; the changes were caused by permanent changes to the rock elastic frame associated with dissolution of mineral. Velocity decreases were observed under both dry and fluid-saturated conditions, and the amount of change was correlated with the initial pore fabrics. Scanning Electron Microscope images of carbonate rock microstructures were taken before and after injection of CO2-rich water. The images reveal enlargement of the pores, dissolution of micrite (micron-scale calcite crystals), and pitting of grain surfaces caused by the fluid- solid chemical reactivity. The magnitude of the changes correlates with the rock microtexture – tight, high surface area samples showed the largest changes in permeability and smallest changes in porosity and elastic stiffness compared to those in rocks with looser texture and larger intergranular pore space. Changes to the pore space also occurred from flow of fine particles with the injected fluid. Carbonates with grain-coating materials, such as residual oil, experienced very little permanent change during injection. In the tight micrite/spar cement component, dissolution is controlled by diffusion: the mass transfer of products and reactants is thus slow and the fluid is expected to be close to thermodynamical equilibrium with the calcite, leading to very little dissolution, or even precipitation. In the microporous rounded micrite and macropores, dissolution is controlled by

  14. Structurally simple complexes of CO2.

    PubMed

    Murphy, Luke J; Robertson, Katherine N; Kemp, Richard A; Tuononen, Heikki M; Clyburne, Jason A C

    2015-03-01

    The ability to bind CO2 through the formation of low-energy, easily-broken, bonds could prove invaluable in a variety of chemical contexts. For example, weak bonds to CO2 would greatly decrease the cost of the energy-intensive sorbent-regeneration step common to most carbon capture technologies. Furthermore, exploration of this field could lead to the discovery of novel CO2 chemistry. Reduction of complexed carbon dioxide might generate chemical feedstocks for the preparation of value-added products, particularly transportation fuels or fuel precursors. Implementation on a large scale could help to drastically reduce CO2 concentrations in the atmosphere. However, literature examples of weakly bonded complexes of CO2 are relatively few and true coordination complexes to a 'naked' CO2 fragment are nearly unheard of. In this review article, a variety of complexes of CO2 featuring diverse binding modes and reactivity will be examined. Topics covered include: (A) inclusion complexes of CO2 in porous materials. (B) Zwitterionic carbamates produced from the reaction of CO2 with polyamines. (C) Carbamate salts produced from reaction of CO2 with two equivalents of an amine. (D) Insertion products of CO2 into acid-base adducts (e.g., metal complexes). (E) Lewis acid-base activated CO2, such as frustrated Lewis pair complexes. (F) Simple base-CO2 adducts, wherein the base-CO2 bond is the only interaction formed. Complexes in the last category are of particular interest, and include imidazol-2-carboxylates (N-heterocyclic carbene adducts of CO2) as well as a few other examples that lie outside NHC chemistry.

  15. Elevated atmospheric CO(2) affects the chemical quality of brassica plants and the growth rate of the specialist, Plutella xylostella, but not the generalist, Spodoptera littoralis.

    PubMed

    Reddy, Gadi V P; Tossavainen, Paula; Nerg, Anne-Marja; Holopainen, Jarmo K

    2004-06-30

    Cabbage, Brassica oleracea subsp. capitata (cv. Lennox and Rinda), and oilseed rape, Brassica rapa subsp. oleifera (cv. Valo and Tuli), plants were grown under ambient CO(2) (360 ppm) or elevated CO(2) (720 ppm) at 23/18 degrees C and under a photoperiod of 22/2 h light (250 micromol m(-)(2) s(-)(1))/dark regime for up to 5 weeks. Afterward, the performance of the crucifer specialist Plutella xylostella (Lepidoptera: Plutellidae) and the generalist Spodoptera littoralis (Lepidoptera: Noctuidae) on those plants was studied. The mean relative growth rate (RGR) of P. xylostella larvae, feeding on both cultivars of oilseed rape or on the Lennox cultivar of cabbage leaves grown at an elevated CO(2) concentration, was significantly reduced as compared to ambient CO(2). A negative larval growth rate at elevated CO(2) was observed for P. xylostella on both oilseed rape cultivars, but the growth rate was reduced but positive on cabbage. Conversely, the RGR of S. littoralis on either plant species was not affected by CO(2) treatment but was lower on cabbage cv. Rinda than on cv. Lennox. The mortality of the larvae was not affected by CO(2) treatment either. At the same time, elevated CO(2) significantly decreased the concentrations of leaf phytochemical constituents in oilseed rape, i.e., total phenolics and total nitrogen, but not in cabbage. The effect of elevated CO(2) on the leaf glucosinolate concentrations of both plant species was marginal. In addition, the observed significant changes in individual glucosinolate concentrations of oilseed rape leaves were not consistent among cultivars. However, our results demonstrate for the first time quite strong effects of CO(2) enrichment on the larval performance of P. xylostella, which is an important pest of Brassica plants around the world. Further studies are still required to increase our understanding of why elevated CO(2) differently affects the performance of specialist and generalist insect herbivores on Brassica

  16. Evidence of the chemical reaction of (18)O-labelled nitrite with CO2 in aqueous buffer of neutral pH and the formation of (18)OCO by isotope ratio mass spectrometry.

    PubMed

    Tsikas, Dimitrios; Böhmer, Anke; Gros, Gerolf; Endeward, Volker

    2016-05-01

    Inorganic nitrite (NO2(-), ON-O(-) ←→ (-)O-NO) is the autoxidation product of nitric oxide (NO). Nitrite can also be formed from inorganic nitrate (ONO2(-)), the major oxidation product of NO in erythrocytes, by the catalytic action of bacterial nitrate reductase in gut and oral microflora. Nitrite can be reduced to NO by certain cellular proteins and enzymes, as well as in the gastric juice under acidic conditions. Hemoglobin, xanthine oxidoreductase and carbonic anhydrase (CA) have been reported to convert nitrite to NO. Renal CA isoforms are involved in the reabsorption of nitrite and may, therefore, play an important role in NO homeostasis. Yet, the mechanisms underlying the action of CA on nitrite are incompletely understood. The nitrate/nitrite system is regarded as a reservoir of NO. We have recently shown that nitrite reacts chemically with carbon dioxide (CO2), the regular substrate of CA. The present communication reports a stable isotope ratio mass spectrometry (IRMS) study on the reaction of NO2(-) and CO2 performed in 50 mM HEPES buffer of pH 7.4 at 37 °C. By using (18)O-labelled nitrite ((18)ON-O(-)/(-18)O-NO) and CO2 we observed formation of (18)O-labelled CO2. This finding is an unequivocal evidence of the chemical reaction of (18)ON-O(-)/(-18)O-NO with CO2. The reaction is rapid and involves nucleophilic attack of the negatively charged nitrite via one of its oxygen atoms on the partially positively charged CO2 molecule to form the putative intermediate (18)ON-O-CO2(-)/(-)O2C-(18)O-NO. The by far largest fraction of this intermediate decomposes back to (18)ON-O(-)/(-18)O-NO and CO2. A very small fraction of the intermediate, however, rearranges and finally decomposes to form (18)OCO and nitrite. This reaction is slower in the presence of an isolated erythrocytic CA isoform II. In summary, NO2(-), CO2 and CA are ubiquitous. The chemical reaction of NO2(-) with CO2 and its modulation by CA isoforms may play important roles in the transport of

  17. CO2 blood test

    MedlinePlus

    Bicarbonate test; HCO3-; Carbon dioxide test; TCO2; Total CO2; CO2 test - serum ... Many medicines can interfere with blood test results. Your health care provider will tell you if you need to stop taking any medicines before you have this test. DO ...

  18. CO2 capture in different carbon materials.

    PubMed

    Jiménez, Vicente; Ramírez-Lucas, Ana; Díaz, José Antonio; Sánchez, Paula; Romero, Amaya

    2012-07-01

    In this work, the CO(2) capture capacity of different types of carbon nanofibers (platelet, fishbone, and ribbon) and amorphous carbon have been measured at 26 °C as at different pressures. The results showed that the more graphitic carbon materials adsorbed less CO(2) than more amorphous materials. Then, the aim was to improve the CO(2) adsorption capacity of the carbon materials by increasing the porosity during the chemical activation process. After chemical activation process, the amorphous carbon and platelet CNFs increased the CO(2) adsorption capacity 1.6 times, whereas fishbone and ribbon CNFs increased their CO(2) adsorption capacity 1.1 and 8.2 times, respectively. This increase of CO(2) adsorption capacity after chemical activation was due to an increase of BET surface area and pore volume in all carbon materials. Finally, the CO(2) adsorption isotherms showed that activated amorphous carbon exhibited the best CO(2) capture capacity with 72.0 wt % of CO(2) at 26 °C and 8 bar.

  19. Effect of chemical functionalization groups on Zr6-AzoBDC to enhance H2, CH4 storage and CO2 capture: a theoretical investigation

    NASA Astrophysics Data System (ADS)

    Trang, Khung M.; Pham, Hung Q.; Pham-Tran, Nguyen-Nguyen

    2015-09-01

    Grand canonical Monte Carlo (GCMC) simulation combined with the ideal adsorbed solution theory (IAST) and a statistical method were utilized to investigate the effect of functional groups on zirconium oxide based metal-organic frameworks (MOFs) Zr6-AzoBDC (Zr6A) for the gases (H2, CH4) adsorption property and CO2/CH4 selectivity under low pressure. The results showed that phenyl groups containing nitrogen (pyridine, pyrimidine) and thiophene group enhance the gas affinity with MOFs, therefore increasing both gravimetric and volumetric uptake. In addition, this behavior can also cause significantly improved selective capture of CO2 from CO2/CH4 gas mixtures. Among functional groups studied, the sulfonic acid group can potentially improve CH4, CO2 uptake and H2 isosteric heat of adsorption. These findings would play a vital role in designing new materials toward gas adsorption properties.

  20. Outsourcing CO2 Emissions

    NASA Astrophysics Data System (ADS)

    Davis, S. J.; Caldeira, K. G.

    2009-12-01

    CO2 emissions from the burning of fossil fuels are the primary cause of global warming. Much attention has been focused on the CO2 directly emitted by each country, but relatively little attention has been paid to the amount of emissions associated with consumption of goods and services in each country. This consumption-based emissions inventory differs from the production-based inventory because of imports and exports of goods and services that, either directly or indirectly, involved CO2 emissions. Using the latest available data and reasonable assumptions regarding trans-shipment of embodied carbon through third-party countries, we developed a global consumption-based CO2 emissions inventory and have calculated associated consumption-based energy and carbon intensities. We find that, in 2004, 24% of CO2 emissions are effectively outsourced to other countries, with much of the developed world outsourcing CO2 emissions to emerging markets, principally China. Some wealthy countries, including Switzerland and Sweden, outsource over half of their consumption-based emissions, with many northern Europeans outsourcing more than three tons of emissions per person per year. The United States is both a big importer and exporter of emissions embodied in trade, outsourcing >2.6 tons of CO2 per person and at the same time as >2.0 tons of CO2 per person are outsourced to the United States. These large flows indicate that CO2 emissions embodied in trade must be taken into consideration when considering responsibility for increasing atmospheric greenhouse gas concentrations.

  1. Vitamin B1-catalyzed acetoin formation from acetaldehyde: a key step for upgrading bioethanol to bulk C₄ chemicals.

    PubMed

    Lu, Ting; Li, Xiukai; Gu, Liuqun; Zhang, Yugen

    2014-09-01

    The production of bulk chemicals and fuels from renewable biobased feedstocks is of significant importance for the sustainability of human society. The production of ethanol from biomass has dramatically increased and bioethanol also holds considerable potential as a versatile building block for the chemical industry. Herein, we report a highly selective process for the conversion of ethanol to C4 bulk chemicals, such as 2,3-butanediol and butene, via a vitamin B1 (thiamine)-derived N-heterocyclic carbene (NHC)-catalyzed acetoin condensation as the key step to assemble two C2 acetaldehydes into a C4 product. The environmentally benign and cheap natural catalyst vitamin B1 demonstrates high selectivity (99%), high efficiency (97% yield), and high tolerance toward ethanol and water impurities in the acetoin reaction. The results enable a novel and efficient process for ethanol upgrading. PMID:25044300

  2. Porous materials with optimal adsorption thermodynamics and kinetics for CO2 separation.

    PubMed

    Nugent, Patrick; Belmabkhout, Youssef; Burd, Stephen D; Cairns, Amy J; Luebke, Ryan; Forrest, Katherine; Pham, Tony; Ma, Shengqian; Space, Brian; Wojtas, Lukasz; Eddaoudi, Mohamed; Zaworotko, Michael J

    2013-03-01

    The energy costs associated with the separation and purification of industrial commodities, such as gases, fine chemicals and fresh water, currently represent around 15 per cent of global energy production, and the demand for such commodities is projected to triple by 2050 (ref. 1). The challenge of developing effective separation and purification technologies that have much smaller energy footprints is greater for carbon dioxide (CO2) than for other gases; in addition to its involvement in climate change, CO2 is an impurity in natural gas, biogas (natural gas produced from biomass), syngas (CO/H2, the main source of hydrogen in refineries) and many other gas streams. In the context of porous crystalline materials that can exploit both equilibrium and kinetic selectivity, size selectivity and targeted molecular recognition are attractive characteristics for CO2 separation and capture, as exemplified by zeolites 5A and 13X (ref. 2), as well as metal-organic materials (MOMs). Here we report that a crystal engineering or reticular chemistry strategy that controls pore functionality and size in a series of MOMs with coordinately saturated metal centres and periodically arrayed hexafluorosilicate (SiF(2-)(6)) anions enables a 'sweet spot' of kinetics and thermodynamics that offers high volumetric uptake at low CO2 partial pressure (less than 0.15 bar). Most importantly, such MOMs offer an unprecedented CO2 sorption selectivity over N2, H2 and CH4, even in the presence of moisture. These MOMs are therefore relevant to CO2 separation in the context of post-combustion (flue gas, CO2/N2), pre-combustion (shifted synthesis gas stream, CO2/H2) and natural gas upgrading (natural gas clean-up, CO2/CH4).

  3. Reactive Transport Modeling of Effects of Different (Physical, Chemical and Computational) Factors on the Convection Process during CO2 Geological Sequestration in Deep Saline Aquifers

    NASA Astrophysics Data System (ADS)

    Zhang, W.; Wang, S.

    2014-12-01

    Density-driven convective activity can significantly accelerate the transformation of the injected CO2 from supercritical or gas phase into liquid phase, thus improving the long-term storage security. It is well known that the convective instability is only caused by the heterogeneity of porous medium. However, we found that numerical perturbation resulted from the spatial and temporal discretization and the convergence criteria will affect the modeling results. Partial simulation results as follows: (1) the increase in vertical permeability (kv) has a strong effect on the convection process compared to the increasing horizontal permeability. The higher kv also can accelerate the downward migration of fingers and the CO2 dissolution; (2) increase in magnitude of medium (porosity and permeability) perturbation promotes the onset of convective activity, but does not affect the evolution of convection. However, for same magnitudes of the medium perturbation, the modification in permeability can lead to a more rapid onset of convective activity than that in porosity; and (3) the geochemical reactions and mineral compositions are important not only to the CO2 dissolution, but also to the dissolution of other species from mineral dissolution, which both can increase the water density. In additional, 3D and 2D modeling results indicated that their effect on the convection onset is similar. The CO2 dissolution rate for the higher-resolution 3D model is greatly slower than that for the higher-resolution 2D model, due to the increase in dimension for 3D model enhances the interaction of fingers. However, we found that once the bottom boundary becomes important, the decrease in CO2 dissolution rate for the 2D model is more significant than that for the 3D model. This is because the more significant interaction of fingers in the 3D model than that in the 2D model delays the downward propagation of fingers and then the impact of the bottom boundary.

  4. Natural Analog for Geologic Storage of CO2: CO2 accumulation in China

    NASA Astrophysics Data System (ADS)

    Liu, L.; Xu, T.; Liu, N.; Zhou, B.

    2012-12-01

    Natural accumulations of CO2 are potential analogues of CO2 geological storage that can provide useful information on the behaviour of supercritical CO2 in reservoirs. Natural CO2 accumulations are common across Northeast China, and, although they occur in a wide variety of geological settings, their distribution is principally controlled by the Mesozoic-Cenozoic rift basins and associated Quaternary volcanism. High CO2 concentrations (>60 CO2%) in natural gas reservoirs are usually related to volcanism and magmatism, and possesses mantle-genetic origin. CO2 reservoirs consist of sandstone, volcanic rocks and carbonate rocks with the buried depth from 2000-3000 m. Dawsonite is recognized in almost all of the CO2-bearing basin, which has been proved to share the same carbon source with CO2 in the reservoirs in Songliao basin, Hailaer basin and Donghai basin. Petrographic data show that dawsonite is abundant in feldspar- rich sandstone, volcanic rock fragment-rich sandstones and tuff. In some cases, high percentage of dawsonite cement constitutes a diagenetic seal, which occurs in the reservoir-mudstone caprock and prevents upward leakage of CO2. Besides dawsonite, mantle-genetic CO2 flux leads to the formation of calcite, ankerite and siderite. The statistics of porosity and permeability measured from the dawsonite-bearing sandstone and dawsonite-absent sandstone with the almost same burial depth in Songliao basin show that the mantle-genetic CO2 flux result in lower reservoir quality, suggesting that mineral trapping for CO2 is significant. Chemical analyses of formation water in Songliao basin and Hailaer basin indicate that the concentrations of TDS, HCO3-,CO32-, Mg2+,Ca2+ and Na+ + K+ in dawsonite-bearing sandstone are higher than that in dawsonite-absent sandstone. Distribution of CO2 and dawsonite is constrainted by the regional caprocks in the Songliao basin. The charging time of the mantle-genetic CO2 in China dates from 50 to 25 Ma.

  5. Increased chemical weathering of olivine in high-energy shelf seas can counteract human CO2 emissions and ocean acidification against a price well below that of CCS and other methods

    NASA Astrophysics Data System (ADS)

    de Boer, Poppe L.; Schuiling, Roelof D.

    2014-05-01

    In the reaction: Mg(Fe)2SiO4 (olivine) + 4 H2O 2 Mg(Fe)2+ + 4 OH- + H4SiO4, followed by 4 OH- + 4 CO2 4 HCO3-, CO2 is consumed, and Mg2+, Fe2+, H4SiO4 and HCO3- are produced. Contrary to the paradigm that olivine weathering in nature is a slow process, flume experiments show a fast reaction, consuming CO2, and raising the pH at short notice. Only under static conditions a silica coating develops that retards the reaction. In high-energy shallow marine environments such silica coatings are abraded so that the chemical reaction can continue. When kept in motion even large olivine grains and gravels, rubbing and bumping against each other and against other sediment grains, weather quickly. Experiments show that fine micron- to silt-sized olivine particles are produced, and that the chemical reaction is fast. The chemical weathering of 7 km3 olivine is needed on a yearly basis in order to compensate the human CO2 emissions. This seems much, but is of the same order of magnitude as the volume of fossil fuels (in oil equivalents ~10 km3) that are burnt annually. Olivine is readily available at the Earth' surface on all continents, and such volume of 7 km3 is exceeded by existing mines; e.g. the Bingham Canyon open pit mine in Utah has an excavated volume of 25 km3. Hydrocarbons, on the other hand, are commonly retrieved with great efforts, from great depths, and often at remote locations. Spreading of large amounts of olivine (and/or serpentinite) in high-energy shelf seas where coarse sand and gravel can be transported, will counteract human CO2 production by fossil fuel burning and ocean acidification against a price well below that of other methods; order of US 10.- per ton CO2. For example part of the continental shelf between the Shetland Isles and France, that is the Southern Bight of the North Sea, the English Channel and the Irish Sea, is covered with sand waves, and in and around the English Channel an area of well over 100,000 km2 experiences bed shear stresses

  6. Direct CO2-Methanation of flue gas

    NASA Astrophysics Data System (ADS)

    Müller, Klaus; Fleige, Michael; Rachow, Fabian; Israel, Johannes; Schmeißer, Dieter

    2013-04-01

    Already discovered by Paul Sabatier in 1902 the Hydrogenation according to CO2 + 4H2 ->CH4 + 2H2O nowadays is discussed in the course of the "Power-to-Gas" approach to utilize excess energy from renewable electricity generation in times of oversupply of electricity. We investigate the behavior of this process in a simulated flue gas atmosphere of conventional base load power plants, which could be used as constant sources of the reactant CO2. In relation to an approach related to carbon capture and cycling, the conversion of CO2 directly from the flue gas of a conventional power plant is a new aspect and has several advantages: The conversion of CO2 into methane could be integrated directly into the combustion process. Even older power plants could be upgraded and used as a possible source for CO2, in the same sense as the amine cleaning of flue gas, as a post combustion process. Further, waste heat of the power plant could be used as process energy for the catalytic reaction. Therefore the influence of different flue gas compositions such as varying contents of nitrogen and residual oxygen are tested in a laboratory scale. The heterogeneous catalysis process is investigated with regard to conversion rates, yield and selectivity and long-term stability of the Ni-catalyst. Also the influence of typical contaminations like SO2 is investigated and will be presented.

  7. Regenerable Sorbent for CO2 Removal

    NASA Technical Reports Server (NTRS)

    Alptekin, Gokhan; Jayaraman, Ambal

    2013-01-01

    A durable, high-capacity regenerable sorbent can remove CO2 from the breathing loop under a Martian atmosphere. The system design allows near-ambient temperature operation, needs only a small temperature swing, and sorbent regeneration takes place at or above 8 torr, eliminating the potential for Martian atmosphere to leak into the regeneration bed and into the breathing loop. The physical adsorbent can be used in a metabolic, heat-driven TSA system to remove CO2 from the breathing loop of the astronaut and reject it to the Martian atmosphere. Two (or more) alternating sorbent beds continuously scrub and reject CO2 from the spacesuit ventilation loop. The sorbent beds are cycled, alternately absorbing CO2 from the vent loop and rejecting the adsorbed material into the environment at a high CO2 partial pressure (above 8 torr). The system does not need to run the adsorber at cryogenic temperatures, and uses a much smaller temperature swing. The sorbent removes CO2 via a weak chemical interaction. The interaction is strong enough to enable CO2 adsorption even at 3 to 7.6 torr. However, because the interaction between the surface adsorption sites and the CO2 is relatively weak, the heat input needed to regenerate the sorbent is much lower than that for chemical absorbents. The sorbent developed in this project could potentially find use in a large commercial market in the removal of CO2 emissions from coal-fired power plants, if regulations are put in place to curb carbon emissions from power plants.

  8. Silvering substrates after CO2 snow cleaning

    NASA Astrophysics Data System (ADS)

    Zito, Richard R.

    2005-09-01

    There have been some questions in the astronomical community concerning the quality of silver coatings deposited on substrates that have been cleaned with carbon dioxide snow. These questions center around the possible existence of carbonate ions left behind on the substrate by CO2. Such carbonate ions could react with deposited silver to produce insoluble silver carbonate, thereby reducing film adhesion and reflectivity. Carbonate ions could be produced from CO2 via the following mechanism. First, during CO2 snow cleaning, a small amount of moisture can condense on a surface. This is especially true if the jet of CO2 is allowed to dwell on one spot. CO2 gas can dissolve in this moisture, producing carbonic acid, which can undergo two acid dissociations to form carbonate ions. In reality, it is highly unlikely that charged carbonate ions will remain stable on a substrate for very long. As condensed water evaporates, Le Chatelier's principle will shift the equilibrium of the chain of reactions that produced carbonate back to CO2 gas. Furthermore, the hydration of CO2 reaction of CO2 with H20) is an extremely slow process, and the total dehydrogenation of carbonic acid is not favored. Living tissues that must carry out the equilibration of carbonic acid and CO2 use the enzyme carbonic anhydrase to speed up the reaction by a factor of one million. But no such enzymatic action is present on a clean mirror substrate. In short, the worst case analysis presented below shows that the ratio of silver atoms to carbonate radicals must be at least 500 million to one. The results of chemical tests presented here support this view. Furthermore, film lift-off tests, also presented in this report, show that silver film adhesion to fused silica substrates is actually enhanced by CO2 snow cleaning.

  9. Chemical composition of the essential oil and supercritical CO2 extract of Commiphora myrrha (Nees) Engl. and of Acorus calamus L.

    PubMed

    Marongiu, Bruno; Piras, Alessandra; Porcedda, Silvia; Scorciapino, Andrea

    2005-10-01

    Volatile concentrates from the oleo-gum resin of Commiphora myrrha (Nees) Engl. and from the rhizomes of Acorus calamus were isolated by supercritical extraction with carbon dioxide. The volatile oil of myrrh was obtained at 9.0 MPa and 50 degrees C and at a CO2 flow of 1.5 kg/h. Acorus calamus was extracted at 9.0 MPa and 45 degrees C and at a CO2 flow of 1.6 kg/h. In both cases, an oil devoid of cuticular waxes was obtained with a single depressurization stage. The SFE myrrh oil had a yield, Y, of 3.2%. Its main components, identified and quantified by GC/MS, were furanoeudesma-1,3-diene, 34.9%; lindestrene, 12.9%; curzerene, 8.5%; and germacrone, 5.8%. The essential oils from the same starting material by hydrodistillation, HD, (Y = 2.8%) and by steam distillation, SD, (Y = 0.4%) were quite similar to the SFE extract. The main components of the SFE oil of A. calamus (Y = 3.5%) were acorenone, 13.4%; iso-acorone, 11.6%; (Z)-sesquilavandulol, 11.0%; dehydroxy isocalamendiol, 7.7%; and beta-asarone, 5.5%. The comparison with hydrodistilled (Y = 1.8%) and steam distilled (Y = 1.0%) oils revealed large differences in the content of iso-acorone and crypto-acorone. PMID:16190653

  10. Chemical composition of the essential oil and supercritical CO2 extract of Commiphora myrrha (Nees) Engl. and of Acorus calamus L.

    PubMed

    Marongiu, Bruno; Piras, Alessandra; Porcedda, Silvia; Scorciapino, Andrea

    2005-10-01

    Volatile concentrates from the oleo-gum resin of Commiphora myrrha (Nees) Engl. and from the rhizomes of Acorus calamus were isolated by supercritical extraction with carbon dioxide. The volatile oil of myrrh was obtained at 9.0 MPa and 50 degrees C and at a CO2 flow of 1.5 kg/h. Acorus calamus was extracted at 9.0 MPa and 45 degrees C and at a CO2 flow of 1.6 kg/h. In both cases, an oil devoid of cuticular waxes was obtained with a single depressurization stage. The SFE myrrh oil had a yield, Y, of 3.2%. Its main components, identified and quantified by GC/MS, were furanoeudesma-1,3-diene, 34.9%; lindestrene, 12.9%; curzerene, 8.5%; and germacrone, 5.8%. The essential oils from the same starting material by hydrodistillation, HD, (Y = 2.8%) and by steam distillation, SD, (Y = 0.4%) were quite similar to the SFE extract. The main components of the SFE oil of A. calamus (Y = 3.5%) were acorenone, 13.4%; iso-acorone, 11.6%; (Z)-sesquilavandulol, 11.0%; dehydroxy isocalamendiol, 7.7%; and beta-asarone, 5.5%. The comparison with hydrodistilled (Y = 1.8%) and steam distilled (Y = 1.0%) oils revealed large differences in the content of iso-acorone and crypto-acorone.

  11. Hydrocarbonaceous material upgrading method

    SciTech Connect

    Brecher, Lee E.; Mones, Charles G.; Guffey, Frank D.

    2015-06-02

    A hydrocarbonaceous material upgrading method may involve a novel combination of heating, vaporizing and chemically reacting hydrocarbonaceous feedstock that is substantially unpumpable at pipeline conditions, and condensation of vapors yielded thereby, in order to upgrade that feedstock to a hydrocarbonaceous material condensate that meets crude oil pipeline specification.

  12. Synthesis, characterization and performance of single-component CO2-binding organic liquids (CO2BOL) for post combustion CO2 capture

    SciTech Connect

    Koech, Phillip K.; Heldebrant, David J.; Rainbolt, James E.; Zheng, Feng; Smurthwaite, Tricia D.

    2010-03-31

    Carbon dioxide (CO2) emission to the atmosphere will increase significantly with the shift to coal powered plants for energy generation. This increase in CO2 emission will contribute to climate change. There is need to capture and sequester large amounts of CO2 emitted from these coal power plants in order to mitigate the environmental effects. Here we report the synthesis, characterization and system performance of multiple third generation CO2 binding organic liquids (CO2BOLs) as a solvent system for post combustion gas capture. Alkanolguanidines and alkanolamidines are single component CO2BOLs that reversibly bind CO2 chemically as liquid zwitterionic amidinium / guanidinium alkylcarbonates. Three different alkanolguanidines and alkanolamidines were synthesized and studied for CO2 capacity and binding energetics. Solvent performance of these three CO2BOLs was evaluated by batch-wise CO2 uptake and release over multiple cycles. Synthesis of CO2BOLs, characterization, CO2 uptake, selectivity towards CO2 as well as solvent tolerance to water will be discussed.

  13. Integrated supply chain design for commodity chemicals production via woody biomass fast pyrolysis and upgrading.

    PubMed

    Zhang, Yanan; Hu, Guiping; Brown, Robert C

    2014-04-01

    This study investigates the optimal supply chain design for commodity chemicals (BTX, etc.) production via woody biomass fast pyrolysis and hydroprocessing pathway. The locations and capacities of distributed preprocessing hubs and integrated biorefinery facilities are optimized with a mixed integer linear programming model. In this integrated supply chain system, decisions on the biomass chipping methods (roadside chipping vs. facility chipping) are also explored. The economic objective of the supply chain model is to maximize the profit for a 20-year chemicals production system. In addition to the economic objective, the model also incorporates an environmental objective of minimizing life cycle greenhouse gas emissions, analyzing the trade-off between the economic and environmental considerations. The capital cost, operating cost, and revenues for the biorefinery facilities are based on techno-economic analysis, and the proposed approach is illustrated through a case study of Minnesota, with Minneapolis-St. Paul serving as the chemicals distribution hub.

  14. Engineered yeast for enhanced CO2 mineralization†

    PubMed Central

    Barbero, Roberto; Carnelli, Lino; Simon, Anna; Kao, Albert; Monforte, Alessandra d’Arminio; Riccò, Moreno; Bianchi, Daniele; Belcher, Angela

    2014-01-01

    In this work, a biologically catalyzed CO2 mineralization process for the capture of CO2 from point sources was designed, constructed at a laboratory scale, and, using standard chemical process scale-up protocols, was modeled and evaluated at an industrial scale. A yeast display system in Saccharomyces cerevisae was used to screen several carbonic anhydrase isoforms and mineralization peptides for their impact on CO2 hydration, CaCO3 mineralization, and particle settling rate. Enhanced rates for each of these steps in the CaCO3 mineralization process were confirmed using quantitative techniques in lab-scale measurements. The effect of these enhanced rates on the CO2 capture cost in an industrial scale CO2 mineralization process using coal fly ash as the CaO source was evaluated. The model predicts a process using bCA2- yeast and fly ash is ~10% more cost effective per ton of CO2 captured than a process with no biological molecules, a savings not realized by wild-type yeast and high-temperature stable recombinant CA2 alone or in combination. The levelized cost of electricity for a power plant using this process was calculated and scenarios in which this process compares favorably to CO2 capture by MEA absorption process are presented. PMID:25289021

  15. CO2 laser preionisation

    NASA Technical Reports Server (NTRS)

    Spiers, Gary D.

    1991-01-01

    The final report for work done during the reporting period of January 25, 1990 to January 24, 1991 is presented. A literature survey was conducted to identify the required parameters for effective preionization in TEA CO2 lasers and the methods and techniques for characterizing preionizers are reviewed. A numerical model of the LP-140 cavity was used to determine the cause of the transverse mode stability improvement obtained when the cavity was lengthened. The measurement of the voltage and current discharge pulses on the LP-140 were obtained and their subsequent analysis resulted in an explanation for the low efficiency of the laser. An assortment of items relating to the development of high-voltage power supplies is also provided. A program for analyzing the frequency chirp data files obtained with the HP time and frequency analyzer is included. A program to calculate the theoretical LIMP chirp is also included and a comparison between experiment and theory is made. A program for calculating the CO2 linewidth and its dependence on gas composition and pressure is presented. The program also calculates the number of axial modes under the FWHM of the line for a given resonator length. A graphical plot of the results is plotted.

  16. CO2 Laser Market

    NASA Astrophysics Data System (ADS)

    Simonsson, Samuel

    1989-03-01

    It gives me a great deal of pleasure to introduce our final speaker of this morning's session for two reasons: First of all, his company has been very much in the news not only in our own community but in the pages of Wall Street Journal and in the world economic press. And, secondly, we would like to welcome him to our shores. He is a temporary resident of the United States, for a few months, forsaking his home in Germany to come here and help with the start up of a new company which we believe, probably, ranks #1 as the world supplier of CO2 lasers now, through the combination of former Spectra Physics Industrial Laser Division and Rofin-Sinar GMBH. Samuel Simonsson is the Chairman of the Board of Rofin-Sinar, Inc., here in the U.S. and managing director of Rofin-Sinar GMBH. It is a pleasure to welcome him.

  17. [Technology upgrades and exposure to chemical agents: results of the PPTP study in the footwear industry].

    PubMed

    Gianoli, Enrica; Brusoni, Daniela; Cornaggia, Nicoletta; Saretto, Gianni

    2012-01-01

    In the present work the chemical compositions of the products used in shoes manufacturing are reported. The data were collected over the period 2004-2007 in 156 shoe factories in Vigevano area during a study aiming the evaluation of safety conditions and occupational exposure to hazardous chemicals of the employees. The study was part of a regional project for "Occupational cancer prevention in the footwear industry". In the first phase of the study an information form on production cycle, products used and their composition was filled during preliminary audit. In the second phase of the study an in depth qualitative/quantitative evaluation of professional exposure was conducted in 13 selected shoe factories. Data analysis showed the increase in use of water-based adhesives at expense of solvent-based adhesives, the reduction to less than 3.5 weight %, and up to 1 weight %, of n-hexane concentration in solvent mixtures, the increase in use of products containing less hazardous ketones, esters, cyclohexane and heptane. Only in very few cases, products containing from 4 to 12 weight% of toluene were used. These data attest a positive trend in workers risks prevention in shoes industry.

  18. Acid Gas Capture Using CO2-Binding Organic Liquids

    SciTech Connect

    Heldebrant, David J.; Koech, Phillip K.; Rainbolt, James E.; Zheng, Feng

    2010-11-10

    Current chemical CO2 scrubbing technology is primarily aqueous alkanolamine based. These systems rapidly bind CO2 (forming water-soluble carbamate and bicarbonate salts) however, the process has serious disadvantages. The concentration of monoethanolamine rarely exceeds 30 wt % due to the corrosive nature of the solution, and this reduces the maximum CO2 volumetric (≤108 g/L) and gravimetric capacity (≤7 wt%) of the CO2 scrubber. The ≤30 wt % loading of ethanolamine also means that a large excess of water must be pumped and heated during CO2 capture and release, and this greatly increases the energy requirements especially considering the high specific heat of water (4 j/g-1K-1). Our approach is to switch to organic systems that chemically bind CO2 as liquid alkylcarbonate salts. Our CO2-binding organic liquids have higher CO2 solubility, lower specific heats, potential for less corrosion and lower binding energies for CO2 than aqueous systems. CO2BOLs also reversibly bind and release mixed sulfur oxides. Furthermore the CO2BOL system can be direct solvent replacements for any solvent based CO2 capture systems because they are commercially available reagents and because they are fluids they would not require extensive process re-engineering.

  19. Volatile Organic Compounds (VOCs) and Elevated Concentrations of Carbon Dioxide (CO2) in Unsaturated-Zone Vapors Near a Chemical and Low-Level Radioactivity Waste-Disposal Facility, Amargosa Desert Research Site, Nye County, Nevada

    NASA Astrophysics Data System (ADS)

    Baker, R. J.; Andraski, B. J.; Walvoord, M. A.; Stonestrom, D. A.; Prudic, D. E.; Luo, W.

    2003-12-01

    As part of its Toxic Substances Hydrology Program, the U.S. Geological Survey is studying contaminant-transport processes in an arid environment at the Amargosa Desert Research Site (http://nevada.usgs.gov/adrs/). The site is near waste-disposal facilities 20 kilometers east of Death Valley National Park. Low-level radioactive waste was buried in unlined trenches of varying depth during 1962-92. Hazardous chemical waste was buried in unlined trenches at an adjacent facility during 1970-88. Mean annual precipitation at the site from 1981 to 2000 was 108 millimeters. The unsaturated zone is aerobic down to the water table, which is about 110 m (meters) deep. Sampling infrastructure south and west of the facility includes a grid of vapor probes 1.5 m deep, a 23.8-m-deep background borehole (JFDB), and two approximately 100-m-deep boreholes (UZB-2 and UZB-3), which are 160 m and 100 m from the nearest trench, respectively, and are instrumented for multi-level sampling. Analytes detected in unsaturated-zone-vapor samples include elevated concentrations of tritium and carbon-14; three chlorofluorocarbon (CFC) compounds, eight chlorinated solvent compounds, and toluene, all at concentrations exceeding 1,000 parts per billion (ppb) in UZB-3, and at lower concentrations in UZB-2 and in the shallow-vapor-probe grid; and CO2 in concentrations up to 2% in UZB-3, whereas maximum CO2 concentrations in JFDB are less than 0.2%. With the notable exception of toluene, VOCs that are known to be highly biodegradable are generally absent or occur at low concentrations (<100 ppb). The trends in the CO2 concentration profiles approximately parallel those of CFCs and radionuclides. The following preliminary conclusions have been drawn from the radionuclide, VOC, and CO2 data: 1. Biodegradation of organic substances is a reasonable explanation for the presence of CO2 in UZB-3 at concentrations greater those in JFDB (background), which are attributed to near-surface natural biological

  20. Capture and Sequestration of CO2 at the Boise White Paper Mill

    SciTech Connect

    B.P. McGrail; C.J. Freeman; G.H. Beeman; E.C. Sullivan; S.K. Wurstner; C.F. Brown; R.D. Garber; D. Tobin E.J. Steffensen; S. Reddy; J.P. Gilmartin

    2010-06-16

    This report documents the efforts taken to develop a preliminary design for the first commercial-scale CO2 capture and sequestration (CCS) project associated with biomass power integrated into a pulp and paper operation. The Boise Wallula paper mill is located near the township of Wallula in Southeastern Washington State. Infrastructure at the paper mill will be upgraded such that current steam needs and a significant portion of the current mill electric power are supplied from a 100% biomass power source. A new biomass power system will be constructed with an integrated amine-based CO2 capture plant to capture approximately 550,000 tons of CO2 per year for geologic sequestration. A customized version of Fluor Corporation’s Econamine Plus™ carbon capture technology will be designed to accommodate the specific chemical composition of exhaust gases from the biomass boiler. Due to the use of biomass for fuel, employing CCS technology represents a unique opportunity to generate a net negative carbon emissions footprint, which on an equivalent emissions reduction basis is 1.8X greater than from equivalent fossil fuel sources (SPATH and MANN, 2004). Furthermore, the proposed project will offset a significant amount of current natural gas use at the mill, equating to an additional 200,000 tons of avoided CO2 emissions. Hence, the total net emissions avoided through this project equates to 1,100,000 tons of CO2 per year. Successful execution of this project will provide a clear path forward for similar kinds of emissions reduction that can be replicated at other energy-intensive industrial facilities where the geology is suitable for sequestration. This project also represents a first opportunity for commercial development of geologic storage of CO2 in deep flood basalt formations. The Boise paper mill site is host to a Phase II pilot study being carried out under DOE’s Regional Carbon Partnership Program. Lessons learned from this pilot study and other separately

  1. Modeling global atmospheric CO2 with improved emission inventories and CO2 production from the oxidation of other carbon species

    SciTech Connect

    Nassar, Ray; Jones, DBA; Suntharalingam, P; Chen, j.; Andres, Robert Joseph; Wecht, K. J.; Yantosca, R. M.; Kulawik, SS; Bowman, K; Worden, JR; Machida, T; Matsueda, H

    2010-01-01

    The use of global three-dimensional (3-D) models with satellite observations of CO2 in inverse modeling studies is an area of growing importance for understanding Earth s carbon cycle. Here we use the GEOS-Chem model (version 8-02-01) CO2 mode with multiple modifications in order to assess their impact on CO2 forward simulations. Modifications include CO2 surface emissions from shipping (0.19 PgC yr 1), 3-D spatially-distributed emissions from aviation (0.16 PgC yr 1), and 3-D chemical production of CO2 (1.05 PgC yr 1). Although CO2 chemical production from the oxidation of CO, CH4 and other carbon gases is recognized as an important contribution to global CO2, it is typically accounted for by conversion from its precursors at the surface rather than in the free troposphere. We base our model 3-D spatial distribution of CO2 chemical production on monthly-averaged loss rates of CO (a key precursor and intermediate in the oxidation of organic carbon) and apply an associated surface correction for inventories that have counted emissions of CO2 precursors as CO2. We also explore the benefit of assimilating satellite observations of CO into GEOS-Chem to obtain an observation-based estimate of the CO2 chemical source. The CO assimilation corrects for an underestimate of atmospheric CO abundances in the model, resulting in increases of as much as 24% in the chemical source during May June 2006, and increasing the global annual estimate of CO2 chemical production from 1.05 to 1.18 Pg C. Comparisons of model CO2 with measurements are carried out in order to investigate the spatial and temporal distributions that result when these new sources are added. Inclusion of CO2 emissions from shipping and aviation are shown to increase the global CO2 latitudinal gradient by just over 0.10 ppm (3%), while the inclusion of CO2 chemical production (and the surface correction) is shown to decrease the latitudinal gradient by about 0.40 ppm (10%) with a complex spatial structure

  2. Ar + CO2 and He + CO2 Plasmas in ASTRAL

    NASA Astrophysics Data System (ADS)

    Boivin, R. F.; Gardner, A.; Munoz, J.; Kamar, O.; Loch, S.

    2007-11-01

    Spectroscopy study of the ASTRAL helicon plasma source running Ar + CO2 and He + CO2 gas mixes is presented. ASTRAL produces plasmas with the following parameters: ne = 10^10 - 10^13 cm-3, Te = 2 - 10 eV and Ti = 0.03 - 0.5 eV, B-field <= 1.3 kGauss, rf power <= 2 kWatt. A 0.33 m scanning monochromator is used for this study. Using Ar + CO2 gas mixes, very different plasmas are observed as the concentration of CO2 is changed. At low CO2 concentration, the bluish plasma is essentially atomic and argon transitions dominate the spectra. Weak C I and O I lines are present in the 750 - 1000 nm range. At higher CO2 concentration, the plasma becomes essentially molecular and is characterized by intense, white plasma columns. Here, spectra are filled with molecular bands (CO2, CO2^+, CO and CO^+). Limited molecular dissociative excitation processes associated with the production of C I and O I emission are also observed. On the other hand, He + CO2 plasmas are different. Here, rf matches are only possible at low CO2 concentration. Under these conditions, the spectra are characterized by strong C I and O I transitions with little or no molecular bands. Strong dissociative processes observed in these plasmas can be link to the high Te associated with He plasmas. An analysis of the spectra with possible scientific and industrial applications will be presented.

  3. CO2 mineralization-bridge between storage and utilization of CO2.

    PubMed

    Geerlings, Hans; Zevenhoven, Ron

    2013-01-01

    CO2 mineralization comprises a chemical reaction between suitable minerals and the greenhouse gas carbon dioxide. The CO2 is effectively sequestered as a carbonate, which is stable on geological timescales. In addition, the variety of materials that can be produced through mineralization could find applications in the marketplace, which makes implementation of the technology more attractive. In this article, we review recent developments and assess the current status of the CO2 mineralization field. In an outlook, we briefly describe a few mineralization routes, which upon further development have the potential to be implemented on a large scale.

  4. Physical and Chemical Effects of Two-Phase Brine/Supercritical-CO2 Fluid Flow on Clastic Rocks: Real-Time Monitoring and NMR Imaging of Flow-Through Core Experiments

    NASA Astrophysics Data System (ADS)

    Shaw, C. A.; Vogt, S.; Maneval, J. E.; Brox, T.; Skidmore, M. L.; Codd, S. L.; Seymour, J. D.

    2010-12-01

    Sandstone core samples were challenged with a supercritical CO2-saturated brine mixture in a laboratory flow-through core reactor system over a range of temperatures and brine strengths. Cores of quartz arenite from the Berea formation were selected to represent ideal ‘clean’ sandstone These laboratory experiments potentially provide an analog for the acidification of pore fluids near the brine/CO2 interface during CO2 flooding of depleted clastic hydrocarbon reservoirs for carbon sequestration. Flow in the reactor was perpendicular to bedding. Initial experiments were run at 50°C and 100°C with brine concentrations of 1g/L and 10g/L (TDS) to test effects of different temperatures and brine compositions. Real-time monitoring of fluid pH and conductivity provided a measure of reaction rates. Introduction of supercritical CO2 into the brine-saturated cores initiated a reduction in pH accompanied by an increase in conductivity. NMR images of fresh cores were compared with images of challenged cores using a protocol for pixel-by-pixel comparison to determine the effects on bulk pore volume and geometry. Two types of imaging experiments were conducted: multi-slice spin echo and 3-D spin echo images. Multi-slice experiments had a slice thickness of 1.5 mm and an in-plane resolution of 0.27 mm x 0.27 mm, and 3-D experiments had a resolution of 0.47 mm x 0.55 mm x 0.55mm. Imaging results reflected the observed changes in the physical and chemical structure post-challenge. Two-dimensional relaxation correlation experiments were also conducted to probe the pore sizes, connectivity and fluid saturation of the rock cores before and after challenging. Chemical analyses and microscopic examination of the challenged cores will provide a better understanding of alteration in the cores and the changes in the volume, geometry and connectivity of pore space.

  5. CO2 laser cutting of natural granite

    NASA Astrophysics Data System (ADS)

    Riveiro, A.; Mejías, A.; Soto, R.; Quintero, F.; del Val, J.; Boutinguiza, M.; Lusquiños, F.; Pardo, J.; Pou, J.

    2016-01-01

    Commercial black granite boards (trade name: "Zimbabwe black granite") 10 mm thick, were successfully cut by a 3.5 kW CO2 laser source. Cutting quality, in terms of kerf width and roughness of the cut wall, was assessed by means of statistically planned experiments. No chemical modification of the material in the cutting walls was detected by the laser beam action. Costs associated to the process were calculated, and the main factors affecting them were identified. Results reported here demonstrate that cutting granite boards could be a new application of CO2 laser cutting machines provided a supersonic nozzle is used.

  6. Development of Novel CO2 Adsorbents for Capture of CO2 from Flue Gas

    SciTech Connect

    Fauth, D.J.; Filburn, T.P.; Gray, M.L.; Hedges, S.W.; Hoffman, J.; Pennline, H.W.; Filburn, T.

    2007-06-01

    Capturing CO2 emissions generated from fossil fuel-based power plants has received widespread attention and is considered a vital course of action for CO2 emission abatement. Efforts are underway at the Department of Energy’s National Energy Technology Laboratory to develop viable energy technologies enabling the CO2 capture from large stationary point sources. Solid, immobilized amine sorbents (IAS) formulated by impregnation of liquid amines within porous substrates are reactive towards CO2 and offer an alternative means for cyclic capture of CO2 eliminating, to some degree, inadequacies related to chemical absorption by aqueous alkanolamine solutions. This paper describes synthesis, characterization, and CO2 adsorption properties for IAS materials previously tested to bind and release CO2 and water vapor in a closed loop life support system. Tetraethylenepentamine (TEPA), acrylonitrile-modified tetraethylenepentamine (TEPAN), and a single formulation consisting of TEPAN and N, N’-bis(2-hydroxyethyl)ethylenediamine (BED) were individually supported on a poly (methyl methacrylate) (PMMA) substrate and examined. CO2 adsorption profiles leading to reversible CO2 adsorption capacities were obtained using thermogravimetry. Under 10% CO2 in nitrogen at 25°C and 1 atm, TEPA supported on PMMA over 60 minutes adsorbed ~3.2 mmol/g{sorbent} whereas, TEPAN supported on PMMA along with TEPAN and BED supported on PMMA adsorbed ~1.7 mmol/g{sorbent} and ~2.3 mmol/g{sorbent} respectively. Cyclic experiments with a 1:1 weight ratio of TEPAN and BED supported on poly (methyl methacrylate) beads utilizing a fixed-bed flow system with 9% CO2, 3.5% O2, nitrogen balance with trace gas constituents were studied. CO2 adsorption capacity was ~ 3 mmols CO2/g{sorbent} at 40°C and 1.4 atm. No beneficial effect on IAS performance was found using a moisture-laden flue gas mixture. Tests with 750 ppmv NO in a humidified gas stream revealed negligible NO sorption onto the IAS. A high SO2

  7. CO2 adsorption isotherm on clay minerals and the CO2 accessibility into the clay interlayer

    NASA Astrophysics Data System (ADS)

    Gensterblum, Yves; Bertier, Pieter; Busch, Andreas; Rother, Gernot; Krooß, Bernhard

    2013-04-01

    Large-scale CO2 storage in porous rock formations at 1-3 km depth is seen as a global warming mitigation strategy. In this process, CO2 is separated from the flue gas of coal or gas power plants, compressed, and pumped into porous subsurface reservoirs with overlying caprocks (seals). Good seals are mechanically and chemically stable caprocks with low porosity and permeability. They prevent leakage of buoyant CO2 from the reservoir. Caprocks are generally comprised of thick layers of shale, and thus mainly consist of clay minerals. These clays can be affected by CO2-induced processes, such as swelling or dissolution. The interactions of CO2 with clay minerals in shales are at present poorly understood. Sorption measurements in combination scattering techniques could provide fundamental insight into the mechanisms governing CO2-clay interaction. Volumetric sorption techniques have assessed the sorption of supercritical CO2 onto coal (Gensterblum et al., 2010; Gensterblum et al., 2009), porous silica (Rother et al., 2012a) and clays as a means of exploring the potential of large-scale storage of anthropogenic CO2 in geological reservoirs (Busch et al., 2008). On different clay minerals and shales, positive values of excess sorption were measured at gas pressures up to 6 MPa, where the interfacial fluid is assumed to be denser than the bulk fluid. However, zero and negative values were obtained at higher densities, which suggests the adsorbed fluid becomes equal to and eventually less dense than the corresponding bulk fluid, or that the clay minerals expand on CO2 charging. Using a combination of neutron diffraction and excess sorption measurements, we recently deduced the interlayer density of scCO2 in Na-montmorillonite clay in its single-layer hydration state (Rother et al., 2012b), and confirmed its low density, as well as the expansion of the basal spacings. We performed neutron diffraction experiments at the FRMII diffractometer on smectite, kaolinite and illite

  8. Is CO2 ice permanent?

    NASA Technical Reports Server (NTRS)

    Lindner, Bernhard Lee

    1992-01-01

    Carbon dioxide ice has been inferred to exist at the south pole in summertime, but Earth based measurements in 1969 of water vapor in the Martian atmosphere suggest that all CO2 ice sublined from the southern polar cap and exposed underlying water ice. This implies that the observed summertime CO2 ice is of recent origin. It appears possible to construct an energy balance model that maintains seasonal CO2 ice at the south pole year round and still reasonably simulates the polar cap regression and atmospheric pressure data. This implies that the CO2 ice observed in the summertime south polar cap could be seasonal in origin, and that minor changes in climate could cause CO2 ice to completely vanish, as would appear to have happened in 1969. However, further research remains before it is certain whether the CO2 ice observed in the summertime south polar cap is seasonal or is part of a permanent reservoir.

  9. India Co2 Emissions

    NASA Astrophysics Data System (ADS)

    Sharan, S.; Diffenbaugh, N. S.

    2010-12-01

    created a balance in between the “developed” and developing countries. If India was producing the same amounts of emissions per capita as the it would have a total of 20 billion metric tons of CO2 emissions annually.

  10. Co2 geological sequestration

    SciTech Connect

    Xu, Tianfu

    2004-11-18

    Human activities are increasingly altering the Earth's climate. A particular concern is that atmospheric concentrations of carbon dioxide (CO{sub 2}) may be rising fast because of increased industrialization. CO{sub 2} is a so-called ''greenhouse gas'' that traps infrared radiation and may contribute to global warming. Scientists project that greenhouse gases such as CO{sub 2} will make the arctic warmer, which would melt glaciers and raise sea levels. Evidence suggests that climate change may already have begun to affect ecosystems and wildlife around the world. Some animal species are moving from one habitat to another to adapt to warmer temperatures. Future warming is likely to exceed the ability of many species to migrate or adjust. Human production of CO{sub 2} from fossil fuels (such as at coal-fired power plants) is not likely to slow down soon. It is urgent to find somewhere besides the atmosphere to put these increased levels of CO{sub 2}. Sequestration in the ocean and in soils and forests are possibilities, but another option, sequestration in geological formations, may also be an important solution. Such formations could include depleted oil and gas reservoirs, unmineable coal seams, and deep saline aquifers. In many cases, injection of CO2 into a geological formation can enhance the recovery of hydrocarbons, providing value-added byproducts that can offset the cost of CO{sub 2} capture and sequestration. Before CO{sub 2} gas can be sequestered from power plants and other point sources, it must be captured. CO{sub 2} is also routinely separated and captured as a by-product from industrial processes such as synthetic ammonia production, H{sub 2} production, and limestone calcination. Then CO{sub 2} must be compressed into liquid form and transported to the geological sequestration site. Many power plants and other large emitters of CO{sub 2} are located near geological formations that are amenable to CO{sub 2} sequestration.

  11. CO2 interaction with geomaterials.

    SciTech Connect

    Guthrie, George D.; Al-Saidi, Wissam A.; Jordan, Kenneth D.; Voora, Vamsee, K.; Romanov, Vyacheslav N.; Lopano, Christina L; Myshakin, Eugene M.; Hur, Tae Bong; Warzinski, Robert P.; Lynn, Ronald J.; Howard, Bret H.; Cygan, Randall Timothy

    2010-09-01

    This work compares the sorption and swelling processes associated with CO2-coal and CO2-clay interactions. We investigated the mechanisms of interaction related to CO2 adsortion in micropores, intercalation into sub-micropores, dissolution in solid matrix, the role of water, and the associated changes in reservoir permeability, for applications in CO2 sequestration and enhanced coal bed methane recovery. The structural changes caused by CO2 have been investigated. A high-pressure micro-dilatometer was equipped to investigate the effect of CO2 pressure on the thermoplastic properties of coal. Using an identical dilatometer, Rashid Khan (1985) performed experiments with CO2 that revealed a dramatic reduction in the softening temperature of coal when exposed to high-pressure CO2. A set of experiments was designed for -20+45-mesh samples of Argonne Premium Pocahontas No.3 coal, which is similar in proximate and ultimate analysis to the Lower Kittanning seam coal that Khan used in his experiments. No dramatic decrease in coal softening temperature has been observed in high-pressure CO2 that would corroborate the prior work of Khan. Thus, conventional polymer (or 'geopolymer') theories may not be directly applicable to CO2 interaction with coals. Clays are similar to coals in that they represent abundant geomaterials with well-developed microporous structure. We evaluated the CO2 sequestration potential of clays relative to coals and investigated the factors that affect the sorption capacity, rates, and permanence of CO2 trapping. For the geomaterials comparison studies, we used source clay samples from The Clay Minerals Society. Preliminary results showed that expandable clays have CO2 sorption capacities comparable to those of coal. We analyzed sorption isotherms, XRD, DRIFTS (infrared reflectance spectra at non-ambient conditions), and TGA-MS (thermal gravimetric analysis) data to compare the effects of various factors on CO2 trapping. In montmorillonite, CO2

  12. Elevated CO(2) and drought stress effects on the chemical composition of maize plants, their ruminal fermentation and microbial diversity in vitro.

    PubMed

    Meibaum, Birgit; Riede, Susanne; Schröder, Bernd; Manderscheid, Remy; Weigel, Hans-Joachim; Breves, Gerhard

    2012-12-01

    Climate changes are supposed to influence productivity and chemical composition of plants. In the present experiments, it was hypothesised that the incubation of plants exposed to elevated atmospheric carbon dioxide concentrations ([CO₂]) and drought stress will result in different ruminal fermentation pattern and microbial diversity compared to unaffected plants. Maize plants were grown, well-watered under ambient (380 ppm CO₂, Variant A) and elevated [CO₂] (550 ppm CO₂, Variant B). Furthermore, each CO₂ treatment was also exposed to drought stress (380 ppm and 550 ppm CO₂,Variants C and D, respectively), which received only half as much water as the well-watered plants. Plant material from these treatments was incubated in a semi-continuous in vitro fermentation experiment using the rumen simulation technique. Single strand conformation polymorphism (SSCP) analysis was conducted for Bacteria and Archaea specific profiles. The analysis of crude nutrients showed higher contents of fibre fraction in drought stress Variants C and D. Crude protein content was increased by drought stress under ambient but not under elevated [CO₂]. Fermentation of drought stress variants resulted in significantly increased pH values, decreased digestibilities of organic matter and increased ammonia-N (NH₃-N) concentrations compared with well-watered variants. Additionally, the 550 ppm CO₂ Variants B and D showed significantly lower NH₃-N concentrations than Variants A and C. The Bacteria- and Archaea-specific SSCP profiles as well as the production rates of short-chain fatty acids and their molar percentages were not affected by treatments. During the first four days of equilibration period, a decrease of molar percentage of acetate and increased molar percentages of propionate were observed for all treatments. These alterations might have been induced by adaptation of the in vitro system to the new substrate. The rumen microflora appeared to be highly adaptive and

  13. Convergent Cenozoic CO2 history

    NASA Astrophysics Data System (ADS)

    Royer, D. L.; Beerling, D. J.

    2011-12-01

    The quality and quantity of Cenozoic CO2 records have increased significantly in the last decade. Gains in quality have come primarily from a fuller accounting of confounding factors; examples include soil respiration rates in the pedogenic carbonate method, alkalinity and seawater δ11B in the boron method, and cell size in the alkenone phytoplankton method. Previously, variability across Cenozoic CO2 estimates in a given time period sometimes exceeded an order of magnitude, but through these improvements variability has been reduced to a factor of two or less. Further improvements in the record can probably be facilitated by more robust quantification of statistical error, generation of CO2 estimates at single locations from multiple methods, and cross-calibration with Pleistocene ice-core CO2 records (Beerling & Royer, 2011, Nature Geoscience 4: 418-420). An improved Cenozoic CO2 record offers opportunities for better understanding Earth system processes. We provide one example related to climate sensitivity. We find a significant relationship between CO2 radiative forcing and global temperature during the Cenozoic, even after accounting for forcings related to solar evolution and paleogeographic changes. Although the calculations are based on simple assumptions and should be taken as provisional, the mean Cenozoic climate sensitivity (3 °C or higher per CO2 doubling) is similar to or higher than calculations for the present-day (~3 °C per CO2 doubling).

  14. Leaves: Elevated CO2 levels

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Burning fossil fuels and land use changes such as deforestation and urbanization have led to a dramatic rise in the concentration of carbon dioxide (CO2) in the atmosphere since the onset of the Industrial Revolution. The highly dilute CO2 from the atmosphere enters plant leaves where it is concentr...

  15. Fluid chemistry of the onshore CO2 sequestration formation at Nagaoka, Japan: 5 years passed since CO2 injection

    NASA Astrophysics Data System (ADS)

    Mito, S.; Asahara, Y.; Xue, Z.

    2011-12-01

    The CO2 injection into structural reservoirs in deep permeable geologic formations is now expected one of the most realizable methods from the point of view of the cost and the CO2 preserving capability of the geological reservoirs. The first Japanese pilot-scale CO2 sequestration project has been done in an onshore saline aquifer at Nagaoka-site, Japan. 10,400 tones of CO2 were injected into a thin aquifer at the depth of 1110 m at a rate of 20-40 tones from July 2003 to January 2005. To investigate a chemical reaction between CO2 fluids and rock forming minerals at the sequestration formation, formation water was collected before and after 1year of the injection (Mito et al., 2008). The result of chemical analyses exhibited a high concentration of HCO3-, Ca, Mg, Fe, Mn and Si in the post-CO2 injection samples compared to the original formation water. The result indicated that a chemical reaction between CO2 and formation water and rock forming minerals had occurred in the sequestration formation at the early stage of CO2 storage. A continuous resistivity monitoring from 2003 to 2011 showed an existence of stagnant free CO2 at the depth of 1110m and gradual spreading of CO2 dissolved water at a top and a bottom of the free CO2 layer (Mito and Xue 2011). This observation suggests that the CO2 trapped by formation water have gradually diffused and chemical trapping of CO2 by surrounding minerals have progressed in the formation. For long-term CO2 storage, we should clarify the reaction between CO2 and minerals occurred at the edge of the spreading CO2 fluids. We are going to collect formation water in the sequestration site at November 2011. We will show the analytical result of the sampled water and discuss about the long-term chemical reaction between the diffused CO2 fluids and rock forming minerals at the Nagaoka sequestration site. References Mito et al., 2008. International Journal of Greenhouse Gas Control, 2, 309-318. Mito and Xue 2011. Energy procedia, 4

  16. CO2 Sequestration short course

    SciTech Connect

    DePaolo, Donald J.; Cole, David R; Navrotsky, Alexandra; Bourg, Ian C

    2014-12-08

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

  17. Leak Path Development in CO2 Wells

    NASA Astrophysics Data System (ADS)

    Torsater, M.; Todorovic, J.; Opedal, N.; Lavrov, A.

    2014-12-01

    Wells have in numerous scientific works been denoted the "weak link" of safe and cost-efficient CO2 Capture and Storage (CCS). Whether they are active or abandoned, all wells are man-made intrusions into the storage reservoir with sealing abilities depending on degradable materials like steel and cement. If dense CO2 is allowed to expand (e.g. due to leakage) it will cool down its surroundings and cause strong thermal and mechanical loading on the wellbore. In addition, CO2 reacts chemically with rock, cement and steel. To ensure long-term underground containment, it is therefore necessary to study how, why, where and when leakage occurs along CO2wells. If cement bonding to rock or casing is poor, leak paths can form already during drilling and completion of the well. In the present work, we have mapped the bonding quality of cement-rock and cement-steel interfaces - and measured their resistance towards CO2 flow. This involved a large experimental matrix including different rocks, steels, cement types and well fluids. The bonding qualities were measured on composite cores using micro computed tomography (µ-CT), and CO2 was flooded through the samples to determine leakage rates. These were further compared to numerical simulations of leakage through the digitalized µ-CT core data, and CO2chemical interactions with the materials were mapped using electron microscopy. We also present a new laboratory set-up for measuring how well integrity is affected by downhole temperature variations - and we showcase some initial results. Our work concludes that leak path development in CO2 wells depends critically on the drilling fluids and presflushes/spacers chosen already during drilling and completion of a well. Fluid films residing on rock and casing surfaces strongly degrade the quality of cement bonding. The operation of the well is also important, as even slight thermal cycling (between 10°C and 95°C on casing) leads to significant de-bonding of the annular cement.

  18. Effects of elevated CO2 concentrations on denitrifying and nitrifying popualtions at terrestrial CO2 leakeage analogous sites

    NASA Astrophysics Data System (ADS)

    Christine, Dictor Marie; Catherine, Joulian; Valerie, Laperche; Stephanie, Coulon; Dominique, Breeze

    2010-05-01

    CO2 capture and geological storage (CCS) is recognized to be an important option for carbon abatement in Europe. One of the risks of CCS is the leakage from storage site. A laboratory was conducted on soil samples sampled near-surface from a CO2 leakage analogous site (Latera, Italy) in order to evaluate the impact of an elevated soil CO2 concentration on terrestrial bacterial ecosystems form near surface terrestrial environments and to determine a potential bacterial indicator of CO2 leakage from storage site. Surveys were conducted along a 50m long transect across the vent centre, providing a spectrum of CO2 flux rates, soil gas concentrations and compositions (Beaubien et al., 2007). A bacterial diversity studies, performed by CE-SSCP technique, on a soil profile with increasing CO2 soil concentrations (from 0.3% to 100%) showed that a change on bacterial diversity was noted when CO2 concentration was above 50 % of CO2. From this result, 3 soil samples were taken at 70 cm depth in 3 distinct zones (background soil CO2 content, soil CO2 content of 20% and soil CO2 content of 50%). Then theses soil samples were incubated under closed jars flushed with different air atmospheres (20, 50 and 90 % of CO2) during 18 months. At initial, 3, 6, 12 and 18 months, some soil samples were collected in order to estimate the denitrifying, nitrifying activities as a function of CO2 concentration content and times. Theses enzymatic activities were chosen because one occurs under anaerobic conditions (denitrification) and the other occurs under aerobic conditions (nitrification). Both of them were involved in the nitrogen cycle and are major actors of soil function and groundwater quality preservation. Metabolic diversity using BIOLOG Ecoplates was determined on every soil samples. Physico-chemical parameters (e.g. pH, bulk chemistry, mineralogy) were analyzed to have some information about the evolution of the soil during the incubation with increasing soil CO2 concentrations

  19. Infrared spectroscopy of Mg-CO2 and Al-CO2 complexes in helium nanodroplets

    NASA Astrophysics Data System (ADS)

    Thomas, Brandon J.; Harruff-Miller, Barbara A.; Bunker, Christopher E.; Lewis, William K.

    2015-05-01

    The catalytic reduction of CO2 to produce hydrocarbon fuels is a topic that has gained significant attention. Development of efficient catalysts is a key enabler to such approaches, and metal-based catalysts have shown promise towards this goal. The development of a fundamental understanding of the interactions between CO2 molecules and metal atoms is expected to offer insight into the chemistry that occurs at the active site of such catalysts. In the current study, we utilize helium droplet methods to assemble complexes composed of a CO2 molecule and a Mg or Al atom. High-resolution infrared (IR) spectroscopy and optically selected mass spectrometry are used to probe the structure and binding of the complexes, and the experimental observations are compared with theoretical results determined from ab initio calculations. In both the Mg-CO2 and Al-CO2 systems, two IR bands are obtained: one assigned to a linear isomer and the other assigned to a T-shaped isomer. In the case of the Mg-CO2 complexes, the vibrational frequencies and rotational constants associated with the two isomers are in good agreement with theoretical values. In the case of the Al-CO2 complexes, the vibrational frequencies agree with theoretical predictions; however, the bands from both structural isomers exhibit significant homogeneous broadening sufficient to completely obscure the rotational structure of the bands. The broadening is consistent with an upper state lifetime of 2.7 ps for the linear isomer and 1.8 ps for the T-shaped isomer. The short lifetime is tentatively attributed to a prompt photo-induced chemical reaction between the CO2 molecule and the Al atom comprising the complex.

  20. Polyurethane Foam-Based Ultramicroporous Carbons for CO2 Capture.

    PubMed

    Ge, Chao; Song, Jian; Qin, Zhangfeng; Wang, Jianguo; Fan, Weibin

    2016-07-27

    A series of sustainable porous carbon materials were prepared from waste polyurethane foam and investigated for capture of CO2. The effects of preparation conditions, such as precarbonization, KOH to carbon precursor weight ratio, and activation temperature, on the porous structure and CO2 adsorption properties were studied for the purpose of controlling pore sizes and nitrogen content and developing high-performance materials for capture of CO2. The sample prepared at optimum conditions shows CO2 adsorption capacities of 6.67 and 4.33 mmol·g(-1) at 0 and 25 °C under 1 bar, respectively, which are comparable to those of the best reported porous carbons prepared from waste materials. The HCl treatment experiment reveals that about 80% of CO2 adsorption capacity arises from physical adsorption, while the other 20% is due to the chemical adsorption originated from the interaction of basic N groups and CO2 molecules. The relationship between CO2 uptake and pore size at different temperatures indicates that the micropores with pore size smaller than 0.86 and 0.70 nm play a dominant role in the CO2 adsorption at 0 and 25 °C, respectively. It was found that the obtained carbon materials exhibited high recyclability and high selectivity to adsorption of CO2 from the CO2 and N2 mixture. PMID:27376177

  1. CO2 Chemistry of Phenolate-Based Ionic Liquids.

    PubMed

    Lee, Tae Bum; Oh, Seungmin; Gohndrone, Thomas R; Morales-Collazo, Oscar; Seo, Samuel; Brennecke, Joan F; Schneider, William F

    2016-03-01

    We synthesized ionic liquids (ILs) comprising an alkylphosphonium cation paired with phenolate, 4-nitrophenolate, and 4-methoxyphenolate anions that span a wide range of predicted reaction enthalpies with CO2. Each phenolate-based IL was characterized by spectroscopic techniques, and their physical properties (viscosity, conductivity, and CO2 solubility) were determined. We use the computational quantum chemical approach paired with experimental results to reveal the reaction mechanism of CO2 with phenolate ILs. Model chemistry shows that the oxygen atom of phenolate associates strongly with phosphonium cations and is able to deprotonate the cation to form an ylide with an affordable activation barrier. The ATR-FTIR and (31)P NMR spectra indicate that the phosphonium ylide formation and its reaction with CO2 are predominantly responsible for the observed CO2 uptake rather than direct anion-CO2 interaction. PMID:26556283

  2. Processes affecting the CO2 concentrations measured in Greenland ice

    NASA Astrophysics Data System (ADS)

    Anklin, Martin; Barnola, Jean-Marc; Schwander, Jakob; Stauffer, Bernhard; Raynaud, Dominique

    1995-09-01

    Detailed CO2 measurements on ice cores from Greenland and Antarctica show different mean CO2 concentrations for samples at the same gas age. The deviation between Antarctic and Greenland CO2 records raises up to 20 ppmv during the last millennium. Based on the present knowledge of the global carbon cycle we can exclude such a high mean interhemispheric difference of the CO2 concentration between high northern and southern latitudes. Diffusive mixing of the air in the firn smoothes out short term variations of the atmospheric CO2 Concentration. Nevertheless, we observe short term CO2 variations in Greenland ice in the range of 10 20 ppmv, which cannot represent atmospheric CO2 variations. Due to the low temperature at Summit, meltlayers can be excluded for most of the ice and they cannot account for the frequent anomalous short term CO2 variations and the elevated mean CO2 concentration in the Greenland ice. In this work we give some clues, that in situ production of CO2 in Greenland ice could build up excess CO2 after pore close of. Possible chemical reactions are the oxidation of organic carbon and the reaction between acidity and carbonate. We conclude that the carbonate-acidity reaction is the most probable process to explain the excess CO2 in the bubbles. The reaction could take place in very small liquid-like veins in cold ice, where the mobility of impurities is higher than in the ice lattice. At present, there exists no technique to measure the carbonate concentration in the ice directly. However, a comparison of CO2 analyses performed with a dry- and a wet-extraction technique allows to estimate the carbonate content of the ice. This estimate indicates a carbonate concentration in Greenland ice of about 0.4±0.2µmol/l and a much lower concentration in Antarctic ice.

  3. Catalytic hydrothermal upgrading of crude bio-oils produced from different thermo-chemical conversion routes of microalgae.

    PubMed

    Duan, Peigao; Wang, Bing; Xu, Yuping

    2015-06-01

    This study presents experimental results that compare the use of hydrothermal liquefaction (HTL), alcoholysis (Al), pyrolysis (Py) and hydropyrolysis (HPy) for the production of bio-oil from a microalga (Chlorella pyrenoidosa) and the catalytic hydrothermal upgrading of crude bio-oils produced by these four conversion routes. The yields and compositions of bio-oil, solid residue, and gases were evaluated and compared. HTL resulted in a bio-oil that has a higher energy density and superior fuel properties, such as thermal and storage stabilities, compared with the other three conversion routes. The N in crude bio-oils produced from Py and HPy is more easily removed than that in the bio-oils produced from HTL and Al. The upgraded bio-oils contain reduced amounts of certain O-containing and N-containing compounds and significantly increased saturated hydrocarbon contents. All of the upgraded bio-oils have a larger fraction boiling below 350°C than their corresponding crude bio-oils. PMID:25802049

  4. Catalytic hydrothermal upgrading of crude bio-oils produced from different thermo-chemical conversion routes of microalgae.

    PubMed

    Duan, Peigao; Wang, Bing; Xu, Yuping

    2015-06-01

    This study presents experimental results that compare the use of hydrothermal liquefaction (HTL), alcoholysis (Al), pyrolysis (Py) and hydropyrolysis (HPy) for the production of bio-oil from a microalga (Chlorella pyrenoidosa) and the catalytic hydrothermal upgrading of crude bio-oils produced by these four conversion routes. The yields and compositions of bio-oil, solid residue, and gases were evaluated and compared. HTL resulted in a bio-oil that has a higher energy density and superior fuel properties, such as thermal and storage stabilities, compared with the other three conversion routes. The N in crude bio-oils produced from Py and HPy is more easily removed than that in the bio-oils produced from HTL and Al. The upgraded bio-oils contain reduced amounts of certain O-containing and N-containing compounds and significantly increased saturated hydrocarbon contents. All of the upgraded bio-oils have a larger fraction boiling below 350°C than their corresponding crude bio-oils.

  5. Breadboard CO2 and humidity control system

    NASA Technical Reports Server (NTRS)

    Boehm, A. M.

    1976-01-01

    A regenerable CO2 and humidity control system is being developed for potential use on shuttle as an alternate to the baseline lithium hydroxide (LiOH)/condensing heat exchanger system. The system utilizes a sorbent material, designated HS-C, to adsorb CO2 and water vapor from the cabin atmosphere. The material is regenerated by exposing it to space vacuum. A half-size breadboard system, utilizing a flight representative HS-C canister, was designed, built, and performance tested to shuttle requirements for total CO2 and total humidity removal. The use of a new chemical matrix material allowed significant optimization of the system design by packing the HS-C chemical into the core of a heat exchanger which is manifolded to form two separate and distinct beds. Breadboard system performance was proven by parametric testing and simulated mission testing over the full range of shuttle crew sizes and metabolic loadings. Vacuum desorption testing demonstrated considerable savings in previously projected shuttle vacuum duct sizing.

  6. Enhancing the Ocean's Role in CO2 Mitigation

    NASA Astrophysics Data System (ADS)

    Rau, G. H.

    2012-12-01

    The possibility of safely increasing the ocean's significant, natural consumption and storage of excess CO2 deserves consideration since land-based efforts are thus far failing to stabilize atmospheric CO2 and associated climate and ocean chemistry impacts. Of the approximately 34 GT/yr of CO2 currently emitted to the atmosphere by human activity, the ocean consumes the equivalent of about 8 GT/yr of these emissions. These fluxes are, however, dwarfed by the annual gross amount of CO2 naturally taken up and released by the ocean, in excess of 300 GT CO2/yr. Additionally, the carbon content in the ocean is about 50 times that of the atmosphere, with the majority in a form (HCO2-) that can, through equilibrium reactions, interact with atmospheric CO2. Marine chemical, biological and physical processes that naturally affect ocean CO2 gain and loss thus intimately influence the natural carbon content of the atmosphere. Indeed, ocean chemistry in conjunction with carbonate and silicate mineral weathering is the primary mechanism that naturally moderates and consumes excess atmospheric CO2 on geologic timescales. The ocean is therefore a logical place to explore means of enhancing atmospheric and anthropogenic carbon uptake and/or sequestration in efforts to stabilize or possibly reduce atmospheric CO2 concentrations. Modification of such global processes (often only relatively slightly) forms the basis for many of the ocean-based CO2 mitigation approaches thus far proposed. These include: 1) the storage in or under the ocean of molecular CO2, or organic or inorganic derivatives that have been captured or formed on land; 2) the removal of ocean/atmosphere CO2 via biological uptake enhanced by artificially increased upwelling or nutrient addition; 3) the chemical, geochemical, or electrochemical alkalization of the ocean to increase ocean CO2 uptake with chemical transformation to bicarbonates or carbonates, and subsequent ocean storage; and 4) increased production and

  7. CO2 Sequestration Crosswell Monitoring

    NASA Astrophysics Data System (ADS)

    Morency, C.; Luo, Y.; Tromp, J.

    2010-12-01

    Geologic sequestration of CO2, a green house gas, represents an effort to reduce the large amount of CO2 generated as a by-product of fossil fuels combustion and emitted into the atmosphere. This process of sequestration involves CO2 storage deep underground into highly permeable porous media sealed by caprock. "4D seismics" is a natural non-intrusive monitoring technique which involves 3D time-lapse seismic surveys. The success of monitoring CO2 movement relies upon a proper description of the physics of the problem. We realize time-lapse migrations comparing acoustic, elastic (with or without Gassmann's formulae), and poroelastic simulations of 4D seismic imaging. This approach highlights the influence of using different physical theories on interpreting seismic data, and, more importantly, on extracting the CO2 signature from the seismic wave field. We investigate various types of inversions using (1) P-wave traveltimes, (2) P- & S-wave traveltimes and (3) P- & S-wave traveltimes and amplitudes. Simulations are performed using a spectral-element method, and finite-frequency sensitivity kernels, used in the non-linear iterative inversions, are calculated based on an adjoint method. Biot's equations are implemented in the forward and adjoint simulations to account for poroelastic effects.

  8. ACCURACY OF CO2 SENSORS

    SciTech Connect

    Fisk, William J.; Faulkner, David; Sullivan, Douglas P.

    2008-10-01

    Are the carbon dioxide (CO2) sensors in your demand controlled ventilation systems sufficiently accurate? The data from these sensors are used to automatically modulate minimum rates of outdoor air ventilation. The goal is to keep ventilation rates at or above design requirements while adjusting the ventilation rate with changes in occupancy in order to save energy. Studies of energy savings from demand controlled ventilation and of the relationship of indoor CO2 concentrations with health and work performance provide a strong rationale for use of indoor CO2 data to control minimum ventilation rates1-7. However, this strategy will only be effective if, in practice, the CO2 sensors have a reasonable accuracy. The objective of this study was; therefore, to determine if CO2 sensor performance, in practice, is generally acceptable or problematic. This article provides a summary of study methods and findings ? additional details are available in a paper in the proceedings of the ASHRAE IAQ?2007 Conference8.

  9. Multiple timescales for neutralization of fossil fuel CO2

    NASA Astrophysics Data System (ADS)

    Archer, David; Kheshgi, Haroon; Maier-Reimer, Ernst

    The long term abiological sinks for anthropogenic CO2 will be dissolution in the oceans and chemical neutralization by reaction with carbonates and basic igneous rocks. We use a detailed ocean/sediment carbon cycle model to simulate the response of the carbonate cycle in the ocean to a range of anthropogenic CO2 release scenarios. CaCO3 will play only a secondary role in buffering the CO2 concentration of the atmosphere because CaCO3 reaction uptake capacity and kinetics are limited by the dynamics of the ocean carbon cycle. Dissolution into ocean water sequesters 70-80% of the CO2 release on a time scale of several hundred years. Chemical neutralization of CO2 by reaction with CaCO3 on the sea floor accounts for another 9-15% decrease in the atmospheric concentration on a time scale of 5.5-6.8 kyr. Reaction with CaCO3 on land accounts for another 3-8%, with a time scale of 8.2 kyr. The final equilibrium with CaCO3 leaves 7.5-8% of the CO2 release remaining in the atmosphere. The carbonate chemistry of the oceans in contact with CaCO3 will act to buffer atmospheric CO2 at this higher concentration until the entire fossil fuel CO2 release is consumed by weathering of basic igneous rocks on a time scale of 200 kyr.

  10. Sequestering CO2 in the Ocean: Options and Consequences

    NASA Astrophysics Data System (ADS)

    Rau, G. H.; Caldeira, K.

    2002-12-01

    The likelihood of negative climate and environmental impacts associated with increasing atmospheric CO2 has prompted serious consideration of various CO2 mitigation strategies. Among these are methods of capturing and storing of CO2 in the ocean. Two approaches that have received the most attention in this regard have been i) ocean fertilization to enhanced biological uptake and fixation of CO2, and ii) the chemical/mechanical capture and injection of CO2 into the deep ocean. Both methods seek to enhance or speed up natural mechanisms of CO2 uptake and storage by the ocean, namely i) the biological CO2 "pump" or ii) the passive diffusion of CO2 into the surface ocean and subsequent mixing into the deep sea. However, as will be reviewed, concerns about the capacity and effectiveness of either strategy in long-term CO2 sequestration have been raised. Both methods are not without potentially significant environmental impacts, and the costs of CO2 capture and injection (option ii) are currently prohibitive. An alternate method of ocean CO2 sequestration would be to react and hydrate CO2 rich waste gases (e.g., power plant flue gas) with seawater and to subsequently neutralize the resulting carbonic acid with limestone to produce calcium and bicarbonate ions in solution. This approach would simply speed up the CO2 uptake and sequestration that naturally (but very slowly) occurs via global carbonate weathering. This would avoid much of the increased acidity associated with direct CO2 injection while obviating the need for costly CO2 separation and capture. The addition of the resulting bicarbonate- and carbonate-rich solution to the ocean would help to counter the decrease in pH and carbonate ion concentration, and hence loss of biological calcification that is presently occurring as anthropogenic CO2 invades the ocean from the atmosphere. However, as with any approach to CO2 mitigation, the costs, impacts, risks, and benefits of this method need to be better understood

  11. Update on CO2 emissions

    SciTech Connect

    Friedingstein, P.; Houghton, R.A.; Marland, Gregg; Hackler, J.; Boden, Thomas A; Conway, T.J.; Canadell, J.G.; Raupach, Mike; Ciais, Philippe; Le Quere, Corrine

    2010-12-01

    Emissions of CO2 are the main contributor to anthropogenic climate change. Here we present updated information on their present and near-future estimates. We calculate that global CO2 emissions from fossil fuel burning decreased by 1.3% in 2009 owing to the global financial and economic crisis that started in 2008; this is half the decrease anticipated a year ago1. If economic growth proceeds as expected2, emissions are projected to increase by more than 3% in 2010, approaching the high emissions growth rates that were observed from 2000 to 20081, 3, 4. We estimate that recent CO2 emissions from deforestation and other land-use changes (LUCs) have declined compared with the 1990s, primarily because of reduced rates of deforestation in the tropics5 and a smaller contribution owing to forest regrowth elsewhere.

  12. The CO2nnect activities

    NASA Astrophysics Data System (ADS)

    Eugenia, Marcu

    2014-05-01

    Climate change is one of the biggest challenges we face today. A first step is the understanding the problem, more exactly what is the challenge and the differences people can make. Pupils need a wide competencies to meet the challenges of sustainable development - including climate change. The CO2nnect activities are designed to support learning which can provide pupils the abilities, skills, attitudes and awareness as well as knowledge and understanding of the issues. The project "Together for a clean and healthy world" is part of "The Global Educational Campaign CO2nnect- CO2 on the way to school" and it was held in our school in the period between February and October 2009. It contained a variety of curricular and extra-curricular activities, adapted to students aged from 11 to 15. These activities aimed to develop in students the necessary skills to understanding man's active role in improving the quality of the environment, putting an end to its degrading process and to reducing the effects of climate changes caused by the human intervention in nature, including transport- a source of CO2 pollution. The activity which I propose can be easily adapted to a wide range of age groups and linked to the curricula of many subjects: - Investigate CO2 emissions from travel to school -Share the findings using an international database -Compare and discuss CO2 emissions -Submit questions to a climate- and transport expert -Partner with other schools -Meet with people in your community to discuss emissions from transport Intended learning outcomes for pupils who participate in the CO2nnect campaign are: Understanding of the interconnected mobility- and climate change issue climate change, its causes and consequences greenhouse-gas emissions from transport and mobility the interlinking of social, environmental, cultural and economic aspects of the local transport system how individual choices and participation can contribute to creating a more sustainable development

  13. CO2CRC's Otway Residual Saturation and Dissolution Test: Using Reactive Ester Tracers to Determine Residual CO2 Saturation

    NASA Astrophysics Data System (ADS)

    Myers, M.; Stalker, L.; LaForce, T.; Pejcic, B.; Dyt, C.; Ho, K.; Ennis-King, J.

    2013-12-01

    Residual trapping, that is CO2 held in the rock pore space due to capillarity, is an important storage mechanism in geo-sequestration of over the short to medium term (up to 1000 years). As such residual CO2 saturation is a critical reservoir parameter for assessing the storage capacity and security of carbon capture and storage (CCS). As a component of the CO2CRC's Residual Gas Saturation and Dissolution Test at the CO2CRC Otway Project site in Victoria (Australia), we have recently tested a suite of reactive esters (triacetin, tripropionin and propylene glycol diacetate) in a single well chemical tracer test to determine residual CO2 saturation. The goal of this project was to assess and validate a suite of possible tests that could be implemented to determine residual CO2 saturation. For this test, the chemical tracers were injected with a saturated CO2/water mixture into the formation (that is already at residual CO2 saturation) where they were allowed to 'soak' for approximately 10 days allowing for the partial hydrolysis of the esters to their corresponding carboxylic acids and alcohols. Water containing the tracers was then produced from the well resulting in over 600 tracer samples over a period of 12 hours. A selection of these samples were analysed for tracer content and to establish tracer breakthrough curves. To understand the behaviour of these chemical tracers in the downhole environment containing residually trapped supercritical CO2 and formation water, it is necessary to determine the supercritical CO2/water partition coefficients. We have previously determined these in the laboratory (Myers et al., 2012) and they are used here to model the tracer behaviour and provide an estimate of the residual CO2 saturation. Two different computational simulators were used to analyse the tracer breakthrough profiles. The first is based on simple chromatographic retardation and has been used extensively in single well chemical tracer tests to determine residual

  14. The LHCb VELO upgrade

    NASA Astrophysics Data System (ADS)

    Dosil Suárez, Álvaro

    2016-07-01

    The upgrade of the LHCb experiment, planned for 2019, will transform the experiment to a trigger-less system reading out the full detector at 40 MHz event rate. All data reduction algorithms will be executed in a high-level software farm. The upgraded detector will run at luminosities of 2×1033 cm-2 s-1 and probe physics beyond the Standard Model in the heavy flavour sector with unprecedented precision. The Vertex Locator (VELO) is the silicon vertex detector surrounding the interaction region. The current detector will be replaced with a hybrid pixel system equipped with electronics capable of reading out at 40 MHz. The detector comprises silicon pixel sensors with 55×55 μm2 pitch, read out by the VeloPix ASIC, based on the TimePix/MediPix family. The hottest region will have pixel hit rates of 900 Mhits/s yielding a total data rate more than 3 Tbit/s for the upgraded VELO. The detector modules are located in a separate vacuum, separated from the beam vacuum by a thin custom made foil. The detector halves are retracted when the beams are injected and closed at stable beams, positioning the first sensitive pixel at 5.1 mm from the beams. The material budget will be minimised by the use of evaporative CO2 coolant circulating in microchannels within 400 μm thick silicon substrates.

  15. Reducing cement's CO2 footprint

    USGS Publications Warehouse

    van Oss, Hendrik G.

    2011-01-01

    The manufacturing process for Portland cement causes high levels of greenhouse gas emissions. However, environmental impacts can be reduced by using more energy-efficient kilns and replacing fossil energy with alternative fuels. Although carbon capture and new cements with less CO2 emission are still in the experimental phase, all these innovations can help develop a cleaner cement industry.

  16. Efficient electrochemical CO2 conversion powered by renewable energy.

    PubMed

    Kauffman, Douglas R; Thakkar, Jay; Siva, Rajan; Matranga, Christopher; Ohodnicki, Paul R; Zeng, Chenjie; Jin, Rongchao

    2015-07-22

    The catalytic conversion of CO2 into industrially relevant chemicals is one strategy for mitigating greenhouse gas emissions. Along these lines, electrochemical CO2 conversion technologies are attractive because they can operate with high reaction rates at ambient conditions. However, electrochemical systems require electricity, and CO2 conversion processes must integrate with carbon-free, renewable-energy sources to be viable on larger scales. We utilize Au25 nanoclusters as renewably powered CO2 conversion electrocatalysts with CO2 → CO reaction rates between 400 and 800 L of CO2 per gram of catalytic metal per hour and product selectivities between 80 and 95%. These performance metrics correspond to conversion rates approaching 0.8-1.6 kg of CO2 per gram of catalytic metal per hour. We also present data showing CO2 conversion rates and product selectivity strongly depend on catalyst loading. Optimized systems demonstrate stable operation and reaction turnover numbers (TONs) approaching 6 × 10(6) molCO2 molcatalyst(-1) during a multiday (36 h total hours) CO2 electrolysis experiment containing multiple start/stop cycles. TONs between 1 × 10(6) and 4 × 10(6) molCO2 molcatalyst(-1) were obtained when our system was powered by consumer-grade renewable-energy sources. Daytime photovoltaic-powered CO2 conversion was demonstrated for 12 h and we mimicked low-light or nighttime operation for 24 h with a solar-rechargeable battery. This proof-of-principle study provides some of the initial performance data necessary for assessing the scalability and technical viability of electrochemical CO2 conversion technologies. Specifically, we show the following: (1) all electrochemical CO2 conversion systems will produce a net increase in CO2 emissions if they do not integrate with renewable-energy sources, (2) catalyst loading vs activity trends can be used to tune process rates and product distributions, and (3) state-of-the-art renewable-energy technologies are sufficient

  17. Efficient electrochemical CO2 conversion powered by renewable energy

    DOE PAGES

    Kauffman, Douglas R.; Thakkar, Jay; Siva, Rajan; Matranga, Christopher; Ohodnicki, Paul R.; Zeng, Chenjie; Jin, Rongchao

    2015-06-29

    Here, the catalytic conversion of CO2 into industrially relevant chemicals is one strategy for mitigating greenhouse gas emissions. Along these lines, electrochemical CO2 conversion technologies are attractive because they can operate with high reaction rates at ambient conditions. However, electrochemical systems require electricity, and CO2 conversion processes must integrate with carbon-free, renewable-energy sources to be viable on larger scales. We utilize Au25 nanoclusters as renewably powered CO2 conversion electrocatalysts with CO2 → CO reaction rates between 400 and 800 L of CO2 per gram of catalytic metal per hour and product selectivities between 80 and 95%. These performance metrics correspondmore » to conversion rates approaching 0.8–1.6 kg of CO2 per gram of catalytic metal per hour. We also present data showing CO2 conversion rates and product selectivity strongly depend on catalyst loading. Optimized systems demonstrate stable operation and reaction turnover numbers (TONs) approaching 6 × 106 mol CO2 molcatalyst–1 during a multiday (36 hours total hours) CO2electrolysis experiment containing multiple start/stop cycles. TONs between 1 × 106 and 4 × 106 molCO2 molcatalyst–1 were obtained when our system was powered by consumer-grade renewable-energy sources. Daytime photovoltaic-powered CO2 conversion was demonstrated for 12 h and we mimicked low-light or nighttime operation for 24 h with a solar-rechargeable battery. This proof-of-principle study provides some of the initial performance data necessary for assessing the scalability and technical viability of electrochemical CO2 conversion technologies. Specifically, we show the following: (1) all electrochemical CO2 conversion systems will produce a net increase in CO2 emissions if they do not integrate with renewable-energy sources, (2) catalyst loading vs activity trends can be used to tune process rates and product distributions, and (3) state-of-the-art renewable-energy technologies

  18. Sedimentary reservoir oxidation during geologic CO2 sequestration

    NASA Astrophysics Data System (ADS)

    Lammers, Laura N.; Brown, Gordon E.; Bird, Dennis K.; Thomas, Randal B.; Johnson, Natalie C.; Rosenbauer, Robert J.; Maher, Katharine

    2015-04-01

    Injection of carbon dioxide into subsurface geologic reservoirs during geologic carbon sequestration (GCS) introduces an oxidizing supercritical CO2 phase into a subsurface geologic environment that is typically reducing. The resulting redox disequilibrium provides the chemical potential for the reduction of CO2 to lower free energy organic species. However, redox reactions involving carbon typically require the presence of a catalyst. Iron oxide minerals, including magnetite, are known to catalyze oxidation and reduction reactions of C-bearing species. If the redox conditions in the reservoir are modified by redox transformations involving CO2, such changes could also affect mineral stability, leading to dissolution and precipitation reactions and alteration of the long-term fate of CO2 in GCS reservoirs. We present experimental evidence that reservoirs with reducing redox conditions are favorable environments for the relatively rapid abiotic reduction of CO2 to organic molecules. In these experiments, an aqueous suspension of magnetite nanoparticles was reacted with supercritical CO2 under pressure and temperature conditions relevant to GCS in sedimentary reservoirs (95-210 °C and ∼100 bars of CO2). Hydrogen production was observed in several experiments, likely caused by Fe(II) oxidation either at the surface of magnetite or in the aqueous phase. Heating of the Fe(II)-rich system resulted in elevated PH2 and conditions favorable for the reduction of CO2 to acetic acid. Implications of these results for the long-term fate of CO2 in field-scale systems were explored using reaction path modeling of CO2 injection into reservoirs containing Fe(II)-bearing primary silicate minerals, with kinetic parameters for CO2 reduction obtained experimentally. The results of these calculations suggest that the reaction of CO2 with reservoir constituents will occur in two primary stages (1) equilibration of CO2 with organic acids resulting in mineral-fluid disequilibrium, and

  19. Is guava phenolic metabolism influenced by elevated atmospheric CO2?

    PubMed

    Mendes de Rezende, Fernanda; Pereira de Souza, Amanda; Silveira Buckeridge, Marcos; Maria Furlan, Cláudia

    2015-01-01

    Seedlings of Psidium guajava cv. Pedro Sato were distributed into four open-top chambers: two with ambient CO(2) (∼390 ppm) and two with elevated CO(2) (∼780 ppm). Monthly, five individuals of each chamber were collected, separated into root, stem and leaves and immediately frozen in liquid nitrogen. Chemical parameters were analyzed to investigate how guava invests the surplus carbon. For all classes of phenolic compounds analyzed only tannins showed significant increase in plants at elevated CO(2) after 90 days. There was no significant difference in dry biomass, but the leaves showed high accumulation of starch under elevated CO(2). Results suggest that elevated CO(2) seems to be favorable to seedlings of P. guajava, due to accumulation of starch and tannins, the latter being an important anti-herbivore substance. PMID:25129845

  20. Is guava phenolic metabolism influenced by elevated atmospheric CO2?

    PubMed

    Mendes de Rezende, Fernanda; Pereira de Souza, Amanda; Silveira Buckeridge, Marcos; Maria Furlan, Cláudia

    2015-01-01

    Seedlings of Psidium guajava cv. Pedro Sato were distributed into four open-top chambers: two with ambient CO(2) (∼390 ppm) and two with elevated CO(2) (∼780 ppm). Monthly, five individuals of each chamber were collected, separated into root, stem and leaves and immediately frozen in liquid nitrogen. Chemical parameters were analyzed to investigate how guava invests the surplus carbon. For all classes of phenolic compounds analyzed only tannins showed significant increase in plants at elevated CO(2) after 90 days. There was no significant difference in dry biomass, but the leaves showed high accumulation of starch under elevated CO(2). Results suggest that elevated CO(2) seems to be favorable to seedlings of P. guajava, due to accumulation of starch and tannins, the latter being an important anti-herbivore substance.

  1. Excitation of CO2/+/ by electron impact on CO2

    NASA Technical Reports Server (NTRS)

    Mentall, J. E.; Coplan, M. A.; Kushlis, R. J.

    1973-01-01

    Consideration of a discrepancy concerning the correct value of the cross section for excitation of the CO2(+) B state by electron impact on CO2. It is suggested that the reason for the disparate results obtained by various authors for the B state can be traced to a calibration error due to scattered light. In particular, the tungsten filament lamps used in the experiments cited have very low intensity at wavelengths below 3000 A where the B state emissions occur, so that even a small amount of scattered light in the spectrometer will produce a large error in the measured cross section. In a remeasurement of the cross section for excitation of the B state at an energy of 150 eV it was found that at 2900 A the scattered light signal, if uncorrected for, would introduce an error of about 50%.

  2. Distribution and nature of CO2 on Enceladus

    NASA Astrophysics Data System (ADS)

    Combe, J. P.; McCord, T. B.; Matson, D.; Johnson, T. V.; Scipioni, F.; Tosi, F.

    2015-12-01

    We present the first global mapping and analysis of CO2 on the surface of Enceladus, and we report the largest concentrations of free CO2 on the southern polar region using the Visual and Infrared Mapping Spectrometer (VIMS) on Cassini. Free CO2 ice and complexed CO2 were already reported near the South Pole (Brown et al., Science, 2006; Hansen, LPSC, 2010). Our work focuses on determining the amount, location and molecular state of CO2 on Enceladus, which could help identify and model geophysical processes that currently occur in the interior. One hypothesis for bringing heat and chemicals to the surface is a warm subsurface ocean containing dissolved gases, mostly CO2 (Postberg F. et al., Nature, 2009). Therefore, our observations are consistent with erupted and condensed materials onto Enceladus' surface (Matson et al., Icarus, 2012; Matson et al. AGU Fall meeting 2015). Free CO2 ice absorbs at 4.268 µm (Sandford and Allamandola, 1990) and CO2 complexed with other molecules absorbs at 4.247 μm (Chaban et al., Icarus, 2007). The Enceladus case is complicated because both free and complexed CO2 are present, and the absorption band of interest is shallow and close to the instrument detection limit. Many of the few Enceladus VIMS data sets have significant and sometimes unusual noise, which we attempted to avoid or remove. We utilized all VIMS data sets available that were collected over ten years of the Cassini mission as a way to improve the detection statistics and signal to noise. We also used wavelengths near 2.7 μm where CO2 has a narrow absorption as a filter to help identify CO2-rich areas. Finally, we selected observations that have spatial resolution better than 100 km in order to create a map that can be compared with the largest fractures, known as Tiger Stripes, in the southern polar region.

  3. Wavelength measurement of tunable TEA CO2 laser

    NASA Astrophysics Data System (ADS)

    Qu, Yanchen; Ren, Deming; Hu, Xiaoyong; Liu, Fengmei; Zhang, Lili; Chen, Chunyu

    2005-01-01

    Due to their interesting physical and chemical parameters, tunable transversely excited atmospheric-pressure(TEA) CO2 lasers are widely utilized in scientific and industrial applications. The CO2 differential absorption lidar (DIAL) is an effective tool for remote measurement of pollutant gaseous concentration of the atmosphere over large areas. Many pollutant gases have strong absorption lines within the spectral range of CO2 laser wavelength tuning. In addition, the radiation of CO2 laser is well distributed in the atmosphere, coinciding with the "transparency window" of the atmosphere. Therefore the wavelength tunable TEA CO2 laser is an ideal optical source for DIAL. Most existing instruments for measuring the laser wavelength are only suitable for the measurement of continuous wave and stable frequency output. With the attempt of measuring the wavelength of pulsed TEA CO2 laser, an experimental setup is established which consists of two main portions, namely auto-scanning grating monochromator as the color dispersion system and Boxcar integrator. In the experiment of tuning TEA CO2 laser, the wavelength of CO2 laser is observed and measured by means of integrating method. The accuracy of measurement in the mid-infrared region attains 1nm.

  4. CO2/Brine transport into shallow aquifers along fault zones.

    PubMed

    Keating, Elizabeth H; Newell, Dennis L; Viswanathan, Hari; Carey, J W; Zyvoloski, G; Pawar, Rajesh

    2013-01-01

    Unintended release of CO(2) from carbon sequestration reservoirs poses a well-recognized risk to groundwater quality. Research has largely focused on in situ CO(2)-induced pH depression and subsequent trace metal mobilization. In this paper we focus on a second mechanism: upward intrusion of displaced brine or brackish-water into a shallow aquifer as a result of CO(2) injection. Studies of two natural analog sites provide insights into physical and chemical mechanisms controlling both brackish water and CO(2) intrusion into shallow aquifers along fault zones. At the Chimayó, New Mexico site, shallow groundwater near the fault is enriched in CO(2) and, in some places, salinity is significantly elevated. In contrast, at the Springerville, Arizona site CO(2) is leaking upward through brine aquifers but does not appear to be increasing salinity in the shallow aquifer. Using multiphase transport simulations we show conditions under which significant CO(2) can be transported through deep brine aquifers into shallow layers. Only a subset of these conditions favor entrainment of salinity into the shallow aquifer: high aspect-ratio leakage pathways and viscous coupling between the fluid phases. Recognition of the conditions under which salinity is favored to be cotransported with CO(2) into shallow aquifers will be important in environmental risk assessments. PMID:22799449

  5. CO2 Acquisition Membrane (CAM)

    NASA Technical Reports Server (NTRS)

    Mason, Larry W.; Way, J. Douglas; Vlasse, Marcus

    2003-01-01

    The objective of CAM is to develop, test, and analyze thin film membrane materials for separation and purification of carbon dioxide (CO2) from mixtures of gases, such as those found in the Martian atmosphere. The membranes are targeted toward In Situ Resource Utilization (ISRU) applications that will operate in extraterrestrial environments and support future unmanned and human space missions. A primary application is the Sabatier Electrolysis process that uses Mars atmosphere CO2 as raw material for producing water, oxygen, and methane for rocket fuel and habitat support. Other applications include use as an inlet filter to collect and concentrate Mars atmospheric argon and nitrogen gases for habitat pressurization, and to remove CO2 from breathing gases in Closed Environment Life Support Systems (CELSS). CAM membrane materials include crystalline faujasite (FAU) zeolite and rubbery polymers such as silicone rubber (PDMS) that have been shown in the literature and via molecular simulation to favor adsorption and permeation of CO2 over nitrogen and argon. Pure gas permeation tests using commercial PDMS membranes have shown that both CO2 permeance and the separation factor relative to other gases increase as the temperature decreases, and low (Delta)P(Sub CO2) favors higher separation factors. The ideal CO2/N2 separation factor increases from 7.5 to 17.5 as temperature decreases from 22 C to -30 C. For gas mixtures containing CO2, N2, and Ar, plasticization decreased the separation factors from 4.5 to 6 over the same temperature range. We currently synthesize and test our own Na(+) FAU zeolite membranes using standard formulations and secondary growth methods on porous alumina. Preliminary tests with a Na(+) FAU membrane at 22 C show a He/SF6 ideal separation factor of 62, exceeding the Knudsen diffusion selectivity by an order of magnitude. This shows that the membrane is relatively free from large defects and associated non-selective (viscous flow) transport

  6. Reducing CO2 from shipping - do non-CO2 effects matter?

    NASA Astrophysics Data System (ADS)

    Eide, M. S.; Dalsøren, S. B.; Endresen, Ø.; Samset, B.; Myhre, G.; Fuglestvedt, J.; Berntsen, T.

    2013-04-01

    Shipping is a growing sector in the global economy, and it contributions to global CO2 emissions are expected to increase. CO2 emissions from the world shipping fleet will likely be regulated in the near future, and studies have shown that significant emission reductions can be achieved at low cost. Regulations are being discussed for both existing ships as well as for future additions to the fleet. In this study a plausible CO2 emission reduction inventory is constructed for the cargo fleet existing in 2010, as well as for container ships, bulk ships and tankers separately. In the reduction inventories, CO2 emissions are reduced by 25-32% relative to baseline by applying 15 technical and operational emission reduction measures in accordance with a ship-type-specific cost-effectiveness criterion, and 9 other emission compounds are changed as a technical implication of reducing CO2. The overall climate and environmental effects of the changes to all 10 emission components in the reduction inventory are assessed using a chemical transport model, radiative forcing (RF) models and a simple climate model. We find substantial environmental and health benefits with up to 5% reduction in surface ozone levels, 15% reductions in surface sulfate and 10% reductions in wet deposition of sulfate in certain regions exposed to heavy ship traffic. The major ship types show distinctly different contributions in specific locations. For instance, the container fleet contributes 50% of the sulfate decline on the west coast of North America. The global radiative forcing from a 1 yr emission equal to the difference between baseline and reduction inventory shows an initial strong positive forcing from non-CO2 compounds. This warming effect is due to reduced cooling by aerosols and methane. After approximately 25 yr, the non-CO2 forcing is balanced by the CO2 forcing. For the global mean temperature change, we find a shift from warming to cooling after approximately 60 yr. The major ship

  7. Isotopic disequilibrium during uptake of atmospheric CO2 into mine process waters: implications for CO2 sequestration.

    PubMed

    Wilson, Siobhan A; Barker, Shaun L L; Dipple, Gregory M; Atudorei, Viorel

    2010-12-15

    Dypingite, a hydrated Mg-carbonate mineral, was precipitated from high-pH, high salinity solutions to investigate controls on carbon fixation and to identify the isotopic characteristics of mineral sequestration in mine tailings. δ(13)C values of dissolved inorganic carbon content and synthetic dypingite are significantly more negative than those predicted for equilibrium exchange of CO(2) gas between the atmosphere and solution. The measured δ(13)C of aqueous carbonate species is consistent with a kinetic fractionation that results from a slow diffusion of atmospheric CO(2) into solution. During dypingite precipitation, dissolved inorganic carbon concentrations decrease and δ(13)C values become more negative, indicating that the rate of CO(2) uptake into solution was outpaced by the rate of carbon fixation within the precipitate. This implies that CO(2) gas uptake is rate-limiting to CO(2) fixation. δ(13)C of carbonate mineral precipitates in mine tailings and of DIC in mine process waters display similar (13)C-depletions that are inconsistent with equilibrium fractionation. Thus, the rate of carbon fixation in mine tailings may also be limited by supply of CO(2). Carbon sequestration could be accelerated by increasing the partial pressure of CO(2) in tailings ponds or by using chemicals that enhance the uptake of gaseous CO(2) into aqueous solution.

  8. Intercomparison of two cavity ring-down spectroscopy analyzers for atmospheric 13CO2 / 12CO2 measurement

    NASA Astrophysics Data System (ADS)

    Pang, Jiaping; Wen, Xuefa; Sun, Xiaomin; Huang, Kuan

    2016-08-01

    Isotope ratio infrared spectroscopy (IRIS) permits continuous in situ measurement of CO2 isotopic composition under ambient conditions. Previous studies have mainly focused on single IRIS instrument performance; few studies have considered the comparability among different IRIS instruments. In this study, we carried out laboratory and ambient measurements using two Picarro CO2δ13C analyzers (G1101-i and G2201-i (newer version)) and evaluated their performance and comparability. The best precision was 0.08-0.15 ‰ for G1101-i and 0.01-0.04 ‰ for G2201-i. The dependence of δ13C on CO2 concentration was 0.46 ‰ per 100 ppm and 0.09 ‰ per 100 ppm, the instrument drift ranged from 0.92-1.09 ‰ and 0.19-0.37 ‰, and the sensitivity of δ13C to the water vapor mixing ratio was 1.01 ‰ / % H2O and 0.09 ‰ / % H2O for G1101-i and G2201-i, respectively. The accuracy after correction by the two-point mixing ratio gain and offset calibration method ranged from -0.04-0.09 ‰ for G1101-i and -0.13-0.03 ‰ for G2201-i. The sensitivity of δ13C to the water vapor mixing ratio improved from 1.01 ‰ / % H2O before the upgrade of G1101-i (G1101-i-original) to 0.15 ‰ / % H2O after the upgrade of G1101-i (G1101-i-upgraded). Atmospheric δ13C measured by G1101-i and G2201-i captured the rapid changes in atmospheric δ13C signals on hourly to diurnal cycle scales, with a difference of 0.07 ± 0.24 ‰ between G1101-i-original and G2201-i and 0.05 ± 0.30 ‰ between G1101-i-upgraded and G2201-i. A significant linear correlation was observed between the δ13C difference of G1101-i-original and G2201-i and the water vapor concentration, but there was no significant correlation between the δ13C difference of G1101-i-upgraded and G2201-i and the water vapor concentration. The difference in the Keeling intercept values decreased from 1.24 ‰ between G1101-i-original and G2201-i to 0.36 ‰ between G1101-i-upgraded and G2201-i, which indicates the importance of consistency

  9. Estimation of continuous anthropogenic CO2 using CO2, CO, δ13C(CO2) and Δ14C(CO2)

    NASA Astrophysics Data System (ADS)

    Vardag, S. N.; Gerbig, C.; Janssens-Maenhout, G.; Levin, I.

    2015-07-01

    We investigate different methods for estimating anthropogenic CO2 using modelled continuous atmospheric concentrations of CO2 alone, as well as CO2 in combination with the surrogate tracers CO, δ13C(CO2) and Δ14C(CO2). These methods are applied at three hypothetical stations representing rural, urban and polluted conditions. We find that independent of the tracer used, an observation-based estimate of continuous anthropogenic CO2 is not feasible at rural measurement sites due to the low signal to noise ratio of anthropogenic CO2 estimates at such settings. At urban and polluted sites, potential future continuous Δ14C(CO2) measurements with a precision of 5 ‰ or better are most promising for anthropogenic CO2 determination (precision ca. 10-20%), but the insensitivity against CO2 contributions from biofuel emissions may reduce its accuracy in the future. Other tracers, such as δ13C(CO2) and CO could provide an accurate and already available alternative if all CO2 sources in the catchment area are well characterized with respect to their isotopic signature and CO to anthropogenic CO2 ratio. We suggest a strategy for calibrating these source characteristics on an annual basis using precise Δ14C(CO2) measurements on grab samples. The precision of anthropogenic CO2 determination using δ13C(CO2) is largely determined by the measurement precision of δ13C(CO2) and CO2. The precision when using the CO-method is mainly limited by the variation of natural CO sources and CO sinks. At present, continuous anthropogenic CO2 could be determined using the tracers δ13C(CO2) and/or CO with a precision of about 30 %, a mean bias of about 10 % and without significant diurnal discrepancies. This allows significant improvement, validation and bias reduction of highly resolved emission inventories using atmospheric observation and regional modelling.

  10. Technological advances in CO2 conversion electro-biorefinery: A step toward commercialization.

    PubMed

    ElMekawy, Ahmed; Hegab, Hanaa M; Mohanakrishna, Gunda; Elbaz, Ashraf F; Bulut, Metin; Pant, Deepak

    2016-09-01

    The global atmospheric warming due to increased emissions of carbon dioxide (CO2) has attracted great attention in the last two decades. Although different CO2 capture and storage platforms have been proposed, the utilization of captured CO2 from industrial plants is progressively prevalent strategy due to concerns about the safety of terrestrial and aquatic CO2 storage. Two utilization forms were proposed, direct utilization of CO2 and conversion of CO2 to chemicals and energy products. The latter strategy includes the bioelectrochemical techniques in which electricity can be used as an energy source for the microbial catalytic production of fuels and other organic products from CO2. This approach is a potential technique in which CO2 emissions are not only reduced, but it also produce more value-added products. This review article highlights the different methodologies for the bioelectrochemical utilization of CO2, with distinctive focus on the potential opportunities for the commercialization of these techniques.

  11. Synthesis, characterization and application of alkanolamidines and alkanolguanidines in CO(2) capture

    SciTech Connect

    Koech, Phillip K; Heldebrant, David J; Lee, Suh-Jane; Rainbolt, James E; Smurthwaite, Tricia D

    2011-03-01

    Global carbon dioxide (CO2) emission to the atmosphere is partly responsible for climate change. In order to mitigate these environmental effects CO2 capture and storage is required. Solvents currently used for this application are the energy intensive aqueous amines. Here we present the synthesis, characterization and CO2 uptake of new advanced solvents called alkanolamidines and alkanolguanidines otherwise known as CO2-binding organic Liquids (CO2BOLs). These solvents have been designed to have decreased vapor pressure and low viscosity in order to increase the CO2 uptake capacity while minimizing evaporative losses. Alkanolamidines were synthesized in 1-3 steps from commercially available materials. These compounds bind CO2 chemically via the alcohol moiety forming zwitterionic alkylcarbonates. The alkanolamidines can be regenerated thermally by heating the alkylcarbonate to 75 °C. CO2 binding capacities up to 10 wt% were achieved using these compounds. These compounds have the potential to be energy efficient CO2 capture solvents.

  12. Technological advances in CO2 conversion electro-biorefinery: A step toward commercialization.

    PubMed

    ElMekawy, Ahmed; Hegab, Hanaa M; Mohanakrishna, Gunda; Elbaz, Ashraf F; Bulut, Metin; Pant, Deepak

    2016-09-01

    The global atmospheric warming due to increased emissions of carbon dioxide (CO2) has attracted great attention in the last two decades. Although different CO2 capture and storage platforms have been proposed, the utilization of captured CO2 from industrial plants is progressively prevalent strategy due to concerns about the safety of terrestrial and aquatic CO2 storage. Two utilization forms were proposed, direct utilization of CO2 and conversion of CO2 to chemicals and energy products. The latter strategy includes the bioelectrochemical techniques in which electricity can be used as an energy source for the microbial catalytic production of fuels and other organic products from CO2. This approach is a potential technique in which CO2 emissions are not only reduced, but it also produce more value-added products. This review article highlights the different methodologies for the bioelectrochemical utilization of CO2, with distinctive focus on the potential opportunities for the commercialization of these techniques. PMID:27020396

  13. Surface Condensation of CO2 onto Kaolinite

    SciTech Connect

    Schaef, Herbert T.; Glezakou, Vassiliki Alexandra; Owen, Antionette T.; Ramprasad, Sudhir; Martin, Paul F.; McGrail, B. Peter

    2014-02-11

    The fundamental adsorption behavior of gaseous and supercritical carbon dioxide (CO2) onto poorly crystalline kaolinite (KGa-2) at conditions relevant to geologic sequestration has been investigated using a quartz crystal microbalance (QCM) and density functional theory (DFT) methods. The QCM data indicated linear adsorption of CO2 (0-0.3 mmol CO2/g KGa-2) onto the kaolinite surface up through the gaseous state (0.186 g/cm3). However in the supercritical region, CO2 adsorption increases dramatically, reaching a peak (0.9-1.0 mmol CO2/g KGa-2) near 0.43 g/cm3, before declining rapidly to surface adsorption values equivalent or below gaseous CO2. This adsorption profile was not observed with He or N2. Comparative density functional studies of CO2 interactions with kaolinite surface models rule out CO2 intercalation and confirm that surface adsorption is favored up to approximately 0.35 g/cm3 of CO2, showing distorted T-shaped CO2-CO2 clustering, typical of supercritical CO2 aggregation over the surface as the density increases. Beyond this point, the adsorption energy gain for any additional CO2 becomes less than the CO2 interaction energy (~0.2 eV) in the supercritical medium resulting in overall desorption of CO2 from the kaolinite surface.

  14. Molecular Dynamics Simulations of CO2/Water/Quartz Interfacial Properties: Impact of CO2 Dissolution in Water.

    PubMed

    Javanbakht, Gina; Sedghi, Mohammad; Welch, William; Goual, Lamia

    2015-06-01

    The safe trapping of carbon dioxide (CO2) in deep saline aquifers is one of the major concerns of CO2 sequestration. The amount of capillary trapping is dominated by the capillary pressure of water and CO2 inside the reservoir, which in turn is controlled by the interfacial tension (IFT) and the contact angle (CA) of CO2/water/rock systems. The measurement of IFT and CA could be very challenging at reservoir conditions, especially in the presence of toxic cocontaminants. Thus, the ability to accurately predict these interfacial properties at reservoir conditions is very advantageous. Although the majority of existing molecular dynamics (MD) studies of CO2/water/mineral systems were able to capture the trends in IFT and CA variations with pressure and temperature, their predictions often deviated from experimental data, possibly due to erroneous models and/or overlooked chemical reactions. The objective of this study was to improve the MD predictions of IFT and CA of CO2/water/quartz systems at various pressure and temperature conditions by (i) considering the chemical reactions between CO2 and water and (ii) using a new molecular model for α-quartz surface. The results showed that the presence of carbonic acid at the CO2/water interface improved the predictions of IFT, especially at low temperature and high pressure where more CO2 dissolution occurs. On the other hand, the effect on CA was minor. The slight decrease in CA observed across the pressure range investigated could be attributed to an increase in the total number of H-bonds between fluid molecules and quartz surface.

  15. Environmental potential of the use of CO2 from alcoholic fermentation processes. The CO2-AFP strategy.

    PubMed

    Alonso-Moreno, Carlos; García-Yuste, Santiago

    2016-10-15

    A novel Carbon Dioxide Utilization (CDU) approach from a relatively minor CO2 emission source, i.e., alcoholic fermentation processes (AFP), is presented. The CO2 produced as a by-product from the AFP is estimated by examining the EtOH consumed per year reported by the World Health Organization in 2014. It is proposed that the extremely pure CO2 from the AFP is captured in NaOH solutions to produce one of the Top 10 commodities in the chemical industry, Na2CO3, as a good example of an atomic economy process. The novel CDU strategy could yield over 30.6Mt of Na2CO3 in oversaturated aqueous solution on using ca. 12.7Mt of captured CO2 and this process would consume less energy than the synthetic methodology (Solvay ammonia soda process) and would not produce low-value by-products. The quantity of Na2CO3 obtained by this strategy could represent ca. 50% of the world Na2CO3 production in one year. In terms of the green economy, the viability of the strategy is discussed according to the recommendations of the CO2Chem network, and an estimation of the CO2negative emission achieved suggests a capture of around 280.0Mt of CO2 from now to 2020 or ca. 1.9Gt from now to 2050. Finally, the results obtained for this new CDU proposal are discussed by considering different scenarios; the CO2 production in a typical winemaking corporation, the CO2 released in the most relevant wine-producing countries, and the use of CO2 from AFP as an alternative for the top Na2CO3-producing countries. PMID:27300565

  16. Environmental potential of the use of CO2 from alcoholic fermentation processes. The CO2-AFP strategy.

    PubMed

    Alonso-Moreno, Carlos; García-Yuste, Santiago

    2016-10-15

    A novel Carbon Dioxide Utilization (CDU) approach from a relatively minor CO2 emission source, i.e., alcoholic fermentation processes (AFP), is presented. The CO2 produced as a by-product from the AFP is estimated by examining the EtOH consumed per year reported by the World Health Organization in 2014. It is proposed that the extremely pure CO2 from the AFP is captured in NaOH solutions to produce one of the Top 10 commodities in the chemical industry, Na2CO3, as a good example of an atomic economy process. The novel CDU strategy could yield over 30.6Mt of Na2CO3 in oversaturated aqueous solution on using ca. 12.7Mt of captured CO2 and this process would consume less energy than the synthetic methodology (Solvay ammonia soda process) and would not produce low-value by-products. The quantity of Na2CO3 obtained by this strategy could represent ca. 50% of the world Na2CO3 production in one year. In terms of the green economy, the viability of the strategy is discussed according to the recommendations of the CO2Chem network, and an estimation of the CO2negative emission achieved suggests a capture of around 280.0Mt of CO2 from now to 2020 or ca. 1.9Gt from now to 2050. Finally, the results obtained for this new CDU proposal are discussed by considering different scenarios; the CO2 production in a typical winemaking corporation, the CO2 released in the most relevant wine-producing countries, and the use of CO2 from AFP as an alternative for the top Na2CO3-producing countries.

  17. Reaction of CO2 and Carbonate Mineral in Seawater for Mitigation of CO2 and Ocean Acidity

    NASA Astrophysics Data System (ADS)

    Rau, G. H.

    2010-12-01

    A lab-scale seawater/mineral carbonate gas scrubber was found to remove up to 97% of CO2 in a simulated flue gas stream at ambient temperature and pressure, with a large fraction of this carbon ultimately converted to dissolved calcium bicarbonate. Contrary to predictions based on classical carbonate chemistry, up to 85% of the captured carbon was retained in solution, i.e., it did not degas or precipitate, even after full equilibration with air. This is because abiotic precipitation of CaCO3 from seawater is chemically inhibited up to dissolved concentrations approaching 20X supersaturation. Thus, above-ground CO2 hydration with seawater, reaction with mineral carbonate, and conversion to dissolved Ca(HCO3)2 may provide a relatively simple point-source CO2 capture and storage scheme at coastal locations. This approach is analogous to wet limestone scrubbing of flue gas that is commonly used for SO2 removal. Such low-tech CO2 mitigation could be especially relevant for retrofitting to existing coastal power plants and for deployment in the developing world, the primary source of future CO2 emissions. An electrochemically powered version of the preceding has been demonstrated for air capture of CO2. In any case, the addition of the resulting alkaline solution to the ocean would benefit marine ecosystems that are currently challenged by acidification. This is indicated by the widespread use of miniature CO2/carbonate mineral/seawater reactors in saltwater aquaria to generate alkalinity for preserving or enhancing coral and shellfish growth. Large-scale applications would thus allow use of the planet’s largest saline reservoir, the ocean, to safely and effectively store anthropogenic carbon in a form other than molecular CO2 or carbonic acid. This approach in essence hastens Nature's own very effective but slow CO2 mitigation process; carbonate mineral weathering is a major consumer of excess atmospheric CO2 and ocean acidity on geologic times scales.

  18. Sorption enhanced CO2 methanation.

    PubMed

    Borgschulte, Andreas; Gallandat, Noris; Probst, Benjamin; Suter, Riccardo; Callini, Elsa; Ferri, Davide; Arroyo, Yadira; Erni, Rolf; Geerlings, Hans; Züttel, Andreas

    2013-06-28

    The transformation from the fatuous consumption of fossil energy towards a sustainable energy circle is most easily marketable by not changing the underlying energy carrier but generating it from renewable energy. Hydrocarbons can be principally produced from renewable hydrogen and carbon dioxide collected by biomass. However, research is needed to increase the energetic and economic efficiency of the process. We demonstrate the enhancement of CO2 methanation by sorption enhanced catalysis. The preparation and catalytic activity of sorption catalysts based on Ni particles in zeolites is reported. The functioning of the sorption catalysis is discussed together with the determination of the reaction mechanism, providing implications for new ways in catalysis. PMID:23673365

  19. Isentropic transport and the seasonal cycle amplitude of CO2

    NASA Astrophysics Data System (ADS)

    Barnes, Elizabeth A.; Parazoo, Nicholas; Orbe, Clara; Denning, A. Scott

    2016-07-01

    Carbon-concentration feedbacks and carbon-climate feedbacks constitute one of the largest sources of uncertainty in future climate. Since the beginning of the modern atmospheric CO2 record, seasonal variations in CO2 have been recognized as a signal of the metabolism of land ecosystems, and quantitative attribution of changes in the seasonal cycle amplitude (SCA) of CO2 to ecosystem processes is critical for understanding and projecting carbon-climate feedbacks far into the 21st Century. Here the impact of surface carbon fluxes on the SCA of CO2 throughout the Northern Hemisphere troposphere is investigated, paying particular attention to isentropic transport across latitudes. The analysis includes both a chemical transport model GOES-Chem and an idealized tracer in a gray-radiation aquaplanet. The results of the study can be summarized by two main conclusions: (1) the SCA of CO2 roughly follows surfaces of constant potential temperature, which can explain the observed increase in SCA with latitude along pressure surfaces and (2) increasing seasonal fluxes in lower latitudes have a larger impact on the SCA of CO2 throughout most of the troposphere compared to increasing seasonal fluxes in higher latitudes. These results provide strong evidence that recently observed changes in the SCA of CO2 at high northern latitudes (poleward of 60°N) are likely driven by changes in midlatitude surface fluxes, rather than changes in Arctic fluxes.

  20. The Nanoscale Basis of CO2 Trapping for Geologic Storage.

    PubMed

    Bourg, Ian C; Beckingham, Lauren E; DePaolo, Donald J

    2015-09-01

    Carbon capture and storage (CCS) is likely to be a critical technology to achieve large reductions in global carbon emissions over the next century. Research on the subsurface storage of CO2 is aimed at reducing uncertainties in the efficacy of CO2 storage in sedimentary rock formations. Three key parameters that have a nanoscale basis and that contribute uncertainty to predictions of CO2 trapping are the vertical permeability kv of seals, the residual CO2 saturation Sg,r in reservoir rocks, and the reactive surface area ar of silicate minerals. This review summarizes recent progress and identifies outstanding research needs in these areas. Available data suggest that the permeability of shale and mudstone seals is heavily dependent on clay fraction and can be extremely low even in the presence of fractures. Investigations of residual CO2 trapping indicate that CO2-induced alteration in the wettability of mineral surfaces may significantly influence Sg,r. Ultimately, the rate and extent of CO2 conversion to mineral phases are uncertain due to a poor understanding of the kinetics of slow reactions between minerals and fluids. Rapidly improving characterization techniques using X-rays and neutrons, and computing capability for simulating chemical interactions, provide promise for important advances.

  1. The Nanoscale Basis of CO2 Trapping for Geologic Storage.

    PubMed

    Bourg, Ian C; Beckingham, Lauren E; DePaolo, Donald J

    2015-09-01

    Carbon capture and storage (CCS) is likely to be a critical technology to achieve large reductions in global carbon emissions over the next century. Research on the subsurface storage of CO2 is aimed at reducing uncertainties in the efficacy of CO2 storage in sedimentary rock formations. Three key parameters that have a nanoscale basis and that contribute uncertainty to predictions of CO2 trapping are the vertical permeability kv of seals, the residual CO2 saturation Sg,r in reservoir rocks, and the reactive surface area ar of silicate minerals. This review summarizes recent progress and identifies outstanding research needs in these areas. Available data suggest that the permeability of shale and mudstone seals is heavily dependent on clay fraction and can be extremely low even in the presence of fractures. Investigations of residual CO2 trapping indicate that CO2-induced alteration in the wettability of mineral surfaces may significantly influence Sg,r. Ultimately, the rate and extent of CO2 conversion to mineral phases are uncertain due to a poor understanding of the kinetics of slow reactions between minerals and fluids. Rapidly improving characterization techniques using X-rays and neutrons, and computing capability for simulating chemical interactions, provide promise for important advances. PMID:26266820

  2. Ozone Radiative Feedback in Global Warming Simulations with CO2 and non-CO2 Forcings

    NASA Astrophysics Data System (ADS)

    Ponater, M.; Rieger, V.; Dietmüller, S.

    2015-12-01

    It has been found that ozone radiative feedback acts to reduce the climate sensitivity in global warming simulations including interactive atmospheric chemistry, if the radiative forcing origins from CO2 increase. The effect can be traced to a negative feedback from stratospheric ozone changes and it is amplified by a reduced positive feedback from stratospheric water vapor.These findings cannot be simply transferred to simulations in which the warming is driven by a non-CO2 radiative forcing. Using a perturbation of surface NOx and CO emissions as an example, we demonstrate that a tropospheric ozone feedback may have significant impacts on physical feedbacks. These interactions can act to an extent that the effect of a negative ozone feedback can be reversed by changes in other feedbacks, thus increasing the climate sensitivity instead of reducing it. We also address some conceptual issues showing up as chemical feedbacks are added to set of physical feedbacks in simulation with interactive chemistry.

  3. Supersonic Technology for CO2 Capture: A High Efficiency Inertial CO2 Extraction System

    SciTech Connect

    2010-07-01

    IMPACCT Project: Researchers at ATK and ACENT Laboratories are developing a device that relies on aerospace wind-tunnel technologies to turn CO2 into a condensed solid for collection and capture. ATK’s design incorporates a special nozzle that converges and diverges to expand flue gas, thereby cooling it off and turning the CO2 into solid particles which are removed from the system by a cyclonic separator. This technology is mechanically simple, contains no moving parts and generates no chemical waste, making it inexpensive to construct and operate, readily scalable, and easily integrated into existing facilities. The increase in the cost to coal-fired power plants associated with introduction of this system would be 50% less than current technologies.

  4. Emission of CO2 from seafioor hydrothermal systems at Mariana Trough

    NASA Astrophysics Data System (ADS)

    Maeda, Y.; Shitashima, K.

    2007-12-01

    Hydrothermal vent fluids are highly enriched in CO2 and the CO2 rich fluids are released into the ocean as a hydrothermal plume. Especially, the emission of hydrothermal-related liquid CO2 from the seafloor (about 1500m) was discovered at the Okinawa Trough and Mariana Trough. At these areas, it is considered that the liquid CO2 rises up to shallow depth as a CO2 droplet and that the rising CO2 droplet dissolves gradually in ambient seawater. The observation of the hydrothermal-related CO2 would provide the opportunity for understanding the physic-chemical behavior and diffusion process of liquid CO2 in the ocean. Newly developed in-situ pH/pCO2 sensor can detect precisely and rapidly the changes of pH and pCO2 derived from high CO2 concentration. At southern Mariana Trough, the pH/pCO2 sensor was installed onto the manned submersible and in-situ pH and pCO2 data were measured every 10 seconds during the operation on the hydrothermal active site. Mapping survey of low pH and pCO2 distribution was performed on the hydrothermal active site by the grid navigation of the manned submersible that installed the pH/pCO2 sensor. The results of pH mapping survey showed only localized pH depression at the hydrothermal active site. At NW Eifuku submarine volcano, hydrothermal-related liquid CO2 dispersion was observed by using a towing multi-layer monitoring system. This system can observe the dispersion behavior of CO2 by towing several in-situ pH/pCO2 sensors and SSBL transponders in the high CO2 plume. Low pH plume of 100m high and 200m wide was detected above the summit of NW Eifuku submarine volcano.

  5. CO2-induced changes in mineral stoichiometry of wheat grains

    NASA Astrophysics Data System (ADS)

    Broberg, Malin; Pleijel, Håkan; Högy, Petra

    2016-04-01

    positive environmental effect and possibly as a result of reduced transpiration under eCO2, since uptake and transport of Cd is known to be related to transpiration. For elements with substantial data the response in OTC and FACE exposure systems could be compared and no large differences were observed. Our study shows that eCO2 has a significant effect on the mineral composition of wheat grain. This has strong implications for human nutrition in a world of rising CO2 concentrations. An altered chemical composition of biomass under eCO2 is also of great importance for the biogeochemical cycling of elements in general.

  6. CO2 Utilization and Storage in Shale Gas Reservoirs

    NASA Astrophysics Data System (ADS)

    Schaef, T.; Glezakou, V.; Owen, T.; Miller, Q.; Loring, J.; Davidson, C.; McGrail, P.

    2013-12-01

    supercritical CO2. Additional experiments were conducted with pressurized attenuated total reflectance infrared spectroscopy technique that tracked clay hydration, gas adsorption, and water concentrations in the fluids during exposure to CO2 and CH4. These fundamental physico-chemical data are being collected into a database for parameterization of multiphase flow and reactive transport simulations of the CO2 injection, trapping, and secondary methane in fractured shales.

  7. The influence of fracture anisotropy on CO2 flow

    NASA Astrophysics Data System (ADS)

    Bond, Clare E.; Wightman, Ruth; Ringrose, Philip S.

    2013-04-01

    gas mitigation through geological storage of carbon dioxide is dependent on rock formations storing CO2 effectively. Secure containment for periods of 100 × 105 years nee7ds to be verifiable. The effectiveness of geological storage is reliant on the chemical and physical properties of the geological storage complex and its ability to inhibit migration of CO2. Petroleum reservoir data and field evidence show that fracture networks often act as pathways for fluid movement, potentially allowing fluids to migrate to the surface within the time scale of interest. We demonstrate the importance of predicting the effects of fracture networks on flow, using a case study from the In Salah CO2 storage site, and show how fracture permeability is closely controlled by the stress regime determining the conductive fracture network. Our results demonstrate that fracture network prediction combined with present-day stress analysis can be used to successfully predict CO2 movement in the subsurface.

  8. CO2 laser induced refractive index changes in optical polymers.

    PubMed

    Liu, Qing; Chiang, Kin Seng; Reekie, Laurence; Chow, Yuk Tak

    2012-01-01

    We study the infrared photosensitivity properties of two optical polymer materials, benzocyclobutene (BCB) and epoxy OPTOCAST 3505, with a 10.6 μm CO2 laser. We discover that the CO2 laser radiation can lower the refractive index of BCB by as much as 5.5 × 10(-3), while inducing no measurable index change in the epoxy. As confirmed by Fourier transform infrared spectroscopy, the observed index change in BCB can be attributed to photothermal modification of chemical bonds in the material by the CO2 laser radiation. Our findings open up a new possibility of processing polymer materials with a CO2 laser, which could be further developed for application in the areas of post-processing and direct-writing of polymer waveguide devices.

  9. Simulation of CO2-water-rock interactions on geologic CO2 sequestration under geological conditions of China.

    PubMed

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

    2013-11-15

    The main purpose of this study focused on the feasibility of geologic CO2 sequestration within the actual geological conditions of the first Carbon Capture and Storage (CCS) project in China. This study investigated CO2-water-rock interactions under simulated hydrothermal conditions via physicochemical analyses and scanning electron microscopy (SEM). Mass loss measurement and SEM showed that corrosion of feldspars, silica, and clay minerals increased with increasing temperature. Corrosion of sandstone samples in the CO2-containing fluid showed a positive correlation with temperature. During reaction at 70°C, 85°C, and 100°C, gibbsite (an intermediate mineral product) formed on the sample surface. This demonstrated mineral capture of CO2 and supported the feasibility of geologic CO2 sequestration. Chemical analyses suggested a dissolution-reprecipitation mechanism underlying the CO2-water-rock interactions. The results of this study suggested that mineral dissolution, new mineral precipitation, and carbonic acid formation-dissociation are closely interrelated in CO2-water-rock interactions.

  10. Passive CO2 concentration in higher plants.

    PubMed

    Sage, Rowan F; Khoshravesh, Roxana

    2016-06-01

    Photorespiratory limitations on C3 photosynthesis are substantial in warm, low CO2 conditions. To compensate, certain plants evolved mechanisms to actively concentrate CO2 around Rubisco using ATP-supported CO2 pumps such as C4 photosynthesis. Plants can also passively accumulate CO2 without additional ATP expenditure by localizing the release of photorespired and respired CO2 around Rubisco that is diffusively isolated from peripheral air spaces. Passive accumulation of photorespired CO2 occurs when glycine decarboxylase is localized to vascular sheath cells in what is termed C2 photosynthesis, and through forming sheaths of chloroplasts around the periphery of mesophyll cells. The peripheral sheaths require photorespired CO2 to re-enter chloroplasts where it can be refixed. Passive accumulation of respiratory CO2 is common in organs such as stems, fruits and flowers, due to abundant heterotrophic tissues and high diffusive resistance along the organ periphery. Chloroplasts within these organs are able to exploit this high CO2 to reduce photorespiration. CO2 concentration can also be enhanced passively by channeling respired CO2 from roots and rhizomes into photosynthetic cells of stems and leaves via lacunae, aerenchyma and the xylem stream. Through passive CO2 concentration, C3 species likely improved their carbon economy and maintained fitness during episodes of low atmospheric CO2.

  11. Sources/sinks analysis with satellite sensing for exploring global atmospheric CO2 distributions

    NASA Astrophysics Data System (ADS)

    Shim, C.; Nassar, R.; Kim, J.

    2010-12-01

    There is growing interest in CO2 budget analysis since space-borne measurements of global CO2 distribution have been conducted (e.g, GOSAT project). Here we simulated the global CO2 distribution to estimate individual source/sink contributions. The chemical transport model (GEOS-Chem) was used in order to simulate the global CO2 distribution with updated global sources/sinks with 2°x2.5° horizontal resolution. In addition, 3-D emissions from aviation and chemical oxidation of CO are implemented. The model simulated CO2 amounts were compared with the GOSAT column averaged CO2 column (SWIR L2 data) from April 2009 to May 2010. The seasonal cycles of CO2 concentration were compared and the regional patterns of CO2 distribution are explained by the model with a systemic difference by 1 ~ 2% in the CO2 concentration. In other work, the GEOS-Chem CO2 concentrations show reasonable agreement with GLOBALVIEW-CO2. We further estimated the sources/sinks contributions to the global CO2 budget through 9 tagged CO2 tracers (fossil fuels, ocean exchanges, biomass burning, biofuel burning, balanced biosphere, net terrestrial exchange, ship emissions, aviation emissions, and oxidation from carbon precursors) over the years 2005-2009. Global CO2 concentration shows an increase of 2.1 ppbv/year in which the human fossil fuel and cement emissions are the main driving force (5.0 ppbv/year) for the trend. Net terrestrial and oceanic exchange of CO2 are main sinks (-2.1 ppbv/year and -0.7 ppbv/year, respectively). Our model results will help to suggest the level of reduction in global human CO2 emissions which could control the global CO2 trends in 21th century.

  12. Sulfur implantation in CO and CO2 ices

    NASA Astrophysics Data System (ADS)

    Lv, X. Y.; Boduch, P.; Ding, J. J.; Domaracka, A.; Langlinay, T.; Palumbo, M. E.; Rothard, H.; Strazzulla, G.

    2014-02-01

    We present new experimental results concerning the implantation of multiply charged sulfur ions (90 and 176 keV) in frozen CO and CO2. CO2 layers have been capped with a water ice layer to study chemical reactions induced at the interface between the two species. The results indicate that SO2 is formed after implantation in both CO and CO2 and the respective formation yields are 0.20 ± 0.05 and 0.38 ± 0.20 molecules ion-1 for 176-keV S11+ in CO and 90-keV S9+ in CO2, respectively. Possibly, CS2 has been produced in CO2 and OCS in CO. Ion implantation produces also all of the chemical modifications observed with other ion beam. In particular a large number of carbon chains are formed after implantation in CO. Chemical reactions and mixing are induced at the water/carbon dioxide interface and lead to the formation of carbonic acid (H2CO3). The results are discussed in the light of their relevance in some astrophysical environments both in the star-forming regions and in the Solar system.

  13. Optical properties of heusler alloys Co2FeSi, Co2FeAl, Co2CrAl, and Co2CrGa

    NASA Astrophysics Data System (ADS)

    Shreder, E. I.; Svyazhin, A. D.; Belozerova, K. A.

    2013-11-01

    The results of an investigation of optical properties and the calculations of the electronic structure of Co2FeSi, Co2FeAl, Co2CrAl, and Co2CrGa Heusler alloys are presented. The main focus of our attention is the study of the spectral dependence of the real part (ɛ1) and imaginary part (ɛ2) of the dielectric constant in the range of wavelengths λ = 0.3-13 μm using the ellipsometric method. An anomalous behavior of the optical conductivity σ(ω) has been found in the infrared range in the Co2CrAl and Co2CrGa alloys, which differs substantially from that in the Co2FeSi and Co2FeAl alloys. The results obtained are discussed based on the calculations of the electronic structure.

  14. CO2 Sequestration and Recycle by Photosynthesis

    SciTech Connect

    Steven S.C. Chuang

    2004-02-01

    Visible light-photocatalysis could provide a cost-effective route to recycle CO2 to useful chemicals or fuels. Research is planned to study the reactivity of adsorbates, their role in the photosynthesis reaction, and their relation to the nature of surface sites during photosynthesis of methanol and hydrocarbons from CO{sub 2}/H{sub 2}O. The year two research focus catalyst screening and IR studies. Key research results show Pd/TiO2 exhibits the highest activity for hydrocarbon synthesis from photocatalytic reactions. The in situ IR could successfully monitor the adsorbate hydrocarbon species on Cu/TiO2. Year III research will focus on developing a better understanding of the key factors which control the catalyst activity.

  15. Experimental evaluation of in situ CO2-water-rock reactions during CO2 injection in basaltic rocks: Implications for geological CO2 sequestration

    NASA Astrophysics Data System (ADS)

    Matter, Juerg M.; Takahashi, Taro; Goldberg, David

    2007-02-01

    Deep aquifers are potential long-term storage sites for anthropogenic CO2 emissions. The retention time and environmental safety of the injected CO2 depend on geologic and physical factors and on the chemical reactions between the CO2, the aquifer water, and the host rocks. The pH buffer capacity of the aquifer water and the acid neutralization potential of the host rocks are important factors for the permanent stabilization of the injected CO2. Mafic rocks, such as basalt, which primarily consists of Ca, Mg silicate minerals, have a high acid neutralization capacity by providing alkaline earth elements that form stable carbonate minerals. The carbonate minerals formed thus sequester CO2 in a chemically stable and environmentally benign form. In this study, we present results from a small-scale CO2 injection test in mafic and metasedimentary rocks. The injection test was conducted using a single-well push-pull test strategy. CO2 saturated water (pH = 3.5) was injected into a hydraulically isolated and permeable aquifer interval to study the acid neutralization capacity of Ca, Mg silicate rocks and to estimate in situ cation release rates. Release rates for Ca, Mg, and Na were calculated by use of solute compositions of water samples retrieved after the CO2 injection, the incubation time of the injected solution within the aquifer, and geometric estimates of the reactive surface area of the host rocks. Our results confirm rapid acid neutralization rates and water-rock reactions sufficient for safe and permanent storage of CO2. Carbonic acid was neutralized within hours of injection into a permeable mafic aquifer by two processes: mixing between the injected solution and the aquifer water, and water-rock reactions. Calculated cation release rates decrease with increasing pH that is confirmed by laboratory-based experiments. Large differences between release rates obtained from the field and laboratory experiments may be mainly due to uncertainties in the estimation

  16. Investigation of CO2 release pressures in pipeline cracks

    NASA Astrophysics Data System (ADS)

    Gorenz, Paul; Herzog, Nicoleta; Egbers, Christoph

    2013-04-01

    The CCS (Carbon Capture and Storage) technology can prevent or reduce the emissions of carbon dioxide. The main idea of this technology is the segregation and collection of CO2 from facilities with a high emission of that greenhouse gas, i.e. power plants which burn fossil fuels. To segregate CO2 from the exhaust gas the power plant must be upgraded. Up to now there are three possible procedures to segregate the carbon dioxide with different advantages and disadvantages. After segregation the carbon dioxide will be transported by pipeline to a subsurface storage location. As CO2 is at normal conditions (1013,25 Pa; 20 °C) in a gaseous phase state it must be set under high pressure to enter denser phase states to make a more efficient pipeline transport possible. Normally the carbon dioxide is set into the liquid or supercritical phase state by compressor stations which compress the gas up to 15 MPa. The pressure drop makes booster stations along the pipeline necessary which keep the CO2 in a dens phase state. Depending on the compression pressure CO2 can be transported over 300km without any booster station. The goal of this work is the investigation of release pressures in pipeline cracks. The high pressurised pipeline system consists of different parts with different failure probabilities. In most cases corrosion or obsolescence is the reason for pipeline damages. In case of a crack CO2 will escape from the pipeline and disperse into the atmosphere. Due to its nature CO2 can remain unattended for a long time. There are some studies of the CO2 dispersion process, e.g. Mazzoldi et al. (2007, 2008 and 2011) and Wang et al. (2008), but with different assumptions concerning the pipeline release pressures. To give an idea of realistic release pressures investigations with the CFD tool OpenFOAM were carried out and are presented within this work. To cover such a scenario with an accidental release of carbon dioxide a pipeline section with different diameters and

  17. CO2 mitigation via accelerated limestone weathering

    USGS Publications Warehouse

    Rau, G.H.; Knauss, K.G.; Langer, W.H.; Caldeira, K.

    2004-01-01

    The climate and environmental impacts of the current, carbon-intensive energy usage demands that effective and practical energy alternatives and CO2 mitigation strategies be found. A discussion on CO2 mitigation via accelerated limestone weathering covers limestone and seawater availability and cost; reaction rates and densities; effectiveness in CO2 sequestration; and environmental impacts and benefits.

  18. Understanding chemical reactions of CO2 and its isoelectronic molecules with 1-butyl-3-methylimidazolium acetate by changing the nature of the cation: the case of CS2 in 1-butyl-1-methylpyrrolidinium acetate studied by NMR spectroscopy and density functional theory calculations.

    PubMed

    Cabaço, M Isabel; Besnard, Marcel; Chávez, Fabián Vaca; Pinaud, Noël; Sebastião, Pedro J; Coutinho, João A P; Danten, Yann

    2014-06-28

    NMR spectroscopy ((1)H, (13)C, (15)N) shows that carbon disulfide reacts spontaneously with 1-butyl-1-methylpyrrolidinium acetate ([BmPyrro][Ac]) in the liquid phase. It is found that the acetate anions play an important role in conditioning chemical reactions with CS2 leading, via coupled complex reactions, to the degradation of this molecule to form thioacetate anion (CH3COS(-)), CO2, OCS, and trithiocarbonate (CS3 (2-)). In marked contrast, the cation does not lead to the formation of any adducts allowing to conclude that, at most, its role consists in assisting indirectly these reactions. The choice of the [BmPyrro](+) cation in the present study allows disentangling the role of the anion and the cation in the reactions. As a consequence, the ensemble of results already reported on CS2-[Bmim][Ac] (1), OCS-[Bmim][Ac] (2), and CO2-[Bmim][Ac] (3) systems can be consistently rationalized. It is argued that in system (1) both anion and cation play a role. The CS2 reacts with the acetate anion leading to the formation of CH3COS(-), CO2, and OCS. After these reactions have proceeded the nascent CO2 and OCS interact with the cation to form imidazolium-carboxylate ([Bmim] CO2) and imidazolium-thiocarboxylate ([Bmim] COS). The same scenario also applies to system (2). In contrast, in the CO2-[Bmim] [Ac] system a concerted cooperative process between the cation, the anion, and the CO2 molecule takes place. A carbene issued from the cation reacts to form the [Bmim] CO2, whereas the proton released by the ring interacts with the anion to produce acetic acid. In all these systems, the formation of adduct resulting from the reaction between the solute molecule and the carbene species originating from the cation is expected. However, this species was only observed in systems (2) and (3). The absence of such an adduct in system (1) has been theoretically investigated using DFT calculations. The values of the energetic barrier of the reactions show that the formation of [Bmim

  19. Using CO2:CO Correlations to Improve Inverse Analyses of Carbon Fluxes

    NASA Technical Reports Server (NTRS)

    Palmer, Paul I.; Suntharalingam, Parvadha; Jones, Dylan B. A.; Jacob, Daniel J.; Streets, David G.; Fu, Qingyan; Vay, Stephanie A.; Sachse, Glen W.

    2006-01-01

    Observed correlations between atmospheric concentrations of CO2 and CO represent potentially powerful information for improving CO2 surface flux estimates through coupled CO2-CO inverse analyses. We explore the value of these correlations in improving estimates of regional CO2 fluxes in east Asia by using aircraft observations of CO2 and CO from the TRACE-P campaign over the NW Pacific in March 2001. Our inverse model uses regional CO2 and CO surface fluxes as the state vector, separating biospheric and combustion contributions to CO2. CO2-CO error correlation coefficients are included in the inversion as off-diagonal entries in the a priori and observation error covariance matrices. We derive error correlations in a priori combustion source estimates of CO2 and CO by propagating error estimates of fuel consumption rates and emission factors. However, we find that these correlations are weak because CO source uncertainties are mostly determined by emission factors. Observed correlations between atmospheric CO2 and CO concentrations imply corresponding error correlations in the chemical transport model used as the forward model for the inversion. These error correlations in excess of 0.7, as derived from the TRACE-P data, enable a coupled CO2-CO inversion to achieve significant improvement over a CO2-only inversion for quantifying regional fluxes of CO2.

  20. Removal of headspace CO2 increases biological hydrogen production.

    PubMed

    Park, Wooshin; Hyun, Seung H; Oh, Sang-Eun; Logan, Bruce E; Kim, In S

    2005-06-15

    For biological hydrogen production by fermentation to be a useful method of hydrogen generation, molar yields of hydrogen must be increased. While heat treatment of a soil inoculum increases hydrogen yields by preventing loss of hydrogen to methanogenesis, hydrogen is still lost to acetic acid generation from hydrogen and CO2. To reduce hydrogen losses via acetogenesis, CO2 concentrations in the headspace were substantially reduced during hydrogen production using a chemical scavenger (KOH). CO2 in the headspace was decreased from 24.5% (control) to a maximum of 5.2% during the highest gas production phase, resulting in a hydrogen partial pressure of 87.4%. This reduction in CO2 increased the hydrogen yield by 43% (from 1.4 to 2.0 mol of H2/mol of glucose). The soluble byproducts in all tests consisted primarily of acetate and ethanol. Higher concentrations of ethanol (10.9 mM) remained in solution from bottles with CO2 removal than in the control (1.2 mM), likely as a result of hydrogen inhibition of biological ethanol conversion to acetic acid. These results show that hydrogen production can be increased by removing CO2 in the reactor vessel, likely as a result of suppression of acetogenesis.

  1. Sorbents for CO2 capture from high carbon fly ashes.

    PubMed

    Maroto-Valer, M Mercedes; Lu, Zhe; Zhang, Yinzhi; Tang, Zhong

    2008-11-01

    Fly ashes with high-unburned-carbon content, referred to as fly ash carbons, are an increasing problem for the utility industry, since they cannot be marketed as a cement extender and, therefore, have to be disposed. Previous work has explored the potential development of amine-enriched fly ash carbons for CO2 capture. However, their performance was lower than that of commercially available sorbents, probably because the samples investigated were not activated prior to impregnation and, therefore, had a very low surface area. Accordingly, the work described here focuses on the development of activated fly ash derived sorbents for CO2 capture. The samples were steam activated at 850 degrees C, resulting in a significant increase of the surface area (1075 m2/g). The activated samples were impregnated with different amine compounds, and the resultant samples were tested for CO2 capture at different temperatures. The CO2 adsorption of the parent and activated samples is typical of a physical adsorption process. The impregnation process results in a decrease of the surface areas, indicating a blocking of the porosity. The highest adsorption capacity at 30 and 70 degrees C for the amine impregnated activated carbons was probably due to a combination of physical adsorption inherent from the parent sample and chemical adsorption of the loaded amine groups. The CO2 adsorption capacities for the activated amine impregnated samples are higher than those previously published for fly ash carbons without activation (68.6 vs. 45 mg CO2/g sorbent).

  2. Throwing new light on the reduction of CO2.

    PubMed

    Ozin, Geoffrey A

    2015-03-18

    While the chemical energy in fossil fuels has enabled the rapid rise of modern civilization, their utilization and accompanying anthropogenic CO2 emissions is occurring at a rate that is outpacing nature's carbon cycle. Its effect is now considered to be irreversible and this could lead to the demise of human society. This is a complex issue without a single solution, yet from the burgeoning global research activity and development in the field of CO2 capture and utilization, there is light at the end of the tunnel. In this article a couple of recent advances are illuminated. Attention is focused on the discovery of gas-phase, light-assisted heterogeneous catalytic materials and processes for CO2 photoreduction that operate at sufficiently high rates and conversion efficiencies, and under mild conditions, to open a new pathway for an energy transition from today's "fossil fuel economy" to a new and sustainable "CO2 economy". Whichever of the competing CO2 capture and utilization approaches proves to be the best way forward for the development of a future CO2-based solar fuels economy, hopefully this can occur in a period short enough to circumvent the predicted adverse consequences of greenhouse gas climate change.

  3. Public Acceptance for Geological CO2-Storage

    NASA Astrophysics Data System (ADS)

    Schilling, F.; Ossing, F.; Würdemann, H.; Co2SINK Team

    2009-04-01

    for public, press, NGOs,…). - being open for visitors (first of all for the local!) often we informed the public together with the mining authorities - being open for podium discussions and presentation etc. - organized by NGOs, Student groups, press, politics, scientific meetings… Since people usually trust scientists more than politicians and companies, scientists have an enhanced responsibility while informing the public. Once again - always tell the truth and take care of your credibility! In this case, it was most helpful that the project was embedded in the broad scientific activity of research centre which seems to have given the project a positive neutral background. As many people have an undefined fear of all operations in the underground, we tried to address all issues related to storage. Ranging from the transport, injection facility, technical installation, safety of the storage site, the wells, hydraulic system, chemical reactions etc.. When addressing all major concerns before people ask, confidence to the scientists is kept high. We never said that there is absolutely no risk (by the way, nobody would believe that!) we weighted the risk with respect to health, safety and environmental HSE issues. We explained in detail the different trapping mechanisms of the storage operation. This has to be done according to the social groups involved. For the broad public common analogues were helpful: - Trapping in the pore space - a sponge - Trapping through a tight cap rock - a bottle of mineral water with a crown cap as seal - Chemical Trapping - opening of a bottle of mineral water - Well bore integrity - problem of retightening of a bottle with a crown cap - Sucking in of fluid -instead of releasing a sandstone sample standing partly in water - Injecting of CO2 - using a soda machine - Often the concern of burning gas is addressed - showing a CO2 fire extinguisher -CO is poisonous, CO2 not: - drinking soda or even better? champaigne Beyond information of

  4. Effects of small-scale chemical reactions between supercritical CO2 and arkosic sandstone on large-scale permeability fields: An experimental study with implications for geologic carbon sequestration

    NASA Astrophysics Data System (ADS)

    Luhmann, A. J.; Ding, K.; Saar, M. O.; Seyfried, W. E.

    2011-12-01

    During geologic carbon sequestration, small, pore-scale changes in mineralogy due to dissolution and precipitation reactions can modify bulk porosity. Porosity/permeability relationships are then typically used to infer large-scale permeability field changes. However, these relationships have limited use because they do not account for changes in pore geometry. Therefore, in connection with a DOE sponsored program, involving CO2 sequestration with geothermal energy usage, we constructed a novel hydrothermal flow system that allows simultaneous determination of changes in fluid chemistry and associated changes in permeability at elevated temperatures and high CO2 pressure. Initial experiments were conducted with an arkosic sandstone core of the Eau Claire Formation from southeastern Minnesota. The core was disaggregated and then wet sieved to yield a grain size distribution of 90-120 μm that was used to fill the Teflon sleeve held within the stainless steel pressure vessel. Initial water chemistry consisted of CO2 dissolved in deionized water. Outlet pressure was set to 11 MPa, and confinement pressure was 20 MPa. Flow rates produced inlet pressures between these two extremes, allowing CO2 solubility up to 1.1 mol/kg water. Rates of fluid flow ranged from 0.04 to 1.5 mL/min at a temperature of 21°C over the course of 33 days. Based on these data, the in-situ permeability of ~1E-14 to 9E-14 m2 for the arkosic sandstone was calculated. The reaction cell temperature was then increased to 50°C, and eventually 100°C. Each temperature step was associated with a sharp decrease in permeability, such that at 100°C the permeability had decreased by approximately three orders of magnitude from the starting condition. Fluid samples indicate release of dissolved Na, Ca, Mg, K, Al, SiO2, and Cl from minerals in the core, suggesting dissolution of primary mineral components. Charge balance constraints indicate a pH of approximately 4.2 at the highest temperature run condition

  5. Forest succession at elevated CO2

    SciTech Connect

    Clark, James S.; Schlesinger, William H.

    2002-02-01

    We tested hypotheses concerning the response of forest succession to elevated CO2 in the FACTS-1 site at the Duke Forest. We quantified growth and survival of naturally recruited seedlings, tree saplings, vines, and shrubs under ambient and elevated CO2. We planted seeds and seedlings to augment sample sites. We augmented CO2 treatments with estimates of shade tolerance and nutrient limitation while controlling for soil and light effects to place CO2 treatments within the context of natural variability at the site. Results are now being analyzed and used to parameterize forest models of CO2 response.

  6. Isotopic CO2 Instrumentation for UAV Measurements

    NASA Astrophysics Data System (ADS)

    Gomez, A.; Silver, J.

    2013-12-01

    Carbon dioxide is the largest component of anthroprogenic green house gas emissions. Knowing atmospheric 13CO2/12CO2 ratios precisely is important for understanding biogenic and anthroprogenic sources and sinks for carbon. Instrumentation mounted on UAV aircraft would enable important spatial isotopic CO2 information. However, current isotopic CO2 instrumentation have unfavorable attributes for UAV use, such as high power requirements, high cost, high weight, and large size. Here we present the early development of a compact isotopic CO2 instrument that is designed to nullify effects of pressure, temperature and moisture, and will ultimately be suitable for UAV deployment.

  7. Storing CO2 underground shows promising results

    NASA Astrophysics Data System (ADS)

    Zweigel, Peter; Gale, John

    Long-term underground storage of CO2 is an important element in concepts to reduce atmospheric CO2 emissions as the use of fossil fuels continues. The first results of a multinational research project evaluating the injection of CO2 into a saline aquifer in the North Sea are validating this method of CO2 reduction, and are serving to further define the research needed to develop the technology for large-scale applicability. Reducing the emission of substances that have potentially harmful effects on global climate— for example, CO2—has become a central issue of environmental policy at least since the 1997 Kyoto conference on climate change.

  8. Aminosilicone solvents for CO(2) capture.

    PubMed

    Perry, Robert J; Grocela-Rocha, Teresa A; O'Brien, Michael J; Genovese, Sarah; Wood, Benjamin R; Lewis, Larry N; Lam, Hubert; Soloveichik, Grigorii; Rubinsztajn, Malgorzata; Kniajanski, Sergei; Draper, Sam; Enick, Robert M; Johnson, J Karl; Xie, Hong-bin; Tapriyal, Deepak

    2010-08-23

    This work describes the first report of the use of an aminosilicone solvent mix for the capture of CO(2). To maintain a liquid state, a hydroxyether co-solvent was employed which allowed enhanced physisorption of CO(2) in the solvent mixture. Regeneration of the capture solvent system was demonstrated over 6 cycles and absorption isotherms indicate a 25-50 % increase in dynamic CO(2) capacity over 30 % MEA. In addition, proof of concept for continuous CO(2) absorption was verified. Additionally, modeling to predict heats of reaction of aminosilicone solvents with CO(2) was in good agreement with experimental results.

  9. Reversible Acid Gas Capture Using CO2-Binding Organic Liquids

    SciTech Connect

    Heldebrant, David J.; Koech, Phillip K.; Yonker, Clement R.; Rainbolt, James E.; Zheng, Feng

    2010-08-31

    Acid gas scrubbing technology is predominantly aqueous alkanolamine based. Of the acid gases, CO2, H2S and SO2 have been shown to be reversible, however there are serious disadvantages with corrosion and high regeneration costs. The primary scrubbing system composed of monoethanolamine is limited to 30% by weight because of the highly corrosive solution. This gravimetric limitation limits the CO2 volumetric (≤108 g/L) and gravimetric capacity (≤7 wt%) of the system. Furthermore the scrubbing system has a large energy penalty from pumping and heating the excess water required to dissolve the MEA bicarbonate salt. Considering the high specific heat of water (4 j/g-1K-1), low capacities and the high corrosion we set out to design a fully organic solvent that can chemically bind all acid gases i.e. CO2 as reversible alkylcarbonate ionic liquids or analogues thereof. Having a liquid acid gas carrier improves process economics because there is no need for excess solvent to pump and to heat. We have demonstrated illustrated in Figure 1, that CO2-binding organic liquids (CO2BOLs) have a high CO2 solubility paired with a much lower specific heat (<1.5 J/g-1K-1) than aqueous systems. CO2BOLs are a subsection of a larger class of materials known as Binding Organic Liquids (BOLs). Our BOLs have been shown to reversibly bind and release COS, CS2, and SO2, which we denote COSBOLS, CS2BOLs and SO2BOLs. Our BOLs are highly tunable and can be designed for post or pre-combustion gas capture. The design and testing of the next generation zwitterionic CO2BOLs and SO2BOLs are presented.

  10. CO2 Annual and Semiannual Cycles from Satellite Retrievals and Models

    NASA Astrophysics Data System (ADS)

    Jiang, X.; Crisp, D.; Olsen, E. T.; Kulawik, S. S.; Miller, C. E.; Pagano, T. S.; Yung, Y. L.

    2014-12-01

    We have compared satellite CO2 retrievals from the Greenhouse gases Observing SATellite (GOSAT), Atmospheric Infrared Sounder (AIRS), and Tropospheric Emission Spectrometer (TES) with in-situ measurements from the Earth System Research Laboratory (NOAA-ESRL) Surface CO2 and Total Carbon Column Observing Network (TCCON), and utilized zonal means to characterize variability and distribution of CO2. In general, zonally averaged CO2 from the three satellite data sets are consistent with the surface and TCCON XCO2 data. Retrievals of CO2 from the three satellites show more (less) CO2 in the northern hemisphere than that in the southern hemisphere in the northern hemispheric winter (summer) season. The difference between the three satellite CO2 retrievals might be related to the different averaging kernels in the satellites CO2 retrievals. A multiple regression method was used to calculate the CO2 annual cycle and semiannual cycle amplitudes from different satellite CO2 retrievals. The CO2 annual cycle and semiannual cycle amplitudes are largest at the surface, as seen in the NOAA-ESRL CO2 data sets. The CO2 annual cycle and semiannual cycle amplitudes in the GOSAT XCO2, AIRS mid-tropospheric CO2, and TES mid-tropospheric CO2 are smaller compared with those from the surface CO2. Similar regression analysis was applied to the Model for OZone And Related chemical Tracers-2 (MOZART-2) and CarbonTracker model CO2. The convolved model CO2 annual cycle and semiannual cycle amplitudes are similar to those from the satellite CO2 retrievals, although the model tends to under-estimate the CO2 seasonal cycle amplitudes in the northern hemisphere mid-latitudes from the comparison with GOSAT and TES CO2 and underestimate the CO2 semi-annual cycle amplitudes in the high latitudes from the comparison with AIRS CO2. The difference between model and satellite CO2 can be used to identify possible deficiency in the model and improve the model in the future.

  11. Residual CO2 trapping in Indiana limestone.

    PubMed

    El-Maghraby, Rehab M; Blunt, Martin J

    2013-01-01

    We performed core flooding experiments on Indiana limestone using the porous plate method to measure the amount of trapped CO(2) at a temperature of 50 °C and two pressures: 4.2 and 9 MPa. Brine was mixed with CO(2) for equilibration, then the mixture was circulated through a sacrificial core. Porosity and permeability tests conducted before and after 884 h of continuous core flooding confirmed negligible dissolution. A trapping curve for supercritical (sc)CO(2) in Indiana showing the relationship between the initial and residual CO(2) saturations was measured and compared with that of gaseous CO(2). The results were also compared with scCO(2) trapping in Berea sandstone at the same conditions. A scCO(2) residual trapping end point of 23.7% was observed, indicating slightly less trapping of scCO(2) in Indiana carbonates than in Berea sandstone. There is less trapping for gaseous CO(2) (end point of 18.8%). The system appears to be more water-wet under scCO(2) conditions, which is different from the trend observed in Berea; we hypothesize that this is due to the greater concentration of Ca(2+) in brine at higher pressure. Our work indicates that capillary trapping could contribute to the immobilization of CO(2) in carbonate aquifers.

  12. Microbial Growth under Supercritical CO2

    PubMed Central

    Peet, Kyle C.; Freedman, Adam J. E.; Hernandez, Hector H.; Britto, Vanya; Boreham, Chris; Ajo-Franklin, Jonathan B.

    2015-01-01

    Growth of microorganisms in environments containing CO2 above its critical point is unexpected due to a combination of deleterious effects, including cytoplasmic acidification and membrane destabilization. Thus, supercritical CO2 (scCO2) is generally regarded as a sterilizing agent. We report isolation of bacteria from three sites targeted for geologic carbon dioxide sequestration (GCS) that are capable of growth in pressurized bioreactors containing scCO2. Analysis of 16S rRNA genes from scCO2 enrichment cultures revealed microbial assemblages of varied complexity, including representatives of the genus Bacillus. Propagation of enrichment cultures under scCO2 headspace led to isolation of six strains corresponding to Bacillus cereus, Bacillus subterraneus, Bacillus amyloliquefaciens, Bacillus safensis, and Bacillus megaterium. Isolates are spore-forming, facultative anaerobes and capable of germination and growth under an scCO2 headspace. In addition to these isolates, several Bacillus type strains grew under scCO2, suggesting that this may be a shared feature of spore-forming Bacillus spp. Our results provide direct evidence of microbial activity at the interface between scCO2 and an aqueous phase. Since microbial activity can influence the key mechanisms for permanent storage of sequestered CO2 (i.e., structural, residual, solubility, and mineral trapping), our work suggests that during GCS microorganisms may grow and catalyze biological reactions that influence the fate and transport of CO2 in the deep subsurface. PMID:25681188

  13. CO2 Sequestration in Unmineable Coal Seams: Potential Environmental Impacts

    SciTech Connect

    Hedges, S.W.; Soong, Yee; McCarthy Jones, J.R.; Harrison, D.K.; Irdi, G.A.; Frommell, E.A.; Dilmore, R.M.; Pique, P.J.; Brown, T.D

    2005-09-01

    An initial investigation into the potential environmental impacts of CO2 sequestration in unmineable coal seams has been conducted, focusing on changes in the produced water during enhanced coalbed methane (ECBM) production using a CO2 injection process (CO2-ECBM). Two coals have been used in this study, the medium volatile bituminous Upper Freeport coal (APCS 1) of the Argonne Premium Coal Samples series, and an as-mined Pittsburgh #8 coal, which is a high volatile bituminous coal. Coal samples were reacted with either synthetic produced water or field collected produced water and gaseous carbon dioxide at 40 οC and 50 bar to evaluate the potential for mobilizing toxic metals during CO2-ECBM/sequestration. Microscopic and x-ray diffraction analysis of the post-reaction coal samples clearly show evidence of chemical reaction, and chemical analysis of the produced water shows substantial changes in composition. These results suggest that changes to the produced water chemistry and the potential for mobilizing toxic trace elements from coalbeds are important factors to be considered when evaluating deep, unmineable coal seams for CO2 sequestration.

  14. CO2/H(+) sensing: peripheral and central chemoreception.

    PubMed

    Lahiri, Sukhamay; Forster, Robert E

    2003-10-01

    H(+) is maintained constant in the internal environment at a given body temperature independent of external environment according to Bernard's principle of "milieu interieur". But CO2 relates to ventilation and H(+) to kidney. Hence, the title of the chapter. In order to do this, sensors for H(+) in the internal environment are needed. The sensor-receptor is CO2/H(+) sensing. The sensor-receptor is coupled to integrate and to maintain the body's chemical environment at equilibrium. This chapter dwells on this theme of constancy of H(+) of the blood and of the other internal environments. [H(+)] is regulated jointly by respiratory and renal systems. The respiratory response to [H(+)] originates from the activities of two groups of chemoreceptors in two separate body fluid compartments: (A) carotid and aortic bodies which sense arterial P(O2) and H(+); and (B) the medullary H(+) receptors on the ventrolateral medulla of the central nervous system (CNS). The arterial chemoreceptors function to maintain arterial P(O2) and H(+) constant, and medullary H(+) receptors to maintain H(+) of the brain fluid constant. Any acute change of H(+) in these compartments is taken care of almost instantly by pulmonary ventilation, and slowly by the kidney. This general theme is considered in Section 1. The general principles involving cellular CO2 reactions mediated by carbonic anhydrase (CA), transport of CO2 and H(+) are described in Section 2. Since the rest of the chapter is dependent on these key mechanisms, they are given in detail, including the role of Jacobs-Stewart Cycle and its interaction with carbonic anhydrase. Also, this section deals briefly with the mechanisms of membrane depolarization of the chemoreceptor cells because this is one mechanism on which the responses depend. The metabolic impact of endogenous CO2 appears in the section with a historical twist, in the context of acclimatization to high altitude (Section 3). Because low P(O2) at high altitude stimulates

  15. Assessment of full-scale biological nutrient removal systems upgraded with physico-chemical processes for the removal of emerging pollutants present in wastewaters from Mexico.

    PubMed

    Estrada-Arriaga, Edson Baltazar; Cortés-Muñoz, Juana Enriqueta; González-Herrera, Arturo; Calderón-Mólgora, César Guillermo; de Lourdes Rivera-Huerta, Ma; Ramírez-Camperos, Esperanza; Montellano-Palacios, Leticia; Gelover-Santiago, Silvia Lucila; Pérez-Castrejón, Sara; Cardoso-Vigueros, Lina; Martín-Domínguez, Alejandra; García-Sánchez, Liliana

    2016-11-15

    Two full-scale biological nutrient removal systems upgraded with three physico-chemical processes (coagulation, chemical precipitation, and neutral Fenton) were evaluated in order to determine the removal of emerging pollutants (EPs) present in municipal wastewater from Mexico. Between 41 and 55 EPs were detected in the influents of two wastewater treatment plants (WWTPs), including personal care products (PPCPs), antibiotics, analgesics, antiepileptics, antilipidemics, antihypertensives, antiseptics, stimulants, and hormones. Emerging pollutants were detected at concentrations ranging from 0.69ng/L to 94,600ng/L. High concentrations of emerging pollutants were found during dry season. WWTP 1, integrated by oxidation ditches and UV light lamps, showed removal efficiencies of EPs between 20% and 22%. On the other hand, WWTP 2 consisted of anaerobic/anoxic/aerobic tanks coupled with two disinfection processes; chlorine dioxide and UV light lamps, for which the removal of EPs was significant (up to 80%). The concentrations of emerging pollutants in WWTP 1 effluent was found within a range

  16. Assessment of full-scale biological nutrient removal systems upgraded with physico-chemical processes for the removal of emerging pollutants present in wastewaters from Mexico.

    PubMed

    Estrada-Arriaga, Edson Baltazar; Cortés-Muñoz, Juana Enriqueta; González-Herrera, Arturo; Calderón-Mólgora, César Guillermo; de Lourdes Rivera-Huerta, Ma; Ramírez-Camperos, Esperanza; Montellano-Palacios, Leticia; Gelover-Santiago, Silvia Lucila; Pérez-Castrejón, Sara; Cardoso-Vigueros, Lina; Martín-Domínguez, Alejandra; García-Sánchez, Liliana

    2016-11-15

    Two full-scale biological nutrient removal systems upgraded with three physico-chemical processes (coagulation, chemical precipitation, and neutral Fenton) were evaluated in order to determine the removal of emerging pollutants (EPs) present in municipal wastewater from Mexico. Between 41 and 55 EPs were detected in the influents of two wastewater treatment plants (WWTPs), including personal care products (PPCPs), antibiotics, analgesics, antiepileptics, antilipidemics, antihypertensives, antiseptics, stimulants, and hormones. Emerging pollutants were detected at concentrations ranging from 0.69ng/L to 94,600ng/L. High concentrations of emerging pollutants were found during dry season. WWTP 1, integrated by oxidation ditches and UV light lamps, showed removal efficiencies of EPs between 20% and 22%. On the other hand, WWTP 2 consisted of anaerobic/anoxic/aerobic tanks coupled with two disinfection processes; chlorine dioxide and UV light lamps, for which the removal of EPs was significant (up to 80%). The concentrations of emerging pollutants in WWTP 1 effluent was found within a range

  17. Fourier Transform Microwave Spectra of CO{2}-ETHYLENE Sulfide, CO{2}-ETHYLENE Oxide and CO{2}-PROPYLENE Oxide Complexes

    NASA Astrophysics Data System (ADS)

    Orita, Yukari; Kawashima, Yoshiyuki; Hirota, Eizi

    2010-06-01

    We have previously examined the difference in roles of O and S in structure and dynamics of the CO-ethylene oxide (EO) and CO-ethylene sulfide (ES) complexes. We have extended the investigation to CO{2}-EO and CO{2}-ES for comparison. We have also observed the CO{2}-propylene oxide (PO) complex, which is an important intermediate in the reaction of PO with CO{2} leading to polycarbonate. Both a-type and b-type transitions were observed for the CO{2}-EO and CO{2}-ES, but no c-type transitions were observed at all. We also detected the {34}S and {13}C isotopic species in natural abundance and the species containing {18}OCO and C{18}O% {2}, which were synthesized by burning paper in an {18}O{2} and{% 16}O{2} mixture. By analyzing the observed spectra we concluded the CO{2} moiety of CO{2}-EO and CO{2}-ES located in a plane % prependicular to the three-membered ring and bisecting the COC or CSC angle of EO or ES, respectively, as in the case of CO-EO and CO-ES complexes. An % ab initio MO calculation at the level of MP2/6-311G(d, p) yielded an optimized structure in good agreement with the experimental result. We have derived from the observed spectra the distance, the stretching force constant, and the binding energy of the bonds between the constituents of the CO{2}-EO and CO{2}-ES complexes and have found that the distances of the two complexes were shorter by 0.2Å than those in CO-EO and CO-ES, respectively, and that the intermolecular bonds were two times stronger in the CO{2} complexes than in the corresponding CO complexes. We have concluded from the observed spectra that the CO{2} moiety in CO{2}-PO is located on the PO three-membered ring plane opposite to the methyl group. The constituents in CO{2}-PO were more weakly bound than those in CO{2}-EO and CO{2}-ES. S. Sato, Y. Kawashima, Y. Tatamitani, and E. Hirota, 63rd International Symposium on Molecular Spectroscopy, WF05 (2008).

  18. Simulation of CO 2 concentrations at Tsukuba tall tower using WRF-CO 2 tracer transport model

    NASA Astrophysics Data System (ADS)

    Ballav, Srabanti; Patra, Prabir K.; Sawa, Yousuke; Matsueda, Hidekazu; Adachi, Ahoro; Onogi, Shigeru; Takigawa, Masayuki; de, Utpal K.

    2016-02-01

    Simulation of carbon dioxide (CO2) at hourly/weekly intervals and fine vertical resolution at the continental or coastal sites is challenging because of coarse horizontal resolution of global transport models. Here the regional Weather Research and Forecasting (WRF) model coupled with atmospheric chemistry is adopted for simulating atmospheric CO2 (hereinafter WRF-CO2) in nonreactive chemical tracer mode. Model results at horizontal resolution of 27 × 27 km and 31 vertical levels are compared with hourly CO2 measurements from Tsukuba, Japan (36.05°N, 140.13 oE) at tower heights of 25 and 200 m for the entire year 2002. Using the wind rose analysis, we find that the fossil fuel emission signal from the megacity Tokyo dominates the diurnal, synoptic and seasonal variations observed at Tsukuba. Contribution of terrestrial biosphere fluxes is of secondary importance for CO2 concentration variability. The phase of synoptic scale variability in CO2 at both heights are remarkably well simulated the observed data (correlation coefficient >0.70) for the entire year. The simulations of monthly mean diurnal cycles are in better agreement with the measurements at lower height compared to that at the upper height. The modelled vertical CO2 gradients are generally greater than the observed vertical gradient. Sensitivity studies show that the simulation of observed vertical gradient can be improved by increasing the number of vertical levels from 31 in the model WRF to 37 (4 below 200 m) and using the Mellor-Yamada-Janjic planetary boundary scheme. These results have large implications for improving transport model simulation of CO2 over the continental sites.

  19. Nutrient removal and biogas upgrading by integrating freshwater algae cultivation with piggery anaerobic digestate liquid treatment.

    PubMed

    Xu, Jie; Zhao, Yongjun; Zhao, Guohua; Zhang, Hui

    2015-08-01

    An integrated approach that combined freshwater microalgae Scenedesmus obliquus (FACHB-31) cultivation with piggery anaerobic digestate liquid treatment was investigated in this study. The characteristics of algal growth, biogas production, and nutrient removal were examined using photobioreactor bags (PBRbs) to cultivate S. obliquus (FACHB-31) in digestate with various digestate dilutions (the concentration levels of 3200, 2200, 1600, 1200, 800, and 400 mg L(-1) chemical oxygen demand (COD)) during 7-day period. The effects of the level of pollutants on nutrient removal efficiency and CO2 removal process were investigated to select the optimum system for effectively upgrade biogas and simultaneously reduce the nutrient content in digestate. The treatment performance displayed that average removal rates of COD, total nitrogen (TN), total phosphorous (TP), and CO2 were 61.58-75.29, 58.39-74.63, 70.09-88.79, and 54.26-73.81 %, respectively. All the strains grew well under any the dilution treatments. With increased initial nutrient concentration to a certain range, the CO4 content (v/v) of raw biogas increased. Differences in the biogas enrichment of S. obliquus (FACHB-31) in all treatments mainly resulted from variations in biomass productivity and CO2 uptake. Notably, the diluted digestate sample of 1600 mg L(-1) COD provided an optimal nutrient concentration for S. obliquus (FACHB-31) cultivation, where the advantageous nutrient and CO2 removals, as well as the highest productivities of biomass and biogas upgrading, were revealed. Results showed that microalgal biomass production offered real opportunities to address issues such as CO2 sequestration, wastewater treatment, and biogas production.

  20. Nutrient removal and biogas upgrading by integrating freshwater algae cultivation with piggery anaerobic digestate liquid treatment.

    PubMed

    Xu, Jie; Zhao, Yongjun; Zhao, Guohua; Zhang, Hui

    2015-08-01

    An integrated approach that combined freshwater microalgae Scenedesmus obliquus (FACHB-31) cultivation with piggery anaerobic digestate liquid treatment was investigated in this study. The characteristics of algal growth, biogas production, and nutrient removal were examined using photobioreactor bags (PBRbs) to cultivate S. obliquus (FACHB-31) in digestate with various digestate dilutions (the concentration levels of 3200, 2200, 1600, 1200, 800, and 400 mg L(-1) chemical oxygen demand (COD)) during 7-day period. The effects of the level of pollutants on nutrient removal efficiency and CO2 removal process were investigated to select the optimum system for effectively upgrade biogas and simultaneously reduce the nutrient content in digestate. The treatment performance displayed that average removal rates of COD, total nitrogen (TN), total phosphorous (TP), and CO2 were 61.58-75.29, 58.39-74.63, 70.09-88.79, and 54.26-73.81 %, respectively. All the strains grew well under any the dilution treatments. With increased initial nutrient concentration to a certain range, the CO4 content (v/v) of raw biogas increased. Differences in the biogas enrichment of S. obliquus (FACHB-31) in all treatments mainly resulted from variations in biomass productivity and CO2 uptake. Notably, the diluted digestate sample of 1600 mg L(-1) COD provided an optimal nutrient concentration for S. obliquus (FACHB-31) cultivation, where the advantageous nutrient and CO2 removals, as well as the highest productivities of biomass and biogas upgrading, were revealed. Results showed that microalgal biomass production offered real opportunities to address issues such as CO2 sequestration, wastewater treatment, and biogas production. PMID:25808519

  1. Geophysical Implications of Enceladus' CO2 Frost

    NASA Astrophysics Data System (ADS)

    Matson, D.; Davies, A. G.; Johnson, T. V.; Castillo, J. C.; Lunine, J. I.

    2013-12-01

    CO2 frost has been reported on the surface of Enceladus [1]. We suggest that the frost originated from shallow gas pockets below the surface. These pockets are a natural consequence of the ocean water circulation hypothesis [2]. They are different from the plume chambers [3] and would constitute a previously unrecognized structure in the surface. The oceanic circulation uses gas bubbles to make seawater buoyant and bring up water, chemicals, and heat from a warm ocean at depth [2]. The ocean water rises through the icy crust and near the surface it spreads out laterally beneath a relatively thin ice cap, following the pattern indicated by the thermal anomalies identified in Cassini data [4,5]. Topography on the bottom of this cap ice is conducive to the formation of gas pockets. As the ocean water flows horizontally, the gas bubbles in it continue to rise vertically. Even though their vertical migration may be slow and even if the flow is relatively turbulent, some bubbles reach recesses in the bottom of the ice cap and, over time, pop and form gas pockets. The gas pockets are envisioned as being ruptured by the regular fissuring of ice in the South Polar Region. Hurford et al. [6] have modelled the tidally controlled openings of rifts in the SPR. If one of these rifts reaches a gas pocket, CO2 gas may come to the surface. The tortuosity and other properties of its route will determine if it vents as a seep or a jet. If enough gas is vented and the molecules in the transient cloud have many collisions, some of them will be scattered to the surface and freeze. It was noted by Brown, et al. [1] that the frost deposits may not be permanent and that an active replenishment processes might be necessary. Studies of CO2 frost on Iapetus suggest that migration can be significant [7]. This work was performed at the Jet Propulsion Laboratory, California Institute of Technology, under contract to NASA. al., Science 311, 1425-1428, 2006. [2] Matson D. L. et al., Icarus 221, 53

  2. Exogenously produced CO2 doubles the CO2 efflux from three north temperate lakes

    NASA Astrophysics Data System (ADS)

    Wilkinson, Grace M.; Buelo, Cal D.; Cole, Jonathan J.; Pace, Michael L.

    2016-03-01

    It is well established that lakes are typically sources of CO2 to the atmosphere. However, it remains unclear what portion of CO2 efflux is from endogenously processed organic carbon or from exogenously produced CO2 transported into lakes. We estimated high-frequency CO2 and O2 efflux from three north temperate lakes in summer to determine the proportion of the total CO2 efflux that was exogenously produced. Two of the lakes were amended with nutrients to experimentally enhance endogenous CO2 uptake. In the unfertilized lake, 50% of CO2 efflux was from exogenous sources and hydrology had a large influence on efflux. In the fertilized lakes, endogenous CO2 efflux was negative (into the lake) yet exogenous CO2 made the lakes net sources of CO2 to the atmosphere. Shifts in hydrologic regimes and nutrient loading have the potential to change whether small lakes act primarily as reactors or vents in the watershed.

  3. Energyless CO2 Absorption, Generation, and Fixation Using Atmospheric CO2.

    PubMed

    Inagaki, Fuyuhiko; Okada, Yasuhiko; Matsumoto, Chiaki; Yamada, Masayuki; Nakazawa, Kenta; Mukai, Chisato

    2016-01-01

    From an economic and ecological perspective, the efficient utilization of atmospheric CO2 as a carbon resource should be a much more important goal than reducing CO2 emissions. However, no strategy to harvest CO2 using atmospheric CO2 at room temperature currently exists, which is presumably due to the extremely low concentration of CO2 in ambient air (approximately 400 ppm=0.04 vol%). We discovered that monoethanolamine (MEA) and its derivatives efficiently absorbed atmospheric CO2 without requiring an energy source. We also found that the absorbed CO2 could be easily liberated with acid. Furthermore, a novel CO2 generator enabled us to synthesize a high value-added material (i.e., 2-oxazolidinone derivatives based on the metal catalyzed CO2-fixation at room temperature) from atmospheric CO2.

  4. CO2 transport over complex terrain

    USGS Publications Warehouse

    Sun, Jielun; Burns, Sean P.; Delany, A.C.; Oncley, S.P.; Turnipseed, A.A.; Stephens, B.B.; Lenschow, D.H.; LeMone, M.A.; Monson, Russell K.; Anderson, D.E.

    2007-01-01

    CO2 transport processes relevant for estimating net ecosystem exchange (NEE) at the Niwot Ridge AmeriFlux site in the front range of the Rocky Mountains, Colorado, USA, were investigated during a pilot experiment. We found that cold, moist, and CO2-rich air was transported downslope at night and upslope in the early morning at this forest site situated on a ???5% east-facing slope. We found that CO2 advection dominated the total CO2 transport in the NEE estimate at night although there are large uncertainties because of partial cancellation of horizontal and vertical advection. The horizontal CO2 advection captured not only the CO2 loss at night, but also the CO2 uptake during daytime. We found that horizontal CO2 advection was significant even during daytime especially when turbulent mixing was not significant, such as in early morning and evening transition periods and within the canopy. Similar processes can occur anywhere regardless of whether flow is generated by orography, synoptic pressure gradients, or surface heterogeneity as long as CO2 concentration is not well mixed by turbulence. The long-term net effect of all the CO2 budget terms on estimates of NEE needs to be investigated. ?? 2007 Elsevier B.V. All rights reserved.

  5. Pseudo-data Inversions of California CO2 Fluxes Combining Tower Measurements of CO2 and 14CO2 with OCO2 Column CO2 Retrievals

    NASA Astrophysics Data System (ADS)

    Fischer, M. L.; Jeong, S.; Bagley, J.; Frankenberg, C.; Parazoo, N.; Keeling, R. F.; Graven, H. D.

    2014-12-01

    The majority (~ 80 %) of California's greenhouse gas (GHG) emissions are likely CO2 produced by fossil fuel combustion (ffCO2). While bottom-up estimates of State-annual total ffCO2 emissions are expected to be accurate to ~ 5-10% (68% confidence), net CO2 exchange at smaller spatial and temporal scales (and emissions of other GHGs) are likely less certain. Here, we report initial results of a Carbon Monitoring System (CMS) pseudo-data inversion study combining simulated total and radiocarbon CO2 sampling from a 10-site ground-based tower network with OCO2 satellite column CO2 retrievals. Fossil and biosphere CO2 signals are computed for tower and OCO2 observations across urban and rural areas of California including the South Coast Air Basin (SoCAB), Central Valley, and San Francisco Bay Area using the WRF-STILT transport model simulations coupled with prior fluxes from VULCAN (ffCO2) and CASA (bioCO2) fluxes respectively. Nominal uncertainties are assigned to the prior ffCO2 fluxes and estimated for the model-measurement differences including WRF and STILT model uncertainties and background subtraction. Reductions in posterior uncertainties for regional ffCO2 emissions are estimated for the tower pseudo-data using Bayesian inversions for monthly periods in multiple seasons. Ongoing work will include incorporation of OCO2 pseudo-data to estimate additional uncertainty reductions obtained for ffCO2 and bioCO2 exchange signals across California's urban and rural regions.

  6. Chances and challenges of forest scale CO2 enrichment

    NASA Astrophysics Data System (ADS)

    Körner, Christian

    2016-04-01

    Rising CO2 is changing the biosphere's diet. As with any dietary change, both amount and quality of food matter. Atmospheric CO2 enrichment is clearly providing a rather one-sided, C-rich diet. Hence, the reaiistic experimental simulation of its effect on the single biggest C reservoir of the biosphere, that is forest, requires experimental conditions that resemble exactly that situation. In the past, trees where most commonly exposed to elevated CO2 while provided with ample other constituents of a plant's diet (soil nutrients), yielding exaggerated growth stimulation, unlikely to reflect real world responses. So, by either selecting fertile soils, disturbing the system by fire or planting activities, offering ample soil space to isolated individuals or even adding fertilizer, almost any CO2-response can be 'designed'. The 'art' of designing future Free Air CO2 Enrichment (FACE) experiments will be to avoid exactly these pitfalls. Plants can incorporate additional C only to the extent the provision of chemical elements other than C will permit, given the stoichiometry of life. Site selection (soil fertility), degree of canopy closure, recent disturbance regime or successional stage will influence CO2 effects. It is the fundamental dilemma in CO2-enrichment research that simple, homogenous, artificial test systems offer statistical power, while systems that account for 'naturalness' and species diversity do not. Any new FACE program needs to handle that tradeoff between precision and relevance. In this presentation I will advocate a pragmatic approach that will inevitably have to lean on individual tree responses, across a wide as possible range of neighborhoods, age and growth conditions, with the statistical power depending in obtaining the best possible pre-treatment traits and responses. By illustrating the results of 15 years of FACE with 30-40 m tall forest trees, I will caution against over-optimistic ecosystem scale approaches with just ONE technology

  7. CO2 sequestration: Storage capacity guideline needed

    USGS Publications Warehouse

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

    2006-01-01

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

  8. Fate of liquid CO2 discharged from the hydrothermal area in the Okinawa Trough

    NASA Astrophysics Data System (ADS)

    Shitashima, K.; Maeda, Y.

    2005-12-01

    Deep-sea hydrothermal systems are suitable for the on-site field analysis of a high CO2 environment in the ocean. Hydrothermal fluids are highly enriched in CO2 and show lower pH (about pH2-3) relative to seawater. The observation of the hydrothermal CO2 would provide the opportunity for understanding the physic-chemical behavior and diffusion process of CO2 in the ocean. Furthermore, the information on the hydrothermal ecosystem in the high CO2 environment is important for an environment impact assessment of the CO2 ocean sequestration. The observation of behavior of natural CO2 droplets (8-10?, 0.5ml) was carried out in the deep-sea hydrothermal system at the Okinawa Trough. The natural CO2 droplet contains CO2 of 95-98%, H2S of 2-3% and other gas species. The rising CO2 droplets were tracked by an ROV, and depth, temperature, salinity, pH and pCO2 in seawater near the CO2 droplets were measured during their ascent by using CTD and in-situ pH/pCO2 sensor. The behavior of the rising CO2 droplets was observed with an HDTV camera on an ROV. Mapping survey (400m X 400m, 3 layers) of low pH distribution was performed on the natural CO2 venting area by the grid navigation of the ROV that installed a pH/pCO2 sensor. The droplet size and the rise rate of CO2 droplets decreased during their ascent in water column (from 1470m to 900m depth). The CO2 droplets dissolved gradually and became small CO2 clathrate while rising, and the rising clathrate materials were found to disappear at 918m depth (552m above the bottom). Although the pH just above the sea floor CO2 vents showed pH 5, the pH depression in seawater surrounding the rising CO2 droplets was not observed. The results of pH mapping survey showed only localized pH depression at the CO2 venting site.

  9. Production of solar fuels by CO2 plasmolysis

    NASA Astrophysics Data System (ADS)

    Goede, Adelbert P. H.; Bongers, Waldo A.; Graswinckel, Martijn F.; M. C. M van de Sanden, Richard; Leins, Martina; Kopecki, Jochen; Schulz, Andreas; Walker, Mathias

    2014-12-01

    A storage scheme for Renewable Energy (RE) based on the plasmolysis of CO2into CO and O2 has been experimentally investigated, demonstrating high energy efficiency (>50%) combined with high energy density, rapid start-stop and no use of scarce materials. The key parameter controlling energy efficiency has been identified as the reduced electric field. Basic plasma parameters including density and temperature are derived from a simple particle and energy balance model, allowing parameter specification of an upscale 100 kW reactor. With RE powered plasmolysis as the critical element, a CO2 neutral energy system becomes feasible when complemented by effective capture of CO2 at the input and separation of CO from the output gas stream followed by downstream chemical processing into hydrocarbon fuels.

  10. Thermodynamic and kinetic stabilities of CO2 oligomers.

    PubMed

    Dunlap, Brett I; Schweigert, Igor V; Purdy, Andrew P; Snow, Arthur W; Hu, Anguang

    2013-04-01

    Density-functional and coupled cluster calculations suggest that the stability, against unimolecular dissociation, of the cyclic D(3h) trimer of CO2, 1,3,5-trioxetanetrione, is greater than all but one other chemically bound oligomer of CO2. It requires far less energy to produce, on a per CO2 basis, than the low-symmetry cyclic 1,2 dioxetanedione dimer, but its kinetic stability against unimolecular dissociation is much lower. The extreme stability of the dimer, which makes it an excellent intermediate in chemiluminescence, is caused by an extreme range of geometric change to its transition state leading to a trapezoidal potential energy surface. The thermodynamically more stable trimer affords a low pressure pathway from molecular carbon dioxide to the extended covalent structure at high pressure. PMID:23574224

  11. Thermodynamic and kinetic stabilities of CO2 oligomers

    NASA Astrophysics Data System (ADS)

    Dunlap, Brett I.; Schweigert, Igor V.; Purdy, Andrew P.; Snow, Arthur W.; Hu, Anguang

    2013-04-01

    Density-functional and coupled cluster calculations suggest that the stability, against unimolecular dissociation, of the cyclic D3h trimer of CO2, 1,3,5-trioxetanetrione, is greater than all but one other chemically bound oligomer of CO2. It requires far less energy to produce, on a per CO2 basis, than the low-symmetry cyclic 1,2 dioxetanedione dimer, but its kinetic stability against unimolecular dissociation is much lower. The extreme stability of the dimer, which makes it an excellent intermediate in chemiluminescence, is caused by an extreme range of geometric change to its transition state leading to a trapezoidal potential energy surface. The thermodynamically more stable trimer affords a low pressure pathway from molecular carbon dioxide to the extended covalent structure at high pressure.

  12. First-principles-guided design of ionic liquids for CO2 capture.

    PubMed

    Wu, Chao; Senftle, Thomas P; Schneider, William F

    2012-10-14

    The identification of sorbents that combine selectively and reversibly with CO(2) is essential for efficient and economical abatement of ever-increasing CO(2) emissions. Room temperature ionic liquids (ILs) are a promising class of potential absorbents, especially when modified to chemically combine with CO(2). In this perspective we describe the evolution of IL-based CO(2) capture chemistries over the last ten years and in particular the important role that first principles simulations have played in helping guide those developments. Current anion-functionalized ILs achieve high CO(2) capture efficiencies tailorable to a wide range of separation conditions and avoid the viscosity problems that plagued the earliest amine-functionalized, CO(2)-reactive ILs. Further progress is needed to develop ILs able to meet all the requirements of a CO(2) separation system, and simulations will play a central role in those developments. PMID:22948394

  13. Lidar measurements of the column CO2 mixing ratio made by NASA Goddard's CO2 Sounder during the NASA ASCENDS 2014 Airborne campaign.

    NASA Astrophysics Data System (ADS)

    Ramanathan, A. K.; Mao, J.; Abshire, J. B.; Kawa, S. R.

    2015-12-01

    Remote sensing measurements of CO2 from space can help improve our understanding of the carbon cycle and help constrain the global carbon budget. However, such measurements need to be sufficiently accurate to detect small (1 ppm) changes in the CO2 mixing ratio (XCO2) against a large background (~ 400 ppm). Satellite measurements of XCO2 using passive spectrometers, such as those from the Japanese GOSAT (Greenhouse gas Observing Satellite) and the NASA OCO-2 (Orbiting Carbon Observatory-2) are limited to daytime sunlit portions of the Earth and are susceptible to biases from clouds and aerosols. For this reason, NASA commissioned the formulation study of ASCENDS a space-based lidar mission. NASA Goddard Space Flight Center's CO2 Sounder lidar is one candidate approach for the ASCENDS mission. The NASA GSFC CO2 Sounder measures the CO2 mixing ratio using a pulsed multi-wavelength integrated path differential absorption (IPDA) approach. The CO2 Sounder has flown in the 2011, 2013 and 2014 ASCENDS airborne campaigns over the continental US, and has produced measurements in close agreement with in situ measurements of the CO2 column. In 2014, the CO2 Sounder upgraded its laser with a precision step-locked diode laser source to improve the lidar wavelength position accuracy. It also improved its optical receiver with a low-noise, high efficiency, HgCdTe avalanche photo diode detector. The combination of these two technologies enabled lidar XCO2 measurements with unprecedented accuracy. In this presentation, we show analysis from the ASCENDS 2014 field campaign, exploring: (1) Horizontal XCO2 gradients measured by the lidar, (2) Comparisons of lidar XCO2 measurements against the Parameterized Chemistry Transport Model (PCTM), and (3) Lidar column water vapor measurements using a HDO absorption line that occurs next to the CO2 absorption line. This can reduce the uncertainty in the dry air column used in XCO2 retrievals.

  14. R&D100: CO2 Memzyme

    SciTech Connect

    Rempe, Susan; Brinker, Jeff; Jiang, Ying-Bing; Vanegas, Juan

    2015-11-19

    By combining a water droplet loaded with CO2 enzymes in an ultrathin nanopore on a flexible substrate, researchers at Sandia National Laboratories realized the first technology that meets and exceeds DOE targets for cost-effective CO2 capture. When compared with the nearest membrane competitor, this technology delivers a three times permeation rate, twenty times higher selectivity, and ten time lower fabrication cost. The CO2 Memzyme has the potential to remove 90% of CO2 emissions and is forecasted to save the U.S. coal industry $90 billion a year compared to conventional technology.

  15. CO2 MITIGATION VIA ACCELERATED LIMESTONE WEATHERING

    SciTech Connect

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

    2004-02-27

    The climate and environmental impacts of our current, carbon-intensive energy usage demands that effective and practical energy alternatives and CO2 mitigation strategies be found. As part of this effort, various means of capturing and storing CO2 generated from fossil-fuel-based energy production are being investigated. One of the proposed methods involves a geochemistry-based capture and sequestration process that hydrates point-source, waste CO2 with water to produce a carbonic acid solution. This in turn is reacted and neutralized with limestone, thus converting the original CO2 gas to calcium bicarbonate in solution, the overall reaction being:

  16. TCS Upgrade

    NASA Astrophysics Data System (ADS)

    Grossnickle, J. A.; Miller, K. E.

    2004-11-01

    The original TCS experiment has demonstrated the robust ability to form and sustain FRCs in steady-state using Rotating Magnetic Fields (RMF). Radiation levels, which are due in large part to Oxygen, are seen to increase dramatically after the initial formation phase ( ˜0.5 msec), causing a severe drop in the plasma temperature. Since the RMF magnitude and frequency determine the plasma density, as the temperature is limited, so is the FRC's external field and energy confinement time. In order to improve temperatures and flux levels, TCS is being extensively upgraded. All o-ring sealed flanges will be replaced with wire sealed flanges, and heating blankets installed to bake the system to 200 C. Internal flux rings, shielded with Tantalum, will be installed to shield the quartz and stainless steel vacuum wall from the plasma. Unique aspects of this design are related to the interface between the quartz section needed to allow penetration of the RMF from the external antennas and the adjacent stainless steel vacuum chambers. Wall conditioning will include glow discharge, Ti gettering, siliconization, and/or boronization. The total system will be described.

  17. A Critical Assessment of Microbiological Biogas to Biomethane Upgrading Systems.

    PubMed

    Rittmann, Simon K-M R

    2015-01-01

    Microbiological biogas upgrading could become a promising technology for production of methane (CH(4)). This is, storage of irregular generated electricity results in a need to store electricity generated at peak times for use at non-peak times, which could be achieved in an intermediate step by electrolysis of water to molecular hydrogen (H(2)). Microbiological biogas upgrading can be performed by contacting carbon dioxide (CO(2)), H(2) and hydrogenotrophic methanogenic Archaea either in situ in an anaerobic digester, or ex situ in a separate bioreactor. In situ microbiological biogas upgrading is indicated to require thorough bioprocess development, because only low volumetric CH(4) production rates and low CH(4) fermentation offgas content have been achieved. Higher volumetric production rates are shown for the ex situ microbiological biogas upgrading compared to in situ microbiological biogas upgrading. However, the ex situ microbiological biogas upgrading currently suffers from H(2) gas liquid mass transfer limitation, which results in low volumetric CH(4) productivity compared to pure H(2)/CO(2) conversion to CH(4). If waste gas utilization from biological and industrial sources can be shown without reduction in volumetric CH(4) productivity, as well as if the aim of a single stage conversion to a CH(4) fermentation offgas content exceeding 95 vol% can be demonstrated, ex situ microbiological biogas upgrading with pure or enrichment cultures of methanogens could become a promising future technology for almost CO(2)-neutral biomethane production.

  18. Role of CO2 in the formation of gold deposits.

    PubMed

    Phillips, G N; Evans, K A

    2004-06-24

    Much of global gold production has come from deposits with uneconomic concentrations of base metals, such as copper, lead and zinc. These 'gold-only' deposits are thought to have formed from hot, aqueous fluids rich in carbon dioxide, but only minor significance has been attached to the role of the CO2 in the process of gold transport. This is because chemical bonding between gold ions and CO2 species is not strong, and so it is unlikely that CO2 has a direct role in gold transport. An alternative indirect role for CO2 as a weak acid that buffers pH has also appeared unlikely, because previously inferred pH values for such gold-bearing fluids are variable. Here we show that such calculated pH values are unlikely to record conditions of gold transport, and propose that CO2 may play a critical role during gold transport by buffering the fluid in a pH range where elevated gold concentration can be maintained by complexation with reduced sulphur. Our conclusions, which are supported by geochemical modelling, may provide a platform for new gold exploration methods.

  19. A novel CO 2 gas analyzer based on IR absorption

    NASA Astrophysics Data System (ADS)

    Zhang, Guangjun; Wu, Xiaoli

    2004-08-01

    Carbon dioxide (CO 2) gas analyzer can be widely used in many fields. A novel CO 2 gas analyzer based on infrared ray (IR) absorption is presented sufficiently in this paper. Applying Lambert-Beer Law, a novel space-double-beam optical structure is established successfully. The optical structure includes an IR source, a gas cell, a bandpass filter with a transmission wavelength at 4.26 μm, another bandpass filter with a transmission wavelength at 3.9 μm, and two IR detectors. Based on Redial Basic Function (RBF) artificial neural network, the measuring model of IR CO 2 analyzer is established with a high accuracy. A dynamic compensation filter is effectively designed to improve the dynamic characteristic of the IR CO 2 analyzer without gas pump. The IR CO 2 analyzer possesses the advantages of high accuracy and mechanical reliability with small volume, lightweight, and low-power consumption. Therefore, it can be used in such relevant fields as environmental protection, processing control, chemical analysis, medical diagnosis, and space environmental and control systems.

  20. CO2 Interaction with Geomaterials (Invited)

    NASA Astrophysics Data System (ADS)

    Romanov, V.; Howard, B. H.; Lynn, R. J.; Warzinski, R. P.; Hur, T.; Myshakin, E. M.; Lopano, C. L.; Voora, V. K.; Al-Saidi, W. A.; Jordan, K. D.; Cygan, R. T.; Guthrie, G. D.

    2010-12-01

    This work compares the sorption and swelling processes associated with CO2-coal and CO2-clay interactions. We investigated the mechanisms of interaction related to CO2 adsortion in micropores, intercalation into sub-micropores, dissolution in solid matrix, the role of water, and the associated changes in reservoir permeability, for applications in CO2 sequestration and enhanced coal bed methane recovery. The structural changes caused by CO2 have been investigated. A high-pressure micro-dilatometer was equipped to investigate the effect of CO2 pressure on the thermoplastic properties of coal. Using an identical dilatometer, Rashid Khan (1985) performed experiments with CO2 that revealed a dramatic reduction in the softening temperature of coal when exposed to high-pressure CO2. A set of experiments was designed for -20+45-mesh samples of Argonne Premium Pocahontas #3 coal, which is similar in proximate and ultimate analysis to the Lower Kittanning seam coal that Khan used in his experiments. No dramatic decrease in coal softening temperature has been observed in high-pressure CO2 that would corroborate the prior work of Khan. Thus, conventional polymer (or “geopolymer”) theories may not be directly applicable to CO2 interaction with coals. Clays are similar to coals in that they represent abundant geomaterials with well-developed microporous structure. We evaluated the CO2 sequestration potential of clays relative to coals and investigated the factors that affect the sorption capacity, rates, and permanence of CO2 trapping. For the geomaterials comparison studies, we used source clay samples from The Clay Minerals Society. Preliminary results showed that expandable clays have CO2 sorption capacities comparable to those of coal. We analyzed sorption isotherms, XRD, DRIFTS (infrared reflectance spectra at non-ambient conditions), and TGA-MS (thermal gravimetric analysis) data to compare the effects of various factors on CO2 trapping. In montmorillonite, CO2

  1. CO2 Leak Detection Using Hyperspectral Plant Signatures During the 2008 ZERT CO2 Sequestration Field Experiment in Bozeman, MT

    NASA Astrophysics Data System (ADS)

    Male, E. J.; Pickles, W. L.; Silver, E. A.; Lewicki, J. L.; Apple, M.; Burton, E. A.

    2008-12-01

    Geologic sequestration of carbon dioxide is a potential method of mitigating increased carbon dioxide (CO2) emissions into the atmosphere. However, the impact CO2 sequestration would have on various physical, chemical, and biological systems needs to be explored in order to effectively utilize this technique long term. We used plants to detect the effects of releasing pure carbon dioxide gas through a 100-meter long horizontal well, varying between 1 and 2.5 meters below ground surface, at a flow rate of 0.3 tons per day for 29 days, beginning on July 9th, 2008. An influx of CO2 gas into the soil induces stress on vegetation, which can be observed in their visible to near infrared reflectance spectral signatures. We followed the health of a 20 meter by 30 meter patch of plants (including alfalfa, dandelion, Timothy grass, Tall fescue grass, and Orchard grass), located along and across the injection well. 68 sites were chosen within the plant patch where spectral signatures were measured almost daily with an Analytical Spectral Devices "FieldSpec Pro" spectrometer. These sites were located over the injection well and up to 10 meters off the well. This array gave us data both within and outside of the CO2 leak zone so we could normalize our observations for all other environmental factors affecting the plants. On August 5, 2008, airborne hyperspectral imagery was also acquired from a low flying aircraft using a hyperspectral camera developed by Resonon, Inc. of Bozeman, MT. In addition, other groups participating in the ZERT experiment measured various parameters of the field site, such as CO2 flux mapping, soil CO2 concentrations, atmospheric CO2 concentrations, plant isotopics, soil moisture, groundwater chemistry, and depth to groundwater. Four to five days after the start of the CO2 injection, stress was observed in the spectral signatures of plants within 1 meter of the well. After approximately ten days of CO2 injection, plants located up to 2.5 meters from the

  2. Potential of satellite CO2 data to infer CO2 fluxes, using atmospheric inversion: influence of data uncertainty correlations

    NASA Astrophysics Data System (ADS)

    Montandon, V.; Peylin, P.; Bousquet, P.; Ciais, P.; Breon, F.-M.

    2003-04-01

    Knowledge of present surface sources and sinks of atmospheric CO2 is crucial to quantify the future man-induced green-house effect. Measurements of radiation from space potentially offer denser samplings of CO2 column amount, both in time and space than in situ measurements. This could allow in turn to decrease the uncertainties of CO2 flux estimates, depending on the achievable precision of CO2 retrievals from space, and on the removal of any spatially coherent bias. In the framework of the COCO project, shaped to take advantage of the sooncoming or present satellite missions, we enriched some investigations about the satellite observations potential to improve the atmospheric CO2 sinks and sources knowledge. Our particular study dealt with the introduction of spatial correlations between the individual measurement errors of CO2 column amount, to inverstigate possible coherent biases between satellite data. One year of pseudo-data was generated according to the CARBOSAT project instrumental and orbital characteristics. These individual data were then grouped month by month onto the grid of the LMDZ transport model. The classical independance assumption made in all priors study about the measurement errors lead to a large decrease of the final satellite data uncertainty. However, spatially coherent bias would bring correlated data uncertainties, a feature that would largely affect the results. We quantified here the influence of these correlations on the retrieved CO2 flux uncertainties. Several transport model grids (regular / non regular) were used to aggregate the individual measurements, and their influence is also discussed. Such results could also be applied to other reactive chemical species like CH4, CO, ...

  3. Conversion of CO2 into biomass by microalgae: how realistic a contribution may it be to significant CO2 removal?

    PubMed

    Acién Fernández, F Gabriel; González-López, C V; Fernández Sevilla, J M; Molina Grima, E

    2012-11-01

    Microalgae have been proposed as a CO(2) removal option to contribute to climate change avoidance and problems coming from the use of fossil fuels. However, even though microalgae can be used to fix CO(2) from air or flue gases, they do not permit long-term CO(2) storage because they are easily decomposed. On the other hand, microalgae can contribute to an enhancement in human sustainability by producing biofuels as an alternative to fossil fuels in addition to the production of other useful chemicals and commodities. Moreover, microalgae can contribute to enhancing the sustainability of waste treatment processes, reducing the energy consumed, and improving the recycling of nutrients contained within them. This paper reviews the potential contribution of these processes and the existing knowledge in these areas. PMID:22923096

  4. Characterization of CO2 leakage into the freshwater body

    NASA Astrophysics Data System (ADS)

    Singh, Ashok; Delfs, Jens-Olaf; Shao, Habing; Kolditz, Olaf

    2013-04-01

    Current research into Carbon dioxide Capture and Storage (CCS) is dominated by improving the CO2 storage capacity. However, potential leakage of CO2 can cause environmental problems, particularly if freshwater resources are nearby. In this regards, it is important to understand the chemistry of CO2 and the water system. CO2 leakage across the fluid interface (CO2 and water) is controlled by the difference in the partial pressure of CO2 in the storage and in the freshwater body. Once the CO2 is in solution, it equilibrates with the bicarbonate and carbonate ions. According to Millero (1994)such a system can be characterized by two parameters out of the four: total alkalinity (TA), total carbonate (TCO2), fugacity of CO2(fCO2) and pH. In the present modeling study, we are interested in the (i) CO2 leakage into a freshwater body (while injecting CO2 for storage) through an inclined fracture and (ii) characterization of the system by measuring fugacity of CO2 and pH. According to work presented by Singh et al. (2012), about 31% of injected CO2 leaks into the freshwater body. Solubility of CO2 in water follows Henry's law, while the Henry constant, K0 is calculated by an empirical relation developed by Murray and Riley (1971), which is a function of salinity and temperature. According to our results, pH and fugacity both appear to be a linear function of temperature. To simulate the discussed problem, a corresponding numerical module has been developed for multi-component fluid flow coupled with heat and mass transport processes. Governing equations and Volume Translated Peng-Robinson equations of state are implemented within the object-oriented finite element code OpenGeoSys (Kolditz et al., 2012; www.opengeosys.org). Primary variables are pressure, temperature and salinity which are obtained by solving the governing equations in a monolithic way The governing equations are discretized spatially within the context of a Galerkin approach, whereas the temporal

  5. CO2 annual and semiannual cycles from multiple satellite retrievals and models

    NASA Astrophysics Data System (ADS)

    Jiang, Xun; Crisp, David; Olsen, Edward T.; Kulawik, Susan S.; Miller, Charles E.; Pagano, Thomas S.; Liang, Maochang; Yung, Yuk L.

    2016-02-01

    Satellite CO2 retrievals from the Greenhouse gases Observing SATellite (GOSAT), Atmospheric Infrared Sounder (AIRS), and Tropospheric Emission Spectrometer (TES) and in situ measurements from the National Oceanic and Atmospheric Administration - Earth System Research Laboratory (NOAA-ESRL) Surface CO2 and Total Carbon Column Observing Network (TCCON) are utilized to explore the CO2 variability at different altitudes. A multiple regression method is used to calculate the CO2 annual cycle and semiannual cycle amplitudes from different data sets. The CO2 annual cycle and semiannual cycle amplitudes for GOSAT XCO2 and TCCON XCO2 are consistent but smaller than those seen in the NOAA-ESRL surface data. The CO2 annual and semiannual cycles are smallest in the AIRS midtropospheric CO2 compared with other data sets in the Northern Hemisphere. The amplitudes for the CO2 annual cycle and semiannual cycle from GOSAT, TES, and AIRS CO2 are small and comparable to each other in the Southern Hemisphere. Similar regression analysis is applied to the Model for OZone And Related chemical Tracers-2 and CarbonTracker model CO2. The convolved model CO2 annual cycle and semiannual cycle amplitudes are similar to those from the satellite CO2 retrievals, although the models tend to underestimate the CO2 seasonal cycle amplitudes in the Northern Hemisphere midlatitudes and underestimate the CO2 semiannual cycle amplitudes in the high latitudes. These results can be used to better understand the vertical structures for the CO2 annual cycle and semiannual cycle and help identify deficiencies in the models, which are very important for the carbon budget study.

  6. Improved quantification of Chinese carbon fluxes using CO2/CO correlations in Asian outflow

    NASA Astrophysics Data System (ADS)

    Suntharalingam, Parvadha; Jacob, Daniel J.; Palmer, Paul I.; Logan, Jennifer A.; Yantosca, Robert M.; Xiao, Yaping; Evans, Mathew J.; Streets, David G.; Vay, Stephanie L.; Sachse, Glen W.

    2004-09-01

    We use observed CO2:CO correlations in Asian outflow from the TRACE-P aircraft campaign (February-April 2001), together with a three-dimensional global chemical transport model (GEOS-CHEM), to constrain specific components of the east Asian CO2 budget including, in particular, Chinese emissions. The CO2/CO emission ratio varies with the source of CO2 (different combustion types versus the terrestrial biosphere) and provides a characteristic signature of source regions and source type. Observed CO2/CO correlation slopes in east Asian boundary layer outflow display distinct regional signatures ranging from 10-20 mol/mol (outflow from northeast China) to 80 mol/mol (over Japan). Model simulations using best a priori estimates of regional CO2 and CO sources from [2003] (anthropogenic), the CASA model (biospheric), and [2003] (biomass burning) overestimate CO2 concentrations and CO2/CO slopes in the boundary layer outflow. Constraints from the CO2/CO slopes indicate that this must arise from an overestimate of the modeled regional net biospheric CO2 flux. Our corrected best estimate of the net biospheric source of CO2 from China for March-April 2001 is 3200 Gg C/d, which represents a 45% reduction of the net flux from the CASA model. Previous analyses of the TRACE-P data had found that anthropogenic Chinese CO emissions must be ˜50% higher than in 's [2003] inventory. We find that such an adjustment improves the simulation of the CO2/CO slopes and that it likely represents both an underreporting of sector activity (domestic and industrial combustion) and an underestimate of CO emission factors. Increases in sector activity would imply increases in Chinese anthropogenic CO2 emissions and would also imply a further reduction of the Chinese biospheric CO2 source to reconcile simulated and observed CO2 concentrations.

  7. CO2 Capture with Enzyme Synthetic Analogue

    SciTech Connect

    Cordatos, Harry

    2010-11-08

    Overview of an ongoing, 2 year research project partially funded by APRA-E to create a novel, synthetic analogue of carbonic anhydrase and incorporate it into a membrane for removal of CO2 from flue gas in coal power plants. Mechanism background, preliminary feasibility study results, molecular modeling of analogue-CO2 interaction, and program timeline are provided.

  8. Capturing CO2 via reactions in nanopores.

    SciTech Connect

    Leung, Kevin; Nenoff, Tina Maria; Criscenti, Louise Jacqueline; Tang, Z; Dong, J. H.

    2008-10-01

    This one-year exploratory LDRD aims to provide fundamental understanding of the mechanism of CO2 scrubbing platforms that will reduce green house gas emission and mitigate the effect of climate change. The project builds on the team members expertise developed in previous LDRD projects to study the capture or preferential retention of CO2 in nanoporous membranes and on metal oxide surfaces. We apply Density Functional Theory and ab initio molecular dynamics techniques to model the binding of CO2 on MgO and CaO (100) surfaces and inside water-filled, amine group functionalized silica nanopores. The results elucidate the mechanisms of CO2 trapping and clarify some confusion in the literature. Our work identifies key future calculations that will have the greatest impact on CO2 capture technologies, and provides guidance to science-based design of platforms that can separate the green house gas CO2 from power plant exhaust or even from the atmosphere. Experimentally, we modify commercial MFI zeolite membranes and find that they preferentially transmit H2 over CO2 by a factor of 34. Since zeolite has potential catalytic capability to crack hydrocarbons into CO2 and H2, this finding paves the way for zeolite membranes that can convert biofuel into H2 and separate the products all in one step.

  9. CO2 Capture with Enzyme Synthetic Analogue

    SciTech Connect

    Cordatos, Harry

    2010-03-01

    Project overview provides background on carbonic anhydrase transport mechanism for CO2 in the human body and proposed approach for ARPA-E project to create a synthetic enzyme analogue and utilize it in a membrane for CO2 capture from flue gas.

  10. Liquid CO2 venting on the seafloor: Yonaguni Knoll IV hydrothermal system, Okinawa Trough

    NASA Astrophysics Data System (ADS)

    Konno, Uta; Tsunogai, Urumu; Nakagawa, Fumiko; Nakaseama, Miwako; Ishibashi, Jun-ichiro; Nunoura, Takuro; Nakamura, Ko-ichi

    2006-08-01

    We determined the chemical and isotopic compositions of the liquid CO2 found on Yonaguni IV knoll hydrothermal site, as well as those in hydrothermal fluid venting from the surrounding chimneys. The δ13C of both CO2 and CH4 in the liquid CO2 almost coincide with those in the hydrothermal fluid, suggesting that the liquid CO2 must be derived from the hydrothermal fluid. While showing homogeneous δ13C, the hydrothermal fluids exhibit wide variation in gas contents. Active phase separation must be taking place within the conduits. Besides, H2-depletion in the liquid CO2 suggests formation of solid CO2-hydrate must also precede the venting of liquid CO2. In conclusion, liquid CO2 must be produced through following subseafloor processes: phase separation of hydrothermal fluid due to boiling, formation of solid CO2-hydrate due to cooling of vapor phase, and melting of the solid CO2-hydrate to liquid CO2 due to a temperature increase within the sedimentary layer.

  11. Rate of CO2 attack on hydrated Class H well cement under geologic sequestration conditions.

    PubMed

    Kutchko, Barbara G; Strazisar, Brian R; Lowry, Gregory V; Dzombak, David A; Thaulow, Niels

    2008-08-15

    Experiments were conducted to study the degradation of hardened cement paste due to exposure to CO2 and brine under geologic sequestration conditions (T = 50 degrees C and 30.3 MPa). The goal was to determine the rate of reaction of hydrated cement exposed to supercritical CO2 and to CO2-saturated brine to assess the potential impact of degradation in existing wells on CO2 storage integrity. Two different forms of chemical alteration were observed. The supercritical CO2 alteration of cement was similar in process to cement in contact with atmospheric CO2 (ordinary carbonation), while alteration of cement exposed to CO2-saturated brine was typical of acid attack on cement. Extrapolation of the hydrated cement alteration rate measured for 1 year indicates a penetration depth range of 1.00 +/- 0.07 mm for the CO2-saturated brine and 1.68 +/- 0.24 mm for the supercritical CO2 after 30 years. These penetration depths are consistent with observations of field samples from an enhanced oil recovery site after 30 years of exposure to CO2-saturated brine under similar temperature and pressure conditions. These results suggest that significant degradation due to matrix diffusion of CO2 in intact Class H neat hydrated cement is unlikely on time scales of decades. PMID:18767693

  12. Evasion of CO2 Injected into the Ocean in the Context of CO2 Stabilization

    NASA Astrophysics Data System (ADS)

    Kheshgi, H. S.

    2002-05-01

    The injection captured CO2 into the deep ocean is one potential option for sequestering CO2 from the atmosphere. Aspects of this potential option include cost, effects on the marine environment and the eventual evasion of injected CO2 to the atmosphere. Estimates of evasion are considered in the context of long-term scenarios for future CO2 emissions, including illustrative cases leading to stabilization of CO2 concentration at various levels. Ocean carbon cycle model results are used to illustrate how the timing of evasion of injected CO2 fits with current conceptions of the timing of future changes in atmospheric CO2 concentration. Of course, some CO2 emissions would be immediately incurred from the effort required to capture, transport and inject CO2. Modeled residence time for CO2 injected into the deep ocean exceeds the 100 year time scale usually considered in scenarios for future emissions, and the potential impacts of climate change. Illustrative cases leading monotonically to constant CO2 concentration have been highlighted by the Intergovernmental Panel on Climate Change to give guidance on possible timing of emission reductions that may be required to stabilize CO2 concentrations at various levels. For cases considered, significant modeled evasion does not occur until long after CO2 emissions have reached a maximum and begun to decline. Illustrative cases can also lead to a maximum in CO2 concentration followed by a decline to lower, possibly constant, concentrations. In such cases, injection of emissions into the deep ocean leads to lower maximum CO2 concentrations, with less effect on concentrations later on in time. Alternative illustrative cases leading to stabilization of CO2 concentration provide a perspective to view evasion of injected CO2 in relation to emissions from technologies in the distant future.

  13. A model for the evolution of CO2 on Mars

    NASA Technical Reports Server (NTRS)

    Haberle, Robert M.; Tyler, Daniel; Mckay, Christopher P.; Davis, Wanda L.

    1994-01-01

    We have constructed a model that predicts the evolution of CO2 on Mars from the end of the heavy bombardment period to the present. The model draws on published estimates of the main processes believed to affect the fate of CO2 during this period: chemical weathering, regolith uptake, polar cap formation, and atmospheric escape. Except for escape, the rate at which these processes act is controlled by surface temperatures which we calculate using a modified version of the Gierasch and Toon energy balance model. The modifications account for the change in solar luminosity with time, the greenhouse effect, and a polar and equatorial energy budget. Using published estimates for the main parameters, we find no evolutionary scenario in which CO2 is capable of producing a warm (global mean temperatures greater than 250 K) and wet (surface pressures greater than 30 mbar) early climate, and then evolves to present conditions with approximately 7 mbar in the atmosphere, less than 300 mbar in the regolith, and less than 5 mbar in the caps. Such scenarios would only exist if the early sun were brighter than standard solar models suggest, if greenhouse gases other than CO2 were present in the early atmosphere, or if the polar albedo were significantly lower than 0.75. However, these scenarios generally require the storage of large amounts of CO2 (greater than 1 bar) in the carbonate reservoir. If the warm and wet early Mars constraint is relaxed, then we find best overall agreement with present day reservoirs for initial CO2 inventories of 0.5-1.0 bar. We also find that the polar caps can have a profound effect on how the system evolves. If the initial amount of CO2 is less than some critical value, then there is not enough heating of the poles to prevent permanent caps from forming. Once formed, these caps control how the system evolves, because they set the surface pressure and, hence, the thermal environment. If the initial amount of CO2 is greater than this critical value

  14. A model for the evolution of CO2 on Mars.

    PubMed

    Haberle, R M; Tyler, D; McKay, C P; Davis, W L

    1994-05-01

    We have constructed a model that predicts the evolution of CO2 on Mars from the end of the heavy bombardment period to the present. The model draws on published estimates of the main processes believed to affect the fate of CO2 during this period: chemical weathering, regolith uptake, polar cap formation, and atmospheric escape. Except for escape, the rate at which these processes act is controlled by surface temperatures which we calculate using a modified version of the Gierasch and Toon energy balance model (1973, J. Atmos. Sci. 30, 1502-1508). The modifications account for the change in solar luminosity with time, the greenhouse effect, and a polar and solar equatorial energy budget. Using published estimates for the main parameters, we find no evolutionary scenario in which CO2 is capable of producing a warm (global mean temperatures>250 K) and wet (surface pressures>30 mbar) early climate, and then evolves to present conditions with approximately 7 mbar in the atmosphere, <300 mbar in the regolith, and <5 mbar in the caps. Such scenarios would only exist if the early sun were brighter than standard solar models suggest, if greenhouse gases other than CO2 were present in the early atmosphere, or if the polar albedo were significantly lower than 0.75. However, these scenarios generally require the storage of large amounts of CO2 (>1 bar) in the carbonate reservoir. If the warm and wet early Mars constraint is relaxed, then we find best overall agreement with present day reservoirs for initial CO2 inventories of 0.5-1.0 bar. We also find that the polar caps can a profound effect on how the system evolves. If the initial amount of CO2 is less than some critical value, then there is not enough heating of the poles to prevent permanent caps from forming. Once formed, these caps control how the system evolves, because they set the surface pressure and, hence, the thermal environment. If the initial amount of CO2 is greater than this critical value, then caps do not

  15. A model for the evolution of CO2 on Mars.

    PubMed

    Haberle, R M; Tyler, D; McKay, C P; Davis, W L

    1994-05-01

    We have constructed a model that predicts the evolution of CO2 on Mars from the end of the heavy bombardment period to the present. The model draws on published estimates of the main processes believed to affect the fate of CO2 during this period: chemical weathering, regolith uptake, polar cap formation, and atmospheric escape. Except for escape, the rate at which these processes act is controlled by surface temperatures which we calculate using a modified version of the Gierasch and Toon energy balance model (1973, J. Atmos. Sci. 30, 1502-1508). The modifications account for the change in solar luminosity with time, the greenhouse effect, and a polar and solar equatorial energy budget. Using published estimates for the main parameters, we find no evolutionary scenario in which CO2 is capable of producing a warm (global mean temperatures>250 K) and wet (surface pressures>30 mbar) early climate, and then evolves to present conditions with approximately 7 mbar in the atmosphere, <300 mbar in the regolith, and <5 mbar in the caps. Such scenarios would only exist if the early sun were brighter than standard solar models suggest, if greenhouse gases other than CO2 were present in the early atmosphere, or if the polar albedo were significantly lower than 0.75. However, these scenarios generally require the storage of large amounts of CO2 (>1 bar) in the carbonate reservoir. If the warm and wet early Mars constraint is relaxed, then we find best overall agreement with present day reservoirs for initial CO2 inventories of 0.5-1.0 bar. We also find that the polar caps can a profound effect on how the system evolves. If the initial amount of CO2 is less than some critical value, then there is not enough heating of the poles to prevent permanent caps from forming. Once formed, these caps control how the system evolves, because they set the surface pressure and, hence, the thermal environment. If the initial amount of CO2 is greater than this critical value, then caps do not

  16. Geophysical monitoring technology for CO2 sequestration

    NASA Astrophysics Data System (ADS)

    Ma, Jin-Feng; Li, Lin; Wang, Hao-Fan; Tan, Ming-You; Cui, Shi-Ling; Zhang, Yun-Yin; Qu, Zhi-Peng; Jia, Ling-Yun; Zhang, Shu-Hai

    2016-06-01

    Geophysical techniques play key roles in the measuring, monitoring, and verifying the safety of CO2 sequestration and in identifying the efficiency of CO2-enhanced oil recovery. Although geophysical monitoring techniques for CO2 sequestration have grown out of conventional oil and gas geophysical exploration techniques, it takes a long time to conduct geophysical monitoring, and there are many barriers and challenges. In this paper, with the initial objective of performing CO2 sequestration, we studied the geophysical tasks associated with evaluating geological storage sites and monitoring CO2 sequestration. Based on our review of the scope of geophysical monitoring techniques and our experience in domestic and international carbon capture and sequestration projects, we analyzed the inherent difficulties and our experiences in geophysical monitoring techniques, especially, with respect to 4D seismic acquisition, processing, and interpretation.

  17. Zinc depolarized electrochemical CO2 concentration

    NASA Technical Reports Server (NTRS)

    Woods, R. R.; Marshall, R. D.; Schubert, F. H.

    1975-01-01

    Two zinc depolarized electrochemical carbon dioxide concentrator concepts were analytically and experimentally evaluated for portable life support system carbon dioxide (CO2) removal application. The first concept, referred to as the zinc hydrogen generator electrochemical depolarized CO2 concentrator, uses a ZHG to generate hydrogen for direct use in an EDC. The second concept, referred to as the zinc/electrochemical depolarized concentrator, uses a standard EDC cell construction modified for use with the Zn anode. The Zn anode is consumed and subsequently regenerated, thereby eliminating the need to supply H2 to the EDC for the CO2 removal process. The evaluation was based primarily on an analytical evaluation of the two ZnDCs at projected end item performance and hardware design levels. Both ZnDC concepts for PLSS CO2 removal application were found to be noncompetitive in both total equivalent launch weight and individual extravehicular activity mission volume when compared to other candidate regenerable PLSS CO2 scrubbers.

  18. Venting of CO2 at Enceladus’ Surface

    NASA Astrophysics Data System (ADS)

    Matson, Dennis L.; Davies, Ashley G.; Johnson, Torrence V.; Combe, Jean-Philippe; McCord, Tom B.; Radebaugh, Jani

    2015-11-01

    Enceladus has CO2 surface deposits in its South Polar Region that have been recently mapped by J.-P. Combe et al. (2015 AGU Fall Meeting). Assuming that these are CO2 frost, we show how they can be formed. We use an ocean-water circulation model [1] that specifies pressure gradients that drive water to the surface from a relatively gas-rich, subsurface ocean. We now examine the movement of CO2 to the surface; formation of shallow CO2 gas pockets in the ice; and the venting of CO2, when at least some of the gas freezes to form frost. If the local heat flow is known (cf. [2]), then the depths of the corresponding gas pockets can be calculated. References: [1] Matson et al. (2012) Icarus, 221, 53-62. [2] Howett et al. (2011) J. Geophys. Res. 116, E03003. Acknowledgements: AGD thanks the NASA OPR Program for support.

  19. The ins and outs of CO2.

    PubMed

    Raven, John A; Beardall, John

    2016-01-01

    It is difficult to distinguish influx and efflux of inorganic C in photosynthesizing tissues; this article examines what is known and where there are gaps in knowledge. Irreversible decarboxylases produce CO2, and CO2 is the substrate/product of enzymes that act as carboxylases and decarboxylases. Some irreversible carboxylases use CO2; others use HCO3(-). The relative role of permeation through the lipid bilayer versus movement through CO2-selective membrane proteins in the downhill, non-energized, movement of CO2 is not clear. Passive permeation explains most CO2 entry, including terrestrial and aquatic organisms with C3 physiology and biochemistry, terrestrial C4 plants and all crassulacean acid metabolism (CAM) plants, as well as being part of some mechanisms of HCO3(-) use in CO2 concentrating mechanism (CCM) function, although further work is needed to test the mechanism in some cases. However, there is some evidence of active CO2 influx at the plasmalemma of algae. HCO3(-) active influx at the plasmalemma underlies all cyanobacterial and some algal CCMs. HCO3(-) can also enter some algal chloroplasts, probably as part of a CCM. The high intracellular CO2 and HCO3(-) pools consequent upon CCMs result in leakage involving CO2, and occasionally HCO3(-). Leakage from cyanobacterial and microalgal CCMs involves up to half, but sometimes more, of the gross inorganic C entering in the CCM; leakage from terrestrial C4 plants is lower in most environments. Little is known of leakage from other organisms with CCMs, though given the leakage better-examined organisms, leakage occurs and increases the energetic cost of net carbon assimilation.

  20. The ins and outs of CO2

    PubMed Central

    Raven, John A.; Beardall, John

    2016-01-01

    It is difficult to distinguish influx and efflux of inorganic C in photosynthesizing tissues; this article examines what is known and where there are gaps in knowledge. Irreversible decarboxylases produce CO2, and CO2 is the substrate/product of enzymes that act as carboxylases and decarboxylases. Some irreversible carboxylases use CO2; others use HCO3 –. The relative role of permeation through the lipid bilayer versus movement through CO2-selective membrane proteins in the downhill, non-energized, movement of CO2 is not clear. Passive permeation explains most CO2 entry, including terrestrial and aquatic organisms with C3 physiology and biochemistry, terrestrial C4 plants and all crassulacean acid metabolism (CAM) plants, as well as being part of some mechanisms of HCO3 – use in CO2 concentrating mechanism (CCM) function, although further work is needed to test the mechanism in some cases. However, there is some evidence of active CO2 influx at the plasmalemma of algae. HCO3 – active influx at the plasmalemma underlies all cyanobacterial and some algal CCMs. HCO3 – can also enter some algal chloroplasts, probably as part of a CCM. The high intracellular CO2 and HCO3 – pools consequent upon CCMs result in leakage involving CO2, and occasionally HCO3 –. Leakage from cyanobacterial and microalgal CCMs involves up to half, but sometimes more, of the gross inorganic C entering in the CCM; leakage from terrestrial C4 plants is lower in most environments. Little is known of leakage from other organisms with CCMs, though given the leakage better-examined organisms, leakage occurs and increases the energetic cost of net carbon assimilation. PMID:26466660

  1. Stomatal proxy record of CO2 concentrations from the last termination suggests an important role for CO2 at climate change transitions

    NASA Astrophysics Data System (ADS)

    Steinthorsdottir, Margret; Wohlfarth, Barbara; Kylander, Malin E.; Blaauw, Maarten; Reimer, Paula J.

    2013-05-01

    A new stomatal proxy-based record of CO2 concentrations ([CO2]), based on Betula nana (dwarf birch) leaves from the Hässeldala Port sedimentary sequence in south-eastern Sweden, is presented. The record is of high chronological resolution and spans most of Greenland Interstadial 1 (GI-1a to 1c, Allerød pollen zone), Greenland Stadial 1 (GS-1, Younger Dryas pollen zone) and the very beginning of the Holocene (Preboreal pollen zone). The record clearly demonstrates that i) [CO2] were significantly higher than usually reported for the Last Termination and ii) the overall pattern of CO2 evolution through the studied time period is fairly dynamic, with significant abrupt fluctuations in [CO2] when the climate moved from interstadial to stadial state and vice versa. A new loss-on-ignition chemical record (used here as a proxy for temperature) lends independent support to the Hässeldala Port [CO2] record. The large-amplitude fluctuations around the climate change transitions may indicate unstable climates and that “tipping-point” situations were involved in Last Termination climate evolution. The scenario presented here is in contrast to [CO2] records reconstructed from air bubbles trapped in ice, which indicate lower concentrations and a gradual, linear increase of [CO2] through time. The prevalent explanation for the main climate forcer during the Last Termination being ocean circulation patterns needs to re-examined, and a larger role for atmospheric [CO2] considered.

  2. Stomatal proxy record of CO2 concentrations during the Last Termination demonstrates dynamic climate behaviour and an important role for CO2.

    NASA Astrophysics Data System (ADS)

    Steinthorsdottir, Margret; Wohlfarth, Barbara; Kylander, Malin E.; Blaauw, Maarten; Reimer, Paula J.

    2013-04-01

    We present a new stomatal proxy-based record of CO2 concentrations spanning Greenland Interstadial 1 (Allerød pollen zone, GI-1a to 1c), Greenland Stadial 1 (Younger Dryas pollen zone, GS-1) and the first part of the Holocene (Preboreal pollen zone). The calibrated atmospheric CO2 concentrations are based on Betula nana (dwarf birch) leaves from a fossil lake sedimentary sequence in south-eastern Sweden. The stomatal proxy method relies on the inverse relationship between stomatal density on plant leaves and atmospheric CO2 concentrations to reconstruct variations in past CO2 concentrations. The record presented here demonstrates that the overall pattern of CO2 evolution during this period was dynamic, with significant abrupt fluctuations in CO2 concentration when the climate moved from interstadial to stadial state and vice versa. The cooling at the GI-1/GS-1 transition was preceded by an abrupt warming, and the warming at the GS-1/Holocene transition was preceded by an abrupt cooling. This scenario is in contrast to CO2 records reconstructed from air bubbles trapped in ice, which indicate a gradual increase in concentrations, but largely in alignment with previously published stomatal proxy-based CO2 records. A new loss-on-ignition chemical record (used here as a proxy for temperature), from the same locality, lends independent support to the CO2 record.

  3. Experimental multi-phase H2O-CO2 brine interactions at elevated temperature and pressure: Implications for CO2 sequestration in deep-saline aquifers

    USGS Publications Warehouse

    Rosenbauer, R.; Koksalan, T.

    2004-01-01

    The burning of fossil fuel and other anthropogenic activities have caused a continuous and dramatic 30% increase of atmospheric CO2 over the past 150 yr. CO2 sequestration is increasingly being viewed as a tool for managing these anthropogenic CO2 emissions to the atmosphere. CO2-saturated brine-rock experiments were carried out to evaluate the effects of multiphase H2O-CO2 fluids on mineral equilibria and the potential for CO2 sequestration in mineral phases within deep-saline aquifers. Experimental results were generally consistent with theoretical thermodynamic calculations. The solubility of CO2 was enhanced in brines in the presence of both limestone and sandstone relative to brines alone. Reactions between CO2 saturated brines and arkosic sandstones were characterized by desiccation of the brine and changes in the chemical composition of the brine suggesting fixation of CO2 in mineral phases. These reactions were occurring on a measurable but kinetically slow time scale at 120??C.

  4. Dynamics of CO2 fluxes and concentrations during a shallow subsurface CO2 release

    SciTech Connect

    Lewicki, J.L.; Hilley, G.E.; Dobeck, L.; Spangler, L.

    2009-09-01

    A field facility located in Bozeman, Montana provides the opportunity to test methods to detect, locate, and quantify potential CO2 leakage from geologic storage sites. From 9 July to 7 August 2008, 0.3 t CO2 d{sup -1} were injected from a 100-m long, {approx}2.5 m deep horizontal well. Repeated measurements of soil CO2 fluxes on a grid characterized the spatio-temporal evolution of the surface leakage signal and quantified the surface leakage rate. Infrared CO2 concentration sensors installed in the soil at 30 cm depth at 0 to 10 m from the well and at 4 cm above the ground at 0 and 5 m from the well recorded surface breakthrough of CO2 leakage and migration of CO2 leakage through the soil. Temporal variations in CO2 concentrations were correlated with atmospheric and soil temperature, wind speed, atmospheric pressure, rainfall, and CO2 injection rate.

  5. Investigation of Wyoming Bentonite Hydration in Dry to Water-Saturated Supercritical CH4 and CH4/CO2 Mixtures: Implications for CO2-Enhanced Gas Production

    NASA Astrophysics Data System (ADS)

    Loring, J.

    2015-12-01

    Injection of CO2 into low permeability shale formations leads to additional gas recovery and reduces the flux of CO2 into the atmosphere, thus combining a strong economic incentive with a permanent storage option for CO2. Reduced formation transmissivity due to clay swelling is a concern in CO2-enhanced gas production. Clay minerals partly determine the physical (i.e. permeability, brittleness) and certain chemical properties (i.e. wetting ability, gas adsorption) of shales, and montmorillonites are of particular interest because they swell by the uptake of species in their interlayer. In this study, the hydration and expansion of Na-, Cs-, and NH4+-saturated montmorillonite (Na-, Cs-, and NH4-SWy-2) in high-pressure (90 bar) and moderate temperature (50 °C) methane, carbon dioxide, and CO2/CH4 mixtures (3 and 25 mole% CO2) were investigated using in situ IR spectroscopic titrations, in situ XRD, in situ MAS-NMR, and ab initio electronic structure calculations. The overarching goal was to better understand the hydration/expansion behavior of Na-SWy-2 in CO2/CH4 fluid mixtures by comparison to Cs-, and NH4+-saturated clays. Specific aims were to (1) determine if CH4 intercalates the clays, (2) probe the effects of increasing dissolved CO2 and H2O concentrations, and (3) understand the role of cation solvation by H2O and/or CO2. In pure CH4, no evidence of CH4 intercalation was detected by IR for any of the clays. Similarly, no measurable changes to the basal spacing were observed by XRD in the presence of pure CH4. However, when dry Cs- and NH4-SWy-2 were exposed to dry fluids containing CO2, IR showed maximum CO2 penetrated the interlayer, XRD indicated the clays expanded, and NMR showed evidence for cation solvation by CO2, in line with theoretical predictions. IR titration of these clays with water showed sorbed H2O concentrations decreased with increasing dissolved CO2, suggesting competition for interlayer residency by CO2 and H2O. For Na-SWy-2, on the other

  6. CO2 (dry ice) cleaning system

    NASA Technical Reports Server (NTRS)

    Barnett, Donald M.

    1995-01-01

    Tomco Equipment Company has participated in the dry ice (solid carbon dioxide, CO2) cleaning industry for over ten years as a pioneer in the manufacturer of high density, dry ice cleaning pellet production equipment. For over four years Tomco high density pelletizers have been available to the dry ice cleaning industry. Approximately one year ago Tomco introduced the DI-250, a new dry ice blast unit making Tomco a single source supplier for sublimable media, particle blast, cleaning systems. This new blast unit is an all pneumatic, single discharge hose device. It meters the insertion of 1/8 inch diameter (or smaller), high density, dry ice pellets into a high pressure, propellant gas stream. The dry ice and propellant streams are controlled and mixed from the blast cabinet. From there the mixture is transported to the nozzle where the pellets are accelerated to an appropriate blasting velocity. When directed to impact upon a target area, these dry ice pellets have sufficient energy to effectively remove most surface coatings through dry, abrasive contact. The meta-stable, dry ice pellets used for CO2 cleaning, while labeled 'high density,' are less dense than alternate, abrasive, particle blast media. In addition, after contacting the target surface, they return to their equilibrium condition: a superheated gas state. Most currently used grit blasting media are silicon dioxide based, which possess a sharp tetrahedral molecular structure. Silicon dioxide crystal structures will always produce smaller sharp-edged replicas of the original crystal upon fracture. Larger, softer dry ice pellets do not share the same sharp-edged crystalline structures as their non-sublimable counterparts when broken. In fact, upon contact with the target surface, dry ice pellets will plastically deform and break apart. As such, dry ice cleaning is less harmful to sensitive substrates, workers and the environment than chemical or abrasive cleaning systems. Dry ice cleaning system

  7. CO2 (dry ice) cleaning system

    NASA Astrophysics Data System (ADS)

    Barnett, Donald M.

    1995-03-01

    Tomco Equipment Company has participated in the dry ice (solid carbon dioxide, CO2) cleaning industry for over ten years as a pioneer in the manufacturer of high density, dry ice cleaning pellet production equipment. For over four years Tomco high density pelletizers have been available to the dry ice cleaning industry. Approximately one year ago Tomco introduced the DI-250, a new dry ice blast unit making Tomco a single source supplier for sublimable media, particle blast, cleaning systems. This new blast unit is an all pneumatic, single discharge hose device. It meters the insertion of 1/8 inch diameter (or smaller), high density, dry ice pellets into a high pressure, propellant gas stream. The dry ice and propellant streams are controlled and mixed from the blast cabinet. From there the mixture is transported to the nozzle where the pellets are accelerated to an appropriate blasting velocity. When directed to impact upon a target area, these dry ice pellets have sufficient energy to effectively remove most surface coatings through dry, abrasive contact. The meta-stable, dry ice pellets used for CO2 cleaning, while labeled 'high density,' are less dense than alternate, abrasive, particle blast media. In addition, after contacting the target surface, they return to their equilibrium condition: a superheated gas state. Most currently used grit blasting media are silicon dioxide based, which possess a sharp tetrahedral molecular structure. Silicon dioxide crystal structures will always produce smaller sharp-edged replicas of the original crystal upon fracture. Larger, softer dry ice pellets do not share the same sharp-edged crystalline structures as their non-sublimable counterparts when broken. In fact, upon contact with the target surface, dry ice pellets will plastically deform and break apart. As such, dry ice cleaning is less harmful to sensitive substrates, workers and the environment than chemical or abrasive cleaning systems. Dry ice cleaning system

  8. Ab initio Quantum Chemical Studies of Reactions in Astrophysical Ices. Reactions Involving CH3OH, CO2, CO, HNCO in H2CO/NH3/H2O Ices

    NASA Technical Reports Server (NTRS)

    Woon, David E.

    2006-01-01

    While reactions between closed shell molecules generally involve prohibitive barriers in the gas phase, prior experimental and theoretical studies have demonstrated that some of these reactions are significantly enhanced when confined within an icy grain mantle and can occur efficiently at temperatures below 100 K with no additional energy processing. The archetypal case is the reaction of formaldehyde (H2CO) and ammonia (NH3) to yield hydroxymethylamine (NH2CH2OH). In the present work we have characterized reactions involving methanol (CH3OH), carbon dioxide (CO2), carbon monoxide (CO), and isocyanic acid (HNCO) in search of other favorable cases. Most of the emphasis is on CH3OH, which was investigated in the two-body reaction with one H2CO and the three-body reaction with two H2CO molecules. The addition of a second H2CO to the product of the reaction between CH3OH and H2CO was also considered as an alternative route to longer polyoxymethylene polymers of the -CH2O- form. The reaction between HNCO and NH3 was studied to determine if it can compete against the barrierless charge transfer process that yields OCN(-) and NH4(+). Finally, the H2CO + NH3 reaction was revisited with additional benchmark calculations that confirm that little or no barrier is present when it occurs in ice.

  9. Advances in post AFM repair cleaning of photomask with CO2 cryogenic aerosol technology

    NASA Astrophysics Data System (ADS)

    Bowers, Charles; Varghese, Ivin; Balooch, Mehdi; Brandt, Werner

    2009-04-01

    As the mask technology matures, critical printing features and sub-resolution assist features (SRAF) shrink below 100 nm, forcing critical cleaning processes to face significant challenges. These challenges include use of new materials, oxidation, chemical contamination sensitivity, proportionally decreasing printable defect size, and a requirement for a damage-free clean. CO2 cryogenic aerosol cleaning has the potential to offer a wide process window for meeting these new challenges, if residue adder issues and damage can be eliminated. Some key differentiations of CO2 cryogenic aerosol cleaning are the non-oxidizing and non-etching properties compared to conventional chemical wet clean processes with or without megasonics. In prior work, the feasibility of CO2 cryogenic aerosol in post AFM repair photomask cleaning was demonstrated. In this paper, recent advancements of CO2 cryogenic aerosol cleaning technology are presented, focusing on the traditional problem areas of particle adders, electrostatic discharge (ESD), and mask damage mitigation. Key aspects of successful CO2 cryogenic aerosol cleaning include the spray nozzle design, CO2 liquid purity, and system design. The design of the nozzle directly controls the size, density, and velocity of the CO2 snow particles. Methodology and measurements of the solid CO2 particle size and velocity distributions will be presented, and their responses to various control parameters will be discussed. Adder control can be achieved only through use of highly purified CO2 and careful materials selection. Recent advances in CO2 purity will be discussed and data shown. The mask cleaning efficiency by CO2 cryogenic aerosol and damage control is essentially an optimization of the momentum of the solid CO2 particles and elimination of adders. The previous damage threshold of 150 nm SRAF structures has been reduced to 70nm and data will be shown indicating 60 nm is possible in the near future. Data on CO2 tribocharge mitigation

  10. Performance of a biogas upgrading process based on alkali absorption with regeneration using air pollution control residues.

    PubMed

    Baciocchi, Renato; Carnevale, Ennio; Costa, Giulia; Gavasci, Renato; Lombardi, Lidia; Olivieri, Tommaso; Zanchi, Laura; Zingaretti, Daniela

    2013-12-01

    This work analyzes the performance of an innovative biogas upgrading method, Alkali absorption with Regeneration (AwR) that employs industrial residues and allows to permanently store the separated CO2. This process consists in a first stage in which CO2 is removed from the biogas by means of chemical absorption with KOH or NaOH solutions followed by a second stage in which the spent absorption solution is contacted with waste incineration Air Pollution Control (APC) residues. The latter reaction leads to the regeneration of the alkali reagent in the solution and to the precipitation of calcium carbonate and hence allows to reuse the regenerated solution in the absorption process and to permanently store the separated CO2 in solid form. In addition, the final solid product is characterized by an improved environmental behavior compared to the untreated residues. In this paper the results obtained by AwR tests carried out in purposely designed demonstrative units installed in a landfill site are presented and discussed with the aim of verifying the feasibility of this process at pilot-scale and of identifying the conditions that allow to achieve all of the goals targeted by the proposed treatment. Specifically, the CO2 removal efficiency achieved in the absorption stage, the yield of alkali regeneration and CO2 uptake resulting for the regeneration stage, as well as the leaching behavior of the solid product are analyzed as a function of the type and concentration of the alkali reagent employed for the absorption reaction.

  11. CIUDENs Pilot Project for CO2 Biomonitoring Tools (PISCO2)

    NASA Astrophysics Data System (ADS)

    García, D.; Bruno, J.; Credoz, A.; Grandia, F.; Fuentes, J.; Calabuig, E.; Montoto, M.; Ciuden's Co2 Geological Storage Programme

    2011-12-01

    This paper describes CIUDENs Pilot Project for CO2 Biomonitoring Tools (PISCO2) in NW Spain; focusing on the development of biomonitoring of potential CO2 leakages through testing biogeochemical effects of CO2 injection in soils. CIUDEN is a Spanish National foundation created in 2006 dedicated to different projects related to energy and environment. One of the main activities is the construction and operation of various facilities for Research and Development in CCS. The PISCO2 installation consists of 18 cells excavated in the ground and isolated by concrete. Each cell has a 40 m3. The cells will be filled with different soils from various sites in Spain including the Hontomín site in Burgos, where CIUDENs CO2 Storage Technological Development Plant is under construction. The cells are be equipped with systems for (i) controlled CO2 injection at different depths, (ii) control of irrigation and drainage in the unsaturated soil, (iii) sampling of groundwater and gases, and (iv) monitoring of different parameters; such as water content, pH, CO2 flux, microbiological, botanical, and biogeochemical alterations and the chemical composition of water. The main objectives are: the detection of potential diffuse leakage during/after the injection operations; the use of native species as bio-indicators of early leakage; the calibration and optimization of monitoring sensors & methodologies; the optimization of existing multiphase reactive transport models and the comprehension improvement of the biogeochemical processes. The facility is planned to be fully operational in November 2011. Its configuration makes it unique and suitable for international R&D programs. CIUDEN is open for cooperative research projects with institutions all over the world. Results are expected to significantly contribute to the development of new, useful, economical and ecological biomonitoring tools for wide areas. The paper will focus on the presentation of the technical caracteristics and the

  12. Mineral CO2 sequestration by steel slag carbonation.

    PubMed

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

    2005-12-15

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

  13. Role of Rective Mineral Surface Area on the CO2 Mineralisation of CO2 Under Natural Conditions

    NASA Astrophysics Data System (ADS)

    Zuddas, P.; Rillard, J.

    2011-12-01

    The understanding of complex reactions between CO2 rich fluids and rock is fundamental to secured, long-term CO2 storage in geological reservoirs. A natural hydrothermal field is considered to be a useful analogue of carbon dioxide mineralization because it integrates the long-term interaction signal. The hydrothermal field of Galicia (Spain) is characterized by co-genetic fluids resulting from a mostly homogeneous granite reservoir with pCO2 partial pressure ranging from 104 to105 Pa and pH from 10 to 6. Fluids are characterized by an increase of major elements (Ca, Mg, K and Na) and alkalinity, both correlated to pCO2. We evaluated the effects of deep CO2 perturbation on the fluid-rock interaction system. Mineral reactivity which produces changes in the fluid mineral composition is mainly dependent on the 'real' reactive surface area. The mineral surface area participating in reactions resulting from this pCO2 gradient was estimated by an inverse model approach. Input data was based on the chemical composition of the fluids we sampled. The rate of mineral dissolution was estimated by the observed pH and equilibrium conditions. Moreover, the major elemental concentrations allowed us to quantify the variation of the reactive surface area of minerals involved with the overall water-rock interaction. The irreversible mass transfer process, ruled by the continuum equilibrium condition, was defined by the overall degree of reaction advancement, using a set of polynomial equations solved independently of time scale. We found that reactive surface area of calcite, albite and K-feldspar increases by 2 orders of magnitude over the entire CO2 fluid-rock interaction process, while the reactive surface area of biotite increases by 4 orders of magnitude. This shows that fluid neutralisation and consequent CO2 mineralization under the form of carbonate species is greatly dependent on the behaviour of the reactive surface area of the mineral association in this geological

  14. CO2 Accounting and Risk Analysis for CO2 Sequestration at Enhanced Oil Recovery Sites.

    PubMed

    Dai, Zhenxue; Viswanathan, Hari; Middleton, Richard; Pan, Feng; Ampomah, William; Yang, Changbing; Jia, Wei; Xiao, Ting; Lee, Si-Yong; McPherson, Brian; Balch, Robert; Grigg, Reid; White, Mark

    2016-07-19

    Using CO2 in enhanced oil recovery (CO2-EOR) is a promising technology for emissions management because CO2-EOR can dramatically reduce sequestration costs in the absence of emissions policies that include incentives for carbon capture and storage. This study develops a multiscale statistical framework to perform CO2 accounting and risk analysis in an EOR environment at the Farnsworth Unit (FWU), Texas. A set of geostatistical-based Monte Carlo simulations of CO2-oil/gas-water flow and transport in the Morrow formation are conducted for global sensitivity and statistical analysis of the major risk metrics: CO2/water injection/production rates, cumulative net CO2 storage, cumulative oil/gas productions, and CO2 breakthrough time. The median and confidence intervals are estimated for quantifying uncertainty ranges of the risk metrics. A response-surface-based economic model has been derived to calculate the CO2-EOR profitability for the FWU site with a current oil price, which suggests that approximately 31% of the 1000 realizations can be profitable. If government carbon-tax credits are available, or the oil price goes up or CO2 capture and operating expenses reduce, more realizations would be profitable. The results from this study provide valuable insights for understanding CO2 storage potential and the corresponding environmental and economic risks of commercial-scale CO2-sequestration in depleted reservoirs.

  15. CO2 Accounting and Risk Analysis for CO2 Sequestration at Enhanced Oil Recovery Sites.

    PubMed

    Dai, Zhenxue; Viswanathan, Hari; Middleton, Richard; Pan, Feng; Ampomah, William; Yang, Changbing; Jia, Wei; Xiao, Ting; Lee, Si-Yong; McPherson, Brian; Balch, Robert; Grigg, Reid; White, Mark

    2016-07-19

    Using CO2 in enhanced oil recovery (CO2-EOR) is a promising technology for emissions management because CO2-EOR can dramatically reduce sequestration costs in the absence of emissions policies that include incentives for carbon capture and storage. This study develops a multiscale statistical framework to perform CO2 accounting and risk analysis in an EOR environment at the Farnsworth Unit (FWU), Texas. A set of geostatistical-based Monte Carlo simulations of CO2-oil/gas-water flow and transport in the Morrow formation are conducted for global sensitivity and statistical analysis of the major risk metrics: CO2/water injection/production rates, cumulative net CO2 storage, cumulative oil/gas productions, and CO2 breakthrough time. The median and confidence intervals are estimated for quantifying uncertainty ranges of the risk metrics. A response-surface-based economic model has been derived to calculate the CO2-EOR profitability for the FWU site with a current oil price, which suggests that approximately 31% of the 1000 realizations can be profitable. If government carbon-tax credits are available, or the oil price goes up or CO2 capture and operating expenses reduce, more realizations would be profitable. The results from this study provide valuable insights for understanding CO2 storage potential and the corresponding environmental and economic risks of commercial-scale CO2-sequestration in depleted reservoirs. PMID:27362472

  16. CO2 deserts: implications of existing CO2 supply limitations for carbon management.

    PubMed

    Middleton, Richard S; Clarens, Andres F; Liu, Xiaowei; Bielicki, Jeffrey M; Levine, Jonathan S

    2014-10-01

    Efforts to mitigate the impacts of climate change will require deep reductions in anthropogenic CO2 emissions on the scale of gigatonnes per year. CO2 capture and utilization and/or storage technologies are a class of approaches that can substantially reduce CO2 emissions. Even though examples of this approach, such as CO2-enhanced oil recovery, are already being practiced on a scale >0.05 Gt/year, little attention has been focused on the supply of CO2 for these projects. Here, facility-scale data newly collected by the U.S. Environmental Protection Agency was processed to produce the first comprehensive map of CO2 sources from industrial sectors currently supplying CO2 in the United States. Collectively these sources produce 0.16 Gt/year, but the data reveal the presence of large areas without access to CO2 at an industrially relevant scale (>25 kt/year). Even though some facilities with the capability to capture CO2 are not doing so and in some regions pipeline networks are being built to link CO2 sources and sinks, much of the country exists in "CO2 deserts". A life cycle analysis of the sources reveals that the predominant source of CO2, dedicated wells, has the largest carbon footprint further confounding prospects for rational carbon management strategies.

  17. Glacial CO2 Cycles: A Composite Scenario

    NASA Astrophysics Data System (ADS)

    Broecker, W. S.

    2015-12-01

    There are three main contributors to the glacial drawdown of atmospheric CO2 content: starvation of the supply of carbon to the ocean-atmosphere reservoir, excess CO2 storage in the deep sea, and surface-ocean cooling. In this talk, I explore a scenario in which all three play significant roles. Key to this scenario is the assumption that deep ocean storage is related to the extent of nutrient stratification of the deep Atlantic. The stronger this stratification, the larger the storage of respiration CO2. Further, it is my contention that the link between Milankovitch insolation cycles and climate is reorganizations of the ocean's thermohaline circulation leading to changes in the deep ocean's CO2 storage. If this is the case, the deep Atlantic d13C record kept in benthic foraminifera shells tells us that deep ocean CO2 storage follows Northern Hemisphere summer insolation cycles and thus lacks the downward ramp so prominent in the records of sea level, benthic 18O and CO2. Rather, the ramp is created by the damping of planetary CO2 emissions during glacial time intervals. As it is premature to present a specific scenario, I provide an example as to how these three contributors might be combined. As their magnitudes and shapes remain largely unconstrained, the intent of this exercise is to provoke creative thinking.

  18. A Numerical Study on Combining CO2 Mineral Carbonation and Geothermal Energy Development

    NASA Astrophysics Data System (ADS)

    Wan, Y.; Xu, T.; Pruess, K.

    2010-12-01

    There is growing interest in the novel concept of operating Enhanced Geothermal Systems (EGS) with CO2 instead of water as heat transmission fluid. Initial studies have suggested that CO2 may achieve larger rates of heat extraction, and can offer geologic storage of carbon as an ancillary benefit. A fully developed EGS with CO2 would consist of three distinct zones, (1) a central zone or “core” in which all aqueous phase has been removed by dissolution into the flowing CO2 stream, so that the reservoir fluid is a single supercritical CO2 phase; (2) a surrounding intermediate zone, in which the reservoir fluid consists of a two-phase water-CO2 mixture; and (3) an outer or peripheral zone, in which the reservoir fluid is a single aqueous phase with dissolved CO2. Fluid-rock interactions in EGS operated with CO2 are expected to be vastly different in zones with an aqueous phase present, as compared to the central reservoir zone with anhydrous supercritical CO2. We have performed chemically reactive transport (TOUGHREACT ) modeling to investigate fluid-rock interactions and CO2 mineral carbonation of an EGS operated with CO2. The quartz monzodiorite unit at the Enhanced Geothermal Systems (EGS) site at Desert Peak (Nevada) was taken as an example. A geothermal injection well system with supercritical CO2 injection was simulated to (1) investigate mineral dissolution/precipitation and associated porosity changes, and (2) impacts on reservoir growth and longevity, with ramifications for sustaining energy recovery, for estimating CO2 loss rates, and for figuring tradeoffs between power generation and CO2 mineralization (geologic storage).

  19. CO2 dynamics in the Amargosa Desert: Fluxes and isotopic speciation in a deep unsaturated zone

    USGS Publications Warehouse

    Walvoord, M.A.; Striegl, R.G.; Prudic, D.E.; Stonestrom, D.A.

    2005-01-01

    Natural unsaturated-zone gas profiles at the U.S. Geological Survey's Amargosa Desert Research Site, near Beatty, Nevada, reveal the presence of two physically and isotopically distinct CO2 sources, one shallow and one deep. The shallow source derives from seasonally variable autotrophic and heterotrophic respiration in the root zone. Scanning electron micrograph results indicate that at least part of the deep CO2 source is associated with calcite precipitation at the 110-m-deep water table. We use a geochemical gas-diffusion model to explore processes of CO2 production and behavior in the unsaturated zone. The individual isotopic species 12CO2, 13CO2, and 14CO2 are treated as separate chemical components that diffuse and react independently. Steady state model solutions, constrained by the measured PCO2 ??13C (in CO2), and ??14C (in CO2) profiles, indicate that the shallow CO2 source from root and microbial respiration composes ???97% of the annual average total CO2 production at this arid site. Despite the small contribution from deep CO2 production amounting to ???0.1 mol m-2 yr-1, upward diffusion from depth strongly influences the distribution of CO2 and carbon isotopes in the deep unsaturated zone. In addition to diffusion from deep CO2 production, 14C exchange with a sorbed CO2 phase is indicated by the modeled ??14C profiles, confirming previous work. The new model of carbon-isotopic profiles provides a quantitative approach for evaluating fluxes of carbon under natural conditions in deep unsaturated zones.

  20. Estimating lake-atmosphere CO2 exchange

    USGS Publications Warehouse

    Anderson, D.E.; Striegl, R.G.; Stannard, D.I.; Michmerhuizen, C.M.; McConnaughey, T.A.; LaBaugh, J.W.

    1999-01-01

    Lake-atmosphere CO2 flux was directly measured above a small, woodland lake using the eddy covariance technique and compared with fluxes deduced from changes in measured lake-water CO2 storage and with flux predictions from boundary-layer and surface-renewal models. Over a 3-yr period, lake-atmosphere exchanges of CO2 were measured over 5 weeks in spring, summer, and fall. Observed springtime CO2 efflux was large (2.3-2.7 ??mol m-2 s-1) immediately after lake-thaw. That efflux decreased exponentially with time to less than 0.2 ??mol m-2 s-1 within 2 weeks. Substantial interannual variability was found in the magnitudes of springtime efflux, surface water CO2 concentrations, lake CO2 storage, and meteorological conditions. Summertime measurements show a weak diurnal trend with a small average downward flux (-0.17 ??mol m-2 s-1) to the lake's surface, while late fall flux was trendless and smaller (-0.0021 ??mol m-2 s-1). Large springtime efflux afforded an opportunity to make direct measurement of lake-atmosphere fluxes well above the detection limits of eddy covariance instruments, facilitating the testing of different gas flux methodologies and air-water gas-transfer models. Although there was an overall agreement in fluxes determined by eddy covariance and those calculated from lake-water storage change in CO2, agreement was inconsistent between eddy covariance flux measurements and fluxes predicted by boundary-layer and surface-renewal models. Comparison of measured and modeled transfer velocities for CO2, along with measured and modeled cumulative CO2 flux, indicates that in most instances the surface-renewal model underpredicts actual flux. Greater underestimates were found with comparisons involving homogeneous boundary-layer models. No physical mechanism responsible for the inconsistencies was identified by analyzing coincidentally measured environmental variables.

  1. Geological factors affecting CO2 plume distribution

    USGS Publications Warehouse

    Frailey, S.M.; Leetaru, H.

    2009-01-01

    Understanding the lateral extent of a CO2 plume has important implications with regards to buying/leasing pore volume rights, defining the area of review for an injection permit, determining the extent of an MMV plan, and managing basin-scale sequestration from multiple injection sites. The vertical and lateral distribution of CO2 has implications with regards to estimating CO2 storage volume at a specific site and the pore pressure below the caprock. Geologic and flow characteristics such as effective permeability and porosity, capillary pressure, lateral and vertical permeability anisotropy, geologic structure, and thickness all influence and affect the plume distribution to varying degrees. Depending on the variations in these parameters one may dominate the shape and size of the plume. Additionally, these parameters do not necessarily act independently. A comparison of viscous and gravity forces will determine the degree of vertical and lateral flow. However, this is dependent on formation thickness. For example in a thick zone with injection near the base, the CO2 moves radially from the well but will slow at greater radii and vertical movement will dominate. Generally the CO2 plume will not appreciably move laterally until the caprock or a relatively low permeability interval is contacted by the CO2. Conversely, in a relatively thin zone with the injection interval over nearly the entire zone, near the wellbore the CO2 will be distributed over the entire vertical component and will move laterally much further with minimal vertical movement. Assuming no geologic structure, injecting into a thin zone or into a thick zone immediately under a caprock will result in a larger plume size. With a geologic structure such as an anticline, CO2 plume size may be restricted and injection immediately below the caprock may have less lateral plume growth because the structure will induce downward vertical movement of the CO2 until the outer edge of the plume reaches a spill

  2. Atmospheric CO2 Removal by Enhancing Weathering

    NASA Astrophysics Data System (ADS)

    Koster van Groos, A. F.; Schuiling, R. D.

    2014-12-01

    The increase of the CO2 content in the atmosphere by the release of anthropogenic CO2 may be addressed by the enhancement of weathering at the surface of the earth. The average emission of mantle-derived CO2 through volcanism is ~0.3 Gt/year (109 ton/year). Considering the ~3.000 Gt of CO2 present in the atmosphere, the residence time of CO2 in the earth's atmosphere is ~10,000 years. Because the vast proportion of carbon in biomass is recycled through the atmosphere, CO2 is continuously removed by a series of weathering reactions of silicate minerals and stored in calcium and magnesium carbonates. The addition of anthropogenic CO2 from fossil fuel and cement production, which currently exceeds 35 Gt/year and dwarfs the natural production 100-fold, cannot be compensated by current rates of weathering, and atmospheric CO2 levels are rising rapidly. To address this increase in CO2 levels, weathering rates would have to be accelerated on a commensurate scale. Olivine ((Mg,Fe)2SiO4) is the most reactive silicate mineral in the weathering process. This mineral is the major constituent in relatively common ultramafic rocks such as dunites (olivine content > 90%). To consume the current total annual anthropogenic release of CO2, using a simplified weathering reaction (Mg2SiO4 + 4CO2 + 4H2O --> 2 Mg2+ + 4HCO3- + H4SiO4) would require ~30 Gt/year or ~8-9 km3/year of dunite. This is a large volume; it is about double the total amount of ore and gravel currently mined (~ 17 Gt/year). To mine and crush these rocks to <100 μm costs ~ 8/ton. The transport and distribution over the earth's surface involves additional costs, that may reach 2-5/ton. Thus, the cost of remediation for the release of anthropogenic CO2 is 300-400 billion/year. This compares to a 2014 global GDP of ~80 trillion. Because weathering reactions require the presence of water and proceed more rapidly at higher temperatures, the preferred environments to enhance weathering are the wet tropics. From a socio

  3. The Oceanic Sink for Anthropogenic CO2

    SciTech Connect

    Sabine, Chris; Feely, R. A.; Gruber, N.; Key, Robert; Lee, K.; Bullister, J.L.; Wanninkhof, R.; Wong, C. S.; Wallace, D.W.R.; Tilbrook, B.; Millero, F. J.; Peng, T.-H.; Kozyr, Alexander; Ono, Tsueno

    2004-01-01

    Using inorganic carbon measurements from an international survey effort in the 1990s and a tracer-based separation technique, we estimate a global oceanic anthropogenic carbon dioxide (CO2) sink for the period from 1800 to 1994 of 118 19 petagrams of carbon. The oceanic sink accounts for ~48% of the total fossil-fuel and cement-manufacturing emissions, implying that the terrestrial biosphere was a net source of CO2 to the atmosphere of about 39 28 petagrams of carbon for this period. The current fraction of total anthropogenic CO2 emissions stored in the ocean appears to be about one-third of the long-term potential.

  4. The oceanic sink for anthropogenic CO2.

    PubMed

    Sabine, Christopher L; Feely, Richard A; Gruber, Nicolas; Key, Robert M; Lee, Kitack; Bullister, John L; Wanninkhof, Rik; Wong, C S; Wallace, Douglas W R; Tilbrook, Bronte; Millero, Frank J; Peng, Tsung-Hung; Kozyr, Alexander; Ono, Tsueno; Rios, Aida F

    2004-07-16

    Using inorganic carbon measurements from an international survey effort in the 1990s and a tracer-based separation technique, we estimate a global oceanic anthropogenic carbon dioxide (CO2) sink for the period from 1800 to 1994 of 118 +/- 19 petagrams of carbon. The oceanic sink accounts for approximately 48% of the total fossil-fuel and cement-manufacturing emissions, implying that the terrestrial biosphere was a net source of CO2 to the atmosphere of about 39 +/- 28 petagrams of carbon for this period. The current fraction of total anthropogenic CO2 emissions stored in the ocean appears to be about one-third of the long-term potential.

  5. CO2 Driven Mineral Transformations in Fractured Reservoir

    NASA Astrophysics Data System (ADS)

    Schaef, T.

    2015-12-01

    Engineering fracture systems in low permeable formations to increase energy production, accelerate heat extraction, or to enhance injectivity for storing anthropogenic CO2, is a challenging endeavor. To complicate matters, caprocks, essential components of subsurface reservoirs, need to maintain their sealing integrity in this modified subsurface system. Supercritical CO2 (scCO2), a proposed non-aqueous based working fluid, is capable of driving mineral transformations in fracture environments. Water dissolution in scCO2 significantly impacts the reactivity of this fluid, largely due to the development of thin adsorbed H2O films on the surfaces of exposed rocks and minerals. Adsorbed H2O films are geochemically complex microenvironments that host mineral dissolution and precipitation processes that could be tailored to influence overall formation permeability. Furthermore, manipulating the composition of injected CO2 (e.g., moisture content and/or reactive gases such as O2, NOx, or SOx) could stimulate targeted mineral transformations that enhance or sustain reservoir performance. PNNL has developed specialized experimental techniques that can be used to characterize chemical reactions occurring between minerals and pressurized gases. For example, hydration of a natural shale sample (Woodford Shale) has been characterized by an in situ infrared spectroscopic technique as water partitions from the scCO2 onto the shale. Mineral dissolution and carbonate precipitation reactions were tracked by monitoring changes of Si-O and C-O stretching bands, respectively Structural changes indicated expandable clays in the shale such as montmorillonite are intercalated with scCO2, a process not observed with the non-expandable kaolinite component. Extreme scale ab initio molecular dynamics simulations were used in conjunction with model mineral systems to identify the driving force and mechanism of water films. They showed that the film nucleation and formation on minerals is

  6. Liquid CO2 venting on the seafloor: Yonaguni Knoll IV hydrothermal system, Okinawa Trough

    NASA Astrophysics Data System (ADS)

    Konno, U.; Tsunogai, U.; Nakagawa, F.; Nakaseama, M.; Ishibashi, J.; Nunoura, T.; Nakamura, K.

    2006-12-01

    In 2000, an active hydrothermal site, venting high-temperature fluid up to 300 oC, was discovered by Shinkai 6500 on the top of Yonaguni Knoll IV during YK 00-06 cruise in Okinawa Trough. During the subsequent subseafloor survey using Shinkai 6500 in 2003 (YK03-05), vents of liquid CO2 droplets were found at the site. Similar liquid CO2 droplets had previously been found at the active hydrothermal sites at JADE hydrothermal field, Okinawa Trough, during the extensive seafloor survey using submersibles in 1989 [Sakai et al., 1990]. Besides, similar liquid CO2 venting has also been recognized in NW Eifuku hydrothermal site on Izu-Bonin- Mariana arc. It thus appears that liquid CO2 venting might be usual phenomenon in some submarine arc volcanoes. The detailed relation between seafloor venting liquid CO2 and the surrounding high-temperature hydrothermal fluid, however, was not clarified in their studies. Furthermore, no definite evidence was obtained for the presence of CO2-hydrate in the subsurface. In this study, in order to discuss the subseafloor processes responsible for producing liquid CO2 at the Yonaguni Knoll IV site, as well as the possibility of the occurrence of solid CO2-hydrate within the sediments, we determined the chemical and isotopic compositions of the liquid CO2 found on the site, as well as those in hydrothermal fluid venting from the surrounding chimneys. In consequence, the ^13C of both CO2 and CH4 in the liquid CO2 almost coincide with those in the hydrothermal fluid, suggesting that the liquid CO2 must be derived from the hydrothermal fluid. While showing homogeneous ^13C, the hydrothermal fluids exhibit wide variation in gas contents. Active phase separation must be taking place within the conduits. Besides, H2-depletion in the liquid CO2 suggests formation of solid CO2-hydrate must also precede the venting of liquid CO2. In conclusion, liquid CO2 must be produced through following subseafloor processes: phase separation of hydrothermal

  7. Detecting small scale CO2 emission structures using OCO-2

    NASA Astrophysics Data System (ADS)

    Schwandner, Florian M.; Eldering, Annmarie; Verhulst, Kristal R.; Miller, Charles E.; Nguyen, Hai M.; Oda, Tomohiro; O'Dell, Christopher; Rao, Preeti; Kahn, Brian; Crisp, David; Gunson, Michael R.; Sanchez, Robert M.; Ashok, Manasa; Pieri, David; Linick, Justin P.; Yuen, Karen

    2016-04-01

    Localized carbon dioxide (CO2) emission structures cover spatial domains of less than 50 km diameter and include cities and transportation networks, as well as fossil fuel production, upgrading and distribution infra-structure. Anthropogenic sources increasingly upset the natural balance between natural carbon sources and sinks. Mitigation of resulting climate change impacts requires management of emissions, and emissions management requires monitoring, reporting and verification. Space-borne measurements provide a unique opportunity to detect, quantify, and analyze small scale and point source emissions on a global scale. NASA's first satellite dedicated to atmospheric CO2 observation, the July 2014 launched Orbiting Carbon Observatory (OCO-2), now leads the afternoon constellation of satellites (A-Train). Its continuous swath of 2 to 10 km in width and eight footprints across can slice through coincident emission plumes and may provide momentary cross sections. First OCO-2 results demonstrate that we can detect localized source signals in the form of urban total column averaged CO2 enhancements of ~2 ppm against suburban and rural backgrounds. OCO-2's multi-sounding swath observing geometry reveals intra-urban spatial structures reflected in XCO2 data, previously unobserved from space. The transition from single-shot GOSAT soundings detecting urban/rural differences (Kort et al., 2012) to hundreds of soundings per OCO-2 swath opens up the path to future capabilities enabling urban tomography of greenhouse gases. For singular point sources like coal fired power plants, we have developed proxy detections of plumes using bands of imaging spectrometers with sensitivity to SO2 in the thermal infrared (ASTER). This approach provides a means to automate plume detection with subsequent matching and mining of OCO-2 data for enhanced detection efficiency and validation. © California Institute of Technology

  8. Long-term pCO2 trends in Adirondack Lakes

    NASA Astrophysics Data System (ADS)

    Seekell, David A.; Gudasz, Cristian

    2016-05-01

    Lakes are globally significant sources of CO2 to the atmosphere. However, there are few temporally resolved records of lake CO2 concentrations and long-term patterns are poorly characterized. We evaluated annual trends in the partial pressure of CO2 (pCO2) based on chemical measurements from 31 Adirondack Lakes taken monthly over an 18 year period. All lakes were supersaturated with CO2 and were sources of CO2 to the atmosphere. There were significant pCO2 trends in 29% of lakes. The median magnitude of significant positive trends was 32.1 µatm yr-1. Overall, 52% of lakes had pCO2 trends greater than those reported for the atmosphere and ocean. Significant trends in lake pCO2 were attributable to regional recovery from acid deposition and changing patterns of ice cover. These results illustrate that lake pCO2 can respond rapidly to environmental change, but the lack of significant trend in 71% of lakes indicates substantial lake-to-lake variation in magnitude of response.

  9. Reversible CO2 Capture by Conjugated Ionic Liquids through Dynamic Covalent Carbon-Oxygen Bonds.

    PubMed

    Pan, Mingguang; Cao, Ningning; Lin, Wenjun; Luo, Xiaoyan; Chen, Kaihong; Che, Siying; Li, Haoran; Wang, Congmin

    2016-09-01

    The strong chemisorption of CO2 is always accompanied by a high absorption enthalpy, and traditional methods to reduce the absorption enthalpy lead to decreased CO2 capacities. Through the introduction of a large π-conjugated structure into the anion, a dual-tuning approach for the improvement of CO2 capture by anion-functionalized ionic liquids (ILs) resulted in a high capacity of up to 0.96 molCO2  mol-1IL and excellent reversibility. The increased capacity and improved desorption were supported by quantum chemical calculations, spectroscopic investigations, and thermogravimetric analysis. The increased capacity may be a result of the strengthened dynamic covalent bonds in these π-electron-conjugated structures through anion aggregation upon the uptake of CO2 , and the improved desorption originates from the charge dispersion of interaction sites through the large π-electron delocalization. These results provide important insights into effective strategies for CO2 capture. PMID:27458723

  10. Reversible CO2 Capture by Conjugated Ionic Liquids through Dynamic Covalent Carbon-Oxygen Bonds.

    PubMed

    Pan, Mingguang; Cao, Ningning; Lin, Wenjun; Luo, Xiaoyan; Chen, Kaihong; Che, Siying; Li, Haoran; Wang, Congmin

    2016-09-01

    The strong chemisorption of CO2 is always accompanied by a high absorption enthalpy, and traditional methods to reduce the absorption enthalpy lead to decreased CO2 capacities. Through the introduction of a large π-conjugated structure into the anion, a dual-tuning approach for the improvement of CO2 capture by anion-functionalized ionic liquids (ILs) resulted in a high capacity of up to 0.96 molCO2  mol-1IL and excellent reversibility. The increased capacity and improved desorption were supported by quantum chemical calculations, spectroscopic investigations, and thermogravimetric analysis. The increased capacity may be a result of the strengthened dynamic covalent bonds in these π-electron-conjugated structures through anion aggregation upon the uptake of CO2 , and the improved desorption originates from the charge dispersion of interaction sites through the large π-electron delocalization. These results provide important insights into effective strategies for CO2 capture.

  11. Effects of diffusion impairment on O2 and CO2 time courses in pulmonary capillaries.

    NASA Technical Reports Server (NTRS)

    Wagner, P. D.; West, J. B.

    1972-01-01

    Simultaneous time courses for O2 and CO2 exchange along the capillary have been calculated for homogeneous lungs, allowing for O2-CO2 interactions, dissolved O2, and chemical reaction rates. As diffusing capacity (Dl) was reduced, the transfer of CO2 and O2 was impaired by similar amounts, in spite of the 20-fold greater diffusing capacity for CO2. The reason why CO2 is affected so much is that the slope of the content against partial pressure is so much greater in blood than tissue for this gas. Because of the shapes of their respective dissociation curves, O2 transfer was most affected at normal ventilation-perfusion ratios, whereas CO2 was most affected at high ratios. Exercise exaggerated the impairment of transfer of both gases.

  12. CO2 Sensing and CO2 Regulation of Stomatal Conductance: Advances and Open Questions.

    PubMed

    Engineer, Cawas B; Hashimoto-Sugimoto, Mimi; Negi, Juntaro; Israelsson-Nordström, Maria; Azoulay-Shemer, Tamar; Rappel, Wouter-Jan; Iba, Koh; Schroeder, Julian I

    2016-01-01

    Guard cells form epidermal stomatal gas-exchange valves in plants and regulate the aperture of stomatal pores in response to changes in the carbon dioxide (CO2) concentration ([CO2]) in leaves. Moreover, the development of stomata is repressed by elevated CO2 in diverse plant species. Evidence suggests that plants can sense [CO2] changes via guard cells and via mesophyll tissues in mediating stomatal movements. We review new discoveries and open questions on mechanisms mediating CO2-regulated stomatal movements and CO2 modulation of stomatal development, which together function in the CO2 regulation of stomatal conductance and gas exchange in plants. Research in this area is timely in light of the necessity of selecting and developing crop cultivars that perform better in a shifting climate. PMID:26482956

  13. 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.

  14. Translucent CO2 ice on Mars ?

    NASA Astrophysics Data System (ADS)

    Schmidt, Frederic; Andrieu, Francois; Douté, Sylvain; Schmitt, Bernard

    2016-10-01

    The Martian climate is driven by the condensation/sublimation of CO2 representing 95% of the atmosphere. Many active surface features (such dark spot, dark flows), have been potentially linked to CO2 exchange. Understanding the surface/atmosphere interactions is a major issue, for both atmospheric but also surface science. This study aims at estimating the physical properties of the seasonal CO2 ice deposits. Are these deposits granular or compact? What is the thickness of the ice? How much impurities are included within the ice? These questions have been highly debated in the literature, in particular the presence of a translucent slab ice, the link with the H2O cycle. In particular the cold jet geyser model requires translucent CO2 ice. We use radiative transfer models to simulate spectroscopic data from the CRISM instrument and perform an inversion to estimate model's parameters though time. We then discuss the consistency of the results with other datasets.

  15. Fabry-Perot Interferometer for Column CO2

    NASA Technical Reports Server (NTRS)

    Heaps, William S.; Kawa, Randolph; Bhartia, P. K. (Technical Monitor)

    2002-01-01

    Global atmospheric CO2 measurements are essential to resolving significant discrepancies in our understanding of the global carbon budget and, hence, humankind's role in global climate change. The science measurement requirements for CO2 are extremely demanding (precision approx. 0.3%). No atmospheric chemical species has ever been measured from space with this precision. We are developing a novel application of a Fabry-Perot interferometer to detect spectral absorption of reflected sunlight by CO2 and O2 in the atmosphere. Preliminary design studies indicate that the method will be able to achieve the sensitivity and signal-to-noise detection required to measure column CO2 at the target specification. The objective of this program is to construct a prototype instrument for deployment on an aircraft to test the instrument performance and our ability to retrieve the data in the real atmosphere. To date we have assembled a laboratory bench system to begin testing the optical and electronic components. We are also measuring signal and noise levels in actual sunlight to evaluate component performance.

  16. Fabry-Perot Interferometer for Column CO2

    NASA Technical Reports Server (NTRS)

    Heaps, William S.; Kawa, S. Randolph; Krebs, Carolyn A. (Technical Monitor)

    2002-01-01

    Global atmospheric CO2 measurements are essential to resolving significant discrepancies in our understanding of the global carbon budget and, hence, humankind's role in global climate change. The science measurement requirements for CO2 are extremely demanding (precision is less than .3%). No atmospheric chemical species has ever been measured from space with this precision. We are developing a novel application of a Fabry-Perot interferometer to detect spectral absorption of reflected sunlight by CO2 and O2 in the atmosphere. Preliminary design studies indicate that the method will be able to achieve the sensitivity and signal-to-noise detection required to measure column CO2 at the target specification. The objective of this program is to construct a prototype instrument for deployment on an aircraft to test the instrument performance and our ability to retrieve the data in the real atmosphere. To date we have assembled a laboratory bench system to begin testing the optical and electronic components. We are also undertaking some measurements of signal and noise levels for actual sunlight reflecting from the ground in order to evaluate the potential of some components to meet the exacting requirements of this measurement.

  17. Performance of photoperiod and light intensity on biogas upgrade and biogas effluent nutrient reduction by the microalgae Chlorella sp.

    PubMed

    Yan, Cheng; Zheng, Zheng

    2013-07-01

    Biogas is an environment-friendly fuel but that must be upgraded before being utilized. The method about removing CO2 from biogas by microalgal culturing using biogas effluent as nutrient medium in this study could effectively upgrade biogas and simultaneously reduce the biogas effluent nutrient. Results showed that the optimum parameters for microalgal growth and biogas effluent nutrient reduction was moderate light intensity with middle photoperiod. While low light intensity with long photoperiod and moderate light intensity with middle photoperiod obtained the best biogas CO2 removal and biogas upgrade effects. Therefore, the optimal parameters were moderate light intensity 350 μmol m(-2)s(-1) with middle photoperiod 14 h light:10h dark. Under this condition, the microalgal dry weight, CH4 concentration, reduction efficiency of chemical oxygen demand, total nitrogen, and total phosphorus was 615.84 ± 33.07 mg L(-1), 92.16 ± 2.83% (v/v), 88.74 ± 3.45%, 83.94 ± 3.51%, and 80.43 ± 4.17%, respectively.

  18. Thermodynamics and kinetics of CO2, CO, and H+ binding to the metal centre of CO2 reduction catalysts.

    PubMed

    Schneider, Jacob; Jia, Hongfei; Muckerman, James T; Fujita, Etsuko

    2012-03-21

    In our developing world, carbon dioxide has become one of the most abundant greenhouse gases in the atmosphere. It is a stable, inert, small molecule that continues to present significant challenges toward its chemical activation as a useful carbon end product. This tutorial review describes one approach to the reduction of carbon dioxide to carbon fuels, using cobalt and nickel molecular catalysts, with particular focus on studying the thermodynamics and kinetics of CO(2) binding to metal catalytic sites.

  19. How secure is subsurface CO2 storage? Controls on leakage in natural CO2 reservoirs

    NASA Astrophysics Data System (ADS)

    Miocic, Johannes; Gilfillan, Stuart; McDermott, Christopher; Haszeldine, Stuart

    2014-05-01

    Carbon Capture and Storage (CCS) is the only industrial scale technology available to directly reduce carbon dioxide (CO2) emissions from fossil fuelled power plants and large industrial point sources to the atmosphere. The technology includes the capture of CO2 at the source and transport to subsurface storage sites, such as depleted hydrocarbon reservoirs or saline aquifers, where it is injected and stored for long periods of time. To have an impact on the greenhouse gas emissions it is crucial that there is no or only a very low amount of leakage of CO2 from the storage sites to shallow aquifers or the surface. CO2 occurs naturally in reservoirs in the subsurface and has often been stored for millions of years without any leakage incidents. However, in some cases CO2 migrates from the reservoir to the surface. Both leaking and non-leaking natural CO2 reservoirs offer insights into the long-term behaviour of CO2 in the subsurface and on the mechanisms that lead to either leakage or retention of CO2. Here we present the results of a study on leakage mechanisms of natural CO2 reservoirs worldwide. We compiled a global dataset of 49 well described natural CO2 reservoirs of which six are leaking CO2 to the surface, 40 retain CO2 in the subsurface and for three reservoirs the evidence is inconclusive. Likelihood of leakage of CO2 from a reservoir to the surface is governed by the state of CO2 (supercritical vs. gaseous) and the pressure in the reservoir and the direct overburden. Reservoirs with gaseous CO2 is more prone to leak CO2 than reservoirs with dense supercritical CO2. If the reservoir pressure is close to or higher than the least principal stress leakage is likely to occur while reservoirs with pressures close to hydrostatic pressure and below 1200 m depth do not leak. Additionally, a positive pressure gradient from the reservoir into the caprock averts leakage of CO2 into the caprock. Leakage of CO2 occurs in all cases along a fault zone, indicating that

  20. Study on CO2 global recycling system.

    PubMed

    Takeuchi, M; Sakamoto, Y; Niwa, S

    2001-09-28

    In order to assist in finding ways to mitigate CO2 emission and to slow the depletion of fossil fuels we have established and evaluated a representative system, which consists of three technologies developed in our laboratory. These technologies were in CO2 recovery, hydrogen production and methanol synthesis and in addition we established the necessary supporting systems. Analysis of outline designs of the large scale renewable energy power generation system and this system and energy input for building plant, energy input for running plant has been conducted based on a case using this system for a 1000-MW coal fired power plant, followed by an evaluation of the material balance and energy balance. The results are as follows. Energy efficiency is 34%, the CO2 reduction rate is 41%, the balance ratio of the energy and CO2 of the system is 2.2 and 1.8, respectively, on the assumption that the primary renewable energy is solar thermal power generation, the stationary CO2 emission source is a coal-fired power plant and the generation efficiency of the methanol power plant is 60%. By adopting the system, 3.7 million tons of CO2 can be recovered, approximately 2.7 million tons of methanol can be produced, and 15.4 billion kWh of electricity can be generated per year. Compared to generating all electrical power using only coal, approximately 2.6 million tons of coal per year can be saved and approximately 2.15 million tons of CO2 emission can be reduced. Therefore, it is clearly revealed that this system would be effective to reduce CO2 emissions and to utilize renewable energy.

  1. Trapping atmospheric CO2 with gold.

    PubMed

    Collado, Alba; Gómez-Suárez, Adrián; Webb, Paul B; Kruger, Hedi; Bühl, Michael; Cordes, David B; Slawin, Alexandra M Z; Nolan, Steven P

    2014-10-01

    The ability of gold-hydroxides to fix CO2 is reported. [Au(IPr)(OH)] and [{Au(IPr)}2(μ-OH)][BF4] react with atmospheric CO2 to form the trigold carbonate complex [{Au(IPr)}3(μ(3)-CO3)][BF4]. Reactivity studies revealed that this complex behaves as two basic and one cationic Au centres, and that it is catalytically active. DFT calculations and kinetic experiments have been carried out.

  2. On the Vertical Gradient in CO2

    NASA Astrophysics Data System (ADS)

    Stine, A. R.; Fung, I. Y.

    2008-12-01

    Attempts to constrain surface fluxes of carbon from atmospheric measurements of carbon dioxide have primarily focused on surface boundary layer measurements, because information about surface fluxes is least diluted close to the locations where the fluxes occur. However, errors in model ventilation of air in the vertical can be misinterpreted as local surface fluxes. Satellites which measure column integrated CO2 are expected to represent a major advance in part because they observe the entire atmospheric column. Recent work has highlighted the fact that vertical gradients in carbon concentrations can give us information about where vertical mixing errors are likely to be misinterpreted as local surface fluxes, but passive tracer evidence suggests that models that capture vertical profiles on the ocean do poorly on the land (and vice versa), suggesting that the problem of correctly treating vertical mixing in inverse studies is more fundamental than picking the "best" model. We consider observations of the vertical gradient in CO2 from aircrafts and from a comparison of satellites that observe in the near infrared (which observe the column integrated CO2 field) and the thermal infrared (which observe the upper troposphere). We evaluate the feasibility of using these satellites for determining the vertical gradient in CO2. We examine how observations of the vertical gradient of CO2 allow us to differentiate the imprint of vertical mixing and the imprint in surface fluxes on the observed field of atmospheric CO2.

  3. Advanced CO2 Removal and Reduction System

    NASA Technical Reports Server (NTRS)

    Alptekin, Gokhan; Dubovik, Margarita; Copeland, Robert J.

    2011-01-01

    An advanced system for removing CO2 and H2O from cabin air, reducing the CO2, and returning the resulting O2 to the air is less massive than is a prior system that includes two assemblies . one for removal and one for reduction. Also, in this system, unlike in the prior system, there is no need to compress and temporarily store CO2. In this present system, removal and reduction take place within a single assembly, wherein removal is effected by use of an alkali sorbent and reduction is effected using a supply of H2 and Ru catalyst, by means of the Sabatier reaction, which is CO2 + 4H2 CH4 + O2. The assembly contains two fixed-bed reactors operating in alternation: At first, air is blown through the first bed, which absorbs CO2 and H2O. Once the first bed is saturated with CO2 and H2O, the flow of air is diverted through the second bed and the first bed is regenerated by supplying it with H2 for the Sabatier reaction. Initially, the H2 is heated to provide heat for the regeneration reaction, which is endothermic. In the later stages of regeneration, the Sabatier reaction, which is exothermic, supplies the heat for regeneration.

  4. The overlooked tropical oceanic CO2 sink

    NASA Astrophysics Data System (ADS)

    Ibánhez, J. Severino P.; Araujo, Moacyr; Lefèvre, Nathalie

    2016-04-01

    The intense rainfall in the tropical Atlantic spatially overlaps with the spread of the Amazon plume. Based on remote-sensed sea surface salinity and rainfall, we removed the contribution of rainfall to the apparent Amazon plume area, thus refining the quantification of its extension (0.84 ± 0.06 × 106 km2 to 0.89 ± 0.06 × 106 km2). Despite the previous overestimation of the Amazon plume area due to the influence of rainfall (>16%), our calculated annual CO2 flux based on rainfall-corrected sea surface CO2 fugacity confirms that the Amazon River plume is an atmospheric CO2 sink of global importance (-7.61 ± 1.01 to -7.85 ± 1.02 Tg C yr-1). Yet we show that current sea-air CO2 flux assessments for the tropical Atlantic could be overestimated in about 10% by neglecting the CO2 sink associated to the Amazon plume. Thus, including the Amazon plume, the sea-air CO2 exchange for the tropical Atlantic is estimated to be 81.1 ± 1.1 to 81.5 ± 1.1 Tg C yr-1.

  5. Density of aqueous solutions of CO2

    SciTech Connect

    Garcia, Julio E.

    2001-10-10

    In this report, we present a numerical representation for the partial molar volume of CO2 in water and the calculation of the corresponding aqueous solution density. The motivation behind this work is related to the importance of having accurate representations for aqueous phase properties in the numerical simulation of carbon dioxide disposal into aquifers as well as in geothermal applications. According to reported experimental data the density of aqueous solutions of CO2 can be as much as 2-3% higher than pure water density. This density variation might produce an influence on the groundwater flow regime. For instance, in geologic sequestration of CO2, convective transport mixing might occur when, several years after injection of carbon dioxide has stopped, the CO2-rich gas phase is concentrated at the top of the formation, just below an overlaying caprock. In this particular case the heavier CO2 saturated water will flow downward and will be replaced by water with a lesser CO2 content.

  6. CO2 Acquisition Membrane (CAM) Project

    NASA Technical Reports Server (NTRS)

    Mason, Larry W.

    2003-01-01

    The CO2 Acquisition Membrane (CAM) project was performed to develop, test, and analyze thin film membrane materials for separation and purification of carbon dioxide (CO2) from mixtures of gases, such as those found in the Martian atmosphere. The membranes developed in this project are targeted toward In Situ Resource Utilization (ISRU) applications, such as In Situ Propellant Production (ISPP) and In Situ Consumables Production (ISCP). These membrane materials may be used in a variety of ISRU systems, for example as the atmospheric inlet filter for an ISPP process to enhance the concentration of CO2 for use as a reactant gas, to passively separate argon and nitrogen trace gases from CO2 for habitat pressurization, to provide a system for removal of CO2 from breathing gases in a closed environment, or within a process stream to selectively separate CO2 from other gaseous components. The membranes identified and developed for CAM were evaluated for use in candidate ISRU processes and other gas separation applications, and will help to lay the foundation for future unmanned sample return and human space missions. CAM is a cooperative project split among three institutions: Lockheed Martin Astronautics (LMA), the Colorado School of Mines (CSM), and Marshall Space Flight Center (MSFC).

  7. Investigating 14CO2 chamber methodologies

    NASA Astrophysics Data System (ADS)

    Egan, J. E.; Phillips, C. L.; Nickerson, N. R.; Risk, D. A.

    2012-12-01

    The radiogenic isotope of carbon (14C) is an exceptionally useful tool in studying soil respired CO2, providing information about soil turnover rates, depths of production and the biological sources of production through partitioning. Unfortunately, little work has been done to thoroughly investigate the possibility of inherent biases in the current measurement techniques for 14CO2, caused by disturbances to the soil's natural diffusive regime, because of high costs and sampling logistics. Our aim in this study is to investigate the degree of bias present in the current sampling methodologies using a numerical model and laboratory calibration device. Four chamber techniques were tested numerically with varying fraction modern of production, δ13C of production, collar lengths, flux rates and diffusivities. Two of the chambers were then tested on the lab calibration device. One of these chambers, Iso-FD, has recently been tested for its use as a 13CO2 chamber and it does not induce gas transport fractionation biases present in other 13CO2 sampling methodologies. We then implemented it in the field to test its application as a 14CO2 chamber because of its excellent performance as a 13CO2chamber. Presented here are the results from the numerical modeling experiment, the laboratory calibration experiment and preliminary field results from the Iso-FD chamber.

  8. CO2 cooling in terrestrial planet thermospheres

    NASA Technical Reports Server (NTRS)

    Bougher, S. W.; Hunten, D. M.; Roble, R. G.

    1994-01-01

    We examine the recent progress in the debate on the CO2-O relaxation rate, its temperature dependence, and its corresponding impact on the thermospheric heat budgets of Venus, Earth, and Mars. This comparative approach provides the broadest range of conditions under which a common CO2-O relaxation rate should provide consistent results. New global mean calculations are presented for the heat budgets of these three planets using large CO2-O relaxation rates that have been inferred recently from Earth CO2 radiance measurements and laboratory studies. Results indicate that available Venus and Mars data constrain the CO2-O relaxation rate to be 2-4 x 10(exp -12)/cu cm/s at 300 K. For Venus, this strong cooling serves as an effective thermostat that gives rise to a small variation of thermospheric temperatures over the solar cycle, just as observed. Conversely, CO2 cooling does not appear to be dominant in the dayside heat budget of the Mars thermosphere over most of the solar cycle. For the Earth, this strong cooling implies that the lower thermosphere does not typically require significant eddy diffusion or heat conduction. However, global-scale dynamics or an additional heating mechanism may be needed to restore calculated temperatures to observed values when relaxation rates exceeding 2 x 10(exp -12)/cu cm/s are employed.

  9. Geochemistry of Wellbore Integrity in CO2 Sequestration: Portland Cement-Steel-Brine-CO2 Interactions (Invited)

    NASA Astrophysics Data System (ADS)

    Carey, J. W.

    2013-12-01

    Effective geologic sequestration of CO2 requires long-term storage with very low leak rates. Numerous studies have identified wells as one of the key risk factors for CO2 leakage including purpose-built injection and monitoring wells in addition to older wells in and above the storage reservoir. All wells have the potential to leak due to faulty construction or other defects. However, geochemical reactions induced by CO2 could result in damage to Portland cement and steel that are used in the well to isolate reservoir fluids from underground drinking water sources and the surface. This concern is based on the thermodynamic incompatibility of CO2-saturated aqueous fluids with Portland cement and steel, which leads to relatively rapidly reactions that form, principally, calcium carbonate and iron carbonate. Despite this thermodynamic fate, wellbore materials perform and maintain zonal isolation in field and experimental observations. This is understood as a consequence of coupled behavior between flow of reactants (CO2-water) and the rate of dissolution and precipitation of cement or corrosion of steel. In the restricted flow environments found in wellbore systems, cements are carbonated but do not suffer significant deterioration of hydrologic or mechanical properties. In fact, cement carbonation often results in reduced permeability and enhanced mechanical strength. While steel is susceptible to corrosion, wellbore environments allow development of protective iron carbonate scale. In addition, the presence of Portland cement, even carbonated cement, provides protection against significant rates of corrosion. The impact of geochemical reactions in the wellbore environment cannot be separated from coupled flow, thermal and mechanical processes. CO2-induced chemical reactions migrating upward from a storage reservoir will not result in the creation of defects or the wholesale dissolution of cement or steel. Defects must exist that allow CO2×brine to flow and to come

  10. Experimental multi-phase CO2-brine-rock interactions at elevated temperature and pressure: Implications for CO2 sequestration in deep-saline aquifers

    USGS Publications Warehouse

    Rosenbauer, R.J.; Koksalan, T.

    2004-01-01

    Long-term CO2 saturated brine-rock experiments were conducted to evaluate the effects of multiphase H2O-CO2 fluids on mineral equilibria and the potential for CO2 sequestration mineral phases within deep-saline aquifers. Experimental results were consistent with theoretical thermodynamic calculations when CO2-saturated brines were reacted with limestone rocks. The CO2-saturated brine-limestone reactions were characterized by compositional and mineralogical-changes in the aquifer fluid and formation rocks that were dependent on initial brine composition as were the changes in formation porosity, especially dissolved sulfate. The solubility of CO2 was enhanced in brines in the presence of both limestone and sandstone rocks relative to brines alone. Reactions between CO2 saturated brines and arkosic sandstones were characterized by desiccation of the brine and changes in the chemical composition of the brine suggesting fixation of CO2 in mineral phases. These reactions occured on a measurable but kinetically slow time scale at 120??C.

  11. CO2 Absorption in an Alcoholic Solution of Heavily Hindered Alkanolamine: Reaction Mechanism of 2-(tert-Butylamino)ethanol with CO2 Revisited.

    PubMed

    Xie, Hong-Bin; Wei, Xiaoxuan; Wang, Pan; He, Ning; Chen, Jingwen

    2015-06-18

    To advance the optimal design of amines for postcombustion CO2 capture, a sound mechanistic understanding of the chemical process of amines with good CO2 capture performance is advantageous. A sterically hindered alkanolamine, 2-(tert-butylamino)ethanol (TBAE), in ethylene glycol (EG) solution was recently reported to have better CO2 capture performance and unusual reactivity toward CO2, in comparison with those of the prototypical alkanolamines. However, the reaction mechanism of TBAE with CO2 in EG solution is unclear. Here, various quantum chemistry methods were employed to probe the reaction mechanism of TBAE with CO2 in EG and aqueous solution. Six reaction pathways involving three kinds of possible reactive centers of TBAE solution were considered. The results indicated that the formation of anionic hydroxyethyl carbonate by the attack of -OH of EG on CO2 is the most favorable, which is confirmed by complementary high-resolution mass spectrum experiments. This clarified that the speculated zwitterionic carbonate species is not the main product in EG solution. The reaction process of TBAE in aqueous solution is similar to that in EG solution, leading to bicarbonate, which agrees with experimental observations. On the basis of the unveiled reaction mechanisms of TBAE + CO2, the role of the key tert-butyl functional group of TBAE was revealed. PMID:25993508

  12. Will atmospheric CO2 concentration continue to increase if anthropogenic CO2 emissions cease?

    NASA Astrophysics Data System (ADS)

    MacDougall, A. H.; Eby, M.; Weaver, A. J.

    2013-12-01

    If anthropogenic CO2 emissions were to suddenly cease, the evolution of the atmospheric CO2 concentration would depend on the magnitude and sign of natural carbon sources and sinks. Experiments using Earth system models indicate that overall carbon sinks would dominate. However, these models have typically neglected the permafrost carbon pool, which has the potential to introduce an additional terrestrial source of carbon to the atmosphere. Here we use the University of Victoria Earth System Climate Model, which has recently been expanded to include permafrost carbon stocks and exchanges with the atmosphere. In a scenario of zeroed CO2 and sulphate aerosol emissions, we assess whether the warming induced by specified constant concentrations of non-CO2 greenhouse gases could slow the CO2 decline following zero emissions, or even reverse this trend and cause CO2 to increase over time. We find that a radiative forcing from non-CO2 gases of approximately 0.6 W m-2 results in a near balance of CO2 emissions from the terrestrial biosphere and uptake of CO2 by the oceans, resulting in near-constant atmospheric CO2 concentrations for at least a century after emissions are eliminated. At higher values of non-CO2 radiative forcing, CO2 concentrations increase over time, regardless of when emissions cease during the 21st century. Given that the present-day radiative forcing from non-CO2 greenhouse gases is about 0.95 W m-2, our results suggest that if we were to eliminate all CO2 and aerosols emissions without also decreasing non-CO2 greenhouse gas emissions, CO2 levels would increase over time, resulting in a small increase in climate warming. The sudden and total cessation of anthropogenic CO2 emissions is an unlikely future scenario. However, such cessation experiments provide a useful method for evaluating the relative strength of the terrestrial and oceanic carbon cycle feedbacks in the presence of forcing from non-CO2 greenhouse gasses.

  13. Global CO2 simulation using GOSAT-based surface CO2 flux estimates

    NASA Astrophysics Data System (ADS)

    Takagi, H.; Oda, T.; Saito, M.; Valsala, V.; Belikov, D.; Saeki, T.; Saito, R.; Morino, I.; Uchino, O.; Yoshida, Y.; Yokota, Y.; Bril, A.; Oshchepkov, S.; Andres, R. J.; Maksyutov, S.

    2012-04-01

    Investigating the distribution and temporal variability of surface CO2 fluxes is an active research topic in the field of contemporary carbon cycle dynamics. The technique central to this effort is atmospheric inverse modeling with which surface CO2 fluxes are estimated by making corrections to a priori flux estimates such that mismatches between model-predicted and observed CO2 concentrations are minimized. Past investigations were carried out by utilizing CO2 measurements collected in global networks of surface-based monitoring sites. Now, datasets of column-averaged CO2 dry air mole fraction (XCO2) retrieved from spectral soundings collected by GOSAT are available for complementing the surface-based CO2 observations. These space-based XCO2 data are expected to enhance the spatiotemporal coverage of the existing surface observation network and thus reduce uncertainty associated with the surface flux estimates. We estimated monthly CO2 fluxes in 64 sub-continental regions from a subset of the surface-based GLOBALVIEW CO2 data and the GOSAT FTS SWIR Level 2 XCO2 retrievals. We further simulated CO2 concentrations in 3-D model space using the surface flux estimates obtained. In this presentation, we report the result of a comparison between the simulated CO2 concentrations and independent surface observations. As part of an effort in inter-comparing GOSAT-based surface CO2 flux estimates, we also look at results yielded with XCO2 data retrieved with the PPDF-DOAS algorithm and those made available by the NASA Atmospheric CO2 Observations from Space team. For this study, we used version 08.1 of the National Institute for Environmental Studies atmospheric transport model, which was driven by the Japan Meteorological Agency's JCDAS wind analysis data. The CO2 forward simulations were performed on 2.5° × 2.5° horizontal grids at 32 vertical levels between the surface and the top of the atmosphere. The a priori flux dataset used was comprised of the sum of four

  14. NREL's Cyanobacteria Engineering Shortens Biofuel Production Process, Captures CO2

    SciTech Connect

    2015-09-01

    This highlight describes NREL's work to systematically analyze the flow of energy in a photosynthetic microbe and show how the organism adjusts its metabolism to meet the increased energy demand for making ethylene. This work successfully demonstrates that the organism could cooperate by stimulating photosynthesis. The results encourage further genetic engineering for the conversion of CO2 to biofuels and chemicals. This highlight is being developed for the September 2015 Alliance S&T Board meeting. biofuels and chemicals. This highlight is being developed for the September 2015 Alliance S&T Board meeting.

  15. Primary, secondary, and tertiary amines for CO2 capture: designing for mesoporous CO2 adsorbents.

    PubMed

    Ko, Young Gun; Shin, Seung Su; Choi, Ung Su

    2011-09-15

    CO(2) emissions, from fossil-fuel-burning power plants, the breathing, etc., influence the global worming on large scale and the man's work efficiency on small scale. The reversible capture of CO(2) is a prominent feature of CO(2) organic-inorganic hybrid adsorbent to sequester CO(2). Herein, (3-aminopropyl) trimethoxysilane (APTMS), [3-(methylamino)propyl] trimethoxysilane (MAPTMS), and [3-(diethylamino) propyl] trimethoxysilane (DEAPTMS) are immobilized on highly ordered mesoporous silicas (SBA-15) to catch CO(2) as primary, secondary, and tertiary aminosilica adsorbents. X-ray photoelectron spectroscopy was used to analyze the immobilized APTMS, MAPTMS, and DEAPTMS on the SBA-15. We report an interesting discovery that the CO(2) adsorption and desorption on the adsorbent depend on the amine type of the aminosilica adsorbent. The adsorbed CO(2) was easily desorbed from the adsorbent with the low energy consumption in the order of tertiary, secondary, and primary amino-adsorbents while the adsorption amount and the bonding-affinity increased in the reverse order. The effectiveness of amino-functionalized (1(o), 2(o), and 3(o) amines) SBA-15s as a CO(2) capturing agent was investigated in terms of adsorption capacity, adsorption-desorption kinetics, and thermodynamics. This work demonstrates apt amine types to catch CO(2) and regenerate the adsorbent, which may open new avenues to designing "CO(2) basket". PMID:21708387

  16. Commitment accounting for CO2 emissions

    NASA Astrophysics Data System (ADS)

    Davis, S. J.; Socolow, R. H.

    2013-12-01

    Long-lived energy infrastructure that burns fossil fuels represents a multi-decade 'commitment' to emit CO2. Today's global power sector, alone, represents hundreds of billions of tons of still unrealized 'committed emissions' of CO2. And every year, substantial new commitments to future emissions are made, as new power plants are built. The socioeconomic inertia of these commitments is a major barrier to climate change mitigation. Here, we quantify these annual commitments by a bottom-up analysis of all power plants commissioned between 1950 and 2011; assigning emission commitments to the year when each generator came on line. We find, assuming 40-year commitments, that the global commitment to future emissions from the world's generators in 2011 (the most recent year in our analysis) was 318 Gt CO2, of which 216 Gt CO2 were commitments from the world's coal-fired generators and 134 Gt CO2 were commitments from China's generators. Annual new global commitments exceeded 15 Gt CO2 per year in every year since 2000. Moreover, between 2005-2010 (the latest year of available emissions data), new global commitments were more than twice as large as actual emissions from all power plants. Country-specific ratios of new committed emissions to actual emissions, averaged over 1990-2010 were 4.1 for China, 2.6 for India, 0.9 for the EU, and 0.6 for the US. We urge that the reporting of annual CO2 emissions, already widely institutionalized, be augmented by 'commitment accounting' which makes these future emissions salient. Annual committed emissions and annual emissions of primary power infrastructure. New committed emissions (light green) have grown from approximately 4 Gt CO2 per year in 1960 to roughly 10 Gt CO2 per year between 1970-1995, and then to more than 15 Gt CO2 per year since 2000. Throughout this period, new committed emissions have exceeded annual emissions (blue curve, source: IEA). Although the commitments made 30-40 years ago have largely been realized (dark

  17. Precursory volcanic CO2 signals from space

    NASA Astrophysics Data System (ADS)

    Schwandner, Florian M.; Carn, Simon A.; Kataoka, Fumie; Kuze, Akihiko; Shiomi, Kei; Goto, Naoki

    2016-04-01

    Identification of earliest signals heralding volcanic unrest benefits from the unambiguous detection of precursors that reflect deviation of magmatic systems from metastable background activity. Ascent and emplacement of new basaltic magma at depth may precede eruptions by weeks to months. Transient localized carbon dioxide (CO2) emissions stemming from exsolution from depressurized magma are expected, and have been observed weeks to months ahead of magmatic surface activity. Detecting such CO2 precursors by continuous ground-based monitoring operations is unfortunately not a widely implemented method yet, save a handful of volcanoes. Detecting CO2 emissions from space offers obvious advantages - however it is technologically challenging, not the least due to the increasing atmospheric burden of CO2, against which a surface emission signal is hard to discern. In a multi-year project, we have investigated the feasibility of space-borne detection of pre-eruptive volcanic CO2 passive degassing signals using observations from the Greenhouse Gas Observing SATellite (GOSAT). Since 2010, we have observed over 40 active volcanoes from space using GOSAT's special target mode. Over 72% of targets experienced at least one eruption over that time period, demonstrating the potential utility of space-borne CO2 observations in non-imaging target-mode (point source monitoring mode). While many eruption precursors don't produce large enough CO2 signals to exceed space-borne detection thresholds of current satellite sensors, some of our observations have nevertheless already shown significant positive anomalies preceding eruptions at basaltic volcanoes. In 2014, NASA launched its first satellite dedicated to atmospheric CO2 observation, the Orbiting Carbon Observatory (OCO-2). Its observation strategy differs from the single-shot GOSAT instrument. At the expense of GOSAT's fast time series capability (3-day repeat cycle, vs. 16 for OCO-2), its 8-footprint continuous swath can slice

  18. Exercise carbon dioxide (CO2) retention with inhaled CO2 and breathing resistance.

    PubMed

    Shykoff, Barbara E; Warkander, Dan E

    2012-01-01

    Combined effects on respiratory minute ventilation (VE)--and thus, on end-tidal carbon dioxide partial pressure (P(ET)CO2)--of breathing resistance and elevated inspired carbon dioxide (CO2) had not been determined during heavy exercise. In this Institutional Review Board-approved, dry, sea-level study, 12 subjects in each of three phases exercised to exhaustion at 85% peak oxygen uptake while V(E) and P(ET)CO2 were measured. Participants inhaled 0%, 1%, 2% or 3% CO2 in air, or 0% or 2% CO2 in oxygen, with or without breathing resistance, mimicking the U.S. Navy's MK 16 rebreather underwater breathing apparatus (UBA). Compared to air baseline (0% inspired CO2 in air without resistance): (1) Oxygen decreased baseline V(E) (p < 0.01); (2) Inspired CO2 increased V(E) and P(ET)CO2 (p < 0.01); (3) Resistance decreased V(E) (p < 0.01); (4) Inspired CO2 with resistance elevated P(ET)CO2 (p < 0.01). In air, V(E) did not change from that with resistance alone. In oxygen, V(E) returned to oxygen baseline. End-exercise P(ET)CO2 exceeded 60 Torr (8.0 kPa) in three tests. Subjects identified hypercapnia poorly. Results support dual optimization of arterial carbon dioxide partial pressure and respiratory effort. Because elevated CO2 may not increase V(E) if breathing resistance and VE are high, rebreather UBA safety requires very low inspired CO2.

  19. Fingerprinting captured CO2 using natural tracers: Determining CO2 fate and proving ownership

    NASA Astrophysics Data System (ADS)

    Flude, Stephanie; Gilfillan, Stuart; Johnston, Gareth; Stuart, Finlay; Haszeldine, Stuart

    2016-04-01

    In the long term, captured CO2 will most likely be stored in large saline formations and it is highly likely that CO2 from multiple operators will be injected into a single saline formation. Understanding CO2 behavior within the reservoir is vital for making operational decisions and often uses geochemical techniques. Furthermore, in the event of a CO2 leak, being able to identify the owner of the CO2 is of vital importance in terms of liability and remediation. Addition of geochemical tracers to the CO2 stream is an effective way of tagging the CO2 from different power stations, but may become prohibitively expensive at large scale storage sites. Here we present results from a project assessing whether the natural isotopic composition (C, O and noble gas isotopes) of captured CO2 is sufficient to distinguish CO2 captured using different technologies and from different fuel sources, from likely baseline conditions. Results include analytical measurements of CO2 captured from a number of different CO2 capture plants and a comprehensive literature review of the known and hypothetical isotopic compositions of captured CO2 and baseline conditions. Key findings from the literature review suggest that the carbon isotope composition will be most strongly controlled by that of the feedstock, but significant fractionation is possible during the capture process; oxygen isotopes are likely to be controlled by the isotopic composition of any water used in either the industrial process or the capture technology; and noble gases concentrations will likely be controlled by the capture technique employed. Preliminary analytical results are in agreement with these predictions. Comparison with summaries of likely storage reservoir baseline and shallow or surface leakage reservoir baseline data suggests that C-isotopes are likely to be valuable tracers of CO2 in the storage reservoir, while noble gases may be particularly valuable as tracers of potential leakage.

  20. Inserting CO2 into Aryl C-H Bonds of Metal-Organic Frameworks: CO2 Utilization for Direct Heterogeneous C-H Activation.

    PubMed

    Gao, Wen-Yang; Wu, Haifan; Leng, Kunyue; Sun, Yinyong; Ma, Shengqian

    2016-04-25

    Described for the first time is that carbon dioxide (CO2 ) can be successfully inserted into aryl C-H bonds of the backbone of a metal-organic framework (MOF) to generate free carboxylate groups, which serve as Brønsted acid sites for efficiently catalyzing the methanolysis of epoxides. The work delineates the very first example of utilizing CO2 for heterogeneous C-H activation and carboxylation reactions on MOFs, and opens a new avenue for CO2 chemical transformations under mild reaction conditions.

  1. CO2 evaporative cooling: The future for tracking detector thermal management

    NASA Astrophysics Data System (ADS)

    Tropea, P.; Daguin, J.; Petagna, P.; Postema, H.; Verlaat, B.; Zwalinski, L.

    2016-07-01

    In the last few years, CO2 evaporative cooling has been one of the favourite technologies chosen for the thermal management of tracking detectors at LHC. ATLAS Insertable B-Layer and CMS Pixel phase 1 upgrade have adopted it and their systems are now operational or under commissioning. The CERN PH-DT team is now merging the lessons learnt on these two systems in order to prepare the design and construction of the cooling systems for the new Upstream Tracker and the Velo upgrade in LHCb, due by 2018. Meanwhile, the preliminary design of the ATLAS and CMS full tracker upgrades is started, and both concepts heavily rely on CO2 evaporative cooling. This paper highlights the performances of the systems now in operation and the challenges to overcome in order to scale them up to the requirements of the future generations of trackers. In particular, it focuses on the conceptual design of a new cooling system suited for the large phase 2 upgrade programmes, which will be validated with the construction of a common prototype in the next years.

  2. Advanced CO2 Removal Technology Development

    NASA Technical Reports Server (NTRS)

    Finn, John E.; Verma, Sunita; Forrest, Kindall; LeVan, M. Douglas

    2001-01-01

    The Advanced CO2 Removal Technical Task Agreement covers three active areas of research and development. These include a study of the economic viability of a hybrid membrane/adsorption CO2 removal system, sorbent materials development, and construction of a database of adsorption properties of important fixed gases on several adsorbent material that may be used in CO2 removal systems. The membrane/adsorption CO2 removal system was proposed as a possible way to reduce the energy consumption of the four-bed molecular sieve system now in use. Much of the energy used by the 4BMS is used to desorb water removed in the device s desiccant beds. These beds might be replaced by a desiccating membrane that moves the water from [he incoming stream directly into the outlet stream. The approach may allow the CO2 removal beds to operate at a lower temperature. A comparison between models of the 4BMS and hybrid systems is underway at Vanderbilt University. NASA Ames Research Center has been investigating a Ag-exchanged zeolites as a possible improvement over currently used Ca and Na zeolites for CO2 removal. Silver ions will complex with n:-bonds in hydrocarbons such as ethylene, giving remarkably improved selectivity for adsorption of those materials. Bonds with n: character are also present in carbon oxides. NASA Ames is also continuing to build a database for adsorption isotherms of CO2, N2, O2, CH4, and Ar on a variety of sorbents. This information is useful for analysis of existing hardware and design of new processes.

  3. Photolytic production of CO2 on Iapetus

    NASA Astrophysics Data System (ADS)

    Palmer, Eric; Brown, R. H.

    2008-09-01

    Carbon Dioxide has been detected on the surface of Iapetus by Cassini's VIMS instrument at the 4.26 micron band. This CO2 is concentrated on the equatorial leading side, where we also see an abundance of dark material. The residence time of free CO2 on the surface of Iapetus is very short, thus the CO2 is unlikely to be in the form of frost; it is more likely that the CO2 is tightly bound in the form of complexed molecules. We explore the possibility of photolytically generating CO2 from a mixture of the carbon rich material and water ice that matches the expected composition of the dark material on Iapetus' surface. An ice regolith was created with flash frozen water that was crushed into sub-millimeter shards and mixed with amorphous 13C. The regolith was placed in a vacuum chamber with a surface area of 10 cm2 and a thickness of 2 cm and exposed to UV light from a deuterium lamp with peaks of flux centered around 121 and 160 nm. Temperatures were varied between 60 and 130K at a pressure of 10-8 torr. Both CO and CO2 were produced by photolytic reactions and detected by a mass spectrometer. Applying these results to Iapetus, Jeans escape calculations show that CO2 generated by photolysis will remain gravitationally bound to Iapetus for between 100 and 200 years, ballistically scattering across the surface until it is sequestered in a polar cold trap or escapes to space. The average particle will interact with the surface more than 1000 times before escaping unless interactions with surface grains causes it to become complexed, such as adsorption. We are continuing to evaluate the photochemistry for this simulated Iapetus surface using a Nicolet IR spectrometer to identify all the products generated and estimate the associated production rate.

  4. CO(2) Fixation in Opuntia Roots.

    PubMed

    Ting, I P; Dugger, W M

    1966-03-01

    Nonautotrophic CO(2) metabolism in Opuntia echinocarpa roots was studied with techniques of manometry and radiometry. The roots were grown in a one-quarter strength nutrient solution for several days; the distal 2 cm was used for physiological studies. The roots assimilated significant quantities of (14)CO(2) and appeared to show a crassulacean-type acid metabolism with respect to quality and quantity. Most of the (14)C activity was associated with the distal portion of the elongating root indicating correlation with metabolic activity. The (14)CO(2) assimilation was comparable to a crassulacean leaf succulent, but 3 times greater than that found for stem tissue of the same Opuntia species.The rates of O(2) and CO(2) exchange and estimated CO(2) fixation were 180, 123, and 57 mul/g per hour. A respiratory quotient of 0.66 was found.The products of (14)CO(2) fixation were similar in most respects to reported experiments with leaf succulents. Equilibration of the predominant malic acid with isocitric, succinic, and fumaric acids was not evident. The latter observation was interpreted as metabolic isolation of the fixation products rather than poor citric acid cycle activity.A rapid turnover of the fixed (14)CO(2) was measured by following decarboxlyation kinetics and by product analysis after a postincubation period. The first order rate constant for the steady state release was 4.4 x 10(-3) min(-1) with a half-time of 157.5 minutes. Amino acids decayed at a more rapid rate than organic acids.

  5. Continuously Regenerable Freeze-Out CO2 Control Technology

    NASA Technical Reports Server (NTRS)

    Fricker, John; Dyer, Chris; Myers, Jeff; Patten, Rich; Paul, Heather

    2007-01-01

    Carbon dioxide (CO2) removal technology development for portable life support systems (PLSS) has traditionally concentrated in the areas of solid and liquid chemical sorbents and semi-permeable membranes. Most of these systems are too heavy in gravity environments, require prohibitive amounts of consumables for operation on long term planetary missions, or are inoperable on the surface of Mars due to the presence of a CO2 atmosphere. This paper describes the effort performed to mature an innovative CO2 removal technology that meets NASA s planetary mission needs while adhering to the important guiding principles of simplicity, reliability, and operability. A breadboard cryogenic carbon dioxide scrubber (Cryo Scrubber) for a closed loop cryogenic PLSS was developed, designed, and tested, and a conceptual design suitable for a PLSS was developed based on the results of the breadboard testing. The Cryo Scrubber freezes CO2 and other trace contaminants out of expired vent loop gas using cooling available from a liquid oxygen (LOX) based PLSS. The device is continuously regenerable, with solid CO2 being removed from the cold freeze-out surfaces, sublimated, and vented overboard. Duration is limited only by the supply of LOX stored in the PLSS. Simplicity, reliability, and operability are universally important criteria for critical hardware on long duration Lunar or Mars missions. The Cryo Scrubber has no moving parts, requires no additional consumables, and uses no electrical power, contributing to its simplicity and reliability. It is easy to use; no operator action is required to prepare, use, or shut down the Cryo Scrubber, and it does not require charging or regeneration. The versatility of the concept allows for operation on earth, the moon, and Mars, and in microgravity.

  6. Carbon Dioxide Clusters: (CO_2)_6 to (CO_2)13

    NASA Astrophysics Data System (ADS)

    McKellar, A. R. W.; Oliaee, J. Norooz; Dehghany, M.; Moazzen-Ahmadi, N.

    2011-06-01

    We recenty reported assignments of specific infrared bands in the CO_2 νb{3} region (˜2350 wn) to (CO_2)_6, (CO_2)_7, (CO_2)_9, (CO_2)10, (CO_2)11, (CO_2)12, and (CO_2)13. Spectra are obtained by direct absorption using a rapid-scan tuneable diode laser spectrometer to probe a pulsed supersonic slit-jet expansion and assignments are facilitated by recent calculations of Takeuchi based on the Murthy potential. (CO_2)_6 is a symmetric top with S_6 point group symmetry which can be thought of as a stack of two planar cyclic trimers. (CO_2)13 is also an S_6 symmetric top, and consists of a single CO_2 monomer surrounded by an slightly distorted icosahedral cage. The remaining clusters are asymmetric tops without symmetry. Here we report additional CO_2 cluster results. Calculations based on the SAPT-s potential indicate that the structure of (CO_2)10 may be slightly different from that given by Takeuchi/Murthy. An additional band is observed for each of (CO_2)13 and (CO_2)10. A feature observed at 2378.2 wn is assigned as a (CO_2)_6 parallel combination band involving the sum of a fundamental and a low-lying intermolecular vibration. Most significantly, two bands are assigned to a second isomer of (CO_2)_6. This is also a symmetric top, but now with S_4 symmetry. The two symmetric hexamer isomers observed spectroscopically correspond well with the lowest energy structures given by both the SAPT-s and Murthy intermolecular potentials. [1] J. Norooz Oliaee, M. Dehgany, N. Moazzen-Ahmadi, and A.R.W. McKellar, Phys. Chem. Chem. Phys. 13, 1297 (2011). [2] H. Takeuchi, J. Phys. Chem. A 107, 5703 (2008); C.S. Murthy, S.F. O'Shea, and I.R. McDonald, Mol. Phys. 50, 531 (1983). [3] R. Bukowski, J. Sadlej, B. Jeziorski, P. Jankowski, K. Szalewicz, S.A. Kucharski, H.L. Williams, and B.M. Rice, J. Chem. Phys. 110, 3785 (1999)

  7. Kinetics of CO2 Reduction over Nonstoichiometric Ceria

    PubMed Central

    2015-01-01

    The kinetics of CO2 reduction over nonstoichimetric ceria, CeO2−δ, a material of high potential for thermochemical conversion of sunlight to fuel, has been investigated for a wide range of nonstoichiometries (0.02 ≤ δ ≤ 0.25), temperatures (693 ≤ T ≤ 1273 K), and CO2 concentrations (0.005 ≤ pCO2 ≤ 0.4 atm). Samples were reduced thermally at 1773 K to probe low nonstoichiometries (δ < 0.05) and chemically at lower temperatures in a H2 atmosphere to prevent particle sintering and probe the effect of higher nonstoichiometries (δ < 0.25). For extents greater than δ = 0.2, oxidation rates at a given nonstoichiometry are hindered for the duration of the reaction, presumably because of near-order changes, such as lattice compression, as confirmed via Raman Spectroscopy. Importantly, this behavior is reversible and oxidation rates are not affected at lower δ. Following thermal reduction at very low δ, however, oxidation rates are an order of magnitude slower than those of chemically reduced samples, and rates monotonically increase with the initial nonstoichiometry (up to δ = 0.05). This dependence may be attributed to the formation of stable defect complexes formed between oxygen vacancies and polarons. When the same experiments are performed with 10 mol % Gd3+ doped ceria, in which defect complexes are less prevalent than in pure ceria, this dependence is not observed. PMID:26693270

  8. Effects of CO2 and Temperature on Tritrophic Interactions

    PubMed Central

    Dyer, Lee A.; Richards, Lora A.; Short, Stephanie A.; Dodson, Craig D.

    2013-01-01

    There has been a significant increase in studies of how global change parameters affect interacting species or entire communities, yet the combined or interactive effects of increased atmospheric CO2 and associated increases in global mean temperatures on chemically mediated trophic interactions are mostly unknown. Thus, predictions of climate-induced changes on plant-insect interactions are still based primarily on studies of individual species, individual global change parameters, pairwise interactions, or parameters that summarize communities. A clear understanding of community response to global change will only emerge from studies that examine effects of multiple variables on biotic interactions. We examined the effects of increased CO2 and temperature on simple laboratory communities of interacting alfalfa, chemical defense, armyworm caterpillars, and parasitoid wasps. Higher temperatures and CO2 caused decreased plant quality, decreased caterpillar development times, developmental asynchrony between caterpillars and wasps, and complete wasp mortality. The effects measured here, along with other effects of global change on natural enemies suggest that biological control and other top-down effects of insect predators will decline over the coming decades. PMID:23638105

  9. CO2 and CO Simulations and Their Source Signature Indicated by CO/CO2

    NASA Technical Reports Server (NTRS)

    Kawa, Randy; Huisheng, Bian

    2004-01-01

    Three years (2000-2002) atmospheric CO2 and CO fields are simulated by a Chemistry Transport Model driven by the assimilated meteorological fields from GEOS-4. The simulated CO2 and CO are evaluated by measurements from surface (CMDL), satellite (MOPITT/CO), and aircraft. The model-observation comparisons indicate reasonable agreement in both source and remote regions, and in the lower and upper troposphere. The simulation also captures the seasonality of CO2 and CO variations. The ratios of CO/CO2 are analyzed over different representative regions to identify the source signature, since the anthropogenic CO comes fiom the same combustion processes as CO2. This work enables us to improve satellite inversion estimates of CO2 sources and sinks by simultaneously using satellite CO measurement.

  10. The Effect of Excess Electron and hole on CO2 Adsorption and Activation on Rutile (110) surface.

    PubMed

    Yin, Wen-Jin; Wen, Bo; Bandaru, Sateesh; Krack, Matthias; Lau, M W; Liu, Li-Min

    2016-01-01

    CO2 capture and conversion into useful chemical fuel attracts great attention from many different fields. In the reduction process, excess electron is of key importance as it participates in the reaction, thus it is essential to know whether the excess electrons or holes affect the CO2 conversion. Here, the first-principles calculations were carried out to explore the role of excess electron on adsorption and activation of CO2 on rutile (110) surface. The calculated results demonstrate that CO2 can be activated as CO2 anions or CO2 cation when the system contains excess electrons and holes. The electronic structure of the activated CO2 is greatly changed, and the lowest unoccupied molecular orbital of CO2 can be even lower than the conduction band minimum of TiO2, which greatly facilities the CO2 reduction. Meanwhile, the dissociation process of CO2 undergoes an activated CO2(-) anion in bend configuration rather than the linear, while the long crossing distance of proton transfer greatly hinders the photocatalytic reduction of CO2 on the rutile (110) surface. These results show the importance of the excess electrons on the CO2 reduction process. PMID:26984417

  11. The Effect of Excess Electron and hole on CO2 Adsorption and Activation on Rutile (110) surface

    NASA Astrophysics Data System (ADS)

    Yin, Wen-Jin; Wen, Bo; Bandaru, Sateesh; Krack, Matthias; Lau, Mw; Liu, Li-Min

    2016-03-01

    CO2 capture and conversion into useful chemical fuel attracts great attention from many different fields. In the reduction process, excess electron is of key importance as it participates in the reaction, thus it is essential to know whether the excess electrons or holes affect the CO2 conversion. Here, the first-principles calculations were carried out to explore the role of excess electron on adsorption and activation of CO2 on rutile (110) surface. The calculated results demonstrate that CO2 can be activated as CO2 anions or CO2 cation when the system contains excess electrons and holes. The electronic structure of the activated CO2 is greatly changed, and the lowest unoccupied molecular orbital of CO2 can be even lower than the conduction band minimum of TiO2, which greatly facilities the CO2 reduction. Meanwhile, the dissociation process of CO2 undergoes an activated CO2‑ anion in bend configuration rather than the linear, while the long crossing distance of proton transfer greatly hinders the photocatalytic reduction of CO2 on the rutile (110) surface. These results show the importance of the excess electrons on the CO2 reduction process.

  12. The Effect of Excess Electron and hole on CO2 Adsorption and Activation on Rutile (110) surface

    PubMed Central

    Yin, Wen-Jin; Wen, Bo; Bandaru, Sateesh; Krack, Matthias; Lau, MW; Liu, Li-Min

    2016-01-01

    CO2 capture and conversion into useful chemical fuel attracts great attention from many different fields. In the reduction process, excess electron is of key importance as it participates in the reaction, thus it is essential to know whether the excess electrons or holes affect the CO2 conversion. Here, the first-principles calculations were carried out to explore the role of excess electron on adsorption and activation of CO2 on rutile (110) surface. The calculated results demonstrate that CO2 can be activated as CO2 anions or CO2 cation when the system contains excess electrons and holes. The electronic structure of the activated CO2 is greatly changed, and the lowest unoccupied molecular orbital of CO2 can be even lower than the conduction band minimum of TiO2, which greatly facilities the CO2 reduction. Meanwhile, the dissociation process of CO2 undergoes an activated CO2− anion in bend configuration rather than the linear, while the long crossing distance of proton transfer greatly hinders the photocatalytic reduction of CO2 on the rutile (110) surface. These results show the importance of the excess electrons on the CO2 reduction process. PMID:26984417

  13. Monitoring of near surface CO2

    NASA Astrophysics Data System (ADS)

    Faber, E.; Möller, I.; Teschner, M.; Poggenburg, J.; Spickenbom, K.; Schulz, H. J.

    2009-04-01

    Monitoring of near surface CO2 ECKHARD FABER1, INGO MÖLLER1, MANFRED TESCHNER1, JÜRGEN POGGENBURG1, KAI SPICKENBOM1, HANS-MARTIN SCHULZ1,2 1Bundesanstalt für Geowissenschaften und Rohstoffe (BGR), Stilleweg 2, D-30655 Hannover, e.faber@bgr.de 2present adress: GeoForschungsZentrum Potsdam (GFZ), Telegrafenberg, D-14473 Potsdam Underground gas storage and sequestration of carbon dioxide is one of the methods to reduce the input of antropogenic CO2 into the atmosphere and its greenhouse effect. Storage of CO2 is planned in depleted reservoirs, in aquifers and in salt caverns. Storage sites must have very small leakage rates to safely store the CO2 for centuries. Thus, a careful investigation and site selection is crucial. However, any leakage of CO2 to the surface is potentially dangerous for humans and environment. Therefore, instruments and systems for the detection of any CO2 escaping the storage sites and reaching the atmosphere have to be developed. Systems to monitor gases in deep wells, groundwater and surface sediments for leaking CO2 are developed, tested and are contnuously improved. Our group is mainly analysing CO2 in shallow (down to 3 m) soil samples using automatically operating monitoring systems. The systems are equipped with sensors to measure CO2 (and other gases) concentrations and other environmental parameters (atmospheric pressure, ambient and soil temperatures, etc.). Data are measured in short intervals (minute to subminute), are stored locally and are transferred by telemetrical systems into the BGR laboratory (Weinlich et al., 2006). In addition to soil gases monitoring systems technical equipment is available for continuous underwater gas flow measurements. Several of those monitoring systems are installed in different areas like Czech Republic, Austria, Italy and Germany. To detect any leaking gas from a sequestration site after CO2 injection, the naturally existing CO2 concentration (before injection) must be known. Thus, the natural

  14. On CO2 Behavior in the Subsurface, Following Leakage from aGeologic Storage Reservoir

    SciTech Connect

    Pruess, Karsten

    2006-02-09

    and demonstrate that CO2 can be injected and stored safely ingeologic formations. This requires an understanding of the risks andhazards associated with geologic storage, and a demonstration that therisks are acceptably small or can be mitigated. Much work is currentlyunderway to develop comprehensive approaches towards risk assessment froma systems analysis perspective, which in general requires a simplifieddescription of physical and chemical processes (Maul, et al., 2004,Espie, 2004; Wildenborg, et al., 2004; Walton, et al., 2004). This typeof approach is very important, but needs to be complemented withdevelopment of an understanding of the physical and chemical processesassociated with CO2 storage and leakage (Evans, et al.,2004).

  15. Geochemical signatures of the diffuse CO2 emission from Brava volcanic system, Cape Verde

    NASA Astrophysics Data System (ADS)

    Rodriguez, F.; Bandomo, Z.; Barros, I.; Dias Fonseca, J.; Fernandes, P.; Rodrigues, J.; Melian Rodriguez, G.; Padron, E.; Dionis, S.; Sonia, S.; Gonçalves, A.; Fernandes, A.; Hernandez Perez, P. A.; Perez, N.

    2010-12-01

    Brava (67 km2) the smallest of the populated Cape Verde islands, lies at the southwestern end of the archipelagic crescent. Brava volcanic system has no documented historical eruptions, but its youthful volcanic morphology and the fact that earthquake swarms still occur indicate the potential for future eruptions. A geochemical survey of diffuse gas emissions was carried out in Brava island during February and March 2010. For this survey 228 sampling sites were selected all over the island to perform soil CO2 efflux measurements, using a portable accumulation chamber and an IR sensor, and soil temperature measurements at a depth of 30-50 cm. Soil gas samples were collected at 40 cm depth for chemical (He, H2, N2, CO2, CH4, Ar and O2) and isotopic (δ13C-CO2) analysis in 32 selected sampling sites. CO2 efflux values ranged from non-detectable up to 1.343 g m-2 d-1. To quantify the total diffuse CO2 emission from Brava volcanic system, a CO2 efflux map was constructed using sequential Gaussian simulations (sGs). Most of the studied area showed background levels of CO2 efflux (˜2 g m-2 d-1), while peak levels (>1300 g m-2 d-1) were mainly identified at Vinagre and Baleia areas. The total diffuse CO2 output from Brava volcanic system was estimated about 41.6 t d-1. The analysis of the carbon isotopic signature of the CO2 in the soil atmosphere provides an insight for evaluating the origin of the diffuse CO2 emission. Observed δ13C-CO2 values ranged from -20.86 to -1.26 ‰. A binary plot of CO2 concentrations versus δ13C-CO2 values allows us to represent three major geochemical reservoirs (atmospheric air, volcanic gas, and biogenic gas) and their related mixing lines. The chemical and isotopic analysis of Brava soil gas samples suggest a mixing with deep-seated CO2 and biogenic gas for the diffuse CO2 emission from Brava volcanic system. The lack of visible volcanic gas emission in Brava highlights the importance of monitoring diffuse CO2 emission to improve its

  16. Climate balance of biogas upgrading systems.

    PubMed

    Pertl, A; Mostbauer, P; Obersteiner, G

    2010-01-01

    One of the numerous applications of renewable energy is represented by the use of upgraded biogas where needed by feeding into the gas grid. The aim of the present study was to identify an upgrading scenario featuring minimum overall GHG emissions. The study was based on a life-cycle approach taking into account also GHG emissions resulting from plant cultivation to the process of energy conversion. For anaerobic digestion two substrates have been taken into account: (1) agricultural resources and (2) municipal organic waste. The study provides results for four different upgrading technologies including the BABIU (Bottom Ash for Biogas Upgrading) method. As the transport of bottom ash is a critical factor implicated in the BABIU-method, different transport distances and means of conveyance (lorry, train) have been considered. Furthermore, aspects including biogas compression and energy conversion in a combined heat and power plant were assessed. GHG emissions from a conventional energy supply system (natural gas) have been estimated as reference scenario. The main findings obtained underlined how the overall reduction of GHG emissions may be rather limited, for example for an agricultural context in which PSA-scenarios emit only 10% less greenhouse gases than the reference scenario. The BABIU-method constitutes an efficient upgrading method capable of attaining a high reduction of GHG emission by sequestration of CO(2).

  17. CO2 flux estimation accuracy evaluation of Global and Regional atmospheric CO2 mission concepts

    NASA Astrophysics Data System (ADS)

    Lee, M.; Miller, C.; Weidner, R. J.; Duren, R. M.; Sander, S.; Eldering, A.

    2012-12-01

    We developed an observing system simulation experiment (OSSE) framework to evaluate mission-science-return quantitatively as a function of instrument payload, observation frequency, orbit, and sampling strategy for space-based remote sensing. The OSSE framework integrates GEOSChem and its adjoint system to perform forward/inverse modeling of the simulated measurements. During 2011-2012, we extended the OSSE framework to evaluate CO2 mission concepts in collaboration with the NASA's carbon monitoring system (CMS) flux pilot project team. In this paper, we employ the OSSE framework to analyze the science impact of multiple, simultaneous space-based column CO2 observations from simulated combinations of GOSAT, OCO-2, OCO-3, and a geo-stationary mission concept (GEOFTS). The OSSE process involved generating a CO2 concentration forecast, sampling the CO2 field at the appropriate time and location for each satellite sensor, incorporating realistic cloud climatologies to generate accurate clear-sky viewing statistics, retrieving CO2 profile simulaton in the presence of measurement noise, and finally assimilating the simulated column CO2 retrievals to estimate CO2 fluxes and flux uncertainty reductions. The OSSE process was applied over one-year-long mission period (2009/Jan - 2009/Dec) and the CO2 flux estimation error was analyzed to compute the probability density function (PDF) of CO2 flux estimation-error-reduction. The global OSSEs were performed in 2deg x 2.5 deg spatial resolution with the monthly-average CO2 flux estimation-error-reduction as the science-impact metric. Regional OSSEs were performed in 0.5 deg by 0.666 deg over N. America and the weekly average of the CO2 flux estimation-error-reduction was employed as the science-impact metric. We discuss the results and the projected performance of planned and potential space-based CO2 observing systems.

  18. Direct Copolymerization of CO2 and Diols.

    PubMed

    Tamura, Masazumi; Ito, Kazuki; Honda, Masayoshi; Nakagawa, Yoshinao; Sugimoto, Hiroshi; Tomishige, Keiichi

    2016-01-01

    Direct polymerization of CO2 and diols is promising as a simple and environmental-benign method in place of conventional processes using high-cost and/or hazardous reagents such as phosgene, carbon monoxide and epoxides, however, there are no reports on the direct method due to the inertness of CO2 and severe equilibrium limitation of the reaction. Herein, we firstly substantiate the direct copolymerization of CO2 and diols using CeO2 catalyst and 2-cyanopyridine promotor, providing the alternating cooligomers in high diol-based yield (up to 99%) and selectivity (up to >99%). This catalyst system is applicable to various diols including linear C4-C10 α,ω-diols to provide high yields of the corresponding cooligomers, which cannot be obtained by well-known methods such as copolymerization of CO2 and cyclic ethers and ring-opening polymerization of cyclic carbonates. This process provides us a facile synthesis method for versatile polycarbonates from various diols and CO2 owing to simplicity of diols modification. PMID:27075987

  19. The supply chain of CO2 emissions

    PubMed Central

    Davis, Steven J.; Peters, Glen P.; Caldeira, Ken

    2011-01-01

    CO2 emissions from the burning of fossil fuels are conventionally attributed to the country where the emissions are produced (i.e., where the fuels are burned). However, these production-based accounts represent a single point in the value chain of fossil fuels, which may have been extracted elsewhere and may be used to provide goods or services to consumers elsewhere. We present a consistent set of carbon inventories that spans the full supply chain of global CO2 emissions, finding that 10.2 billion tons CO2 or 37% of global emissions are from fossil fuels traded internationally and an additional 6.4 billion tons CO2 or 23% of global emissions are embodied in traded goods. Our results reveal vulnerabilities and benefits related to current patterns of energy use that are relevant to climate and energy policy. In particular, if a consistent and unavoidable price were imposed on CO2 emissions somewhere along the supply chain, then all of the parties along the supply chain would seek to impose that price to generate revenue from taxes collected or permits sold. The geographical concentration of carbon-based fuels and relatively small number of parties involved in extracting and refining those fuels suggest that regulation at the wellhead, mine mouth, or refinery might minimize transaction costs as well as opportunities for leakage. PMID:22006314

  20. Direct Copolymerization of CO2 and Diols

    PubMed Central

    Tamura, Masazumi; Ito, Kazuki; Honda, Masayoshi; Nakagawa, Yoshinao; Sugimoto, Hiroshi; Tomishige, Keiichi

    2016-01-01

    Direct polymerization of CO2 and diols is promising as a simple and environmental-benign method in place of conventional processes using high-cost and/or hazardous reagents such as phosgene, carbon monoxide and epoxides, however, there are no reports on the direct method due to the inertness of CO2 and severe equilibrium limitation of the reaction. Herein, we firstly substantiate the direct copolymerization of CO2 and diols using CeO2 catalyst and 2-cyanopyridine promotor, providing the alternating cooligomers in high diol-based yield (up to 99%) and selectivity (up to >99%). This catalyst system is applicable to various diols including linear C4-C10 α,ω-diols to provide high yields of the corresponding cooligomers, which cannot be obtained by well-known methods such as copolymerization of CO2 and cyclic ethers and ring-opening polymerization of cyclic carbonates. This process provides us a facile synthesis method for versatile polycarbonates from various diols and CO2 owing to simplicity of diols modification. PMID:27075987

  1. Atmospheric CO2 stabilization and ocean acidification

    NASA Astrophysics Data System (ADS)

    Cao, Long; Caldeira, Ken

    2008-10-01

    We use a coupled climate/carbon-cycle model to examine the consequences of stabilizing atmospheric CO2 at different levels for ocean chemistry. Our simulations show the potential for major damage to at least some ocean ecosystems at atmospheric CO2 stabilization levels as low as 450 ppm. Before the industrial revolution, more than 98% of corals reefs were surrounded by waters that were >3.5 times saturated with respect to their skeleton materials (aragonite). If atmospheric CO2 is stabilized at 450 ppm only 8% of existing coral reefs will be surrounded by water with this saturation level. Also at this CO2 level 7% of the ocean South of 60°S will become undersaturated with respect to aragonite, and parts of the high latitude ocean will experience a decrease in pH by more than 0.2 units. Results presented here provide an independent and additional basis for choosing targets of atmospheric CO2 stabilization levels.

  2. Direct Copolymerization of CO2 and Diols

    NASA Astrophysics Data System (ADS)

    Tamura, Masazumi; Ito, Kazuki; Honda, Masayoshi; Nakagawa, Yoshinao; Sugimoto, Hiroshi; Tomishige, Keiichi

    2016-04-01

    Direct polymerization of CO2 and diols is promising as a simple and environmental-benign method in place of conventional processes using high-cost and/or hazardous reagents such as phosgene, carbon monoxide and epoxides, however, there are no reports on the direct method due to the inertness of CO2 and severe equilibrium limitation of the reaction. Herein, we firstly substantiate the direct copolymerization of CO2 and diols using CeO2 catalyst and 2-cyanopyridine promotor, providing the alternating cooligomers in high diol-based yield (up to 99%) and selectivity (up to >99%). This catalyst system is applicable to various diols including linear C4-C10 α,ω-diols to provide high yields of the corresponding cooligomers, which cannot be obtained by well-known methods such as copolymerization of CO2 and cyclic ethers and ring-opening polymerization of cyclic carbonates. This process provides us a facile synthesis method for versatile polycarbonates from various diols and CO2 owing to simplicity of diols modification.

  3. Development of new measuring technique using sound velocity for CO2 concentration in Cameroonian volcanic lakes

    NASA Astrophysics Data System (ADS)

    Sanemasa, M.; Saiki, K.; Kaneko, K.; Ohba, T.; Kusakabe, M.; Tanyileke, G.; Hell, J.

    2012-12-01

    1. Introduction Limnic eruptions at Lakes Monoun and Nyos in Cameroon, which are sudden degassing of magmatic CO2 dissolved in the lake water, occurred in 1984 and 1986, respectively. The disasters killed about 1800 people around the lakes. Because of ongoing CO2 accumulation in the bottom water of the lakes, tragedy of limnic eruptions will possibly occur again. To prevent from further disasters, artificial degassing of CO2 from the lake waters has been undergoing. Additionally, CO2 monitoring of the lake waters is needed. Nevertheless, CO2 measurement is done only once or twice a year because current methods of CO2 measurement, which require chemical analysis of water samples, are not suitable for frequent measurement. In engineering field, on the other hand, a method to measure salt concentration using sound velocity has been proposed (Kleis and Sanchez, 1990). This method allows us to evaluate solute concentration fast. We applied the method to dissolved CO2 and examined the correlation between sound velocity and CO2 concentration in laboratory experiment. Furthermore, using the obtained correlation, we tried to estimate the CO2 concentration of waters in the Cameroonian lakes. 2. Laboratory experiment We examined the correlation between sound velocity and CO2 concentration. A profiler (Minos X, made by AML oceanography) and pure water were packed in cylindrical stainless vessel and high-pressure CO2 gas was injected to produce carbonated water. The profiler recorded temperature, pressure and sound velocity. Change of sound velocity was defined as difference of sound velocity between carbonated water and pure water under the same temperature and pressure conditions. CO2 concentration was calculated by Henry's law. The result indicated that the change of sound velocity [m s-1] is proportional to CO2 concentration [mmol kg-1], and the coefficient is 0.021 [m kg s-1 mmol-1]. 3. Field application Depth profiles of sound velocity, pressure, and temperature of Lakes

  4. Impact of Wellbore Cement Degradation on CO2 Storage Integrity

    NASA Astrophysics Data System (ADS)

    Kutchko, B.; Strazisar, B.; Lowry, G.; Dzombak, D.; Thaulow, N.

    2007-12-01

    The sequestration of CO2 in underground geologic formations requires a thorough evaluation of potential leakage of the sequestered CO2 through the numerous existing wellbores which penetrate them. Leakage rates of less than 1% per 100 years have been deemed necessary for geologic sequestration to be viable. Well bores are of particular interest because the cement used to line and/or plug the well, may be vulnerable to acid attack. Injected CO2 will dissolve, becoming carbonic acid, which can readily react with calcium hydroxide and calcium silicate hydrate, key components in hardened cement. Laboratory experiments have been performed in order to determine the physical and chemical changes, as well as the rate of degradation of the cement under simulated sequestration reservoir conditions, including both aqueous and supercritical CO2. Upon exposure to aqueous CO2, hardened cement formed well-defined reaction zones by a 2-step process. The first step is the dissolution of Ca(OH) 2 (s) and subsequent precipitation of CaCO3 (s). The formation of CaCO3 (s) has been reported to decrease cement permeability and increase its compressive strength. The second step is the dissolution of CaCO3 (s) resulting in a leaching of calcium from the cement matrix. The resulting cement paste has a significant increase in porosity, is primarily composed of amorphous silica gel, and lacks structural integrity. Although it is clear that cement is degraded, the results of this study suggest that the reactions involved are slow. In fact, long term experiments show that the rate of degradation decreases over time, likely due to the precipitation of CaCO3 (s) within the pore space of the cement. This phenomenon should limit the negative impact that chemical degradation will have on well bores. Supercritical CO2 exposure (saturated with water vapor) led to a very different process by which CaCO3 (s) was deposited throughout the matrix and on the surface, rather than within an isolated reaction

  5. CO2-Binding-Organic-Liquids-Enhanced CO2 Capture using Polarity-Swing-Assisted Regeneration

    SciTech Connect

    Zhang, Jian; Kutnyakov, Igor; Koech, Phillip K.; Zwoster, Andy; Howard, Chris; Zheng, Feng; Freeman, Charles J.; Heldebrant, David J.

    2013-01-01

    A new solvent-based CO2 capture process couples the unique attributes of non-aqueous, CO2-binding organic liquids (CO2BOLs) with the newly discovered polarity-swing-assisted regeneration (PSAR) process that is unique to switchable ionic liquids. Laboratory measurements with PSAR indicate the ability to achieve a regeneration effect at 75°C comparable to that at 120°C using thermal regeneration only. Initial measurements also indicate that the kinetic behavior of CO2 release is also improved with PSAR. Abstract cleared PNWD-SA-9743

  6. Light-duty vehicle CO2 targets consistent with 450 ppm CO2 stabilization.

    PubMed

    Winkler, Sandra L; Wallington, Timothy J; Maas, Heiko; Hass, Heinz

    2014-06-01

    We present a global analysis of CO2 emission reductions from the light-duty vehicle (LDV) fleet consistent with stabilization of atmospheric CO2 concentration at 450 ppm. The CO2 emission reductions are described by g CO2/km emission targets for average new light-duty vehicles on a tank-to-wheel basis between 2010 and 2050 that we call CO2 glide paths. The analysis accounts for growth of the vehicle fleet, changing patterns in driving distance, regional availability of biofuels, and the changing composition of fossil fuels. New light-duty vehicle fuel economy and CO2 regulations in the U.S. through 2025 and in the EU through 2020 are broadly consistent with the CO2 glide paths. The glide path is at the upper end of the discussed 2025 EU range of 68-78 g CO2/km. The proposed China regulation for 2020 is more stringent than the glide path, while the 2017 Brazil regulation is less stringent. Existing regulations through 2025 are broadly consistent with the light-duty vehicle sector contributing to stabilizing CO2 at approximately 450 ppm. The glide paths provide long-term guidance for LDV powertrain/fuel development. PMID:24798684

  7. Surface CO2 leakage during the first shallow subsurface CO2release experiment

    SciTech Connect

    Lewicki, J.L.; Oldenburg, C.; Dobeck, L.; Spangler, L.

    2007-09-15

    A new field facility was used to study CO2 migrationprocesses and test techniques to detect and quantify potential CO2leakage from geologic storage sites. For 10 days starting 9 July 2007,and for seven days starting 5 August 2007, 0.1 and 0.3 t CO2 d-1,respectively, were released from a ~;100-m long, sub-water table (~;2.5-mdepth) horizontal well. The spatio-temporal evolution of leakage wasmapped through repeated grid measurements of soil CO2 flux (FCO2). Thesurface leakage onset, approach to steady state, and post-release declinematched model predictions closely. Modeling suggested that minimal CO2was taken up by groundwater through dissolution, and CO2 spread out ontop of the water table. FCO2 spatial patterns were related to well designand soil physical properties. Estimates of total CO2 discharge along withsoil respiration and leakage discharge highlight the influence ofbackground CO2 flux variations on detection of CO2 leakagesignals.

  8. Sensitivity analysis of a model of CO2 exchange in tundra ecosystems by the adjoint method

    NASA Technical Reports Server (NTRS)

    Waelbroek, C.; Louis, J.-F.

    1995-01-01

    A model of net primary production (NPP), decomposition, and nitrogen cycling in tundra ecosystems has been developed. The adjoint technique is used to study the sensitivity of the computed annual net CO2 flux to perturbation in initial conditions, climatic inputs, and model's main parameters describing current seasonal CO2 exchange in wet sedge tundra at Barrow, Alaska. The results show that net CO2 flux is most sensitive to parameters characterizing litter chemical composition and more sensitive to decomposition parameters than to NPP parameters. This underlines the fact that in nutrient-limited ecosystems, decomposition drives net CO2 exchange by controlling mineralization of main nutrients. The results also indicate that the short-term (1 year) response of wet sedge tundra to CO2-induced warming is a significant increase in CO2 emission, creating a positive feedback to atmosphreic CO2 accumulation. However, a cloudiness increase during the same year can severely alter this response and lead to either a slight decrease or a strong increase in emitted CO2, depending on its exact timing. These results demonstrate that the adjoint method is well suited to study systems encountering regime changes, as a single run of the adjoint model provides sensitivities of the net CO2 flux to perturbations in all parameters and variables at any time of the year. Moreover, it is shown that large errors due to the presence of thresholds can be avoided by first delimiting the range of applicability of the adjoint results.

  9. Sensitivity analysis of a model of CO2 exchange in tundra ecosystems by the adjoint method

    SciTech Connect

    Waelbroek, C.; Louis, J.F. |

    1995-02-01

    A model of net primary production (NPP), decomposition, and nitrogen cycling in tundra ecosystems has been developed. The adjoint technique is used to study the sensitivity of the computed annual net CO2 flux to perturbation in initial conditions, climatic inputs, and model`s main parameters describing current seasonal CO2 exchange in wet sedge tundra at Barrow, Alaska. The results show that net CO2 flux is most sensitive to parameters characterizing litter chemical composition and more sensitive to decomposition parameters than to NPP parameters. This underlines the fact that in nutrient-limited ecosystems, decomposition drives net CO2 exchange by controlling mineralization of main nutrients. The results also indicate that the short-term (1 year) response of wet sedge tundra to CO2-induced warming is a significant increase in CO2 emission, creating a positive feedback to atmosphreic CO2 accumulation. However, a cloudiness increase during the same year can severely alter this response and lead to either a slight decrease or a strong increase in emitted CO2, depending on its exact timing. These results demonstrate that the adjoint method is well suited to study systems encountering regime changes, as a single run of the adjoint model provides sensitivities of the net CO2 flux to perturbations in all parameters and variables at any time of the year. Moreover, it is shown that large errors due to the presence of thresholds can be avoided by first delimiting the range of applicability of the adjoint results.

  10. Impact of episodic vertical fluxes on sea surface pCO2.

    PubMed

    Mahadevan, A; Tagliabue, A; Bopp, L; Lenton, A; Mémery, L; Lévy, M

    2011-05-28

    Episodic events like hurricanes, storms and frontal- and eddy-driven upwelling can alter the partial pressure of CO(2) (pCO(2)) at the sea surface by entraining subsurface waters into the surface mixed layer (ML) of the ocean. Since pCO(2) is a function of total dissolved inorganic carbon (DIC), temperature (T), salinity and alkalinity, it responds to the combined impacts of physical, chemical and biological changes. Here, we present an analytical framework for assessing the relative magnitude and sign in the short-term perturbation of surface pCO(2) arising from vertical mixing events. Using global, monthly, climatological datasets, we assess the individual, as well as integrated, contribution of various properties to surface pCO(2) in response to episodic mixing. The response depends on the relative vertical gradients of properties beneath the ML. Many areas of the ocean exhibit very little sensitivity to mixing owing to the compensatory effects of DIC and T on pCO(2), whereas others, such as the eastern upwelling margins, have the potential to generate large positive/negative anomalies in surface pCO(2). The response varies seasonally and spatially and becomes more intense in subtropical and subpolar regions during summer. Regions showing a greater pCO(2) response to vertical mixing are likely to exhibit higher spatial variability in surface pCO(2) on time scales of days.

  11. Development of a laser remote sensing instrument to measure sub-aerial volcanic CO2 fluxes

    NASA Astrophysics Data System (ADS)

    Queisser, Manuel; Burton, Mike

    2016-04-01

    A thorough quantification of volcanic CO2 fluxes would lead to an enhanced understanding of the role of volcanoes in the geological carbon cycle. This would enable a more subtle understanding of human impact on that cycle. Furthermore, variations in volcanic CO2 emissions are a key to understanding volcanic processes such as eruption phenomenology. However, measuring fluxes of volcanic CO2 is challenging as volcanic CO2 concentrations are modest compared with the ambient CO2 concentration (~400 ppm) . Volcanic CO2 quickly dilutes with the background air. For Mt. Etna (Italy), for instance, 1000 m downwind from the crater, dispersion modelling yields a signal of ~4 ppm only. It is for this reason that many magmatic CO2 concentration measurements focus on in situ techniques, such as direct sampling Giggenbach bottles, chemical sensors, IR absorption spectrometers or mass spectrometers. However, emission rates are highly variable in time and space. Point measurements fail to account for this variability. Inferring 1-D or 2-D gas concentration profiles, necessary to estimate gas fluxes, from point measurements may thus lead to erroneous flux estimations. Moreover, in situ probing is time consuming and, since many volcanoes emit toxic gases and are dangerous as mountains, may raise safety concerns. In addition, degassing is often diffuse and spatially extended, which makes a measurement approach with spatial coverage desirable. There are techniques that allow to indirectly retrieve CO2 fluxes from correlated SO2 concentrations and fluxes. However, they still rely on point measurements of CO2 and are prone to errors of SO2 fluxes due to light dilution and depend on blue sky conditions. Here, we present a new remote sensing instrument, developed with the ERC project CO2Volc, which measures 1-D column amounts of CO2 in the atmosphere with sufficient sensitivity to reveal the contribution of magmatic CO2. Based on differential absorption LIDAR (DIAL) the instrument measures

  12. Infrared absorption of t-HOCO+, H+(CO2)2, and HCO2- produced in electron bombardment of CO2 in solid para-H2

    NASA Astrophysics Data System (ADS)

    Das, Prasanta; Tsuge, Masashi; Lee, Yuan-Pern

    2016-07-01

    We have employed electron bombardment during matrix deposition of CO2 (or 13CO2, C18O2) and para-hydrogen (p-H2) at 3.2 K and recorded infrared (IR) spectra of t-HOCO+, H+(CO2)2, HCO2-, CO2-, t-HOCO, and other species isolated in solid p-H2. After the matrix was maintained in darkness for 13 h, intensities of absorption features of t-HOCO+ at 2403.5 (ν1), 2369.9 (ν2), 1018.1 (ν4), and 606.5 (ν6) cm-1 and those of H+(CO2)2 at 1341.1, 883.6, and 591.5 cm-1 decreased. Corresponding lines of isotopologues were observed when 13CO2 or C18O2 replaced CO2. In contrast, lines of HCO2- at 2522.4 (ν1), 1616.1 (ν5), 1327.9 (ν2), and 745.6 (ν3) cm-1 increased in intensity; corresponding lines of H13CO2- or HC18O2- were also observed. Lines of t-DOCO+ and DCO2- were observed in an electron bombarded CO2 /normal-deuterium (n-D2) matrix. Data of ν6 of t-HOCO+ and all observed modes of H18OC18O+ and HC18O2- are new. The assignments were made according to expected chemical behavior, observed isotopic shifts, and comparisons with vibrational wavenumbers and relative intensities of previous reports and calculations with the B3PW91/aug-cc-pVQZ method. The ν1 line of t-HOCO+ in solid p-H2 (2403.5 cm-1), similar to the line at 2673 cm-1 of t-HOCO+ tagged with an Ar atom, is significantly red-shifted from that reported for gaseous t-HOCO+ (3375.37 cm-1) due to partial proton sharing between CO2 and H2 or Ar. The ν1 line of HCO2- in solid p-H2 (2522.4 cm-1) is blue shifted from that reported for HCO2- in solid Ne (2455.7 cm-1) and that of HCO2- tagged with Ar (2449 cm-1); this can be explained by the varied solvation effects by Ne, Ar, or H2 on the mixing of H+ + CO2 and H + CO2- surfaces. Possible formation mechanisms of t-HOCO+, H+(CO2)2, HCO2-, CO2-, t-HOCO, H2O, and t-HCOOH are discussed.

  13. Oxygen isotope fractionation in stratospheric CO2

    NASA Technical Reports Server (NTRS)

    Thiemens, M. H.; Jackson, T.; Mauersberger, K.; Schueler, B.; Morton, J.

    1991-01-01

    A new cryogenic collection system has been flown on board a balloon gondola to obtain separate samples of ozone and carbon dioxide without entrapping major atmospheric gases. Precision laboratory isotopic analysis of CO2 samples collected between 26 and 35.5 km show a mass-independent enrichment in both O-17 and O-18 of about 11 per mil above tropospheric values. Ozone enrichment in its heavy isotopes was 9 to 16 percent in O3-50 and 8 to 11 percent in O3-49, respectively (Schueler et al., 1990). A mechanism to explain the isotope enrichment in CO2 has been recently proposed by Yung et al. (1991). The model is based on the isotope exchange between CO2 and O3 via O(1D), resulting in a transfer of the ozone isotope enrichment to carbon dioxide. Predicted enrichment and measured values agree well.

  14. CO2 mitigation via accelerated limestone weathering

    USGS Publications Warehouse

    Rau, G.H.; Knauss, K.G.; Langer, W.H.; Caldeira, K.

    2004-01-01

    Accelerated weathering of limestone (AWL: CO22+ + CaCO3 + H2O ??? Ca2+ + 2HCO3- as a low-tech, inexpensive, high-capacity, environmentally-friendly CO2 capture and sequestration technology was evaluated. With access to seawater and limestone being essential to this approach, significant limestone resources were close to most CO2-emitting power plants along the coastal US. Waste fines, representing > 20% of current US crushed limestone production (> 109 tons/yr), could be used as an inexpensive source of AWL carbonate. AWL end-solution disposal in the ocean would significantly reduce effects on ocean pH and carbonate chemistry relative to those caused by direct atmospheric or ocean CO2 disposal. Indeed, the increase in ocean Ca2+ and bicarbonate offered by AWL should enhance growth of corals and other calcifying marine organisms.

  15. Sequestration of CO2 by concrete carbonation.

    PubMed

    Galan, Isabel; Andrade, Carmen; Mora, Pedro; Sanjuan, Miguel A

    2010-04-15

    Carbonation of reinforced concrete is one of the causes of corrosion, but it is also a way to sequester CO2. The characteristics of the concrete cover should ensure alkaline protection for the steel bars but should also be able to combine CO2 to a certain depth. This work attempts to advance the knowledge of the carbon footprint of cement. As it is one of the most commonly used materials worldwide, it is very important to assess its impact on the environment. In order to quantify the capacity of cement based materials to combine CO2 by means of the reaction with hydrated phases to produce calcium carbonate, Thermogravimetry and the phenolphthalein indicator have been used to characterize several cement pastes and concretes exposed to different environments. The combined effect of the main variables involved in this process is discussed. The moisture content of the concrete seems to be the most influential parameter. PMID:20225850

  16. Influence of O2 on the dielectric properties of CO2 at the elevated temperatures

    NASA Astrophysics Data System (ADS)

    Rong, Mingzhe; Sun, Hao; Yang, Fei; Wu, Yi; Chen, Zhexin; Wang, Xiaohua; Wu, Mingliang

    2014-11-01

    SF6 gas is widely used in the high voltage circuit breakers but considering its high global warming potential other substitutes are being sought. Among them CO2 was investigated and even has been used in some practical products. However, at room temperature, the dielectric properties of CO2 are relatively lower than SF6 and air. The goal of this work is to investigate a CO2-based gas to improve the performance of the pure CO2. In this paper, the dielectric properties of hot CO2/O2 mixtures related to the dielectric recovery phase of the circuit breaker were investigated in the temperature range from 300 K to 4000 K and in the pressure range from 0.01 MPa to 1.0 MPa. The species compositions of hot CO2/O2 were obtained based on Gibbs free energy minimization under the assumptions of local thermodynamic equilibrium and local chemical equilibrium. The reduced critical electric field strength of CO2/O2 was determined by balancing electron generation and loss. These were calculated using the electron energy distribution function by solving the Boltzmann transport equation. The validity of the calculation method and the cross sections data was confirmed by comparing the measurements and calculations of the electron swarm data in previous work. The results indicate that in pure CO2 the critical electric field strength is higher only in higher temperature range. By adding the O2 into the CO2, the critical electric field strength at lower temperature is effectively enhanced. CO2/O2 mixtures have a much better dielectric strength than both the pure CO2 and air and thus have the potential to improve the CO2-based gas circuit breakers. Similar conclusions can also be found in others' work, which further confirm the validity of these results.

  17. Direct Numerical Simulation of Pore Scale Flow and Reactive Transport of CO2 in Porous Media.

    NASA Astrophysics Data System (ADS)

    Alizadeh Nomeli, M.

    2014-12-01

    Recently, the need to decrease CO2 concentration in the atmosphere has been recognized because of the role of CO2 as a greenhouse gas that contributes to global warming. Carbon Capture and Sequestration (CCS) is one of the most promising long term solutions for the reduction of CO2 in the atmosphere. To this end, injection of CO2 into deep geological formations has been proposed and investigated theoretically and experimentally in the last years. The fracture permeability, an important parameter controlling CO2 migration throughout sequestration, affects the amount of mineralization trapping of CO2 which enhances the long-term CO2 storage. A long-term geochemical modeling of subsurface CO2 storage is carried out in a single fracture to investigate its impact on CO2 transport and storage capacity. We model the fracture by considering flow of CO2 between finite plates. CO2 is initially dissolved in the brine and then precipitates during the geochemical reactions between H2O-CO2 and minerals. We study the physics and the critical time of blockage for a fracture to interpret the results. We employ direct numerical simulation tools and algorithms to simulate incompressible flow along with necessary transport equations that capture the kinetics of relevant chemical reactions. The numerical model is based on a finite difference method using a sequential non-iterative approach. It is found that mineral precipitation has an important effect on reservoir porosity and permeability. The fracture ceases to be a fluid channel because of the precipitation of minerals.

  18. Molybdenum carbide as alternative catalysts to precious metals for highly selective reduction of CO2 to CO.

    PubMed

    Porosoff, Marc D; Yang, Xiaofang; Boscoboinik, J Anibal; Chen, Jingguang G

    2014-06-23

    Rising atmospheric CO2 is expected to have negative effects on the global environment from its role in climate change and ocean acidification. Utilizing CO2 as a feedstock to make valuable chemicals is potentially more desirable than sequestration. A substantial reduction of CO2 levels requires a large-scale CO2 catalytic conversion process, which in turn requires the discovery of low-cost catalysts. Results from the current study demonstrate the feasibility of using the non-precious metal material molybdenum carbide (Mo2C) as an active and selective catalyst for CO2 conversion by H2.

  19. CO2 Orbital Trends in Comets

    NASA Astrophysics Data System (ADS)

    Kelley, Michael; Bodewits, Dennis; Feaga, Lori; Knight, Matthew; McKay, Adam; Snodgrass, Colin; Wooden, Diane

    2016-08-01

    Carbon dioxide is a primary volatile in comet nuclei, and potentially a major contributor to comet activity (i.e., the process of mass loss). However, CO2 cannot be observed directly from the ground, and past surveys of this molecule in comets were limited to space-borne snapshot observations. This situation limits our understanding of the behavior of CO2 in comets, and its role in driving comet mass loss. To address this deficiency, we were awarded a Cy11 Spitzer program designed to quantify the production rate of CO2 on >month-long timescales for 21 comets. We request an additional 269~hr in Cy13 to complete the Spitzer portion of our survey, and to add three more comets (46P/Wirtanen and 2 Target of Opportunity Oort cloud comets). Our survey is designed to probe the orbital trends of CO2 production in the comet population. We aim to: 1) examine the role of CO2 in the persistent post-perihelion activity observed in Jupiter-family comets; 2) measure the seasonal variations of CO2/H2O as a proxy for nucleus heterogeneity, when possible; 3) search for orbital trends sensitive to cumulative insolation as a proxy for nucleus layering; and 4) examine how Oort cloud comets evolve by comparing dynamically new and old targets. The final data set will allow us to investigate the effects of heating on the evolution of comets, if nucleus structures can be inferred through activity, and set the stage for JWST investigations into comet activity and composition.

  20. Geochemical Monitoring for Potential Environmental Impacts of Geologic Sequestration of CO2

    NASA Astrophysics Data System (ADS)

    Thomas, B.; Kharaka, Y. K.; Cole, D. R.; Thordsen, J. J.; Conaway, C. H.; Gans, K. D.

    2013-12-01

    Geologically sequestered CO2 is buoyant, has a low viscosity and, when dissolved in brine, becomes reactive to minerals, cements and well pipes. These properties of CO2 may cause it to leak upward from the major storage reservoirs, possibly contaminating underground sources of drinking water. We have participated in several multi-laboratory field experiments to investigate the changes in chemical and isotopic parameters and added tracers that are applicable to the monitoring of the flow of injected CO2 in reservoirs and leakage into potable shallow groundwater. Geochemical results from the Frio Brine I and II pilot tests located near Dayton, Texas and from the SECARB Phase III tests at Cranfield oil field, Mississippi, proved powerful tools in: 1- Tracking the successful injection and flow of CO2 into the injection sandstones; 2- showing major changes in the chemical (pH, alkalinity, and major divalent cations) and isotopic (δ13C values of CO2, and δ18O values of CO2, and brine) compositions of formation water; 3-. showing mobilization of metals, including Fe Mn and Pb, and organic compounds , including DOC, BTEX, PAHs, and phenols following CO2 injection; and 4- showing that some of the CO2 injected into the Frio 'C' sandstone was detected in the overlying 'B' sandstone that is separated by 15 m of shale and muddy siltstone. Rapid, significant and systematic changes were also observed in the isotopic and chemical compositions of shallow groundwater at the ZERT site located in Bozeman, MT, in response to four yearly controlled injections of CO2 gas through a slotted pipe placed horizontally at a depth of ~2 m below ground level. The observed changes, included the lowering of groundwater pH from ~7.0 to values as low as 5.6, increases in the alkalinity from about 400 mg/L as HCO3 to values of up to 1330 mg/L, increases in the electrical conductance from ~600 μS/cm to up to 1800 μS/cm, as well as increases in the concentrations of cations and metals following CO2

  1. Why capture CO2 from the atmosphere?

    PubMed

    Keith, David W

    2009-09-25

    Air capture is an industrial process for capturing CO2 from ambient air; it is one of an emerging set of technologies for CO2 removal that includes geological storage of biotic carbon and the acceleration of geochemical weathering. Although air capture will cost more than capture from power plants when both are operated under the same economic conditions, air capture allows one to apply industrial economies of scale to small and mobile emission sources and enables a partial decoupling of carbon capture from the energy infrastructure, advantages that may compensate for the intrinsic difficulty of capturing carbon from the air.

  2. Why Capture CO2 from the Atmosphere?

    NASA Astrophysics Data System (ADS)

    Keith, David W.

    2009-09-01

    Air capture is an industrial process for capturing CO2 from ambient air; it is one of an emerging set of technologies for CO2 removal that includes geological storage of biotic carbon and the acceleration of geochemical weathering. Although air capture will cost more than capture from power plants when both are operated under the same economic conditions, air capture allows one to apply industrial economies of scale to small and mobile emission sources and enables a partial decoupling of carbon capture from the energy infrastructure, advantages that may compensate for the intrinsic difficulty of capturing carbon from the air.

  3. CO2 Acquisition Membrane (CAM) Project

    NASA Technical Reports Server (NTRS)

    Mason, L. W.; Way, J. D.; Vlasse, M.

    2001-01-01

    The CO2 Acquisition Membrane (CAM) project will develop, test, and analyze membrane materials for separation and purification of carbon dioxide (CO2) from mixtures of gases, such as those found in the Martian atmosphere. The CAM technology will enable passive separation of these gases, allow energy efficient acquisition and purification of these important resources, and lay the foundation for future unmanned sample return and human space missions. The CAM membranes are targeted toward In Situ Resource Utilization (ISRU) applications, such as In Situ Propellant Production (ISPP) and In Situ Consumables Production (ISCP).

  4. 10 MW Supercritical CO2 Turbine Test

    SciTech Connect

    Turchi, Craig

    2014-01-29

    The Supercritical CO2 Turbine Test project was to demonstrate the inherent efficiencies of a supercritical carbon dioxide (s-CO2) power turbine and associated turbomachinery under conditions and at a scale relevant to commercial concentrating solar power (CSP) projects, thereby accelerating the commercial deployment of this new power generation technology. The project involved eight partnering organizations: NREL, Sandia National Laboratories, Echogen Power Systems, Abengoa Solar, University of Wisconsin at Madison, Electric Power Research Institute, Barber-Nichols, and the CSP Program of the U.S. Department of Energy. The multi-year project planned to design, fabricate, and validate an s-CO2 power turbine of nominally 10 MWe that is capable of operation at up to 700°C and operates in a dry-cooled test loop. The project plan consisted of three phases: (1) system design and modeling, (2) fabrication, and (3) testing. The major accomplishments of Phase 1 included: Design of a multistage, axial-flow, s-CO2 power turbine; Design modifications to an existing turbocompressor to provide s-CO2 flow for the test system; Updated equipment and installation costs for the turbomachinery and associated support infrastructure; Development of simulation tools for the test loop itself and for more efficient cycle designs that are of greater commercial interest; Simulation of s-CO2 power cycle integration into molten-nitrate-salt CSP systems indicating a cost benefit of up to 8% in levelized cost of energy; Identification of recuperator cost as a key economic parameter; Corrosion data for multiple alloys at temperatures up to 650ºC in high-pressure CO2 and recommendations for materials-of-construction; and Revised test plan and preliminary operating conditions based on the ongoing tests of related equipment. Phase 1 established that the cost of the facility needed to test the power turbine at its full power and temperature would exceed the planned funding for Phases 2 and 3. Late

  5. Selective Oxytrifluoromethylation of Allylamines with CO2.

    PubMed

    Ye, Jian-Heng; Song, Lei; Zhou, Wen-Jun; Ju, Tao; Yin, Zhu-Bao; Yan, Si-Shun; Zhang, Zhen; Li, Jing; Yu, Da-Gang

    2016-08-16

    Reported is the first oxy-trifluoromethylation of allylamines with carbon dioxide (CO2 ) using copper catalysis, thus leading to important CF3 -containing 2-oxazolidones. It is also the first time CO2 , a nontoxic and easily available greenhouse gas, has been used to tune the difunctionalization of alkenes from amino- to oxy-trifluoromethylation. Of particular note, this multicomponent reaction is highly chemo-, regio-, and diastereoselective under redox-neutral and mild reaction conditions. Moreover, these reactions feature good functional-group tolerance, broad substrate scope, easy scalability and facile product diversification. The important products could also be formed with either spirocycles or two adjacent tetrasubstituted carbon centers. PMID:27411560

  6. Crystallization of CO2 ice and the absence of amorphous CO2 ice in space

    PubMed Central

    Escribano, Rafael M.; Muñoz Caro, Guillermo M.; Cruz-Diaz, Gustavo A.; Rodríguez-Lazcano, Yamilet; Maté, Belén

    2013-01-01

    Carbon dioxide (CO2) is one of the most relevant and abundant species in astrophysical and atmospheric media. In particular, CO2 ice is present in several solar system bodies, as well as in interstellar and circumstellar ice mantles. The amount of CO2 in ice mantles and the presence of pure CO2 ice are significant indicators of the temperature history of dust in protostars. It is therefore important to know if CO2 is mixed with other molecules in the ice matrix or segregated and whether it is present in an amorphous or crystalline form. We apply a multidisciplinary approach involving IR spectroscopy in the laboratory, theoretical modeling of solid structures, and comparison with astronomical observations. We generate an unprecedented highly amorphous CO2 ice and study its crystallization both by thermal annealing and by slow accumulation of monolayers from the gas phase under an ultrahigh vacuum. Structural changes are followed by IR spectroscopy. We also devise theoretical models to reproduce different CO2 ice structures. We detect a preferential in-plane orientation of some vibrational modes of crystalline CO2. We identify the IR features of amorphous CO2 ice, and, in particular, we provide a theoretical explanation for a band at 2,328 cm−1 that dominates the spectrum of the amorphous phase and disappears when the crystallization is complete. Our results allow us to rule out the presence of pure and amorphous CO2 ice in space based on the observations available so far, supporting our current view of the evolution of CO2 ice. PMID:23858474

  7. Carbon Dioxide, Hydrographic, and Chemical Data Obtained During the R/V Ronald H. Brown Repeat Hydrography Cruise in the Atlantic Ocean: CLIVAR CO2 Section A16S_2005 (11 January - 24 February, 2005)

    SciTech Connect

    Kozyr, Alex

    2006-08-30

    This report presents methods, and analytical and quality control procedures for salinity, oxygen, nutrient, inorganic carbon, organic carbon, chlorofluorocarbon (CFC), and bomb 14C system parameters performed during the A16S_2005 cruise, which took place from January 11 to February 24, 2005, aboard research vessel (R/V) Ronald H. Brown under the auspices of the National Oceanic and Atmospheric Administration (NOAA). The R/V Ronald H. Brown departed Punta Arenas, Chile, on January 11, 2005, and ended its cruise in Fortaleza, Brazil, on February 24, 2005. The research conducted was one of a series of repeat hydrography sections jointly funded by NOAA and the National Science Foundation as part of the CLIVAR/CO2/repeat hydrography/tracer program. Samples were taken from 36 depths at 121 stations. The data presented in this report include the analyses of water samples for total inorganic carbon (TCO2), fugacity of CO2 (fCO2), total alkalinity (TALK), pH, dissolved organic carbon (DOC), CFC, 14C, hydrographic, and other chemical measurements. The R/V Ronald H. Brown A16S_2005 data set is available free of charge as a numeric data package (NDP) from the Carbon Dioxide Information Analysis Center (CDIAC). The NDP consists of the oceanographic data files and this printed documentation, which describes the procedures and methods used to obtain the data.

  8. Reducing the cost of Ca-based direct air capture of CO2.

    PubMed

    Zeman, Frank

    2014-10-01

    Direct air capture, the chemical removal of CO2 directly from the atmosphere, may play a role in mitigating future climate risk or form the basis of a sustainable transportation infrastructure. The current discussion is centered on the estimated cost of the technology and its link to "overshoot" trajectories, where atmospheric CO2 levels are actively reduced later in the century. The American Physical Society (APS) published a report, later updated, estimating the cost of a one million tonne CO2 per year air capture facility constructed today that highlights several fundamental concepts of chemical air capture. These fundamentals are viewed through the lens of a chemical process that cycles between removing CO2 from the air and releasing the absorbed CO2 in concentrated form. This work builds on the APS report to investigate the effect of modifications to the air capture system based on suggestions in the report and subsequent publications. The work shows that reduced carbon electricity and plastic packing materials (for the contactor) may have significant effects on the overall price, reducing the APS estimate from $610 to $309/tCO2 avoided. Such a reduction does not challenge postcombustion capture from point sources, estimated at $80/tCO2, but does make air capture a feasible alternative for the transportation sector and a potential negative emissions technology. Furthermore, air capture represents atmospheric reductions rather than simply avoided emissions. PMID:25207956

  9. Reducing the cost of Ca-based direct air capture of CO2.

    PubMed

    Zeman, Frank

    2014-10-01

    Direct air capture, the chemical removal of CO2 directly from the atmosphere, may play a role in mitigating future climate risk or form the basis of a sustainable transportation infrastructure. The current discussion is centered on the estimated cost of the technology and its link to "overshoot" trajectories, where atmospheric CO2 levels are actively reduced later in the century. The American Physical Society (APS) published a report, later updated, estimating the cost of a one million tonne CO2 per year air capture facility constructed today that highlights several fundamental concepts of chemical air capture. These fundamentals are viewed through the lens of a chemical process that cycles between removing CO2 from the air and releasing the absorbed CO2 in concentrated form. This work builds on the APS report to investigate the effect of modifications to the air capture system based on suggestions in the report and subsequent publications. The work shows that reduced carbon electricity and plastic packing materials (for the contactor) may have significant effects on the overall price, reducing the APS estimate from $610 to $309/tCO2 avoided. Such a reduction does not challenge postcombustion capture from point sources, estimated at $80/tCO2, but does make air capture a feasible alternative for the transportation sector and a potential negative emissions technology. Furthermore, air capture represents atmospheric reductions rather than simply avoided emissions.

  10. Simulation of altering residual water saturation near wellbore for CO2 injectivity

    NASA Astrophysics Data System (ADS)

    Park, Y.; Lee, T.; Lee, S.; Park, K.

    2014-12-01

    Volumetric CO2 storage capacity in brine aquifers is one of the most important factor for large scale CCS projects. The maximum sustainable injection rate or the injectivity is another important criterion which is dependent on many reservoir specific properties including permeability, porosity, formation thickness, areal extent, pressure and relative permeability. Among those parameters, we focused on the residual wetting phase saturation expressed in relative permeability curve. From previous experiments, residual brine saturation is typically between 0.4 and 0.6. Higher displacement efficiency cannot be expected with those values because the displacement efficiency is inversely proportional to the residual oil saturation. Also, it is natural that the end-point relative permeability for CO2 should be low. The reason is that the high CO2-brine interfacial tension disturbs CO2 invasion into small pores. In this study, chemical flooding was assumed with surfactants or intermediate fluid which is miscible with both water and CO2 to reduce the interfacial tension. We didn't use the chemicals to improve the displacement efficiency all over the field but intend to improve the injectivity at least near the wellbore region swept by the chemicals. Once lower residual brine saturation was achieved, the higher CO2 saturation could be maintained and the better CO2 injectivity was shown. Injection tests using a commercial model showed that the increase of the injectivity was not very high but the enhancement was meaningful.

  11. TES/Aura L2 Carbon Dioxide (CO2) Nadir (TL2CO2N)

    Atmospheric Science Data Center

    2015-01-30

    TES/Aura L2 Carbon Dioxide (CO2) Nadir (TL2CO2N) News:  TES News ... L2 Platform:  TES/Aura L2 Carbon Dioxide Spatial Coverage:  5.2 x 8.5 km nadir ... Subset Data: TES Order Tool Parameters:  Carbon Dioxide Order Data:  Reverb:   Order Data ...

  12. TES/Aura L2 Carbon Dioxide (CO2) Nadir (TL2CO2NS)

    Atmospheric Science Data Center

    2015-01-30

    TES/Aura L2 Carbon Dioxide (CO2) Nadir (TL2CO2NS) News:  TES News ... L2 Platform:  TES/Aura L2 Carbon Dioxide Spatial Coverage:  5.3 x 8.5 km nadir ... Subset Data: TES Order Tool Parameters:  Carbon Dioxide Order Data:  Reverb:   Order Data ...

  13. CO2 dispersion modelling over Paris region within the CO2-MEGAPARIS project

    NASA Astrophysics Data System (ADS)

    Lac, C.; Donnelly, R. P.; Masson, V.; Pal, S.; Donier, S.; Queguiner, S.; Tanguy, G.; Ammoura, L.; Xueref-Remy, I.

    2012-10-01

    Accurate simulation of the spatial and temporal variability of tracer mixing ratios over urban areas is challenging, but essential in order to utilize CO2 measurements in an atmospheric inverse framework to better estimate regional CO2 fluxes. This study investigates the ability of a high-resolution model to simulate meteorological and CO2 fields around Paris agglomeration, during the March field campaign of the CO2-MEGAPARIS project. The mesoscale atmospheric model Meso-NH, running at 2 km horizontal resolution, is coupled with the Town-Energy Balance (TEB) urban canopy scheme and with the Interactions between Soil, Biosphere and Atmosphere CO2-reactive (ISBA-A-gs) surface scheme, allowing a full interaction of CO2 between the surface and the atmosphere. Statistical scores show a good representation of the Urban Heat Island (UHI) and urban-rural contrasts. Boundary layer heights (BLH) at urban, sub-urban and rural sites are well captured, especially the onset time of the BLH increase and its growth rate in the morning, that are essential for tall tower CO2 observatories. Only nocturnal BLH at sub-urban sites are slightly underestimated a few nights, with a bias less than 50 m. At Eiffel tower, the observed spikes of CO2 maxima occur every morning exactly at the time at which the Atmospheric Boundary Layer (ABL) growth reaches the measurement height. The timing of the CO2 cycle is well captured by the model, with only small biases on CO2 concentrations, mainly linked to the misrepresentation of anthropogenic emissions, as the Eiffel site is at the heart of trafic emission sources. At sub-urban ground stations, CO2 measurements exhibit maxima at the beginning and at the end of each night, when the ABL is fully contracted, with a very strong spatio-temporal variability. The CO2 cycle at these sites is generally well reproduced by the model, even if some biases on the nocturnal maxima appear in the Paris plume parly due to small errors on the vertical transport, or in

  14. Elevated CO2 increases constitutive phenolics and trichomes, but decreases inducibility of phenolics in Brassica rapa (Brassicaceae).

    PubMed

    Karowe, David N; Grubb, Christopher

    2011-12-01

    Increasing global atmospheric CO2 has been shown to affect important plant traits, including constitutive levels of defensive compounds. However, little is known about the effects of elevated CO2 on the inducibility of chemical defenses or on plant mechanical defenses. We grew Brassica rapa (oilseed rape) under ambient and elevated CO2 to determine the effects of elevated CO2 on constitutive levels and inducibility of carbon-based phenolic compounds, and on constitutive trichome densities. Trichome density increased by 57% under elevated CO2. Constitutive levels of simple, complex, and total phenolics also increased under elevated CO2, but inducibility of each decreased. Induction of simple phenolics occurred only under ambient CO2. Although induction of complex and total phenolics occurred under both ambient and elevated CO2, the damage-induced increases were 64% and 75% smaller, respectively, under elevated CO2. Constitutive phenolic levels were positively correlated with leaf C:N ratio, and inducibility was positively correlated with leaf N and negatively correlated with leaf C:N ratio, as would be expected if inducibility were constrained by nitrogen availability under elevated CO2. We conclude that B. rapa is likely to exhibit higher constitutive levels of both chemical and mechanical defenses in the future, but is also likely to be less able to respond to herbivore damage by inducing phenolic defenses. To our knowledge, this is only the second study to report a negative effect of elevated CO2 on the inducibility of any plant defense.

  15. Carbon Dioxide Laser Absorption Spectrometer (CO2LAS) Aircraft Measurements of CO2

    NASA Technical Reports Server (NTRS)

    Christensen, Lance E.; Spiers, Gary D.; Menzies, Robert T.; Jacob, Joseph C.; Hyon, Jason

    2011-01-01

    The Jet Propulsion Laboratory Carbon Dioxide Laser Absorption Spectrometer (CO2LAS) utilizes Integrated Path Differential Absorption (IPDA) at 2.05 microns to obtain CO2 column mixing ratios weighted heavily in the boundary layer. CO2LAS employs a coherent detection receiver and continuous-wave Th:Ho:YLF laser transmitters with output powers around 100 milliwatts. An offset frequency-locking scheme coupled to an absolute frequency reference enables the frequencies of the online and offline lasers to be held to within 200 kHz of desired values. We describe results from 2009 field campaigns when CO2LAS flew on the Twin Otter. We also describe spectroscopic studies aimed at uncovering potential biases in lidar CO2 retrievals at 2.05 microns.

  16. Extraction of lipids from microalgae using CO2-expanded methanol and liquid CO2.

    PubMed

    Paudel, Ashok; Jessop, Michael J; Stubbins, Spencer H; Champagne, Pascale; Jessop, Philip G

    2015-05-01

    The use of CO2-expanded methanol (cxMeOH) and liquid carbon dioxide (lCO2) is proposed to extract lipids from Botryococcus braunii. When compressed CO2 dissolves in methanol, the solvent expands in volume, decreases in polarity and so increases in its selectivity for biodiesel desirable lipids. Solid phase extraction of the algal extract showed that the cxMeOH extracted 21 mg of biodiesel desirable lipids per mL of organic solvent compared to 3mg/mL using either neat methanol or chloroform/methanol mixture. The non-polar lCO2 showed a high affinity for non-polar lipids. Using lCO2, it is possible to extract up to 10% neutral lipids relative to the mass of dry algae. Unlike extractions using conventional solvents, these new methods require little to no volatile, flammable, or chlorinated organic solvents.

  17. CO2 Dissociation using the Versatile Atmospheric Dielectric Barrier Discharge Experiment (VADER)

    NASA Astrophysics Data System (ADS)

    Lindon, Michael Allen

    As of 2013, the Carbon Dioxide Information Analysis Center (CDIAC) estimates that the world emits approximately 36 trillion metric tons of Carbon Dioxide (CO2) into the atmosphere every year. These large emissions have been correlated to global warming trends that have many consequences across the globe, including glacial retraction, ocean acidification and increased severity of weather events. With green technologies still in the infancy stage, it can be expected that CO2 emissions will stay this way for along time to come. Approximately 41% of the emissions are due to electricity production, which pump out condensed forms of CO2. This danger to our world is why research towards new and innovative ways of controlling CO2 emissions from these large sources is necessary. As of now, research is focused on two primary methods of CO2 reduction from condensed CO2 emission sources (like fossil fuel power plants): Carbon Capture and Sequestration (CCS) and Carbon Capture and Utilization (CCU). CCS is the process of collecting CO2 using absorbers or chemicals, extracting the gas from those absorbers and finally pumping the gas into reservoirs. CCU on the other hand, is the process of reacting CO2 to form value added chemicals, which can then be recycled or stored chemically. A Dielectric Barrier discharge (DBD) is a pulsed, low temperature, non-thermal, atmospheric pressure plasma which creates high energy electrons suitable for dissociating CO2 into its components (CO and O) as one step in the CCU process. Here I discuss the viability of using a DBD for CO2 dissociation on an industrial scale as well as the fundamental physics and chemistry of a DBD for CO2 dissociation. This work involved modeling the DBD discharge and chemistry, which showed that there are specific chemical pathways and plasma parameters that can be adjusted to improve the CO2 reaction efficiencies and rates. Experimental studies using the Versatile Atmospheric dielectric barrier Discharge Expe

  18. Stereotactic CO2 laser therapy for hydrocephalus

    NASA Astrophysics Data System (ADS)

    Kozodoy-Pins, Rebecca L.; Harrington, James A.; Zazanis, George A.; Nosko, Michael G.; Lehman, Richard M.

    1994-05-01

    A new fiber-optic delivery system for CO2 radiation has been used to successfully treat non-communicating hydrocephalus. This system consists of a hollow sapphire waveguide employed in the lumen of a stereotactically-guided neuroendoscope. CO2 gas flows through the bore of the hollow waveguide, creating a path for the laser beam through the cerebrospinal fluid (CSF). This delivery system has the advantages of both visualization and guided CO2 laser radiation without the same 4.3 mm diameter scope. Several patients with hydrocephalus were treated with this new system. The laser was used to create a passage in the floor of the ventricle to allow the flow of CSF from the ventricles to the sub-arachnoid space. Initial postoperative results demonstrated a relief of the clinical symptoms. Long-term results will indicate if this type of therapy will be superior to the use of implanted silicone shunts. Since CO2 laser radiation at 10.6 micrometers is strongly absorbed by the water in tissue and CSF, damage to tissue surrounding the lesion with each laser pulse is limited. The accuracy and safety of this technique may prove it to be an advantageous therapy for obstructive hydrocephalus.

  19. 76 FR 43489 - Deferral for CO2

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-07-20

    ... dioxide CO 2 e carbon dioxide equivalents EO Executive Order EPA U.S. Environmental Protection Agency FR... as the Tailoring Rule; 75 FR 31514), setting thresholds for GHG emissions that define when permits... bioenergy and other biogenic sources (75 FR 41173). The purpose of this CFI was to request comment...

  20. Photoemission study of SmCo2

    NASA Astrophysics Data System (ADS)

    Kang, J.-S.; Yang, C. J.; Lee, Y. P.; Olson, C. G.; Cho, E.-J.; Oh, S.-J.; Anderson, R. O.; Liu, L. Z.; Park, J.-H.; Allen, J. W.; Ellis, W. P.

    1993-10-01

    The electronic structure of SmCo2 is investigated with photoemission spectroscopy (PES). All the PES spectra are consistent in showing that the bulk Sm ions are trivalent, but that the surface has divalent Sm ions and is probably inhomogeneously mixed valent. Both the Sm 4f valence band and Sm 3d core level PES spectra are found to be substantially broader than those of Sm metal. The observed larger linewidths for SmCo2, as compared to those of pure Sm metal, suggest a larger lifetime broadening, probably due to an increased number of valence-band electrons, and a larger 4f hybridization, mainly to Co 3d states. Weak satellite structures are observed in the Co 3d valence band and Co 2p core level PES spectra, indicating Co 3d correlation effects. The comparison of the experimental valence-band PES spectrum with the theoretical Co 3d projected local density of states also suggests that Co 3d correlation effects in SmCo2 are non-negligible.

  1. CO2 laser used in cosmetology

    NASA Astrophysics Data System (ADS)

    Su, Chenglie

    1993-03-01

    Cases of various kinds of warts, nevi, papillomas, skin angiomas, ephilises, skin vegetation, scars and brandy noses were vaporized and solidified with a 2.5 - 8 W low power CO2 laser with an overall satisfaction rate up to 99.8% and the satisfaction rate for one time 92%.

  2. CO 2 laser surgery in hemophilia treatment.

    PubMed

    Santos-Dias, A

    1992-08-01

    The use of CO 2 laser surgery between 1985 and 1991 in South Africa and Portugal for treatment of disorders in patients with mild to moderate cases of hemophilia A is discussed. Six cases of oral procedures and excision of skin tumors performed during this period are reported. In most of the cases of mild hemophilia no pre- or postoperative infusion of Factor VIII or desmopressin (DDAVP) was required. In some cases of moderate hemophilia, patients were infused with desmopressin (0.3 mug/kg body weight) and were treated postoperatively with the use of nasal desmopressin spray (150 mug to each nostril for four weeks following surgery). Factor VIII levels were measured before surgery. Follow up of four weeks was uneventful. The mean average power of the CO 2 laser was 20 W continuous and the pulse duration was 0.1 s for ablational procedures. For dermatologic procedures, a flexible plastic CO 2 laser hollow fiber was used (Flexilase, Sharplan, Allandale, NJ). We concluded that CO 2 laser surgery for hemophiliacs has a confirmed place in modern laser technology provided the standard precautions are taken and facilities are available.

  3. Porous Hexacyanometalates for CO2 capture applications

    SciTech Connect

    Motkuri, Radha K.; Thallapally, Praveen K.; McGrail, B. Peter

    2013-07-30

    Prussian blue analogues of M3[Fe(CN)6]2 x H2O (where M=Fe, Mn and Ni) were synthesized, characterized and tested for their gas sorption capabilities. The sorption studies reveal that, these Prussian blue materials preferentially sorb CO2 over N2 and CH4 at low pressure (1bar).

  4. Uncooled receivers for CO2 laser radiation

    NASA Astrophysics Data System (ADS)

    Granovskii, A. B.; Iakovlev, V. A.

    1986-01-01

    Published data on low-inertia, uncooled, single-element and matrix-type radiation receivers that have a high degree of reliability and are immune from interference from various external sources are systematically summarized. Three basic types of receivers are examined: photonic receivers, thermal receivers, and receivers based on wave interaction. Principal attention is given to the CO2 laser radiation receiver.

  5. Blackbody-pumped CO2 laser experiment

    NASA Astrophysics Data System (ADS)

    Christiansen, W. H.; Insuik, R. J.

    1983-07-01

    Thermal radiation from a high temperature oven was used as an optical pump to achieve lasing from CO2 mixtures. Laser output as a function of blackbody temperature and gas conditions is described. This achievement represents the first blackbody cavity pumped laser and has potential for solar pumping. Previously announced in STAR as N83-10420

  6. CO2 laser in stapes surgery

    NASA Astrophysics Data System (ADS)

    Jovanovic, Sergije; Schoenfeld, Uwe; Berghaus, Andreas; Fischer, R.; Scherer, Hans H.

    1993-07-01

    Stapedotomy is not only one of the most successful interventions in otology but also one of the most dangerous for the inner ear. To reduce the risk of damaging middle and inner ear structures through manipulations with conventional instruments, the CO2 laser beam is used for perforating the footplate and removing the suprastructures. This non-contact technique aims at precise and controlled management of middle ear structures. Consideration is given to the impact of experimental data on the clinical application of the CO2 laser in stapes surgery. The discussion covers the advantages and disadvantages with regard to optical and tissue-related properties and points out possible dangers to the inner ear. Our experimental and clinical experience is taken as a basis for examining the surgical technique and the varying demands made on the laser beam in treating the stapedial tendon, crura and footplate. Attention is called to the need for additional instruments. Effective energy parameters for CO2 laser stapedeotomy are evaluated for different lasers. Application of the CO2 laser contributes towards optimization of this high-precision intervention and promises to reduce the incidence of inner ear damages in large numbers of cases. This technique appears useful particularly in difficult anatomic situations and, above all, for revisional operations.

  7. Artificial photosynthesis - CO2 towards methanol

    NASA Astrophysics Data System (ADS)

    Nazimek, D.; Czech, B.

    2011-03-01

    The new insight into the problem of carbon dioxide utilization into valuable compound - methanol and then its transformation into fuel is presented. Because the highly endothermic requirements of the reaction of CO2 hydrogenation a photocatalytic route is applied. Combining of the two reactions: water splitting and CO2 hydrogenation using H2O as a source of hydrogen at the same time and place are proposed. The studies over modified TiO2 catalysts supported on Al2O3 were conducted in a self-designed circulated photocatalytic reaction system under at room temperature and constant pressure. Experimental results indicated that the highest yield of the photoreduction of CO2 with H2O were obtained using TiO2 with the active anatase phase modified by Ru and WO3 addition. The conversion was very high - almost 97% of CO2 was transformed mainly into methanol (14%vol.) and into small amount of formic and acetic acid and ester.

  8. Agriculture waste and rising CO2

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Currently, there are many uncertainties concerning agriculture’s role in global environmental change including the effects of rising atmospheric CO2 concentration. A viable and stable world food supply depends on productive agricultural systems, but environmental concerns within agriculture have to...