WorldWideScience

Sample records for carbon chemistry model

  1. The Chemistry of Extragalactic Carbon Stars

    Science.gov (United States)

    Woods, Paul; Walsh, C.; Cordiner, M. A.; Kemper, F.

    2013-01-01

    Prompted by the ongoing interest in Spitzer Infrared Spectrometer spectra of carbon stars in the Large Magellanic Cloud, we have investigated the circumstellar chemistry of carbon stars in low-metallicity environments. Consistent with observations, our models show that acetylene is particularly abundant in the inner regions of low metallicity carbon-rich asymptotic giant branch stars - more abundant than carbon monoxide. As a consequence, larger hydrocarbons have higher abundances at the metallicities of the Magellanic Clouds than in stars with solar metallicity. We also find that the oxygen and nitrogen chemistry is suppressed at lower metallicity, as expected. Finally, we calculate molecular line emission from carbon stars in the Large and Small Magellanic Cloud and find that several molecules should be readily detectable with the Atacama Large Millimeter Array at Full Science operations.

  2. Carbon dioxide, climate and the deep ocean circulation: Carbon chemistry model

    International Nuclear Information System (INIS)

    Menawat, A.S.

    1992-01-01

    The objective of this study was to investigate the role of oceanic carbon chemistry in modulating the atmospheric levels of CO 2 . It is well known that the oceans are the primary sink of the excess carbon pumped into the atmosphere since the beginning of the industrial period. The suspended particulate and the dissolved organic matters in the deep ocean play important roles as carriers of carbon and other elements critical to the fate of CO 2 . In addition, the suspended particulate matter provides sites for oxidation-reduction reactions and microbial activities. The problem is of an intricate system with complex chemical, physical and biological processes. This report describes a methodology to describe the interconversions of different forms of the organic and inorganic nutrients, that may be incorporated in the ocean circulation models. Our approach includes the driving force behind the transfers in addition to balancing the elements. Such thermodynamic considerations of describing the imbalance in the chemical potentials is a new and unique feature of our approach

  3. A comparison of atmospheric composition using the Carbon Bond and Regional Atmospheric Chemistry MechanismsChemistry Mechanisms

    Science.gov (United States)

    We incorporate the recently developed Regional Atmospheric Chemistry Mechanism (version 2, RACM2) into the Community Multiscale Air Quality modeling system for comparison with the existing 2005 Carbon Bond mechanism with updated toluene chemistry (CB05TU). Compared to CB05TU, RAC...

  4. Carbon chemistry in dense molecular clouds: Theory and observational constraints

    International Nuclear Information System (INIS)

    Blake, G.A.

    1990-01-01

    For the most part, gas phase models of the chemistry of dense molecular clouds predict the abundances of simple species rather well. However, for larger molecules and even for small systems rich in carbon these models often fail spectacularly. Researchers present a brief review of the basic assumptions and results of large scale modeling of the carbon chemistry in dense molecular clouds. Particular attention is to the influence of the gas phase C/O ratio in molecular clouds, and the likely role grains play in maintaining this ratio as clouds evolve from initially diffuse objects to denser cores with associated stellar and planetary formation. Recent spectral line surveys at centimeter and millimeter wavelengths along with selected observations in the submillimeter have now produced an accurate inventory of the gas phase carbon budget in several different types of molecular clouds, though gaps in our knowledge clearly remain. The constraints these observations place on theoretical models of interstellar chemistry can be used to gain insights into why the models fail, and show also which neglected processes must be included in more complete analyses. Looking toward the future, larger molecules are especially difficult to study both experimentally and theoretically in such dense, cold regions, and some new methods are therefore outlined which may ultimately push the detectability of small carbon chains and rings to much heavier species

  5. Carbon Isotope Chemistry in Molecular Clouds

    Science.gov (United States)

    Robertson, Amy N.; Willacy, Karen

    2012-01-01

    Few details of carbon isotope chemistry are known, especially the chemical processes that occur in astronomical environments like molecular clouds. Observational evidence shows that the C-12/C-13 abundance ratios vary due to the location of the C-13 atom within the molecular structure. The different abundances are a result of the diverse formation pathways that can occur. Modeling can be used to explore the production pathways of carbon molecules in an effort to understand and explain the chemical evolution of molecular clouds.

  6. Photosynthesis-dependent isoprene emission from leaf to planet in a global carbon-chemistry-climate model

    Science.gov (United States)

    Unger, N.; Harper, K.; Zheng, Y.; Kiang, N. Y.; Aleinov, I.; Arneth, A.; Schurgers, G.; Amelynck, C.; Goldstein, A.; Guenther, A.; Heinesch, B.; Hewitt, C. N.; Karl, T.; Laffineur, Q.; Langford, B.; McKinney, K. A.; Misztal, P.; Potosnak, M.; Rinne, J.; Pressley, S.; Schoon, N.; Serça, D.

    2013-10-01

    We describe the implementation of a biochemical model of isoprene emission that depends on the electron requirement for isoprene synthesis into the Farquhar-Ball-Berry leaf model of photosynthesis and stomatal conductance that is embedded within a global chemistry-climate simulation framework. The isoprene production is calculated as a function of electron transport-limited photosynthesis, intercellular and atmospheric carbon dioxide concentration, and canopy temperature. The vegetation biophysics module computes the photosynthetic uptake of carbon dioxide coupled with the transpiration of water vapor and the isoprene emission rate at the 30 min physical integration time step of the global chemistry-climate model. In the model, the rate of carbon assimilation provides the dominant control on isoprene emission variability over canopy temperature. A control simulation representative of the present-day climatic state that uses 8 plant functional types (PFTs), prescribed phenology and generic PFT-specific isoprene emission potentials (fraction of electrons available for isoprene synthesis) reproduces 50% of the variability across different ecosystems and seasons in a global database of 28 measured campaign-average fluxes. Compared to time-varying isoprene flux measurements at 9 select sites, the model authentically captures the observed variability in the 30 min average diurnal cycle (R2 = 64-96%) and simulates the flux magnitude to within a factor of 2. The control run yields a global isoprene source strength of 451 TgC yr-1 that increases by 30% in the artificial absence of plant water stress and by 55% for potential natural vegetation.

  7. Photosynthesis-dependent Isoprene Emission from Leaf to Planet in a Global Carbon-chemistry-climate Model

    Science.gov (United States)

    Unger, N.; Harper, K.; Zeng, Y.; Kiang, N. Y.; Alienov, I.; Arneth, A.; Schurgers, G.; Amelynck, C.; Goldstein, A.; Guenther, A.; hide

    2013-01-01

    We describe the implementation of a biochemical model of isoprene emission that depends on the electron requirement for isoprene synthesis into the FarquharBallBerry leaf model of photosynthesis and stomatal conductance that is embedded within a global chemistry-climate simulation framework. The isoprene production is calculated as a function of electron transport-limited photosynthesis, intercellular and atmospheric carbon dioxide concentration, and canopy temperature. The vegetation biophysics module computes the photosynthetic uptake of carbon dioxide coupled with the transpiration of water vapor and the isoprene emission rate at the 30 min physical integration time step of the global chemistry-climate model. In the model, the rate of carbon assimilation provides the dominant control on isoprene emission variability over canopy temperature. A control simulation representative of the present-day climatic state that uses 8 plant functional types (PFTs), prescribed phenology and generic PFT-specific isoprene emission potentials (fraction of electrons available for isoprene synthesis) reproduces 50 of the variability across different ecosystems and seasons in a global database of 28 measured campaign-average fluxes. Compared to time-varying isoprene flux measurements at 9 select sites, the model authentically captures the observed variability in the 30 min average diurnal cycle (R2 6496) and simulates the flux magnitude to within a factor of 2. The control run yields a global isoprene source strength of 451 TgC yr1 that increases by 30 in the artificial absence of plant water stress and by 55 for potential natural vegetation.

  8. Photosynthesis-dependent isoprene emission from leaf to planet in a global carbon-chemistry-climate model

    Energy Technology Data Exchange (ETDEWEB)

    Unger, N.; Harper, K.; Zheng, Y.; Kiang, N. Y.; Aleinov, I.; Arneth, Almut; Schurgers, G.; Amelynck, C.; Goldstein, Allen H.; Guenther, Alex B.; Heinesch, B.; Hewitt, C. N.; Karl, T.; Laffineur, Q.; Langford, B.; McKinney, Karena A.; Misztal, P.; Potosnak, M.; Rinne, J.; Pressley, S.; Schoon, N.; Serca, D.

    2013-10-22

    We describe the implementation of a biochemical model of isoprene emission that depends on the electron requirement for isoprene synthesis into the Farquhar/Ball- Berry leaf model of photosynthesis and stomatal conductance that is embedded within a global chemistry-climate simulation framework. The isoprene production is calculated as a function of electron transport-limited photosynthesis, intercellular carbon dioxide concentration, and canopy temperature. The vegetation biophysics module computes the photosynthetic uptake of carbon dioxide coupled with the transpiration of water vapor and the isoprene emission rate at the 30 min physical integration time step of the global chemistry-climate model. In the model, the rate of carbon assimilation provides the dominant control on isoprene emission variability over canopy temperature. A control simulation representative of the present day climatic state that uses plant functional types (PFTs), prescribed phenology and generic PFT-specific isoprene emission potentials (fraction of electrons available for isoprene synthesis) reproduces 50% of the variability across different ecosystems and seasons in a global database of measured campaign-average fluxes. Compared to time-varying isoprene flux measurements at select sites, the model authentically captures the observed variability in the 30 min average diurnal cycle (R2 = 64-96 %) and simulates the flux magnitude to within a factor of 2. The control run yields a global isoprene source strength of 451 TgC yr-1 that increases by 30% in the artificial absence of plant water stress and by 55% for potential natural vegetation.

  9. Photosynthesis-dependent isoprene emission from leaf to planet in a global carbon-chemistry-climate model

    OpenAIRE

    Unger, N.; Harper, K.; Zheng, Y.; Kiang, N. Y.; Aleinov, I.; Arneth, A.; Schurgers, G.; Amelynyck, C.; Goldstein, A.; Guenther, A.; Heinesch, B.; Hewitt, C. N.; Karl, T.; Laffineur, Q.; Langford, B.

    2013-01-01

    We describe the implementation of a biochemical model of isoprene emission that depends on the electron requirement for isoprene synthesis into the Farquhar–Ball–Berry leaf model of photosynthesis and stomatal conductance that is embedded within a global chemistry-climate simulation framework. The isoprene production is calculated as a function of electron transport-limited photosynthesis, intercellular and atmospheric carbon dioxide concentration, and canopy temperature. Th...

  10. Photosynthesis-dependent isoprene emission from leaf to planet in a global carbon-chemistry-climate model

    Directory of Open Access Journals (Sweden)

    N. Unger

    2013-10-01

    Full Text Available We describe the implementation of a biochemical model of isoprene emission that depends on the electron requirement for isoprene synthesis into the Farquhar–Ball–Berry leaf model of photosynthesis and stomatal conductance that is embedded within a global chemistry-climate simulation framework. The isoprene production is calculated as a function of electron transport-limited photosynthesis, intercellular and atmospheric carbon dioxide concentration, and canopy temperature. The vegetation biophysics module computes the photosynthetic uptake of carbon dioxide coupled with the transpiration of water vapor and the isoprene emission rate at the 30 min physical integration time step of the global chemistry-climate model. In the model, the rate of carbon assimilation provides the dominant control on isoprene emission variability over canopy temperature. A control simulation representative of the present-day climatic state that uses 8 plant functional types (PFTs, prescribed phenology and generic PFT-specific isoprene emission potentials (fraction of electrons available for isoprene synthesis reproduces 50% of the variability across different ecosystems and seasons in a global database of 28 measured campaign-average fluxes. Compared to time-varying isoprene flux measurements at 9 select sites, the model authentically captures the observed variability in the 30 min average diurnal cycle (R2 = 64–96% and simulates the flux magnitude to within a factor of 2. The control run yields a global isoprene source strength of 451 TgC yr−1 that increases by 30% in the artificial absence of plant water stress and by 55% for potential natural vegetation.

  11. Refining the Neoproterozoic and Early Paleozoic record of carbon cycling and seawater chemistry using quantitative geochemical models of redox dynamics and carbonate diagenesis

    DEFF Research Database (Denmark)

    Ahm, Anne-Sofie Crüger

    based records. Despite the prevalence of diagenesis in sedimentary rocks there are currently few robust geochemical tools capable of providing quantitative information on the extent of alteration from the primary signal. In order to fill this gap, Chapter 3 presents a numerical model of marine carbonate...... through diagenesis and provide more robust estimates for past seawater chemistry. Ancient carbonate rocks with extreme negative carbon isotopes are found worldwide bracketing the Marinoan glaciation (∼635 Ma). There is no scientific consensus as to whether these excursions originate from a primary...... perturbation in the carbon cycle or from diagenetic alterations. Chapter 4 merges new measurements of calcium, magnesium, and strontium isotopes in these sediments with the diagenetic model developed in Chapter 3 to offer new insights into the potential origin of these extreme isotope anomalies....

  12. Hot atom chemistry of carbon

    International Nuclear Information System (INIS)

    Wolf, A.P.

    1975-01-01

    The chemistry of energetic carbon atoms is discussed. The experimental approach to studies that have been carried out is described and the mechanistic framework of hot carbon atom reactions is considered in some detail. Finally, the direction that future work might take is examined, including the relationship of experimental to theoretical work. (author)

  13. Chemistry of carbon in dynamic sodium

    Energy Technology Data Exchange (ETDEWEB)

    Lievens, F; Casteels, F [SCK/CEN, Mol (Belgium)

    1980-05-01

    The chemistry of carbon in sodium is described by its chemical activity measurements using alloy monitor foils, by its behaviour in the heat exchanger of the Na 2 sodium loop after 60,000 hours of operation, and by measurements with on-line meters. Efforts toward the identification of the carbon chemical states present in dynamic sodium, and responsible for the carbon chemical activity, are described. (author)

  14. Chemistry of carbon in dynamic sodium

    International Nuclear Information System (INIS)

    Lievens, F.; Casteels, F.

    1980-01-01

    The chemistry of carbon in sodium is described by its chemical activity measurements using alloy monitor foils, by its behaviour in the heat exchanger of the Na 2 sodium loop after 60,000 hours of operation, and by measurements with on-line meters. Efforts toward the identification of the carbon chemical states present in dynamic sodium, and responsible for the carbon chemical activity, are described. (author)

  15. Soil Carbon Chemistry and Greenhouse Gas Production in Global Peatlands

    Science.gov (United States)

    Normand, A. E.; Turner, B. L.; Lamit, L. J.; Smith, A. N.; Baiser, B.; Clark, M. W.; Hazlett, C.; Lilleskov, E.; Long, J.; Grover, S.; Reddy, K. R.

    2017-12-01

    Peatlands play a critical role in the global carbon cycle because they contain approximately 30% of the 1500 Pg of carbon stored in soils worldwide. However, the stability of these vast stores of carbon is under threat from climate and land-use change, with important consequences for global climate. Ecosystem models predict the impact of peatland perturbation on carbon fluxes based on total soil carbon pools, but responses could vary markedly depending on the chemical composition of soil organic matter. Here we combine experimental and observational studies to quantify the chemical nature and response to perturbation of soil organic matter in peatlands worldwide. We quantified carbon functional groups in a global sample of 125 freshwater peatlands using solid-state 13C nuclear magnetic resonance (NMR) spectroscopy to determine the drivers of molecular composition of soil organic matter. We then incubated a representative subset of the soils under aerobic and anaerobic conditions to determine how organic matter composition influences carbon dioxide (CO2) and methane (CH4) emissions following drainage or flooding. The functional chemistry of peat varied markedly at large and small spatial scales, due to long-term land use change, mean annual temperature, nutrient status, and vegetation, but not pH. Despite this variation, we found predictable responses of greenhouse gas production following drainage based on soil carbon chemistry, defined by a novel Global Peat Stability Index, with greater CO2 and CH4 fluxes from soils enriched in oxygen-containing organic carbon (O-alkyl C) and depleted in aromatic and hydrophobic compounds. Incorporation of the Global Peat Stability Index of peatland organic matter into earth system models and management strategies, which will improve estimates of GHG fluxes from peatlands and ultimately advance management to reduce carbon loss from these sensitive ecosystems.

  16. Sol-Gel Chemistry for Carbon Dots.

    Science.gov (United States)

    Malfatti, Luca; Innocenzi, Plinio

    2018-03-14

    Carbon dots are an emerging class of carbon-based nanostructures produced by low-cost raw materials which exhibit a widely-tunable photoluminescence and a high quantum yield. The potential of these nanomaterials as a substitute of semiconductor quantum dots in optoelectronics and biomedicine is very high, however they need a customized chemistry to be integrated in host-guest systems or functionalized in core-shell structures. This review is focused on recent advances of the sol-gel chemistry applied to the C-dots technology. The surface modification, the fine tailoring of the chemical composition and the embedding into a complex nanostructured material are the main targets of combining sol-gel processing with C-dots chemistry. In addition, the synergistic effect of the sol-gel precursor combined with the C-dots contribute to modify the intrinsic chemo-physical properties of the dots, empowering the emission efficiency or enabling the tuning of the photoluminescence over a wide range of the visible spectrum. © 2018 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Effects of changes in carbonate chemistry speciation on Coccolithus braarudii: a discussion of coccolithophorid sensitivities

    Directory of Open Access Journals (Sweden)

    U. Riebesell

    2011-03-01

    Full Text Available Ocean acidification and associated shifts in carbonate chemistry speciation induced by increasing levels of atmospheric carbon dioxide (CO2 have the potential to impact marine biota in various ways. The process of biogenic calcification, for instance, is usually shown to be negatively affected. In coccolithophores, an important group of pelagic calcifiers, changes in cellular calcification rates in response to changing ocean carbonate chemistry appear to differ among species. By applying a wider CO2 range we show that a species previously reported insensitive to seawater acidification, Coccolithus braarudii, responds both in terms of calcification and photosynthesis, although at higher levels of CO2. Thus, observed differences between species seem to be related to individual sensitivities while the underlying mechanisms could be the same. On this basis we develop a conceptual model of coccolithophorid calcification and photosynthesis in response to CO2-induced changes in seawater carbonate chemistry speciation.

  18. Green chemistry of carbon nanomaterials.

    Science.gov (United States)

    Basiuk, Elena V; Basiuk, Vladimir A

    2014-01-01

    The global trend of looking for more ecologically friendly, "green" techniques manifested itself in the chemistry of carbon nanomaterials. The main principles of green chemistry emphasize how important it is to avoid the use, or at least to reduce the consumption, of organic solvents for a chemical process. And it is precisely this aspect that was systematically addressed and emphasized by our research group since the very beginning of our work on the chemistry of carbon nanomaterials in early 2000s. The present review focuses on the results obtained to date on solvent-free techniques for (mainly covalent) functionalization of fullerene C60, single-walled and multi-walled carbon nanotubes (SWNTs and MWNTs, respectively), as well as nanodiamonds (NDs). We designed a series of simple and fast functionalization protocols based on thermally activated reactions with chemical compounds stable and volatile at 150-200 degrees C under reduced pressure, when not only the reactions take place at a high rate, but also excess reagents are spontaneously removed from the functionalized material, thus making its purification unnecessary. The main two classes of reagents are organic amines and thiols, including bifunctional ones, which can be used in conjunction with different forms of nanocarbons. The resulting chemical processes comprise nucleophilic addition of amines and thiols to fullerene C60 and to defect sites of pristine MWNTs, as well as direct amidation of carboxylic groups of oxidized nanotubes (mainly SWNTs) and ND. In the case of bifunctional amines and thiols, reactions of the second functional group can give rise to cross-linking effects, or be employed for further derivatization steps.

  19. Carbonate chemistry, water quality, coral measurements

    Data.gov (United States)

    U.S. Environmental Protection Agency — Carbonate chemistry parameters (pH, total alkalinity, and pCO2), water quality parameters (Temperature, salinity, Ca, Mg, PO4, NH3 and NO3) as well as all coral...

  20. Adsorption of perfluoroalkyl acids by carbonaceous adsorbents: Effect of carbon surface chemistry

    International Nuclear Information System (INIS)

    Zhi, Yue; Liu, Jinxia

    2015-01-01

    Adsorption by carbonaceous sorbents is among the most feasible processes to remove perfluorooctane sulfonic (PFOS) and carboxylic acids (PFOA) from drinking and ground waters. However, carbon surface chemistry, which has long been recognized essential for dictating performance of such sorbents, has never been considered for PFOS and PFOA adsorption. Thus, the role of surface chemistry was systematically investigated using sorbents with a wide range in precursor material, pore structure, and surface chemistry. Sorbent surface chemistry overwhelmed physical properties in controlling the extent of uptake. The adsorption affinity was positively correlated carbon surface basicity, suggesting that high acid neutralizing or anion exchange capacity was critical for substantial uptake of PFOS and PFOA. Carbon polarity or hydrophobicity had insignificant impact on the extent of adsorption. Synthetic polymer-based Ambersorb and activated carbon fibers were more effective than activated carbon made of natural materials in removing PFOS and PFOA from aqueous solutions. - Highlights: • Adsorption of PFOS and PFOA by ten carbonaceous adsorbents were compared. • Surface chemistry of the adsorbents controlled adsorption affinity. • Carbon surface basicity was positively correlated with the extent of PFOS and PFOA uptake. • Carbon polarity or hydrophobicity was not correlated with adsorption affinity. • Synthetic polymer-based adsorbents were more effective in removing PFOS and PFOA. - Carbon surface basicity is the primary factor that influences adsorption affinity of the carbonaceous sorbents for perfluorooctane sulfonic and carboxylic acids

  1. New Carbons Made by Soft Chemistry

    Czech Academy of Sciences Publication Activity Database

    Kavan, Ladislav

    2001-01-01

    Roč. 200, Supplement (2001), s. 223-224 ISSN 0371-5345 R&D Projects: GA MŠk OC D14.10 Institutional research plan: CEZ:AV0Z4040901 Keywords : carbon * nanostructures * chemical modification Subject RIV: CF - Physical ; Theoretical Chemistry

  2. Carbonate-silicate cycle models of the long-term carbon cycle, carbonate accumulation in the oceans, and climate

    International Nuclear Information System (INIS)

    Caldeira, K.G.

    1991-01-01

    Several models of the long-term carbon cycle, incorporating models of the carbonate-silicate cycle, were developed and utilized to investigate issues relating to global climate and the causes and consequences of changes in calcium carbonate accumulation in the oceans. Model results indicate that the marked mid-Cretaceous (120 Ma) global warming could be explained by increased rates of release of carbon dioxide from subduction-zone metamorphism and mid-ocean-ridges, in conjunction with paleogeographic factors. Since the mid-Cretaceous, the primary setting for calcium carbonate accumulation in the oceans has shifted from shallow-water to deep-water environments. Model results suggest that this shift could have major consequences for the carbonate-silicate cycle and climate, and lead to significant increases in the flux of metamorphic carbon dioxide to the atmosphere. Increases in pelagic carbonate productivity, and decreases in tropical shallow-water area available for neritic carbonate accumulation, have both been proposed as the primary cause of this shift. Two lines of evidence developed here (one involving a statistical analysis of Tertiary carbonate-accumulation and oxygen-isotope data, and another based on modeling the carbonate-silicate cycle and ocean chemistry) suggest that a decrease in tropical shallow-water area was more important than increased pelagic productivity in explaining this shift. Model investigations of changes in ocean chemistry at the Cretaceous/Tertiary (K/T) boundary (66 Ma) indicate that variations in deep-water carbonate productivity may affect shallow-water carbonate accumulation rates through a mechanism involving surface-water carbonate-ion concentration. In the aftermath of the K/T boundary event, deep-water carbonate production and accumulation were significantly reduced as a result of the extinction of calcareous plankton

  3. Net Community Metabolism and Seawater Carbonate Chemistry Scale Non-intuitively with Coral Cover

    Directory of Open Access Journals (Sweden)

    Heather N. Page

    2017-05-01

    highlight the need to consider the natural complexity of reefs and additional biological and physical factors that influence seawater carbonate chemistry on larger spatial and longer temporal scales. Coordinated efforts combining various research approaches (e.g., experiments, field studies, and models will be required to better understand how benthic metabolism integrates across functional, spatial, and temporal scales, and for making predictions on how coral reefs will respond to climate change.

  4. Carbon Stable Isotope Values in Plankton and Mussels Reflect Changes in Carbonate Chemistry Associated with Nutrient Enhanced Net Production

    Directory of Open Access Journals (Sweden)

    Autumn Oczkowski

    2018-02-01

    Full Text Available Coastal ecosystems are inherently complex and potentially adaptive as they respond to changes in nutrient loads and climate. We documented the role that carbon stable isotope (δ13C measurements could play in understanding that adaptation with a series of three Ecostat (i.e., continuous culture experiments. We quantified linkages among δ13C, nutrients, carbonate chemistry, primary, and secondary production in temperate estuarine waters. Experimental culture vessels (9.1 L containing 33% whole and 67% filtered (0.2 μm seawater were amended with dissolved inorganic nitrogen (N and phosphorous (P in low (3 vessels; 5 μM N, 0.3 μM P, moderate (3 vessels; 25 μM N, 1.6 μM P, and high amounts (3 vessels; 50 μM N, 3.1 μM P. The parameters necessary to calculate carbonate chemistry, chlorophyll-a concentrations, and particulate δ13C values were measured throughout the 14 day experiments. Outflow lines from the experimental vessels fed 250 ml containers seeded with juvenile blue mussels (Mytilus edulis. Mussel subsamples were harvested on days 0, 7, and 14 and their tissues were analyzed for δ13C values. We consistently observed that particulate δ13C values were positively correlated with chlorophyll-a, carbonate chemistry, and to changes in the ratio of bicarbonate to dissolved carbon dioxide (HCO3-:CO2. While the relative proportion of HCO3- to CO2 increased over the 14 days, concentrations of each declined, reflecting the drawdown of carbon associated with enhanced production. Plankton δ13C values, like chlorophyll-a concentrations, increased over the course of each experiment, with the greatest increases in the moderate and high treatments. Trends in δ13C over time were also observed in the mussel tissues. Despite ecological variability and different plankton abundances the experiments consistently demonstrated how δ13C values in primary producers and consumers reflected nutrient availability, via its impact on carbonate chemistry. We

  5. A unifying concept of coccolithophore sensitivity to changing carbonate chemistry embedded in an ecological framework

    Science.gov (United States)

    Bach, Lennart Thomas; Riebesell, Ulf; Gutowska, Magdalena A.; Federwisch, Luisa; Schulz, Kai Georg

    2015-06-01

    Coccolithophores are a group of unicellular phytoplankton species whose ability to calcify has a profound influence on biogeochemical element cycling. Calcification rates are controlled by a large variety of biotic and abiotic factors. Among these factors, carbonate chemistry has gained considerable attention during the last years as coccolithophores have been identified to be particularly sensitive to ocean acidification. Despite intense research in this area, a general concept harmonizing the numerous and sometimes (seemingly) contradictory responses of coccolithophores to changing carbonate chemistry is still lacking to date. Here, we present the "substrate-inhibitor concept" which describes the dependence of calcification rates on carbonate chemistry speciation. It is based on observations that calcification rate scales positively with bicarbonate (HCO3-), the primary substrate for calcification, and carbon dioxide (CO2), which can limit cell growth, whereas it is inhibited by protons (H+). This concept was implemented in a model equation, tested against experimental data, and then applied to understand and reconcile the diverging responses of coccolithophorid calcification rates to ocean acidification obtained in culture experiments. Furthermore, we (i) discuss how other important calcification-influencing factors (e.g. temperature and light) could be implemented in our concept and (ii) embed it in Hutchinson's niche theory, thereby providing a framework for how carbonate chemistry-induced changes in calcification rates could be linked with changing coccolithophore abundance in the oceans. Our results suggest that the projected increase of H+ in the near future (next couple of thousand years), paralleled by only a minor increase of inorganic carbon substrate, could impede calcification rates if coccolithophores are unable to fully adapt. However, if calcium carbonate (CaCO3) sediment dissolution and terrestrial weathering begin to increase the oceans' HCO3

  6. Influence of surface chemistry on inkjet printed carbon nanotube films

    International Nuclear Information System (INIS)

    Hopkins, Alan R.; Straw, David C.; Spurrell, Kathryn C.

    2011-01-01

    Carbon nanotube ink chemistry and the proper formulation are crucial for direct-write printing of nanotubes. Moreover, the correct surface chemistry of the self-assembled monolayers that assist the direct deposition of carbon nanotubes onto the substrate is equally important to preserve orientation of the printed carbon nanotubes. We report that the successful formulation of two single walled carbon nanotube (SWNT) inks yields a consistent, homogenous printing pattern possessing the requisite viscosities needed for flow through the microcapillary nozzles of the inkjet printer with fairly modest drying times. The addition of an aqueous sodium silicate allows for a reliable method for forming a uniform carbon nanotube network deposited directly onto unfunctionalized surfaces such as glass or quartz via inkjet deposition. Furthermore, this sodium silicate ingredient helps preserve applied orientation to the printed SWNT solution. Sheet resistivity of this carbon nanotube ink formula printed on quartz decreases as a function of passes and is independent of the substrate. SWNTs were successfully patterned on Au. This amine-based surface chemistry dramatically helps improve the isolation stabilization of the printed SWNTs as seen in the atomic force microscopy (AFM) image. Lastly, using our optimized SWNT ink formula and waveform parameters in the Fuji materials printer, we are able to directly write/print SWNTs into 2D patterns. Dried ink pattern expose and help orient roped carbon nanotubes that are suspended in ordered arrays across the cracks.

  7. Electrical conductivity of conductive carbon blacks: influence of surface chemistry and topology

    International Nuclear Information System (INIS)

    Pantea, Dana; Darmstadt, Hans; Kaliaguine, Serge; Roy, Christian

    2003-01-01

    Conductive carbon blacks from different manufacturers were studied in order to obtain some insight into the relation between their electrical conductivity and their surface properties. The surface chemistry was studied by X-ray photoelectron spectroscopy (XPS) and static secondary ion mass spectroscopy (SIMS), whereas the topology of the carbon black surface was investigated using low-pressure nitrogen adsorption. All these techniques yield information on the graphitic character of the surface. In general, the electrical conductivity of the conductive blacks increases with the graphitic character of the surface. For low surface area conductive blacks, the electrical conductivity correlates well with the surface chemistry. In the case of the XPS and SIMS data, this correlation is also valid when other types of carbon blacks such as thermal and furnace blacks are included, confirming the determining influence of the carbon black surface chemistry on the electrical conductivity

  8. Computational materials chemistry for carbon capture using porous materials

    International Nuclear Information System (INIS)

    Sharma, Abhishek; Malani, Ateeque; Huang, Runhong; Babarao, Ravichandar

    2017-01-01

    Control over carbon dioxide (CO 2 ) release is extremely important to decrease its hazardous effects on the environment such as global warming, ocean acidification, etc. For CO 2 capture and storage at industrial point sources, nanoporous materials offer an energetically viable and economically feasible approach compared to chemisorption in amines. There is a growing need to design and synthesize new nanoporous materials with enhanced capability for carbon capture. Computational materials chemistry offers tools to screen and design cost-effective materials for CO 2 separation and storage, and it is less time consuming compared to trial and error experimental synthesis. It also provides a guide to synthesize new materials with better properties for real world applications. In this review, we briefly highlight the various carbon capture technologies and the need of computational materials design for carbon capture. This review discusses the commonly used computational chemistry-based simulation methods for structural characterization and prediction of thermodynamic properties of adsorbed gases in porous materials. Finally, simulation studies reported on various potential porous materials, such as zeolites, porous carbon, metal organic frameworks (MOFs) and covalent organic frameworks (COFs), for CO 2 capture are discussed. (topical review)

  9. Chemistry of Fluorinated Carbon Acids: Synthesis, Physicochemical Properties, and Catalysis.

    Science.gov (United States)

    Yanai, Hikaru

    2015-01-01

    The bis[(trifluoromethyl)sulfonyl]methyl (Tf2CH; Tf=SO2CF3) group is known to be one of the strongest carbon acid functionalities. The acidity of such carbon acids in the gas phase is stronger than that of sulfuric acid. Our recent investigations have demonstrated that this type of carbon acids work as novel acid catalysts. In this paper, recent achievements in carbon acid chemistry by our research group, including synthesis, physicochemical properties, and catalysis, are summarized.

  10. Environmental Green Chemistry Applications of Nanoporous Carbons

    Energy Technology Data Exchange (ETDEWEB)

    Matos, J.; Garcia, A; Poon, P

    2010-01-01

    Influence of surface properties of nanoporous carbons on activity and selectivity during the photooxidation of 4-chlorophenol on UV-irradiated TiO{sub 2} was performed. Characterization by infrared spectroscopy, X-ray photoelectronic spectroscopy and X-ray absorption near edge structure spectroscopy confirm the presence of a contact interface between both solids and suggest the coordination of some functional organic groups of the carbon surface, mainly ethers and carboxylic acids, to metallic centre Ti{sup +4} in TiO{sub 2}. Changes in surface pH of carbons from basic to neutral or acid remarkably increase the production of 4-chlorocathecol by a factor of 22 on TiO{sub 2}-Carbon in comparison of TiO{sub 2} alone. A scheme of interaction between TiO{sub 2} and carbon is proposed to the increased photoactivity of TiO{sub 2} and a reaction mechanism for the different intermediate products detected is also proposed. Results showed that TiO{sub 2}-Carbon can be used as an alternative photocatalyst for environmental green chemistry and selective organic synthesis applications.

  11. Benthic metabolic feedbacks to carbonate chemistry on coral reefs:implications for ocean acidification

    Science.gov (United States)

    Price, N.; Rohwer, F. L.; Stuart, S. A.; Andersson, A.; Smith, J.

    2012-12-01

    The metabolic activity of resident organisms can cause spatio-temporal variability in carbonate chemistry within the benthic boundary layer, and thus potentially buffer the global impacts of ocean acidification. But, little is known about the capacity for particular species assemblages to contribute to natural daily variability in carbonate chemistry. We encapsulated replicate areas (~3m2) of reef across six Northern Line Islands in the central Pacific for 24 hrs to quantify feedbacks to carbonate chemistry within the benthic boundary layer from community metabolism. Underneath each 'tent', we quantified relative abundance and biomass of each species of corals and algae. We coupled high temporal resolution time series data on the natural diurnal variability in pH, dissolved oxygen, salinity, and temperature (using autonomous sensors) with resident organisms' net community calcification and productivity rates (using change in total dissolved carbon and total alkalinity over time) to examine feedbacks from reef metabolism to boundary layer carbonate chemistry. These reefs experienced large ranges in pH (> 0.2 amplitude) each day, similar to the magnitude of 'acidification' expected over the next century. Daily benthic pH, pCO2, and aragonite saturation state (Ωaragonite) were contrasted with seasonal threshold values estimated from open ocean climatological data extrapolated at each island to determine relative inter-island feedbacks. Diurnal amplitude in pH, pCO2, and Ωaragonite at each island was dependent upon the resident species assemblage of the benthos and was particularly reliant upon the biomass, productivity, and calcification rate of Halimeda. Net primary productivity of fleshy algae (algal turfs and Lobophora spp.) predominated on degraded, inhabited islands where net community calcification was negligible. In contrast, the chemistry over reefs on 'pristine', uninhabited islands was driven largely by net calcification of calcareous algae and stony

  12. Models of gas-grain chemistry in interstellar cloud cores with a stochastic approach to surface chemistry

    Science.gov (United States)

    Stantcheva, T.; Herbst, E.

    2004-08-01

    We present a gas-grain model of homogeneous cold cloud cores with time-independent physical conditions. In the model, the gas-phase chemistry is treated via rate equations while the diffusive granular chemistry is treated stochastically. The two phases are coupled through accretion and evaporation. A small network of surface reactions accounts for the surface production of the stable molecules water, formaldehyde, methanol, carbon dioxide, ammonia, and methane. The calculations are run for a time of 107 years at three different temperatures: 10 K, 15 K, and 20 K. The results are compared with those produced in a totally deterministic gas-grain model that utilizes the rate equation method for both the gas-phase and surface chemistry. The results of the different models are in agreement for the abundances of the gaseous species except for later times when the surface chemistry begins to affect the gas. The agreement for the surface species, however, is somewhat mixed. The average abundances of highly reactive surface species can be orders of magnitude larger in the stochastic-deterministic model than in the purely deterministic one. For non-reactive species, the results of the models can disagree strongly at early times, but agree to well within an order of magnitude at later times for most molecules. Strong exceptions occur for CO and H2CO at 10 K, and for CO2 at 20 K. The agreement seems to be best at a temperature of 15 K. As opposed to the use of the normal rate equation method of surface chemistry, the modified rate method is in significantly better agreement with the stochastic-deterministic approach. Comparison with observations of molecular ices in dense clouds shows mixed agreement.

  13. Impact of seawater carbonate chemistry on the calcification of marine bivalves

    Science.gov (United States)

    Thomsen, J.; Haynert, K.; Wegner, K. M.; Melzner, F.

    2015-07-01

    Bivalve calcification, particularly of the early larval stages, is highly sensitive to the change in ocean carbonate chemistry resulting from atmospheric CO2 uptake. Earlier studies suggested that declining seawater [CO32-] and thereby lowered carbonate saturation affect shell production. However, disturbances of physiological processes such as acid-base regulation by adverse seawater pCO2 and pH can affect calcification in a secondary fashion. In order to determine the exact carbonate system component by which growth and calcification are affected it is necessary to utilize more complex carbonate chemistry manipulations. As single factors, pCO2 had no effects and [HCO3-] and pH had only limited effects on shell growth, while lowered [CO32-] strongly impacted calcification. Dissolved inorganic carbon (CT) limiting conditions led to strong reductions in calcification, despite high [CO32-], indicating that [HCO3-] rather than [CO32-] is the inorganic carbon source utilized for calcification by mytilid mussels. However, as the ratio [HCO3-] / [H+] is linearly correlated with [CO32-] it is not possible to differentiate between these under natural seawater conditions. An equivalent of about 80 μmol kg-1 [CO32-] is required to saturate inorganic carbon supply for calcification in bivalves. Below this threshold biomineralization rates rapidly decline. A comparison of literature data available for larvae and juvenile mussels and oysters originating from habitats differing substantially with respect to prevailing carbonate chemistry conditions revealed similar response curves. This suggests that the mechanisms which determine sensitivity of calcification in this group are highly conserved. The higher sensitivity of larval calcification seems to primarily result from the much higher relative calcification rates in early life stages. In order to reveal and understand the mechanisms that limit or facilitate adaptation to future ocean acidification, it is necessary to better

  14. Gas-Grain Models for Interstellar Anion Chemistry

    Science.gov (United States)

    Cordiner, M. A.; Charnely, S. B.

    2012-01-01

    Long-chain hydrocarbon anions C(sub n) H(-) (n = 4, 6, 8) have recently been found to be abundant in a variety of interstellar clouds. In order to explain their large abundances in the denser (prestellar/protostellar) environments, new chemical models are constructed that include gas-grain interactions. Models including accretion of gas-phase species onto dust grains and cosmic-ray-induced desorption of atoms are able to reproduce the observed anion-to-neutral ratios, as well as the absolute abundances of anionic and neutral carbon chains, with a reasonable degree of accuracy. Due to their destructive effects, the depletion of oxygen atoms onto dust results in substantially greater polyyne and anion abundances in high-density gas (with n(sub H2) approx > / cubic cm). The large abundances of carbon-chain-bearing species observed in the envelopes of protostars such as L1527 can thus be explained without the need for warm carbon-chain chemistry. The C6H(-) anion-to-neutral ratio is found to be most sensitive to the atomic O and H abundances and the electron density. Therefore, as a core evolves, falling atomic abundances and rising electron densities are found to result in increasing anion-to-neutral ratios. Inclusion of cosmic-ray desorption of atoms in high-density models delays freeze-out, which results in a more temporally stable anion-to-neutral ratio, in better agreement with observations. Our models include reactions between oxygen atoms and carbon-chain anions to produce carbon-chain-oxide species C6O, C7O, HC6O, and HC7O, the abundances of which depend on the assumed branching ratios for associative electron detachment

  15. Rapid changes in surface water carbonate chemistry during Antarctic sea ice melt

    Science.gov (United States)

    Jones, Elizabeth M.; Bakker, Dorothee C. E.; Venables, Hugh J.; Whitehouse, Michael J.; Korb, Rebecca E.; Watson, Andrew J.

    2010-11-01

    ABSTRACT The effect of sea ice melt on the carbonate chemistry of surface waters in the Weddell-Scotia Confluence, Southern Ocean, was investigated during January 2008. Contrasting concentrations of dissolved inorganic carbon (DIC), total alkalinity (TA) and the fugacity of carbon dioxide (fCO2) were observed in and around the receding sea ice edge. The precipitation of carbonate minerals such as ikaite (CaCO3.6H2O) in sea ice brine has the net effect of decreasing DIC and TA and increasing the fCO2 in the brine. Deficits in DIC up to 12 +/- 3 μmol kg-1 in the marginal ice zone (MIZ) were consistent with the release of DIC-poor brines to surface waters during sea ice melt. Biological utilization of carbon was the dominant processes and accounted for 41 +/- 1 μmol kg-1 of the summer DIC deficit. The data suggest that the combined effects of biological carbon uptake and the precipitation of carbonates created substantial undersaturation in fCO2 of 95 μatm in the MIZ during summer sea ice melt. Further work is required to improve the understanding of ikaite chemistry in Antarctic sea ice and its importance for the sea ice carbon pump.

  16. Mukilteo water sensor time series - Field work coupling measurements of carbon chemistry and distribution of free-living organisms

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — To estimate the carbon chemistry conditions experienced by free-living organisms, we will conduct coupled biological/carbon chemistry sampling for key zooplankton...

  17. Data assimilation in atmospheric chemistry models: current status and future prospects for coupled chemistry meteorology models

    OpenAIRE

    M. Bocquet; H. Elbern; H. Eskes; M. Hirtl; R. Žabkar; G. R. Carmichael; J. Flemming; A. Inness; M. Pagowski; J. L. Pérez Camaño; P. E. Saide; R. San Jose; M. Sofiev; J. Vira; A. Baklanov

    2015-01-01

    Data assimilation is used in atmospheric chemistry models to improve air quality forecasts, construct re-analyses of three-dimensional chemical (including aerosol) concentrations and perform inverse modeling of input variables or model parameters (e.g., emissions). Coupled chemistry meteorology models (CCMM) are atmospheric chemistry models that simulate meteorological processes and chemical transformations jointly. They offer the possibility to assimilate both meteorologica...

  18. Simulated Carbon Cycling in a Model Microbial Mat.

    Science.gov (United States)

    Decker, K. L.; Potter, C. S.

    2006-12-01

    We present here the novel addition of detailed organic carbon cycling to our model of a hypersaline microbial mat ecosystem. This ecosystem model, MBGC (Microbial BioGeoChemistry), simulates carbon fixation through oxygenic and anoxygenic photosynthesis, and the release of C and electrons for microbial heterotrophs via cyanobacterial exudates and also via a pool of dead cells. Previously in MBGC, the organic portion of the carbon cycle was simplified into a black-box rate of accumulation of simple and complex organic compounds based on photosynthesis and mortality rates. We will discuss the novel inclusion of fermentation as a source of carbon and electrons for use in methanogenesis and sulfate reduction, and the influence of photorespiration on labile carbon exudation rates in cyanobacteria. We will also discuss the modeling of decomposition of dead cells and the ultimate release of inorganic carbon. The detailed modeling of organic carbon cycling is important to the accurate representation of inorganic carbon flux through the mat, as well as to accurate representation of growth models of the heterotrophs under different environmental conditions. Because the model ecosystem is an analog of ancient microbial mats that had huge impacts on the atmosphere of early earth, this MBGC can be useful as a biological component to either early earth models or models of other planets that potentially harbor life.

  19. Containment Sodium Chemistry Models in MELCOR.

    Energy Technology Data Exchange (ETDEWEB)

    Louie, David [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Humphries, Larry L. [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Denman, Matthew R [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

    2017-04-01

    To meet regulatory needs for sodium fast reactors’ future development, including licensing requirements, Sandia National Laboratories is modernizing MELCOR, a severe accident analysis computer code developed for the U.S. Nuclear Regulatory Commission (NRC). Specifically, Sandia is modernizing MELCOR to include the capability to model sodium reactors. However, Sandia’s modernization effort primarily focuses on the containment response aspects of the sodium reactor accidents. Sandia began modernizing MELCOR in 2013 to allow a sodium coolant, rather than water, for conventional light water reactors. In the past three years, Sandia has been implementing the sodium chemistry containment models in CONTAIN-LMR, a legacy NRC code, into MELCOR. These chemistry models include spray fire, pool fire and atmosphere chemistry models. Only the first two chemistry models have been implemented though it is intended to implement all these models into MELCOR. A new package called “NAC” has been created to manage the sodium chemistry model more efficiently. In 2017 Sandia began validating the implemented models in MELCOR by simulating available experiments. The CONTAIN-LMR sodium models include sodium atmosphere chemistry and sodium-concrete interaction models. This paper presents sodium property models, the implemented models, implementation issues, and a path towards validation against existing experimental data.

  20. Invariance of the carbonate chemistry of the South China Sea from the glacial period to the Holocene and its implications to the Pacific Ocean carbonate system

    Science.gov (United States)

    Luo, Yiming; Kienast, Markus; Boudreau, Bernard P.

    2018-06-01

    Substantial and correlated changes in marine carbonate (CaCO3) content of oceanic sediments commonly accompany the transitions from cold glacial periods to warm interglacial periods. The South China Sea (SCS) is said to be ocean-dominated at depth, and its CaCO3 records should reflect and preserve the effects of changes in the carbonate chemistry of the (western) Pacific Ocean. Using published and newly acquired CaCO3 data and a model for carbonate compensation dynamics, we show that a significant change with respect to carbonate saturation is unlikely to have occurred in the SCS during the last glacial-interglacial transition. Instead, the results from a carbonate deposition model argue that the saturation state of the SCS was largely invariant; a separate diagenetic model argues that changes in sediment CaCO3 content can be explained by alterations in lithogenic input. In turn, this could indicate that the carbonate ion concentration of the (western) Pacific at depths shallower than the sill to the SCS (ca. 2,400 m) has not changed appreciably between the last glacial period and the present interglacial.

  1. From simple to complex prebiotic chemistry in a carbon-rich universe

    Science.gov (United States)

    Lage, C.; Janot-Pacheco, E.; Domiciano de Souza, A.; Suárez, O.; Bendjoya, P.; Gadotti, D. A.

    2012-09-01

    It is well known that the main components of important biomolecules are quite common not only in the Solar System, but also in other planetary systems and in the Galactic ISM. The ubiquitous presence of C in the Universe and the unique carbon chemical properties and carbon bonding thermodynamics supports the spontaneous self-replication of monomers into larger polymers, yielding the formation of large molecules. The detection of an ever increasing number of organic molecules in the interstellar medium (ISM) by radio-telescopes and chemical analysis of meteorites boosted astrochemical theories on radiation-induced chemistry, supported by laboratory experiments. In this scenario of exogenous origin of carbon compounds, polyaromatic hydrocarbons (PAHs) may represent a resilient way of accumulating carbon as a robust cosmic reservoir. Consisting of a family of compounds with fused aromatic rings, the abundances of its larger members (50-100 carbon atoms) were estimated to be on top scores just after H2 and CO. PAHs have been detected in the ISM, in star-forming regions, ~14% of low-mass premainsequence stars, and, remarkably, in some 54% of intermediate mass stars. They have also been detected by SPITZER in distant galaxies up to z = 3. PAHs were promptly photolysed into a family of radicals if exposed to UV and oxygen-bearing molecules in laboratory. The presence of oxygenbearing molecules was shown in the laboratory to bring aromatic rings into an unstable chemistry leading to the production of e.g. alcohols, ketones and ether radicals. It has already been observed that carbon-and oxygen-rich stellar envelopes give rise to richer carbon chemistry. It appears very tempting to think that key prebiotic fragments should appear along planetary formation as C-O reaction byproducts such as methanol (CH3OH), formaldehyde (H2CO) and also simpler hydrocarbons as methyl acetylene (CH3CCH). Under an Astrobiology perspective it is plausible to map PAHs and oxygen compounds

  2. Contributions for the chemistry, physics and technology of the elementary carbon in various states for the Carbon '76

    International Nuclear Information System (INIS)

    Delle, W.W.

    1976-07-01

    This report is the compilation of a number of papers prepared by KFA Juelich for the 2nd International Carbon Conference CARBON '76 at Baden-Baden, June 28th - July 2nd, 1976. The presentations deal with objectives of chemistry, physics and technology of the elementary carbon in various states including irradiation induced effects on graphite and pyrolytic carbon. The work was partly sponsored by the Bundesministerium fuer Forschung und Technologie of the Federal Republic of Germany as well as by the Government of North-Rhine-Westfalia. (orig.) [de

  3. Functionalization of carbon nanofibers with elastomeric block copolymer using carbodiimide chemistry

    International Nuclear Information System (INIS)

    Mapkar, Javed A.; Iyer, Ganesh; Coleman, Maria R.

    2009-01-01

    Surface functionalization of carbon nanofibers (CNFs) with aminopropyl terminated polydimethylsiloxane [(PDMS-NH 2 )] and other organic diamines was achieved using carbodiimide chemistry. The carbodiimide chemistry provides faster reaction rate so that the reaction occurs at lower temperature compared to amidation and acylation-amidation chemistry. CNF functionalized with PDMS-NH 2 fibers were further functionalized with oligomer of polyimide (6FDA-BisP) using imidization reaction. The formation of block copolymer on the surface of CNF is proposed as an effective method to engineer the interphase between the fiber and the polymer, which is essential to modulate and enhance the properties of the nanocomposite. The efficiency of the carbodiimide chemistry to functionalize amine terminated groups on CNF and the functionalization of block copolymer was characterized using thermal gravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) and UV-vis spectroscopy.

  4. Functionalization of carbon nanofibers with elastomeric block copolymer using carbodiimide chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Mapkar, Javed A.; Iyer, Ganesh [Chemical and Environmental Engineering Department, University of Toledo, Mail Stop 305, 2801 W Bancroft St., Toledo, OH 43606 (United States); Coleman, Maria R., E-mail: maria.coleman6@utoledo.edu [Chemical and Environmental Engineering Department, University of Toledo, Mail Stop 305, 2801 W Bancroft St., Toledo, OH 43606 (United States)

    2009-02-15

    Surface functionalization of carbon nanofibers (CNFs) with aminopropyl terminated polydimethylsiloxane [(PDMS-NH{sub 2})] and other organic diamines was achieved using carbodiimide chemistry. The carbodiimide chemistry provides faster reaction rate so that the reaction occurs at lower temperature compared to amidation and acylation-amidation chemistry. CNF functionalized with PDMS-NH{sub 2} fibers were further functionalized with oligomer of polyimide (6FDA-BisP) using imidization reaction. The formation of block copolymer on the surface of CNF is proposed as an effective method to engineer the interphase between the fiber and the polymer, which is essential to modulate and enhance the properties of the nanocomposite. The efficiency of the carbodiimide chemistry to functionalize amine terminated groups on CNF and the functionalization of block copolymer was characterized using thermal gravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) and UV-vis spectroscopy.

  5. Impact of seawater carbonate chemistry on the calcification of marine bivalves

    OpenAIRE

    Thomsen Jörn; Haynert Kristin; Wegner K Mathias; Melzner Frank

    2015-01-01

    Bivalve calcification, particular of the early larval stages is highly sensitive to the change of ocean carbonate chemistry resulting from atmospheric CO2 uptake. Earlier studies suggested that declining seawater [CO32−] and thereby lowered carbonate saturation affect shell production. However, disturbances of physiological processes such as acid-base regulation by adverse seawater pCO2 and pH can affect calcification in a secondary fashion. In order to determine the e...

  6. Atmospheric chemistry, sources and sinks of carbon suboxide, C3O2

    Science.gov (United States)

    Keßel, Stephan; Cabrera-Perez, David; Horowitz, Abraham; Veres, Patrick R.; Sander, Rolf; Taraborrelli, Domenico; Tucceri, Maria; Crowley, John N.; Pozzer, Andrea; Stönner, Christof; Vereecken, Luc; Lelieveld, Jos; Williams, Jonathan

    2017-07-01

    Carbon suboxide, O = C = C = C = O, has been detected in ambient air samples and has the potential to be a noxious pollutant and oxidant precursor; however, its lifetime and fate in the atmosphere are largely unknown. In this work, we collect an extensive set of studies on the atmospheric chemistry of C3O2. Rate coefficients for the reactions of C3O2 with OH radicals and ozone were determined as kOH = (2.6 ± 0.5) × 10-12 cm3 molecule-1 s-1 at 295 K (independent of pressure between ˜ 25 and 1000 mbar) and kO3 chemistry-general circulation model. The results indicate sub-pptv levels at the Earth's surface, up to about 10 pptv in regions with relatively strong sources, e.g. influenced by biomass burning, and a mean lifetime of ˜ 3.2 days. These predictions carry considerable uncertainty, as more measurement data are needed to determine ambient concentrations and constrain the source strengths.

  7. Interaction between carbon fibers and polymer sizing: Influence of fiber surface chemistry and sizing reactivity

    Science.gov (United States)

    Moosburger-Will, Judith; Bauer, Matthias; Laukmanis, Eva; Horny, Robert; Wetjen, Denise; Manske, Tamara; Schmidt-Stein, Felix; Töpker, Jochen; Horn, Siegfried

    2018-05-01

    Different aspects of the interaction of carbon fibers and epoxy-based polymer sizings are investigated, e.g. the wetting behavior, the strength of adhesion between fiber and sizing, and the thermal stability of the sizing layer. The influence of carbon fiber surface chemistry and sizing reactivity is investigated using fibers of different degree of anodic oxidation and sizings with different number of reactive epoxy groups per molecule. Wetting of the carbon fibers by the sizing dispersion is found to be specified by both, the degree of fiber activation and the sizing reactivity. In contrast, adhesion strength between fibers and sizing is dominated by the surface chemistry of the carbon fibers. Here, the number of surface oxygen groups seems to be the limiting factor. We also find that the sizing and the additional functionalities induced by anodic oxidation are removed by thermal treatment at 600 °C, leaving the carbon fiber in its original state after carbonization.

  8. Modeling the atmospheric chemistry of TICs

    Science.gov (United States)

    Henley, Michael V.; Burns, Douglas S.; Chynwat, Veeradej; Moore, William; Plitz, Angela; Rottmann, Shawn; Hearn, John

    2009-05-01

    An atmospheric chemistry model that describes the behavior and disposition of environmentally hazardous compounds discharged into the atmosphere was coupled with the transport and diffusion model, SCIPUFF. The atmospheric chemistry model was developed by reducing a detailed atmospheric chemistry mechanism to a simple empirical effective degradation rate term (keff) that is a function of important meteorological parameters such as solar flux, temperature, and cloud cover. Empirically derived keff functions that describe the degradation of target toxic industrial chemicals (TICs) were derived by statistically analyzing data generated from the detailed chemistry mechanism run over a wide range of (typical) atmospheric conditions. To assess and identify areas to improve the developed atmospheric chemistry model, sensitivity and uncertainty analyses were performed to (1) quantify the sensitivity of the model output (TIC concentrations) with respect to changes in the input parameters and (2) improve, where necessary, the quality of the input data based on sensitivity results. The model predictions were evaluated against experimental data. Chamber data were used to remove the complexities of dispersion in the atmosphere.

  9. Ethanolic carbon-11 chemistry: The introduction of green radiochemistry

    International Nuclear Information System (INIS)

    Shao, Xia; Fawaz, Maria V.; Jang, Keunsam; Scott, Peter J.H.

    2014-01-01

    The principles of green chemistry have been applied to a radiochemistry setting. Eleven carbon-11 labeled radiopharmaceuticals have been prepared using ethanol as the only organic solvent throughout the entire manufacturing process. The removal of all other organic solvents from the process simplifies production and quality control (QC) testing, moving our PET Center towards the first example of a green radiochemistry laboratory. All radiopharmaceutical doses prepared are suitable for clinical use. - Highlights: • We report application of the principles of green chemistry to a radiochemistry setting. • Radiopharmaceuticals are prepared using ethanol as the only organic solvent. • Green radiochemistry simplifies production and QC in busy clinical production laboratories. • Residual solvent analysis can be relegated to a quarterly or annual QC test

  10. Kinetic chemistry of dense interstellar clouds

    International Nuclear Information System (INIS)

    Graedel, T.E.; Langer, W.D.; Frerking, M.A.

    1982-01-01

    A detailed model of the time-dependent chemistry of dense interstellar clouds has been developed to study the dominant chemical processes in carbon and oxygen isotope fractionation, formation of nitrogen-containing molecules, evolution of product molecules as a function of cloud density and temperature, and other topics of interest. The full computation involves 328 individual reactions (expanded to 1067 to study carbon and oxygen isotope chemistry); photodegradation processes are unimportant in these dense clouds and are excluded

  11. Tropical seagrass meadows modify seawater carbon chemistry: implications for coral reefs impacted by ocean acidification

    International Nuclear Information System (INIS)

    Unsworth, Richard K F; Collier, Catherine J; Henderson, Gideon M; McKenzie, Len J

    2012-01-01

    Highly productive tropical seagrasses often live adjacent to or among coral reefs and utilize large amounts of inorganic carbon. In this study, the effect of seagrass productivity on seawater carbonate chemistry and coral calcification was modelled on the basis of an analysis of published data. Published data (11 studies, 64 records) reveal that seagrass meadows in the Indo-Pacific have an 83% chance of being net autotrophic, resulting in an average net sink of 155 gC m −2 yr −1 . The capacities for seagrass productivity were analysed using an empirical model to examine the effect on seawater carbonate chemistry. Our analyses indicate that increases in pH of up to 0.38 units, and Ω arag increases of 2.9 are possible in the presence of seagrass meadows (compared to their absence) with the precise values of these increases dependent on water residence time (tidal flushing) and water depth. In shallow water reef environments, Scleractinian coral calcification downstream of seagrass has the potential to be ≈18% greater than in an environment without seagrass. If this potential benefit to reef calcifiers is supported by further study it offers a potential tool in marine park management at a local scale. The applicability of this will depend upon local physical conditions as well as the spatial configuration of habitats, and the factors that influence their productivity. This novel study suggests that, in addition to their importance to fisheries, sediment stabilization and primary production, seagrass meadows may enhance coral reef resilience to future ocean acidification. (letter)

  12. Recent results from the chemistry of recoiling carbon and silicon atoms: The interplay between hot atom chemistry and gas kinetics

    International Nuclear Information System (INIS)

    Gaspar, P.P.; Garmestani, K.; Ferrieri, R.A.; Wolf, A.P.

    1990-01-01

    Recent results from the chemistry of recoiling carbon and silicon atoms illustrate the power of an experimental approach to the solution of complex mechanistic problems that combines the study of the reactions of recoiling atoms with conventional gas kinetic techniques. Included will be the reactions of 11 C atoms with anisole, addressing the question whether an aromatic pi-electron system can compete as a reactive site with carbon-hydrogen bonds

  13. A Model of Titan-like Chemistry to Connect Experiments and Cassini Observations

    Science.gov (United States)

    Raymond, Alexander W.; Sciamma-O’Brien, Ella; Salama, Farid; Mazur, Eric

    2018-02-01

    A numerical model is presented for interpreting the chemical pathways that lead to the experimental mass spectra acquired in the Titan Haze Simulation (THS) laboratory experiments and for comparing the electron density and temperature of the THS plasma to observations made at Titan by the Cassini spacecraft. The THS plasma is a pulsed glow-discharge experiment designed to simulate the reaction of N2/CH4-dominated gas in Titan's upper atmosphere. The transient, one-dimensional model of THS chemistry tracks the evolution of more than 120 species in the direction of the plasma flow. As the minor species C2H2 and C2H4 are added to the N2/CH4-based mixture, the model correctly predicts the emergence of reaction products with up to five carbon atoms in relative abundances that agree well with measured mass spectra. Chemical growth in Titan's upper atmosphere transpires through ion–neutral and neutral–neutral chemistry, and the main reactions involving a series of known atmospheric species are retrieved from the calculation. The model indicates that the electron density and chemistry are steady during more than 99% of the 300 μs long discharge pulse. The model also suggests that the THS ionization fraction and electron temperature are comparable to those measured in Titan's upper atmosphere. These findings reaffirm that the THS plasma is a controlled analog environment for studying the first and intermediate steps of chemistry in Titan's upper atmosphere.

  14. Variability of the carbonate chemistry in a shallow, seagrass-dominated ecosystem: implications for ocean acidification experiments

    Science.gov (United States)

    Challener, Roberta; Robbins, Lisa L.; Mcclintock, James B.

    2016-01-01

    Open ocean observations have shown that increasing levels of anthropogenically derived atmospheric CO2 are causing acidification of the world's oceans. Yet little is known about coastal acidification and studies are just beginning to characterise the carbonate chemistry of shallow, nearshore zones where many ecologically and economically important organisms occur. We characterised the carbonate chemistry of seawater within an area dominated by seagrass beds (Saint Joseph Bay, Florida) to determine the extent of variation in pH and pCO2 over monthly and daily timescales. Distinct diel and seasonal fluctuations were observed at daily and monthly timescales respectively, indicating the influence of photosynthetic and respiratory processes on the local carbonate chemistry. Over the course of a year, the range in monthly values of pH (7.36-8.28), aragonite saturation state (0.65-5.63), and calculated pCO2 (195-2537 μatm) were significant. When sampled on a daily basis the range in pH (7.70-8.06), aragonite saturation state (1.86-3.85), and calculated pCO2 (379-1019 μatm) also exhibited significant range and indicated variation between timescales. The results of this study have significant implications for the design of ocean acidification experiments where nearshore species are utilised and indicate that coastal species are experiencing far greater fluctuations in carbonate chemistry than previously thought.

  15. Modeling Ne-21 NMR parameters for carbon nanosystems

    Czech Academy of Sciences Publication Activity Database

    Kupka, T.; Nieradka, M.; Kaminský, Jakub; Stobinski, L.

    2013-01-01

    Roč. 51, č. 10 (2013), s. 676-681 ISSN 0749-1581 R&D Projects: GA ČR GAP208/11/0105; GA MŠk(CZ) LH11033 Grant - others:AV ČR(CZ) M200551205 Institutional support: RVO:61388963 Keywords : Ne-21 NMR * GIAO NMR * molecular modeling * carbon nanostructures Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.559, year: 2013

  16. Influence of changing carbonate chemistry on morphology and weight of coccoliths formed by Emiliania huxleyi

    Directory of Open Access Journals (Sweden)

    K. G. Schulz

    2012-08-01

    Full Text Available The coccolithophore Emiliania huxleyi is a marine phytoplankton species capable of forming small calcium carbonate scales (coccoliths which cover the organic part of the cell. Calcification rates of E. huxleyi are known to be sensitive to changes in seawater carbonate chemistry. It has, however, not yet been clearly determined how these changes are reflected in size and weight of individual coccoliths and which specific parameter(s of the carbonate system drive morphological modifications. Here, we compare data on coccolith size, weight, and malformation from a set of five experiments with a large diversity of carbonate chemistry conditions. This diversity allows distinguishing the influence of individual carbonate chemistry parameters such as carbon dioxide (CO2, bicarbonate (HCO3−, carbonate ion (CO32−, and protons (H+ on the measured parameters. Measurements of fine-scale morphological structures reveal an increase of coccolith malformation with decreasing pH suggesting that H+ is the major factor causing malformations. Coccolith distal shield area varies from about 5 to 11 μm2. Changes in size seem to be mainly induced by varying [HCO3−] and [H+] although influence of [CO32−] cannot be entirely ruled out. Changes in coccolith weight were proportional to changes in size. Increasing CaCO3 production rates are reflected in an increase in coccolith weight and an increase of the number of coccoliths formed per unit time. The combined investigation of morphological features and coccolith production rates presented in this study may help to interpret data derived from sediment cores, where coccolith morphology is used to reconstruct calcification rates in the water column.

  17. Physical and Biological Controls on the Carbonate Chemistry of Coral Reef Waters: Effects of Metabolism, Wave Forcing, Sea Level, and Geomorphology

    Science.gov (United States)

    Falter, James L.; Lowe, Ryan J.; Zhang, Zhenlin; McCulloch, Malcolm

    2013-01-01

    We present a three-dimensional hydrodynamic-biogeochemical model of a wave-driven coral-reef lagoon system using the circulation model ROMS (Regional Ocean Modeling System) coupled with the wave transformation model SWAN (Simulating WAves Nearshore). Simulations were used to explore the sensitivity of water column carbonate chemistry across the reef system to variations in benthic reef metabolism, wave forcing, sea level, and system geomorphology. Our results show that changes in reef-water carbonate chemistry depend primarily on the ratio of benthic metabolism to the square root of the onshore wave energy flux as well as on the length and depth of the reef flat; however, they are only weakly dependent on channel geometry and the total frictional resistance of the reef system. Diurnal variations in pCO2, pH, and aragonite saturation state (Ωar) are primarily dependent on changes in net production and are relatively insensitive to changes in net calcification; however, net changes in pCO2, pH, and Ωar are more strongly influenced by net calcification when averaged over 24 hours. We also demonstrate that a relatively simple one-dimensional analytical model can provide a good description of the functional dependence of reef-water carbonate chemistry on benthic metabolism, wave forcing, sea level, reef flat morphology, and total system frictional resistance. Importantly, our results indicate that any long-term (weeks to months) net offsets in reef-water pCO2 relative to offshore values should be modest for reef systems with narrow and/or deep lagoons. Thus, the long-term evolution of water column pCO2 in many reef environments remains intimately connected to the regional-scale oceanography of offshore waters and hence directly influenced by rapid anthropogenically driven increases in pCO2. PMID:23326411

  18. Physical and biological controls on the carbonate chemistry of coral reef waters: effects of metabolism, wave forcing, sea level, and geomorphology.

    Science.gov (United States)

    Falter, James L; Lowe, Ryan J; Zhang, Zhenlin; McCulloch, Malcolm

    2013-01-01

    We present a three-dimensional hydrodynamic-biogeochemical model of a wave-driven coral-reef lagoon system using the circulation model ROMS (Regional Ocean Modeling System) coupled with the wave transformation model SWAN (Simulating WAves Nearshore). Simulations were used to explore the sensitivity of water column carbonate chemistry across the reef system to variations in benthic reef metabolism, wave forcing, sea level, and system geomorphology. Our results show that changes in reef-water carbonate chemistry depend primarily on the ratio of benthic metabolism to the square root of the onshore wave energy flux as well as on the length and depth of the reef flat; however, they are only weakly dependent on channel geometry and the total frictional resistance of the reef system. Diurnal variations in pCO(2), pH, and aragonite saturation state (Ω(ar)) are primarily dependent on changes in net production and are relatively insensitive to changes in net calcification; however, net changes in pCO(2), pH, and Ω(ar) are more strongly influenced by net calcification when averaged over 24 hours. We also demonstrate that a relatively simple one-dimensional analytical model can provide a good description of the functional dependence of reef-water carbonate chemistry on benthic metabolism, wave forcing, sea level, reef flat morphology, and total system frictional resistance. Importantly, our results indicate that any long-term (weeks to months) net offsets in reef-water pCO(2) relative to offshore values should be modest for reef systems with narrow and/or deep lagoons. Thus, the long-term evolution of water column pCO(2) in many reef environments remains intimately connected to the regional-scale oceanography of offshore waters and hence directly influenced by rapid anthropogenically driven increases in pCO(2).

  19. Strain-specific responses of Emiliania huxleyi to changing seawater carbonate chemistry

    Directory of Open Access Journals (Sweden)

    P. Ziveri

    2009-11-01

    Full Text Available Four strains of the coccolithophore E. huxleyi (RCC1212, RCC1216, RCC1238, RCC1256 were grown in dilute batch culture at four CO2 levels ranging from ~200 μatm to ~1200 μatm. Growth rate, particulate organic carbon content, and particulate inorganic carbon content were measured, and organic and inorganic carbon production calculated. The four strains did not show a uniform response to carbonate chemistry changes in any of the analysed parameters and none of the four strains displayed a response pattern previously described for this species. We conclude that the sensitivity of different strains of E. huxleyi to acidification differs substantially and that this likely has a genetic basis. We propose that this can explain apparently contradictory results reported in the literature.

  20. Effect of water chemistry on the aggregation and photoluminescence behavior of carbon dots.

    Science.gov (United States)

    Bayati, Mohamed; Dai, Jingjing; Zambrana, Austin; Rees, Chloe; Fidalgo de Cortalezzi, Maria

    2018-03-01

    Carbon dots are rapidly emerging carbon-based nanomaterials that, due to their growing applications, will inevitable find their way to natural waters; however, their environmental fate is mostly unknown. Carbon dots with different surface functionality were fabricated and characterized by TEM and FT-IR. Their surface charge, given by the zeta potential, and their hydrodynamic diameter in suspension were investigated under a variety of environmentally relevant conditions. The effect of ionic strength was studied in the presence of monovalent (NaCl) and divalent (CaCl 2 ) cations, for pH levels from 3 to 11; humic acid was used as a model for dissolved natural organic matter. Total potential energies of interactions were modeled by classical DLVO theory. The experimental results showed that water chemistry altered the surface charge of the nanomaterials, but their hydrodynamic size could not be correlated to those changes. Evidence of specific interactions was found for the amino functionalized particles in most cases, as well as the plain carbon dots in the presence of Ca 2+ and humic acid. Nanoparticles remained largely stable in suspension, with some exception at the highest ionic strength considered. DLVO theory did not adequately capture the aggregation behavior of the system. Moreover, cation and/or humic acid adsorption negatively affected the emission intensity of the particles, suggesting limitations to their use in natural water sensing applications. The particular stability shown by the carbon dots results in exposure to organisms in the water column and the possibility of contamination transported to significant distances from their source. Copyright © 2017. Published by Elsevier B.V.

  1. Mineralogy, early marine diagenesis, and the chemistry of shallow-water carbonate sediments

    Science.gov (United States)

    Higgins, J. A.; Blättler, C. L.; Lundstrom, E. A.; Santiago-Ramos, D. P.; Akhtar, A. A.; Crüger Ahm, A.-S.; Bialik, O.; Holmden, C.; Bradbury, H.; Murray, S. T.; Swart, P. K.

    2018-01-01

    Shallow-water carbonate sediments constitute the bulk of sedimentary carbonates in the geologic record and are widely used archives of Earth's chemical and climatic history. One of the main limitations in interpreting the geochemistry of ancient carbonate sediments is the potential for post-depositional diagenetic alteration. In this study, we use paired measurements of calcium (44Ca/40Ca or δ44Ca) and magnesium (26Mg/24Mg or δ26Mg) isotope ratios in sedimentary carbonates and associated pore-fluids as a tool to understand the mineralogical and diagenetic history of Neogene shallow-water carbonate sediments from the Bahamas and southwest Australia. We find that the Ca and Mg isotopic composition of bulk carbonate sediments at these sites exhibits systematic stratigraphic variability that is related to both mineralogy and early marine diagenesis. The observed variability in bulk sediment Ca isotopes is best explained by changes in the extent and style of early marine diagenesis from one where the composition of the diagenetic carbonate mineral is determined by the chemistry of the fluid (fluid-buffered) to one where the composition of the diagenetic carbonate mineral is determined by the chemistry of the precursor sediment (sediment-buffered). Our results indicate that this process, together with variations in carbonate mineralogy (aragonite, calcite, and dolomite), plays a fundamental and underappreciated role in determining the regional and global stratigraphic expressions of geochemical tracers (δ13C, δ18O, major, minor, and trace elements) in shallow-water carbonate sediments in the geologic record. Our results also provide evidence that a large shallow-water carbonate sink that is enriched in 44Ca can explain the mismatch between the δ44/40Ca value of rivers and deep-sea carbonate sediments and call into question the hypothesis that the δ44/40Ca value of seawater depends on the mineralogy of primary carbonate precipitations (e.g. 'aragonite seas' and

  2. Modelling stratospheric chemistry in a global three-dimensional chemical transport model

    Energy Technology Data Exchange (ETDEWEB)

    Rummukainen, M [Finnish Meteorological Inst., Sodankylae (Finland). Sodankylae Observatory

    1996-12-31

    Numerical modelling of atmospheric chemistry aims to increase the understanding of the characteristics, the behavior and the evolution of atmospheric composition. These topics are of utmost importance in the study of climate change. The multitude of gases and particulates making up the atmosphere and the complicated interactions between them affect radiation transfer, atmospheric dynamics, and the impacts of anthropogenic and natural emissions. Chemical processes are fundamental factors in global warming, ozone depletion and atmospheric pollution problems in general. Much of the prevailing work on modelling stratospheric chemistry has so far been done with 1- and 2-dimensional models. Carrying an extensive chemistry parameterisation in a model with high spatial and temporal resolution is computationally heavy. Today, computers are becoming powerful enough to allow going over to 3-dimensional models. In order to concentrate on the chemistry, many Chemical Transport Models (CTM) are still run off-line, i.e. with precalculated and archived meteorology and radiation. In chemistry simulations, the archived values drive the model forward in time, without interacting with the chemical evolution. This is an approach that has been adopted in stratospheric chemistry modelling studies at the Finnish Meteorological Institute. In collaboration with the University of Oslo, a development project was initiated in 1993 to prepare a stratospheric chemistry parameterisation, fit for global 3-dimensional modelling. This article presents the parameterisation approach. Selected results are shown from basic photochemical simulations

  3. Modelling stratospheric chemistry in a global three-dimensional chemical transport model

    Energy Technology Data Exchange (ETDEWEB)

    Rummukainen, M. [Finnish Meteorological Inst., Sodankylae (Finland). Sodankylae Observatory

    1995-12-31

    Numerical modelling of atmospheric chemistry aims to increase the understanding of the characteristics, the behavior and the evolution of atmospheric composition. These topics are of utmost importance in the study of climate change. The multitude of gases and particulates making up the atmosphere and the complicated interactions between them affect radiation transfer, atmospheric dynamics, and the impacts of anthropogenic and natural emissions. Chemical processes are fundamental factors in global warming, ozone depletion and atmospheric pollution problems in general. Much of the prevailing work on modelling stratospheric chemistry has so far been done with 1- and 2-dimensional models. Carrying an extensive chemistry parameterisation in a model with high spatial and temporal resolution is computationally heavy. Today, computers are becoming powerful enough to allow going over to 3-dimensional models. In order to concentrate on the chemistry, many Chemical Transport Models (CTM) are still run off-line, i.e. with precalculated and archived meteorology and radiation. In chemistry simulations, the archived values drive the model forward in time, without interacting with the chemical evolution. This is an approach that has been adopted in stratospheric chemistry modelling studies at the Finnish Meteorological Institute. In collaboration with the University of Oslo, a development project was initiated in 1993 to prepare a stratospheric chemistry parameterisation, fit for global 3-dimensional modelling. This article presents the parameterisation approach. Selected results are shown from basic photochemical simulations

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

    Science.gov (United States)

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

    2015-01-01

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

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

    Science.gov (United States)

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

    2015-10-01

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

  6. Predicting tropospheric ozone and hydroxyl radical in a global, three-dimensional, chemistry, transport, and deposition model

    Energy Technology Data Exchange (ETDEWEB)

    Atherton, C.S.

    1995-01-05

    Two of the most important chemically reactive tropospheric gases are ozone (O{sub 3}) and the hydroxyl radical (OH). Although ozone in the stratosphere is a necessary protector against the sun`s radiation, tropospheric ozone is actually a pollutant which damages materials and vegetation, acts as a respiratory irritant, and is a greenhouse gas. One of the two main sources of ozone in the troposphere is photochemical production. The photochemistry is initiated when hydrocarbons and carbon monoxide (CO) react with nitrogen oxides (NO{sub x} = NO + NO{sub 2}) in the presence of sunlight. Reaction with the hydroxyl radical, OH, is the main sink for many tropospheric gases. The hydroxyl radical is highly reactive and has a lifetime on the order of seconds. Its formation is initiated by the photolysis of tropospheric ozone. Tropospheric chemistry involves a complex, non-linear set of chemical reactions between atmospheric species that vary substantially in time and space. To model these and other species on a global scale requires the use of a global, three-dimensional chemistry, transport, and deposition (CTD) model. In this work, I developed two such three dimensional CTD models. The first model incorporated the chemistry necessary to model tropospheric ozone production from the reactions of nitrogen oxides with carbon monoxide (CO) and methane (CH{sub 4}). The second also included longer-lived alkane species and the biogenic hydrocarbon isoprene, which is emitted by growing plants and trees. The models` ability to predict a number of key variables (including the concentration of O{sub 3}, OH, and other species) were evaluated. Then, several scenarios were simulated to understand the change in the chemistry of the troposphere since preindustrial times and the role of anthropogenic NO{sub x} on present day conditions.

  7. Desorption of 1,3,5-Trichlorobenzene from Multi-Walled Carbon Nanotubes: Impact of Solution Chemistry and Surface Chemistry

    Directory of Open Access Journals (Sweden)

    Sheikh Uddin

    2013-05-01

    Full Text Available The strong affinity of carbon nanotubes (CNTs to environmental contaminants has raised serious concern that CNTs may function as a carrier of environmental pollutants and lead to contamination in places where the environmental pollutants are not expected. However, this concern will not be realized until the contaminants are desorbed from CNTs. It is well recognized that the desorption of environmental pollutants from pre-laden CNTs varies with the environmental conditions, such as the solution pH and ionic strength. However, comprehensive investigation on the influence of solution chemistry on the desorption process has not been carried out, even though numerous investigations have been conducted to investigate the impact of solution chemistry on the adsorption of environmental pollutants on CNTs. The main objective of this study was to determine the influence of solution chemistry (e.g., pH, ionic strength and surface functionalization on the desorption of preloaded 1,3,5-trichlorobenzene (1,3,5-TCB from multi-walled carbon nanotubes (MWNTs. The results suggested that higher pH, ionic strength and natural organic matter in solution generally led to higher desorption of 1,3,5-TCB from MWNTs. However, the extent of change varied at different values of the tested parameters (e.g., pH 7. In addition, the impact of these parameters varied with MWNTs possessing different surface functional groups, suggesting that surface functionalization could considerably alter the environmental behaviors and impact of MWNTs.

  8. Activated Carbon Textile via Chemistry of Metal Extraction for Supercapacitors.

    Science.gov (United States)

    Lam, Do Van; Jo, Kyungmin; Kim, Chang-Hyun; Kim, Jae-Hyun; Lee, Hak-Joo; Lee, Seung-Mo

    2016-12-27

    Carbothermic reduction in the chemistry of metal extraction (MO(s) + C(s) → M(s) + CO(g)) using carbon as a sacrificial agent has been used to smelt metals from diverse oxide ores since ancient times. Here, we paid attention to another aspect of the carbothermic reduction to prepare an activated carbon textile for high-rate-performance supercapacitors. On the basis of thermodynamic reducibility of metal oxides reported by Ellingham, we employed not carbon, but metal oxide as a sacrificial agent in order to prepare an activated carbon textile. We conformally coated ZnO on a bare cotton textile using atomic layer deposition, followed by pyrolysis at high temperature (C(s) + ZnO(s) → C'(s) + Zn(g) + CO(g)). We figured out that it leads to concurrent carbonization and activation in a chemical as well as mechanical way. Particularly, the combined effects of mechanical buckling and fracture that occurred between ZnO and cotton turned out to play an important role in carbonizing and activating the cotton textile, thereby significantly increasing surface area (nearly 10 times) compared with the cotton textile prepared without ZnO. The carbon textiles prepared by carbothermic reduction showed impressive combination properties of high power and energy densities (over 20-fold increase) together with high cyclic stability.

  9. Boron incorporation in the foraminifer Amphistegina lessonii under a decoupled carbonate chemistry

    Science.gov (United States)

    Kaczmarek, K.; Langer, G.; Nehrke, G.; Horn, I.; Misra, S.; Janse, M.; Bijma, J.

    2015-03-01

    A number of studies have shown that the boron isotopic composition (δ11B) and the B / Ca ratio of biogenic carbonates (mostly foraminifers) can serve as proxies for two parameters of the ocean's carbonate chemistry, rendering it possible to calculate the entire carbonate system. However, the B incorporation mechanism into marine carbonates is still not fully understood and analyses of field samples show species-specific and hydrographic effects on the B proxies complicating their application. Identifying the carbonate system parameter influencing boron incorporation is difficult due to the co-variation of pH, CO32- and B(OH)4-. To shed light on the question which parameter of the carbonate system is related to the boron incorporation, we performed culture experiments with the benthic symbiont-bearing foraminifer Amphistegina lessonii using a decoupled pH-CO32- chemistry. The determination of the δ11B and B / Ca ratios was performed simultaneously by means of a new in situ technique combining optical emission spectroscopy and laser ablation MC-ICP-MS. The boron isotopic composition in the tests gets heavier with increasing pH and B / Ca increases with increasing B(OH)4- / HCO3- of the culture media. The latter indicates that boron uptake of A. lessonii features a competition between B(OH)4- and HCO3-. Furthermore, the simultaneous determination of B / Ca and δ11B on single specimens allows for assessing the relative variability of these parameters. Among different treatments the B / Ca shows an increasing variability with increasing boron concentration in the test whereas the variability in the isotope distribution is constant.

  10. Chemistry resolved kinetic flow modeling of TATB based explosives

    Science.gov (United States)

    Vitello, Peter; Fried, Laurence E.; William, Howard; Levesque, George; Souers, P. Clark

    2012-03-01

    Detonation waves in insensitive, TATB-based explosives are believed to have multiple time scale regimes. The initial burn rate of such explosives has a sub-microsecond time scale. However, significant late-time slow release in energy is believed to occur due to diffusion limited growth of carbon. In the intermediate time scale concentrations of product species likely change from being in equilibrium to being kinetic rate controlled. We use the thermo-chemical code CHEETAH linked to an ALE hydrodynamics code to model detonations. We term our model chemistry resolved kinetic flow, since CHEETAH tracks the time dependent concentrations of individual species in the detonation wave and calculates EOS values based on the concentrations. We present here two variants of our new rate model and comparison with hot, ambient, and cold experimental data for PBX 9502.

  11. Factors Influencing NO2 Adsorption/Reduction on Microporous Activated Carbon: Porosity vs. Surface Chemistry

    Directory of Open Access Journals (Sweden)

    Imen Ghouma

    2018-04-01

    Full Text Available The textural properties and surface chemistry of different activated carbons, prepared by the chemical activation of olive stones, have been investigated in order to gain insight on the NO2 adsorption mechanism. The parent chemical activated carbon was prepared by the impregnation of olive stones in phosphoric acid followed by thermal carbonization. Then, the textural properties and surface chemistry were modified by chemical treatments including nitric acid, sodium hydroxide and/or a thermal treatment at 900 °C. The main properties of the parent and modified activated carbons were analyzed by N2-adsorption, scanning electron microscopy (SEM, and Fourier transform infrared spectroscopy (FTIR techniques, in order to enlighten the modifications issued from the chemical and thermal treatments. The NO2 adsorption capacities of the different activated carbons were measured in fixed bed experiments under 500 ppmv NO2 concentrations at room temperature. Temperature programmed desorption (TPD was applied after adsorption tests in order to quantify the amount of the physisorbed and chemisorbed NO2. The obtained results showed that the development of microporosity, the presence of oxygen-free sites, and the presence of basic surface groups are key factors for the efficient adsorption of NO2.

  12. Effect of water chemistry on flow accelerated corrosion rate of carbon steel measured by on-line corrosion-monitoring system

    International Nuclear Information System (INIS)

    Fujiwara, K.; Domae, M.; Yoneda, K.; Inada, F.

    2010-01-01

    Flow Accelerated Corrosion (FAC) of carbon steel is one of the most important subjects in coolant systems of power plants. FAC is influenced by material, flow condition, temperature, and water chemistry. Iron and chromium solubility should be the most effective factor to determine the effect of water chemistry on the FAC. It is very important to evaluate the correlation between the solubility and the FAC rate of the carbon steel. In the present study, the effects of pH and Cr concentration of material on the FAC rate of carbon steel were evaluated by using high temperature loop equipment with on-line corrosion-monitoring system. Effect of dissolved oxygen concentration at pH 7 was also evaluated. The experimental FAC rates were compared with the calculation result, which was obtained from a FAC model developed previously by the authors' group. The tube specimens made of STPT 480 carbon steel were used for the FAC tests. The Cr concentration of STPT 480 was specially adjusted to 0.001 and 0.08 %. The inner diameters of the tubes were 1.6, 2.4, and 3.2 mm. The solutions were fed to the specimens with the flow rate of 1.5 l/min. The temperature of the solution at the specimen was controlled at 140 o C. Test solutions were demineralized water or NH 3 solutions of pH 8.0, 9.2, and 10.0. The increase in pH more than 9 decreased the FAC rates of both 0.001 and 0.08 % Cr specimens at 140 o C. Increase of the Cr concentration of the material decreased the FAC rate in the solution of pH 7.0, 8.0, 9.2, and 10.0. The FAC model reproduced well dependence of the experimental FAC behavior on water chemistry. It was confirmed that effect of pH and Cr concentration of material on the FAC rate were closely related to the solubility and diffusion of iron and chromium. (author)

  13. Seawater Carbonate Chemistry of Deep-sea Coral Beds off the Northwestern Hawaiian Islands

    Science.gov (United States)

    Brooks, J.; Shamberger, K.; Roark, E. B.; Miller, K.; Baco-Taylor, A.

    2016-02-01

    Many species of deep-sea octocorals produce calcium carbonate (CaCO3) skeletons and form coral beds that support diverse ecosystems crucial to fisheries. The geochemistry of deep-sea coral skeletons can provide valuable paleoceanographic information on ocean circulation and nutrient cycling. Deep-sea corals in the older bottom waters of the Pacific are naturally exposed to higher carbon dioxide (CO2) concentrations and lower pH than in the Atlantic where much of the previous deep-sea coral work has occurred. Therefore, some Pacific deep-sea corals may live and calcify in waters that are corrosive to their skeletons, but there have been few current seawater carbonate chemistry measurements of the waters surrounding deep-sea coral beds to assess this. The input of anthropogenic atmospheric CO2 known as ocean acidification (OA) lowers ocean pH and causes an expansion of these corrosive waters. Seawater carbonate chemistry must be characterized before accurate predictions can be made for the effects of OA on these important ecosystems. Total Alkalinity (TA) and Dissolved Inorganic Carbon (DIC) samples were collected in the fall of 2014 and 2015 from the surface to 1450 m depth off the Northwestern Hawaiian Island chain where deep-sea octocorals are found. The partial pressure of CO2 increased and pH, calcite saturation state (Ωca) and aragonite saturation state (Ωar) decreased with increasing latitude and depth. Notably, waters were undersaturated with respect to calcite and aragonite (Ωca and Ωar less than 1) below 800 m and 500 m, respectively. Therefore, deep-sea corals below these depths must calcify in waters that are thermodynamically favorable for CaCO3 dissolution. How deep-sea octocorals cope with such adverse seawater chemistry is critical to understanding future effects of OA. It is not known whether OA is currently negatively impacting deep-sea octocorals, but their naturally acidified environments could make them particularly susceptible to OA.

  14. Computing the carbonate chemistry of the coral calcifying medium and its response to ocean acidification.

    Science.gov (United States)

    Raybaud, Virginie; Tambutté, Sylvie; Ferrier-Pagès, Christine; Reynaud, Stéphanie; Venn, Alexander A; Tambutté, Éric; Nival, Paul; Allemand, Denis

    2017-07-07

    Critical to determining vulnerability or resilience of reef corals to Ocean Acidification (OA) is a clearer understanding of the extent to which corals can control carbonate chemistry in their Extracellular Calcifying Medium (ECM) where the CaCO 3 skeleton is produced. Here, we employ a mathematical framework to calculate ECM aragonite saturation state (Ω arag.(ECM) ) and carbonate system ion concentration using measurements of calcification rate, seawater characteristics (temperature, salinity and pH) and ECM pH (pH (ECM) ). Our calculations of ECM carbonate chemistry at current-day seawater pH, indicate that Ω arag.(ECM) ranges from ∼10 to 38 (mean 20.41), i.e. about 5 to 6-fold higher than seawater. Accordingly, Dissolved Inorganic Carbon (DIC) and Total Alkalinity (TA) were calculated to be around 3 times higher in the ECM than in seawater. We also assessed the effects of acidification on ECM chemical properties of the coral Stylophora pistillata. At reduced seawater pH our calculations indicate that Ω arag.(ECM) remains almost constant. DIC (ECM) and TA (ECM) gradually increase as seawater pH declines, reaching values about 5 to 6-fold higher than in seawater, respectively for DIC and TA. We propose that these ECM characteristics buffer the effect of acidification and explain why certain corals continue to produce CaCO 3 even when seawater chemistry is less favourable. Copyright © 2017 Elsevier Ltd. All rights reserved.

  15. Experimental and modeling studies of small molecule chemistry in expanding spherical flames

    Science.gov (United States)

    Santner, Jeffrey

    Accurate models of flame chemistry are required in order to predict emissions and flame properties, such that clean, efficient engines can be designed more easily. There are three primary methods used to improve such combustion chemistry models - theoretical reaction rate calculations, elementary reaction rate experiments, and combustion system experiments. This work contributes to model improvement through the third method - measurements and analysis of the laminar burning velocity at constraining conditions. Modern combustion systems operate at high pressure with strong exhaust gas dilution in order to improve efficiency and reduce emissions. Additionally, flames under these conditions are sensitized to elementary reaction rates such that measurements constrain modeling efforts. Measurement conditions of the present work operate within this intersection between applications and fundamental science. Experiments utilize a new pressure-release, heated spherical combustion chamber with a variety of fuels (high hydrogen content fuels, formaldehyde (via 1,3,5-trioxane), and C2 fuels) at pressures from 0.5--25 atm, often with dilution by water vapor or carbon dioxide to flame temperatures below 2000 K. The constraining ability of these measurements depends on their uncertainty. Thus, the present work includes a novel analytical estimate of the effects of thermal radiative heat loss on burning velocity measurements in spherical flames. For 1,3,5-trioxane experiments, global measurements are sufficiently sensitive to elementary reaction rates that optimization techniques are employed to indirectly measure the reaction rates of HCO consumption. Besides the influence of flame chemistry on propagation, this work also explores the chemistry involved in production of nitric oxide, a harmful pollutant, within flames. We find significant differences among available chemistry models, both in mechanistic structure and quantitative reaction rates. There is a lack of well

  16. Seasonal Carbonate Chemistry Covariation with Temperature, Oxygen, and Salinity in a Fjord Estuary: Implications for the Design of Ocean Acidification Experiments

    Science.gov (United States)

    Reum, Jonathan C. P.; Alin, Simone R.; Feely, Richard A.; Newton, Jan; Warner, Mark; McElhany, Paul

    2014-01-01

    Carbonate chemistry variability is often poorly characterized in coastal regions and patterns of covariation with other biologically important variables such as temperature, oxygen concentration, and salinity are rarely evaluated. This absence of information hampers the design and interpretation of ocean acidification experiments that aim to characterize biological responses to future pCO2 levels relative to contemporary conditions. Here, we analyzed a large carbonate chemistry data set from Puget Sound, a fjord estuary on the U.S. west coast, and included measurements from three seasons (winter, summer, and fall). pCO2 exceeded the 2008–2011 mean atmospheric level (392 µatm) at all depths and seasons sampled except for the near-surface waters (aragonite were widespread (Ωar<1). We show that pCO2 values were relatively uniform throughout the water column and across regions in winter, enriched in subsurface waters in summer, and in the fall some values exceeded 2500 µatm in near-surface waters. Carbonate chemistry covaried to differing levels with temperature and oxygen depending primarily on season and secondarily on region. Salinity, which varied little (27 to 31), was weakly correlated with carbonate chemistry. We illustrate potential high-frequency changes in carbonate chemistry, temperature, and oxygen conditions experienced simultaneously by organisms in Puget Sound that undergo diel vertical migrations under present-day conditions. We used simple calculations to estimate future pCO2 and Ωar values experienced by diel vertical migrators based on an increase in atmospheric CO2. Given the potential for non-linear interactions between pCO2 and other abiotic variables on physiological and ecological processes, our results provide a basis for identifying control conditions in ocean acidification experiments for this region, but also highlight the wide range of carbonate chemistry conditions organisms may currently experience in this and similar coastal

  17. Multi-scale modeling of carbon capture systems

    Energy Technology Data Exchange (ETDEWEB)

    Kress, Joel David [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2017-03-03

    The development and scale up of cost effective carbon capture processes is of paramount importance to enable the widespread deployment of these technologies to significantly reduce greenhouse gas emissions. The U.S. Department of Energy initiated the Carbon Capture Simulation Initiative (CCSI) in 2011 with the goal of developing a computational toolset that would enable industry to more effectively identify, design, scale up, operate, and optimize promising concepts. The first half of the presentation will introduce the CCSI Toolset consisting of basic data submodels, steady-state and dynamic process models, process optimization and uncertainty quantification tools, an advanced dynamic process control framework, and high-resolution filtered computationalfluid- dynamics (CFD) submodels. The second half of the presentation will describe a high-fidelity model of a mesoporous silica supported, polyethylenimine (PEI)-impregnated solid sorbent for CO2 capture. The sorbent model includes a detailed treatment of transport and amine-CO2- H2O interactions based on quantum chemistry calculations. Using a Bayesian approach for uncertainty quantification, we calibrate the sorbent model to Thermogravimetric (TGA) data.

  18. Influence of porous texture and surface chemistry on the CO₂ adsorption capacity of porous carbons: acidic and basic site interactions.

    Science.gov (United States)

    Sánchez-Sánchez, Angela; Suárez-García, Fabián; Martínez-Alonso, Amelia; Tascón, Juan M D

    2014-12-10

    Doped porous carbons exhibiting highly developed porosity and rich surface chemistry have been prepared and subsequently applied to clarify the influence of both factors on carbon dioxide capture. Nanocasting was selected as synthetic route, in which a polyaramide precursor (3-aminobenzoic acid) was thermally polymerized inside the porosity of an SBA-15 template in the presence of different H3PO4 concentrations. The surface chemistry and the porous texture of the carbons could be easily modulated by varying the H3PO4 concentration and carbonization temperature. Porous texture was found to be the determinant factor on carbon dioxide adsorption at 0 °C, while surface chemistry played an important role at higher adsorption temperatures. We proved that nitrogen functionalities acted as basic sites and oxygen and phosphorus groups as acidic ones toward adsorption of CO2 molecules. Among the nitrogen functional groups, pyrrolic groups exhibited the highest influence, while the positive effect of pyridinic and quaternary functionalities was smaller. Finally, some of these N-doped carbons exhibit CO2 heats of adsorption higher than 42 kJ/mol, which make them excellent candidates for CO2 capture.

  19. Update of the water chemistry effect on the flow-accelerated corrosion rate of carbon steel: influence of hydrazine, boric acid, ammonia, morpholine and ethanolamine

    International Nuclear Information System (INIS)

    Pavageau, E.-M.; De Bouvier, O.; Trevin, S.; Bretelle, J.-L.; Dejoux, L.

    2007-01-01

    The influence of the water chemistry on Flow-Accelerated Corrosion (FAC) affecting carbon steel components has been studied for many years and is relatively well known and taken into account by the models. Nonetheless, experimental studies were conducted in the last few years at EDF on the CIROCO loop in order to check the influence of the water chemistry parameters (hydrazine, boric acid, ammonia, morpholine and ethanolamine) on the FAC rate of carbon steel in one phase flow conditions. The hydrazine impact on the FAC rate was shown to be minor in EDF's chemistry recommendation range, compared to other parameters' effects such as the pH effect. The presence of boric acid in the nominal secondary circuit conditions was negligible. Finally, as expected, the nature of the chemical conditioning (ammonia, morpholine or ethanolamine) did not modify the FAC rate, the influencing chemical variable being the at-temperature pH in one-phase flow conditions. (author)

  20. Seasonal carbonate chemistry covariation with temperature, oxygen, and salinity in a fjord estuary: implications for the design of ocean acidification experiments.

    Directory of Open Access Journals (Sweden)

    Jonathan C P Reum

    Full Text Available Carbonate chemistry variability is often poorly characterized in coastal regions and patterns of covariation with other biologically important variables such as temperature, oxygen concentration, and salinity are rarely evaluated. This absence of information hampers the design and interpretation of ocean acidification experiments that aim to characterize biological responses to future pCO2 levels relative to contemporary conditions. Here, we analyzed a large carbonate chemistry data set from Puget Sound, a fjord estuary on the U.S. west coast, and included measurements from three seasons (winter, summer, and fall. pCO2 exceeded the 2008-2011 mean atmospheric level (392 µatm at all depths and seasons sampled except for the near-surface waters (< 10 m in the summer. Further, undersaturated conditions with respect to the biogenic carbonate mineral aragonite were widespread (Ωar<1. We show that pCO2 values were relatively uniform throughout the water column and across regions in winter, enriched in subsurface waters in summer, and in the fall some values exceeded 2500 µatm in near-surface waters. Carbonate chemistry covaried to differing levels with temperature and oxygen depending primarily on season and secondarily on region. Salinity, which varied little (27 to 31, was weakly correlated with carbonate chemistry. We illustrate potential high-frequency changes in carbonate chemistry, temperature, and oxygen conditions experienced simultaneously by organisms in Puget Sound that undergo diel vertical migrations under present-day conditions. We used simple calculations to estimate future pCO2 and Ωar values experienced by diel vertical migrators based on an increase in atmospheric CO2. Given the potential for non-linear interactions between pCO2 and other abiotic variables on physiological and ecological processes, our results provide a basis for identifying control conditions in ocean acidification experiments for this region, but also highlight

  1. Seasonal carbonate chemistry covariation with temperature, oxygen, and salinity in a fjord estuary: implications for the design of ocean acidification experiments.

    Science.gov (United States)

    Reum, Jonathan C P; Alin, Simone R; Feely, Richard A; Newton, Jan; Warner, Mark; McElhany, Paul

    2014-01-01

    Carbonate chemistry variability is often poorly characterized in coastal regions and patterns of covariation with other biologically important variables such as temperature, oxygen concentration, and salinity are rarely evaluated. This absence of information hampers the design and interpretation of ocean acidification experiments that aim to characterize biological responses to future pCO2 levels relative to contemporary conditions. Here, we analyzed a large carbonate chemistry data set from Puget Sound, a fjord estuary on the U.S. west coast, and included measurements from three seasons (winter, summer, and fall). pCO2 exceeded the 2008-2011 mean atmospheric level (392 µatm) at all depths and seasons sampled except for the near-surface waters (Salinity, which varied little (27 to 31), was weakly correlated with carbonate chemistry. We illustrate potential high-frequency changes in carbonate chemistry, temperature, and oxygen conditions experienced simultaneously by organisms in Puget Sound that undergo diel vertical migrations under present-day conditions. We used simple calculations to estimate future pCO2 and Ωar values experienced by diel vertical migrators based on an increase in atmospheric CO2. Given the potential for non-linear interactions between pCO2 and other abiotic variables on physiological and ecological processes, our results provide a basis for identifying control conditions in ocean acidification experiments for this region, but also highlight the wide range of carbonate chemistry conditions organisms may currently experience in this and similar coastal ecosystems.

  2. Porous structure and surface chemistry of phosphoric acid activated carbon from corncob

    Science.gov (United States)

    Sych, N. V.; Trofymenko, S. I.; Poddubnaya, O. I.; Tsyba, M. M.; Sapsay, V. I.; Klymchuk, D. O.; Puziy, A. M.

    2012-11-01

    Active carbons have been prepared from corncob using chemical activation with phosphoric acid at 400 °C using varied ratio of impregnation (RI). Porous structure of carbons was characterized by nitrogen adsorption and scanning electron microscopy. Surface chemistry was studied by IR and potentiometric titration method. It has been shown that porosity development was peaked at RI = 1.0 (SBET = 2081 m2/g, Vtot = 1.1 cm3/g), while maximum amount of acid surface groups was observed at RI = 1.25. Acid surface groups of phosphoric acid activated carbons from corncob includes phosphate and strongly acidic carboxylic (pK = 2.0-2.6), weakly acidic carboxylic (pK = 4.7-5.0), enol/lactone (pK = 6.7-7.4; 8.8-9.4) and phenol (pK = 10.1-10.7). Corncob derived carbons showed high adsorption capacity to copper, especially at low pH. Maximum adsorption of methylene blue and iodine was observed for carbon with most developed porosity (RI = 1.0).

  3. Quantifying atmospheric transport, chemistry, and mixing using a new trajectory-box model and a global atmospheric-chemistry GCM

    Directory of Open Access Journals (Sweden)

    H. Riede

    2009-12-01

    Full Text Available We present a novel method for the quantification of transport, chemistry, and mixing along atmospheric trajectories based on a consistent model hierarchy. The hierarchy consists of the new atmospheric-chemistry trajectory-box model CAABA/MJT and the three-dimensional (3-D global ECHAM/MESSy atmospheric-chemistry (EMAC general circulation model. CAABA/MJT employs the atmospheric box model CAABA in a configuration using the atmospheric-chemistry submodel MECCA (M, the photochemistry submodel JVAL (J, and the new trajectory submodel TRAJECT (T, to simulate chemistry along atmospheric trajectories, which are provided offline. With the same chemistry submodels coupled to the 3-D EMAC model and consistent initial conditions and physical parameters, a unique consistency between the two models is achieved. Since only mixing processes within the 3-D model are excluded from the model consistency, comparisons of results from the two models allow to separate and quantify contributions of transport, chemistry, and mixing along the trajectory pathways. Consistency of transport between the trajectory-box model CAABA/MJT and the 3-D EMAC model is achieved via calculation of kinematic trajectories based on 3-D wind fields from EMAC using the trajectory model LAGRANTO. The combination of the trajectory-box model CAABA/MJT and the trajectory model LAGRANTO can be considered as a Lagrangian chemistry-transport model (CTM moving isolated air parcels. The procedure for obtaining the necessary statistical basis for the quantification method is described as well as the comprehensive diagnostics with respect to chemistry.

    The quantification method presented here allows to investigate the characteristics of transport, chemistry, and mixing in a grid-based 3-D model. The analysis of chemical processes within the trajectory-box model CAABA/MJT is easily extendable to include, for example, the impact of different transport pathways or of mixing processes onto

  4. Gas-grain chemistry in cold interstellar cloud cores with a microscopic Monte Carlo approach to surface chemistry

    Science.gov (United States)

    Chang, Q.; Cuppen, H. M.; Herbst, E.

    2007-07-01

    Aims:We have recently developed a microscopic Monte Carlo approach to study surface chemistry on interstellar grains and the morphology of ice mantles. The method is designed to eliminate the problems inherent in the rate-equation formalism to surface chemistry. Here we report the first use of this method in a chemical model of cold interstellar cloud cores that includes both gas-phase and surface chemistry. The surface chemical network consists of a small number of diffusive reactions that can produce molecular oxygen, water, carbon dioxide, formaldehyde, methanol and assorted radicals. Methods: The simulation is started by running a gas-phase model including accretion onto grains but no surface chemistry or evaporation. The starting surface consists of either flat or rough olivine. We introduce the surface chemistry of the three species H, O and CO in an iterative manner using our stochastic technique. Under the conditions of the simulation, only atomic hydrogen can evaporate to a significant extent. Although it has little effect on other gas-phase species, the evaporation of atomic hydrogen changes its gas-phase abundance, which in turn changes the flux of atomic hydrogen onto grains. The effect on the surface chemistry is treated until convergence occurs. We neglect all non-thermal desorptive processes. Results: We determine the mantle abundances of assorted molecules as a function of time through 2 × 105 yr. Our method also allows determination of the abundance of each molecule in specific monolayers. The mantle results can be compared with observations of water, carbon dioxide, carbon monoxide, and methanol ices in the sources W33A and Elias 16. Other than a slight underproduction of mantle CO, our results are in very good agreement with observations.

  5. Energy and carbon for green chemistry

    International Nuclear Information System (INIS)

    Jacquelin, Louis-Marie; Bucy, Jacques de; Caujolle, Alexis

    2015-04-01

    Since 2006, massive shale gas exploration and development in the United States has enabled the country to reduce the price of gas by a factor of 3. Taking instantaneously advantage of this unique situation, the chemical sector has planned more than 100 billion dollars of investment in new industrial capacity, creating a tremendous environment for its domestic chemical industry. In Europe, despite a high capacity for innovation, the chemical industry is suffering from ageing facilities and high production costs. It must contend with ferocious competition from the United States but also from Asia, which currently represents 46% of the global market, and the Middle East that is benefiting from the 50 billion dollars invested in the chemical sector since the early 2000's. Lower energy prices and labor costs in the United States are negatively impacting the competitiveness of European industrial companies but their capacity to innovate can help them to re-bounce. By reducing the environmental impact of their products, they can generate added value that is important to their direct customers, end users and also governments. In this article, to assist industrial companies, ENEA, a consulting firm specialized in energy and sustainable development, examines two strategic principles of green chemistry: energy efficiency and the use of renewable feedstock. It addresses all of the topics linked to energy and carbon in chemistry, from supply (bio-feedstocks, CO 2 reuse) to the end products (life-cycle analysis, recyclability) while also covering the processes (energy sobriety, bio-refineries, use of microalgae)

  6. Dilution physics modeling: Dissolution/precipitation chemistry

    International Nuclear Information System (INIS)

    Onishi, Y.; Reid, H.C.; Trent, D.S.

    1995-09-01

    This report documents progress made to date on integrating dilution/precipitation chemistry and new physical models into the TEMPEST thermal-hydraulics computer code. Implementation of dissolution/precipitation chemistry models is necessary for predicting nonhomogeneous, time-dependent, physical/chemical behavior of tank wastes with and without a variety of possible engineered remediation and mitigation activities. Such behavior includes chemical reactions, gas retention, solids resuspension, solids dissolution and generation, solids settling/rising, and convective motion of physical and chemical species. Thus this model development is important from the standpoint of predicting the consequences of various engineered activities, such as mitigation by dilution, retrieval, or pretreatment, that can affect safe operations. The integration of a dissolution/precipitation chemistry module allows the various phase species concentrations to enter into the physical calculations that affect the TEMPEST hydrodynamic flow calculations. The yield strength model of non-Newtonian sludge correlates yield to a power function of solids concentration. Likewise, shear stress is concentration-dependent, and the dissolution/precipitation chemistry calculations develop the species concentration evolution that produces fluid flow resistance changes. Dilution of waste with pure water, molar concentrations of sodium hydroxide, and other chemical streams can be analyzed for the reactive species changes and hydrodynamic flow characteristics

  7. Instructional Model and Thinking Skill in Chemistry Class

    Science.gov (United States)

    Langkudi, H. H.

    2018-02-01

    Chemistry course are considered a difficult lesson for students as evidenced by low learning outcomes on daily tests, mid-semester tests as well as final semester tests. This research intended to investigate the effect of instructional model, thinking skill and the interaction of these variables on students’ achievement in chemistry. Experimental method was applying used 2 x 2 factorial design. The results showed that the use of instructional model with thinking skill influences student’s learning outcomes, so that the chemistry teacher is recommended to pay attention to the learning model, and adjusted to the student’s skill thinking on the chemistry material being taught. The conclusion of this research is that discovery model is suitable for students who have formal thinking skill and conventional model is fit for the students that have concrete thinking skill.

  8. DISEQUILIBRIUM CARBON, OXYGEN, AND NITROGEN CHEMISTRY IN THE ATMOSPHERES OF HD 189733b AND HD 209458b

    International Nuclear Information System (INIS)

    Moses, Julianne I.; Visscher, C.; Fortney, J. J.; Showman, A. P.; Lewis, N. K.; Griffith, C. A.; Klippenstein, S. J.; Shabram, M.; Friedson, A. J.; Marley, M. S.; Freedman, R. S.

    2011-01-01

    We have developed a one-dimensional photochemical and thermochemical kinetics and diffusion model to study the effects of disequilibrium chemistry on the atmospheric composition of 'hot-Jupiter' exoplanets. Here we investigate the coupled chemistry of neutral carbon, hydrogen, oxygen, and nitrogen species on HD 189733b and HD 209458b and we compare the model results with existing transit and eclipse observations. We find that the vertical profiles of molecular constituents are significantly affected by transport-induced quenching and photochemistry, particularly on the cooler HD 189733b; however, the warmer stratospheric temperatures on HD 209458b help maintain thermochemical equilibrium and reduce the effects of disequilibrium chemistry. For both planets, the methane and ammonia mole fractions are found to be enhanced over their equilibrium values at pressures of a few bar to less than an mbar due to transport-induced quenching, but CH 4 and NH 3 are photochemically removed at higher altitudes. Disequilibrium chemistry also enhances atomic species, unsaturated hydrocarbons (particularly C 2 H 2 ), some nitriles (particularly HCN), and radicals like OH, CH 3 , and NH 2 . In contrast, CO, H 2 O, N 2 , and CO 2 more closely follow their equilibrium profiles, except at pressures ∼ 2 O, and N 2 are photochemically destroyed and CO 2 is produced before its eventual high-altitude destruction. The enhanced abundances of CH 4 , NH 3 , and HCN are expected to affect the spectral signatures and thermal profiles of HD 189733b and other relatively cool, transiting exoplanets. We examine the sensitivity of our results to the assumed temperature structure and eddy diffusion coefficients and discuss further observational consequences of these models.

  9. The Irminger Sea and the Iceland Sea time series measurements of sea water carbon and nutrient chemistry 1983–2008

    Directory of Open Access Journals (Sweden)

    J. Olafsson

    2010-03-01

    Full Text Available This paper describes the ways and means of assembling and quality controling the Irminger Sea and Iceland Sea time-series biogeochemical data which are included in the CARINA data set. The Irminger Sea and the Iceland Sea are hydrographically different regions where measurements of sea water carbon and nutrient chemistry were started in 1983. The sampling is seasonal, four times a year. The carbon chemistry is studied with measurements of the partial pressure of carbon dioxide in seawater, pCO2, and total dissolved inorganic carbon, TCO2. The carbon chemistry data are for surface waters only until 1991 when water column sampling was initiated. Other measured parameters are salinity, dissolved oxygen and the inorganic nutrients nitrate, phosphate and silicate. Because of the CARINA criteria for secondary quality control, depth >1500 m, the IRM-TS could not be included in the routine QC and the IS-TS only in a limited way. However, with the information provided here, the quality of the data can be assessed, e.g. on the basis of the results obtained with the use of reference materials.

  10. A regression model using sediment chemistry for the evaluation of marine environmental impacts associated with salmon aquaculture cage wastes

    International Nuclear Information System (INIS)

    Chou, C.L.; Haya, K.; Paon, L.A.; Moffatt, J.D.

    2004-01-01

    This study was undertaken to develop an approach for modelling changes of sediment chemistry related to the accumulation of aquaculture waste. Metal composition of sediment Al, Cu, Fe, Li, Mn, and Zn; organic carbon and 2 =0.945 compared to R 2 =0.653 for the regression model using unadjusted EMP for assessing the environmental conditions

  11. Impact of RACM2, halogen chemistry, and updated ozone deposition velocity onhemispheric ozone predictions

    Science.gov (United States)

    We incorporate the Regional Atmospheric Chemistry Mechanism (RACM2) into the Community Multiscale Air Quality (CMAQ) hemispheric model and compare model predictions to those obtained using the existing Carbon Bond chemical mechanism with the updated toluene chemistry (CB05TU). Th...

  12. Synthesis and carbonization chemistry of a phosphorous-nitrogen based intumescent flame retardant

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Haiyun, E-mail: mahaiyun@gmail.com [College of Chemistry and Environmental Science, HeBei University, Baoding, Hebei Province 071002 (China); Fang, Zhengping [MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Institute of Polymer Composites, Zhejiang University, Hangzhou 310027 (China); Laboratory of Polymer Materials and Engineering, Ningbo Institute of Technology, Zhejiang University, Ningbo 315100 (China)

    2012-09-10

    Graphical abstract: The carbonization chemistry and mechanism of a novel synthesized intumescent flame retardant. The final chars showed a complex P-O-Ph and aromatic/graphitic structure containing architecture. Highlights: Black-Right-Pointing-Pointer The IFR synthesized is polymeric and has high molecular weight. Black-Right-Pointing-Pointer The IFR has a higher thermal stability than most of the commercial IFRs. Black-Right-Pointing-Pointer The final chars of IFR showed a complex P-O-Ph and aromatic/graphitic structure. - Abstract: In this work, a polymeric phosphorous-nitrogen containing intumescent flame retardant, named poly(diaminodiphenyl methane spirocyclic pentaerythritol bisphosphonate) (PDSPB), was synthesized. The carbonization chemistry was investigated. FTIR and {sup 1}H NMR were used to confirm the chemical structure of PDSPB. Thermogravimetric analysis (TGA), scanning electron microscopy (SEM), transmission electron microscopy (TEM), in situ FTIR and energy dispersive X-ray (EDX) were used to investigate and monitor the chemical structural changes during thermal degradation. PDSPB demonstrated a three-step degradation behavior. PDSPB oligomers continuously polymerized and generated a higher macromolecular weight during the first step (200-250 Degree-Sign C). The phosphate ester bonds were broken down and phosphoric acid was released which dehydrated the carbon source to form chars during the second step (280-320 Degree-Sign C). The residues will be further degraded and form final chars during the final weight loss step (400-450 Degree-Sign C). The final chars showed a complex P-O-Ph and aromatic/graphitic structure containing architecture.

  13. Synthesis and carbonization chemistry of a phosphorous–nitrogen based intumescent flame retardant

    International Nuclear Information System (INIS)

    Ma, Haiyun; Fang, Zhengping

    2012-01-01

    Graphical abstract: The carbonization chemistry and mechanism of a novel synthesized intumescent flame retardant. The final chars showed a complex P-O-Ph and aromatic/graphitic structure containing architecture. Highlights: ► The IFR synthesized is polymeric and has high molecular weight. ► The IFR has a higher thermal stability than most of the commercial IFRs. ► The final chars of IFR showed a complex P-O-Ph and aromatic/graphitic structure. - Abstract: In this work, a polymeric phosphorous–nitrogen containing intumescent flame retardant, named poly(diaminodiphenyl methane spirocyclic pentaerythritol bisphosphonate) (PDSPB), was synthesized. The carbonization chemistry was investigated. FTIR and 1 H NMR were used to confirm the chemical structure of PDSPB. Thermogravimetric analysis (TGA), scanning electron microscopy (SEM), transmission electron microscopy (TEM), in situ FTIR and energy dispersive X-ray (EDX) were used to investigate and monitor the chemical structural changes during thermal degradation. PDSPB demonstrated a three-step degradation behavior. PDSPB oligomers continuously polymerized and generated a higher macromolecular weight during the first step (200–250 °C). The phosphate ester bonds were broken down and phosphoric acid was released which dehydrated the carbon source to form chars during the second step (280–320 °C). The residues will be further degraded and form final chars during the final weight loss step (400–450 °C). The final chars showed a complex P-O-Ph and aromatic/graphitic structure containing architecture.

  14. Simplified Model for Reburning Chemistry

    DEFF Research Database (Denmark)

    Glarborg, Peter; Hansen, Stine

    2010-01-01

    In solid fuel flames, reburn-type reactions are often important for the concentrations of NOx in the near-burner region. To be able to model the nitrogen chemistry in these flames, it is necessary to have an adequate model for volatile/NO interactions. Simple models consisting of global steps...

  15. Controls of Ca/Mg/Fe activity ratios in pore water chemistry models of the Callovian-Oxfordian clay formation

    International Nuclear Information System (INIS)

    Lerouge, C.; Grangeon, S.; Wille, G.; Flehoc, C.; Gailhanou, H.; Gaucher, E.C.; Tournassat, C.; Vinsot, A.; Made, B.; Altmann, S.

    2013-01-01

    In the pore water chemistry model of the Callovian-Oxfordian clay formation, the divalent cations Ca, Mg, and Fe are controlled by equilibrium reactions with pure carbonates: calcite for Ca, dolomite for Mg, and siderite for Fe. Results of a petrological study and computing of the Ca/Mg and Ca/Fe activity ratios based on natural pore water chemistry provide evidence that equilibrium with pure calcite and pure dolomite is a reasonable assumption for undisturbed pore waters; on the other hand, siderite cannot be considered at equilibrium with pore waters at the formation scale. (authors)

  16. Controls of Ca/Mg/Fe activity ratios in pore water chemistry models of the Callovian-Oxfordian clay formation

    Energy Technology Data Exchange (ETDEWEB)

    Lerouge, C.; Grangeon, S.; Wille, G.; Flehoc, C.; Gailhanou, H.; Gaucher, E.C.; Tournassat, C. [BRGM av. Claude Guillemin BP6009 45060 Orleans cedex 2 (France); Vinsot, A. [ANDRA Meuse/Haute-Marne Underground research Laboratory (URL), RD 960, 55290 Bure (France); Made, B.; Altmann, S. [ANDRA - Parc de la Croix Blanche, 1-7 rue Jean Monnet, 92298 Chatenay-Malabry Cedex (France)

    2013-07-01

    In the pore water chemistry model of the Callovian-Oxfordian clay formation, the divalent cations Ca, Mg, and Fe are controlled by equilibrium reactions with pure carbonates: calcite for Ca, dolomite for Mg, and siderite for Fe. Results of a petrological study and computing of the Ca/Mg and Ca/Fe activity ratios based on natural pore water chemistry provide evidence that equilibrium with pure calcite and pure dolomite is a reasonable assumption for undisturbed pore waters; on the other hand, siderite cannot be considered at equilibrium with pore waters at the formation scale. (authors)

  17. Microelectrode characterization of coral daytime interior pH and carbonate chemistry.

    Science.gov (United States)

    Cai, Wei-Jun; Ma, Yuening; Hopkinson, Brian M; Grottoli, Andréa G; Warner, Mark E; Ding, Qian; Hu, Xinping; Yuan, Xiangchen; Schoepf, Verena; Xu, Hui; Han, Chenhua; Melman, Todd F; Hoadley, Kenneth D; Pettay, D Tye; Matsui, Yohei; Baumann, Justin H; Levas, Stephen; Ying, Ye; Wang, Yongchen

    2016-04-04

    Reliably predicting how coral calcification may respond to ocean acidification and warming depends on our understanding of coral calcification mechanisms. However, the concentration and speciation of dissolved inorganic carbon (DIC) inside corals remain unclear, as only pH has been measured while a necessary second parameter to constrain carbonate chemistry has been missing. Here we report the first carbonate ion concentration ([CO3(2-)]) measurements together with pH inside corals during the light period. We observe sharp increases in [CO3(2-)] and pH from the gastric cavity to the calcifying fluid, confirming the existence of a proton (H(+)) pumping mechanism. We also show that corals can achieve a high aragonite saturation state (Ωarag) in the calcifying fluid by elevating pH while at the same time keeping [DIC] low. Such a mechanism may require less H(+)-pumping and energy for upregulating pH compared with the high [DIC] scenario and thus may allow corals to be more resistant to climate change related stressors.

  18. CARBON-CHAIN SPECIES IN WARM-UP MODELS

    International Nuclear Information System (INIS)

    Hassel, George E.; Harada, Nanase; Herbst, Eric

    2011-01-01

    In previous warm-up chemical models of the low-mass star-forming region L1527, we investigated the evolution of carbon-chain unsaturated hydrocarbon species when the envelope temperature is slightly elevated to T ≈ 30 K. These models demonstrated that enhanced abundances of such species can be explained by gas-phase ion-molecule chemistry following the partial sublimation of methane from grain surfaces. We also concluded that the abundances of hydrocarbon radicals such as the C n H family should be further enhanced as the temperatures increase to higher values, but this conclusion stood in contrast with the lack of unambiguous detection of these species toward hot core and corino sources. Meanwhile, observational surveys have identified C 2 H, C 4 H, CH 3 CCH, and CH 3 OH toward hot corinos (especially IRAS 16293–2422) as well as toward L1527, with lower abundances for the carbon-chain radicals and higher abundances for the other two species toward the hot corinos. In addition, the Herschel Space Telescope has detected the bare linear chain C 3 in 50 K material surrounding young high-mass stellar objects. To understand these new results, we revisit previous warm-up models with an augmented gas-grain network that incorporated reactions from a gas-phase network that was constructed for use with increased temperature up to 800 K. Some of the newly adopted reactions between carbon-chain species and abundant H 2 possess chemical activation energy barriers. The revised model results now better reproduce the observed abundances of unsaturated carbon chains under hot corino (100 K) conditions and make predictions for the abundances of bare carbon chains in the 50 K regions observed by the Herschel HIFI detector.

  19. Functionalization of multilayer fullerenes (carbon nano-onions) using diazonium compounds and "click" chemistry.

    Science.gov (United States)

    Flavin, Kevin; Chaur, Manuel N; Echegoyen, Luis; Giordani, Silvia

    2010-02-19

    A novel versatile approach for the functionalization of multilayer fullerenes (carbon nano-onions) has been developed, which involves the facile introduction of a variety of simple functionalities onto their surface by treatment with in situ generated diazonium compounds. This approach is complemented by use of "click" chemistry which was used for the covalent introduction of more complex porphyrin molecules.

  20. Chemistry models in the Victoria code

    International Nuclear Information System (INIS)

    Grimley, A.J. III

    1988-01-01

    The VICTORIA Computer code consists of the fission product release and chemistry models for the MELPROG severe accident analysis code. The chemistry models in VICTORIA are used to treat multi-phase interactions in four separate physical regions: fuel grains, gap/open porosity/clad, coolant/aerosols, and structure surfaces. The physical and chemical environment of each region is very different from the others and different models are required for each. The common thread in the modelling is the use of a chemical equilibrium assumption. The validity of this assumption along with a description of the various physical constraints applicable to each region will be discussed. The models that result from the assumptions and constraints will be presented along with samples of calculations in each region

  1. Chemistry and palynology of carbon seams and associated rocks from the Witwatersrand goldfields, South Africa

    Science.gov (United States)

    Ebert, L.B.; Robbins, E.I.; Rose, K.D.; Kastrup, R.V.; Scanlon, J.C.; Gebhard, L.A.; Garcia, A.R.

    1990-01-01

    Carbon seams in the Witwatersrand System of South Africa host some of the richest gold concentrations in the world. A study of the microscopic characteristics in thin sections and acid residues, and of the chemical and physical nature of the carbon-bearing phases, was undertaken to gain some understanding of the biological precursors and thermal changes that have occurred since the seams were buried. The HClHF acid-resistant organic tissues in this Early Proterozoic coal are filamentous and spherical, which are typical morphologies for microorganisms. The tissues are carbonized black as would be expected for metamorphic rocks, so usual palynological techniques were of limited use. Therefore, the chemical and physical nature of the organic remains was studied by H C ratios, X-ray diffraction (XRD), 13C nuclear magnetic resonance (NMR), reductive chemistry, crosspolarization/magic angle spinning NMR (CP/MAS), and electron spin resonance (ESR). The H C ratios of the samples examined are similar to those of semi-anthracite and petroleum cokes from delayed cokers. XRD shows graphite is not present and that the gold is in elemental form, not chemically bound or intercalated between carbon planes. NMR shows that both aromatic and paraffinic carbons are present. Integration of the carbon NMR spectra suggests that 80% of the carbon is sp2-hybridized and 20% is sp3-hybridized. Reductive chemistry shows that the benzenoid entities are larger than common polynuclear aromatic hydrocarbons such as perylene and decacyclene. Dipolar dephasing CP/MAS NMR suggests the presence of two types of paraffinic carbons, a rigid methylene group and a rotating methyl group. The narrowing of the ESR linewidth between room temperature and 300??C shows that the materials examined have not previously been subjected to temperatures as high as 300??C. ?? 1990.

  2. Assessment of the surface chemistry of carbon blacks by TGA-MS, XPS and inverse gas chromatography using statistical chemometric analysis

    International Nuclear Information System (INIS)

    Strzemiecka, Beata; Voelkel, Adam; Donate-Robles, Jessica; Martín-Martínez, José Miguel

    2014-01-01

    Highlights: • Carbon blacks with lower specific surface area had basic character (electron donor) due to C=O and C-O groups. • Carbon blacks with higher specific surface area had acidic character (acceptor electron) due to OH groups. • Total surface energy and its dispersive component of carbon blacks increased by increasing their specific surface area. (table) - Abstract: Four carbon blacks with different specific surface areas and surface chemistries (C32, C71, C159 and C178) were analyzed by transmission electron microscopy (TEM) and nitrogen adsorption isotherms at 77 K. Their surface chemistries were analyzed by X-ray photoelectron spectroscopy (XPS), thermal gravimetric analysis coupled with mass spectrometry (TGA-MS) and inverse gas chromatography (IGC). The carbon blacks contained 2.7–5.8 wt% volatiles corresponding to -OH, C-O, C=O and COO groups. The surface chemistry parameters obtained with the different experimental techniques were inter-related by using chemometric statistical analysis tools. The application of this methodology showed that the carbon blacks with lower specific surface area (C32 and C71) had basic character (electron donor) mainly due to C=O and C-O groups, whereas the carbon black with the highest specific surface area (C178) showed acidic character (acceptor electron) due to its high content of OH groups. Moreover, the total surface energy and the dispersive component of the surface energy of the carbon blacks increased with the increase of their specific surface area. In general the specific interactions of the carbon blacks also increased with the increase of their specific surface area although C71 is exceptional due to higher oxygen content corresponding to C-O groups

  3. “Impact of RACM2, halogen chemistry, and updated ozonedeposition velocity on hemispheric ozone predictions”

    Science.gov (United States)

    We incorporate the Regional Atmospheric Chemistry Mechanism (RACM2) into the Community Multiscale Air Quality (CMAQ) hemispheric model and compare model predictions to those obtained using the existing Carbon Bond chemical mechanism with updated toluene chemistry (CB05TU). The RA...

  4. Modeling local chemistry in PWR steam generator crevices

    International Nuclear Information System (INIS)

    Millett, P.J.

    1997-01-01

    Over the past two decades steam generator corrosion damage has been a major cost impact to PWR owners. Crevices and occluded regions create thermal-hydraulic conditions where aggressive impurities can become highly concentrated, promoting localized corrosion of the tubing and support structure materials. The type of corrosion varies depending on the local conditions, with stress corrosion cracking being the phenomenon of most current concern. A major goal of the EPRI research in this area has been to develop models of the concentration process and resulting crevice chemistry conditions. These models may then be used to predict crevice chemistry based on knowledge of bulk chemistry, thereby allowing the operator to control corrosion damage. Rigorous deterministic models have not yet been developed; however, empirical approaches have shown promise and are reflected in current versions of the industry-developed secondary water chemistry guidelines

  5. A rechargeable iodine-carbon battery that exploits ion intercalation and iodine redox chemistry.

    Science.gov (United States)

    Lu, Ke; Hu, Ziyu; Ma, Jizhen; Ma, Houyi; Dai, Liming; Zhang, Jintao

    2017-09-13

    Graphitic carbons have been used as conductive supports for developing rechargeable batteries. However, the classic ion intercalation in graphitic carbon has yet to be coupled with extrinsic redox reactions to develop rechargeable batteries. Herein, we demonstrate the preparation of a free-standing, flexible nitrogen and phosphorus co-doped hierarchically porous graphitic carbon for iodine loading by pyrolysis of polyaniline coated cellulose wiper. We find that heteroatoms could provide additional defect sites for encapsulating iodine while the porous carbon skeleton facilitates redox reactions of iodine and ion intercalation. The combination of ion intercalation with redox reactions of iodine allows for developing rechargeable iodine-carbon batteries free from the unsafe lithium/sodium metals, and hence eliminates the long-standing safety issue. The unique architecture of the hierarchically porous graphitic carbon with heteroatom doping not only provides suitable spaces for both iodine encapsulation and cation intercalation but also generates efficient electronic and ionic transport pathways, thus leading to enhanced performance.Carbon-based electrodes able to intercalate Li + and Na + ions have been exploited for high performing energy storage devices. Here, the authors combine the ion intercalation properties of porous graphitic carbons with the redox chemistry of iodine to produce iodine-carbon batteries with high reversible capacities.

  6. Using advanced surface complexation models for modelling soil chemistry under forests: Solling forest, Germany

    Energy Technology Data Exchange (ETDEWEB)

    Bonten, Luc T.C., E-mail: luc.bonten@wur.nl [Alterra-Wageningen UR, Soil Science Centre, P.O. Box 47, 6700 AA Wageningen (Netherlands); Groenenberg, Jan E. [Alterra-Wageningen UR, Soil Science Centre, P.O. Box 47, 6700 AA Wageningen (Netherlands); Meesenburg, Henning [Northwest German Forest Research Station, Abt. Umweltkontrolle, Sachgebiet Intensives Umweltmonitoring, Goettingen (Germany); Vries, Wim de [Alterra-Wageningen UR, Soil Science Centre, P.O. Box 47, 6700 AA Wageningen (Netherlands)

    2011-10-15

    Various dynamic soil chemistry models have been developed to gain insight into impacts of atmospheric deposition of sulphur, nitrogen and other elements on soil and soil solution chemistry. Sorption parameters for anions and cations are generally calibrated for each site, which hampers extrapolation in space and time. On the other hand, recently developed surface complexation models (SCMs) have been successful in predicting ion sorption for static systems using generic parameter sets. This study reports the inclusion of an assemblage of these SCMs in the dynamic soil chemistry model SMARTml and applies this model to a spruce forest site in Solling Germany. Parameters for SCMs were taken from generic datasets and not calibrated. Nevertheless, modelling results for major elements matched observations well. Further, trace metals were included in the model, also using the existing framework of SCMs. The model predicted sorption for most trace elements well. - Highlights: > Surface complexation models can be well applied in field studies. > Soil chemistry under a forest site is adequately modelled using generic parameters. > The model is easily extended with extra elements within the existing framework. > Surface complexation models can show the linkages between major soil chemistry and trace element behaviour. - Surface complexation models with generic parameters make calibration of sorption superfluous in dynamic modelling of deposition impacts on soil chemistry under nature areas.

  7. Using advanced surface complexation models for modelling soil chemistry under forests: Solling forest, Germany

    International Nuclear Information System (INIS)

    Bonten, Luc T.C.; Groenenberg, Jan E.; Meesenburg, Henning; Vries, Wim de

    2011-01-01

    Various dynamic soil chemistry models have been developed to gain insight into impacts of atmospheric deposition of sulphur, nitrogen and other elements on soil and soil solution chemistry. Sorption parameters for anions and cations are generally calibrated for each site, which hampers extrapolation in space and time. On the other hand, recently developed surface complexation models (SCMs) have been successful in predicting ion sorption for static systems using generic parameter sets. This study reports the inclusion of an assemblage of these SCMs in the dynamic soil chemistry model SMARTml and applies this model to a spruce forest site in Solling Germany. Parameters for SCMs were taken from generic datasets and not calibrated. Nevertheless, modelling results for major elements matched observations well. Further, trace metals were included in the model, also using the existing framework of SCMs. The model predicted sorption for most trace elements well. - Highlights: → Surface complexation models can be well applied in field studies. → Soil chemistry under a forest site is adequately modelled using generic parameters. → The model is easily extended with extra elements within the existing framework. → Surface complexation models can show the linkages between major soil chemistry and trace element behaviour. - Surface complexation models with generic parameters make calibration of sorption superfluous in dynamic modelling of deposition impacts on soil chemistry under nature areas.

  8. The 1-way on-line coupled atmospheric chemistry model system MECO(n – Part 1: Description of the limited-area atmospheric chemistry model COSMO/MESSy

    Directory of Open Access Journals (Sweden)

    A. Kerkweg

    2012-01-01

    Full Text Available The numerical weather prediction model of the Consortium for Small Scale Modelling (COSMO, maintained by the German weather service (DWD, is connected with the Modular Earth Submodel System (MESSy. This effort is undertaken in preparation of a new, limited-area atmospheric chemistry model. Limited-area models require lateral boundary conditions for all prognostic variables. Therefore the quality of a regional chemistry model is expected to improve, if boundary conditions for the chemical constituents are provided by the driving model in consistence with the meteorological boundary conditions. The new developed model is as consistent as possible, with respect to atmospheric chemistry and related processes, with a previously developed global atmospheric chemistry general circulation model: the ECHAM/MESSy Atmospheric Chemistry (EMAC model. The combined system constitutes a new research tool, bridging the global to the meso-γ scale for atmospheric chemistry research. MESSy provides the infrastructure and includes, among others, the process and diagnostic submodels for atmospheric chemistry simulations. Furthermore, MESSy is highly flexible allowing model setups with tailor made complexity, depending on the scientific question. Here, the connection of the MESSy infrastructure to the COSMO model is documented and also the code changes required for the generalisation of regular MESSy submodels. Moreover, previously published prototype submodels for simplified tracer studies are generalised to be plugged-in and used in the global and the limited-area model. They are used to evaluate the TRACER interface implementation in the new COSMO/MESSy model system and the tracer transport characteristics, an important prerequisite for future atmospheric chemistry applications. A supplementary document with further details on the technical implementation of the MESSy interface into COSMO with a complete list of modifications to the COSMO code is provided.

  9. Coral calcifying fluid pH is modulated by seawater carbonate chemistry not solely seawater pH.

    Science.gov (United States)

    Comeau, S; Tambutté, E; Carpenter, R C; Edmunds, P J; Evensen, N R; Allemand, D; Ferrier-Pagès, C; Tambutté, S; Venn, A A

    2017-01-25

    Reef coral calcification depends on regulation of pH in the internal calcifying fluid (CF) in which the coral skeleton forms. However, little is known about calcifying fluid pH (pH CF ) regulation, despite its importance in determining the response of corals to ocean acidification. Here, we investigate pH CF in the coral Stylophora pistillata in seawater maintained at constant pH with manipulated carbonate chemistry to alter dissolved inorganic carbon (DIC) concentration, and therefore total alkalinity (A T ). We also investigate the intracellular pH of calcifying cells, photosynthesis, respiration and calcification rates under the same conditions. Our results show that despite constant pH in the surrounding seawater, pH CF is sensitive to shifts in carbonate chemistry associated with changes in [DIC] and [A T ], revealing that seawater pH is not the sole driver of pH CF Notably, when we synthesize our results with published data, we identify linear relationships of pH CF with the seawater [DIC]/[H + ] ratio, [A T ]/ [H + ] ratio and [[Formula: see text

  10. Molecular-level chemistry of model single-crystal oxide surfaces with model halogenated compounds

    Science.gov (United States)

    Adib, Kaveh

    Synchrotron-based X-ray photoelectron spectroscopy (XPS), temperature-programmed desorption (TPD) and low energy electron diffraction (LEED) have been used to investigate, at a molecular level, the chemistry of different terminations of single crystal iron-oxide surfaces with probe molecules (CCl4 and D2O). Comparisons of the reactivity of these surfaces towards CCl4, indicate that the presence of an uncapped surface Fe cation (strong Lewis acid site) and an adjacent oxygen site capped by that cation can effect the C-Cl bond cleavage in CCl4, resulting in dissociatively adsorbed Cl-adatoms and carbon-containing fragments. If in addition to these sites, an uncapped surface oxygen (Lewis base) site is also available, the carbon-containing moiety can then move that site, coordinate itself with that uncapped oxygen, and stabilize itself. At a later step, the carbon-containing fragment may form a strong covalent bond with the uncapped oxygen and may even abstract that surface oxygen. On the other hand, if an uncapped oxygen is not available to stabilize the carbon-containing fragment, the surface coordination will not occur and upon the subsequent thermal annealing of the surface the Cl-adatoms and the carbon-containing fragments will recombine and desorb as CCl4. Finally, the presence of surface deuteroxyls blocking the strong Lewis acid and base sites of the reactive surface, passivates this surface. Such a deuteroxylated surface will be unreactive towards CCl 4. Such a molecular level understanding of the surface chemistry of metal-oxides will have applications in the areas of selective catalysis, including environmental catalysis, and chemical sensor technology.

  11. Inverse Modeling of Water-Rock-CO2 Batch Experiments: Potential Impacts on Groundwater Resources at Carbon Sequestration Sites.

    Science.gov (United States)

    Yang, Changbing; Dai, Zhenxue; Romanak, Katherine D; Hovorka, Susan D; Treviño, Ramón H

    2014-01-01

    This study developed a multicomponent geochemical model to interpret responses of water chemistry to introduction of CO2 into six water-rock batches with sedimentary samples collected from representative potable aquifers in the Gulf Coast area. The model simulated CO2 dissolution in groundwater, aqueous complexation, mineral reactions (dissolution/precipitation), and surface complexation on clay mineral surfaces. An inverse method was used to estimate mineral surface area, the key parameter for describing kinetic mineral reactions. Modeling results suggested that reductions in groundwater pH were more significant in the carbonate-poor aquifers than in the carbonate-rich aquifers, resulting in potential groundwater acidification. Modeled concentrations of major ions showed overall increasing trends, depending on mineralogy of the sediments, especially carbonate content. The geochemical model confirmed that mobilization of trace metals was caused likely by mineral dissolution and surface complexation on clay mineral surfaces. Although dissolved inorganic carbon and pH may be used as indicative parameters in potable aquifers, selection of geochemical parameters for CO2 leakage detection is site-specific and a stepwise procedure may be followed. A combined study of the geochemical models with the laboratory batch experiments improves our understanding of the mechanisms that dominate responses of water chemistry to CO2 leakage and also provides a frame of reference for designing monitoring strategy in potable aquifers.

  12. An artificial interphase enables reversible magnesium chemistry in carbonate electrolytes

    Energy Technology Data Exchange (ETDEWEB)

    Son, Seoung-Bum; Gao, Tao; Harvey, Steve P.; Steirer, K. Xerxes; Stokes, Adam; Norman, Andrew; Wang, Chunsheng; Cresce, Arthur; Xu, Kang; Ban, Chunmei

    2018-04-02

    Magnesium-based batteries possess potential advantages over their lithium counterparts. However, reversible Mg chemistry requires a thermodynamically stable electrolyte at low potential, which is usually achieved with corrosive components and at the expense of stability against oxidation. In lithium-ion batteries the conflict between the cathodic and anodic stabilities of the electrolytes is resolved by forming an anode interphase that shields the electrolyte from being reduced. This strategy cannot be applied to Mg batteries because divalent Mg2+ cannot penetrate such interphases. Here, we engineer an artificial Mg2+-conductive interphase on the Mg anode surface, which successfully decouples the anodic and cathodic requirements for electrolytes and demonstrate highly reversible Mg chemistry in oxidation-resistant electrolytes. The artificial interphase enables the reversible cycling of a Mg/V2O5 full-cell in the water-containing, carbonate-based electrolyte. This approach provides a new avenue not only for Mg but also for other multivalent-cation batteries facing the same problems, taking a step towards their use in energy-storage applications.

  13. An artificial interphase enables reversible magnesium chemistry in carbonate electrolytes

    Science.gov (United States)

    Son, Seoung-Bum; Gao, Tao; Harvey, Steve P.; Steirer, K. Xerxes; Stokes, Adam; Norman, Andrew; Wang, Chunsheng; Cresce, Arthur; Xu, Kang; Ban, Chunmei

    2018-05-01

    Magnesium-based batteries possess potential advantages over their lithium counterparts. However, reversible Mg chemistry requires a thermodynamically stable electrolyte at low potential, which is usually achieved with corrosive components and at the expense of stability against oxidation. In lithium-ion batteries the conflict between the cathodic and anodic stabilities of the electrolytes is resolved by forming an anode interphase that shields the electrolyte from being reduced. This strategy cannot be applied to Mg batteries because divalent Mg2+ cannot penetrate such interphases. Here, we engineer an artificial Mg2+-conductive interphase on the Mg anode surface, which successfully decouples the anodic and cathodic requirements for electrolytes and demonstrate highly reversible Mg chemistry in oxidation-resistant electrolytes. The artificial interphase enables the reversible cycling of a Mg/V2O5 full-cell in the water-containing, carbonate-based electrolyte. This approach provides a new avenue not only for Mg but also for other multivalent-cation batteries facing the same problems, taking a step towards their use in energy-storage applications.

  14. Inorganic carbon acquisition in potentially toxic and non-toxic diatoms: the effect of pH-induced changes in the seawater carbonate chemistry

    DEFF Research Database (Denmark)

    Trimborn, S; Lundholm, Nina; Thoms, S

    2008-01-01

    . In terms of carbon source, all species took up both CO2 and HCO3-. K-1/2 values for inorganic carbon uptake decreased with increasing pH in two species, while in N. navis-varingica apparent affinities did not change. While the contribution of HCO3- to net fixation was more than 85% in S. stellaris......The effects of pH-induced changes in seawater carbonate chemistry on inorganic carbon (C-i) acquisition and domoic acid (DA) production were studied in two potentially toxic diatom species, Pseudo-nitzschia multiseries and Nitzschia navis-varingica, and the non-toxic Stellarima stellaris. In vivo...... activities of carbonic anhydrase (CA), photosynthetic O-2 evolution and CO2 and HCO3- uptake rates were measured by membrane inlet MS in cells acclimated to low (7.9) and high pH (8.4 or 8.9). Species-specific differences in the mode of carbon acquisition were found. While extracellular carbonic anhydrase (e...

  15. Chemistry of organic carbon in soil with relationship to the global carbon cycle

    International Nuclear Information System (INIS)

    Post, W.M. III.

    1988-01-01

    Various ecosystem disturbances alter the balances between production of organic matter and its decomposition and therefore change the amount of carbon in soil. The most severe perturbation is conversion of natural vegetation to cultivated crops. Conversion of natural vegetation to cultivated crops results in a lowered input of slowly decomposing material which causes a reduction in overall carbon levels. Disruption of soil matrix structure by cultivation leads to lowered physical protection of organic matter resulting in an increased net mineralization rate of soil carbon. Climate change is another perturbation that affects the amount and composition of plant production, litter inputs, and decomposition regimes but does not affect soil structure directly. Nevertheless, large changes in soil carbon storage are probable with anticipated CO 2 induced climate change, particularly in northern latitudes where anticipated climate change will be greatest (MacCracken and Luther 1985) and large amounts of soil organic matter are found. It is impossible, given the current state of knowledge of soil organic matter processes and transformations to develop detailed process models of soil carbon dynamics. Largely phenomenological models appear to be developing into predictive tools for understanding the role of soil organic matter in the global carbon cycle. In particular, these models will be useful in quantifying soil carbon changes due to human land-use and to anticipated global climate and vegetation changes. 47 refs., 7 figs., 2 tabs

  16. Effect of electrochemical treatments on the surface chemistry of activated carbon

    OpenAIRE

    Berenguer Betrián, Raúl; Marco Lozar, Juan Pablo; Quijada Tomás, César; Cazorla Amorós, Diego; Morallón Núñez, Emilia

    2008-01-01

    The effect of the electrochemical treatment (galvanostatic electrolysis in a filter-press electrochemical cell) on the surface chemistry and porous structure of a granular activated carbon (GAC) has been analyzed by means of temperature-programmed desorption and N2 (at 77 K) and CO2 (at 273 K) adsorption isotherms. The anodic and cathodic treatments, the applied current (between 0.2 and 2.0 A) and the type of electrolyte (NaOH, H2SO4 and NaCl)have been studied as electrochemical variables. Bo...

  17. GEOS-5 Chemistry Transport Model User's Guide

    Science.gov (United States)

    Kouatchou, J.; Molod, A.; Nielsen, J. E.; Auer, B.; Putman, W.; Clune, T.

    2015-01-01

    The Goddard Earth Observing System version 5 (GEOS-5) General Circulation Model (GCM) makes use of the Earth System Modeling Framework (ESMF) to enable model configurations with many functions. One of the options of the GEOS-5 GCM is the GEOS-5 Chemistry Transport Model (GEOS-5 CTM), which is an offline simulation of chemistry and constituent transport driven by a specified meteorology and other model output fields. This document describes the basic components of the GEOS-5 CTM, and is a user's guide on to how to obtain and run simulations on the NCCS Discover platform. In addition, we provide information on how to change the model configuration input files to meet users' needs.

  18. Environmental carbonate chemistry selects for phenotype of recently isolated strains of Emiliania huxleyi

    Science.gov (United States)

    Rickaby, Rosalind E. M.; Hermoso, Michaël; Lee, Renee B. Y.; Rae, Benjamin D.; Heureux, Ana M. C.; Balestreri, Cecilia; Chakravarti, Leela; Schroeder, Declan C.; Brownlee, Colin

    2016-05-01

    Coccolithophorid algae, particularly Emiliania huxleyi, are prolific biomineralisers that, under many conditions, dominate communities of marine eukaryotic plankton. Their ability to photosynthesise and form calcified scales (coccoliths) has placed them in a unique position in the global carbon cycle. Contrasting reports have been made with regards to the response of E. huxleyi to ocean acidification. Therefore, there is a pressing need to further determine the fate of this key organism in a rising CO2 world. In this paper, we investigate the phenotype of newly isolated, genetically diverse, strains of E. huxleyi from UK Ocean Acidification Research Programme (UKOA) cruises around the British Isles, the Arctic, and the Southern Ocean. We find a continuum of diversity amongst the physiological and photosynthetic parameters of different strains of E. huxleyi morphotype A under uniform, ambient conditions imposed in the laboratory. This physiology is best explained by adaptation to carbonate chemistry in the former habitat rather than being prescribed by genetic fingerprints such as the coccolithophore morphology motif (CMM). To a first order, the photosynthetic capacity of each strain is a function of both aqueous CO2 availability, and calcification rate, suggestive of a link between carbon concentrating ability and calcification. The calcification rate of each strain is related linearly to the natural environmental [CO32-] at the site of isolation, but a few exceptional strains display low calcification rates at the highest [CO32-] when calcification is limited by low CO2 availability and/or a lack of a carbon concentrating mechanism. We present O2-electrode measurements alongside coccolith oxygen isotopic composition and the uronic acid content (UAC) of the coccolith associated polysaccharide (CAP), that act as indirect tools to show the differing carbon concentrating ability of the strains. The environmental selection revealed amongst our recently isolated strain

  19. Disequilibrium Chemistry in the Solar Nebula and Early Solar System: Implications for the Chemistry of Comets

    Science.gov (United States)

    Fegley, Bruce, Jr.

    1997-12-01

    A growing body of observations demonstrates that comets, like the chondritic meteorites, are disequilibrium assemblages, whose chemistry and molecular composition cannot be explained solely on the basis of models of equilibrium condensation in the solar nebula. These observations include: (1) The coexistence of reduced (e.g., CH4 and organics) and oxidized (e.g., CO, CO2, and H2CO) carbon compounds observed in the gas and dust emitted by comet P/Halley; (2) The coexistence of reduced (e.g., NH3) and oxidized (e.g., N2) nitrogen compounds in the gas emitted by comet P/Halley; (3) The observation of large amounts of formaldehyde in the gas emitted by comet P/Halley (H2CO/H2O approx. 1.5 - 4%) and by comet Machholz (1988j). Formaldehyde would be rapidly destroyed by thermal processing in the solar nebula and must be formed by some disequilibrating process either in the solar nebula or in some presolar environment. (4) The observation of large amounts of the oxidized carbon gases CO and CO2 in comet P/Halley at levels far exceeding those predicted by chemical equilibrium models of solar nebula carbon chemistry. In fact, oxidized carbon gases (CO+ C02 + H2CO) are the most abundant volatile (after water vapor) emitted by comet P/Halley. (5) The observation of HCN, which is not a predicted low temperature condensate in the solar nebula (e.g., Lewis 1972), in comet P/Halley (e.g., Schloerb et al. 1987) and in comet Kohoutek. (6) The observation of S2, which is argued to be a parent molecule vaporized from the nucleus, in comet IRAS-Araki-Alcock (1983d) by A'Hearn et aL (1983) and Feldman et al. (1984). This molecule is not an equilibrium condensate in the solar nebula and must result from disequilibrium chemistry. (7) The deduction that organic grains (C-H-O-N particles) comprise about 30% of the dust emitted by comet P/Halley and that about 75% of the total carbon inventory of Halley is in these grains also implies substantial disequilibrium chemistry. (8) The deductions

  20. Porous structure and surface chemistry of phosphoric acid activated carbon from corncob

    International Nuclear Information System (INIS)

    Sych, N.V.; Trofymenko, S.I.; Poddubnaya, O.I.; Tsyba, M.M.; Sapsay, V.I.; Klymchuk, D.O.; Puziy, A.M.

    2012-01-01

    Highlights: ► Phosphoric acid activation results in formation of carbons with acidic surface groups. ► Maximum amount of surface groups is introduced at impregnation ratio 1.25. ► Phosphoric acid activated carbons show high capacity to copper. ► Phosphoric acid activated carbons are predominantly microporous. ► Maximum surface area and pore volume achieved at impregnation ratio 1.0. - Abstract: Active carbons have been prepared from corncob using chemical activation with phosphoric acid at 400 °C using varied ratio of impregnation (RI). Porous structure of carbons was characterized by nitrogen adsorption and scanning electron microscopy. Surface chemistry was studied by IR and potentiometric titration method. It has been shown that porosity development was peaked at RI = 1.0 (S BET = 2081 m 2 /g, V tot = 1.1 cm 3 /g), while maximum amount of acid surface groups was observed at RI = 1.25. Acid surface groups of phosphoric acid activated carbons from corncob includes phosphate and strongly acidic carboxylic (pK = 2.0–2.6), weakly acidic carboxylic (pK = 4.7–5.0), enol/lactone (pK = 6.7–7.4; 8.8–9.4) and phenol (pK = 10.1–10.7). Corncob derived carbons showed high adsorption capacity to copper, especially at low pH. Maximum adsorption of methylene blue and iodine was observed for carbon with most developed porosity (RI = 1.0).

  1. Porous structure and surface chemistry of phosphoric acid activated carbon from corncob

    Energy Technology Data Exchange (ETDEWEB)

    Sych, N.V.; Trofymenko, S.I.; Poddubnaya, O.I.; Tsyba, M.M. [Institute for Sorption and Endoecology Problems, National Academy of Sciences of Ukraine, 13 General Naumov St., 03164 Kyiv (Ukraine); Sapsay, V.I.; Klymchuk, D.O. [M.G. Kholodny Institute of Botany, National Academy of Sciences of Ukraine, 2 Tereshchenkivska St., 01601 Kyiv (Ukraine); Puziy, A.M., E-mail: alexander.puziy@ispe.kiev.ua [Institute for Sorption and Endoecology Problems, National Academy of Sciences of Ukraine, 13 General Naumov St., 03164 Kyiv (Ukraine)

    2012-11-15

    Highlights: Black-Right-Pointing-Pointer Phosphoric acid activation results in formation of carbons with acidic surface groups. Black-Right-Pointing-Pointer Maximum amount of surface groups is introduced at impregnation ratio 1.25. Black-Right-Pointing-Pointer Phosphoric acid activated carbons show high capacity to copper. Black-Right-Pointing-Pointer Phosphoric acid activated carbons are predominantly microporous. Black-Right-Pointing-Pointer Maximum surface area and pore volume achieved at impregnation ratio 1.0. - Abstract: Active carbons have been prepared from corncob using chemical activation with phosphoric acid at 400 Degree-Sign C using varied ratio of impregnation (RI). Porous structure of carbons was characterized by nitrogen adsorption and scanning electron microscopy. Surface chemistry was studied by IR and potentiometric titration method. It has been shown that porosity development was peaked at RI = 1.0 (S{sub BET} = 2081 m{sup 2}/g, V{sub tot} = 1.1 cm{sup 3}/g), while maximum amount of acid surface groups was observed at RI = 1.25. Acid surface groups of phosphoric acid activated carbons from corncob includes phosphate and strongly acidic carboxylic (pK = 2.0-2.6), weakly acidic carboxylic (pK = 4.7-5.0), enol/lactone (pK = 6.7-7.4; 8.8-9.4) and phenol (pK = 10.1-10.7). Corncob derived carbons showed high adsorption capacity to copper, especially at low pH. Maximum adsorption of methylene blue and iodine was observed for carbon with most developed porosity (RI = 1.0).

  2. Organic chemistry in the atmosphere. [laboratory modeling of Titan atmosphere

    Science.gov (United States)

    Sagan, C.

    1974-01-01

    The existence of an at least moderately complex organic chemistry on Titan is stipulated based on clear evidence of methane, and at least presumptive evidence of hydrogen in its atmosphere. The ratio of methane to hydrogen is the highest of any atmosphere in the solar system. Irradiation of hydrogen/methane mixtures produces aromatic and aliphatic hydrocarbons. A very reasonable hypothesis assumes that the red cloud cover of Titan is made of organic chemicals. Two-carbon hydrocarbons experimentally produced from irradiated mixtures of methane, ammonia, water, and hydrogen bear out the possible organic chemistry of the Titanian environment.

  3. A four-dimensional variational chemistry data assimilation scheme for Eulerian chemistry transport modeling

    Science.gov (United States)

    Eibern, Hendrik; Schmidt, Hauke

    1999-08-01

    The inverse problem of data assimilation of tropospheric trace gas observations into an Eulerian chemistry transport model has been solved by the four-dimensional variational technique including chemical reactions, transport, and diffusion. The University of Cologne European Air Pollution Dispersion Chemistry Transport Model 2 with the Regional Acid Deposition Model 2 gas phase mechanism is taken as the basis for developing a full four-dimensional variational data assimilation package, on the basis of the adjoint model version, which includes the adjoint operators of horizontal and vertical advection, implicit vertical diffusion, and the adjoint gas phase mechanism. To assess the potential and limitations of the technique without degrading the impact of nonperfect meteorological analyses and statistically not established error covariance estimates, artificial meteorological data and observations are used. The results are presented on the basis of a suite of experiments, where reduced records of artificial "observations" are provided to the assimilation procedure, while other "data" is retained for performance control of the analysis. The paper demonstrates that the four-dimensional variational technique is applicable for a comprehensive chemistry transport model in terms of computational and storage requirements on advanced parallel platforms. It is further shown that observed species can generally be analyzed, even if the "measurements" have unbiased random errors. More challenging experiments are presented, aiming to tax the skill of the method (1) by restricting available observations mostly to surface ozone observations for a limited assimilation interval of 6 hours and (2) by starting with poorly chosen first guess values. In this first such application to a three-dimensional chemistry transport model, success was also achieved in analyzing not only observed but also chemically closely related unobserved constituents.

  4. Surface chemistry of first wall materials - From fundamental data to modeling

    International Nuclear Information System (INIS)

    Linsmeier, Ch.; Reinelt, M.; Schmid, K.

    2011-01-01

    The application of different materials at the first wall of fusion devices, like beryllium, carbon, and tungsten in the case of ITER, unavoidably leads to the formation of compounds. These compounds are created dynamically during operation and depend on the local parameters like surface temperature, incoming particle energies and species. In dedicated, well-defined laboratory experiments, using mainly X-ray photoelectron spectroscopy and Rutherford backscattering analysis for qualitative and quantitative chemical surface analysis, the parameter space in relevant element combinations are investigated. These studies lead to a deep understanding of the reaction mechanisms under the applied conditions and to a quantitative description of reaction and diffusion processes. These data can be parameterized and integrated into a modeling approach which combines dynamic surface chemistry with the modeling of the transport in the plasma. Two different approaches for surface reaction modeling are compared and benchmarked with experimental data.

  5. OBSERVATIONS OF WARM CARBON CHAIN CHEMISTRY IN NGC 3576

    Energy Technology Data Exchange (ETDEWEB)

    Saul, M. [School of Physics, University of New South Wales, Sydney, NSW 2052 (Australia); Tothill, N. F. H. [Faculty of Computing, Engineering and Mathematics, University of Western Sydney, Locked Bag 1797, Penrith South DC, NSW 1797 (Australia); Purcell, C. R., E-mail: msaul@phys.unsw.edu.au, E-mail: n.tothill@uws.edu.au, E-mail: Cormac.Purcell@sydney.edu.au [Institute for Astronomy, University of Sydney, Sydney, NSW 2006 (Australia)

    2015-01-01

    We report observations of warm carbon chain chemistry (WCCC) in NGC 3576, including high angular resolution imaging of an ionization source candidate and the first detection of C{sub 5}H in a massive star-forming region. In order to investigate the environment associated with birthline emergence, we ask how observed chemical conditions relate to Class 0/1 core differentiation: a systemic shift in peak position between species correlates with giant molecular cloud core gradients in turbulence and age. Emission in several molecular lines including HC{sub 3}N (11-10), NH{sub 3} (1, 1), and C{sub 5}H supports the G291.3-0.7 ionization front—transitional pre-main-sequence core interaction regulating the WCCC environment.

  6. LOSCAR: Long-term Ocean-atmosphere-Sediment CArbon cycle Reservoir Model v2.0.4

    Directory of Open Access Journals (Sweden)

    R. E. Zeebe

    2012-01-01

    Full Text Available The LOSCAR model is designed to efficiently compute the partitioning of carbon between ocean, atmosphere, and sediments on time scales ranging from centuries to millions of years. While a variety of computationally inexpensive carbon cycle models are already available, many are missing a critical sediment component, which is indispensable for long-term integrations. One of LOSCAR's strengths is the coupling of ocean-atmosphere routines to a computationally efficient sediment module. This allows, for instance, adequate computation of CaCO3 dissolution, calcite compensation, and long-term carbon cycle fluxes, including weathering of carbonate and silicate rocks. The ocean component includes various biogeochemical tracers such as total carbon, alkalinity, phosphate, oxygen, and stable carbon isotopes. LOSCAR's configuration of ocean geometry is flexible and allows for easy switching between modern and paleo-versions. We have previously published applications of the model tackling future projections of ocean chemistry and weathering, pCO2 sensitivity to carbon cycle perturbations throughout the Cenozoic, and carbon/calcium cycling during the Paleocene-Eocene Thermal Maximum. The focus of the present contribution is the detailed description of the model including numerical architecture, processes and parameterizations, tuning, and examples of input and output. Typical CPU integration times of LOSCAR are of order seconds for several thousand model years on current standard desktop machines. The LOSCAR source code in C can be obtained from the author by sending a request to loscar.model@gmail.com.

  7. A comparison of atmospheric composition using the Carbon Bond and Regional Atmospheric Chemistry Mechanisms

    Directory of Open Access Journals (Sweden)

    G. Sarwar

    2013-10-01

    Full Text Available We incorporate the recently developed Regional Atmospheric Chemistry Mechanism (version 2, RACM2 into the Community Multiscale Air Quality modeling system for comparison with the existing 2005 Carbon Bond mechanism with updated toluene chemistry (CB05TU. Compared to CB05TU, RACM2 enhances the domain-wide monthly mean hydroxyl radical concentrations by 46% and nitric acid by 26%. However, it reduces hydrogen peroxide by 2%, peroxyacetic acid by 94%, methyl hydrogen peroxide by 19%, peroxyacetyl nitrate by 40%, and organic nitrate by 41%. RACM2 enhances ozone compared to CB05TU at all ambient levels. Although it exhibited greater overestimates at lower observed concentrations, it displayed an improved performance at higher observed concentrations. The RACM2 ozone predictions are also supported by increased ozone production efficiency that agrees better with observations. Compared to CB05TU, RACM2 enhances the domain-wide monthly mean sulfate by 10%, nitrate by 6%, ammonium by 10%, anthropogenic secondary organic aerosols by 42%, biogenic secondary organic aerosols by 5%, and in-cloud secondary organic aerosols by 7%. Increased inorganic and organic aerosols with RACM2 agree better with observed data. Any air pollution control strategies developed using the two mechanisms do not differ appreciably.

  8. High fidelity chemistry and radiation modeling for oxy -- combustion scenarios

    Science.gov (United States)

    Abdul Sater, Hassan A.

    To account for the thermal and chemical effects associated with the high CO2 concentrations in an oxy-combustion atmosphere, several refined gas-phase chemistry and radiative property models have been formulated for laminar to highly turbulent systems. This thesis examines the accuracies of several chemistry and radiative property models employed in computational fluid dynamic (CFD) simulations of laminar to transitional oxy-methane diffusion flames by comparing their predictions against experimental data. Literature review about chemistry and radiation modeling in oxy-combustion atmospheres considered turbulent systems where the predictions are impacted by the interplay and accuracies of the turbulence, radiation and chemistry models. Thus, by considering a laminar system we minimize the impact of turbulence and the uncertainties associated with turbulence models. In the first section of this thesis, an assessment and validation of gray and non-gray formulations of a recently proposed weighted-sum-of-gray gas model in oxy-combustion scenarios was undertaken. Predictions of gas, wall temperatures and flame lengths were in good agreement with experimental measurements. The temperature and flame length predictions were not sensitive to the radiative property model employed. However, there were significant variations between the gray and non-gray model radiant fraction predictions with the variations in general increasing with decrease in Reynolds numbers possibly attributed to shorter flames and steeper temperature gradients. The results of this section confirm that non-gray model predictions of radiative heat fluxes are more accurate than gray model predictions especially at steeper temperature gradients. In the second section, the accuracies of three gas-phase chemistry models were assessed by comparing their predictions against experimental measurements of temperature, species concentrations and flame lengths. The chemistry was modeled employing the Eddy

  9. The link between physics and chemistry in track modelling

    International Nuclear Information System (INIS)

    Green, N.J.B.; Bolton, C.E.; Spencer-Smith, R.D.

    1999-01-01

    The physical structure of a radiation track provides the initial conditions for the modelling of radiation chemistry. These initial conditions are not perfectly understood, because there are important gaps between what is provided by a typical track structure model and what is required to start the chemical model. This paper addresses the links between the physics and chemistry of tracks, with the intention of identifying those problems that need to be solved in order to obtain an accurate picture of the initial conditions for the purposes of modelling chemistry. These problems include the reasons for the increased yield of ionisation relative to homolytic bond breaking in comparison with the gas phase. A second area of great importance is the physical behaviour of low-energy electrons in condensed matter (including thermolisation and solvation). Many of these processes are not well understood, but they can have profound effects on the transient chemistry in the track. Several phenomena are discussed, including the short distance between adjacent energy loss events, the molecular nature of the underlying medium, dissociative attachment resonances and the ability of low-energy electrons to excite optically forbidden molecular states. Each of these phenomena has the potential to modify the transient chemistry substantially and must therefore be properly characterised before the physical model of the track can be considered to be complete. (orig.)

  10. Tunable Luminescent Carbon Nanospheres with Well-Defined Nanoscale Chemistry for Synchronized Imaging and Therapy.

    Science.gov (United States)

    Mukherjee, Prabuddha; Misra, Santosh K; Gryka, Mark C; Chang, Huei-Huei; Tiwari, Saumya; Wilson, William L; Scott, John W; Bhargava, Rohit; Pan, Dipanjan

    2015-09-01

    In this work, we demonstrate the significance of defined surface chemistry in synthesizing luminescent carbon nanomaterials (LCN) with the capability to perform dual functions (i.e., diagnostic imaging and therapy). The surface chemistry of LCN has been tailored to achieve two different varieties: one that has a thermoresponsive polymer and aids in the controlled delivery of drugs, and the other that has fluorescence emission both in the visible and near-infrared (NIR) region and can be explored for advanced diagnostic modes. Although these particles are synthesized using simple, yet scalable hydrothermal methods, they exhibit remarkable stability, photoluminescence and biocompatibility. The photoluminescence properties of these materials are tunable through careful choice of surface-passivating agents and can be exploited for both visible and NIR imaging. Here the synthetic strategy demonstrates the possibility to incorporate a potent antimetastatic agent for inhibiting melanomas in vitro. Since both particles are Raman active, their dispersion on skin surface is reported with Raman imaging and utilizing photoluminescence, their depth penetration is analysed using fluorescence 3D imaging. Our results indicate a new generation of tunable carbon-based probes for diagnosis, therapy or both. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    Science.gov (United States)

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

    2017-07-01

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

  12. Carbon-11 and fluorine-18 chemistry devoted to molecular probes for imaging the brain with positron emission tomography.

    Science.gov (United States)

    Dollé, Frédéric

    2013-01-01

    Exploration of the living human brain in real-time and in a noninvasive way was for centuries only a dream, made, however, possible today with the remarkable development during the four last decades of powerful molecular imaging techniques, and especially positron emission tomography (PET). Molecular PET imaging relies, from a chemical point of view, on the use and preparation of a positron-emitting radiolabelled probe or radiotracer, notably compounds incorporating one of two short-lived radionuclides fluorine-18 (T1/2 : 109.8 min) and carbon-11 (T1/2 : 20.38 min). The growing availability and interest for the radiohalogen fluorine-18 in radiopharmaceutical chemistry undoubtedly results from its convenient half-life and the successful use in clinical oncology of 2-[(18) F]fluoro-2-deoxy-d-glucose ([(18) F]FDG). The special interest of carbon-11 is not only that carbon is present in virtually all biomolecules and drugs allowing therefore for isotopic labelling of their chemical structures but also that a given molecule could be radiolabelled at different functions or sites, permitting to explore (or to take advantage of) in vivo metabolic pathways. PET chemistry includes production of these short-lived radioactive isotopes via nuclear transmutation reactions using a cyclotron, and is directed towards the development of rapid synthetic methods, at the trace level, for the introduction of these nuclides into a molecule, as well as the use of fast purification, analysis and formulation techniques. PET chemistry is the driving force in molecular PET imaging, and this special issue of the Journal of Labelled Compounds and Radiopharmaceuticals, which is strongly chemistry and radiochemistry-oriented, aims at illustrating, be it in part only, the state-of-the-art arsenal of reactions currently available and its potential for the research and development of specific molecular probes labelled with the positron emitters carbon-11 and fluorine-18, with optimal imaging

  13. Modeling UTLS water vapor: Transport/Chemistry interactions

    International Nuclear Information System (INIS)

    Gulstad, Line

    2005-01-01

    This thesis was initially meant to be a study on the impact on chemistry and climate from UTLS water vapor. However, the complexity of the UTLS water vapor and its recent changes turned out to be a challenge by it self. In the light of this, the overall motivation for the thesis became to study the processes controlling UTLS water vapor and its changes. Water vapor is the most important greenhouse gas, involved in important climate feedback loops. Thus, a good understanding of the chemical and dynamical behavior of water vapor in the atmosphere is crucial for understanding the climate changes in the last century. Additionally, parts of the work was motivated by the development of a coupled climate chemistry model based on the CAM3 model coupled with the Chemical Transport Model Oslo CTM2. The future work will be concentrated on the UTLS water vapor impact on chemistry and climate. We are currently studying long term trends in UTLS water vapor, focusing on identification of the different processes involved in the determination of such trends. The study is based on natural as well as anthropogenic climate forcings. The ongoing work on the development of a coupled climate chemistry model will continue within our group, in collaboration with Prof. Wei-Chyung Wang at the State University of New York, Albany. Valuable contacts with observational groups are established during the work on this thesis. These collaborations will be continued focusing on continuous model validation, as well as identification of trends and new features in UTLS water vapor, and other tracers in this region. (Author)

  14. Carbonate Chemistry and Isotope Characteristics of Groundwater of Ljubljansko Polje and Ljubljansko Barje Aquifers in Slovenia

    Directory of Open Access Journals (Sweden)

    Sonja Cerar

    2013-01-01

    Full Text Available Ljubljansko polje and Ljubljansko Barje aquifers are the main groundwater resources for the needs of Ljubljana, the capital of Slovenia. Carbonate chemistry and isotope analysis of the groundwater were performed to acquire new hydrogeological data, which should serve as a base for improvement of hydrogeological conceptual models of both aquifers. A total of 138 groundwater samples were collected at 69 sampling locations from both aquifers. Major carbonate ions and the stable isotope of oxygen were used to identify differences in the recharging areas of aquifers. Four groups of groundwater were identified: (1 Ljubljansko polje aquifer, with higher Ca2+ values, as limestone predominates in its recharge area, (2 northern part of Ljubljansko Barje aquifer, with prevailing dolomite in its recharge area, (3 central part of Ljubljansko Barje aquifer, which lies below surface cover of impermeable clay and is poor in carbonate, and (4 Brest and Iški vršaj aquifer in the southern part of Ljubljansko Barje with higher Mg2+ in groundwater and dolomite prevailing in its recharge area. The radioactive isotope tritium was also used to estimate the age of groundwater. Sampled groundwater is recent with tritium activity between 4 and 8 TU and residence time of up to 10 years.

  15. Carbon Chemistry in Transitional Clouds from the GOT C+ Survey of CII 158 micron Emission in the Galactic Plane

    Science.gov (United States)

    Langer, W. D.; Velusamy, T.; Pineda, J.; Willacy, K.; Goldsmith, P. F.

    2011-05-01

    In understanding the lifecycle and chemistry of the interstellar gas, the transition from diffuse atomic to molecular gas clouds is a very important stage. The evolution of carbon from C+ to C0 and CO is a fundamental part of this transition, and C+ along with its carbon chemistry is a key diagnostic. Until now our knowledge of interstellar gas has been limited primarily to the diffuse atomic phase traced by HI and the dense molecular H2 phase traced by CO. However, we have generally been missing an important layer in diffuse and transition clouds, which is denoted by the warm "dark gas'', that is mostly H2 and little HI and CO, and is best traced with C+. Here, we discuss the chemistry in the transition from C+ to C0 and CO in these clouds as understood by a survey of the CII 1.9 THz (158 micron) line from a sparse survey of the inner galaxy over about 40 degrees in longitude as part of the Galactic Observations of Terahertz C+ (GOT C+) program, a Herschel Space Observatory Open Time Key Program to study interstellar clouds by sampling ionized carbon. Using the first results from GOT C+ along 11 LOSs, in a sample of 53 transition clouds, Velusamy, Langer et al. (A&A 521, L18, 2010) detected an excess of CII intensities indicative of a thick H2 layer (a significant warm H2, "dark gas'' component) around the 12CO core. Here we present a much larger, statistically significant sample of a few hundred diffuse and transition clouds traced by CII, along with auxiliary HI and CO data in the inner Galaxy between l=-30° and +30°. Our new and more extensive sample of transition clouds is used to elucidate the time dependent physical and carbon chemical evolution of diffuse to transition clouds, and transition layers. We consider the C+ to CO conversion pathways such as H++ O and C+ + H2 chemistry for CO production to constrain the physical parameters such as the FUV intensity and cosmic ray ionization rate that drive the CO chemistry in the diffuse transition clouds.

  16. Structure and chemistry of model catalysts in ultrahigh vacuum

    Science.gov (United States)

    Walker, Joshua D.

    The study of catalysis is a key area of focus not only in the industrial sector but also in the nature and biological systems. The market for catalysis is a multi-billion dollar industry. Many of the materials and products we use on a daily basis are formed through a catalytic process. The quest to understanding and improving catalytic mechanisms is ongoing. Many model catalysts use transition metals as a support for chemical reactions to take place due to their selectivity and activity. Palladium, gold, and copper metals are studied in this work and show the ability to be catalytically reactive. It is important to understand the characteristics and properties of these surfaces. A well-known example of catalysis is the conversion of carbon monoxide (CO), a very harmful gas to carbon dioxide (CO2) which is less harmful. This reaction is mainly seen in the automotive industry. This reaction is investigated in this work on a Au(111) single crystal, which is normally inert but becomes reactivity with the adsorption of oxygen on the surface. Temperature Programmed Desorption (TPD) is used to understand some of the chemistry and effects with and without the addition of H2O. The oxidation of CO is shown to be enhanced by the addition of water, but warrants further analysis too fully understand the different mechanisms and reaction pathways existing. The field of nano-electronics is rapidly growing as technology continues to challenge scientists to create innovative ideas. The trend to produce smaller electronic products is increasing as consumer demands persist. It has been shown previously that 1,4-phenlyene diisocyanobenzene (1,4-PDI) on Au(111) react to form one-dimensional oligomer chains comprising alternating gold and 1,4-PDI units on the Au(111) surface. A similar compound 1,3-phenlyene diisocyanobenzene (1,3-PDI) was studied in order to investigate whether the oligomerization found for 1,4-PDI is a general phenomenon and to ultimately explore the effect of

  17. Influence of surface chemistry of carbon materials on their interactions with inorganic nitrogen contaminants in soil and water.

    Science.gov (United States)

    Sumaraj; Padhye, Lokesh P

    2017-10-01

    Inorganic nitrogen contaminants (INC) (NH 4 + , NO 3 - , NO 2 - , NH 3 , NO, NO 2 , and N 2 O) pose a growing risk to the environment, and their remediation methods are highly sought after. Application of carbon materials (CM), such as biochar and activated carbon, to remediate INC from agricultural fields and wastewater treatment plants has gained a significant interest since past few years. Understanding the role of surface chemistry of CM in adsorption of various INC is highly critical to increase adsorption efficiency as well as to assess the long term impact of using these highly recalcitrant CM for remediation of INC. Critical reviews of adsorption studies related to INC have revealed that carbon surface chemistry (surface functional groups, pH, Eh, elemental composition, and mineral content) has significant influence on adsorption of INC. Compared to basic functional groups, oxygen containing surface functional groups have been found to be more influential for adsorption of INC. However, basic sites on carbon materials still play an important role in chemisorption of anionic INC. Apart from surface functional groups, pH, Eh and pH zpc of CM and elemental and mineral composition of its surface are important properties capable of altering INC interactions with CM. This review summarizes our current understanding of INC interactions with CM's surface through the known chemisorption mechanisms: electrostatic interaction, hydrogen bonding, electron donor-acceptor mechanism, hydrophobic and hydrophilic interaction, chemisorption aided by minerals, and interactions influenced by pH and elemental composition. Change in surface chemistry of CM in soil during aging is also discussed. Copyright © 2017 Elsevier Ltd. All rights reserved.

  18. Evaluation of Preindustrial to Present-day Black Carbon and its Albedo Forcing from Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP)

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Y. H.; Lamarque, J.-F.; Flanner, M. G.; Jiao, C.; Shindell, Drew; Berntsen, T.; Bisiauxs, M.; Cao, J.; Collins, W. J.; Curran, M.; Edwards, R.; Faluvegi, G.; Ghan, Steven J.; Horowitz, L.; McConnell, J.R.; Ming, J.; Myhre, G.; Nagashima, T.; Naik, Vaishali; Rumbold, S.; Skeie, R. B.; Sudo, K.; Takemura, T.; Thevenon, F.; Xu, B.; Yoon, Jin-Ho

    2013-03-05

    As a part of the Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP), we evaluate the historical black carbon (BC) aerosols simulated by 8 ACCMIP models against the observations including 12 ice core records, a long-term surface mass concentrations and recent Arctic BC snowpack measurements. We also estimate BC albedo forcing by performing additional simulations using the NCAR Community Land and Sea-Ice model 4 with prescribed meteorology from 1996-2000, which includes the SNICAR BC-snow model. We evaluated the vertical profile of BC snow concentrations from these offline simulations to using recent BC snowpack measurements. Despite using the same BC emissions, global BC burden differs by approximately a factor of 3 among models due to the differences in aerosol removal parameterizations and simulated meteorology among models; 34 Gg to 103 Gg in 1850 and 82 Gg to 315 Gg in 2000. However,models agree well on 2.5~3 times increase in the global BC burden from preindustrial to present-day, which matches with the 2.5 times increase in BC emissions. We find a large model diversity at both NH and SH high latitude regions for BC burden and at SH high latitude regions for deposition fluxes. The ACCMIP simulations match the observed BC mass concentrations well in Europe and North America except at Jungfrauch and Ispra. However, the models fail to capture the Arctic BC seasonality due tosevere underestimations during winter and spring. Compared to recent snowpack measurements, the simulated vertically resolved BC snow concentrations are, on average, within a factor of 2-3 of observations except for Greenland and Arctic Ocean. However, model and observation differ widely due to missing interannual variations in emissions and possibly due to the choice of the prescribed meteorology period (i.e., 1996-2000).

  19. Chemistry education based on concepts represented by mental models

    OpenAIRE

    Gibin, Gustavo Bizarria; Ferreira, Luiz Henrique

    2010-01-01

    The current legislation determines that the chemist must have a solid comprehension about chemical concepts. Literature presents the concept of mental model, which is determinant to the learning of phenomena and concepts. This paper presents some mental models that students of the Chemistry course at UFSCar have about chemical concepts. A lot of incoherence was observed in student's mental models, which is an evidence that there are problems in the learning of chemistry education.

  20. Reactive transport modelling of groundwater chemistry in a chalk aquifer at the watershed scale.

    Science.gov (United States)

    Mangeret, A; De Windt, L; Crançon, P

    2012-09-01

    This study investigates thermodynamics and kinetics of water-rock interactions in a carbonate aquifer at the watershed scale. A reactive transport model is applied to the unconfined chalk aquifer of the Champagne Mounts (France), by considering both the chalk matrix and the interconnected fracture network. Major element concentrations and main chemical parameters calculated in groundwater and their evolution along flow lines are in fair agreement with field data. A relative homogeneity of the aquifer baseline chemistry is rapidly reached in terms of pH, alkalinity and Ca concentration since calcite equilibrium is achieved over the first metres of the vadose zone. However, incongruent chalk dissolution slowly releases Ba, Mg and Sr in groundwater. Introducing dilution effect by rainwater infiltration and a local occurrence of dolomite improves the agreement between modelling and field data. The dissolution of illite and opal-CT, controlling K and SiO(2) concentrations in the model, can be approximately tackled by classical kinetic rate laws, but not the incongruent chalk dissolution. An apparent kinetic rate has therefore been fitted on field data by inverse modelling: 1.5×10(-5) mol(chalk)L (-1) water year (-1). Sensitivity analysis indicates that the CO(2) partial pressure of the unsaturated zone is a critical parameter for modelling the baseline chemistry over the whole chalk aquifer. Copyright © 2012 Elsevier B.V. All rights reserved.

  1. PEGylation of carbon nanotubes via mussel inspired chemistry: Preparation, characterization and biocompatibility evaluation

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Xiaoyong; Zeng, Guangjian; Tian, Jianwen; Wan, Qing; Huang, Qiang [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Wang, Ke; Zhang, Qingsong [Department of Chemistry and the Tsinghua Center for Frontier Polymer Research, Tsinghua University, Beijing 100084 (China); Liu, Meiying; Deng, Fengjie [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang 330031 (China); Wei, Yen, E-mail: xiaoyongzhang1980@gmail.com [Department of Chemistry and the Tsinghua Center for Frontier Polymer Research, Tsinghua University, Beijing 100084 (China)

    2015-10-01

    Graphical abstract: Water dispersible and biocompatible PEGylated carbon nanotubes were prepared via a novel mussel inspired strategy for the first time. - Highlights: • Surface modification of CNTs via bioinspired chemistry. • CNTs with high water dispersibility and excellent biocompatibility. • PEGytion of CNTs via Michael addition reaction. • Preparation of aminated PEG molecules via chain transfer polymerization. - Abstract: A novel strategy for surface modification of multi-walled carbon nanotubes (MWCNT) was developed via combination of mussel inspired chemistry and Michael addition reaction. In this procedure, pristine MWCNT were first coated with polydopamine (PDA) through self polymerization of dopamine. The PDA functionalized CNT (CNT-PDA) were further functionalized with amino-terminated polymers (polyPEGMA), which were synthesized via free radical polymerization using cysteamine hydrochloride as the chain transfer agent and poly(ethylene glycol) monomethyl ether methacylate as the monomer. The successful modification of CNT was ascertained by a series of characterization techniques including transmission electron microscopy, Fourier transform infrared spectroscopy, thermal gravimetric analysis and X-ray photoelectron spectrometry. The polymer modified CNT showed enhanced dispersibility in aqueous and organic solution. Cytotoxicity evaluation of polymers modified CNT showed that these modified CNT are biocompatible with cells. Finally, due to the universal adhesive of PDA and chain transfer free radical polymerization, this strategy developed in this work can also be extended for surface modification of many other nanomaterials with different functional polymers.

  2. A Conceptual Model for Projecting Coccolithophorid Growth, Calcification and Photosynthetic Carbon Fixation Rates in Response to Global Ocean Change

    Directory of Open Access Journals (Sweden)

    Natasha A. Gafar

    2018-01-01

    Full Text Available Temperature, light and carbonate chemistry all influence the growth, calcification and photosynthetic rates of coccolithophores to a similar degree. There have been multiple attempts to project the responses of coccolithophores to changes in carbonate chemistry, but the interaction with light and temperature remains elusive. Here we devise a simple conceptual model to derive a fit equation for coccolithophorid growth, photosynthetic and calcification rates in response to simultaneous changes in carbonate chemistry, temperature and light conditions. The fit equation is able to account for up to 88% of the variability in measured metabolic rates. Equation projections indicate that temperature, light and carbonate chemistry all have different modulating effects on both optimal growth conditions and the sensitivity of responses to extreme environmental conditions. Calculations suggest that a single extreme environmental condition (CO2, temperature, light will reduce maximum rates regardless of how optimal the other environmental conditions may be. Thus, while the response of coccolithophores to ocean change depends on multiple variables, the one which is least optimal will have the most impact on overall rates. Finally, responses to ocean change are usually reported in terms of cellular rates. However, changes in cellular rates can be a poor predictor for assessing changes in production at the community level. We therefore introduce a new metric, the calcium carbonate production potential (CCPP, which combines the independent effects of changes in growth rate and cellular calcium carbonate content to assess how environmental changes will impact coccolith production. Direct comparison of CO2 impacts on cellular CaCO3 production rates and CCPP shows that while the former is still at 45% of its pre-industrial capacity at 1,000 μatm, the latter is reduced to 10%.

  3. Chemistry Teachers' Knowledge and Application of Models

    Science.gov (United States)

    Wang, Zuhao; Chi, Shaohui; Hu, Kaiyan; Chen, Wenting

    2014-01-01

    Teachers' knowledge and application of model play an important role in students' development of modeling ability and scientific literacy. In this study, we investigated Chinese chemistry teachers' knowledge and application of models. Data were collected through test questionnaire and analyzed quantitatively and qualitatively. The result indicated…

  4. he Impact of Primary Marine Aerosol on Atmospheric Chemistry, Radiation and Climate: A CCSM Model Development Study

    Energy Technology Data Exchange (ETDEWEB)

    Keene, William C. [University of Virginia; Long, Michael S. [University of Virginia

    2013-05-20

    This project examined the potential large-scale influence of marine aerosol cycling on atmospheric chemistry, physics and radiative transfer. Measurements indicate that the size-dependent generation of marine aerosols by wind waves at the ocean surface and the subsequent production and cycling of halogen-radicals are important but poorly constrained processes that influence climate regionally and globally. A reliable capacity to examine the role of marine aerosol in the global-scale atmospheric system requires that the important size-resolved chemical processes be treated explicitly. But the treatment of multiphase chemistry across the breadth of chemical scenarios encountered throughout the atmosphere is sensitive to the initial conditions and the precision of the solution method. This study examined this sensitivity, constrained it using high-resolution laboratory and field measurements, and deployed it in a coupled chemical-microphysical 3-D atmosphere model. First, laboratory measurements of fresh, unreacted marine aerosol were used to formulate a sea-state based marine aerosol source parameterization that captured the initial organic, inorganic, and physical conditions of the aerosol population. Second, a multiphase chemical mechanism, solved using the Max Planck Institute for Chemistry's MECCA (Module Efficiently Calculating the Chemistry of the Atmosphere) system, was benchmarked across a broad set of observed chemical and physical conditions in the marine atmosphere. Using these results, the mechanism was systematically reduced to maximize computational speed. Finally, the mechanism was coupled to the 3-mode modal aerosol version of the NCAR Community Atmosphere Model (CAM v3.6.33). Decadal-scale simulations with CAM v.3.6.33, were run both with and without reactive-halogen chemistry and with and without explicit treatment of particulate organic carbon in the marine aerosol source function. Simulated results were interpreted (1) to evaluate influences

  5. ECHMERIT: A new on-line global mercury-chemistry model

    Science.gov (United States)

    Jung, G.; Hedgecock, I. M.; Pirrone, N.

    2009-04-01

    Mercury is a volatile metal, that is of concern because when deposited and transformed to methylmercury accumulates within the food-web. Due to the long lifetime of elemental mercury, which is the dominant fraction of mercury species in the atmosphere, mercury is prone to long-range transport and therefore distributed over the globe, transported and hence deposited even in regions far from anthropogenic emission sources. Mercury is released to the atmosphere from a variety of natural and anthropogenic sources, in elementary and oxidised forms, and as particulate mercury. It is then transported, but also transformed chemically in the gaseous phase, as well as in aqueous phase within cloud and rain droplets. Mercury (particularly its oxidised forms) is removed from the atmosphere though wet and dry deposition processes, a large fraction of deposited mercury is, after chemical or biological reduction, re-emitted to the atmosphere as elementary mercury. To investigate mercury chemistry and transport processes on the global scale, the new, global model ECHMERIT has been developed. ECHMERIT simulates meteorology, transport, deposition, photolysis and chemistry on-line. The general circulation model on which ECHMERIT is based is ECHAM5. Sophisticated chemical modules have been implemented, including gas phase chemistry based on the CBM-Z chemistry mechanism, as well as aqueous phase chemistry, both of which have been adapted to include Hg chemistry and Hg species gas-droplet mass transfer. ECHMERIT uses the fast-J photolysis routine. State-of-the-art procedures simulating wet and dry deposition and emissions were adapted and included in the model as well. An overview of the model structure, development, validation and sensitivity studies is presented.

  6. Geochemical modelling of CO2-water-rock interactions for carbon storage : data requirements and outputs

    International Nuclear Information System (INIS)

    Kirste, D.

    2008-01-01

    A geochemical model was used to predict the short-term and long-term behaviour of carbon dioxide (CO 2 ), formation water, and reservoir mineralogy at a carbon sequestration site. Data requirements for the geochemical model included detailed mineral petrography; formation water chemistry; thermodynamic and kinetic data for mineral phases; and rock and reservoir physical characteristics. The model was used to determine the types of outputs expected for potential CO 2 storage sites and natural analogues. Reaction path modelling was conducted to determine the total reactivity or CO 2 storage capability of the rock by applying static equilibrium and kinetic simulations. Potential product phases were identified using the modelling technique, which also enabled the identification of the chemical evolution of the system. Results of the modelling study demonstrated that changes in porosity and permeability over time should be considered during the site selection process.

  7. Chemistry in an evolving protoplanetary disk: Effects on terrestrial planet composition

    International Nuclear Information System (INIS)

    Moriarty, John; Fischer, Debra; Madhusudhan, Nikku

    2014-01-01

    The composition of planets is largely determined by the chemical and dynamical evolution of the disk during planetesimal formation and growth. To predict the diversity of exoplanet compositions, previous works modeled planetesimal composition as the equilibrium chemical composition of a protoplanetary disk at a single time. However, planetesimals form over an extended period of time, during which elements sequentially condense out of the gas as the disk cools and are accreted onto planetesimals. To account for the evolution of the disk during planetesimal formation, we couple models of disk chemistry and dynamics with a prescription for planetesimal formation. We then follow the growth of these planetesimals into terrestrial planets with N-body simulations of late-stage planet formation to evaluate the effect of sequential condensation on the bulk composition of planets. We find that our model produces results similar to those of earlier models for disks with C/O ratios close to the solar value (0.54). However, in disks with C/O ratios greater than 0.8, carbon-rich planetesimals form throughout a much larger radial range of the disk. Furthermore, our model produces carbon-rich planetesimals in disks with C/O ratios as low as ∼0.65, which is not possible in the static equilibrium chemistry case. These results suggest that (1) there may be a large population of short-period carbon-rich planets around moderately carbon-enhanced stars (0.65 < C/O < 0.8) and (2) carbon-rich planets can form throughout the terrestrial planet region around carbon-rich stars (C/O > 0.8).

  8. Constraining Phosphorus Chemistry in Carbon- and Oxygen-Rich Circumstellar Envelopes: Observations of PN, HCP, and CP

    Science.gov (United States)

    Milam, S. N.; Halfen, D. T.; Tenenbaum, E. D.; Apponi, A. J.; Woolf, N. J.; Ziurys, L. M.

    2008-09-01

    Millimeter-wave observations of PN, CP, and HCP have been carried out toward circumstellar envelopes of evolved stars using the Arizona Radio Observatory (ARO). HCP and PN have been identified in the carbon-rich source CRL 2688 via observations at 1 mm using the Submillimeter Telescope (SMT) and 2-3 mm with the Kitt Peak 12 m. An identical set of measurements were carried out toward IRC +10216, as well as observations of CP at 1 mm. PN was also observed toward VY Canis Majoris (VY CMa), an oxygen-rich supergiant star. The PN and HCP line profiles in CRL 2688 and IRC +10216 are roughly flat topped, indicating unresolved, optically thin emission; CP, in contrast, has a distinct "U" shape in IRC +10216. Modeling of the line profiles suggests abundances, relative to H2, of f(PN) ~ (3-5) × 10-9 and f(HCP) ~ 2 × 10-7 in CRL 2688, about an order of magnitude higher than in IRC +10216. In VY CMa, f(PN) is ~4 × 10-8. The data in CRL 2688 and IRC +10216 are consistent with LTE formation of HCP and PN in the inner envelope, as predicted by theoretical calculations, with CP a photodissociation product at larger radii. The observed abundance of PN in VY CMa is a factor of 100 higher than LTE predictions. In IRC +10216, the chemistry of HCP/CP mimics that of HCN/CN and suggests an N2 abundance of f ~ 1 × 10-7. The chemistry of phosphorus appears active in both carbon- and oxygen-rich envelopes of evolved stars.

  9. Sources of uncertainties in modelling black carbon at the global scale

    Directory of Open Access Journals (Sweden)

    E. Vignati

    2010-03-01

    Full Text Available Our understanding of the global black carbon (BC cycle is essentially qualitative due to uncertainties in our knowledge of its properties. This work investigates two source of uncertainties in modelling black carbon: those due to the use of different schemes for BC ageing and its removal rate in the global Transport-Chemistry model TM5 and those due to the uncertainties in the definition and quantification of the observations, which propagate through to both the emission inventories, and the measurements used for the model evaluation.

    The schemes for the atmospheric processing of black carbon that have been tested with the model are (i a simple approach considering BC as bulk aerosol and a simple treatment of the removal with fixed 70% of in-cloud black carbon concentrations scavenged by clouds and removed when rain is present and (ii a more complete description of microphysical ageing within an aerosol dynamics model, where removal is coupled to the microphysical properties of the aerosol, which results in a global average of 40% in-cloud black carbon that is scavenged in clouds and subsequently removed by rain, thus resulting in a longer atmospheric lifetime. This difference is reflected in comparisons between both sets of modelled results and the measurements. Close to the sources, both anthropogenic and vegetation fire source regions, the model results do not differ significantly, indicating that the emissions are the prevailing mechanism determining the concentrations and the choice of the aerosol scheme does not influence the levels. In more remote areas such as oceanic and polar regions the differences can be orders of magnitude, due to the differences between the two schemes. The more complete description reproduces the seasonal trend of the black carbon observations in those areas, although not always the magnitude of the signal, while the more simplified approach underestimates black carbon concentrations by orders of

  10. Drivers of inorganic carbon dynamics in first-year sea ice: A model study

    DEFF Research Database (Denmark)

    Moreau, Sebastien; Vancoppenolle, Martin; Delille, Bruno

    2015-01-01

    , of total dissolved inorganic carbon (DIC) and total alkalinity (TA) are represented using fluid transport equa- tions. Carbonate chemistry, the consumption, and release of CO2 by primary production and respiration, the precipitation and dissolution of ikaite (CaCO3ﰀ6H2O) and ice-air CO2 fluxes, are also...... included. The model is evaluated using observations from a 6 month field study at Point Barrow, Alaska, and an ice-tank experi- ment. At Barrow, results show that the DIC budget is mainly driven by physical processes, wheras brine-air CO2 fluxes, ikaite formation, and net primary production, are secondary...

  11. The extrapolar SWIFT-model: Fast stratospheric ozone chemistry for global climate models

    OpenAIRE

    Kreyling, Daniel

    2016-01-01

    The goal of this PhD-thesis was the development of a fast yet accurate chemistry scheme for an interactive calculation of the extrapolar stratospheric ozone layer. The SWIFT-model is mainly intended for use in Global Climate Models (GCMs). For computing-time reasons GCMs often do not employ full stratospheric chemistry modules, but use prescribed ozone instead. This method does not consider the interaction between atmospheric dynamics and the ozone layer and can neither resolve the inter-annu...

  12. (Chemistry of the global atmosphere)

    Energy Technology Data Exchange (ETDEWEB)

    Marland, G.

    1990-09-27

    The traveler attended the conference The Chemistry of the Global Atmosphere,'' and presented a paper on the anthropogenic emission of carbon dioxide (CO{sub 2}) to the atmosphere. The conference included meetings of the International Global Atmospheric Chemistry (IGAC) programme, a core project of the International Geosphere/Biosphere Programme (IGBP) and the traveler participated in meetings on the IGAC project Development of Global Emissions Inventories'' and agreed to coordinate the working group on CO{sub 2}. Papers presented at the conference focused on the latest developments in analytical methods, modeling and understanding of atmospheric CO{sub 2}, CO, CH{sub 4}, N{sub 2}O, SO{sub 2}, NO{sub x}, NMHCs, CFCs, and aerosols.

  13. Predictive Modeling in Actinide Chemistry and Catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Ping [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2016-05-16

    These are slides from a presentation on predictive modeling in actinide chemistry and catalysis. The following topics are covered in these slides: Structures, bonding, and reactivity (bonding can be quantified by optical probes and theory, and electronic structures and reaction mechanisms of actinide complexes); Magnetic resonance properties (transition metal catalysts with multi-nuclear centers, and NMR/EPR parameters); Moving to more complex systems (surface chemistry of nanomaterials, and interactions of ligands with nanoparticles); Path forward and conclusions.

  14. Stratospheric General Circulation with Chemistry Model (SGCCM)

    Science.gov (United States)

    Rood, Richard B.; Douglass, Anne R.; Geller, Marvin A.; Kaye, Jack A.; Nielsen, J. Eric; Rosenfield, Joan E.; Stolarski, Richard S.

    1990-01-01

    In the past two years constituent transport and chemistry experiments have been performed using both simple single constituent models and more complex reservoir species models. Winds for these experiments have been taken from the data assimilation effort, Stratospheric Data Analysis System (STRATAN).

  15. Teaching Chemistry with Electron Density Models

    Science.gov (United States)

    Shusterman, Gwendolyn P.; Shusterman, Alan J.

    1997-07-01

    Linus Pauling once said that a topic must satisfy two criteria before it can be taught to students. First, students must be able to assimilate the topic within a reasonable amount of time. Second, the topic must be relevant to the educational needs and interests of the students. Unfortunately, the standard general chemistry textbook presentation of "electronic structure theory", set as it is in the language of molecular orbitals, has a difficult time satisfying either criterion. Many of the quantum mechanical aspects of molecular orbitals are too difficult for most beginning students to appreciate, much less master, and the few applications that are presented in the typical textbook are too limited in scope to excite much student interest. This article describes a powerful new method for teaching students about electronic structure and its relevance to chemical phenomena. This method, which we have developed and used for several years in general chemistry (G.P.S.) and organic chemistry (A.J.S.) courses, relies on computer-generated three-dimensional models of electron density distributions, and largely satisfies Pauling's two criteria. Students find electron density models easy to understand and use, and because these models are easily applied to a broad range of topics, they successfully convey to students the importance of electronic structure. In addition, when students finally learn about orbital concepts they are better prepared because they already have a well-developed three-dimensional picture of electronic structure to fall back on. We note in this regard that the types of models we use have found widespread, rigorous application in chemical research (1, 2), so students who understand and use electron density models do not need to "unlearn" anything before progressing to more advanced theories.

  16. The impact of Future Land Use and Land Cover Changes on Atmospheric Chemistry-Climate Interactions

    NARCIS (Netherlands)

    Ganzeveld, L.N.; Bouwman, L.

    2010-01-01

    To demonstrate potential future consequences of land cover and land use changes beyond those for physical climate and the carbon cycle, we present an analysis of large-scale impacts of land cover and land use changes on atmospheric chemistry using the chemistry-climate model EMAC (ECHAM5/MESSy

  17. Non-detection of HC11N towards TMC-1: constraining the chemistry of large carbon-chain molecules

    Science.gov (United States)

    Loomis, Ryan A.; Shingledecker, Christopher N.; Langston, Glen; McGuire, Brett A.; Dollhopf, Niklaus M.; Burkhardt, Andrew M.; Corby, Joanna; Booth, Shawn T.; Carroll, P. Brandon; Turner, Barry; Remijan, Anthony J.

    2016-12-01

    Bell et al. reported the first detection of the cyanopolyyne HC11N towards the cold dark cloud TMC-1; no subsequent detections have been reported towards any source. Additional observations of cyanopolyynes and other carbon-chain molecules towards TMC-1 have shown a log-linear trend between molecule size and column density, and in an effort to further explore the underlying chemical processes driving this trend, we have analysed Green Bank Telescope observations of HC9N and HC11N towards TMC-1. Although we find an HC9N column density consistent with previous values, HC11N is not detected and we derive an upper limit column density significantly below that reported in Bell et al. Using a state-of-the-art chemical model, we have investigated possible explanations of non-linearity in the column density trend. Despite updating the chemical model to better account for ion-dipole interactions, we are not able to explain the non-detection of HC11N, and we interpret this as evidence of previously unknown carbon-chain chemistry. We propose that cyclization reactions may be responsible for the depleted HC11N abundance, and that products of these cyclization reactions should be investigated as candidate interstellar molecules.

  18. Atmospheric chemistry and environmental impact of the use of amines in carbon capture and storage (CCS).

    Science.gov (United States)

    Nielsen, Claus J; Herrmann, Hartmut; Weller, Christian

    2012-10-07

    This critical review addresses the atmospheric gas phase and aqueous phase amine chemistry that is relevant to potential emissions from amine-based carbon capture and storage (CCS). The focus is on amine, nitrosamine and nitramine degradation, and nitrosamine and nitramine formation processes. A comparison between the relative importance of the various atmospheric sinks for amines, nitrosamines and nitramines is presented.

  19. Observable Signatures of Wind-driven Chemistry with a Fully Consistent Three-dimensional Radiative Hydrodynamics Model of HD 209458b

    Science.gov (United States)

    Drummond, B.; Mayne, N. J.; Manners, J.; Carter, A. L.; Boutle, I. A.; Baraffe, I.; Hébrard, É.; Tremblin, P.; Sing, D. K.; Amundsen, D. S.; Acreman, D.

    2018-03-01

    We present a study of the effect of wind-driven advection on the chemical composition of hot-Jupiter atmospheres using a fully consistent 3D hydrodynamics, chemistry, and radiative transfer code, the Met Office Unified Model (UM). Chemical modeling of exoplanet atmospheres has primarily been restricted to 1D models that cannot account for 3D dynamical processes. In this work, we couple a chemical relaxation scheme to the UM to account for the chemical interconversion of methane and carbon monoxide. This is done consistently with the radiative transfer meaning that departures from chemical equilibrium are included in the heating rates (and emission) and hence complete the feedback between the dynamics, thermal structure, and chemical composition. In this Letter, we simulate the well studied atmosphere of HD 209458b. We find that the combined effect of horizontal and vertical advection leads to an increase in the methane abundance by several orders of magnitude, which is directly opposite to the trend found in previous works. Our results demonstrate the need to include 3D effects when considering the chemistry of hot-Jupiter atmospheres. We calculate transmission and emission spectra, as well as the emission phase curve, from our simulations. We conclude that gas-phase nonequilibrium chemistry is unlikely to explain the model–observation discrepancy in the 4.5 μm Spitzer/IRAC channel. However, we highlight other spectral regions, observable with the James Webb Space Telescope, where signatures of wind-driven chemistry are more prominant.

  20. SWIFT: Semi-empirical and numerically efficient stratospheric ozone chemistry for global climate models

    OpenAIRE

    Kreyling, Daniel; Wohltmann, Ingo; Lehmann, Ralph; Rex, Markus

    2015-01-01

    The SWIFT model is a fast yet accurate chemistry scheme for calculating the chemistry of stratospheric ozone. It is mainly intended for use in Global Climate Models (GCMs), Chemistry Climate Models (CCMs) and Earth System Models (ESMs). For computing time reasons these models often do not employ full stratospheric chem- istry modules, but use prescribed ozone instead. This can lead to insufficient representation between stratosphere and troposphere. The SWIFT stratospheric ozone chem...

  1. Polymer chemistry (revised edition)

    International Nuclear Information System (INIS)

    Kim, Jae Mum

    1987-02-01

    This book deals with polymer chemistry, which is divided into fourteen chapters. The contents of this book are development of polymer chemistry, conception of polymer, measurement of polymer chemistry, conception of polymer, measurement of polymer, molecule structure of polymer, thermal prosperities of solid polymer, basic theory of polymerization, radical polymerization, ion polymerization, radical polymerization, copolymerization, polymerization by step-reaction, polymer reaction, crown polymer and inorganic polymer on classification and process of creation such as polymeric sulfur and carbon fiber.

  2. Modelling electric discharge chemistry

    International Nuclear Information System (INIS)

    McFarlane, J.; Wren, J.C.

    1991-07-01

    The chemistry occurring in a electric discharge was modelled to predict how it would be influenced by discharge conditions. The discharge was characterized by a calculated Boltzmann electron-energy distribution, from which rate constants for electron-molecule processes in air were determined. These rate constants were used in a chemical kinetics calculation that also included reactions between neutral molecules, ions, free radicals and electronically excited species. The model describes how the discharge chemistry was influenced by humidity, electric field, electron number density, and concentrations of key reagents identified in the study. The use of an electric discharge to destroy airborne contaminant molecules was appraised, the targeted contaminants being CF 2 Cl 2 , HCN, and SO 2 . The modelling results indicate that an electric discharge should be able to remove HCN and CF 2 Cl 2 effectively, especially if the discharge conditions have been optimized. Effective destruction is achieved with a moderate electric field (over 1 x 10 -15 V.cm 2 ), a substantial electron number density (over 1 x 10 12 cm -3 ), and the presence of H 2 0 in the process air. The residence time in the discharge was also shown to be important in contaminant destruction. An attempt was made to explain the results of the electric discharge abatement of SO 2 , a component of a simulated flue-gas mixture. Results from the model indicate that the discharge parameters that increase the concentration of hydroxyl radical also increase the rate of decomposition of SO 2 . An objective of the study was to explain the apparent enhancement of SO 2 destruction by the presence of a small amount of NO 2 . It was thought that a likely explanation would be the stabilization of HOSO 2 , an important intermediate in the oxidation of SO 2 by NO 2 . (49 figs., 14 tabs., 75 refs.)

  3. Multi-frequency observations of seawater carbonate chemistry on the central coast of the western Antarctic Peninsula

    Directory of Open Access Journals (Sweden)

    Julie B. Schram

    2015-07-01

    Full Text Available Assessments of benthic coastal seawater carbonate chemistry in Antarctica are sparse. The studies have generally been short in duration, during the austral spring/summer, under sea ice, or offshore in ice-free water. Herein we present multi-frequency measurements for seawater collected from the shallow coastal benthos on a weekly schedule over one year (May 2012–May 2013, daily schedule over three months (March–May 2013 and semidiurnal schedule over five weeks (March–April 2013. A notable pH increase (max pH = 8.62 occurred in the late austral spring/summer (November–December 2012, coinciding with sea-ice break-out and subsequent increase in primary productivity. We detected semidiurnal variation in seawater pH with a maximum variation of 0.13 pH units during the day and 0.11 pH units during the night. Daily variation in pH is likely related to biological activity, consistent with previous research. We calculated the variation in dissolved inorganic carbon (DIC over each seawater measurement frequency, focusing on the primary DIC drivers in the Palmer Station region. From this, we estimated net biological activity and found it accounts for the greatest variations in DIC. Our seasonal data suggest that this coastal region tends to act as a carbon dioxide source during austral winter months and as a strong sink during the summer. These data characterize present-day seawater carbonate chemistry and the extent to which these measures vary over multiple time scales. This information will inform future experiments designed to evaluate the vulnerability of coastal benthic Antarctic marine organisms to ocean acidification.

  4. Virtually going green: The role of quantum computational chemistry in reducing pollution and toxicity in chemistry

    Science.gov (United States)

    Stevens, Jonathan

    2017-07-01

    Continuing advances in computational chemistry has permitted quantum mechanical calculation to assist in research in green chemistry and to contribute to the greening of chemical practice. Presented here are recent examples illustrating the contribution of computational quantum chemistry to green chemistry, including the possibility of using computation as a green alternative to experiments, but also illustrating contributions to greener catalysis and the search for greener solvents. Examples of applications of computation to ambitious projects for green synthetic chemistry using carbon dioxide are also presented.

  5. Adsorption of a Textile Dye on Commercial Activated Carbon: A Simple Experiment to Explore the Role of Surface Chemistry and Ionic Strength

    Science.gov (United States)

    Martins, Angela; Nunes, Nelson

    2015-01-01

    In this study, an adsorption experiment is proposed using commercial activated carbon as adsorbent and a textile azo dye, Mordant Blue-9, as adsorbate. The surface chemistry of the activated carbon is changed through a simple oxidation treatment and the ionic strength of the dye solution is also modified, simulating distinct conditions of water…

  6. PISCES-v2: an ocean biogeochemical model for carbon and ecosystem studies

    Directory of Open Access Journals (Sweden)

    O. Aumont

    2015-08-01

    of marine ecosystems (phytoplankton, microzooplankton and mesozooplankton and the biogeochemical cycles of carbon and of the main nutrients (P, N, Fe, and Si. The model is intended to be used for both regional and global configurations at high or low spatial resolutions as well as for short-term (seasonal, interannual and long-term (climate change, paleoceanography analyses. There are 24 prognostic variables (tracers including two phytoplankton compartments (diatoms and nanophytoplankton, two zooplankton size classes (microzooplankton and mesozooplankton and a description of the carbonate chemistry. Formulations in PISCES-v2 are based on a mixed Monod–quota formalism. On the one hand, stoichiometry of C / N / P is fixed and growth rate of phytoplankton is limited by the external availability in N, P and Si. On the other hand, the iron and silicon quotas are variable and the growth rate of phytoplankton is limited by the internal availability in Fe. Various parameterizations can be activated in PISCES-v2, setting, for instance, the complexity of iron chemistry or the description of particulate organic materials. So far, PISCES-v2 has been coupled to the Nucleus for European Modelling of the Ocean (NEMO and Regional Ocean Modeling System (ROMS systems. A full description of PISCES-v2 and of its optional functionalities is provided here. The results of a quasi-steady-state simulation are presented and evaluated against diverse observational and satellite-derived data. Finally, some of the new functionalities of PISCES-v2 are tested in a series of sensitivity experiments.

  7. Implementation of an Online Chemistry Model to a Large Eddy Simulation Model (PALM-4U0

    Science.gov (United States)

    Mauder, M.; Khan, B.; Forkel, R.; Banzhaf, S.; Russo, E. E.; Sühring, M.; Kanani-Sühring, F.; Raasch, S.; Ketelsen, K.

    2017-12-01

    Large Eddy Simulation (LES) models permit to resolve relevant scales of turbulent motion, so that these models can capture the inherent unsteadiness of atmospheric turbulence. However, LES models are so far hardly applied for urban air quality studies, in particular chemical transformation of pollutants. In this context, BMBF (Bundesministerium für Bildung und Forschung) funded a joint project, MOSAIK (Modellbasierte Stadtplanung und Anwendung im Klimawandel / Model-based city planning and application in climate change) with the main goal to develop a new highly efficient urban climate model (UCM) that also includes atmospheric chemical processes. The state-of-the-art LES model PALM; Maronga et al, 2015, Geosci. Model Dev., 8, doi:10.5194/gmd-8-2515-2015), has been used as a core model for the new UCM named as PALM-4U. For the gas phase chemistry, a fully coupled 'online' chemistry model has been implemented into PALM. The latest version of the Kinetic PreProcessor (KPP) Version 2.3, has been utilized for the numerical integration of chemical species. Due to the high computational demands of the LES model, compromises in the description of chemical processes are required. Therefore, a reduced chemistry mechanism, which includes only major pollutants namely O3, NO, NO2, CO, a highly simplified VOC chemistry and a small number of products have been implemented. This work shows preliminary results of the advection, and chemical transformation of atmospheric pollutants. Non-cyclic boundaries have been used for inflow and outflow in east-west directions while periodic boundary conditions have been implemented to the south-north lateral boundaries. For practical applications, our approach is to go beyond the simulation of single street canyons to chemical transformation, advection and deposition of air pollutants in the larger urban canopy. Tests of chemistry schemes and initial studies of chemistry-turbulence, transport and transformations are presented.

  8. Modeling of iodine radiation chemistry in the presence of organic compounds

    International Nuclear Information System (INIS)

    Taghipour, Fariborz; Evans, Greg J.

    2002-01-01

    A kinetic-based model was developed that simulates the radiation chemistry of iodine in the presence of organic compounds. The model's mechanistic description of iodine chemistry and generic semi-mechanistic reactions for various classes of organics, provided a reasonable representation of experimental results. The majority of the model and experimental results of iodine volatilization rates were in agreement within an order of magnitude

  9. MIANN models in medicinal, physical and organic chemistry.

    Science.gov (United States)

    González-Díaz, Humberto; Arrasate, Sonia; Sotomayor, Nuria; Lete, Esther; Munteanu, Cristian R; Pazos, Alejandro; Besada-Porto, Lina; Ruso, Juan M

    2013-01-01

    Reducing costs in terms of time, animal sacrifice, and material resources with computational methods has become a promising goal in Medicinal, Biological, Physical and Organic Chemistry. There are many computational techniques that can be used in this sense. In any case, almost all these methods focus on few fundamental aspects including: type (1) methods to quantify the molecular structure, type (2) methods to link the structure with the biological activity, and others. In particular, MARCH-INSIDE (MI), acronym for Markov Chain Invariants for Networks Simulation and Design, is a well-known method for QSAR analysis useful in step (1). In addition, the bio-inspired Artificial-Intelligence (AI) algorithms called Artificial Neural Networks (ANNs) are among the most powerful type (2) methods. We can combine MI with ANNs in order to seek QSAR models, a strategy which is called herein MIANN (MI & ANN models). One of the first applications of the MIANN strategy was in the development of new QSAR models for drug discovery. MIANN strategy has been expanded to the QSAR study of proteins, protein-drug interactions, and protein-protein interaction networks. In this paper, we review for the first time many interesting aspects of the MIANN strategy including theoretical basis, implementation in web servers, and examples of applications in Medicinal and Biological chemistry. We also report new applications of the MIANN strategy in Medicinal chemistry and the first examples in Physical and Organic Chemistry, as well. In so doing, we developed new MIANN models for several self-assembly physicochemical properties of surfactants and large reaction networks in organic synthesis. In some of the new examples we also present experimental results which were not published up to date.

  10. Identification of Chemistry Learning Problems Viewed From Conceptual Change Model

    OpenAIRE

    Redhana, I. W; Sudria, I. B. N; Hidayat, I; Merta, L. M

    2017-01-01

    This study aimed at describing and explaining chemistry learning problems viewed from conceptual change model and misconceptions of students. The study was qualitative research of case study type conducted in one class of SMAN 1 Singaraja. Subjects of the study were a chemistry teacher and students. Data were obtained through classroom observation, interviews, and conception tests. The chemistry learning problems were grouped based on aspects of necessity, intelligibility, plausibility, and f...

  11. Flow-Tube Reactor Experiments on the High Temperature Oxidation of Carbon Weaves

    Science.gov (United States)

    Panerai, Francesco; White, Jason D.; Robertson, Robert; Borner, Arnaud; Ferguson, Joseph C.; Mansour, Nagi N.

    2017-01-01

    Under entry conditions carbon weaves used in thermal protection systems (TPS) decompose via oxidation. Modeling this phenomenon is challenging due to the different regimes encountered along a flight trajectory. Approaches using equilibrium chemistry may lead to over-estimated mass loss and recession at certain conditions. Concurrently, there is a shortcoming of experimental data on carbon weaves to enable development of improved models. In this work, a flow-tube test facility was used to measure the oxidation of carbon weaves at temperatures up to 1500 K. The material tested was the 3D carbon weave used for the heat shield of the NASA Adaptive Deployable Entry and Placement Technology, ADEPT. Oxidation was characterized by quantifying decomposition gases (CO and CO2), by mass measurements, and by microscale surface analysis. The current set of measurements contributes to the development of finite rate chemistry models for carbon fabrics used in woven TPS materials.

  12. The influence of feedstock and production temperature on biochar carbon chemistry: A solid-state 13C NMR study

    International Nuclear Information System (INIS)

    McBeath, Anna V.; Smernik, Ronald J.; Krull, Evelyn S.; Lehmann, Johannes

    2014-01-01

    Solid-state 13 C nuclear magnetic resonance (NMR) spectroscopy was used to evaluate the carbon chemistry of twenty-six biochars produced from eleven different feedstocks at production temperatures ranging from 350 °C to 600 °C. Carbon-13 NMR spectra were acquired using both cross-polarisation (CP) and direct polarisation (DP) techniques. Overall, the corresponding CP and DP spectra were similar, although aromaticity was slightly higher and observability much higher when DP was used. The relative size and purity of the aromatic ring structures (i.e. aromatic condensation) were also gauged using the ring current technique. Both aromaticity and aromatic condensation increased with increasing production temperature, regardless of the feedstock source. However, there were clear differences in these two measures for biochars produced at the same temperature but from different feedstocks. Based on a relationship previously established in a long-term incubation study between aromatic condensation and the mean residence time (MRT) of biochar, the MRT of the biochars was estimated to range from 1400 years. This study demonstrates how the combination of feedstock composition and production temperature influences the composition of aromatic domains in biochars, which in turn is likely to be related to their recalcitrance and ultimately their carbon sequestration value. -- Highlights: • Sensitive NMR techniques were used to gauge differences in biochar carbon chemistry. • Varying pyrolysis conditions influences biochars recalcitrant properties. • The MRT of contrasting biochars varies considerably from 1400 years

  13. The global change research center atmospheric chemistry model

    Energy Technology Data Exchange (ETDEWEB)

    Moraes, Jr., Francis Perry [Oregon Graduate Inst. of Science and Technology, Portland, OR (United States)

    1995-01-01

    This work outlines the development of a new model of the chemistry of the natural atmosphere. The model is 2.5-dimensional, having spatial coordinates height, latitude, and, the half-dimension, land and ocean. The model spans both the troposphere and stratosphere, although the troposphere is emphasized and the stratosphere is simple and incomplete. The chemistry in the model includes the Ox, HOx, NOx, and methane cycles in a highly modular fashion which allows model users great flexibility in selecting simulation parameters. A detailed modeled sensitivity analysis is also presented. A key aspect of the model is its inclusion of clouds. The model uses current understanding of the distribution and optical thickness of clouds to determine the true radiation distribution in the atmosphere. As a result, detailed studies of the radiative effects of clouds on the distribution of both oxidant concentrations and trace gas removal are possible. This work presents a beginning of this study with model results and discussion of cloud effects on the hydroxyl radical.

  14. BWR water chemistry impurity studies

    International Nuclear Information System (INIS)

    Ljungberg, L.G.; Korhonen, S.; Renstroem, K.; Hofling, C.G.; Rebensdorff, B.

    1990-03-01

    Laboratory studies were made on the effect of water impurities on environmental cracking in simulated BWR water of stainless steel, low alloy steel and nickel-base alloys. Constant elongation rate tensile (CERT) tests were run in simulated normal water chemistry (NWC), hydrogen water chemistry (HWC), or start-up environment. Sulfate, chloride and copper with chloride added to the water at levels of a fraction of a ppM were found to be extremely deleterious to all kinds of materials except Type 316 NG. Other detrimental impurities were fluoride, silica and some organic acids, although acetic acid was beneficial. Nitrate and carbon dioxide were fairly inoccuous. Corrosion fatigue and constant load tests on compact tension specimens were run in simulated normal BWR water chemistry (NWC) or hydrogen water chemistry (HWC), without impurities or with added sulfate or carbon dioxide. For sensitized Type 304 SS in NWC, 0.1 ppM sulfate increased crack propagation rates in constant load tests by up to a factor of 100, and in fatigue tests up to a factor of 10. Also, cracking in Type 316 nuclear grade SS and Alloy 600 was enhanced, but to a smaller degree. Carbon dioxide was less detrimental than sulfate. 3 figs., 4 tabs

  15. Solid state chemistry and its applications

    CERN Document Server

    West, Anthony R

    2013-01-01

    Solid State Chemistry and its Applications, 2nd Edition: Student Edition is an extensive update and sequel to the bestselling textbook Basic Solid State Chemistry, the classic text for undergraduate teaching in solid state chemistry worldwide. Solid state chemistry lies at the heart of many significant scientific advances from recent decades, including the discovery of high-temperature superconductors, new forms of carbon and countless other developments in the synthesis, characterisation and applications of inorganic materials. Looking forward, solid state chemistry will be crucial for the

  16. Modeling the carbon isotope composition of bivalve shells (Invited)

    Science.gov (United States)

    Romanek, C.

    2010-12-01

    The stable carbon isotope composition of bivalve shells is a valuable archive of paleobiological and paleoenvironmental information. Previous work has shown that the carbon isotope composition of the shell is related to the carbon isotope composition of dissolved inorganic carbon (DIC) in the ambient water in which a bivalve lives, as well as metabolic carbon derived from bivalve respiration. The contribution of metabolic carbon varies among organisms, but it is generally thought to be relatively low (e.g., 90%) in the shells from terrestrial organisms. Because metabolic carbon contains significantly more C-12 than DIC, negative excursions from the expected environmental (DIC) signal are interpreted to reflect an increased contribution of metabolic carbon in the shell. This observation contrasts sharply with modeled carbon isotope compositions for shell layers deposited from the inner extrapallial fluid (EPF). Previous studies have shown that growth lines within the inner shell layer of bivalves are produced during periods of anaerobiosis when acidic metabolic byproducts (e.g., succinic acid) are neutralized (or buffered) by shell dissolution. This requires the pH of EPF to decrease below ambient levels (~7.5) until a state of undersaturation is achieved that promotes shell dissolution. This condition may occur when aquatic bivalves are subjected to external stressors originating from ecological (predation) or environmental (exposure to atm; low dissolved oxygen; contaminant release) pressures; normal physiological processes will restore the pH of EPF when the pressure is removed. As a consequence of this process, a temporal window should also exist in EPF at relatively low pH where shell carbonate is deposited at a reduced saturation state and precipitation rate. For example, EPF chemistry should remain slightly supersaturated with respect to aragonite given a drop of one pH unit (6.5), but under closed conditions, equilibrium carbon isotope fractionation

  17. Modelling the chemistry of iodine

    International Nuclear Information System (INIS)

    Paquette, J.

    1989-01-01

    We have assembled a kinetic model, based on elementary chemical reactions, that describes the chemical behaviour of iodine in aqueous solution as a function of time and various parameters such as pH, concentration and radiation field. The model is conceptually divided into six section: aqueous iodine chemistry, aqueous organic iodide chemistry, water radiolysis, radiolysis of iodine solutions, radiolysis of organic iodide solutions and mass transfer. The model indicates that, in the absence of a radiation field, the rate of production of volatile iodine species is controlled by the rate of oxidation of the iodide ion. The volatile iodine species are dominated by organic iodides if organic impurities are present. The single most important parameter controlling iodine volatility is the pH of the solution; high pH values tend to minimize iodine volatility. In the presence of a radiation field, the volatility of iodine is controlled by the radiation-induced oxidation of the iodide ion. Again, iodine volatility is dominated by organic iodides if organic impurities are present. High pH values minimize iodine volatility. A sensitivity analysis has been performed on some sections of the model to identify reactions to which the volatility of iodine is most sensitive. In the absence of a radiation field, the volatility is most sensitive, first, to the rate of oxidation of the iodide ion, and, second, to the rate of mass transfer of volatile species between the aqueous and the gaseous phases. This approach should be useful in identifying reactions for which accurate rate constants are required and in decreasing the complexity of the model. 37 refs

  18. Modeling emissions for three-dimensional atmospheric chemistry transport models.

    Science.gov (United States)

    Matthias, Volker; Arndt, Jan A; Aulinger, Armin; Bieser, Johannes; Denier Van Der Gon, Hugo; Kranenburg, Richard; Kuenen, Jeroen; Neumann, Daniel; Pouliot, George; Quante, Markus

    2018-01-24

    Poor air quality is still a threat for human health in many parts of the world. In order to assess measures for emission reductions and improved air quality, three-dimensional atmospheric chemistry transport modeling systems are used in numerous research institutions and public authorities. These models need accurate emission data in appropriate spatial and temporal resolution as input. This paper reviews the most widely used emission inventories on global and regional scale and looks into the methods used to make the inventory data model ready. Shortcomings of using standard temporal profiles for each emission sector are discussed and new methods to improve the spatio-temporal distribution of the emissions are presented. These methods are often neither top-down nor bottom-up approaches but can be seen as hybrid methods that use detailed information about the emission process to derive spatially varying temporal emission profiles. These profiles are subsequently used to distribute bulk emissions like national totals on appropriate grids. The wide area of natural emissions is also summarized and the calculation methods are described. Almost all types of natural emissions depend on meteorological information, which is why they are highly variable in time and space and frequently calculated within the chemistry transport models themselves. The paper closes with an outlook for new ways to improve model ready emission data, for example by using external databases about road traffic flow or satellite data to determine actual land use or leaf area. In a world where emission patterns change rapidly, it seems appropriate to use new types of statistical and observational data to create detailed emission data sets and keep emission inventories up-to-date. Emission data is probably the most important input for chemistry transport model (CTM) systems. It needs to be provided in high temporal and spatial resolution and on a grid that is in agreement with the CTM grid. Simple

  19. Proceedings of the ninth national conference on solid state chemistry and allied areas

    International Nuclear Information System (INIS)

    Singh, N.B.; Shukla, S.K.; Abbas, N.S.; Bharadvaja, Anand

    2015-01-01

    Solid State Chemistry and Materials Science is the backbone of many industrial developments. Research on advanced materials makes a strong connection between different fields in basic science, engineering and medical sciences. This conference aims to cover wide range of interdisciplinary topics dealing with various aspects of solid state chemistry and advanced materials such as Nanomaterials, Catalysts, Active Packaging, High Energy Materials, Cementations, Materials , Nuclear Materials, Carbon Materials, Chalcogenides, Superconductor, Conducting Polymers, Photovoltaic, Sensors, Luminescence, Super conductors, Liquid Crystals, Modeling and Molecular Simulation,Biomaterials, Biosensors, Drug Delivery, Tissue Engineering, Bioplastics, Carbon Nanomaterials, Organ, Transplant, Dentisty, Bioimplant, Materials for Engineering and Environment, Nanocomposite, Biodegradable Polymers, etc

  20. A Simple and Accurate Network for Hydrogen and Carbon Chemistry in the Interstellar Medium

    Science.gov (United States)

    Gong, Munan; Ostriker, Eve C.; Wolfire, Mark G.

    2017-07-01

    Chemistry plays an important role in the interstellar medium (ISM), regulating the heating and cooling of the gas and determining abundances of molecular species that trace gas properties in observations. Although solving the time-dependent equations is necessary for accurate abundances and temperature in the dynamic ISM, a full chemical network is too computationally expensive to incorporate into numerical simulations. In this paper, we propose a new simplified chemical network for hydrogen and carbon chemistry in the atomic and molecular ISM. We compare results from our chemical network in detail with results from a full photodissociation region (PDR) code, and also with the Nelson & Langer (NL99) network previously adopted in the simulation literature. We show that our chemical network gives similar results to the PDR code in the equilibrium abundances of all species over a wide range of densities, temperature, and metallicities, whereas the NL99 network shows significant disagreement. Applying our network to 1D models, we find that the CO-dominated regime delimits the coldest gas and that the corresponding temperature tracks the cosmic-ray ionization rate in molecular clouds. We provide a simple fit for the locus of CO-dominated regions as a function of gas density and column. We also compare with observations of diffuse and translucent clouds. We find that the CO, {{CH}}x, and {{OH}}x abundances are consistent with equilibrium predictions for densities n=100{--}1000 {{cm}}-3, but the predicted equilibrium C abundance is higher than that seen in observations, signaling the potential importance of non-equilibrium/dynamical effects.

  1. Pteropod Ecology and Physiology in Relation to Natural Variability in Carbonate Chemistry

    Science.gov (United States)

    Lawson, G. L.; Maas, A. E.; Wang, A. Z.; Bergan, A. J.; Wiebe, P. H.; Blanco-Bercial, L.; Lavery, A.; Copley, N. J.

    2016-02-01

    The thecosomatous pteropods are a group of aragonite-shelled zooplankton thought to be particularly vulnerable to ocean acidification. We seek to gain insight into both basic questions of pteropod biology and potential responses to ocean acidification by combining field sampling with shipboard experimental manipulations, capitalizing on natural spatial variability in modern-day carbonate chemistry between and within the Atlantic and Pacific Oceans. Two cruises were conducted, in 2011 and 2012, along open-ocean transects running between 35 and 50°N in the NW Atlantic and NE Pacific; strong differences in environmental conditions exist between these regions, as well as along the Pacific transect, notably in aragonite compensation and oxygen minimum depths. The transects overlapped with portions of WOCE/CLIVAR lines A20 and P17N and measurements of carbonate chemistry provided insight into rates of chemical change as well as information on the pteropods' chemical environment. The abundance and diversity of pteropods varied substantially within and between the study regions. Depth-stratified net sampling during day and night indicated that multiple pteropod species undertook the typical diel vertical migration employed by many zooplankton species as an anti-predation strategy; the amplitude of this migration differed among species as well as within sub-populations of certain cosmopolitan species found in both oceans. Shipboard experiments of short-duration (<18 hrs, intended to mimic the duration of diel vertical migrations to depth) exposing eight species of pteropod to high CO2 and low O2 found no effect of CO2 alone on metabolic rate and an effect of low O2 or interactive effect of CO2 and O2 only in two Atlantic species not known to naturally encounter low oxygen in their biogeographic range. The implications of these various findings to our understanding of the response of pteropods to environmental change will be discussed.

  2. Modeling the Explicit Chemistry of Anthropogenic and Biogenic Organic Aerosols

    Energy Technology Data Exchange (ETDEWEB)

    Madronich, Sasha [Univ. Corporation for Atmospheric Research, Boulder, CO (United States)

    2015-12-09

    The atmospheric burden of Secondary Organic Aerosols (SOA) remains one of the most important yet uncertain aspects of the radiative forcing of climate. This grant focused on improving our quantitative understanding of SOA formation and evolution, by developing, applying, and improving a highly detailed model of atmospheric organic chemistry, the Generation of Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A) model. Eleven (11) publications have resulted from this grant.

  3. Regionally variable chemistry, auto-heterotrophic coupling and vertical carbon flux in the northwestern Indian Ocean: A case study for biochemical pump

    Digital Repository Service at National Institute of Oceanography (India)

    Rajendran, A; Biddanda, B.

    Large scale regional differences in surface productivity as well as water column chemistry exist in the Arabian Sea environment in north-south direction. The available primary productivity data are incorporated into existing global ocean carbon flux...

  4. Online-coupled meteorology and chemistry models: history, current status, and outlook

    Directory of Open Access Journals (Sweden)

    Y. Zhang

    2008-06-01

    Full Text Available The climate-chemistry-aerosol-cloud-radiation feedbacks are important processes occurring in the atmosphere. Accurately simulating those feedbacks requires fully-coupled meteorology, climate, and chemistry models and presents significant challenges in terms of both scientific understanding and computational demand. This paper reviews the history and current status of the development and application of online-coupled meteorology and chemistry models, with a focus on five representative models developed in the US including GATOR-GCMOM, WRF/Chem, CAM3, MIRAGE, and Caltech unified GCM. These models represent the current status and/or the state-of-the science treatments of online-coupled models worldwide. Their major model features, typical applications, and physical/chemical treatments are compared with a focus on model treatments of aerosol and cloud microphysics and aerosol-cloud interactions. Aerosol feedbacks to planetary boundary layer meteorology and aerosol indirect effects are illustrated with case studies for some of these models. Future research needs for model development, improvement, application, as well as major challenges for online-coupled models are discussed.

  5. A greenhouse-scale photosynthetic microbial bioreactor for carbon sequestration in magnesium carbonate minerals.

    Science.gov (United States)

    McCutcheon, Jenine; Power, Ian M; Harrison, Anna L; Dipple, Gregory M; Southam, Gordon

    2014-08-19

    A cyanobacteria dominated consortium collected from an alkaline wetland located near Atlin, British Columbia, Canada accelerated the precipitation of platy hydromagnesite [Mg5(CO3)4(OH)2·4H2O] in a linear flow-through experimental model wetland. The concentration of magnesium decreased rapidly within 2 m of the inflow point of the 10-m-long (∼1.5 m(2)) bioreactor. The change in water chemistry was monitored over two months along the length of the channel. Carbonate mineralization was associated with extra-cellular polymeric substances in the nutrient-rich upstream portion of the bioreactor, while the lower part of the system, which lacked essential nutrients, did not exhibit any hydromagnesite precipitation. A mass balance calculation using the water chemistry data produced a carbon sequestration rate of 33.34 t of C/ha per year. Amendment of the nutrient deficiency would intuitively allow for increased carbonation activity. Optimization of this process will have application as a sustainable mining practice by mediating magnesium carbonate precipitation in ultramafic mine tailings storage facilities.

  6. Guided-Inquiry Experiments for Physical Chemistry: The POGIL-PCL Model

    Science.gov (United States)

    Hunnicutt, Sally S.; Grushow, Alexander; Whitnell, Robert

    2015-01-01

    The POGIL-PCL project implements the principles of process-oriented, guided-inquiry learning (POGIL) in order to improve student learning in the physical chemistry laboratory (PCL) course. The inquiry-based physical chemistry experiments being developed emphasize modeling of chemical phenomena. In each experiment, students work through at least…

  7. Risks to coral reefs from ocean carbonate chemistry changes in recent earth system model projections

    International Nuclear Information System (INIS)

    Ricke, K L; Caldeira, K; Orr, J C; Schneider, K

    2013-01-01

    Coral reefs are among the most biodiverse ecosystems in the world. Today they are threatened by numerous stressors, including warming ocean waters and coastal pollution. Here we focus on the implications of ocean acidification for the open ocean chemistry surrounding coral reefs, as estimated from earth system models participating in the Coupled Model Intercomparison Project, Phase 5 (CMIP5). We project risks to reefs in the context of three potential aragonite saturation (Ωa) thresholds. We find that in preindustrial times, 99.9% of reefs adjacent to open ocean in the CMIP5 ensemble were located in regions with Ωa > 3.5. Under a business-as-usual scenario (RCP 8.5), every coral reef considered will be surrounded by water with Ωa 2 emissions abatement, the Ωa threshold for reefs is critical to projecting their fate. Our results indicate that to maintain a majority of reefs surrounded by waters with Ωa > 3.5 to the end of the century, very aggressive reductions in emissions are required. The spread of Ωa projections across models in the CMIP5 ensemble is narrow, justifying a high level of confidence in these results. (letter)

  8. The phosphorus and the transition metals chemistry

    International Nuclear Information System (INIS)

    Mathey, F.

    1988-01-01

    The 1988 progress report, concerning the Polytechnic School unit (France), which studies the phosphorus and the transition metals chemistry, is presented. The laboratory activities are related to the following topics: the phosporus heterocyclic chemistry, the phosphorus-carbon double bonds chemistry, the new transition metals phosphorus compounds, the phosphonates and their uses. Some practical applications of homogeneous catalysis and new materials synthesis are investigated. The main results obtained are: the discovery of the tetra-phosphafulvalenes, the utilization of a new synthesis method of the phosphorus-carbon double bonds and the stabilization of the α-phosphonyled carbanions by the lithium diisopropylamidourea. The papers, the congress communications and the thesis are also shown [fr

  9. In-Package Chemistry Abstraction

    Energy Technology Data Exchange (ETDEWEB)

    E. Thomas

    2004-11-09

    package has been breached but the drip shield remains intact, so all of the seepage flow is diverted from the waste package. The chemistry from the vapor influx case is used to determine the stability of colloids and the solubility of radionuclides available for transport by diffusion, and to determine the degradation rates for the waste forms. TSPA-LA uses the water influx case for the seismic scenario, where the waste package has been breached and the drip shield has been damaged such that seepage flow is actually directed into the waste package. The chemistry from the water influx case that is a function of the flow rate is used to determine the stability of colloids and the solubility of radionuclides available for transport by diffusion and advection, and to determine the degradation rates for the CSNF and HLW glass. TSPA-LA does not use this model for the igneous scenario. Outputs from the in-package chemistry model implemented inside TSPA-LA include pH, ionic strength, and total carbonate concentration. These inputs to TSPA-LA will be linked to the following principle factors: dissolution rates of the CSNF and HLWG, dissolved concentrations of radionuclides, and colloid generation.

  10. In-Package Chemistry Abstraction

    International Nuclear Information System (INIS)

    E. Thomas

    2004-01-01

    breached but the drip shield remains intact, so all of the seepage flow is diverted from the waste package. The chemistry from the vapor influx case is used to determine the stability of colloids and the solubility of radionuclides available for transport by diffusion, and to determine the degradation rates for the waste forms. TSPA-LA uses the water influx case for the seismic scenario, where the waste package has been breached and the drip shield has been damaged such that seepage flow is actually directed into the waste package. The chemistry from the water influx case that is a function of the flow rate is used to determine the stability of colloids and the solubility of radionuclides available for transport by diffusion and advection, and to determine the degradation rates for the CSNF and HLW glass. TSPA-LA does not use this model for the igneous scenario. Outputs from the in-package chemistry model implemented inside TSPA-LA include pH, ionic strength, and total carbonate concentration. These inputs to TSPA-LA will be linked to the following principle factors: dissolution rates of the CSNF and HLWG, dissolved concentrations of radionuclides, and colloid generation

  11. Constraining the climate and ocean pH of the early Earth with a geological carbon cycle model.

    Science.gov (United States)

    Krissansen-Totton, Joshua; Arney, Giada N; Catling, David C

    2018-04-17

    The early Earth's environment is controversial. Climatic estimates range from hot to glacial, and inferred marine pH spans strongly alkaline to acidic. Better understanding of early climate and ocean chemistry would improve our knowledge of the origin of life and its coevolution with the environment. Here, we use a geological carbon cycle model with ocean chemistry to calculate self-consistent histories of climate and ocean pH. Our carbon cycle model includes an empirically justified temperature and pH dependence of seafloor weathering, allowing the relative importance of continental and seafloor weathering to be evaluated. We find that the Archean climate was likely temperate (0-50 °C) due to the combined negative feedbacks of continental and seafloor weathering. Ocean pH evolves monotonically from [Formula: see text] (2σ) at 4.0 Ga to [Formula: see text] (2σ) at the Archean-Proterozoic boundary, and to [Formula: see text] (2σ) at the Proterozoic-Phanerozoic boundary. This evolution is driven by the secular decline of pCO 2 , which in turn is a consequence of increasing solar luminosity, but is moderated by carbonate alkalinity delivered from continental and seafloor weathering. Archean seafloor weathering may have been a comparable carbon sink to continental weathering, but is less dominant than previously assumed, and would not have induced global glaciation. We show how these conclusions are robust to a wide range of scenarios for continental growth, internal heat flow evolution and outgassing history, greenhouse gas abundances, and changes in the biotic enhancement of weathering. Copyright © 2018 the Author(s). Published by PNAS.

  12. Surface modification of carbon nanotubes via combination of mussel inspired chemistry and chain transfer free radical polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Wan, Qing; Tian, Jianwen; Liu, Meiying; Zeng, Guangjian; Huang, Qiang [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang, 330031 (China); Wang, Ke; Zhang, Qingsong [Department of Chemistry and the Tsinghua Center for Frontier Polymer Research, Tsinghua University, Beijing, 100084 (China); Deng, Fengjie, E-mail: fengjiedeng@aliyun.com [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang, 330031 (China); Zhang, Xiaoyong, E-mail: xiaoyongzhang1980@gmail.com [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang, 330031 (China); Wei, Yen, E-mail: weiyen@tsinghua.edu.cn [Department of Chemistry and the Tsinghua Center for Frontier Polymer Research, Tsinghua University, Beijing, 100084 (China)

    2015-08-15

    Graphical abstract: A novel strategy combination of mussel inspired chemistry and chain transfer free radical polymerization has been developed for surface modification of carbon nanotubes with polymers for the first time. - Highlights: • Surface modification of CNTs via mussel inspired chemistry. • Preparation of aminated polymers through free radical polymerization. • Functionalized CNTs with aminated polymers via Michael addition reaction. • Highly dispersed CNTs in organic and aqueous solution. - Abstract: In this work, a novel strategy for surface modification of carbon nanotubes (CNTs) was developed via combination of mussel inspired chemistry and chain transfer free radical polymerization. First, pristine CNTs were functionalized with polydopamine (PDA), which is formed via self-polymerization of dopamine in alkaline conditions. These PDA functionalized CNTs can be further reacted with amino-terminated polymers (named as PDMC), which was synthesized through chain transfer free radical polymerization using cysteamine hydrochloride as chain transfer agent and methacryloxyethyltrimethyl ammonium chloride as the monomer. PDMC perfectly conjugated with CNT-PDA was ascertained by a series of characterization techniques including transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), thermal gravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS). The dispersibility of obtained CNT nanocomposites (named as CNT-PDA-PDMC) was further examined. Results showed that the dispersibility of CNT-PDA-PDMC in aqueous and organic solutions was obviously enhanced. Apart from PDMC, many other amino-terminated polymers can also be used to functionalization of CNTs via similar strategy. Therefore, the method described in this work should be a general strategy for fabrication various polymer nanocomposites.

  13. Modeling Carbon Exchange

    Science.gov (United States)

    Sellers, Piers

    2012-01-01

    Model results will be reviewed to assess different methods for bounding the terrestrial role in the global carbon cycle. It is proposed that a series of climate model runs could be scoped that would tighten the limits on the "missing sink" of terrestrial carbon and could also direct future satellite image analyses to search for its geographical location and understand its seasonal dynamics.

  14. Long Carbon Chains in the Warm Carbon-chain-chemistry Source L1527: First Detection of C7H in Molecular Clouds

    Science.gov (United States)

    Araki, Mitsunori; Takano, Shuro; Sakai, Nami; Yamamoto, Satoshi; Oyama, Takahiro; Kuze, Nobuhiko; Tsukiyama, Koichi

    2017-09-01

    Long carbon-chain molecules were searched for toward the low-mass star-forming region L1527, which is a prototypical source of warm carbon-chain chemistry (WCCC), using the 100 m Green Bank Telescope. Long carbon-chain molecules, C7H (2Π1/2), C6H (2Π3/2 and 2Π1/2), CH3C4H, and C6H2 (cumulene carbene, CCCCCCH2), and cyclic species of C3H and C3H2O were detected. In particular, C7H was detected for the first time in molecular clouds. The column density of C7H is determined to be 6 × 1010 cm-2. The column densities of the carbon-chain molecules including CH3C4H and C6H in L1527 relative to those in the starless dark cloud Taurus Molecular Cloud-1 Cyanopolyyne Peak (TMC-1 CP) tend to be systematically lower for long carbon-chain lengths. However, the column densities of C7H and C6H2 do not follow this trend and are found to be relatively abundant in L1527. This result implies that these long carbon-chain molecules are remnants of the cold starless phase. The results—that both the remnants and WCCC products are observed toward L1527—are consistent with the suggestion that the protostar can also be born in the parent core at a relatively early stage in the chemical evolution.

  15. An Ocean Acidification Acclimatised Green Tide Alga Is Robust to Changes of Seawater Carbon Chemistry but Vulnerable to Light Stress.

    Directory of Open Access Journals (Sweden)

    Guang Gao

    Full Text Available Ulva is the dominant genus in the green tide events and is considered to have efficient CO2 concentrating mechanisms (CCMs. However, little is understood regarding the impacts of ocean acidification on the CCMs of Ulva and the consequences of thalli's acclimation to ocean acidification in terms of responding to environmental factors. Here, we grew a cosmopolitan green alga, Ulva linza at ambient (LC and elevated (HC CO2 levels and investigated the alteration of CCMs in U. linza grown at HC and its responses to the changed seawater carbon chemistry and light intensity. The inhibitors experiment for photosynthetic inorganic carbon utilization demonstrated that acidic compartments, extracellular carbonic anhydrase (CA and intracellular CA worked together in the thalli grown at LC and the acquisition of exogenous carbon source in the thalli could be attributed to the collaboration of acidic compartments and extracellular CA. Contrastingly, when U. linza was grown at HC, extracellular CA was completely inhibited, acidic compartments and intracellular CA were also down-regulated to different extents and thus the acquisition of exogenous carbon source solely relied on acidic compartments. The down-regulated CCMs in U. linza did not affect its responses to changes of seawater carbon chemistry but led to a decrease of net photosynthetic rate when thalli were exposed to increased light intensity. This decrease could be attributed to photodamage caused by the combination of the saved energy due to the down-regulated CCMs and high light intensity. Our findings suggest future ocean acidification might impose depressing effects on green tide events when combined with increased light exposure.

  16. Soil carbon model alternatives for ECHAM5/JSBACH climate model: Evaluation and impacts on global carbon cycle estimates

    DEFF Research Database (Denmark)

    Thum, T.; Raisanen, P.; Sevanto, S.

    2011-01-01

    The response of soil organic carbon to climate change might lead to significant feedbacks affecting global warming. This response can be studied by coupled climate-carbon cycle models but so far the description of soil organic carbon cycle in these models has been quite simple. In this work we used...... the coupled climate-carbon cycle model ECHAM5/JSBACH (European Center/Hamburg Model 5/Jena Scheme for Biosphere-Atmosphere Coupling in Hamburg) with two different soil carbon modules, namely (1) the original soil carbon model of JSBACH called CBALANCE and (2) a new soil carbon model Yasso07, to study...... the interaction between climate variability and soil organic carbon. Equivalent ECHAM5/JSBACH simulations were conducted using both soil carbon models, with freely varying atmospheric CO2 for the last 30 years (1977-2006). In this study, anthropogenic CO2 emissions and ocean carbon cycle were excluded. The new...

  17. The synergy of ultrasonic treatment and organic modifiers for tuning the surface chemistry and conductivity of multiwalled carbon nanotubes

    Czech Academy of Sciences Publication Activity Database

    Omastová, M.; Mičušík, M.; Fedorko, P.; Pionteck, J.; Kovářová, Jana; Chehimi, M. M.

    2014-01-01

    Roč. 46, 10-11 (2014), s. 940-944 ISSN 0142-2421. [European Conference on Applications of Surface and Interface Analysis /15./ - ECASIA 2013. Cagliari, 13.10.2013-18.10.2013] Institutional support: RVO:61389013 Keywords : carbon nanotubes * surface modification * surfactant Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.245, year: 2014

  18. Quantum chemistry and scientific calculus

    International Nuclear Information System (INIS)

    Gervais, H.P.

    1988-01-01

    The 1988 progress report of the Polytechnic School research team, concerning the quantum chemistry and the scientific calculus. The research program involves the following topics: the transition metals - carbon monoxide systems, which are a suitable model for the chemisorption phenomena; the introduction of the vibronic perturbations in the magnetic screen constants; the gauge invariance method (used in the calculation of the magnetic perturbations), extended to the case of the static or dynamic electrical polarizabilities. The published papers, the congress communications and the thesis are listed [fr

  19. Surface chemistry of polyacrylonitrile- and rayon-based activated carbon fibers after post-heat treatment

    International Nuclear Information System (INIS)

    Chiang Yuchun; Lee, C.-Y.; Lee, H.-C.

    2007-01-01

    Polyacrylonitrile- and rayon-based activated carbon fibers (ACFs) subject to heat treatment were investigated by means of elemental analyzer, and X-ray photoelectron spectroscopy (XPS). The total ash content of all ACFs was also analyzed. The adsorption of benzene, carbon tetrachloride and water vapor on ACFs was determined to shed light on the role of surface chemistry on gas adsorption. Results show that different precursors resulted in various elemental compositions and imposed diverse influence upon surface functionalities after heat treatment. The surface of heat-treated ACFs became more graphitic and hydrophobic. Three distinct peaks due to C, N, and O atoms were identified by XPS, and the high-resolution revealed the existence of several surface functionalities. The presence of nitride-like species, aromatic N-imines, or chemisorbed nitrogen oxides was found to be of great advantage to adsorption of water vapor or benzene, but the pyridine-N was not. Unstable complexes on the surface would hinder the fibers from adsorption of carbon tetrachloride. The rise in total ash content or hydrogen composition was of benefit to the access of water vapor. Modifications of ACFs by heat treatment have effectively improved adsorption performance

  20. [Impact of Rocky Desertification Treatment on Underground Water Chemistry and Dissolved Inorganic Carbon Isotope in Karst Areas].

    Science.gov (United States)

    Xiao, Shi-zhen; Xiong, Kang-ning; Lan, Jia-cheng; Zhang, Hui; Yang, Long

    2015-05-01

    Five springs representing different land-use types and different karst rocky desertification treatment models were chosen at the Huajiang Karst Rocky Desertification Treatment Demonstration Site in Guanling-Zhenfeng Counties in Guizhou, to analyze the features of underground water chemistry and dissolved inorganic carbon isotopes (δ13C(DIC)) and reveal the effect of rocky desertification treatment on karstification and water quality. It was found that, the underground water type of the research area was HCO3-Ca; the water quality of the springs which were relatively less affected by human activities including Shuijingwan Spring (SJW) , Gebei Spring (GB), and Maojiawan Spring (MJW) was better than those relatively more affected by human activities including Diaojing Spring (DJ) and Tanjiazhai Spring (TJZ) , the main ion concentrations and electrical conductivity of which were higher; pH, SIc and pCO2 were sensitive to land-use types and rocky desertification treatment, which could be shown by the higher pH and SIc and lower pCO2 in MJW than those in the other four springs; (Ca(2+) + Mg2+)/HCO(3-) of SJW, MJW and GB were nearly 1:1, dominated by carbonate rock weathering by carbon acid, while the (Ca(2+) + Mg2+) of DJ and TJZ was much higher than HCO3-, suggesting that sulfate and nitrate might also dissolve carbonate rock because of the agricultural activities; δ13C(DIC) was lighter in wet season because of the higher biological activities; the average δ13C(DIC) was in the order of DJ (-12.79 per thousand) desertification and lighter after the rocky desertification are treated and controlled.

  1. General chemistry

    International Nuclear Information System (INIS)

    Kwon, Yeong Sik; Lee, Dong Seop; Ryu, Haung Ryong; Jang, Cheol Hyeon; Choi, Bong Jong; Choi, Sang Won

    1993-07-01

    The book concentrates on the latest general chemistry, which is divided int twenty-three chapters. It deals with basic conception and stoichiometry, nature of gas, structure of atoms, quantum mechanics, symbol and structure of an electron of ion and molecule, chemical thermodynamics, nature of solid, change of state and liquid, properties of solution, chemical equilibrium, solution and acid-base, equilibrium of aqueous solution, electrochemistry, chemical reaction speed, molecule spectroscopy, hydrogen, oxygen and water, metallic atom; 1A, IIA, IIIA, carbon and atom IVA, nonmetal atom and an inert gas, transition metals, lanthanons, and actinoids, nuclear properties and radioactivity, biochemistry and environment chemistry.

  2. Effects of `Environmental Chemistry' Elective Course Via Technology-Embedded Scientific Inquiry Model on Some Variables

    Science.gov (United States)

    Çalik, Muammer; Özsevgeç, Tuncay; Ebenezer, Jazlin; Artun, Hüseyin; Küçük, Zeynel

    2014-06-01

    The purpose of this study is to examine the effects of `environmental chemistry' elective course via Technology-Embedded Scientific Inquiry (TESI) model on senior science student teachers' (SSSTs) conceptions of environmental chemistry concepts/issues, attitudes toward chemistry, and technological pedagogical content knowledge (TPACK) levels. Within one group pre-test-post-test design, the study was conducted with 117 SSSTs (68 females and 49 males—aged 21-23 years) enrolled in an `environmental chemistry' elective course in the spring semester of 2011-2012 academic-years. Instruments for data collection comprised of Environmental Chemistry Conceptual Understanding Questionnaire, TPACK survey, and Chemistry Attitudes and Experiences Questionnaire. Significant increases in the SSSTs' conceptions of environmental chemistry concepts/issues, attitudes toward chemistry, and TPACK levels are attributed to the SSSTs learning how to use the innovative technologies in the contexts of the `environmental chemistry' elective course and teaching practicum. The study implies that the TESI model may serve a useful purpose in experimental science courses that use the innovative technologies. However, to generalize feasibility of the TESI model, it should be evaluated with SSSTs in diverse learning contexts.

  3. The GEOS Chemistry Climate Model: Comparisons to Satellite Data

    Science.gov (United States)

    Stolarski, R. S.; Douglass, A. R.

    2008-05-01

    The Goddard Earth Observing System Chemistry Climate Model (GEOS CCM) has been developed by combining the atmospheric chemistry and transport modules developed over the years at Goddard and the GEOS general circulation model, also developed at Goddard. We will compare model simulations of ozone, and the minor constituents that affect ozone, for the period around 1980 with newly released revised data from the Limb Infrared Monitor of the Stratosphere (LIMS) instrument on Nimbus 4. We will also compare model simulations for the period of the early 2000s with the data from the Microwave Limb Sounder (MLS) and the High Resolution Dynamic Limb Sounder (HRDLS) on the Aura satellite. We will use these comparisons to examine the performance of the model for the present atmosphere and for the change that has occurred during the last 2 decades of ozone loss due to chlorine and bromine compounds released from chlorofluorocarbons and halons.

  4. Frontiers in Atmospheric Chemistry Modelling

    Science.gov (United States)

    Colette, Augustin; Bessagnet, Bertrand; Meleux, Frederik; Rouïl, Laurence

    2013-04-01

    The first pan-European kilometre-scale atmospheric chemistry simulation is introduced. The continental-scale air pollution episode of January 2009 is modelled with the CHIMERE offline chemistry-transport model with a massive grid of 2 million horizontal points, performed on 2000 CPU of a high performance computing system hosted by the Research and Technology Computing Center at the French Alternative Energies and Atomic Energy Commission (CCRT/CEA). Besides the technical challenge, which demonstrated the robustness of the selected air quality model, we discuss the added value in terms of air pollution modelling and decision support. The comparison with in-situ observations shows that model biases are significantly improved despite some spurious added spatial variability attributed to shortcomings in the emission downscaling process and coarse resolution of the meteorological fields. The increased spatial resolution is clearly beneficial for the detection of exceedances and exposure modelling. We reveal small scale air pollution patterns that highlight the contribution of city plumes to background air pollution levels. Up to a factor 5 underestimation of the fraction of population exposed to detrimental levels of pollution can be obtained with a coarse simulation if subgrid scale correction such as urban increments are ignored. This experiment opens new perspectives for environmental decision making. After two decades of efforts to reduce air pollutant emissions across Europe, the challenge is now to find the optimal trade-off between national and local air quality management strategies. While the first approach is based on sectoral strategies and energy policies, the later builds upon new alternatives such as urban development. The strategies, the decision pathways and the involvement of individual citizen differ, and a compromise based on cost and efficiency must be found. We illustrated how high performance computing in atmospheric science can contribute to this

  5. Theoretical chemistry periodicities in chemistry and biology

    CERN Document Server

    Eyring, Henry

    1978-01-01

    Theoretical Chemistry: Periodicities in Chemistry and Biology, Volume 4 covers the aspects of theoretical chemistry. The book discusses the stably rotating patterns of reaction and diffusion; the chemistry of inorganic systems exhibiting nonmonotonic behavior; and population cycles. The text also describes the mathematical modeling of excitable media in neurobiology and chemistry; oscillating enzyme reactions; and oscillatory properties and excitability of the heart cell membrane. Selected topics from the theory of physico-chemical instabilities are also encompassed. Chemists, mechanical engin

  6. Climate effects of anthropogenic sulfate: Simulations from a coupled chemistry/climate model

    International Nuclear Information System (INIS)

    Chuang, C.C.; Penner, J.E.; Taylor, K.E.; Walton, J.J.

    1993-09-01

    In this paper, we use a more comprehensive approach by coupling a climate model with a 3-D global chemistry model to investigate the forcing by anthropogenic aerosol sulfate. The chemistry model treats the global-scale transport, transformation, and removal of SO 2 , DMS and H 2 SO 4 species in the atmosphere. The mass concentration of anthropogenic sulfate from fossil fuel combustion and biomass burning is calculated in the chemistry model and provided to the climate model where it affects the shortwave radiation. We also investigate the effect, with cloud nucleation parameterized in terms of local aerosol number, sulfate mass concentration and updraft velocity. Our simulations indicate that anthropogenic sulfate may result in important increases in reflected solar radiation, which would mask locally the radiative forcing from increased greenhouse gases. Uncertainties in these results will be discussed

  7. A detailed chemistry model for transient hydrogen and carbon monoxide catalytic recombination on parallel flat Pt surfaces implemented in an integral code

    International Nuclear Information System (INIS)

    Jimenez, Miguel A.; Martin-Valdepenas, Juan M.; Martin-Fuertes, Francisco; Fernandez, Jose A.

    2007-01-01

    A detailed chemistry model has been adapted and developed for surface chemistry, heat and mass transfer between H 2 /CO/air/steam/CO 2 mixtures and vertical parallel Pt-coated surfaces. This model is based onto a simplified Deutschmann reaction scheme for methane surface combustion and the analysis by Elenbaas for buoyancy-induced heat transfer between parallel plates. Mass transfer is treated by the heat and mass transfer analogy. The proposed model is able to simulate the H 2 /CO recombination phenomena characteristic of parallel-plate Passive Autocatalytic Recombiners (PARs), which have been proposed and implemented as a promising hydrogen-control strategy in the safety of nuclear power stations or other industries. The transient model is able to approach the warm-up phase of the PAR and its shut-down as well as the dynamic changes within the surrounding atmosphere. The model has been implemented within the MELCOR code and assessed against results of the Battelle Model Containment tests of the Zx series. Results show accurate predictions and a better performance than traditional methods in integral codes, i.e. empirical correlations, which are also much case-specific. Influence of CO present in the mixture on the PAR performance is also addressed in this paper

  8. In-Package Chemistry Abstraction

    Energy Technology Data Exchange (ETDEWEB)

    P.S. Domski

    2003-07-21

    The work associated with the development of this model report was performed in accordance with the requirements established in ''Technical Work Plan for Waste Form Degradation Modeling, Testing, and Analyses in Support of SR and LA'' (BSC 2002a). The in-package chemistry model and in-package chemistry model abstraction are developed to predict the bulk chemistry inside of a failed waste package and to provide simplified expressions of that chemistry. The purpose of this work is to provide the abstraction model to the Performance Assessment Project and the Waste Form Department for development of geochemical models of the waste package interior. The scope of this model report is to describe the development and validation of the in-package chemistry model and in-package chemistry model abstraction. The in-package chemistry model will consider chemical interactions of water with the waste package materials and the waste form for commercial spent nuclear fuel (CSNF) and codisposed high-level waste glass (HLWG) and N Reactor spent fuel (CDNR). The in-package chemistry model includes two sub-models, the first a water vapor condensation (WVC) model, where water enters a waste package as vapor and forms a film on the waste package components with subsequent film reactions with the waste package materials and waste form--this is a no-flow model, the reacted fluids do not exit the waste package via advection. The second sub-model of the in-package chemistry model is the seepage dripping model (SDM), where water, water that may have seeped into the repository from the surrounding rock, enters a failed waste package and reacts with the waste package components and waste form, and then exits the waste package with no accumulation of reacted water in the waste package. Both of the submodels of the in-package chemistry model are film models in contrast to past in-package chemistry models where all of the waste package pore space was filled with water. The

  9. In-Package Chemistry Abstraction

    International Nuclear Information System (INIS)

    P.S. Domski

    2003-01-01

    The work associated with the development of this model report was performed in accordance with the requirements established in ''Technical Work Plan for Waste Form Degradation Modeling, Testing, and Analyses in Support of SR and LA'' (BSC 2002a). The in-package chemistry model and in-package chemistry model abstraction are developed to predict the bulk chemistry inside of a failed waste package and to provide simplified expressions of that chemistry. The purpose of this work is to provide the abstraction model to the Performance Assessment Project and the Waste Form Department for development of geochemical models of the waste package interior. The scope of this model report is to describe the development and validation of the in-package chemistry model and in-package chemistry model abstraction. The in-package chemistry model will consider chemical interactions of water with the waste package materials and the waste form for commercial spent nuclear fuel (CSNF) and codisposed high-level waste glass (HLWG) and N Reactor spent fuel (CDNR). The in-package chemistry model includes two sub-models, the first a water vapor condensation (WVC) model, where water enters a waste package as vapor and forms a film on the waste package components with subsequent film reactions with the waste package materials and waste form--this is a no-flow model, the reacted fluids do not exit the waste package via advection. The second sub-model of the in-package chemistry model is the seepage dripping model (SDM), where water, water that may have seeped into the repository from the surrounding rock, enters a failed waste package and reacts with the waste package components and waste form, and then exits the waste package with no accumulation of reacted water in the waste package. Both of the submodels of the in-package chemistry model are film models in contrast to past in-package chemistry models where all of the waste package pore space was filled with water. The current in

  10. Modelling neutral and plasma chemistry with DSMC

    International Nuclear Information System (INIS)

    Bartel, Timothy J.

    2003-01-01

    The Direct Simulation Monte Carlo (DSMC) method is a powerful method for modelling chemically reacting flows. It is a statistical method which simulates the Boltzmann equation by interacting computational particles which represent a large number of a single species type. A statistical problem will occur when trace concentrations are required to be accurately modelled; the traditional strategy is to use more computational particles per cell or simply obtain lower statistics and thus have higher uncertainty for the trace concentrations. A new method, cell based chemistry (CBC), based on an integral balancing concept, allows all chemistry, including trace reactions, to be efficiently modelled in the framework of DSMC. This strategy first separates the collision phase from the reacting phase. Then a strategy is presented which conserves both the collision and reaction frequencies in a consistent manner. The illustrative problem is a chemically reacting glow discharge plasma; the ion concentrations typically are at a 0.1% mole fraction but dominant the physical mechanism of the system. Comparisons will be made to a chlorine plasma in a Gaseous Electronics Conference (GEC) reference cell with an inductive coil at approximately 20 mtorr system pressure

  11. Modeling nitrogen chemistry in combustion

    DEFF Research Database (Denmark)

    Glarborg, Peter; Miller, James A.; Ruscic, Branko

    2018-01-01

    the accuracy of engineering calculations and thereby the potential of primary measures for NOx control. In this review our current understanding of the mechanisms that are responsible for combustion-generated nitrogen-containing air pollutants is discussed. The thermochemistry of the relevant nitrogen...... via NNH or N2O are discussed, along with the chemistry of NO removal processes such as reburning and Selective Non-Catalytic Reduction of NO. Each subset of the mechanism is evaluated against experimental data and the accuracy of modeling predictions is discussed....

  12. Constraining the climate and ocean pH of the early Earth with a geological carbon cycle model

    Science.gov (United States)

    Krissansen-Totton, Joshua; Arney, Giada N.; Catling, David C.

    2018-04-01

    The early Earth’s environment is controversial. Climatic estimates range from hot to glacial, and inferred marine pH spans strongly alkaline to acidic. Better understanding of early climate and ocean chemistry would improve our knowledge of the origin of life and its coevolution with the environment. Here, we use a geological carbon cycle model with ocean chemistry to calculate self-consistent histories of climate and ocean pH. Our carbon cycle model includes an empirically justified temperature and pH dependence of seafloor weathering, allowing the relative importance of continental and seafloor weathering to be evaluated. We find that the Archean climate was likely temperate (0–50 °C) due to the combined negative feedbacks of continental and seafloor weathering. Ocean pH evolves monotonically from 6.6‑0.4+0.6 (2σ) at 4.0 Ga to 7.0‑0.5+0.7 (2σ) at the Archean–Proterozoic boundary, and to 7.9‑0.2+0.1 (2σ) at the Proterozoic–Phanerozoic boundary. This evolution is driven by the secular decline of pCO2, which in turn is a consequence of increasing solar luminosity, but is moderated by carbonate alkalinity delivered from continental and seafloor weathering. Archean seafloor weathering may have been a comparable carbon sink to continental weathering, but is less dominant than previously assumed, and would not have induced global glaciation. We show how these conclusions are robust to a wide range of scenarios for continental growth, internal heat flow evolution and outgassing history, greenhouse gas abundances, and changes in the biotic enhancement of weathering.

  13. Dynamic-chemistry-aerosol modelling interaction: the ESCOMPTE 2001 experiment

    International Nuclear Information System (INIS)

    Cousin, F.

    2004-09-01

    After most pollution studies independently devoted to gases and aerosols, there now appears an urgent need to consider their interactions. In this view, an aerosol module has been implemented in the Meso-NH-C model to simulate two IOPs documented during the ESCOMPTE campaign which took place in the Marseille/Fos-Berre region in June-July 2001. First, modelled dynamic parameters (winds, temperatures, boundary layer thickness) and gaseous chemistry have been validated with measurements issued from the exhaustive ESCOMPTE database. Sensitivity analysis have also been performed using different gaseous emission inventories at various resolution. These simulations have illustrated the deep impact of both synoptic and local dynamics on observed ozone concentrations on June 24 (IOP2b) in the ESCOMPTE domain. Afterwards, the ORISAM aerosol module has been introduced into the Meso-NH-C model. Dynamics, gaseous chemistry and aerosol processes have thus been coupled on-line. The particulate pollution episode on June 24 (IOP2b) has been characterised through a satisfactory comparison, specially from sub-micron particles, between modelling and measurements at different representative stations in the domain. This study, with validation of the particulate emission inventory has also highlighted the need for future improvements, such as further characterisation of organic and inorganic aerosol species and consideration of coarse particles. Aerosol impact on gaseous chemistry has been preliminary approached in view of future development and modification to be given to the Meso-NH-C model. (author)

  14. Combustion chemistry of alcohols: Experimental and modeled structure of a premixed 2-methylbutanol flame

    KAUST Repository

    Lucassen, Arnas

    2014-06-14

    This paper presents a detailed investigation of 2-methylbutanol combustion chemistry in low-pressure premixed flames. This chemistry is of particular interest to study because this compound is potentially a lignocellulosic-based, next-generation biofuel. The detailed chemical structure of a stoichiometric low-pressure (25 Torr) flame was determined using flame-sampling molecular-beam mass spectrometry. A total of 55 species were identified and subsequently quantitative mole fraction profiles as function of distance from the burner surface were determined. In an independent effort, a detailed flame chemistry model for 2-methylbutanol was assembled based on recent knowledge gained from combustion chemistry studies for butanol isomers ([Sarathy et al. Combust. Flame 159 (6) (2012) 2028-2055]) and iso-pentanol (3-methylbutanol) [Sarathy et al. Combust. Flame 160 (12) (2013) 2712-2728]. Experimentally determined and modeled mole fraction profiles were compared to demonstrate the model\\'s capabilities. Examples of individual mole fraction profiles are discussed together with the most significant fuel consumption pathways to highlight the combustion chemistry of 2-methylbutanol. Discrepancies between experimental and modeling results are used to suggest areas where improvement of the kinetic model would be needed. © 2014.

  15. SITE 94. Modelling of groundwater chemistry at Aespoe Hard Rock Laboratory

    Energy Technology Data Exchange (ETDEWEB)

    Emren, A.T. [Chalmers Univ. of Technology, Goeteborg (Sweden). Dept. of Nuclear Chemistry

    1999-02-01

    of the groundwater appears to be mostly a consequence of chemical reactions between water and fracture filling minerals. This has been studied in simulations where rain has been allowed to enter a fracture. Although there are some differences, the results found in this modelling generally are similar to the observed values. The deviations suggest that the fracture filling minerals alone are not enough to explain the observed groundwater chemistry. This should not be expected, since the old waters found hundreds of meters below the surface have been able to react with other mineral sets as well. In the CRACKER simulations it has been found that the simulated waters are similar to observations with respect to redox properties. The Aespoe groundwaters have iron concentrations which are low compared to those found in other deep Swedish groundwaters. By inhibiting reactions in the simulations, it has been found unlikely that the Fe(II) - Fe(III) redox couple is the main controller of the redox properties in Aespoe groundwaters. Rather, it appears that the redox properties can be maintained even if reactions with this couple are inhibited. According to the simulation results, reactions in which dissolved hydrogen, carbonates and methane are participating are important. This does not mean that iron species and minerals are not involved in redox processes. The simulation methods have been applied to possible future events and processes. As examples of such, the effects of elevated temperature on the groundwater properties have been investigated as well as a prediction on possible effects of Baltic Sea water intrusion 58 refs, figs

  16. SITE 94. Modelling of groundwater chemistry at Aespoe Hard Rock Laboratory

    International Nuclear Information System (INIS)

    Emren, A.T.

    1999-02-01

    of the groundwater appears to be mostly a consequence of chemical reactions between water and fracture filling minerals. This has been studied in simulations where rain has been allowed to enter a fracture. Although there are some differences, the results found in this modelling generally are similar to the observed values. The deviations suggest that the fracture filling minerals alone are not enough to explain the observed groundwater chemistry. This should not be expected, since the old waters found hundreds of meters below the surface have been able to react with other mineral sets as well. In the CRACKER simulations it has been found that the simulated waters are similar to observations with respect to redox properties. The Aespoe groundwaters have iron concentrations which are low compared to those found in other deep Swedish groundwaters. By inhibiting reactions in the simulations, it has been found unlikely that the Fe(II) - Fe(III) redox couple is the main controller of the redox properties in Aespoe groundwaters. Rather, it appears that the redox properties can be maintained even if reactions with this couple are inhibited. According to the simulation results, reactions in which dissolved hydrogen, carbonates and methane are participating are important. This does not mean that iron species and minerals are not involved in redox processes. The simulation methods have been applied to possible future events and processes. As examples of such, the effects of elevated temperature on the groundwater properties have been investigated as well as a prediction on possible effects of Baltic Sea water intrusion

  17. Evaluation of dynamics and equilibrium models for the sorption of Basic Violet 3 on activated carbon prepared from Moringa Oleifera fruit shell waste

    Directory of Open Access Journals (Sweden)

    C. Sumithra

    2014-03-01

    Full Text Available The feasibility of activated carbon prepared from Moringa oleifera fruit shell waste to remove Basic Violet 3 from aqueous solution was investigated through batch mode contact time studies. The surface chemistry of activated carbon is studied using Boehm titrations and pH of PZC measurements indicates that the surface oxygenated groups are mainly basic in nature. The surface area of the activated carbon is determined using BET method. The kinetics of Basic Violet 3 adsorption are observed to be pH dependent. The experimental data can be explained by Pseudo second order kinetic model. For, Basic Violet 3, the Langmuir model is best suited to stimulate the adsorption isotherms.

  18. Solving vertical transport and chemistry in air pollution models

    International Nuclear Information System (INIS)

    Berkvens, P.J.F.; Botchev, M.A.; Verwer, J.G.; Krol, M.C.; Peters, W.

    2000-01-01

    For the time integration of stiff transport-chemistry problems from air pollution modelling, standard ODE solvers are not feasible due to the large number of species and the 3D nature. The popular alternative, standard operator splitting, introduces artificial transients for short-lived species. This complicates the chemistry solution, easily causing large errors for such species. In the framework of an operational global air pollution model, we focus on the problem formed by chemistry and vertical transport, which is based on diffusion, cloud-related vertical winds, and wet deposition. Its specific nature leads to full Jacobian matrices, ruling out standard implicit integration. We compare Strang operator splitting with two alternatives: source splitting and an (unsplit) Rosenbrock method with approximate matrix factorization, all having equal computational cost. The comparison is performed with real data. All methods are applied with half-hour time steps, and give good accuracies. Rosenbrock is the most accurate, and source splitting is more accurate than Strang splitting. Splitting errors concentrate in short-lived species sensitive to solar radiation and species with strong emissions and depositions. 30 refs

  19. Water temperature, carbonate chemistry, and growth rates of Acropora cervicornis from the Florida keys, 2014-05-23 to 2016-07-26 (NCEI Accession 0164322)

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — Data were collected as part of the CRCP-funded project "Coral restoration in natural ocean acidification refugia." Carbonate chemistry parameters and temperature...

  20. A depositional model for spherulitic carbonates associated with alkaline, volcanic lakes

    NARCIS (Netherlands)

    Mercedes-Martín, Ramon; Brasier, Alexander T.; Rogerson, Mike; Reijmer, John J.G.; Vonhof, Hubert; Pedley, Martyn

    2017-01-01

    The South Atlantic Aptian ‘Pre-salt’ reservoirs are formed by a combination of spherulitic carbonates and Mg-rich clays accumulated in volcanic alkaline lake settings with exotic chemistries. So far, outcrop analogues characterised by metre-thick successions deposited in lacustrine scenarios are

  1. Hitch code capabilities for modeling AVT chemistry

    International Nuclear Information System (INIS)

    Leibovitz, J.

    1985-01-01

    Several types of corrosion have damaged alloy 600 tubing in the secondary side of steam generators. The types of corrosion include wastage, denting, intergranular attack, stress corrosion, erosion-corrosion, etc. The environments which cause attack may originate from leaks of cooling water into the condensate, etc. When the contaminated feedwater is pumped into the generator, the impurities may concentrate first 200 to 400 fold in the bulk water, depending on the blowdown, and then further to saturation and dryness in heated tube support plate crevices. Characterization of local solution chemistries is the first step to predict and correct the type of corrosion that can occur. The pH is of particular importance because it is a major factor governing the rate of corrosion reactions. The pH of a solution at high temperature is not the same as the ambient temperature, since ionic dissociation constants, solubility and solubility products, activity coefficients, etc., all change with temperature. Because the high temperature chemistry of such solutions is not readily characterized experimentally, modeling techniques were developed under EPRI sponsorship to calculate the high temperature chemistry of the relevant solutions. In many cases, the effects of cooling water impurities on steam generator water chemistry with all volatile treatment (AVT), upon concentration by boiling, and in particular the resulting acid or base concentration can be calculated by a simple code, the HITCH code, which is very easy to use. The scope and applicability of the HITCH code are summarized

  2. Description and Evaluation of IAP-AACM: A Global-regional Aerosol Chemistry Model for the Earth System Model CAS-ESM

    Science.gov (United States)

    Wei, Y.; Chen, X.

    2017-12-01

    We present a first description and evaluation of the IAP Atmospheric Aerosol Chemistry Model (IAP-AACM) which has been integrated into the earth system model CAS-ESM. In this way it is possible to research into interaction of clouds and aerosol by its two-way coupling with the IAP Atmospheric General Circulation Model (IAP-AGCM). The model has a nested global-regional grid based on the Global Environmental Atmospheric Transport Model (GEATM) and the Nested Air Quality Prediction Modeling System (NAQPMS). The AACM provides two optional gas chemistry schemes, the CBM-Z gas chemistry as well as a sulfur oxidize box designed specifically for the CAS-ESM. Now the model driven by AGCM has been applied to a 1-year simulation of tropospheric chemistry both on global and regional scales for 2014, and been evaluated against various observation datasets, including aerosol precursor gas concentration, aerosol mass and number concentrations. Furthermore, global budgets in AACM are compared with other global aerosol models. Generally, the AACM simulations are within the range of other global aerosol model predictions, and the model has a reasonable agreement with observations of gases and particles concentration both on global and regional scales.

  3. The Chemistry of Atmosphere-Forest Exchange (CAFE Model – Part 1: Model description and characterization

    Directory of Open Access Journals (Sweden)

    G. M. Wolfe

    2011-01-01

    Full Text Available We present the Chemistry of Atmosphere-Forest Exchange (CAFE model, a vertically-resolved 1-D chemical transport model designed to probe the details of near-surface reactive gas exchange. CAFE integrates all key processes, including turbulent diffusion, emission, deposition and chemistry, throughout the forest canopy and mixed layer. CAFE utilizes the Master Chemical Mechanism (MCM and is the first model of its kind to incorporate a suite of reactions for the oxidation of monoterpenes and sesquiterpenes, providing a more comprehensive description of the oxidative chemistry occurring within and above the forest. We use CAFE to simulate a young Ponderosa pine forest in the Sierra Nevada, CA. Utilizing meteorological constraints from the BEARPEX-2007 field campaign, we assess the sensitivity of modeled fluxes to parameterizations of diffusion, laminar sublayer resistance and radiation extinction. To characterize the general chemical environment of this forest, we also present modeled mixing ratio profiles of biogenic hydrocarbons, hydrogen oxides and reactive nitrogen. The vertical profiles of these species demonstrate a range of structures and gradients that reflect the interplay of physical and chemical processes within the forest canopy, which can influence net exchange.

  4. Results of an interactively coupled atmospheric chemistry - general circulation model. Comparison with observations

    Energy Technology Data Exchange (ETDEWEB)

    Hein, R.; Dameris, M.; Schnadt, C. [and others

    2000-01-01

    An interactively coupled climate-chemistry model which enables a simultaneous treatment of meteorology and atmospheric chemistry and their feedbacks is presented. This is the first model, which interactively combines a general circulation model based on primitive equations with a rather complex model of stratospheric and tropospheric chemistry, and which is computational efficient enough to allow long-term integrations with currently available computer resources. The applied model version extends from the Earth's surface up to 10 hPa with a relatively high number (39) of vertical levels. We present the results of a present-day (1990) simulation and compare it to available observations. We focus on stratospheric dynamics and chemistry relevant to describe the stratospheric ozone layer. The current model version ECHAM4.L39(DLR)/CHEM can realistically reproduce stratospheric dynamics in the Arctic vortex region, including stratospheric warming events. This constitutes a major improvement compared to formerly applied model versions. However, apparent shortcomings in Antarctic circulation and temperatures persist. The seasonal and interannual variability of the ozone layer is simulated in accordance with observations. Activation and deactivation of chlorine in the polar stratospheric vortices and their interhemispheric differences are reproduced. The consideration of the chemistry feedback on dynamics results in an improved representation of the spatial distribution of stratospheric water vapor concentrations, i.e., the simulated meriodional water vapor gradient in the stratosphere is realistic. The present model version constitutes a powerful tool to investigate, for instance, the combined direct and indirect effects of anthropogenic trace gas emissions, and the future evolution of the ozone layer. (orig.)

  5. Fluorination of vertically aligned carbon nanotubes: from CF4 plasma chemistry to surface functionalization.

    Science.gov (United States)

    Struzzi, Claudia; Scardamaglia, Mattia; Colomer, Jean-François; Verdini, Alberto; Floreano, Luca; Snyders, Rony; Bittencourt, Carla

    2017-01-01

    The surface chemistry of plasma fluorinated vertically aligned carbon nanotubes (vCNT) is correlated to the CF 4 plasma chemical composition. The results obtained via FTIR and mass spectrometry are combined with the XPS and Raman analysis of the sample surface showing the dependence on different plasma parameters (power, time and distance from the plasma region) on the resulting fluorination. Photoemission and absorption spectroscopies are used to investigate the evolution of the electronic properties as a function of the fluorine content at the vCNT surface. The samples suffer a limited ageing effect, with a small loss of fluorine functionalities after two weeks in ambient conditions.

  6. Fluorination of vertically aligned carbon nanotubes: from CF4 plasma chemistry to surface functionalization

    Directory of Open Access Journals (Sweden)

    Claudia Struzzi

    2017-08-01

    Full Text Available The surface chemistry of plasma fluorinated vertically aligned carbon nanotubes (vCNT is correlated to the CF4 plasma chemical composition. The results obtained via FTIR and mass spectrometry are combined with the XPS and Raman analysis of the sample surface showing the dependence on different plasma parameters (power, time and distance from the plasma region on the resulting fluorination. Photoemission and absorption spectroscopies are used to investigate the evolution of the electronic properties as a function of the fluorine content at the vCNT surface. The samples suffer a limited ageing effect, with a small loss of fluorine functionalities after two weeks in ambient conditions.

  7. Using Transport Diagnostics to Understand Chemistry Climate Model Ozone Simulations

    Science.gov (United States)

    Strahan, S. E.; Douglass, A. R.; Stolarski, R. S.; Akiyoshi, H.; Bekki, S.; Braesicke, P.; Butchart, N.; Chipperfield, M. P.; Cugnet, D.; Dhomse, S.; hide

    2010-01-01

    We demonstrate how observations of N2O and mean age in the tropical and midlatitude lower stratosphere (LS) can be used to identify realistic transport in models. The results are applied to 15 Chemistry Climate Models (CCMs) participating in the 2010 WMO assessment. Comparison of the observed and simulated N2O/mean age relationship identifies models with fast or slow circulations and reveals details of model ascent and tropical isolation. The use of this process-oriented N2O/mean age diagnostic identifies models with compensating transport deficiencies that produce fortuitous agreement with mean age. We compare the diagnosed model transport behavior with a model's ability to produce realistic LS O3 profiles in the tropics and midlatitudes. Models with the greatest tropical transport problems show the poorest agreement with observations. Models with the most realistic LS transport agree more closely with LS observations and each other. We incorporate the results of the chemistry evaluations in the SPARC CCMVal Report (2010) to explain the range of CCM predictions for the return-to-1980 dates for global (60 S-60 N) and Antarctic column ozone. Later (earlier) Antarctic return dates are generally correlated to higher (lower) vortex Cl(sub y) levels in the LS, and vortex Cl(sub y) is generally correlated with the model's circulation although model Cl(sub y) chemistry or Cl(sub y) conservation can have a significant effect. In both regions, models that have good LS transport produce a smaller range of predictions for the return-to-1980 ozone values. This study suggests that the current range of predicted return dates is unnecessarily large due to identifiable model transport deficiencies.

  8. Disciplines, models, and computers: the path to computational quantum chemistry.

    Science.gov (United States)

    Lenhard, Johannes

    2014-12-01

    Many disciplines and scientific fields have undergone a computational turn in the past several decades. This paper analyzes this sort of turn by investigating the case of computational quantum chemistry. The main claim is that the transformation from quantum to computational quantum chemistry involved changes in three dimensions. First, on the side of instrumentation, small computers and a networked infrastructure took over the lead from centralized mainframe architecture. Second, a new conception of computational modeling became feasible and assumed a crucial role. And third, the field of computa- tional quantum chemistry became organized in a market-like fashion and this market is much bigger than the number of quantum theory experts. These claims will be substantiated by an investigation of the so-called density functional theory (DFT), the arguably pivotal theory in the turn to computational quantum chemistry around 1990.

  9. Combustion chemistry of alcohols: Experimental and modeled structure of a premixed 2-methylbutanol flame

    KAUST Repository

    Lucassen, Arnas; Park, Sungwoo; Hansen, Nils; Sarathy, Mani

    2014-01-01

    This paper presents a detailed investigation of 2-methylbutanol combustion chemistry in low-pressure premixed flames. This chemistry is of particular interest to study because this compound is potentially a lignocellulosic-based, next-generation biofuel. The detailed chemical structure of a stoichiometric low-pressure (25 Torr) flame was determined using flame-sampling molecular-beam mass spectrometry. A total of 55 species were identified and subsequently quantitative mole fraction profiles as function of distance from the burner surface were determined. In an independent effort, a detailed flame chemistry model for 2-methylbutanol was assembled based on recent knowledge gained from combustion chemistry studies for butanol isomers ([Sarathy et al. Combust. Flame 159 (6) (2012) 2028-2055]) and iso-pentanol (3-methylbutanol) [Sarathy et al. Combust. Flame 160 (12) (2013) 2712-2728]. Experimentally determined and modeled mole fraction profiles were compared to demonstrate the model's capabilities. Examples of individual mole fraction profiles are discussed together with the most significant fuel consumption pathways to highlight the combustion chemistry of 2-methylbutanol. Discrepancies between experimental and modeling results are used to suggest areas where improvement of the kinetic model would be needed. © 2014.

  10. Adsorption of Naphthol Green B on unburned carbon: 2- and 3- parameter linear and non-linear equilibrium modelling

    Czech Academy of Sciences Publication Activity Database

    Bartoňová, L.; Ruppenthalová, Lucie; Ritz, M.

    2017-01-01

    Roč. 25, č. 1 (2017), s. 37-44 ISSN 1004-9541 R&D Projects: GA MŠk(CZ) LO1406; GA MŠk ED2.1.00/03.0082 Institutional support: RVO:68145535 Keywords : adsorption * unburned carbon * Naphthol Green B * isotherms * Redlich–Peterson model Subject RIV: CB - Analytical Chemistry, Separation OBOR OECD: Analytical chemistry Impact factor: 1.174, year: 2016 http://ac.els-cdn.com/S100495411630218X/1-s2.0-S100495411630218X-main.pdf?_tid=cac3f0e4-9a87-11e6-a1c5-00000aacb360&acdnat=1477382049_e99a7a8e381310d60cafbb816571cdd5

  11. Carbon paste electrodes in electroanalytical chemistry

    Directory of Open Access Journals (Sweden)

    KAREL VYTŘAS

    2009-09-01

    Full Text Available An overview is given dealing with the applications of carbon paste electrodes in equilibrium potentiometry as well as in electrochemical stripping analysis using both voltammetric and potentiometric modes. Various modifications of carbon pastes and carbon paste-based biosensors are also mentioned. The main emphasis in this article is directed at summarizing recent results of the authors’ research group during the past few years.

  12. Chemistry and physics

    International Nuclear Information System (INIS)

    Broerse, J.J.; Barendsen, G.W.; Kal, H.B.; Kogel, A.J. van der

    1983-01-01

    This book contains the extended abstracts of the contributions of the poster workshop sessions on chemistry and physics of the 7th international congress of radiation research. They cover the following main topics: primary processes in radiation physics and chemistry, general chemistry in radiation chemistry, DNA and model systems in radiation chemistry, molecules of biological interest in radiation chemistry, techniques in radiation chemistry, hot atom chemistry. refs.; figs.; tabs

  13. Repeat synoptic sampling reveals drivers of change in carbon and nutrient chemistry of Arctic catchments

    Science.gov (United States)

    Zarnetske, J. P.; Abbott, B. W.; Bowden, W. B.; Iannucci, F.; Griffin, N.; Parker, S.; Pinay, G.; Aanderud, Z.

    2017-12-01

    Dissolved organic carbon (DOC), nutrients, and other solute concentrations are increasing in rivers across the Arctic. Two hypotheses have been proposed to explain these trends: 1. distributed, top-down permafrost degradation, and 2. discrete, point-source delivery of DOC and nutrients from permafrost collapse features (thermokarst). While long-term monitoring at a single station cannot discriminate between these mechanisms, synoptic sampling of multiple points in the stream network could reveal the spatial structure of solute sources. In this context, we sampled carbon and nutrient chemistry three times over two years in 119 subcatchments of three distinct Arctic catchments (North Slope, Alaska). Subcatchments ranged from 0.1 to 80 km2, and included three distinct types of Arctic landscapes - mountainous, tundra, and glacial-lake catchments. We quantified the stability of spatial patterns in synoptic water chemistry and analyzed high-frequency time series from the catchment outlets across the thaw season to identify source areas for DOC, nutrients, and major ions. We found that variance in solute concentrations between subcatchments collapsed at spatial scales between 1 to 20 km2, indicating a continuum of diffuse- and point-source dynamics, depending on solute and catchment characteristics (e.g. reactivity, topography, vegetation, surficial geology). Spatially-distributed mass balance revealed conservative transport of DOC and nitrogen, and indicates there may be strong in-stream retention of phosphorus, providing a network-scale confirmation of previous reach-scale studies in these Arctic catchments. Overall, we present new approaches to analyzing synoptic data for change detection and quantification of ecohydrological mechanisms in ecosystems in the Arctic and beyond.

  14. Modelling of the local chemistry in stagnant areas in the PWR primary circuit

    International Nuclear Information System (INIS)

    Reid, Rick; Fruzzetti, Keith; Ahluwalia, Al; Summe, Alex; Dame, Cecile; Schmitt, Kyle

    2014-01-01

    MRP-236 demonstrated a correlation between stagnant or low flow conditions and stress corrosion cracking (SCC) of stainless steel components in the PWR primary system. Of the approximately 140 SCC events documented (affecting 15 different components), 83% involved stagnant or low flow conditions that were likely to be associated with chemical environments different from the well mixed bulk coolant. The chemistry in such locations is typically not monitored, and sampling is difficult or impossible. Actions to improve chemistry in regions of low or no coolant flow, such as flushing, cycling of components and imposition of more stringent make up water chemistry controls affect both operational costs and outage schedules. Similarly, design changes to improve flow in affected areas are costly or impracticable. Improving the understanding of the factors controlling chemistry in such areas and development of the capability to predict typical and worst case conditions will allow an informed assessment of procedural actions and/or design changes to improve local chemistry and thereby reduce SCC susceptibility. A project was undertaken to develop a model to predict local chemistry conditions in stagnant locations. The model comprises the iterative application of the EPRI MULTEQ solution chemistry equilibrium code and standard thermodynamic relationships to predict local chemistry conditions considered likely to have been present at the surfaces of components when SCC was initiated. The starting chemistry conditions are based on PWR primary system chemistry from different plant maneuvers (e.g., startup and shutdown conditions). The model was applied to three example components where SCC has occurred in the field. The selected components were: control rod drive mechanism canopy seals; valve drain lines; and reactor vessel o-ring leak-off lines. This paper provides a summary of the model and predicted local chemistry conditions that develop for the three example component as a

  15. Adsorption Energies of Carbon, Nitrogen, and Oxygen Atoms on the Low-temperature Amorphous Water Ice: A Systematic Estimation from Quantum Chemistry Calculations

    Science.gov (United States)

    Shimonishi, Takashi; Nakatani, Naoki; Furuya, Kenji; Hama, Tetsuya

    2018-03-01

    We propose a new simple computational model to estimate the adsorption energies of atoms and molecules to low-temperature amorphous water ice, and we present the adsorption energies of carbon (3 P), nitrogen (4 S), and oxygen (3 P) atoms based on quantum chemistry calculations. The adsorption energies were estimated to be 14,100 ± 420 K for carbon, 400 ± 30 K for nitrogen, and 1440 ± 160 K for oxygen. The adsorption energy of oxygen is consistent with experimentally reported values. We found that the binding of a nitrogen atom is purely physisorption, while that of a carbon atom is chemisorption, in which a chemical bond to an O atom of a water molecule is formed. That of an oxygen atom has a dual character, with both physisorption and chemisorption. The chemisorption of atomic carbon also implies the possibility of further chemical reactions to produce molecules bearing a C–O bond, though this may hinder the formation of methane on water ice via sequential hydrogenation of carbon atoms. These properties would have a large impact on the chemical evolution of carbon species in interstellar environments. We also investigated the effects of newly calculated adsorption energies on the chemical compositions of cold dense molecular clouds with the aid of gas-ice astrochemical simulations. We found that abundances of major nitrogen-bearing molecules, such as N2 and NH3, are significantly altered by applying the calculated adsorption energy, because nitrogen atoms can thermally diffuse on surfaces, even at 10 K.

  16. Chemistry Cube Game - Exploring Basic Principles of Chemistry by Turning Cubes.

    Science.gov (United States)

    Müller, Markus T

    2018-02-01

    The Chemistry Cube Game invites students at secondary school level 1 and 2 to explore basic concepts of chemistry in a playful way, either as individuals or in teams. It consists of 15 different cubes, 9 cubes for different acids, their corresponding bases and precursors, and 6 cubes for different reducing and oxidising agents. The cubes can be rotated in those directions indicated. Each 'allowed' vertical or horizontal rotation of 90° stands for a chemical reaction or a physical transition. Two different games and playing modes are presented here: First, redox chemistry is introduced for the formation of salts from elementary metals and non-metals. Second, the speciation of acids and bases at different pH-values is shown. The cubes can be also used for games about environmental chemistry such as the carbon and sulphur cycle, covering the topic of acid rain, or the nitrogen cycle including ammoniac synthesis, nitrification and de-nitrification.

  17. Misconceptions of Concepts in Chemistry among Senior Secondary ...

    African Journals Online (AJOL)

    This study examined the misconceptions by chemistry teachers of senior secondary three (SSIII) in Cross River State, Nigeria. Concepts investigated were hydrocarbons, alkanols, alkanoic acids, pollution, classification and nomenclature of carbon compounds, natural products, chemistry in industry, extraction of metals, fats ...

  18. Meso-scale modeling of air pollution transport/chemistry/deposition and its application

    International Nuclear Information System (INIS)

    Kitada, Toshihiro

    2007-01-01

    Transport/chemistry/deposition model for atmospheric trace chemical species is now regarded as an important tool for an understanding of the effects of various human activities, such as fuel combustion and deforestation, on human health, eco-system, and climate and for planning of appropriate control of emission sources. Several 'comprehensive' models have been proposed such as RADM (Chang, et al., 1987), STEM-II (Carmichael, et al., 1986), and CMAQ (Community Multi-scale Air Quality model, e.g., EPA website, 2003); the 'comprehensive' models include not only gas/aerosol phase chemistry but also aqueous phase chemistry in cloud/rain water in addition to the processes of advection, diffusion, wet deposition (mass transfer between aqueous and gas/aerosol phases), and dry deposition. The target of the development of the 'comprehensive' model will be that the model can correctly reproduce mass balance of various chemical species in the atmosphere with keeping adequate accuracy for calculated concentration distributions of chemical species. For the purpose, one of the important problems is a reliable wet deposition modeling, and here, we introduce two types of methods of 'cloud-resolving' and 'non-cloud-resolving' modeling for the wet deposition of pollutants. (author)

  19. Adsorption of benzene and toluene from aqueous solutions onto activated carbon and its acid and heat treated forms: influence of surface chemistry on adsorption.

    Science.gov (United States)

    Wibowo, N; Setyadhi, L; Wibowo, D; Setiawan, J; Ismadji, S

    2007-07-19

    The influence of surface chemistry and solution pH on the adsorption of benzene and toluene on activated carbon and its acid and heat treated forms were studied. A commercial coal-based activated carbon F-400 was chosen as carbon parent. The carbon samples were obtained by modification of F-400 by means of chemical treatment with HNO3 and thermal treatment under nitrogen flow. The treatment with nitric acid caused the introduction of a significant number of oxygenated acidic surface groups onto the carbon surface, while the heat treatment increases the basicity of carbon. The pore characteristics were not significantly changed after these modifications. The dispersive interactions are the most important factor in this adsorption process. Activated carbon with low oxygenated acidic surface groups (F-400Tox) has the best adsorption capacity.

  20. NWCA 2011 Soil Chemistry - Data

    Data.gov (United States)

    U.S. Environmental Protection Agency — NWCA 2011 Soil Chemistry Data. This dataset is associated with the following publication: Nahlik, A., and M.S. Fennessy. Carbon storage in US wetlands. Nature...

  1. DEPLETION OF CCS IN A CANDIDATE WARM-CARBON-CHAIN-CHEMISTRY SOURCE L483

    International Nuclear Information System (INIS)

    Hirota, Tomoya; Sakai, Nami; Yamamoto, Satoshi

    2010-01-01

    We have carried out an observation of the CCS (J N = 2 1 -1 0 ) line with the Very Large Array in its D-configuration toward a protostellar core L483 (IRAS 18140-0440). This is a candidate source of the newly found carbon-chain-rich environment called 'Warm-Carbon-Chain-Chemistry (WCCC)', according to the previous observations of carbon-chain molecules. The CCS distribution in L483 is found to consist of two clumps aligned in the northwest-southeast direction, well tracing the CCS ridge observed with the single-dish radio telescope. The most remarkable feature is that CCS is depleted at the core center. Such a CCS distribution with the central hole is consistent with those of previously observed prestellar and protostellar cores, but it is rather unexpected for L483. This is because the distribution of CS, which is usually similar to that of CCS, is centrally peaked. Our results imply that the CCS (J N = 2 1 -1 0 ) line would selectively trace the outer cold envelope in the chemically less evolved phase that is seriously resolved out with the interferometric observation. Thus, it is most likely that the high abundance of CCS in L483 relative to the other WCCC sources is not due to the activity of the protostar, although it would be related to its younger chemical evolutionary stage, or a short timescale of the prestellar phase.

  2. Colour chemistry in water

    OpenAIRE

    Cardona, Maria

    2015-01-01

    Atmospheric carbon dioxide (CO2) levels have increased dramatically in the last few decades. Famous for causing global warming, CO2 is also resulting in the acidification of seas and oceans. http://www.um.edu.mt/think/colour-chemistry-in-water/

  3. Modeling seasonal changes of atmospheric carbon dioxide and carbon 13

    International Nuclear Information System (INIS)

    Gillette, D.A.; Box, E.O.

    1986-01-01

    A two-dimensional (latitude-altitude) model of atmospheric CO 2 and δ 13 C was constructed to simulate some features of seasonal carbon cycle fluctuations. The model simulates air-sea exchange, atmospheric diffusion, and fossil fuel carbon sources, which are functions of time and latitude. In addition, it uses biosphere-atmosphere fluxes of carbon that are based on global-scale biological models of vegetation growth and decay. Results of the model show fair agreement with observational results for CO 2 and δ 13 C seasonal fluctuations. Their model results have far northern fluctuations with smaller amplitudes than are observed. Analysis of sources of CO 2 change at given latitudes shows that, for far southern latitudes, southern hemisphere biospheric fluxes are dominant in affecting the seasonal CO 2 fluctuations. Long-term decrease of δ 13 C for the model is larger than for observations. This may be due to errors in the formulation for oceanic fluxes for 13 C in the model or to a net uptake of carbon by the biosphere

  4. Results of an interactively coupled atmospheric chemistry – general circulation model: Comparison with observations

    Directory of Open Access Journals (Sweden)

    R. Hein

    Full Text Available The coupled climate-chemistry model ECHAM4.L39(DLR/CHEM is presented which enables a simultaneous treatment of meteorology and atmospheric chemistry and their feedbacks. This is the first model which interactively combines a general circulation model with a chemical model, employing most of the important reactions and species necessary to describe the stratospheric and upper tropospheric ozone chemistry, and which is computationally fast enough to allow long-term integrations with currently available computer resources. This is possible as the model time-step used for the chemistry can be chosen as large as the integration time-step for the dynamics. Vertically the atmosphere is discretized by 39 levels from the surface up to the top layer which is centred at 10 hPa, with a relatively high vertical resolution of approximately 700 m near the extra-tropical tropopause. We present the results of a control simulation representing recent conditions (1990 and compare it to available observations. The focus is on investigations of stratospheric dynamics and chemistry relevant to describe the stratospheric ozone layer. ECHAM4.L39(DLR/CHEM reproduces main features of stratospheric dynamics in the arctic vortex region, including stratospheric warming events. This constitutes a major improvement compared to earlier model versions. However, apparent shortcomings in Antarctic circulation and temperatures persist. The seasonal and interannual variability of the ozone layer is simulated in accordance with observations. Activation and deactivation of chlorine in the polar stratospheric vortices and their inter-hemispheric differences are reproduced. Considering methane oxidation as part of the dynamic-chemistry feedback results in an improved representation of the spatial distribution of stratospheric water vapour concentrations. The current model constitutes a powerful tool to investigate, for instance, the combined direct and indirect effects of anthropogenic

  5. Carbon-14 Graphitization Chemistry

    Science.gov (United States)

    Miller, James; Collon, Philippe; Laverne, Jay

    2014-09-01

    Accelerator Mass Spectrometry (AMS) is a process that allows for the analysis of mass of certain materials. It is a powerful process because it results in the ability to separate rare isotopes with very low abundances from a large background, which was previously impossible. Another advantage of AMS is that it only requires very small amounts of material for measurements. An important application of this process is radiocarbon dating because the rare 14C isotopes can be separated from the stable 14N background that is 10 to 13 orders of magnitude larger, and only small amounts of the old and fragile organic samples are necessary for measurement. Our group focuses on this radiocarbon dating through AMS. When performing AMS, the sample needs to be loaded into a cathode at the back of an ion source in order to produce a beam from the material to be analyzed. For carbon samples, the material must first be converted into graphite in order to be loaded into the cathode. My role in the group is to convert the organic substances into graphite. In order to graphitize the samples, a sample is first combusted to form carbon dioxide gas and then purified and reduced into the graphite form. After a couple weeks of research and with the help of various Physics professors, I developed a plan and began to construct the setup necessary to perform the graphitization. Once the apparatus is fully completed, the carbon samples will be graphitized and loaded into the AMS machine for analysis.

  6. A coordination chemistry approach for modeling trace element adsorption

    International Nuclear Information System (INIS)

    Bourg, A.C.M.

    1986-01-01

    The traditional distribution coefficient, Kd, is highly dependent on the water chemistry and the surface properties of the geological system being studied and is therefore quite inappropriate for use in predictive models. Adsorption, one of the many processes included in Kd values, is described here using a coordination chemistry approach. The concept of adsorption of cationic trace elements by solid hydrous oxides can be applied to natural solids. The adsorption process is thus understood in terms of a classical complexation leading to the formation of surface (heterogeneous) ligands. Applications of this concept to some freshwater, estuarine and marine environments are discussed. (author)

  7. Carbon accumulation and changes in soil chemistry in reclaimed open-cast coal mining heaps near Sokolov using repeated measurement of chronosequence sites

    Czech Academy of Sciences Publication Activity Database

    Bartuška, Martin; Frouz, J.

    2015-01-01

    Roč. 66, 1 /SI/ (2015), s. 104-111 ISSN 1351-0754 Grant - others:GA ČR(CZ) GAP504/12/1288 Program:GA Institutional support: RVO:60077344 Keywords : carbon accumulation * changes in soil chemistry * post mining sites * chronosequence Subject RIV: DF - Soil Science Impact factor: 3.425, year: 2015

  8. The Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP): Overview and Description of Models, Simulations and Climate Diagnostics

    Science.gov (United States)

    Lamarque, J.-F.; Shindell, D. T.; Naik, V.; Plummer, D.; Josse, B.; Righi, M.; Rumbold, S. T.; Schulz, M.; Skeie, R. B.; Strode, S.; hide

    2013-01-01

    The Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP) consists of a series of time slice experiments targeting the long-term changes in atmospheric composition between 1850 and 2100, with the goal of documenting composition changes and the associated radiative forcing. In this overview paper, we introduce the ACCMIP activity, the various simulations performed (with a requested set of 14) and the associated model output. The 16 ACCMIP models have a wide range of horizontal and vertical resolutions, vertical extent, chemistry schemes and interaction with radiation and clouds. While anthropogenic and biomass burning emissions were specified for all time slices in the ACCMIP protocol, it is found that the natural emissions are responsible for a significant range across models, mostly in the case of ozone precursors. The analysis of selected present-day climate diagnostics (precipitation, temperature, specific humidity and zonal wind) reveals biases consistent with state-of-the-art climate models. The model-to- model comparison of changes in temperature, specific humidity and zonal wind between 1850 and 2000 and between 2000 and 2100 indicates mostly consistent results. However, models that are clear outliers are different enough from the other models to significantly affect their simulation of atmospheric chemistry.

  9. Enhanced Electro-Static Modulation of Ionic Diffusion through Carbon Nanotube Membranes by Diazonium Grafting Chemistry

    Science.gov (United States)

    Majumder, Mainak; Keis, Karin; Zhan, Xin; Meadows, Corey; Cole, Jeggan

    2013-01-01

    A membrane structure consisting of an aligned array of open ended carbon nanotubes (~ 7 nm i.d.) spanning across an inert polymer matrix allows the diffusive transport of aqueous ionic species through CNT cores. The plasma oxidation process that opens CNTs tips inherently introduces carboxylic acid groups at the CNT tips, which allows for a limited amount of chemical functional at the CNT pore entrance. However for numerous applications, it is important to increase the density of carboxylic acid groups at the pore entrance for effective separation processes. Aqueous diazonium based electro-chemistry significantly increases the functional density of carboxylic acid groups. pH dependent dye adsorption-desorption and interfacial capacitance measurements indicate ~ 5–6 times increase in functional density. To further control the spatial location of the functional chemistry, a fast flowing inert liquid column inside the CNT core is found to restrict the diazonium grafting to the CNT tips only. This is confirmed by the increased flux of positively charged Ru(bi-py)3+2 with anionic functionality. The electrostatic enhancement of ion diffusion is readily screened in 0.1(M) electrolyte solution consistent with the membrane pore geometry and increased functional density. PMID:25132719

  10. The Extrapolar SWIFT model (version 1.0): fast stratospheric ozone chemistry for global climate models

    Science.gov (United States)

    Kreyling, Daniel; Wohltmann, Ingo; Lehmann, Ralph; Rex, Markus

    2018-03-01

    The Extrapolar SWIFT model is a fast ozone chemistry scheme for interactive calculation of the extrapolar stratospheric ozone layer in coupled general circulation models (GCMs). In contrast to the widely used prescribed ozone, the SWIFT ozone layer interacts with the model dynamics and can respond to atmospheric variability or climatological trends.The Extrapolar SWIFT model employs a repro-modelling approach, in which algebraic functions are used to approximate the numerical output of a full stratospheric chemistry and transport model (ATLAS). The full model solves a coupled chemical differential equation system with 55 initial and boundary conditions (mixing ratio of various chemical species and atmospheric parameters). Hence the rate of change of ozone over 24 h is a function of 55 variables. Using covariances between these variables, we can find linear combinations in order to reduce the parameter space to the following nine basic variables: latitude, pressure altitude, temperature, overhead ozone column and the mixing ratio of ozone and of the ozone-depleting families (Cly, Bry, NOy and HOy). We will show that these nine variables are sufficient to characterize the rate of change of ozone. An automated procedure fits a polynomial function of fourth degree to the rate of change of ozone obtained from several simulations with the ATLAS model. One polynomial function is determined per month, which yields the rate of change of ozone over 24 h. A key aspect for the robustness of the Extrapolar SWIFT model is to include a wide range of stratospheric variability in the numerical output of the ATLAS model, also covering atmospheric states that will occur in a future climate (e.g. temperature and meridional circulation changes or reduction of stratospheric chlorine loading).For validation purposes, the Extrapolar SWIFT model has been integrated into the ATLAS model, replacing the full stratospheric chemistry scheme. Simulations with SWIFT in ATLAS have proven that the

  11. The surface chemistry of divalent metal carbonate minerals; a critical assessment of surface charge and potential data using the charge distribution multi-site ion complexation model

    NARCIS (Netherlands)

    Wolthers, M.; Charlet, L.; Van Cappellen, P.

    2008-01-01

    The Charge Distribution MUltiSite Ion Complexation or CD–MUSIC modeling approach is used to describe the chemical structure of carbonate mineralaqueous solution interfaces. The new model extends existing surface complexation models of carbonate minerals, by including atomic scale information on

  12. Modelling carbon emissions in electric systems

    International Nuclear Information System (INIS)

    Lau, E.T.; Yang, Q.; Forbes, A.B.; Wright, P.; Livina, V.N.

    2014-01-01

    Highlights: • We model carbon emissions in electric systems. • We estimate emissions in generated and consumed energy with UK carbon factors. • We model demand profiles with novel function based on hyperbolic tangents. • We study datasets of UK Elexon database, Brunel PV system and Irish SmartGrid. • We apply Ensemble Kalman Filter to forecast energy data in these case studies. - Abstract: We model energy consumption of network electricity and compute Carbon emissions (CE) based on obtained energy data. We review various models of electricity consumption and propose an adaptive seasonal model based on the Hyperbolic tangent function (HTF). We incorporate HTF to define seasonal and daily trends of electricity demand. We then build a stochastic model that combines the trends and white noise component and the resulting simulations are estimated using Ensemble Kalman Filter (EnKF), which provides ensemble simulations of groups of electricity consumers; similarly, we estimate carbon emissions from electricity generators. Three case studies of electricity generation and consumption are modelled: Brunel University photovoltaic generation data, Elexon national electricity generation data (various fuel types) and Irish smart grid data, with ensemble estimations by EnKF and computation of carbon emissions. We show the flexibility of HTF-based functions for modelling realistic cycles of energy consumption, the efficiency of EnKF in ensemble estimation of energy consumption and generation, and report the obtained estimates of the carbon emissions in the considered case studies

  13. Final Report - Low Temperature Combustion Chemistry And Fuel Component Interactions

    Energy Technology Data Exchange (ETDEWEB)

    Wooldridge, Margaret [Univ. of Michigan, Ann Arbor, MI (United States)

    2017-02-24

    Recent research into combustion chemistry has shown that reactions at “low temperatures” (700 – 1100 K) have a dramatic influence on ignition and combustion of fuels in virtually every practical combustion system. A powerful class of laboratory-scale experimental facilities that can focus on fuel chemistry in this temperature range is the rapid compression facility (RCF), which has proven to be a versatile tool to examine the details of fuel chemistry in this important regime. An RCF was used in this project to advance our understanding of low temperature chemistry of important fuel compounds. We show how factors including fuel molecular structure, the presence of unsaturated C=C bonds, and the presence of alkyl ester groups influence fuel auto-ignition and produce variable amounts of negative temperature coefficient behavior of fuel ignition. We report new discoveries of synergistic ignition interactions between alkane and alcohol fuels, with both experimental and kinetic modeling studies of these complex interactions. The results of this project quantify the effects of molecular structure on combustion chemistry including carbon bond saturation, through low temperature experimental studies of esters, alkanes, alkenes, and alcohols.

  14. Radiation chemistry of salicylic and methyl substituted salicylic acids: Models for the radiation chemistry of pharmaceutical compounds

    International Nuclear Information System (INIS)

    Ayatollahi, Shakiba; Kalnina, Daina; Song, Weihua; Turks, Maris; Cooper, William J.

    2013-01-01

    Salicylic acid and its derivatives are components of many medications and moieties found in numerous pharmaceutical compounds. They have been used as models for various pharmaceutical compounds in pharmacological studies, for the treatment of pharmaceuticals and personal care products (PPCPs), and, reactions with natural organic matter (NOM). In this study, the radiation chemistry of benzoic acid, salicylic acid and four methyl substituted salicylic acids (MSA) is reported. The absolute bimolecular reaction rate constants for hydroxyl radical reaction with benzoic and salicylic acids as well as 3-methyl-, 4-methyl-, 5-methyl-, and 6-methyl-salicylic acid were determined (5.86±0.54)×10 9 , (1.07±0.07)×10 10 , (7.48±0.17)×10 9 , (7.31±0.29)×10 9 , (5.47±0.25)×10 9 , (6.94±0.10)×10 9 (M −1 s −1 ), respectively. The hydrated electron reaction rate constants were measured (3.02±0.10)×10 9 , (8.98±0.27)×10 9 , (5.39±0.21)×10 9 , (4.33±0.17)×10 9 , (4.72±0.15)×10 9 , (1.42±0.02)×10 9 (M −1 s −1 ), respectively. The transient absorption spectra for the six model compounds were examined and their role as model compounds for the radiation chemistry of pharmaceuticals investigated. - Highlights: • Free radical chemistry of salicylic and 4 methyl salicylic acids is investigated. • The transient absorptions spectra for model compounds are measured. • Absolute bimolecular reaction rate constants for hydroxyl radical are determined. • Solvated electron reaction rate constants are calculated. • The use of salicylic acids as models for pharmaceuticals is explored

  15. Use of the HadGEM2 climate-chemistry model to investigate interannual variability in methane sources

    Science.gov (United States)

    Hayman, Garry; O'Connor, Fiona; Clark, Douglas; Huntingford, Chris; Gedney, Nicola

    2013-04-01

    The global mean atmospheric concentration of methane (CH4) has more than doubled during the industrial era [1] and now constitutes ? 20% of the anthropogenic climate forcing by greenhouse gases [2]. The globally-averaged CH4 growth rate, derived from surface measurements, has fallen significantly from a high of 16 ppb yr-1 in the late 1970s/early 1980s and was close to zero between 1999 and 2006 [1]. This overall period of declining or low growth was however interspersed with years of positive growth-rate anomalies (e.g., in 1991-1992, 1998-1999 and 2002-2003). Since 2007, renewed growth has been evident [1, 3], with the largest increases observed over polar northern latitudes and the Southern Hemisphere in 2007 and in the tropics in 2008. The observed inter-annual variability in atmospheric methane concentrations and the associated changes in growth rates have variously been attributed to changes in different methane sources and sinks [1, 4]. In this paper, we report results from runs of the HadGEM2 climate-chemistry model [5] using year- and month-specific emission datasets. The HadGEM2 model includes the comprehensive atmospheric chemistry and aerosol package, the UK Chemistry Aerosol community model (UKCA, http://www.ukca.ac.uk/wiki/index.php). The Standard Tropospheric Chemistry scheme was selected for this work. This chemistry scheme simulates the Ox, HOx and NOx chemical cycles and the oxidation of CO, methane, ethane and propane. Year- and month-specific emission datasets were generated for the period from 1997 to 2009 for the emitted species in the chemistry scheme (CH4, CO, NOx, HCHO, C2H6, C3H8, CH3CHO, CH3CHOCH3). The approach adopted varied depending on the source sector: Anthropogenic: The emissions from anthropogenic sources were based on decadal-averaged emission inventories compiled by [6] for the Coupled Carbon Cycle Climate Model Intercomparison Project (C4MIP). These were then used to derive year-specific emission datasets by scaling the

  16. A simple one-step chemistry model for partially premixed hydrocarbon combustion

    Energy Technology Data Exchange (ETDEWEB)

    Fernandez-Tarrazo, Eduardo [Instituto Nacional de Tecnica Aeroespacial, Madrid (Spain); Sanchez, Antonio L. [Area de Mecanica de Fluidos, Universidad Carlos III de Madrid, Leganes 28911 (Spain); Linan, Amable [ETSI Aeronauticos, Pl. Cardenal Cisneros 3, Madrid 28040 (Spain); Williams, Forman A. [Department of Mechanical and Aerospace Engineering, University of California San Diego, La Jolla, CA 92093-0411 (United States)

    2006-10-15

    This work explores the applicability of one-step irreversible Arrhenius kinetics with unity reaction order to the numerical description of partially premixed hydrocarbon combustion. Computations of planar premixed flames are used in the selection of the three model parameters: the heat of reaction q, the activation temperature T{sub a}, and the preexponential factor B. It is seen that changes in q with equivalence ratio f need to be introduced in fuel-rich combustion to describe the effect of partial fuel oxidation on the amount of heat released, leading to a universal linear variation q(f) for f>1 for all hydrocarbons. The model also employs a variable activation temperature T{sub a}(f) to mimic changes in the underlying chemistry in rich and very lean flames. The resulting chemistry description is able to reproduce propagation velocities of diluted and undiluted flames accurately over the whole flammability limit. Furthermore, computations of methane-air counterflow diffusion flames are used to test the proposed chemistry under nonpremixed conditions. The model not only predicts the critical strain rate at extinction accurately but also gives near-extinction flames with oxygen leakage, thereby overcoming known predictive limitations of one-step Arrhenius kinetics. (author)

  17. Effect of carbonate chemistry alteration on the early embryonic development of the Pacific oyster (Crassostrea gigas).

    Science.gov (United States)

    Gazeau, Frédéric; Gattuso, Jean-Pierre; Greaves, Mervyn; Elderfield, Henry; Peene, Jan; Heip, Carlo H R; Middelburg, Jack J

    2011-01-01

    Ocean acidification, due to anthropogenic CO₂ absorption by the ocean, may have profound impacts on marine biota. Calcareous organisms are expected to be particularly sensitive due to the decreasing availability of carbonate ions driven by decreasing pH levels. Recently, some studies focused on the early life stages of mollusks that are supposedly more sensitive to environmental disturbances than adult stages. Although these studies have shown decreased growth rates and increased proportions of abnormal development under low pH conditions, they did not allow attribution to pH induced changes in physiology or changes due to a decrease in aragonite saturation state. This study aims to assess the impact of several carbonate-system perturbations on the growth of Pacific oyster (Crassostrea gigas) larvae during the first 3 days of development (until shelled D-veliger larvae). Seawater with five different chemistries was obtained by separately manipulating pH, total alkalinity and aragonite saturation state (calcium addition). Results showed that the developmental success and growth rates were not directly affected by changes in pH or aragonite saturation state but were highly correlated with the availability of carbonate ions. In contrast to previous studies, both developmental success into viable D-shaped larvae and growth rates were not significantly altered as long as carbonate ion concentrations were above aragonite saturation levels, but they strongly decreased below saturation levels. These results suggest that the mechanisms used by these organisms to regulate calcification rates are not efficient enough to compensate for the low availability of carbonate ions under corrosive conditions.

  18. Effect of carbonate chemistry alteration on the early embryonic development of the Pacific oyster (Crassostrea gigas.

    Directory of Open Access Journals (Sweden)

    Frédéric Gazeau

    Full Text Available Ocean acidification, due to anthropogenic CO₂ absorption by the ocean, may have profound impacts on marine biota. Calcareous organisms are expected to be particularly sensitive due to the decreasing availability of carbonate ions driven by decreasing pH levels. Recently, some studies focused on the early life stages of mollusks that are supposedly more sensitive to environmental disturbances than adult stages. Although these studies have shown decreased growth rates and increased proportions of abnormal development under low pH conditions, they did not allow attribution to pH induced changes in physiology or changes due to a decrease in aragonite saturation state. This study aims to assess the impact of several carbonate-system perturbations on the growth of Pacific oyster (Crassostrea gigas larvae during the first 3 days of development (until shelled D-veliger larvae. Seawater with five different chemistries was obtained by separately manipulating pH, total alkalinity and aragonite saturation state (calcium addition. Results showed that the developmental success and growth rates were not directly affected by changes in pH or aragonite saturation state but were highly correlated with the availability of carbonate ions. In contrast to previous studies, both developmental success into viable D-shaped larvae and growth rates were not significantly altered as long as carbonate ion concentrations were above aragonite saturation levels, but they strongly decreased below saturation levels. These results suggest that the mechanisms used by these organisms to regulate calcification rates are not efficient enough to compensate for the low availability of carbonate ions under corrosive conditions.

  19. Solving vertical transport and chemistry in air pollution models

    NARCIS (Netherlands)

    Berkvens, P.J.F.; Bochev, M.A.; Krol, M.C.; Peters, W.; Verwer, J.G.; Chock, David P.; Carmichael, Gregory R.; Brick, Patricia

    2002-01-01

    For the time integration of stiff transport-chemistry problems from air pollution modelling, standard ODE solvers are not feasible due to the large number of species and the 3D nature. The popular alternative, standard operator splitting, introduces artificial transients for short-lived species.

  20. Solving Vertical Transport and Chemistry in Air Pollution Models

    NARCIS (Netherlands)

    Berkvens, P.J.F.; Bochev, M.A.; Verwer, J.G.; Krol, M.C.; Peters, W.

    For the time integration of stiff transport-chemistry problems from air pollution modelling, standard ODE solvers are not feasible due to the large number of species and the 3D nature. The popular alternative, standard operator splitting, introduces artificial transients for short-lived species.

  1. Transport of oxidized multi-walled carbon nanotubes through silica based porous media: influences of aquatic chemistry, surface chemistry, and natural organic matter.

    Science.gov (United States)

    Yang, Jin; Bitter, Julie L; Smith, Billy A; Fairbrother, D Howard; Ball, William P

    2013-12-17

    This paper provides results from studies of the transport of oxidized multi-walled carbon nanotubes (O-MWCNTs) of varying surface oxygen concentrations under a range of aquatic conditions and through uniform silica glass bead media. In the presence of Na(+), the required ionic strength (IS) for maximum particle attachment efficiency (i.e., the critical deposition concentration, or CDC) increased as the surface oxygen concentration of the O-MWCNTs or pH increased, following qualitative tenets of theories based on electrostatic interactions. In the presence of Ca(2+), CDC values were lower than those with Na(+) present, but were no longer sensitive to surface oxygen content, suggesting that Ca(2+) impacts the interactions between O-MWCNTs and glass beads by mechanisms other than electrostatic alone. The presence of Suwannee River natural organic matter (SRNOM) decreased the attachment efficiency of O-MWCNTs in the presence of either Na(+) or Ca(2+), but with more pronounced effects when Na(+) was present. Nevertheless, low concentrations of SRNOM (organic carbon) were sufficient to mobilize all O-MWCNTs studied at CaCl2 concentrations as high as 10 mM. Overall, this study reveals that NOM content, pH, and cation type show more importance than surface chemistry in affecting O-MWCNTs deposition during transport through silica-based porous media.

  2. GEM-AQ, an on-line global multiscale chemical weather modelling system: model description and evaluation of gas phase chemistry processes

    Directory of Open Access Journals (Sweden)

    J. W. Kaminski

    2008-06-01

    Full Text Available Tropospheric chemistry and air quality processes were implemented on-line in the Global Environmental Multiscale weather prediction model. The integrated model, GEM-AQ, was developed as a platform to investigate chemical weather at scales from global to urban. The current chemical mechanism is comprised of 50 gas-phase species, 116 chemical and 19 photolysis reactions, and is complemented by a sectional aerosol module with 5 aerosols types. All tracers are advected using the semi-Lagrangian scheme native to GEM. The vertical transport includes parameterized subgrid-scale turbulence and large scale deep convection. Dry deposition is included as a flux boundary condition in the vertical diffusion equation. Wet deposition of gas-phase species is treated in a simplified way, and only below-cloud scavenging is considered. The emissions used include yearly-averaged anthropogenic, and monthly-averaged biogenic, ocean, soil, and biomass burning emission fluxes, as well as NOx from lightning. In order to evaluate the ability to simulate seasonal variations and regional distributions of trace gases such as ozone, nitrogen dioxide and carbon monoxide, the model was run for a period of five years (2001–2005 on a global uniform 1.5°×1.5° horizontal resolution domain and 28 hybrid levels extending up to 10 hPa. Model results were compared with observations from satellites, aircraft measurement campaigns and balloon sondes. We find that GEM-AQ is able to capture the spatial details of the chemical fields in the middle and lower troposphere. The modelled ozone consistently shows good agreement with observations, except over tropical oceans. The comparison of carbon monoxide and nitrogen dioxide with satellite measurements emphasizes the need for more accurate, year-specific emissions fluxes for biomass burning and anthropogenic sources. Other species also compare well with available observations.

  3. Organic chemistry of Murchison meteorite: Carbon isotopic fractionation

    Science.gov (United States)

    Yuen, G. U.; Blair, N. E.; Desmarais, D. J.; Cronin, J. R.; Chang, S.

    1986-01-01

    The carbon isotopic composition of individual organic compounds of meteoritic origin remains unknown, as most reported carbon isotopic ratios are for bulk carbon or solvent extractable fractions. The researchers managed to determine the carbon isotopic ratios for individual hydrocarbons and monocarboxylic acids isolated from a Murchison sample by a freeze-thaw-ultrasonication technique. The abundances of monocarboxylic acids and saturated hydrocarbons decreased with increasing carbon number and the acids are more abundant than the hydrocarbon with the same carbon number. For both classes of compounds, the C-13 to C-12 ratios decreased with increasing carbon number in a roughly parallel manner, and each carboxylic acid exhibits a higher isotopic number than the hydrocarbon containing the same number of carbon atoms. These trends are consistent with a kinetically controlled synthesis of higher homologues for lower ones.

  4. Online coupled regional meteorology chemistry models in Europe : Current status and prospects

    NARCIS (Netherlands)

    Baklanov, A.; Schlünzen, K.; Suppan, P.; Baldasano, J.; Brunner, D.; Aksoyoglu, S.; Carmichael, G.; Douros, J.; Flemming, J.; Forkel, R.; Galmarini, S.; Gauss, M.; Grell, G.; Hirtl, M.; Joffre, S.; Jorba, O.; Kaas, E.; Kaasik, M.; Kallos, G.; Kong, X.; Korsholm, U.; Kurganskiy, A.; Kushta, J.; Lohmann, U.; Mahura, A.; Manders-Groot, A.; Maurizi, A.; Moussiopoulos, N.; Rao, S.T.; Savage, N.; Seigneur, C.; Sokhi, R.S.; Solazzo, E.; Solomos, S.; Sørensen, B.; Tsegas, G.; Vignati, E.; Vogel, B.; Zhang, Y.

    2014-01-01

    Online coupled mesoscale meteorology atmospheric chemistry models have undergone a rapid evolution in recent years. Although mainly developed by the air quality modelling community, these models are also of interest for numerical weather prediction and regional climate modelling as they can consider

  5. Kinetic modeling of microbially-driven redox chemistry of radionuclides in subsurface environments: Coupling transport, microbial metabolism and geochemistry

    International Nuclear Information System (INIS)

    Wang, Yifeng; Papenguth, Hans W.

    2000-01-01

    Microbial degradation of organic matter is a driving force in many subsurface geochemical systems, and therefore may have significant impacts on the fate of radionuclides released into subsurface environments. In this paper, the authors present a general reaction-transport model for microbial metabolism, redox chemistry, and radionuclide migration in subsurface systems. The model explicitly accounts for biomass accumulation and the coupling of radionuclide redox reactions with major biogeochemical processes. Based on the consideration that the biomass accumulation in subsurface environments is likely to achieve a quasi-steady state, they have accordingly modified the traditional microbial growth kinetic equation. They justified the use of the biogeochemical models without the explicit representation of biomass accumulation, if the interest of modeling is in the net impact of microbial reactions on geochemical processes. They then applied their model to a scenario in which an oxic water flow containing both uranium and completing organic ligands is recharged into an oxic aquifer in a carbonate formation. The model simulation shows that uranium can be reduced and therefore immobilized in the anoxic zone created by microbial degradation

  6. Kinetic modeling of microbially-driven redox chemistry of radionuclides in subsurface environments: Coupling transport, microbial metabolism and geochemistry

    Energy Technology Data Exchange (ETDEWEB)

    WANG,YIFENG; PAPENGUTH,HANS W.

    2000-05-04

    Microbial degradation of organic matter is a driving force in many subsurface geochemical systems, and therefore may have significant impacts on the fate of radionuclides released into subsurface environments. In this paper, the authors present a general reaction-transport model for microbial metabolism, redox chemistry, and radionuclide migration in subsurface systems. The model explicitly accounts for biomass accumulation and the coupling of radionuclide redox reactions with major biogeochemical processes. Based on the consideration that the biomass accumulation in subsurface environments is likely to achieve a quasi-steady state, they have accordingly modified the traditional microbial growth kinetic equation. They justified the use of the biogeochemical models without the explicit representation of biomass accumulation, if the interest of modeling is in the net impact of microbial reactions on geochemical processes. They then applied their model to a scenario in which an oxic water flow containing both uranium and completing organic ligands is recharged into an oxic aquifer in a carbonate formation. The model simulation shows that uranium can be reduced and therefore immobilized in the anoxic zone created by microbial degradation.

  7. Tropospheric jet response to Antarctic ozone depletion: An update with Chemistry-Climate Model Initiative (CCMI) models

    Science.gov (United States)

    Son, Seok-Woo; Han, Bo-Reum; Garfinkel, Chaim I.; Kim, Seo-Yeon; Park, Rokjin; Abraham, N. Luke; Akiyoshi, Hideharu; Archibald, Alexander T.; Butchart, N.; Chipperfield, Martyn P.; Dameris, Martin; Deushi, Makoto; Dhomse, Sandip S.; Hardiman, Steven C.; Jöckel, Patrick; Kinnison, Douglas; Michou, Martine; Morgenstern, Olaf; O’Connor, Fiona M.; Oman, Luke D.; Plummer, David A.; Pozzer, Andrea; Revell, Laura E.; Rozanov, Eugene; Stenke, Andrea; Stone, Kane; Tilmes, Simone; Yamashita, Yousuke; Zeng, Guang

    2018-05-01

    The Southern Hemisphere (SH) zonal-mean circulation change in response to Antarctic ozone depletion is re-visited by examining a set of the latest model simulations archived for the Chemistry-Climate Model Initiative (CCMI) project. All models reasonably well reproduce Antarctic ozone depletion in the late 20th century. The related SH-summer circulation changes, such as a poleward intensification of westerly jet and a poleward expansion of the Hadley cell, are also well captured. All experiments exhibit quantitatively the same multi-model mean trend, irrespective of whether the ocean is coupled or prescribed. Results are also quantitatively similar to those derived from the Coupled Model Intercomparison Project phase 5 (CMIP5) high-top model simulations in which the stratospheric ozone is mostly prescribed with monthly- and zonally-averaged values. These results suggest that the ozone-hole-induced SH-summer circulation changes are robust across the models irrespective of the specific chemistry-atmosphere-ocean coupling.

  8. Innovation Developments of Coal Chemistry Science in L.M. Litvinenko Institute of Physical-Organic Chemistry and Coal Chemistry of NAS of Ukraine

    Directory of Open Access Journals (Sweden)

    Shendrik, T.G.

    2015-11-01

    Full Text Available The article presents short historical review and innovation developments of Coal Chemistry Department of L.M. Litvinenko Institute, NAS of Ukraine connected with coal mine exploitation problems, search for decisions toward prevention of spontaneous combustion, dust control in mines, establishing structural chemical features of coal with different genesis and stages of metamorphism with the aim to develop new methods of their modification and rational use. The methods of obtaining inexpensive sorbents from Ukrainian raw materials (including carbon containing waste are proposed. The problems of modern coal chemistry science in IPOCC of NAS of Ukraine are outlined.

  9. Proceedings of the DAE-BRNS fifth interdisciplinary symposium on materials chemistry

    International Nuclear Information System (INIS)

    Jafar, Mohsin; Tyagi, Adish; Tyagi, Deepak

    2014-12-01

    The focus of the present symposium on materials chemistry was on research areas in materials chemistry like: nuclear materials; high purity materials; nanomaterials and clusters; carbon based materials; fuel cell materials and other electro-ceramics; biomaterials; polymers and soft condensed matter; materials for energy conversion; thin films and surface chemistry; magnetic materials; catalysis; chemical sensors; organic and organometallic compounds; computational material chemistry etc. Papers relevant to INIS are indexed separately

  10. How does Interactive Chemistry Influence the Representation of Stratosphere-Troposphere Coupling in a Climate Model?

    Science.gov (United States)

    Haase, S.; Matthes, K. B.

    2017-12-01

    Changes in stratospheric ozone can trigger tropospheric circulation changes. In the Southern hemisphere (SH), the observed shift of the Southern Annular Mode was attributed to the observed trend in lower stratospheric ozone. In the Northern Hemisphere (NH), a recent study showed that extremely low stratospheric ozone conditions during spring produce robust anomalies in the troposphere (zonal wind, temperature and precipitation). This could only be reproduced in a coupled chemistry climate model indicating that chemical-dynamical feedbacks are also important on the NH. To further investigate the importance of interactive chemistry for surface climate, we conducted a set of experiments using NCAR's Community Earth System Model (CESM1) with the Whole Atmosphere Community Climate Model (WACCM) as the atmosphere component. WACCM contains a fully interactive stratospheric chemistry module in its standard configuration. It also allows for an alternative configuration, referred to as SC-WACCM, in which the chemistry (O3, NO, O, O2, CO2 and chemical and shortwave heating rates) is specified as a 2D field in the radiation code. A comparison of the interactive vs. the specified chemistry version enables us to evaluate the relative importance of interactive chemistry by systematically inhibiting the feedbacks between chemistry and dynamics. To diminish the effect of temporal interpolation when prescribing ozone, we use daily resolved zonal mean ozone fields for the specified chemistry run. Here, we investigate the differences in stratosphere-troposphere coupling between the interactive and specified chemistry simulations for the mainly chemically driven SH as well as for the mainly dynamically driven NH. We will especially consider years that are characterized by extremely low stratospheric ozone on the one hand and by large dynamical disturbances, i.e. Sudden Stratospheric Warmings, on the other hand.

  11. Non-Equilibrium Chemistry of O-Rich AGB Stars as Revealed by ALMA

    Science.gov (United States)

    Wong, Ka Tat

    2018-04-01

    Chemical models suggest that pulsation driven shocks propagating from the stellar surfaces of oxygen-rich evolved stars to the dust formation zone trigger non-equilibrium chemistry in the shocked gas near the star, including the formation of carbon-bearing molecules in the stellar winds dominated by oxygen-rich chemistry. Recent long-baseline ALMA observations are able to give us a detailed view of the molecular line emission and absorption at an angular resolution of a few stellar radii. I am going to present the latest results from the ALMA observations of IK Tau and o Cet in late 2017, with a particular focus on HCN.

  12. Effects of '"Environmental Chemistry" Elective Course via Technology-Embedded Scientific Inquiry Model on Some Variables

    Science.gov (United States)

    Çalik, Muammer; Özsevgeç, Tuncay; Ebenezer, Jazlin; Artun, Hüseyin; Küçük, Zeynel

    2014-01-01

    The purpose of this study is to examine the effects of "environmental chemistry" elective course via Technology-Embedded Scientific Inquiry (TESI) model on senior science student teachers' (SSSTs) conceptions of environmental chemistry concepts/issues, attitudes toward chemistry, and technological pedagogical content knowledge…

  13. The chemistry-climate model ECHAM6.3-HAM2.3-MOZ1.0

    Science.gov (United States)

    Schultz, Martin G.; Stadtler, Scarlet; Schröder, Sabine; Taraborrelli, Domenico; Franco, Bruno; Krefting, Jonathan; Henrot, Alexandra; Ferrachat, Sylvaine; Lohmann, Ulrike; Neubauer, David; Siegenthaler-Le Drian, Colombe; Wahl, Sebastian; Kokkola, Harri; Kühn, Thomas; Rast, Sebastian; Schmidt, Hauke; Stier, Philip; Kinnison, Doug; Tyndall, Geoffrey S.; Orlando, John J.; Wespes, Catherine

    2018-05-01

    The chemistry-climate model ECHAM-HAMMOZ contains a detailed representation of tropospheric and stratospheric reactive chemistry and state-of-the-art parameterizations of aerosols using either a modal scheme (M7) or a bin scheme (SALSA). This article describes and evaluates the model version ECHAM6.3-HAM2.3-MOZ1.0 with a focus on the tropospheric gas-phase chemistry. A 10-year model simulation was performed to test the stability of the model and provide data for its evaluation. The comparison to observations concentrates on the year 2008 and includes total column observations of ozone and CO from IASI and OMI, Aura MLS observations of temperature, HNO3, ClO, and O3 for the evaluation of polar stratospheric processes, an ozonesonde climatology, surface ozone observations from the TOAR database, and surface CO data from the Global Atmosphere Watch network. Global budgets of ozone, OH, NOx, aerosols, clouds, and radiation are analyzed and compared to the literature. ECHAM-HAMMOZ performs well in many aspects. However, in the base simulation, lightning NOx emissions are very low, and the impact of the heterogeneous reaction of HNO3 on dust and sea salt aerosol is too strong. Sensitivity simulations with increased lightning NOx or modified heterogeneous chemistry deteriorate the comparison with observations and yield excessively large ozone budget terms and too much OH. We hypothesize that this is an impact of potential issues with tropical convection in the ECHAM model.

  14. Next Generation Carbon-Nitrogen Dynamics Model

    Science.gov (United States)

    Xu, C.; Fisher, R. A.; Vrugt, J. A.; Wullschleger, S. D.; McDowell, N. G.

    2012-12-01

    Nitrogen is a key regulator of vegetation dynamics, soil carbon release, and terrestrial carbon cycles. Thus, to assess energy impacts on the global carbon cycle and future climates, it is critical that we have a mechanism-based and data-calibrated nitrogen model that simulates nitrogen limitation upon both above and belowground carbon dynamics. In this study, we developed a next generation nitrogen-carbon dynamic model within the NCAR Community Earth System Model (CESM). This next generation nitrogen-carbon dynamic model utilized 1) a mechanistic model of nitrogen limitation on photosynthesis with nitrogen trade-offs among light absorption, electron transport, carboxylation, respiration and storage; 2) an optimal leaf nitrogen model that links soil nitrogen availability and leaf nitrogen content; and 3) an ecosystem demography (ED) model that simulates the growth and light competition of tree cohorts and is currently coupled to CLM. Our three test cases with changes in CO2 concentration, growing temperature and radiation demonstrate the model's ability to predict the impact of altered environmental conditions on nitrogen allocations. Currently, we are testing the model against different datasets including soil fertilization and Free Air CO2 enrichment (FACE) experiments across different forest types. We expect that our calibrated model will considerably improve our understanding and predictability of vegetation-climate interactions.itrogen allocation model evaluations. The figure shows the scatter plots of predicted and measured Vc,max and Jmax scaled to 25 oC (i.e.,Vc,max25 and Jmax25) at elevated CO2 (570 ppm, test case one), reduced radiation in canopy (0.1-0.9 of the radiation at the top of canopy, test case two) and reduced growing temperature (15oC, test case three). The model is first calibrated using control data under ambient CO2 (370 ppm), radiation at the top of the canopy (621 μmol photon/m2/s), the normal growing temperature (30oC). The fitted model

  15. Three-dimensional decomposition models for carbon productivity

    International Nuclear Information System (INIS)

    Meng, Ming; Niu, Dongxiao

    2012-01-01

    This paper presents decomposition models for the change in carbon productivity, which is considered a key indicator that reflects the contributions to the control of greenhouse gases. Carbon productivity differential was used to indicate the beginning of decomposition. After integrating the differential equation and designing the Log Mean Divisia Index equations, a three-dimensional absolute decomposition model for carbon productivity was derived. Using this model, the absolute change of carbon productivity was decomposed into a summation of the absolute quantitative influences of each industrial sector, for each influence factor (technological innovation and industrial structure adjustment) in each year. Furthermore, the relative decomposition model was built using a similar process. Finally, these models were applied to demonstrate the decomposition process in China. The decomposition results reveal several important conclusions: (a) technological innovation plays a far more important role than industrial structure adjustment; (b) industry and export trade exhibit great influence; (c) assigning the responsibility for CO 2 emission control to local governments, optimizing the structure of exports, and eliminating backward industrial capacity are highly essential to further increase China's carbon productivity. -- Highlights: ► Using the change of carbon productivity to measure a country's contribution. ► Absolute and relative decomposition models for carbon productivity are built. ► The change is decomposed to the quantitative influence of three-dimension. ► Decomposition results can be used for improving a country's carbon productivity.

  16. Integrated modeling and characterization of local crack chemistry

    International Nuclear Information System (INIS)

    Savchik, J.A.; Burke, M.S.

    1996-01-01

    The MULTEQ computer program has become an industry wide tool which can be used to calculate the chemical composition in a flow occluded region as the solution within concentrates due to a local boiling process. These results can be used to assess corrosion concerns in plant equipment such as steam generators. Corrosion modeling attempts to quantify corrosion assessments by accounting for the mass transport processes involved in the corrosion mechanism. MULTEQ has played an ever increasing role in defining the local chemistry for such corrosion models. This paper will outline how the integration of corrosion modeling with the analysis of corrosion films and deposits can lead to the development of a useful modeling tool, wherein MULTEQ is interactively linked to a diffusion and migration transport process. This would provide a capability to make detailed inferences of the local crack chemistry based on the analyses of the local corrosion films and deposits inside a crack and thus provide guidance for chemical fixes to avoid cracking. This methodology is demonstrated for a simple example of a cracked tube. This application points out the utility of coupling MULTEQ with a mass transport process and the feasibility of an option in a future version of MULTEQ that would permit relating film and deposit analyses to the local chemical environment. This would increase the amount of information obtained from removed tube analyses and laboratory testing that can contribute to an overall program for mitigating tubing and crevice corrosion

  17. Integrated modeling and characterization of local crack chemistry

    International Nuclear Information System (INIS)

    Savchik, J.A.; Burke, M.S.

    1995-01-01

    The MULTEQ computer program has become an industry wide tool which can be used to calculate the chemical composition in a flow occluded region as the solution within concentrates due to a local boiling process. These results can be used to assess corrosion concerns in plant equipment such as steam generators. Corrosion modeling attempts to quantify corrosion assessments by accounting for the mass transport processes involved in the corrosion mechanism. MULTEQ has played an ever increasing role in defining the local chemistry for such corrosion models. This paper will outline how the integration of corrosion modeling with the analysis of corrosion films and deposits can lead to the development of a useful modeling tool, wherein MULTEQ is interactively linked to a diffusion and migration transport process. This would provide a capability to make detailed inferences of the local crack chemistry based on the analyses of the local corrosion films and deposits inside a crack and thus provide guidance for chemical fixes to avoid cracking. This methodology is demonstrated for a simple example of a cracked tube. This application points out the utility of coupling MULTEQ with a mass transport process and the feasibility of an option in a future version of MULTEQ that would permit relating film and deposit analyses to the local chemical environment. This would increase the amount of information obtained from removed tube analyses and laboratory testing that can contribute to an overall program for mitigating tubing and crevice corrosion

  18. porewater chemistry experiment at Mont Terri rock laboratory. Reactive transport modelling including bacterial activity

    International Nuclear Information System (INIS)

    Tournassat, Christophe; Gaucher, Eric C.; Leupin, Olivier X.; Wersin, Paul

    2010-01-01

    Document available in extended abstract form only. An in-situ test in the Opalinus Clay formation, termed pore water Chemistry (PC) experiment, was run for a period of five years. It was based on the concept of diffusive equilibration whereby traced water with a composition close to that expected in the formation was continuously circulated and monitored in a packed off borehole. The main original focus was to obtain reliable data on the pH/pCO 2 of the pore water, but because of unexpected microbially- induced redox reactions, the objective was then changed to elucidate the biogeochemical processes happening in the borehole and to understand their impact on pH/pCO 2 and pH in the low permeability clay formation. The biologically perturbed chemical evolution of the PC experiment was simulated with reactive transport models. The aim of this modelling exercise was to develop a 'minimal-' model able to reproduce the chemical evolution of the PC experiment, i.e. the chemical evolution of solute inorganic and organic compounds (organic carbon, dissolved inorganic carbon etc...) that are coupled with each other through the simultaneous occurrence of biological transformation of solute or solid compounds, in-diffusion and out-diffusion of solute species and precipitation/dissolution of minerals (in the borehole and in the formation). An accurate description of the initial chemical conditions in the surrounding formation together with simplified kinetics rule mimicking the different phases of bacterial activities allowed reproducing the evolution of all main measured parameters (e.g. pH, TOC). Analyses from the overcoring and these simulations evidence the high buffer capacity of Opalinus clay regarding chemical perturbations due to bacterial activity. This pH buffering capacity is mainly attributed to the carbonate system as well as to the clay surfaces reactivity. Glycerol leaching from the pH-electrode might be the primary organic source responsible for

  19. Size-dependent response of foraminiferal calcification to seawater carbonate chemistry

    Science.gov (United States)

    Henehan, Michael J.; Evans, David; Shankle, Madison; Burke, Janet E.; Foster, Gavin L.; Anagnostou, Eleni; Chalk, Thomas B.; Stewart, Joseph A.; Alt, Claudia H. S.; Durrant, Joseph; Hull, Pincelli M.

    2017-07-01

    The response of the marine carbon cycle to changes in atmospheric CO2 concentrations will be determined, in part, by the relative response of calcifying and non-calcifying organisms to global change. Planktonic foraminifera are responsible for a quarter or more of global carbonate production, therefore understanding the sensitivity of calcification in these organisms to environmental change is critical. Despite this, there remains little consensus as to whether, or to what extent, chemical and physical factors affect foraminiferal calcification. To address this, we directly test the effect of multiple controls on calcification in culture experiments and core-top measurements of Globigerinoides ruber. We find that two factors, body size and the carbonate system, strongly influence calcification intensity in life, but that exposure to corrosive bottom waters can overprint this signal post mortem. Using a simple model for the addition of calcite through ontogeny, we show that variable body size between and within datasets could complicate studies that examine environmental controls on foraminiferal shell weight. In addition, we suggest that size could ultimately play a role in determining whether calcification will increase or decrease with acidification. Our models highlight that knowledge of the specific morphological and physiological mechanisms driving ontogenetic change in calcification in different species will be critical in predicting the response of foraminiferal calcification to future change in atmospheric pCO2.

  20. A simple global carbon and energy coupled cycle model for global warming simulation: sensitivity to the light saturation effect

    International Nuclear Information System (INIS)

    Ichii, Kazuhito; Murakami, Kazutaka; Mukai, Toshikazu; Yamaguchi, Yasushi; Ogawa, Katsuro

    2003-01-01

    A simple Earth system model, the Four-Spheres Cycle of Energy and Mass (4-SCEM) model, has been developed to simulate global warming due to anthropogenic CO 2 emission. The model consists of the Atmosphere-Earth Heat Cycle (AEHC) model, the Four Spheres Carbon Cycle (4-SCC) model, and their feedback processes. The AEHC model is a one-dimensional radiative convective model, which includes the greenhouse effect of CO 2 and H 2 O, and one cloud layer. The 4-SCC model is a box-type carbon cycle model, which includes biospheric CO 2 fertilization, vegetation area variation, the vegetation light saturation effect and the HILDA oceanic carbon cycle model. The feedback processes between carbon cycle and climate considered in the model are temperature dependencies of water vapor content, soil decomposition and ocean surface chemistry. The future status of the global carbon cycle and climate was simulated up to the year 2100 based on the 'business as usual' (IS92a) emission scenario, followed by a linear decline in emissions to zero in the year 2200. The atmospheric CO 2 concentration reaches 645 ppmv in 2100 and a peak of 760 ppmv approximately in the year 2170, and becomes a steady state with 600 ppmv. The projected CO 2 concentration was lower than those of the past carbon cycle studies, because we included the light saturation effect of vegetation. The sensitivity analysis showed that uncertainties derived from the light saturation effect of vegetation and land use CO 2 emissions were the primary cause of uncertainties in projecting future CO 2 concentrations. The climate feedback effects showed rather small sensitivities compared with the impacts of those two effects. Satellite-based net primary production trends analyses can somewhat decrease the uncertainty in quantifying CO 2 emissions due to land use changes. On the other hand, as the estimated parameter in vegetation light saturation was poorly constrained, we have to quantify and constrain the effect more

  1. Presidential Green Chemistry Challenge: 1997 Academic Award

    Science.gov (United States)

    Presidential Green Chemistry Challenge 1997 award winner, Professor Joseph M. DeSimone, developed surfactants that allow carbon dioxide to be a solvent for chemical manufacturing, replacing hazardous chemical solvents.

  2. A Model for Nitrogen Chemistry in Oxy-Fuel Combustion of Pulverized Coal

    DEFF Research Database (Denmark)

    Hashemi, Hamid; Hansen, Stine; Toftegaard, Maja Bøg

    2011-01-01

    , heating and devolatilization of particles, and gas–solid reactions. The model is validated by comparison with entrained flow reactor results from the present work and from the literature on pulverized coal combustion in O2/CO2 and air, covering the effects of fuel, mixing conditions, temperature......In this work, a model for the nitrogen chemistry in the oxy-fuel combustion of pulverized coal has been developed. The model is a chemical reaction engineering type of model with a detailed reaction mechanism for the gas-phase chemistry, together with a simplified description of the mixing of flows......, stoichiometry, and inlet NO level. In general, the model provides a satisfactory description of NO formation in air and oxy-fuel combustion of coal, but under some conditions, it underestimates the impact on NO of replacing N2 with CO2. According to the model, differences in the NO yield between the oxy...

  3. Green chemistry: to rethink chemistry for tomorrow's world. Press briefing of 20 January 2015

    International Nuclear Information System (INIS)

    Legrand, Francois

    2015-01-01

    This document discusses various issues related to the development of the green chemistry sector, and mentions and presents activities performed by the CEA in this respect. A first part outlines how green chemistry is an answer to stakes for a sustainable development. The second part addresses metal recycling: recovery of silver from photovoltaic cells, avoiding tensions related to rare earth supply. The third part discusses how to replace dangerous or costly compounds (chromium in aircraft paintings, platinum in fuel cells, ruthenium in photovoltaic cells, rare earth in magnetic wire). The fourth part addresses how to transform wastes into useful products (production of formamides, of aromatic compounds, and of methanol, respectively from waste recycling, natural lignin, and CO_2). The fifth part presents new concepts for chemical synthesis: chemistry under ultrasounds, production of hydrogen from water. The sixth part presents contributions of life sciences to green chemistry: reduction of carbon dioxide emissions, bioremediation (biology for soil rehabilitation), production of molecules of interest by using micro algae, enzymes or bacteria. The last part discusses issues which outline that chemistry is at the heart of challenges for a sustainable nuclear in terms of materials, for a closed fuel cycle, in terms of fuel cycle processes, of installation sanitation and dismantling. Appendices formulate 5 societal challenges for green chemistry, and 12 background principles of green chemistry

  4. Chemistry and Transport In a Multi-Dimensional Model

    Science.gov (United States)

    Yung, Yuk L.; Allen, M.; Zurek, R. W.; Salawitch, R. J.

    2002-01-01

    The focus of the work funded under this proposal is the exchange between the stratosphere and the troposphere, and between the troposphere and the blaspheme. These two interfaces represent the frontiers of atmospheric chemistry. It is the combination of exchange processes at both interfaces that ultimately controls how the blaspheme (including human activities) affects the ozone layer. The modeling work was motivated by and attempts to integrate information obtained by aircraft, spacecraft, shuttle and oceanic measurements. The model development and research activities accomplished in the past three years provide a technical and intellectual basis for the research in this group. The innovative part of our research program is related to the IAV of ozone and the hydrological cycle. Other related but independently supported work include the study of isotopic fractionation of atmospheric species, e.g., N2O and CO2. Our theory suggests that we now have the ability to probe the middle atmosphere at a level of sensitivity where subtle details such as the isotopic composition of simple molecules can yield measurable systematic effects. This creates the possibility for probing the chemistry and dynamics of the middle atmosphere using all of the N2O and CO2 isotopologues. In the following we will briefly describe the model development and review the highlights of recent accomplishments.

  5. An advanced modeling study on the impacts and atmospheric implications of multiphase dimethyl sulfide chemistry

    Science.gov (United States)

    Hoffmann, Erik Hans; Tilgner, Andreas; Schrödner, Roland; Bräuer, Peter; Wolke, Ralf; Herrmann, Hartmut

    2016-01-01

    Oceans dominate emissions of dimethyl sulfide (DMS), the major natural sulfur source. DMS is important for the formation of non-sea salt sulfate (nss-SO42−) aerosols and secondary particulate matter over oceans and thus, significantly influence global climate. The mechanism of DMS oxidation has accordingly been investigated in several different model studies in the past. However, these studies had restricted oxidation mechanisms that mostly underrepresented important aqueous-phase chemical processes. These neglected but highly effective processes strongly impact direct product yields of DMS oxidation, thereby affecting the climatic influence of aerosols. To address these shortfalls, an extensive multiphase DMS chemistry mechanism, the Chemical Aqueous Phase Radical Mechanism DMS Module 1.0, was developed and used in detailed model investigations of multiphase DMS chemistry in the marine boundary layer. The performed model studies confirmed the importance of aqueous-phase chemistry for the fate of DMS and its oxidation products. Aqueous-phase processes significantly reduce the yield of sulfur dioxide and increase that of methyl sulfonic acid (MSA), which is needed to close the gap between modeled and measured MSA concentrations. Finally, the simulations imply that multiphase DMS oxidation produces equal amounts of MSA and sulfate, a result that has significant implications for nss-SO42− aerosol formation, cloud condensation nuclei concentration, and cloud albedo over oceans. Our findings show the deficiencies of parameterizations currently used in higher-scale models, which only treat gas-phase chemistry. Overall, this study shows that treatment of DMS chemistry in both gas and aqueous phases is essential to improve the accuracy of model predictions. PMID:27688763

  6. CARBON-RICH GIANT PLANETS: ATMOSPHERIC CHEMISTRY, THERMAL INVERSIONS, SPECTRA, AND FORMATION CONDITIONS

    Energy Technology Data Exchange (ETDEWEB)

    Madhusudhan, Nikku [Department of Astrophysical Sciences, Princeton University, Princeton, NJ 08544 (United States); Mousis, Olivier [Institut UTINAM, CNRS-UMR 6213, Observatoire de Besancon, BP 1615, F-25010 Besancon Cedex (France); Johnson, Torrence V. [Jet Propulsion Laboratory, California Institute of Technology, Pasadena, CA 91109 (United States); Lunine, Jonathan I., E-mail: nmadhu@astro.princeton.edu [Department of Astronomy, Cornell University, Ithaca, NY 14853 (United States)

    2011-12-20

    The recent inference of a carbon-rich atmosphere, with C/O {>=} 1, in the hot Jupiter WASP-12b motivates the exotic new class of carbon-rich planets (CRPs). We report a detailed study of the atmospheric chemistry and spectroscopic signatures of carbon-rich giant (CRG) planets, the possibility of thermal inversions in their atmospheres, the compositions of icy planetesimals required for their formation via core accretion, and the apportionment of ices, rock, and volatiles in their envelopes. Our results show that CRG atmospheres probe a unique region in composition space, especially at high temperature (T). For atmospheres with C/O {>=} 1, and T {approx}> 1400 K in the observable atmosphere, most of the oxygen is bound up in CO, while H{sub 2}O is depleted and CH{sub 4} is enhanced by up to two or three orders of magnitude each, compared to equilibrium compositions with solar abundances (C/O = 0.54). These differences in the spectroscopically dominant species for the different C/O ratios cause equally distinct observable signatures in the spectra. As such, highly irradiated transiting giant exoplanets form ideal candidates to estimate atmospheric C/O ratios and to search for CRPs. We also find that the C/O ratio strongly affects the abundances of TiO and VO, which have been suggested to cause thermal inversions in highly irradiated hot Jupiter atmospheres. A C/O = 1 yields TiO and VO abundances of {approx}100 times lower than those obtained with equilibrium chemistry assuming solar abundances, at P {approx} 1 bar. Such a depletion is adequate to rule out thermal inversions due to TiO/VO even in the most highly irradiated hot Jupiters, such as WASP-12b. We estimate the compositions of the protoplanetary disk, the planetesimals, and the envelope of WASP-12b, and the mass of ices dissolved in the envelope, based on the observed atmospheric abundances. Adopting stellar abundances (C/O = 0.44) for the primordial disk composition and low-temperature formation conditions

  7. A general method for the inclusion of radiation chemistry in astrochemical models.

    Science.gov (United States)

    Shingledecker, Christopher N; Herbst, Eric

    2018-02-21

    In this paper, we propose a general formalism that allows for the estimation of radiolysis decomposition pathways and rate coefficients suitable for use in astrochemical models, with a focus on solid phase chemistry. Such a theory can help increase the connection between laboratory astrophysics experiments and astrochemical models by providing a means for modelers to incorporate radiation chemistry into chemical networks. The general method proposed here is targeted particularly at the majority of species now included in chemical networks for which little radiochemical data exist; however, the method can also be used as a starting point for considering better studied species. We here apply our theory to the irradiation of H 2 O ice and compare the results with previous experimental data.

  8. Multimodel simulations of carbon monoxide: comparison with observations and projected near-future changes

    NARCIS (Netherlands)

    Shindell, D.T.; Krol, M.C.

    2006-01-01

    We analyze present-day and future carbon monoxide (CO) simulations in 26 state-ofthe- art atmospheric chemistry models run to study future air quality and climate change. In comparison with near-global satellite observations from the MOPITT instrument and local surface measurements, the models show

  9. Surface chemistry of a viscose-based activated carbon cloth modified by treatment with ammonia and steam

    Energy Technology Data Exchange (ETDEWEB)

    Boudou, J.P. [University of Paris, Paris (France)

    2003-07-01

    The influence of ammonia treatment at 800{sup o}C on the catalytic activity of a viscose-based activated carbon cloth (ACC) was evaluated for the oxidative retention of H{sub 2}S or SO{sub 2} at room temperature. Change in the surface chemistry was observed by X-ray spectroscopy of nitrogen (N1s) and by temperature programmed desorption (TPD). Dynamic adsorption of H{sub 2}S or SO{sub 2} in moist air onto a packed bed of activated carbon cloth was monitored by measurement of the breakthrough curves at room temperature. ACC modified by ammonia showed noteworthy enhanced SO{sub 2} and H{sub 2}S loading relative to the untreated ACC. Improved SO{sub 2} retention rate could be replicated several times after regeneration by washing at room temperature, in contrast to the case with H{sub 2}S. The likely reasons for the behavior of H{sub 2}S and SO{sub 2} on the ammonia-treated ACC are discussed with reference to the recent literature.

  10. Sketching the Invisible to Predict the Visible: From Drawing to Modeling in Chemistry.

    Science.gov (United States)

    Cooper, Melanie M; Stieff, Mike; DeSutter, Dane

    2017-10-01

    Sketching as a scientific practice goes beyond the simple act of inscribing diagrams onto paper. Scientists produce a wide range of representations through sketching, as it is tightly coupled to model-based reasoning. Chemists in particular make extensive use of sketches to reason about chemical phenomena and to communicate their ideas. However, the chemical sciences have a unique problem in that chemists deal with the unseen world of the atomic-molecular level. Using sketches, chemists strive to develop causal mechanisms that emerge from the structure and behavior of molecular-level entities, to explain observations of the macroscopic visible world. Interpreting these representations and constructing sketches of molecular-level processes is a crucial component of student learning in the modern chemistry classroom. Sketches also serve as an important component of assessment in the chemistry classroom as student sketches give insight into developing mental models, which allows instructors to observe how students are thinking about a process. In this paper we discuss how sketching can be used to promote such model-based reasoning in chemistry and discuss two case studies of curricular projects, CLUE and The Connected Chemistry Curriculum, that have demonstrated a benefit of this approach. We show how sketching activities can be centrally integrated into classroom norms to promote model-based reasoning both with and without component visualizations. Importantly, each of these projects deploys sketching in support of other types of inquiry activities, such as making predictions or depicting models to support a claim; sketching is not an isolated activity but is used as a tool to support model-based reasoning in the discipline. Copyright © 2017 Cognitive Science Society, Inc.

  11. Functionalization of single-walled carbon nanotubes with protein by click chemistry as sensing platform for sensitized electrochemical immunoassay

    International Nuclear Information System (INIS)

    Qi Honglan; Ling Chen; Huang Ru; Qiu Xiaoying; Shangguan Li; Gao Qiang; Zhang Chengxiao

    2012-01-01

    Highlights: ► Single-walled carbon nanotubes were functionalized with protein by click chemistry. ► The SWNTs conjugated with protein showed excellent dispersion in water and kept good bioacitvity. ► A competitive electrochemical immunoassay for the determination of anti-IgG was developed with high sensitivity and good stability. - Abstract: The application of the Cu(I)-catalyzed [3 + 2] Huisgen cycloaddition to the functionalization of single-walled carbon nanotubes (SWNTs) with the protein and the use of the artificial SWNTs as a sensing platform for sensitive immunoassay were reported. Covalent functionalization of azide decorated SWNTs with alkyne modified protein was firstly accomplished by the Cu(I)-catalyzed [3 + 2] Huisgen cycloaddition. FT-IR spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy and transmission electron micrograph were used to characterize the protein-functionalized SWNTs. It was found that the SWNTs conjugated with the proteins showed excellent dispersion in water and kept good bioacitivity when immunoglobulin (IgG) and horseradish peroxidase (HRP) were chosen as model proteins. As a proof-of-concept, IgG-functionalized SWNTs were immobilized onto the surface of a glassy carbon electrode by simple casting method as immunosensing platform and a sensitive competitive electrochemical immunoassay was developed for the determination of anti-immunoglobulin (anti-IgG) using HRP as enzyme label. The fabrication of the immunosensor were characterized by cyclic voltammetry and electrochemical impedance spectroscopy with the redox probe [Fe(CN) 6 ] 3−/4− . The SWNTs as immobilization platform showed better sensitizing effect, a detection limit of 30 pg mL −1 (S/N = 3) was obtained for anti-IgG. The proposed strategy provided a stable immobilization method and sensitized recognition platform for analytes. This work demonstrated that the click coupling of SWNTs with protein was an effective

  12. Nanocarbons Made by Soft Chemistry

    Czech Academy of Sciences Publication Activity Database

    Kavan, Ladislav

    2002-01-01

    Roč. 386, - (2002), s. 167-172 ISSN 1058-725X R&D Projects: GA ČR GA203/99/1015 Institutional research plan: CEZ:AV0Z4040901 Keywords : carbon nanotubes * fullerenes * perfluorinated hydrocarbons Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 0.457, year: 2002

  13. In vitro adsorption study of fluoxetine in activated carbons and activated carbon fibres

    Energy Technology Data Exchange (ETDEWEB)

    Nabais, J.M. Valente; Mouquinho, A.; Galacho, C.; Carrott, P.J.M.; Ribeiro Carrott, M.M.L. [Centro de Quimica de Evora e Departamento de Quimica da Universidade de Evora, Rua Romao Ramalho no. 59, 7000-671 Evora (Portugal)

    2008-05-15

    We study the in vitro adsorption of fluoxetine hydrochloride by different adsorbents in simulated gastric and intestinal fluid, pH 1.2 and 7.5, respectively. The tested materials were two commercial activated carbons, carbomix and maxsorb MSC30, one activated carbon fibre produced in our laboratory and also three MCM-41 samples, also produced by us. Selected samples were modified by liquid phase oxidation and thermal treatment in order to change the surface chemistry without significant modifications to the porous characteristics. The fluoxetine adsorption follows the Langmuir model. The calculated Q{sub 0} values range from 54 to 1112 mg/g. A different adsorption mechanism was found for the adsorption of fluoxetine in activated carbon fibres and activated carbons. In the first case the most relevant factors are the molecular sieving effect and the dispersive interactions whereas in the activated carbons the mechanism seams to be based on the electrostatic interactions between the fluoxetine molecules and the charged carbon surface. Despite the different behaviours most of the materials tested have potential for treating potential fluoxetine intoxications. (author)

  14. Drivers of the Seasonal Carbon Cycle in the Coastal Gulf of Alaska

    Science.gov (United States)

    Pilcher, D.; Siedlecki, S. A.; Hermann, A. J.; Coyle, K. O.; Mathis, J. T.

    2016-02-01

    The Coastal Gulf of Alaska serves as a significant carbon sink annually, but varies seasonally from net carbon efflux in winter, to net carbon uptake from spring through fall. This significant uptake of anthropogenic CO2 combined with the naturally cold, low calcium carbonate surface waters is expected to accelerate ocean acidification. Observational evidence has already detected subsurface aragonite undersaturation, likely resulting from carbon remineralization of sinking organic matter. Other processes such as storm-induced vertical mixing, glacial runoff, temperature change, and nutrient supply can further modify the carbon cycle. Improving knowledge of these seasonal processes is critical for the region's fisheries that provide substantial ecosystem services and can be adversely impacted by sub-optimal aragonite saturation conditions. We use a regional model of the Coastal Gulf of Alaska coupled to an ecosystem model with full carbonate chemistry to investigate the physical and biogeochemical mechanisms that drive the seasonal carbon cycle. Boundary conditions are set from the coarser Northeast Pacific model, with alkalinity and carbon concentrations determined from empirical relationships with salinity. Model output from a 2009 hindcast simulation is compared to observations of alkalinity and dissolved inorganic carbon concentrations for model verification and to elucidate seasonal mechanisms.

  15. Southwest Pacific deep water carbonate chemistry linked to high southern latitude climate and atmospheric CO2 during the Last Glacial Termination

    Science.gov (United States)

    Allen, Katherine A.; Sikes, Elisabeth L.; Hönisch, Bärbel; Elmore, Aurora C.; Guilderson, Thomas P.; Rosenthal, Yair; Anderson, Robert F.

    2015-08-01

    A greater amount of CO2 was stored in the deep sea during glacial periods, likely via greater efficiency of the biologic pump and increased uptake by a more alkaline ocean. Reconstructing past variations in seawater carbonate ion concentration (a major component of alkalinity) enables quantification of the relative roles of different oceanic CO2 storage mechanisms and also places constraints on the timing, magnitude, and location of subsequent deep ocean ventilation. Here, we present a record of deep-water inorganic carbon chemistry since the Last Glacial Maximum (LGM; ∼19-23 ka BP), derived from sediment core RR0503-83 raised from 1627 m in New Zealand's Bay of Plenty. The core site lies within the upper limit of southern-sourced Circumpolar Deep Water (CDW), just below the lower boundary of Antarctic Intermediate Water (AAIW). We reconstruct past changes in bottom water inorganic carbon chemistry from the trace element and stable isotopic composition of calcite shells of the epibenthic foraminifer Cibicidoides wuellerstorfi. A record of ΔCO32-(ΔCO32- = [COCO32-] in situ - [CO32-] saturation) derived from the foraminiferal boron to calcium ratio (B/Ca) provides evidence for greater ice-age storage of respired CO2 and reveals abrupt deglacial shifts in [CO32-] in situ of up to 30 μmol/kg (5 times larger than the difference between average LGM and Holocene values). The rapidity of these changes suggests the influence of changing water mass structure and atmospheric circulation in addition to a decrease in CO2 content of interior waters.

  16. Modelling interactions of carbon dioxide, forests, and climate

    International Nuclear Information System (INIS)

    Luxmoore, R.J.; Baldocchi, D.D.

    1994-01-01

    Atmospheric carbon dioxide is rising and forests and climate is changing exclamation point This combination of fact and premise may be evaluated at a range of temporal and spatial scales with the aid of computer simulators describing the interrelationships between forest vegetation, litter and soil characteristics, and appropriate meteorological variables. Some insights on the effects of climate on the transfers of carbon and the converse effect of carbon transfer on climate are discussed as a basis for assessing the significance of feedbacks between vegetation and climate under conditions of rising atmospheric carbon dioxide. Three main classes of forest models are reviewed. These are physiologically-based models, forest succession simulators based on the JABOWA model, and ecosystem-carbon budget models that use compartment transfer rates with empirically estimated coefficients. Some regression modeling approaches are also outlined. Energy budget models applied to forests and grasslands are also reviewed. This review presents examples of forest models; a comprehensive discussion of all available models is not undertaken

  17. Aspects and prospects of the chemistry of organic heterocycles (review)

    International Nuclear Information System (INIS)

    Schroth, W.

    1986-01-01

    The systematics of heterocycles, their place in organic chemistry, and their significance for theory and practice are discussed. Problems of the chemistry of heterocycles are discussed on the examples of systems with various types of conjugation and ring sizes. The focus is on the principles of synthesis of heterocycles, in particular, those based on acetylene, various C 3 fragments, carbon disulfide, and maleic anhydride. Individual sections of the survey are devoted to the role of heterocycles in biosynthesis, as well as certain problems common to the chemistry of heterocycles, biochemistry, and macromolecular chemistry

  18. A unique model system of microbial carbonate precipitation: Stromatolites of Lagoa Vermelha, Brazil

    Science.gov (United States)

    Warthmann, R. J.; Vasoncelos, C.; van Lith, Y.; Visscher, P. T.; McKenzie, J. A.

    2003-04-01

    Modern stromatolites are recognized as analogues to fossil laminated structures, which are remains of microbial activity that are widely found in sedimentary rocks beginning in the Neo-Archean, but are quite rare today. The key difference of modern microbial mats and stromatolites compared to ancient examples is the type of lithification. A few marine and hypersaline microbial mats have been observed to precipitate carbonates, and only in Shark Bay (Western, Australia) and Highborne Cay (Bahamas) has the formation of continuous laminae of carbonates been observed. Lagoa Vermelha, a moderate hypersaline lagoon in Rio de Janeiro, Brazil, offers the ideal conditions to promote lithification. Calcified, sometimes dolomitic stromatolites grow on the sediment surface, whereas within the sediments dolomite precipitates. The factors controlling carbonate precipitation in Lagoa Vermelha are the changing water chemistry and the special hydrology, combined with a high primary production by cyanobacteria, a high rate of respiration and the absence of higher organisms. Here, we present a study of the physico-chemical parameters, microbial processes and bio-minerals associated with these stromatolites and microbial mats. This approach provides boundary conditions to better understand dolomite formation. Several discrete lithified calcium carbonate layers are present. The first lithified layer is found beneath a 2-mm-thick biofilm, which contains Gloeocapsa. Below the underlying dense Microcoleus layer, the second micrite deposit is observed at 4-5 mm depth. Successive micritic laminae are preserved in the layer of decaying cyanobacteria that harbors large numbers of purple sulfur bacteria, heterotrophic microbes and sulfate-reducing bacteria. C-isotope studies of the carbonate layers indicate a contribution of organic derived carbon associated with microbial processes, such as sulfate reduction. The O-isotopic values indicate an evaporitic enrichment of the water. Understanding

  19. Modelling the urban air quality in Hamburg with the new city-scale chemistry transport model CityChem

    Science.gov (United States)

    Karl, Matthias; Ramacher, Martin; Aulinger, Armin; Matthias, Volker; Quante, Markus

    2017-04-01

    Air quality modelling plays an important role by providing guidelines for efficient air pollution abatement measures. Currently, most urban dispersion models treat air pollutants as passive tracer substances or use highly simplified chemistry when simulating air pollutant concentrations on the city-scale. The newly developed urban chemistry-transport model CityChem has the capability of modelling the photochemical transformation of multiple pollutants along with atmospheric diffusion to produce pollutant concentration fields for the entire city on a horizontal resolution of 100 m or even finer and a vertical resolution of 24 layers up to 4000 m height. CityChem is based on the Eulerian urban dispersion model EPISODE of the Norwegian Institute for Air Research (NILU). CityChem treats the complex photochemistry in cities using detailed EMEP chemistry on an Eulerian 3-D grid, while using simple photo-stationary equilibrium on a much higher resolution grid (receptor grid), i.e. close to industrial point sources and traffic sources. The CityChem model takes into account that long-range transport contributes to urban pollutant concentrations. This is done by using 3-D boundary concentrations for the city domain derived from chemistry-transport simulations with the regional air quality model CMAQ. For the study of the air quality in Hamburg, CityChem was set-up with a main grid of 30×30 grid cells of 1×1 km2 each and a receptor grid of 300×300 grid cells of 100×100 m2. The CityChem model was driven with meteorological data generated by the prognostic meteorology component of the Australian chemistry-transport model TAPM. Bottom-up inventories of emissions from traffic, industry, households were based on data of the municipality of Hamburg. Shipping emissions for the port of Hamburg were taken from the Clean North Sea Shipping project. Episodes with elevated ozone (O3) were of specific interest for this study, as these are associated with exceedances of the World

  20. Controlling Processes on Carbonate Chemistry across the Pacific

    Science.gov (United States)

    Hartman, S. E.

    2016-12-01

    The SWIRE NOC Ocean Monitoring System (SNOMS) project is an innovative programme helping to answer important questions about global climate change by using a commercial ship of opportunity to measure carbon in the surface of the ocean. Daily sampling coupled to continuous underway observation from a ship of opportunity (MV Shengking) provides new insights into the processes controlling variability in the carbonate system across the Pacific. The ships track runs from Vancouver (Canada) to Brisbane (Australia). Daily samples were taken on-board and measurements of Total alkalinity (TA) and total dissolved inorganic carbon (DIC) were determined. This was alongside measurements of nutrients and continuous records of temperature, salinity, chlorophyll-fluorescence, carbon dioxide and dissolved oxygen (DO). These sensor based measurements were validated using the discrete samples. Carbon dioxide calculated from DIC and TA showed an offset from the sensor data of up to 8uatm. This and comparisons with climatology were used to calibrate the sensor data. The data have been compared with previous data from the MV Pacific Celebes that ran a similar route until 2012. The data show a clear increase in seawater carbon dioxide, tracking the atmospheric increases. Along track the partial pressure of seawater carbon dioxide varied by over 150 uatm. The highest values were seen just south of the equator in the Pacific, which is an important source region for carbon dioxide to the atmosphere.

  1. Multimodel simulations of carbon monoxide: Comparison with observations and projected near-future changes

    NARCIS (Netherlands)

    Shindell, D.T.; Faluvegi, G.; Stevenson, D.S.; Krol, M.C.; Emmons, L.K.; Lamarque, J.F.; Petron, G.; Dentener, F.J.; Ellingsen, K.; Schultz, M.G.; Wild, O.; Amann, M.; Atherton, C.S.; Bergmann, D.J.; Bey, I.; Butler, T.; Cofala, J.; Collins, W.J.; Derwent, R.G.; Doherty, R.M.; Drevet, J.; Eskes, H.J.; Fiore, A.M.; Gauss, M.; Hauglustaine, D.A.; Horowitz, L.W.; Isaksen, I.S.A.; Lawrence, M.G.; Montanaro, V.; Muller, J.F.; Pitari, G.; Prather, M.J.; Pyle, J.A.; Rast, S.; Rodriguez, J.M.; Sanderson, M.G.; Savage, N.H.; Strahan, S.E.; Sudo, K.; Szopa, S.; Unger, N.; Noije, van T.P.C.; Zeng, G.

    2006-01-01

    We analyze present-day and future carbon monoxide (CO) simulations in 26 state-of-the-art atmospheric chemistry models run to study future air quality and climate change. In comparison with near-global satellite observations from the MOPITT instrument and local surface measurements, the models show

  2. Carbohydrate Chemistry from Fischer to Now

    Indian Academy of Sciences (India)

    In this brief article, this intriguing field of natural products chemistry is ... six carbon atoms, five hydroxyl groups (one primary and the other ..... to elucidate the mechanism of ..... As a postscript, a quotation from the review by P H Seeberger and.

  3. Effect of fullerenol surface chemistry on nanoparticle binding-induced protein misfolding

    Science.gov (United States)

    Radic, Slaven; Nedumpully-Govindan, Praveen; Chen, Ran; Salonen, Emppu; Brown, Jared M.; Ke, Pu Chun; Ding, Feng

    2014-06-01

    Fullerene and its derivatives with different surface chemistry have great potential in biomedical applications. Accordingly, it is important to delineate the impact of these carbon-based nanoparticles on protein structure, dynamics, and subsequently function. Here, we focused on the effect of hydroxylation -- a common strategy for solubilizing and functionalizing fullerene -- on protein-nanoparticle interactions using a model protein, ubiquitin. We applied a set of complementary computational modeling methods, including docking and molecular dynamics simulations with both explicit and implicit solvent, to illustrate the impact of hydroxylated fullerenes on the structure and dynamics of ubiquitin. We found that all derivatives bound to the model protein. Specifically, the more hydrophilic nanoparticles with a higher number of hydroxyl groups bound to the surface of the protein via hydrogen bonds, which stabilized the protein without inducing large conformational changes in the protein structure. In contrast, fullerene derivatives with a smaller number of hydroxyl groups buried their hydrophobic surface inside the protein, thereby causing protein denaturation. Overall, our results revealed a distinct role of surface chemistry on nanoparticle-protein binding and binding-induced protein misfolding.Fullerene and its derivatives with different surface chemistry have great potential in biomedical applications. Accordingly, it is important to delineate the impact of these carbon-based nanoparticles on protein structure, dynamics, and subsequently function. Here, we focused on the effect of hydroxylation -- a common strategy for solubilizing and functionalizing fullerene -- on protein-nanoparticle interactions using a model protein, ubiquitin. We applied a set of complementary computational modeling methods, including docking and molecular dynamics simulations with both explicit and implicit solvent, to illustrate the impact of hydroxylated fullerenes on the structure and

  4. Soil Carbon and Nitrogen Cycle Modeling

    Science.gov (United States)

    Woo, D.; Chaoka, S.; Kumar, P.; Quijano, J. C.

    2012-12-01

    Second generation bioenergy crops, such as miscanthus (Miscantus × giganteus) and switchgrass (Panicum virgatum), are regarded as clean energy sources, and are an attractive option to mitigate the human-induced climate change. However, the global climate change and the expansion of perennial grass bioenergy crops have the power to alter the biogeochemical cycles in soil, especially, soil carbon storages, over long time scales. In order to develop a predictive understanding, this study develops a coupled hydrological-soil nutrient model to simulate soil carbon responses under different climate scenarios such as: (i) current weather condition, (ii) decreased precipitation by -15%, and (iii) increased temperature up to +3C for four different crops, namely miscanthus, switchgrass, maize, and natural prairie. We use Precision Agricultural Landscape Modeling System (PALMS), version 5.4.0, to capture biophysical and hydrological components coupled with a multilayer carbon and ¬nitrogen cycle model. We apply the model at daily time scale to the Energy Biosciences Institute study site, located in the University of Illinois Research Farms, in Urbana, Illinois. The atmospheric forcing used to run the model was generated stochastically from parameters obtained using available data recorded in Bondville Ameriflux Site. The model simulations are validated with observations of drainage and nitrate and ammonium concentrations recorded in drain tiles during 2011. The results of this study show (1) total soil carbon storage of miscanthus accumulates most noticeably due to the significant amount of aboveground plant carbon, and a relatively high carbon to nitrogen ratio and lignin content, which reduce the litter decomposition rate. Also, (2) the decreased precipitation contributes to the enhancement of total soil carbon storage and soil nitrogen concentration because of the reduced microbial biomass pool. However, (3) an opposite effect on the cycle is introduced by the increased

  5. Modeling Human Serum Albumin Tertiary Structure to Teach Upper-Division Chemistry Students Bioinformatics and Homology Modeling Basics

    Science.gov (United States)

    Petrovic, Dus?an; Zlatovic´, Mario

    2015-01-01

    A homology modeling laboratory experiment has been developed for an introductory molecular modeling course for upper-division undergraduate chemistry students. With this experiment, students gain practical experience in homology model preparation and assessment as well as in protein visualization using the educational version of PyMOL…

  6. North American Carbon Project (NACP) Regional Model-Model and Model-Data Intercomparison Project

    Science.gov (United States)

    Huntzinger, D. N.; Post, W. M.; Jacobson, A. R.; Cook, R. B.

    2009-05-01

    Available observations are localized and widely separated in both space and time, so we depend heavily on models to characterize, understand, and predict carbon fluxes at regional and global scales. The results from each model differ because they use different approaches (forward vs. inverse), modeling strategies (detailed process, statistical, observation based), process representation, boundary conditions, initial conditions, and driver data. To investigate these differences we conducted a model-model and model-data comparison using available forward ecosystem model and atmospheric inverse output, along with regional scale inventory data. Forward or "bottom-up" models typically estimate carbon fluxes through a set of physiological relationships, and are based on our current mechanistic understanding of how carbon is exchanged within ecosystems. Inverse or "top-down" analyses use measured atmospheric concentrations of CO2, coupled with an atmospheric transport model to infer surface flux distributions. Although bottom-up models do fairly well at reproducing measured fluxes (i.e., net ecosystem exchange) at a given location, they vary considerably in their estimates of carbon flux over regional or continental scales, suggesting difficulty in scaling mechanistic relationships to large areas and/or timescales. Conversely, top-down inverse models predict fluxes that are quantitatively consistent with atmospheric measurements, suggesting that they are capturing large scale variability in flux quite well, but offer limited insights into the processes controlling this variability and how fluxes vary at fine spatial scales. The analyses focused on identifying and quantifying spatial and temporal patterns of carbon fluxes among the models; quantifying across-model variability, as well as comparing simulated or estimated surface fluxes and biomass to observed values at regional to continental scales for the period 2000-2005. The analysis focused on the following three

  7. Calibration of a Chemistry Test Using the Rasch Model

    Directory of Open Access Journals (Sweden)

    Nancy Coromoto Martín Guaregua

    2011-11-01

    Full Text Available The Rasch model was used to calibrate a general chemistry test for the purpose of analyzing the advantages and information the model provides. The sample was composed of 219 college freshmen. Of the 12 questions used, good fit was achieved in 10. The evaluation shows that although there are items of variable difficulty, there are gaps on the scale; in order to make the test complete, it will be necessary to design new items to fill in these gaps.

  8. A Global Assessment of the Chemical Recalcitrance of Seagrass Tissues: Implications for Long-Term Carbon Sequestration

    Directory of Open Access Journals (Sweden)

    Stacey M. Trevathan-Tackett

    2017-06-01

    Full Text Available Seagrass ecosystems have recently been identified for their role in climate change mitigation due to their globally-significant carbon sinks; yet, the capacity of seagrasses to sequester carbon has been shown to vary greatly among seagrass ecosystems. The recalcitrant nature of seagrass tissues, or the resistance to degradation back into carbon dioxide, is one aspect thought to influence sediment carbon stocks. In this study, a global survey investigated how the macromolecular chemistry of seagrass leaves, sheaths/stems, rhizomes and roots varied across 23 species from 16 countries. The goal was to understand how this seagrass chemistry might influence the capacity of seagrasses to contribute to sediment carbon stocks. Three non-destructive analytical chemical analyses were used to investigate seagrass chemistry: thermogravimetric analysis (TGA and solid state 13C-NMR and infrared spectroscopy. A strong latitudinal influence on carbon quality was found, whereby temperate seagrasses contained 5% relatively more labile carbon, and tropical seagrasses contained 3% relatively more refractory carbon. Sheath/stem tissues significantly varied across taxa, with larger morphologies typically containing more refractory carbon than smaller morphologies. Rhizomes were characterized by a higher proportion of labile carbon (16% of total organic matter compared to 8–10% in other tissues; however, high rhizome biomass production and slower remineralization in anoxic sediments will likely enhance these below-ground tissues' contributions to long-term carbon stocks. Our study provides a standardized and global dataset on seagrass carbon quality across tissue types, taxa and geography that can be incorporated in carbon sequestration and storage models as well as ecosystem valuation and management strategies.

  9. On the use of mass-conserving wind fields in chemistry-transport models

    Directory of Open Access Journals (Sweden)

    B. Bregman

    2003-01-01

    Full Text Available A new method has been developed that provides mass-conserving wind fields for global chemistry-transport models. In previous global Eulerian modeling studies a mass-imbalance was found between the model mass transport and the surface pressure tendencies. Several methods have been suggested to correct for this imbalance, but so far no satisfactory solution has been found. Our new method solves these problems by using the wind fields in a spherical harmonical form (divergence and vorticity by mimicing the physics of the weather forecast model as closely as possible. A 3-D chemistry-transport model was used to show that the calculated ozone fields with the new processing method agree remarkably better with ozone observations in the upper troposphere and lower stratosphere. In addition, the calculated age of air in the lower stratosphere show better agreement with observations, although the air remains still too young in the extra-tropical stratosphere.

  10. Carbon source in the future chemical industries

    Science.gov (United States)

    Hofmann, Peter; Heinrich Krauch, Carl

    1982-11-01

    Rising crude oil prices favour the exploitation of hitherto unutilised energy carriers and the realisation of new technologies in all sectors where carbon is used. These changed economic constraints necessitate both savings in conventional petrochemistry and a change to oil-independent carbon sources in the chemical industry. While, in coal chemistry, the synthesis and process principles of petrochemistry — fragmentation of the raw material and subsequent buildup of molecular structures — can be maintained, the raw material structure largely remains unchanged in the chemistry of renewable raw materials. This lecture is to demonstrate the structural as well as the technological and energy criteria of the chemistry of alternative carbon sources, to forecast the chances of commercial realization and to discuss some promising fields of research and development.

  11. Tracking chemistry self-efficacy and achievement in a preparatory chemistry course

    Science.gov (United States)

    Garcia, Carmen Alicia

    Self-efficacy is a person's own perception about performing a task with a certain level of proficiency (Bandura, 1986). An important affective aspect of learning chemistry is chemistry self-efficacy (CSE). Several researchers have found chemistry self-efficacy to be a fair predictor of achievement in chemistry. This study was done in a college preparatory chemistry class for science majors exploring chemistry self-efficacy and its change as it relates to achievement. A subscale of CAEQ, Chemistry Attitudes and Experiences Questionnaire (developed by Dalgety et al, 2003) as well as student interviews were used to determine student chemistry self-efficacy as it changed during the course. The questionnaire was given to the students five times during the semester: in the first class and the class before each the four tests taken through the semester. Twenty-six students, both men and women, of the four major races/ethnicities were interviewed three times during the semester and events that triggered changes in CSE were followed through the interviews. HLM (hierarchical linear modeling) was used to model the results of the CSE surveys. Among the findings, women who started at significantly lower CSE than men accomplished a significant gain by the end of the semester. Blacks' CSE trends through the semester were found to be significantly different from the rest of the ethnicities.

  12. Progress in the medicinal chemistry of silicon: C/Si exchange and beyond.

    Science.gov (United States)

    Fujii, Shinya; Hashimoto, Yuichi

    2017-04-01

    Application of silyl functionalities is one of the most promising strategies among various 'elements chemistry' approaches for the development of novel and distinctive drug candidates. Replacement of one or more carbon atoms of various biologically active compounds with silicon (so-called sila-substitution) has been intensively studied for decades, and is often effective for alteration of activity profile and improvement of metabolic profile. In addition to simple C/Si exchange, several novel approaches for utilizing silicon in medicinal chemistry have been suggested in recent years, focusing on the intrinsic differences between silicon and carbon. Sila-substitution offers great potential for enlarging the chemical space of medicinal chemistry, and provides many options for structural development of drug candidates.

  13. Ion sorption onto hydrous ferric oxides: Effect on major element fluid chemistry at Aespoe, Sweden

    International Nuclear Information System (INIS)

    Bruton, C.J.; Viani, B.E.

    1996-06-01

    The observed variability of fluid chemistry at the Aespoe Hard Rock Laboratory is not fully described by conservative fluid mixing models. Ion exchange may account for some of the observed discrepancies. It is also possible that variably charged solids such as oxyhydroxides of Fe can serve as sources and sinks of anions and cations through surface complexation. Surface complexation reactions on hydrous ferric oxides involve sorption of both cations and anions. Geochemical modeling of the surface chemistry of hydrous ferric oxides (HFOs) in equilibrium with shallow HBH02 and deep KA0483A waters shows that HFOs can serve as significant, pH-sensitive sources and sinks for cations and anions. Carbonate sorption is favored especially at below-neutral pH. A greater mass of carbonate is sorbed onto HFO surfaces than is contained in the fluid when 10 g goethite, used as a proxy for HFOs, is in contact with 1 kg H 2 O. The masses of sorbent required to significantly impact fluid chemistry through sorption/desorption reactions seem to be reasonable when compared to the occurrences of HFOs at Aespoe. Thus, it is possible that small changes in fluid chemistry can cause significant releases of cations or anions from HFOs into the fluid phase or, alternately, result in uptake of aqueous species onto HFO surfaces. Simulations of the mixing of shallow HBH02 and native KA0483A waters in the presence of a fixed mass of goethite show that surface complexation does not cause the concentrations of Ca, Sr, and SO 4 to deviate from those that are predicted using conservative mixing models. Results for HCO 3 are more difficult to interpret and cannot be addressed adequately at this time

  14. Low temperature nitrogen chemistry. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Glarborg, P.; Dam-Johansen, K.; Kristensen, P.G.; Alzueta, M.; Roejel, H.

    1997-04-01

    The results of a two tasks program on Natural Gas Reburning are reported. The work involved an experimental and theoretical study of the reburning and hybrid reburning/SNCR chemistry in the 1000-1500 K range. The interactions between hydrocarbon and nitrogen chemistry under fuel-rich conditions were investigated in order to assess the NO{sub x} reduction potential of low temperature reburning. The effect of reburn fuel(carbon monoxide, methane, acetylene, ethylene, ethane, and methane/ethane mixture), temperature, stoichiometry, reactant dilution, reaction time, and inlet NO level were studied. The results indicate a significant NO reduction potential even below 1400 K, but extrapolation to practical conditions are complicated by inadequate knowledge of the detailed chemistry as well as of the effect of mixing. The possibilities of enhancing the conversion to N{sub 2} instead of NO by adding selective reducing agents (hybrid reburning/SNCR) were evaluated. Our results indicate little synergistic effect between reburn and SNCR. The most simple configuration, where the selective reducing agent is injected together with the burnout air, is not expected to be effective, unless the N-agent is injected in form of an aqueous solution. A chemical kinetic model for reburning and reburn/SNCR is listed and can be obtained by e-mail from pgl(commerical at)kt.dtu.dk.(au) 145 refs.

  15. A new 2D climate model with chemistry and self consistent eddy-parameterization. The impact of airplane NO{sub x} on the chemistry of the atmosphere

    Energy Technology Data Exchange (ETDEWEB)

    Gepraegs, R.; Schmitz, G.; Peters, D. [Institut fuer Atmosphaerenphysik, Kuehlungsborn (Germany)

    1997-12-31

    A 2D version of the ECHAM T21 climate model has been developed. The new model includes an efficient spectral transport scheme with implicit diffusion. Furthermore, photodissociation and chemistry of the NCAR 2D model have been incorporated. A self consistent parametrization scheme is used for eddy heat- and momentum flux in the troposphere. It is based on the heat flux parametrization of Branscome and mixing-length formulation for quasi-geostrophic vorticity. Above 150 hPa the mixing-coefficient K{sub yy} is prescribed. Some of the model results are discussed, concerning especially the impact of aircraft NO{sub x} emission on the model chemistry. (author) 6 refs.

  16. A new 2D climate model with chemistry and self consistent eddy-parameterization. The impact of airplane NO{sub x} on the chemistry of the atmosphere

    Energy Technology Data Exchange (ETDEWEB)

    Gepraegs, R; Schmitz, G; Peters, D [Institut fuer Atmosphaerenphysik, Kuehlungsborn (Germany)

    1998-12-31

    A 2D version of the ECHAM T21 climate model has been developed. The new model includes an efficient spectral transport scheme with implicit diffusion. Furthermore, photodissociation and chemistry of the NCAR 2D model have been incorporated. A self consistent parametrization scheme is used for eddy heat- and momentum flux in the troposphere. It is based on the heat flux parametrization of Branscome and mixing-length formulation for quasi-geostrophic vorticity. Above 150 hPa the mixing-coefficient K{sub yy} is prescribed. Some of the model results are discussed, concerning especially the impact of aircraft NO{sub x} emission on the model chemistry. (author) 6 refs.

  17. CO chemistry/research trends in CO chemistry in the US

    Energy Technology Data Exchange (ETDEWEB)

    Cantacuzene, M

    1978-10-01

    Research trends in CO chemistry in the U.S. include the development of stable and selective homogeneous catalysts which would facilitate the removal of the heat of reaction and be resistant to sulfur poisoning for the methanation reaction, methanol synthesis, and Fischer-Tropsch synthesis; development of low-temperature homogeneous water gas shift catalysts; and research on the coordination chemistry and photochemical conversions of CO/sub 2/. In 1977, the National Science Foundation awarded 16 contracts for a total of $720,000 to promote the research in this field, including studies on chemisorption and heterogeneous catalysis (four contracts) and on transition metal complexes (ten contracts, of which seven are dedicated to metal clusters). Carbon monoxide-based processes, including water gas shift reactions, CO reduction to alkanes and alcohols, hydroformylation, and homogeneous carbonylation processes, recently developed in the U.S. are listed.

  18. Carbonate chemistry of an in-situ free-ocean CO2 enrichment experiment (antFOCE) in comparison to short term variation in Antarctic coastal waters.

    Science.gov (United States)

    Stark, J S; Roden, N P; Johnstone, G J; Milnes, M; Black, J G; Whiteside, S; Kirkwood, W; Newbery, K; Stark, S; van Ooijen, E; Tilbrook, B; Peltzer, E T; Berry, K; Roberts, D

    2018-02-12

    Free-ocean CO 2 enrichment (FOCE) experiments have been deployed in marine ecosystems to manipulate carbonate system conditions to those predicted in future oceans. We investigated whether the pH/carbonate chemistry of extremely cold polar waters can be manipulated in an ecologically relevant way, to represent conditions under future atmospheric CO 2 levels, in an in-situ FOCE experiment in Antarctica. We examined spatial and temporal variation in local ambient carbonate chemistry at hourly intervals at two sites between December and February and compared these with experimental conditions. We successfully maintained a mean pH offset in acidified benthic chambers of -0.38 (±0.07) from ambient for approximately 8 weeks. Local diel and seasonal fluctuations in ambient pH were duplicated in the FOCE system. Large temporal variability in acidified chambers resulted from system stoppages. The mean pH, Ω arag and fCO 2 values in the acidified chambers were 7.688 ± 0.079, 0.62 ± 0.13 and 912 ± 150 µatm, respectively. Variation in ambient pH appeared to be mainly driven by salinity and biological production and ranged from 8.019 to 8.192 with significant spatio-temporal variation. This experiment demonstrates the utility of FOCE systems to create conditions expected in future oceans that represent ecologically relevant variation, even under polar conditions.

  19. Drivers of inorganic carbon dynamics in first-year sea ice: A model study

    Science.gov (United States)

    Moreau, Sébastien; Vancoppenolle, Martin; Delille, Bruno; Tison, Jean-Louis; Zhou, Jiayun; Kotovich, Marie; Thomas, David; Geilfus, Nicolas-Xavier; Goosse, Hugues

    2015-04-01

    Sea ice is an active source or a sink for carbon dioxide (CO2), although to what extent is not clear. Here, we analyze CO2 dynamics within sea ice using a one-dimensional halo-thermodynamic sea ice model including gas physics and carbon biogeochemistry. The ice-ocean fluxes, and vertical transport, of total dissolved inorganic carbon (DIC) and total alkalinity (TA) are represented using fluid transport equations. Carbonate chemistry, the consumption and release of CO2 by primary production and respiration, the precipitation and dissolution of ikaite (CaCO3•6H2O) and ice-air CO2 fluxes, are also included. The model is evaluated using observations from a 6-month field study at Point Barrow, Alaska and an ice-tank experiment. At Barrow, results show that the DIC budget is mainly driven by physical processes, wheras brine-air CO2 fluxes, ikaite formation, and net primary production, are secondary factors. In terms of ice-atmosphere CO2 exchanges, sea ice is a net CO2 source and sink in winter and summer, respectively. The formulation of the ice-atmosphere CO2 flux impacts the simulated near-surface CO2 partial pressure (pCO2), but not the DIC budget. Because the simulated ice-atmosphere CO2 fluxes are limited by DIC stocks, and therefore < 2 mmol m-2 day-1, we argue that the observed much larger CO2 fluxes from eddy covariance retrievals cannot be explained by a sea ice direct source and must involve other processes or other sources of CO2. Finally, the simulations suggest that near surface TA/DIC ratios of ~2, sometimes used as an indicator of calcification, would rather suggest outgassing.

  20. Cohesive zone model of carbon nanotube-coated carbon fiber/polyester composites

    International Nuclear Information System (INIS)

    Agnihotri, Prabhat Kamal; Kar, Kamal K; Basu, Sumit

    2012-01-01

    It has been previously reported that the average properties of carbon nanotube-coated carbon fiber/polyester multiscale composites critically depend on the length and density of nanotubes on the fiber surface. In this paper the effect of nanotube length and density on the interfacial properties of the carbon nanotube-coated carbon fiber–polymer interface has been studied using shear lag and a cohesive zone model. The latter model incorporates frictional sliding after complete debonding between the fiber and matrix and has been developed to quantify the effect of nanotube coating on various interfacial characterizing parameters. Our numerical results indicate that fibers with an optimal coverage and length of nanotubes significantly increase the interfacial strength and friction between the fiber and polymer. However, they also embrittle the interface compared with bare fibers. (paper)

  1. Adsorption of dyes by ACs prepared from waste tyre reinforcing fibre. Effect of texture, surface chemistry and pH.

    Science.gov (United States)

    Acevedo, Beatriz; Rocha, Raquel P; Pereira, Manuel F R; Figueiredo, José L; Barriocanal, Carmen

    2015-12-01

    This paper compares the importance of the texture and surface chemistry of waste tyre activated carbons in the adsorption of commercial dyes. The adsorption of two commercial dyes, Basic Astrazon Yellow 7GLL and Reactive Rifafix Red 3BN on activated carbons made up of reinforcing fibres from tyre waste and low-rank bituminous coal was studied. The surface chemistry of activated carbons was modified by means of HCl-HNO3 treatment in order to increase the number of functional groups. Moreover, the influence of the pH on the process was also studied, this factor being of great importance due to the amphoteric characteristics of activated carbons. The activated carbons made with reinforcing fibre and coal had the highest SBET, but the reinforcing fibre activated carbon samples had the highest mesopore volume. The texture of the activated carbons was not modified upon acid oxidation treatment, unlike their surface chemistry which underwent considerable modification. The activated carbons made with a mixture of reinforcing fibre and coal experienced the largest degree of oxidation, and so had more acid surface groups. The adsorption of reactive dye was governed by the mesoporous volume, whilst surface chemistry played only a secondary role. However, the surface chemistry of the activated carbons and dispersive interactions played a key role in the adsorption of the basic dye. The adsorption of the reactive dye was more favored in a solution of pH 2, whereas the basic dye was adsorbed more easily in a solution of pH 12. Copyright © 2015 Elsevier Inc. All rights reserved.

  2. Chemistry of Carbon Rich Star IRAS 15194–5115 A. Ali

    Indian Academy of Sciences (India)

    We have constructed two gas-phase models to study the chem- ... 1. Introduction. IRAS 15194–5115 is the third brightest carbon star at 12 µm and the brightest one ..... The main formation routes of CN, HCN and HNC in the inner part are.

  3. Carbonate system parameters of an algal-dominated reef along west Maui

    Science.gov (United States)

    Prouty, Nancy G.; Yates, Kimberly K.; Smiley, Nathan A.; Gallagher, Christopher; Cheriton, Olivia; Storlazzi, Curt

    2018-01-01

    Constraining coral reef metabolism and carbon chemistry dynamics are fundamental for understanding and predicting reef vulnerability to rising coastal CO2 concentrations and decreasing seawater pH. However, few studies exist along reefs occupying densely inhabited shorelines with known input from land-based sources of pollution. The shallow coral reefs off Kahekili, West Maui, are exposed to nutrient-enriched, low-pH submarine groundwater discharge (SGD) and are particularly vulnerable to the compounding stressors from land-based sources of pollution and lower seawater pH. To constrain the carbonate chemistry system, nutrients and carbonate chemistry were measured along the Kahekili reef flat every 4 h over a 6-d sampling period in March 2016. Abiotic process – primarily SGD fluxes – controlled the carbonate chemistry adjacent to the primary SGD vent site, with nutrient-laden freshwater decreasing pH levels and favoring undersaturated aragonite saturation (Ωarag) conditions. In contrast, diurnal variability in the carbonate chemistry at other sites along the reef flat was driven by reef community metabolism. Superimposed on the diurnal signal was a transition during the second sampling period to a surplus of total alkalinity (TA) and dissolved inorganic carbon (DIC) compared to ocean end-member TA and DIC measurements. A shift from net community production and calcification to net respiration and carbonate dissolution was identified. This transition occurred during a period of increased SGD-driven nutrient loading, lower wave height, and reduced current speeds. This detailed study of carbon chemistry dynamics highlights the need to incorporate local effects of nearshore oceanographic processes into predictions of coral reef vulnerability and resilience.

  4. Precision Controlled Carbon Materials for Next-Generation Optoelectronic and Photonic Devices

    Science.gov (United States)

    2018-01-08

    engineer next-generation carbon-based optoelectronic and photonic devices with superior performance and capabilities. These devices include carbon...electronics; (4) nanostructured graphene plasmonics; and (5) polymer-nanotube conjugate chemistry . (1) Semiconducting carbon nanotube-based...applications (In Preparation, 2018). (5) Polymer-nanotube conjugate chemistry Conjugated polymers can be exploited as agents for selectively wrapping and

  5. Connections between radiation and positronium chemistry

    International Nuclear Information System (INIS)

    Hirade, Tetsuya

    2007-01-01

    Some of the important connections between radiation chemistry and positronium chemistry started from the establishment of the spur reaction model proposed by Mogensen. Now, the modified model, the blob model proposed by Stepanov and Byakov, is making it possible to have the quantitative or semi-quantitative view of the positronium formation by using the distributions of positrons and excess electrons. Some of the interesting topics will be picked up here to understand the connections between radiation chemistry and positronium chemistry

  6. Vegetation and Carbon Cycle Dynamics in the High-Resolution Transient Holocene Simulations Using the MPI Earth System Model

    Science.gov (United States)

    Brovkin, V.; Lorenz, S.; Raddatz, T.; Claussen, M.; Dallmeyer, A.

    2017-12-01

    One of the interesting periods to investigate a climatic role of terrestrial biosphere is the Holocene, when, despite of the relatively steady global climate, the atmospheric CO2 grew by about 20 ppm from 7 kyr BP to pre-industrial. We use a new setup of the Max Planck Institute Earth System Model MPI-ESM1 consisting of the latest version of the atmospheric model ECHAM6, including the land surface model JSBACH3 with carbon cycle and vegetation dynamics, coupled to the ocean circulation model MPI-OM, which includes the HAMOCC model of ocean biogeochemistry. The model has been run for several simulations over the Holocene period of the last 8000 years under the forcing data sets of orbital insolation, atmospheric greenhouse gases, volcanic aerosols, solar irradiance and stratospheric ozone, as well as land-use changes. In response to this forcing, the land carbon storage increased by about 60 PgC between 8 and 4 kyr BP, stayed relatively constant until 2 kyr BP, and decreased by about 90 PgC by 1850 AD due to land use changes. At 8 kyr BP, vegetation cover was much denser in Africa, mainly due to increased rainfall in response to the orbital forcing. Boreal forests moved northward in both, North America and Eurasia. The boreal forest expansion in North America is much less pronounced than in Eurasia. Simulated physical ocean fields, including surface temperatures and meridional overturning, do not change substantially in the Holocene. Carbonate ion concentration in deep ocean decreases in both, prescribed and interactive CO2simulations. Comparison with available proxies for terrestrial vegetation and for the ocean carbonate chemistry will be presented. Vegetation and soil carbon changes significantly affected atmospheric CO2 during the periods of strong volcanic eruptions. In response to the eruption-caused cooling, the land initially stores more carbon as respiration decreases, but then it releases even more carbon die to productivity decrease. This decadal

  7. An exploratory study of proficient undergraduate Chemistry II students' application of Lewis's model

    Science.gov (United States)

    Lewis, Sumudu R.

    This exploratory study was based on the assumption that proficiency in chemistry must not be determined exclusively on students' declarative and procedural knowledge, but it should be also described as the ability to use variety of reasoning strategies that enrich and diversify procedural methods. The study furthermore assumed that the ability to describe the structure of a molecule using Lewis's model and use it to predict its geometry as well as some of its properties is indicative of proficiency in the essential concepts of covalent bonding and molecule structure. The study therefore inquired into the reasoning methods and procedural techniques of proficient undergraduate Chemistry II students when solving problems, which require them to use Lewis's model. The research design included an original survey, designed by the researcher for this study, and two types of interviews, with students and course instructors. The purpose of the survey was two-fold. First and foremost, the survey provided a base for the student interview selection, and second it served as the foundation for the inquiry into the strategies the student use when solving survey problems. Twenty two students were interviewed over the course of the study. The interview with six instructors allowed to identify expected prior knowledge and skills, which the students should have acquired upon completion of the Chemistry I course. The data, including videos, audios, and photographs of the artifacts produced by students during the interviews, were organized and analyzed manually and using QSR NVivo 10. The research found and described the differences between proficient and non-proficient students' reasoning and procedural strategies when using Lewis's model to describe the structure of a molecule. One of the findings clearly showed that the proficient students used a variety of cues to reason, whereas other students used one memorized cue, or an algorithm, which often led to incorrect representations in

  8. Numerical Modeling of Climate-Chemistry Connections: Recent Developments and Future Challenges

    Directory of Open Access Journals (Sweden)

    Patrick Jöckel

    2013-05-01

    Full Text Available This paper reviews the current state and development of different numerical model classes that are used to simulate the global atmospheric system, particularly Earth’s climate and climate-chemistry connections. The focus is on Chemistry-Climate Models. In general, these serve to examine dynamical and chemical processes in the Earth atmosphere, their feedback, and interaction with climate. Such models have been established as helpful tools in addition to analyses of observational data. Definitions of the global model classes are given and their capabilities as well as weaknesses are discussed. Examples of scientific studies indicate how numerical exercises contribute to an improved understanding of atmospheric behavior. There, the focus is on synergistic investigations combining observations and model results. The possible future developments and challenges are presented, not only from the scientific point of view but also regarding the computer technology and respective consequences for numerical modeling of atmospheric processes. In the future, a stronger cross-linkage of subject-specific scientists is necessary, to tackle the looming challenges. It should link the specialist discipline and applied computer science.

  9. Using Demonstrations Involving Combustion and Acid-Base Chemistry to Show Hydration of Carbon Dioxide, Sulfur Dioxide, and Magnesium Oxide and Their Relevance for Environmental Climate Science

    Science.gov (United States)

    Shaw, C. Frank, III; Webb, James W.; Rothenberger, Otis

    2016-01-01

    The nature of acidic and basic (alkaline) oxides can be easily illustrated via a series of three straightforward classroom demonstrations for high school and general chemistry courses. Properties of carbon dioxide, sulfur dioxide, and magnesium oxide are revealed inexpensively and safely. Additionally, the very different kinetics of hydration of…

  10. Metadynamics for training neural network model chemistries: A competitive assessment

    Science.gov (United States)

    Herr, John E.; Yao, Kun; McIntyre, Ryker; Toth, David W.; Parkhill, John

    2018-06-01

    Neural network model chemistries (NNMCs) promise to facilitate the accurate exploration of chemical space and simulation of large reactive systems. One important path to improving these models is to add layers of physical detail, especially long-range forces. At short range, however, these models are data driven and data limited. Little is systematically known about how data should be sampled, and "test data" chosen randomly from some sampling techniques can provide poor information about generality. If the sampling method is narrow, "test error" can appear encouragingly tiny while the model fails catastrophically elsewhere. In this manuscript, we competitively evaluate two common sampling methods: molecular dynamics (MD), normal-mode sampling, and one uncommon alternative, Metadynamics (MetaMD), for preparing training geometries. We show that MD is an inefficient sampling method in the sense that additional samples do not improve generality. We also show that MetaMD is easily implemented in any NNMC software package with cost that scales linearly with the number of atoms in a sample molecule. MetaMD is a black-box way to ensure samples always reach out to new regions of chemical space, while remaining relevant to chemistry near kbT. It is a cheap tool to address the issue of generalization.

  11. Presidential Green Chemistry Challenge: 2007 Small Business Award

    Science.gov (United States)

    Presidential Green Chemistry Challenge 2007 award winner, NovaSterilis, invented a way to sterilize delicate biological materials such as graft tissue without harming them, using supercritical carbon dioxide and a peroxide.

  12. Carbon nanotubes and graphene in analytical sciences

    International Nuclear Information System (INIS)

    Perez-Lopez, B.; Merkoci, A.

    2012-01-01

    Nanosized carbon materials are offering great opportunities in various areas of nanotechnology. Carbon nanotubes and graphene, due to their unique mechanical, electronic, chemical, optical and electrochemical properties, represent the most interesting building blocks in various applications where analytical chemistry is of special importance. The possibility of conjugating carbon nanomaterials with biomolecules has received particular attention with respect to the design of chemical sensors and biosensors. This review describes the trends in this field as reported in the last 6 years in (bio)analytical chemistry in general, and in biosensing in particular. (author)

  13. Chemistry conditions in crevices of carbon steel and stainless steel: a comparative study

    International Nuclear Information System (INIS)

    Pushpalata, R.; Veena, S.; Chandran, Sinu; Mohan, T.V.K.; Rangarajan, S.; Narasimhan, S.V.

    2008-01-01

    Occurrence of crevice corrosion in the steam generator tubes of nuclear power plants may lead to transport of radioactivity to the secondary side. It is expected that effect of crevice corrosion will be more pronounced in a passive material like stainless steel (SS) as compared to carbon steel (CS). Theoretical modeling of the dynamics of crevice chemistry calls for experimental data with respect to various water chemistry parameters like pH, conductivity and concentrations of the ionic species in typical crevices of different geometry (aspect ratio of length and width). This paper presents the experimental results obtained with crevices in CS -106 B, SS-304 (nano grain) and SS 316 blocks (varying dimensions) exposed to a medium containing 1 ppm of lithium and chloride ion each for 10 days in static autoclave at 245 deg C. The bulk solution pH showed a reduction in alkalinity and slight increase in conductivity. In case of CS about 58 times increase in Cl - was observed in the smaller crevice of dimension 1 mm (width) x 25 mm (depth) whereas it was only ∼ 12 times in the bigger crevice (2 mm x 39 mm). Other anionic impurities like SO 4 2- and Br - present as impurities in NaCI were also found to be concentrated in the crevices whereas not much increase in cationic impurities was observed. In a similar experiment with SS blocks with crevice dimension comparable to diffusion layer thickness, appreciable increase in chloride concentration was observed. Electrochemical experiments were also carried out in deaerated NaCI (3.5%) solution at 25 deg C with CS, SS-304 (nano grain) and SS-316 (normal-grain) coupons. The OCP was -297 mV for SS-316 whereas for SS-304 coupon the OCP was -339 mV. Potentiodynamic anodic polarization curve showed a passive behavior up to 0.0V and then a sudden increase in anodic current. On nano-grained SS, a yellowish film on the surface was observed with a large number of pits whereas severe general corrosion was observed in the normal

  14. Organics in environmental ices: sources, chemistry, and impacts

    Directory of Open Access Journals (Sweden)

    V. F. McNeill

    2012-10-01

    Full Text Available The physical, chemical, and biological processes involving organics in ice in the environment impact a number of atmospheric and biogeochemical cycles. Organic material in snow or ice may be biological in origin, deposited from aerosols or atmospheric gases, or formed chemically in situ. In this manuscript, we review the current state of knowledge regarding the sources, properties, and chemistry of organic materials in environmental ices. Several outstanding questions remain to be resolved and fundamental data gathered before an accurate model of transformations and transport of organic species in the cryosphere will be possible. For example, more information is needed regarding the quantitative impacts of chemical and biological processes, ice morphology, and snow formation on the fate of organic material in cold regions. Interdisciplinary work at the interfaces of chemistry, physics and biology is needed in order to fully characterize the nature and evolution of organics in the cryosphere and predict the effects of climate change on the Earth's carbon cycle.

  15. Using measurements for evaluation of black carbon modeling

    Directory of Open Access Journals (Sweden)

    S. Gilardoni

    2011-01-01

    Full Text Available The ever increasing use of air quality and climate model assessments to underpin economic, public health, and environmental policy decisions makes effective model evaluation critical. This paper discusses the properties of black carbon and light attenuation and absorption observations that are the key to a reliable evaluation of black carbon model and compares parametric and nonparametric statistical tools for the quantification of the agreement between models and observations. Black carbon concentrations are simulated with TM5/M7 global model from July 2002 to June 2003 at four remote sites (Alert, Jungfraujoch, Mace Head, and Trinidad Head and two regional background sites (Bondville and Ispra. Equivalent black carbon (EBC concentrations are calculated using light attenuation measurements from January 2000 to December 2005. Seasonal trends in the measurements are determined by fitting sinusoidal functions and the representativeness of the period simulated by the model is verified based on the scatter of the experimental values relative to the fit curves. When the resolution of the model grid is larger than 1° × 1°, it is recommended to verify that the measurement site is representative of the grid cell. For this purpose, equivalent black carbon measurements at Alert, Bondville and Trinidad Head are compared to light absorption and elemental carbon measurements performed at different sites inside the same model grid cells. Comparison of these equivalent black carbon and elemental carbon measurements indicates that uncertainties in black carbon optical properties can compromise the comparison between model and observations. During model evaluation it is important to examine the extent to which a model is able to simulate the variability in the observations over different integration periods as this will help to identify the most appropriate timescales. The agreement between model and observation is accurately described by the overlap of

  16. Variational data assimilation schemes for transport and transformation models of atmospheric chemistry

    Science.gov (United States)

    Penenko, Alexey; Penenko, Vladimir; Tsvetova, Elena; Antokhin, Pavel

    2016-04-01

    The work is devoted to data assimilation algorithm for atmospheric chemistry transport and transformation models. In the work a control function is introduced into the model source term (emission rate) to provide flexibility to adjust to data. This function is evaluated as the constrained minimum of the target functional combining a control function norm with a norm of the misfit between measured data and its model-simulated analog. Transport and transformation processes model is acting as a constraint. The constrained minimization problem is solved with Euler-Lagrange variational principle [1] which allows reducing it to a system of direct, adjoint and control function estimate relations. This provides a physically-plausible structure of the resulting analysis without model error covariance matrices that are sought within conventional approaches to data assimilation. High dimensionality of the atmospheric chemistry models and a real-time mode of operation demand for computational efficiency of the data assimilation algorithms. Computational issues with complicated models can be solved by using a splitting technique. Within this approach a complex model is split to a set of relatively independent simpler models equipped with a coupling procedure. In a fine-grained approach data assimilation is carried out quasi-independently on the separate splitting stages with shared measurement data [2]. In integrated schemes data assimilation is carried out with respect to the split model as a whole. We compare the two approaches both theoretically and numerically. Data assimilation on the transport stage is carried out with a direct algorithm without iterations. Different algorithms to assimilate data on nonlinear transformation stage are compared. In the work we compare data assimilation results for both artificial and real measurement data. With these data we study the impact of transformation processes and data assimilation to the performance of the modeling system [3]. The

  17. Chemical Oceanography and the Marine Carbon Cycle

    Science.gov (United States)

    Emerson, Steven; Hedges, John

    The principles of chemical oceanography provide insight into the processes regulating the marine carbon cycle. The text offers a background in chemical oceanography and a description of how chemical elements in seawater and ocean sediments are used as tracers of physical, biological, chemical and geological processes in the ocean. The first seven chapters present basic topics of thermodynamics, isotope systematics and carbonate chemistry, and explain the influence of life on ocean chemistry and how it has evolved in the recent (glacial-interglacial) past. This is followed by topics essential to understanding the carbon cycle, including organic geochemistry, air-sea gas exchange, diffusion and reaction kinetics, the marine and atmosphere carbon cycle and diagenesis in marine sediments. Figures are available to download from www.cambridge.org/9780521833134. Ideal as a textbook for upper-level undergraduates and graduates in oceanography, environmental chemistry, geochemistry and earth science and a valuable reference for researchers in oceanography.

  18. Physics and chemistry of irradiated protostars

    DEFF Research Database (Denmark)

    Lindberg, Johan

    not resemble so-called hot corinos or warm carbon-chain chemistry sources (the previously known types of low-mass Class 0 objects as defined by their chemistry). The absence of complex organic molecules in combination with high abundances of radicals such as cyanide (CN) and hydroxyl (OH) suggest...... that the chemistry is dominated by radiation from R CrA. In the high-resolution interferometry data we also detect signs of a 100 AU Keplerian disc around the Class 0/I object IRS7B. The disc may be responsible for the lack of detections of complex organic molecules on the smaller scales as it may have flattened......) and chemistry (such as molecular abundances) in low-mass protostellar envelopes is studied. The work studies the nearby low-mass star-forming region Corona Australis, in which a large proportion of the youngest low-mass protostars (so-called Class 0 and Class I objects) are located in a dense cloud situated...

  19. CARBON ISOTOPE FRACTIONATION IN PROTOPLANETARY DISKS

    International Nuclear Information System (INIS)

    Woods, Paul M.; Willacy, Karen

    2009-01-01

    We investigate the gas-phase and grain-surface chemistry in the inner 30 AU of a typical protoplanetary disk (PPD) using a new model which calculates the gas temperature by solving the gas heating and cooling balance and which has an improved treatment of the UV radiation field. We discuss inner-disk chemistry in general, obtaining excellent agreement with recent observations which have probed the material in the inner regions of PPDs. We also apply our model to study the isotopic fractionation of carbon. Results show that the fractionation ratio, 12 C/ 13 C, of the system varies with radius and height in the disk. Different behavior is seen in the fractionation of different species. We compare our results with 12 C/ 13 C ratios in the solar system comets, and find a stark contrast, indicative of reprocessing.

  20. High-Latitude Stratospheric Sensitivity to QBO Width in a Chemistry-Climate Model with Parameterized Ozone Chemistry

    Science.gov (United States)

    Hurwitz, M. M.; Braesicke, P.; Pyle, J. A.

    2010-01-01

    In a pair of idealized simulations with a simplified chemistry-climate model, the sensitivity of the wintertime Arctic stratosphere to variability in the width of the quasi-biennial oscillation (QBO) is assessed. The width of the QBO appears to have equal influence on the Arctic stratosphere as does the phase (i.e. the Holton-Tan mechanism). In the model, a wider QBO acts like a preferential shift toward the easterly phase of the QBO, where zonal winds at 60 N tend to be relatively weaker, while 50 hPa geopotential heights and polar ozone values tend to be higher.

  1. Carbon Dioxide Emission Pathways Avoiding Dangerous Ocean Impacts

    OpenAIRE

    Kvale, K.; Zickfeld, K.; Bruckner, T.; Meissner, K. J.; Tanaka, K.; Weaver, A. J.

    2012-01-01

    Anthropogenic emissions of greenhouse gases could lead to undesirable effects on oceans in coming centuries. Drawing on recommendations published by the German Advisory Council on Global Change, levels of unacceptable global marine change (so-called guardrails) are defined in terms of global mean temperature, sea level rise, and ocean acidification. A global-mean climate model [the Aggregated Carbon Cycle, Atmospheric Chemistry and Climate Model (ACC2)] is coupled with an economic module [tak...

  2. Evaluation of preindustrial to present-day black carbon and its albedo forcing from Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP

    Directory of Open Access Journals (Sweden)

    Y. H. Lee

    2013-03-01

    Full Text Available As part of the Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP, we evaluate the historical black carbon (BC aerosols simulated by 8 ACCMIP models against observations including 12 ice core records, long-term surface mass concentrations, and recent Arctic BC snowpack measurements. We also estimate BC albedo forcing by performing additional simulations using offline models with prescribed meteorology from 1996–2000. We evaluate the vertical profile of BC snow concentrations from these offline simulations using the recent BC snowpack measurements. Despite using the same BC emissions, the global BC burden differs by approximately a factor of 3 among models due to differences in aerosol removal parameterizations and simulated meteorology: 34 Gg to 103 Gg in 1850 and 82 Gg to 315 Gg in 2000. However, the global BC burden from preindustrial to present-day increases by 2.5–3 times with little variation among models, roughly matching the 2.5-fold increase in total BC emissions during the same period. We find a large divergence among models at both Northern Hemisphere (NH and Southern Hemisphere (SH high latitude regions for BC burden and at SH high latitude regions for deposition fluxes. The ACCMIP simulations match the observed BC surface mass concentrations well in Europe and North America except at Ispra. However, the models fail to predict the Arctic BC seasonality due to severe underestimations during winter and spring. The simulated vertically resolved BC snow concentrations are, on average, within a factor of 2–3 of the BC snowpack measurements except for Greenland and the Arctic Ocean. For the ice core evaluation, models tend to adequately capture both the observed temporal trends and the magnitudes at Greenland sites. However, models fail to predict the decreasing trend of BC depositions/ice core concentrations from the 1950s to the 1970s in most Tibetan Plateau ice cores. The distinct temporal trend at the Tibetan

  3. Evaluation of preindustrial to present-day black carbon and its albedo forcing from Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP)

    Science.gov (United States)

    Lee, Y. H.; Lamarque, J.-F.; Flanner, M. G.; Jiao, C.; Shindell, D. T.; Bernsten, T.; Bisiaux, M. M.; Cao, J.; Collins, W. J.; Curran, M.; hide

    2013-01-01

    As part of the Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP), we evaluate the historical black carbon (BC) aerosols simulated by 8 ACCMIP models against observations including 12 ice core records, long-term surface mass concentrations, and recent Arctic BC snowpack measurements. We also estimate BC albedo forcing by performing additional simulations using offline models with prescribed meteorology from 1996-2000. We evaluate the vertical profile of BC snow concentrations from these offline simulations using the recent BC snowpack measurements. Despite using the same BC emissions, the global BC burden differs by approximately a factor of 3 among models due to differences in aerosol removal parameterizations and simulated meteorology: 34 Gg to 103 Gg in 1850 and 82 Gg to 315 Gg in 2000. However, the global BC burden from preindustrial to present-day increases by 2.5-3 times with little variation among models, roughly matching the 2.5-fold increase in total BC emissions during the same period.We find a large divergence among models at both Northern Hemisphere (NH) and Southern Hemisphere (SH) high latitude regions for BC burden and at SH high latitude regions for deposition fluxes. The ACCMIP simulations match the observed BC surface mass concentrations well in Europe and North America except at Ispra. However, the models fail to predict the Arctic BC seasonality due to severe underestimations during winter and spring. The simulated vertically resolved BC snow concentrations are, on average, within a factor of 2-3 of the BC snowpack measurements except for Greenland and the Arctic Ocean. For the ice core evaluation, models tend to adequately capture both the observed temporal trends and the magnitudes at Greenland sites. However, models fail to predict the decreasing trend of BC depositions/ice core concentrations from the 1950s to the 1970s in most Tibetan Plateau ice cores. The distinct temporal trend at the Tibetan Plateau ice cores

  4. Chemistry in Titan

    Science.gov (United States)

    Plessis, S.; Carrasco, N.; Pernot, P.

    2009-04-01

    Modelling the chemical composition of Titan's ionosphere is a very challenging issue. Latest works perform either inversion of CASSINI's INMS mass spectra (neutral[1] or ion[2]), or design coupled ion-neutral chemistry models[3]. Coupling ionic and neutral chemistry has been reported to be an essential feature of accurate modelling[3]. Electron Dissociative Recombination (EDR), where free electrons recombine with positive ions to produce neutral species, is a key component of ion-neutral coupling. There is a major difficulty in EDR modelling: for heavy ions, the distribution of neutral products is incompletely characterized by experiments. For instance, for some hydrocarbon ions only the carbon repartition is measured, leaving the hydrogen repartition and thus the exact neutral species identity unknown[4]. This precludes reliable deterministic modelling of this process and of ion-neutral coupling. We propose a novel stochastic description of the EDR chemical reactions which enables efficient representation and simulation of the partial experimental knowledge. The description of products distribution in multi-pathways reactions is based on branching ratios, which should sum to unity. The keystone of our approach is the design of a probability density function accounting for all available informations and physical constrains. This is done by Dirichlet modelling which enables one to sample random variables whose sum is constant[5]. The specifics of EDR partial uncertainty call for a hierarchiral Dirichlet representation, which generalizes our previous work[5]. We present results on the importance of ion-neutral coupling based on our stochastic model. C repartition H repartition (measured) (unknown ) → C4H2 + 3H2 + H .. -→ C4 . → C4H2 + 7H → C3H8. + CH C4H+9 + e- -→ C3 + C .. → C3H3 + CH2 + 2H2 → C2H6 + C2H2 + H .. -→ C2 + C2 . → 2C2H2 + 2H2 + H (1) References [1] J. Cui, R.V. Yelle, V. Vuitton, J.H. Waite Jr., W.T. Kasprzak

  5. Computational Study of Nonequilibrium Chemistry in High Temperature Flows

    Science.gov (United States)

    Doraiswamy, Sriram

    Recent experimental measurements in the reflected shock tunnel CUBRC LENS-I facility raise questions about our ability to correctly model the recombination processes in high enthalpy flows. In the carbon dioxide flow, the computed shock standoff distance over the Mars Science Laboratory (MSL) shape was less than half of the experimental result. For the oxygen flows, both pressure and heat transfer data on the double cone geometry were not correctly predicted. The objective of this work is to investigate possible reasons for these discrepancies. This process involves systematically addressing different factors that could possibly explain the differences. These factors include vibrational modeling, role of electronic states and chemistry-vibrational coupling in high enthalpy flows. A state-specific vibrational model for CO2, CO, O2 and O system is devised by taking into account the first few vibrational states of each species. All vibrational states with energies at or below 1 eV are included in the present work. Of the three modes of vibration in CO2 , the antisymmetric mode is considered separately from the symmetric stretching mode and the doubly degenerate bending modes. The symmetric and the bending modes are grouped together since the energy transfer rates between the two modes are very large due to Fermi resonance. The symmetric and bending modes are assumed to be in equilibrium with the translational and rotational modes. The kinetic rates for the vibrational-translation energy exchange reactions, and the intermolecular and intramolecular vibrational-vibrational energy exchange reactions are based on experimental data to the maximum extent possible. Extrapolation methods are employed when necessary. This vibrational model is then coupled with an axisymmetric computational fluid dynamics code to study the expansion of CO2 in a nozzle. The potential role of low lying electronic states is also investigated. Carbon dioxide has a single excited state just below

  6. Modeling and preparation of activated carbon for methane storage II. Neural network modeling and experimental studies of the activated carbon preparation

    International Nuclear Information System (INIS)

    Namvar-Asl, Mahnaz; Soltanieh, Mohammad; Rashidi, Alimorad

    2008-01-01

    This study describes the activated carbon (AC) preparation for methane storage. Due to the need for the introduction of a model, correlating the effective preparation parameters with the characteristic parameters of the activated carbon, a model was developed by neural networks. In a previous study [Namvar-Asl M, Soltanieh M, Rashidi A, Irandoukht A. Modeling and preparation of activated carbon for methane storage: (I) modeling of activated carbon characteristics with neural networks and response surface method. Proceedings of CESEP07, Krakow, Poland; 2007.], the model was designed with the MATLAB toolboxes providing the best response for the correlation of the characteristics parameters and the methane uptake of the activated carbon. Regarding this model, the characteristics of the activated carbon were determined for a target methane uptake. After the determination of the characteristics, the demonstrated model of this work guided us to the selection of the effective AC preparation parameters. According to the modeling results, some samples were prepared and their methane storage capacity was measured. The results were compared with those of a target methane uptake (special amount of methane storage). Among the designed models, one of them illustrated the methane storage capacity of 180 v/v. It was finally found that the neural network modeling for the assay of the efficient AC preparation parameters was financially feasible, with respect to the determined methane storage capacity. This study could be useful for the development of the Adsorbed Natural Gas (ANG) technology

  7. Predictive geochemical modeling of uranium and other contaminants in laboratory columns in relatively oxidizing, carbonate-rich solutions

    International Nuclear Information System (INIS)

    Longmire, P.; Turney, W.R.; Mason, C.F.V.

    1994-01-01

    Carbonate heap leaching of uranium-contaminated soils and sediments represents a viable, cost-effective remediation technology. Column experiments have been conducted using 0.1, 0.25, and 0.5 M Na 2 CO 3 /NaHCO 3 solutions for leaching uranium from soils located adjacent to an incinerator at the Fernald Environmental Management Project (FEMP) site. Results from column experiments and geochemical modeling are used to quantitatively evaluate the effectiveness of heap leaching. Leach efficiencies of up to 72 wt.% of total uranium in CaO-agglomerated soil result from dissolution of uranium (U(VI)-dominated) minerals, formation of the soluble complex UO 2 (CO 3 ) 3 4- , and uranium desorption from clay minerals, ferric hydroxides, and humic acids. Parameters that control the extent of uranium extraction include pH, Eh, temperature, carbonate concentration, lixiviant-flow rate, pore-solution chemistry, solid phases, and soil texture

  8. Integrating chemistry into 3D climate models: Detailed kinetics in the troposphere and stratosphere of a global climate model

    Energy Technology Data Exchange (ETDEWEB)

    Kao, C.Y.J.; Elliott, S. [Los Alamos National Lab., NM (United States). Earth and Environmental Sciences Div.; Turco, R.P.; Zhao, X. [Univ. of California, Los Angeles, CA (United States)

    1997-11-01

    This is the final report of a three-year, Laboratory Directed Research and Development (LDRD) project at Los Alamos National Laboratory (LANL). The motivation for the project is to create the first complete, three-dimensional climate model that enfolds atmospheric photochemistry. The LANL chemical global climate model (GCM) not only distributes the trace greenhouse gases and modifies their concentrations within the detailed photochemical web, but also permits them to influence the radiation field and so force their own transport. Both atmospheric chemistry and fluid dynamics are nonlinear and zonally asymmetric phenomena. They can only be adequately modeled in three dimensions on the global grid. The kinetics-augmented GCM is the only program within the atmospheric community capable of investigating interaction involving chemistry and transport. The authors have conducted case studies of timely three-dimensional chemistry issues. Examples include ozone production from biomass burning plumes, kinetic feedbacks in zonally asymmetric transport phenomena with month- to year-long time scales, and volcano sulfate aerosols with respect to their potential effects on tropospheric ozone depletion.

  9. College Chemistry Students' Mental Models of Acids and Acid Strength

    Science.gov (United States)

    McClary, LaKeisha; Talanquer, Vicente

    2011-01-01

    The central goal of this study was to characterize the mental models of acids and acid strength expressed by advanced college chemistry students when engaged in prediction, explanation, and justification tasks that asked them to rank chemical compounds based on their relative acid strength. For that purpose we completed a qualitative research…

  10. Actinide chemistry research supporting the Waste Isolation Pilot Plant (WIPP): FY94 results

    Energy Technology Data Exchange (ETDEWEB)

    Novak, C.F. [ed.

    1995-08-01

    This document contains six reports on actinide chemistry research supporting the Waste Isolation Pilot Plant (WIPP). These reports, completed in FY94, are relevant to the estimation of the potential dissolved actinide concentrations in WIPP brines under repository breach scenarios. Estimates of potential dissolved actinide concentrations are necessary for WIPP performance assessment calculations. The specific topics covered within this document are: the complexation of oxalate with Th(IV) and U(VI); the stability of Pu(VI) in one WIPP-specific brine environment both with and without carbonate present; the solubility of Nd(III) in a WIPP Salado brine surrogate as a function of hydrogen ion concentration; the steady-state dissolved plutonium concentrations in a synthetic WIPP Culebra brine surrogate; the development of a model for Nd(III) solubility and speciation in dilute to concentrated sodium carbonate and sodium bicarbonate solutions; and the development of a model for Np(V) solubility and speciation in dilute to concentrated sodium Perchlorate, sodium carbonate, and sodium chloride media.

  11. Actinide chemistry research supporting the Waste Isolation Pilot Plant (WIPP): FY94 results

    International Nuclear Information System (INIS)

    Novak, C.F.

    1995-08-01

    This document contains six reports on actinide chemistry research supporting the Waste Isolation Pilot Plant (WIPP). These reports, completed in FY94, are relevant to the estimation of the potential dissolved actinide concentrations in WIPP brines under repository breach scenarios. Estimates of potential dissolved actinide concentrations are necessary for WIPP performance assessment calculations. The specific topics covered within this document are: the complexation of oxalate with Th(IV) and U(VI); the stability of Pu(VI) in one WIPP-specific brine environment both with and without carbonate present; the solubility of Nd(III) in a WIPP Salado brine surrogate as a function of hydrogen ion concentration; the steady-state dissolved plutonium concentrations in a synthetic WIPP Culebra brine surrogate; the development of a model for Nd(III) solubility and speciation in dilute to concentrated sodium carbonate and sodium bicarbonate solutions; and the development of a model for Np(V) solubility and speciation in dilute to concentrated sodium Perchlorate, sodium carbonate, and sodium chloride media

  12. Effect of surface chemistry, solution pH, and ionic strength on the removal of herbicides diuron and amitrole from water by an activated carbon fiber.

    Science.gov (United States)

    Fontecha-Cámara, M A; López-Ramón, M V; Alvarez-Merino, M A; Moreno-Castilla, C

    2007-01-30

    A study was conducted on the effects of carbon surface chemistry, solution pH, and ionic strength on the removal of diuron and amitrole from aqueous solutions by adsorption on an as-received and oxidized activated carbon fiber. Results obtained were explained by the surface characteristics of the adsorbents and the characteristics of the herbicide molecules. Under the experimental conditions used, diuron uptake was much higher than that of amitrole, despite its larger molecular dimensions, due to the lesser water solubility, greater hydrophobicity, and larger dipolar moment of diuron compared with amitrole. Uptake variations associated with differences in carbon surface oxidation, solution pH, and ionic strength were explained by corresponding changes in electrostatic, hydrophobic, and van der Waals interactions.

  13. Spatiotemporal variability of dimethylsulphoniopropionate on a fringing coral reef: the role of reefal carbonate chemistry and environmental variability.

    Directory of Open Access Journals (Sweden)

    Heidi L Burdett

    Full Text Available Oceanic pH is projected to decrease by up to 0.5 units by 2100 (a process known as ocean acidification, OA, reducing the calcium carbonate saturation state of the oceans. The coastal ocean is expected to experience periods of even lower carbonate saturation state because of the inherent natural variability of coastal habitats. Thus, in order to accurately project the impact of OA on the coastal ocean, we must first understand its natural variability. The production of dimethylsulphoniopropionate (DMSP by marine algae and the release of DMSP's breakdown product dimethylsulphide (DMS are often related to environmental stress. This study investigated the spatiotemporal response of tropical macroalgae (Padina sp., Amphiroa sp. and Turbinaria sp. and the overlying water column to natural changes in reefal carbonate chemistry. We compared macroalgal intracellular DMSP and water column DMSP+DMS concentrations between the environmentally stable reef crest and environmentally variable reef flat of the fringing Suleman Reef, Egypt, over 45-hour sampling periods. Similar diel patterns were observed throughout: maximum intracellular DMSP and water column DMS/P concentrations were observed at night, coinciding with the time of lowest carbonate saturation state. Spatially, water column DMS/P concentrations were highest over areas dominated by seagrass and macroalgae (dissolved DMS/P and phytoplankton (particulate DMS/P rather than corals. This research suggests that macroalgae may use DMSP to maintain metabolic function during periods of low carbonate saturation state. In the reef system, seagrass and macroalgae may be more important benthic producers of dissolved DMS/P than corals. An increase in DMS/P concentrations during periods of low carbonate saturation state may become ecologically important in the future under an OA regime, impacting larval settlement and increasing atmospheric emissions of DMS.

  14. Why has the bohr-sommerfeld model of the atom been ignoredby general chemistry textbooks?

    Science.gov (United States)

    Niaz, Mansoor; Cardellini, Liberato

    2011-12-01

    Bohr's model of the atom is considered to be important by general chemistry textbooks. A major shortcoming of this model was that it could not explain the spectra of atoms containing more than one electron. In order to increase the explanatory power of the model, Sommerfeld hypothesized the existence of elliptical orbits. This study has the following objectives: 1) Formulation of criteria based on a history and philosophy of science framework; and 2) Evaluation of university-level general chemistry textbooks based on the criteria, published in Italy and U.S.A. Presentation of a textbook was considered to be "satisfactory" if it included a description of the Bohr-Sommerfeld model along with diagrams of the elliptical orbits. Of the 28 textbooks published in Italy that were analyzed, only five were classified as "satisfactory". Of the 46 textbooks published in U.S.A., only three were classified as "satisfactory". This study has the following educational implications: a) Sommerfeld's innovation (auxiliary hypothesis) by introducing elliptical orbits, helped to restore the viability of Bohr's model; b) Bohr-Sommerfeld's model went no further than the alkali metals, which led scientists to look for other models; c) This clearly shows that scientific models are tentative in nature; d) Textbook authors and chemistry teachers do not consider the tentative nature of scientific knowledge to be important; e) Inclusion of the Bohr-Sommerfeld model in textbooks can help our students to understand how science progresses.

  15. 21 CFR 862.1160 - Bicarbonate/carbon dioxide test system.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Bicarbonate/carbon dioxide test system. 862.1160 Section 862.1160 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) MEDICAL DEVICES CLINICAL CHEMISTRY AND CLINICAL TOXICOLOGY DEVICES Clinical Chemistry Test Systems § 862.1160 Bicarbonate/carbon dioxide...

  16. USGS Arctic Ocean carbon cruise 2010: field activity H-03-10-AR to collect carbon data in the Arctic Ocean, August - September 2010

    Science.gov (United States)

    Robbins, Lisa L.; Yates, Kimberly K.; Gove, Matthew D.; Knorr, Paul O.; Wynn, Jonathan; Byrne, Robert H.; Liu, Xuewu

    2013-01-01

    Carbon dioxide (CO2) in the atmosphere is absorbed at the surface of the ocean by reacting with seawater to form carbonic acid, a weak, naturally occurring acid. As atmospheric carbon dioxide increases, the concentration of carbonic acid in seawater also increases, causing a decrease in ocean pH and carbonate mineral saturation states, a process known as ocean acidification. The oceans have absorbed approximately 525 billion tons of carbon dioxide from the atmosphere, or about one-quarter to one-third of the anthropogenic carbon emissions released since the beginning of the Industrial Revolution (Sabine and others, 2004). Global surveys of ocean chemistry have revealed that seawater pH has decreased by about 0.1 units (from a pH of 8.2 to 8.1) since the 1700s due to absorption of carbon dioxide (Caldeira and Wickett, 2003; Orr and others, 2005; Raven and others, 2005). Modeling studies, based on Intergovernmental Panel on Climate Change (IPCC) CO2 emission scenarios, predict that atmospheric carbon dioxide levels could reach more than 500 parts per million (ppm) by the middle of this century and 800 ppm by the year 2100, causing an additional decrease in surface water pH of 0.3 pH units. Ocean acidification is a global threat and is already having profound and deleterious effects on the geology, biology, chemistry, and socioeconomic resources of coastal and marine habitats (Raven and others, 2005; Ruttiman, 2006). The polar and sub-polar seas have been identified as the bellwethers for global ocean acidification.

  17. USGS Arctic Ocean carbon cruise 2011: field activity H-01-11-AR to collect carbon data in the Arctic Ocean, August - September 2011

    Science.gov (United States)

    Robbins, Lisa L.; Yates, Kimberly K.; Knorr, Paul O.; Wynn, Jonathan; Lisle, John; Buczkowski, Brian J.; Moore, Barbara; Mayer, Larry; Armstrong, Andrew; Byrne, Robert H.; Liu, Xuewu

    2013-01-01

    Carbon dioxide (CO2) in the atmosphere is absorbed at the surface of the ocean by reacting with seawater to form a weak, naturally occurring acid called carbonic acid. As atmospheric carbon dioxide increases, the concentration of carbonic acid in seawater also increases, causing a decrease in ocean pH and carbonate mineral saturation states, a process known as ocean acidification. The oceans have absorbed approximately 525 billion tons of carbon dioxide from the atmosphere, or about one-quarter to one-third of the anthropogenic carbon emissions released since the beginning of the Industrial Revolution (Sabine and others, 2004). Global surveys of ocean chemistry have revealed that seawater pH has decreased by about 0.1 units (from a pH of 8.2 to 8.1) since the 1700s due to absorption of carbon dioxide (Caldeira and Wickett, 2003; Orr and others, 2005; Raven and others, 2005). Modeling studies, based on Intergovernmental Panel on Climate Change (IPCC) CO2 emission scenarios, predict that atmospheric carbon dioxide levels could reach more than 500 parts per million (ppm) by the middle of this century and 800 ppm by the year 2100, causing an additional decrease in surface water pH of 0.3 pH units. Ocean acidification is a global threat and is already having profound and deleterious effects on the geology, biology, chemistry, and socioeconomic resources of coastal and marine habitats (Raven and others, 2005; Ruttiman, 2006). The polar and sub-polar seas have been identified as the bellwethers for global ocean acidification.

  18. Carbonate system parameters of an algal-dominated reef along West Maui

    Science.gov (United States)

    Prouty, Nancy G.; Yates, Kimberly K.; Smiley, Nathan; Gallagher, Chris; Cheriton, Olivia; Storlazzi, Curt D.

    2018-04-01

    Constraining coral reef metabolism and carbon chemistry dynamics are fundamental for understanding and predicting reef vulnerability to rising coastal CO2 concentrations and decreasing seawater pH. However, few studies exist along reefs occupying densely inhabited shorelines with known input from land-based sources of pollution. The shallow coral reefs off Kahekili, West Maui, are exposed to nutrient-enriched, low-pH submarine groundwater discharge (SGD) and are particularly vulnerable to the compounding stressors from land-based sources of pollution and lower seawater pH. To constrain the carbonate chemistry system, nutrients and carbonate chemistry were measured along the Kahekili reef flat every 4 h over a 6-day sampling period in March 2016. Abiotic process - primarily SGD fluxes - controlled the carbonate chemistry adjacent to the primary SGD vent site, with nutrient-laden freshwater decreasing pH levels and favoring undersaturated aragonite saturation (Ωarag) conditions. In contrast, diurnal variability in the carbonate chemistry at other sites along the reef flat was driven by reef community metabolism. Superimposed on the diurnal signal was a transition during the second sampling period to a surplus of total alkalinity (TA) and dissolved inorganic carbon (DIC) compared to ocean endmember TA and DIC measurements. A shift from positive net community production and positive net community calcification to negative net community production and negative net community calcification was identified. This transition occurred during a period of increased SGD-driven nutrient loading, lower wave height, and reduced current speeds. This detailed study of carbon chemistry dynamics highlights the need to incorporate local effects of nearshore oceanographic processes into predictions of coral reef vulnerability and resilience.

  19. Modelling iodide – iodate speciation in atmospheric aerosol: Contributions of inorganic and organic iodine chemistry

    Directory of Open Access Journals (Sweden)

    S. Pechtl

    2007-01-01

    Full Text Available The speciation of iodine in atmospheric aerosol is currently poorly understood. Models predict negligible iodide concentrations but accumulation of iodate in aerosol, both of which is not confirmed by recent measurements. We present an updated aqueous phase iodine chemistry scheme for use in atmospheric chemistry models and discuss sensitivity studies with the marine boundary layer model MISTRA. These studies show that iodate can be reduced in acidic aerosol by inorganic reactions, i.e., iodate does not necessarily accumulate in particles. Furthermore, the transformation of particulate iodide to volatile iodine species likely has been overestimated in previous model studies due to negligence of collision-induced upper limits for the reaction rates. However, inorganic reaction cycles still do not seem to be sufficient to reproduce the observed range of iodide – iodate speciation in atmospheric aerosol. Therefore, we also investigate the effects of the recently suggested reaction of HOI with dissolved organic matter to produce iodide. If this reaction is fast enough to compete with the inorganic mechanism, it would not only directly lead to enhanced iodide concentrations but, indirectly via speed-up of the inorganic iodate reduction cycles, also to a decrease in iodate concentrations. Hence, according to our model studies, organic iodine chemistry, combined with inorganic reaction cycles, is able to reproduce observations. The presented chemistry cycles are highly dependent on pH and thus offer an explanation for the large observed variability of the iodide – iodate speciation in atmospheric aerosol.

  20. Selection of carbon beam therapy: biophysical models of carbon beam therapy.

    Science.gov (United States)

    Matsufuji, Naruhiro

    2018-03-01

    Variation in the relative biological effectiveness (RBE) within the irradiation field of a carbon beam makes carbon-ion radiotherapy unique and advantageous in delivering the therapeutic dose to a deep-seated tumor, while sparing surrounding normal tissues. However, it is crucial to consider the RBE, not only in designing the dose distribution during treatment planning, but also in analyzing the clinical response retrospectively. At the National Institute of Radiological Sciences, the RBE model was established based on the response of human salivary gland cells. The response was originally handled with a linear-quadratic model, and later with a microdosimetric kinetic model. Retrospective analysis with a tumor-control probability model of non-small cell cancer treatment revealed a steep dose response in the tumor, and that the RBE of the tumor was adequately estimated using the model. A commonly used normal tissue complication probability model has not yet fully been accountable for the variable RBE of carbon ions; however, analysis of rectum injury after prostate cancer treatment suggested a highly serial-organ structure for the rectum, and a steep dose response similar to that observed for tumors.

  1. Polyhedral boron-containing cluster chemistry: Aspects of architecture beyond the icosahedron

    Czech Academy of Sciences Publication Activity Database

    Shea, S. L.; Bould, J.; Londesborough, M. G. S.; Perea, S. D.; Franken, A.; Ormsby, D. L.; Jelínek, Tomáš; Štíbr, Bohumil; Holub, Josef; Kilner, C. A.; Thorton-Pett, M.; Kennedy, J. D.

    2003-01-01

    Roč. 75, č. 9 (2003), s. 1239-1248 ISSN 0033-4545 R&D Projects: GA MŠk LN00A028 Grant - others:UK EPRC(GB) J56929 Institutional research plan: CEZ:AV0Z4032918 Keywords : molecular chemistry * carbon hydrides Subject RIV: CA - Inorganic Chemistry Impact factor: 1.471, year: 2003

  2. Surface chemistry of carbon removal from indium tin oxide by base and plasma treatment, with implications on hydroxyl termination

    International Nuclear Information System (INIS)

    Chaney, John A.; Koh, Sharon E.; Dulcey, Charles S.; Pehrsson, Pehr E.

    2003-01-01

    The surface chemistry of carbon removal from indium tin oxide (ITO) has been investigated with Auger electron spectroscopy (AES), high-resolution electron energy loss spectroscopy (HREELS), and high-resolution energy loss spectroscopy (HR-ELS). A vibrating Kelvin probe (KP) was used to monitor the work function (PHI) of ITO after cleaning, either by base-cleaning with alcoholic-KOH or by O 2 plasma-cleaning. Base-cleaning lowered PHI ITO as seen in the KP analysis, whereas plasma-cleaning slightly increased PHI ITO by an oxidative process. The degree of PHI ITO depression by base-cleaning was seen to depend on the initial surface, but the PHI depression itself was nonreductive to the ITO, as seen in the In-MNN AES lineshape. The nonreductive depression of PHI ITO by base-cleaning was further supported by a constant charge carrier density, as estimated from the HR-ELS. Base-cleaning was slightly more effective than the oxygen plasma in removing carbon from the ITO surface. However, base-cleaning preferentially removed graphitic carbon while leaving significant hydrocarbon contaminants, as determined by vibrational analysis with HREELS. All other ITO surfaces retained a significant carbon and hydrocarbon contamination as evidenced by AES and HREELS. There was little evidence of the formation of surface hydroxyl species, as expected for such an inherently contaminated surface as ITO

  3. Proceedings of DAE-BRNS third international symposium on materials chemistry

    International Nuclear Information System (INIS)

    Tyagi, Deepak; Banerjee, Atindra Mohan; Nigam, Sandeep; Varma, Salil; Tripathi, Arvind Kumar; Bharadwaj, Shyamala Rajkumar; Das, Dasarathi

    2010-12-01

    The present volume consists of the proceedings of the DAE-BRNS Third International Symposium on Materials Chemistry. In order to keep pace with the advancements made in the area of materials chemistry, new topics like materials for energy conversion, biomaterials, carbon based materials, soft condensed materials, thin films, surface chemistry, polymer based materials, organic and organometallics, magnetic materials and high purity materials have been included in this symposium while topics like nuclear materials, nanomaterials and clusters, catalysis, chemical sensors, fuel cell materials and computational research in materials chemistry have been continued as important features of the symposium. Papers relevant to INIS are indexed separately

  4. Experimental and modelling studies of the near-field chemistry for Nirex repository concepts

    International Nuclear Information System (INIS)

    Atkinson, A.; Ewart, F.T.; Pugh, S.Y.R.; Rees, J.H.; Sharland, S.M.; Tasker, P.W.; Wilkins, J.D.

    1988-02-01

    A research programme is described which is designed to investigate the chemical conditions in the near field of a concrete based repository and the behaviour of the radiologically important nuclides under these conditions. The chemical conditions are determined by the corrosion of the iron components of the repository and by the soluble components of the concrete. Both of these have been investigated experimentally and models developed which have been validated by further experiment. The effect of these reactions on the repository pH and Eh, and how these develop in time and space have been modelled using a coupled chemical equilibrium and transport code. The solubility of the important nuclides are being studied experimentally under these conditions, and under sensible variations. These data have been used to refine the thermodynamic data base used for the geochemical code PHREEQE. The sorption behaviour of plutonium and americium, under the same conditions, have been studied; the sorption coefficients were found to be large and independent of the concrete formulation, particle size and solid liquid ratio. Recent experimental results from sorption/exchange experiments with lead and 14-carbon are also reported. The programme has also investigated experimentally the possible perturbation of the repository chemistry by microbial action and by natural and added organic material. A final set of experiments combine all the repository components and the waste in a long term equilibration experiment. (author)

  5. Spatially Resolved Artificial Chemistry

    DEFF Research Database (Denmark)

    Fellermann, Harold

    2009-01-01

    Although spatial structures can play a crucial role in chemical systems and can drastically alter the outcome of reactions, the traditional framework of artificial chemistry is a well-stirred tank reactor with no spatial representation in mind. Advanced method development in physical chemistry has...... made a class of models accessible to the realms of artificial chemistry that represent reacting molecules in a coarse-grained fashion in continuous space. This chapter introduces the mathematical models of Brownian dynamics (BD) and dissipative particle dynamics (DPD) for molecular motion and reaction...

  6. Spatially Resolved Artificial Chemistry

    DEFF Research Database (Denmark)

    Fellermann, Harold

    2009-01-01

    made a class of models accessible to the realms of artificial chemistry that represent reacting molecules in a coarse-grained fashion in continuous space. This chapter introduces the mathematical models of Brownian dynamics (BD) and dissipative particle dynamics (DPD) for molecular motion and reaction......Although spatial structures can play a crucial role in chemical systems and can drastically alter the outcome of reactions, the traditional framework of artificial chemistry is a well-stirred tank reactor with no spatial representation in mind. Advanced method development in physical chemistry has...

  7. Implementation and evaluation of pH-dependent cloud chemistry and wetdeposition in the chemical transport model REM-Calgrid

    NARCIS (Netherlands)

    Banzhaf, S.; Schaap, M.; Kerschbaumer, A.; Reimer, E.; Stern, R.; Swaluw, E. van der; Builtjes, P.

    2012-01-01

    The Chemistry Transport Model REM-Calgrid (RCG) has been improved by implementing an enhanced description of aqueous-phase chemistry and wet deposition processes including droplet pH. A sensitivity study on cloud and rain droplet pH has been performed to investigate its impact on model sulphate

  8. Yucca Mountain Area Saturated Zone Dissolved Organic Carbon Isotopic Data

    International Nuclear Information System (INIS)

    Thomas, James; Decker, David; Patterson, Gary; Peterman, Zell; Mihevc, Todd; Larsen, Jessica; Hershey, Ronald

    2007-01-01

    Groundwater samples in the Yucca Mountain area were collected for chemical and isotopic analyses and measurements of water temperature, pH, specific conductivity, and alkalinity were obtained at the well or spring at the time of sampling. For this project, groundwater samples were analyzed for major-ion chemistry, deuterium, oxygen-18, and carbon isotopes of dissolved inorganic carbon (DIC) and dissolved organic carbon (DOC). The U.S. Geological Survey (USGS) performed all the fieldwork on this project including measurement of water chemistry field parameters and sample collection. The major ions dissolved in the groundwater, deuterium, oxygen-18, and carbon isotopes of dissolved inorganic carbon (DIC) were analyzed by the USGS. All preparation and processing of samples for DOC carbon isotopic analyses and geochemical modeling were performed by the Desert Research Institute (DRI). Analysis of the DOC carbon dioxide gas produced at DRI to obtain carbon-13 and carbon-14 values was conducted at the University of Arizona Accelerator Facility (a NSHE Yucca Mountain project QA qualified contract facility). The major-ion chemistry, deuterium, oxygen-18, and carbon isotopes of DIC were used in geochemical modeling (NETPATH) to determine groundwater sources, f ow paths, mixing, and ages. The carbon isotopes of DOC were used to calculate groundwater ages that are independent of DIC model corrected carbon-14 ages. The DIC model corrected carbon-14 calculated ages were used to evaluate groundwater travel times for mixtures of water including water beneath Yucca Mountain. When possible, groundwater travel times were calculated for groundwater flow from beneath Yucca Mountain to down gradient sample sites. DOC carbon-14 groundwater ages were also calculated for groundwaters in the Yucca Mountain area. When possible, groundwater travel times were estimated for groundwater flow from beneath Yucca Mountain to down gradient groundwater sample sites using the DOC calculated

  9. Center for Applications of Single-Walled Carbon Nanotubes

    Energy Technology Data Exchange (ETDEWEB)

    Resasco, Daniel E

    2008-02-21

    This report describes the activities conducted under a Congressional Direction project whose goal was to develop applications for Single-walled carbon nanotubes, under the Carbon Nanotube Technology Center (CANTEC), a multi-investigator program that capitalizes on OU’s advantageous position of having available high quality carbon nanotubes. During the first phase of CANTEC, 11 faculty members and their students from the College of Engineering developed applications for carbon nanotubes by applying their expertise in a number of areas: Catalysis, Reaction Engineering, Nanotube synthesis, Surfactants, Colloid Chemistry, Polymer Chemistry, Spectroscopy, Tissue Engineering, Biosensors, Biochemical Engineering, Cell Biology, Thermal Transport, Composite Materials, Protein synthesis and purification, Molecular Modeling, Computational Simulations. In particular, during this phase, the different research groups involved in CANTEC made advances in the tailoring of Single-Walled Carbon Nanotubes (SWNT) of controlled diameter and chirality by Modifying Reaction Conditions and the Nature of the catalyst; developed kinetic models that quantitatively describe the SWNT growth, created vertically oriented forests of SWNT by varying the density of metal nanoparticles catalyst particles, and developed novel nanostructured SWNT towers that exhibit superhydrophobic behavior. They also developed molecular simulations of the growth of Metal Nanoparticles on the surface of SWNT, which may have applications in the field of fuell cells. In the area of biomedical applications, CANTEC researchers fabricated SWNT Biosensors by a novel electrostatic layer-by-layer (LBL) deposition method, which may have an impact in the control of diabetes. They also functionalized SWNT with proteins that retained the protein’s biological activity and also retained the near-infrared light absorbance, which finds applications in the treatment of cancer.

  10. Carbon-nitrogen-water interactions: is model parsimony fruitful?

    Science.gov (United States)

    Puertes, Cristina; González-Sanchis, María; Lidón, Antonio; Bautista, Inmaculada; Lull, Cristina; Francés, Félix

    2017-04-01

    It is well known that carbon and nitrogen cycles are highly intertwined and both should be explained through the water balance. In fact, in water-controlled ecosystems nutrient deficit is related to this water scarcity. For this reason, the present study compares the capability of three models in reproducing the interaction between the carbon and nitrogen cycles and the water cycle. The models are BIOME-BGCMuSo, LEACHM and a simple carbon-nitrogen model coupled to the hydrological model TETIS. Biome-BGCMuSo and LEACHM are two widely used models that reproduce the carbon and nitrogen cycles adequately. However, their main limitation is that these models are quite complex and can be too detailed for watershed studies. On the contrary, the TETIS nutrient sub-model is a conceptual model with a vertical tank distribution over the active soil depth, dividing it in two layers. Only the input of the added litter and the losses due to soil respiration, denitrification, leaching and plant uptake are considered as external fluxes. Other fluxes have been neglected. The three models have been implemented in an experimental plot of a semi-arid catchment (La Hunde, East of Spain), mostly covered by holm oak (Quercus ilex). Plant transpiration, soil moisture and runoff have been monitored daily during nearly two years (26/10/2012 to 30/09/2014). For the same period, soil samples were collected every two months and taken to the lab in order to obtain the concentrations of dissolved organic carbon, microbial biomass carbon, ammonium and nitrate. In addition, between field trips soil samples were placed in PVC tubes with resin traps and were left incubating (in situ buried cores). Thus, mineralization and nitrification accumulated fluxes for two months, were obtained. The ammonium and nitrate leaching accumulated for two months were measured using ion-exchange resin cores. Soil respiration was also measured every field trip. Finally, water samples deriving from runoff, were collected

  11. Chemistry of carbon nanomaterials: Uses of lithium nanotube salts in organic syntheses and functionalization of graphite

    Science.gov (United States)

    Chattopadhyay, Jayanta

    transfer (SET) mechanism to functionalize carbon nanotubes with different alkyl/aryl groups. Using the reductive alkylation approach, we can also functionalize graphites by alkyl/carboxylic acid groups, making graphite soluble in organic solvents and water. Tailoring of graphite layers is also accomplished by using different metals in liquid ammonia. Finally, SWNT-epoxides/graphite epoxides are synthesized using m-CPBA. Quantification of the epoxide substituents on the nanotube/graphite surface is evaluated through the catalytic de-epoxidation reaction using MeReO 3/PPh3 as heterogeneous catalyst. In summary, the proposed covalent functionalization methods yield derivatized nanomaterials that can provide a solid platform for a number of exciting applications, ranging from material science to biomedical devices. Furthermore, the results presented in this thesis provide insight into the molecular chemistry at nano-resolution.

  12. Water chemistry and materials degradation in LWR'S

    International Nuclear Information System (INIS)

    Haenninen, H.; Toerroenen, K.; Aaltonen, P.

    1994-01-01

    Water chemistry plays a major role in corrosion, in erosion corrosion and in activity transport in NPPs; it impacts upon the operational safety of LWRs in two main ways: integrity of pressure boundary materials and activity transport and out-of-core radiation fields. A good control of water chemistry can significantly reduce these problems and improve plant safety, but economic pressures are leading to more rigorous operating conditions: fuel burnups are to be increased, higher efficiencies are to be achieved by running at higher temperatures and plant lifetimes are to be extended. Typical water chemistry specifications used in PWR and BWR plants are presented and the chemistry optimization is discussed. The complex interplay of metallurgical, mechanical and environmental factors in environmental sensitive cracking is shown, with details on studies for carbon steels, stainless steels and nickel base alloys. 20 refs., 8 figs., 4 tabs

  13. Integrating microbial diversity in soil carbon dynamic models parameters

    Science.gov (United States)

    Louis, Benjamin; Menasseri-Aubry, Safya; Leterme, Philippe; Maron, Pierre-Alain; Viaud, Valérie

    2015-04-01

    Faced with the numerous concerns about soil carbon dynamic, a large quantity of carbon dynamic models has been developed during the last century. These models are mainly in the form of deterministic compartment models with carbon fluxes between compartments represented by ordinary differential equations. Nowadays, lots of them consider the microbial biomass as a compartment of the soil organic matter (carbon quantity). But the amount of microbial carbon is rarely used in the differential equations of the models as a limiting factor. Additionally, microbial diversity and community composition are mostly missing, although last advances in soil microbial analytical methods during the two past decades have shown that these characteristics play also a significant role in soil carbon dynamic. As soil microorganisms are essential drivers of soil carbon dynamic, the question about explicitly integrating their role have become a key issue in soil carbon dynamic models development. Some interesting attempts can be found and are dominated by the incorporation of several compartments of different groups of microbial biomass in terms of functional traits and/or biogeochemical compositions to integrate microbial diversity. However, these models are basically heuristic models in the sense that they are used to test hypotheses through simulations. They have rarely been confronted to real data and thus cannot be used to predict realistic situations. The objective of this work was to empirically integrate microbial diversity in a simple model of carbon dynamic through statistical modelling of the model parameters. This work is based on available experimental results coming from a French National Research Agency program called DIMIMOS. Briefly, 13C-labelled wheat residue has been incorporated into soils with different pedological characteristics and land use history. Then, the soils have been incubated during 104 days and labelled and non-labelled CO2 fluxes have been measured at ten

  14. Computational Tools To Model Halogen Bonds in Medicinal Chemistry.

    Science.gov (United States)

    Ford, Melissa Coates; Ho, P Shing

    2016-03-10

    The use of halogens in therapeutics dates back to the earliest days of medicine when seaweed was used as a source of iodine to treat goiters. The incorporation of halogens to improve the potency of drugs is now fairly standard in medicinal chemistry. In the past decade, halogens have been recognized as direct participants in defining the affinity of inhibitors through a noncovalent interaction called the halogen bond or X-bond. Incorporating X-bonding into structure-based drug design requires computational models for the anisotropic distribution of charge and the nonspherical shape of halogens, which lead to their highly directional geometries and stabilizing energies. We review here current successes and challenges in developing computational methods to introduce X-bonding into lead compound discovery and optimization during drug development. This fast-growing field will push further development of more accurate and efficient computational tools to accelerate the exploitation of halogens in medicinal chemistry.

  15. Chemistry in T Tauri winds

    Energy Technology Data Exchange (ETDEWEB)

    Rawlings, J M.C.; Williams, D A; Canto, J

    1988-02-15

    The chemistry occurring in the winds of T Tauri stars is investigated. On the assumption that the wind is dust-free, then routes to H/sub 2/ are inhibited under the conditions in the wind, and subsequent chemistry does not produce substantial molecular abundances. The major losses to the chemical network lie in the geometrical dilution and collisional dissociation rather than in chemical destruction and photodissociation. Mass loading of the wind with dust and H/sub 2/ may, however, occur. This stimulates the chemistry and may in some circumstances lead to a conversion of approx.1-10 per cent of carbon into CO. This gives a column density of CO which is marginally detectable. A positive detection of CO at high wind velocities would imply that the winds must be cool and that mixing of molecular material from a disc, which may play a role in collimating the wind, or the remnants of a disc, must occur.

  16. Redox-controlled carbon and phosphorus burial: A mechanism for enhanced organic carbon sequestration during the PETM

    Science.gov (United States)

    Komar, Nemanja; Zeebe, Richard E.

    2017-12-01

    Geological records reveal a major perturbation in carbon cycling during the Paleocene-Eocene Thermal Maximum (PETM, ∼56 Ma), marked by global warming of more than 5 °C and a prominent negative carbon isotope excursion of at least 2.5‰ within the marine realm. The entire event lasted about 200,000 yr and was associated with a massive release of light carbon into the ocean-atmosphere system over several thousands of years. Here we focus on the terminal stage of the PETM, during which the ocean-atmosphere system rapidly recovered from the carbon cycle perturbation. We employ a carbon-cycle box model to examine the feedbacks between surface ocean biological production, carbon, oxygen, phosphorus, and carbonate chemistry during massive CO2 release events, such as the PETM. The model results indicate that the redox-controlled carbon-phosphorus feedback is capable of producing enhanced organic carbon sequestration during large carbon emission events. The locale of carbon oxidation (ocean vs. atmosphere) does not affect the amount of carbon sequestered. However, even though the model produces trends consistent with oxygen, excess accumulation rates of organic carbon (∼1700 Pg C during the recovery stage), export production and δ13 C data, it fails to reproduce the magnitude of change of sediment carbonate content and the CCD over-deepening during the recovery stage. The CCD and sediment carbonate content overshoot during the recovery stage is muted by a predicted increase in CaCO3 rain. Nonetheless, there are indications that the CaCO3 export remained relatively constant during the PETM. If this was indeed true, then an initial pulse of 3,000 Pg C followed by an additional, slow leak of 2,500 Pg C could have triggered an accelerated nutrient supply to the surface ocean instigating enhanced organic carbon export, consequently increasing organic carbon sequestration, resulting in an accelerated restoration of ocean-atmosphere biogeochemistry during the termination

  17. Unconventional Constraints on Nitrogen Chemistry using DC3 Observations and Trajectory-based Chemical Modeling

    Science.gov (United States)

    Shu, Q.; Henderson, B. H.

    2017-12-01

    Chemical transport models underestimate nitrogen dioxide observations in the upper troposphere (UT). Previous research in the UT succeeded in combining model predictions with field campaign measurements to demonstrate that the nitric acid formation rate (HO + NO2 → HNO3 (R1)) is overestimated by 22% (Henderson et al., 2012). A subsequent publication (Seltzer et al., 2015) demonstrated that single chemical constraint alters ozone and aerosol formation/composition. This work attempts to replicate previous chemical constraints with newer observations and a different modeling framework. We apply the previously successful constraint framework to Deep Convection Clouds and Chemistry (DC3). DC3 is a more recent field campaign where simulated nitrogen imbalances still exist. Freshly convected air parcels, identified in the DC3 dataset, as initial coordinates to initiate Lagrangian trajectories. Along each trajectory, we simulate the air parcel chemical state. Samples along the trajectories will form ensembles that represent possible realizations of UT air parcels. We then apply Bayesian inference to constrain nitrogen chemistry and compare results to the existing literature. Our anticipated results will confirm overestimation of HNO3 formation rate in previous work and provide further constraints on other nitrogen reaction rate coefficients that affect terminal products from NOx. We will particularly focus on organic nitrate chemistry that laboratory literature has yet to fully address. The results will provide useful insights into nitrogen chemistry that affects climate and human health.

  18. A time-dependent anisotropic plasma chemistry model of the Io plasma torus

    Science.gov (United States)

    Arridge, C. S.

    2016-12-01

    The physics of the Io plasma torus is typically modelled using one box neutral-plasma chemistry models, often referred to as neutral cloud theory models (e.g., Barbosa 1994; Delamere and Bagenal 2003). These models incorporate electron impact and photoionisation, charge exchange, molecular dissociation/recombination reactions, atomic radiatiative losses and Coulomb collisional heating. Isotropic Maxwellian distributions are usually assumed in the implementation of these models. Observationally a population of suprathermal electrons has been identified in the plasma torus and theoretically they have been shown to be important in reproducing the observed ionisation balance in the torus (e.g., Barbosa 1994). In this paper we describe an anisotropic plasma chemistry model for the Io torus that is inspired by ion cyclotron wave observations (Huddleston et al. 1994; Leisner et al. 2011), ion anisotropies due to pick up (Wilson et al. 2008), and theoretical ideas on the maintenance of the suprathermal electron population (Barbosa 1994). We present both steady state calculations and also time varying solutions (e.g., Delamere et al. 2004) where increases in the neutral source rate in the torus generates perturbations in ion anisotropies that subsequently decay over a timescale much longer than the duration of the initial perturbation. We also present a method for incorporating uncertainties in reaction rates into the model.

  19. Tropospheric ozone changes, radiative forcing and attribution to emissions in the Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP

    Directory of Open Access Journals (Sweden)

    D. S. Stevenson

    2013-03-01

    Full Text Available Ozone (O3 from 17 atmospheric chemistry models taking part in the Atmospheric Chemistry and Climate Model Intercomparison Project (ACCMIP has been used to calculate tropospheric ozone radiative forcings (RFs. All models applied a common set of anthropogenic emissions, which are better constrained for the present-day than the past. Future anthropogenic emissions follow the four Representative Concentration Pathway (RCP scenarios, which define a relatively narrow range of possible air pollution emissions. We calculate a value for the pre-industrial (1750 to present-day (2010 tropospheric ozone RF of 410 mW m−2. The model range of pre-industrial to present-day changes in O3 produces a spread (±1 standard deviation in RFs of ±17%. Three different radiation schemes were used – we find differences in RFs between schemes (for the same ozone fields of ±10%. Applying two different tropopause definitions gives differences in RFs of ±3%. Given additional (unquantified uncertainties associated with emissions, climate-chemistry interactions and land-use change, we estimate an overall uncertainty of ±30% for the tropospheric ozone RF. Experiments carried out by a subset of six models attribute tropospheric ozone RF to increased emissions of methane (44±12%, nitrogen oxides (31 ± 9%, carbon monoxide (15 ± 3% and non-methane volatile organic compounds (9 ± 2%; earlier studies attributed more of the tropospheric ozone RF to methane and less to nitrogen oxides. Normalising RFs to changes in tropospheric column ozone, we find a global mean normalised RF of 42 mW m−2 DU−1, a value similar to previous work. Using normalised RFs and future tropospheric column ozone projections we calculate future tropospheric ozone RFs (mW m−2; relative to 1750 for the four future scenarios (RCP2.6, RCP4.5, RCP6.0 and RCP8.5 of 350, 420, 370 and 460 (in 2030, and 200, 300, 280 and 600 (in 2100. Models show some coherent responses of ozone to climate change

  20. Controls on dripwater chemistry of Oregon Caves National Monument, northwestern United States

    Science.gov (United States)

    Rushdi, Ahmed I.; Ersek, Vasile; Mix, Alan C.; Clark, Peter U.

    2018-02-01

    Cave dripwater chemistry of Oregon Caves National Monument (OCNM) was studied, where the parameters pH, total alkalinity, calcium, magnesium, strontium, sodium and barium were analyzed at quasi-monthly intervals from 2005 to 2007. Different statistical analyses have been used to investigate the variability of the chemical parameters in the different sites in the OCNM cave system. The dripwater varies in response to seasonal changes in rainfall. The drip rates range from zero in summer to continuous flow in winter, closely following the rainfall intensity. Spatial variations of dripwater chemistry, which is nonlinearly related to dripwater discharge likely, reflect the chemical composition of bedrock and overlying soil, and the residence time of the ground water within the aquifer. The residence time of infiltrated water in bedrock cracks control the dissolution carbonate bedrock, reprecipitation of calcium carbonate and the degree of saturation of dripwater with respect to calcium carbonate minerals. Spatiotemporal fluctuations of dripwater Mg/Ca and Sr/Ca ratios are controlled by dissolution of carbonate bedrock and the degree of calcite reprecipitation in bedrock cracks. This suggests that trace elements in speleothem deposits at the OCNM may serve as paleoclimatological proxies for precipitation, if interpreted within the context of understanding local bedrock chemistry.

  1. Multi-wall carbon nanotubes with nitrogen-containing carbon coating

    Czech Academy of Sciences Publication Activity Database

    Tomšík, Elena; Morávková, Zuzana; Stejskal, Jaroslav; Trchová, Miroslava; Šálek, Petr; Kovářová, Jana; Zemek, Josef; Cieslar, M.; Prokeš, J.

    2013-01-01

    Roč. 67, č. 8 (2013), s. 1054-1065 ISSN 0366-6352 R&D Projects: GA ČR GPP108/11/P763; GA ČR GAP205/12/0911; GA ČR GA202/09/0428 Institutional support: RVO:61389013 ; RVO:68378271 Keywords : polyaniline coating * carbon ization * multi-wall carbon nanotubes Subject RIV: CD - Macromolecular Chemistry; BM - Solid Matter Physics ; Magnetism (FZU-D) Impact factor: 1.193, year: 2013

  2. D-region ion-neutral coupled chemistry (Sodankylä Ion Chemistry, SIC) within the Whole Atmosphere Community Climate Model (WACCM 4) - WACCM-SIC and WACCM-rSIC

    Science.gov (United States)

    Kovács, Tamás; Plane, John M. C.; Feng, Wuhu; Nagy, Tibor; Chipperfield, Martyn P.; Verronen, Pekka T.; Andersson, Monika E.; Newnham, David A.; Clilverd, Mark A.; Marsh, Daniel R.

    2016-09-01

    This study presents a new ion-neutral chemical model coupled into the Whole Atmosphere Community Climate Model (WACCM). The ionospheric D-region (altitudes ˜ 50-90 km) chemistry is based on the Sodankylä Ion Chemistry (SIC) model, a one-dimensional model containing 307 ion-neutral and ion recombination, 16 photodissociation and 7 photoionization reactions of neutral species, positive and negative ions, and electrons. The SIC mechanism was reduced using the simulation error minimization connectivity method (SEM-CM) to produce a reaction scheme of 181 ion-molecule reactions of 181 ion-molecule reactions of 27 positive and 18 negative ions. This scheme describes the concentration profiles at altitudes between 20 km and 120 km of a set of major neutral species (HNO3, O3, H2O2, NO, NO2, HO2, OH, N2O5) and ions (O2+, O4+, NO+, NO+(H2O), O2+(H2O), H+(H2O), H+(H2O)2, H+(H2O)3, H+(H2O)4, O3-, NO2-, O-, O2, OH-, O2-(H2O), O2-(H2O)2, O4-, CO3-, CO3-(H2O), CO4-, HCO3-, NO2-, NO3-, NO3-(H2O), NO3-(H2O)2, NO3-(HNO3), NO3-(HNO3)2, Cl-, ClO-), which agree with the full SIC mechanism within a 5 % tolerance. Four 3-D model simulations were then performed, using the impact of the January 2005 solar proton event (SPE) on D-region HOx and NOx chemistry as a test case of four different model versions: the standard WACCM (no negative ions and a very limited set of positive ions); WACCM-SIC (standard WACCM with the full SIC chemistry of positive and negative ions); WACCM-D (standard WACCM with a heuristic reduction of the SIC chemistry, recently used to examine HNO3 formation following an SPE); and WACCM-rSIC (standard WACCM with a reduction of SIC chemistry using the SEM-CM method). The standard WACCM misses the HNO3 enhancement during the SPE, while the full and reduced model versions predict significant NOx, HOx and HNO3 enhancements in the mesosphere during solar proton events. The SEM-CM reduction also identifies the important ion-molecule reactions that affect the partitioning of

  3. Improving Students' Understanding of Molecular Structure through Broad-Based Use of Computer Models in the Undergraduate Organic Chemistry Lecture

    Science.gov (United States)

    Springer, Michael T.

    2014-01-01

    Several articles suggest how to incorporate computer models into the organic chemistry laboratory, but relatively few papers discuss how to incorporate these models broadly into the organic chemistry lecture. Previous research has suggested that "manipulating" physical or computer models enhances student understanding; this study…

  4. Adsorption of Remazol Black B dye on Activated Carbon Felt

    Directory of Open Access Journals (Sweden)

    Donnaperna Lucio

    2008-11-01

    Full Text Available The adsorption of Remazol Black B (anionic dye on a microporous activated carbon felt is investigated from its aqueous solution. The surface chemistry of activated carbon is studied using X-ray microanalysis, "Boehm" titrations and pH of PZC measurements which indicates that the surface oxygenated groups are mainly acidic in nature. The kinetics of Remazol Black B adsorption is observed to be pH dependent and governed by the diffusion of the dye molecules. The experimental data can be explained by "intra-particle diffusion model". For Remazol Black B, the Khan model is best suited to simulate the adsorption isotherms.

  5. Heterogeneity of activated carbons in adsorption of aniline from aqueous solutions

    Science.gov (United States)

    Podkościelny, P.; László, K.

    2007-08-01

    The heterogeneity of activated carbons (ACs) prepared from different precursors is investigated on the basis of adsorption isotherms of aniline from dilute aqueous solutions at various pH values. The APET carbon prepared from polyethyleneterephthalate (PET), as well as, commercial ACP carbon prepared from peat were used. Besides, to investigate the influence of carbon surface chemistry, the adsorption was studied on modified carbons based on ACP carbon. Its various oxygen surface groups were changed by both nitric acid and thermal treatments. The Dubinin-Astakhov (DA) equation and Langmuir-Freundlich (LF) one have been used to model the phenomenon of aniline adsorption from aqueous solutions on heterogeneous carbon surfaces. Adsorption-energy distribution (AED) functions have been calculated by using an algorithm based on a regularization method. Analysis of these functions for activated carbons studied provides important comparative information about their surface heterogeneity.

  6. Synthesis and Characterization of Multiwalled Carbon Nanotubes/Poly(HEMA-co-MMA) by Utilizing Click Chemistry.

    Science.gov (United States)

    Bach, Long Giang; Cao, Xuan Thang; Islam, Md Rafiqul; Jeong, Yeon Tae; Kim, Jong Su; Lim, Kwon Taek

    2016-03-01

    The hybrid material consisting of multi walled carbon nanotubes (MWNTs) and poly(2-hydroxyethylmethacrylate-co-methylmethacrylate) [poly(HEMA-co-MMA)] was synthesized by a combination of RAFT and Click chemistry. In the primary stage, the copolymer poly(HEMA-co-MMA) was prepared by applying RAFT technique. Alkynyl side groups were incorporated onto the poly(HEMA-co-MMA) backbone by esterification reaction. Then, MWNTs-N3 was prepared by treating MWNTs with 4-azidobutylamine. The click coupling reaction between azide-functionalized MWNTs (MWNTs-N3) and the alkyne-functionalized random copolymer ((HEMA-co-MMA)-Alkyne) with the Cu(I)-catalyzed [3+2] Huisgen cycloaddition afforded the hybrid compound. The structure and properties of poly(MMA-co-HEMA)-g-MWNTs were investigated by FT-IR, EDX and TGA measurements. The copolymer brushes were observed to be immobilized onto the functionalized MWNTs by SEM and TEM analysis.

  7. Carbonate rock depositional models: A microfacies approach

    Energy Technology Data Exchange (ETDEWEB)

    Carozzi, A.V.

    1988-01-01

    Carbonate rocks contain more than 50% by weight carbonate minerals such as calcite, dolomite, and siderite. Understanding how these rocks form can lead to more efficient methods of petroleum exploration. Micofacies analysis techniques can be used as a method of predicting models of sedimentation for carbonate rocks. Micofacies in carbonate rocks can be seen clearly only in thin sections under a microscope. This section analysis of carbonate rocks is a tool that can be used to understand depositional environments, diagenetic evolution of carbonate rocks, and the formation of porosity and permeability in carbonate rocks. The use of micofacies analysis techniques is applied to understanding the origin and formation of carbonate ramps, carbonate platforms, and carbonate slopes and basins. This book will be of interest to students and professionals concerned with the disciplines of sedimentary petrology, sedimentology, petroleum geology, and palentology.

  8. Simulating atmospheric composition over a South-East Asian tropical rainforest: performance of a chemistry box model

    Directory of Open Access Journals (Sweden)

    T. A. M. Pugh

    2010-01-01

    Full Text Available Atmospheric composition and chemistry above tropical rainforests is currently not well established, particularly for south-east Asia. In order to examine our understanding of chemical processes in this region, the performance of a box model of atmospheric boundary layer chemistry is tested against measurements made at the top of the rainforest canopy near Danum Valley, Malaysian Borneo. Multi-variate optimisation against ambient concentration measurements was used to estimate average canopy-scale emissions for isoprene, total monoterpenes and nitric oxide. The excellent agreement between estimated values and measured fluxes of isoprene and total monoterpenes provides confidence in the overall modelling strategy, and suggests that this method may be applied where measured fluxes are not available, assuming that the local chemistry and mixing are adequately understood. The largest contributors to the optimisation cost function at the point of best-fit are OH (29%, NO (22% and total peroxy radicals (27%. Several factors affect the modelled VOC chemistry. In particular concentrations of methacrolein (MACR and methyl-vinyl ketone (MVK are substantially overestimated, and the hydroxyl radical (OH concentration is substantially underestimated; as has been seen before in tropical rainforest studies. It is shown that inclusion of dry deposition of MACR and MVK and wet deposition of species with high Henry's Law values substantially improves the fit of these oxidised species, whilst also substantially decreasing the OH sink. Increasing OH production arbitrarily, through a simple OH recycling mechanism , adversely affects the model fit for volatile organic compounds (VOCs. Given the constraints on isoprene flux provided by measurements, a substantial decrease in the rate of reaction of VOCs with OH is the only remaining option to explain the measurement/model discrepancy for OH. A reduction in the isoprene+OH rate constant of 50%, in conjunction with

  9. On Calcium Carbonates: from Fundamental Research to Application

    OpenAIRE

    Brečević, Ljerka; Kralj, Damir

    2007-01-01

    Appearance of a solid phase from aqueous solution, known as precipitation, is responsible for the formation of numerous natural materials and technological products. Therefore, the knowledge on mechanisms of elementary processes involved in precipitation should be considered in the areas such as geology, oceanology, biomineralization, medicine, basic chemical and pharmaceutical industries, analytical and materials chemistry in particular. Calcium carbonates are a very suitable model system fo...

  10. The Hamburg oceanic carbon cycle circulation model. Cycle 1

    International Nuclear Information System (INIS)

    Maier-Reimer, E.; Heinze, C.

    1992-02-01

    The carbon cycle model calculates the prognostic fields of oceanic geochemical carbon cycle tracers making use of a 'frozen' velocity field provided by a run of the LSG oceanic circulation model (see the corresponding manual, LSG=Large Scale Geostrophic). The carbon cycle model includes a crude approximation of interactions between sediment and bottom layer water. A simple (meridionally diffusive) one layer atmosphere model allows to calculate the CO 2 airborne fraction resulting from the oceanic biogeochemical interactions. (orig.)

  11. Presidential Green Chemistry Challenge: 2010 Academic Award - James C. Liao and Easel Biotechnologies, LLC

    Science.gov (United States)

    Presidential Green Chemistry Challenge 2010 award winner, Dr. James C. Liao, genetically engineered microorganisms to make higher alcohols (with 3 to 8 carbon atoms) from glucose or directly from carbon dioxide (CO2).

  12. Twin carbons: The carbonization of cellulose or carbonized cellulose coated with a conducting polymer, polyaniline

    Czech Academy of Sciences Publication Activity Database

    Bober, Patrycja; Kovářová, Jana; Pfleger, Jiří; Stejskal, Jaroslav; Trchová, Miroslava; Novák, I.; Berek, D.

    2016-01-01

    Roč. 109, November (2016), s. 836-842 ISSN 0008-6223 R&D Projects: GA ČR(CZ) GA13-00270S Institutional support: RVO:61389013 Keywords : cellulose * carbon * polyaniline Subject RIV: CD - Macromolecular Chemistry Impact factor: 6.337, year: 2016

  13. Primary Water Chemistry Control during a Planned Outage at Bruce Power

    International Nuclear Information System (INIS)

    Ma, Guoping; Nashiem, Rod; Matheson, Shane; Yabar, Berman; Harper, Bill; Roberts, John G.

    2012-09-01

    Bruce Power has developed a comprehensive outage water chemistry program, which includes both primary and secondary chemistry requirements during planned outages. The purpose of the program is to emphasize the chemistry requirements during outages and subsequent start-ups in order to maintain the integrity of the systems, minimise activity transport and radiation fields, reduce the Carbon-14 release, and to ensure that the requirements are integrated with the outage management program. Prior to a planned outage, Station Chemical Technical Sections identify outage chemistry requirements to Operations and Outage Planning and ensure that work necessary to correct system chemistry issues is within outage work scope. The outage water chemistry program provides direction for establishing alternative sampling locations as demanded by the system configuration during the outage and identifies outage prerequisites for nuclear system purification capabilities. These requirements are contained in an outage checklist. The paper mainly highlights the primary water chemistry issues and chemistry control strategies during planned outages and discusses challenges and successes. (authors)

  14. Increase of carbon cycle feedback with climate sensitivity: results from a coupled climate and carbon cycle model

    International Nuclear Information System (INIS)

    Govindasamy, B.; Thompson, S.; Mirin, A.; Wickett, M.; Caldeira, K.; Delire, C.

    2005-01-01

    Coupled climate and carbon cycle modelling studies have shown that the feedback between global warming and the carbon cycle, in particular the terrestrial carbon cycle, could accelerate climate change and result in greater warming. In this paper we investigate the sensitivity of this feedback for year 2100 global warming in the range of 0 to 8 K. Differing climate sensitivities to increased CO 2 content are imposed on the carbon cycle models for the same emissions. Emissions from the SRES A2 scenario are used. We use a fully coupled climate and carbon cycle model, the INtegrated Climate and CArbon model (INCCA), the NCAR/DOE Parallel Climate Model coupled to the IBIS terrestrial biosphere model and a modified OCMIP ocean biogeochemistry model. In our integrated model, for scenarios with year 2100 global warming increasing from 0 to 8 K, land uptake decreases from 47% to 29% of total CO 2 emissions. Due to competing effects, ocean uptake (16%) shows almost no change at all. Atmospheric CO 2 concentration increases are 48% higher in the run with 8 K global climate warming than in the case with no warming. Our results indicate that carbon cycle amplification of climate warming will be greater if there is higher climate sensitivity to increased atmospheric CO 2 content; the carbon cycle feedback factor increases from 1.13 to 1.48 when global warming increases from 3.2 to 8 K

  15. Liquid surface model for carbon nanotube energetics

    DEFF Research Database (Denmark)

    Solov'yov, Ilia; Mathew, Maneesh; Solov'yov, Andrey V.

    2008-01-01

    an important insight in the energetics and stability of nanotubes of different chirality and might be important for the understanding of nanotube growth process. For the computations we use empirical Brenner and Tersoff potentials and discuss their applicability to the study of carbon nanotubes. From......In the present paper we developed a model for calculating the energy of single-wall carbon nanotubes of arbitrary chirality. This model, which we call as the liquid surface model, predicts the energy of a nanotube with relative error less than 1% once its chirality and the total number of atoms...... the calculated energies we determine the elastic properties of the single-wall carbon nanotubes (Young modulus, curvature constant) and perform a comparison with available experimental measurements and earlier theoretical predictions....

  16. Presidential Green Chemistry Challenge: 2013 Designing Greener Chemicals Award

    Science.gov (United States)

    Presidential Green Chemistry Challenge 2013 award winner, Cargill, Inc., developed a vegetable-oil-based transformer fluid that is much less flammable, provides superior performance, is less toxic, and has a substantially lower carbon footprint.

  17. A multi-layer box model of carbon dynamics in soil

    International Nuclear Information System (INIS)

    Kuc, T.

    2005-01-01

    A multi-layer box model (MLB) for quantification of carbon fluxes between soil and atmosphere has been developed. In the model, soil carbon reservoir is represented by two boxes: fast decomposition box (FDB) and slow decomposition box (SDB), characterised by substantially different turnover time (TT) of carbon compounds. Each box has an internal structure (sub-compartments) accounting for carbon deposited in consecutive time intervals. The rate of decomposition of carbon compounds in each sub-compartment is proportional to the carbon content. With the aid of the MLB model and the 14 C signature of carbon dioxide, the fluxes entering and leaving the boxes, turnover time of carbon in each box, and the ratio of mass of carbon in the slow and fast box (M s /M f ) were calculated. The MBL model yields the turnover time of carbon in the FDB (TT f ) ca. 14 for typical investigated soils of temperate climate ecosystems. The calculated contribution of the CO 2 flux originating from the slow box (F s ) to the total CO 2 flux into the atmosphere ranges from 12% to 22%. These values are in agreement with experimental observations at different locations. Assuming that the input flux of carbon (F i n) to the soil system is doubled within the period of 100 years, the soil buffering capacity for excess carbon predicted by the MLB model for typical soil parameters may vary in the range between 26% and 52%. The highest values are obtained for soils characterised by long TTf, and well developed old carbon pool. (author)

  18. Detailed Numerical Simulation of Single-Walled Carbon Nanotube Synthesis in a Radio-Frequency Induction Thermal Plasma System

    International Nuclear Information System (INIS)

    Esfarjani, S Arabzadeh; Mostaghimi, J; Dworkin, S B; Kim, K S; Kingston, C T; Simard, B; Soucy, G

    2012-01-01

    2D axisymmetric numerical calculations are conducted to model the thermo-fluid fields and chemical reactions leading to the formation of SWCNTs in an RF plasma system. A modified version of the SWCNT “reduced” chemical model is used to estimate the formation of SWCNT in an RF plasma system for the first time. The “reduced” model incorporates 14 species and 36 chemical reactions to predict the formation of metal and carbon clusters and SWCNTs. By combing the chemistry model into the RF plasma CFD code, the formation and development of carbon and metal catalyst clusters and their reactions which produce SWCNTs are shown. The chemistry model is shown to under-predict the yield rate of SWCNT. In order to better predict the yield rate, a sensitivity analysis is performed to modify the dominant reaction rates. The modified model predicts the yield of SWCNTs correctly within the range reported experimentally. However, more studies should be conducted to validate the accuracy of the model for different operating conditions.

  19. A carbon in molten carbonate anode model for a direct carbon fuel cell

    Energy Technology Data Exchange (ETDEWEB)

    Li Hongjiao; Liu Qinghua [Tianjin Key Laboratory of Catalysis Science and Technology, School of Chemical Engineering, Tianjin University, Weijing Road 92, Tianjin 300072 (China); State Key Laboratory for Chemical Engineering (Tianjin University), School of Chemical Engineering, Tianjin University, Weijing Road 92, Tianjin 300072 (China); Li Yongdan, E-mail: ydli@tju.edu.c [Tianjin Key Laboratory of Catalysis Science and Technology, School of Chemical Engineering, Tianjin University, Weijing Road 92, Tianjin 300072 (China); State Key Laboratory for Chemical Engineering (Tianjin University), School of Chemical Engineering, Tianjin University, Weijing Road 92, Tianjin 300072 (China)

    2010-02-15

    The electrochemical oxidation of carbon at the anode of a direct carbon fuel cell (DCFC) includes charge transfer steps and chemical steps. A microstructural model of carbon particle is built, in which perfect graphene stacks are taken as the basic building blocks of carbon. A modified mechanism taking account of the irreversibility of the process and supposing that the electrochemical oxidation of carbon takes place only at the edges of the graphene sheets is proposed. A Tafel type overall rate equation is deduced along with expressions of exchange current density (j{sub 0}) and activation polarization (eta{sub act}). The performance of carbon black and graphite as the fuel of DCFC is examined. It has been found that j{sub 0} is in the range of 0.10-6.12 mA cm{sup -2} at 923-1123 K and eta{sub act} is in the range of 0.024-0.28 V at 923-1123 K with current density in 10-120 mA cm{sup -2}. Analysis of the j{sub 0}, eta{sub act} values and the product composition reveals that the charge transfer steps as well as the oxygen ion absorption steps are both important for the reaction rate. The activity of the carbon material with respect to atom location is introduced to the open circuit potential difference (OCP) calculation with Nernst equation.

  20. Modelling soil nitrogen: The MAGIC model with nitrogen retention linked to carbon turnover using decomposer dynamics

    International Nuclear Information System (INIS)

    Oulehle, F.; Cosby, B.J.; Wright, R.F.; Hruška, J.; Kopáček, J.; Krám, P.; Evans, C.D.; Moldan, F.

    2012-01-01

    We present a new formulation of the acidification model MAGIC that uses decomposer dynamics to link nitrogen (N) cycling to carbon (C) turnover in soils. The new model is evaluated by application to 15–30 years of water chemistry data at three coniferous-forested sites in the Czech Republic where deposition of sulphur (S) and N have decreased by >80% and 40%, respectively. Sulphate concentrations in waters have declined commensurately with S deposition, but nitrate concentrations have shown much larger decreases relative to N deposition. This behaviour is inconsistent with most conceptual models of N saturation, and with earlier versions of MAGIC which assume N retention to be a first-order function of N deposition and/or controlled by the soil C/N ratio. In comparison with earlier versions, the new formulation more correctly simulates observed short-term changes in nitrate leaching, as well as long-term retention of N in soils. The model suggests that, despite recent deposition reductions and recovery, progressive N saturation will lead to increased future nitrate leaching, ecosystem eutrophication and re-acidification. - Highlights: ► New version of the biogeochemical model MAGIC developed to simulate C/N dynamics. ► New formulation of N retention based directly on the decomposer processes. ► The new formulation simulates observed changes in nitrate leaching and in soil C/N. ► The model suggests progressive N saturation at sites examined. ► The model performance meets a growing need for realistic process-based simulations. - Process-based modelling of nitrogen dynamics and acidification in forest ecosystems.

  1. Towards a paradigm shift in the modeling of soil organic carbon decomposition for earth system models

    Science.gov (United States)

    He, Yujie

    Soils are the largest terrestrial carbon pools and contain approximately 2200 Pg of carbon. Thus, the dynamics of soil carbon plays an important role in the global carbon cycle and climate system. Earth System Models are used to project future interactions between terrestrial ecosystem carbon dynamics and climate. However, these models often predict a wide range of soil carbon responses and their formulations have lagged behind recent soil science advances, omitting key biogeochemical mechanisms. In contrast, recent mechanistically-based biogeochemical models that explicitly account for microbial biomass pools and enzyme kinetics that catalyze soil carbon decomposition produce notably different results and provide a closer match to recent observations. However, a systematic evaluation of the advantages and disadvantages of the microbial models and how they differ from empirical, first-order formulations in soil decomposition models for soil organic carbon is still needed. This dissertation consists of a series of model sensitivity and uncertainty analyses and identifies dominant decomposition processes in determining soil organic carbon dynamics. Poorly constrained processes or parameters that require more experimental data integration are also identified. This dissertation also demonstrates the critical role of microbial life-history traits (e.g. microbial dormancy) in the modeling of microbial activity in soil organic matter decomposition models. Finally, this study surveys and synthesizes a number of recently published microbial models and provides suggestions for future microbial model developments.

  2. Recent Developments in Carbonylation Chemistry Using [13 C]CO, [11 C]CO and [14 C]CO.

    Science.gov (United States)

    Nielsen, Dennis U; Neumann, Karoline T; Lindhardt, Anders T; Skrydstrup, Troels

    2018-06-01

    Carbon monoxide represents the most important C1-building block for the chemical industry, both for the production of bulk and fine chemicals, but also for synthetic fuels. Yet, its toxicity and subsequently its cautious handling has limited its applications in medicinal chemistry research and in particular for the synthesis of pharmaceutically relevant molecules. Recent years have nevertheless witnessed a considerable headway on the development of carbon monoxide surrogates and reactor systems, which provide an ideal setting for performing carbonylation chemistry with stoichiometric and sub-stoichiometric carbon monoxide. Such set-ups are particularly ideal for the introduction of isotope labels such as carbon-11, carbon-13 and carbon-14 into bioactive compounds. This review summarizes this growing field and examines the large number of carbonylation reactions that can be exploited for the introduction of a carbon isotope. This article is protected by copyright. All rights reserved.

  3. Remote sensing of atmospheric chemistry; Proceedings of the Meeting, Orlando, FL, Apr. 1-3, 1991

    Science.gov (United States)

    McElroy, James L.; McNeal, Robert J.

    The present volume on remote sensing of atmospheric chemistry discusses special remote sensing space observations and field experiments to study chemical change in the atmosphere, network monitoring for detection of stratospheric chemical change, stratospheric chemistry studies, and the combining of model, in situ, and remote sensing in atmospheric chemistry. Attention is given to the measurement of tropospheric carbon monoxide using gas filter radiometers, long-path differential absorption measurements of tropospheric molecules, air quality monitoring with the differential optical absorption spectrometer, and a characterization of tropospheric methane through space-based remote sensing. Topics addressed include microwave limb sounder experiments for UARS and EOS, an overview of the spectroscopy of the atmosphere using an FIR emission experiment, the detection of stratospheric ozone trends by ground-based microwave observations, and a FIR Fabry-Perot spectrometer for OH measurements. (For individual items see A93-31377 to A93-31412)

  4. Predicting steam generator crevice chemistry

    International Nuclear Information System (INIS)

    Burton, G.; Strati, G.

    2006-01-01

    'Full text:' Corrosion of steam cycle components produces insoluble material, mostly iron oxides, that are transported to the steam generator (SG) via the feedwater and deposited on internal surfaces such as the tubes, tube support plates and the tubesheet. The build up of these corrosion products over time can lead to regions of restricted flow with water chemistry that may be significantly different, and potentially more corrosive to SG tube material, than the bulk steam generator water chemistry. The aim of the present work is to predict SG crevice chemistry using experimentation and modelling as part of AECL's overall strategy for steam generator life management. Hideout-return experiments are performed under CANDU steam generator conditions to assess the accumulation of impurities in hideout, and return from, model crevices. The results are used to validate the ChemSolv model that predicts steam generator crevice impurity concentrations, and high temperature pH, based on process parameters (e.g., heat flux, primary side temperature) and blowdown water chemistry. The model has been incorporated into ChemAND, AECL's system health monitoring software for chemistry monitoring, analysis and diagnostics that has been installed at two domestic and one international CANDU station. ChemAND provides the station chemists with the only method to predict SG crevice chemistry. In one recent application, the software has been used to evaluate the crevice chemistry based on the elevated, but balanced, SG bulk water impurity concentrations present during reactor startup, in order to reduce hold times. The present paper will describe recent hideout-return experiments that are used for the validation of the ChemSolv model, station experience using the software, and improvements to predict the crevice electrochemical potential that will permit station staff to ensure that the SG tubes are in the 'safe operating zone' predicted by Lu (AECL). (author)

  5. Parameterization of dust emissions in the global atmospheric chemistry-climate model EMAC: impact of nudging and soil properties

    OpenAIRE

    Astitha, M.; Lelieveld, J.; Kader, M. Abdel; Pozzer, A.; de Meij, A.

    2012-01-01

    Airborne desert dust influences radiative transfer, atmospheric chemistry and dynamics, as well as nutrient transport and deposition. It directly and indirectly affects climate on regional and global scales. Two versions of a parameterization scheme to compute desert dust emissions are incorporated into the atmospheric chemistry general circulation model EMAC (ECHAM5/MESSy2.41 Atmospheric Chemistry). One uses a global...

  6. Flowfield and Radiation Analysis of Missile Exhaust Plumes Using a Turbulent-Chemistry Interaction Model

    National Research Council Canada - National Science Library

    Calhoon, W. H; Kenzakowski, D. C

    2000-01-01

    ... components and missile defense systems. Current engineering level models neglect turbulent-chemistry interactions and typically underpredict the intensity of plume afterburning and afterburning burnout...

  7. Water chemistry in WWER reactors

    International Nuclear Information System (INIS)

    Yurmanov, V.A.; Mamet, V.A.; Shestakov, Yu.M.; Amosov, M.M.

    1997-01-01

    In this paper ''Water Chemistry in WWER Reactors'', are briefly described the 30 WWERs in Russian and the Ukraine, and are pointed out the essential differences between the 440s and 1000s. The primary coolant in the six loops of the former type operates at 270-290 deg. C, while the four loops of the latter type are at 290-320 deg. C. Performance of the fuel has been generally good with some fission product activities emanating from tramp uranium. Incidents causing unusually high fission product levels were overheating of the 16th fuel load at Kola NPP in 1990 by a reduced coolant flow, and fuel defects at Novovoronezh NPP resulting from deposits of carbon and corrosion products. Organic carbon, depositing from the coolant in regions of high turbulence (i.e. at the spacer grids), provokes corrosion product deposition. The source of the organic is not known. New chemistry guidelines have been implemented since 1992-93 for Russian and Ukrainian WWERs. These include higher pH T values (7.0-7.1 as opposed to 6.6-6.9) and tighter controls on oxygen and impurities. Lower dose rates in steam generator channels are reported. Significant reduction in operator doses are achieved by these methods coupled with a ''soft decontamination'' involving changing the KOH concentration and, hence, the pH T before shutdown. The benefits of hydrazine treatment for deoxygenating feedwater and coolant prior to start up, for injecting before shutdown and for general chemistry control on radiation fields are described. (author). 7 refs, 9 figs, 8 tabs

  8. Water chemistry in WWER reactors

    Energy Technology Data Exchange (ETDEWEB)

    Yurmanov, V A; Mamet, V A; Shestakov, Yu M; Amosov, M M [All-Russian Scientific Research Inst. for Nuclear Power Plants Operation, Moscow (Russian Federation)

    1997-02-01

    In this paper ``Water Chemistry in WWER Reactors``, are briefly described the 30 WWERs in Russian and the Ukraine, and are pointed out the essential differences between the 440s and 1000s. The primary coolant in the six loops of the former type operates at 270-290 deg. C, while the four loops of the latter type are at 290-320 deg. C. Performance of the fuel has been generally good with some fission product activities emanating from tramp uranium. Incidents causing unusually high fission product levels were overheating of the 16th fuel load at Kola NPP in 1990 by a reduced coolant flow, and fuel defects at Novovoronezh NPP resulting from deposits of carbon and corrosion products. Organic carbon, depositing from the coolant in regions of high turbulence (i.e. at the spacer grids), provokes corrosion product deposition. The source of the organic is not known. New chemistry guidelines have been implemented since 1992-93 for Russian and Ukrainian WWERs. These include higher pH{sub T} values (7.0-7.1 as opposed to 6.6-6.9) and tighter controls on oxygen and impurities. Lower dose rates in steam generator channels are reported. Significant reduction in operator doses are achieved by these methods coupled with a ``soft decontamination`` involving changing the KOH concentration and, hence, the pH{sub T} before shutdown. The benefits of hydrazine treatment for deoxygenating feedwater and coolant prior to start up, for injecting before shutdown and for general chemistry control on radiation fields are described. (author). 7 refs, 9 figs, 8 tabs.

  9. The carbon budget in the outer solar nebula

    International Nuclear Information System (INIS)

    Simonelli, D.P.; Pollack, J.B.; Mckay, C.P.; Reynolds, R.T.; Summers, A.L.

    1989-01-01

    The compositional contrast between the giant-planet satellites and the significantly rockier Pluto/Charon system is indicative of different formation mechanisms; cosmic abundance calculations, in conjunction with an assumption of the Pluto/Charon system's direct formation from solar nebula condensates, strongly suggest that most of the carbon in the outer solar nebula was in CO form, in keeping with both the inheritance from the dense molecular clouds in the interstellar medium, and/or the Lewis and Prinn (1980) kinetic-inhibition model of solar nebula chemistry. Laboratory studies of carbonaceous chondrites and Comet Halley flyby studies suggest that condensed organic material, rather than elemental carbon, is the most likely candidate for the small percentage of the carbon-bearing solid in the outer solar nebula. 71 refs

  10. Interfacial charge distributions in carbon-supported palladium catalysts

    DEFF Research Database (Denmark)

    Rao, Radhika G.; Blume, Raoul; Hansen, Thomas Willum

    2017-01-01

    Controlling the charge transfer between a semiconducting catalyst carrier and the supported transition metal active phase represents an elite strategy for fine turning the electronic structure of the catalytic centers, hence their activity and selectivity. These phenomena have been theoretically...... and experimentally elucidated for oxide supports but remain poorly understood for carbons due to their complex nanoscale structure. Here, we combine advanced spectroscopy and microscopy on model Pd/C samples to decouple the electronic and surface chemistry effects on catalytic performance. Our investigations reveal...... treatments can be used to tune the interfacial charge distribution, hereby providing a strategy to rationally design carbon-supported catalysts.Control over charge transfer in carbon-supported metal nanoparticles is essential for designing new catalysts. Here, the authors show that thermal treatments...

  11. Modeling of the chemistry in oxidation flow reactors with high initial NO

    Science.gov (United States)

    Peng, Zhe; Jimenez, Jose L.

    2017-10-01

    Oxidation flow reactors (OFRs) are increasingly employed in atmospheric chemistry research because of their high efficiency of OH radical production from low-pressure Hg lamp emissions at both 185 and 254 nm (OFR185) or 254 nm only (OFR254). OFRs have been thought to be limited to studying low-NO chemistry (in which peroxy radicals (RO2) react preferentially with HO2) because NO is very rapidly oxidized by the high concentrations of O3, HO2, and OH in OFRs. However, many groups are performing experiments by aging combustion exhaust with high NO levels or adding NO in the hopes of simulating high-NO chemistry (in which RO2 + NO dominates). This work systematically explores the chemistry in OFRs with high initial NO. Using box modeling, we investigate the interconversion of N-containing species and the uncertainties due to kinetic parameters. Simple initial injection of NO in OFR185 can result in more RO2 reacted with NO than with HO2 and minor non-tropospheric photolysis, but only under a very narrow set of conditions (high water mixing ratio, low UV intensity, low external OH reactivity (OHRext), and initial NO concentration (NOin) of tens to hundreds of ppb) that account for a very small fraction of the input parameter space. These conditions are generally far away from experimental conditions of published OFR studies with high initial NO. In particular, studies of aerosol formation from vehicle emissions in OFRs often used OHRext and NOin several orders of magnitude higher. Due to extremely high OHRext and NOin, some studies may have resulted in substantial non-tropospheric photolysis, strong delay to RO2 chemistry due to peroxynitrate formation, VOC reactions with NO3 dominating over those with OH, and faster reactions of OH-aromatic adducts with NO2 than those with O2, all of which are irrelevant to ambient VOC photooxidation chemistry. Some of the negative effects are the worst for alkene and aromatic precursors. To avoid undesired chemistry, vehicle emissions

  12. Econometric modelling of international carbon tax regimes

    International Nuclear Information System (INIS)

    Smith, Clare; Hall, Stephen; Mabey, N.

    1995-01-01

    An economometric model of fossil fuel demand has been estimated for eight OECD countries, relating coal, oil and gas demands to GDP and prices. In addition a model of endogenous technical progress has been estimated, aiming to include both price induced innovation in energy and structural change in the economy as long-term determinants of energy consumption. A number of possible international carbon/energy tax agreements are simulated, showing the impacts on carbon dioxide emissions and comparing the two models. (author)

  13. Presidential Green Chemistry Challenge: 1996 Greener Reaction Conditions Award

    Science.gov (United States)

    Presidential Green Chemistry Challenge 1996 award winner, Dow Chemical Company, developed a process to manufacture polystyrene foam sheet packaging that uses carbon dioxide (CO2) as a blowing agent, eliminating CFC-12 and HCFC-22.

  14. 40th anniversary of 'ALSTOM Power Plant Chemistry' in Mannheim

    International Nuclear Information System (INIS)

    Leidich, F.U.; Seipp, H.G.

    2008-01-01

    The power plant chemistry department of Alstom in Mannheim was founded in 1967. The presentation summarizes our contributions to the development of new power plant technologies over the past four decades. In addition, an overview of the future activities of our department is presented. In the retrospective the following examples are mentioned: nuclear power, combined cycles, supercritical steam generators and the contributions of Alstom's power plant chemistry department to, for example, the VGB guidelines. The outlook includes the expected contribution of power plant chemistry to solving challenges in connection with 700 C technology steam power plants, oxyfuel processes and carbon capture. (orig.)

  15. Modelling carbon dynamics from urban land conversion: fundamental model of city in relation to a local carbon cycle

    Directory of Open Access Journals (Sweden)

    Schellnhuber Hans-Joachim

    2006-08-01

    Full Text Available Abstract Background The main task is to estimate the qualitative and quantitative contribution of urban territories and precisely of the process of urbanization to the Global Carbon Cycle (GCC. Note that, on the contrary to many investigations that have considered direct anthropogenic emission of CO2(urbanized territories produce ca. 96–98% of it, we are interested in more subtle, and up until the present time, weaker processes associated with the conversion of the surrounding natural ecosystems and landscapes into urban lands. Such conversion inevitably takes place when cities are sprawling and additional "natural" lands are becoming "urbanized". Results In order to fulfil this task, we first develop a fundamental model of urban space, since the type of land cover within a city makes a difference for a local carbon cycle. Hence, a city is sub-divided by built-up, „green" (parks, etc. and informal settlements (favelas fractions. Another aspect is a sub-division of the additional two regions, which makes the total number reaching eight regions, while the UN divides the world by six. Next, the basic model of the local carbon cycle for urbanized territories is built. We consider two processes: carbon emissions as a result of conversion of natural lands caused by urbanization; and the transformation of carbon flows by "urbanized" ecosystems; when carbon, accumulated by urban vegetation, is exported to the neighbouring territories. The total carbon flow in the model depends, in general, on two groups of parameters. The first includes the NPP, and the sum of living biomass and dead organic matter of ecosystems involved in the process of urbanization, and namely them we calculate here, using a new more realistic approach and taking into account the difference in regional cities' evolution. Conclusion There is also another group of parameters, dealing with the areas of urban territories, and their annual increments. A method of dynamic forecasting

  16. The Breath of Chemistry

    DEFF Research Database (Denmark)

    Josephsen, Jens

    The present preliminary text is a short thematic presentation in biological inorganic chemistry meant to illustrate general and inorganic (especially coordination) chemistry in biochemistry. The emphasis is on molecular models to explain features of the complicated mechanisms essential to breathing...

  17. Exploring global carbon turnover and radiocarbon cycling in terrestrial biosphere models

    Science.gov (United States)

    Graven, H. D.; Warren, H.

    2017-12-01

    The uptake of carbon into terrestrial ecosystems through net primary productivity (NPP) and the turnover of that carbon through various pathways are the fundamental drivers of changing carbon stocks on land, in addition to human-induced and natural disturbances. Terrestrial biosphere models use different formulations for carbon uptake and release, resulting in a range of values in NPP of 40-70 PgC/yr and biomass turnover times of about 25-40 years for the preindustrial period in current-generation models from CMIP5. Biases in carbon uptake and turnover impact simulated carbon uptake and storage in the historical period and later in the century under changing climate and CO2 concentration, however evaluating global-scale NPP and carbon turnover is challenging. Scaling up of plot-scale measurements involves uncertainty due to the large heterogeneity across ecosystems and biomass types, some of which are not well-observed. We are developing the modelling of radiocarbon in terrestrial biosphere models, with a particular focus on decadal 14C dynamics after the nuclear weapons testing in the 1950s-60s, including the impact of carbon flux trends and variability on 14C cycling. We use an estimate of the total inventory of excess 14C in the biosphere constructed by Naegler and Levin (2009) using a 14C budget approach incorporating estimates of total 14C produced by the weapons tests and atmospheric and oceanic 14C observations. By simulating radiocarbon in simple biosphere box models using carbon fluxes from the CMIP5 models, we find that carbon turnover is too rapid in many of the simple models - the models appear to take up too much 14C and release it too quickly. Therefore many CMIP5 models may also simulate carbon turnover that is too rapid. A caveat is that the simple box models we use may not adequately represent carbon dynamics in the full-scale models. Explicit simulation of radiocarbon in terrestrial biosphere models would allow more robust evaluation of biosphere

  18. Bayesian Evaluation of Dynamical Soil Carbon Models Using Soil Carbon Flux Data

    Science.gov (United States)

    Xie, H. W.; Romero-Olivares, A.; Guindani, M.; Allison, S. D.

    2017-12-01

    2016 was Earth's hottest year in the modern temperature record and the third consecutive record-breaking year. As the planet continues to warm, temperature-induced changes in respiration rates of soil microbes could reduce the amount of carbon sequestered in the soil organic carbon (SOC) pool, one of the largest terrestrial stores of carbon. This would accelerate temperature increases. In order to predict the future size of the SOC pool, mathematical soil carbon models (SCMs) describing interactions between the biosphere and atmosphere are needed. SCMs must be validated before they can be chosen for predictive use. In this study, we check two SCMs called CON and AWB for consistency with observed data using Bayesian goodness of fit testing that can be used in the future to compare other models. We compare the fit of the models to longitudinal soil respiration data from a meta-analysis of soil heating experiments using a family of Bayesian goodness of fit metrics called information criteria (IC), including the Widely Applicable Information Criterion (WAIC), the Leave-One-Out Information Criterion (LOOIC), and the Log Pseudo Marginal Likelihood (LPML). These IC's take the entire posterior distribution into account, rather than just one outputted model fit line. A lower WAIC and LOOIC and larger LPML indicate a better fit. We compare AWB and CON with fixed steady state model pool sizes. At equivalent SOC, dissolved organic carbon, and microbial pool sizes, CON always outperforms AWB quantitatively by all three IC's used. AWB monotonically improves in fit as we reduce the SOC steady state pool size while fixing all other pool sizes, and the same is almost true for CON. The AWB model with the lowest SOC is the best performing AWB model, while the CON model with the second lowest SOC is the best performing model. We observe that AWB displays more changes in slope sign and qualitatively displays more adaptive dynamics, which prevents AWB from being fully ruled out for

  19. Ocean uptake of carbon dioxide

    International Nuclear Information System (INIS)

    Peng, Tsung-Hung; Takahashi, Taro

    1993-01-01

    Factors controlling the capacity of the ocean for taking up anthropogenic C0 2 include carbon chemistry, distribution of alkalinity, pCO 2 and total concentration of dissolved C0 2 , sea-air pCO 2 difference, gas exchange rate across the sea-air interface, biological carbon pump, ocean water circulation and mixing, and dissolution of carbonate in deep sea sediments. A general review of these processes is given and models of ocean-atmosphere system based on our understanding of these regulating processes axe used to estimate the magnitude of C0 2 uptake by the ocean. We conclude that the ocean can absorb up to 35% of the fossil fuel emission. Direct measurements show that 55% Of C0 2 from fossil fuel burning remains in the atmosphere. The remaining 10% is not accounted for by atmospheric increases and ocean uptake. In addition, it is estimated that an amount equivalent to 30% of recent annual fossil fuel emissions is released into the atmosphere as a result of deforestation and farming. To balance global carbon budget, a sizable carbon sink besides the ocean is needed. Storage of carbon in terrestrial biosphere as a result of C0 2 fertilization is a potential candidate for such missing carbon sinks

  20. Overview on the history of organofluorine chemistry from the viewpoint of material industry

    OpenAIRE

    Okazoe, Takashi

    2009-01-01

    Fluorine (from ?le fluor?, meaning ?to flow?) is a second row element of Group 17 in the periodic table. When bound to carbon it forms the strongest bond in organic chemistry to give organofluorine compounds. The scientific field treating them, organofluorine chemistry, started before elemental fluorine itself was isolated. Applying the fruits in academia, industrial organofluorine chemistry has developed over 80 years via dramatic changes during World War II. Nowadays, it provides various ma...

  1. Proceedings of the DAE-BRNS fourth interdisciplinary symposium on materials chemistry

    International Nuclear Information System (INIS)

    Tyagi, D.; Banerjee, A.M.; Bhattacharyya, K.; Nigam, S.; Varma, S.; Tripathi, A.K.; Das, D.

    2012-12-01

    This symposium covers almost all the contemporary research areas of materials chemistry like materials for energy conversion, biomaterials, carbon based materials, chemical sensors, fuel cell materials and other electro-ceramics, polymers and soft condensed matters, thin films and surface chemistry, organic and organometallics, high purity materials, nanomaterials and clusters to acquaint ourselves with the advancement made in these emerging areas. Topics like nuclear materials, magnetic materials, catalysis and computational materials chemistry continue to be important facet of ISMC series of symposia. Papers relevant to INIS are indexed separately

  2. Chemistry of Carbon Nanotubes for Everyone

    Science.gov (United States)

    Basu-Dutt, Sharmistha; Minus, Marilyn L.; Jain, Rahul; Nepal, Dhriti; Kumar, Satish

    2012-01-01

    Carbon nanotubes (CNTs) have the extraordinary potential to change our lives by improving existing products and enabling new ones. Current and future research and industrial workforce professionals are very likely to encounter some aspects of nanotechnology including CNT science and technology in their education or profession. The simple structure…

  3. Chemistry of the aqueous medium - Determining factor of corrosion in carbon steel components of secondary circuit

    International Nuclear Information System (INIS)

    Radulescu, M.; Pirvan, I.; Dinu, A.; Velciu, L.

    2003-01-01

    The interplay of chemistry of aqueous medium and corrosion processes followed by deposition and/or release of corrosion products determines both formation and growth of superficial films as well as the kinetics of ion release from materials into the aqueous medium. Material corrosion in the secondary circuit of a NPP can be minimized by choosing the materials of the components and by a rigorous inspection of the chemistry of aqueous agent. The chemical inspection helps in minimizing: - the corrosion of the components immersed in feedwater and vapor and of Steam Generator components; - 'dirtying' of the systems particularly of the surfaces implied in heat transfer; - the amount of insoluble chemical species resulting in corrosion process and carried along the circuit; - the corrosion of secondary circuit components during revisions or outages. An important role among the chemical parameters of the fluids circulated in NPP tubing appears to be the pH. In CANDU reactors it must be kept within the range of 8.7 to 9.4 by treating the medium with volatile amines (morpholine and cyclohexylamine). A plot is presented giving the corrosion rate of carbon steels as a function of the pH of the medium. Besides, the oxygen concentration dissolved in the aqueous medium must be maintained under 5 μg per water kg. Other factors determining the corrosion rates are also discussed. The paper gives the results of the experiments done with various materials, solutions and analysis methods

  4. Redox Models in Chemistry Textbooks for the Upper Secondary School: Friend or Foe?

    Science.gov (United States)

    Osterlund, Lise-Lotte; Berg, Anders; Ekborg, Margareta

    2010-01-01

    We have investigated how chemistry textbooks use models of redox reactions in different subject areas, how they change models between and within the topics, and how they deal with specific learning difficulties identified in the literature. The textbooks examined were published for use in the natural science programme in Swedish upper secondary…

  5. Dimethylsulfide Chemistry: Annual, Seasonal, and Spatial Impacts on Sulfate

    Science.gov (United States)

    We incorporated oceanic emissions and atmospheric chemistry of dimethylsulfide (DMS) into the hemispheric Community Multiscale Air Quality model and performed annual model simulations without and with DMS chemistry. The model without DMS chemistry predicts higher concentrations o...

  6. Evidence for long-range transport of carbon monoxide in the Southern Hemisphere from SCIAMACHY observations

    NARCIS (Netherlands)

    Gloudemans, A.M.S.; Krol, M.C.; Meirink, J.F.; de Laat, A.T.J.; van der Werf, G.R.; Schrijver, H.; van den Broek, M.M.P.; Aben, I.

    2006-01-01

    The SCIAMACHY satellite instrument shows enhanced carbon monoxide (CO) columns in the Southern Hemisphere during the local Spring. Chemistry-transport model simulations using the new GFEDv2 biomass-burning emission database show a similar temporal and spatial CO distribution, indicating that the

  7. The Origin of Carbon-bearing Volatiles in Surprise Valley Hot Springs in the Great Basin: Carbon Isotope and Water Chemistry Characterizations

    Science.gov (United States)

    Fu, Qi; Socki, Richard A.; Niles, Paul B.; Romanek, Christopher; Datta, Saugata; Darnell, Mike; Bissada, Adry K.

    2013-01-01

    There are numerous hydrothermal fields within the Great Basin of North America, some of which have been exploited for geothermal resources. With methane and other carbon-bearing compounds being observed, in some cases with high concentrations, however, their origins and formation conditions remain unknown. Thus, studying hydrothermal springs in this area provides us an opportunity to expand our knowledge of subsurface (bio)chemical processes that generate organic compounds in hydrothermal systems, and aid in future development and exploration of potential energy resources as well. While isotope measurement has long been used for recognition of their origins, there are several secondary processes that may generate variations in isotopic compositions: oxidation, re-equilibration of methane and other alkanes with CO2, mixing with compounds of other sources, etc. Therefore, in addition to isotopic analysis, other evidence, including water chemistry and rock compositions, are necessary to identify volatile compounds of different sources. Surprise Valley Hot Springs (SVHS, 41 deg 32'N, 120 deg 5'W), located in a typical basin and range province valley in northeastern California, is a terrestrial hydrothermal spring system of the Great Basin. Previous geophysical studies indicated the presence of clay-rich volcanic and sedimentary rocks of Tertiary age beneath the lava flows in late Tertiary and Quaternary. Water and gas samples were collected for a variety of chemical and isotope composition analyses, including in-situ pH, alkalinity, conductivity, oxidation reduction potential (ORP), major and trace elements, and C and H isotope measurements. Fluids issuing from SVHS can be classified as Na-(Cl)-SO4 type, with the major cation and anion being Na+ and SO4(2-), respectively. Thermodynamic calculation using ORP and major element data indicated that sulfate is the most dominant sulfur species, which is consistent with anion analysis results. Aquifer temperatures at depth

  8. Mineral Carbonation Employing Ultramafic Mine Waste

    Science.gov (United States)

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

    2014-12-01

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

  9. Development of collaborative-creative learning model using virtual laboratory media for instrumental analytical chemistry lectures

    Science.gov (United States)

    Zurweni, Wibawa, Basuki; Erwin, Tuti Nurian

    2017-08-01

    The framework for teaching and learning in the 21st century was prepared with 4Cs criteria. Learning providing opportunity for the development of students' optimal creative skills is by implementing collaborative learning. Learners are challenged to be able to compete, work independently to bring either individual or group excellence and master the learning material. Virtual laboratory is used for the media of Instrumental Analytical Chemistry (Vis, UV-Vis-AAS etc) lectures through simulations computer application and used as a substitution for the laboratory if the equipment and instruments are not available. This research aims to design and develop collaborative-creative learning model using virtual laboratory media for Instrumental Analytical Chemistry lectures, to know the effectiveness of this design model adapting the Dick & Carey's model and Hannafin & Peck's model. The development steps of this model are: needs analyze, design collaborative-creative learning, virtual laboratory media using macromedia flash, formative evaluation and test of learning model effectiveness. While, the development stages of collaborative-creative learning model are: apperception, exploration, collaboration, creation, evaluation, feedback. Development of collaborative-creative learning model using virtual laboratory media can be used to improve the quality learning in the classroom, overcome the limitation of lab instruments for the real instrumental analysis. Formative test results show that the Collaborative-Creative Learning Model developed meets the requirements. The effectiveness test of students' pretest and posttest proves significant at 95% confidence level, t-test higher than t-table. It can be concluded that this learning model is effective to use for Instrumental Analytical Chemistry lectures.

  10. Development of a Grid-Independent Geos-Chem Chemical Transport Model (v9-02) as an Atmospheric Chemistry Module for Earth System Models

    Science.gov (United States)

    Long, M. S.; Yantosca, R.; Nielsen, J. E; Keller, C. A.; Da Silva, A.; Sulprizio, M. P.; Pawson, S.; Jacob, D. J.

    2015-01-01

    The GEOS-Chem global chemical transport model (CTM), used by a large atmospheric chemistry research community, has been re-engineered to also serve as an atmospheric chemistry module for Earth system models (ESMs). This was done using an Earth System Modeling Framework (ESMF) interface that operates independently of the GEOSChem scientific code, permitting the exact same GEOSChem code to be used as an ESM module or as a standalone CTM. In this manner, the continual stream of updates contributed by the CTM user community is automatically passed on to the ESM module, which remains state of science and referenced to the latest version of the standard GEOS-Chem CTM. A major step in this re-engineering was to make GEOS-Chem grid independent, i.e., capable of using any geophysical grid specified at run time. GEOS-Chem data sockets were also created for communication between modules and with external ESM code. The grid-independent, ESMF-compatible GEOS-Chem is now the standard version of the GEOS-Chem CTM. It has been implemented as an atmospheric chemistry module into the NASA GEOS- 5 ESM. The coupled GEOS-5-GEOS-Chem system was tested for scalability and performance with a tropospheric oxidant-aerosol simulation (120 coupled species, 66 transported tracers) using 48-240 cores and message-passing interface (MPI) distributed-memory parallelization. Numerical experiments demonstrate that the GEOS-Chem chemistry module scales efficiently for the number of cores tested, with no degradation as the number of cores increases. Although inclusion of atmospheric chemistry in ESMs is computationally expensive, the excellent scalability of the chemistry module means that the relative cost goes down with increasing number of cores in a massively parallel environment.

  11. Theoretical modelling of carbon deposition processes

    International Nuclear Information System (INIS)

    Marsh, G.R.; Norfolk, D.J.; Skinner, R.F.

    1985-01-01

    Work based on capsule experiments in the BNL Gamma Facility, aimed at elucidating the chemistry involved in the formation of carbonaceous deposit on CAGR fuel pin surfaces is described. Using a data-base derived from capsule experiments together with literature values for the kinetics of the fundamental reactions, a chemical model of the gas-phase processes has been developed. This model successfully reproduces the capsule results, whilst preliminary application to the WAGR coolant circuit indicates the likely concentration profiles of various radical species within the fuel channels. (author)

  12. Large-scale separation of single-walled carbon nanotubes by electronic type using click chemistry

    Science.gov (United States)

    Um, Jo-Eun; Song, Sun Gu; Yoo, Pil J.; Song, Changsik; Kim, Woo-Jae

    2018-01-01

    Single-walled carbon nanotubes (SWCNTs) can be either metallic or semiconducting, making their separation critical for applications in nanoelectronics, biomedical materials, and solar cells. Herein, we investigate a novel solution-phase separation method based on click chemistry (azide-alkyne Huisgen cycloaddition) and determine its efficiency and scalability. In this method, metallic SWCNTs in metallic/semiconducting SWCNT mixtures are selectively functionalized with alkyne groups by being reacted with 4-propargyloxybenezenediazonium tetrafluoroborate. Subsequently, silica nanoparticles are functionalized with azide groups and reacted with alkyne-bearing metallic SWCNTs in the SWCNT mixture in the presence of a Cu catalyst. As a result, metallic SWCNTs are anchored on silica powder, whereas non-functionalized semiconducting SWCNTs remain in solution. Low-speed centrifugation effectively removes the silica powder with attached metallic SWCNTs, furnishing a solution of highly pure semiconducting SWCNTs, as confirmed by Raman and UV-vis/near-infrared absorption measurements. This novel separation scheme exhibits the advantage of simultaneously separating both metallic and semiconducting SWCNTs from their mixtures, being cost-effective and therefore applicable at an industrial scale.

  13. Phosphorus and nitrogen-containing carbons obtained by the carbonization of conducting polyaniline complex with phosphites

    Czech Academy of Sciences Publication Activity Database

    Bober, Patrycja; Trchová, Miroslava; Morávková, Zuzana; Kovářová, Jana; Vulić, I.; Gavrilov, N.; Pašti, I. A.; Stejskal, Jaroslav

    2017-01-01

    Roč. 246, 20 August (2017), s. 443-450 ISSN 0013-4686 R&D Projects: GA ČR(CZ) GA16-02787S Institutional support: RVO:61389013 Keywords : carbonization * conducting polymer * nitrogen-containing carbon Subject RIV: CD - Macromolecular Chemistry OBOR OECD: Polymer science Impact factor: 4.798, year: 2016

  14. The atmospheric chemistry general circulation model ECHAM5/MESSy1: consistent simulation of ozone from the surface to the mesosphere

    Directory of Open Access Journals (Sweden)

    P. Jöckel

    2006-01-01

    Full Text Available The new Modular Earth Submodel System (MESSy describes atmospheric chemistry and meteorological processes in a modular framework, following strict coding standards. It has been coupled to the ECHAM5 general circulation model, which has been slightly modified for this purpose. A 90-layer model setup up to 0.01 hPa was used at spectral T42 resolution to simulate the lower and middle atmosphere. With the high vertical resolution the model simulates the Quasi-Biennial Oscillation. The model meteorology has been tested to check the influence of the changes to ECHAM5 and the radiation interactions with the new representation of atmospheric composition. In the simulations presented here a Newtonian relaxation technique was applied in the tropospheric part of the domain to weakly nudge the model towards the analysed meteorology during the period 1998–2005. This allows an efficient and direct evaluation with satellite and in-situ data. It is shown that the tropospheric wave forcing of the stratosphere in the model suffices to reproduce major stratospheric warming events leading e.g. to the vortex split over Antarctica in 2002. Characteristic features such as dehydration and denitrification caused by the sedimentation of polar stratospheric cloud particles and ozone depletion during winter and spring are simulated well, although ozone loss in the lower polar stratosphere is slightly underestimated. The model realistically simulates stratosphere-troposphere exchange processes as indicated by comparisons with satellite and in situ measurements. The evaluation of tropospheric chemistry presented here focuses on the distributions of ozone, hydroxyl radicals, carbon monoxide and reactive nitrogen compounds. In spite of minor shortcomings, mostly related to the relatively coarse T42 resolution and the neglect of inter-annual changes in biomass burning emissions, the main characteristics of the trace gas distributions are generally reproduced well. The MESSy

  15. A universal model for nanoporous carbon supercapacitors applicable to diverse pore regimes, carbon materials, and electrolytes.

    Science.gov (United States)

    Huang, Jingsong; Sumpter, Bobby G; Meunier, Vincent

    2008-01-01

    Supercapacitors, commonly called electric double-layer capacitors (EDLCs), are emerging as a novel type of energy-storage device with the potential to substitute batteries in applications that require high power densities. In response to the latest experimental breakthrough in nanoporous carbon supercapacitors, we propose a heuristic theoretical model that takes pore curvature into account as a replacement for the EDLC model, which is based on a traditional parallel-plate capacitor. When the pore size is in the mesopore regime (2-50 nm), counterions enter mesoporous carbon materials and approach the pore wall to form an electric double-cylinder capacitor (EDCC); in the micropore regime (electric wire-in-cylinder capacitor (EWCC). In the macropore regime (>50 nm) at which pores are large enough so that pore curvature is no longer significant, the EDCC model can be reduced naturally to the EDLC model. We present density functional theory calculations and detailed analyses of available experimental data in various pore regimes, which show the significant effects of pore curvature on the supercapacitor properties of nanoporous carbon materials. It is shown that the EDCC/EWCC model is universal for carbon supercapacitors with diverse carbon materials, including activated carbon materials, template carbon materials, and novel carbide-derived carbon materials, and with diverse electrolytes, including organic electrolytes, such as tetraethylammonium tetrafluoroborate (TEABF(4)) and tetraethylammonium methylsulfonate (TEAMS) in acetonitrile, aqueous H(2)SO(4) and KOH electrolytes, and even an ionic liquid electrolyte, such as 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (EMI-TFSI). The EDCC/EWCC model allows the supercapacitor properties to be correlated with pore size, specific surface area, Debye length, electrolyte concentration and dielectric constant, and solute ion size It may lend support for the systematic optimization of the properties of carbon

  16. Multivariate Calibration and Model Integrity for Wood Chemistry Using Fourier Transform Infrared Spectroscopy

    Directory of Open Access Journals (Sweden)

    Chengfeng Zhou

    2015-01-01

    Full Text Available This research addressed a rapid method to monitor hardwood chemical composition by applying Fourier transform infrared (FT-IR spectroscopy, with particular interest in model performance for interpretation and prediction. Partial least squares (PLS and principal components regression (PCR were chosen as the primary models for comparison. Standard laboratory chemistry methods were employed on a mixed genus/species hardwood sample set to collect the original data. PLS was found to provide better predictive capability while PCR exhibited a more precise estimate of loading peaks and suggests that PCR is better for model interpretation of key underlying functional groups. Specifically, when PCR was utilized, an error in peak loading of ±15 cm−1 from the true mean was quantified. Application of the first derivative appeared to assist in improving both PCR and PLS loading precision. Research results identified the wavenumbers important in the prediction of extractives, lignin, cellulose, and hemicellulose and further demonstrated the utility in FT-IR for rapid monitoring of wood chemistry.

  17. Volatile Organic Molecules Sorption onto Carbon Nanotubes: Experiment and Molecular Modeling

    Czech Academy of Sciences Publication Activity Database

    Simha Martynková, G.; Plachá, D.; Plevová, Eva

    2016-01-01

    Roč. 12, č. 1 (2016), s. 142-146 ISSN 2211-8128 R&D Projects: GA MŠk ED1.1.00/02.0070 Institutional support: RVO:68145535 Keywords : carbon nanotubes * sorption * naphthalene * formaldehyde Subject RIV: CB - Analytical Chemistry, Separation http://ac.els-cdn.com/S2211812816000341/1-s2.0-S2211812816000341-main.pdf?_tid=a9631cda-969b-11e6-9761-00000aab0f01&acdnat=1476950778_b6de7ebc7654df3afb52d7e7fb4c0986

  18. Testing isotherm models and recovering empirical relationships for adsorption in microporous carbons using virtual carbon models and grand canonical Monte Carlo simulations

    International Nuclear Information System (INIS)

    Terzyk, Artur P; Furmaniak, Sylwester; Gauden, Piotr A; Harris, Peter J F; Wloch, Jerzy

    2008-01-01

    Using the plausible model of activated carbon proposed by Harris and co-workers and grand canonical Monte Carlo simulations, we study the applicability of standard methods for describing adsorption data on microporous carbons widely used in adsorption science. Two carbon structures are studied, one with a small distribution of micropores in the range up to 1 nm, and the other with micropores covering a wide range of porosity. For both structures, adsorption isotherms of noble gases (from Ne to Xe), carbon tetrachloride and benzene are simulated. The data obtained are considered in terms of Dubinin-Radushkevich plots. Moreover, for benzene and carbon tetrachloride the temperature invariance of the characteristic curve is also studied. We show that using simulated data some empirical relationships obtained from experiment can be successfully recovered. Next we test the applicability of Dubinin's related models including the Dubinin-Izotova, Dubinin-Radushkevich-Stoeckli, and Jaroniec-Choma equations. The results obtained demonstrate the limits and applications of the models studied in the field of carbon porosity characterization

  19. New structural concept for carbonized coals

    Energy Technology Data Exchange (ETDEWEB)

    Marzec, A. [Polish Academy of Sciences, Gliwice (Poland). Inst. of Coal Chemistry

    1997-07-01

    The aim of this study was to present a model of structure for solid products of bituminous coal carbonization carried out at end temperatures (ETCs) in the 600-750{degree}C range. The products are of interest since they are used as raw materials for production of activated carbons. Moreover a layer of such products occurring in coke ovens seems to play a crucial role in generation of excessive coking pressure in industrial coking. The experimental data used in modeling were derived from the following: carbonization studies of coals and individual aromatic hydrocarbons, X-ray diffraction, transmission electron microscopy, pyrolysis-field ionization mass spectrometry, and electrical resistivity measurements. The final step of model preparation relied on application of computational chemistry for search of stable conformers and for calculations of molecular orbitals. According to the model, semicokes contain two structural components: (1) oligomers that form nonplanar 3D networks of aromatic clusters (an extended system of conjugated {pi}-orbitals unites clusters of the networks despite the fact they are not coplanar) and (2) planar aggregates that arise from products of dehydrocyclization reaction (the aggregates fill space between oligomeric networks). The two structural components represent optically isotropic and anisotropic phases, respectively. 21 refs., 7 figs.

  20. Traceable components of terrestrial carbon storage capacity in biogeochemical models.

    Science.gov (United States)

    Xia, Jianyang; Luo, Yiqi; Wang, Ying-Ping; Hararuk, Oleksandra

    2013-07-01

    Biogeochemical models have been developed to account for more and more processes, making their complex structures difficult to be understood and evaluated. Here, we introduce a framework to decompose a complex land model into traceable components based on mutually independent properties of modeled biogeochemical processes. The framework traces modeled ecosystem carbon storage capacity (Xss ) to (i) a product of net primary productivity (NPP) and ecosystem residence time (τE ). The latter τE can be further traced to (ii) baseline carbon residence times (τ'E ), which are usually preset in a model according to vegetation characteristics and soil types, (iii) environmental scalars (ξ), including temperature and water scalars, and (iv) environmental forcings. We applied the framework to the Australian Community Atmosphere Biosphere Land Exchange (CABLE) model to help understand differences in modeled carbon processes among biomes and as influenced by nitrogen processes. With the climate forcings of 1990, modeled evergreen broadleaf forest had the highest NPP among the nine biomes and moderate residence times, leading to a relatively high carbon storage capacity (31.5 kg cm(-2) ). Deciduous needle leaf forest had the longest residence time (163.3 years) and low NPP, leading to moderate carbon storage (18.3 kg cm(-2) ). The longest τE in deciduous needle leaf forest was ascribed to its longest τ'E (43.6 years) and small ξ (0.14 on litter/soil carbon decay rates). Incorporation of nitrogen processes into the CABLE model decreased Xss in all biomes via reduced NPP (e.g., -12.1% in shrub land) or decreased τE or both. The decreases in τE resulted from nitrogen-induced changes in τ'E (e.g., -26.7% in C3 grassland) through carbon allocation among plant pools and transfers from plant to litter and soil pools. Our framework can be used to facilitate data model comparisons and model intercomparisons via tracking a few traceable components for all terrestrial carbon

  1. SYSTEMATIC THEORETICAL STUDY ON THE INTERSTELLAR CARBON CHAIN MOLECULES

    Energy Technology Data Exchange (ETDEWEB)

    Etim, Emmanuel E.; Arunan, Elangannan [Inorganic and Physical Chemistry Department, Indian Institute of Science Bangalore, 560012 (India); Gorai, Prasanta; Das, Ankan [Indian Centre for Space Physics, 43 Chalantika, Garia Station Road, Kolkata 700 084 (India); Chakrabarti, Sandip K., E-mail: ankan.das@gmail.com [Department of Chemical Sciences, Federal University Wukari,  Katsina-Ala Road, P.M.B. 1020 Wukari, Taraba State (Nigeria)

    2016-12-01

    In an effort to further our interest in understanding the basic chemistry of interstellar molecules, here we carry out an extensive investigation of the stabilities of interstellar carbon chains; C{sub n}, H{sub 2}C{sub n}, HC{sub n}N and C{sub n}X (X = N, O, Si, S, H, P, H{sup −}, N{sup −}). These sets of molecules account for about 20% of all the known interstellar and circumstellar molecules. Their high abundances, therefore, demand serious attention. High-level ab initio quantum chemical calculations are employed to accurately estimate the enthalpy of formation, chemical reactivity indices, global hardness and softness, and other chemical parameters of these molecules. Chemical modeling of the abundances of these molecular species has also been performed. Of the 89 molecules considered from these groups, 47 have been astronomically observed, and these observed molecules are found to be more stable with respect to other members of the group. Of the 47 observed molecules, 60% are odd-numbered carbon chains. Interstellar chemistry is not actually driven by thermodynamics, but it is primarily dependent on various kinetic parameters. However, we found that the detectability of the odd-numbered carbon chains could be correlated due to the fact that they are more stable than the corresponding even-numbered carbon chains. Based on this aspect, the next possible carbon chain molecule for astronomical observation in each group is proposed. The effect of kinetics in the formation of some of these carbon chain molecules is also discussed.

  2. IN-PACKAGE CHEMISTRY ABSTRACTION

    Energy Technology Data Exchange (ETDEWEB)

    E. Thomas

    2005-07-14

    This report was developed in accordance with the requirements in ''Technical Work Plan for Postclosure Waste Form Modeling'' (BSC 2005 [DIRS 173246]). The purpose of the in-package chemistry model is to predict the bulk chemistry inside of a breached waste package and to provide simplified expressions of that chemistry as a function of time after breach to Total Systems Performance Assessment for the License Application (TSPA-LA). The scope of this report is to describe the development and validation of the in-package chemistry model. The in-package model is a combination of two models, a batch reactor model, which uses the EQ3/6 geochemistry-modeling tool, and a surface complexation model, which is applied to the results of the batch reactor model. The batch reactor model considers chemical interactions of water with the waste package materials, and the waste form for commercial spent nuclear fuel (CSNF) waste packages and codisposed (CDSP) waste packages containing high-level waste glass (HLWG) and DOE spent fuel. The surface complexation model includes the impact of fluid-surface interactions (i.e., surface complexation) on the resulting fluid composition. The model examines two types of water influx: (1) the condensation of water vapor diffusing into the waste package, and (2) seepage water entering the waste package as a liquid from the drift. (1) Vapor-Influx Case: The condensation of vapor onto the waste package internals is simulated as pure H{sub 2}O and enters at a rate determined by the water vapor pressure for representative temperature and relative humidity conditions. (2) Liquid-Influx Case: The water entering a waste package from the drift is simulated as typical groundwater and enters at a rate determined by the amount of seepage available to flow through openings in a breached waste package.

  3. IN-PACKAGE CHEMISTRY ABSTRACTION

    International Nuclear Information System (INIS)

    E. Thomas

    2005-01-01

    This report was developed in accordance with the requirements in ''Technical Work Plan for Postclosure Waste Form Modeling'' (BSC 2005 [DIRS 173246]). The purpose of the in-package chemistry model is to predict the bulk chemistry inside of a breached waste package and to provide simplified expressions of that chemistry as a function of time after breach to Total Systems Performance Assessment for the License Application (TSPA-LA). The scope of this report is to describe the development and validation of the in-package chemistry model. The in-package model is a combination of two models, a batch reactor model, which uses the EQ3/6 geochemistry-modeling tool, and a surface complexation model, which is applied to the results of the batch reactor model. The batch reactor model considers chemical interactions of water with the waste package materials, and the waste form for commercial spent nuclear fuel (CSNF) waste packages and codisposed (CDSP) waste packages containing high-level waste glass (HLWG) and DOE spent fuel. The surface complexation model includes the impact of fluid-surface interactions (i.e., surface complexation) on the resulting fluid composition. The model examines two types of water influx: (1) the condensation of water vapor diffusing into the waste package, and (2) seepage water entering the waste package as a liquid from the drift. (1) Vapor-Influx Case: The condensation of vapor onto the waste package internals is simulated as pure H 2 O and enters at a rate determined by the water vapor pressure for representative temperature and relative humidity conditions. (2) Liquid-Influx Case: The water entering a waste package from the drift is simulated as typical groundwater and enters at a rate determined by the amount of seepage available to flow through openings in a breached waste package

  4. The chemical bond in inorganic chemistry the bond valence model

    CERN Document Server

    Brown, I David

    2016-01-01

    The bond valence model is a version of the ionic model in which the chemical constraints are expressed in terms of localized chemical bonds formed by the valence charge of the atoms. Theorems derived from the properties of the electrostatic flux predict the rules obeyed by both ionic and covalent bonds. They make quantitative predictions of coordination number, crystal structure, bond lengths and bond angles. Bond stability depends on the matching of the bonding strengths of the atoms, while the conflicting requirements of chemistry and space lead to the structural instabilities responsible for the unusual physical properties displayed by some materials. The model has applications in many fields ranging from mineralogy to molecular biology.

  5. Minimizing the wintertime low bias of Northern Hemisphere carbon monoxide in global model simulations

    Science.gov (United States)

    Stein, Olaf; Schultz, Martin G.; Bouarar, Idir; Clark, Hannah; Huijnen, Vincent; Gaudel, Audrey; George, Maya; Clerbaux, Cathy

    2015-04-01

    Carbon monoxide (CO) is a product of incomplete combustion and is also produced from oxidation of volatile organic compounds (VOC) in the atmosphere. It is of interest as an indirect greenhouse gas and an air pollutant causing health effects and is thus subject to emission restrictions. CO acts as a major sink for the OH radical and as a precursor for tropospheric ozone and affects the oxidizing capacity of the atmosphere as well as regional air quality. Despite the developments in the global modelling of chemistry and of the parameterization of the physical processes, CO concentrations remain underestimated during NH winter by most state-of-the-art chemical transport models. The resulting model bias can in principle originate from either an underestimation of CO sources or an overestimation of its sinks. We address both the role of sources and sinks with a series of MOZART chemistry transport model sensitivity simulations for the year 2008 and compare our results to observational data from ground-based stations, satellite observations, and from MOZAIC tropospheric profile measurements on passenger aircraft. Our base case simulation using the MACCity emission inventory (Granier et al. 2011) underestimates the near-surface Northern Hemispheric CO mixing ratios by more than 20 ppb from December to April with a maximal bias of 40 ppb in January. The bias is strongest for the European region (up to 75 ppb in January). From our sensitivity studies the mismatch between observed and modelled atmospheric CO concentrations can be explained by a combination of the following emission inventory shortcuts: (i) missing anthropogenic wintertime CO emissions from traffic or other combustion processes, (ii) missing anthropogenic VOC emissions, (iii) an exaggerated downward trend in the RCP8.5 scenario underlying the MACCity inventory, (iv) a lack of knowledge about the seasonality of emissions. Deficiencies in the parameterization of the dry deposition velocities can also lead to

  6. Ocean acidification 2.0: Managing our Changing Coastal Ocean Chemistry

    OpenAIRE

    Strong, AL; Kroeker, KJ; Teneva, LT; Mease, LA; Kelly, RP

    2014-01-01

    Ocean acidification (OA) is rapidly emerging as a significant problem for organisms, ecosystems, and human societies. Globally, addressing OA and its impacts requires international agreements to reduce rising atmospheric carbon dioxide concentrations. However, the complex suite of drivers of changing carbonate chemistry in coastal environments also requires regional policy analysis, mitigation, and adaptation responses. In order to fundamentally address the threat of OA, environmental manager...

  7. The UK transport carbon model: An integrated life cycle approach to explore low carbon futures

    International Nuclear Information System (INIS)

    Brand, Christian; Tran, Martino; Anable, Jillian

    2012-01-01

    Current debate focuses on the need for the transport sector to contribute to more ambitious carbon emission reduction targets. In the UK, various macro-economic and energy system wide, top-down models are used to explore the potential for energy demand and carbon emissions reduction in the transport sector. These models can lack the bottom-up, sectoral detail needed to simulate the effects of integrated demand and supply-side policy strategies to reduce emissions. Bridging the gap between short-term forecasting and long-term scenario “models”, this paper introduces a newly developed strategic transport, energy, emissions and environmental impacts model, the UK Transport Carbon Model (UKTCM). The UKTCM covers the range of transport–energy–environment issues from socio-economic and policy influences on energy demand reduction through to life cycle carbon emissions and external costs. The model is demonstrated in this paper by presenting the results of three single policies and one policy package scenario. Limitations of the model are also discussed. Developed under the auspices of the UK Energy Research Centre (UKERC) the UKTCM can be used to develop transport policy scenarios that explore the full range of technological, fiscal, regulatory and behavioural change policy interventions to meet UK climate change and energy security goals. - Research highlights: ►New strategic transport, energy, emissions and environmental impacts model. ►Tool to develop and analyse full consequences of multiple scenarios of transport policy packages. ►Novel approach to modelling demand for new vehicles by market and technology. ►Model available for use by research community via http://www.ukerc.ac.uk/support/tiki-index.php?page=UK+Transport+Carbon+Model.

  8. A global predictive model of carbon in mangrove soils

    Science.gov (United States)

    Jardine, Sunny L.; Siikamäki, Juha V.

    2014-10-01

    Mangroves are among the most threatened and rapidly vanishing natural environments worldwide. They provide a wide range of ecosystem services and have recently become known for their exceptional capacity to store carbon. Research shows that mangrove conservation may be a low-cost means of reducing CO2 emissions. Accordingly, there is growing interest in developing market mechanisms to credit mangrove conservation projects for associated CO2 emissions reductions. These efforts depend on robust and readily applicable, but currently unavailable, localized estimates of soil carbon. Here, we use over 900 soil carbon measurements, collected in 28 countries by 61 independent studies, to develop a global predictive model for mangrove soil carbon. Using climatological and locational data as predictors, we explore several predictive modeling alternatives, including machine-learning methods. With our predictive model, we construct a global dataset of estimated soil carbon concentrations and stocks on a high-resolution grid (5 arc min). We estimate that the global mangrove soil carbon stock is 5.00 ± 0.94 Pg C (assuming a 1 meter soil depth) and find this stock is highly variable over space. The amount of carbon per hectare in the world’s most carbon-rich mangroves (approximately 703 ± 38 Mg C ha-1) is roughly a 2.6 ± 0.14 times the amount of carbon per hectare in the world’s most carbon-poor mangroves (approximately 272 ± 49 Mg C ha-1). Considerable within country variation in mangrove soil carbon also exists. In Indonesia, the country with the largest mangrove soil carbon stock, we estimate that the most carbon-rich mangroves contain 1.5 ± 0.12 times as much carbon per hectare as the most carbon-poor mangroves. Our results can aid in evaluating benefits from mangrove conservation and designing mangrove conservation policy. Additionally, the results can be used to project changes in mangrove soil carbon stocks based on changing climatological predictors, e.g. to

  9. Thermodynamic modelling of bentonite-groundwater interaction and implications for near field chemistry in a repository for spent fuel

    International Nuclear Information System (INIS)

    Wanner, H.; Wersin, P.; Sierro, N.

    1992-11-01

    Predictions of near field geochemistry are made using a thermodynamic model for bentonite/ground interaction. This model is a refinement and extension of the model developed by the senior author. It is based on recent experiments performed at high solid/water ratio and adapted to the Swedish type of HLW repository design. Thus, from the obtained experimental results on solution composition, the model includes chemical reactions resulting from both the impurities and the main clay fraction within the bentonite. Ion exchange reactions are treated both with and without the contribution of edge sites. Due to its thermodynamic basis, the model exhibits prediction capability over a wide range of conditions in terms of solid/water ratio. The modelling of repository conditions implies, due to the lack of experimental information, simplifications with regard to thermodynamic properties of the bentonite. This mainly involves the non-consideration of the temperature effects and of the acid/base properties of the solid. Nevertheless, our results yield insight into important processes affecting porewater chemistry. Thus, the model suggests that proton exchange reactions may exert a strong control on calcite dissolution within highly compacted bentonite. Estimations of chemical changes over time in the bentonite were done in the basis of a mixing tank model. These results indicate transformation of Na-bentonite to Ca-bentonite over time. The extent of this process, however, critically depends on the amount of carbonate present in the bentonite. (authors) (34 refs.)

  10. Modeling Chemistry for Effective Chemical Education: An Interview with Ronald J. Gillespie

    Science.gov (United States)

    Cardellini, Liberato

    2010-01-01

    Ronald J. Gillespie, the inventor of the Valence Shell Electron Pair Repulsion (VSEPR) model, relates how his career as researcher in Christopher Ingold's laboratories started. Gillespie developed a passion for chemistry and chemical education, searching for more appropriate and interesting ways to transmit the essential knowledge and enthusiasm…

  11. Irrigation, fertilization and initial substrate quality effects on decomposing Loblolly pine litter chemistry

    Science.gov (United States)

    Felipe G. Sanchez

    2004-01-01

    Changes in carbon chemistry (i.e., carbon compound classes such as aromatics, phenolics, etc.) of loblolly pine (Pinus taeda L.) litter were examined during three years of decomposition under factorial combinations of irrigation and fertilization treatments. Cross polarization magic angle spinning 13C nuclear magnetic resonance...

  12. Modelling Sublimation of Carbon Dioxide

    Science.gov (United States)

    Winkel, Brian

    2012-01-01

    In this article, the author reports results in their efforts to model sublimation of carbon dioxide and the associated kinetics order and parameter estimation issues in their model. They have offered the reader two sets of data and several approaches to determine the rate of sublimation of a piece of solid dry ice. They presented several models…

  13. Molecular investigations into a globally important carbon pool: permafrost-protected carbon in Alaskan soils

    Science.gov (United States)

    M.P. Waldrop; K.P. Wickland; R. White; A.A. Berhe; J.W. Harden; V.E. Romanovsky

    2010-01-01

    The fate of carbon (C) contained within permafrost in boreal forest environments is an important consideration for the current and future carbon cycle as soils warm in northern latitudes. Currently, little is known about the microbiology or chemistry of permafrost soils that may affect its decomposition once soils thaw. We tested the hypothesis that low microbial...

  14. Preparation and characterisation of activated carbon

    International Nuclear Information System (INIS)

    Badri bin Muhammad; Karen binti Badri; Mohd Zobir bin Hussein; Zulkarnain bin Zainal; W.M. Daud bin W Yunus; Ramli bin Ibrahim

    1994-01-01

    Activated carbon was prepared from Agricultural wastes, such as coconut shell, Palm oil Shell and mangrove trunk by destructive distillation under vakuum. Chemical and Physical properties of the activated carbon were studied and some potentially useful application in the fields of chemistry was also carried out

  15. Effect of condenser water in-leakage on steam generator water chemistry

    International Nuclear Information System (INIS)

    Balakrishnan, P.V.

    1978-01-01

    Corrosive environments may be generated within steam genrators from condenser cooling water in-leakage. Theoretical as well as experimental evaluation of the aggressiveness of such environments is being carried out for the condenser-cooling waters used at CANDU-PHW nuclear power stations. Calculations have shown that highly concentrated chloride solutions - acidic in the case of sea-water in-leakage, and alkaline in the rest of the cases considered - would be produced within the steam generator. Experiments in a model boiler showed that sea-water in-leakage caused rapid corrosion of carbon steel components when only AVT (all volatile treatment) was used for water chemistry control. Use of a non-volatile reagent, as in the congruent phosphate treatment, avoided the rapid corrosion of carbon steel. On the basis of our studies, congruent phosphate treatment during sea water in-leakage appears desirable. (author)

  16. Modeling of the global carbon cycle - isotopic data requirements

    International Nuclear Information System (INIS)

    Ciais, P.

    1994-01-01

    Isotopes are powerful tools to constrain carbon cycle models. For example, the combinations of the CO 2 and the 13 C budget allows to calculate the net-carbon fluxes between atmosphere, ocean, and biosphere. Observations of natural and bomb-produced radiocarbon allow to estimate gross carbon exchange fluxes between different reservoirs and to deduce time scales of carbon overturning in important reservoirs. 18 O in CO 2 is potentially a tool to make the deconvolution of C fluxes within the land biosphere (assimilation vs respirations). The scope of this article is to identify gaps in our present knowledge about isotopes in the light of their use as constraint for the global carbon cycle. In the following we will present a list of some future data requirements for carbon cycle models. (authors)

  17. Projections of Ocean Acidification Under the U.N. Framework Convention of Climate Change Using a Reduced-Form Climate Carbon-Cycle Model

    Science.gov (United States)

    Hartin, C.

    2016-02-01

    Ocean chemistry is quickly changing in response to continued anthropogenic emissions of carbon to the atmosphere. Mean surface ocean pH has already decreased by 0.1 units relative to the preindustrial era. We use an open-source, simple climate and carbon cycle model ("Hector") to investigate future changes in ocean acidification (pH and calcium carbonate saturations) under the climate agreement from the United Nations Convention on Climate Change Conference (UNFCCC) of Parties in Paris 2015 (COP 21). Hector is a reduced-form, very fast-executing model that can emulate the global mean climate of the CMIP5 models, as well as the inorganic carbon cycle in the upper ocean, allowing us to investigate future changes in ocean acidification. We ran Hector under three different emissions trajectories, using a sensitivity analysis approach to quantify model uncertainty and capture a range of possible ocean acidification changes. The first trajectory is a business-as-usual scenario comparable to a Representative Concentration Pathway (RCP) 8.5, the second a scenario with the COP 21 commitments enacted, and the third an idealized scenario keeping global temperature change to 2°C, comparable to a RCP 2.6. Preliminary results suggest that under the COP 21 agreements ocean pH at 2100 will decrease by 0.2 units and surface saturations of aragonite (calcite) will decrease by 0.9 (1.4) units relative to 1850. Under the COP 21 agreement the world's oceans will be committed to a degree of ocean acidification, however, these changes may be within the range of natural variability evident in some paleo records.

  18. The Learner Characteristics, Features of Desktop 3D Virtual Reality Environments, and College Chemistry Instruction: A Structural Equation Modeling Analysis

    Science.gov (United States)

    Merchant, Zahira; Goetz, Ernest T.; Keeney-Kennicutt, Wendy; Kwok, Oi-man; Cifuentes, Lauren; Davis, Trina J.

    2012-01-01

    We examined a model of the impact of a 3D desktop virtual reality environment on the learner characteristics (i.e. perceptual and psychological variables) that can enhance chemistry-related learning achievements in an introductory college chemistry class. The relationships between the 3D virtual reality features and the chemistry learning test as…

  19. Fracture of Carbon Nanotube - Amorphous Carbon Composites: Molecular Modeling

    Science.gov (United States)

    Jensen, Benjamin D.; Wise, Kristopher E.; Odegard, Gregory M.

    2015-01-01

    Carbon nanotubes (CNTs) are promising candidates for use as reinforcements in next generation structural composite materials because of their extremely high specific stiffness and strength. They cannot, however, be viewed as simple replacements for carbon fibers because there are key differences between these materials in areas such as handling, processing, and matrix design. It is impossible to know for certain that CNT composites will represent a significant advance over carbon fiber composites before these various factors have been optimized, which is an extremely costly and time intensive process. This work attempts to place an upper bound on CNT composite mechanical properties by performing molecular dynamics simulations on idealized model systems with a reactive forcefield that permits modeling of both elastic deformations and fracture. Amorphous carbon (AC) was chosen for the matrix material in this work because of its structural simplicity and physical compatibility with the CNT fillers. It is also much stiffer and stronger than typical engineering polymer matrices. Three different arrangements of CNTs in the simulation cell have been investigated: a single-wall nanotube (SWNT) array, a multi-wall nanotube (MWNT) array, and a SWNT bundle system. The SWNT and MWNT array systems are clearly idealizations, but the SWNT bundle system is a step closer to real systems in which individual tubes aggregate into large assemblies. The effect of chemical crosslinking on composite properties is modeled by adding bonds between the CNTs and AC. The balance between weakening the CNTs and improving fiber-matrix load transfer is explored by systematically varying the extent of crosslinking. It is, of course, impossible to capture the full range of deformation and fracture processes that occur in real materials with even the largest atomistic molecular dynamics simulations. With this limitation in mind, the simulation results reported here provide a plausible upper limit on

  20. Monitoring, modelling and managing Canada's forest carbon cycle

    International Nuclear Information System (INIS)

    Kurz, W.

    2005-01-01

    This paper presents information concerning the management of carbon stocks both globally and in Canada, with reference to the fact that forests may contribute to carbon emissions problems. Global fossil carbon emissions statistics were provided, as well as data of forest area per capita in Canada and various countries. Details of forest management options and carbon accounting with reference to the Kyoto Protocol were reviewed. An explanation of forest management credits in national accounts was provided. An explanation of carbon sinks and carbon sources was also presented, along with details of stand level carbon dynamics. A model for calculating landscape level carbon stocks was presented, with reference to increasing and decreasing disturbances. A hypothetical landscape example was provided. It was concluded that age-class structure affect the amount of carbon stored in landscape; age-class structure also affect carbon dynamics; and responses reflect the change in disturbance regimes. An overview of international reporting requirements was presented. Canadian harvests equal 54,000 tonnes of carbon per year. It was recommended that managed forests could increase carbon in forests while also managing carbon harvests to meet society's needs. A chart presenting forest management details was presented, along with a hypothetical landscape example and a forecast for cumulative changes after 50 years, The benefits and challenges of forest management were reviewed as well as options regarding salvaging and deforestation avoidance. A carbon budget model was presented. It was concluded that forests in Canada could be used in a greenhouse gas management strategy. However, changes in disturbance may mean the difference between net source or net sink. Details of biomass were presented and multi-mode combustion facilities. The feasibility of biomass as a fuel source was discussed, with reference to hydrogen fuel. Gas composition profiles were provided, as well as details of

  1. Optical excitation of carbon nanotubes drives stoichiometric reaction with diazonium salts

    Science.gov (United States)

    Powell, Lyndsey; Piao, Yanmei; Wang, Yuhuang; YuHuang Wang Research Group Team

    Covalent chemistry is known to lack the precision required to tailor the physical properties of carbon nanostructures. Here we show that, for the first time, light can be used to drive a typically inefficient reaction with single-walled carbon nanotubes in a more stoichiometric fashion. Specifically, our experimental results suggest that light can enhance the reaction rate of diazonium salt with carbon nanotubes by as much as 35-fold, making possible stoichiometric control of the covalent bonding of a functional group to the sp2 carbon lattice. This light-controlled reaction paves the way for the possibility of highly selective and precise chemistry on single-walled carbon nanotubes and other graphitic nanostructures.

  2. Sorption of organic compounds to activated carbons. Evaluation of isotherm models

    NARCIS (Netherlands)

    Pikaar, I.; Koelmans, A.A.; Noort, van P.C.M.

    2006-01-01

    Sorption to 'hard carbon' (black carbon, coal, kerogen) in soils and sediments is of major importance for risk assessment of organic pollutants. We argue that activated carbon (AC) may be considered a model sorbent for hard carbon. Here, we evaluate six sorption models on a literature dataset for

  3. A Performance Enhanced Interactive Learning Workshop Model as a Supplement for Organic Chemistry Instruction

    Science.gov (United States)

    Phillips, Karen E. S.; Grose-Fifer, Jilliam

    2011-01-01

    In this study, the authors describe a Performance Enhanced Interactive Learning (PEIL) workshop model as a supplement for organic chemistry instruction. This workshop model differs from many others in that it includes public presentations by students and other whole-class-discussion components that have not been thoroughly investigated in the…

  4. An Integrated Visualization and Basic Molecular Modeling Laboratory for First-Year Undergraduate Medicinal Chemistry

    Science.gov (United States)

    Hayes, Joseph M.

    2014-01-01

    A 3D model visualization and basic molecular modeling laboratory suitable for first-year undergraduates studying introductory medicinal chemistry is presented. The 2 h practical is embedded within a series of lectures on drug design, target-drug interactions, enzymes, receptors, nucleic acids, and basic pharmacokinetics. Serving as a teaching aid…

  5. The Origin of Carbon-bearing Volatiles in Surprise Valley Hot Springs in the Great Basin: Carbon Isotope aud Water Chemistry Characterizations

    Science.gov (United States)

    Fu, Qi; Socki, Richard A.; Niles, Paul B.; Romanek, Christopher; Datta, Saugata; Darnell, Mike; Bissada, Adry K.

    2013-01-01

    There are numerous hydrothermal fields within the Great Basin of North America, some of which have been exploited for geothermal resources. With methane and other carbon-bearing compounds being observed, in some cases with high concentrations, however, their origins and formation conditions remain unknown. Thus, studying hydrothermal springs in this area provides us an opportunity to expand our knowledge of subsurface (bio)chemical processes that generate organic compounds in hydrothermal systems, and aid in future development and exploration of potential energy resources as well. While isotope measurement has long been used for recognition of their origins, there are several secondary processes that may generate variations in isotopic compositions: oxidation, re-equilibration of methane and other alkanes with CO2, mixing with compounds of other sources, etc. Therefore, in addition to isotopic analysis, other evidence, including water chemistry and rock compositions, are necessary to identify volatile compounds of different sources. Surprise Valley Hot Springs (SVHS, 41º32'N, 120º5'W), located in a typical basin and range province valley in northeastern California, is a terrestrial hydrothermal spring system of the Great Basin. Previous geophysical studies indicated the presence of clay-rich volcanic and sedimentary rocks of Tertiary age beneath the lava flows in late Tertiary and Quaternary. Water and gas samples were collected for a variety of chemical and isotope composition analyses, including in-situ pH, alkalinity, conductivity, oxidation reduction potential (ORP), major and trace elements, and C and H isotope measurements. Fluids issuing from SVHS can be classified as Na-(Cl)-SO4 type, with the major cation and anion being Na+ and SO4 2-, respectively. Thermodynamic calculation using ORP and major element data indicated that sulfate is the most dominant sulfur species, which is consistent with anion analysis results. Aquifer temperatures at depth estimated

  6. NWFSC OA facility water chemistry - Ocean acidification species exposure experimental facility

    Data.gov (United States)

    National Oceanic and Atmospheric Administration, Department of Commerce — We have developed a unique facility for conducting high-quality experiments on marine organisms in seawater with controlled carbon chemistry conditions. The...

  7. A New Way to Produce Cellobiose Carbonates Using Green Chemistry.

    Science.gov (United States)

    Khiari, R; Brochier-Salon, M-C; Mhenni, M F; Mauret, E; Belgacem, M N

    2016-08-23

    The preparation of cellulose derivatives using green (i.e., environmentally friendly) reagents would improve sustainability and reduce concerns arising from the use of non-green reagents. The objective of this work was to prepare cellobiose carbonate using a green reagent, dimethyl carbonate. The carbonation reaction was carried out in the presence of ethanolic potassium hydroxide solution and dimethyl carbonate for 6 h at a range of temperatures (25-70 °C). A cellobiose derivative was successfully prepared with a recovered yield of more than 70 % and characterized by FTIR and NMR spectroscopy techniques. The presence of a grafted disaccharide with a degree of substitution higher than 2 was determined by (13) C NMR analysis. The spectra of the prepared cellobiose carbonate exhibited peaks that were associated with cellulose molecules (C1 -C6 ) and corresponded to carbonate functions at around 159.4 ppm. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Chemistry and radiation in oxy-fuel combustion