Effects of salinity and the extent of water on supercritical CO2-induced phlogopite dissolution and secondary mineral formation.

PubMed

Shao, Hongbo; Ray, Jessica R; Jun, Young-Shin

2011-02-15

To ensure the viability of geologic CO2 sequestration (GCS), we need a holistic understanding of reactions at supercritical CO2 (scCO2)-saline water-rock interfaces and the environmental factors affecting these interactions. This research investigated the effects of salinity and the extent of water on the dissolution and surface morphological changes of phlogopite [KMg2.87Si3.07Al1.23O10(F,OH)2], a model clay mineral in potential GCS sites. Salinity enhanced the dissolution of phlogopite and affected the location, shape, size, and phase of secondary minerals. In low salinity solutions, nanoscale particles of secondary minerals formed much faster, and there were more nanoparticles than in high salinity solutions. The effect of water extent was investigated by comparing scCO2-H2O(g)-phlogopite and scCO2-H2O(l)-phlogopite interactions. Experimental results suggested that the presence of a thin water film adsorbed on the phlogopite surface caused the formation of dissolution pits and a surface coating of secondary mineral phases that could change the physical properties of rocks. These results provide new information for understanding reactions at scCO2-saline water-rock interfaces in deep saline aquifers and will help design secure and environmentally sustainable CO2 sequestration projects.

Estimating lake-atmosphere CO2 exchange

USGS Publications Warehouse

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

1999-01-01

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

Comparative Investigation on the Heat Transfer Characteristics of Gaseous CO2 and Gaseous Water Flowing Through a Single Granite Fracture

NASA Astrophysics Data System (ADS)

He, Yuanyuan; Bai, Bing; Li, Xiaochun

2017-11-01

CO2 and water are two commonly employed heat transmission fluids in several fields. Their temperature and pressure determine their phase states, thus affecting the heat transfer performance of the water/CO2. The heat transfer characteristics of gaseous CO2 and gaseous water flowing through fractured hot dry rock still need a great deal of investigation, in order to understand and evaluate the heat extraction in enhanced geothermal systems. In this work, we develop a 2D numerical model to compare the heat transfer performance of gaseous CO2 and gaseous water flowing through a single fracture aperture of 0.2 mm in a φ 50 × 50 mm cylindrical granite sample with a confining temperature of 200°C under different inlet mass flow rates. Our results indicate that: (1) the final outlet temperatures of the fluid are very close to the outer surface temperature under low inlet mass flow rate, regardless of the sample length. (2) Both the temperature of the fluid (gaseous CO2/gaseous water) and inner surface temperature rise sharply at the inlet, and the inner surface temperature is always higher than the fluid temperature. However, their temperature difference becomes increasingly small. (3) Both the overall heat transfer coefficient (OHTC) and local heat transfer coefficient (LHTC) of gaseous CO2 and gaseous water increase with increasing inlet mass flow rates. (4) Both the OHTC and LHTC of gaseous CO2 are lower than those of gaseous water under the same conditions; therefore, the heat mining performance of gaseous water is superior to gaseous CO2 under high temperature and low pressure.

Global carbon dioxide emissions from inland waters

USGS Publications Warehouse

Raymond, Peter A.; Hartmann, Jens; Lauerwald, Ronny; Sobek, Sebastian; McDonald, Cory P.; Hoover, Mark; Butman, David; Striegl, Robert G.; Mayorga, Emilio; Humborg, Christoph; Kortelainen, Pirkko; Durr, Hans H.; Meybeck, Michel; Ciais, Philippe; Guth, Peter

2013-01-01

Carbon dioxide (CO2) transfer from inland waters to the atmosphere, known as CO2 evasion, is a component of the global carbon cycle. Global estimates of CO2 evasion have been hampered, however, by the lack of a framework for estimating the inland water surface area and gas transfer velocity and by the absence of a global CO2 database. Here we report regional variations in global inland water surface area, dissolved CO2 and gas transfer velocity. We obtain global CO2 evasion rates of 1.8   petagrams of carbon (Pg C) per year from streams and rivers and 0.32  Pg C yr−1 from lakes and reservoirs, where the upper and lower limits are respectively the 5th and 95th confidence interval percentiles. The resulting global evasion rate of 2.1 Pg C yr−1 is higher than previous estimates owing to a larger stream and river evasion rate. Our analysis predicts global hotspots in stream and river evasion, with about 70 per cent of the flux occurring over just 20 per cent of the land surface. The source of inland water CO2 is still not known with certainty and new studies are needed to research the mechanisms controlling CO2 evasion globally.

The Martian paleoclimate and enhanced atmospheric carbon dioxide

NASA Technical Reports Server (NTRS)

Cess, R. D.; Owen, T.; Ramanathan, V.

1980-01-01

Current evidence indicates that the Martian surface is abundant with water presently in the form of ice, while the atmosphere was at one time more massive with a past surface pressure of as much as 1 atm of CO2. In an attempt to understand the Martian paleoclimate, a past CO2-H2O greenhouse was modeled and global temperatures which are consistent with an earlier presence of liquid surface water are found in agreement with the extensive evidence for past fluvial erosion. An important aspect of the CO2-H2O greenhouse model is the detailed inclusion of CO2 hot bands. For a surface pressure of 1 atm of CO2, the present greenhouse model predicts a global mean surface temperature of 294 K, but if the hot bands are excluded, a surface temperature of only 250 K is achieved.

Spatial and temporal variability of seawater pCO2 within the Canadian Arctic Archipelago and Baffin Bay during the summer and autumn 2011

NASA Astrophysics Data System (ADS)

Geilfus, N.-X.; Pind, M. L.; Else, B. G. T.; Galley, R. J.; Miller, L. A.; Thomas, H.; Gosselin, M.; Rysgaard, S.; Wang, F.; Papakyriakou, T. N.

2018-03-01

The partial pressure of CO2 in surface water (pCO2sw) measured within the Canadian Arctic Archipelago (CAA) and Baffin Bay was highly variable with values ranging from strongly undersaturated (118 μatm) to slightly supersaturated (419 μatm) with respect to the atmospheric levels ( 386 μatm) during summer and autumn 2011. During summer, melting sea ice contributed to cold and fresh surface water and enhanced the ice-edge bloom, resulting in strong pCO2sw undersaturation. Coronation Gulf was the only area with supersaturated pCO2sw, likely due to warm CO2-enriched freshwater input from the Coppermine River. During autumn, the entire CAA (including Coronation Gulf) was undersaturated, despite generally increasing pCO2sw. Coronation Gulf was the one place where pCO2sw decreased, likely due to seasonal reduction in discharge from the Coppermine River and the decreasing sea surface temperature. The seasonal summer-to-autumn increase in pCO2sw across the archipelago is attributed in part to the continuous uptake of atmospheric CO2 through both summer and autumn and to the seasonal deepening of the surface mixed layer, bringing CO2-rich waters to the surface. These observations demonstrate how freshwater from sea ice melt and rivers affect pCO2sw differently. The general pCO2sw undersaturation during summer-autumn 2011 throughout the CAA and Baffin Bay give an estimated net oceanic sink for atmospheric CO2 over the study period of 11.4 mmol CO2 m-2 d-1, assuming no sea-air CO2 flux exchange across the sea-ice covered areas.

Outgassing of the Eastern Equatorial Pacific during the Pliocene period.

NASA Astrophysics Data System (ADS)

Guillermic, M.; Tripati, A.

2016-12-01

The transition from the warm, ice-free conditions of the early Cenozoic to present-day glacial state with ice sheets in both hemispheres has been ascribed to long- and short-term changes in atmospheric CO2. The processes causing long-term changes in atmospheric CO2 levels are of debate. One possible explanation for changes in atmospheric CO2 relates to changes in air-sea exchange due to fluctuations in ocean carbon sources and sinks, as modulated by the stratification of surface waters. While nutrient consumption in low-latitude environments and associated export of CO2 to the deep sea works to sequester CO2 in the ocean interior, the return of deep water to the surface in the high latitudes and upwelling at the equator and in the eastern portion of ocean basins releases CO2. Quantitative estimates for surface water pH and pCO2 in different regions of the ocean and identification of CO2-sources and sinks are needed to better understand the role of the ocean in driving and/or amplifying variations in the atmospheric CO2 reservoir and climate change. Here we present preliminary results of surface water pH for the early Pliocene to Holocene based on boron isotope measurements of planktic foraminifera for the Eastern Equatorial Pacific. We develop records of B/Ca, Mg/Ca ratios, boron isotopes, and oxygen isotopes measurements in foraminifera tests (Globigeneroides sacculifer, Globigeneroides ruber, Neogloboquadrina dutertrei). We reconstruct changes in ocean CO2 outgassing in the Eastern Equatorial Pacific using records from ODP Site 847 (0°N, 95°W, 3373 m water depth). These data are used to examine if there is evidence for changes in stratification and CO2 outgassing during the early Pliocene warm period and during Pliocene intensification of Northern Hemisphere glaciation.

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

NASA Astrophysics Data System (ADS)

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

2015-12-01

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

Glass shell manufacturing in space. [residual gases in spherical shells made from metal-organic gels

NASA Technical Reports Server (NTRS)

Nolen, R. J.; Ebner, M. A.; Downs, R. L.

1980-01-01

Residual gases always found in glass shells are CO2, O2 and N2. In those cases where high water vapor pressure is maintained in the furnace, water is also found in the shells. Other evidence for the existence of water in shells is the presence of water-induced surface weathering of the interior shell surface. Water and CO2 are the predominant volatiles generated by the pyrolysis of both inorganic and hydrolyzed metal-organic gels. The pyrolysates of unhydrolyzed metal-organic gels also contain, in addition to water and CO2, significant levels of organic volatiles, such as ethanol and some hydrocarbons; on complete oxidation, these produce CO2 and water as well. Water is most likely the initial blowing agent, it is produced copiously during the initial stages of heating. In the later stages, CO2 becomes the dominant gas as H2O is lost at increasing rates. Water in the shell arises mainly from gel dehydration, CO2 by sodium bicarbonate/carbonate decomposition and carbon oxidation, and O2 and N2 by permeation of the ambient furnace air through the molten shell wall.

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

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

Determination of the magnetic contribution to the heat capacity of cobalt oxide nanoparticles and the thermodynamic properties of the hydration layers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Spencer, Elinor; Ross, Dr. Nancy; Parker, Stewart F.

2011-01-01

We present low temperature (11 K) inelastic neutron scattering (INS) data on four hydrated nanoparticle systems: 10 nm CoO 0.10H2O (1), 16 nmCo3O4 0.40H2O (2), 25 nm Co3O4 0.30H2O (3) and 40 nmCo3O4 0.026H2O (4). The vibrational densities of states were obtained for all samples and from these the isochoric heat capacity and vibrational energy for the hydration layers confined to the surfaces of these nanoparticle systems have been elucidated. The results show that water on the surface of CoO nanoparticles is more tightly bound than water confined to the surface of Co3O4, and this is reflected in the reducedmore » heat capacity and vibrational entropy for water on CoO relative to water on Co3O4 nanoparticles. This supports the trend, seen previously, for water to be more tightly bound in materials with higher surface energies. The INS spectra for the antiferromagnetic Co3O4 particles (2 4) also show sharp and intense magnetic excitation peaks at 5 meV, and from this the magnetic contribution to the heat capacity of Co3O4 nanoparticles has been calculated; this represents the first example of use of INS data for determining the magnetic contribution to the heat capacity of any magnetic nanoparticle system.« less

Heterogeneous water oxidation: surface activity versus amorphization activation in cobalt phosphate catalysts.

PubMed

González-Flores, Diego; Sánchez, Irene; Zaharieva, Ivelina; Klingan, Katharina; Heidkamp, Jonathan; Chernev, Petko; Menezes, Prashanth W; Driess, Matthias; Dau, Holger; Montero, Mavis L

2015-02-16

Is water oxidation catalyzed at the surface or within the bulk volume of solid oxide materials? This question is addressed for cobalt phosphate catalysts deposited on inert electrodes, namely crystallites of pakhomovskyite (Co3(PO4)2⋅8 H2O, Pak) and phosphate-containing Co oxide (CoCat). X-ray spectroscopy reveals that oxidizing potentials transform the crystalline Pak slowly (5-8 h) but completely into the amorphous CoCat. Electrochemical analysis supports high-TOF surface activity in Pak, whereas its amorphization results in dominating volume activity of the thereby formed CoCat material. In the directly electrodeposited CoCat, volume catalysis prevails, but not at very low levels of the amorphous material, implying high-TOF catalysis at surface sites. A complete picture of heterogeneous water oxidation requires insight in catalysis at the electrolyte-exposed "outer surface", within a hydrated, amorphous volume phase, and modes and kinetics of restructuring upon operation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Core-shell CoFe2O4@Co-Fe-Bi nanoarray: a surface-amorphization water oxidation catalyst operating at near-neutral pH.

PubMed

Ji, Xuqiang; Hao, Shuai; Qu, Fengli; Liu, Jingquan; Du, Gu; Asiri, Abdullah M; Chen, Liang; Sun, Xuping

2017-06-14

The exploration of high-performance and earth-abundant water oxidation catalysts operating under mild conditions is highly attractive and challenging. In this communication, core-shell CoFe 2 O 4 @Co-Fe-Bi nanoarray on carbon cloth (CoFe 2 O 4 @Co-Fe-Bi/CC) was successfully fabricated by in situ surface amorphization of CoFe 2 O 4 nanoarray on CC (CoFe 2 O 4 /CC). As a 3D water oxidation electrode, CoFe 2 O 4 @Co-Fe-Bi/CC shows outstanding activity with an overpotential of 460 mV to drive a geometrical catalytic current density of 10 mA cm -2 in 0.1 M potassium borate (pH 9.2). Notably, it also demonstrates superior long-term durability for at least 20 h with 96% Faradic efficiency. Density functional theory calculations indicate that the conversion from OOH* to O 2 is the rate-limiting step and the high water oxidation activity of CoFe 2 O 4 @Co-Fe-Bi/CC is associated with the lower free energy of 1.84 eV on a Co-Fe-Bi shell.

Adsorption of CO on oxide and water ice surfaces - Implications for the Martian atmosphere

NASA Technical Reports Server (NTRS)

Leu, M.-T.; Blamont, J. E.; Anbar, A. D.; Keyser, L. F.; Sander, S. P.

1992-01-01

The adsorption of carbon monoxide (CO) on water ice and on the oxides Fe2O3, Fe3O4, Al2O3, SiO2, CaO, MgO, and TiO2 (rutile and anatase) has been investigated in a flow reactor. A mass spectrometer was employed as a detector to monitor the temporal concentrations of CO. Adsorption coefficients as large as 1 x 10 exp -4 were measured for CO on TiO2 solids in helium at 196 K. The fractional surface coverage for CO on TiO2 solids in helium was also determined to be approximately 10 percent at 196 K. The upper limits of the fractional surface coverage for the other oxides (Fe2O3, Fe3O4, Al2O3, SiO2, CaO, and MgO) and water ice were also measured to be less than 1 percent. The implications for the stability of CO2 in the Martian atmosphere and the 'CO hole' observed by the Phobos/ISM experiment are discussed.

Carbon dioxide catastrophes: Past and future menace

NASA Technical Reports Server (NTRS)

Baur, Mario E.

1988-01-01

Carbon dioxide is important in its role as coupler of the terrestrial biosphere to inorganic chemical processes and as the principal greenhouse gas controlling Earth's surface temperature. The hypothesis that atmospheric CO2 levels have diminished with time, with the resulting cooling effect offsetting an increase in the solar constant, seems firmly established, and it is shown that feedback mechanisms exist which can maintain the terrestrial surface in a relatively narrow temperature range over geological time. Of the factors involved in such CO2 variation, the oceanic reservoir appears the most important. Surface waters are probably in approximate equilibrium with regard to CO2 exchange with the ambient atmosphere in most regions, but data from deep-ocean water sampling indicates that such waters are somewhat undersaturated in the sense that they would tend to absorb CO2 from the atmosphere if brought to the surface without change in composition or temperature. If major impacts into the ocean can result in loss of a substantial portion of the atmospheric CO2 reservoir, then any such future event could imperil the continuation of most higher forms of life on Earth. The most likely candidate for an inverse Nyos global event in previous Earth history is the Cretaceous-Tertiary terminal extinction event. The Cretaceous was characterized by warm, equable temperatures presumably indicative of relatively high CO2 levels and an intense greenhouse heating. Cooling of the oceans in absence of massive transfer of CO2 to the oceanic reservoir in itself would promote a condition of CO2 undersaturation in abyssal waters, and this is made even more extreme by the pattern of ocean water circulation. It is possible to envision a situation in which deep ocean waters were at least occasionally profoundly undersaturated with regard to CO2. Turnover of a major fraction of such an ocean would then remove, on a very short time scale, as much as 90 percent of the atmospheric CO2 inventory.

Surface radiation fluxes in transient climate simulations

NASA Astrophysics Data System (ADS)

Garratt, J. R.; O'Brien, D. M.; Dix, M. R.; Murphy, J. M.; Stephens, G. L.; Wild, M.

1999-01-01

Transient CO 2 experiments from five coupled climate models, in which the CO 2 concentration increases at rates of 0.6-1.1% per annum for periods of 75-200 years, are used to document the responses of surface radiation fluxes, and associated atmospheric properties, to the CO 2 increase. In all five models, the responses of global surface temperature and column water vapour are non-linear and fairly tightly constrained. Thus, global warming lies between 1.9 and 2.7 K at doubled, and between 3.1 and 4.1 K at tripled, CO 2, whilst column water vapour increases by between 3.5 and 4.5 mm at doubled, and between 7 and 8 mm at tripled, CO 2. Global cloud fraction tends to decrease by 1-2% out to tripled CO 2, mainly the result of decreases in low cloud. Global increases in column water, and differences in these increases between models, are mainly determined by the warming of the tropical oceans relative to the middle and high latitudes; these links are emphasised in the zonal profiles of warming and column water vapour increase, with strong water vapour maxima in the tropics. In all models the all-sky shortwave flux to the surface S↓ (global, annual average) changes by less than 5 W m -2 out to tripled CO 2, in some cases being essentially invariant in time. In contrast, the longwave flux to the surface L↓ increases significantly, by 25 W m -2 typically at tripled CO 2. The variations of S↓ and L↓ (clear-sky and all-sky fluxes) with increase in CO 2 concentration are generally non-linear, reflecting the effects of ocean thermal inertia, but as functions of global warming are close to linear in all five models. This is best illustrated for the clear-sky downwelling fluxes, and the net radiation. Regionally, as illustrated in zonal profiles and global distributions, greatest changes in both S↓ and L↓ are the result primarily of local maxima in warming and column water vapour increases.

Effects of Hydration and Oxygen Vacancy on CO2 Adsorption and Activation on β-Ga2O3(100)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pan, Yunxiang; Liu, Chang-jun; Mei, Donghai

The effects of hydration and oxygen vacancy on CO2 adsorption on the β-Ga2O3(100) surface have been studied using density functional theory slab calculations. Adsorbed CO2 is activated on the dry perfect β-Ga2O3(100) surface, resulting in a carbonate species. This adsorption is slightly endothermic, with an adsorption energy of 0.07 eV. Water is preferably adsorbed molecularly on the dry perfect β-Ga2O3(100) surface with an adsorption energy of -0.56 eV, producing a hydrated perfect β-Ga2O3(100) surface. Adsorption of CO2 on the hydrated surface as a carbonate species is also endothermic, with an adsorption energy of 0.14 eV, indicating a slight repulsive interactionmore » when H2O and CO2 are coadsorbed. The carbonate species on the hydrated perfect surface can be protonated by the co-adsorbed H2O to a bicarbonate species, making the overall process exothermic with an adsorption energy of -0.13 eV. The effect of defects on CO2 adsorption and activation has been examined by creating an oxygen vacancy on the dry β-Ga2O3(100) surface. The formation of an oxygen vacancy is endothermic, by 0.34 eV, with respect to a free O2 molecule in the gas phase. Presence of the oxygen vacancy promoted the adsorption and activation of CO2. In the most stable CO2 adsorption configuration on the dry defective β-Ga2O3(100) surface with an oxygen vacancy, one of the oxygen atoms of the adsorbed CO2 occupies the oxygen vacancy site and the CO2 adsorption energy is -0.31 eV. Water favors dissociative adsorption at the oxygen vacancy site on the defective surface. This process is instantaneous with an adsorption energy of -0.62 eV. These results indicate that, when water and CO2 are both present in the adsorption system simultaneously, the water molecule will compete with CO2 for the oxygen vacancy sites and impact CO2 adsorption and conversion negatively. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy. A portion of the computing time was granted by the scientific user projects using the Molecular Science Computing Facility in the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL). The EMSL is a DOE national scientific user facility located at PNNL, and supported by the DOE’s Office of Science, Biological and Environmental Research.« less

Modelling CO2 emissions from water surface of a boreal hydroelectric reservoir.

PubMed

Wang, Weifeng; Roulet, Nigel T; Kim, Youngil; Strachan, Ian B; Del Giorgio, Paul; Prairie, Yves T; Tremblay, Alain

2018-01-15

To quantify CO 2 emissions from water surface of a reservoir that was shaped by flooding the boreal landscape, we developed a daily time-step reservoir biogeochemistry model. We calibrated the model using the measured concentrations of dissolved organic and inorganic carbon (C) in a young boreal hydroelectric reservoir, Eastmain-1 (EM-1), in northern Quebec, Canada. We validated the model against observed CO 2 fluxes from an eddy covariance tower in the middle of EM-1. The model predicted the variability of CO 2 emissions reasonably well compared to the observations (root mean square error: 0.4-1.3gCm -2 day -1 , revised Willmott index: 0.16-0.55). In particular, we demonstrated that the annual reservoir surface effluxes were initially high, steeply declined in the first three years, and then steadily decreased to ~115gCm -2 yr -1 with increasing reservoir age over the estimated "engineering" reservoir lifetime (i.e., 100years). Sensitivity analyses revealed that increasing air temperature stimulated CO 2 emissions by enhancing CO 2 production in the water column and sediment, and extending the duration of open water period over which emissions occur. Increasing the amount of terrestrial organic C flooded can enhance benthic CO 2 fluxes and CO 2 emissions from the reservoir water surface, but the effects were not significant over the simulation period. The model is useful for the understanding of the mechanism of C dynamics in reservoirs and could be used to assist the hydro-power industry and others interested in the role of boreal hydroelectric reservoirs as sources of greenhouse gas emissions. Copyright © 2017 Elsevier B.V. All rights reserved.

Air-water CO2 and CH4 fluxes along a river-reservoir continuum: Case study in the Pengxi River, a tributary of the Yangtze River in the Three Gorges Reservoir, China.

PubMed

Huang, Yang; Yasarer, Lindsey M W; Li, Zhe; Sturm, Belinda S M; Zhang, Zengyu; Guo, Jinsong; Shen, Yu

2017-05-01

Water surface greenhouse gas (GHG) emissions in freshwater reservoirs are closely related to limnological processes in the water column. Affected by both reservoir operation and seasonal changes, variations in the hydro-morphological conditions in the river-reservoir continuum will create distinctive patterns in water surface GHG emissions. A one-year field survey was carried out in the Pengxi River-reservoir continuum, a part of the Three Gorges Reservoir (TGR) immediately after the TGR reached its maximum water level. The annual average water surface CO 2 and CH 4 emissions at the riverine background sampling sites were 6.23 ± 0.93 and 0.025 ± 0.006 mmol h -1  m -2 , respectively. The CO 2 emissions were higher than those in the downstream reservoirs. The development of phytoplankton controlled the downstream decrease in water surface CO 2 emissions. The presence of thermal stratification in the permanent backwater area supported extensive phytoplankton blooms, resulting in a carbon sink during several months of the year. The CH 4 emissions were mainly impacted by water temperature and dissolved organic carbon. The greatest water surface CH 4 emission was detected in the fluctuating backwater area, likely due to a shallower water column and abundant organic matter. The Pengxi River backwater area did not show significant increase in water surface GHG emissions reported in tropical reservoirs. In evaluating the net GHG emissions by the impoundment of TGR, the net change in the carbon budget and the contribution of nitrogen and phosphorus should be taken into consideration in this eutrophic river-reservoir continuum.

Carbon Dioxide Removal from Air using Seafloor Peridotite

NASA Astrophysics Data System (ADS)

Kelemen, P. B.; Brandt, A. R.; Benson, S. M.

2016-12-01

We describe a method for Carbon Dioxide Removal from Air (CDR) using CO2 uptake via mineral carbonation, about half the cost of that proposed by Kelemen & Matter [1,2]. Reaction of CO2-bearing fluids and gases with peridotite rapidly forms inert, non-toxic carbonate minerals. In proposed methods for combined capture and storage of ambient CO2 via reaction of seawater or ground water with peridotite [1-5], return of depleted water to the surface draws down CO2 from air. Because they use available chemical and thermal energy that drive spontaneous natural reactions, they may be the least expensive methods for capture of CO2 from air. We focus on subsurface CO2 uptake during flow of surface water through fractured peridotite. Previously [1-3], we envisioned a design similar to enhanced geothermal systems (EGS), involving two large diameter boreholes, subject to the challenges of achieving rapid, efficient return flow that limit the success of EGS. Recent discussions yielded a less expensive, more robust design: A single well produces ambient, CO2-depleted pore water from seafloor peridotite. Such water has low carbon and high pH [6,7,8]. Where such waters are delivered to the surface, observations reveal rapid CO2 uptake from air [1,3,8-10]. Delivery to the sea surface would also reduce local acidification. Thermal buoyancy and pumps powered by wave and tidal energy would bring warm formation water from wells to the surface through conduits surrounded by colder seawater. Recharge would be via flow in natural or enhanced fracture networks in unconfined submarine aquifers. This method could be tested and scaled-up in coastal, sub-seafloor peridotite with onshore drilling off Oman, New Caledonia and Papua New Guinea, Spain, Morocco, USA, etc. It is possible to achieve much larger scale. Giant volumes of peridotite are exposed on the seafloor along slow-spreading mid-ocean ridges [3]. Robotic drills could install wells that deliver CO2-depleted water through fabric tubes to the sea surface. Does anyone know James Cameron's phone number? [1] Kelemen & Matter PNAS 08 [2] Kelemen & Matter AGU Fall 14 [3] Kelemen et al AREPS 11 [4] Wilson et al IJGHGC 14 [5] Schuiling & Krijgsman Climate Change 06 [6] Barnes & O'Neil GSA Bull 69 [7] Kelley et al Science 01 [8] Paukert et al Chem Geol 12 [9] Mervine et al GCA 13 [10] Mervine et al Chem Geol 15

Diurnal dynamics of the CO2 concentration in water of the coastal zone of lake Baikal in the ice period (testing of the DIEL - CO2 method for assessment of lake metabolic rate)

NASA Astrophysics Data System (ADS)

Panchenko, M. V.; Domysheva, V. M.; Pestunov, D. A.; Sakirko, M. V.; Ivanov, V. G.; Shamrin, A. M.

2017-11-01

Results of three long cycles of 24-hour measurements of the carbon dioxide content in the surface and bottom water in the ice period of 2014-2016 in the Baikal coastal zone are analyzed. The diurnal dynamics of the CO2 concentration in the subglacial water, in which photosynthesis plays the leading role, is described. It is found that, in comparison with the surface subglacial water (that is, directly adjacent to the ice bottom), the more pronounced diurnal rhythm of CO2 is observed in the bottom layer in all realizations. This rhythm is well correlated with pyranometer readings. The data on the diurnal dynamics of CO2 are used to estimate the gross primary production in the bottom water with the DIEL method based on the analysis of temporal variability of the carbon dioxide concentration in water in situ.

Modification of land-atmosphere interactions by CO2 effects: Implications for summer dryness and heat wave amplitude

NASA Astrophysics Data System (ADS)

Lemordant, Léo.; Gentine, Pierre; Stéfanon, Marc; Drobinski, Philippe; Fatichi, Simone

2016-10-01

Plant stomata couple the energy, water, and carbon cycles. We use the framework of Regional Climate Modeling to simulate the 2003 European heat wave and assess how higher levels of surface CO2 may affect such an extreme event through land-atmosphere interactions. Increased CO2 modifies the seasonality of the water cycle through stomatal regulation and increased leaf area. As a result, the water saved during the growing season through higher water use efficiency mitigates summer dryness and the heat wave impact. Land-atmosphere interactions and CO2 fertilization together synergistically contribute to increased summer transpiration. This, in turn, alters the surface energy budget and decreases sensible heat flux, mitigating air temperature rise. Accurate representation of the response to higher CO2 levels and of the coupling between the carbon and water cycles is therefore critical to forecasting seasonal climate, water cycle dynamics, and to enhance the accuracy of extreme event prediction under future climate.

Reaction Mechanisms for the Electrochemical Reduction of CO 2 to CO and Formate on the Cu(100) Surface at 298 K from Quantum Mechanics Free Energy Calculations with Explicit Water

DOE PAGES

Cheng, Tao; Xiao, Hai; Goddard, William A.

2016-10-11

Copper is the only elemental metal that reduces a significant fraction of CO 2 to hydrocarbons and alcohols, but the atomistic reaction mechanism that controls the product distributions is not known because it has not been possible to detect the reaction intermediates on the electrode surface experimentally, or to carry out Quantum Mechanics (QM) calculations with a realistic description of the electrolyte (water). We carry out QM calculations with an explicit description of water on the Cu(100) surface (experimentally shown to be stable under CO 2 reduction reaction conditions) to examine the initial reaction pathways to form CO and formatemore » (HCOO –) from CO 2 through free energy calculations at 298 K and pH 7. We find that CO formation proceeds from physisorbed CO 2 to chemisorbed CO 2 (*CO 2 δ-), with a free energy barrier of ΔG ‡ = 0.43 eV, the rate-determining step (RDS). The subsequent barriers of protonating *CO 2 δ- to form COOH* and then dissociating COOH* to form *CO are 0.37 and 0.30 eV, respectively. HCOO– formation proceeds through a very different pathway in which physisorbed CO 2 reacts directly with a surface H* (along with electron transfer), leading to ΔG ‡ = 0.80 eV. Thus, the competition between CO formation and HCOO – formation occurs in the first electron-transfer step. On Cu(100), the RDS for CO formation is lower, making CO the predominant product. Therefore, to alter the product distribution, we need to control this first step of CO 2 binding, which might involve controlling pH, alloying, or changing the structure at the nanoscale.« less

Reaction Mechanisms for the Electrochemical Reduction of CO2 to CO and Formate on the Cu(100) Surface at 298K from Quantum Mechanics Free Energy Calculations with Explicit Water.

PubMed

Cheng, Tao; Xiao, Hai; Goddard, William A

2016-10-11

Copper is the only elemental metal that reduces a significant fraction of CO 2 to hydrocarbons and alcohols, but the atomistic reaction mechanism that controls the product distributions are not known because it has not been possible to detect the reaction intermediates on the electrode surface experimentally, or carry out Quantum Mechanics (QM) calculations with a realistic description of the electrolyte (water). Here, we carry out Quantum Mechanics (QM) calculations with an explicit description of water on the Cu(100) surface (experimentally shown to be stable under CO2RR conditions) to examine the initial reaction pathways to form CO and formate (HCOO - ) from CO 2 through free energy calculations at 298K and pH 7. We find that CO formation proceeds from physisorbed CO 2 to chemisorbed CO 2 (*CO 2 δ- ), with a free energy barrier of ΔG ‡ =0.43 eV, the rate determining step (RDS). The subsequent barriers of protonating *CO 2 δ- to form COOH* and then dissociating COOH* to form *CO are 0.37 eV and 0.30 eV, respectively. HCOO - formation proceeds through a very different pathway in which physisorbed CO 2 reacts directly with a surface H* (along with electron transfer), leading to ΔG ‡ = 0.80 eV. Thus, the competition between CO formation and HCOO - formation occurs in the first electron transfer step. On Cu(100), the RDS for CO formation is lower, making CO the predominant product. Thus, to alter the product distribution we need to control this first step of CO 2 binding, which might involve alloying or changing the structure at the nanoscale.

The Relative Influence of H2O and CO2 on the Primitive Surface Conditions and Evolution of Rocky Planets

NASA Astrophysics Data System (ADS)

Salvador, A.; Massol, H.; Davaille, A.; Marcq, E.; Sarda, P.; Chassefiere, E.

2016-12-01

Recent literature reveals how different the telluric planets' water content can be, depending on the formation processes and origins of water. Furthermore, for Earth mass planets, estimates of their atmospheric water content range between 0.3 to 1000 water oceans. We simulate the secular convective cooling and solidification of a 1D magma ocean (hereafter "MO") in interaction with the outgassed atmosphere. We vary the initial CO2 and H2O contents (respectively from 0.1×10-2 to 14×10-2wt% and from 0.05 to 2.2 times the Earth Ocean current mass (MEO)), the solar distance - from 0.63 to 1.30 AU -, the radiative heat transfer in the atmosphere (grey or non-grey, with or without clouds) and investigate the relative influence of these parameters on an Earth like planet's surface conditions at the MO phase term, and especially its ability to form a water ocean. We define the end of the MO as the time when the heat flux from the vigorous convecting mantle becomes negligible compared to the incident solar flux, linked to the dramatic increase of viscosity as the MO solidification reaches the surface, which considerably reduces the convection intensity and the heat transfer. This particular time coincides with the possible apparition of a water ocean and with the development of a thermal boundary layer at the surface, thick enough to limit the interactions between the two reservoirs. As a first step, we assume a bottom-up solidification of the MO. The planetary surface pressure-temperature conditions, resulting from the solidification, are conditioned by the sun-planet distance and the initial CO2 and H2O contents. There is a critical sun-planet distance Rc below which water will never condense, whatever the initial volatile content. For distances larger than Rc, water condensation strongly depends on the relative proportion of CO2 and H2O. The higher the H2O content, the easier it is to reach the equilibrium water vapor pressure and therefore to condense water, for the tested range of CO2 contents. Otherwise, for [H2O]t0<1.8 MEO , too much CO2 precludes the formation of a water ocean by greenhouse effect. In order to study exoplanets surface conditions, and the wide diversity of these gas rich extrasolar worlds, we propose a simple scaling law to explain the relative influence of the tested parameters on the water condensation.

A doping technique that suppresses undesirable H2 evolution derived from overall water splitting in the highly selective photocatalytic conversion of CO2 in and by water.

PubMed

Teramura, Kentaro; Wang, Zheng; Hosokawa, Saburo; Sakata, Yoshihisa; Tanaka, Tsunehiro

2014-08-04

Photocatalytic conversion of CO2 to reduction products, such as CO, HCOOH, HCHO, CH3OH, and CH4, is one of the most attractive propositions for producing green energy by artificial photosynthesis. Herein, we found that Ga2O3 photocatalysts exhibit high conversion of CO2. Doping of Zn species into Ga2O3 suppresses the H2 evolution derived from overall water splitting and, consequently, Zn-doped, Ag-modified Ga2O3 exhibits higher selectivity toward CO evolution than bare, Ag-modified Ga2O3. We observed stoichiometric amounts of evolved O2 together with CO. Mass spectrometry clarified that the carbon source of the evolved CO is not the residual carbon species on the photocatalyst surface, but the CO2 introduced in the gas phase. Doping of the photocatalyst with Zn is expected to ease the adsorption of CO2 on the catalyst surface. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Formation of a nanobubble and its effect on the structural ordering of water in a CH4-N2-CO2-H2O mixture.

PubMed

Kaur, Surinder Pal; Sujith, K S; Ramachandran, C N

2018-04-04

The replacement of methane (CH4) from its hydrate by a mixture of nitrogen (N2) and carbon dioxide (CO2) involves the dissociation of methane hydrate leading to the formation of a CH4-N2-CO2-H2O mixture that can significantly influence the subsequent steps of the replacement process. In the present work, we study the evolution of dissolved gas molecules in this mixture by applying classical molecular dynamics simulations. Our study shows that a higher CO2 : N2 ratio in the mixture enhances the formation of nanobubbles composed of N2, CH4 and CO2 molecules. To understand how the CO2 : N2 ratio affects nanobubble nucleation, the distribution of molecules in the bubble formed is examined. It is observed that unlike N2 and CH4, the density of CO2 in the bubble reaches a maximum at the surface of the bubble. The accumulation of CO2 molecules at the surface makes the bubble more stable by decreasing the excess pressure inside the bubble as well as surface tension at its interface with water. It is found that a frequent exchange of gas molecules takes place between the bubble and the surrounding liquid and an increase in concentration of CO2 in the mixture leads to a decrease in the number of such exchanges. The effect of nanobubbles on the structural ordering of water molecules is examined by determining the number of water rings formed per unit volume in the mixture. The role of nanobubbles in water structuring is correlated to the dynamic nature of the bubble arising from the exchange of gas molecules between the bubble and the liquid.

Water dissociation and CO oxidation over Au/anatase catalyst. A DFT-D2 study

NASA Astrophysics Data System (ADS)

Saqlain, Muhammad Adnan; Hussain, Akhtar; Siddiq, Muhammad; Leitão, Alexandre A.

2018-03-01

With the help of DFT-D2 methodology, we have investigated the adsorption of water on clean anatase(001) and Au/anatase(001). In the former case, adsorption energies of H2O differ to small extent computed employing GGA = PW91 and DFT-D2 methods. While the GGA = PW91 predicts that water would desorb close to 650 K on the TiO2 surface, the DFT-D2 predicts that desorption is most likely to occur above 700 K. A comparison of water adsorption on TiO2 and Au/TiO2 surfaces shows that the TiO2 prefers dimer adsorption whereas the Au/TiO2 prefers monomer adsorption. We found that the diffusion of surface hydroxyls on to the Au cluster from the Au/TiO2 periphery is unlikely and it seems that the CO oxidation would occur at the Au/TiO2 boundary. The results show that water dissociation and CO oxidation steps occur easily on Au/TiO2 indicating that this could be good alternative catalyst for water gas shift reaction industry.

Blue water tradeoffs with ecosystems in a CO2-enriched climate

NASA Astrophysics Data System (ADS)

Mankin, J. S.; Smerdon, J. E.; Cook, B. I.; Williams, A. P.; Seager, R.

2017-12-01

Present and future freshwater availability and drought risks are physically tied to the competing responses of surface vegetation to increasing CO2, which includes radiative and plant physiological forcing, as well as their consequences for plant phenology, water use efficiency, and CO2 fertilization. Because Earth system models (ESMs) have increased their sophistication in representing the coupling among biogeochemical and biogeophysical processes at the land surface, projected linkages among ecosystem responses to CO2 and blue water (runoff) can be explored. A detailed analysis of the Western US demonstrates that CO2- and radiatively-induced vegetation growth drives projected decreases in soil moisture and runoff in the NCAR CESM LENS, creating a curious pattern of colocated 'greening' and 'drying.' Here we explore these responses at the global-scale and the consequences of such vegetation-driven drying on blue water availability for people. We present a simple metric that quantifies the tradeoff that occurs between ecosystems and blue water and link their occurrence to changes in daily-scale precipitation extremes, plant functional types, and changes in leaf areas. These results have implications for blue water availability for people and raise important questions about model representations of vegetation-water responses to high CO2.

CO2 hydrate nucleation kinetics enhanced by an organo-mineral complex formed at the montmorillonite-water interface.

PubMed

Kyung, Daeseung; Lim, Hyung-Kyu; Kim, Hyungjun; Lee, Woojin

2015-01-20

In this study, we investigated experimentally and computationally the effect of organo-mineral complexes on the nucleation kinetics of CO2 hydrate. These complexes formed via adsorption of zwitter-ionic glycine (Gly-zw) onto the surface of sodium montmorillonite (Na-MMT). The electrostatic attraction between the −NH3(+) group of Gly-zw, and the negatively charged Na-MMT surface, provides the thermodynamic driving force for the organo-mineral complexation. We suggest that the complexation of Gly-zw on the Na-MMT surface accelerates CO2 hydrate nucleation kinetics by increasing the mineral–water interfacial area (thus increasing the number of effective hydrate-nucleation sites), and also by suppressing the thermal fluctuation of solvated Na(+) (a well-known hydrate formation inhibitor) in the vicinity of the mineral surface by coordinating with the −COO(–) groups of Gly-zw. We further confirmed that the local density of hydrate-forming molecules (i.e., reactants of CO2 and water) at the mineral surface (regardless of the presence of Gly-zw) becomes greater than that of bulk phase. This is expected to promote the hydrate nucleation kinetics at the surface. Our study sheds new light on CO2 hydrate nucleation kinetics in heterogeneous marine environments, and could provide knowledge fundamental to successful CO2 sequestration under seabed sediments.

Physical Controls on Carbon Flux from a Temperate Lake During Autumn Cooling

NASA Astrophysics Data System (ADS)

Czikowsky, M. J.; Miller, S. D.; Tedford, E. W.; MacIntyre, S.

2011-12-01

Seasonally-stratified temperate lakes are a source of carbon dioxide to the atmosphere during autumn overturning as CO2 trapped below the thermocline becomes available to the surface for release to the atmosphere. We made continuous measurements of the vertical profile of pCO2 in a ~600 ha temperate lake (Lake Pleasant, maximum depth ~24 m) in southwestern Adirondack Park, New York from mid-September to mid-October 2010 from a moored pontoon boat. Continuous eddy covariance flux measurements of momentum, sensible and latent heat, and CO2 were made in situ, and the water column thermal structure was measured using thermistor chains. The spatial variability (horizontal and vertical) of pCO2 throughout the lake was characterized periodically using a roving profiling system. At the beginning of the study interval, pCO2 at the pontoon boat varied from 500 ppm at the surface to > 3000 ppm below the thermocline. The vertical profile of pCO2 changed markedly during the campaign due to the effects of wind forcing and evaporation (buoyancy), with nearly uniform, high pCO2 throughout the water column at the end of the campaign (Figure 1). The elevated surface water pCO2 increased CO2 emission to the atmosphere.

Blue Water Trade-Offs With Vegetation in a CO2-Enriched Climate

NASA Astrophysics Data System (ADS)

Mankin, Justin S.; Seager, Richard; Smerdon, Jason E.; Cook, Benjamin I.; Williams, A. Park; Horton, Radley M.

2018-04-01

Present and future freshwater availability and drought risks are physically tied to the responses of surface vegetation to increasing CO2. A single-model large ensemble identifies the occurrence of colocated warming- and CO2-induced leaf area index increases with summer soil moisture declines. This pattern of "greening" and "drying," which occurs over 42% of global vegetated land area, is largely attributable to changes in the partitioning of precipitation at the land surface away from runoff and toward terrestrial vegetation ecosystems. Changes in runoff and ecosystem partitioning are inversely related, with changes in runoff partitioning being governed by changes in precipitation (mean and extremes) and ecosystem partitioning being governed by ecosystem water use and surface resistance to evapotranspiration (ET). Projections show that warming-influenced and CO2-enriched terrestrial vegetation ecosystems use water that historically would have been partitioned to runoff over 48% of global vegetated land areas, largely in Western North America, the Amazon, and Europe, many of the same regions with colocated greening and drying. These results have implications for how water available for people will change in response to anthropogenic warming and raise important questions about model representations of vegetation water responses to high CO2.

No Mystery! Water Carved the Outflow Channels on Mars

NASA Astrophysics Data System (ADS)

Coleman, N.

2002-12-01

The enormous outflow channels of Chryse Planitia provide the best evidence that large amounts of water were once released onto the martian surface. The role of water has recently been challenged by the White Mars hypothesis, which claims that the channels were cut by CO2 gas-supported debris flows that also resurfaced the northern plains. Hoffman [Icarus, 2000] refers to a volumetric "misfit" between outburst channels and the chaos source zones. He explains that chaos collapse "...involves regolith alone which generates its own fluids from liquid CO2 and CO2-bearing ices within its own volume." Hoffman [LPSC 32, #1257] argues that release of liquid CO2 produced Aromatum Chaos, and a hypothetical energetic "jet" of gas and debris carved Ravi Vallis. He notes that water would have had to be locally recharged in many episodes to provide enough discharge to form the chaos and channel. However, these assertions appear incorrect because the fluid source was a distant surface impoundment, not local recharge. Carr [Water on Mars, 1996] describes a 400-km-long zone of subsidence that extends northward from Ganges Chasma to the source of Shalbatana Vallis. MOLA data reveal that this subsidence also extends eastward to Aromatum Chaos, the source of Ravi Vallis. The field relations show that a liquid-filled impoundment in Ganges Chasma drained northward via subterranean flowpaths to maintain surface flows in Shalbatana and Ravi Valles. The fact that the flows began at a surface impoundment virtually eliminates liquid CO2 as the flowing agent. Liquid CO2 would not be stable at the surface unless the atmospheric pressure exceeded 5 atm. A recent study by Stewart and Nimmo [JGR, in press] suggests that CO2 in liquid, solid, or clathrate form could not be preserved within the crust over geologic time. Liquid water is much closer to its stability field even on present-day Mars. Large outflow channels, such as Kasei and Tiu-Simud Valles, likely formed through the release of floodwaters dammed by ice and debris, analogous to the scabland flooding of eastern Washington. The water sources were probably ice-covered impoundments in ancestral Valles Marineris canyons. Subice volcanism was a possible source of heat to create liquid water. The former existence of transient water bodies near the surface can help to calibrate models of a volcanic-hydrologic climax during the Hesperian.

Reactions of water and C1 molecules on carbide and metal-modified carbide surfaces

DOE PAGES

Wan, Weiming; Tackett, Brian M.; Chen, Jingguang G.

2017-02-23

The formation of carbides can significantly modify the physical and chemical properties of the parent metals. In the current review, we summarize the general trends in the reactions of water and C1 molecules over transition metal carbide (TMC) and metal-modified TMC surfaces and thin films. Although the primary focus of the current review is on the theoretical and experimental studies of reactions of C1 molecules (CO, CO 2, CH 3OH, etc.), the reactions of water will also be reviewed because water plays an important role in many of the C1 transformation reactions. This review is organized by discussing separately thermalmore » reactions and electrochemical reactions, which provides insights into the application of TMCs in heterogeneous catalysis and electrocatalysis, respectively. In thermal reactions, we discuss the thermal decomposition of water and methanol, as well as the reactions of CO and CO 2 over TMC surfaces. In electrochemical reactions, we summarize recent studies in the hydrogen evolution reaction, electrooxidation of methanol and CO, and electroreduction of CO 2. Lastly, future research opportunities and challenges associated with using TMCs as catalysts and electrocatalysts are also discussed.« less

Diffusion and Clustering of Carbon Dioxide on Non-porous Amorphous Solid Water

DOE Office of Scientific and Technical Information (OSTI.GOV)

He, Jiao; Emtiaz, Shahnewaj M.; Vidali, Gianfranco

2017-03-01

Observations by ISO and Spitzer toward young stellar objects showed that CO{sub 2} segregates in the icy mantles covering dust grains. Thermal processing of the ice mixture was proposed as being responsible for the segregation. Although several laboratories studied thermally induced segregation, a satisfying quantification is still missing. We propose that the diffusion of CO{sub 2} along pores inside water ice is the key to quantify segregation. We combined Temperature Programmed Desorption and Reflection Absorption InfraRed Spectroscopy to study how CO{sub 2} molecules interact on a non-porous amorphous solid water (np-ASW) surface. We found that CO{sub 2} diffuses significantly onmore » an np-ASW surface above 65 K and clusters are formed at well below one monolayer. A simple rate equation simulation finds that the diffusion energy barrier of CO{sub 2} on np-ASW is 2150 ± 50 K, assuming a diffusion pre-exponential factor of 10{sup 12} s{sup −1}. This energy should also apply to the diffusion of CO{sub 2} on the wall of pores. The binding energy of CO{sub 2} from CO{sub 2} clusters and CO{sub 2} from H{sub 2}O ice has been found to be 2415 ± 20 K and 2250 ± 20 K, respectively, assuming the same prefactor for desorption. CO{sub 2}–CO{sub 2} interaction is stronger than CO{sub 2}–H{sub 2}O interaction, in agreement with the experimental finding that CO{sub 2} does not wet the np-ASW surface. For comparison, we carried out similar experiments with CO on np-ASW, and found that the CO–CO interaction is always weaker than CO–H{sub 2}O. As a result, CO wets the np-ASW surface. This study should be of help to uncover the thermal history of CO{sub 2} on the icy mantles of dust grains.« less

CO2 and circulation in the deglacial North Pacific

NASA Astrophysics Data System (ADS)

Taylor, B.; Rae, J. W. B.; Gray, W. R.; Rees-Owen, R. L.; Burke, A.

2017-12-01

The North Pacific is the largest carbon reservoir in the global ocean, but has not typically been thought to play an active role in deglacial CO2 rise based on its modern stratified state. Recent studies (Okazaki et al., 2010; Rae et al., 2014; Max et al., 2017), however, have suggested that a more dynamic circulation regime operated in the glacial and deglacial North Pacific and, as such, the role of the North Pacific in deglacial CO2 rise may have been underestimated. We present two new high-resolution boron isotope records of surface water pCO2 from the North West and North East Pacific spanning the last 22 kyrs. The two records show remarkable coherence over key intervals during the last deglaciation and highlight major changes over a number of abrupt climate events. At both sites, following the LGM, pCO2(sw) rises, coincident with a younging of North Pacific intermediate and deep waters. This suggests that increased local overturning mixed CO2-rich deep waters throughout the water column, likely contributing to CO2 outgassing during Heinrich Stadial 1 (HS1). Both records exhibit decreases in pCO2(sw) during the latter stages of HS1, which are immediately followed by a rapid increase in pCO2(sw) at the onset of the Bølling-Allerød (B/A). Radiocarbon and δ13C data indicate a collapse in North Pacific Intermediate Water formation at the onset of the B/A, which, combined with enhanced wind stress curl, would have allowed CO2-rich waters to mix into the surface ocean from intermediate-depths. The combination of high nutrient availability and a seasonally well-stratified mixed layer likely led to the abrupt increase in export productivity across the region; the excess surface water CO2 shows that alleviation of iron or light limitation could not have been its primary cause. Our new records highlight the importance of overturning circulation in the North Pacific in controlling productivity and CO2 release on glacial/interglacial timescales.

Spatial and Temporal Variations in the Partial Pressure and Emission of CO2 and CH4 in and Amazon Floodplain Lake

NASA Astrophysics Data System (ADS)

Forsberg, B. R.; Amaral, J. H.; Barbosa, P.; Kasper, D.; MacIntyre, S.; Cortes, A.; Sarmento, H.; Borges, A. V.; Melack, J. M.; Farjalla, V.

2015-12-01

The Amazon floodplain contains a variety of wetland environments which contribute CO2 and CH4 to the regional and global atmospheres. The partial pressure and emission of these greenhouse gases (GHGs) varies: 1) between habitats, 2) seasonally, as the characteristics these habitats changes and 3) diurnally, in response to diurnal stratification. In this study, we investigated the combined influence of these factors on the partial pressure and emission of GHGs in Lago Janauacá, a central Amazon floodplain lake (3o23' S; 60o18' O). All measurements were made between August of 2014 and April of 2015 at two different sites and in three distinct habitats: open water, flooded forest, flooded macrophytes. Concentrations of CO2 and CH4 in air were measured continuously with a cavity enhanced absorption spectrometer, Los Gatos Research´s Ultraportable Greenhouse Gas Analyzer (UGGA). Vertical profiles o pCO2 and pCH4 were measured using the UGGA connected to an electric pump and equilibrator. Diffusive surface emissions were estimated with the UGGA connected to a static floating chamber. To investigate the influence of vertical stratification and mixing on GHG partial pressure and emissions, a meteorological station and submersible sensor chain were deployed at each site. Meteorological sensors included wind speed and direction. The submersible chains included thermistors and oxygen sensors. Depth profiles of partial pressure and diffusive emissions for both CO2 and CH4 varied diurnally, seasonally and between habitats. Both pCO2 and pCH4 were consistently higher in bottom than surface waters with the largest differences occurring at high water when thermal stratification was most stable. Methane emissions and partial pressures were highest at low water while pCO2 and CO2 fluxes were highest during high water periods, with 35% of CO2 fluxes at low water being negative. The highest average surface value of pCO2 (5491 μatm), encountered during rising water, was ~3 times higher than that encountered at low water (1708 μatm). Partial pressures and emissions of both CO2 and CH4 were greatest in open water habitats and consistently higher at night. These patterns reflected the higher levels of wind driven mixing and turbulence in open water environments and higher convective mixing at night which promoted diffusive emission.

Observational constraints on the global atmospheric CO2 budget

NASA Technical Reports Server (NTRS)

Tans, Pieter P.; Fung, Inez Y.; Takahashi, Taro

1990-01-01

Observed atmospheric concentrations of CO2 and data on the partial pressures of CO2 in surface ocean waters are combined to identify globally significant sources and sinks of CO2. The atmospheric data are compared with boundary layer concentrations calculated with the transport fields generated by a general circulation model (GCM) for specified source-sink distributions. In the model the observed north-south atmospheric concentration gradient can be maintained only if sinks for CO2 are greater in the Northern than in the Southern Hemisphere. The observed differences between the partial pressure of CO2 in the surface waters of the Northern Hemisphere and the atmosphere are too small for the oceans to be the major sink of fossil fuel CO2. Therefore, a large amount of the CO2 is apparently absorbed on the continents by terrestrial ecosystems.

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

PubMed

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.

Eastern equatorial pacific productivity and related-CO2 changes since the last glacial period.

PubMed

Calvo, Eva; Pelejero, Carles; Pena, Leopoldo D; Cacho, Isabel; Logan, Graham A

2011-04-05

Understanding oceanic processes, both physical and biological, that control atmospheric CO(2) is vital for predicting their influence during the past and into the future. The Eastern Equatorial Pacific (EEP) is thought to have exerted a strong control over glacial/interglacial CO(2) variations through its link to circulation and nutrient-related changes in the Southern Ocean, the primary region of the world oceans where CO(2)-enriched deep water is upwelled to the surface ocean and comes into contact with the atmosphere. Here we present a multiproxy record of surface ocean productivity, dust inputs, and thermocline conditions for the EEP over the last 40,000 y. This allows us to detect changes in phytoplankton productivity and composition associated with increases in equatorial upwelling intensity and influence of Si-rich waters of sub-Antarctic origin. Our evidence indicates that diatoms outcompeted coccolithophores at times when the influence of Si-rich Southern Ocean intermediate waters was greatest. This shift from calcareous to noncalcareous phytoplankton would cause a lowering in atmospheric CO(2) through a reduced carbonate pump, as hypothesized by the Silicic Acid Leakage Hypothesis. However, this change does not seem to have been crucial in controlling atmospheric CO(2), as it took place during the deglaciation, when atmospheric CO(2) concentrations had already started to rise. Instead, the concomitant intensification of Antarctic upwelling brought large quantities of deep CO(2)-rich waters to the ocean surface. This process very likely dominated any biologically mediated CO(2) sequestration and probably accounts for most of the deglacial rise in atmospheric CO(2).

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

Hurricane Arthur and its effect on the short-term variability of pCO2 on the Scotian Shelf, NW Atlantic

NASA Astrophysics Data System (ADS)

Lemay, Jonathan; Thomas, Helmuth; Craig, Susanne E.; Burt, William J.; Fennel, Katja; Greenan, Blair J. W.

2018-04-01

The understanding of the seasonal variability of carbon cycling on the Scotian Shelf in the NW Atlantic Ocean has improved in recent years; however, very little information is available regarding its short-term variability. In order to shed light on this aspect of carbon cycling on the Scotian Shelf we investigate the effects of Hurricane Arthur, which passed the region on 5 July 2014. The hurricane caused a substantial decline in the surface water partial pressure of CO2 (pCO2), even though the Scotian Shelf possesses CO2-rich deep waters. High-temporal-resolution data of moored autonomous instruments demonstrate that there is a distinct layer of relatively cold water with low dissolved inorganic carbon (DIC) slightly above the thermocline, presumably due to a sustained population of phytoplankton. Strong storm-related wind mixing caused this cold intermediate layer with high phytoplankton biomass to be entrained into the surface mixed layer. At the surface, phytoplankton begin to grow more rapidly due to increased light. The combination of growth and the mixing of low DIC water led to a short-term reduction in the partial pressure of CO2 until wind speeds relaxed and allowed for the restratification of the upper water column. These hurricane-related processes caused a (net) CO2 uptake by the Scotian Shelf region that is comparable to the spring bloom, thus exerting a major impact on the annual CO2 flux budget.

Structural equation modelling reveals factors regulating surface sediment organic carbon content and CO2 efflux in a subtropical mangrove.

PubMed

Ouyang, Xiaoguang; Lee, Shing Yip; Connolly, Rod M

2017-02-01

Mangroves are blue carbon ecosystems that sequester significant carbon but release CO 2 , and to a lesser extent CH 4, from the sediment through oxidation of organic carbon or from overlying water when flooded. Previous studies, e.g. Leopold et al. (2015), have investigated sediment organic carbon (SOC) content and CO 2 flux separately, but could not provide a holistic perspective for both components of blue carbon. Based on field data from a mangrove in southeast Queensland, Australia, we used a structural equation model to elucidate (1) the biotic and abiotic drivers of surface SOC (10cm) and sediment CO 2 flux; (2) the effect of SOC on sediment CO 2 flux; and (3) the covariation among the environmental drivers assessed. Sediment water content, the percentage of fine-grained sediment (<63μm), surface sediment chlorophyll and light condition collectively drive sediment CO 2 flux, explaining 41% of their variation. Sediment water content, the percentage of fine sediment, season, landform setting, mangrove species, sediment salinity and chlorophyll collectively drive surface SOC, explaining 93% of its variance. Sediment water content and the percentage of fine sediment have a negative impact on sediment CO 2 flux but a positive effect on surface SOC content, while sediment chlorophyll is a positive driver of both. Surface SOC was significantly higher in Avicennia marina (2994±186gm -2 , mean±SD) than in Rhizophora stylosa (2383±209gm -2 ). SOC was significantly higher in winter (2771±192gm -2 ) than in summer (2599±211gm -2 ). SOC significantly increased from creek-side (865±89gm -2 ) through mid (3298±137gm -2 ) to landward (3933±138gm -2 ) locations. Sediment salinity was a positive driver of SOC. Sediment CO 2 flux without the influence of biogenic structures (crab burrows, aerial roots) averaged 15.4mmolm -2 d -1 in A. marina stands under dark conditions, lower than the global average dark flux (61mmolm -2 d -1 ) for mangroves. Copyright © 2016 Elsevier B.V. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thompson, Christopher J.; Martin, Paul F.; Chen, Jeffrey

A fully automated titration system with infrared detection was developed for investigating interfacial chemistry at high pressures. The apparatus consists of a high-pressure fluid generation and delivery system coupled to a high-pressure cell with infrared optics. A manifold of electronically actuated valves is used to direct pressurized fluids into the cell. Precise reagent additions to the pressurized cell are made with calibrated tubing loops that are filled with reagent and placed in-line with the cell and a syringe pump. The cell’s infrared optics facilitate both transmission and attenuated total reflection (ATR) measurements to monitor bulk-fluid composition and solid-surface phenomena suchmore » as adsorption, desorption, complexation, dissolution, and precipitation. Switching between the two measurement modes is accomplished with moveable mirrors that direct radiation from a Fourier transform infrared spectrometer into the cell along transmission or ATR light paths. The versatility of the high-pressure IR titration system is demonstrated with three case studies. First, we titrated water into supercritical CO2 (scCO2) to generate an infrared calibration curve and determine the solubility of water in CO2 at 50 °C and 90 bar. Next, we characterized the partitioning of water between a montmorillonite clay and scCO2 at 50 °C and 90 bar. Transmission-mode spectra were used to quantify changes in the clay’s sorbed water concentration as a function of scCO2 hydration, and ATR measurements provided insights into competitive residency of water and CO2 on the clay surface and in the interlayer. Finally, we demonstrated how time-dependent studies can be conducted with the system by monitoring the carbonation reaction of forsterite (Mg2SiO4) in water-bearing scCO2 at 50 °C and 90 bar. Immediately after water dissolved in the scCO2, a thin film of adsorbed water formed on the mineral surface, and the film thickness increased with time as the forsterite began to dissolve. However, after approximately 2.5 hours, the trend reversed, and a carbonate precipitate began to form on the forsterite surface, exposing dramatic chemical changes in the thin-water film. Collectively, these applications illustrate how the high-pressure IR titration system can provide molecular-level information about the interactions between variably wet scCO2 and minerals relevant to underground storage of CO2 (geologic carbon sequestration). The apparatus could also be utilized to study high-pressure interfacial chemistry in other areas such as catalysis, polymerization, food processing, and oil and gas recovery.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thompson, Christopher J., E-mail: chris.thompson@pnnl.gov; Martin, Paul F.; Chen, Jeffrey

A fully automated titration system with infrared detection was developed for investigating interfacial chemistry at high pressures. The apparatus consists of a high-pressure fluid generation and delivery system coupled to a high-pressure cell with infrared optics. A manifold of electronically actuated valves is used to direct pressurized fluids into the cell. Precise reagent additions to the pressurized cell are made with calibrated tubing loops that are filled with reagent and placed in-line with the cell and a syringe pump. The cell's infrared optics facilitate both transmission and attenuated total reflection (ATR) measurements to monitor bulk-fluid composition and solid-surface phenomena suchmore » as adsorption, desorption, complexation, dissolution, and precipitation. Switching between the two measurement modes is accomplished with moveable mirrors that direct the light path of a Fourier transform infrared spectrometer into the cell along transmission or ATR light paths. The versatility of the high-pressure IR titration system was demonstrated with three case studies. First, we titrated water into supercritical CO{sub 2} (scCO{sub 2}) to generate an infrared calibration curve and determine the solubility of water in CO{sub 2} at 50 °C and 90 bar. Next, we characterized the partitioning of water between a montmorillonite clay and scCO{sub 2} at 50 °C and 90 bar. Transmission-mode spectra were used to quantify changes in the clay's sorbed water concentration as a function of scCO{sub 2} hydration, and ATR measurements provided insights into competitive residency of water and CO{sub 2} on the clay surface and in the interlayer. Finally, we demonstrated how time-dependent studies can be conducted with the system by monitoring the carbonation reaction of forsterite (Mg{sub 2}SiO{sub 4}) in water-bearing scCO{sub 2} at 50 °C and 90 bar. Immediately after water dissolved in the scCO{sub 2}, a thin film of adsorbed water formed on the mineral surface, and the film thickness increased with time as the forsterite began to dissolve. However, after approximately 2.5 h, the trend reversed, and a carbonate precipitate began to form on the forsterite surface, exposing dramatic chemical changes in the thin-water film. Collectively, these applications illustrate how the high-pressure IR titration system can provide molecular-level information about the interactions between variably wet scCO{sub 2} and minerals relevant to underground storage of CO{sub 2} (geologic carbon sequestration). The apparatus could also be utilized to study high-pressure interfacial chemistry in other areas such as catalysis, polymerization, food processing, and oil and gas recovery.« less

Extreme diel dissolved oxygen and carbon cycles in shallow vegetated lakes.

PubMed

Andersen, Mikkel R; Kragh, Theis; Sand-Jensen, Kaj

2017-09-13

A common perception in limnology is that shallow lakes are homogeneously mixed owing to their small water volume. However, this perception is largely gained by downscaling knowledge from large lakes to their smaller counterparts. Here we show that shallow vegetated lakes (less than 0.6 m), in fact, undergo recurring daytime stratification and nocturnal mixing accompanied by extreme chemical variations during summer. Dense submerged vegetation effectively attenuates light and turbulence generating separation between warm surface waters and much colder bottom waters. Photosynthesis in surface waters produces oxygen accumulation and CO 2 depletion, whereas respiration in dark bottom waters causes anoxia and CO 2 accumulation. High daytime pH in surface waters promotes precipitation of CaCO 3 which is re-dissolved in bottom waters. Nocturnal convective mixing re-introduces oxygen into bottom waters for aerobic respiration and regenerated inorganic carbon into surface waters, which supports intense photosynthesis. Our results reconfigure the basic understanding of local environmental gradients in shallow lakes, one of the most abundant freshwater habitats globally. © 2017 The Author(s).

Linking water and carbon cycles through salinity observed from space

NASA Astrophysics Data System (ADS)

Xie, X.; Liu, W. T.

2017-12-01

The association of ocean surface salinity in global hydrological cycle and climate change has been traditionally studied through the examination of its tendency and advection as manifestation of ocean's heat and water fluxes with the atmosphere. The variability of surface heat and water fluxes are linked to top of atmosphere radiation, whose imbalance is the main cause of global warming. Besides the link of salinity to greenhouse warming through water balance, this study will focus on the effect of changing salinity on carbon dioxide flux between the ocean and the atmosphere. We have built statistical models to estimate the partial pressure of carbon dioxide (pCO2) and ocean acidification (in terms of total alkalinity and pH) using spacebased data. PCO2 is a critical parameter governing ocean as source and sink of the accumulated greenhouse gas in the atmosphere. The exchange also causes ocean acidification, which is detrimental to marine lives and ecology. Before we had sufficient spacebased salinity measurements coincident with in situ pCO2 measurement, we trained our statistical models to use satellite sea surface temperature and chlorophyll, with one model using salinity climatology and the other without. We found significant differences between the two models in regions of strong water input through river discharge and surface water flux. The pCO2 output follows the seasonal salinity advection of the Amazon outflow. The seasonal salinity advection between Bay of Bengal and Arabian Sea are followed by change of pCO2 and total alkalinity. At shorter time scales, the signatures of rain associated with intraseasonal organized convection of summer monsoon can be detected. We have observed distribution agreement of among pCO2, surface salinity, and surface water flux for variation from a few days to a few years under the Pacific ITCZ; the agreement varies slightly with season and longitudes and the reason is under study.

Dual-Templated Cobalt Oxide for Photochemical Water Oxidation.

PubMed

Deng, Xiaohui; Bongard, Hans-Josef; Chan, Candace K; Tüysüz, Harun

2016-02-19

Mesoporous Co3 O4 was prepared using a dual templating approach whereby mesopores inside SiO2 nanospheres, as well as the void spaces between the nanospheres, were used as templates. The effect of calcination temperature on the crystallinity, morphology, and textural parameters of the Co3 O4 replica was investigated. The catalytic activity of Co3 O4 for photochemical water oxidation in a [Ru(bpy)3 ](2+) [S2 O8 ](2-) system was evaluated. The Co3 O4 replica calcined at the lowest temperature (150 °C) exhibited the best performance as a result of the unique nanostructure and high surface area arising from the dual templating. The performance of Co3 O4 with highest surface area was further examined in electrochemical water oxidation. Superior activity over high temperature counterpart and decent stability was observed. Furthermore, CoO with identical morphology was prepared from Co3 O4 using an ethanol reduction method and a higher turnover-frequency number for photochemical water oxidation was obtained. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Composition and stability of the condensate observed at the Viking Lander 2 site on Mars

NASA Astrophysics Data System (ADS)

Hart, H. M.; Jakosky, B. M.

1986-04-01

Surface energy balance and near-surface temperature data from the Viking Lander 2 site taken during the first winter that condensated were observed and analyzed to determine the relative stability of CO2 and H2O frosts. The CO2 frost stability is calculated with an equilibrium surface energy balance model, i.e., the total energy incident on a frost surface is compared with the blackbody energy emitted by the surface. The energy sources considered were IR emission from the atmosphere, sunlight, and the sensible heat flux from the atmosphere. H2O stability was examined as a function of buoyant diffusion and turbulent mixing processes which could remove saturated near-surface gases. The CO2 frost is found to be sufficiently unstable at the time the condensate was observed on the ground, so all CO2 ice deposited at night would boil away in a few hours of sunlight. CO2 ice would not form during a dust storm. Water frost would be stable during the condensate observations, since sublimation would occur at a rate below 1 micron/day. A stable winter thickness of 10 microns is projected for the water ice.

Composition and stability of the condensate observed at the Viking Lander 2 site on Mars

NASA Technical Reports Server (NTRS)

Hart, H. M.; Jakosky, B. M.

1986-01-01

Surface energy balance and near-surface temperature data from the Viking Lander 2 site taken during the first winter that condensated were observed and analyzed to determine the relative stability of CO2 and H2O frosts. The CO2 frost stability is calculated with an equilibrium surface energy balance model, i.e., the total energy incident on a frost surface is compared with the blackbody energy emitted by the surface. The energy sources considered were IR emission from the atmosphere, sunlight, and the sensible heat flux from the atmosphere. H2O stability was examined as a function of buoyant diffusion and turbulent mixing processes which could remove saturated near-surface gases. The CO2 frost is found to be sufficiently unstable at the time the condensate was observed on the ground, so all CO2 ice deposited at night would boil away in a few hours of sunlight. CO2 ice would not form during a dust storm. Water frost would be stable during the condensate observations, since sublimation would occur at a rate below 1 micron/day. A stable winter thickness of 10 microns is projected for the water ice.

Different Apparent Gas Exchange Coefficients for CO2 and CH4: Comparing a Brown-Water and a Clear-Water Lake in the Boreal Zone during the Whole Growing Season.

PubMed

Rantakari, Miitta; Heiskanen, Jouni; Mammarella, Ivan; Tulonen, Tiina; Linnaluoma, Jessica; Kankaala, Paula; Ojala, Anne

2015-10-06

The air-water exchange of carbon dioxide (CO2) and methane (CH4) is a central process during attempts to establish carbon budgets for lakes and landscapes containing lakes. Lake-atmosphere diffusive gas exchange is dependent on the concentration gradient between air and surface water and also on the gas transfer velocity, often described with the gas transfer coefficient k. We used the floating-chamber method in connection with surface water gas concentration measurements to estimate the gas transfer velocity of CO2 (kCO2) and CH4 (kCH4) weekly throughout the entire growing season in two contrasting boreal lakes, a humic oligotrophic lake and a clear-water productive lake, in order to investigate the earlier observed differences between kCO2 and kCH4. We found that the seasonally averaged gas transfer velocity of CH4 was the same for both lakes. When the lakes were sources of CO2, the gas transfer velocity of CO2 was also similar between the two study lakes. The gas transfer velocity of CH4 was constantly higher than that of CO2 in both lakes, a result also found in other studies but for reasons not yet fully understood. We found no differences between the lakes, demonstrating that the difference between kCO2 and kCH4 is not dependent on season or the characteristics of the lake.

Negative CO2 emissions via subsurface mineral carbonation in fractured peridotite

NASA Astrophysics Data System (ADS)

Kelemen, P. B.; Matter, J.

2014-12-01

Uptake of CO2 from surface water via mineral carbonation in peridotite can be engineered to achieve negative CO2 emissions. Reaction with peridotite, e.g., CO2 + olivine (A), serpentine (B) and brucite (C), forms inert, non-toxic, solid carbonates such as magnesite. Experimental studies show that A can be 80% complete in a few hours with 30 micron powders and elevated P(CO2) [1,2,3]. B is slower, but in natural systems the rate of B+C is significant [4]. Methods for capture of dilute CO2 via mineral carbonation [4,5,6,7] are not well known, though CO2 storage via mineral carbonation has been discussed for decades [8,9]. Where crushed peridotite is available, as in mine tailings, increased air or water flow could enhance CO2 uptake at a reasonable cost [4,5]. Here we focus on enhancing subsurface CO2 uptake from surface water flowing in fractured peridotite, in systems driven by thermal convection such as geothermal power plants. Return of depleted water to the surface would draw down CO2 from the air [6,7]. CO2 uptake from water, rate limited by flow in input and output wells, could exceed 1000 tons CO2/yr [7]. If well costs minus power sales were 0.1M to 1M and each system lasts 10 years this costs < 10 to 100 per ton CO2. As for other CCS methods, upscaling requires infrastructure resembling the oil industry. Uptake of 1 Gt CO2/yr at 1000 t/well/yr requires 1M wells, comparable to the number of producing oil and gas wells in the USA. Subsurface CO2 uptake could first be applied in coastal, sub-seafloor peridotite with onshore drilling. Sub-seafloor peridotite is extensive off Oman, New Caledonia and Papua New Guinea, with smaller amounts off Spain, Morocco, USA, etc. This would be a regional contribution, used in parallel with other methods elsewhere. To achieve larger scale is conceivable. There is a giant mass of seafloor peridotite along slow-spreading mid-ocean ridges. Could robotic drills enhance CO2 uptake at a reasonable cost, while fabric chimneys transport CO2-depleted water to the sea surface? Does anyone know James Cameron's phone number? [1] O'Connor et al DOE Report 04 [2] Chizmeshya et al DOE Report 07 [3] Gadikota et al Phys Chem Chem Phys 14 [4] Wilson et al IJGHGC 14 [5] Schuiling & Krijgsman Climate Change 06 [6] Kelemen & Matter PNAS 08 [7] Kelemen et al AREPS 11 [8] Seifritz Nature 90 [9] Lackner et al Energy 95

Effect of Sampling Depth on Air-Sea CO2 Flux Estimates in River-Stratified Arctic Coastal Waters

NASA Astrophysics Data System (ADS)

Miller, L. A.; Papakyriakou, T. N.

2015-12-01

In summer-time Arctic coastal waters that are strongly influenced by river run-off, extreme stratification severely limits wind mixing, making it difficult to effectively sample the surface 'mixed layer', which can be as shallow as 1 m, from a ship. During two expeditions in southwestern Hudson Bay, off the Nelson, Hayes, and Churchill River estuaries, we confirmed that sampling depth has a strong impact on estimates of 'surface' pCO2 and calculated air-sea CO2 fluxes. We determined pCO2 in samples collected from 5 m, using a typical underway system on the ship's seawater supply; from the 'surface' rosette bottle, which was generally between 1 and 3 m; and using a niskin bottle deployed at 1 m and just below the surface from a small boat away from the ship. Our samples confirmed that the error in pCO2 derived from typical ship-board versus small-boat sampling at a single station could be nearly 90 μatm, leading to errors in the calculated air-sea CO2 flux of more than 0.1 mmol/(m2s). Attempting to extrapolate such fluxes over the 6,000,000 km2 area of the Arctic shelves would generate an error approaching a gigamol CO2/s. Averaging the station data over a cruise still resulted in an error of nearly 50% in the total flux estimate. Our results have implications not only for the design and execution of expedition-based sampling, but also for placement of in-situ sensors. Particularly in polar waters, sensors are usually deployed on moorings, well below the surface, to avoid damage and destruction from drifting ice. However, to obtain accurate information on air-sea fluxes in these areas, it is necessary to deploy sensors on ice-capable buoys that can position the sensors in true 'surface' waters.

Elevated [CO2] mitigates the effect of surface drought by stimulating root growth to access sub-soil water.

PubMed

Uddin, Shihab; Löw, Markus; Parvin, Shahnaj; Fitzgerald, Glenn J; Tausz-Posch, Sabine; Armstrong, Roger; O'Leary, Garry; Tausz, Michael

2018-01-01

Through stimulation of root growth, increasing atmospheric CO2 concentration ([CO2]) may facilitate access of crops to sub-soil water, which could potentially prolong physiological activity in dryland environments, particularly because crops are more water use efficient under elevated [CO2] (e[CO2]). This study investigated the effect of drought in shallow soil versus sub-soil on agronomic and physiological responses of wheat to e[CO2] in a glasshouse experiment. Wheat (Triticum aestivum L. cv. Yitpi) was grown in split-columns with the top (0-30 cm) and bottom (31-60 cm; 'sub-soil') soil layer hydraulically separated by a wax-coated, root-penetrable layer under ambient [CO2] (a[CO2], ∼400 μmol mol-1) or e[CO2] (∼700 μmol mol-1) [CO2]. Drought was imposed from stem-elongation in either the top or bottom soil layer or both by withholding 33% of the irrigation, resulting in four water treatments (WW, WD, DW, DD; D = drought, W = well-watered, letters denote water treatment in top and bottom soil layer, respectively). Leaf gas exchange was measured weekly from stem-elongation until anthesis. Above-and belowground biomass, grain yield and yield components were evaluated at three developmental stages (stem-elongation, anthesis and maturity). Compared with a[CO2], net assimilation rate was higher and stomatal conductance was lower under e[CO2], resulting in greater intrinsic water use efficiency. Elevated [CO2] stimulated both above- and belowground biomass as well as grain yield, however, this stimulation was greater under well-watered (WW) than drought (DD) throughout the whole soil profile. Imposition of drought in either or both soil layers decreased aboveground biomass and grain yield under both [CO2] compared to the well-watered treatment. However, the greatest 'CO2 fertilisation effect' was observed when drought was imposed in the top soil layer only (DW), and this was associated with e[CO2]-stimulation of root growth especially in the well-watered bottom layer. We suggest that stimulation of belowground biomass under e[CO2] will allow better access to sub-soil water during grain filling period, when additional water is converted into additional yield with high efficiency in Mediterranean-type dryland agro-ecosystems. If sufficient water is available in the sub-soil, e[CO2] may help mitigating the effect of drying surface soil.

A review on wetting and water condensation - Perspectives for CO2 condensation.

PubMed

Snustad, Ingrid; Røe, Ingeborg T; Brunsvold, Amy; Ervik, Åsmund; He, Jianying; Zhang, Zhiliang

2018-06-01

Liquefaction of vapor is a necessary, but energy intensive step in several important process industries. This review identifies possible materials and surface structures for promoting dropwise condensation, known to increase efficiency of condensation heat transfer. Research on superhydrophobic and superomniphobic surfaces promoting dropwise condensation constitutes the basis of the review. In extension of this, knowledge is extrapolated to condensation of CO 2 . Global emissions of CO 2 need to be minimized in order to reduce global warming, and liquefaction of CO 2 is a necessary step in some carbon capture, transport and storage (CCS) technologies. The review is divided into three main parts: 1) An overview of recent research on superhydrophobicity and promotion of dropwise condensation of water, 2) An overview of recent research on superomniphobicity and dropwise condensation of low surface tension substances, and 3) Suggested materials and surface structures for dropwise CO 2 condensation based on the two first parts. Copyright © 2018 Elsevier B.V. All rights reserved.

Carbon Cycling and pH regulation on the Scotian Shelf, NW Atlantic

NASA Astrophysics Data System (ADS)

Thomas, Helmuth

2015-04-01

This presentation intends to describe the biogeochemical context for ocean acidification studies on the Scotian Shelf. The seasonality of the dominant processes, regulating surface ocean CO2 conditions, including pH, will be assessed as well as cross-shelf transports of CO2, acidity and nutrient, the latter ones exerting the "subsurface control" of CO2 air-sea fluxes and surface pH. Methods summary: The seasonal variability of inorganic carbon in the surface waters of the Scotian Shelf region of the Canadian northwestern Atlantic Ocean was assessed using hourly measurements of the partial pressure of CO2 (pCO2), and hydrographic variables obtained by an autonomous moored instrument (44.3°N and 63.3°W). These measurements were complemented by seasonal shipboard sampling of dissolved inorganic carbon (DIC), total alkalinity (TA), and pCO2, at the mooring site, and over the larger spatial scale. The Scotian Shelf is a 700 km long section of the continental shelf off Nova Scotia. Bounded by the Laurentian Channel to the northeast, and by the Northeast Channel and the Gulf of Maine to the southwest, it varies in width from 120 to 240 km covering roughly 120,000 km2 with an average depth of 90 m . Convective mixin in winter time and coastal upwelling and the associated favorable wind conditions on the Scotian Shelf have long been recognized. Strong winds of speeds greater than 10 m s-1, blowing to the northeast, and persisting for several days force relatively cold, saline, water toward the surface, displacing the warmer, fresher water offshore. Upwelling events have frequently been observed in the region in winter, and modeling studies have reproduced these observed events. Furthermore, these events may play a role in initiating and sustaining the spring phytoplankton bloom by displacing nutrient-depleted surface water and bring nutrient-rich waters up to the surface. Biological processes were found to be the dominant control on mixed-layer DIC, with the delivery of carbon-rich subsurface waters also playing an important role. The region acts as a net source of CO2 to the atmosphere at the annual scale, with a reversal of this trend occurring only during the diatom dominated spring phytoplankton bloom, when a pronounced undersaturation of the surface waters is reached for a short period. During that time, the pH is at its annual maximum (pH≈8.15), while the Aragonite saturation state reaches its minimum just before the onset of the spring bloom in late March. After of the spring bloom period, the competing effects of temperature and biology influence surface pCO2 in roughly equal magnitude. During that time carbon fixation is driven by the smaller phytoplankton size classes, which can grow in warmer, nutrient poor conditions. In the Scotian Shelf region the summertime population these numerically abundant small cells accounts for approximately 10-20% of annual carbon uptake. The regional mean surface water pH is roughly 7.8 in April and increases to greater than 8.0 in September; subsurface pH is approximately 7.6 throughout the region and indicates a seasonal decrease due to the respiration of organic matter at depth. The surface aragonite saturation state increases from less than 2.0 to values as high as 3.2 between April and September; the region as a whole exhibits relatively low saturation states, however values approaching 1.0 were only observed in the Cabot Strait at depths below roughly 100m. Subsurface onshore gradients of CO2 and nutrient species yield onshore carbon, nutrient and hydrogen ion (H+) fluxes in subsurface waters, which in turn regulate surface pH and fuel the CO2 outgassing from the Scotian Shelf.

Storm Driven Upwelling Responsible for pCO2-rich Water Intrusion in the South Atlantic Bight

NASA Astrophysics Data System (ADS)

Noakes, S.; Gledhill, D. K.

2016-02-01

Gray's Reef National Marine Sanctuary (GRNMS) is located approximately 20 miles offshore Georgia along the inner to middle shelf of the South Atlantic Bight (SAB). The University of Georgia (UGA) and the Pacific Marine Environmental Lab have maintained a high resolution pCO2 system for almost a decade on the National Data Buoy Center's buoy moored at GRNMS. To support the surface monitoring and set the stage for benthic monitoring at GRNMS, UGA and GRNMS have established a seafloor observatory that monitors pCO2, pH and water quality parameters. Traditional thought had held that given the relatively shallow water depth at GRNMS, the pCO2 measured on the surface could be extrapolated to the seafloor and utilized to monitor the benthic community. However, seafloor pCO2 data collected to date have revealed unusual episodes of subsurface pCO2-rich water moving through GRNMS that had not been previously identified by surface monitoring. Many of these events correspond with major storms that have either formed off the SAB or passed nearby GRNMS. Based on the surface data collected to date, temperature driven seasonal pCO2 changes occur naturally on an annual scale in the SAB which also affects the pH. However, the storms appear to have induced upwelling of pCO2-rich water from the deep Atlantic Ocean pushing it inward over the long continental shelf towards GRNMS. The result of the upwelling is a sharp increase of subsurface pCO2 lasting only days to weeks as compared to the seasonal cycle. It is part of the natural weather patterns for storms to form off the SAB or pass nearby, but depending on if the storm frequency increases due to global climate change, this process may become more of an impact on the benthic community. How this affects the benthic community has yet to be determined, but it is clear that they have adapted to seasonal fluctuations for survival. These upwellings are obviously adding to the SAB total carbon budget and affecting the benthic water quality, but to what extent have yet to be determined.

[Distribution, flux and biological consumption of carbon monoxide in the East China Sea and the South Yellow Sea in summer].

PubMed

Wang, Jing; Lu, Xiao-Lan; Yang, Gui-Peng; Xu, Guan-Qiu

2014-11-01

Carbon monoxide (CO) concentration distribution, sea-to-air flux and microbial consumption rate constant, along with atmospheric CO mixing ratio, were measured in the East China Sea and the South Yellow Sea in summer. Atmospheric CO mixing ratios varied from 68 x 10(-9) -448 x 10(-9), with an average of 117 x 10(-9) (SD = 68 x 10(-9), n = 36). Overall, the concentrations of atmospheric CO displayed a decreasing trend from the coastal stations to the offshore stations. The surface water CO concentrations in the investigated area ranged from 0.23-7.10 nmol x L(-1), with an average of 2.49 nmol x L(-1) (SD = 2.11, n = 36). The surface water CO concentrations were significantly affected by sunlight. Vertical profiles showed that CO concentrations rapidly declined with depth, with the maximum values appearing in the surface water. CO concentrations exhibited obvious diurnal variations in the study area, with the maximum values being 6-40 folds higher than the minimum values. Minimal concentrations of CO all occurred before dawn. However, the maximal concentrations of CO occurred at noon. Marked diurnal variation in the concentrations of CO in the water column indicated that CO was produced primarily by photochemistry. The surface CO concentrations were oversaturated relative to the atmospheric concentrations and the saturation factors ranged from 1.99-99.18, with an average of 29.36 (SD = 24.42, n = 29). The East China Sea and the South Yellow Sea was a net source of atmospheric CO. The sea-to-air fluxes of CO in the East China Sea and the South Yellow Sea ranged 0.37-44.84 μmol x (m2 x d)(-1), with an average of 12.73 μmol x (m2 x d)(-1) (SD = 11.40, n = 29). In the incubation experiments, CO concentrations decreased exponentially with incubation time and the processes conformed to the first order reaction characteristics. The microbial CO consumption rate constants (K(co)) in the surface water ranged from 0.12 to 1.45 h(-1), with an average of 0.47 h(-1) (SD = 0.55, n = 5). A negative correlation between K(co) and salinity was observed in the present study.

A long history of equatorial deep-water upwelling in the Pacific Ocean

NASA Astrophysics Data System (ADS)

Zhang, Yi Ge; Pagani, Mark; Henderiks, Jorijntje; Ren, Haojia

2017-06-01

Cold, nutrient- and CO2-rich waters upwelling in the eastern equatorial Pacific (EEP) give rise to the Pacific cold tongue. Quasi-periodic subsidence of the thermocline and attenuation in wind strength expressed by El Niño conditions decrease upwelling rates, increase surface-water temperatures in the EEP, and lead to changes in regional climates both near and far from the equatorial Pacific. EEP surface waters have elevated CO2 concentrations during neutral (upwelling) or La Niña (strong upwelling) conditions. In contrast, approximate air-sea CO2 equilibrium characterizes El Niño events. One hypothesis proposes that changes in physical oceanography led to the establishment of a deep tropical thermocline and expanded mixed-layer prior to 3 million years ago. These effects are argued to have substantially reduced deep-water upwelling rates in the EEP and promoted a "permanent El Niño-like" climate state. For this study, we test this supposition by reconstructing EEP "excess CO2" and upwelling history for the past 6.5 million years using the alkenone-pCO2 methodology. Contrary to previous assertions, our results indicate that average temporal conditions in the EEP over the past ∼6.5 million years were characterized by substantial CO2 disequilibrium and high nutrient delivery to surface waters - characteristics that imply strong upwelling of deep waters. Upwelling appears most vigorous between ∼6.5 to 4.5 million years ago coinciding with high accumulation rates of biogenic material during the late Miocene - early Pliocene "biogenic bloom".

The Dynamics of Energy and CO2 Transport above a Subtropical Rice Paddy

NASA Astrophysics Data System (ADS)

Hsieh, C.; Huang, C.; Cheng, S.

2013-12-01

An eddy-covariance system was established to understand the dynamics of turbulent transport of sensible heat, water vapor, and CO2 above a subtropical rice paddy in north Taiwan (24°48'07.958'N, 121°47'58.665'E). The results showed that, during crop season, about 25% of net radiation was used for latent heat flux, 10% for sensible heat flux, and the rest (65%) was absorbed by the water and soil in the rice paddy. However, during fallow period, where there was no rice in the paddy, both water vapor and sensible heat fluxes occupied about 18% of the net radiation. Also, Penman-Monteith equation was found to reproduce the water vapor flux well with surface resistance close to 190 s m-1. We also found that, under small Bowen ratio (< 0.2) conditions, water vapor and CO2 were transported more efficiently than heat. However, when Bowen ration was large (> 0.5), sensible heat was transported about 10% more efficiently than both water vapor and CO2. During crop season the maximum CO2 uptake was about 22 micro mol m-2 s-1. In fallow period, the maximum CO2 emission rate from the soil-water surface was around 5 micro mol m-2 s-1, which was about the same as the growing season.

Critical Role of Water and Oxygen Defects in C-O Scission during CO2 Reduction on Zn2GeO4(010).

PubMed

Yang, Jing; Li, Yanlu; Zhao, Xian; Fan, Weiliu

2018-03-27

Exploration of catalyst structure and environmental sensitivity for C-O bond scission is essential for improving the conversion efficiency because of the inertness of CO 2 . We performed density functional theory calculations to understand the influence of the properties of adsorbed water and the reciprocal action with oxygen vacancy on the CO 2 dissociation mechanism on Zn 2 GeO 4 (010). When a perfect surface was hydrated, the introduction of H 2 O was predicted to promote the scission step by two modes based on its appearance, with the greatest enhancement from dissociative adsorbed H 2 O. The dissociative H 2 O lowers the barrier and reaction energy of CO 2 dissociation through hydrogen bonding to preactivate the C-O bond and assisted scission via a COOH intermediate. The perfect surface with bidentate-binding H 2 O was energetically more favorable for CO 2 dissociation than the surface with monodentate-binding H 2 O. Direct dissociation was energetically favored by the former, whereas monodentate H 2 O facilitated the H-assisted pathway. The defective surface exhibited a higher reactivity for CO 2 decomposition than the perfect surface because the generation of oxygen vacancies could disperse the product location. When the defective surface was hydrated, the reciprocal action for vacancy and surface H 2 O on CO 2 dissociation was related to the vacancy type. The presence of H 2 O substantially decreased the reaction energy for the direct dissociation of CO 2 on O 2c1 - and O 3c2 -defect surfaces, which converts the endoergic reaction to an exoergic reaction. However, the increased decomposition barrier made the step kinetically unfavorable and reduced the reaction rate. When H 2 O was present on the O 2c2 -defect surface, both the barrier and reaction energy for direct dissociation were invariable. This result indicated that the introduction of H 2 O had little effect on the kinetics and thermodynamics. Moreover, the H-assisted pathway was suppressed on all hydrated defect surfaces. These results provide a theoretical perspective for the design of highly efficient catalysts.

Surface-Bound Intermediates in Low-Temperature Methanol Synthesis on Copper. Participants and Spectators

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Yong; Mei, Donghai; Peden, Charles H.F.

The reactivity of surface adsorbed species present on copper catalysts during methanol synthesis at low temperatures was studied by simultaneous infrared spectroscopy (IR) and mass spectroscopy (MS) measurements during “titration” (transient surface reaction) experiments with isotopic tracing. The results show that adsorbed formate is a major bystander species present on the surface under steady-state methanol synthesis reaction conditions, but it cannot be converted to methanol by reaction with pure H 2, nor with H 2 plus added water. Formate-containing surface adlayers for these experiments were produced during steady state catalysis in (a) H 2:CO 2 (with substantial formate coverage) andmore » (b) moist H 2:CO (with no IR visible formate species). Both these reaction conditions produce methanol at steady state with relatively high rates. Adlayers containing formate were also produced by (c) formic acid adsorption. Various "titration" gases were used to probe these adlayers at modest temperatures (T = 410-450K) and 6 bar total pressure. Methanol gas (up to ~1% monolayer equivalent) was produced in "titration" from the H 2:CO 2 catalytic adlayers by H 2 plus water, but not by dry hydrogen. The decay in the formate IR features accelerated in the presence of added water vapor. The H 2:CO:H 2O catalytic adlayer produced similar methanol titration yields in H 2 plus water but showed no surface formate features in IR (less than 0.2% monolayer coverage). Finally, formate from formic acid chemisorption produced no methanol under any titration conditions. Even under (H 2:CO 2) catalytic reaction conditions, isotope tracing showed that pre-adsorbed formate from formic acid did not contribute to the methanol produced. Although non-formate intermediates exist during low temperature methanol synthesis on copper which can be converted to methanol gas by titration with pure H 2 plus water in sufficient quantities for that intermediate to be observable by IR, formate itself is only a "spectator" in this reaction and gives no observable methanol upon any titration we performed with H 2 or H 2 plus water.« less

Photosynthesis sensitivity to climate change in land surface models

NASA Astrophysics Data System (ADS)

Manrique-Sunen, Andrea; Black, Emily; Verhoef, Anne; Balsamo, Gianpaolo

2016-04-01

Accurate representation of vegetation processes within land surface models is key to reproducing surface carbon, water and energy fluxes. Photosynthesis determines the amount of CO2 fixated by plants as well as the water lost in transpiration through the stomata. Photosynthesis is calculated in land surface models using empirical equations based on plant physiological research. It is assumed that CO2 assimilation is either CO2 -limited, radiation -limited ; and in some models export-limited (the speed at which the products of photosynthesis are used by the plant) . Increased levels of atmospheric CO2 concentration tend to enhance photosynthetic activity, but the effectiveness of this fertilization effect is regulated by environmental conditions and the limiting factor in the photosynthesis reaction. The photosynthesis schemes at the 'leaf level' used by land surface models JULES and CTESSEL have been evaluated against field photosynthesis observations. Also, the response of photosynthesis to radiation, atmospheric CO2 and temperature has been analysed for each model, as this is key to understanding the vegetation response that climate models using these schemes are able to reproduce. Particular emphasis is put on the limiting factor as conditions vary. It is found that while at present day CO2 concentrations export-limitation is only relevant at low temperatures, as CO2 levels rise it becomes an increasingly important restriction on photosynthesis.

Carbonation of wollastonite(001) competing hydration: microscopic insights from ion spectroscopy and density functional theory.

PubMed

Longo, Roberto C; Cho, Kyeongjae; Brüner, Philipp; Welle, Alexander; Gerdes, Andreas; Thissen, Peter

2015-03-04

In this paper, we report about the influence of the chemical potential of water on the carbonation reaction of wollastonite (CaSiO3) as a model surface of cement and concrete. Total energy calculations based on density functional theory combined with kinetic barrier predictions based on nudge elastic band method show that the exposure of the water-free wollastonite surface to CO2 results in a barrier-less carbonation. CO2 reacts with the surface oxygen and forms carbonate (CO3(2-)) complexes together with a major reconstruction of the surface. The reaction comes to a standstill after one carbonate monolayer has been formed. In case one water monolayer is covering the wollastonite surface, the carbonation is no more barrier-less, yet ending in a localized monolayer. Covered with multilayers of water, the thermodynamic ground state of the wollastonite completely changes due to a metal-proton exchange reaction (also called early stage hydration) and Ca(2+) ions are partially removed from solid phase into the H2O/wollastonite interface. Mobile Ca(2+) reacts again with CO2 and forms carbonate complexes, ending in a delocalized layer. By means of high-resolution time-of-flight secondary-ion mass spectrometry images, we confirm that hydration can lead to a partially delocalization of Ca(2+) ions on wollastonite surfaces. Finally, we evaluate the impact of our model surface results by the meaning of low-energy ion-scattering spectroscopy combined with careful discussion about the competing reactions of carbonation vs hydration.

Interactions and exchange of CO2 and H2O in coals: an investigation by low-field NMR relaxation

NASA Astrophysics Data System (ADS)

Sun, Xiaoxiao; Yao, Yanbin; Liu, Dameng; Elsworth, Derek; Pan, Zhejun

2016-01-01

The mechanisms by which CO2 and water interact in coal remain unclear and these are key questions for understanding ECBM processes and defining the long-term behaviour of injected CO2. In our experiments, we injected helium/CO2 to displace water in eight water-saturated samples. We used low-field NMR relaxation to investigate CO2 and water interactions in these coals across a variety of time-scales. The injection of helium did not change the T2 spectra of the coals. In contrast, the T2 spectra peaks of micro-capillary water gradually decreased and those of macro-capillary and bulk water increased with time after the injection of CO2. We assume that the CO2 diffuses through and/or dissolves into the capillary water to access the coal matrix interior, which promotes desorption of water molecules from the surfaces of coal micropores and mesopores. The replaced water mass is mainly related to the Langmuir adsorption volume of CO2 and increases as the CO2 adsorption capacity increases. Other factors, such as mineral composition, temperature and pressure, also influence the effective exchange between water and CO2. Finally, we built a quantified model to evaluate the efficiency of water replacement by CO2 injection with respect to temperature and pressure.

Interactions and exchange of CO2 and H2O in coals: an investigation by low-field NMR relaxation.

PubMed

Sun, Xiaoxiao; Yao, Yanbin; Liu, Dameng; Elsworth, Derek; Pan, Zhejun

2016-01-28

The mechanisms by which CO2 and water interact in coal remain unclear and these are key questions for understanding ECBM processes and defining the long-term behaviour of injected CO2. In our experiments, we injected helium/CO2 to displace water in eight water-saturated samples. We used low-field NMR relaxation to investigate CO2 and water interactions in these coals across a variety of time-scales. The injection of helium did not change the T2 spectra of the coals. In contrast, the T2 spectra peaks of micro-capillary water gradually decreased and those of macro-capillary and bulk water increased with time after the injection of CO2. We assume that the CO2 diffuses through and/or dissolves into the capillary water to access the coal matrix interior, which promotes desorption of water molecules from the surfaces of coal micropores and mesopores. The replaced water mass is mainly related to the Langmuir adsorption volume of CO2 and increases as the CO2 adsorption capacity increases. Other factors, such as mineral composition, temperature and pressure, also influence the effective exchange between water and CO2. Finally, we built a quantified model to evaluate the efficiency of water replacement by CO2 injection with respect to temperature and pressure.

Interactions and exchange of CO2 and H2O in coals: an investigation by low-field NMR relaxation

PubMed Central

Sun, Xiaoxiao; Yao, Yanbin; Liu, Dameng; Elsworth, Derek; Pan, Zhejun

2016-01-01

The mechanisms by which CO2 and water interact in coal remain unclear and these are key questions for understanding ECBM processes and defining the long-term behaviour of injected CO2. In our experiments, we injected helium/CO2 to displace water in eight water-saturated samples. We used low-field NMR relaxation to investigate CO2 and water interactions in these coals across a variety of time-scales. The injection of helium did not change the T2 spectra of the coals. In contrast, the T2 spectra peaks of micro-capillary water gradually decreased and those of macro-capillary and bulk water increased with time after the injection of CO2. We assume that the CO2 diffuses through and/or dissolves into the capillary water to access the coal matrix interior, which promotes desorption of water molecules from the surfaces of coal micropores and mesopores. The replaced water mass is mainly related to the Langmuir adsorption volume of CO2 and increases as the CO2 adsorption capacity increases. Other factors, such as mineral composition, temperature and pressure, also influence the effective exchange between water and CO2. Finally, we built a quantified model to evaluate the efficiency of water replacement by CO2 injection with respect to temperature and pressure. PMID:26817784

Migration of carbon dioxide included micro-nano bubble water in porous media and its monitoring

NASA Astrophysics Data System (ADS)

Takemura, T.; Hamamoto, S.; Suzuki, K.; Koichi, O.

2017-12-01

The distributed CO2 storage is the small scale storage and its located near the emission areas. In the distributed CO2 storage, the CO2 is neutralized by sediment and underground water in the subsurface region (300-500m depth). Carbon dioxide (CO2) included micro-nano bubbles is one approach in neutralizing CO2 and sediments by increasing CO2 volume per unit volume of water and accelerating the chemical reaction. In order to design underground treatment for CO2 gas in the subsurface, it is required to elucidate the behavior of CO2 included micro-nano bubbles in the water. In this study, we carried out laboratory experiment using the soil tank, and measure the amount of leakage of CO2 gas at the surface. In addition, the process of migration of carbon dioxide included micro-nano bubble was monitored by the nondestructive method, wave velocity and resistivity.

Liquid water on Mars - an energy balance climate model for CO2/H2O atmospheres

NASA Astrophysics Data System (ADS)

Hoffert, M. I.; Callegari, A. J.; Hsieh, T.; Ziegler, W.

1981-07-01

A simple climatic model is developed for a Mars atmosphere containing CO2 and sufficient liquid water to account for the observed hydrologic surface features by the existence of a CO2/H2O greenhouse effect. A latitude-resolved climate model originally devised for terrestrial climate studies is applied to Martian conditions, with the difference between absorbed solar flux and emitted long-wave flux to space per unit area attributed to the divergence of the meridional heat flux and the poleward heat flux assumed to equal the atmospheric eddy heat flux. The global mean energy balance is calculated as a function of atmospheric pressure to assess the CO2/H2O greenhouse liquid water hypothesis, and some latitude-resolved cases are examined in detail in order to clarify the role of atmospheric transport and temperature-albedo feedback. It is shown that the combined CO2/H2O greenhouse at plausible early surface pressures may account for climates hot enough to support a hydrological cycle and running water at present-day insolation and visible albedo levels.

Liquid water on Mars - An energy balance climate model for CO2/H2O atmospheres

NASA Technical Reports Server (NTRS)

Hoffert, M. I.; Callegari, A. J.; Hsieh, C. T.; Ziegler, W.

1981-01-01

A simple climatic model is developed for a Mars atmosphere containing CO2 and sufficient liquid water to account for the observed hydrologic surface features by the existence of a CO2/H2O greenhouse effect. A latitude-resolved climate model originally devised for terrestrial climate studies is applied to Martian conditions, with the difference between absorbed solar flux and emitted long-wave flux to space per unit area attributed to the divergence of the meridional heat flux and the poleward heat flux assumed to equal the atmospheric eddy heat flux. The global mean energy balance is calculated as a function of atmospheric pressure to assess the CO2/H2O greenhouse liquid water hypothesis, and some latitude-resolved cases are examined in detail in order to clarify the role of atmospheric transport and temperature-albedo feedback. It is shown that the combined CO2/H2O greenhouse at plausible early surface pressures may account for climates hot enough to support a hydrological cycle and running water at present-day insolation and visible albedo levels.

Effect of the greenhouse gases (CO2, H2O, SO2) on Martian paleoclimate

NASA Technical Reports Server (NTRS)

Postawko, S. E.; Kuhn, W. R.

1986-01-01

There is general agreement that certain surface features on Mars are indicative of the presence of liquid water at various times in the geologic past. In particular, the valley networks are difficult to explain by a mechanism other than the flow of liquid water. It has been suggested in several studies that a thick CO2 atmosphere on Mars early in its history could have provided a greenhouse warming that would have allowed the flow of water either on the surface or just below the surface. However, this effect was examined with a detailed radiation model, and it was found that if reduced solar luminosity early in the history of the solar system is taken into account, even three bars of CO2 will not provide sufficient greeenhouse warming. The addition of water vapor and sulflur dioxide (both plausible gases that may have been emitted by Martian volcanoes) to the atmosphere also fail to warm the surface above 273 K for reduced solar luminosity conditions. The increase in temperature may be large enough, however, for the formation of these features by brines.

Dewetting of silica surfaces upon reactions with supercritical CO2 and brine: pore-scale studies in micromodels.

PubMed

Kim, Yongman; Wan, Jiamin; Kneafsey, Timothy J; Tokunaga, Tetsu K

2012-04-03

Wettability of reservoir minerals and rocks is a critical factor controlling CO(2) mobility, residual trapping, and safe-storage in geologic carbon sequestration, and currently is the factor imparting the greatest uncertainty in predicting capillary behavior in porous media. Very little information on wettability in supercritical CO(2) (scCO(2))-mineral-brine systems is available. We studied pore-scale wettability and wettability alteration in scCO(2)-silica-brine systems using engineered micromodels (transparent pore networks), at 8.5 MPa and 45 °C, over a wide range of NaCl concentrations up to 5.0 M. Dewetting of silica surfaces upon reactions with scCO(2) was observed through water film thinning, water droplet formation, and contact angle increases within single pores. The brine contact angles increased from initial values near 0° up to 80° with larger increases under higher ionic strength conditions. Given the abundance of silica surfaces in reservoirs and caprocks, these results indicate that CO(2) induced dewetting may have important consequences on CO(2) sequestration including reducing capillary entry pressure, and altering quantities of CO(2) residual trapping, relative permeability, and caprock integrity.

Remote-Raman and Micro-Raman Studies of Solid CO2, CH4, Gas Hydrates and Ice

NASA Technical Reports Server (NTRS)

Sharma, S. K.; Misra, A. K.; Lucey, P. G.; Exarhos, G. J.; Windisch, C. F., Jr.

2004-01-01

It is well known that on Mars CO2 is the principal constituent of the thin atmosphere and on a seasonal basis CO2 snow and frost coats the polar caps. Also over 25% of the Martian atmosphere freezes out and sublimes again each year. The Mars Odyssey Emission Imaging system (THEMIS) has discovered water ice exposed near the edge of Mars southern perennials cap. In recent years, it has been suggested that in Martian subsurface CO2 may exist as gas hydrate (8CO2 + 44 H2O) with melting temperature of 10C. Since the crust of Mars has been stable for enough time there is also a possibility that methane formed by magmatic processes and/or as a byproduct of anaerobic deep biosphere activity to have raised toward the planet s surface. This methane would have been captured and stored as methane hydrate, which concentrates methane and water. Determination of abundance and distribution of these ices on the surface and in the near surface are of fundamental importance for understanding Martian atmosphere, and for future exploration of Mars. In this work, we have evaluated feasibility of using remote Raman and micro-Raman spectroscopy as potential nondestructive and non-contact techniques for detecting solid CO2, CH4 gas, and gas hydrates as well as water-ice on planetary surfaces.

Energy, chemical disequilibrium, and geological constraints on Europa.

PubMed

Hand, Kevin P; Carlson, Robert W; Chyba, Christopher F

2007-12-01

Europa is a prime target for astrobiology. The presence of a global subsurface liquid water ocean and a composition likely to contain a suite of biogenic elements make it a compelling world in the search for a second origin of life. Critical to these factors, however, may be the availability of energy for biological processes on Europa. We have examined the production and availability of oxidants and carbon-containing reductants on Europa to better understand the habitability of the subsurface ocean. Data from the Galileo Near-Infrared Mapping Spectrometer were used to constrain the surface abundance of CO(2) to 0.036% by number relative to water. Laboratory results indicate that radiolytically processed CO(2)-rich ices yield CO and H(2)CO(3); the reductants H(2)CO, CH(3)OH, and CH(4) are at most minor species. We analyzed chemical sources and sinks and concluded that the radiolytically processed surface of Europa could serve to maintain an oxidized ocean even if the surface oxidants (O(2), H(2)O(2), CO(2), SO(2), and SO(4) (2)) are delivered only once every approximately 0.5 Gyr. If delivery periods are comparable to the observed surface age (30-70 Myr), then Europa's ocean could reach O(2) concentrations comparable to those found in terrestrial surface waters, even if approximately 10(9) moles yr(1) of hydrothermally delivered reductants consume most of the oxidant flux. Such an ocean would be energetically hospitable for terrestrial marine macrofauna. The availability of reductants could be the limiting factor for biologically useful chemical energy on Europa.

Controllable Surface Reorganization Engineering on Cobalt Phosphide Nanowire Arrays for Efficient Alkaline Hydrogen Evolution Reaction.

PubMed

Xu, Kun; Cheng, Han; Lv, Haifeng; Wang, Jingyu; Liu, Linqi; Liu, Si; Wu, Xiaojun; Chu, Wangsheng; Wu, Changzheng; Xie, Yi

2018-01-01

Developing highly efficient hydrogen evolution reaction (HER) catalysts in alkaline media is considered significant and valuable for water splitting. Herein, it is demonstrated that surface reorganization engineering by oxygen plasma engraving on electocatalysts successfully realizes a dramatically enhanced alkaline HER activity. Taking CoP nanowire arrays grown on carbon cloth (denoted as CoP NWs/CC) as an example, the oxygen plasma engraving can trigger moderate CoO x species formation on the surface of the CoP NWs/CC, which is visually verified by the X-ray absorption fine structure, high-resolution transmission electron microscopy, and energy-dispersive spectrometer (EDS) mapping. Benefiting from the moderate CoO x species formed on the surface, which can promote the water dissociation in alkaline HER, the surface reorganization of the CoP NWs/CC realizes almost fourfold enhanced alkaline HER activity and a 180 mV decreased overpotential at 100 mA cm -2 , compared with the pristine ones. More interestingly, this surface reorganization strategy by oxygen plasma engraving can also be effective to other electrocatalysts such as free-standing CoP, Co 4 N, O-CoSe 2 , and C-CoSe 2 nanowires, which verifies the universality of the strategy. This work thus opens up new avenues for designing alkaline HER electrocatalysts based on oxygen plasma engraving. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Aluminosilicate Dissolution and Silicate Carbonation during Geologic CO2 Sequestration

NASA Astrophysics Data System (ADS)

Min, Yujia

Geologic CO2 sequestration (GCS) is considered a promising method to reduce anthropogenic CO2 emission. Assessing the supercritical CO2 (scCO2) gas or liquid phase water (g, l)-mineral interactions is critical to evaluating the viability of GCS processes. This work contributes to our understanding of geochemical reactions at CO 2-water (g, l)-mineral interfaces, by investigating the dissolution of aluminosilicates in CO2-acidified water (l). Plagioclase and biotite were chosen as model minerals in reservoir rock and caprock, respectively. To elucidate the effects of brine chemistry, first, the influences of cations in brine including Na, Ca, and K, have been investigated. In addition to the cations, the effects of abundant anions including sulfate and oxalate were also examined. Besides the reactions in aqueous phase, we also examine the carbonation of silicates in water (g)-bearing supercritical CO2 (scCO2) under conditions relevant to GCS. For the metal carbonation, in particular, the effects of particle sizes, water, temperature, and pressure on the carbonation of wollastonite were systematically examined. For understanding the cations effects in brine, the impacts of Na concentrations up to 4 M on the dissolution of plagioclase and biotite were examined. High concentrations of Na significantly inhibited plagioclase dissolution by competing adsorption with proton and suppressing proton-promoted dissolution. Ca has a similar effect to Na, and their effects did not suppress each other when Na and Ca co-existed. For biotite, the inhibition effects of Na coupled with an enhancing effect due to ion exchange reaction between Na and interlayer K, which cracked the basal surfaces of biotite. The K in aqueous phase significantly inhibited the dissolution. If the biotite is equilibrated with NaCl solutions initially, the biotite dissolved faster than the original biotite and the dissolution was inhibited by Na and K in brine. The outcomes improve our current knowledge of silicates dissolution to the high salinity conditions in subsurface environments. In addition to cations, the role of anions in geochemical reactions in subsurfaces are important. This study investigated the anion effects by studying sulfate and oxalate. Sulfate formed monodentate surface complexes with the Al sites on plagioclase surface and enhanced the dissolution. Oxalate was also found to enhance the plagioclase dissolution. Co-existing oxalate and sulfate suppressed the effects of sulfate on plagioclase dissolution. This information provides useful insights for understanding the roles of sulfate and organic compounds on the CO2 water-mineral interactions during scCO2 enhanced oil recovery. The results also aid in formulating a scientific guideline of the proper amount of SO2 co-injection with CO2. Water in GCS sites can exist in water-bearing scCO2 in addition to the aqueous phase in brine. Thus, it is important to understand the effects of water-bearing scCO2 on the carbonation of silicates. To address the gap between the nano- and micro-sized particles used in the laboratory to the large grains in field sites, we utilized wollastonite and investigated the effects of particle sizes on the wollastonite carbonation in water-bearing scCO2. The thickness of the reacted layer on the particle surfaces was found to be constant for different sized particles. The amorphous silica layer formed act as a diffusion barrier for water-bearing scCO2. In addition, the reaction extent was higher with more water, lower temperature, and higher pressure. Further, higher water saturation percentage and lower temperature can lead to the formation of more permeable amorphous silica layers. This thesis included the investigations of both liquid phase and vapor phase water that contacted with scCO2, and the effects of cations and anions on both formation and caprock minerals. The findings from this work improve our knowledge of the geochemical reactions at CO2-water-mineral interfaces, which will help us design a safer GCS operation and assess the impacts of GCS on the environmental safety and quality.

Wettability of supercritical carbon dioxide/water/quartz systems: simultaneous measurement of contact angle and interfacial tension at reservoir conditions.

PubMed

Saraji, Soheil; Goual, Lamia; Piri, Mohammad; Plancher, Henry

2013-06-11

Injection of carbon dioxide in deep saline aquifers is considered as a method of carbon sequestration. The efficiency of this process is dependent on the fluid-fluid and rock-fluid interactions inside the porous media. For instance, the final storage capacity and total amount of capillary-trapped CO2 inside an aquifer are affected by the interfacial tension between the fluids and the contact angle between the fluids and the rock mineral surface. A thorough study of these parameters and their variations with temperature and pressure will provide a better understanding of the carbon sequestration process and thus improve predictions of the sequestration efficiency. In this study, the controversial concept of wettability alteration of quartz surfaces in the presence of supercritical carbon dioxide (sc-CO2) was investigated. A novel apparatus for measuring interfacial tension and contact angle at high temperatures and pressures based on Axisymmetric Drop Shape Analysis with no-Apex (ADSA-NA) method was developed and validated with a simple system. Densities, interfacial tensions, and dynamic contact angles of CO2/water/quartz systems were determined for a wide range of pressures and temperatures relevant to geological sequestration of CO2 in the subcritical and supercritical states. Image analysis was performed with ADSA-NA method that allows the determination of both interfacial tensions and contact angles with high accuracy. The results show that supercritical CO2 alters the wettability of quartz surface toward less water-wet conditions compared to subcritical CO2. Also we observed an increase in the water advancing contact angles with increasing temperature indicating less water-wet quartz surfaces at higher temperatures.

Undoped and Ni-doped CoO x surface modification of porous BiVO 4 photoelectrodes for water oxidation

DOE PAGES

Liu, Ya; Guo, Youhong; Schelhas, Laura T.; ...

2016-09-29

Surface modification of photoanodes with oxygen evolution reaction (OER) catalysts is an effective approach to enhance water oxidation kinetics, to reduce external bias, and to improve the energy harvesting efficiency of photoelectrochemical (PEC) water oxidation. Here, the surface of porous BiVO 4 photoanodes was modified by the deposition of undoped and Ni-doped CoO x via nitrogen flow assisted electrostatic spray pyrolysis. This newly developed atmospheric pressure deposition technique allows for surface coverage throughout the porous structure with thickness and composition control. PEC testing of modified BiVO 4 photoanodes shows that after deposition of an undoped CoO x surface layer, themore » onset potential shifts negatively by ca. 420 mV and the photocurrent density reaches 2.01 mA cm –2 at 1.23 vs V RHE under AM 1.5G illumination. Modification with Ni-doped CoO x produces even more effective OER catalysis and yields a photocurrent density of 2.62 mA cm –2 at 1.23 V RHE under AM 1.5G illumination. Furthermore, the valence band X-ray photoelectron spectroscopy and synchrotron-based X-ray absorption spectroscopy results show the Ni doping reduces the Fermi level of the CoO x layer; the increased surface band bending produced by this effect is partially responsible for the superior PEC performance.« less

OpenGeoSys: An Open-Source Initiative for Numerical Simulation of Thermo-Hydro-Mechanical/Chemical (THM/C) Processes in Porous Media

NASA Astrophysics Data System (ADS)

Watanabe, N.; Bilke, L.; Fischer, T.; Kalbacher, T.; Nagel, T.; Naumov, D.; Rink, K.; Shao, H.; Wang, W.; Kolditz, O.

2014-12-01

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

The nature of the air-cleaved mica surface

NASA Astrophysics Data System (ADS)

Christenson, Hugo K.; Thomson, Neil H.

2016-06-01

The accepted image of muscovite mica is that of an inert and atomically smooth surface, easily prepared by cleavage in an ambient atmosphere. Consequently, mica is extensively used a model substrate in many fundamental studies of surface phenomena and as a substrate for AFM imaging of biomolecules. In this review we present evidence from the literature that the above picture is not quite correct. The mica used in experimental work is almost invariably cleaved in laboratory air, where a reaction between the mica surface, atmospheric CO2 and water occurs immediately after cleavage. The evidence suggests very strongly that as a result the mica surface becomes covered by up to one formula unit of K2CO3 per nm2, which is mobile under humid conditions, and crystallises under drier conditions. The properties of mica in air or water vapour cannot be fully understood without reference to the surface K2CO3, and many studies of the structure of adsorbed water on mica surfaces may need to be revisited. With this new insight, however, the air-cleaved mica should provide exciting opportunities to study phenomena such as two-dimensional ion diffusion, electrolyte effects on surface conductivity, and two-dimensional crystal nucleation.

Variability of pCO2 in surface waters and development of prediction model.

PubMed

Chung, Sewoong; Park, Hyungseok; Yoo, Jisu

2018-05-01

Inland waters are substantial sources of atmospheric carbon, but relevant data are rare in Asian monsoon regions including Korea. Emissions of CO 2 to the atmosphere depend largely on the partial pressure of CO 2 (pCO 2 ) in water; however, measured pCO 2 data are scarce and calculated pCO 2 can show large uncertainty. This study had three objectives: 1) to examine the spatial variability of pCO 2 in diverse surface water systems in Korea; 2) to compare pCO 2 calculated using pH-total alkalinity (Alk) and pH-dissolved inorganic carbon (DIC) with pCO 2 measured by an in situ submersible nondispersive infrared detector; and 3) to characterize the major environmental variables determining the variation of pCO 2 based on physical, chemical, and biological data collected concomitantly. Of 30 samples, 80% were found supersaturated in CO 2 with respect to the overlying atmosphere. Calculated pCO 2 using pH-Alk and pH-DIC showed weak prediction capability and large variations with respect to measured pCO 2 . Error analysis indicated that calculated pCO 2 is highly sensitive to the accuracy of pH measurements, particularly at low pH. Stepwise multiple linear regression (MLR) and random forest (RF) techniques were implemented to develop the most parsimonious model based on 10 potential predictor variables (pH, Alk, DIC, Uw, Cond, Turb, COD, DOC, TOC, Chla) by optimizing model performance. The RF model showed better performance than the MLR model, and the most parsimonious RF model (pH, Turb, Uw, Chla) improved pCO 2 prediction capability considerably compared with the simple calculation approach, reducing the RMSE from 527-544 to 105μatm at the study sites. Copyright © 2017 Elsevier B.V. All rights reserved.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bryan, Charles R.; Dewers, Thomas A.; Heath, Jason E.

2013-09-01

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

Carbon dioxide and methane emissions from the Yukon River system

USGS Publications Warehouse

Striegl, Robert G.; Dornblaser, Mark M.; McDonald, Cory P.; Rover, Jennifer R.; Stets, Edward G.

2012-01-01

Carbon dioxide (CO2) and methane (CH4) emissions are important, but poorly quantified, components of riverine carbon (C) budgets. This is largely because the data needed for gas flux calculations are sparse and are spatially and temporally variable. Additionally, the importance of C gas emissions relative to lateral C exports is not well known because gaseous and aqueous fluxes are not commonly measured on the same rivers. We couple measurements of aqueous CO2 and CH4 partial pressures (pCO2, pCH4) and flux across the water-air interface with gas transfer models to calculate subbasin distributions of gas flux density. We then combine those flux densities with remote and direct observations of stream and river water surface area and ice duration, to calculate C gas emissions from flowing waters throughout the Yukon River basin. CO2emissions were 7.68 Tg C yr−1 (95% CI: 5.84 −10.46), averaging 750 g C m−2 yr−1 normalized to water surface area, and 9.0 g C m−2 yr−1 normalized to river basin area. River CH4 emissions totaled 55 Gg C yr−1 or 0.7% of the total mass of C emitted as CO2 plus CH4 and ∼6.4% of their combined radiative forcing. When combined with lateral inorganic plus organic C exports to below head of tide, C gas emissions comprised 50% of total C exported by the Yukon River and its tributaries. River CO2 and CH4 derive from multiple sources, including groundwater, surface water runoff, carbonate equilibrium reactions, and benthic and water column microbial processing of organic C. The exact role of each of these processes is not yet quantified in the overall river C budget.

Effect of water vapor on evolution of a thick Pt-layer modified oxide on the NiCoCrAl alloy at high temperature

NASA Astrophysics Data System (ADS)

Song, Peng; He, Xuan; Xiong, Xiping; Ma, Hongqing; Song, Qunling; Lü, Jianguo; Lu, Jiansheng

2018-03-01

To investigate the effect of water vapor on the novel Pt-containing oxide growth behavior, Pt-addition within the oxide layer on the surface of NiCoCrAl coating and furnace cycle tests were carried out at 1050 °C in air and air plus water vapor. The thick Pt-containing oxide layer on NiCoCrAl exhibits a different oxidation growth behavior compared to the conventional Pt-diffusion metallic coatings. The Pt-containing oxide after oxidation in air plus water vapor showed a much thicker oxide layer compare to the ones without Pt addition, and also presented a much better coating adhesion. During the oxidation process in air, Pt promotes the spinel (NiCr2O4) formation. However, the Cr2O3 formed in air with water vapor and fixed Pt within the complex oxide layer. The water vapor promoted the Ni and Co outer-diffusion, and combined with Pt to form CoPt compounds on the surface of the NiCoCrAl coating system.

Interactions between iron and organic matter may influence the fate of permafrost carbon in the Arctic

NASA Astrophysics Data System (ADS)

Cory, R. M.; Trusiak, A.; Ward, C.; Kling, G. W.; Tfaily, M.; Paša-Tolić, L.; Noel, V.; Bargar, J.

2017-12-01

The ongoing thawing of permafrost soils is the only environmental change that allows tremendous stores of organic carbon (C) to be converted into carbon dioxide (CO2) on decadal time scales, thus providing a positive and accelerating feedback to global warming. Evidence suggests that iron enhances abiotic reactions that convert dissolved organic matter (DOM) to CO2 in dark soils and in sunlit surface waters depending on its redox state and association with DOM (i.e., iron-DOM complexation). However, the complexation of iron in surface waters and soils remains too poorly understood to predict how iron influences the rates of oxidation of DOM to CO2. To address this knowledge gap, we characterized iron-DOM complexation in iron-rich soil and surface waters of the Arctic, in combination with measurements of DOM oxidation to CO2. These waters contain high concentrations of dissolved iron and DOM (up to 1 and 2 mM, respectively), and low concentrations of other potential ligands for iron such as sulfide, carbonate, chloride, or bromide. Ultra-high resolution mass spectrometry (FT-ICR MS) was used to identify ligands for iron within the DOM pool, and synchrotron based X-ray analysis (XAS and EXAFS) was used to assess iron's oxidation state, to detect iron complexation, and to constrain the chemical composition of the complexes. Across a natural gradient of dissolved iron and DOM concentrations, many potential ligands were identified within DOM that are expected to complex with iron (e.g., aromatic acids). EXAFS showed substantial complexation of reduced ferrous iron (Fe(II)) to DOM in arctic soil waters, on the basis of comparison to Fe(II)-DOM reference spectra. Identification of iron complexed to DOM in soil waters is consistent with strongly co-varying iron and DOM concentrations in arctic soil and surface waters, and supports our hypothesis that complexation of iron by DOM influences dark and light redox reactions that oxidize DOM to CO2. Understanding the molecular controls on the biogeochemical reactions that convert permafrost carbon to CO2 is critical for understanding the role of the Arctic in current and future climate change.

Early stages in the evolution of the atmosphere and climate on the Earth-group planets

NASA Technical Reports Server (NTRS)

Moroz, V. I.; Mukhin, L. M.

1977-01-01

The early evolution of the atmospheres and climate of the Earth, Mars and Venus is discussed, based on a concept of common initial conditions and main processes (besides known differences in chemical composition and outgassing rate). It is concluded that: (1) liquid water appeared on the surface of the earth in the first few hundred million years; the average surface temperature was near the melting point for about the first two eons; CO2 was the main component of the atmosphere in the first 100-500 million years; (2) much more temperate outgassing and low solar heating led to the much later appearance of liquid water on the Martian surface, only one to two billion years ago; the Martian era of rivers, relatively dense atmosphere and warm climate ended as a result of irreversible chemical bonding of CO2 by Urey equilibrium processes; (3) a great lack of water in the primordial material of Venus is proposed; liquid water never was present on the surface of the planet, and there was practically no chemical bonding of CO2; the surface temperature was over 600 K four billion years ago.

Energetics of CO2 and H2O adsorption on zinc oxide.

PubMed

Gouvêa, Douglas; Ushakov, Sergey V; Navrotsky, Alexandra

2014-08-05

Adsorption of H2O and CO2 on zinc oxide surfaces was studied by gas adsorption calorimetry on nanocrystalline samples prepared by laser evaporation in oxygen to minimize surface impurities and degassed at 450 °C. Differential enthalpies of H2O and CO2 chemisorption are in the range -150 ±10 kJ/mol and -110 ±10 kJ/mol up to a coverage of 2 molecules per nm(2). Integral enthalpy of chemisorption for H2O is -96.8 ±2.5 kJ/mol at 5.6 H2O/nm(2) when enthalpy of water condensation is reached, and for CO2 is -96.6 ±2.5 kJ/mol at 2.6 CO2/nm(2) when adsorption ceases. These values are consistent with those reported for ZnO prepared by other methods after similar degas conditions. The similar energetics suggests possible competition of CO2 and H2O for binding to ZnO surfaces. Exposure of bulk and nanocrystalline ZnO with preadsorbed CO2 to water vapor results in partial displacement of CO2 by H2O. In contrast, temperature-programmed desorption (TPD) indicates that a small fraction of CO2 is retained on ZnO surfaces up to 800 °C, under conditions where all H2O is desorbed, with adsorption energies near -200 kJ/mol. Although molecular mechanisms of adsorption were not studied, the thermodynamic data are consistent with dissociative adsorption of H2O at low coverage and with several different modes of CO2 binding.

Surface chemistry of carbon dioxide revisited

NASA Astrophysics Data System (ADS)

Taifan, William; Boily, Jean-François; Baltrusaitis, Jonas

2016-12-01

This review discusses modern developments in CO2 surface chemistry by focusing on the work published since the original review by H.J. Freund and M.W. Roberts two decades ago (Surface Science Reports 25 (1996) 225-273). It includes relevant fundamentals pertaining to the topics covered in that earlier review, such as conventional metal and metal oxide surfaces and CO2 interactions thereon. While UHV spectroscopy has routinely been applied for CO2 gas-solid interface analysis, the present work goes further by describing surface-CO2 interactions under elevated CO2 pressure on non-oxide surfaces, such as zeolites, sulfides, carbides and nitrides. Furthermore, it describes additional salient in situ techniques relevant to the resolution of the interfacial chemistry of CO2, notably infrared spectroscopy and state-of-the-art theoretical methods, currently used in the resolution of solid and soluble carbonate species in liquid-water vapor, liquid-solid and liquid-liquid interfaces. These techniques are directly relevant to fundamental, natural and technological settings, such as heterogeneous and environmental catalysis and CO2 sequestration.

Subsurface capture of carbon dioxide

DOEpatents

Blount, Gerald; Siddal, Alvin A.; Falta, Ronald W.

2014-07-22

A process and apparatus of separating CO.sub.2 gas from industrial off-gas source in which the CO.sub.2 containing off-gas is introduced deep within an injection well. The CO.sub.2 gases are dissolved in the, liquid within the injection well while non-CO.sub.2 gases, typically being insoluble in water or brine, are returned to the surface. Once the CO.sub.2 saturated liquid is present within the injection well, the injection well may be used for long-term geologic storage of CO.sub.2 or the CO.sub.2 saturated liquid can be returned to the surface for capturing a purified CO.sub.2 gas.

Atmospheric Collapse on Early Mars: The Role of CO2 Clouds

NASA Technical Reports Server (NTRS)

Kahre, M. A.; Haberle, R. M.; Steakley, K. E.; Murphy, J. R.; Kling, A.

2017-01-01

The abundance of evidence that liquid water flowed on the surface early in Mars' history strongly implies that the early Martian atmosphere was significantly more massive than it is today. While it seems clear that the total CO2 inventory was likely substantially larger in the past, the fundamental question about the physical state of that CO2 is not completely understood. Because the temperature at which CO2 condenses increases with surface pressure, surface CO2 ice is more likely to form and persist as the atmospheric mass increases. For the atmosphere to remain stable against collapse, there must be enough energy, distributed planet wide, to stave off the formation of permanent CO2 caps that leads to atmospheric collapse. The presence of a "faint young sun" that was likely about 25 percent less luminous 3.8 billion years ago than the sun today makes this even more difficult. Several physical processes play a role in the ultimate stability of a CO2 atmosphere. The system is regulated by the energy balance between solar insolation, the radiative effects of the atmosphere and its constituents, atmospheric heat transport, heat exchange between the surface and the atmosphere, and latent heating/cooling. Specific considerations in this balance for a given orbital obliquity/eccentricity and atmospheric mass are the albedo of the caps, the dust content of the atmosphere, and the presence of water and/or CO2 clouds. Forget et al. show that, for Mars' current obliquity (in a circular orbit), CO2 atmospheres ranging in surface pressure from 500 hectopascals to 3000 hectopascals would have been stable against collapsing into permanent surface ice reservoirs. Soto et al. examined a similar range in initial surface pressure to investigate atmospheric collapse and to compute collapse rates. CO2 clouds and their radiative effects were included in Forget et al. but they were not included in Soto et al. Here we focus on how CO2 clouds affect the stability of the atmosphere against collapse.

Process-based approach for the detection of deep gas invading the surface

DOEpatents

Romanak, Katherine; Bennett, Philip C.

2017-05-09

The present invention includes a method for determining the level of deep gas in a near surface formation that includes: measuring CO.sub.2, O.sub.2, CH.sub.4, and N.sub.2 levels in percent by volume from one or more surface or near surface geological samples; adding the water vapor content to the measured CO.sub.2, O.sub.2, CH.sub.4, and N.sub.2 levels in percent by volume; normalizing the gas mixture to 100% by volume or 1 atmospheric total pressure; and determining the ratios of: O.sub.2 versus CO.sub.2 to distinguish in-situ vadose zone CO.sub.2 from exogenous deep leakage CO.sub.2; CO.sub.2 versus N.sub.2 to distinguish whether CO.sub.2 is being removed from the near surface formation or CO.sub.2 is added from an exogenous deep leakage input; or CO.sub.2 versus N.sub.2/O.sub.2 to determine the degree of oxygen influx, consumption, or both; wherein the ratios are indicative of natural in situ CO.sub.2 or CO.sub.2 from the exogenous deep leakage input.

CO2-Water-Rock Wettability: Variability, Influencing Factors, and Implications for CO2 Geostorage.

PubMed

Iglauer, Stefan

2017-05-16

Carbon geosequestration (CGS) has been identified as a key technology to reduce anthropogenic greenhouse gas emissions and thus significantly mitigate climate change. In CGS, CO 2 is captured from large point-source emitters (e.g., coal fired power stations), purified, and injected deep underground into geological formations for disposal. However, the CO 2 has a lower density than the resident formation brine and thus migrates upward due to buoyancy forces. To prevent the CO 2 from leaking back to the surface, four trapping mechanisms are used: (1) structural trapping (where a tight caprock acts as a seal barrier through which the CO 2 cannot percolate), (2) residual trapping (where the CO 2 plume is split into many micrometer-sized bubbles, which are immobilized by capillary forces in the pore network of the rock), (3) dissolution trapping (where CO 2 dissolves in the formation brine and sinks deep into the reservoir due to a slight increase in brine density), and (4) mineral trapping (where the CO 2 introduced into the subsurface chemically reacts with the formation brine or reservoir rock or both to form solid precipitates). The efficiency of these trapping mechanisms and the movement of CO 2 through the rock are strongly influenced by the CO 2 -brine-rock wettability (mainly due to the small capillary-like pores in the rock which form a complex network), and it is thus of key importance to rigorously understand CO 2 -wettability. In this context, a substantial number of experiments have been conducted from which several conclusions can be drawn: of prime importance is the rock surface chemistry, and hydrophilic surfaces are water-wet while hydrophobic surfaces are CO 2 -wet. Note that CO 2 -wet surfaces dramatically reduce CO 2 storage capacities. Furthermore, increasing pressure, salinity, or dissolved ion valency increases CO 2 -wettability, while the effect of temperature is not well understood. Indeed theoretical understanding of CO 2 -wettability and the ability to quantitatively predict it are currently limited although recent advances have been made. Moreover, data for real storage rock and real injection gas (which contains impurities) is scarce and it is an open question how realistic subsurface conditions can be reproduced in laboratory experiments. In conclusion, however, it is clear that in principal CO 2 -wettability can vary drastically from completely water-wet to almost completely CO 2 -wet, and this possible variation introduces a large uncertainty into trapping capacity and containment security predictions.

Acidification at the Surface in the East Sea: A Coupled Climate-carbon Cycle Model Study

NASA Astrophysics Data System (ADS)

Park, Young-Gyu; Seol, Kyung-Hee; Boo, Kyung-On; Lee, Johan; Cho, Chunho; Byun, Young-Hwa; Seo, Seongbong

2018-05-01

This modeling study investigates the impacts of increasing atmospheric CO2 concentration on acidification in the East Sea. A historical simulation for the past three decades (1980 to 2010) was performed using the Hadley Centre Global Environmental Model (version 2), a coupled climate model with atmospheric, terrestrial and ocean cycles. As the atmospheric CO2 concentration increased, acidification progressed in the surface waters of the marginal sea. The acidification was similar in magnitude to observations and models of acidification in the global ocean. However, in the global ocean, the acidification appears to be due to increased in-situ oceanic CO2 uptake, whereas local processes had stronger effects in the East Sea. pH was lowered by surface warming and by the influx of water with higher dissolved inorganic carbon (DIC) from the northwestern Pacific. Due to the enhanced advection of DIC, the partial pressure of CO2 increased faster than in the overlying air; consequently, the in-situ oceanic uptake of CO2 decreased.

Effect of Leaf Water Potential on Internal Humidity and CO 2 Dissolution: Reverse Transpiration and Improved Water Use Efficiency under Negative Pressure

DOE PAGES

Vesala, Timo; Sevanto, Sanna; Grönholm, Tiia; ...

2017-02-06

The pull of water from the soil to the leaves causes water in the transpiration stream to be under negative pressure decreasing the water potential below zero. The osmotic concentration also contributes to the decrease in leaf water potential but with much lesser extent. Thus, the surface tension force is approximately balanced by a force induced by negative water potential resulting in concavely curved water-air interfaces in leaves. The lowered water potential causes a reduction in the equilibrium water vapor pressure in internal (sub-stomatal/intercellular) cavities in relation to that over water with the potential of zero, i.e., over the flatmore » surface. The curved surface causes a reduction also in the equilibrium vapor pressure of dissolved CO 2, thus enhancing its physical solubility to water. Although the water vapor reduction is acknowledged by plant physiologists its consequences for water vapor exchange at low water potential values have received very little attention. Consequences of the enhanced CO 2 solubility to a leaf water-carbon budget have not been considered at all before this study. We use theoretical calculations and modeling to show how the reduction in the vapor pressures affects transpiration and carbon assimilation rates. Here, our results indicate that the reduction in vapor pressures of water and CO 2 could enhance plant water use efficiency up to about 10% at a leaf water potential of -2 MPa, and much more when water potential decreases further. The low water potential allows for a direct stomatal water vapor uptake from the ambient air even at sub-100% relative humidity values. This alone could explain the observed rates of foliar water uptake by e.g., the coastal redwood in the fog belt region of coastal California provided the stomata are sufficiently open. Lastly, the omission of the reduction in the water vapor pressure causes a bias in the estimates of the stomatal conductance and leaf internal CO 2 concentration based on leaf gas exchange measurements. Manufactures of leaf gas exchange measurement systems should incorporate leaf water potentials in measurement set-ups.« less

Effect of Leaf Water Potential on Internal Humidity and CO 2 Dissolution: Reverse Transpiration and Improved Water Use Efficiency under Negative Pressure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vesala, Timo; Sevanto, Sanna; Grönholm, Tiia

The pull of water from the soil to the leaves causes water in the transpiration stream to be under negative pressure decreasing the water potential below zero. The osmotic concentration also contributes to the decrease in leaf water potential but with much lesser extent. Thus, the surface tension force is approximately balanced by a force induced by negative water potential resulting in concavely curved water-air interfaces in leaves. The lowered water potential causes a reduction in the equilibrium water vapor pressure in internal (sub-stomatal/intercellular) cavities in relation to that over water with the potential of zero, i.e., over the flatmore » surface. The curved surface causes a reduction also in the equilibrium vapor pressure of dissolved CO 2, thus enhancing its physical solubility to water. Although the water vapor reduction is acknowledged by plant physiologists its consequences for water vapor exchange at low water potential values have received very little attention. Consequences of the enhanced CO 2 solubility to a leaf water-carbon budget have not been considered at all before this study. We use theoretical calculations and modeling to show how the reduction in the vapor pressures affects transpiration and carbon assimilation rates. Here, our results indicate that the reduction in vapor pressures of water and CO 2 could enhance plant water use efficiency up to about 10% at a leaf water potential of -2 MPa, and much more when water potential decreases further. The low water potential allows for a direct stomatal water vapor uptake from the ambient air even at sub-100% relative humidity values. This alone could explain the observed rates of foliar water uptake by e.g., the coastal redwood in the fog belt region of coastal California provided the stomata are sufficiently open. Lastly, the omission of the reduction in the water vapor pressure causes a bias in the estimates of the stomatal conductance and leaf internal CO 2 concentration based on leaf gas exchange measurements. Manufactures of leaf gas exchange measurement systems should incorporate leaf water potentials in measurement set-ups.« less

Effect of Leaf Water Potential on Internal Humidity and CO2 Dissolution: Reverse Transpiration and Improved Water Use Efficiency under Negative Pressure

PubMed Central

Vesala, Timo; Sevanto, Sanna; Grönholm, Tiia; Salmon, Yann; Nikinmaa, Eero; Hari, Pertti; Hölttä, Teemu

2017-01-01

The pull of water from the soil to the leaves causes water in the transpiration stream to be under negative pressure decreasing the water potential below zero. The osmotic concentration also contributes to the decrease in leaf water potential but with much lesser extent. Thus, the surface tension force is approximately balanced by a force induced by negative water potential resulting in concavely curved water-air interfaces in leaves. The lowered water potential causes a reduction in the equilibrium water vapor pressure in internal (sub-stomatal/intercellular) cavities in relation to that over water with the potential of zero, i.e., over the flat surface. The curved surface causes a reduction also in the equilibrium vapor pressure of dissolved CO2, thus enhancing its physical solubility to water. Although the water vapor reduction is acknowledged by plant physiologists its consequences for water vapor exchange at low water potential values have received very little attention. Consequences of the enhanced CO2 solubility to a leaf water-carbon budget have not been considered at all before this study. We use theoretical calculations and modeling to show how the reduction in the vapor pressures affects transpiration and carbon assimilation rates. Our results indicate that the reduction in vapor pressures of water and CO2 could enhance plant water use efficiency up to about 10% at a leaf water potential of −2 MPa, and much more when water potential decreases further. The low water potential allows for a direct stomatal water vapor uptake from the ambient air even at sub-100% relative humidity values. This alone could explain the observed rates of foliar water uptake by e.g., the coastal redwood in the fog belt region of coastal California provided the stomata are sufficiently open. The omission of the reduction in the water vapor pressure causes a bias in the estimates of the stomatal conductance and leaf internal CO2 concentration based on leaf gas exchange measurements. Manufactures of leaf gas exchange measurement systems should incorporate leaf water potentials in measurement set-ups. PMID:28220128

Effect of Leaf Water Potential on Internal Humidity and CO2 Dissolution: Reverse Transpiration and Improved Water Use Efficiency under Negative Pressure.

PubMed

Vesala, Timo; Sevanto, Sanna; Grönholm, Tiia; Salmon, Yann; Nikinmaa, Eero; Hari, Pertti; Hölttä, Teemu

2017-01-01

The pull of water from the soil to the leaves causes water in the transpiration stream to be under negative pressure decreasing the water potential below zero. The osmotic concentration also contributes to the decrease in leaf water potential but with much lesser extent. Thus, the surface tension force is approximately balanced by a force induced by negative water potential resulting in concavely curved water-air interfaces in leaves. The lowered water potential causes a reduction in the equilibrium water vapor pressure in internal (sub-stomatal/intercellular) cavities in relation to that over water with the potential of zero, i.e., over the flat surface. The curved surface causes a reduction also in the equilibrium vapor pressure of dissolved CO 2 , thus enhancing its physical solubility to water. Although the water vapor reduction is acknowledged by plant physiologists its consequences for water vapor exchange at low water potential values have received very little attention. Consequences of the enhanced CO 2 solubility to a leaf water-carbon budget have not been considered at all before this study. We use theoretical calculations and modeling to show how the reduction in the vapor pressures affects transpiration and carbon assimilation rates. Our results indicate that the reduction in vapor pressures of water and CO 2 could enhance plant water use efficiency up to about 10% at a leaf water potential of -2 MPa, and much more when water potential decreases further. The low water potential allows for a direct stomatal water vapor uptake from the ambient air even at sub-100% relative humidity values. This alone could explain the observed rates of foliar water uptake by e.g., the coastal redwood in the fog belt region of coastal California provided the stomata are sufficiently open. The omission of the reduction in the water vapor pressure causes a bias in the estimates of the stomatal conductance and leaf internal CO 2 concentration based on leaf gas exchange measurements. Manufactures of leaf gas exchange measurement systems should incorporate leaf water potentials in measurement set-ups.

Electrochemical CO 2 reduction on Au surfaces: mechanistic aspects regarding the formation of major and minor products

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cave, Etosha R.; Montoya, Joseph H.; Kuhl, Kendra P.

In the future, industrial CO 2 electroreduction using renewable energy sources could be a sustainable means to convert CO 2 and water into commodity chemicals at room temperature and atmospheric pressure. This study focuses on the electrocatalytic reduction of CO 2 on polycrystalline Au surfaces, which have high activity and selectivity for CO evolution. Here, we explore the catalytic behavior of polycrystalline Au surfaces by coupling potentiostatic CO 2 electrolysis experiments in an aqueous bicarbonate solution with high sensitivity product detection methods. We observed the production of methanol, in addition to detecting the known products of CO 2 electroreduction onmore » Au: CO, H 2 and formate. We suggest a mechanism that explains Au's evolution of methanol. Specifically, the Au surface does not favor C-O scission, and thus is more selective towards methanol than methane. These insights could aid in the design of electrocatalysts that are selective for CO 2 electroreduction to oxygenates over hydrocarbons.« less

Electrochemical CO 2 reduction on Au surfaces: mechanistic aspects regarding the formation of major and minor products

DOE PAGES

Cave, Etosha R.; Montoya, Joseph H.; Kuhl, Kendra P.; ...

2017-01-06

In the future, industrial CO 2 electroreduction using renewable energy sources could be a sustainable means to convert CO 2 and water into commodity chemicals at room temperature and atmospheric pressure. This study focuses on the electrocatalytic reduction of CO 2 on polycrystalline Au surfaces, which have high activity and selectivity for CO evolution. Here, we explore the catalytic behavior of polycrystalline Au surfaces by coupling potentiostatic CO 2 electrolysis experiments in an aqueous bicarbonate solution with high sensitivity product detection methods. We observed the production of methanol, in addition to detecting the known products of CO 2 electroreduction onmore » Au: CO, H 2 and formate. We suggest a mechanism that explains Au's evolution of methanol. Specifically, the Au surface does not favor C-O scission, and thus is more selective towards methanol than methane. These insights could aid in the design of electrocatalysts that are selective for CO 2 electroreduction to oxygenates over hydrocarbons.« less

Modification of land-atmosphere interactions by CO2 effects

NASA Astrophysics Data System (ADS)

Lemordant, Leo; Gentine, Pierre

2017-04-01

Plant stomata couple the energy, water and carbon cycles. Increased CO2 modifies the seasonality of the water cycle through stomatal regulation and increased leaf area. As a result, the water saved during the growing season through higher water use efficiency mitigates summer dryness and the impact of potential heat waves. Land-atmosphere interactions and CO2 fertilization together synergistically contribute to increased summer transpiration. This, in turn, alters the surface energy budget and decreases sensible heat flux, mitigating air temperature rise. Accurate representation of the response to higher CO2 levels, and of the coupling between the carbon and water cycles are therefore critical to forecasting seasonal climate, water cycle dynamics and to enhance the accuracy of extreme event prediction under future climate.

High-Performance Overall Water Splitting Electrocatalysts Derived from Cobalt-Based Metal–Organic Frameworks

DOE Office of Scientific and Technical Information (OSTI.GOV)

You, Bo; Jiang, Nan; Sheng, Meili

2015-11-05

The design of active, robust, and nonprecious electrocatalysts with both H 2 and O 2 evolution reaction (HER and OER) activities for overall water splitting is highly desirable but remains a grand challenge. Here in this article, we report a facile two-step method to synthesize porous Co-P/NC nanopolyhedrons composed of CoP x (a mixture of CoP and Co 2P) nanoparticles embedded in N-doped carbon matrices as electrocatalysts for overall water splitting. The Co-P/NC catalysts were prepared by direct carbonization of Co-based zeolitic imidazolate framework (ZIF-67) followed by phosphidation. Benefiting from the large specific surface area, controllable pore texture, and highmore » nitrogen content of ZIF (a subclass of metal–organic frameworks), the optimal Co-P/NC showed high specific surface area of 183 m 2 g -1 and large mesopores, and exhibited remarkable catalytic performance for both HER and OER in 1.0 M KOH, affording a current density of 10 mA cm -2 at low overpotentials of -154 mV for HER and 319 mV for OER, respectively. Furthermore, a Co-P/NC-based alkaline electrolyzer approached 165 mA cm -2 at 2.0 V, superior to that of Pt/IrO 2 couple, along with strong stability. Various characterization techniques including X-ray absorption spectroscopy (XAS) revealed that the superior activity and strong stability of Co-P/NC originated from its 3D interconnected mesoporosity with high specific surface area, high conductivity, and synergistic effect of CoP x encapsulated within N-doped carbon matrices.« less

Using the Bongwana natural CO2 release to understand leakage processes and develop monitoring

NASA Astrophysics Data System (ADS)

Jones, David; Johnson, Gareth; Hicks, Nigel; Bond, Clare; Gilfillan, Stuart; Kremer, Yannick; Lister, Bob; Nkwane, Mzikayise; Maupa, Thulani; Munyangane, Portia; Robey, Kate; Saunders, Ian; Shipton, Zoe; Pearce, Jonathan; Haszeldine, Stuart

2016-04-01

Natural CO2 leakage along the Bongwana Fault in South Africa is being studied to help understand processes of CO2 leakage and develop monitoring protocols. The Bongwana Fault crops out over approximately 80 km in KwaZulu-Natal province, South Africa. In outcrop the fault is expressed as a broad fracture corridor in Dwyka Tillite, with fractures oriented approximately N-S. Natural emissions of CO2 occur at various points along the fault, manifest as travertine cones and terraces, bubbling in the rivers and as gas fluxes through soil. Exposed rock outcrop shows evidence for Fe-staining around fractures and is locally extensively kaolinitised. The gas has also been released through a shallow water well, and was exploited commercially in the past. Preliminary studies have been carried out to better document the surface emissions using near surface gas monitoring, understand the origin of the gas through major gas composition and stable and noble gas isotopes and improve understanding of the structural controls on gas leakage through mapping. In addition the impact of the leaking CO2 on local water sources (surface and ground) is being investigated, along with the seismic activity of the fault. The investigation will help to build technical capacity in South Africa and to develop monitoring techniques and plans for a future CO2 storage pilot there. Early results suggest that CO2 leakage is confined to a relatively small number of spatially-restricted locations along the weakly seismically active fault. Fracture permeability appears to be the main method by which the CO2 migrates to the surface. The bulk of the CO2 is of deep origin with a minor contribution from near surface biogenic processes as determined by major gas composition. Water chemistry, including pH, DO and TDS is notably different between CO2-rich and CO2-poor sites. Soil gas content and flux effectively delineates the fault trace in active leakage sites. The fault provides an effective testing ground for field-based monitoring with results to date indicating the methods and technologies tested successfully detect leaking CO2. Further work will investigate the source of the CO2 and attempt to quantify CO2 flux rates and detection thresholds.

Control of air-sea CO2 disequilibria in the subtropical NE Atlantic by planktonic metabolism under the ocean skin

NASA Astrophysics Data System (ADS)

Calleja, María Ll.; Duarte, Carlos M.; Navarro, Nuria; Agustí, Susana

2005-04-01

The air-sea CO2 gradient at the subtropical NE Atlantic was strongly dependent on the metabolism of the planktonic community within the top cms, but independent of that of the communities deeper in the water column. Gross primary production (GPP) and community respiration (R) of the planktonic community within the top cms exceeded those of the communities deeper in the water column by >10-fold and >7 fold, respectively. Net autotrophic metabolism (GPP > R) at the top cms of the water column in some stations drove CO2 uptake by creating a CO2 deficit at the ocean surface, while net heterotrophic metabolism (GPP < R) at the top cms of the water column in other stations resulted in strong CO2 supersaturation, driving CO2 emissions. These results suggest a strong control of the air-sea pCO2 anomaly by intense biological processes.

Variations of uranium concentrations in a multi-aquifer system under the impact of surface water-groundwater interaction

NASA Astrophysics Data System (ADS)

Wu, Ya; Li, Junxia; Wang, Yanxin; Xie, Xianjun

2018-04-01

Understanding uranium (U) mobility is vital to minimizing its concentrations in potential drinking water sources. In this study, we report spatial-seasonal variations in U speciation and concentrations in a multi-aquifer system under the impact of Sanggan River in Datong basin, northern China. Hydrochemical and H, O, Sr isotopic data, thermodynamic calculations, and geochemical modeling are used to investigate the mechanisms of surface water-groundwater mixing-induced mobilization and natural attenuation of U. In the study site, groundwater U concentrations are up to 30.2 μg/L, and exhibit strong spatial-seasonal variations that are related to pH and Eh values, as well as dissolved Ca2+, HCO3-, and Fe(III) concentrations. For the alkaline aquifers of this site (pH 7.02-8.44), U mobilization is due to the formation and desorption of Ca2UO2(CO3)30 and CaUO2(CO3)32- caused by groundwater Ca2+ elevation via mineral weathering and Na-Ca exchange, incorporated U(VI) release from calcite, and U(IV) oxidation by Fe(OH)3. U immobilization is linked to the adsorption of CaUO2(CO3)32- and UO2(CO3)34- shifted from Ca2UO2(CO3)30 because of HCO3- elevation and Ca2+ depletion, U(VI) co-precipitation with calcite, and U(VI) reduction by adsorbed Fe2+ and FeS. Those results are of great significance for the groundwater resource management of this and similar other surface water-groundwater interaction zones.

Structure and Dynamics of Confined Water and CO2 in Clays under Supercritical Conditions

NASA Astrophysics Data System (ADS)

Glezakou, V.; Lee, M.; Schaef, T.; Loring, J.; Davidson, C.; McGrail, P.

2013-12-01

Carbon dioxide (CO2) driven enhanced gas recovery (EGR) from depleted fractured shale gas reservoirs has the potential for producing economic benefits and providing long term storage options for anthropogenic derived CO2 emissions. However key scientific processes related to CO2:CH4 exchange rates, mineral volume changes, organic mobility, and mineral stability in the presence of acid gas injections are not well understood. In this paper, we conduct atomistic simulations to examine interactions occurring between model clay minerals and supercritical CO2 equilibrated with water or brines to identify parameters controlling adsorption and desorption of gases. Integrated within these simulations are results derived from a set of newly developed experimental techniques designed to characterize physico-chemical reactions at reservoir conditions. In a series of cell optimizations under pressures relevant to sequestration scenarios, molecular simulations within the NVT and NPT ensembles with varying water/CO2 ratios showed a range of interlayer expansion for specific cation-saturated smectites. In conjunction with experimental in situ high pressure x-ray diffraction (HXRD), semi-quantitative concentrations of interlayer H2O and CO2 were established. For example, Ca saturated smectites maintaining sub-single to single hydration states (<1W to 1W), expand approximately 1.7-2.0 Å when exposed to anhydrous supercritical CO2. In contrast, for single to double hydration states (1W-2W), the simulations indicate formation of a quasi-single, metastable state, leading to a reduced interlayer spacing. Partial dehydration of the interlayer spacing while in contact with CO2 is due to a reduction of the interlayer cation coordination number. Structural analysis of the intercalated species shows an increase in the hydrogen bonding between waters during CO2 intercalation coincident with a decrease in the coordination population around the cations. Power spectra reveal rotationally constrained CO2 molecules over the silica layer of the Ca-smectite surface due to the formation of a two dimensional supercritical CO2 network at lower pressures, expanding to three-dimensions as the water content increases. Diffusion coefficients of the interlayer species determined from the molecular trajectories show dependence on the presence of CO2 and hydration state. In agreement with modeling studies, direct observations of volume changes were observed during in situ HXRD experiments when exposure of a 2W Ca-smectite to supercritical CO2 at 50 °C and 90 bar produced a decrease in the interlayer spacing. In addition to intercalation, surface adsorption and desorption are equally important interactions occurring with clay minerals in the presence of supercritical CO2. Processes related to surface condensation of CO2 were examined through a series of modeling exercises and in situ spectroscopic measurements. Results showed that adsorbed CO2 concentrations were low when no water was adsorbed to the clay, but dramatically increased to a maximum when the clay was at ~1W. With continued water adsorption, CO2 concentrations decreased as the water outcompeted CO2 for adsorption/intercalation sites.

How Properties of Solid Surfaces Modulate the Nucleation of Gas Hydrate

PubMed Central

Bai, Dongsheng; Chen, Guangjin; Zhang, Xianren; Sum, Amadeu K.; Wang, Wenchuan

2015-01-01

Molecular dynamics simulations were performed for CO2 dissolved in water near silica surfaces to investigate how the hydrophilicity and crystallinity of solid surfaces modulate the local structure of adjacent molecules and the nucleation of CO2 hydrates. Our simulations reveal that the hydrophilicity of solid surfaces can change the local structure of water molecules and gas distribution near liquid-solid interfaces, and thus alter the mechanism and dynamics of gas hydrate nucleation. Interestingly, we find that hydrate nucleation tends to occur more easily on relatively less hydrophilic surfaces. Different from surface hydrophilicity, surface crystallinity shows a weak effect on the local structure of adjacent water molecules and on gas hydrate nucleation. At the initial stage of gas hydrate growth, however, the structuring of molecules induced by crystalline surfaces are more ordered than that induced by amorphous solid surfaces. PMID:26227239

Climatological mean and decadal change in surface ocean pCO 2, and net sea-air CO 2 flux over the global oceans

NASA Astrophysics Data System (ADS)

Takahashi, Taro; Sutherland, Stewart C.; Wanninkhof, Rik; Sweeney, Colm; Feely, Richard A.; Chipman, David W.; Hales, Burke; Friederich, Gernot; Chavez, Francisco; Sabine, Christopher; Watson, Andrew; Bakker, Dorothee C. E.; Schuster, Ute; Metzl, Nicolas; Yoshikawa-Inoue, Hisayuki; Ishii, Masao; Midorikawa, Takashi; Nojiri, Yukihiro; Körtzinger, Arne; Steinhoff, Tobias; Hoppema, Mario; Olafsson, Jon; Arnarson, Thorarinn S.; Tilbrook, Bronte; Johannessen, Truls; Olsen, Are; Bellerby, Richard; Wong, C. S.; Delille, Bruno; Bates, N. R.; de Baar, Hein J. W.

2009-04-01

A climatological mean distribution for the surface water pCO 2 over the global oceans in non-El Niño conditions has been constructed with spatial resolution of 4° (latitude) ×5° (longitude) for a reference year 2000 based upon about 3 million measurements of surface water pCO 2 obtained from 1970 to 2007. The database used for this study is about 3 times larger than the 0.94 million used for our earlier paper [Takahashi et al., 2002. Global sea-air CO 2 flux based on climatological surface ocean pCO 2, and seasonal biological and temperature effects. Deep-Sea Res. II, 49, 1601-1622]. A time-trend analysis using deseasonalized surface water pCO 2 data in portions of the North Atlantic, North and South Pacific and Southern Oceans (which cover about 27% of the global ocean areas) indicates that the surface water pCO 2 over these oceanic areas has increased on average at a mean rate of 1.5 μatm y -1 with basin-specific rates varying between 1.2±0.5 and 2.1±0.4 μatm y -1. A global ocean database for a single reference year 2000 is assembled using this mean rate for correcting observations made in different years to the reference year. The observations made during El Niño periods in the equatorial Pacific and those made in coastal zones are excluded from the database. Seasonal changes in the surface water pCO 2 and the sea-air pCO 2 difference over four climatic zones in the Atlantic, Pacific, Indian and Southern Oceans are presented. Over the Southern Ocean seasonal ice zone, the seasonality is complex. Although it cannot be thoroughly documented due to the limited extent of observations, seasonal changes in pCO 2 are approximated by using the data for under-ice waters during austral winter and those for the marginal ice and ice-free zones. The net air-sea CO 2 flux is estimated using the sea-air pCO 2 difference and the air-sea gas transfer rate that is parameterized as a function of (wind speed) 2 with a scaling factor of 0.26. This is estimated by inverting the bomb 14C data using Ocean General Circulation models and the 1979-2005 NCEP-DOE AMIP-II Reanalysis (R-2) wind speed data. The equatorial Pacific (14°N-14°S) is the major source for atmospheric CO 2, emitting about +0.48 Pg-C y -1, and the temperate oceans between 14° and 50° in the both hemispheres are the major sink zones with an uptake flux of -0.70 Pg-C y -1 for the northern and -1.05 Pg-C y -1 for the southern zone. The high-latitude North Atlantic, including the Nordic Seas and portion of the Arctic Sea, is the most intense CO 2 sink area on the basis of per unit area, with a mean of -2.5 tons-C month -1 km -2. This is due to the combination of the low pCO 2 in seawater and high gas exchange rates. In the ice-free zone of the Southern Ocean (50°-62°S), the mean annual flux is small (-0.06 Pg-C y -1) because of a cancellation of the summer uptake CO 2 flux with the winter release of CO 2 caused by deepwater upwelling. The annual mean for the contemporary net CO 2 uptake flux over the global oceans is estimated to be -1.6±0.9 Pg-C y -1, which includes an undersampling correction to the direct estimate of -1.4±0.7 Pg-C y -1. Taking the pre-industrial steady-state ocean source of 0.4±0.2 Pg-C y -1 into account, the total ocean uptake flux including the anthropogenic CO 2 is estimated to be -2.0±1.0 Pg-C y -1 in 2000.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wan, Weiming; Tackett, Brian M.; Chen, Jingguang G.

The formation of carbides can significantly modify the physical and chemical properties of the parent metals. In the current review, we summarize the general trends in the reactions of water and C1 molecules over transition metal carbide (TMC) and metal-modified TMC surfaces and thin films. Although the primary focus of the current review is on the theoretical and experimental studies of reactions of C1 molecules (CO, CO 2, CH 3OH, etc.), the reactions of water will also be reviewed because water plays an important role in many of the C1 transformation reactions. This review is organized by discussing separately thermalmore » reactions and electrochemical reactions, which provides insights into the application of TMCs in heterogeneous catalysis and electrocatalysis, respectively. In thermal reactions, we discuss the thermal decomposition of water and methanol, as well as the reactions of CO and CO 2 over TMC surfaces. In electrochemical reactions, we summarize recent studies in the hydrogen evolution reaction, electrooxidation of methanol and CO, and electroreduction of CO 2. Lastly, future research opportunities and challenges associated with using TMCs as catalysts and electrocatalysts are also discussed.« less

Ikaite crystals in melting sea ice - implications for pCO2 and pH levels in Arctic surface waters

NASA Astrophysics Data System (ADS)

Rysgaard, S.; Glud, R. N.; Lennert, K.; Cooper, M.; Halden, N.; Leakey, R. J. G.; Hawthorne, F. C.; Barber, D.

2012-08-01

A major issue of Arctic marine science is to understand whether the Arctic Ocean is, or will be, a source or sink for air-sea CO2 exchange. This has been complicated by the recent discoveries of ikaite (a polymorph of CaCO3·6H2O) in Arctic and Antarctic sea ice, which indicate that multiple chemical transformations occur in sea ice with a possible effect on CO2 and pH conditions in surface waters. Here, we report on biogeochemical conditions, microscopic examinations and x-ray diffraction analysis of single crystals from a melting 1.7 km2 (0.5-1 m thick) drifting ice floe in the Fram Strait during summer. Our findings show that ikaite crystals are present throughout the sea ice but with larger crystals appearing in the upper ice layers. Ikaite crystals placed at elevated temperatures disintegrated into smaller crystallites and dissolved. During our field campaign in late June, melt reduced the ice floe thickness by 0.2 m per week and resulted in an estimated 3.8 ppm decrease of pCO2 in the ocean surface mixed layer. This corresponds to an air-sea CO2 uptake of 10.6 mmol m-2 sea ice d-1 or to 3.3 ton km-2 ice floe week-1. This is markedly higher than the estimated primary production within the ice floe of 0.3-1.3 mmol m-2 sea ice d-1. Finally, the presence of ikaite in sea ice and the dissolution of the mineral during melting of the sea ice and mixing of the melt water into the surface oceanic mixed layer accounted for half of the estimated pCO2 uptake.

The spatial and interannual dynamics of the surface water carbonate system and air-sea CO2 fluxes in the outer shelf and slope of the Eurasian Arctic Ocean

NASA Astrophysics Data System (ADS)

Pipko, Irina I.; Pugach, Svetlana P.; Semiletov, Igor P.; Anderson, Leif G.; Shakhova, Natalia E.; Gustafsson, Örjan; Repina, Irina A.; Spivak, Eduard A.; Charkin, Alexander N.; Salyuk, Anatoly N.; Shcherbakova, Kseniia P.; Panova, Elena V.; Dudarev, Oleg V.

2017-11-01

The Arctic is undergoing dramatic changes which cover the entire range of natural processes, from extreme increases in the temperatures of air, soil, and water, to changes in the cryosphere, the biodiversity of Arctic waters, and land vegetation. Small changes in the largest marine carbon pool, the dissolved inorganic carbon pool, can have a profound impact on the carbon dioxide (CO2) flux between the ocean and the atmosphere, and the feedback of this flux to climate. Knowledge of relevant processes in the Arctic seas improves the evaluation and projection of carbon cycle dynamics under current conditions of rapid climate change. Investigation of the CO2 system in the outer shelf and continental slope waters of the Eurasian Arctic seas (the Barents, Kara, Laptev, and East Siberian seas) during 2006, 2007, and 2009 revealed a general trend in the surface water partial pressure of CO2 (pCO2) distribution, which manifested as an increase in pCO2 values eastward. The existence of this trend was defined by different oceanographic and biogeochemical regimes in the western and eastern parts of the study area; the trend is likely increasing due to a combination of factors determined by contemporary change in the Arctic climate, each change in turn evoking a series of synergistic effects. A high-resolution in situ investigation of the carbonate system parameters of the four Arctic seas was carried out in the warm season of 2007; this year was characterized by the next-to-lowest historic sea-ice extent in the Arctic Ocean, on satellite record, to that date. The study showed the different responses of the seawater carbonate system to the environment changes in the western vs. the eastern Eurasian Arctic seas. The large, open, highly productive water area in the northern Barents Sea enhances atmospheric CO2 uptake. In contrast, the uptake of CO2 was strongly weakened in the outer shelf and slope waters of the East Siberian Arctic seas under the 2007 environmental conditions. The surface seawater appears in equilibrium or slightly supersaturated by CO2 relative to atmosphere because of the increasing influence of river runoff and its input of terrestrial organic matter that mineralizes, in combination with the high surface water temperature during sea-ice-free conditions. This investigation shows the importance of processes that vary on small scales, both in time and space, for estimating the air-sea exchange of CO2. It stresses the need for high-resolution coverage of ocean observations as well as time series. Furthermore, time series must include multi-year studies in the dynamic regions of the Arctic Ocean during these times of environmental change.

Effect of impurities on the corrosion behavior of CO2 transmission pipeline steel in supercritical CO2-water environments.

PubMed

Choi, Yoon-Seok; Nesic, Srdjan; Young, David

2010-12-01

The corrosion property of carbon steel was evaluated using an autoclave under CO(2)-saturated water phase and water-saturated CO(2) phase with impurities (O(2) and SO(2)) at 80 bar CO(2) and 50 °C to simulate the condition of CO(2) transmission pipeline in the carbon capture and storage (CCS) applications. The results showed that the corrosion rate of carbon steel in CO(2)-saturated water was very high and it increased with adding O(2) in the system due to the inhibition effect of O(2) on the formation of protective FeCO(3). It is noteworthy that corrosion took place in the water-saturated CO(2) phase under supercritical condition when no free water is present. The addition of O(2) increased the corrosion rates of carbon steel in water-saturated CO(2) phase. The addition of 0.8 bar SO(2) (1%) in the gas phase dramatically increased the corrosion rate of carbon steel from 0.38 to 5.6 mm/y. This then increased to more than 7 mm/y with addition of both O(2) and SO(2). SO(2) can promote the formation of iron sulfite hydrate (FeSO(3)·3H(2)O) on the steel surface which is less protective than iron carbonate (FeCO(3)), and it is further oxidized to become FeSO(4) and FeOOH when O(2) is present with SO(2) in the CO(2)-rich phase. The corrosion rates of 13Cr steel were very low compared with carbon steel in CO(2)-saturated water environments with O(2), whereas it was as high as carbon steel in a water-saturated CO(2) phase with O(2) and SO(2).

Subsurface oxide plays a critical role in CO2 activation by Cu(111) surfaces to form chemisorbed CO2, the first step in reduction of CO2.

PubMed

Favaro, Marco; Xiao, Hai; Cheng, Tao; Goddard, William A; Yano, Junko; Crumlin, Ethan J

2017-06-27

A national priority is to convert CO 2 into high-value chemical products such as liquid fuels. Because current electrocatalysts are not adequate, we aim to discover new catalysts by obtaining a detailed understanding of the initial steps of CO 2 electroreduction on copper surfaces, the best current catalysts. Using ambient pressure X-ray photoelectron spectroscopy interpreted with quantum mechanical prediction of the structures and free energies, we show that the presence of a thin suboxide structure below the copper surface is essential to bind the CO 2 in the physisorbed configuration at 298 K, and we show that this suboxide is essential for converting to the chemisorbed CO 2 in the presence of water as the first step toward CO 2 reduction products such as formate and CO. This optimum suboxide leads to both neutral and charged Cu surface sites, providing fresh insights into how to design improved carbon dioxide reduction catalysts.

Subsurface oxide plays a critical role in CO2 activation by Cu(111) surfaces to form chemisorbed CO2, the first step in reduction of CO2

PubMed Central

Favaro, Marco; Yano, Junko; Crumlin, Ethan J.

2017-01-01

A national priority is to convert CO2 into high-value chemical products such as liquid fuels. Because current electrocatalysts are not adequate, we aim to discover new catalysts by obtaining a detailed understanding of the initial steps of CO2 electroreduction on copper surfaces, the best current catalysts. Using ambient pressure X-ray photoelectron spectroscopy interpreted with quantum mechanical prediction of the structures and free energies, we show that the presence of a thin suboxide structure below the copper surface is essential to bind the CO2 in the physisorbed configuration at 298 K, and we show that this suboxide is essential for converting to the chemisorbed CO2 in the presence of water as the first step toward CO2 reduction products such as formate and CO. This optimum suboxide leads to both neutral and charged Cu surface sites, providing fresh insights into how to design improved carbon dioxide reduction catalysts. PMID:28607092

Enceladus' near-surface CO2 gas pockets and surface frost deposits

NASA Astrophysics Data System (ADS)

Matson, Dennis L.; Davies, Ashley Gerard; Johnson, Torrence V.; Combe, Jean-Philippe; McCord, Thomas B.; Radebaugh, Jani; Singh, Sandeep

2018-03-01

Solid CO2 surface deposits were reported in Enceladus' South Polar Region by Brown et al. (2006). They noted that such volatile deposits are temporary and posited ongoing replenishment. We present a model for this replenishment by expanding on the Matson et al. (2012) model of subsurface heat and chemical transport in Enceladus. Our model explains the distributions of both CO2 frost and complexed CO2 clathrate hydrate as seen in the Cassini Visual and Infrared Mapping Spectrometer (VIMS) data. We trace the journey of CO2 from a subsurface ocean. The ocean-water circulation model of Matson et al. (2012) brings water up to near the surface where gas exsolves to form bubbles. Some of the CO2 bubbles are trapped and form pockets of gas in recesses at the bottom of the uppermost ice layer. When fissures break open these pockets, the CO2 gas is vented. Gas pocket venting is episodic compared to the more or less continuous eruptive plumes, emanating from the "tiger stripes", that are supported by plume chambers. Two styles of gas pocket venting are considered: (1) seeps, and (2) blowouts. The presence of CO2 frost patches suggests that the pocket gas slowly seeped through fractured, cold ice and when some of the gas reached the surface it was cold enough to condense (i.e., T ∼70 to ∼119 K). If the fissure opening is large, a blowout occurs. The rapid escape of gas and drop in pocket pressure causes water in the pocket to boil and create many small aerosol droplets of seawater. These may be carried along by the erupting gas. Electrically charged droplets can couple to the magnetosphere, and be dragged away from Enceladus. Most of the CO2 blowout gas escapes from Enceladus and the remainder is distributed globally. However, CO2 trapped in a clathrate structure does not escape. It is much heavier and slower moving than the CO2 gas. Its motion is ballistic and has an average range of about 17 km. Thus, it contributes to deposits in the vicinity of the vent. Local heat flow indicates that gas pockets can be located as deep as several tens of meters below the surface. Gas pockets can be reused, and we explore their life cycle.

Acetaldehyde Adsorption and Reaction onCeO2(100) Thin Films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mullins, David R; Albrecht, Peter M

2013-01-01

This study reports and compares the adsorption and dissociation of acetaldehyde on oxidized and reduced CeOX(100) thin films. Acetaldehyde reacts and decomposes on fully oxidized CeO2(100) whereas it desorbs molecularly at low temperature on CeO2(111). The primary products are CO, CO2 and water along with trace amounts of crotonaldehyde and acetylene. The acetaldehyde adsorbs as the 2-acetaldehyde species, dioxyethylene. Decomposition proceeds by dehydrogenation through acetate and enolate intermediates. The reaction pathway is similar on the reduced CeO2-X(100) surface however the inability to react with surface O on the reduced surface results in H2 rather than H2O desorption and C ismore » left on the surface rather than producing CO and CO2. C-O bond cleavage in the enolate intermediate followed by reaction with surface H results in ethylene desorption.« less

A laboratory study of supercritical CO2 adsorption on cap rocks in the geological storage conditions

NASA Astrophysics Data System (ADS)

Jedli, Hedi; Jbara, Abdessalem; Hedfi, Hachem; Bouzgarrou, Souhail; Slimi, Khalifa

2017-04-01

In the present study, various cap rocks have been experimentally reacted in water with supercritical CO2 in geological storage conditions ( P = 8 × 106 Pa and T = 80 °C) for 25 days. To characterize the potential CO2-water-rock interactions, an experimental setup has been built to provide additional information concerning the effects of structure, thermal and surface characteristics changes due to CO2 injection with cap rocks. In addition, CO2 adsorption capacities of different materials (i.e., clay evaporate and sandstone) are measured. These samples were characterized by XRD technique. The BET specific surface area was determined by nitrogen isotherms. In addition, thermal characteristics of untreated adsorbents were analyzed via TGA method and topography surfaces are identified by Scanning Electron Microscope (SEM). Taking into account pressure and temperature, the physical as well as chemical mechanisms of CO2 retention were determined. Isotherm change profiles of samples for relative pressure range indicate clearly that CO2 was adsorbed in different quantities. In accordance with the X-ray diffraction, a crystalline phase was formed due to the carbonic acid attack and precipitation of some carbonate.

Assessment of the water and energy budget simulation of three land surface models: CLM4.5, CoLM2014, and CoLM2005

NASA Astrophysics Data System (ADS)

Li, C.; Lu, H.; Wen, X.

2015-12-01

Land surface model (LSM), which simulates energy, water and momentum exchanges between land and atmosphere, is an important component of Earth System Models (ESM). As shown in CMIP5, different ESMs usually use different LSMs and represent various land surface status. In order to select a land surface model which could be embedded into the ESM developed in Tsinghua University, we firstly evaluate the performance of three LSMs: Community Land Model (CLM4.5) and two different versions of Common Land Model (CoLM2005 and CoLM2014). All of three models were driven by CRUNCEP data and simulation results from 1980 to 2010 were used in this study. Diagnostic data provided by NCAR, global latent and sensible heat flux map estimated by Jung, net radiation from SRB, and in situ observation collected from FluxNet were used as reference data. Two variables, surface runoff and snow depth, were used for evaluating the model performance in water budget simulation, while three variables including net radiation, sensible heat, and latent heat were used for assessing energy budget simulation. For 30 years averaged runoff, global average value of Colm2014 is 0.44mm/day and close to the diagnostic value of 0.75 mm/day, while that of Colm2005 is 0.44mm/day and that of CLM is 0.20mm/day. For snow depth simulation, three models all have overestimation in the Northern Hemisphere and underestimation in the Southern Hemisphere compare to diagnostic data. For 30 years energy budget simulation, at global scale, CoLM2005 performs best in latent heat estimation, CoLM2014 performs best in sensible heat simulation, and CoLM2005 and CoLM2014 make similar performance in net radiation estimation but is still better than CLM. At regional and local scale, comparing to the four years average of flux tower observation, RMSE of CoLM2005 is the smallest for latent heat (9.717 W/m2) , and for sensible heat simulation, RMSE of CoLM2005 (13.048 W/m2) is slightly greater than CLM(10.767 W/m2) but still better than CoLM2014(30.085 W/m2). Our analysis shows that both CoLM 2005 and CoLM 2014 are able to reproduce comparable land surface water and energy fluxes. It implies that the ESM developed in Tsinghua University may use CoLM, a LSM developed and maintained in China, as the land surface component. .

Response of anaerobic carbon cycling to water table manipulation in an Alaskan rich fen

Treesearch

E.S. Kane; M.R. Chivers; M.S. Turetsky; C.C. Treat; D.G. Petersen; M. Waldrop; J.W. Harden; A.D. McGuire

2013-01-01

To test the effects of altered hydrology on organic soil decomposition, we investigated CO2 and CH4 production potential of rich-fen peat (mean surface pH = 6.3) collected from a field water table manipulation experiment including control, raised and lowered water table treatments. Mean anaerobic CO2...

Measured Fluid Flow in an Active H2O-CO2 Geothermal Well as an Analog to Fluid Flow in Fractures on Mars: Preliminary Report

NASA Technical Reports Server (NTRS)

Kieffer, Susan W.; Brown, K. L.; Simmons, Stuart F.; Watson, Arnold

2004-01-01

Water in the Earth's crust generally contains dissolved gases such as CO2. Models for both 'Blue Mars' (H2O-driven processes) and 'White Mars' (CO2-driven processes) predict liquid H2O with dissolved CO2 at depth. The fate of dissolved CO2 as this mixture rises toward the surface has not been quantitatively explored. Our approach is a variation on NASA's 'Follow the Water' as we 'Follow the Fluid' from depth to the surface in hydrothermal areas on Earth and extrapolate our results to Mars. This is a preliminary report on a field study of fluid flow in a producing geothermal well. For proprietary reasons, the name and location of this well cannot be revealed, so we have named it 'Earth1' for this study.

Uptake of CO2, SO2, HNO3 and HCl on calcite (CaCO3) at 300 K: mechanism and the role of adsorbed water.

PubMed

Santschi, Ch; Rossi, M J

2006-06-01

All experimental observations of the uptake of the four title compounds on calcite are consistent with the presence of a reactive bifunctional surface intermediate Ca(OH)(HCO3) that has been proposed in the literature. The uptake of CO2 and SO2 occurs on specific adsorption sites of crystalline CaCO3(s) rather than by dissolution in adsorbed water, H2O(ads). SO2 primarily interacts with the bicarbonate moiety whereas CO2, HNO3 and HCl all react first with the hydroxyl group of the surface intermediate. Subsequently, the latter two react with the bicarbonate group to presumably form Ca(NO3)2 and CaCl2.2H2O. The effective equilibrium constant of the interaction of CO2 with calcite in the presence of H2O(ads) is kappa = deltaCO2/(H2O(ads)[CO2]) = 1.62 x 10(3) bar(-1), where CO2 is the quantity of CO2 adsorbed on CaCO3. The reaction mechanism involves a weakly bound precursor species that is reversibly adsorbed and undergoes rate-controlling concurrent reactions with both functionalities of the surface intermediate. The initial uptake coefficients gamma0 on calcite powder depend on the abundance of H2O(ads) under the present experimental conditions and are on the order of 10(-4) for CO2 and 0.1 for SO2, HNO3 and HCl, with gamma(ss) being significantly smaller than gamma0 for HNO3 and HCl, thus indicating partial saturation of the uptake. At 33% relative humidity and 300 K there are 3.5 layers of H2O adsorbed on calcite that reduce to a fraction of a monolayer of weakly and strongly bound water upon pumping and/or heating.

Self-assembled biomimetic superhydrophobic CaCO3 coating inspired from fouling mineralization in geothermal water.

PubMed

Wang, Gong G; Zhu, Li Q; Liu, Hui C; Li, Wei P

2011-10-18

Inspired from fouling self-mineralization in geothermal water, a novel biomimetic cactuslike CaCO(3) coating with superhydrophobic features is reported in this letter. The structure, morphologies, and phases of the CaCO(3) coating were characterized by X-ray diffractometry, scanning electron microscopy, transmission electron microscopy, and infrared spectrophotometry. After prenucleation treatment, a continuous cactuslike CaCO(3) coating with hierarchical nano- and microstructures was self-assembled on stainless steel surfaces after immersion in simulated geothermal water at 50 °C for 48 h. After being modified with a low-surface-energy monolayer of sodium stearate, the as-prepared coating exhibited superhydrophobic properties with a water contact angle of 158.9° and a sliding angle of 2°. Therefore, this work might open up a new application field of geothermal resources and provide insight into designing multidimensional structures with functional applications, including superhydrophobic surfaces. © 2011 American Chemical Society

Enhancing surface methane fluxes from an oligotrophic lake: exploring the microbubble hypothesis.

PubMed

McGinnis, Daniel F; Kirillin, Georgiy; Tang, Kam W; Flury, Sabine; Bodmer, Pascal; Engelhardt, Christof; Casper, Peter; Grossart, Hans-Peter

2015-01-20

Exchange of the greenhouse gases carbon dioxide (CO2) and methane (CH4) across inland water surfaces is an important component of the terrestrial carbon (C) balance. We investigated the fluxes of these two gases across the surface of oligotrophic Lake Stechlin using a floating chamber approach. The normalized gas transfer rate for CH4 (k600,CH4) was on average 2.5 times higher than that for CO2 (k600,CO2) and consequently higher than Fickian transport. Because of its low solubility relative to CO2, the enhanced CH4 flux is possibly explained by the presence of microbubbles in the lake’s surface layer. These microbubbles may originate from atmospheric bubble entrainment or gas supersaturation (i.e., O2) or both. Irrespective of the source, we determined that an average of 145 L m(–2) d(–1) of gas is required to exit the surface layer via microbubbles to produce the observed elevated k600,CH4. As k600 values are used to estimate CH4 pathways in aquatic systems, the presence of microbubbles could alter the resulting CH4 and perhaps C balances. These microbubbles will also affect the surface fluxes of other sparingly soluble gases in inland waters, including O2 and N2.

Atlantic cod actively avoid CO2 and predator odour, even after long-term CO2 exposure.

PubMed

Jutfelt, Fredrik; Hedgärde, Maria

2013-12-27

The rising atmospheric CO2 level is continuously driving the dissolution of more CO2 into the oceans, and some emission scenarios project that the surface waters may reach 1000 μatm by the end of the century. It is not known if fish can detect moderately elevated CO2 levels, and if they avoid areas with high CO2. If so, avoidance behaviour to water with high CO2 could affect movement patterns and migrations of fish in the future. It is also being increasingly recognized that fish behaviour can be altered by exposure to CO2. Therefore this study investigated how long-term exposure to elevated pCO2 affects predator avoidance and CO2 avoidance in juvenile Atlantic cod (Gadus morhua). The fish were exposed to control water or CO2-enriched water (1000 μatm) for six weeks before being subjected to tests of behaviour. Despite long term exposure to elevated pCO2 the cod still strongly avoided the smell of a predator. These data are surprising because several coral reef fish have demonstrated reversal of olfactory responses after CO2 exposure, turning avoidance of predator cues into preference for predator cues. Fish from both treatment groups also demonstrated strong avoidance of CO2 when presented with the choice of control or CO2-acidified water, indicating that habituation to the CO2 sensory stimuli is negligible. As Atlantic cod maintained normal behavioural responses to olfactory cues, they may be tolerant to CO2-induced behavioural changes. The results also suggest that despite the long-term exposure to CO2-acidified water, the fish still preferred the control water over CO2-acidified water. Therefore, in the future, fish may alter their movements and migrations in search of waters with a lower CO2 content.

Atlantic cod actively avoid CO2 and predator odour, even after long-term CO2 exposure

PubMed Central

2013-01-01

Introduction The rising atmospheric CO2 level is continuously driving the dissolution of more CO2 into the oceans, and some emission scenarios project that the surface waters may reach 1000 μatm by the end of the century. It is not known if fish can detect moderately elevated CO2 levels, and if they avoid areas with high CO2. If so, avoidance behaviour to water with high CO2 could affect movement patterns and migrations of fish in the future. It is also being increasingly recognized that fish behaviour can be altered by exposure to CO2. Therefore this study investigated how long-term exposure to elevated pCO2 affects predator avoidance and CO2 avoidance in juvenile Atlantic cod (Gadus morhua). The fish were exposed to control water or CO2-enriched water (1000 μatm) for six weeks before being subjected to tests of behaviour. Results Despite long term exposure to elevated pCO2 the cod still strongly avoided the smell of a predator. These data are surprising because several coral reef fish have demonstrated reversal of olfactory responses after CO2 exposure, turning avoidance of predator cues into preference for predator cues. Fish from both treatment groups also demonstrated strong avoidance of CO2 when presented with the choice of control or CO2-acidified water, indicating that habituation to the CO2 sensory stimuli is negligible. Conclusions As Atlantic cod maintained normal behavioural responses to olfactory cues, they may be tolerant to CO2-induced behavioural changes. The results also suggest that despite the long-term exposure to CO2-acidified water, the fish still preferred the control water over CO2-acidified water. Therefore, in the future, fish may alter their movements and migrations in search of waters with a lower CO2 content. PMID:24373523

Carbon Dioxide Emissions from Reservoirs in the Lower Jordan Watershed

PubMed Central

Alshboul, Zeyad; Lorke, Andreas

2015-01-01

We have analyzed monthly hydrological, meteorological and water quality data from three irrigation and drinking water reservoirs in the lower Jordan River basin and estimated the atmospheric emission rates of CO2. The data were collected between 2006 and 2013 and show that the reservoirs, which differ in size and age, were net sources of CO2. The estimated surface fluxes were comparable in magnitude to those reported for hydroelectric reservoirs in the tropical and sub-tropical zones. Highest emission rates were observed for a newly established reservoir, which was initially filled during the sampling period. In the two older reservoirs, CO2 partial pressures and fluxes were significantly decreasing during the observation period, which could be related to simultaneously occurring temporal trends in water residence time and chemical composition of the water. The results indicate a strong influence of water and reservoir management (e.g. water consumption) on CO2 emission rates, which is affected by the increasing anthropogenic pressure on the limited water resources in the study area. The low wind speed and relatively high pH favored chemical enhancement of the CO2 gas exchange at the reservoir surfaces, which caused on average a four-fold enhancement of the fluxes. A sensitivity analysis indicates that the uncertainty of the estimated fluxes is, besides pH, mainly affected by the poorly resolved wind speed and resulting uncertainty of the chemical enhancement factor. PMID:26588241

Carbon Dioxide Emissions from Reservoirs in the Lower Jordan Watershed.

PubMed

Alshboul, Zeyad; Lorke, Andreas

2015-01-01

We have analyzed monthly hydrological, meteorological and water quality data from three irrigation and drinking water reservoirs in the lower Jordan River basin and estimated the atmospheric emission rates of CO2. The data were collected between 2006 and 2013 and show that the reservoirs, which differ in size and age, were net sources of CO2. The estimated surface fluxes were comparable in magnitude to those reported for hydroelectric reservoirs in the tropical and sub-tropical zones. Highest emission rates were observed for a newly established reservoir, which was initially filled during the sampling period. In the two older reservoirs, CO2 partial pressures and fluxes were significantly decreasing during the observation period, which could be related to simultaneously occurring temporal trends in water residence time and chemical composition of the water. The results indicate a strong influence of water and reservoir management (e.g. water consumption) on CO2 emission rates, which is affected by the increasing anthropogenic pressure on the limited water resources in the study area. The low wind speed and relatively high pH favored chemical enhancement of the CO2 gas exchange at the reservoir surfaces, which caused on average a four-fold enhancement of the fluxes. A sensitivity analysis indicates that the uncertainty of the estimated fluxes is, besides pH, mainly affected by the poorly resolved wind speed and resulting uncertainty of the chemical enhancement factor.

EGS rock reactions with Supercritical CO2 saturated with water and water saturated with Supercritical CO2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Earl D. Mattson; Travis L. McLing; William Smith

2013-02-01

EGS using CO2 as a working fluid will likely involve hydro-shearing low-permeability hot rock reservoirs with a water solution. After that process, the fractures will be flushed with CO2 that is maintained under supercritical conditions (> 70 bars). Much of the injected water in the main fracture will be flushed out with the initial CO2 injection; however side fractures, micro fractures, and the lower portion of the fracture will contain connate water that will interact with the rock and the injected CO2. Dissolution/precipitation reactions in the resulting scCO2/brine/rock systems have the potential to significantly alter reservoir permeability, so it ismore » important to understand where these precipitates form and how are they related to the evolving ‘free’ connate water in the system. To examine dissolution / precipitation behavior in such systems over time, we have conducted non-stirred batch experiments in the laboratory with pure minerals, sandstone, and basalt coupons with brine solution spiked with MnCl2 and scCO2. The coupons are exposed to liquid water saturated with scCO2 and extend above the water surface allowing the upper portion of the coupons to be exposed to scCO2 saturated with water. The coupons were subsequently analyzed using SEM to determine the location of reactions in both in and out of the liquid water. Results of these will be summarized with regard to significance for EGS with CO2 as a working fluid.« less

Component-specific dynamics of riverine mangrove CO2 efflux in the Florida coastal Everglades

USGS Publications Warehouse

Troxler, Tiffany G.; Barr, Jordan G.; Fuentes, Jose D.; Engel, Victor C.; Anderson, Gordon H.; Sanchez, Christopher; Lagomosino, David; Price, Rene; Davis, Stephen E.

2015-01-01

Carbon cycling in mangrove forests represents a significant portion of the coastal wetland carbon (C) budget across the latitudes of the tropics and subtropics. Previous research suggests fluctuations in tidal inundation, temperature and salinity can influence forest metabolism and C cycling. Carbon dioxide (CO2) from respiration that occurs from below the canopy is contributed from different components. In this study, we investigated variation in CO2 flux among different below-canopy components (soil, leaf litter, course woody debris, soil including pneumatophores, prop roots, and surface water) in a riverine mangrove forest of Shark River Slough estuary, Everglades National Park (Florida, USA). The range in CO2 flux from different components exceeded that measured among sites along the oligohaline-saline gradient. Black mangrove (Avicennia germinans) pneumatophores contributed the largest average CO2 flux. Over a narrow range of estuarine salinity (25–35 practical salinity units (PSU)), increased salinity resulted in lower CO2 flux to the atmosphere. Tidal inundation reduced soil CO2 flux overall but increased the partial pressure of CO2 (pCO2) observed in the overlying surface water upon flooding. Higher pCO2 in surface water is then subject to tidally driven export, largely as HCO3. Integration and scaling of CO2 flux rates to forest scale allowed for improved understanding of the relative contribution of different below-canopy components to mangrove forest ecosystem respiration (ER). Summing component CO2fluxes suggests a more significant contribution of below-canopy respiration to ER than previously considered. An understanding of below-canopy CO2 component fluxes and their contributions to ER can help to elucidate how C cycling will change with discrete disturbance events (e.g., hurricanes) and long-term change, including sea-level rise, and potential impact mangrove forests. As such, key controls on below-canopy ER must be taken into consideration when developing and modeling mangrove forest C budgets.

Spatiotemporal variability of carbon dioxide and methane in a eutrophic lake

NASA Astrophysics Data System (ADS)

Loken, Luke; Crawford, John; Schramm, Paul; Stadler, Philipp; Stanley, Emily

2017-04-01

Lakes are important regulators of global carbon cycling and conduits of greenhouse gases to the atmosphere; however, most efflux estimates for individual lakes are based on extrapolations from a single location. Within-lake variability in carbon dioxide (CO2) and methane (CH4) arises from differences in water sources, physical mixing, and local transformations; all of which can be influenced by anthropogenic disturbances and vary at multiple temporal and spatial scales. During the 2016 open water season (March - December), we mapped surface water concentrations of CO2 and CH4 weekly in a eutrophic lake (Lake Mendota, WI, USA), which has a predominately agricultural and urban watershed. In total we produced 26 maps of each gas based on 10,000 point measurements distributed across the lake surface. Both gases displayed relatively consistent spatial patterns over the stratified period but exhibited remarkable heterogeneity on each sample date. CO2 was generally undersaturated (global mean: 0.84X atmospheric saturation) throughout the lake's pelagic zone and often differed near river inlets and shorelines. The lake was routinely extremely supersaturated with CH4 (global mean: 105X atmospheric saturation) with greater concentrations in littoral areas that contained organic-rich sediments. During fall mixis, both CO2 and CH4 increased substantially, and concentrations were not uniform across the lake surface. CO2 and CH4 were higher on the upwind side of the lake due to upwelling of enriched hypolimnetic water. While the lake acted as a modest sink for atmospheric CO2 during the stratified period, the lake released substantial amounts of CO2 during turnover and continually emitted CH4, offsetting any reduction in atmospheric warming potential from summertime CO2 uptake. These data-rich maps illustrate how lake-wide surface concentrations and lake-scale efflux estimates based on single point measurements diverge from spatially weighted calculations. Both gases are not well represented by a sample collected at lake's central buoy, and thus, extrapolations from a single sampling location may not be adequate to assess lake-wide CO2 and CH4 dynamics in human-dominated landscapes.

Air-surface exchange of H2O, CO2, and O3 at a tallgrass prairie in relation to remotely sensed vegetation indices

NASA Technical Reports Server (NTRS)

Gao, W.; Wesely, M. L.; Cook, D. R.; Hart, R. L.

1992-01-01

Parameters derived from eddy correlation measurements of the air-surface exchange rates of H2O, CO2, and O3 over a tallgrass prairie are examined in terms of their relationships with spectral reflectance data remotely sensed from aircraft and satellites during the four 1987 intensive field campaigns of the First ISLSCP Field Experiment (FIFE). The surface conductances were strongly modulated by photosynthetically active radiation received at the surface when the grass was green and well watered; mesophyll resistances were large for CO2 but negligible for H2O and O3.

Non-destructive estimates of soil carbonic anhydrase activity and associated soil water oxygen isotope composition

NASA Astrophysics Data System (ADS)

Jones, Sam P.; Ogée, Jérôme; Sauze, Joana; Wohl, Steven; Saavedra, Noelia; Fernández-Prado, Noelia; Maire, Juliette; Launois, Thomas; Bosc, Alexandre; Wingate, Lisa

2017-12-01

The contribution of photosynthesis and soil respiration to net land-atmosphere carbon dioxide (CO2) exchange can be estimated based on the differential influence of leaves and soils on budgets of the oxygen isotope composition (δ18O) of atmospheric CO2. To do so, the activity of carbonic anhydrases (CAs), a group of enzymes that catalyse the hydration of CO2 in soils and plants, needs to be understood. Measurements of soil CA activity typically involve the inversion of models describing the δ18O of CO2 fluxes to solve for the apparent, potentially catalysed, rate of CO2 hydration. This requires information about the δ18O of CO2 in isotopic equilibrium with soil water, typically obtained from destructive, depth-resolved sampling and extraction of soil water. In doing so, an assumption is made about the soil water pool that CO2 interacts with, which may bias estimates of CA activity if incorrect. Furthermore, this can represent a significant challenge in data collection given the potential for spatial and temporal variability in the δ18O of soil water and limited a priori information with respect to the appropriate sampling resolution and depth. We investigated whether we could circumvent this requirement by inferring the rate of CO2 hydration and the δ18O of soil water from the relationship between the δ18O of CO2 fluxes and the δ18O of CO2 at the soil surface measured at different ambient CO2 conditions. This approach was tested through laboratory incubations of air-dried soils that were re-wetted with three waters of different δ18O. Gas exchange measurements were made on these soils to estimate the rate of hydration and the δ18O of soil water, followed by soil water extraction to allow for comparison. Estimated rates of CO2 hydration were 6.8-14.6 times greater than the theoretical uncatalysed rate of hydration, indicating that CA were active in these soils. Importantly, these estimates were not significantly different among water treatments, suggesting that this represents a robust approach to assay the activity of CA in soil. As expected, estimates of the δ18O of the soil water that equilibrates with CO2 varied in response to alteration to the δ18O of soil water. However, these estimates were consistently more negative than the composition of the soil water extracted by cryogenic vacuum distillation at the end of the gas measurements with differences of up to -3.94 ‰ VSMOW-SLAP. These offsets suggest that, at least at lower water contents, CO2-H2O isotope equilibration primarily occurs with water pools that are bound to particle surfaces and are depleted in 18O compared to bulk soil water.

Forsterite [Mg 2 SiO 4 )] Carbonation in Wet Supercritical CO 2 : An in Situ High-Pressure X-ray Diffraction Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Todd Schaef, Herbert; McGrail, Bernard P.; Loring, John L.

2013-01-02

Technological advances have been significant in recent years for managing environmentally harmful emissions (mostly CO2) resulting from combustion of fossil fuels. Deep underground geologic formations are emerging as reasonable options for long term storage of CO2 but mechanisms controlling rock and mineral stability in contact with injected supercritical fluids containing water are relatively unknown. In this paper, we discuss mineral transformation reactions occurring with forsterite (Mg2SiO4) exposed to wet supercritical CO2. Forsterite was selected as it is an important olivine group mineral present in igneous and mafic rocks and has been the subject of a large number of aqueous dissolutionmore » studies that can be compared with non-aqueous fluid tests in this study. Transformation reactions were examined by in situ high pressure x-ray diffraction in the presence of supercritical carbon dioxide (scCO2) containing dissolved water at conditions relevant to carbon sequestration. Under modest pressures (90 bar) and temperatures (50°C), scCO2 saturated with water was found to convert >70 wt% forsterite to a hydrated magnesium carbonate, nesquehonite (MgCO3 •3H2O) and magnesite (MgCO3), after 72 hours of reaction. However, comparable tests with scCO2 at only partial water saturation (82%) showed a significantly slower carbonation rate with only ~30-39 wt% conversion to nesquehonite and no evidence of the anhydrous form (MgCO3). Further decreases in water content of the scCO2 continued to reduce the extent of carbonation, until a critical moisture threshold (~30%) was crossed where forsterite no longer reacted in the presence of the wet scCO2 to form crystalline carbonates. Increasing the temperature to 75°C produced anhydrous magnesium carbonate, magnesite (MgCO3), preceded by the intermediate phase, hydromagnesite [Mg(CO3)4(OH)2 •4H2O]. Measurements conducted during in situ IR experiments at 50°C and 30% saturation identified the presence of an amorphous carbonate phase as well as the formation of a thin liquid-like water layer on the forsterite surface. The presence of this water film appears to be critical for the mineral carbonation of forsterite exposed to water bearing scCO2. In contrast, our prior studies with the mineral brucite [Mg(OH)2] showed extensive carbonation in the absence of a condensed water layer on the mineral surface. The contrasts in reaction rate and products formed demonstrated by temperature and water-content dependence highlights the importance of these kinds of studies to help enable better predictions of the long term fate of geologically stored CO2.« less

New measurements of the sticking coefficient and binding energy of molecules on non-porous amorphous solid water in the submonolayer regime

NASA Astrophysics Data System (ADS)

He, Jiao; Acharyya, Kinsuk; Emtiaz, S. M.; Vidali, Gianfranco

2016-06-01

Sticking and adsorption of molecules on dust grains are two important processes in gas-grain interactions. We accurately measured both the sticking coefficient and the binding energy of several key molecules on the surface of amorphous solid water as a function of coverage.A time-resolved scattering technique was used to measure sticking coefficient of H2, D2, N2, O2, CO, CH4, and CO2 on non-porous amorphous solid water (np-ASW) in the low coverage limit over a wide range of surface temperatures. We found that the time-resolved scattering technique is advantageous over the conventional King-Wells method that underestimates the sticking coefficient. Based on the measured values we suggest a useful general formula of the sticking coefficient as a function of grain temperature and molecule-surface binding energy.We measured the binding energy of N2, CO, O2, CH4, and CO2 on np-ASW, and of N2 and CO on porous amorphous solid water (p-ASW). We were able to measure binding energies down to a fraction of 1% of a layer, thus making these measurements more appropriate for astrochemistry than the existing values. We found that CO2 forms clusters on np-ASW surface even at very low coverage; this may help in explaining the segregation of CO2 in ices. The binding energies of N2, CO, O2, and CH4 on np-ASW decrease with coverage in the submonolayer regime. Their values in the low coverage limit are much higher than what is commonly used in gas-grain models. An empirical formula was used to describe the coverage dependence of the binding energies. We used the newly determined binding energy distributions in a simulation of gas-grain chemistry for cold dense clouds and hot core models. We found that owing to the higher value of desorption energy in the sub-monlayer regime a fraction of all these ices stays much longer and to higher temperature on the grain surface compared to the case using single value energies as currently done in astrochemical models.This work was supported in part by a grant to GV from NSF --- Astronomy & Astrophysics Division (#1311958)

Tunneling Rate Constants for H2CO+H on Amorphous Solid Water Surfaces

NASA Astrophysics Data System (ADS)

Song, Lei; Kästner, Johannes

2017-12-01

Formaldehyde (H2CO) is one of the most abundant molecules observed in the icy mantle covering interstellar grains. Studying its evolution can contribute to our understanding of the formation of complex organic molecules in various interstellar environments. In this work, we investigated the hydrogenation reactions of H2CO yielding CH3O, CH2OH, and the hydrogen abstraction resulting in H2+HCO on an amorphous solid water (ASW) surface using a quantum mechanics/molecular mechanics (QM/MM) model. The binding energies of H2CO on the ASW surface vary broadly, from 1000 to 9370 K. No correlation was found between binding energies and activation energies of hydrogenation reactions. Combining instanton theory with QM/MM modeling, we calculated rate constants for the Langmuir-Hinshelwood and the Eley-Rideal mechanisms for the three product channels of H+H2CO surface reactions down to 59 K. We found that the channel producing CH2OH can be ignored, owing to its high activation barrier leading to significantly lower rates than the other two channels. The ASW surface influences the reactivity in favor of formation of CH3O (branching ratio ˜80%) and hinders the H2CO dissociation into H2+HCO. In addition, kinetic isotope effects are strong in all reaction channels and vary strongly between the channels. Finally, we provide fits of the rate constants to be used in astrochemical models.

The Abundance of Atmospheric CO{sub 2} in Ocean Exoplanets: a Novel CO{sub 2} Deposition Mechanism

DOE Office of Scientific and Technical Information (OSTI.GOV)

Levi, A.; Sasselov, D.; Podolak, M., E-mail: amitlevi.planetphys@gmail.com

We consider super-Earth sized planets which have a water mass fraction large enough to form an external mantle composed of high-pressure water-ice polymorphs and also lack a substantial H/He atmosphere. We consider such planets in their habitable zone, so that their outermost condensed mantle is a global, deep, liquid ocean. For these ocean planets, we investigate potential internal reservoirs of CO{sub 2}, the amount of CO{sub 2} dissolved in the ocean for the various saturation conditions encountered, and the ocean-atmosphere exchange flux of CO{sub 2}. We find that, in a steady state, the abundance of CO{sub 2} in the atmospheremore » has two possible states. When wind-driven circulation is the dominant CO{sub 2} exchange mechanism, an atmosphere of tens of bars of CO{sub 2} results, where the exact value depends on the subtropical ocean surface temperature and the deep ocean temperature. When sea-ice formation, acting on these planets as a CO{sub 2} deposition mechanism, is the dominant exchange mechanism, an atmosphere of a few bars of CO{sub 2} is established. The exact value depends on the subpolar surface temperature. Our results suggest the possibility of a negative feedback mechanism, unique to water planets, where a reduction in the subpolar temperature drives more CO{sub 2} into the atmosphere to increase the greenhouse effect.« less

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

NASA Astrophysics Data System (ADS)

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

2015-12-01

To assure long-term security of geologic carbon sequestration site, evaluation of natural CO2 leakage should be preceded before actual construction of the CO2 facility by comparing natural and artificial reservoir systems. The Little Grand Wash fault is located at the northwestern margin of the Paradox Basin and roles on a bypass of deep subsurface CO2 and brine water onto the surface, e.g., cold water geyser, CO2 spring, and surface travertine deposits. CO2 degassed out from brine at the Little Grand Wash fault zone may react with formation water and minerals while migrating through the fault conduit. Leakage observed by soil CO2 flux on the fault trace shows this ongoing transition of CO2, from supersaturated condition in deep subsurface to shallow surface equilibria. The present study aims to investigate the reactions induced by changes in hydrological and mineralogical factors inside of the fault zone. The methodology to develop site-specific geochemical model of the Little Grand Wash Fault combines calculated mechanical movements of each fluid end-member, along with chemical reactions among fluid, free CO2 gas and rock formations. Reactive transport modeling was conducted to simulate these property changes inside of the fault zone, using chemistry dataset based on 86 effluent samples of CO2 geysers, springs and in situ formation water from Entrada, Carmel, and Navajo Sandstone. Meanwhile, one- and two-dimensional models were separately developed to delineate features mentioned above. The results from the 3000-year simulation showed an appearance of self-sealing processes near the surface of the fault conduit. By tracking physicochemical changes at the depth of 15 m on the 2-dimensional model, significant changes induced by fluid mixing were indicated. Calculated rates of precipitation for calcite, illite, and pyrite showed increase in 2.6 x 10-4, 2.25 x 10-5, and 3.0 x 10-6 in mineral volume fraction at the depth of 15m, respectively. Concurrently, permeability and porosity were decreased 4.0 x 10-18 m2 and 3.0 x 10-4 due to precipitation of minerals. At the middle of the fault conduit (400 m), however, indicates consistent dissolution of minerals in formation which enhances vertical fluid migration.

Probing surface sites of TiO2: reactions with [HRe(CO)5] and [CH3Re(CO)5].

PubMed

Lobo-Lapidus, Rodrigo J; Gates, Bruce C

2010-10-04

Two carbonyl complexes of rhenium, [HRe(CO)(5)] and [CH(3)Re(CO)(5)], were used to probe surface sites of TiO(2) (anatase). These complexes were adsorbed from the gas phase onto anatase powder that had been treated in flowing O(2) or under vacuum to vary the density of surface OH sites. Infrared (IR) spectra demonstrate the variation in the number of sites, including Ti(+3)-OH and Ti(+4)-OH. IR and extended X-ray absorption fine structure (EXAFS) spectra show that chemisorption of the rhenium complexes led to their decarbonylation, with formation of surface-bound rhenium tricarbonyls, when [HRe(CO)(5)] was adsorbed, or rhenium tetracarbonyls, when [CH(3)Re(CO)(5)] was adsorbed. These reactions were accompanied by the formation of water and surface carbonates and removal of terminal hydroxyl groups associated with Ti(+3) and Ti(+4) ions on the anatase. Data characterizing the samples after adsorption of [HRe(CO)(5)] or [CH(3)Re(CO)(5)] determined a ranking of the reactivity of the surface OH sites, with the Ti(+3)-OH groups being the more reactive towards the rhenium complexes but the less likely to be dehydroxylated. The two rhenium pentacarbonyl probes provided complementary information, suggesting that the carbonate species originate from carbonyl ligands initially bonded to the rhenium and from hydroxyl groups of the titania surface, with the reaction leading to the formation of water and bridging hydroxyl groups on the titania. The results illustrate the value of using a family of organometallic complexes as probes of oxide surface sites.

Greenhouse gas emissions are enhanced by wastewater discharge into New York City coastal estuaries

NASA Astrophysics Data System (ADS)

Brigham, B. A.; O'Mullan, G. D.; Bird, J. A.

2016-12-01

The Hudson River Estuary (HRE) receives significant inputs of untreated wastewater from sewer overflow from New York City (NYC) and other urban areas. These inputs deliver large, concentrated pulses of carbon (C) and nitrogen (N) into the estuary primarily during storm events. We hypothesized that sewage inputs would increase carbon dioxide (CO2) and methane (CH4) efflux from the HRE via two mechanism: (1) direct input of these gases into estuarine surface waters from NYC's wastewater treatment system; and (2) indirect in-situ microbial production in response to the C and N additions. To test these hypotheses, CO2, CH4, dissolved organic C and inorganic N concentrations were measured in both sewage outflow and in estuarine waters. Efflux of CO2 and CH4 were also quantified from sediment cores sampled from Flushing Bay (FB), which is in close proximity to sewage delivery outlets. Wastewater discharge was found to be both a direct input in wastewater and an indirect source of CO2 and CH4 via microbial respiration. Effluent concentrations of CH4 (125 ppm), CO2 (2200 ρCO2), dissolved organic C, ammonium, and nitrate surface water concentrations, were a minimum of 3 times greater than in estuarine surface water adjacent to the sewage delivery area and up to 20 times greater than concentrations found in regional HRE surface waters. Incubation experiments with FB sediment demonstrated that acetate additions stimulated CO2 efflux by + 1.25 and CH4 efflux by +10 times, compared with unamended controls. The magnitude of CH4 produced was +40 times greater than from sediments incubated from a non-sewage affected area with similar salinity levels. However, total C mineralization (6 µg C day-1 g-1 of dry soil) was a small portion of the C amendment indicating negligible priming. These data warrant study on larger regional scales to assess the broader climate impact likely driven by CH4 efflux that results from discharge of untreated wastewater into urban estuaries.

Far-infrared spectra of CO2 clathrate hydrate frosts

NASA Technical Reports Server (NTRS)

Landry, J. C.; England, A. W.

1993-01-01

As a product of our interest in remote sensing of planetary ices, frost samples of CO2 clathrate hydrate were grown by depositing water vapor on a cooled surface and pressurizing the resulting water frost with CO2 gas. At pressures above the dissociation pressure of the clathrate, the samples exhibit an absorption peak at 75 cm (sup -1). At pressures below the dissociation pressure, the peak disappears. Since the free CO2 molecule does not have rotational or vibrational absorption in this region, the absorption is attributed to a CO2 rattling mode within a clathrate cage.

Evolution of CO2, CH4, and OCS abundances relative to H2O in the coma of comet 67P around perihelion from Rosetta/VIRTIS-H observations

NASA Astrophysics Data System (ADS)

Bockelée-Morvan, Dominique; Crovisier, J.; Erard, S.; Capaccioni, F.; Leyrat, C.; Filacchione, G.; Drossart, P.; Encrenaz, T.; Biver, N.; de Sanctis, M.-C.; Schmitt, B.; Kührt, E.; Capria, M.-T.; Combes, M.; Combi, M.; Fougere, N.; Arnold, G.; Fink, U.; Ip, W.; Migliorini, A.; Piccioni, G.; Tozzi, G.

2016-11-01

Infrared observations of the coma of 67P/Churyumov-Gerasimenko were carried out from 2015 July to September, I.e. around perihelion (2015 August 13), with the high-resolution channel of the Visible and Infrared Thermal Imaging Spectrometer instrument onboard Rosetta. We present the analysis of fluorescence emission lines of H2O, CO2, 13CO2, OCS, and CH4 detected in limb sounding with the field of view at 2.7-5 km from the comet centre. Measurements are sampling outgassing from the illuminated Southern hemisphere, as revealed by H2O and CO2 raster maps, which show anisotropic distributions, aligned along the projected rotation axis. An abrupt increase of water production is observed 6 d after perihelion. In the meantime, CO2, CH4, and OCS abundances relative to water increased by a factor of 2 to reach mean values of 32, 0.47, and 0.18 per cent, respectively, averaging post-perihelion data. We interpret these changes as resulting from the erosion of volatile-poor surface layers. Sustained dust ablation due to the sublimation of water ice maintained volatile-rich layers near the surface until at least the end of the considered period, as expected for low thermal inertia surface layers. The large abundance measured for CO2 should be representative of the 67P nucleus original composition, and indicates that 67P is a CO2-rich comet. Comparison with abundance ratios measured in the Northern hemisphere shows that seasons play an important role in comet outgassing. The low CO2/H2O values measured above the illuminated Northern hemisphere are not original, but the result of the devolatilization of the uppermost layers.

Grafting of carboxyl groups using CO2/C2H4/Ar pulsed plasma: Theoretical modeling and XPS derivatization

NASA Astrophysics Data System (ADS)

Manakhov, Anton; Kiryukhantsev-Korneev, Philip; Michlíček, Miroslav; Permyakova, Elizaveta; Dvořáková, Eva; Polčák, Josef; Popov, Zakhar; Visotin, Maxim; Shtansky, Dmitry V.

2018-03-01

The grafting of carboxyl groups enhances cell adhesion and can be used for immobilization of different biomolecules onto plasma-treated materials. The process, however, was not well optimized due to lack of clear understanding of the mechanisms of carboxylic group incorporation into plasma and their grafting to polymer surface. In this work the deposition of COOH plasma polymers from CO2/C2H4/Ar pulsed discharge has been studied depending on the gas mixture and duty cycle. We have demonstrated that the CO2/C2H4/Ar plasma with adjustable thickness of COOH functionalized layer and high stability of the grafted functions in water is a better solution for the COOH surface functionalization compared to the thoroughly analyzed CO2 plasma. The concentration of different carbon environments and the density of COOH groups have been measured by using chemical derivatization combined with X-ray photoelectron spectroscopy. It has been found that the CO2/C2H4/Ar plasma mainly contains ester groups (COOC), the COOH/COOC ratio being between 0.03 and 0.08. The water stability of the COOH groups was significantly higher compared to ester environment, so immersing in water for 24 h allowed to increase the COOH/COOC ratio by a factor of 3. The mechanisms of the CO2 molecule attachment to hydrocarbon chains on the polymer surface and those located inside the plasma were modeled using ab initio calculations.

Water Vapor Adsorption on Biomass Based Carbons under Post-Combustion CO2 Capture Conditions: Effect of Post-Treatment

PubMed Central

Querejeta, Nausika; Plaza, Marta G.; Rubiera, Fernando; Pevida, Covadonga

2016-01-01

The effect of post-treatment upon the H2O adsorption performance of biomass-based carbons was studied under post-combustion CO2 capture conditions. Oxygen surface functionalities were partially replaced through heat treatment, acid washing, and wet impregnation with amines. The surface chemistry of the final carbon is strongly affected by the type of post-treatment: acid treatment introduces a greater amount of oxygen whereas it is substantially reduced after thermal treatment. The porous texture of the carbons is also influenced by post-treatment: the wider pore volume is somewhat reduced, while narrow microporosity remains unaltered only after acid treatment. Despite heat treatment leading to a reduction in the number of oxygen surface groups, water vapor adsorption was enhanced in the higher pressure range. On the other hand acid treatment and wet impregnation with amines reduce the total water vapor uptake thus being more suitable for post-combustion CO2 capture applications. PMID:28773488

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cheng, Tao; Xiao, Hai; Goddard, William A.

Copper is the only elemental metal that reduces a significant fraction of CO 2 to hydrocarbons and alcohols, but the atomistic reaction mechanism that controls the product distributions is not known because it has not been possible to detect the reaction intermediates on the electrode surface experimentally, or to carry out Quantum Mechanics (QM) calculations with a realistic description of the electrolyte (water). We carry out QM calculations with an explicit description of water on the Cu(100) surface (experimentally shown to be stable under CO 2 reduction reaction conditions) to examine the initial reaction pathways to form CO and formatemore » (HCOO –) from CO 2 through free energy calculations at 298 K and pH 7. We find that CO formation proceeds from physisorbed CO 2 to chemisorbed CO 2 (*CO 2 δ-), with a free energy barrier of ΔG ‡ = 0.43 eV, the rate-determining step (RDS). The subsequent barriers of protonating *CO 2 δ- to form COOH* and then dissociating COOH* to form *CO are 0.37 and 0.30 eV, respectively. HCOO– formation proceeds through a very different pathway in which physisorbed CO 2 reacts directly with a surface H* (along with electron transfer), leading to ΔG ‡ = 0.80 eV. Thus, the competition between CO formation and HCOO – formation occurs in the first electron-transfer step. On Cu(100), the RDS for CO formation is lower, making CO the predominant product. Therefore, to alter the product distribution, we need to control this first step of CO 2 binding, which might involve controlling pH, alloying, or changing the structure at the nanoscale.« less

Geochemical detection of carbon dioxide in dilute aquifers

PubMed Central

2009-01-01

Background Carbon storage in deep saline reservoirs has the potential to lower the amount of CO2 emitted to the atmosphere and to mitigate global warming. Leakage back to the atmosphere through abandoned wells and along faults would reduce the efficiency of carbon storage, possibly leading to health and ecological hazards at the ground surface, and possibly impacting water quality of near-surface dilute aquifers. We use static equilibrium and reactive transport simulations to test the hypothesis that perturbations in water chemistry associated with a CO2 gas leak into dilute groundwater are important measures for the potential release of CO2 to the atmosphere. Simulation parameters are constrained by groundwater chemistry, flow, and lithology from the High Plains aquifer. The High Plains aquifer is used to represent a typical sedimentary aquifer overlying a deep CO2 storage reservoir. Specifically, we address the relationships between CO2 flux, groundwater flow, detection time and distance. The CO2 flux ranges from 103 to 2 × 106 t/yr (0.63 to 1250 t/m2/yr) to assess chemical perturbations resulting from relatively small leaks that may compromise long-term storage, water quality, and surface ecology, and larger leaks characteristic of short-term well failure. Results For the scenarios we studied, our simulations show pH and carbonate chemistry are good indicators for leakage of stored CO2 into an overlying aquifer because elevated CO2 yields a more acid pH than the ambient groundwater. CO2 leakage into a dilute groundwater creates a slightly acid plume that can be detected at some distance from the leak source due to groundwater flow and CO2 buoyancy. pH breakthrough curves demonstrate that CO2 leaks can be easily detected for CO2 flux ≥ 104 t/yr within a 15-month time period at a monitoring well screened within a permeable layer 500 m downstream from the vertical gas trace. At lower flux rates, the CO2 dissolves in the aqueous phase in the lower most permeable unit and does not reach the monitoring well. Sustained pumping in a developed aquifer mixes the CO2-affected water with the ambient water and enhances pH signal for small leaks (103 t/yr) and reduces pH signal for larger leaks (≥ 104t/yr). Conclusion The ability to detect CO2 leakage from a storage reservoir to overlying dilute groundwater is dependent on CO2 solubility, leak flux, CO2 buoyancy, and groundwater flow. Our simulations show that the most likely places to detect CO2 are at the base of the confining layer near the water table where CO2 gas accumulates and is transported laterally in all directions, and downstream of the vertical gas trace where groundwater flow is great enough to transport dissolved CO2 laterally. Our simulations show that CO2 may not rise high enough in the aquifer to be detected because aqueous solubility and lateral groundwater transport within the lower aquifer unit exceeds gas pressure build-up and buoyancy needed to drive the CO2 gas upwards. PMID:19323832

Geochemical detection of carbon dioxide in dilute aquifers.

PubMed

Carroll, Susan; Hao, Yue; Aines, Roger

2009-03-26

Carbon storage in deep saline reservoirs has the potential to lower the amount of CO2 emitted to the atmosphere and to mitigate global warming. Leakage back to the atmosphere through abandoned wells and along faults would reduce the efficiency of carbon storage, possibly leading to health and ecological hazards at the ground surface, and possibly impacting water quality of near-surface dilute aquifers. We use static equilibrium and reactive transport simulations to test the hypothesis that perturbations in water chemistry associated with a CO2 gas leak into dilute groundwater are important measures for the potential release of CO2 to the atmosphere. Simulation parameters are constrained by groundwater chemistry, flow, and lithology from the High Plains aquifer. The High Plains aquifer is used to represent a typical sedimentary aquifer overlying a deep CO2 storage reservoir. Specifically, we address the relationships between CO2 flux, groundwater flow, detection time and distance. The CO2 flux ranges from 10(3) to 2 x 10(6) t/yr (0.63 to 1250 t/m2/yr) to assess chemical perturbations resulting from relatively small leaks that may compromise long-term storage, water quality, and surface ecology, and larger leaks characteristic of short-term well failure. For the scenarios we studied, our simulations show pH and carbonate chemistry are good indicators for leakage of stored CO2 into an overlying aquifer because elevated CO2 yields a more acid pH than the ambient groundwater. CO2 leakage into a dilute groundwater creates a slightly acid plume that can be detected at some distance from the leak source due to groundwater flow and CO2 buoyancy. pH breakthrough curves demonstrate that CO2 leaks can be easily detected for CO2 flux >or= 10(4) t/yr within a 15-month time period at a monitoring well screened within a permeable layer 500 m downstream from the vertical gas trace. At lower flux rates, the CO2 dissolves in the aqueous phase in the lower most permeable unit and does not reach the monitoring well. Sustained pumping in a developed aquifer mixes the CO2-affected water with the ambient water and enhances pH signal for small leaks (10(3) t/yr) and reduces pH signal for larger leaks (>or= 10(4) t/yr). The ability to detect CO2 leakage from a storage reservoir to overlying dilute groundwater is dependent on CO2 solubility, leak flux, CO2 buoyancy, and groundwater flow. Our simulations show that the most likely places to detect CO2 are at the base of the confining layer near the water table where CO2 gas accumulates and is transported laterally in all directions, and downstream of the vertical gas trace where groundwater flow is great enough to transport dissolved CO2 laterally. Our simulations show that CO2 may not rise high enough in the aquifer to be detected because aqueous solubility and lateral groundwater transport within the lower aquifer unit exceeds gas pressure build-up and buoyancy needed to drive the CO2 gas upwards.

Assessing Near-surface Heat, Water Vapor and Carbon Dioxide Exchange Over a Coastal Salt-marsh

NASA Astrophysics Data System (ADS)

Bogoev, I.; O'Halloran, T. L.; LeMoine, J.

2017-12-01

Coastal ecosystems play an important role in mitigating the effects of climate change by storing significant quantities of carbon. A growing number of studies suggest that vegetated estuarine habitats, specifically salt marshes, have high long-term rates of carbon sequestration, perhaps even higher than mature tropical and temperate forests. Large amounts of carbon, accumulated over thousands of years, are stored in the plant materials and sediment. Improved understanding of the factors that control energy and carbon exchange is needed to better guide restoration and conservation management practices. To that end, we recently established an observation system to study marsh-atmosphere interactions within the North Inlet-Winyah Bay National Estuarine Research Reserve. Near-surface fluxes of heat, water vapor (H2O) and carbon dioxide (CO2) were measured by an eddy-covariance system consisting of an aerodynamic open-path H2O / CO2 gas analyzer with a spatially integrated 3D sonic anemometer/thermometer (IRGASON). The IRGASON instrument provides co-located and highly synchronized, fast response H2O, CO2 and air- temperature measurements, which eliminates the need for spectral corrections associated with the separation between the sonic anemometer and the gas analyzer. This facilitates calculating the instantaneous CO2 molar mixing ratio relative to dry air. Fluxes computed from CO2 and H2O mixing ratios, which are conserved quantities, do not require post-processing corrections for air-density changes associated with temperature and water vapor fluctuations. These corrections are particularly important for CO2, because they could be even larger than the measured flux. Here we present the normalized frequency spectra of air temperature, water vapor and CO2, as well as their co-spectra with the co-located vertical wind. We also show mean daily cycles of sensible, latent and CO2 fluxes and analyze correlations with air/water temperature, wind speed and light availability.

Modelling the aqueous and nonaqueous interfaces for CO2 electro-reduction over Sn catalysts

NASA Astrophysics Data System (ADS)

Sheng, Tian; Sun, Shi-Gang

2018-01-01

In CO2 electroreduction, Sn catalysts with a high overpotential for hydrogen evolution reaction and a high selectivity towards formic acid formation are very attractive. Many efforts have been made for improving the catalytic performance and for understanding the mechanisms. In electrochemistry, the role of solvents for surface reactions was deserved to be investigated, in particular for some nonaqueous solvents. Here, we have modeled the aqueous (water) and nonaqueous (acetonitrile and dichloromethane) for investigation of CO2 electroreduction on Sn surface, by constrained ab initio molecular dynamics simulations and thermodynamic integrations, including a number of explicit solvent molecules in computational models. It was found that CO2 reduction is initiated from formate formation and solvents, in particular, water can effectively facilitate the reaction.

Effect of CO2 and Nd:YAG Lasers on Shear Bond Strength of Resin Cement to Zirconia Ceramic.

PubMed

Kasraei, Shahin; Rezaei-Soufi, Loghman; Yarmohamadi, Ebrahim; Shabani, Amanj

2015-09-01

Because of poor bond between resin cement and zirconia ceramics, laser surface treatments have been suggested to improve adhesion. The present study evaluated the effect of CO2 and Nd:YAG lasers on the shear bond strength (SBS) of resin cement to zirconia ceramic. Ninety zirconia disks (6×2 mm) were randomly divided into six groups of 15. In the control group, no surface treatment was used. In the test groups, laser surface treatment was accomplished using CO2 and Nd:YAG lasers, respectively (groups two and three). Composite resin disks (3×2 mm) were fabricated and cemented to zirconia disks with self-etch resin cement and stored in distilled water for 24 hours. In the test groups four-six, the samples were prepared as in groups one-three and then thermocycled and stored in distilled water for six months. The SBS tests were performed (strain rate of 0.5 mm/min). The fracture modes were observed via stereomicroscopy. Data were analyzed with one and two-way ANOVA, independent t and Tukey's tests. The SBS values of Nd:YAG group (18.95±3.46MPa) was significantly higher than that of the CO2 group (14.00±1.96MPa), but lower than that of controls (23.35±3.12MPa). After thermocycling and six months of water storage, the SBS of the untreated group (1.80±1.23 MPa) was significantly lower than that of the laser groups. In groups stored for 24 hours, 60% of the failures were adhesive; however, after thermocycling and six months of water storage, 100% of failures were adhesive. Bonding durability of resin cement to zirconia improved with CO2 and Nd:YAG laser surface treatment of zirconia ceramic.

Effects of ocean acidification, warming and melting of sea ice on aragonite saturation of the Canada Basin surface water

NASA Astrophysics Data System (ADS)

Yamamoto-Kawai, M.; McLaughlin, F. A.; Carmack, E. C.

2011-02-01

In 2008, surface waters in the Canada Basin of the Arctic Ocean were found to be undersaturated with respect to aragonite. This is associated with recent extensive melting of sea ice in this region, as well as elevated sea surface temperature and atmospheric CO2 concentrations. We have estimated the relative contribution of each of these controlling factors to the calcium carbonate saturation state (Ω) from observations of dissolved inorganic carbon, total alkalinity and oxygen isotope ratio. Results indicate that the increase in atmospheric CO2 has lowered surface Ω by ˜0.3 in the Canada Basin since the preindustrial period. Recent melting of sea ice has further lowered mean Ω by 0.4, and of this, half was due to dilution of surface water and half was due to the change in air-sea disequilibrium state. Surface water warming has generally counteracted the mean decrease in Ω by 0.1.

The role of Southern Ocean mixing and upwelling in glacial-interglacial atmospheric CO2 change

NASA Astrophysics Data System (ADS)

Watson, Andrew J.; Naveira Garabato, Alberto C.

2006-02-01

Decreased ventilation of the Southern Ocean in glacial time is implicated in most explanations of lower glacial atmospheric CO2. Today, the deep (>2000 m) ocean south of the Polar Front is rapidly ventilated from below, with the interaction of deep currents with topography driving high mixing rates well up into the water column. We show from a buoyancy budget that mixing rates are high in all the deep waters of the Southern Ocean. Between the surface and ~2000 m depth, water is upwelled by a residual meridional overturning that is directly linked to buoyancy fluxes through the ocean surface. Combined with the rapid deep mixing, this upwelling serves to return deep water to the surface on a short time scale. We propose two new mechanisms by which, in glacial time, the deep Southern Ocean may have been more isolated from the surface. Firstly, the deep ocean appears to have been more stratified because of denser bottom water resulting from intense sea ice formation near Antarctica. The greater stratification would have slowed the deep mixing. Secondly, subzero atmospheric temperatures may have meant that the present-day buoyancy flux from the atmosphere to the ocean surface was reduced or reversed. This in turn would have reduced or eliminated the upwelling (contrary to a common assumption, upwelling is not solely a function of the wind stress but is coupled to the air-sea buoyancy flux too). The observed very close link between Antarctic temperatures and atmospheric CO2 could then be explained as a natural consequence of the connection between the air-sea buoyancy flux and upwelling in the Southern Ocean, if slower ventilation of the Southern Ocean led to lower atmospheric CO2. Here we use a box model, similar to those of previous authors, to show that weaker mixing and reduced upwelling in the Southern Ocean can explain the low glacial atmospheric CO2 in such a formulation.

The Role of H2O in the Carbonation of Forsterite in Supercritical CO2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kwak, Ja Hun; Hu, Jian Z.; Turcu, Romulus VF

2011-07-01

The water concentration dependence of forsterite carbonation in supercritical CO2 (scCO2) at 80°C and 76 bars was investigated by a combination of NMR, XRD, TEM and XPS. Reaction products were not detected using scCO2 alone without added H2O. When trace amounts of water were included, limited reaction was observed. Below saturation, reaction products were a mixture of partially hydrated/hydroxylated magnesium carbonates and hydroxylated silica species that were mainly in an amorphous state, forming a non-resolved layer on the forsterite surface. At water concentrations above saturation, where forsterite was in contact with both a CO2-saturated aqueous fluid and a water-saturated scCO2more » fluid, solid reaction products were magnesite (MgCO3) and an amorphous polymerized SiO2 dominated by Q4, and to a lesser extent by Q3 silica coordination. Formation of these phases implies H2O initially bound in precursor hydrated/hydroxylated reaction products was liberated, inducing further reaction. Hence, for a given fluid/mineral ratio there is a water threshold above which a significant portion of the water serves in a catalytic role where more extensive carbonation reaction occurs. Defining the role of water, even in low water content environments, is therefore critical to determining the long term impact of CO2 reactivity in the subsurface.« less

Water stress impacts on bacterial carbon monoxide oxidation on recent volcanic deposits.

PubMed

Weber, Carolyn F; King, Gary M

2009-12-01

Water availability oscillates dramatically on young volcanic deposits, and may control the distribution and activity of microbes during early stages of biological succession. Carbon monoxide (CO)-oxidizing bacteria are among the pioneering colonists on volcanic deposits and are subjected to these water stresses. We report here the effects of water potential on CO-oxidizing bacteria in unvegetated (bare) and vegetated (canopy) sites on a 1959 volcanic deposit on Kilauea Volcano (Hawai'i). Time course measurements of water potential showed that average water potentials in the surface layer (0-1 cm) of canopy soil remained between -0.1 and 0 MPa, whereas dramatic diurnal oscillations (for example, between -60 and 0 MPa) occur in bare site surface cinders. During a moderate drying event in situ (-1.7 to 0 MPa), atmospheric CO consumption by intact bare site cores decreased 2.7-fold. For bare and canopy surface samples, maximum potential CO oxidation rates decreased 40 and 60%, respectively, when water potentials were lowered from 0 to -1.5 MPa in the laboratory. These observations indicated that CO oxidation is moderately sensitive to changes in water potential. Additional analyses showed that CO oxidation resumes within a few hours of rehydration, even after desiccation at -150 MPa for 63 days. Samples from both sites exposed to multiple cycles of drying and rewetting (-80 to 0 MPa), lost significant activity after the first cycle, but not after subsequent cycles. Similar responses of CO oxidation in both sites suggested that active CO-oxidizing communities in bare and canopy sites do not express differential adaptations to water stress.

Vertical observation of molecular hydrogen and carbon monoxide: Implication for non-photochemical H2 production at ocean surface and subsurface

NASA Astrophysics Data System (ADS)

Kawagucci, S.; Narita, T.; Obata, H.; Ogawa, H.; Gamo, T.

2009-12-01

Biological nitrogen fixation is a key metabolism controlling marine N-cycling and also known as a main H2 source. Recently, it was proposed that a monitoring of surface H2 concentration could be used quickly to figure out the spatial extent of biological nitrogen fixation activity without onboard incubation required for currently used methods for detecting the activity. However, H2 behavior in ocean water was still unresolved. This study carried out vertical observation of H2 and CO concentrations in south of Japan, western North Pacific. Because carbon monoxide, CO, in seawater has no relation with nitrogen fixation metabolism and is produced dominantly by the photochemical reaction, which is an altanative H2 source, simultaneous observation and comparison of H2 and CO concentration is helpful to investigate H2 behavior in ocean water. Reductive gases in seawater were observed during the R/V Tansei-maru KT-08-14 cruise by using a wired CTD-CMS (CTD-carousel multiple sampling) system to conduct vertical sampling (at most 200 m depth) and by using a plastic bucket for sampling surface seawater. The sample in the Niskin-X bottle was directed to the bottom of a 120 mL brown-colored glass vial allowed to overflow by 2 volumes before the tube was slowly withdrawn. After the addition of 0.5 mL HgCl2-saturated solution for poisoning, the PTFE-lined butyl-gum septum was used to cap the vials. Molecular hydrogen (H2) and carbon monoxide (CO) were analyzed at an onboard laboratory within 6 hours after subsampling. 20 mL of sample water was substituted by 20 mL of H2- and CO-free air using a gas-tight syringe; then the vial was put on an automatic shaker and shaken upside down for 6 minutes to achieve a complete equilibrium between the dissolved and head space gases in the vial. The equilibrated headspace was taken by another gas-tight syringe and then injected into a gas chromatograph equipped with a trace reduced gas detector. Vertical distribution of dissolved H2 and CO concentration were observed. Apparently different vertical distributions between H2 and CO concentration were revealed at all the observed stations. At a station where N-nutrient was depleted through surface mixed layer, H2 was supersaturated at the surface while CO concentration was constant through the depths. In contrast, at another station where some amount of terrestrial humic matter was introduced into the surface, H2 concentration was constantly undersaturated through the depth while vertical distribution of CO concentration showed the highest at the surface and exponentially decreased to deep. These facts suggest that H2 production involved with nitrogen fixation played an important role for H2 behavior in ocean water while photochemical H2 production would be a minor process. In addition to the surface, H2 supersaturation accoumpanied with little CO concentration rise were observed at depths just below the mixed layer in pycnocline with Chlorophyll maximum.

CO2-Binding Organic Liquids Gas Capture with Polarity-Swing-Assisted Regeneration Full Technology Feasibility Study B1 - Solvent-based Systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Heldebrant, David J

PNNL, Fluor Corporation and Queens University (Kingston, ON) successfully completed a three year comprehensive study of the CO2BOL water-lean solvent platform with Polarity Swing Assisted Regeneration (PSAR). This study encompassed solvent synthesis, characterization, environmental toxicology, physical, thermodynamic and kinetic property measurements, Aspen Plus™ modeling and bench-scale testing of a candidate CO2BOL solvent molecule. Key Program Findings The key program findings are summarized as follows: • PSAR favorably reduced stripper duties and reboiler temperatures with little/no impact to absorption column • >90% CO2 capture was achievable at reasonable liquid-gas ratios in the absorber • High rich solvent viscosities (up to 600more » cP) were successfully demonstrated in the bench-scale system. However, the projected impacts of high viscosity to capital cost and operational limits compromised the other levelized cost of electricity benefits. • Low thermal conductivity of organics significantly increased the required cross exchanger surface area, and potentially other heat exchange surfaces. • CO2BOL had low evaporative losses during bench-scale testing • There was no evidence of foaming during bench scale testing • Current CO2BOL formulation costs project to be $35/kg • Ecotoxicity (Water Daphnia) was comparable between CO2BOL and MEA (169.47 versus 103.63 mg/L) • Full dehydration of the flue gas was determined to not be economically feasible. However, modest refrigeration (13 MW for the 550 MW reference system) was determined to be potentially economically feasible, and still produce a water-lean condition for the CO2BOLs (5 wt% steady-state water loading). • CO2BOLs testing with 5 wt% water loading did not compromise anhydrous performance behavior, and showed actual enhancement of CO2 capture performance. • Mass transfer of CO2BOLs was not greatly impeded by viscosity • Facile separation of antisolvent from lean CO2BOL was demonstrated on the bench cart • No measurable solvent degradation was observed over 4 months of testing – even with 5 wt% water present« less

Subsurface oxide plays a critical role in CO 2 activation by Cu(111) surfaces to form chemisorbed CO 2, the first step in reduction of CO 2

DOE PAGES

Favaro, Marco; Xiao, Hai; Cheng, Tao; ...

2017-06-12

A national priority is to convert CO 2 into high-value chemical products such as liquid fuels. Because current electrocatalysts are not adequate, we aim to discover new catalysts by obtaining a detailed understanding of the initial steps of CO 2 electroreduction on copper surfaces, the best current catalysts. Using ambient pressure X-ray photoelectron spectroscopy interpreted with quantum mechanical prediction of the structures and free energies, we show that the presence of a thin suboxide structure below the copper surface is essential to bind the CO 2 in the physisorbed configuration at 298 K, and we show that this suboxide ismore » essential for converting to the chemisorbed CO 2 in the presence of water as the first step toward CO 2 reduction products such as formate and CO. This optimum suboxide leads to both neutral and charged Cu surface sites, providing fresh insights into how to design improved carbon dioxide reduction catalysts.« less

Spatiotemporal trends in surface seawater CO2 in the Gulf of Mexico

NASA Astrophysics Data System (ADS)

Kealoha, A. K.; Shamberger, K.

2016-12-01

The Gulf of Mexico (GoM) contains many interconnected ecosystems intimately linked to regional economic stability through fisheries. Yet, numerous human pressures, including eutrophication-induced hypoxia and ocean acidification (OA), threaten the health of this large marine ecosystem. A comprehensive characterization of the drivers of GoM seawater CO2 cycling is required to assess interactions between these local stresses, global climate change, and OA. Several observational and modeling studies have been conducted in an effort to characterize CO2-system trends within the GoM. However, observational studies are limited to specific regions and time-frames, while modeled data are based on parameterizations that often cannot account for all the biogeochemical processes occurring in this complex system. Here, we present a compilation of approximately 510,000 continuous, underway measurements of sea surface temperature, salinity and seawater CO2, collected from 1996-2013 throughout the entire GoM. These data reveal distinct spatial and temporal CO2 trends that are driven primarily by temperature, Mississippi River outflow, biological productivity, and water circulation. For example, during the spring and summer, nutrient input from the Mississippi River stimulates biological productivity that drives surface seawater CO2 below atmospheric levels in the north-central GoM shelf waters. Although open ocean waters are generally a source of CO2 to the atmosphere in the summer, a unique combination of physical processes including high river discharge, offshore currents and eddy activity can transport low CO2 coastal water beyond the shelf causing vast areas, tens of thousands of square kilometers, of the open ocean to switch to a CO2 sink for several months. Since anthropogenic-driven climate change is expected to influence ocean circulation patterns, GoM CO2 source-sink characteristics and regional scale ocean carbon budgets may be altered in the future. We also combine discrete CO2 chemistry data collected in the Flower Garden Banks National Marine Sanctuary with historical underway data to provide insight into the connections between Gulf wide carbon variability and variability within these important coral reef ecosystems.

CO2 sensing of La0.875Ca0.125FeO3 in wet vapor: a comparison of experimental results and first-principles calculations.

PubMed

Wang, Xiaofeng; Chen, Yanping; Qin, Hongwei; Li, Ling; Shi, Changmin; Liu, Liang; Hu, Jifan

2015-05-28

Experimental results show that with an increase of relative humidity, the resistance of La0.875Ca0.125FeO3 decreases at room temperature but increases at higher temperatures (140-360 °C). The humid effect at room temperature is due to the movement of H(+) or H3O(+) inside of the condensed water layer on the surface of La0.875Ca0.125FeO3. Regarding the humid effect at high temperatures, the density functional theory (DFT) calculations show that H2O can be adsorbed onto the La0.875Ca0.125FeO3 surface in the molecular and dissociative adsorption configurations, where the La0.875Ca0.125FeO3 surface gains some electrons from H2O or its dissociative products, consistent with our observation. Experimental results also show that CO2 sensing response at high temperatures decreases with an increase of room-temperature relative humidity. DFT calculations indicate that CO2 adsorbed onto the La0.875Ca0.125FeO3(010) surface, where high concentration oxygen adsorption occurs without water adsorption nearby, releases some electrons into the semiconductor surface, playing the role of a donor. The interaction between CO2 and the local La0.875Ca0.125FeO3(010) surface with pre-adsorption of H2O nearby results in some electron transfer from the La0.875Ca0.125FeO3 surface to CO2, which is responsible for the weakening of CO2 response at high temperatures for La0.875Ca0.125FeO3 with an increase of room-temperature relative humidity.

Gravel bar thermal variability and its potential consequences for CO2 evasion from Alpine coldwater streams

NASA Astrophysics Data System (ADS)

Boodoo, Kyle; Battin, Tom; Schelker, Jakob

2017-04-01

Gravel bars (GB) are ubiquitous in-stream structures with relatively large exposed surfaces, capable of absorbing heat and possibly acting as a heat source to the underlying hyporheic zone (HZ). The distinctive mixing of groundwater and surface water within their HZ largely determines its characteristic physical and biogeochemical properties, including temperature distribution. To study thermal variability within GBs and its possible consequences for CO2 evasion fluxes we analysed high frequency spatio-temporal data for a range of stream and atmospheric physical parameters including the vertical GB temperature, in an Alpine cold water stream (Oberer Seebach, Austria) over the course of a year. We found the vertical temperature profiles within the GB to vary seasonally and with discharge. We extended our study to 13 other gravel bars of varying physical characteristics within the surrounding Ybbs and Erlauf catchments, conducting diurnal spot samplings in summer 2016. Temperatures within the observed permanently wetted hyporheic zone (-56 to -100cm depth below GB surface) of the OSB, were warmer than both end members, surface water and groundwater >18% of the year, particularly during summer. There was a general increase in exceedance within the periodically wetted gravel bar sediment toward the gravel bar surface, further evidencing downward heat transfer to the wetted HZ. Average CO2 flux from the GB was significantly higher than that of streamwater during summer and winter, with significantly higher temperatures and CO2 outgassing rates occurring at the GB tail as compared to streamwater and the head and mid of the GB throughout the year. Higher cumulative (over 6 h) GB seasonal temperatures were associated with increased CO2 evasion fluxes within the OSB, particularly during summer. This enhanced CO2 flux may result from the input of warmer CO2-rich groundwater into the HZ in autumn, while downward heat transfer in summer may enhance GB metabolism and therefore CO2 evasion. Furthermore, catchment CO2 outgassing fluxes significantly exceeded that of the stream, with higher diurnal CO2 outgassing fluxes observed for all 13 GBs within the Ybbs and Erlauf catchments as compared to their respective streams. We found DOC concentration did not significantly correlate to CO2 outgassing. But, vertical temperature gradient as a measure of heat flux to the hyporheic zone explained 55% and 69% of the variability in observed CO2 efflux from the OSB gravel bar (seasonal samplings during summer 2015 - winter 2016) and 11 catchment gravel bars (2 GBs excluded due to equipment malfunction) respectively. These results highlight the effect of temperature on physical and biochemical stream processes, particularly in cold-water streams, due to the occurrence of more frequent and intense warm temperature events, as well as altered flow regimes, likely consequences of climatic change.

Composition and physical properties of Enceladus' surface

USGS Publications Warehouse

Brown, R.H.; Clark, R.N.; Buratti, B.J.; Cruikshank, D.P.; Barnes, J.W.; Mastrapa, R.M.E.; Bauer, J.; Newman, S.; Momary, T.; Baines, K.H.; Bellucci, G.; Capaccioni, F.; Cerroni, P.; Combes, M.; Coradini, A.; Drossart, P.; Formisano, V.; Jaumann, R.; Langavin, Y.; Matson, D.L.; McCord, T.B.; Nelson, R.M.; Nicholson, P.D.; Sicardy, B.; Sotin, Christophe

2006-01-01

Observations of Saturn's satellite Enceladus using Cassini's Visual and Infrared Mapping Spectrometer instrument were obtained during three flybys of Enceladus in 2005. Enceladus' surface is composed mostly of nearly pure water ice except near its south pole, where there are light organics, CO2, and amorphous and crystalline water ice, particularly in the region dubbed the "tiger stripes." An upper limit of 5 precipitable nanometers is derived for CO in the atmospheric column above Enceladus, and 2% for NH 3 in global surface deposits. Upper limits of 140 kelvin (for a filled pixel) are derived for the temperatures in the tiger stripes.

Process for producing methane from gas streams containing carbon monoxide and hydrogen

DOEpatents

Frost, Albert C.

1980-01-01

Carbon monoxide-containing gas streams are passed over a catalyst capable of catalyzing the disproportionation of carbon monoxide so as to deposit a surface layer of active surface carbon on the catalyst essentially without formation of inactive coke thereon. The surface layer is contacted with steam and is thus converted to methane and CO.sub.2, from which a relatively pure methane product may be obtained. While carbon monoxide-containing gas streams having hydrogen or water present therein can be used only the carbon monoxide available after reaction with said hydrogen or water is decomposed to form said active surface carbon. Although hydrogen or water will be converted, partially or completely, to methane that can be utilized in a combustion zone to generate heat for steam production or other energy recovery purposes, said hydrogen is selectively removed from a CO--H.sub.2 -containing feed stream by partial oxidation thereof prior to disproportionation of the CO content of said stream.

In situ mid-infrared spectroscopic titration of forsterite with water in supercritical CO2: Dependence of mineral carbonation on quantitative water speciation

NASA Astrophysics Data System (ADS)

Loring, J. S.; Thompson, C. J.; Wang, Z.; Schaef, H. T.; Martin, P.; Qafoku, O.; Felmy, A. R.; Rosso, K. M.

2011-12-01

Geologic sequestration of carbon dioxide holds promise for helping mitigate CO2 emissions generated from the burning of fossil fuels. Supercritical CO2 (scCO2) plumes containing variable water concentrations (wet scCO2) will displace aqueous solution and dominate the pore space adjacent to caprocks. It is important to understand possible mineral reactions with wet scCO2 to better predict long-term caprock integrity. We introduce novel in situ instrumentation that enables quantitative titrations of reactant minerals with water in scCO2 at temperatures and pressures relevant to target geologic reservoirs. The system includes both transmission and attenuated total reflection mid-infrared optics. Transmission infrared spectroscopy is used to measure concentrations of water dissolved in the scCO2, adsorbed on mineral surfaces, and incorporated into precipitated carbonates. Single-reflection attenuated total reflection infrared spectroscopy is used to monitor water adsorption, mineral dissolution, and carbonate precipitation reactions. Results are presented for the infrared spectroscopic titration of forsterite (Mg2SiO4), a model divalent metal silicate, with water in scCO2 at 100 bar and at both 50 and 75°C. The spectral data demonstrate that the quantitative speciation of water as either dissolved or adsorbed is important for understanding the types, growth rates, and amounts of carbonate precipitates formed. Relationships between dissolved/adsorbed water, water concentrations, and the role of liquid-like adsorbed water are discussed. Our results unify previous in situ studies from our laboratory based on infrared spectroscopy, nuclear magnetic resonance spectroscopy and X-ray diffraction.

Subsurface watering resulted in reduced soil N2O and CO2 emissions and their global warming potentials than surface watering

NASA Astrophysics Data System (ADS)

Wei, Qi; Xu, Junzeng; Yang, Shihong; Liao, Linxian; Jin, Guangqiu; Li, Yawei; Hameed, Fazli

2018-01-01

Water management is an important practice with significant effect on greenhouse gases (GHG) emission from soils. Nitrous oxide (N2O) and carbon dioxide (CO2) emissions and their global warming potentials (GWPs) from subsurface watering soil (SUW) were investigated, with surface watering (SW) as a control. Results indicated that the N2O and CO2 emissions from SUW soils were somewhat different to those from SW soil, with the peak N2O and CO2 fluxes from SUW soil reduced by 28.9% and 19.4%, and appeared 72 h and 168 h later compared with SW. The fluxes of N2O and CO2 from SUW soils were lower than those from SW soil in both pulse and post-pulse periods, and the reduction was significantly (p<0.05) in pulse period. Compare to SW, the cumulative N2O and CO2 emissions and its integrative GWPs from SUW soil decreased by 21.0% (p<0.05), 15.9% and 18.0%, respectively. The contributions of N2O to GWPs were lower than those of CO2 during most of time, except in pulse emission periods, and the proportion of N2O from SUW soil was 1.4% (p>0.1) lower that from SW soil. Moreover, N2O and CO2 fluxes from both watering treatments increased exponentially with increase of soil water-filled pore space (WFPS) and temperature. Our results suggest that watering soil from subsurface could significantly reduce the integrative greenhouse effect caused by N2O and CO2 and is a promising strategy for soil greenhouse gases (GHGs) mitigation. And the pulse period, contributed most to the reduction in emissions of N2O and CO2 from soils between SW and SUW, should be a key period for mitigating GHGs emissions. Response of N2O and CO2 emissions to soil WFPS and temperature illustrated that moisture was the dominant parameters that triggering GHG pulse emissions (especially for N2O), and temperature had a greater effect on the soil microorganism activity than moisture in drier soil. Avoiding moisture and temperature are appropriate for GHG emission at the same time is essential for GHGs mitigation, because peak N2O and CO2 emission were observed only when moisture and temperature are both appropriate.

Modeling climate diversity, tidal dynamics and the fate of volatiles on TRAPPIST-1 planets

NASA Astrophysics Data System (ADS)

Turbet, Martin; Bolmont, Emeline; Leconte, Jeremy; Forget, François; Selsis, Franck; Tobie, Gabriel; Caldas, Anthony; Naar, Joseph; Gillon, Michaël

2018-05-01

TRAPPIST-1 planets are invaluable for the study of comparative planetary science outside our solar system and possibly habitability. Both transit timing variations (TTV) of the planets and the compact, resonant architecture of the system suggest that TRAPPIST-1 planets could be endowed with various volatiles today. First, we derived from N-body simulations possible planetary evolution scenarios, and show that all the planets are likely in synchronous rotation. We then used a versatile 3D global climate model (GCM) to explore the possible climates of cool planets around cool stars, with a focus on the TRAPPIST-1 system. We investigated the conditions required for cool planets to prevent possible volatile species to be lost permanently by surface condensation, irreversible burying or photochemical destruction. We also explored the resilience of the same volatiles (when in condensed phase) to a runaway greenhouse process. We find that background atmospheres made of N2, CO, or O2 are rather resistant to atmospheric collapse. However, even if TRAPPIST-1 planets were able to sustain a thick background atmosphere by surviving early X/EUV radiation and stellar wind atmospheric erosion, it is difficult for them to accumulate significant greenhouse gases like CO2, CH4, or NH3. CO2 can easily condense on the permanent nightside, forming CO2 ice glaciers that would flow toward the substellar region. A complete CO2 ice surface cover is theoretically possible on TRAPPIST-1g and h only, but CO2 ices should be gravitationally unstable and get buried beneath the water ice shell in geologically short timescales. Given TRAPPIST-1 planets large EUV irradiation (at least 103 × Titan's flux), CH4 and NH3 are photodissociated rapidly and are thus hard to accumulate in the atmosphere. Photochemical hazes could then sedimentate and form a surface layer of tholins that would progressively thicken over the age of the TRAPPIST-1 system. Regarding habitability, we confirm that few bars of CO2 would suffice to warm the surface of TRAPPIST-1f and g above the melting point of water. We also show that TRAPPIST-1e is a remarkable candidate for surface habitability. If the planet is today synchronous and abundant in water, then it should very likely sustain surface liquid water at least in the substellar region, whatever the atmosphere considered.

Dynamic interaction of CO/H 2O mixtures with gold nanocrystals: Real-time imaging and local chemical probing

NASA Astrophysics Data System (ADS)

Visart de Bocarmé, Thierry; Chau, Thoi-Dai; Kruse, Norbert

2006-09-01

The dynamic interaction of pure gold nanocrystals ("tips") with H 2O/CO gas mixtures was studied by means of video-field ion microscopy (FIM). While imaging with nano-scale resolution selected areas of the equivalent of ˜200 atomic Au sites were analysed for their chemical composition using short field pulses and injecting respective ions into a time-of-flight mass spectrometer (pulsed field desorption mass spectrometry, PFDMS). At room temperature the exposure of a clean Au sample to water gas at 10 -4 Pa, in the presence of an electric field of ˜10 V/nm, led to water adsorption and formation of bright patterns in FIM. Additional exposure to CO gas at 5 × 10 -3 Pa led to the removal of the water layer. This was associated with the occurrence of bright wave fronts which ignited simultaneously in several regions of the Au surface with no preference for a certain crystallographic surface plane. In some cases wave fronts were seen to collide resulting in more complicated patterns such as concentric rings. Surface areas free of water appeared with low brightness. The phenomena were completely reversible. PFDMS demonstrated water ions to be responsible for image formation. Surface hydroxyl was also detected mass spectrometrically and respective ion intensities decreased during the titration with CO. The results suggest that gold nanocrystals, in the absence of oxidic support materials, may be active in the reaction between water and CO at temperatures as low as 300 K and in the presence of an electric field of ˜10 V/nm.

Heat flow vs. atmospheric greenhouse on early Mars

NASA Technical Reports Server (NTRS)

Fanale, F. P.; Postawko, S. E.

1991-01-01

Researchers derived a quantitative relationship between the effectiveness of an atmospheric greenhouse and internal heat flow in producing the morphological differences between earlier and later Martian terrains. The derivation is based on relationships previously derived by other researchers. The reasoning may be stated as follows: the CO2 mean residence time in the Martian atmosphere is almost certainly much shorter than the total time span over which early climate differences are thought to have been sustained. Therefore, recycling of previously degassed CO2 quickly becomes more important than the ongoing supply of juvenile CO2. If so, then the atmospheric CO2 pressure, and thereby the surface temperature, may be approximated mathematically as a function of the total degassed CO2 in the atmosphere plus buried material and the ratio of the atmospheric and regolith mean residence times. The latter ratio can also be expressed as a function of heat flow. Hence, it follows that the surface temperature may be expressed as a function of heat flow and the total amount of available CO2. However, the depth to the water table can simultaneously be expressed as a function of heat flow and the surface temperature (the boundary condition). Therefore, for any given values of total available CO2 and regolith conductivity, there exist coupled independent equations which relate heat flow, surface temperature, and the depth to the water table. This means we can now derive simultaneous values of surface temperature and the depth of the water table for any value of the heat flow. The derived relationship is used to evaluate the relative importance of the atmospheric greenhouse effect and the internal regolith thermal gradient in producing morphological changes for any value of the heat flow, and to assess the absolute importance of each of the values of the heat flow which are thought to be reasonable on independent geophysical grounds.

Influence of water table on carbon dioxide, carbon monoxide, and methane fluxes from taiga bog microcosms

DOE Office of Scientific and Technical Information (OSTI.GOV)

Funk, D.W.; Pullmann, E.R.; Peterson, K.M.

1994-09-01

Hydrological changes, particularly alterations in water table level, may largely overshadow the more direct effects of global temperature increase upon carbon cycling in arctic and subarctic wetlands. Frozen cores (n=40) of intact soils and vegetation were collected from a bog near Fairbanks, Alaska, and fluxes of CO{sub 2}, CH{sub 4}, and Co in response to water table variation were studied under controlled conditions in the Duke University phytotron. Core microcosms thawed to a 20-cm depth over 30 days under a 20 hour photoperiod with a day/night temperature regime of 20/10{degrees}C. After 30 days the water table in 20 microcosms wasmore » decreased from the soil surface to -15 cm and maintained at the soil surface in 20 control cores. Outward fluxes of CO{sub 2} (9-16 g m{sup -2}d{sup -1}) and CO (3-4 mg m{sup -2}d{sup -1}) were greatest during early thaw and decreased to near zero for both gases before the water table treatment started. Lower water table tripled CO{sub 2} flux to the atmosphere when compared with control cores. Carbon monoxide was emitted at low rates from high water table cores and consumed by low water table cores. Methane fluxes were low (<1 mg m{sup -2}d{sup -1}) in all cores during thaw. High water table cores increased CH{sub 4} flux to 8-9 mg m{sup -2}d{sup -1} over 70 days and remained high relative to the low water table cores (<0.74 mg m{sup -2}d{sup -1}). Although drying of wetland taiga soils may decrease CH{sub 4} emissions to the atmosphere, the associated increase in CO{sub 2} due to aerobic respiration will likely increase the global warming potential of gas emissions from these soils. 43 refs., 4 figs.« less

The combined effects of acidification and hypoxia on pH and aragonite saturation in the coastal waters of the California current ecosystem and the northern Gulf of Mexico

NASA Astrophysics Data System (ADS)

Feely, Richard A.; Okazaki, Remy R.; Cai, Wei-Jun; Bednaršek, Nina; Alin, Simone R.; Byrne, Robert H.; Fassbender, Andrea

2018-01-01

Inorganic carbon chemistry data from the surface and subsurface waters of the West Coast of North America have been compared with similar data from the northern Gulf of Mexico to demonstrate how future changes in CO2 emissions will affect chemical changes in coastal waters affected by respiration-induced hypoxia ([O2] ≤ 60 μmol kg-1). In surface waters, the percentage change in the carbon parameters due to increasing CO2 emissions are very similar for both regions even though the absolute decrease in aragonite saturation is much higher in the warmer waters of the Gulf of Mexico. However, in subsurface waters the changes are enhanced due to differences in the initial oxygen concentration and the changes in the buffer capacity (i.e., increasing Revelle Factor) with increasing respiration from the oxidation of organic matter, with the largest impacts on pH and CO2 partial pressure (pCO2) occurring in the colder West Coast waters. As anthropogenic CO2 concentrations begin to build up in subsurface waters, increased atmospheric CO2 will expose organisms to hypercapnic conditions (pCO2 >1000 μatm) within subsurface depths. Since the maintenance of the extracellular pH appears as the first line of defense against external stresses, many biological response studies have been focused on pCO2-induced hypercapnia. The extent of subsurface exposure will occur sooner and be more widespread in colder waters due to their capacity to hold more dissolved oxygen and the accompanying weaker acid-base buffer capacity. Under present conditions, organisms in the West Coast are exposed to hypercapnic conditions when oxygen concentrations are near 100 μmol kg-1 but will experience hypercapnia at oxygen concentrations of 260 μmol kg-1 by year 2100 under the highest elevated-CO2 conditions. Hypercapnia does not occur at present in the Gulf of Mexico but will occur at oxygen concentrations of 170 μmol kg-1 by the end of the century under similar conditions. The aragonite saturation horizon is currently above the hypoxic zone in the West Coast. With increasing atmospheric CO2, it is expected to shoal up close to surface waters under the IPCC Representative Concentration Pathway (RCP) 8.5 in West Coast waters, while aragonite saturation state will exhibit steeper gradients in the Gulf of Mexico. This study demonstrates how different biological thresholds (e.g., hypoxia, CaCO3 undersaturation, hypercapnia) will vary asymmetrically because of local initial conditions that are affected differently with increasing atmospheric CO2. The direction of change in amplitude of hypercapnia will be similar in both ecosystems, exposing both biological communities from the West Coast and Gulf of Mexico to intensification of stressful conditions. However, the region of lower Revelle factors (i.e., the Gulf of Mexico), currently provides an adequate refuge habitat that might no longer be the case under the most severe RCP scenarios.

Response surface method for modeling the removal of carbon dioxide from a simulated gas using water absorption enhanced with a liquid-film-forming device.

PubMed

Nguyen, Diem-Mai Kim; Imai, Tsuyoshi; Dang, Thanh-Loc Thi; Kanno, Ariyo; Higuchi, Takaya; Yamamoto, Koichi; Sekine, Masahiko

2018-03-01

This paper presents the results from using a physical absorption process to absorb gaseous CO 2 mixed with N 2 using water by producing tiny bubbles via a liquid-film-forming device (LFFD) that improves the solubility of CO 2 in water. The influence of various parameters-pressure, initial CO 2 concentration, gas-to-liquid ratios, and temperature-on the CO 2 removal efficiency and its absorption rate in water were investigated and estimated thoroughly by statistical polynomial models obtained by the utilization of the response surface method (RSM) with a central composite design (CCD). Based on the analysis, a high efficiency of CO 2 capture can be reached in conditions such as low pressure, high CO 2 concentration at the inlet, low gas/liquid ratio, and low temperature. For instance, the highest removal efficiency in the RSM-CCD experimental matrix of nearly 80% occurred for run number 20, which was conducted at 0.30MPa, CO 2 concentration of 35%, gas/liquid ratio of 0.71, and temperature of 15°C. Furthermore, the coefficients of determination, R 2 , were 0.996 for the removal rate and 0.982 for the absorption rate, implying that the predicted values computed by the constructed models correlate strongly and fit well with the experimental values. The results obtained provide essential information for implementing this method properly and effectively and contribute a promising approach to the problem of CO 2 capture in air pollution treatment. Copyright © 2017. Published by Elsevier B.V.

Infrared Spectra and Thermodynamic Properties of Co2/Methanol Ices

NASA Astrophysics Data System (ADS)

Maté, Belén; Gálvez, Óscar; Herrero, Víctor J.; Escribano, Rafael

2009-01-01

Ices of mixtures of carbon dioxide and methanol have been studied in a range of temperatures relevant for star-forming regions, comets, polar caps of planets and satellites, and other solar system bodies. We have performed temperature-programmed desorption measurements and recorded IR spectra of various types of samples. The presence of two slightly different structures of CO2 is manifest. A distorted CO2 structure is characterized by bandshifts between 5 cm-1 (ν3) and 10 cm-1 (ν2) with respect to normal CO2. If the samples are heated above 130 K, the distorted CO2 sublimates and only the normal structure remains. The latter can stay trapped until the sublimation of crystalline methanol (150 K). The desorption energy (E d ~ 20 kJ mol-1) of CO2 from methanol ice, and the specific adsorption surface area (6 m2 g-1) of amorphous CH3OH ice, have been determined. CO2 does not penetrate into crystalline ice. Whereas the desorption energy is similar to that of CO2/H2O samples, the specific surface of methanol is much smaller than that of amorphous solid water (ASW). The interaction of CO2 molecules with water and methanol is similar but ices of CH3OH are much less porous than ASW. The inclusion of CO2 into previously formed ices containing these two species would take place preferentially into ASW. However, in processes of simultaneous deposition, methanol ice can admit a larger amount of CO2 than water ice. CO2/CH3OH ices formed by simultaneous deposition admit two orders of magnitude more CO2 than sequentially deposited ices. These findings can have direct relevance to the interpretation of observations from protostellar environments (e.g., RAFGL7009S) and comet nuclei.

Effect of water on hydrogen permeability

NASA Technical Reports Server (NTRS)

Hulligan, David; Tomazic, William A.

1987-01-01

Doping of hydrogen with CO and CO2 was developed to reduce hydrogen permeation in Stirling engines by forming a low permeability oxide coating on the inner surface of the heater head tubes. Although doping worked well, under certain circumstances the protective oxide could be chemically reduced by the hydrogen in the engine. Some oxygen is required in the hydrogen to prevent reduction. Eventually, all the oxygen in the hydrogen gas - whatever its source - shows up as water. This is the result of hydrogen reducing the CO, CO2, or the protective inner surface oxides. This water can condense in the engine system under the right conditions. If the concentration of water vapor is reduced to a low enough level, the hydrogen can chemically reduce the oxide coating, resulting in an increase in permeability. This work was done to define the minimum water content required to avoid this reduction in the oxide coating. The results of this testing show that a minimum of approximately 750 ppm water is required to prevent an increase in permeability of CG-27, a high temperature metal alloy selected for Stirling engine heater tubes.

Greenhouse gas (CO2 and CH4) emissions from a high altitude hydroelectric reservoir in the tropics (Riogrande II, Colombia)

NASA Astrophysics Data System (ADS)

Guérin, Frédéric; Leon, Juan

2015-04-01

Tropical hydroelectric reservoirs are considered as very significant source of methane (CH4) and carbon dioxide (CO2), especially when flooding dense forest. We report emissions from the Rio Grande II Reservoir located at 2000 m.a.s.l. in the Colombian Andes. The dam was built at the confluence of the Rio Grande and Rio Chico in 1990. The reservoir has a surface of 12 km2, a maximum depth of 40m and a residence time of 2.5 month. Water quality (temperature, oxygen, pH, conductivity), nitrate, ammonium, dissolved and particulate organic carbon (DOC and POC), CO2 and CH4 were monitored bi-monthly during 1.5 year at 9 stations in the reservoir. Diffusive fluxes of CO2 and CH4 and CH4 ebullition were measured at 5 stations. The Rio grande II Reservoir is weakly stratified thermally with surface temperature ranging from 20 to 24°C and a constant bottom temperature of 18°C. The reservoir water column is well oxygenated at the surface and usually anoxic below 10m depth. At the stations close to the tributaries water inputs, the water column is well mixed and oxygenated from the surface to the bottom. As reported for other reservoirs located in "clear water" watersheds, the concentrations of nutrients are low (NO3-<0.1ppm, NH4+<0.2ppm), the concentrations of DOC are high (2-8 mg L-1) and POC concentrations are low (< 3 mg L-1). Surface CH4 concentrations at the central stations of the reservoirs are 0.5 μmol L-1 (0.07-2.14 μmol L-1) and 3 times higher at the stations close to the tributaries inputs (up to 7 μmol L-1). In the hypolimnion, CH4 concentration is <100 μmol L-1 in the wet season and can reach up to 400 μmol L-1 in the dry season. The spatial and temporal variability are lower for CO2. Surface CO2 concentration was on average 72 μmol L-1 (up to 300) and hypolimnic concentration ranged between 250 and 1000 μmol L-1. The CO2 diffusive flux is 517±331 mmol m-2 d-1 with little seasonal and spatial variations. At the center of the reservoir, the median diffusive flux of CH4 is 1.75 mmol m-2 d-1 and sporadic high fluxes (>10 mmol m-2 d-1) were observed during the dry season. Close to the tributaries water inputs where the water column is well mixed, the average diffusive flux is 8 mmol m-2 d-1. CH4 ebullition was 3.5 mmol m-2 d-1 and no ebullition was observed for a water depth higher than 5m. The zone under the influence of the water inputs from tributaries represents 25% of the surface of the reservoir but contributed half of total CH4 emissions from the reservoir (29MgC month-1). Ebullition contributed only to 12% of total CH4 emissions over a year but it contributed up to 60% during the dry season. CH4 emissions from the Rio Grande Reservoir contributed 30% of the total GHG emissions (38GgCO2eq y-1). Overall, this study show that the majority of CH4 emissions from this reservoir occur through hotspot and hot moments and that mountainous reservoir located in the tropics could have emission factors as high as Amazonian reservoirs.

FTIR study of CO2 and H2O/CO2 nanoparticles and their temporal evolution at 80 K.

PubMed

Taraschewski, M; Cammenga, H K; Tuckermann, R; Bauerecker, S

2005-04-21

Fourier transform infrared (FTIR) spectroscopy combined with a long-path collisional cooling cell was used to investigate the temporal evolution of CO2 nanoparticles and binary H2O/CO2 nanocomposites in the aerosol phase at 80 K. The experimental conditions for the formation of different CO2 particle shapes as slab, shell, sphere, cube, and needle have been studied by comparison with calculated data from the literature. The H2O/CO2 nanoparticles were generated with a newly developed multiple-pulse injection technique and with the simpler flow-in technique. The carbon dioxide nu3-vibration band at 2360 cm(-1) and the water ice OH-dangling band at 3700 cm(-1) were used to study the evolution of structure, shape, and contact area of the nanocomposites over 150 s. Different stages of binary nanocomposites with primary water ice cores were identified dependent on the injected CO2 portion: (a) disordered (amorphous) CO2 slabs on water particle surfaces, (b) globular crystalline CO2 humps sticking on the water cores, and (c) water cores being completely enclosed in bigger predominantly crystalline CO2 nanoparticles. However, regular CO2 shell structures on primary water particles showing both longitudinal (LO) and transverse (TO) optical mode features of the nu3-vibration band could not be observed. Experiments with reversed nucleation order indicate that H2O/CO2 composite particles with different initial structures evolve toward similar molecular nanocomposites with separated CO2 and H2O regions.

Atomistic and infrared study of CO-water amorphous ice onto olivine dust grain

NASA Astrophysics Data System (ADS)

Escamilla-Roa, Elizabeth; Moreno, Fernando; López-Moreno, J. Juan; Sainz-Díaz, C. Ignacio

2017-01-01

This work is a study of CO and H2O molecules as adsorbates that interact on the surface of olivine dust grains. Olivine (forsterite) is present on the Earth, planetary dust, in the interstellar medium (ISM) and in particular in comets. The composition of amorphous ice is very important for the interpretation of processes that occur in the solar system and the ISM. Dust particles in ISM are composed of a heterogeneous mixture of amorphous or crystalline silicates (e.g. olivine) organic material, carbon, and other minor constituents. These dust grains are embedded in a matrix of ices, such as H2O, CO, CO2, NH3, and CH4. We consider that any amorphous ice will interact and grow faster on dust grain surfaces. In this work we explore the adsorption of CO-H2O amorphous ice onto several (100) forsterite surfaces (dipolar and non-dipolar), by using first principle calculations based on density functional theory (DFT). These models are applied to two possible situations: i) adsorption of CO molecules mixed into an amorphous ice matrix (gas mixture) and adsorbed directly onto the forsterite surface. This interaction has lower adsorption energy than polar molecules (H2O and NH3) adsorbed on this surface; ii) adsorption of CO when the surface has previously been covered by amorphous water ice (onion model). In this case the calculations show that adsorption energy is low, indicating that this interaction is weak and therefore the CO can be desorbed with a small increase of temperature. Vibration spectroscopy for the most stable complex was also studied and the frequencies were in good agreement with experimental frequency values.

Inhibited proton transfer enhances Au-catalyzed CO2-to-fuels selectivity.

PubMed

Wuttig, Anna; Yaguchi, Momo; Motobayashi, Kenta; Osawa, Masatoshi; Surendranath, Yogesh

2016-08-09

CO2 reduction in aqueous electrolytes suffers efficiency losses because of the simultaneous reduction of water to H2 We combine in situ surface-enhanced IR absorption spectroscopy (SEIRAS) and electrochemical kinetic studies to probe the mechanistic basis for kinetic bifurcation between H2 and CO production on polycrystalline Au electrodes. Under the conditions of CO2 reduction catalysis, electrogenerated CO species are irreversibly bound to Au in a bridging mode at a surface coverage of ∼0.2 and act as kinetically inert spectators. Electrokinetic data are consistent with a mechanism of CO production involving rate-limiting, single-electron transfer to CO2 with concomitant adsorption to surface active sites followed by rapid one-electron, two-proton transfer and CO liberation from the surface. In contrast, the data suggest an H2 evolution mechanism involving rate-limiting, single-electron transfer coupled with proton transfer from bicarbonate, hydronium, and/or carbonic acid to form adsorbed H species followed by rapid one-electron, one-proton, or H recombination reactions. The disparate proton coupling requirements for CO and H2 production establish a mechanistic basis for reaction selectivity in electrocatalytic fuel formation, and the high population of spectator CO species highlights the complex heterogeneity of electrode surfaces under conditions of fuel-forming electrocatalysis.

Propagation of vent CO2 in a subtropical shallow-water ecosystem assessed by stable carbon isotopes

NASA Astrophysics Data System (ADS)

Cheng, Y. F.; Chen, C. T. A.; Liao, Y. M.; Lin, Y. S.

2016-02-01

Carbon cycle of the ocean plays an important role in the global change associated with the emission of CO2. Anthropogenic CO2 dissolves in seawater, changes carbon chemistry of the ocean, and affects marine life in different and complicated ways. In this study, we investigated stable carbon isotope systematics of a shallow-water hydrothermal field near the Kueishantao Islet off NE Taiwan, which has vent gas composition dominated by CO2 and world record breaking low pH hydrothermal fluids. By studying this natural laboratory of ocean acidification, we aim at clarifying to which extent the high dosage of CO2 propagates in the subtropical shallow-water ecosystem, and how it affects the carbon cycle. Samples of seawater and suspended particles were collected from stations of two nearshore-offshore transects, one with hydrothermal vents at the nearshore end (Transect M, 1230 m long) and the other serving as the baseline (Transect B, 1560 m long). Surface seawater of Transect M showed increasing pH in the offshore direction, from 5.8 at the vent mouths to 7.6 at the most distant station. In contrast, pH of surface water decreased seaward from 8.0 to 7.8 in Transect B. The δ13C values of the vent CO2 averaged -6.4‰, consistent with the range attributed to mantle CO2. Seawater DIC δ13C values of Transect M were 13C-depleted (as negative as -2.5‰) at the vent mouths, and became increasingly 13C-enriched till 0.7‰ at the most distant station. This pattern is in clear contrast to that of Transect B, the DIC δ13C values of which decreased from 0.7 to 0.6 ‰ in the offshore direction. We concluded that the vent CO2 has propagated in the surface ocean at least >700 m away from the hydrothermal field. Our next step is to explore how the vent CO2 affects the stable carbon isotopes of particulate organic matter, and to assess the effect of vent CO2 using quantitative approaches.

Molecular dynamics simulations of the electrical double layer on smectite surfaces contacting concentrated mixed electrolyte (NaCl-CaCl2) solutions.

PubMed

Bourg, Ian C; Sposito, Garrison

2011-08-15

We report new molecular dynamics results elucidating the structure of the electrical double layer (EDL) on smectite surfaces contacting mixed NaCl-CaCl(2) electrolyte solutions in the range of concentrations relevant to pore waters in geologic repositories for CO(2) or high-level radioactive waste (0.34-1.83 mol(c) dm(-3)). Our results confirm the existence of three distinct ion adsorption planes (0-, β-, and d-planes), often assumed in EDL models, but with two important qualifications: (1) the location of the β- and d-planes are independent of ionic strength or ion type and (2) "indifferent electrolyte" ions can occupy all three planes. Charge inversion occurred in the diffuse ion swarm because of the affinity of the clay surface for CaCl(+) ion pairs. Therefore, at concentrations ≥0.34 mol(c) dm(-3), properties arising from long-range electrostatics at interfaces (electrophoresis, electro-osmosis, co-ion exclusion, colloidal aggregation) will not be correctly predicted by most EDL models. Co-ion exclusion, typically neglected by surface speciation models, balanced a large part of the clay mineral structural charge in the more concentrated solutions. Water molecules and ions diffused relatively rapidly even in the first statistical water monolayer, contradicting reports of rigid "ice-like" structures for water on clay mineral surfaces. Published by Elsevier Inc.

The Nickel(111)/Alkaline Electrolyte Interface

NASA Technical Reports Server (NTRS)

Wang, Kuilong; Chottiner, G. S.; Scherson, D. A.; Reid, Margaret A.

1991-01-01

The electrochemical properties of Ni (111) prepared and characterized in ultra high vacuum, UHV, by surface analytical techniques have been examined in alkaline media by cyclic voltammetry using an UHV-electrochemical cell transfer system designed and built in this laboratory. Prior to the transfer, the Ni(111) surfaces were exposed to saturation coverages of CO in UHV in an attempt to protect the surface from possible contamination with other gases during the transfer. Temperature Programmed Desorption, TPD, of CO-dosed Ni (111) surfaces displaying sharp c(4x2), LEED patterns, subsequently exposed to water-saturated Ar at atmospheric pressure in an auxiliary UHV compatible chamber and finally transferred back to the main UHV chamber, yielded CO2 and water as the only detectable products. This indicates that the CO-dosed surfaces react with water and/or bicarbonate and hydroxide as the most likely products. Based on the integration of the TPD peaks, the combined amounts of H2O and CO2 were found to be on the order of a single monolayer. The reacted c(4x2)CO/Ni(111) layer seems to protect the surface from undergoing spontaneous oxidation in strongly alkaline solutions. This was evidenced by the fact that the open circuit potential observed immediately after contact with deaerated 0.1 M KOH was about 0.38 V vs. DHE, drifting slightly towards more negative values prior to initiating the voltametric scans. The average ratio of the integrated charge obtained in the first positive linear scan in the range of 0.35 to 1.5 V vs. DHE (initiated at the open circuit potential) and the first (and subsequent) linear negative scans in the same solution yielded for various independent runs a value of 3.5 +/- 0.3. Coulometric analysis of the cyclic voltammetry curves indicate that the electrochemically formed oxyhydroxide layer involves a charge equivalent to 3.2 +/- 0.4 layers of Ni metal.

Investigation of Potassium Feldspar Reactivity in Wet Supercritical CO2 by In Situ Infrared Spectroscopy

NASA Astrophysics Data System (ADS)

Thompson, C.; Widener, C.; Schaef, T.; Loring, J.; McGrail, B. P.

2014-12-01

Capture and subsequent storage of CO2 in deep geologic reservoirs is progressively being considered as a viable approach to reduce anthropogenic greenhouse gas emissions. In the long term, injected CO2 may become permanently entrapped as silicate minerals react with CO2 enriched fluids to form stable carbonate minerals. Potassium feldspars are highly abundant in the earth's crust and are present in the caprocks and storage formations of many target reservoirs. While the dissolution kinetics and carbonation reactions of feldspars have been well studied in the aqueous phase, comparatively little work has focused on K-feldspar reactivity in the CO2-rich fluid. In this study, we used in situ infrared spectroscopy to investigate the carbonation reactions of natural microcline samples. Experiments were carried out at 50 °C and 91 bar by circulating dry or wet supercritical CO2 (scCO2) past a thin film of powdered sample. Water concentrations ranged from 0% to 125% relative to saturation, and transmission-mode absorbance spectra were recorded as a function of time for 48 hours. No discernible reaction was detected when the samples were exposed to anhydrous scCO2. However, in fully water-saturated scCO2, a thin film of liquid-like water was observed on the samples' surfaces, and up to 0.6% of the microcline was converted to a carbonate phase. Potassium carbonate is the most likely reaction product, but minor amounts of sodium carbonate and siderite may also have formed from minor sample impurities. The extent of reaction appears to be related to the thickness of the water film and is likely a consequence of the film's ability to solvate and transport ions in the vicinity of the mineral surface. Other features observed in the spectra correspond to microcline dissolution and precipitation of amorphous silica. Implications about the role of water in these reactions and the relative effectiveness of alkali feldspars for mineral trapping of CO2 will be discussed.

The role of CO 2 as a soft oxidant for dehydrogenation of ethylbenzene to styrene over a high-surface-area ceria catalyst

DOE PAGES

Zhang, Li; Wu, Zili; Nelson, Nicholas; ...

2015-09-22

Catalytic performance and the nature of surface adsorbates were investigated for high-surface-area ceria during ethylbenzene oxidative dehydrogenation (ODH) reaction using CO2 as a soft oxidant. A template assisted method was used to synthesize the high-surface-area ceria. The interactions between ethylbenzene, styrene and CO2 on the surface of ceria and the role of CO2 for the ethylbenzene ODH reaction have been investigated in detail by using activity test, in situ Diffuse Reflectance Infrared and Raman spectroscopy. Not only did CO2 as an oxidant favor the higher yield of styrene, but it also inhibited the deposition of coke during the ethylbenzene ODHmore » reaction. Ethylbenzene ODH reaction over ceria followed a two-step pathway: Ethylbenzene is first dehydrogenated to styrene with H2 formed simultaneously, and then CO2 reacts with H2 via the reverse water gas shift. The styrene produced can easily polymerize to form polystyrene, a key intermediate for coke formation. In the absence of CO2, the polystyrene transforms into graphite-like coke at temperatures above 500 °C, which leads to catalyst deactivation. While in the presence of CO2, the coke deposition can be effectively removed via oxidation with CO2.« less

Structure, spectroscopy and dynamics of layered H2O and CO2 ices

USGS Publications Warehouse

,; Plattner, Nuria; Meuwly, Markus

2012-01-01

Molecular dynamics simulations of structural, spectroscopic and dynamical properties of mixed water–carbon dioxide (H2O–CO2) ices are discussed over temperature ranges relevant to atmospheric and astrophysical conditions. The simulations employ multipolar force fields to represent electrostatic interactions which are essential for spectroscopic and dynamical investigations. It is found that at the water/CO2 interface the water surface acts as a template for the CO2 component. The rotational reorientation times in both bulk phases agree well with experimental observations. A pronounced temperature effect on the CO2 reorientation time is observed between 100 K and 200 K. At the interface, water reorientation times are nearly twice as long compared to water in the bulk. The spectroscopy of such ices is rich in the far-infrared region of the spectrum and can be related to translational and rotational modes. Furthermore, spectroscopic signatures mediated across the water/CO2 interface are found in this frequency range (around 440 cm−1). These results will be particularly important for new airborne experiments such as planned for SOFIA.

Stochastic surface walking reaction sampling for resolving heterogeneous catalytic reaction network: A revisit to the mechanism of water-gas shift reaction on Cu

NASA Astrophysics Data System (ADS)

Zhang, Xiao-Jie; Shang, Cheng; Liu, Zhi-Pan

2017-10-01

Heterogeneous catalytic reactions on surface and interfaces are renowned for ample intermediate adsorbates and complex reaction networks. The common practice to reveal the reaction mechanism is via theoretical computation, which locates all likely transition states based on the pre-guessed reaction mechanism. Here we develop a new theoretical method, namely, stochastic surface walking (SSW)-Cat method, to resolve the lowest energy reaction pathway of heterogeneous catalytic reactions, which combines our recently developed SSW global structure optimization and SSW reaction sampling. The SSW-Cat is automated and massively parallel, taking a rough reaction pattern as input to guide reaction search. We present the detailed algorithm, discuss the key features, and demonstrate the efficiency in a model catalytic reaction, water-gas shift reaction on Cu(111) (CO + H2O → CO2 + H2). The SSW-Cat simulation shows that water dissociation is the rate-determining step and formic acid (HCOOH) is the kinetically favorable product, instead of the observed final products, CO2 and H2. It implies that CO2 and H2 are secondary products from further decomposition of HCOOH at high temperatures. Being a general purpose tool for reaction prediction, the SSW-Cat may be utilized for rational catalyst design via large-scale computations.

MEASUREMENTS OF PAST 14C LEVELS AND 13C/12C RATIOS IN THE SURFACE WATERS OF THE WORLD'S SUBPOLAR OCEANS.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brown, T A

2010-04-22

Under this project we have developed methods that allow the reconstruction of past {sup 14}C levels of the surface waters of the subpolar North Pacific Ocean by measuring the {sup 14}C contents of archived salmon scales. The overall goal of this research was to reduce of the uncertainty in the uptake of fossil CO{sub 2} by the oceans and thereby improve the quantification of the global carbon cycle and to elucidate the fate of anthropogenic CO{sub 2}. Ocean General Circulation Models (OGCMs), with their three dimensional global spatial coverage and temporal modeling capabilities, provide the best route to accurately calculatingmore » the total uptake of CO{sub 2} by the oceans and, hence, to achieving the desired reduction in uncertainty. {sup 14}C has played, and continues to play, a central role in the validation of the OGCMs calculations, particularly with respect to those model components which govern the uptake of CO{sub 2} from the atmosphere and the transport of this carbon within the oceans. Under this project, we have developed time-series records of the {sup 14}C levels of the surface waters of three areas of the subpolar North Pacific Ocean. As the previously available data on the time-history of oceanic surface water {sup 14}C levels are very limited, these time-series records provide significant new {sup 14}C data to constrain and validate the OGCMs.« less

Role of CO2 in the oxy-dehydrogenation of ethylbenzene to styrene on the CeO2(111) surface

NASA Astrophysics Data System (ADS)

Fan, Hong-Xia; Feng, Jie; Li, Wen-Ying; Li, Xiao-Hong; Wiltowski, Tomasz; Ge, Qing-Feng

2018-01-01

The role of CO2 in the ethylbenzene oxy-dehydrogenation to styrene on the CeO2(111) surface was thoroughly investigated by the density functional theory (DFT) calculations. Results show that the first Csbnd H bond of ethylbenzene is activated via the oxo-insertion with a barrier of 1.70 eV, resulting in a 2-phenylethyl species and an H atom adsorbed on two-adjacent-lattice oxygen. The H adatom forms a hydroxyl-like species (denoted as O*H). The subsequent dehydrogenation to styrene can be assisted by either the next lattice oxygen (pathway R1) or the O*H species (pathway R2). The two pathways have almost the same activation energy (0.84 eV for R1 and 0.85 eV for R2), forming a new O*H and desorbing a H2O molecule while leaving an oxygen vacancy on the surface, respectively. In the presence of CO2, it will react with O*H through the reverse water gas shift reaction with an activation barrier of 0.98 eV and reaction energy of 0.30 eV. The reverse water gas shift reaction helps to clear the H adatoms from the lattice oxygen, thereby competing with styrene formation via pathway R2. However, the activation energy following the reverse water gas shift mechanism is 0.13 eV higher than that of styrene formation via pathway R2. Therefore, the formation of oxygen vacancy cannot be inhibited, while CO2 can react with the surface oxygen vacancy to produce CO with a high activation energy of 2.10 eV.

Wettability effect on capillary trapping of supercritical CO2 at pore-scale: micromodel experiment and numerical modeling

NASA Astrophysics Data System (ADS)

Hu, R.; Wan, J.

2015-12-01

Wettability of reservoir minerals along pore surfaces plays a controlling role in capillary trapping of supercritical (sc) CO2 in geologic carbon sequestration. The mechanisms controlling scCO2 residual trapping are still not fully understood. We studied the effect of pore surface wettability on CO2 residual saturation at the pore-scale using engineered high pressure and high temperature micromodel (transparent pore networks) experiments and numerical modeling. Through chemical treatment of the micromodel pore surfaces, water-wet, intermediate-wet, and CO2-wet micromodels can be obtained. Both drainage and imbibition experiments were conducted at 8.5 MPa and 45 °C with controlled flow rate. Dynamic images of fluid-fluid displacement processes were recorded using a microscope with a CCD camera. Residual saturations were determined by analysis of late stage imbibition images of flow path structures. We performed direct numerical simulations of the full Navier-Stokes equations using a volume-of-fluid based finite-volume framework for the primary drainage and the followed imbibition for the micromodel experiments with different contact angles. The numerical simulations agreed well with our experimental observations. We found that more scCO2 can be trapped within the CO2-wet micromodel whereas lower residual scCO2 saturation occurred within the water-wet micromodels in both our experiments and the numerical simulations. These results provide direct and consistent evidence of the effect of wettability, and have important implications for scCO2 trapping in geologic carbon sequestration.

Modelling global nitrogen export to ground and surface water from natural ecosystems: impact of N deposition, climate, and CO2 concentration

NASA Astrophysics Data System (ADS)

Braakhekke, Maarten; Rebel, Karin; Dekker, Stefan; van Beek, Rens; Bierkens, Marc; Smith, Ben; Wassen, Martin

2015-04-01

For large regions in the world strong increases in atmospheric nitrogen (N) deposition are predicted as a result of emissions from fossil fuel combustion and food production. This will cause many previously N limited ecosystems to become N saturated, leading to increased export to ground and surface water and negative impacts on the environment and human health. However, precise N export fluxes are difficult to predict. Due to its strong link to carbon, N in vegetation and soil is also determined by productivity, as affected by rising atmospheric CO2 concentration and temperature, and denitrification. Furthermore, the N concentration of water delivered to streams depends strongly on local hydrological conditions. We aim to study how N delivery to ground and surface water is affected by changes in environmental factors. To this end we are developing a global dynamic modelling system that integrates representations of N cycling in vegetation and soil, and N delivery to ground and surface water. This will be achieved by coupling the dynamic global vegetation model LPJ-GUESS, which includes representations of N cycling, as well as croplands and pasture, to the global water balance model PCR-GLOBWB, which simulates surface runoff, interflow, groundwater recharge, and baseflow. This coupling will allow us to trace N across different systems and estimate the input of N into the riverine system which can be used as input for river biogeochemical models. We will present large scale estimates of N leaching and transport to ground and surface water for natural ecosystems in different biomes, based on a loose coupling of the two models. Furthermore, by means of a factorial model experiment we will explore how these fluxes are influenced by N deposition, temperature, and CO2 concentration.

Superamphiphobic Surfaces Prepared by Coating Multifunctional Nanofluids.

PubMed

Esmaeilzadeh, Pouriya; Sadeghi, Mohammad Taghi; Bahramian, Alireza; Fakhroueian, Zahra; Zarbakhsh, Ali

2016-11-23

Construction of surfaces with the capability of repelling both water and oil is a challenging issue. We report the superamphiphobic properties of mineral surfaces coated with nanofluids based on synthesized Co-doped and Ce-doped Barium Strontium Titanate (CoBST and CeBST) nanoparticles and fluorochemicals of trichloro(1H,1H,2H,2H-perfluorooctyl)silane (PFOS) and polytetrafluoroethylene (PTFE). Coating surfaces with these nanofluids provides both oil (with surface tensions as low as 23 mN/m) and water repellency. Liquids with high surface tension (such as water and ethylene glycol) roll off the coated surface without tilting. A water drop released from 8 mm above the coated surface undergoes first a lateral displacement from its trajectory and shape deformation, striking the surface after 23 ms, bouncing and rolling off freely. These multifunctional coating nanofluids impart properties of self-cleaning. Applications include coating surfaces where cleanliness is paramount such as in hospitals and domestic environments as well as the maintenance of building facades and protection of public monuments from weathering. These superamphiphobic-doped nanofluids have thermal stability up to 180 °C; novel industrial applications include within fracking and the elimination of condensate blockage in gas reservoirs.

Gas-solid carbonation as a current alternative origin for carbonates in Martian regolith

NASA Astrophysics Data System (ADS)

Garenne, A.; Montes-Hernandez, G.; Beck, P.; Schmitt, B.; Brissaud, O.

2011-12-01

Carbonates are abundant sedimentary minerals at the surface and sub-surface of Earth and they have been proposed as tracers of liquid water in extraterrestrial environments (e.g. at Mars surface). Its formation mechanism is since generally associated with aqueous alteration processes. Recently, carbonates minerals have been discovered on Mars surface by different orbital or rovers missions. In particular, the phoenix mission has measured from 1 to 5% of calcium carbonate (calcite type). These occurrences have been reported in area were the relative humidity is significantly high (Boynton et al., 2009). The small concentration of carbonates suggests an alternative process than carbonation in aqueous conditions. Such an observation might rather point toward a possible formation mechanism by dust-gas reaction under current Martian conditions. For this reason, in the present study, we designed an experimental setup consisting of an infrared microscope coupled to a cryogenic reaction cell (IR-CryoCell setup) in order to investigate the gas-solid carbonation of three different mineral precursors for carbonates (Ca and Mg hydroxides, and a hydrated Ca silicate formed from Ca2SiO4) at low temperature (from -10 to 25°C) and at reduced CO2 pressure (from 100 to 1000 mbar). These mineral materials are crucial precursors to form respective Ca and Mg carbonates in humid environments (0 < relative humidity < 100%) at dust-CO2 or dust-water ice-CO2 interfaces. The results have revealed a significant and fast carbonation process for Ca hydroxide and hydrated Ca silicate. Conversely, slight carbonation process was observed for Mg hydroxide. These results suggest that gas-solid carbonation process or carbonate formation at the dust-water ice-CO2 interfaces could be a currently active Mars surface process. We note that the carbonation process at low temperature (<0°C) described in the present study could also have important implications on the dust-water ice-CO2 interactions in cold terrestrial environments (e.g. Antarctic).

CO2 emissions from German drinking water reservoirs.

PubMed

Saidi, Helmi; Koschorreck, Matthias

2017-03-01

Globally, reservoirs are a significant source of atmospheric CO 2 . However, precise quantification of greenhouse gas emissions from drinking water reservoirs on the regional or national scale is still challenging. We calculated CO 2 fluxes for 39 German drinking water reservoirs during a period of 22years (1991-2013) using routine monitoring data in order to quantify total emission of CO 2 from drinking water reservoirs in Germany and to identify major drivers. All reservoirs were a net CO 2 source with a median flux of 167gCm -2 y -1 , which makes gaseous emissions a relevant process for the carbon budget of each reservoir. Fluxes varied seasonally with median fluxes of 13, 48, and 201gCm -2 y -1 in spring, summer, and autumn respectively. Differences between reservoirs appeared to be primarily caused by the concentration of CO 2 in the surface water rather than by the physical gas transfer coefficient. Consideration of short term fluctuations of the gas transfer coefficient due to varying wind speed had only a minor effect on the annual budgets. High CO 2 emissions only occurred in reservoirs with pH<7 and total alkalinity <0.2mEql -1 . Annual CO 2 emissions correlated exponentially with pH but not with dissolved organic carbon (DOC). There was significant correlation between land use in the catchment and CO 2 emissions. In total, German drinking water reservoirs emit 44000t of CO 2 annually, which makes them a negligible CO 2 source (<0.005% of national CO 2 emissions) in Germany. Copyright © 2017 Elsevier B.V. All rights reserved.

The Viking gas exchange experiment results from Chryse and Utopia surface samples

NASA Technical Reports Server (NTRS)

Oyama, V. I.; Berdahl, B. J.

1977-01-01

Immediate gas changes occurred when untreated Martian surface samples were humidified and/or wet by an aqueous nutrient medium in the Viking lander gas exchange experiment. The evolutions of N2, CO2, and Ar are mainly associated with soil surface desorption caused by water vapor, while O2 evolution is primarily associated with decomposition of superoxides inferred to be present on Mars. On recharges with fresh nutrient and test gas, only CO2 was given off, and its rate of evolution decreased with each recharge. This CO2 evolution is thought to come from the oxidation of organics present in the nutrient by gamma Fe2O3 in the surface samples. Atmospheric analyses were also performed at both sites. The mean atmospheric composition from four analyses is N2, 2.3%; O2, not greater than 0.15%; Ar, 1.5% and CO2, 96.2%.

Methods and apparatus for measuring small leaks from carbon dioxide sequestration facilities

DOEpatents

Nelson, Jr., David D.; Herndon, Scott C.

2018-01-02

In one embodiment, a CO.sub.2 leak detection instrument detects leaks from a site (e.g., a CO.sub.2 sequestration facility) using rapid concentration measurements of CO.sub.2, O.sub.2 and optionally water concentration that are achieved, for example, using laser spectroscopy (e.g. direct absorption laser spectroscopy). Water vapor in the sample gas may not be removed, or only partially removed. The sample gas may be collected using a multiplexed inlet assembly from a plurality of locations. CO.sub.2 and O.sub.2 concentrations may be corrected based on the water concentration. A resulting dataset of the CO.sub.2 and O.sub.2 concentrations is analyzed over time intervals to detect any changes in CO.sub.2 concentration that are not anti-correlated with O.sub.2 concentration, and to identify a potential CO.sub.2 leak in response thereto. The analysis may include determining eddy covariance flux measurements of sub-surface potential carbon.

Tidal variability of CO2 and CH4 emissions from the water column within a Rhizophora mangrove forest (New Caledonia).

PubMed

Jacotot, Adrien; Marchand, Cyril; Allenbach, Michel

2018-08-01

We performed a preliminary study to quantify CO 2 and CH 4 emissions from the water column within a Rhizophora spp. mangrove forest. Mean CO 2 and CH 4 emissions during the studied period were 3.35±3.62mmolCm -2 h -1 and 18.30±27.72μmolCm -2 h -1 , respectively. CO 2 and CH 4 emissions were highly variable and mainly driven by tides (flow/ebb, water column thickness, neap/spring). Indeed, an inverse relationship between the magnitude of the emissions and the thickness of the water column above the mangrove soil was observed. δ 13 CO 2 values ranged from -26.88‰ to -8.6‰, suggesting a mixing between CO 2 -enriched pore waters and lagoon incoming waters. In addition, CO 2 and CH 4 emissions were significantly higher during ebb tides, mainly due to the progressive enrichment of the water column by diffusive fluxes as its residence time over the forest floor increased. Eventually, we observed higher CO 2 and CH 4 emissions during spring tides than during neap tides, combined to depleted δ 13 CO 2 values, suggesting a higher contribution of soil-produced gases to the emissions. These higher emissions may result from higher renewable of the electron acceptor and enhanced exchange surface between the soil and the water column. This study shows that CO 2 and CH 4 emissions from the water column were not negligible and must be considered in future carbon budgets in mangroves. Copyright © 2018 Elsevier B.V. All rights reserved.

Self-organization of poly(ethylene oxide) on the surface of aqueous salt solutions.

PubMed

Fuchs, Christian; Hussain, Hazrat; Amado, Elkin; Busse, Karsten; Kressler, Joerg

2015-01-01

It is demonstrated that stable Langmuir films of poly(ethylene oxide) (PEO) can be formed up to surface pressures of 30 mN m(-1) when potassium carbonate K2CO3 is added to the aqueous subphase. Generally, PEO homopolymer cannot stay on the water surface at a surface pressure ≥10 mN m(-1) due to its high water solubility. To prepare stable monolayer films, PEO can be modified with hydrophobic moieties. However, by exploiting the salting out effect by adding certain salts (K2CO3 or MgSO4) into the aqueous subphase, not only very stable films but also unusual self-organization can be achieved by the PEO homopolymer on the surface of the aqueous solution. Thus, a series of OH-terminated PEOs is found to form a stable monolayer at K2CO3 concentrations of 2 M and above in the aqueous subphase, and the stability of the film increases with an increase in K2CO3 concentration. Hysteresis experiments are also carried out. During the phase transition induced by progressive compression, self-organization into well-defined domains with sizes in the micrometer range are observed, and with further compression and holding of the film for 30 min and above the microdomains transform into a crystalline morphology as visualized by Brewster angle microscopy. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Interfacial properties and coal cleaning in the LICADO process

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chi, S.M.B.

1986-01-01

The LICADO LIquid CArbon DiOxide process is currently being investigated as a new technique for cleaning coal. It relies on the relative wettability of clean coal and mineral particles between liquid CO/sub 2/ and water so that when liquid CO/sub 2/ is dispersed into a coal-water slurry, it tends to form agglomerates with the clean coal particles and float them to the liquid CO/sub 2/ phase. The mineral particles, on the other hand, remain in the aqueous phase as refuse. Since the surface/interfacial properties of fine coal particles play such an important role in this coal cleaning operation, an understandingmore » of their behavior becomes indispensable. In order to understand the separation mechanisms involved in the LICADO process, it is necessary to study the interfacial interactions occurring in the CO/sub 2/-water-coal system. It is believed that a relationship between the process performance and the wetting characteristics of the coal/refuse particles can be established. Upper Freeport -200 mesh coal from Indiana County, PA with 23.5% ash content was selected for the experimental work. A specially designed high pressure experimental unit, equipped with necessary optical and photographic accessories, was constructed for this study. Contact angles were also measured on the coal surface under two different sample pretreatment conditions: water-first-wet and liquid CO/sub 2/-first-wet. The results infer that an optimum mixing is necessary to provide sufficient shear force to expose the clean coal particles to the CO/sub 2/ droplets. The coal maceral and mineral association on the coal particle surface was determined based on the reflective grey level distinction between the mineral and Litho-type of various coal components.« less

Corrosion of Pipeline and Wellbore Steel by Liquid CO2 Containing Trace Amounts of Water and SO2

NASA Astrophysics Data System (ADS)

McGrail, P.; Schaef, H. T.; Owen, A. T.

2009-12-01

Carbon dioxide capture and storage in deep saline formations is currently considered the most attractive option to reduce greenhouse gas emissions with continued use of fossil fuels for energy production. Transporting captured CO2 and injection into suitable formations for storage will necessarily involve pipeline systems and wellbores constructed of carbon steels. Industry standards currently require nearly complete dehydration of liquid CO2 to reduce corrosion in the pipeline transport system. However, it may be possible to establish a corrosion threshold based on H2O content in the CO2 that could allow for minor amounts of H2O to remain in the liquid CO2 and thereby eliminate a costly dehydration step. Similarly, trace amounts of sulfur and nitrogen compounds common in flue gas streams are currently removed through expensive desulfurization and catalytic reduction processes. Provided these contaminants could be safely and permanently transported and stored in the geologic reservoir, retrofits of existing fossil-fuel plants could address comprehensive emissions reductions, including CO2 at perhaps nearly the same capital and operating cost. Because CO2-SO2 mixtures have never been commercially transported or injected, both experimental and theoretical work is needed to understand corrosion mechanisms of various steels in these gas mixtures containing varying amounts of water. Experiments were conducted with common tool steel (AISI-01) and pipeline steel (X65) immersed in liquid CO2 at room temperature containing ~1% SO2 and varying amounts of H2O (0 to 2500 ppmw). A threshold concentration of H2O in the liquid CO2-SO2 mixture was established based on the absence of visible surface corrosion. For example, experiments exposing steel to liquid CO2-SO2 containing ~300 ppmw H2O showed a delay in onset of visible corrosion products and minimal surface corrosion was visible after five days of testing. However increasing the water content to 760 ppmw produced extensive surface corrosion after 48 hours at room temperature. Surface characterization by SEM showed one type of morphology that included large circular features radiating outward from a central structure. Chemical analyses obtained by SEM-EDX indicate the phases contained mostly Fe and S with minor amounts of Mn. Corrosion products completely covering the metal coupon surface were identified by XRD as iron sulfite hydrate (FeSO3●3H2O), with lesser amounts of gravegliaite (MnSO3●3H2O), and rozenite (Fe(SO4)●(H2O)4).

Impacts of elevated CO2 concentration on the productivity and surface energy budget of the soybean and maize agroecosystem in the Midwest US

USDA-ARS?s Scientific Manuscript database

The physiological response of vegetation to increasing atmospheric carbon dioxide concentration ([CO2]) modifies productivity and surface energy and water fluxes. Quantifying this response is required for assessments of future climate change. Many global climate models account for this response; how...

Structural implications for oxygen electrocatalysis in earthabundant transition metal oxides

NASA Astrophysics Data System (ADS)

Gardner, Graeme Patrick

Transition metal oxides and related nitrides/nitride-oxides represent a class of materials that have shown great promise as oxygen electrocatalysts to replace the otherwise non-scalable noble metal-based catalysts currently implemented in commercial technologies. That is, compounds in this class of materials have shown promise as electrocatalysts for both the oxygen evolution (OER) and oxygen reduction reactions (ORR). The two aforementioned half-reactions are at the cornerstone of most renewable energy transformations, as oxygen is an inherently practical and abundant source and sink for electrons. In water electrolysis to produce hydrogen, oxygen is inevitably formed, and in a fuel cell the driving force for extracting electrochemical energy from hydrogen is pairing it with the reduction of oxygen to water. If this can be accomplished reversibly, the problem of "transient" renewable energy and its storage can be mitigated. We have examined many metal oxides and related compounds based upon Earth- abundant transition metals (primarily first row) that are crystalline, yet high surface area, for these important electrocatalytic reactions, and found that crystal structure plays a crucial role in determining activity. In fact, while most studies on heterogeneous catalysis focus on the synthesis of defect-rich, high surface area, practically amorphous materials to elicit high activity, we have found that particular crystalline phases possess not only the appropriate activity, but to some degree more importantly, the stability to be named good catalysts. In Chapter 2, we demonstrate that of the two structural types of lithium cobalt oxide (LiCoO2) - layered (R-3m) and cubic (Fd-3m) - only the cubic phase is revealed to be an efficient and stable catalyst for OER. Whether water oxidation is driven photochemically, or electrochemically, the cubic phase LiCoO2 possessing a spinel-like structure (AB 2O4) with [Co4O4] subunits within the crystal is more active. It is seen that electrochemically, both the cubic and layered phases transform to the spinel LiCo2O4 at surface and subsurface levels. This coincides with partial delithiation that is more extensive in layered LiCoO2. It is revealed that the oxidation of CoMn3+ to Co4+ is accompanied by delithiation in aqueous electrolyte to form the active state of the LiCoO2 catalyst. The electronic properties of the cubic spinel allow for localization of electron holes at cubic core active sites to effect water oxidation, whereas holes are more extensively delocalized in layered LiCoO2 in concert with the Li+ deintercalation reaction. In Chapter 3, we investigate the influence of chemical composition on the catalytic water oxidation activity of Co-substituted spinel LiMn 2O4 and Mn-substituted cubic LiCoO2. We find that in the spinel LiMn2O4, CoMn3+ substitution occurs at the B-site for MnMn3+, and the solid solution limit for starts at 1:1 Co:Mn ratio, where Co begins to go into the A-site. The activity for OER increases with increasing Co, owing to the symmetrization of the M4O4 core structure (Jahn-Teller distortions suppressed), which allows for hole delocalization that enables CoMn 3+/4+ oxidation. The more positive redox potential of Co4+ makes for facile water oxidation. Substituting Mn for Co in cubic LiCoO2 allows for retention of MnMn3+, which has been correlated with water oxidation activity in many catalysts. The solid solution limit in this series is also near 1:1 at the B- site. However, the increase in Mn content corresponds to decreasing activity in both water oxidation and oxygen reduction, which correlates well with decreases in pre- catalytic oxidation and reduction peak yields. The results show replacement of CoMn 3+ with MnMn3+ effectively eliminates active sites. Therefore, MnMn3+ in this electronic and structural environment is not active, which agrees well with a recent literature report on corner- shared MnMn3+ octahedral being necessary to produce OER activity in Mn oxides. Finally, in chapter 4, bifunctional oxygen electrocatalysts are explored in depth with a series of cobalt-molybdenum oxides/nitrides. We demonstrate that CoMoN2, with relatively strong M-N interactions, has ideal electronic properties for ORR, and upon oxidation of the surface, yields an active OER catalyst. However, the surface oxidation is found to be irreversible and once oxidized, the activity for ORR significantly decreases. The surface both before and after catalysis was analyzed by XPS, which showed the suppression of Mo and N signals after exposure to OER conditions, meaning the active catalyst is a Co oxide of high valency (3/4+). The results from this study suggests truly reversible, bifunctional oxygen electrocatalysis may be obtained by designing a catalyst whose surface is only partly oxidized and/or can be reversibly reduced in the potential window relevant to OER and ORR.

Low pCO2 under sea-ice melt in the Canada Basin of the western Arctic Ocean

NASA Astrophysics Data System (ADS)

Kosugi, Naohiro; Sasano, Daisuke; Ishii, Masao; Nishino, Shigeto; Uchida, Hiroshi; Yoshikawa-Inoue, Hisayuki

2017-12-01

In September 2013, we observed an expanse of surface water with low CO2 partial pressure (pCO2sea) (< 200 µatm) in the Chukchi Sea of the western Arctic Ocean. The large undersaturation of CO2 in this region was the result of massive primary production after the sea-ice retreat in June and July. In the surface of the Canada Basin, salinity was low (< 27) and pCO2sea was closer to the air-sea CO2 equilibrium (˜ 360 µatm). From the relationships between salinity and total alkalinity, we confirmed that the low salinity in the Canada Basin was due to the larger fraction of meltwater input (˜ 0.16) rather than the riverine discharge (˜ 0.1). Such an increase in pCO2sea was not so clear in the coastal region near Point Barrow, where the fraction of riverine discharge was larger than that of sea-ice melt. We also identified low pCO2sea (< 250 µatm) in the depth of 30-50 m under the halocline of the Canada Basin. This subsurface low pCO2sea was attributed to the advection of Pacific-origin water, in which dissolved inorganic carbon is relatively low, through the Chukchi Sea where net primary production is high. Oxygen supersaturation (> 20 µmol kg-1) in the subsurface low pCO2sea layer in the Canada Basin indicated significant net primary production undersea and/or in preformed condition. If these low pCO2sea layers surface by wind mixing, they will act as additional CO2 sinks; however, this is unlikely because intensification of stratification by sea-ice melt inhibits mixing across the halocline.

Methane and Carbon Dioxide Concentrations and Fluxes in Amazon Floodplains

NASA Astrophysics Data System (ADS)

Melack, J. M.; MacIntyre, S.; Forsberg, B.; Barbosa, P.; Amaral, J. H.

2016-12-01

Field studies on the central Amazon floodplain in representative aquatic habitats (open water, flooded forests, floating macrophytes) combine measurements of methane and carbon dioxide concentrations and fluxes to the atmosphere over diel and seasonal times with deployment of meteorological sensors and high-resolution thermistors and dissolved oxygen sondes. A cavity ringdown spectrometer is used to determine gas concentrations, and floating chambers and bubble collectors are used to measure fluxes. To further understand fluxes, we measured turbulence as rate of dissipation of turbulent kinetic energy based on microstructure profiling. These results allow calculations of vertical mixing within the water column and of air-water exchanges using surface renewal models. Methane and carbon dioxide fluxes varied as a function of season, habitat and water depth. High CO2 fluxes at high water are related to high pCO2; low pCO2 levels at low water result from increased phytoplankton uptake. CO2 fluxes are highest at turbulent open water sites, and pCO2 is highest in macrophyte beds. Fluxes and pCH4 are high in macrophyte beds.

Investigation of Mineral Transformations in Wet Supercritical CO2 by Electron Microscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Arey, Bruce W.; Kovarik, Libor; Wang, Zheming

2011-10-10

The capture and storage of carbon dioxide and other greenhouse gases in deep geologic formations represents one of the most promising options for mitigating the impacts of greenhouse gases on global warming. In this regard, mineral-fluid interactions are of prime importance since such reactions can result in the long term sequestration of CO2 by trapping in mineral phases. Recently it has been recognized that interactions with neat to water-saturated non-aqueous fluids are of prime importance in understanding mineralization reactions since the introduced CO2 is likely to contain water initially or soon after injection and the supercritical CO2 (scCO2) is lessmore » dense than the aqueous phase which can result in a buoyant scCO2 plume contacting the isolating caprock. As a result, unraveling the molecular/microscopic mechanisms of mineral transformation in neat to water saturated scCO2 has taken on an added important. In this study, we are examining the interfacial reactions of the olivine mineral forsterite (Mg2SiO4) over a range of water contents up to and including complete water saturation in scCO2. The surface precipitates that form on the reacted forsterite grains are extremely fragile and difficult to experimentally characterize. In order to address this issue we have developed experimental protocols for preparing and imaging electron-transparent samples from fragile structures. These electron-transparent samples are then examined using a combination of STEM/EDX, FIB-TEM, and helium ion microscope (HIM) imaging (Figures 1-3). This combination of capabilities has provided unique insight into the geochemical processes that occur on scCO2 reacted mineral surfaces. The experimental procedures and protocols that have been developed also have useful applications for examining fragile structures on a wide variety of materials. This research was performed using EMSL, a national scientific user facility sponsored by the Department of Energy's Office of Biological and Environmental Research located at Pacific Northwest National Laboratory.« less

Mapping of the air-sea CO2 flux in the Arctic Ocean and its adjacent seas: Basin-wide distribution and seasonal to interannual variability

NASA Astrophysics Data System (ADS)

Yasunaka, Sayaka; Murata, Akihiko; Watanabe, Eiji; Chierici, Melissa; Fransson, Agneta; van Heuven, Steven; Hoppema, Mario; Ishii, Masao; Johannessen, Truls; Kosugi, Naohiro; Lauvset, Siv K.; Mathis, Jeremy T.; Nishino, Shigeto; Omar, Abdirahman M.; Olsen, Are; Sasano, Daisuke; Takahashi, Taro; Wanninkhof, Rik

2016-09-01

We produced 204 monthly maps of the air-sea CO2 flux in the Arctic north of 60°N, including the Arctic Ocean and its adjacent seas, from January 1997 to December 2013 by using a self-organizing map technique. The partial pressure of CO2 (pCO2) in surface water data were obtained by shipboard underway measurements or calculated from alkalinity and total inorganic carbon of surface water samples. Subsequently, we investigated the basin-wide distribution and seasonal to interannual variability of the CO2 fluxes. The 17-year annual mean CO2 flux shows that all areas of the Arctic Ocean and its adjacent seas were net CO2 sinks. The estimated annual CO2 uptake by the Arctic Ocean was 180 TgC yr-1. The CO2 influx was strongest in winter in the Greenland/Norwegian Seas (>15 mmol m-2 day-1) and the Barents Sea (>12 mmol m-2 day-1) because of strong winds, and strongest in summer in the Chukchi Sea (∼10 mmol m-2 day-1) because of the sea-ice retreat. In recent years, the CO2 uptake has increased in the Greenland/Norwegian Sea and decreased in the southern Barents Sea, owing to increased and decreased air-sea pCO2 differences, respectively.

Photo-induced free radicals on a simulated Martian surface

NASA Technical Reports Server (NTRS)

Tseng, S.-S.; Chang, S.

1974-01-01

Results of an electron spin resonance study of free radicals in the ultraviolet irradiation of a simulated Martian surface suggest that the ultraviolet photolysis of CO or CO2, or a mixture of both, adsorbed on silica gel at minus 170 C involves the formation of OH radicals and possibly of H atoms as the primary process, followed by the formation of CO2H radicals. It is concluded that the photochemical synthesis of organic compounds could occur on Mars if the siliceous surface dust contains enough silanol groups and/or adsorbed H2O in the form of bound water.

A shallow subsurface controlled release facility in Bozeman, Montana, USA, for testing near surface CO2 detection techniques and transport models

USGS Publications Warehouse

Spangler, L.H.; Dobeck, L.M.; Repasky, K.S.; Nehrir, A.R.; Humphries, S.D.; Keith, C.J.; Shaw, J.A.; Rouse, J.H.; Cunningham, A.B.; Benson, S.M.; Oldenburg, C.M.; Lewicki, J.L.; Wells, A.W.; Diehl, J.R.; Strazisar, B.R.; Fessenden, J.E.; Rahn, T.A.; Amonette, J.E.; Barr, J.L.; Pickles, W.L.; Jacobson, J.D.; Silver, E.A.; Male, E.J.; Rauch, H.W.; Gullickson, K.S.; Trautz, R.; Kharaka, Y.; Birkholzer, J.; Wielopolski, L.

2010-01-01

A controlled field pilot has been developed in Bozeman, Montana, USA, to study near surface CO2 transport and detection technologies. A slotted horizontal well divided into six zones was installed in the shallow subsurface. The scale and CO2 release rates were chosen to be relevant to developing monitoring strategies for geological carbon storage. The field site was characterized before injection, and CO2 transport and concentrations in saturated soil and the vadose zone were modeled. Controlled releases of CO2 from the horizontal well were performed in the summers of 2007 and 2008, and collaborators from six national labs, three universities, and the U.S. Geological Survey investigated movement of CO2 through the soil, water, plants, and air with a wide range of near surface detection techniques. An overview of these results will be presented. ?? 2009 The Author(s).

Direct gas-solid carbonation of serpentinite residues in the absence and presence of water vapor: a feasibility study for carbon dioxide sequestration.

PubMed

Veetil, Sanoopkumar Puthiya; Pasquier, Louis-César; Blais, Jean-François; Cecchi, Emmanuelle; Kentish, Sandra; Mercier, Guy

2015-09-01

Mineral carbonation of serpentinite mining residue offers an environmentally secure and permanent storage of carbon dioxide. The strategy of using readily available mining residue for the direct treatment of flue gas could improve the energy demand and economics of CO2 sequestration by avoiding the mineral extraction and separate CO2 capture steps. The present is a laboratory scale study to assess the possibility of CO2 fixation in serpentinite mining residues via direct gas-solid reaction. The degree of carbonation is measured both in the absence and presence of water vapor in a batch reactor. The gas used is a simulated gas mixture reproducing an average cement flue gas CO2 composition of 18 vol.% CO2. The reaction parameters considered are temperature, total gas pressure, time, and concentration of water vapor. In the absence of water vapor, the gas-solid carbonation of serpentinite mining residues is negligible, but the residues removed CO2 from the feed gas possibly due to reversible adsorption. The presence of small amount of water vapor enhances the gas-solid carbonation, but the measured rates are too low for practical application. The maximum CO2 fixation obtained is 0.07 g CO2 when reacting 1 g of residue at 200 °C and 25 barg (pCO2 ≈ 4.7) in a gas mixture containing 18 vol.% CO2 and 10 vol.% water vapor in 1 h. The fixation is likely surface limited and restricted due to poor gas-solid interaction. It was identified that both the relative humidity and carbon dioxide-water vapor ratio have a role in CO2 fixation regardless of the percentage of water vapor.

High net CO2 and CH4 release at a eutrophic shallow lake on a formerly drained fen

NASA Astrophysics Data System (ADS)

Franz, Daniela; Koebsch, Franziska; Larmanou, Eric; Augustin, Jürgen; Sachs, Torsten

2016-05-01

Drained peatlands often act as carbon dioxide (CO2) hotspots. Raising the groundwater table is expected to reduce their CO2 contribution to the atmosphere and revitalise their function as carbon (C) sink in the long term. Without strict water management rewetting often results in partial flooding and the formation of spatially heterogeneous, nutrient-rich shallow lakes. Uncertainties remain as to when the intended effect of rewetting is achieved, as this specific ecosystem type has hardly been investigated in terms of greenhouse gas (GHG) exchange. In most cases of rewetting, methane (CH4) emissions increase under anoxic conditions due to a higher water table and in terms of global warming potential (GWP) outperform the shift towards CO2 uptake, at least in the short term.Based on eddy covariance measurements we studied the ecosystem-atmosphere exchange of CH4 and CO2 at a shallow lake situated on a former fen grassland in northeastern Germany. The lake evolved shortly after flooding, 9 years previous to our investigation period. The ecosystem consists of two main surface types: open water (inhabited by submerged and floating vegetation) and emergent vegetation (particularly including the eulittoral zone of the lake, dominated by Typha latifolia). To determine the individual contribution of the two main surface types to the net CO2 and CH4 exchange of the whole lake ecosystem, we combined footprint analysis with CH4 modelling and net ecosystem exchange partitioning.The CH4 and CO2 dynamics were strikingly different between open water and emergent vegetation. Net CH4 emissions from the open water area were around 4-fold higher than from emergent vegetation stands, accounting for 53 and 13 g CH4 m-2 a-1 respectively. In addition, both surface types were net CO2 sources with 158 and 750 g CO2 m-2 a-1 respectively. Unusual meteorological conditions in terms of a warm and dry summer and a mild winter might have facilitated high respiration rates. In sum, even after 9 years of rewetting the lake ecosystem exhibited a considerable C loss and global warming impact, the latter mainly driven by high CH4 emissions. We assume the eutrophic conditions in combination with permanent high inundation as major reasons for the unfavourable GHG balance.

UV sensitivity of planktonic net community production in ocean surface waters

NASA Astrophysics Data System (ADS)

Regaudie-de-Gioux, Aurore; Agustí, Susana; Duarte, Carlos M.

2014-05-01

The net plankton community metabolism of oceanic surface waters is particularly important as it more directly affects the partial pressure of CO2 in surface waters and thus the air-sea fluxes of CO2. Plankton communities in surface waters are exposed to high irradiance that includes significant ultraviolet blue (UVB, 280-315 nm) radiation. UVB radiation affects both photosynthetic and respiration rates, increase plankton mortality rates, and other metabolic and chemical processes. Here we test the sensitivity of net community production (NCP) to UVB of planktonic communities in surface waters across contrasting regions of the ocean. We observed here that UVB radiation affects net plankton community production at the ocean surface, imposing a shift in NCP by, on average, 50% relative to the values measured when excluding partly UVB. Our results show that under full solar radiation, the metabolic balance shows the prevalence of net heterotrophic community production. The demonstration of an important effect of UVB radiation on NCP in surface waters presented here is of particular relevance in relation to the increased UVB radiation derived from the erosion of the stratospheric ozone layer. Our results encourage design future research to further our understanding of UVB effects on the metabolic balance of plankton communities.

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

PubMed

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

2016-10-20

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

Surface Pressure Dependencies in the GEOS-Chem-Adjoint System and the Impact of the GEOS-5 Surface Pressure on CO2 Model Forecast

NASA Technical Reports Server (NTRS)

Lee, Meemong; Weidner, Richard

2016-01-01

In the GEOS-Chem Adjoint (GCA) system, the total (wet) surface pressure of the GEOS meteorology is employed as dry surface pressure, ignoring the presence of water vapor. The Jet Propulsion Laboratory (JPL) Carbon Monitoring System (CMS) research team has been evaluating the impact of the above discrepancy on the CO2 model forecast and the CO2 flux inversion. The JPL CMS research utilizes a multi-mission assimilation framework developed by the Multi-Mission Observation Operator (M2O2) research team at JPL extending the GCA system. The GCA-M2O2 framework facilitates mission-generic 3D and 4D-variational assimilations streamlining the interfaces to the satellite data products and prior emission inventories. The GCA-M2O2 framework currently integrates the GCA system version 35h and provides a dry surface pressure setup to allow the CO2 model forecast to be performed with the GEOS-5 surface pressure directly or after converting it to dry surface pressure.

Surface Pressure Dependencies in the Geos-Chem-Adjoint System and the Impact of the GEOS-5 Surface Pressure on CO2 Model Forecast

NASA Technical Reports Server (NTRS)

Lee, Meemong; Weidner, Richard

2016-01-01

In the GEOS-Chem Adjoint (GCA) system, the total (wet) surface pressure of the GEOS meteorology is employed as dry surface pressure, ignoring the presence of water vapor. The Jet Propulsion Laboratory (JPL) Carbon Monitoring System (CMS) research team has been evaluating the impact of the above discrepancy on the CO2 model forecast and the CO2 flux inversion. The JPL CMS research utilizes a multi-mission assimilation framework developed by the Multi-Mission Observation Operator (M2O2) research team at JPL extending the GCA system. The GCA-M2O2 framework facilitates mission-generic 3D and 4D-variational assimilations streamlining the interfaces to the satellite data products and prior emission inventories. The GCA-M2O2 framework currently integrates the GCA system version 35h and provides a dry surface pressure setup to allow the CO2 model forecast to be performed with the GEOS-5 surface pressure directly or after converting it to dry surface pressure.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Li; Wu, Zili; Nelson, Nicholas

Catalytic performance and the nature of surface adsorbates were investigated for high-surface-area ceria during ethylbenzene oxidative dehydrogenation (ODH) reaction using CO2 as a soft oxidant. A template assisted method was used to synthesize the high-surface-area ceria. The interactions between ethylbenzene, styrene and CO2 on the surface of ceria and the role of CO2 for the ethylbenzene ODH reaction have been investigated in detail by using activity test, in situ Diffuse Reflectance Infrared and Raman spectroscopy. Not only did CO2 as an oxidant favor the higher yield of styrene, but it also inhibited the deposition of coke during the ethylbenzene ODHmore » reaction. Ethylbenzene ODH reaction over ceria followed a two-step pathway: Ethylbenzene is first dehydrogenated to styrene with H2 formed simultaneously, and then CO2 reacts with H2 via the reverse water gas shift. The styrene produced can easily polymerize to form polystyrene, a key intermediate for coke formation. In the absence of CO2, the polystyrene transforms into graphite-like coke at temperatures above 500 °C, which leads to catalyst deactivation. While in the presence of CO2, the coke deposition can be effectively removed via oxidation with CO2.« less

Recharge of the early atmosphere of Mars by impact-induced release of CO2

USGS Publications Warehouse

Carr, Michael H.

1989-01-01

Channels on the Martian surface suggest that Mars had an early, relatively thick atmosphere. If the atmosphere was thick enough for water to be stable at the surface, CO2 in the atmosphere would have been fixed as carbonates on a relatively short time scale, previously estimated to be 1 bar every 107 years. This loss must have been offset by some replenishment mechanism to account for the numerous valley networks in the oldest surviving terrains. Impacts could have released CO2 into the atmosphere by burial, by shock-induced release during impact events, and by addition of carbon to Mars from the impacting bolides. Depending on the relationship between the transient cavity diameter and the diameter of the resulting crater, burial rates as a result of impact gardening at the end of heavy bombardment are estimated to range from 20 to 45 m/106 years, on the assumption that cratering rates in Mars were similar to those of the Nectarian Period on the Moon. At these rates 0.1-0.2 bar of CO2 could have been released every 107 years as a result of burial to depths where dissociation temperatures of carbonates were reached. Modeling of large impacts suggests that an additional 0.01 to 0.02 bar of CO2 could have been released every 107 years during the actual impacts. In the unlikely event that all the impacting material was composed of carbonaceous chondrites, a further 0.3 bar of CO2 could have been added to the atmosphere every 107 years by oxidation of meteoritic carbon. Even when supplemented by the volcanically induced release of CO2, these release rates are barely sufficient to sustain an early atmosphere if water were continuously present at the surface. The results suggest that water may have been only intermittently present on the surface early in the planet's history.

Investigation into the disparate origin of CO2 and H2O outgassing for Comet 67/P

NASA Astrophysics Data System (ADS)

Fink, Uwe; Doose, Lyn; Rinaldi, Giovanna; Bieler, André; Capaccioni, Fabrizio; Bockelée-Morvan, Dominique; Filacchione, Gianrico; Erard, Stephane; Leyrat, Cedric; Blecka, Maria; Capria, Maria Teresa; Combi, Michael; Crovisier, Jacques; De Sanctis, Maria Cristina; Fougere, Nicolas; Taylor, Fred; Migliorini, Alessandra; Piccioni, Giuseppe

2016-10-01

We present an investigation of the emission intensity of CO2 and H2O and their distribution in the coma of 67P/ Churyumov-Gerasimenko obtained by the VIRTIS-M imaging spectrometer on the Rosetta mission. We analyze 4 data cubes from Feb. 28, and 7 data cubes from April 27, 2015. For both data sets the spacecraft was at a sufficiently large distance from the comet to allow images of the whole nucleus and the surrounding coma. We find that unlike water which has a reasonably predictable behavior and correlates well with the solar illumination, CO2 outgasses mostly in local regions or spots. Furthermore for the data on April 27, the CO2 evolves almost exclusively from the southern hemisphere, a region of the comet that has not received solar illumination since the comet's last perihelion passage. Because CO2 and H2O have such disparate origins, deriving mixing ratios from local column density measurements cannot provide a meaningful measurement of the CO2/H2O ratio in the coma of the comet. We obtain total production rates of H2O and CO2 by integrating the band intensity in an annulus surrounding the nucleus and obtain pro-forma production rate CO2/H2O mixing ratios of ∼5.0% and ∼2.5% for Feb. 28 and April 27, respectively. Because of the highly variable nature of the CO2 evolution from the surface we do not believe that these numbers are diagnostic of the comet's bulk CO2/H2O composition. We believe that our investigation provides an explanation for the large observed variations reported in the literature for the CO2/H2O production rate ratios. Our mixing ratio maps indicate that, besides the difference in vapor pressure of the two gases, this ratio depends on the comet's rotational orientation combined with its complex geometric shape which can result in quite variable rates of erosion for different surface areas such as the northern and southern hemisphere. Our annulus measurement for the total water production for Feb. 28 at 2.21AU from the Sun is 2.5 × 1026 molecules/s while for April 27 at 1.76 AU it is 4.65 × 1026. We find that about 83% of the H2O resides in the illuminated portion of our annulus and about 17% on the night side. We also make an attempt to obtain the fraction of the H2O production coming from the highly active neck of the comet versus the rest of the illuminated surface from the pole-on view of Feb. 28 and estimate that about 60% of the H2O derives from the neck area. A rough estimate of the water surface evaporation rate of the illuminated nucleus for April 27 yields about 5 × 1019 molecules/s/m2. Spatial radial profiles of H2O on April 27 on the illuminated side of the comet, extending from 1.78 to 6.47 km from the nucleus center, show that water follows model predictions quite well, with the gas accelerating as it expands into the coma. Our dayside radial profile allows us to make an empirical determination of the expansion velocity of water. On the night side the spatial profile of water follows 1/ρ. The CO2 profiles do not exhibit any acceleration into the coma but are closely matched by a 1/ρ profile.

Hyperspectral detection of a subsurface CO2 leak in the presence of water stressed vegetation.

PubMed

Bellante, Gabriel J; Powell, Scott L; Lawrence, Rick L; Repasky, Kevin S; Dougher, Tracy

2014-01-01

Remote sensing of vegetation stress has been posed as a possible large area monitoring tool for surface CO2 leakage from geologic carbon sequestration (GCS) sites since vegetation is adversely affected by elevated CO2 levels in soil. However, the extent to which remote sensing could be used for CO2 leak detection depends on the spectral separability of the plant stress signal caused by various factors, including elevated soil CO2 and water stress. This distinction is crucial to determining the seasonality and appropriateness of remote GCS site monitoring. A greenhouse experiment tested the degree to which plants stressed by elevated soil CO2 could be distinguished from plants that were water stressed. A randomized block design assigned Alfalfa plants (Medicago sativa) to one of four possible treatment groups: 1) a CO2 injection group; 2) a water stress group; 3) an interaction group that was subjected to both water stress and CO2 injection; or 4) a group that received adequate water and no CO2 injection. Single date classification trees were developed to identify individual spectral bands that were significant in distinguishing between CO2 and water stress agents, in addition to a random forest classifier that was used to further understand and validate predictive accuracies. Overall peak classification accuracy was 90% (Kappa of 0.87) for the classification tree analysis and 83% (Kappa of 0.77) for the random forest classifier, demonstrating that vegetation stressed from an underground CO2 leak could be accurately discerned from healthy vegetation and areas of co-occurring water stressed vegetation at certain times. Plants appear to hit a stress threshold, however, that would render detection of a CO2 leak unlikely during severe drought conditions. Our findings suggest that early detection of a CO2 leak with an aerial or ground-based hyperspectral imaging system is possible and could be an important GCS monitoring tool.

Hyperspectral Detection of a Subsurface CO2 Leak in the Presence of Water Stressed Vegetation

PubMed Central

Bellante, Gabriel J.; Powell, Scott L.; Lawrence, Rick L.; Repasky, Kevin S.; Dougher, Tracy

2014-01-01

Remote sensing of vegetation stress has been posed as a possible large area monitoring tool for surface CO2 leakage from geologic carbon sequestration (GCS) sites since vegetation is adversely affected by elevated CO2 levels in soil. However, the extent to which remote sensing could be used for CO2 leak detection depends on the spectral separability of the plant stress signal caused by various factors, including elevated soil CO2 and water stress. This distinction is crucial to determining the seasonality and appropriateness of remote GCS site monitoring. A greenhouse experiment tested the degree to which plants stressed by elevated soil CO2 could be distinguished from plants that were water stressed. A randomized block design assigned Alfalfa plants (Medicago sativa) to one of four possible treatment groups: 1) a CO2 injection group; 2) a water stress group; 3) an interaction group that was subjected to both water stress and CO2 injection; or 4) a group that received adequate water and no CO2 injection. Single date classification trees were developed to identify individual spectral bands that were significant in distinguishing between CO2 and water stress agents, in addition to a random forest classifier that was used to further understand and validate predictive accuracies. Overall peak classification accuracy was 90% (Kappa of 0.87) for the classification tree analysis and 83% (Kappa of 0.77) for the random forest classifier, demonstrating that vegetation stressed from an underground CO2 leak could be accurately discerned from healthy vegetation and areas of co-occurring water stressed vegetation at certain times. Plants appear to hit a stress threshold, however, that would render detection of a CO2 leak unlikely during severe drought conditions. Our findings suggest that early detection of a CO2 leak with an aerial or ground-based hyperspectral imaging system is possible and could be an important GCS monitoring tool. PMID:25330232

The effects of elevated CO2 and eutrophication on surface elevation gain in a European salt marsh.

PubMed

Reef, Ruth; Spencer, Tom; Mӧller, Iris; Lovelock, Catherine E; Christie, Elizabeth K; McIvor, Anna L; Evans, Ben R; Tempest, James A

2017-02-01

Salt marshes can play a vital role in mitigating the effects of global environmental change by dissipating incident storm wave energy and, through accretion, tracking increasing water depths consequent upon sea level rise. Atmospheric CO 2 concentrations and nutrient availability are two key variables that can affect the biological processes that contribute to marsh surface elevation gain. We measured the effects of CO 2 concentrations and nutrient availability on surface elevation change in intact mixed-species blocks of UK salt marsh using six open-top chambers receiving CO 2 -enriched (800 ppm) or ambient (400 ppm) air. We found more rapid surface elevation gain in elevated CO 2 conditions: an average increase of 3.4 mm over the growing season relative to ambient CO 2 . Boosted regression analysis to determine the relative influence of different parameters on elevation change identified that a 10% reduction in microbial activity in elevated CO 2 -grown blocks had a positive influence on elevation. The biomass of Puccinellia maritima also had a positive influence on elevation, while other salt marsh species (e.g. Suaeda maritima) had no influence or a negative impact on elevation. Reduced rates of water use by the vegetation in the high CO 2 treatment could be contributing to elevation gain, either directly through reduced soil shrinkage or indirectly by decreasing microbial respiration rates due to lower redox levels in the soil. Eutrophication did not influence elevation change in either CO 2 treatment despite doubling aboveground biomass. The role of belowground processes (transpiration, root growth and decomposition) in the vertical adjustment of European salt marshes, which are primarily minerogenic in composition, could increase as atmospheric CO 2 concentrations rise and should be considered in future wetland models for the region. Elevated CO 2 conditions could enhance resilience in vulnerable systems such as those with low mineral sediment supply or where migration upwards within the tidal frame is constrained. © 2016 John Wiley & Sons Ltd.

Physiological effects on fishes in a high-CO2 world

NASA Astrophysics Data System (ADS)

Ishimatsu, Atsushi; Hayashi, Masahiro; Lee, Kyoung-Seon; Kikkawa, Takashi; Kita, Jun

2005-09-01

Fish are important members of both freshwater and marine ecosystems and constitute a major protein source in many countries. Thus potential reduction of fish resources by high-CO2 conditions due to the diffusion of atmospheric CO2 into the surface waters or direct CO2 injection into the deep sea can be considered as another potential threat to the future world population. Fish, and other water-breathing animals, are more susceptible to a rise in environmental CO2 than terrestrial animals because the difference in CO2 partial pressure (PCO2) of the body fluid of water-breathing animals and ambient medium is much smaller (only a few torr (1 torr = 0.1333 kPa = 1316 μatm)) than in terrestrial animals (typically 30-40 torr). A survey of the literature revealed that hypercapnia acutely affects vital physiological functions such as respiration, circulation, and metabolism, and changes in these functions are likely to reduce growth rate and population size through reproduction failure and change the distribution pattern due to avoidance of high-CO2 waters or reduced swimming activities. This paper reviews the acute and chronic effects of CO2 on fish physiology and tries to clarify necessary areas of future research.

Field evaluation of open and closed-path CO2 flux systems over asphalt surface

NASA Astrophysics Data System (ADS)

Bogoev, I.; Santos, E.

2016-12-01

Eddy covariance (EC) is a widely used method for quantifying surface fluxes of heat, water vapor and carbon dioxide between ecosystems and the atmosphere. A typical EC system consists of an ultrasonic anemometer measuring the 3D wind vector and a fast-response infrared gas analyzer for sensing the water vapor and CO2 density in the air. When using an open-path analyzer that detects the constituent's density in situ a correction for concurrent air temperature and humidity fluctuations must be applied, Webb et al. (1980). In environments with small magnitudes of CO2 flux (<5µmol m-2 s-1) and in the presence of high sensible heat flux, like wintertime over boreal forest, open-path flux measurements have been challenging since the magnitude of the density corrections are as large as the uncorrected CO2 flux itself. A new technology merging the sensing paths of the gas analyzer and the sonic anemometer has been recently developed. This new integrated instrument allows a direct measurement of CO2 mixing ratio in the open air and has the potential to improve the quality of the temperature related density corrections by synchronously measuring the sensible heat flux in the optical path of the gas analyzer. We evaluate the performance and the accuracy of this new sensor over a large parking lot with an asphalt surface where the CO2 fluxes are considered low and the interfering sensible heat fluxes are above 200 Wm-2. A co-located closed-path EC system is used as a reference measurement to examine any systematic biases and apparent CO2 uptake observed with open-path sensors under high sensible heat flux regimes. Half-hour mean and variance of CO2 and water vapor concentrations are evaluated. The relative spectral responses, covariances and corrected turbulent fluxes using a common sonic anemometer are analyzed. The influence of sensor separation and frequency response attenuation on the density corrections is discussed.

Laboratory study on the kinetics of CO2 hydrates in a broad p-T range relevant to Mars

NASA Astrophysics Data System (ADS)

Falenty, A.; Kuhs, W. F.

2007-08-01

Although recent investigations revealed that liquid water was indeed actively reshaping Mars in a distant past, the present cold climate is not favorable for the stability of liquid water at the planet surface or close to it. The discovery of geologically young structures (e.g chaotic terrains, gullies) pushed many authors to search for alternative scenarios to liquid water [1]. Among others a rapid decomposition of CO2 hydrates (CO2 clathrates) formed in the not too distant past has been suggested as a possible source for their formation. CO2 clathrates appear also in considerations about the composition of polar caps and regolith [2]. In contrary to water and CO2 systems that are well established in Martian p-T conditions, CO2 hydrates still carry many unknowns. Only few experimental data exist for the water-CO2-hydrate system below the melting point of water and kinetic data of formation and decomposition did not exist, which motivated our laboratory work. We have performed systematic laboratory formation [3-5] and decomposition studies [6] on CO2 hydrates mimicking Martian surface and sub-surface conditions using in-situ neutron diffraction at ILL Grenoble as well as an in-house p-V-T method combined with x-ray diffraction and ex-situ cryo FE-SEM observations. Hexagonal water ice (Ih) and CO2 gas have been chosen for the experiments as the most probable constituents in the formation reaction. The size of ice particles, temperature and excess of free gas has proven to influence strongly the reaction speed. At p-T conditions close to the Martian poles CO2 hydrates are thermodynamically stable at the surface. Despite of this fact our results show that at these low temperatures the very slow kinetics prevents any significant formation of clathrates. This finding is in agreement with the unsuccessful efforts to detect clathrates by orbital IR spectroscopy. The formation process within the regolith is also limited, as a number of serious difficulties have to be overcome (e.g. sufficient amount of water ice, constant supply of CO2, increased gas pressure). Yet, our studies indicate reasonably short times of transformation for ice particles of sub-μ size suspended in the atmosphere. A number of authors assume that substantial amount of hydrates might have been formed in the planets subsurface. This possibility is confirmed in our work. In further studies, we have investigated possible scenarios for hydrate decomposition and their possible influence on the planet surface and atmosphere. Surprisingly, we have found that ice formed upon clathrate decomposition below 190K is not hexagonal but crystallizes in its "cubic" form (ice Ic). At higher temperatures a defective ice Ih is formed [7]. Ice Ic with its higher specific surface is not only decreasing the time needed for any transformation reaction but also carries other important consequences. The chemical reactivity of ice Ic surfaces differs from the one of ordinary hexagonal ice and should be taken into consideration in surface and atmospheric chemistry processes. In a temperature interval from about 240 to 273 K, we have firmly established a behavior, called "self-preservation" (or "anomalous preservation") [7], that is capable of preservation of CO2hydrates in semi-stable state for geologically long time scales making them an excellent gas storage. This complex micro-structural process is governed by changes on the surface of decomposing hydrates. A layer of small ice crystals [8] (up to 20μm) formed upon decomposition drastically slow down the out-diffusion of gas molecules, thus preventing further decomposition due to annealing and some coarsening processes. Its effect rapidly decreases with the particle size. The destruction of this fragile state above the melting point of water, as speculated, indeed leads to the very rapid, catastrophic decomposition known also from terrestrial examples. Yet, a similar effect below the freezing point of water cannot be expected. Instead, temporary gas outbursts are conceivable. Between 190K and 240K neither annealing of defective ice Ih nor the crystal regrowth is fast enough to effectively slow down outward diffusing gas molecules. In such a scenario slow decomposition is to be expected and therefore the impact on the surface will be very limited. Surprisingly we also have found "self preservation" in a narrow pressure range. The sealing effect is, however, less pronounced as the preservation mechanism differs from the higher temperature one. Therefore only large agglomerations of CO2 hydrates may be effectively saved from further decomposition. [1] J.S.Kargel Mars: A Warmer Wetter Planet, Springer Berlin, 2004. [2] R. Greve, R.A. Mahajan (2005), Icarus 176, 475-485 [3] D.K. Staykova et al. (2003) J. Phys. Chem. B 107,10299-10311 [4] G. Genov et al. (2004), Am. Miner. 89, 1228-1239 [5] W.F. Kuhs et al. (2006) J.Phys.Chem. B 110 (26), 13283-13295 [6] G. Genov PhD thesis, Georg-August Universität, Göttingen, 2004 [7] W. F. Kuhs et al. (2004), Phys. Chem. Chem. Phys. 6, 4917-4920 [8] A. Falenty et al. (2007) In: Physics and Chemistry of Ice (ed. W. F. Kuhs), RSC Publishing, Cambridge, 2007, pp. 171-179

DOE Office of Scientific and Technical Information (OSTI.GOV)

Favaro, Marco; Xiao, Hai; Cheng, Tao

A national priority is to convert CO 2 into high-value chemical products such as liquid fuels. Because current electrocatalysts are not adequate, we aim to discover new catalysts by obtaining a detailed understanding of the initial steps of CO 2 electroreduction on copper surfaces, the best current catalysts. Using ambient pressure X-ray photoelectron spectroscopy interpreted with quantum mechanical prediction of the structures and free energies, we show that the presence of a thin suboxide structure below the copper surface is essential to bind the CO 2 in the physisorbed configuration at 298 K, and we show that this suboxide ismore » essential for converting to the chemisorbed CO 2 in the presence of water as the first step toward CO 2 reduction products such as formate and CO. This optimum suboxide leads to both neutral and charged Cu surface sites, providing fresh insights into how to design improved carbon dioxide reduction catalysts.« less

Hydrochemical Impacts of CO2 Leakage on Fresh Groundwater: a Field Scale Experiment

NASA Astrophysics Data System (ADS)

Lions, J.; Gal, F.; Gombert, P.; Lafortune, S.; Darmoul, Y.; Prevot, F.; Grellier, S.; Squarcioni, P.

2013-12-01

One of the questions related to the emerging technology for Carbon Geological Storage concerns the risk of CO2 migration beyond the geological storage formation. In the event of leakage toward the surface, the CO2 might affect resources in neighbouring formations (geothermal or mineral resources, groundwater) or even represent a hazard for human activities at the surface or in the subsurface. In view of the preservation of the groundwater resources mainly for human consumption, this project studies the potential hydrogeochemical impacts of CO2 leakage on fresh groundwater quality. One of the objectives is to characterize the bio-geochemical mechanisms that may impair the quality of fresh groundwater resources in case of CO2 leakage. To reach the above mentioned objectives, this project proposes a field experiment to characterize in situ the mechanisms that could impact the water quality, the CO2-water-rock interactions and also to improve the monitoring methodology by controlled CO2 leakage in shallow aquifer. The tests were carried out in an experimental site in the chalk formation of the Paris Basin. The site is equipped with an appropriate instrumentation and was previously characterized (8 piezometers, 25 m deep and 4 piezairs 11 m deep). The injection test was preceded by 6 months of monitoring in order to characterize hydrodynamics and geochemical baselines of the site (groundwater, vadose and soil). Leakage into groundwater is simulated via the injection of a small quantity of food-grade CO2 (~20 kg dissolved in 10 m3 of water) in the injection well at a depth of about 20 m. A plume of dissolved CO2 is formed and moves downward according to the direction of groundwater flow and probably by degassing in part to the surface. During the injection test, hydrochemical monitoring of the aquifer is done in situ and by sampling. The parameters monitored in the groundwater are the piezometric head, temperature, pH and electrical conductivity. Analysis on water samples provide chemical elements (major, minor and trace metals), dissolved gases, microbiological diversity and isotopes (13C). The evolution of the composition of the groundwater in terms of major elements, trace elements and isotope signatures is interpreted in terms of geochemical mechanisms, and the water-rock-CO2 interactions are characterized. Modification of the chemical composition of water in the aquifer due to CO2 injection is assessed in term of groundwater quality i.e. metal element release and the possibility of exceeding references and quality of water for human consumption. One outcome of the CIPRES project will be to highlight mechanisms that can impact groundwater quality when a CO2 leakage occurs and to propose recommendations to prevent or/and eliminate negative effects and any risks to the environment and human health. This project is partially funded by the French Research Agency (ANR).

Ikaite crystals in melting sea ice - implications for pCO2 and pH levels in Arctic surface waters

NASA Astrophysics Data System (ADS)

Rysgaard, S.; Glud, R. N.; Lennert, K.; Cooper, M.; Halden, N.; Leakey, R. J. G.; Hawthorne, F. C.; Barber, D.

2012-03-01

A major issue of Arctic marine science is to understand whether the Arctic Ocean is, or will be, a source or sink for air-sea CO2 exchange. This has been complicated by the recent discoveries of ikaite (CaCO3·6H2O) in Arctic and Antarctic sea ice, which indicate that multiple chemical transformations occur in sea ice with a possible effect on CO2 and pH conditions in surface waters. Here we report on biogeochemical conditions, microscopic examinations and x-ray diffraction analysis of single crystals from an actively melting 1.7 km2 (0.5-1 m thick) drifting ice floe in the Fram Strait during summer. Our findings show that ikaite crystals are present throughout the sea ice but with larger crystals appearing in the upper ice layers. Ikaite crystals placed at elevated temperatures gradually disintegrated into smaller crystallites and dissolved. During our field campaign in late June, melt reduced the ice flow thickness by ca. 0.2 m per week and resulted in an estimated 1.6 ppm decrease of pCO2 in the ocean surface mixed layer. This corresponds to an air-sea CO2 uptake of 11 mmol m-2 sea ice d-1 or to 3.5 ton km-2 ice floe week-1.

A catalytic role of surface silanol groups in CO2 capture on the amine-anchored silica support.

PubMed

Cho, Moses; Park, Joonho; Yavuz, Cafer T; Jung, Yousung

2018-05-03

A new mechanism of CO2 capture on the amine-functionalized silica support is demonstrated using density functional theory calculations, in which the silica surface not only acts as a support to anchor amines, but also can actively participate in the CO2 capture process through a facile proton transfer reaction with the amine groups. The surface-mediated proton transfer mechanism in forming a carbamate-ammonium product has lower kinetic barrier (8.1 kcal mol-1) than the generally accepted intermolecular mechanism (12.7 kcal mol-1) under dry conditions, and comparable to that of the water-assisted intermolecular mechanism (6.0 kcal mol-1) under humid conditions. These findings suggest that the CO2 adsorption on the amine-anchored silica surface would mostly occur via the rate-determining proton transfer step that is catalyzed by the surface silanol groups.

Global Distribution of Shallow Water on Mars: Neutron Mapping of Summer-Time Surface by HEND/Odyssey

NASA Technical Reports Server (NTRS)

Mitrofanov, I. G.; Litvak, M. L.; Kozyrev, A. S.; Sanin, A. B.; Tretyakov, V. I.; Boynton, W.; Hamara, D.; Shinohara, C.; Saunders, R. S.; Drake, D.

2003-01-01

Orbital mapping of induced neutrons and gamma-rays by Odyssey has recently successfully proven the applicability of nuclear methods for studying of the elementary composition of Martian upper-most subsurface. In particular, the suite of Gamma-Ray Spectrometer (GRS) has discovered the presence of large water-ice rich regions southward and northward on Mars. The data of neutron mapping of summer-time surface are presented below from the Russian High Energy Neutron Spectrometer (HEND), which is a part of GRS suite. These maps represent the content of water in the soil for summer season at Southern and Northern hemispheres, when the winter deposit of CO2 is absent on the surface. The seasonal evolution of CO2 coverage on Mars is the subject of the complementary paper.

Non-controlled biogenic emissions to the atmosphere from Lazareto landfill, Tenerife, Canary Islands.

PubMed

Nolasco, Dácil; Lima, R Noemí; Hernández, Pedro A; Pérez, Nemesio M

2008-01-01

[corrected] Historically, landfills have been the simplest form of eliminating urban solid waste with the minimum cost. They have been the most usual method for discarding solid waste. However, landfills are considered authentic biochemical reactors that introduce large amounts of contaminants into the environment in the form of gas and leachates. The dynamics of generation and the movement of gas in landfills depend on the input and output parameters, as well as on the structure of the landfill and the kind of waste. The input parameters include water introduced through natural or artificial processes, the characteristics of the urban solid waste, and the input of atmospheric air. The main output parameters for these biochemical reactors include the gases and the leachates that are potentially pollutants for the environment. Control systems are designed and installed to minimize the impact on the environment. However, these systems are not perfect and a significant amount of landfill gas could be released to the atmosphere through the surface in a diffuse form, also known as Non-controlled emission. In this paper, the results of the Non-controlled biogenic gas emissions from the Lazareto landfill in Tenerife, Canary Islands, are presented. The purpose of this study was to evaluate the concentration of CH4 and CO2 in the soil gas of the landfill cover, the CH4 and CO2 efflux from the surface of the landfill and, finally, to compare these parameters with other similar landfills. In this way, a better understanding of the process that controls biogenic gas emissions in landfills is expected. A Non-controlled biogenic gas emission survey of 281 sampling sites was carried out during February and March, 2002. The sampling sites were selected in order to obtain a well-distributed sampling grid. Surface landfill CO2 efflux measurements were carried out at each sampling site on the surface landfill together with soil gas collection and ground temperatures at a depth of 30-40 cm. The CH4 efflux was computed from CO2 efflux and from the ratio CH4/CO2 in the soil gas. Soil gas samples were collected at a depth of 30-40 cm using a metallic probe and 20 cc hypodermic syringes, and later stored in evacuated 10 cc vacutainers for laboratory analysis of bulk composition. The gas sample was introduced in a vacutainer filled with deionized water and displacing the water until the vacutainer was filled with the gas sample in order to avoid air contamination from entering. The surface landfill temperature of the landfill was measured at a depth of 40 cm using a digital thermometer type OMEGA 871A. Landfill gases, CO2 and CH4, were analyzed within 24 hours using a double channel VARIAN micro-GC QUAD CP-2002P, with a 10 meter PORAPLOT-Q column, a TCD detector, and He as a carrier gas. The analysis temperature was 40 degrees C and the injection time was 10 msec. Surface landfill CO2 efflux measurements were performed using a portable NDIR spectrophotometer Licor-800 according to the accumulation chamber method (Chiodini et al. 1996). The data treatment, aimed at drawing the flux map and computing the total gas output, was based on the application of stochastic simulation algorithms provided by the GSLIB program (Deutsch and Journel 1998). Diffuse CH4 and CO2 efflux values range from negligible values up to 7,148 and 30,573 g m(-2) d(-1), respectively. The spatial distribution of the concentration and efflux of CO2, CH4 and soil temperature, show three areas of maximum activity in the landfill, suggesting a non-uniform pattern of diffuse degassing. This correlation between high emissions and concentration of CO2, CH4 and soil temperatures suggests that the areas of higher microbial activity and exothermic reactions are releasing CO2 and CH4 to the atmosphere from the landfill. Taking into consideration the spatial distribution of the CO2 and CH4 efflux values as well as the extension of the landfill, the Non-controlled emission of CO2 and CH4 to the atmosphere by the Lazareto's landfill are of 167 +/- 13.3 and 16 +/- 2.5 t d(-1), respectively. The patterns of gas flow within the landfill seem to be affected by boundary materials at the sides. The basalt layers have a low permeability and the gas flow in these areas is extensive. In this area, where a basalt layer does not exist, the flow gas diffuses toward the sea and the flux emissions at the landfill surface are lower. This behavior reflects the possible dissolution of gases into water and the deflection of gases towards the surface at the basalt boundary. The proximity to the sea, the installation of a palm tree garden and, as a result, the contribution of water coming from the watering of this garden has reactivated the system. The introduction of sea water into the landfill and the type of boundary could be defining the superficial gas discharges. Results from this study indicate that the spatial distribution of Non-controlled emission of CO2 and CH4 at the Lazareto's landfill shows a non-uniform pattern of diffuse degassing. The northeast, central and northwest areas of the Lazareto's landfill are the three areas of high emissions and concentration of CO2 and CH4, and high temperatures. The correlation between high emissions and the concentration of CO2, CH4, and the high temperatures suggest that the areas of higher microbial activity and exothermic reactions are releasing more CO2 and CH4 to the atmosphere from the landfill. A high concentration of CO2 is probably due to the presence of methanotrophic bacteria in the soil atmosphere of the landfill. Patterns of gas flow within the landfill seem to be affected by boundary materials (basalt layers) of low permeability, and side boundaries of the flux emissions at the surface are higher. At the sides of seawater and sediment boundaries, flux emissions at the landfill surface are lower. This behavior reflects a possible dissolution of gases into the water and the deflection of gases towards the surface at the basalt boundary. With this study, we can compare the data obtained in this landfill with other landfills and observe the different levels of emission. The proximity to the sea and the installation of the palm tree garden palms and, as a result, the contribution of water coming from the watering of this garden has reactivated the system. Many landfills worldwide located in similar settings could experience similar gas production processes. The need for investigating and monitoring sea water and sediment quality in these landfills is advisable. Concentrations and fluxes of contaminants and their impact in the area should be assessed. With this study we can compare the data obtained in these landfills with other landfills and observe the different levels of emission.

Method and apparatus for simulating atomospheric absorption of solar energy due to water vapor and CO.sub.2

DOEpatents

Sopori, Bhushan L.

1995-01-01

A method and apparatus for improving the accuracy of the simulation of sunlight reaching the earth's surface includes a relatively small heated chamber having an optical inlet and an optical outlet, the chamber having a cavity that can be filled with a heated stream of CO.sub.2 and water vapor. A simulated beam comprising infrared and near infrared light can be directed through the chamber cavity containing the CO.sub.2 and water vapor, whereby the spectral characteristics of the beam are altered so that the output beam from the chamber contains wavelength bands that accurately replicate atmospheric absorption of solar energy due to atmospheric CO.sub.2 and moisture.

Method and apparatus for simulating atmospheric absorption of solar energy due to water vapor and CO{sub 2}

DOEpatents

Sopori, B.L.

1995-06-20

A method and apparatus for improving the accuracy of the simulation of sunlight reaching the earth`s surface includes a relatively small heated chamber having an optical inlet and an optical outlet, the chamber having a cavity that can be filled with a heated stream of CO{sub 2} and water vapor. A simulated beam comprising infrared and near infrared light can be directed through the chamber cavity containing the CO{sub 2} and water vapor, whereby the spectral characteristics of the beam are altered so that the output beam from the chamber contains wavelength bands that accurately replicate atmospheric absorption of solar energy due to atmospheric CO{sub 2} and moisture. 8 figs.

Emissions of carbon dioxide and methane from a headwater stream network of interior Alaska

USGS Publications Warehouse

Crawford, John T.; Striegl, Robert G.; Wickland, Kimberly P.; Dornblaser, Mark M.; Stanley, Emily H.

2013-01-01

Boreal ecosystems store significant quantities of organic carbon (C) that may be vulnerable to degradation as a result of a warming climate. Despite their limited coverage on the landscape, streams play a significant role in the processing, gaseous emission, and downstream export of C, and small streams are thought to be particularly important because of their close connection with the surrounding landscape. However, ecosystem carbon studies do not commonly incorporate the role of the aquatic conduit. We measured carbon dioxide (CO2) and methane (CH4) concentrations and emissions in a headwater stream network of interior Alaska underlain by permafrost to assess the potential role of stream gas emissions in the regional carbon balance. First-order streams exhibited the greatest variability in fluxes of CO2 and CH4,and the greatest mean pCO2. High-resolution time series of stream pCO2 and discharge at two locations on one first-order stream showed opposing pCO2 responses to storm events, indicating the importance of hydrologic flowpaths connecting CO2-rich soils with surface waters. Repeated longitudinal surveys on the stream showed consistent areas of elevated pCO2 and pCH4, indicative of discrete hydrologic flowpaths delivering soil water and groundwater having varying chemistry. Up-scaled basin estimates of stream gas emissions suggest that streams may contribute significantly to catchment-wide CH4 emissions. Overall, our results indicate that while stream-specific gas emission rates are disproportionately high relative to the terrestrial landscape, both stream surface area and catchment normalized emission rates were lower than those documented for the Yukon River Basin as a whole. This may be due to limitations of C sources and/or C transport to surface waters.

Dependency of Ecosystem Respiration in a Cool Temperate Bog on Peat Temperature and Water Table

NASA Astrophysics Data System (ADS)

Moore, T.; Lafleur, P.; Roulet, N.; Frolking, S.

2003-12-01

We measured ecosystem respiration (ER) from nighttime net ecosystem exchange of carbon dioxide determined from an eddy covariance tower located in a large ombrotrophic bog near Ottawa, Canada. Measurements were made from May to October over 5 years, 1998 to 2002. Ecosystem respiration ranged from <0.05 mg CO2/m2/s in spring (May) and late fall (late October) to 0.10-0.15 mg CO2/m2/s during the summer (July-August). As anticipated, there was a strong relationship between ER and peat temperatures, such as at a depth of 5 cm (r2 = 0.63). Q10 over 5° to 15° C varied from 2.2 to 4.2 depending upon the choice of temperature level and location within a hummock or hollow. Unexpected for a wetland ecosystem, there was only a weak relationship between ER and water table position (r2 = 0.11). Comparison of ER in early and late summer, 2002 with similar surface temperature revealed no significant difference in ER. A laboratory incubation of peat cores at different moisture contents showed that CO2 production was reduced by drying in the surface samples, but there was little decrease in samples from below a depth of 30 cm. We believe that the lack of correlation between ER and water table position in this ecosystem results from an increase in CO2 production at depth compensating a decrease in production of CO2 by heterotrophic respiration in the near surface layers and autotrophic respiration in the moss community.

EPR spin trapping evidence of radical intermediates in the photo-reduction of bicarbonate/CO2 in TiO2 aqueous suspensions.

PubMed

Molinari, Alessandra; Samiolo, Luca; Amadelli, Rossano

2015-05-01

Using the EPR spin trapping technique, we prove that simultaneous reactions take place in illuminated suspensions of TiO2 in aqueous carbonate solutions (pH ≈ 7). The adsorbed HCO3(-) is reduced to formate as directly made evident by the detection of formate radicals (˙CO2(-)). In addition, the amount of OH˙ radicals from the photo-oxidation of water shows a linear dependence on the concentration of bicarbonate, indicating that electron scavenging by HCO3(-) increases the lifetime of holes. In a weakly alkaline medium, photo-oxidation of HCO3(-)/CO3(2-) to ˙CO3(-) interferes with the oxidation of water. A comparative analysis of different TiO2 samples shows that formation of ˙CO2(-) is influenced by factors related to the nature of the surface, once expected surface area effects are accounted for. Modification of the TiO2 surface with noble metal nanoparticles does not have unequivocal benefits: the overall activity improves with Pd and Rh but not with Ru, which favours HCO3(-) photo-oxidation even at pH = 7. In general, identification of radical intermediates of oxidation and reduction reactions can provide useful mechanistic information that may be used in the development of photocatalytic systems for the reduction of CO2 also stored in the form of carbonates.

Derivation of scaled surface reflectances from AVIRIS data

NASA Technical Reports Server (NTRS)

Gao, Bo-Cai; Heidebrecht, Kathleen B.; Goetz, Alexander F. H.

1993-01-01

A method for retrieving 'scaled surface reflectances' assuming horizontal surfaces having Lambertian reflectances from spectral data collected by Airborne Visible/Infrared Imaging Spectrometer (AVIRIS) is presented here. In this method, the integrated water vapor amount on a pixel by pixel basis is derived from the 0.94 micron and 1.14 micron water vapor absorption features. The transmission spectra of H2O, CO2, O3, N2O, CO, CH4, and O2 in the 0.4-2.5 micron region are simulated. The scattering effect due to atmospheric molecules and aerosols is modeled with the 5S computer code. The AVIRIS radiances are divided by solar irradiances above the atmosphere to obtain the apparent reflectances. The scaled surface reflectances are derived from the apparent reflectances using the simulated atmospheric gaseous transmittances and the simulated molecular and aerosol scattering data. The scaled surface reflectances differ from the real surface reflectances by a multiplicative factor. In order to convert the scaled surface reflectances into real surface reflectances, the slopes and aspects of the surfaces must be known.

Deriving a sea surface climatology of CO2 fugacity in support of air-sea gas flux studies

NASA Astrophysics Data System (ADS)

Goddijn-Murphy, L. M.; Woolf, D. K.; Land, P. E.; Shutler, J. D.; Donlon, C.

2014-07-01

Climatologies, or long-term averages, of essential climate variables are useful for evaluating models and providing a baseline for studying anomalies. The Surface Ocean Carbon Dioxide (CO2) Atlas (SOCAT) has made millions of global underway sea surface measurements of CO2 publicly available, all in a uniform format and presented as fugacity, fCO2. fCO2 is highly sensitive to temperature and the measurements are only valid for the instantaneous sea surface temperature (SST) that is measured concurrent with the in-water CO2 measurement. To create a climatology of fCO2 data suitable for calculating air-sea CO2 fluxes it is therefore desirable to calculate fCO2 valid for climate quality SST. This paper presents a method for creating such a climatology. We recomputed SOCAT's fCO2 values for their respective measurement month and year using climate quality SST data from satellite Earth observation and then extrapolated the resulting fCO2 values to reference year 2010. The data were then spatially interpolated onto a 1° × 1° grid of the global oceans to produce 12 monthly fCO2 distributions for 2010. The partial pressure of CO2 (pCO2) is also provided for those who prefer to use pCO2. The CO2 concentration difference between ocean and atmosphere is the thermodynamic driving force of the air-sea CO2 flux, and hence the presented fCO2 distributions can be used in air-sea gas flux calculations together with climatologies of other climate variables.

Experimental Investigation of Mechanical Properties of Black Shales after CO2-Water-Rock Interaction

PubMed Central

Lyu, Qiao; Ranjith, Pathegama Gamage; Long, Xinping; Ji, Bin

2016-01-01

The effects of CO2-water-rock interactions on the mechanical properties of shale are essential for estimating the possibility of sequestrating CO2 in shale reservoirs. In this study, uniaxial compressive strength (UCS) tests together with an acoustic emission (AE) system and SEM and EDS analysis were performed to investigate the mechanical properties and microstructural changes of black shales with different saturation times (10 days, 20 days and 30 days) in water dissoluted with gaseous/super-critical CO2. According to the experimental results, the values of UCS, Young’s modulus and brittleness index decrease gradually with increasing saturation time in water with gaseous/super-critical CO2. Compared to samples without saturation, 30-day saturation causes reductions of 56.43% in UCS and 54.21% in Young’s modulus for gaseous saturated samples, and 66.05% in UCS and 56.32% in Young’s modulus for super-critical saturated samples, respectively. The brittleness index also decreases drastically from 84.3% for samples without saturation to 50.9% for samples saturated in water with gaseous CO2, to 47.9% for samples saturated in water with super-critical carbon dioxide (SC-CO2). SC-CO2 causes a greater reduction of shale’s mechanical properties. The crack propagation results obtained from the AE system show that longer saturation time produces higher peak cumulative AE energy. SEM images show that many pores occur when shale samples are saturated in water with gaseous/super-critical CO2. The EDS results show that CO2-water-rock interactions increase the percentages of C and Fe and decrease the percentages of Al and K on the surface of saturated samples when compared to samples without saturation. PMID:28773784

Carbonate system variability in the Gulf of Trieste (North Adriatic Sea)

NASA Astrophysics Data System (ADS)

Cantoni, Carolina; Luchetta, Anna; Celio, Massimo; Cozzi, Stefano; Raicich, Fabio; Catalano, Giulio

2012-12-01

The seasonal variability of the carbonate system in the waters of the Gulf of Trieste (GoT) was studied at PALOMA station from 2008 to 2009, in order to highlight the effects of biological processes, meteorological forcings and river loads on the dynamics of pHT, CO2 partial pressure (pCO2), dissolved inorganic carbon (DIC), carbonate ion concentration (CO3=), aragonite saturation state (ΩAr) and total alkalinity (AT). During winter, low seawater temperature (9.0 ± 0.4 °C) and a weak biological activity (-10.7 < AOU < 15.7 μmol O2 kg-1) in a homogeneous water column led to the lowest average values of pCO2 (328 ± 19 μatm) and ΩAr (2.91 ± 0.14). In summer, the water column in the area acted as a two-layer system, with production processes prevailing in the upper layer (average AOU = -29.3 μmol O2 kg-1) and respiration processes in the lower layer (average AOU = 26.8 μmol O2 kg-1). These conditions caused the decrease of DIC (50 μmol kg-1) and the increase of ΩAr (1.0) values in the upper layer, whereas opposite trends were observed in the bottom waters. In August 2008, during a hypoxic event (dissolved oxygen DO = 86.9 μmol O2 kg-1), the intense remineralisation of organic carbon caused the rise of pCO2 (1043 μatm) and the decreases of pHT and ΩAr values down to 7.732 and 1.79 respectively. On an annual basis, surface pCO2 was mainly regulated by the pronounced seasonal cycle of seawater temperature. In winter, surface waters in the GoT were under-saturated with respect to atmospheric CO2, thus acting as a sink of CO2, in particular when strong-wind events enhanced air-sea gas exchange (FCO2 up to -11.9 mmol m-2 d-1). During summer, the temperature-driven increase of pCO2 was dampened by biological CO2 uptake, as consequence a slight over-saturation (pCO2 = 409 μatm) turned out. River plumes were generally associated to higher AT and pCO2 values (up to 2859 μmol kg-1 and 606 μatm respectively), but their effect was highly variable in space and time. During winter, the ambient conditions that favour the formation of dense waters on this continental shelf, also favour a high absorption of CO2 in seawater and its consequent acidification (pHT decrease of -0.006 units during a 7-day Bora wind event). This finding indicates a high vulnerability of North Adriatic Dense Water to atmospheric CO2 increase and ocean acidification process.

Cyanobacterial carbon concentrating mechanisms facilitate sustained CO2 depletion in eutrophic lakes

NASA Astrophysics Data System (ADS)

Morales-Williams, Ana M.; Wanamaker, Alan D., Jr.; Downing, John A.

2017-06-01

Phytoplankton blooms are increasing in frequency, intensity, and duration in aquatic ecosystems worldwide. In many eutrophic lakes, these high levels of primary productivity correspond to periods of CO2 depletion in surface waters. Cyanobacteria and other groups of phytoplankton have the ability to actively transport bicarbonate (HCO3-) across their cell membrane when CO2 concentrations are limiting, possibly giving them a competitive advantage over algae not using carbon concentrating mechanisms (CCMs). To investigate whether CCMs can maintain phytoplankton bloom biomass under CO2 depletion, we measured the δ13C signatures of dissolved inorganic carbon (δ13CDIC) and phytoplankton particulate organic carbon (δ13Cphyto) in 16 mesotrophic to hypereutrophic lakes during the ice-free season of 2012. We used mass-balance relationships to determine the dominant inorganic carbon species used by phytoplankton under CO2 stress. We found a significant positive relationship between phytoplankton biomass and phytoplankton δ13C signatures as well as a significant nonlinear negative relationship between water column ρCO2 and isotopic composition of phytoplankton, indicating a shift from diffusive uptake to active uptake by phytoplankton of CO2 or HCO3- during blooms. Calculated photosynthetic fractionation factors indicated that this shift occurs specifically when surface water CO2 drops below atmospheric equilibrium. Our results indicate that active HCO3- uptake via CCMs may be an important mechanism in maintaining phytoplankton blooms when CO2 is depleted. Further increases in anthropogenic pressure, eutrophication, and cyanobacteria blooms are therefore expected to contribute to increased bicarbonate uptake to sustain primary production.

Differential retention and release of CO 2 and CH 4 in kerogen nanopores: Implications for gas extraction and carbon sequestration

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ho, Tuan Anh; Wang, Yifeng; Xiong, Yongliang

Methane (CH 4) and carbon dioxide (CO 2), the two major components generated from kerogen maturation, are stored dominantly in nanometer-sized pores in shale matrix as (1) a compressed gas, (2) an adsorbed surface species and/or (3) a species dissolved in pore water (H 2O). In addition, supercritical CO 2 has been proposed as a fracturing fluid for simultaneous enhanced oil/gas recovery (EOR) and carbon sequestration. A mechanistic understanding of CH 4-CO 2-H 2O interactions in shale nanopores is critical for designing effective operational processes. Using molecular simulations, we show that kerogen preferentially retains CO 2 over CH 4 andmore » that the majority of CO 2 either generated during kerogen maturation or injected in EOR will remain trapped in the kerogen matrix. The trapped CO 2 may be released only if the reservoir pressure drops below the supercritical CO 2 pressure. When water is present in the kerogen matrix, it may block CH 4 release. Furthermore, the addition of CO 2 may enhance CH 4 release because CO 2 can diffuse through water and exchange for adsorbed methane in the kerogen nanopores.« less

Differential retention and release of CO 2 and CH 4 in kerogen nanopores: Implications for gas extraction and carbon sequestration

DOE PAGES

Ho, Tuan Anh; Wang, Yifeng; Xiong, Yongliang; ...

2018-02-06

Methane (CH 4) and carbon dioxide (CO 2), the two major components generated from kerogen maturation, are stored dominantly in nanometer-sized pores in shale matrix as (1) a compressed gas, (2) an adsorbed surface species and/or (3) a species dissolved in pore water (H 2O). In addition, supercritical CO 2 has been proposed as a fracturing fluid for simultaneous enhanced oil/gas recovery (EOR) and carbon sequestration. A mechanistic understanding of CH 4-CO 2-H 2O interactions in shale nanopores is critical for designing effective operational processes. Using molecular simulations, we show that kerogen preferentially retains CO 2 over CH 4 andmore » that the majority of CO 2 either generated during kerogen maturation or injected in EOR will remain trapped in the kerogen matrix. The trapped CO 2 may be released only if the reservoir pressure drops below the supercritical CO 2 pressure. When water is present in the kerogen matrix, it may block CH 4 release. Furthermore, the addition of CO 2 may enhance CH 4 release because CO 2 can diffuse through water and exchange for adsorbed methane in the kerogen nanopores.« less

The comparative limnology of Lakes Nyos and Monoun, Cameroon

USGS Publications Warehouse

Kling, George; Evans, William C; Tanyileke, Gregory

2015-01-01

Lakes Nyos and Monoun are known for the dangerous accumulation of CO2 dissolved in stagnant bottom water, but the shallow waters that conceal this hazard are dilute and undergo seasonal changes similar to other deep crater lakes in the tropics. Here we discuss these changes with reference to climatic and water-column data collected at both lakes during the years following the gas release disasters in the mid-1980s. The small annual range in mean daily air temperatures leads to an equally small annual range of surface water temperatures (ΔT ~6–7 °C), reducing deep convective mixing of the water column. Weak mixing aids the establishment of meromixis, a requisite condition for the gradual buildup of CO2 in bottom waters and perhaps the unusual condition that most explains the rarity of such lakes. Within the mixolimnion, a seasonal thermocline forms each spring and shallow diel thermoclines may be sufficiently strong to isolate surface water and allow primary production to reduce PCO2 below 300 μatm, inducing a net influx of CO2 from the atmosphere. Surface water O2 and pH typically reach maxima at this time, with occasional O2 oversaturation. Mixing to the chemocline occurs in both lakes during the winter dry season, primarily due to low humidity and cool night time air temperature. An additional period of variable mixing, occasionally reaching the chemocline in Lake Monoun, occurs during the summer monsoon season in response to increased frequency of major storms. The mixolimnion encompassed the upper ~40–50 m of Lake Nyos and upper ~15–20 m of Lake Monoun prior to the installation of degassing pipes in 2001 and 2003, respectively. Degassing caused chemoclines to deepen rapidly. Piping of anoxic, high-TDS bottom water to the lake surface has had a complex effect on the mixolimnion. Algal growth stimulated by increased nutrients (N and P) initially stimulated photosynthesis and raised surface water O2 in Lake Nyos, but O2 removal through oxidation of iron was also enhanced and appeared to dominate at Lake Monoun. Depth-integrated O2 contents decreased in both lakes as did water transparency. No dangerous instabilities in water-column structure were detected over the course of degassing. While Nyos-type lakes are extremely rare, other crater lakes can pose dangers from gas releases and monitoring is warranted.

Effect of CO2 and Nd:YAG Lasers on Shear Bond Strength of Resin Cement to Zirconia Ceramic

PubMed Central

Kasraei, Shahin; Yarmohamadi, Ebrahim; Shabani, Amanj

2015-01-01

Objectives: Because of poor bond between resin cement and zirconia ceramics, laser surface treatments have been suggested to improve adhesion. The present study evaluated the effect of CO2 and Nd:YAG lasers on the shear bond strength (SBS) of resin cement to zirconia ceramic. Materials and Methods: Ninety zirconia disks (6×2 mm) were randomly divided into six groups of 15. In the control group, no surface treatment was used. In the test groups, laser surface treatment was accomplished using CO2 and Nd:YAG lasers, respectively (groups two and three). Composite resin disks (3×2 mm) were fabricated and cemented to zirconia disks with self-etch resin cement and stored in distilled water for 24 hours. In the test groups four-six, the samples were prepared as in groups one-three and then thermocycled and stored in distilled water for six months. The SBS tests were performed (strain rate of 0.5 mm/min). The fracture modes were observed via stereomicroscopy. Data were analyzed with one and two-way ANOVA, independent t and Tukey’s tests. Results: The SBS values of Nd:YAG group (18.95±3.46MPa) was significantly higher than that of the CO2 group (14.00±1.96MPa), but lower than that of controls (23.35±3.12MPa). After thermocycling and six months of water storage, the SBS of the untreated group (1.80±1.23 MPa) was significantly lower than that of the laser groups. In groups stored for 24 hours, 60% of the failures were adhesive; however, after thermocycling and six months of water storage, 100% of failures were adhesive. Conclusion: Bonding durability of resin cement to zirconia improved with CO2 and Nd:YAG laser surface treatment of zirconia ceramic. PMID:27148380

Carbon-climate feedbacks accelerate ocean acidification

NASA Astrophysics Data System (ADS)

Matear, Richard J.; Lenton, Andrew

2018-03-01

Carbon-climate feedbacks have the potential to significantly impact the future climate by altering atmospheric CO2 concentrations (Zaehle et al. 2010). By modifying the future atmospheric CO2 concentrations, the carbon-climate feedbacks will also influence the future ocean acidification trajectory. Here, we use the CO2 emissions scenarios from four representative concentration pathways (RCPs) with an Earth system model to project the future trajectories of ocean acidification with the inclusion of carbon-climate feedbacks. We show that simulated carbon-climate feedbacks can significantly impact the onset of undersaturated aragonite conditions in the Southern and Arctic oceans, the suitable habitat for tropical coral and the deepwater saturation states. Under the high-emissions scenarios (RCP8.5 and RCP6), the carbon-climate feedbacks advance the onset of surface water under saturation and the decline in suitable coral reef habitat by a decade or more. The impacts of the carbon-climate feedbacks are most significant for the medium- (RCP4.5) and low-emissions (RCP2.6) scenarios. For the RCP4.5 scenario, by 2100 the carbon-climate feedbacks nearly double the area of surface water undersaturated with respect to aragonite and reduce by 50 % the surface water suitable for coral reefs. For the RCP2.6 scenario, by 2100 the carbon-climate feedbacks reduce the area suitable for coral reefs by 40 % and increase the area of undersaturated surface water by 20 %. The sensitivity of ocean acidification to the carbon-climate feedbacks in the low to medium emission scenarios is important because recent CO2 emission reduction commitments are trying to transition emissions to such a scenario. Our study highlights the need to better characterise the carbon-climate feedbacks and ensure we do not underestimate the projected ocean acidification.

The influence of supercritical carbon dioxide (SC-CO2) processing conditions on drug loading and physicochemical properties.

PubMed

Ahern, Robert J; Crean, Abina M; Ryan, Katie B

2012-12-15

Poor water solubility of drugs can complicate their commercialisation because of reduced drug oral bioavailability. Formulation strategies such as increasing the drug surface area are frequently employed in an attempt to increase dissolution rate and hence, improve oral bioavailability. Maximising the drug surface area exposed to the dissolution medium can be achieved by loading drug onto a high surface area carrier like mesoporous silica (SBA-15). The aim of this work was to investigate the impact of altering supercritical carbon dioxide (SC-CO(2)) processing conditions, in an attempt to enhance drug loading onto SBA-15 and increase the drug's dissolution rate. Other formulation variables such as the mass ratio of drug to SBA-15 and the procedure for combining the drug and SBA-15 were also investigated. A model drug with poor water solubility, fenofibrate, was selected for this study. High drug loading efficiencies were obtained using SC-CO(2), which were influenced by the processing conditions employed. Fenofibrate release rate was enhanced greatly after loading onto mesoporous silica. The results highlighted the potential of this SC-CO(2) drug loading approach to improve the oral bioavailability of poorly water soluble drugs. Copyright © 2012 Elsevier B.V. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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.

Xeromorphic traits help to maintain photosynthesis in the perhumid climate of a Taiwanese cloud forest.

PubMed

Pariyar, Shyam; Chang, Shih-Chieh; Zinsmeister, Daniel; Zhou, Haiyang; Grantz, David A; Hunsche, Mauricio; Burkhardt, Juergen

2017-07-01

Previous flux measurements in the perhumid cloud forest of northeastern Taiwan have shown efficient photosynthesis of the endemic tree species Chamaecyparis obtusa var. formosana even under foggy conditions in which leaf surface moisture would be expected. We hypothesized this to be the result of 'xeromorphic' traits of the Chamaecyparis leaves (hydrophobicity, stomatal crypts, stomatal clustering), which could prevent coverage of stomata by precipitation, fog, and condensation, thereby maintaining CO 2 uptake. Here we studied the amount, distribution, and composition of moisture accumulated on Chamaecyparis leaf surfaces in situ in the cloud forest. We studied the effect of surface tension on gas penetration to stomata using optical O 2 microelectrodes in the laboratory. We captured the dynamics of condensation to the leaf surfaces with an environmental scanning electron microscope (ESEM). In spite of substantial surface hydrophobicity, the mean water film thickness on branchlets under foggy conditions was 80 µm (upper surface) and 40 µm (lower surface). This amount of water could cover stomata and prevent CO 2 uptake. This is avoided by the clustered arrangement of stomata within narrow clefts and the presence of Florin rings. These features keep stomatal pores free from water due to surface tension and provide efficient separation of plant and atmosphere in this perhumid environment. Air pollutants, particularly hygroscopic aerosol, may disturb this functionality by enhancing condensation and reducing the surface tension of leaf surface water.

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

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

Distribution of Surface pH and Total Alkalinity at the Sea of Okhotsk and the East Sea in October 2007

NASA Astrophysics Data System (ADS)

Shim, J.; Kang, D.; Jin, Y.; Obzhirov, A.

2008-12-01

Surface pH, total alkalinity, temperature and salinity were measured at the Sea of Okhotsk and the East Sea (along a track from Vladivostok to the northeastern slope of Sakhalin Island through Soya Strait: 42°N, 132°E - 55°N, 145°E) in October 2007. Continuous pH measurements were conducted using an underway potentiometric pH system modified from Tishchenko et al. (2002) and discrete total alkalinity measurements were made by direct titration with hydrochloric acid. Warm saline surface waters were observed in the East Sea (from Vladivostok to Soya Strait), and relatively cold less-saline waters were observed in the Sea of Okhotsk (at the eastern slopes of Sakhalin Island). In the East Sea and the Sea of Okhotsk, surface pH ranged from 8.063 to 8.158 and 8.047 to 8.226, and total alkalinity normalized to salinity 35 ranged from 2323 to 2344 μmol kg-1 and 2367 to 2422 μmol kg-1, respectively. Due to the freshwater input from rivers and geochemical activity in the water column and sediment, the Sea of Okhotsk generally showed much wider ranges of water properties and richer in carbonate parameters than those of the East Sea. Particularly, water properties changed dramatically at the eastern slopes of Sakhalin Island; surface salinity decreased southward by about 0.5-1 psu and pH and normalized total alkalinity increased southward by about 0.05-0.1 and 20-50 μmol kg-1, respectively. Thus, pCO2 concentration calculated from pH and total alkalinity, ranged from 350-375 μatm in the north to 280-300 μatm in the south of the Okhotsk Sea. The high pH and normalized total alkalinity, and low pCO2 and salinity in the south might be the result of surface water mixing with fresh water discharge from rivers and/or the results of massive primary production along the eastern coast of Sakhalin Island. In the most study area, surface pCO2 ranged from 280 to 370 μatm and was undersaturated relative to atmosphere. Therefore, the Sea of Okhotsk and the East Sea acted as effective CO2 sinks during the study period

Saturn's satellites: Predictions for Cassini

NASA Astrophysics Data System (ADS)

Delitsky, M. L.; Hibbitts, C. A.

2004-11-01

Saturn's satellites are subjected to a variety of energy inputs (from photons, magnetospheric and solar ions and electrons) which will affect their surface composition. The Saturn magnetosphere contains an assortment of ions, including O+ and H+ from sputtering of water ice on the inner satellites and N+ from sputtering of Titan's atmosphere. Implantation of these ions onto the surfaces of the satellites may produce compounds possibly detectable by Cassini instruments. The satellites contain water ice and carbon dioxide ice (and possibly organics, on Phoebe). In Delitsky and Lane (2002), chemistry resulting from nitrogen ion implantation into water ice and carbon dioxide ice was outlined. From deposition of N+ ions into H2O/CO2, a complicated C-H-N-O chemistry may result, including formation of isocyanates, nitriles, nitrogen oxides and amino acids. Upon irradiation, H2O/CO2 mixtures will yield esters, ketones, alcohols, carboxylic acids and other interesting compounds. Cassini's infrared instruments CIRS and VIMS have spectral ranges that can detect many bands of these compounds. VIMS spectral range is 0.35 - 5.1 microns; CIRS covers the spectral range 7 - 100 microns, although its Mid-IR interferometer portion (7 -16 microns) is where organic materials are particularly spectrally active. Weak features are present in the short IR for NO (1.91 microns), NO2 (1.95), NH3 (2.00, 2.24), CH3OH (2.27, 2.34), and CO2 (1.965, 2.01) [Quirico et al.,1999]. Some molecules have stronger absorption features at these wavelengths: [CO2: 4.25 - 4.27 microns; NH3: 3 microns and 9.2 microns (important because the 3 micron band can be masked by water); H2CO3: 3.88 microns (weak); HCOOH: 8.2 microns; O2: 9.7 microns]. These molecules may exist as ices, or as molecules trapped in the surface. CH- and CN-containing molecules absorb at 3.2 - 3.4 microns, and 4.6 microns, respectively. H2O2, detected on Europa by its 3.5 micron band, may exist in the icy surfaces of the Saturn satellites as well.

Corrosion due to use of carbon dioxide for enhanced oil recovery. Final report. SumX No. 78-003

DOE Office of Scientific and Technical Information (OSTI.GOV)

DeBerry, D.W.; Clark, W.S.

1979-09-01

This study documents the specific effects of CO/sub 2/ on corrosion and identifies promising methods for controlling corrosion in fields using CO/sub 2/ injection. Information has been assembled on: CO/sub 2/ corrosion problems in general, surface and downhole corrosion problems specifically associated with CO/sub 2/ enhanced oil recovery, and methods to reduce corrosion problems in CO/sub 2/ environments. Corrosion mechanisms, kinetic behavior, and the effects of various parameters on corrosion by CO/sub 2/ are presented in this study. Engineering metals are not attacked by CO/sub 2/ under oil field environments unless liquid water is also present. Plain and low alloymore » steels are attacked by mixtures of CO/sub 2/ and liquid water. Attack on these bare metals may become serious at a CO/sub 2/ partial pressure as low as 4 psi and it increases with CO/sub 2/ partial pressure although not in direct proportion. Fluid flow rate is an important factor in CO/sub 2//water corrosion. Practically all stainless steels and similar resistant alloys are not particularly subject to corrosion by CO/sub 2//water mixtures alone, even at high CO/sub 2/ pressures. Elevated levels of CO/sub 2/ can aggravate the corrosive effects of other species such as hydrogen sulfide, oxygen, and chloride. Mixtures of CO/sub 2/, carbon monoxide (CO), and water can cause stress corrosion cracking of plain steels. Corrosion problems in CO/sub 2/ systems should be circumvented when possible by avoiding combination of the corrosive components. Although water cannot be excluded throughout the CO/sub 2/ injection-oil production-CO/sub 2/ and water reinjection chain, air in-leakage can be minimized and oxygen scavengers used to remove any residual. Exclusion of oxygen is important to the successful use of other corrosion control measures. A discussion is given of the main control methods including metal selection, protective coatings and nonmetallic materials, and chemical inhibition. (DLC)« less

Climatic modification by CO2, H2O, and aerosol

NASA Technical Reports Server (NTRS)

Rasool, I.

1972-01-01

Research is reported on the effects of increasing the CO2, aerosols, and water content of the atmosphere on the surface temperature and climatology. An atmospheric model is described with the incoming solar radiation for a planetary albedo of 33 percent, surface temperature of 288 K, relative humidity of 75 percent, cloud cover of 48 percent, CO2 of 0.3 parts per thousand, and aerosol density of two million per square centimeter. The results show that if the CO2 increases by a factor of 1000 or more, the total pressure of the atmosphere increases, and the earth may become as hot as Venus. It is also shown that as the amount of dust particles in the atmosphere increases, the solar radiation decreases, and the surface temperature lowers.

Decorating CoP and Pt Nanoparticles on Graphitic Carbon Nitride Nanosheets to Promote Overall Water Splitting by Conjugated Polymers.

PubMed

Pan, Zhiming; Zheng, Yun; Guo, Fangsong; Niu, Pingping; Wang, Xinchen

2017-01-10

The splitting of water into H 2 and O 2 using solar energy is one of the key steps in artificial photosynthesis for the future production of renewable energy. Here, we show the first use of CoP and Pt nanoparticles as dual co-catalysts to modify graphitic carbon nitride (g-C 3 N 4 ) polymer to achieve overall water splitting under visible light irradiation. Our findings demonstrate that loading dual co-catalysts on delaminated g-C 3 N 4 imparts surface redox sites on the g-C 3 N 4 nanosheets that can not only promote catalytic kinetics but also promote charge separation and migration in the soft interface, thus improving the photocatalytic efficiency for overall water splitting. This robust, abundant, and stable photocatalyst based on covalent organic frameworks is demonstrated to hold great promise by forming heterojunctions with CoP and Pt for catalyzing the direct splitting of water into stoichiometric H 2 and O 2 using energy from photons. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

White Mars: A New Model for Mars' Surface and Atmosphere Based on CO 2

NASA Astrophysics Data System (ADS)

Hoffman, Nick

2000-08-01

A new model is presented for the Amazonian outburst floods on Mars. Rather than the working fluid being water, with the associated difficulties in achieving warm and wet conditions on Mars and on collecting and removing the water before and after the floods, instead this model suggests that CO 2 is the active agent in the "floods." The flow is not a conventional liquid flood but is instead a gas-supported density flow akin to terrestrial volcanic pyroclastic flows and surges and at cryogenic temperatures with support from degassing of CO 2-bearing ices. The flows are not sourced from volcanic vents, but from the collapse of thick layered regolith containing liquid CO 2 to form zones of chaotic terrain, as shown by R. St. J. Lambert and V. E. Chamberlain (1978, Icarus34, 568-580; 1992, Workshop on the Evolution of the Martian Atmosphere). Submarine turbidites are also analagous in the flow mechanism, but the martian cryogenic flows were both dry and subaerial, so there is no need for a warm and wet epoch nor an ocean on Mars. Armed with this new model for the floods we review the activity of volatiles on the surface of Mars in the context of a cold ice world—"White Mars." We find that many of the recognized paradoxes about Mars' surface and atmosphere are resolved. In particular, the lack of carbonates on Mars is due to the lack of liquid water. The CO 2 of the primordial atmosphere and the H 2O inventory remain largely sequestered in subsurface ices. The distribution of water ice on modern Mars is also reevaluated, with important potential consequences for future Mars exploration. The model for collapse of terrain due to ices that show decompression melting, and the generation of nonaqueous flows in these circumstances may also be applicable to outer Solar System bodies, where CO 2, SO 2, N 2, and other ices are stable.

Effects of selective handling of pyritic, acid-forming materials on the chemistry of pore gas and ground water at a reclaimed surface coal mine in Clarion County, PA, USA

USGS Publications Warehouse

Cravotta,, Charles A.; Dugas, Diana L.; Brady, Keith; Kovalchuck, Thomas E.

1994-01-01

A change from dragline to “selective handling” mining methods at a reclaimed surface coal mine in western Pennsylvania did not significantly affect concentrations of metals in ground water because oxidation of pyrite and dissolution of siderite were not abated. Throughout the mine, placement of pyritic material near the land surface facilitated the oxidation of pyrite, causing the consumption of oxygen (O2) and release of acid, iron, and sulfate ions. Locally in the unsaturated zone, water sampled within or near pyritic zones was acidic, with concentrations of sulfate exceeding 3,000 milligrams per liter (mg/L). However, acidic conditions generally did not persist below the water table because of neutralization by carbonate minerals. Dissolution of calcite, dolomite, and siderite in unsaturated and saturated zones produced elevated concentrations of carbon dioxide (CO2), alkalinity, calcium, magnesium, iron, and manganese. Alkalinity concentrations of 600 to 800 mg/L as CaCO3 were common in water samples from the unsaturated zone in spoil, and alkalinities of 100 to 400 mg/L as CaCO3 were common in ground-water samples from the underlying saturated zone in spoil and bedrock. Saturation indices indicated that siderite could dissolve in water throughout the spoil, but that calcite dissolution or precipitation could occur locally. Calcite dissolution could be promoted as a result of pyrite oxidation, gypsum precipitation, and calcium ion exchange for sodium. Calcite precipitation could be promoted by evapotranspiration and siderite dissolution, and corresponding increases in concentrations of alkalinity and other solutes. Partial pressures of O2 (Po2) and CO2 (Pco2) in spoil pore gas indicated that oxidation of pyrite and precipitation of ferric hydroxide, coupled with dissolution of calcite, dolomite, and siderite were the primary reactions affecting water quality. Highest vertical gradients in Po2, particularly in the near-surface zone (0-1 m), did not correlate with concentrations of total sulfur in spoil. This lack of correlation could indicate that total sulfur concentrations in spoil do not reflect the amount of reactive pyrite or that oxidation rates can be controlled more by rates of O2 diffusion than the amount of pyrite. Hence, if placed in O2-rich zones near the land surface, even small amounts of disseminated pyritic material can be relatively significant sources of acid and mineralized water.

Atmospheric mass and the record of liquid water on Mars

NASA Astrophysics Data System (ADS)

Halevy, I.; Head, J. W., III

2017-12-01

Widespread evidence for the action of liquid water on early Mars is generally accepted to require the presence of atmospheric greenhouse agents other than CO2. Much of this activity clusters in the late Noachian and early Hesperian (3.9-3.6 Ga), and appears to coincide with a long maximum in extrusive and explosive volcanic activity. Among other suggestions, a role for S-bearing volcanic gases has been proposed, but these and any other non-CO2 greenhouse gases or atmospheric components require a background CO2 atmosphere of several hundred mbar. Global climate models suggest that even if the surface reservoir of CO2 were much larger than today, this reservoir would be mostly trapped as CO2 ice, and only a few to tens of mbar would be in the atmosphere. Thus, at the long-term steady state, sustained warmth is difficult to achieve in the face of a fainter Sun. We suggest that episodic volcanism released the CO2 trapped as ice at the planet's surface in two ways. First, the emission of S-bearing greenhouse gases (mostly SO2) would lead to warming of a few Kelvins. Second, the deposition of volcanic ash on water and CO2 ice surfaces would push the local energy budget to favor sublimation, and would also decrease the planetary albedo and lead to additional warming. Inflation of the CO2 atmosphere has been shown in global climate models to shift the distribution of snowfall to high elevations, as opposed to a latitude-dependent distribution at low atmospheric pressure. We suggest that seasonal melting of this snow carved the valley networks and filled basin lakes. The duration of warm periods was limited by the timescale for atmospheric collapse by condensation, which is 102-103 years. Repeated inflation episodes over the duration of active volcanism led to an integrated duration of aqueous activity of 106-107 years, enough to carve the valley networks. The S-bearing gases emitted by eruptions formed sulfate minerals, initially uniformly dispersed, then remobilized and locally redeposited at low latitudes during periods of aqueous activity. As volcanic activity waned in the mid-Hesperian, fewer instances of atmospheric inflation occurred, and CO2 was trapped as high-latitude surface ice. Decreasing volcanic input and gradual atmospheric escape ultimately resulted in the remaining reservoir of CO2 observed today.

Geochemical Impacts of CO2 Intrusion into Ground Water due to Carbon Dioxide Release from Geologic Sequestration Projects: Overview of ORD Research

EPA Science Inventory

Abstract: Even with the large physical separation between storage reservoirs and surficial environments, there is concern that CO2 stored in reservoirs may eventually leak back to the surface through abandoned wells or along geological features such as faults. Leakage of CO2 into...

Understorey productivity in temperate grassy woodland responds to soil water availability but not to elevated [CO2 ].

PubMed

Collins, Luke; Bradstock, Ross A; Resco de Dios, Victor; Duursma, Remko A; Velasco, Sabrina; Boer, Matthias M

2018-06-01

Rising atmospheric [CO 2 ] and associated climate change are expected to modify primary productivity across a range of ecosystems globally. Increasing aridity is predicted to reduce grassland productivity, although rising [CO 2 ] and associated increases in plant water use efficiency may partially offset the effect of drying on growth. Difficulties arise in predicting the direction and magnitude of future changes in ecosystem productivity, due to limited field experimentation investigating climate and CO 2 interactions. We use repeat near-surface digital photography to quantify the effects of water availability and experimentally manipulated elevated [CO 2 ] (eCO 2 ) on understorey live foliage cover and biomass over three growing seasons in a temperate grassy woodland in south-eastern Australia. We hypothesised that (i) understorey herbaceous productivity is dependent upon soil water availability, and (ii) that eCO 2 will increase productivity, with greatest stimulation occurring under conditions of low water availability. Soil volumetric water content (VWC) determined foliage cover and growth rates over the length of the growing season (August to March), with low VWC (<0.1 m 3  m -3 ) reducing productivity. However, eCO 2 did not increase herbaceous cover and biomass over the duration of the experiment, or mitigate the effects of low water availability on understorey growth rates and cover. Our findings suggest that projected increases in aridity in temperate woodlands are likely to lead to reduced understorey productivity, with little scope for eCO 2 to offset these changes. © 2018 John Wiley & Sons Ltd.

A Polymethyl Methacrylate-Based Acrylic Dental Resin Surface Bound with a Photoreactive Polymer Inhibits Accumulation of Bacterial Plaque.

PubMed

Fukunishi, Miya; Inoue, Yuuki; Morisaki, Hirobumi; Kuwata, Hirotaka; Ishihara, Kazuhiko; Baba, Kazuyoshi

The aim of this study was to examine the ability of a poly(2-methacryloyloxyethyl phosphorylcholine-co-n-butylmethacrylate-co-2-methacryloyloxyethyloxy-p-azidobenzoate) (PMBPAz) coating on polymethyl methacrylate (PMMA)-based dental resin to inhibit bacterial plaque formation, as well as the polymer's durability against water soaking and chemical exposure. Successful application of PMBPAz on PMMA surfaces was confirmed by x-ray photoelectron spectroscopy (XPS) and measuring the static air contact angle in water. The anti-adhesive effects to bacterial plaque were evaluated using Streptococcus mutans biofilm formation assay. The mechanical and chemical durabilities of the PMBPAz coating on the PMMA surfaces were examined using soaking and immersion tests, respectively. XPS signals for phosphorus and nitrogen atoms and hydrophilic status on PMMA surfaces treated with PMBPAz were observed, indicating the presence of the polymer on the substrates. The treated PMMA surfaces showed significant inhibition of S mutans biofilm formation compared to untreated surfaces. The PMBPAz coating was preserved after water soaking and chemical exposure. In addition, water soaking did not decrease the ability of treated PMMA to inhibit biofilm formation compared to treated PMMA specimens not subjected to water soaking. This study suggests that PMBPAz coating may represent a useful modification to PMMA surfaces for inhibiting denture plaque accumulation.

Distance-dependent radiation chemistry: Oxidation versus hydrogenation of CO in electron-irradiated H2O/CO/H2O ices

DOE Office of Scientific and Technical Information (OSTI.GOV)

Petrik, Nikolay G.; Monckton, Rhiannon J.; Koehler, Sven

Electron-stimulated oxidation of CO in layered H2O/CO/H2O ices was investigated with infrared reflection-absorption spectroscopy (IRAS) as function of the distance of the CO layer from the water/vacuum interface. The results show that while both oxidation and reduction reactions occur within the irradiated water films, there are distinct regions where either oxidation or reduction reactions are dominant. At depths less than ~ 15 ML, CO oxidation dominates over the sequential hydrogenation of CO to methanol (CH3OH), and CO2 is the major product of CO oxidation, consistent with previous observations. At its highest yield, CO2 accounts for ~45% of all the reactedmore » CO. Another oxidation product is identified as the formate anion (HCO2-). In contrast, for CO buried more than ~ 35 ML below the water/vacuum interface, the CO-to-methanol conversion efficiency is close to 100%. Production of CO2 and formate are not observed for the more deeply buried CO layers, where hydrogenation dominates. Experiments with CO dosed on pre-irradiated ASW samples suggest that OH radicals are primarily responsible for the oxidation reactions. Possible mechanisms of CO oxidation, involving primary and secondary processes of water radiolysis at low temperature, are discussed. The observed distance-dependent radiation chemistry results from the higher mobility of hydrogen atoms that are created by the interaction of the 100 eV electrons with the water films. These hydrogen atoms, which are primarily created at or near the water/vacuum interface, can desorb from or diffuse into the water films, while the less-mobile OH radicals remain in the near-surface zone resulting in preferential oxidation reactions there. The diffusing hydrogen atoms are responsible for the hydrogenation reactions that are dominant for the more deeply buried CO layers.« less

Seasonal patterns and controls on net ecosystem CO2 exchange in a boreal peatland complex

NASA Astrophysics Data System (ADS)

Bubier, Jill L.; Crill, Patrick M.; Moore, Tim R.; Savage, Kathleen; Varner, Ruth K.

1998-12-01

We measured seasonal patterns of net ecosystem exchange (NEE) of CO2 in a diverse peatland complex underlain by discontinuous permafrost in northern Manitoba, Canada, as part of the Boreal Ecosystems Atmosphere Study (BOREAS). Study sites spanned the full range of peatland trophic and moisture gradients found in boreal environments from bog (pH 3.9) to rich fen (pH 7.2). During midseason (July-August, 1996), highest rates of NEE and respiration followed the trophic sequence of bog (5.4 to -3.9 μmol CO2 m-2 s-1) < poor fen (6.3 to -6.5 μmol CO2 m-2 s-1) < intermediate fen (10.5 to -7.8 μmol CO2 m-2 s-1) < rich fen (14.9 to -8.7 μmol CO2m-2 s-1). The sequence changed during spring (May-June) and fall (September-October) when ericaceous shrub (e.g., Chamaedaphne calyculata) bogs and sedge (Carex spp.) communities in poor to intermediate fens had higher maximum CO2 fixation rates than deciduous shrub-dominated (Salix spp. and Betula spp.) rich fens. Timing of snowmelt and differential rates of peat surface thaw in microtopographic hummocks and hollows controlled the onset of carbon uptake in spring. Maximum photosynthesis and respiration were closely correlated throughout the growing season with a ratio of approximately 1/3 ecosystem respiration to maximum carbon uptake at all sites across the trophic gradient. Soil temperatures above the water table and timing of surface thaw and freeze-up in the spring and fall were more important to net CO2 exchange than deep soil warming. This close coupling of maximum CO2 uptake and respiration to easily measurable variables, such as trophic status, peat temperature, and water table, will improve models of wetland carbon exchange. Although trophic status, aboveground net primary productivity, and surface temperatures were more important than water level in predicting respiration on a daily basis, the mean position of the water table was a good predictor (r2 = 0.63) of mean respiration rates across the range of plant community and moisture gradients. Q10 values ranged from 3.0 to 4.1 from bog to rich fen, but when normalized by above ground vascular plant biomass, the Q10 for all sites was 3.3.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tang Shaochun; Vongehr, Sascha; Wang Yang

Highly uniform, porous {beta}-Co(OH){sub 2} nanostructures with an appearance reminding of certain spherical corals were synthesized via a facile, one-step hydrothermal route using ethanol-water mixtures as solvents. The rough surfaces of the nanostructures consist of numerous randomly distributed, interconnecting nanoflakes, resulting in a network-like structure with many cavities. The coral-like product has a high Brunauer-Emmet-Teller specific surface area of 163 m{sup 2}/g. The diameter of the coral-like {beta}-Co(OH){sub 2} nanostructures is adjustable from 800 nm to 2 {mu}m. The effects of the ethanol/water ratio, the Co{sup 2+} concentration, the hydrothermal temperature, and the reaction time on the formation of themore » coral-like structures were investigated. Cyclic voltammetry and galvanostatic charge-discharge tests show that the {beta}-Co(OH){sub 2} possesses excellent capacitive properties. This is mainly attributed to the high porosity, which allows a deep penetration by electrolytes. - Abstract: Coral-like {beta}-Co(OH){sub 2} nanostructures were synthesized via a facile ethanol-assisted hydrothermal route. Their high porosity facilitates a deep penetration by electrolytes and thus contributes to the excellent capacitive properties.« less

Cobalt phosphide based nanostructures as bifunctional electrocatalysts for low temperature alkaline water splitting

DOE PAGES

Lambert, Timothy N.; Vigil, Julian A.; Christensen, Ben

2016-08-22

Cobalt phosphide based thin films and nanoparticles were prepared by the thermal phosphidation of spinel Co 3O 4 precursor films and nanoparticles, respectively. CoP films were prepared with overall retention of the Co 3O 4 nanoplatelet morphology while the spherical/cubic Co 3O 4 and Ni 0.15Co 2.85O 4 nanoparticles were converted to nanorods or nanoparticles, respectively. The inclusion of nickel in the nanoparticles resulted in a 2.5 fold higher surface area leading to higher gravimetric performance. In each case high surface area structures were obtained with CoP as the primary phase. All materials were found to act as effective bifunctionalmore » electrocatalysts for both the HER and the OER and compared well to commercial precious metal benchmark materials in alkaline electrolyte. As a result, a symmetrical water electrolysis cell prepared from the CoP-based film operated at a low overpotential of 0.41-0.51 V.« less

pCO2 Observations from a Vertical Profiler on the upper continental slope off Vancouver Island: Physical controls on biogeochemical processes.

NASA Astrophysics Data System (ADS)

Mihaly, S. F.

2016-02-01

We analyse two six month sets of data collected from a vertical profiler on Ocean Networks Canada's NEPTUNE observatory over the summer and early fall of 2012 and 2014. The profiler is in 400 m of water on the upper slope of the continental shelf. The site is away from direct influence of canyons, but is in a region of strong internal tide generation. Both seasonally varying semidiurnal internal tidal currents and diurnal shelf waves are observed. The near surface mean flow is weak and seasonally alternates between the California and Alaskan Currents. Mid-depth waters are influenced by the poleward flowing Californian undercurrent and the deep waters by seasonally varying wind-driven Ekman transport. The profiling package consists of a CTD, an oxygen optode, a pCO2 sensor, Chlorophyll fluorometer/turbidity, CDOM and is co-located with an upward-looking bottom-mounted 75kHz ADCP that measures currents to 30 m below sea surface. With these first deep-sea profiled time series measurements of pCO2, we endeavor to model how the local physical dynamics exert control over the variability of water properties over the slope and shelf and what the variability of the non-conservative tracers of pCO2 and O2 can tell us about the biogeochemistry of the region.

Influence of Polyoxometalate Protecting Ligands on Catalytic Aerobic Oxidation at the Surfaces of Gold Nanoparticles in Water.

PubMed

Zhang, Mingfu; Hao, Jingcheng; Neyman, Alevtina; Wang, Yifeng; Weinstock, Ira A

2017-03-06

Metal oxide cluster-anion (polyoxometalate, or POM) protecting ligands, [α-PW 11 O 39 ] 7- (1), modify the rates at which 14 nm gold nanoparticles (Au NPs) catalyze an important model reaction, the aerobic (O 2 ) oxidation of CO to CO 2 in water. At 20 °C and pH 6.2, the following stoichiometry was observed: CO + O 2 + H 2 O = CO 2 + H 2 O 2 . After control experiments verified that the H 2 O 2 product was sufficiently stable and did not react with 1 under turnover conditions, quantitative analysis of H 2 O 2 was used to monitor the rates of CO oxidation, which increased linearly with the percent coverage of the Au NPs by 1 (0-64% coverage, with the latter value corresponding to 211 ± 19 surface-bound molecules of 1). X-ray photoelectron spectroscopy of Au NPs protected by a series of POM ligands (K + salts): 1, the Wells-Dawson ion [α-P 2 W 18 O 62 ] 6- (2) and the monodefect Keggin anion [α-SiW 11 O 39 ] 8- (3) revealed that binding energies of electrons in the Au 4f 7/2 and 4f 5/2 atomic orbitals decreased as a linear function of the POM charge and percent coverage of Au NPs, providing a direct correlation between the electronic effects of the POMs bound to the surfaces of the Au NPs and the rates of CO oxidation by O 2 . Additional data show that this effect is not limited to POMs but occurs, albeit to a lesser extent, when common anions capable of binding to Au-NP surfaces, such as citrate or phosphate, are present.

Horizon Partitioning of Soil CO2 Sources and their Isotopic Composition (13C) in a Pinus Sylvestris Stand

NASA Astrophysics Data System (ADS)

Goffin, S.; Parent, F.; Plain, C.; Maier, M.; Schack-Kirchner, H.; Aubinet, M.; Longdoz, B.

2012-12-01

The overall aim of this study is to contribute to a better understanding of mechanisms behind soil CO2 efflux using carbon stable isotopes. The approach combines a soil multilayer analysis and the isotopic tool in an in situ study. The specific goal of this work is to quantify the origin and the determinism of 13CO2 and 12CO2 production processes in the different soil layers using the gradient-efflux approach. To meet this, the work includes an experimental setup and a modeling approach. The experimental set up (see also communication of Parent et al., session B008) comprised a combination of different systems, which were installed in a Scot Pine temperate forest at the Hartheim site (Southwestern Germany). Measurements include (i) half hourly vertical profiles of soil CO2 concentration (using soil CO2 probes), soil water content and temperature; (ii) half hourly soil surface CO2 effluxes (automatic chambers); (iii) half hourly isotopic composition of surface CO2 efflux and soil CO2 concentration profile and (iv) estimation of soil diffusivity through laboratory measurements conducted on soil samples taken at several depths. Using the data collected in the experimental part, we developed and used a diffusive transport model to simulate CO2 (13CO2 and 12CO2) flows inside and out of the soil based on Fick's first law. Given the horizontal homogeneity of soil physical parameters in Hartheim, we treated the soil as a structure consisting of distinctive layers of 5 cm thick and expressed the Fick's first law in a discrete formalism. The diffusion coefficient used in each layer was derived from (i) horizon specific relationships, obtained from laboratory measurements, between soil relative diffusivity and its water content and (ii) the soil water content values measured in situ. The concentration profile was obtained from in situ measurements. So, the main model inputs are the profiles of (i) CO2 (13CO2 and 12CO2) concentration, (ii) soil diffusion coefficient and (iii) soil water content. Once the diffusive fluxes deduced at each layer interface, the CO2 (13CO2 and 12CO2) production profile was calculated using the (discretized) mass balance equation in each layer. The results of the Hartheim measurement campaign will be presented. The CO2 source vertical profile and its link with the root and the Carbon organic content distribution will be showed. The dynamic of CO2 sources and their isotopic signature will be linked to climatic variables such soil temperature and soil water content. For example, we will show that the dynamics of CO2 sources was mainly related to temperature while changing of isotopic signature was more correlated to soil moisture.

Surface Complexation Modeling of Calcite Zeta Potential Measurement in Mixed Brines for Carbonate Wettability Characterization

NASA Astrophysics Data System (ADS)

Song, J.; Zeng, Y.; Biswal, S. L.; Hirasaki, G. J.

2017-12-01

We presents zeta potential measurements and surface complexation modeling (SCM) of synthetic calcite in various conditions. The systematic zeta potential measurement and the proposed SCM provide insight into the role of four potential determining cations (Mg2+, SO42- , Ca2+ and CO32-) and CO2 partial pressure in calcite surface charge formation and facilitate the revealing of calcite wettability alteration induced by brines with designed ionic composition ("smart water"). Brines with varying potential determining ions (PDI) concentration in two different CO2 partial pressure (PCO2) are investigated in experiments. Then, a double layer SCM is developed to model the zeta potential measurements. Moreover, we propose a definition for contribution of charged surface species and quantitatively analyze the variation of charged species contribution when changing brine composition. After showing our model can accurately predict calcite zeta potential in brines containing mixed PDIs, we apply it to predict zeta potential in ultra-low and pressurized CO2 environments for potential applications in carbonate enhanced oil recovery including miscible CO2 flooding and CO2 sequestration in carbonate reservoirs. Model prediction reveals that pure calcite surface will be positively charged in all investigated brines in pressurized CO2 environment (>1atm). Moreover, the sensitivity of calcite zeta potential to CO2 partial pressure in the various brine is found to be in the sequence of Na2CO3 > Na2SO4 > NaCl > MgCl2 > CaCl2 (Ionic strength=0.1M).

Impact of water vapour and carbon dioxide on surface composition of C{sub 3}A polymorphs studied by X-ray photoelectron spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dubina, E.; Plank, J.; Black, L., E-mail: l.black@leeds.ac.uk

2015-07-15

The surface specific analytical method, X-ray photoelectron spectroscopy (XPS), has been used to study the effects of water vapour and CO{sub 2} on the cubic and orthorhombic polymorphs of C{sub 3}A. Significant differences between the two polymorphs were observed in the XPS spectra. Upon exposure to water vapour, both polymorphs produced C{sub 4}AH{sub 13} on their surfaces. Additionally, the sodium-doped o-C{sub 3}A developed NaOH and traces of C{sub 3}AH{sub 6} on its surface. Subsequent carbonation yielded mono carboaluminate on both polymorphs. Large amounts of Na{sub 2}CO{sub 3} also formed on the surface of o-C{sub 3}A as a result of carbonationmore » of NaOH. Furthermore, the extent of carbonation was much more pronounced for o-C{sub 3}A{sub o} than for c-C{sub 3}A.« less

Sulfate-enhanced catalytic destruction of 1,1,1-trichlorethane over Pt(111).

PubMed

Lee, Adam F; Wilson, Karen

2006-01-19

The catalytic destruction of 1,1,1-trichloroethane (TCA) over model sulfated Pt(111) surfaces has been investigated by fast X-ray photoelectron spectroscopy and mass spectrometry. TCA adsorbs molecularly over SO4 precovered Pt(111) at 100 K, with a saturation coverage of 0.4 monolayer (ML) comparable to that on the bare surface. Surface crowding perturbs both TCA and SO4 species within the mixed adlayer, evidenced by strong, coverage-dependent C 1s and Cl and S 2p core-level shifts. TCA undergoes complete dechlorination above 170 K, accompanied by C-C bond cleavage to form surface CH3, CO, and Cl moieties. These in turn react between 170 and 350 K to evolve gaseous CO2, C2H6, and H2O. Subsequent CH3 dehydrogenation and combustion occurs between 350 and 450 K, again liberating CO2 and water. Combustion is accompanied by SO4 reduction, with the coincident evolution of gas phase SO2 and CO2 suggesting the formation of a CO-SOx surface complex. Reactively formed HCl desorbs in a single state at 400 K. Only trace (<0.06 ML) residual atomic carbon and chlorine remain on the surface by 500 K.

The OceanFlux Greenhouse Gases methodology for deriving a sea surface climatology of CO2 fugacity in support of air-sea gas flux studies

NASA Astrophysics Data System (ADS)

Goddijn-Murphy, L. M.; Woolf, D. K.; Land, P. E.; Shutler, J. D.; Donlon, C.

2015-07-01

Climatologies, or long-term averages, of essential climate variables are useful for evaluating models and providing a baseline for studying anomalies. The Surface Ocean CO2 Atlas (SOCAT) has made millions of global underway sea surface measurements of CO2 publicly available, all in a uniform format and presented as fugacity, fCO2. As fCO2 is highly sensitive to temperature, the measurements are only valid for the instantaneous sea surface temperature (SST) that is measured concurrently with the in-water CO2 measurement. To create a climatology of fCO2 data suitable for calculating air-sea CO2 fluxes, it is therefore desirable to calculate fCO2 valid for a more consistent and averaged SST. This paper presents the OceanFlux Greenhouse Gases methodology for creating such a climatology. We recomputed SOCAT's fCO2 values for their respective measurement month and year using monthly composite SST data on a 1° × 1° grid from satellite Earth observation and then extrapolated the resulting fCO2 values to reference year 2010. The data were then spatially interpolated onto a 1° × 1° grid of the global oceans to produce 12 monthly fCO2 distributions for 2010, including the prediction errors of fCO2 produced by the spatial interpolation technique. The partial pressure of CO2 (pCO2) is also provided for those who prefer to use pCO2. The CO2 concentration difference between ocean and atmosphere is the thermodynamic driving force of the air-sea CO2 flux, and hence the presented fCO2 distributions can be used in air-sea gas flux calculations together with climatologies of other climate variables.

Comparative Reactivity Study of Forsterite and Antigorite in Wet Supercritical CO2 by In Situ Infrared Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thompson, Christopher J.; Loring, John S.; Rosso, Kevin M.

2013-10-01

The carbonation reactions of forsterite (Mg2SiO4) and antigorite [Mg3Si2O5(OH)4], representatives of olivine and serpentine minerals, in dry and wet supercritical carbon dioxide (scCO2) at conditions relevant to geologic carbon sequestration (35 °C and 100 bar) were studied by in-situ Fourier transform infrared (FT-IR) spectroscopy. Our results confirm that water plays a critical role in the reactions between metal silicate minerals and scCO2. For neat scCO2, no reaction was observed in 24 hr for either mineral. When water was added to the scCO2, a thin water film formed on the minerals’ surfaces, and the reaction rates and extents increased as themore » water saturation level was raised from 54% to 116% (excess water). For the first time, the presence of bicarbonate, a key reaction intermediate for metal silicate reactions with scCO2, was observed in a heterogeneous system where mineral solids, an adsorbed water film, and bulk scCO2 co-exist. In excess-water experiments, approximately 4% of forsterite and less than 2% of antigorite transformed into hydrated Mg-carbonates. A precipitate similar to nesquehonite (MgCO3•3H2O) was observed for forsterite within 6 hr of reaction time, but no such precipitate was formed from antigorite until after water was removed from the scCO2 following a 24-hr reaction period. The reduced reactivity and carbonate-precipitation behavior of antigorite was attributed to slower, incongruent dissolution of the mineral and lower concentrations of Mg2+ and HCO3- in the water film. The in situ measurements employed in this work make it possible to quantify metal carbonate precipitates and key reaction intermediates such as bicarbonate for the investigation of carbonation reaction mechanisms relevant to geologic carbon sequestration.« less

Arctic Ocean CO2 uptake: an improved multiyear estimate of the air-sea CO2 flux incorporating chlorophyll a concentrations

NASA Astrophysics Data System (ADS)

Yasunaka, Sayaka; Siswanto, Eko; Olsen, Are; Hoppema, Mario; Watanabe, Eiji; Fransson, Agneta; Chierici, Melissa; Murata, Akihiko; Lauvset, Siv K.; Wanninkhof, Rik; Takahashi, Taro; Kosugi, Naohiro; Omar, Abdirahman M.; van Heuven, Steven; Mathis, Jeremy T.

2018-03-01

We estimated monthly air-sea CO2 fluxes in the Arctic Ocean and its adjacent seas north of 60° N from 1997 to 2014. This was done by mapping partial pressure of CO2 in the surface water (pCO2w) using a self-organizing map (SOM) technique incorporating chlorophyll a concentration (Chl a), sea surface temperature, sea surface salinity, sea ice concentration, atmospheric CO2 mixing ratio, and geographical position. We applied new algorithms for extracting Chl a from satellite remote sensing reflectance with close examination of uncertainty of the obtained Chl a values. The overall relationship between pCO2w and Chl a was negative, whereas the relationship varied among seasons and regions. The addition of Chl a as a parameter in the SOM process enabled us to improve the estimate of pCO2w, particularly via better representation of its decline in spring, which resulted from biologically mediated pCO2w reduction. As a result of the inclusion of Chl a, the uncertainty in the CO2 flux estimate was reduced, with a net annual Arctic Ocean CO2 uptake of 180 ± 130 Tg C yr-1. Seasonal to interannual variation in the CO2 influx was also calculated.

Liquid CO 2/Coal Slurry for Feeding Low Rank Coal to Gasifiers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Marasigan, Jose; Goldstein, Harvey; Dooher, John

2013-09-30

This study investigates the practicality of using a liquid CO 2/coal slurry preparation and feed system for the E-Gas™ gasifier in an integrated gasification combined cycle (IGCC) electric power generation plant configuration. Liquid CO 2 has several property differences from water that make it attractive for the coal slurries used in coal gasification-based power plants. First, the viscosity of liquid CO 2 is much lower than water. This means it should take less energy to pump liquid CO 2 through a pipe compared to water. This also means that a higher solids concentration can be fed to the gasifier, whichmore » should decrease the heat requirement needed to vaporize the slurry. Second, the heat of vaporization of liquid CO 2 is about 80% lower than water. This means that less heat from the gasification reactions is needed to vaporize the slurry. This should result in less oxygen needed to achieve a given gasifier temperature. And third, the surface tension of liquid CO 2 is about 2 orders of magnitude lower than water, which should result in finer atomization of the liquid CO 2 slurry, faster reaction times between the oxygen and coal particles, and better carbon conversion at the same gasifier temperature. EPRI and others have recognized the potential that liquid CO 2 has in improving the performance of an IGCC plant and have previously conducted systemslevel analyses to evaluate this concept. These past studies have shown that a significant increase in IGCC performance can be achieved with liquid CO 2 over water with certain gasifiers. Although these previous analyses had produced some positive results, they were still based on various assumptions for liquid CO 2/coal slurry properties.« less

Reactive Transport Analysis of Fault 'Self-sealing' Associated with CO2 Storage

NASA Astrophysics Data System (ADS)

Patil, V.; McPherson, B. J. O. L.; Priewisch, A.; Franz, R. J.

2014-12-01

We present an extensive hydrologic and reactive transport analysis of the Little Grand Wash fault zone (LGWF), a natural analog of fault-associated leakage from an engineered CO2 repository. Injecting anthropogenic CO2 into the subsurface is suggested for climate change mitigation. However, leakage of CO2 from its target storage formation into unintended areas is considered as a major risk involved in CO2 sequestration. In the event of leakage, permeability in leakage pathways like faults may get sealed (reduced) due to precipitation or enhanced (increased) due to dissolution reactions induced by CO2-enriched water, thus influencing migration and fate of the CO2. We hypothesize that faults which act as leakage pathways can seal over time in presence of CO2-enriched waters. An example of such a fault 'self-sealing' is found in the LGWF near Green River, Utah in the Paradox basin, where fault outcrop shows surface and sub-surface fractures filled with calcium carbonate (CaCO3). The LGWF cuts through multiple reservoirs and seal layers piercing a reservoir of naturally occurring CO2, allowing it to leak into overlying aquifers. As the CO2-charged water from shallower aquifers migrates towards atmosphere, a decrease in pCO2 leads to supersaturation of water with respect to CaCO3, which precipitates in the fractures of the fault damage zone. In order to test the nature, extent and time-frame of the fault sealing, we developed reactive flow simulations of the LGWF. Model parameters were chosen based on hydrologic measurements from literature. Model geochemistry was constrained by water analysis of the adjacent Crystal Geyser and observations from a scientific drilling test conducted at the site. Precipitation of calcite in the top portion of the fault model led to a decrease in the porosity value of the damage zone, while clay precipitation led to a decrease in the porosity value of the fault core. We found that the results were sensitive to the fault architecture, relative permeability functions, kinetic parameters for mineral reactions and treatment of molecular diffusion. Major conclusions from this analysis are that a failed (leaking) engineered sequestration site may behave very similar to the LGWF and that under similar conditions some faults are likely to seal over time.

The carbon cycle and biogeochemical dynamics in lake sediments

USGS Publications Warehouse

Dean, W.E.

1999-01-01

The concentrations of organic carbon (OC) and CaCO3 in lake sediments are often inversely related. This relation occurs in surface sediments from different locations in the same lake, surface sediments from different lakes, and with depth in Holocene sediments. Where data on accumulation rates are available, the relation holds for organic carbon and CaCO3 accumulation rates as well. An increase of several percent OC is accompanied by a decrease of several tens of percent CaCO3 indicating that the inverse relation is not due to simple dilution of one component by another. It appears from core data that once the OC concentration in the sediments becomes greater than about 12%, the CO2 produced by decomposition of that OC and production of organic acids lowers the pH of anoxic pore waters enough to dissolve any CaCO3 that reaches the sediment-water interface. In a lake with a seasonally anoxic hypolimnion, processes in the water column also can produce an inverse relation between OC and CaCO3 over time. If productivity of the lake increases, the rain rate of OC from the epilimnion increases. Biogenic removal of CO2 and accompanying increase in pH also may increase the production of CaCO3. However, the decomposition of organic matter in the hypolimnion will decrease the pH of the hypolimnion causing greater dissolution of CaCO3 and therefore a decrease in the rain rate of CaCO3 to the sediment-water interface.

The Effects of Radiation on the Adsorption of CO2 by Nonice Materials Relevant to Icy Satellites

NASA Astrophysics Data System (ADS)

Hibbitts, C.; Stockstill-Cahill, K.; Paranicas, C.; Wing, B. R.

2017-12-01

Water-ice and water-rich non-ice materials dominate the surfaces of the icy satellites of Jupiter and Saturn, with CO2 detected at trace amounts largely in the nonice materials [1,2]. Although, the mechanism by which CO2 is entrained within the nonice material has not yet been understood, one hypothesis is adsorption by van der Waals forces or induced dipole interactions, with laboratory measurements demonstrating some analog materials can stably retain adsorbed CO2 while under vacuum at the temperatures of the icy satellites [3,4]. The strength and spectral signature of the adsorbed CO2 is dependent upon the composition and temperature of the host material. So far, the most adsorptive analogs are complex expansive clays, probably because of the large microporosity and presence of charge compensating cations to act as adsorption sites. However, the surfaces of the airless Galilean and Saturnian satellites are bombarded by high-energy particles from the planetary magnetospheres, which could alter the nonice material affecting adsorptivity towards CO2 (and other volatiles). Thus, we have conducted experiments to explore the possibility that irradiation could increase the adsorptivity of other analogs more consistent with the expected composition of the satellites surfaces. This hypothesis is explored for CO2 adsorption onto pressed powder pellets that are cooled to the surface temperatures of the satellites' surfaces under solar illumination ( 125-150 K) and dosed with CO2 from directly above the surface of the pellet, while collecting spectra of the asymmetric stretch fundamental of the CO2 absorption band near 4.25 microns. After this initial spectrum, the pellet is warmed to degas any adsorbed CO2 and then recooled. The pellet is then irradiated with 40 keV electrons for 48-72 hours at a fluence of 80 microamps and the adsorption experiment is repeated. The infrared spectrum is a bidirectional reflectance measurement using a Bruker Vertex 70 FTIR with and external MCT detector and the chamber pressure 1e-8 torr or lower. References: [1] McCord et al. 1998. J. Geophys. Res., 103, E4, 8603-8626; [2] Clark et al. 2005. Nature, 435, 66-69; [3] Hibbitts, C.A. and J. Szanyi. 2007. Icarus, 191, 371-380; [4] Berlanga, G. et al., 2016. Icarus, 280, 366-377.

Uptake and storage of anthropogenic CO2 in the pacific ocean estimated using two modeling approaches

NASA Astrophysics Data System (ADS)

Li, Yangchun; Xu, Yongfu

2012-07-01

A basin-wide ocean general circulation model (OGCM) of the Pacific Ocean is employed to estimate the uptake and storage of anthropogenic CO2 using two different simulation approaches. The simulation (named BIO) makes use of a carbon model with biological processes and full thermodynamic equations to calculate surface water partial pressure of CO2, whereas the other simulation (named PTB) makes use of a perturbation approach to calculate surface water partial pressure of anthropogenic CO2. The results from the two simulations agree well with the estimates based on observation data in most important aspects of the vertical distribution as well as the total inventory of anthropogenic carbon. The storage of anthropogenic carbon from BIO is closer to the observation-based estimate than that from PTB. The Revelle factor in 1994 obtained in BIO is generally larger than that obtained in PTB in the whole Pacific, except for the subtropical South Pacific. This, to large extent, leads to the difference in the surface anthropogenic CO2 concentration between the two runs. The relative difference in the annual uptake between the two runs is almost constant during the integration processes after 1850. This is probably not caused by dissolved inorganic carbon (DIC), but rather by a factor independent of time. In both runs, the rate of change in anthropogenic CO2 fluxes with time is consistent with the rate of change in the growth rate of atmospheric partial pressure of CO2.

Gas-solid carbonation as a possible source of carbonates in cold planetary environments

NASA Astrophysics Data System (ADS)

Garenne, A.; Montes-Hernandez, G.; Beck, P.; Schmitt, B.; Brissaud, O.; Pommerol, A.

2013-02-01

Carbonates are abundant sedimentary minerals at the surface and sub-surface of the Earth and they have been proposed as tracers of liquid water in extraterrestrial environments. Their formation mechanism is since generally associated with aqueous alteration processes. Recently, carbonate minerals have been discovered on Mars' surface by different orbitals or rover missions. In particular, the phoenix mission has measured from 1% to 5% of calcium carbonate (calcite type) within the soil (Smith et al., 2009). These occurrences have been reported in area where the relative humidity is significantly high (Boynton et al., 2009). The small concentration of carbonates suggests an alternative process on mineral grain surfaces (as suggested by Shaheen et al., 2010) than carbonation in aqueous conditions. Such an observation could rather point toward a possible formation mechanism by dust-gas reaction under current Martian conditions. To understand the mechanism of carbonate formation under conditions relevant to current Martian atmosphere and surface, we designed an experimental setup consisting of an infrared microscope coupled to a cryogenic reaction cell (IR-CryoCell setup). Three different mineral precursors of carbonates (Ca and Mg hydroxides, and a hydrated Ca silicate formed from Ca2SiO4), low temperature (from -10 to +30 °C), and reduced CO2 pressure (from 100 to 2000 mbar) were utilized to investigate the mechanism of gas-solid carbonation at mineral surfaces. These mineral materials are crucial precursors to form Ca and Mg carbonates in humid environments (0%

Molecular dynamics computations of brine-CO2 interfacial tensions and brine-CO2-quartz contact angles and their effects on structural and residual trapping mechanisms in carbon geo-sequestration.

PubMed

Iglauer, S; Mathew, M S; Bresme, F

2012-11-15

In the context of carbon geo-sequestration projects, brine-CO(2) interfacial tension γ and brine-CO(2)-rock surface water contact angles θ directly impact structural and residual trapping capacities. While γ is fairly well understood there is still large uncertainty associated with θ. We present here an investigation of γ and θ using a molecular approach based on molecular dynamics computer simulations. We consider a system consisting of CO(2)/water/NaCl and an α-quartz surface, covering a brine salinity range between 0 and 4 molal. The simulation models accurately reproduce the dependence of γ on pressure below the CO(2) saturation pressure at 300 K, and over predict γ by ~20% at higher pressures. In addition, in agreement with experimental observations, the simulations predict that γ increases slightly with temperature or salinity. We also demonstrate that for non-hydroxylated quartz surfaces, θ strongly increases with pressure at subcritical and supercritical conditions. An increase in temperature significantly reduces the contact angle, especially at low-intermediate pressures (1-10 MPa), this effect is mitigated at higher pressures, 20 MPa. We also found that θ only weakly depends on salinity for the systems investigated in this work. Copyright © 2012 Elsevier Inc. All rights reserved.

Organics and other molecules in the surfaces of Callisto and Ganymede

USGS Publications Warehouse

McCord, T.B.; Carlson, R.W.; Smythe, W.D.; Hansen, G.B.; Clark, R.N.; Hibbitts, C.A.; Fanale, F.P.; Granahan, J.C.; Segura, M.; Matson, D.L.; Johnson, T.V.; Martin, P.D.

1997-01-01

Five absorption features are reported at wavelengths of 3.4, 3.88, 4.05, 4.25, and 4.57 micrometers in the surface materials of the Galilean satellites Callisto and Ganymede from analysis of reflectance spectra returned by the Galileo mission near-infrared mapping spectrometer. Candidate materials include CO2, organic materials (such as tholins containing C???N and C-H), SO2, and compounds containing an SH-functional group; CO2, SO2, and perhaps cyanogen [(CN)2] may be present within the surface material itself as collections of a few molecules each. The spectra indicate that the primary surface constituents are water ice and hydrated minerals.

Effect of softening precipitate composition and surface characteristics on natural organic matter adsorption.

PubMed

Russell, Caroline G; Lawler, Desmond F; Speitel, Gerald E; Katz, Lynn E

2009-10-15

Natural organic matter (NOM) removal during water softening is thought to occur through adsorption onto or coprecipitation with calcium and magnesium solids. However, details of precipitate composition and surface chemistry and subsequent interactions with NOM are relatively unknown. In this study, zeta potentiometry analyses of precipitates formed from inorganic solutions under varying conditions (e.g., Ca-only, Mg-only, Ca + Mg, increasing lime or NaOH dose) indicated that both CaCO3 and Mg(OH)2 were positively charged at higher lime (Ca(OH)2) and NaOH doses (associated with pH values above 11.5), potentially yielding a greater affinity for adsorbing negatively charged organic molecules. Environmental scanning electron microscopy (ESEM) images of CaCO3 solids illustrated the rhombohedral shape characteristic of calcite. In the presence of increasing concentrations of magnesium, the CaCO3 rhombs shifted to more elongated crystals. The CaCO3 solids also exhibited increasingly positive surface charge from Mg incorporation into the crystal lattice, potentially creating more favorable conditions for adsorption of organic matter. NOM adsorption experiments using humic substances extracted from Lake Austin and Missouri River water elucidated the role of surface charge and surface area on adsorption.

Factors Influencing the Formation of Corrosive Conditions in Puget Sound and the Extreme Conditions Observed During Summer 2015 Associated with the NE Pacific Warm Anomaly (a.k.a. The Blob)

NASA Astrophysics Data System (ADS)

Alin, S. R.; Curry, B.; Newton, J.; Feely, R. A.; Sutton, A.

2016-02-01

Puget Sound is a complex glacial estuarine system that receives input from many rivers and streams, in addition to runoff from the urban and agricultural environments surrounding the southern part of the Salish Sea ecosystem. A series of glacial sills restrict estuarine circulation such that intrusions of seawater only occur episodically, resulting in long residence times in some parts of the basin. Through survey cruises and stationary time-series, we have observed the dynamic biogeochemical cycles in various sub-basins of Puget Sound since 2008. Areas of Puget Sound with restricted circulation may experience conditions of high pCO2, low pH, and low aragonite saturation state throughout the year. Historically, the highest pCO2 and lowest pH and aragonite saturation states have been observed in early fall in Hood Canal. Upwelling of dense, nutrient- and CO2-rich but oxygen-poor water along the coast provides the marine source water for Puget Sound's deep waters. We estimate that marine waters entering Puget Sound via the Strait of Juan de Fuca are now corrosive 95% of the time, representing a 26% increase in frequency since the preindustrial era. Both river inputs and intense primary production in surface waters drive remineralization in deep waters of Puget Sound basins, contributing to the formation of corrosive conditions in waters below the productive surface. In addition, we estimate that regionally enhanced atmospheric CO2 content may result in an increase in CO2 uptake in the region. In 2015 many features of the seasonal carbon cycle were accelerated relative to earlier years, as a result of the influence of the NE Pacific warm anomaly. In southern Hood Canal, the surface spring bloom began weeks earlier than usual, and in July, we saw the lowest estimated pH and aragonite saturation values in deep waters observed to date in Washington marine environments, which was about two months earlier than historical seasonal minima in pH and aragonite saturation.

Co3 O4 Nanowire Arrays toward Superior Water Oxidation Electrocatalysis in Alkaline Media by Surface Amorphization.

PubMed

Zhou, Dan; He, Liangbo; Zhang, Rong; Hao, Shuai; Hou, Xiandeng; Liu, Zhiang; Du, Gu; Asiri, Abdullah M; Zheng, Chengbin; Sun, Xuping

2017-11-07

It is highly desirable to develop a simple, fast and straightforward method to boost the alkaline water oxidation of metal oxide catalysts. In this communication, we report our recent finding that the generation of amorphous Co-borate layer on Co 3 O 4 nanowire arrays supported on Ti mesh (Co 3 O 4 @Co-Bi NA/TM) leads to significantly boosted OER activity. The as-prepared Co 3 O 4 @Co-Bi NA/TM demands overpotential of 304 mV to drive a geometrical current density of 20 mA cm -2 in 1.0 M KOH, which is 109 mV less than that for Co 3 O 4 NA/TM, with its catalytic activity being preserved for at least 20 h. It suggests that the existence of amorphous Co-Bi layer promotes more CoO x (OH) y generation on Co 3 O 4 surface. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

ALARA efforts in nordic BWRs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ingemansson, T.; Lundgren, K.; Elkert, J.

1995-03-01

Some ALARA-related ABB Atom projects are currently under investigation. One of the projects has been ordered by the Swedish Radiation Protection Institute, and two others by the Nordic BWR utilities. The ultimate objective of the projects is to identify and develop methods to significantly decrease the future exposure levels in the Nordic BWRS. As 85% to 90% of the gamma radiation field in the Nordic BWRs originates from Co-60, the only way to significantly decrease the radiation doses is to effect Co and Co-60. The strategy to do this is to map the Co sources and estimate the source strengthmore » of Co from these sources, and to study the possibility to affect the release of Co-60 from the core surfaces and the uptake on system surfaces. Preliminary results indicate that corrosion/erosion of a relatively small number of Stellite-coated valves and/or dust from grinding of Stellite valves may significantly contribute to the Co input to the reactors. This can be seen from a high measured Co/Ni ratio in the feedwater and in the reactor water. If stainless steel is the only source of Co, the Co/Ni ratio would be less than 0.02 as the Co content in the steel is less than 0.2%. The Co/Ni ratio in the reactor water, however, is higher than 0.1, indicating that the major fraction of the Co originates from Stellite-coated valves. There are also other possible explanations for an increase of the radiation fields. The Co-60 inventory on the core surfaces increases approximately as the square of the burn-up level. If the burn-up is increased from 35 to 5 MWd/kgU, the Co-60 inventory on the core surfaces will be doubled. Also the effect on the behavior of Co-60 of different water chemistry and materials conditions is being investigated. Examples of areas studied are Fe and Zn injection, pH-control, and different forms of surface pre-treatments.« less

Continuous measurements of stable isotopes of carbon dioxide and water vapour in an urban atmosphere: isotopic variations associated with meteorological conditions.

PubMed

Wada, Ryuichi; Matsumi, Yutaka; Nakayama, Tomoki; Hiyama, Tetsuya; Fujiyoshi, Yasushi; Kurita, Naoyuki; Muramoto, Kenichiro; Takanashi, Satoru; Kodama, Naomi; Takahashi, Yoshiyuki

2017-12-01

Isotope ratios of carbon dioxide and water vapour in the near-surface air were continuously measured for one month in an urban area of the city of Nagoya in central Japan in September 2010 using laser spectroscopic techniques. During the passages of a typhoon and a stationary front in the observation period, remarkable changes in the isotope ratios of CO 2 and water vapour were observed. The isotope ratios of both CO 2 and water vapour decreased during the typhoon passage. The decreases can be attributed to the air coming from an industrial area and the rainout effects of the typhoon, respectively. During the passage of the stationary front, δ 13 C-CO 2 and δ 18 O-CO 2 increased, while δ 2 H-H 2 Ov and δ 18 O-H 2 Ov decreased. These changes can be attributed to the air coming from rural areas and the air surrounding the observational site changing from a subtropical air mass to a subpolar air mass during the passage of the stationary front. A clear relationship was observed between the isotopic CO 2 and water vapour and the meteorological phenomena. Therefore, isotopic information of CO 2 and H 2 Ov could be used as a tracer of meteorological information.

Carbon dioxide supersaturation in the surface waters of lakes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cole, J.J.; Caraco, N.F.; Kling, G.W.

1994-09-09

Data on the partial pressure of carbon dioxide (CO{sub 2}) in the surface waters from a large number of lakes (1835) with a worldwide distribution show that only a small proportion of the 4665 samples analyzed (less than 10 percent) were within {+-}20 percent of equilibrium with the atmosphere and that most samples (87 percent) were supersaturated. The mean partial pressure of CO{sub 2} averaged 1036 microatmospheres, about three times the value in the overlying atmosphere, indicating that lakes are sources rather than sinks of atmospheric CO{sub 2}. On a global scale, the potential efflux of CO{sub 2} from lakesmore » (about 0.14 x 10{sup 15} grams of carbon per year) is about half as large as riverine transport of organic plus inorganic carbon to the ocean. Lakes are a small but potentially important conduit for carbon for terrestrial sources to the atmospheric sink. 18 refs., 2 figs., 1 tab.« less

A Multi-scale Approach for CO2 Accounting and Risk Analysis in CO2 Enhanced Oil Recovery Sites

NASA Astrophysics Data System (ADS)

Dai, Z.; Viswanathan, H. S.; Middleton, R. S.; Pan, F.; Ampomah, W.; Yang, C.; Jia, W.; Lee, S. Y.; McPherson, B. J. O. L.; Grigg, R.; White, M. D.

2015-12-01

Using carbon dioxide in enhanced oil recovery (CO2-EOR) is a promising technology for emissions management because CO2-EOR can dramatically reduce carbon sequestration costs in the absence of greenhouse gas emissions policies that include incentives for carbon capture and storage. This study develops a multi-scale approach to perform CO2 accounting and risk analysis for understanding CO2 storage potential within an EOR environment at the Farnsworth Unit of the Anadarko Basin in northern Texas. A set of geostatistical-based Monte Carlo simulations of CO2-oil-water flow and transport in the Marrow formation are conducted for global sensitivity and statistical analysis of the major risk metrics: CO2 injection rate, CO2 first breakthrough time, CO2 production rate, cumulative net CO2 storage, cumulative oil and CH4 production, and water injection and production rates. A global sensitivity analysis indicates that reservoir permeability, porosity, and thickness are the major intrinsic reservoir parameters that control net CO2 injection/storage and oil/CH4 recovery rates. The well spacing (the distance between the injection and production wells) and the sequence of alternating CO2 and water injection are the major operational parameters for designing an effective five-spot CO2-EOR pattern. The response surface analysis shows that net CO2 injection rate increases with the increasing reservoir thickness, permeability, and porosity. The oil/CH4 production rates are positively correlated to reservoir permeability, porosity and thickness, but negatively correlated to the initial water saturation. The mean and confidence intervals are estimated for quantifying the uncertainty ranges of the risk metrics. The results from this study provide useful insights for understanding the CO2 storage potential and the corresponding risks of commercial-scale CO2-EOR fields.

Effects of sea-ice and biogeochemical processes and storms on under-ice water fCO2 during the winter-spring transition in the high Arctic Ocean: Implications for sea-air CO2 fluxes

NASA Astrophysics Data System (ADS)

Fransson, Agneta; Chierici, Melissa; Skjelvan, Ingunn; Olsen, Are; Assmy, Philipp; Peterson, Algot K.; Spreen, Gunnar; Ward, Brian

2017-07-01

We performed measurements of carbon dioxide fugacity (fCO2) in the surface water under Arctic sea ice from January to June 2015 during the Norwegian young sea ICE (N-ICE2015) expedition. Over this period, the ship drifted with four different ice floes and covered the deep Nansen Basin, the slopes north of Svalbard, and the Yermak Plateau. This unique winter-to-spring data set includes the first winter-time under-ice water fCO2 observations in this region. The observed under-ice fCO2 ranged between 315 µatm in winter and 153 µatm in spring, hence was undersaturated relative to the atmospheric fCO2. Although the sea ice partly prevented direct CO2 exchange between ocean and atmosphere, frequently occurring leads and breakup of the ice sheet promoted sea-air CO2 fluxes. The CO2 sink varied between 0.3 and 86 mmol C m-2 d-1, depending strongly on the open-water fractions (OW) and storm events. The maximum sea-air CO2 fluxes occurred during storm events in February and June. In winter, the main drivers of the change in under-ice water fCO2 were dissolution of CaCO3 (ikaite) and vertical mixing. In June, in addition to these processes, primary production and sea-air CO2 fluxes were important. The cumulative loss due to CaCO3 dissolution of 0.7 mol C m-2 in the upper 10 m played a major role in sustaining the undersaturation of fCO2 during the entire study. The relative effects of the total fCO2 change due to CaCO3 dissolution was 38%, primary production 26%, vertical mixing 16%, sea-air CO2 fluxes 16%, and temperature and salinity insignificant.

Cross-linked trimetallic nanopetals for electrocatalytic water splitting

NASA Astrophysics Data System (ADS)

Qu, Shanqing; Chen, Wei; Yu, Jinsong; Chen, Guangliang; Zhang, Rui; Chu, Sijun; Huang, Jun; Wang, Xingquan; Li, Chaorong; Ostrikov, Kostya (Ken)

2018-06-01

A facile and effective approach for fabricating a 3D nanostructured catalyst based on nonprecious metals for water splitting is reported. The Ni-Fe foam (NFF) is pretreated by a dielectric barrier discharge (DBD) plasma under ambient conditions, resulting in numerous microtrenches on the NFF surface. Meanwhile, some NiO and Fe2O3 spots appear on the NFF foam upon exposure to hot filaments generated in DBD plasmas in air. Cross-linked 3D CoS/Ni3S2-FeS nanopetals emerge on plasma treated NFF surface (PNFF) through sulfurization of Co nanosheets electrodeposited on PNFF. The produced CoS/Ni3S2-FeS/PNFF nanocomposite exhibited high electrocatalytic activity and stability for the overall water splitting. Benefiting from the 3D hierarchical nanoarchitecture of CoS/Ni3S2-FeS/PNFF with a large surface area, fast electron transport, and low free energy for adsorption, a current density of 10 mA cm-2 is achieved for the HER and OER with ultralow overpotentials of 75 mV and 136 mV, respectively. The amounts of H2 and O2 produced at a normalized current density of 10 mA cm-2 in 1 M KOH are about 680 μmol h-1 and 1230 μmol h-1, respectively. These values are very competitive compared with the state-of-the-art results reported for noble metal-free electrodes in alkaline media.

Water and Carbon Dioxide Adsorption at Olivine Surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kerisit, Sebastien N.; Bylaska, Eric J.; Felmy, Andrew R.

2013-11-14

Plane-wave density functional theory (DFT) calculations were performed to simulate water and carbon dioxide adsorption at the (010) surface of five olivine minerals, namely, forsterite (Mg2SiO4), calcio-olivine (Ca2SiO4), tephroite (Mn2SiO4), fayalite (Fe2SiO4), and Co-olivine (Co2SiO4). Adsorption energies per water molecule obtained from energy minimizations varied from -78 kJ mol-1 for fayalite to -128 kJ mol-1 for calcio-olivine at sub-monolayer coverage and became less exothermic as coverage increased. In contrast, carbon dioxide adsorption energies at sub-monolayer coverage ranged from -20 kJ mol-1 for fayalite to -59 kJ mol-1 for calcio-olivine. Therefore, the DFT calculations show a strong driving force for carbonmore » dioxide displacement by water at the surface of all olivine minerals in a competitive adsorption scenario. Additionally, adsorption energies for both water and carbon dioxide were found to be more exothermic for the alkaline-earth (AE) olivines than for the transition-metal (TM) olivines and to not correlate with the solvation enthalpies of the corresponding divalent cations. However, a correlation was obtained with the charge of the surface divalent cation indicating that the more ionic character of the AE cations in the olivine structure relative to the TM cations leads to greater interactions with adsorbed water and carbon dioxide molecules at the surface and thus more exothermic adsorption energies for the AE olivines. For calcio-olivine, which exhibits the highest divalent cation charge of the five olivines, ab initio molecular dynamics simulations showed that this effect leads both water and carbon dioxide to react with the surface and form hydroxyl groups and a carbonate-like species, respectively.« less

A statistical test for the habitable zone concept

NASA Astrophysics Data System (ADS)

Checlair, J.; Abbot, D. S.

2017-12-01

Traditional habitable zone theory assumes that the silicate-weathering feedback regulates the atmospheric CO2 of planets within the habitable zone to maintain surface temperatures that allow for liquid water. There is some non-definitive evidence that this feedback has worked in Earth history, but it is untested in an exoplanet context. A critical prediction of the silicate-weathering feedback is that, on average, within the habitable zone planets that receive a higher stellar flux should have a lower CO2 in order to maintain liquid water at their surface. We can test this prediction directly by using a statistical approach involving low-precision CO2 measurements on many planets with future instruments such as JWST, LUVOIR, or HabEx. The purpose of this work is to carefully outline the requirements for such a test. First, we use a radiative-transfer model to compute the amount of CO2 necessary to maintain surface liquid water on planets for different values of insolation and planetary parameters. We run a large ensemble of Earth-like planets with different masses, atmospheric masses, inert atmospheric composition, cloud composition and level, and other greenhouse gases. Second, we post-process this data to determine the precision with which future instruments such as JWST, LUVOIR, and HabEx could measure the CO2. We then combine the variation due to planetary parameters and observational error to determine the number of planet measurements that would be needed to effectively marginalize over uncertainties and resolve the predicted trend in CO2 vs. stellar flux. The results of this work may influence the usage of JWST and will enhance mission planning for LUVOIR and HabEx.

Earth 2075 (CO2) - can Ocean-Amplified Carbon Capture (oacc) Impart Atmospheric CO2-SINKING Ability to CCS Fossil Energy?

NASA Astrophysics Data System (ADS)

Fry, R.; Routh, M.; Chaudhuri, S.; Fry, S.; Ison, M.; Hughes, S.; Komor, C.; Klabunde, K.; Sethi, V.; Collins, D.; Polkinghorn, W.; Wroobel, B.; Hughes, J.; Gower, G.; Shkolnik, J.

2017-12-01

Previous attempts to capture atmospheric CO2 by algal blooming were stalled by ocean viruses, zooplankton feeding, and/or bacterial decomposition of surface blooms, re-releasing captured CO2 instead of exporting it to seafloor. CCS fossil energy coupling could bypass algal bloom limits—enabling capture of 10 GtC/yr atmospheric CO2 by selective emiliania huxleyi (EHUX) blooming in mid-latitude open oceans, far from coastal waters and polar seas. This could enable a 500 GtC drawdown, 350 ppm restoration by 2050, 280 ppm CO2 by 2075, and ocean pH 8.2. White EHUX blooms could also reflect sunlight back into outer space and seed extra ocean cloud cover, via DMS release, to raise albedo 1.8%—restoring preindustrial temperature (ΔT = 0°C) by 2030. Open oceans would avoid post-bloom anoxia, exclusively a coastal water phenomenon. The EHUX calcification reaction initially sources CO2, but net sinking prevails in follow-up equilibration reactions. Heavier-than-water EHUX sink captured CO2 to the sea floor before surface decomposition occurs. Seeding EHUX high on their nonlinear growth curve could accelerate short-cycle secondary open-ocean blooming—overwhelming mid-latitude viruses, zooplankton, and competition from other algae. Mid-latitude "ocean deserts" exhibit low viral, zooplankton, and bacterial counts. Thermocline prevents nutrient upwelling that would otherwise promote competing algae. Adding nitrogen nutrient would foster exclusive EHUX blooming. Elevated EHUX seed levels could arise from sealed, pH-buffered, floating, seed-production bioreactors infused with 10% CO2 from carbon feedstock supplied by inland CCS fossil power plants capturing 90% of emissions as liquid CO2. Deep-water SPAR platforms extract natural gas from beneath the sea floor. On-platform Haber and pH processing could convert extracted CH4 to buffered NH4+ nutrient, enabling ≥0.7 GtC/yr of bioreactor seed production and 10 GtC/yr of amplified secondary open-ocean CO2 capture—making CCS fossil energy 1400% carbon negative.

Comparison on pore development of activated carbon produced by chemical and physical activation from palm empty fruit bunch

NASA Astrophysics Data System (ADS)

Hidayat, A.; Sutrisno, B.

2016-11-01

It is well-known that activated carbon is considered to be the general adsorbent due to the large range of applications. Numerous works are being continuously published concerning its use as adsorbent for: treatment of potable water; purification of air; retention of toxins by respirators; removal of organic and inorganic pollutants from flue gases and industrial waste gases and water; recuperation of solvents and hydrocarbons volatilized from petroleum derivatives; catalysis; separation of gas mixtures (molecularsieve activated carbons); storage of natural gas and hydrogen; energy storage in supercapacitors; recovery of gold, silver and othernoble metals; etc. This work presents producing activated carbons from palm empty fruit bunch using both physical activation with CO2 and chemical activation with KOH. The resultant activated carbons were characterized by measuring their porosities and pore size distributions. A comparison of the textural characteristics and surface chemistry of the activated carbon from palm empty fruit bunch by the CO2 and the KOH activation leads to the following findings: An activated carbon by the CO2 activation under the optimum conditions has a BET surface area of 717 m2/g, while that by the KOH activation has a BET surface area of 613 m2/g. The CO2 activation generated a highly microporous carbon (92%) with a Type-I isotherm, while the KOH activation generated a mesoporous one (70%) with a type-IV isotherm, the pore volumes are 0.2135 and 0.7426 cm3.g-1 respectively. The average pore size of the activated carbons is 2.72 and 2.56 nm for KOH activation and CO2 activation, respectively. The FT-IR spectra indicated significant variation in the surface functional groups are quite different for the KOH activated and CO2 activated carbons.

Boosting photocatalytic overall water splitting by Co doping into Mn3O4 nanoparticles as oxygen evolution cocatalysts.

PubMed

Yoshinaga, Taizo; Saruyama, Masaki; Xiong, Anke; Ham, Yeilin; Kuang, Yongbo; Niishiro, Ryo; Akiyama, Seiji; Sakamoto, Masanori; Hisatomi, Takashi; Domen, Kazunari; Teranishi, Toshiharu

2018-06-14

The effect of cobalt doping into a manganese oxide (tetragonal spinel Mn 3 O 4 ) nanoparticle cocatalyst up to Co/(Co + Mn) = 0.4 (mol/mol) on the activity of photocatalytic water oxidation was studied. Monodisperse ∼10 nm Co y Mn 1-y O (0 ≤y≤ 0.4) nanoparticles were uniformly loaded onto photocatalysts and converted to Co x Mn 3-x O 4 nanoparticles through calcination. 40 mol% cobalt-doped Mn 3 O 4 nanoparticle-loaded Rh@Cr 2 O 3 /SrTiO 3 photocatalyst exhibited 1.8 times-higher overall water splitting activity than that with pure Mn 3 O 4 nanoparticles. Investigation on the band structure and electrocatalytic water oxidation activity of Co x Mn 3-x O 4 nanoparticles revealed that the Co doping mainly contributes to the improvement of water oxidation kinetics on the surface of the cocatalyst nanoparticles.

Elevated CO2 facilitates C and N accumulation in a rice paddy ecosystem.

PubMed

Guo, Jia; Zhang, Mingqian; Wang, Xiaowen; Zhang, Weijian

2015-03-01

Elevated CO2 can stimulate wetland carbon (C) and nitrogen (N) exports through gaseous and dissolved pathways, however, the consequent influences on the C and N pools are still not fully known. Therefore, we set up a free-air CO2 enrichment experiment in a paddy field in Eastern China. After five year fumigation, we studied C and N in the plant-water-soil system. The results showed: (1) elevated CO2 stimulated rice aboveground biomass and N accumulations by 19.1% and 12.5%, respectively. (2) Elevated CO2 significantly increased paddy soil TOC and TN contents by 12.5% and 15.5%, respectively in the 0-15 cm layer, and 22.7% and 26.0% in the 15-30 cm soil layer. (3) Averaged across the rice growing period, elevated CO2 greatly increased TOC and TN contents in the surface water by 7.6% and 11.4%, respectively. (4) The TOC/TN ratio and natural δ15N value in the surface soil showed a decreasing trend under elevated CO2. The above results indicate that elevated CO2 can benefit C and N accumulation in paddy fields. Given the similarity between the paddies and natural wetlands, our results also suggest a great potential for long-term C and N accumulation in natural wetlands under future climate patterns. Copyright © 2015. Published by Elsevier B.V.

Microwave Extraction of Volatiles for Mars Science and ISRU

NASA Technical Reports Server (NTRS)

Ethridge, Edwin C.; Kaulker, William F.

2012-01-01

The greatest advantage of microwave heating for volatiles extraction is that excavation can be greatly reduced. Surface support operations would be simple consisting of rovers with drilling capability for insertion of microwaves down bore holes to heat at desired depths. The rovers would also provide support to scientific instruments for volatiles analysis and for volatiles collection and storage. The process has the potential for a much lower mass and a less complex system than other in-situ processes. Microwave energy penetrates the surface heating within with subsequent sublimation of water or decomposition of volatile containing minerals. On Mars the volatiles should migrate to the surface to be captured with a cold trap. The water extraction and transport process coupled with atmospheric CO2 collection could readily lead to a propellant production process, H2O + CO2 yields CH4 + O2.

Molecular Gibbs Surface Excess and CO2-Hydrate Density Determine the Strong Temperature- and Pressure-Dependent Supercritical CO2-Brine Interfacial Tension.

PubMed

Ji, Jiayuan; Zhao, Lingling; Tao, Lu; Lin, Shangchao

2017-06-29

In CO 2 geological storage, the interfacial tension (IFT) between supercritical CO 2 and brine is critical for the storage capacitance design to prevent CO 2 leakage. IFT relies not only on the interfacial molecule properties but also on the environmental conditions at different storage sites. In this paper, supercritical CO 2 -NaCl solution systems are modeled at 343-373 K and 6-35 MPa under the salinity of 1.89 mol/L using molecular dynamics simulations. After computing and comparing the molecular density profile across the interface, the atomic radial distribution function, the molecular orientation distribution, the molecular Gibbs surface excess (derived from the molecular density profile), and the CO 2 -hydrate number density under the above environmental conditions, we confirm that only the molecular Gibbs surface excess of CO 2 molecules and the CO 2 -hydrate number density correlate strongly with the temperature- and pressure-dependent IFTs. We also compute the populations of two distinct CO 2 -hydrate structures (T-type and H-type) and attribute the observed dependence of IFTs to the dominance of the more stable, surfactant-like T-type CO 2 -hydrates at the interface. On the basis of these new molecular mechanisms behind IFT variations, this study could guide the rational design of suitable injecting environmental pressure and temperature conditions. We believe that the above two molecular-level metrics (Gibbs surface excess and hydrate number density) are of great fundamental importance for understanding the supercritical CO 2 -water interface and engineering applications in geological CO 2 storage.

Designed polar cosolvent-modified supercritical CO2 removing caffeine from and retaining catechins in green tea powder using response surface methodology.

PubMed

Huang, Kuo-Jong; Wu, Jia-Jiuan; Chiu, Yung-Ho; Lai, Cheng-Yung; Chang, Chieh-Ming J

2007-10-31

This study examines cosolvent-modified supercritical carbon dioxide (SC-CO2) to remove caffeine from and to retain catechins in green tea powder. The response surface method was adopted to determine the optimal operation conditions in terms of the extraction efficiencies and concentration factors of caffeine and catechins during the extractions. When SC-CO2 was used at 333 K and 300 bar, 91.5% of the caffeine was removed and 80.8% of catechins were retained in the tea: 3600 g of carbon dioxide was used in the extraction of 4 g of tea soaked with 1 g of water. Under the same extraction conditions, 10 g of water was added to <800 g of carbon dioxide in an extraction that completely removed caffeine (that is, the caffeine extraction efficiency was 100%). The optimal result as predicted by three-factor response surface methodology and supported by experimental data was that in 1.5 h of extraction, 640 g of carbon dioxide at 323 K and 275 bar with the addition of 6 g of water extracted 71.9% of the caffeine while leaving 67.8% of the catechins in 8 g of tea. Experimental data indicated that supercritical carbon dioxide decaffeination increased the concentrations of caffeine in the SC-CO2 extracts at 353 K.

Quantifying the flux of CaCO3 and organic carbon from the surface ocean using in situ measurements of O2, N2, pCO2, and pH

NASA Astrophysics Data System (ADS)

Emerson, Steven; Sabine, Christopher; Cronin, Meghan F.; Feely, Richard; Cullison Gray, Sarah E.; Degrandpre, Mike

2011-09-01

Ocean acidification from anthropogenic CO2 has focused our attention on the importance of understanding the rates and mechanisms of CaCO3 formation so that changes can be monitored and feedbacks predicted. We present a method for determining the rate of CaCO3 production using in situ measureme nts of fCO2 and pH in surface waters of the eastern subarctic Pacific Ocean. These quantities were determined on a surface mooring every 3 h for a period of about 9 months in 2007 at Ocean Station Papa (50°N, 145°W). We use the data in a simple surface ocean, mass balance model of dissolved inorganic carbon (DIC) and alkalinity (Alk) to constrain the CaCO3: organic carbon (OC) production ratio to be approximately 0.5. A CaCO3 production rate of 8 mmol CaCO3 m-2 d-1 in the summer of 2007 (1.2 mol m-2 yr-1) is derived by combining the CaCO3: OC ratio with the a net organic carbon production rate (2.5 mol C m-2 yr-1) determined from in situ measurements of oxygen and nitrogen gas concentrations measured on the same mooring (Emerson and Stump, 2010). Carbonate chemistry data from a meridional hydrographic section in this area in 2008 indicate that isopycnal surfaces that outcrop in the winter in the subarctic Pacific and deepen southward into the subtropics are a much stronger source for alkalinity than vertical mixing. This pathway has a high enough Alk:DIC ratio to support the CaCO3:OC production rate implied by the fCO2 and pH data.

Role of water and carbonates in photocatalytic transformation of CO{sub 2} to CH{sub 4} on titania.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dimitrijevic, N. M.; Vijayan, B. K.; Poluektov, O. G.

Using the electron paramagnetic resonance technique, we have elucidated the multiple roles of water and carbonates in the overall photocatalytic reduction of carbon dioxide to methane over titania nanoparticles. The formation of H atoms (reduction product) and {center_dot}OH radicals (oxidation product) from water, and CO{sub 3}{sup -} radical anions (oxidation product) from carbonates, was detected in CO{sub 2}-saturated titania aqueous dispersion under UV illumination. Additionally, methoxyl, {center_dot}OCH{sub 3}, and methyl, {center_dot}CH{sub 3}, radicals were identified as reaction intermediates. The two-electron, one-proton reaction proposed as an initial step in the reduction of CO{sub 2} on the surface of TiO{sub 2} ismore » supported by the results of first-principles calculations.« less

Role of Water and Carbonates in Photocatalytic Transformation of CO2 to CH4 on Titania

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dimitrijevic, Nada; Vijayan, Baiju K.; Poluektov, Oleg G.

Using the electron paramagnetic resonance technique, we have elucidated the multiple roles of water and carbonates in the overall photocatalytic reduction of carbon dioxide to methane over titania nanoparticles. The formation of H atoms (reduction product) and {sm_bullet}OH radicals (oxidation product) from water, and CO{sub 3}{sup -} radical anions (oxidation product) from carbonates, was detected in CO{sub 2}-saturated titania aqueous dispersion under UV illumination. Additionally, methoxyl, {sm_bullet}OCH{sub 3}, and methyl, {sm_bullet}CH{sub 3}, radicals were identified as reaction intermediates. The two-electron, one-proton reaction proposed as an initial step in the reduction of CO{sub 2}, on the surface of TiO{sub 2}, ismore » supported by the results of first-principles calculations.« less

Multi-property modeling of ocean basin carbon fluxes

NASA Technical Reports Server (NTRS)

Volk, Tyler

1988-01-01

The objectives of this project were to elucidate the causal mechanisms in some of the most important features of the global ocean/atomsphere carbon system. These included the interaction of physical and biological processes in the seasonal cycle of surface water pCo2, and links between productivity, surface chlorophyll, and the carbon cycle that would aid global modeling efforts. In addition, several other areas of critical scientific interest involving links between the marine biosphere and the global carbon cycle were successfully pursued; specifically, a possible relation between phytoplankton emitted DMS and climate, and a relation between the location of calcium carbonate burial in the ocean and metamorphic source fluxes of CO2 to the atmosphere. Six published papers covering the following topics are summarized: (1) Mass extinctions, atmospheric sulphur and climatic warming at the K/T boundary; (2) Sensitivity of climate and atmospheric CO2 to deep-ocean and shallow-ocean carbonate burial; (3) Controls on CO2 sources and sinks in the earthscale surface ocean; (4) pre-anthropogenic, earthscale patterns of delta pCO2 between ocean and atmosphere; (5) Effect on atmospheric CO2 from seasonal variations in the high latitude ocean; and (6) Limitations or relating ocean surface chlorophyll to productivity.

Evaluation of the effect of sulfate, alkalinity and disinfector on iron release of iron pipe and iron corrosion scale characteristics under water quality changing condition using response surface methodology

NASA Astrophysics Data System (ADS)

Yang, Fan; Shi, Baoyou; Zhang, Weiyu; Guo, Jianbo; Wu, Nana; Liu, Xinyuan

2018-02-01

The response surface methodology (RSM), particularly Box-Behnken design model, was used in this study to evaluate the sulfate, alkalinity and free chlorine on iron release of pipe with groundwater supply history and its iron corrosion scale characteristics under water quality changing experiment. The RSM results together with response surface contour plots indicated that the iron release of pipe section reactors was positively related with Larson Ratio and free chlorine. The thin Corrosion scales with groundwater supply history upon collection site contained Fe3O4 (18%), α-FeOOH (64%), FeCO3 (9%), β-FeOOH (8%) and γ-FeOOH (5%), besides their averaged amorphous iron oxide content was 13.6%. After the RSM water quality changing experiment, Fe3O4, amorphous iron oxide and intermediate iron products (FeCO3, Green Rust (GR)) content on scale of Cl2Rs increased, while their α-FeOOH contents decreased and β-FeOOH disappeared. The high iron released Cl2Rs receiving higher LR water (1.40-2.04) contained highest FeCO3 (20%) and amorphous iron oxide (42%), while the low iron release Cl2Rs receiving lower LR water (0.52-0.73) had higher GR(6.5%) and the amorphous iron oxide (23.7%). In high LR water (>0.73), the thin and non-protective corrosion scale containing higher amorphous iron oxide, Fe(II) derived from new produced Fe3O4 or FeCO3 or GR was easy for oxidants and sulfate ions penetration, and had higher iron release. However the same unstable corrosion scale didn’t have much iron release in low LR water (≤0.73). RSM experiment indicated that iron release of these unstable corrosion scales had close relationship with water quality (Larson Ratio and disinfectant). Optimizing the water quality of new source water and using reasonable water purification measures can help to eliminate the red water case.

Inorganic C-sources for Lemanea, Cladophora and Ranunculus in a fast-flowing stream: Measurements of gas exchange and of carbon isotope ratio and their ecological implications.

PubMed

Raven, John; Beardall, John; Griffiths, Howard

1982-04-01

CO 2 -and O 2 -exchange characteristics and δ 13 C values have been measured in a rhodophycean haptophyte (Lemanea mamillosa), a chlorophycean haptophyte (Cladophora glomerata) and a magnoliophyte rhizophyte (Ranunculus sp.) from a 5 m stretch of the Dichty Burn near Dundee. Light-and CO 2 -saturated rates of photosynthesis are greatest on a dry weight basis for Cladophora and lowest for Lemanea; the order is reversed on a surface area basis. The CO 2 concentration at pH 6.5 at which photosynthesis is half-saturated is 25-40 μM, with Lemanea rather lower than Cladophora or Ranunculus; these half-saturation values are similar to the free CO 2 concentration in the Burn water. Lemanea cannot use HCO 3 - in photosynthesis, while Cladophora and Ranunculus can. Despite being within a factor or two of saturation with free CO 2 in terms of the bulk water concentration, the growth habit of Cladophora and, particularly, Ranunculus means that the high water velocity in the Burn does not necessarily prevent C depletion effects around the plants, thus providing a possible role for HCO 3 - use by these plants. Lemanea lives in the fastest-growing parts of the Burn, and its growth habit insures that it is exposed to this high water velocity, thus minimising CO 2 depletion during photosynthesis despite the low surface/volume ratio for this plant. δ 13 C measurements on the inorganic C in the Burn water are consistent with at least part of its excess (above air-equilibrium) inorganic C levels coming from heterotrophic activity. Lemanea has the most negative δ 13 C value of the three plants, consistent with CO 2 use and small diffusion resistances. Ranunculus has the least negative δ 13 C value, consistent with some CO 2 depletion and/or HCO 3 - use in situ related to a high diffusion resistance in a rhizophyte which does not have to obtain all of its N and P from the bulk water but can obtain some from the sediments. Cladophora is intermediate, suggesting some CO 2 depletion and/or HCO 3 - use in this densely growing haptophyte.

Conditions for oceans on Earth-like planets orbiting within the habitable zone: importance of volcanic CO{sub 2} degassing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kadoya, S.; Tajika, E., E-mail: kadoya@astrobio.k.u-tokyo.ac.jp, E-mail: tajika@astrobio.k.u-tokyo.ac.jp

2014-08-01

Earth-like planets in the habitable zone (HZ) have been considered to have warm climates and liquid water on their surfaces if the carbonate-silicate geochemical cycle is working as on Earth. However, it is known that even the present Earth may be globally ice-covered when the rate of CO{sub 2} degassing via volcanism becomes low. Here we discuss the climates of Earth-like planets in which the carbonate-silicate geochemical cycle is working, with focusing particularly on insolation and the CO{sub 2} degassing rate. The climate of Earth-like planets within the HZ can be classified into three climate modes (hot, warm, and snowballmore » climate modes). We found that the conditions for the existence of liquid water should be largely restricted even when the planet is orbiting within the HZ and the carbonate-silicate geochemical cycle is working. We show that these conditions should depend strongly on the rate of CO{sub 2} degassing via volcanism. It is, therefore, suggested that thermal evolution of the planetary interiors will be a controlling factor for Earth-like planets to have liquid water on their surface.« less

In situ XPS study of methanol reforming on PdGa near-surface intermetallic phases

PubMed Central

Rameshan, Christoph; Stadlmayr, Werner; Penner, Simon; Lorenz, Harald; Mayr, Lukas; Hävecker, Michael; Blume, Raoul; Rocha, Tulio; Teschner, Detre; Knop-Gericke, Axel; Schlögl, Robert; Zemlyanov, Dmitry; Memmel, Norbert; Klötzer, Bernhard

2012-01-01

In situ X-ray photoelectron spectroscopy and low-energy ion scattering were used to study the preparation, (thermo)chemical and catalytic properties of 1:1 PdGa intermetallic near-surface phases. Deposition of several multilayers of Ga metal and subsequent annealing to 503–523 K led to the formation of a multi-layered 1:1 PdGa near-surface state without desorption of excess Ga to the gas phase. In general, the composition of the PdGa model system is much more variable than that of its PdZn counterpart, which results in gradual changes of the near-surface composition with increasing annealing or reaction temperature. In contrast to near-surface PdZn, in methanol steam reforming, no temperature region with pronounced CO2 selectivity was observed, which is due to the inability of purely intermetallic PdGa to efficiently activate water. This allows to pinpoint the water-activating role of the intermetallic/support interface and/or of the oxide support in the related supported PdxGa/Ga2O3 systems, which exhibit high CO2 selectivity in a broad temperature range. In contrast, corresponding experiments starting on the purely bimetallic model surface in oxidative methanol reforming yielded high CO2 selectivity already at low temperatures (∼460 K), which is due to efficient O2 activation on PdGa. In situ detected partial and reversible oxidative Ga segregation on intermetallic PdGa is associated with total oxidation of intermediate C1 oxygenates to CO2. PMID:22875996

Response of CO and H2 uptake to extremes of water stress in saline and non-saline soils

NASA Astrophysics Data System (ADS)

King, G.

2017-12-01

Neither carbon monoxide (CO) nor hydrogen (H2) have direct impacts on radiative forcing, but both play important roles in tropospheric chemistry. Soils affect both the fate and significance of atmospheric CO and H2 by acting as strong global gas sinks ( 15% and >75 %, respectively), but much remains unknown about the microbiology of these gases, including responses to key environmental drivers. The role of water availability, measured as water potential, has been addressed to a limited extent by earlier studies with results suggesting that CO and H2 uptake are strongly limited by water stress. However recent results indicate a much greater tolerance of water stress than previously suspected. Ex situ assays have shown that non-saline playa soils from the Alvord Basin (Oregon, USA) consumed atmospheric and exogenous hydrogen and CO under conditions of severe water stress. CO uptake occurred at water potentials < -30 MPa, which are far below values considered optimal for terrestrial bacterial growth. Surface soils that had been exposed to water potentials as low as -300 MPa also oxidized CO and H2 after brief equilibration at higher potentials (less water stress), indicating remarkable tolerance of desiccating conditions. Tolerance to water stress for CO and H2 uptake was also observed for soils from a montane rainforest (Hawai`i, USA). However, unlike playa soils rainforest soils seldom experience extended drought that would select for desiccation tolerance. While CO uptake by forest soils was more sensitive to water stress (limits -10MPa) than in playa soils, H2 uptake was observed at -90 MPa to -100 MPa. Tolerance at these levels might be due to the formation of intracellular water that limits the local effects of stress. Comparisons of water stress responses between saline and non-saline soils further suggested that communities of CO- and H2-oxidizing were generally robust with respect to stresses resulting from solute and matric effects. Collectively the results indicate that models of global CO and H2 dynamics might be improved by incorporating responses to soil water stress that could be estimated using relative humidity regimes calibrated for different soil types and systems. Incorporating water stress responses into models offers a means for assessing potential climate change impacts on two important trace gases.

On the feasibility of borehole-to-surface electromagnetics for monitoring CO2 sequestration

NASA Astrophysics Data System (ADS)

Wilson, G. A.; Zhdanov, M. S.; Hibbs, A. D.; Black, N.; Gribenko, A. V.; Cuma, M.; Agundes, A.; Eiskamp, G.

2012-12-01

Carbon capture and storage (CCS) projects rely on storing supercritical CO2 in deep saline reservoirs where buoyancy forces drive the injected CO2 upward into the aquifer until a seal is reached. The permanence of the sequestration depends entirely on the long-term geological integrity of the seal. Active geophysical monitoring of the sequestration is critical for informing CO2 monitoring, accounting and verification (MVA) decisions. During injection, there exists a correlation between the changes in CO2 and water saturations in a saline reservoir. Dissolved salts react with the CO2 to precipitate out as carbonates, thereby generally decreasing the electrical resistivity. As a result, there is a correlation between the change in fluid saturation and measured electromagnetic (EM) fields. The challenge is to design an EM survey appropriate for monitoring large, deep reservoirs. Borehole-to-surface electromagnetic (BSEM) surveys consist of borehole-deployed galvanic transmitters and a surface-based array of electric and magnetic field sensors. During a recent field trial, it was demonstrated that BSEM could successfully identify the oil-water contact in the water-injection zone of a carbonate reservoir. We review the BSEM methodology, and perform full-field BSEM modeling. The 3D resistivity models used in this study are based on dynamic reservoir simulations of CO2 injection into a saline reservoir. Although the electric field response at the earth's surface is low, we demonstrate that it can be accurately measured and processed with novel methods of noise cancellation and sufficient stacking over the period of monitoring to increase the signal-to-noise ratio for subsequent seismic- and well-constrained 3D inversion. For long-term or permanent monitoring, we discuss the deployment of novel electric field sensors with chemically inert electrodes that couple to earth in a capacitive manner. This capacitive coupling is a purely EM phenomenon, which, to first order, has no temperature, ionic concentration or corrosion effects and has unprecedented fidelity. This makes the capacitive E-field sensor ideal for CCS applications which require very stable operation over a wide range of ground temperature and moisture level variation, for extended periods of time.

Stable Aluminum Metal-Organic Frameworks (Al-MOFs) for Balanced CO2 and Water Selectivity.

PubMed

Li, Haiwei; Feng, Xiao; Ma, Dou; Zhang, Mengxi; Zhang, Yuanyuan; Liu, Yi; Zhang, Jinwei; Wang, Bo

2018-01-31

Three new Al-MOFs in the formation of [Al 4 (OH) 2 (OCH 3 ) 4 (OH-BDC) 3 ]·xH 2 O (BIT-72), [Al 4 (OH) 2 (OCH 3 ) 4 (CH 3 -BDC) 3 ]·xH 2 O (BIT-73) and {Al 4 (OH) 2 (OCH 3 ) 4 [(CH 3 ) 2 -BDC] 3 }·xH 2 O (BIT-74) have been synthesized by assembling Al 3+ ion with terephthalic acid ions decorated with monohydroxyl, monomethyl or dimethyl groups, respectively. All of these three MOFs exhibit high stability in boiling water and acidic conditions. Among them, BIT-72 shows the highest surface area of 1618 m 2 ·g -1 and IAST CO 2 /N 2 selectivity of 48, while BIT-73 and BIT-74 present moderate IAST CO 2 /N 2 selectivity and much lower H 2 O capacity below P/P 0 = 0.3. The high CO 2 /N 2 selectivity together with alleviative H 2 O sorption at low water relative pressure may provide promising potential in postcombustion CO 2 capture.

Monodisperse Metal-Organic Framework Nanospheres with Encapsulated Core-Shell Nanoparticles Pt/Au@Pd@{Co2(oba)4(3-bpdh)2}4H2O for the Highly Selective Conversion of CO2 to CO.

PubMed

Zhao, Xi; Xu, Haitao; Wang, XiaoXiao; Zheng, Zhizhong; Xu, Zhenliang; Ge, Jianping

2018-05-02

A new microporous metal-organic framework (MOF) with formula {Co 2 (oba) 4 (3-bpdh) 2 }4H 2 O [oba = 4,4'-oxybis(benzoic acid); 3-bpdh = N, N'-bis-(1-pyridine-3-yl-ethylidene)-hydrazine] was assembled, and its morphology was found to undergo a microrod-to-nanosphere transformation with temperature variation. Core-shell Au@Pd functional nanoparticles (NPs) were successfully encapsulated in the center of the monodisperse nanospheres, and Pt NPs were well-dispersed and fully immobilized on the surface of Au@Pd@1Co to build the Pt/Au@Pd@1Co composites, which exhibited NPs catalytic activity for the reverse water gas shift reaction. The core-shell Au@Pd NPs in MOF significantly enchanced the CO selectivity of the catalyst, and the Pt NP loading on the surface of the nanosphere afforded a desirable CO 2 conversion.

Origin of carbon released from ecosystems affected by permafrost degradation in Northern Siberia

NASA Astrophysics Data System (ADS)

Gandois, L.; Hoyt, A.; Xu, X.; Hatte, C.; Teisserenc, R.; Tananaev, N.

2016-12-01

Permafrost soils and peatlands store half of the soil organic carbon stock worldwide, and are rapidly evolving as a result of permafrost thaw. Determining the origin (permafrost or recent photosynthesis) of carbon which is released to surface waters and the atmosphere is crucial to assess Arctic ecosystems' potential feedback to climate change. In order to evaluate it, we investigated the stable and radioactive content of carbon in solid organic matter, dissolved organic matter (DOM) and dissolved CO2 and CH4 in a discontinuous permafrost area of Siberia affected by permafrost degradation (Igarka, Graviyka catchment (67°27'11''N, 86°32'07''E)). We collected samples from the active layer, permafrost, surface water and bubbles from thermokarst lakes. We further investigated DOM and dissolved CO2 and CH4 in porewater profiles, streams and the catchment outlet. In thermokarst lakes, DOM of surface water as well as CO2 and CH4 from bubbles from lake sediments predominantly originate from modern carbon. In two locations, CO2 and CH4 from bubbles have relatively low 14C contents, with ages greater than 700 yr BP, but still younger that what was previously reported in Eastern Siberia. In all samples the Δ14C of CH4 and CO2 were strongly correlated, with CH4 being consistently older than CO2, indicating strong interrelation between CO2 and CH4 cycles. In our study, permafrost influenced CO2 and CH4 is found in small ponds where palsa collapse and the resulting bank erosion has mobilized sequestered carbon. In peatland porewater, the Δ14C of DOM, CO2 and CH4 increases with depth (DOM: 1385 ±45 yr BP at 2m), indicating a contribution from Holocene peatlands affected by permafrost. In deep layers, CO2 reduction is the dominant pathway of CH4 production, whereas acetate fermentation dominates in thermokarst lakes. In summary, the majority of dissolved CO2 and CH4 analyzed from thermokarst lakes and degraded peatlands is modern and originates from recently fixed carbon. Additionally, the DOM exported in small streams draining peatlands is also modern. However, at the catchment scale, an additional contribution from deep groundwater or thawing permafrost results in an intermediate Δ14C of DOM (300-400 yr BP) at the outlet of the Graviyka River.

A multi-decade record of high-quality fCO2 data in version 3 of the Surface Ocean CO2 Atlas (SOCAT)

USGS Publications Warehouse

Bakker, Dorothee; Landa, Camilla S.; Pfeil, Benjamin; Metzl, Nicolas; O’Brien, Kevin; Olsen, Are; Smith, Karl; Cosca, Cathy; Harasawa, Sumiko; Nakaoka, Shin-ichiro; Jones, Stephen; Nojiri, Yukihiro; Steinhoff, Tobias; Sweeney, Colm; Schuster, Ute; Takahashi, Taro; Tilbrook, Bronte; Wada, Chisato; Wanninkhof, Rik; Alin, Simone R.; Balestrini, Carlos F.; Barbero, Leticia; Bates, Nicholas; Bianchi, Alejandro A.; Bonou, Frédéric; Boutin, Jacqueline; Bozec, Yann; Burger, Eugene F.; Cai, Wei-Jun; Castle, Robert D.; Chen, Liqi; Chierici, Melissa; Currie, Kim; Evans, Wiley; Featherstone, Charles; Feely, Richard; Fransson, Agneta; Goyet, Catherine; Greenwood, Naomi; Gregor, Luke; Hankin, Steven C.; Hardman-Mountford, Nick J.; Harlay, Jérôme; Hauck, Judith; Hoppema, Mario; Humphreys, Matthew P.; Hunt, Christopher W.; Huss, Betty; Ibánhez, J. Severino P.; Johannessen, Truls; Keeling, Ralph F.; Kitidis, Vassilis; Körtzinger, Arne; Kozyr, Alex; Krasakopoulou, Evangelia; Kuwata, Akira; Landschützer, Peter; Lauvset, Siv K.; Lefèvre, Nathalie; Lo Monaco, Claire; Manke, Ansley; Mathis, Jeremy T.; Merlivat, Liliane; Millero, Frank J.; Monteiro, Pedro M. S.; Munro, David R.; Murata, Akihiko; Newberger, Timothy; Omar, Abdirahman M.; Ono, Tsuneo; Paterson, Kristina; Pearce, David; Pierrot, Denis; Robbins, Lisa L.; Saito, Shu; Salisbury, Joe; Schlitzer, Reiner; Schneider, Bernd; Schweitzer, Roland; Sieger, Rainer; Skjelvan, Ingunn; Sullivan, Kevin F.; Sutherland, Stewart C.; Sutton, Adrienne J.; Tadokoro, Kazuaki; Telszewski, Maciej; Tuma, Matthias; van Heuven, Steven M. A. C.; Vandemark, Douglas; Ward, Brian; Watson, Andrew J.; Xu, Suqing

2016-01-01

The Surface Ocean CO2 Atlas (SOCAT) is a synthesis of quality-controlled f CO2 (fugacity of carbon dioxide) values for the global surface oceans and coastal seas with regular updates. Version 3 of SOCAT has 14.7 million f CO2 values from 3646 data sets covering the years 1957 to 2014. This latest version has an additional 4.6 million f CO2 values relative to version 2 and extends the record from 2011 to 2014. Version 3 also significantly increases the data availability for 2005 to 2013. SOCAT has an average of approximately 1.2 million surface water f CO2 values per year for the years 2006 to 2012. Quality and documentation of the data has improved. A new feature is the data set quality control (QC) flag of E for data from alternative sensors and platforms. The accuracy of surface water f CO2 has been defined for all data set QC flags. Automated range checking has been carried out for all data sets during their upload into SOCAT. The upgrade of the interactive Data Set Viewer (previously known as the Cruise Data Viewer) allows better interrogation of the SOCAT data collection and rapid creation of high-quality figures for scientific presentations. Automated data upload has been launched for version 4 and will enable more frequent SOCAT releases in the future. High-profile scientific applications of SOCAT include quantification of the ocean sink for atmospheric carbon dioxide and its long-term variation, detection of ocean acidification, as well as evaluation of coupled-climate and ocean-only biogeochemical models. Users of SOCAT data products are urged to acknowledge the contribution of data providers, as stated in the SOCAT Fair Data Use Statement. This ESSD (Earth System Science Data) “living data” publication documents the methods and data sets used for the assembly of this new version of the SOCAT data collection and compares these with those used for earlier versions of the data collection (Pfeil et al., 2013; Sabine et al., 2013; Bakker et al., 2014). 

The effects of phosphorus additions on the sedimentation of contaminants in a uranium mine pit-lake.

PubMed

Dessouki, Tarik C E; Hudson, Jeff J; Neal, Brian R; Bogard, Matthew J

2005-08-01

We investigated the usefulness of phytoplankton for the removal of surface water contaminants. Nine large mesocosms (92.2m(3)) were suspended in the flooded DJX uranium pit at Cluff Lake (Saskatchewan, Canada), and filled with highly contaminated mine water. Each mesocosm was fertilized with a different amount of phosphorus throughout the 35 day experiment to stimulate phytoplankton growth, and to create a range in phosphorus load (g) to examine how contaminants may be affected by different nutrient regimes. Algal growth was rapid in fertilized mesocosms (as demonstrated by chlorophyll a profiles). As phosphorus loads increased there were significant declines (p<0.05) in the surface water concentrations of As, Co, Cu, Mn, Ni, and Zn. This decline was near significant for uranium (p=0.065). The surface water concentrations of Ra-226, Mo, and Se showed no relationship to phosphorus load. Contaminant concentrations in sediment traps suspended at the bottom of each mesocosm generally showed the opposite trend to that observed in the surface water, with most contaminants (As, Co, Cu, Mn, Ni, Ra-226, U, and Zn) exhibiting a significant positive relationship (p<0.05) with phosphorus load. Selenium and Mo did not respond to nutrient treatments. Our results suggest that phytoremediation has the potential to lower many surface water contaminants through the sedimentation of phytoplankton. Based on our results, we estimate that the Saskatchewan Surface Water Quality Objectives (SSWQO) for DJX pit would be met in approximately 45 weeks for Co, 65 weeks for Ni, 15 weeks for U, and 5 weeks for Zn.

Organics and other molecules in the surfaces of Callisto and Ganymede.

PubMed

McCord, T B; Carlson, R W; Smythe, W D; Hansen, G B; Clark, R N; Hibbitts, C A; Fanale, F P; Granahan, J C; Segura, M; Matson, D L; Johnson, T V; Martin, P D

1997-10-10

Five absorption features are reported at wavelengths of 3.4, 3.88, 4. 05, 4.25, and 4.57 micrometers in the surface materials of the Galilean satellites Callisto and Ganymede from analysis of reflectance spectra returned by the Galileo mission near-infrared mapping spectrometer. Candidate materials include CO2, organic materials (such as tholins containing C(triple bond)N and C-H), SO2, and compounds containing an SH-functional group; CO2, SO2, and perhaps cyanogen [(CN)2] may be present within the surface material itself as collections of a few molecules each. The spectra indicate that the primary surface constituents are water ice and hydrated minerals.

Using Iron-Manganese Co-Oxide Filter Film to Remove Ammonium from Surface Water

PubMed Central

Zhang, Ruifeng; Huang, Tinglin; Wen, Gang; Chen, Yongpan; Cao, Xin; Zhang, Beibei

2017-01-01

An iron-manganese co-oxide filter film (MeOx) has been proven to be a good catalyst for the chemical catalytic oxidation of ammonium in groundwater. Compared with groundwater, surface water is generally used more widely and has characteristics that make ammonium removal more difficult. In this study, MeOx was used to remove ammonium from surface water. It indicated that the average ammonium removal efficiency of MeOx was greater than 90%, even though the water quality changed dramatically and the water temperature was reduced to about 6–8 °C. Then, through inactivating microorganisms, it showed that the removal capability of MeOx included both biological (accounted for about 41.05%) and chemical catalytic oxidation and chemical catalytic oxidation (accounted for about 58.95%). The investigation of the characterizations suggested that MeOx was formed by abiotic ways and the main elements on the surface of MeOx were distributed homogenously. The analysis of the catalytic oxidation process indicated that ammonia nitrogen may interact with MeOx as both ammonia molecules and ammonium ions and the active species of O2 were possibly •O and O2−. PMID:28753939

Consequences of CO2-rich water intrusion into the Critical Zone

NASA Astrophysics Data System (ADS)

Gal, Frédérick; Lions, Julie

2017-04-01

From a geochemical point of view, the sensitivity of the Critical Zone to hazards is not only linked to its proximity to the surface. It may also be linked to - albeit less common - intrusion of upward migrating fluids. One of the hazard scenarios to observe these pathways in surface environments is the occurrence of CO2-rich fluid leakage from deeper horizons and especially leakage from reservoir in the case of underground storage such as Carbon Storage applications. Much effort is done to prevent this risk but it necessary to consider the mitigation of this leak to insure safe storage. Numerous active or planned CO2 storage sites belong to large sedimentary basins. In that perspective, a CO2 injection has been performed in a multi-layered - carbonated aquifer (Beauce aquifer) from the Paris basin as this basin has been considered for such applications. The aquifer mineralogy of the targeted site is dominated by calcite (95 to 98%) with traces of quartz and clay minerals. Around 10,000 liters of CO2 were injected at 50 m depth during a series of gaseous pulsed injections for 5 days. After 3 days of incubation in the aquifer, the groundwater was pumped during 5 days allowing the recovery of 140 m3 of backward water. Physico-chemical parameters, major and trace elements concentrations and dissolved CO2 concentrations were monitored to evaluate water-rock interactions occurring within the aquifer and impacts onto water quality. Main changes that were observed during the CO2 release are in good agreement with results from previous experiments performed worldwide. A strong decrease of the pH value (2 units), a rise of the electrical conductivity (2 fold) and changes in the redox conditions (from oxidising to less oxidising) are monitored few hours after the initiation of the pumping. The dissolution of CO2 induces a drop of pH that favours water-rock interaction processes. The kinetic of reactions appears to be dominated by the dissolution of carbonate, mainly calcite, and probably by desorption processes onto clay minerals. Thus higher concentrations in HCO3 (+225%), Ca (+95%), Mg (+45%), Na (+14%) and SiO2 (+11%) as major elements and in Sr, Mn, Ba, B, As or Li as trace elements (2 to 3 fold increase) were monitored. Congruent rise in the concentration in dissolved CO2 is also observed. Nonetheless, the effects onto water physico-chemical parameters and water chemistry are transient and vanished in few days (4-5) when pumping is done. In the case of a punctual leakage event, even if pumping was not performed, natural flow of the water will also have induced natural attenuation and progressive vanish of anomalies. From a site management perspective, this suggests that sudden and time limited events may not be noticeable in the near surface if the monitoring locations are located remotely from the source. This highlights the need to have extensive site characterization prior setting a storage site.

Temperature, grain size, and CO2-clathrate hydrates maps of Enceladus and Dione

NASA Astrophysics Data System (ADS)

Taffin, C.; Combe, J.; Grasset, O.; Le Menn, E.; McCord, T. B.; Bollengier, O.; Oancea, A.; Giraud, M.; Tobie, G.

2011-12-01

Reflectance spectra of water ice have absorption bands at 1.30 and 1.50 μm that depend on temperature and grain size. Band shape measurements can be used to characterize the surface properties of icy celestial bodies1,2,3. Moreover, CO2-clathrates have a diagnostic and unique absorption band at 2.7 μm. Mapping of these properties and components of the surface can be used to better constrain the internal activity and surface tectonics. We present an analysis of the 1.30 and 1.50 μm water ice absorption bands and the 2.7-μm CO2-clathrates absorption band in reflectance spectra from VIMS on Cassini in order to understand the geological history of the South Pole of Enceladus and an equatorial area of Dione. We have synthesized samples of pure ice Ih grains and acquired reflectance spectra between 1 and 5 μm with a Nicolet Fourier Transform spectrometer to investigate the characteristics of near-IR spectra using temperature and pressure ranges relevant for the icy satellites of Saturn. Forty-seven spectra of crystalline water ice have been acquired. We have derived two empirical laws to calculate temperature and grain size from pure crystalline water ice spectrum4. We have also synthesized samples of CO2-clathrates and acquired reflectance spectra for the band. These two spectra have been used as end-member. A linear sum is computed using the end-member spectra: [CRF×(clathrate)+(1-CRF)×(pure water ice)], where CRF is the to-be-determined clathrate ratio factor, 'clathrate' and 'pure water ice' are the reference spectra (end-member). Figure 1 shows results on one equatorial area where craters and ridges can be observed. Temperature appears to be higher besides the ridges (Figure 1f), but this may indicate that water ice is amorphous, which results in overestimating the temperature. Along the ridge, grain size is larger (Figure 1e), and CO2-clathrates have higher concentration near the ridges (Figure 1d). All these clues indicate a recent activity that we are planning to interpret in more details. 1)Fink and Larson, Icarus, 1975. 2)Leto et al. Mem. S.A.It. Suppl. 2005. 3)Grundy, Icarus, 1999. 4)Taffin et al., PSS, 2011

Pleistocene atmospheric CO2 change linked to Southern Ocean nutrient utilization

NASA Astrophysics Data System (ADS)

Ziegler, M.; Diz, P.; Hall, I. R.; Zahn, R.

2011-12-01

Biological uptake of CO2 by the ocean and its subsequent storage in the abyss is intimately linked with the global carbon cycle and constitutes a significant climatic force1. The Southern Ocean is a particularly important region because its wind-driven upwelling regime brings CO2 laden abyssal waters to the surface that exchange CO2 with the atmosphere. The Subantarctic Zone (SAZ) is a CO2 sink and also drives global primary productivity as unutilized nutrients, advected with surface waters from the south, are exported via Subantarctic Mode Water (SAMW) as preformed nutrients to the low latitudes where they fuel the biological pump in upwelling areas. Recent model estimates suggest that up to 40 ppm of the total 100 ppm atmospheric pCO2 reduction during the last ice age were driven by increased nutrient utilization in the SAZ and associated feedbacks on the deep ocean alkalinity. Micro-nutrient fertilization by iron (Fe), contained in the airborne dust flux to the SAZ, is considered to be the prime factor that stimulated this elevated photosynthetic activity thus enhancing nutrient utilization. We present a millennial-scale record of the vertical stable carbon isotope gradient between subsurface and deep water (Δδ13C) in the SAZ spanning the past 350,000 years. The Δδ13C gradient, derived from planktonic and benthic foraminifera, reflects the efficiency of biological pump and is highly correlated (rxy = -0.67 with 95% confidence interval [0.63; 0.71], n=874) with the record of dust flux preserved in Antarctic ice cores6. This strongly suggests that nutrient utilization in the SAZ was dynamically coupled to dust-induced Fe fertilization across both glacial-interglacial and faster millennial timescales. In concert with ventilation changes of the deep Southern Ocean this drove ocean-atmosphere CO2 exchange and, ultimately, atmospheric pCO2 variability during the late Pleistocene.

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

PubMed

Krauze, Patryk; Kämpf, Horst; Horn, Fabian; Liu, Qi; Voropaev, Andrey; Wagner, Dirk; Alawi, Mashal

2017-01-01

The Cheb Basin (NW Bohemia, Czech Republic) is a shallow, neogene intracontinental basin. It is a non-volcanic region which features frequent earthquake swarms and large-scale diffuse degassing of mantle-derived CO 2 at the surface that occurs in the form of CO 2 -rich mineral springs and wet and dry mofettes. So far, the influence of CO 2 degassing onto the microbial communities has been studied for soil environments, but not for aquatic systems. We hypothesized, that deep-trenching CO 2 conduits interconnect the subsurface with the surface. This admixture of deep thermal fluids should be reflected in geochemical parameters and in the microbial community compositions. In the present study four mineral water springs and two wet mofettes were investigated through an interdisciplinary survey. The waters were acidic and differed in terms of organic carbon and anion/cation concentrations. Element geochemical and isotope analyses of fluid components were used to verify the origin of the fluids. Prokaryotic communities were characterized through quantitative PCR and Illumina 16S rRNA gene sequencing. Putative chemolithotrophic, anaerobic and microaerophilic organisms connected to sulfur (e.g., Sulfuricurvum, Sulfurimonas ) and iron (e.g., Gallionella, Sideroxydans ) cycling shaped the core community. Additionally, CO 2 -influenced waters form an ecosystem containing many taxa that are usually found in marine or terrestrial subsurface ecosystems. Multivariate statistics highlighted the influence of environmental parameters such as pH, Fe 2+ concentration and conductivity on species distribution. The hydrochemical and microbiological survey introduces a new perspective on mofettes. Our results support that mofettes are either analogs or rather windows into the deep biosphere and furthermore enable access to deeply buried paleo-sediments.

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

PubMed Central

Krauze, Patryk; Kämpf, Horst; Horn, Fabian; Liu, Qi; Voropaev, Andrey; Wagner, Dirk; Alawi, Mashal

2017-01-01

The Cheb Basin (NW Bohemia, Czech Republic) is a shallow, neogene intracontinental basin. It is a non-volcanic region which features frequent earthquake swarms and large-scale diffuse degassing of mantle-derived CO2 at the surface that occurs in the form of CO2-rich mineral springs and wet and dry mofettes. So far, the influence of CO2 degassing onto the microbial communities has been studied for soil environments, but not for aquatic systems. We hypothesized, that deep-trenching CO2 conduits interconnect the subsurface with the surface. This admixture of deep thermal fluids should be reflected in geochemical parameters and in the microbial community compositions. In the present study four mineral water springs and two wet mofettes were investigated through an interdisciplinary survey. The waters were acidic and differed in terms of organic carbon and anion/cation concentrations. Element geochemical and isotope analyses of fluid components were used to verify the origin of the fluids. Prokaryotic communities were characterized through quantitative PCR and Illumina 16S rRNA gene sequencing. Putative chemolithotrophic, anaerobic and microaerophilic organisms connected to sulfur (e.g., Sulfuricurvum, Sulfurimonas) and iron (e.g., Gallionella, Sideroxydans) cycling shaped the core community. Additionally, CO2-influenced waters form an ecosystem containing many taxa that are usually found in marine or terrestrial subsurface ecosystems. Multivariate statistics highlighted the influence of environmental parameters such as pH, Fe2+ concentration and conductivity on species distribution. The hydrochemical and microbiological survey introduces a new perspective on mofettes. Our results support that mofettes are either analogs or rather windows into the deep biosphere and furthermore enable access to deeply buried paleo-sediments. PMID:29321765

Behavior of water in supercritical CO2: adsorption and capillary condensation in porous media

NASA Astrophysics Data System (ADS)

Heath, J. E.; Bryan, C. R.; Dewers, T. A.; Wang, Y.

2011-12-01

The chemical potential of water in supercritical CO2 (scCO2) may play an important role in water adsorption, capillary condensation, and evaporation under partially saturated conditions at geologic CO2 storage sites, especially if initially anhydrous CO2 is injected. Such processes may affect residual water saturations, relative permeability, shrink/swell of clays, and colloidal transport. We have developed a thermodynamic model of water or brine film thickness as a function of water relative humidity in scCO2. The model is based on investigations of liquid water configuration in the vadose zone and uses the augmented Young-Laplace equation, which incorporates both adsorptive and capillary components. The adsorptive component is based on the concept of disjoining pressure, which reflects force per area normal to the solid and water/brine-scCO2 interfaces. The disjoining pressure includes van der Waals, electrostatic, and structural interactions. The van der Waals term includes the effects of mutual dissolution of CO2 and water in the two fluid phases on partial molar volumes, dielectric coefficients, and refractive indices. Our approach treats the two interfaces as asymmetric surfaces in terms of charge densities and electrostatic potentials. We use the disjoining pressure isotherm to evaluate the type of wetting (e.g., total or partial wetting) for common reservoir and caprock minerals and kerogen. The capillary component incorporates water activity and is applied to simple pore geometries with slits and corners. Finally, we compare results of the model to a companion study by the coauthors on measurement of water adsorption to mineral phases using a quartz-crystal microbalance. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

Cosmic ion bombardment of the icy moons of Jupiter

NASA Astrophysics Data System (ADS)

Strazzulla, G.

2011-05-01

A large number of experiments have been performed in many laboratories in the world with the aim to investigate the physico-chemical effects induced by fast ions irradiating astrophysical relevant materials. The laboratory in Catania (Italy) has given a contribution to some experimental works. In this paper I review the results of two class of experiments performed by the Catania group, namely implantation of reactive (H+, C+, N+, O+ and S+) ions in ices and the ion irradiation induced synthesis of molecules at the interface between water ice and carbonaceous or sulfurous solid materials. The results, discussed in the light of some questions concerning the surfaces of the Galilean moons, contribute to understand whether minor molecular species (CO2, SO2, H2SO4, etc.) observed on those objects are endogenic i.e. native from the satellite or are produced by exogenic processes, such as ion implantation.The results indicate that:C-ion implantation is not the dominant formation mechanism of CO2 on Europa, Ganimede and Callisto.Implantation of sulfur ions into water ice produces hydrated sulfuric acid with high efficiency such to give a very important contribution to the sulfur cycle on the surface of Europa and other satellites.Implantation of protons into carbon dioxide produces some species containing the projectile (H2CO3, and O-H in poly-water).Implantation of protons into sulfur dioxide produces SO3, polymers, and O3 but not H-S bonds.Water ice has been deposited on refractory carbonaceous materials: a general finding is the formation of a noteworthy quantity of CO2. We suggest that this is the primary mechanism to explain the presence of carbon dioxide on the surfaces of the Galilean satellites.Water ice has been deposited on refractory sulfurous materials originating from SO2 or H2S irradiation. No evidence for an efficient synthesis of SO2 has been found.

Surface Ocean pCO2 Seasonality and Sea-Air CO2 Flux Estimates for the North American East Coast

NASA Technical Reports Server (NTRS)

Signorini, Sergio; Mannino, Antonio; Najjar, Raymond G., Jr.; Friedrichs, Marjorie A. M.; Cai, Wei-Jun; Salisbury, Joe; Wang, Zhaohui Aleck; Thomas, Helmuth; Shadwick, Elizabeth

2013-01-01

Underway and in situ observations of surface ocean pCO2, combined with satellite data, were used to develop pCO2 regional algorithms to analyze the seasonal and interannual variability of surface ocean pCO2 and sea-air CO2 flux for five physically and biologically distinct regions of the eastern North American continental shelf: the South Atlantic Bight (SAB), the Mid-Atlantic Bight (MAB), the Gulf of Maine (GoM), Nantucket Shoals and Georges Bank (NS+GB), and the Scotian Shelf (SS). Temperature and dissolved inorganic carbon variability are the most influential factors driving the seasonality of pCO2. Estimates of the sea-air CO2 flux were derived from the available pCO2 data, as well as from the pCO2 reconstructed by the algorithm. Two different gas exchange parameterizations were used. The SS, GB+NS, MAB, and SAB regions are net sinks of atmospheric CO2 while the GoM is a weak source. The estimates vary depending on the use of surface ocean pCO2 from the data or algorithm, as well as with the use of the two different gas exchange parameterizations. Most of the regional estimates are in general agreement with previous studies when the range of uncertainty and interannual variability are taken into account. According to the algorithm, the average annual uptake of atmospheric CO2 by eastern North American continental shelf waters is found to be between 3.4 and 5.4 Tg C/yr (areal average of 0.7 to 1.0 mol CO2 /sq m/yr) over the period 2003-2010.

Quantifying the drivers of ocean-atmosphere CO2 fluxes

NASA Astrophysics Data System (ADS)

Lauderdale, Jonathan M.; Dutkiewicz, Stephanie; Williams, Richard G.; Follows, Michael J.

2016-07-01

A mechanistic framework for quantitatively mapping the regional drivers of air-sea CO2 fluxes at a global scale is developed. The framework evaluates the interplay between (1) surface heat and freshwater fluxes that influence the potential saturated carbon concentration, which depends on changes in sea surface temperature, salinity and alkalinity, (2) a residual, disequilibrium flux influenced by upwelling and entrainment of remineralized carbon- and nutrient-rich waters from the ocean interior, as well as rapid subduction of surface waters, (3) carbon uptake and export by biological activity as both soft tissue and carbonate, and (4) the effect on surface carbon concentrations due to freshwater precipitation or evaporation. In a steady state simulation of a coarse-resolution ocean circulation and biogeochemistry model, the sum of the individually determined components is close to the known total flux of the simulation. The leading order balance, identified in different dynamical regimes, is between the CO2 fluxes driven by surface heat fluxes and a combination of biologically driven carbon uptake and disequilibrium-driven carbon outgassing. The framework is still able to reconstruct simulated fluxes when evaluated using monthly averaged data and takes a form that can be applied consistently in models of different complexity and observations of the ocean. In this way, the framework may reveal differences in the balance of drivers acting across an ensemble of climate model simulations or be applied to an analysis and interpretation of the observed, real-world air-sea flux of CO2.

Photocatalytic overall water splitting promoted by an α-β phase junction on Ga2O3.

PubMed

Wang, Xiang; Xu, Qian; Li, Mingrun; Shen, Shuai; Wang, Xiuli; Wang, Yaochuan; Feng, Zhaochi; Shi, Jingying; Han, Hongxian; Li, Can

2012-12-21

When Alpha met Beta: a tuneable α-β surface phase junction on Ga(2)O(3) can significantly improve photocatalytic overall water splitting into H(2) and O(2) over individual α-Ga(2)O(3) or β-Ga(2)O(3) surface phases. This enhanced photocatalytic performance is mainly attributed to the efficient charge separation and transfer across the α-β phase junction. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reaction mechanism of WGS and PROX reactions catalyzed by Pt/oxide catalysts revealed by an FeO(111)/Pt(111) inverse model catalyst.

PubMed

Xu, Lingshun; Wu, Zongfang; Jin, Yuekang; Ma, Yunsheng; Huang, Weixin

2013-08-07

We have employed XPS and TDS to study the adsorption and surface reactions of H2O, CO and HCOOH on an FeO(111)/Pt(111) inverse model catalyst. The FeO(111)-Pt(111) interface of the FeO(111)/Pt(111) inverse model catalyst exposes coordination-unsaturated Fe(II) cations (Fe(II)CUS) and the Fe(II)CUS cations are capable of modifying the reactivity of neighbouring Pt sites. Water facilely dissociates on the Fe(II)CUS cations at the FeO(111)-Pt(111) interface to form hydroxyls that react to form both water and H2 upon heating. Hydroxyls on the Fe(II)CUS cations can react with CO(a) on the neighbouring Pt(111) sites to produce CO2 at low temperatures. Hydroxyls act as the co-catalyst in the CO oxidation by hydroxyls to CO2 (PROX reaction), while they act as one of the reactants in the CO oxidation by hydroxyls to CO2 and H2 (WGS reaction), and the recombinative reaction of hydroxyls to produce H2 is the rate-limiting step in the WGS reaction. A comparison of reaction behaviors between the interfacial CO(a) + OH reaction and the formate decomposition reaction suggest that formate is the likely surface intermediate of the CO(a) + OH reaction. These results provide some solid experimental evidence for the associative reaction mechanism of WGS and PROX reactions catalyzed by Pt/oxide catalysts.

Carbonate saturation state of surface waters in the Ross Sea and Southern Ocean: controls and implications for the onset of aragonite undersaturation

NASA Astrophysics Data System (ADS)

DeJong, H. B.; Dunbar, R. B.; Mucciarone, D. A.; Koweek, D.

2016-02-01

Predicting when surface waters of the Ross Sea and Southern Ocean will become undersaturated with respect to biogenic carbonate minerals is challenging in part due to the lack of baseline high resolution carbon system data. Here we present 1700 surface total alkalinity measurements from the Ross Sea and along a transect between the Ross Sea and southern Chile from the austral autumn (February-March 2013). We calculate the saturation state of aragonite (ΩAr) and calcite (ΩCa) using measured total alkalinity and pCO2. In the Ross Sea and south of the Polar Front, variability in carbonate saturation state (Ω) is mainly driven by algal photosynthesis. Freshwater dilution and calcification have minimal influence on Ω variability. We estimate an early spring surface water ΩAr value of 1.2 for the Ross Sea using a total alkalinity-salinity relationship and historical pCO2 measurements. Our results suggest that the Ross Sea is not likely to become undersaturated with respect to aragonite until the year 2070.

Reactivity of formic acid (HCOOD and DCOOH) at uranium and UO 2.0 surfaces

NASA Astrophysics Data System (ADS)

Manner, William L.; Lloyd, Jane A.; Paffett, Mark T.

1999-10-01

Interactions of DCOOH and HCOOD with uranium and UO 2.0 surfaces have been examined using surface-specific techniques of thermal desorption mass spectroscopy (TDMS), X-ray photoelectron spectroscopy (XPS), and static secondary ion mass spectroscopy (SSIMS). On the clean uranium surface, formate is the predominant product following formic acid adsorption at 100 K. A wide range of products is observed after annealing to 200 K, including formate, hydroxyl, O ads, and H ads (D ads) groups. Adsorbed formate decomposes by 300 K increasing the concentration of the remaining surface products. Surface-adsorbed carbon following TDMS measurements remains as the carbide, as indicated from XPS and SSIMS measurements. The only gaseous species created in high yields from the clean surface upon annealing are H 2, HD, and D 2. On the oxide surface (UO 2.0), adsorbed formate groups are more stable toward dissociation in comparison with the clean uranium surface. Between 100 and 300 K the predominant species on the UO 2.0 surface are surface formate and hydroxyl groups. Hydroxyl groups react between 300 and 350 K to release water from the surface. Adsorbed formate groups decompose between 400 and 500 K to release CO and H 2CO (D 2CO) groups from the oxide surface. Carbon was not detected on the oxide surface by XPS or SSIMS after annealing to 500 K, indicating that all carbon-containing species either desorb in the form of CO-containing products or migrate into the surface.

Dryland Flood-Irrigation and its Impact on CO2 Production and the Accumulation of Pedogenic Carbonate in West Texas

NASA Astrophysics Data System (ADS)

Ortiz, A. C.; Jin, L.

2016-12-01

Agricultural fields in drylands are intensively irrigated. Indeed, pecan orchards at the El Paso, TX region are flooded with over one meter of water per growing season. The waters are usually oversaturated in calcite (CaCO3) and continuous evapotranspiration drives CaCO3 precipitation, releasing CO2. As such, the loading of CaCO3 through flood irrigation in drylands impacts Ca and C cycles greatly. We characterized soil, soil gas and soil water samples to quantify rates of pedogenic carbonate accumulation and CO2 release, identify the sources of C and Ca in pedogenic carbonates, and investigate kinetic and environmental controls of CaCO3 formation. Simple calculations show that up to 112000kg/km2/yr of Ca is loaded onto the fields by irrigation, evidenced by high water-soluble and acid-leachable Ca in soils, especially in clayey soils. We used 87Sr/86Sr ratios to quantify the relative importance of different Ca end-members including flood irrigation. Data show that water-soluble soil leachates have similar 87Sr/86Sr ratios as irrigation waters at depth, but lighter signatures at surface, probably due dust and fertilizer inputs. We measured daily soil-atmosphere CO2 efflux, δ13CCO2 and concentrations of CO2 gas samples at different soil depths between two irrigation events and at two sites with sandy versus clayey soils. These data help determine if sources of soil CO2 change with depth, irrigation event and if CO2 transport is controlled by texture. Correlations of δ13CCO2 and soil CO2 concentrations indicate mixing of organically respired, atmospheric and CaCO3-derived CO2. We found co-variation of δ13CCO2 and soil CO2 with time, where soil CO2 became heavier in carbon isotopes and more abundant in concentrations, illustrating shifts from soil respired CO2, characterized by lighter C, to increased proportions of CaCO3-derived CO2 with heavier C. Efflux data show peak values as soils dried, indicating supersaturation of soil waters and precipitation of pedogenic calcite. This efflux is also controlled by soil texture, as sandy soils emitted more CO2 than clayey soils, even if fine-textured soils contained more CaCO3. These findings can significantly impact CO2 modeling and can aid in extrapolating to larger scales.

Modeling CO2 degassing and pH in a stream-aquifer system

USGS Publications Warehouse

Choi, J.; Hulseapple, S.M.; Conklin, M.H.; Harvey, J.W.

1998-01-01

Pinal Creek, Arizona receives an inflow of ground water with high dissolved inorganic carbon (57-75 mg/l) and low pH (5.8-6.3). There is an observed increase of in-stream pH from approximately 6.0-7.8 over the 3 km downstream of the point of groundwater inflow. We hypothesized that CO2 gas-exchange was the most important factor causing the pH increase in this stream-aquifer system. An existing transport model, for coupled ground water-surface water systems (OTIS), was modified to include carbonate equilibria and CO2 degassing, used to simulate alkalinity, total dissolved inorganic carbon (C(T)), and pH in Pinal Creek. Because of the non-linear relation between pH and C(T), the modified transport model used the numerical iteration method to solve the non-linearity. The transport model parameters were determined by the injection of two tracers, bromide and propane. The resulting simulations of alkalinity, C(T) and pH reproduced, without fitting, the overall trends in downstream concentrations. A multi-parametric sensitivity analysis (MPSA) was used to identify the relative sensitivities of the predictions to six of the physical and chemical parameters used in the transport model. MPSA results implied that C(T) and pH in stream water were controlled by the mixing of ground water with stream water and CO2 degassing. The relative importance of these two processes varied spatially depending on the hydrologic conditions, such as stream flow velocity and whether a reach gained or lost stream water caused by the interaction with the ground water. The coupled transport model with CO2 degassing and generalized sensitivity analysis presented in this study can be applied to evaluate carbon transport and pH in other coupled stream-ground water systems.An existing transport model for coupled groundwater-surface water systems was modified to include carbonate equilibria and CO2 degassing. The modified model was used to simulate alkalinity, total dissolved inorganic carbon (CT) and pH in Pinal Creek. The model used the numerical iteration method to solve the nonlinear relation between pH and CT. A multi-parametric sensitivity analysis (MPSA) was used to identify the relative sensitivities of the predictions to six of the physical and chemical parameters used in the transport model. MPSA results implied that CT and pH in the stream water were controlled by the mixing of groundwater with stream water and CO2 degassing.

Characterization of Water and CO2 Adsorption by Stores 3A Desiccant Samples Using Thermal Gravimetric Analysis and Fourier Transform Infrared Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

RIVERA, DION A.; ALAM, M. KATHLEEN; MARTIN, LAURA

2003-02-01

Two lots of manufactured Type 3a zeolite samples were compared by TGA/IR analysis. The first lot, obtained from Davidson Chemical, a commercial vendor, was characterized during the previous study cycle for its water and water-plus-CO{sub 2} uptake in order to determine whether CO{sub 2} uptake prevented water adsorption by the zeolite. It was determined that CO{sub 2} did not hamper water adsorption using the Davidson zeolite. CO{sub 2} was found on the zeolite surface at dewpoints below -40 C, however it was found to be reversibly adsorbed. During the course of the previous studies, chemical analyses revealed that the Davidsonmore » 3a zeolite contained calcium in significant quantities, along with the traditional counterions potassium and sodium. Chemical analysis of a Type 3a zeolite sample retrieved from Kansas City (heretofore referred to as the ''Stores 3a'' sample) indicated that the Stores sample was a more traditional Type 3a zeolite, containing no calcium. TGA/IR studies this year focused on obtaining CO{sub 2} and water absorbance data from the Stores 3a zeolite. Within the Stores 3a sample, CO{sub 2} was found to be reversibly absorbed within the sample, but only at and below -60 C with 5% CO{sub 2} loading. The amount of CO{sub 2} observed eluting from the Stores zeolite at this condition was similar to what was observed from the Davidson zeolite sample but with a greater uncertainty in the measured value. The results of the Stores 3a studies are summarized within this report.« less

Carbon Fluxes in Dissolved and Gaseous Forms for a Restored Peatland in British Columbia, Canada

NASA Astrophysics Data System (ADS)

D'Acunha, B.; Johnson, M. S.; Lee, S. C.; Christen, A.

2016-12-01

Peatlands are wetlands where gross primary production exceeds organic matter decomposition causing an accumulation of partially decomposed matter, also called peat. These ecosystems can accumulate more carbon than tropical rainforests. However, dissolved and gaseous fluxes of carbon (as dissolved organic carbon (DOC), CO2 and methane (CH4)) must also be considered to determine if these ecosystems are net sinks or sources of greenhouse gases (GHGs) to the atmosphere, which depends in part on the environmental conditions and the state of the ecosystem. We conducted research in Burns Bog, Delta, BC, Canada, a raised domed peat bog located in the Fraser River Delta and one of the largest raised peat bogs on the west coast of the Americas, but which has been heavily impacted by a range of human activities. Currently, ecological restoration efforts are underway by a large-scale ditch blocking program, with the aim to re-establish a high water table. This is approached in partnership with research on the ecosystem services that the bog provides, including its role in a regional GHG inventory. Here we present data on ecosystem-scale fluxes of CO2 and CH4 determined by eddy covariance (EC) on a floating tower platform, and complementary data on (i) evasion fluxes of CO2, CH4 and nitrous oxide (N2O) from the water surface to the atmosphere, and (ii) the flux and composition of dissolved organic carbon in water draining Burns Bog. Concentrations of dissolved CO2, CH4 and N2O were determined by headspace equilibration, and evasion rates from the water surface were quantified and are used to estimate the role of the hydrosphere in the ecosystem-scale measurements. Water samples collected from five saturated areas in the flux tower footprint were analyzed for DOC concentrations and composition. Results indicated that, even though the whole system is a net C sink, the water surface behaved as a source of CO2 and CH4, and a sink for N2O throughout the study period. Drainage waters were high in DOC (> 30 mg L-1). DOC export was found to offset about 20% of the apparent net C uptake determined by EC, indicating that the EC system overestimates carbon accumulation by not accounting for DOC drainage.

Carbon dioxide partial pressure and 13C content of north temperate and boreal lakes at spring ice melt

USGS Publications Warehouse

Striegl, Robert G.; Kortelainen, Pirkko; Chanton, J.P.; Wickland, K.P.; Bugna, G.C.; Rantakari, M.

2001-01-01

Carbon dioxide (CO2) accumulates under lake ice in winter and degasses to the atmosphere after ice melt. This large springtime CO2 pulse is not typically considered in surface-atmosphere flux estimates, because most field studies have not sampled through ice during late winter. Measured CO2 partial pressure (pCO2) of lake surface water ranged from 8.6 to 4,290 Pa (85-4,230 ??atm) in 234 north temperate and boreal lakes prior to ice melt during 1998 and 1999. Only four lakes had surface pCO2 less than or equal to atmospheric pCO2, whereas 75% had pCO2 >5 times atmospheric. The ??13CDIC (DIC = ??CO2) of 142 of the lakes ranged from -26.28??? to +0.95.???. Lakes with the greatest pCO2 also had the lightest ??13CDIC, which indicates respiration as their primary CO2 source. Finnish lakes that received large amounts of dissolved organic carbon from surrounding peatlands had the greatest pCO2. Lakes set in noncarbonate till and bedrock in Minnesota and Wisconsin had the smallest pCO2 and the heaviest ??13CDIC, which indicates atmospheric and/or mineral sources of C for those lakes. Potential emissions for the period after ice melt were 2.36 ?? 1.44 mol CO2 m-2 for lakes with average pCO2 values and were as large as 13.7 ?? 8.4 mol CO2 m-2 for lakes with high pCO2 values.

Solubility of C-O-H volatiles in graphite-saturated martian basalts and application to martian atmospheric evolution

NASA Astrophysics Data System (ADS)

Stanley, B. D.; Hirschmann, M. M.; Withers, A. C.

2012-12-01

The modern martian atmosphere is thin, leading to surface conditions too cold to support liquid water. Yet, there is evidence of liquid surface water early in martian history that is commonly thought to require a thick CO2 atmosphere. Our previous work follows the analysis developed by Holloway and co-workers (Holloway et al. 1992; Holloway 1998), which predicts a linear relationship between CO2 and oxygen fugacity (fO2) in graphite-saturated silicate melts. At low oxygen fugacity, the solubility of CO2 in silicate melts is therefore very low. Such low calculated solubilities under reducing conditions lead to small fluxes of CO2 associated with martian magmatism, and therefore production of a thick volcanogenic CO2 atmosphere could require a prohibitively large volume of mantle-derived magma. The key assumption in these previous calculations is that the carbonate ion is the chief soluble C-O-H species. The results of the calculations would not be affected appreciably if molecular CO2, rather than carbonate ion, were an important species, but could be entirely different if there were other appreciable C-species such as CO, carbonyl (C=O) complexes, carbide (Si-C), or CH4. Clearly, graphite-saturated experiments are required to explore how much volcanogenic C may be degassed by reduced martian lavas. A series of piston-cylinder experiments were performed on synthetic martian starting materials over a range of oxygen fugacities (IW+2.3 to IW-0.9), and at pressures of 1-3 GPa and temperatures of 1340-1600 °C in Pt-graphite double capsules. CO2 contents in experimental glasses were determined using Fourier transform infrared spectroscopy (FTIR) and range from 0.0026-0.50 wt%. CO2 solubilities change by one order of magnitude with an order of magnitude change in oxygen fugacity, as predicted by previous work. Secondary ion mass spectrometry (SIMS) determinations of C contents in glasses range from 0.0131-0.2626 wt%. C contents determined by SIMS are consistently higher than CO2 contents determined by FTIR. This difference, termed excess C, is attributed to the presence of other reduced C-species, such as carbonyls and amides (which have C=O and N-H bonds), detected using FTIR in reduced graphite-saturated martian basalts. An atmosphere produced by degassing of magmas similar to this study would be richer in C-O-H species than previously modeled using only CO2 and could create a much warmer climate that stabilizes liquid water on the ancient martian surface.

Southern Ocean biogeochemical control of glacial/interglacial carbon dioxide change

NASA Astrophysics Data System (ADS)

Sigman, D. M.

2014-12-01

In the effort to explain the lower atmospheric CO2 concentrations observed during ice ages, two of the first hypotheses involved redistributing dissolved inorganic carbon (DIC) within the ocean. Broecker (1982) proposed a strengthening of the ocean's biological pump during ice ages, which increased the dissolved inorganic carbon gradient between the dark, voluminous ocean interior and the surface ocean's sun-lit, wind-mixed layer. Boyle (1988) proposed a deepening in the ocean interior's pool of DIC associated with organic carbon regeneration, with its concentration maximum shifting from intermediate to abyssal depths. While not irrefutable, evidence has arisen that these mechanisms can explain much of the ice age CO2 reduction and that both were activated by changes in the Southern Ocean. In the Antarctic Zone, reduced exchange of water between the surface and the underlying ocean sequestered more DIC in the ocean interior (the biological pump mechanism). Dust-borne iron fertilization of the Subantarctic surface lowered CO2 partly by the biological pump mechanism and partly by Boyle's carbon deepening. Each mechanism owes a part of its CO2 effect to a transient increase in seafloor calcium carbonate dissolution, which raised the ice age ocean's alkalinity, causing it to absorb more CO2. However, calcium carbonate cycling also sets limits on these mechanisms and their CO2 effects, such that the combination of Antarctic and Subantarctic changes is needed to achieve the full (80-100 ppm) ice age CO2 decline. Data suggest that these changes began at different phases in the development of the last ice age, 110 and 70 ka, respectively, explaining a 40 ppm CO2 drop at each time. We lack a robust understanding of the potential causes for both the implied reduction in Antarctic surface/deep exchange and the increase in Subantarctic dust supply during ice ages. Thus, even if the evidence for these Southern Ocean changes were to become incontrovertible, conceptual gaps stand in the way of a theory of glacial cycles that includes Southern Ocean-driven CO2 change. There are more compelling proposals for the causes of deglacial change, with a sharp reduction in North Atlantic deep water formation implicated as a trigger of increased surface/deep exchange in the Antarctic and the resulting release of CO2 to the atmosphere.

The effects of cooling systems on CO2-lased human enamel.

PubMed

Lian, H J; Lan, W H; Lin, C P

1996-12-01

The thermal effects on dentin during CO2 laser irradiation on human enamel were investigated. To simulate the clinical practice, two cooling methods (air and water spray) were applied immediately after laser exposure, whereas one group without cooling was served as control. Three hundred and sixty uniform tooth blocks were obtained from freshly extracted human third molars. Temperature change measurements were made via electrical thermocouple implanted within the tooth block 2 mm away from the enamel surface. Experimental treatments consisted of lasing without cooling, lasing with 0.5-ml/sec water cooling, and lasing with 15-psi air cooling. Our results indicated that (1) both air- and water-cooling groups could reduce temperature elevation significantly; (2) the larger power energy resulted in the higher temperature elevation. In conclusion, for CO2 laser irradiation on human enamel both water- and air-cooling methods may be effective on prevention of thermal damage of pulp.

The Role of CO2 Clouds on the Stability of the Early Mars Atmosphere Against Collapse

NASA Astrophysics Data System (ADS)

Kahre, Melinda A.; Haberle, Robert; Steakley, Kathryn; Murphy, Jim; Kling, Alexandre

2017-10-01

The early Mars atmosphere was likely significantly more massive than it is today, given the growing body of evidence that liquid water flowed on the surface early in the planet’s history. Although the CO2 inventory was likely larger in the past, there is much we still do not understand about the state of that CO2. As surface pressure increases, the temperature at which CO2 condenses also increases, making it more likely that CO2 ice would form and persist on the surface when the atmospheric mass increases. An atmosphere that is stable against collapse must contain enough energy, distributed globally, to prohibit the formation of permanents CO2 ice reservoirs that lead to collapse. The presence of the “faint young sun” compounds this issue. Previous global climate model (GCM) investigations show that atmospheres within specific ranges of obliquities and atmospheric masses are stable against collapse. We use the NASA Ames Mars GCM to expand on these works by focusing specifically on the role of CO2 clouds in atmospheric stability. Two end member simulations are executed, one that includes CO2 cloud formation and one that does not. The simulation that explicitly includes CO2 clouds is stable, while the simulation without CO2 clouds collapses into permanent surface CO2 reservoirs. In both cases, significant atmospheric condensation is occurring in the atmosphere throughout the year. In the case without CO2 clouds, all atmospheric condensation (even if it occurs at altitude) leads directly to the accumulation of surface ice, whereas in the case with CO2 clouds, there is a finite settling timescale for the cloud particles. Depending on this timescale and the local conditions, the cloud particles could stay aloft or sublimate as they fall toward the surface. Thus, the striking difference between these two cases illustrates the important role of CO2 clouds. We plan to conduct and present further simulations to better understand how atmospheric stability depends on the details of CO2 cloud microphysical processes and assumptions.

Chemical and biological impacts of ocean acidification along the west coast of North America

NASA Astrophysics Data System (ADS)

Feely, Richard A.; Alin, Simone R.; Carter, Brendan; Bednaršek, Nina; Hales, Burke; Chan, Francis; Hill, Tessa M.; Gaylord, Brian; Sanford, Eric; Byrne, Robert H.; Sabine, Christopher L.; Greeley, Dana; Juranek, Lauren

2016-12-01

The continental shelf region off the west coast of North America is seasonally exposed to water with a low aragonite saturation state by coastal upwelling of CO2-rich waters. To date, the spatial and temporal distribution of anthropogenic CO2 (Canth) within the CO2-rich waters is largely unknown. Here we adapt the multiple linear regression approach to utilize the GO-SHIP Repeat Hydrography data from the northeast Pacific to establish an annually updated relationship between Canth and potential density. This relationship was then used with the NOAA Ocean Acidification Program West Coast Ocean Acidification (WCOA) cruise data sets from 2007, 2011, 2012, and 2013 to determine the spatial variations of Canth in the upwelled water. Our results show large spatial differences in Canth in surface waters along the coast, with the lowest values (37-55 μmol kg-1) in strong upwelling regions off southern Oregon and northern California and higher values (51-63 μmol kg-1) to the north and south of this region. Coastal dissolved inorganic carbon concentrations are also elevated due to a natural remineralized component (Cbio), which represents carbon accumulated through net respiration in the seawater that has not yet degassed to the atmosphere. Average surface Canth is almost twice the surface remineralized component. In contrast, Canth is only about one third and one fifth of the remineralized component at 50 m and 100 m depth, respectively. Uptake of Canth has caused the aragonite saturation horizon to shoal by approximately 30-50 m since the preindustrial period so that undersaturated waters are well within the regions of the continental shelf that affect the shell dissolution of living pteropods. Our data show that the most severe biological impacts occur in the nearshore waters, where corrosive waters are closest to the surface. Since the pre-industrial times, pteropod shell dissolution has, on average, increased approximately 19-26% in both nearshore and offshore waters.

Applications of low temperature CO-oxidation catalysts to breathable gases

NASA Technical Reports Server (NTRS)

Noordally, Ehsan; Richmond, John R.

1990-01-01

Modifications of tin oxide/precious metal catalysts described for use in CO2 lasers have also been developed for use in other applications; namely, as low temperature CO oxidation components in fire escape hoods/masks for mines, aircrafts, hotels, and offices and in sealed environments, such as hyperbaric chambers and submarines. Tin oxide/precious metal catalysts have been prepared on a variety of high surface area cloth substrates for application in fire escape hoods. These show high and stable CO oxidation capability (10 to the 4th power ppm CO reduced to 10 to the 1st power ppm CO) at GHSV of 37,000 h(-1) with water saturated inlet gas at body heat (37 C) and below. Water vapor plays an important role in the surface state/performance of tin oxide catalyst. Water-resistant formulations have been produced by the introduction of transition metal promoters. Tin oxide/precious metal catalysts have also been developed for CO oxidation in the North Sea diving environment. These are currently in use in a variety of hyperbaric chambers and diving vehicles. Ambient temperature operation and resistance to atmospheric water vapor have been demonstrated, and as a result, they offer a viable alternative to hopcalite or heated catalyst systems. A new range of non-tin oxide based low temperature CO oxidation catalysts is described. They are based on reducible metal oxides promoted with previous metals. Preliminary data on selected materials in the form of both cloth artifacts and shaped pellets are presented. They are expected to be applicable both to the breathable gas application area and to CO2 lasers.

Biofilm-like properties of the sea surface and predicted effects on air-sea CO2 exchange

NASA Astrophysics Data System (ADS)

Wurl, Oliver; Stolle, Christian; Van Thuoc, Chu; The Thu, Pham; Mari, Xavier

2016-05-01

Because the sea surface controls various interactions between the ocean and the atmosphere, it has a profound function for marine biogeochemistry and climate regulation. The sea surface is the gateway for the exchange of climate-relevant gases, heat and particles. Thus, in order to determine how the ocean and the atmosphere interact and respond to environmental changes on a global scale, the characterization and understanding of the sea surface are essential. The uppermost part of the water column is defined as the sea-surface microlayer and experiences strong spatial and temporal dynamics, mainly due to meteorological forcing. Wave-damped areas at the sea surface are caused by the accumulation of surface-active organic material and are defined as slicks. Natural slicks are observed frequently but their biogeochemical properties are poorly understood. In the present study, we found up to 40 times more transparent exopolymer particles (TEP), the foundation of any biofilm, in slicks compared to the underlying bulk water at multiple stations in the North Pacific, South China Sea, and Baltic Sea. We found a significant lower enrichment of TEP (up to 6) in non-slick sea surfaces compared to its underlying bulk water. Moreover, slicks were characterized by a large microbial biomass, another shared feature with conventional biofilms on solid surfaces. Compared to non-slick samples (avg. pairwise similarity of 70%), the community composition of bacteria in slicks was increasingly (avg. pairwise similarity of 45%) different from bulk water communities, indicating that the TEP-matrix creates specific environments for its inhabitants. We, therefore, conclude that slicks can feature biofilm-like properties with the excessive accumulation of particles and microbes. We also assessed the potential distribution and frequency of slick-formation in coastal and oceanic regions, and their effect on air-sea CO2 exchange based on literature data. We estimate that slicks can reduce CO2 fluxes by up to 15%, and, therefore, play important local and regional roles in regulating air-sea interactions.

A deep-time CO2 barometer based on triple oxygen isotope compositions of dinosaurian eggshell carbonate

NASA Astrophysics Data System (ADS)

Hu, H.; Passey, B. H.; Montanari, S.; Levin, N.; Li, S.

2013-12-01

Photochemical reactions in the stratosphere lead to mass independent fractionation of oxygen isotopes: oxygen exchange among O2, O3, and CO2 produces 17O-enriched O3 and CO2, and 17O-depleted O2. This effect increases with increasing atmospheric CO2 concentration, and thus the 17O anomaly of O2, Δ17O (O2), is reflective of pCO2. Animals incorporate this signal into body water via respiration, and minerals such as bioapatite and eggshell calcite forming in equilibrium with body water can preserve the signal for millions of years. We contribute to the development of this new pCO2 barometer by developing analytical methods for high-precision triple oxygen isotope analysis of carbonates, by developing an ecophysiological model of body water triple oxygen isotopes, and by applying the method to eggshell from modern birds and late Cretaceous (Campanian and Maastrichtian) dinosaur eggshells. Our findings include the following: (1) If animal ecophysiology and climatic context are perfectly known, the sensitivity of Δ17O (body water) to atmospheric CO2 is on the order of 0.01 ‰ per 100 ppm CO2; our analytical precision is ~ 0.01 ‰, thus ultimately permitting sub -100 ppm - level pCO2 reconstructions. (2) However, the effect of ecophysiology and climate can lead to a range in Δ17O (body water) of about 0.15 ‰ for animals living under the same Δ17O (O2); this prediction, confirmed by analyses of eggshells and body water of modern birds, translates to an apparent pCO2 range of about 1500 ppm. (3) Animals that are highly dependent on unevaporated free surface water ('drinking water') and live in humid climates have Δ17O (body water) signals that mimic low pCO2, whereas animals that consume primarily evaporated water (e.g., leaf water) and living in arid environments have Δ17O (body water) signals that mimic high pCO2. (4) There is an upper limit to this 'evaporation / aridity' effect mimicking high pCO2, so Δ17O (fossil eggshell) can be modeled assuming such upper limits to produce conservative lower limits on estimates of past pCO2. (5) We find that late Cretaceous Δ17O (fossil eggshell) is generally lower than modern Δ17O (eggshell), implying generally higher pCO2 during the late Cretaceous. The lowest observed Δ17O (fossil eggshell) value implies CO2 levels of at least 1200 ppm, and probably closer to 2000 ppm, for at least a short interval of Campanian time. Overall, this triple oxygen isotope approach shows promise for placing constraints on past CO2 levels. While somewhat limited in precision, it has the benefits of little appreciable loss of sensitivity with increasing pCO2, no presently-known mechanism for generating 'false positive' estimates of high pCO2 (except for extremely low atmospheric O2 levels and low primary productivity), and a basis that is fundamentally different from existing methods, thus allowing for independent new constraints on past CO2 levels.

Carbon dioxide and energy fluxes over a large shallow lake in China

NASA Astrophysics Data System (ADS)

Zhao, Xiaosong

2017-04-01

The turbulent exchange of carbon dioxide and energy between water and atmosphere over lakes differ from those over vegetated surfaces due to high heat capacity of water and different water ecological environment. For a shallow lake, the underlying surface generally changes between water covered and land covered with water level fluctuation, which significantly influences carbon dioxide and energy fluxes. Continuous measurement of the carbon dioxide (CO2), latent (LE) and sensible (H) heat fluxes was made using the eddy covariance method over the Poyang Lake, the largest fresh lake in China, from August 2013 to December 2015. Results indicated that the surface energy budget has a strong seasonal pattern, with peaks in LE and H observed in early August and September. There was 10 days delay between the net radiation and the latent heat flux. More net radiation (Rn) was allocated to the LE rather than H through the year, with monthly mean LE/Rn of 0.65 and H/Rn of 0.11, which caused Bowen ratio was 0.15 in water-covered period, lower than that in land-covered period. The water heat storage experienced shifting from heat storage to heat release, with maximum heat storage in July and maximum heat release in September. The water heat advection was account for 4% to 10% of Rn and peaked in June. The annual evaporation is 875 mm, 893 mm and 1019 mm in 2013 (from August 2013 to July 2014), 2014 and 2015, which was account for approximately 57% of precipitation in the three years. The large lake acted as a CO2 source in inundating period and a CO2 sink in exposure period. The energy fluxes were controlled by environmental factors with timescale dependence. On daily scale, the LE and H were highly correlated with product of wind speed and vapor pressure deficit (UVPD) or wind speed (U) in the water-covered period, and with Rn in the land-covered period. Monthly LE, H and annual H were controlled by Rn, while annual LE was primarily dependent on water depth. Annual CO2 budget was regulated by duration of inundating period.

Mg/Ca- Δ CO3porewater2- -temperature calibration for Globobulimina spp.: A sensitive paleothermometer for deep-sea temperature reconstruction

NASA Astrophysics Data System (ADS)

Weldeab, Syee; Arce, Adam; Kasten, Sabine

2016-03-01

Existing benthic foraminiferal Mg/Ca-temperature calibrations are surrounded by substantial uncertainties mainly due to low temperature sensitivity of Mg/Ca in most benthic foraminifers and the effect of carbonate ion concentration on benthic foraminiferal Mg/Ca. Here we present Mg/Ca analysis of Rose Bengal stained and exceptionally well-preserved tests of the infaunal benthic foraminifer Globobulimina spp. from 39 eastern equatorial Atlantic core top samples. Mg/Ca in Globobulimina spp. varies between 2.5 mmol/mol and 9.1 mmol/mol corresponding to bottom water temperatures (BWT) between 1.8 °C and 19.1 °C and Δ CO3pore water2- between 33.7 ± 4 and - 34.3 ± 4 μmol /kg in sediment depths between 1 and 10 cm. Mg/Ca and BWT are linearly correlated with a best fit of Mg/Ca [mmol/mol] = (0.36 ± 0.02) * BWT [°C] + 2.22 ± 0.19 (r2 = 0.92, p-value: 11 *10-20, and n = 39). Using total alkalinity and pH data of pore water samples from 64 Atlantic multi-corer sites, we obtained Δ CO3pore water2- data from the depth habitat range of Globobulimina spp. (≥1 cm ≤ 10 cm below sediment surface). We show that Δ CO3pore waterSUP>2- is significantly lower than and linearly co-varies with the ΔCO2-3 of the overlying bottom water: Δ CO3pore water2- = (0.67 ± 0.05) * Δ CO3bottom water2- - (39.84 ± 1.98); r2 = 0.75, p-value: 6 *10-20, n = 64. We found a Mg/Ca sensitivity of 0.009 ± 0.0044 mmol /mol per μmol/kg Δ CO3pore water2- and Mg/Ca temperature sensitivity of 0.32 ± 0.06 mmol /mol / °C after a correction for the Δ CO3pore water2- effect. This study provides a robust Mg/Ca-temperature calibration, highlights that Δ CO3pore water2- is spatially and most likely temporally variable, and contradicts the notion that infaunal foraminiferal Mg/Ca is relatively immune from ΔCO2-3 changes in the overlying bottom water. Furthermore, comparison of down core Mg/Ca data of Cibicides pachyderma and Globobulimina spp. demonstrates that the high temperature sensitivity of Mg/Ca in Globobulimina spp. presents a more robust paleothermometer to reconstruct past changes in the thermal state of the deep ocean.

Adsorption kinetics of CO2, CH4, and their equimolar mixture on coal from the Black Warrior Basin, West-Central Alabama

USGS Publications Warehouse

Gruszkiewicz, M.S.; Naney, M.T.; Blencoe, J.G.; Cole, D.R.; Pashin, J.C.; Carroll, R.E.

2009-01-01

Laboratory experiments were conducted to investigate the adsorption kinetic behavior of pure and mixed gases (CO2, CH4, approximately equimolar CO2 + CH4 mixtures, and He) on a coal sample obtained from the Black Warrior Basin at the Littleton Mine (Twin Pine Coal Company), Jefferson County, west-central Alabama. The sample was from the Mary Lee coal zone of the Pottsville Formation (Lower Pennsylvanian). Experiments with three size fractions (45-150????m, 1-2??mm, and 5-10??mm) of crushed coal were performed at 40????C and 35????C over a pressure range of 1.4-6.9??MPa to simulate coalbed methane reservoir conditions in the Black Warrior Basin and provide data relevant for enhanced coalbed methane recovery operations. The following key observations were made: (1) CO2 adsorption on both dry and water-saturated coal is much more rapid than CH4 adsorption; (2) water saturation decreases the rates of CO2 and CH4 adsorption on coal surfaces, but it appears to have minimal effects on the final magnitude of CO2 or CH4 adsorption if the coal is not previously exposed to CO2; (3) retention of adsorbed CO2 on coal surfaces is significant even with extreme pressure cycling; and (4) adsorption is significantly faster for the 45-150????m size fraction compared to the two coarser fractions. ?? 2008 Elsevier B.V.

Theoretical Insights into a CO Dimerization Mechanism in CO2 Electroreduction.

PubMed

Montoya, Joseph H; Shi, Chuan; Chan, Karen; Nørskov, Jens K

2015-06-04

In this work, we present DFT simulations that demonstrate the ability of Cu to catalyze CO dimerization in CO2 and CO electroreduction. We describe a previously unreported CO dimer configuration that is uniquely stabilized by a charged water layer on both Cu(111) and Cu(100). Without this charged water layer at the metal surface, the formation of the CO dimer is prohibitively endergonic. Our calculations also demonstrate that dimerization should have a lower activation barrier on Cu(100) than Cu(111), which, along with a more exergonic adsorption energy and a corresponding higher coverage of *CO, is consistent with experimental observations that Cu(100) has a high activity for C-C coupling at low overpotentials. We also demonstrate that this effect is present with cations other than H(+), a finding that is consistent with the experimentally observed pH independence of C2 formation on Cu.

Amorphous cobalt potassium phosphate microclusters as efficient photoelectrochemical water oxidation catalyst

NASA Astrophysics Data System (ADS)

Zhang, Ye; Zhao, Chunsong; Dai, Xuezeng; Lin, Hong; Cui, Bai; Li, Jianbao

2013-12-01

A novel amorphous cobalt potassium phosphate hydrate compound (KCoPO4·H2O) is identified to be active photocatalyst for oxygen evolution reaction (OER) to facilitate hydrogen generation from water photolysis. It has been synthesized through a facile and cost-effective solution-based precipitation method using earth-abundant materials. Its highly porous structure and large surface areas are found to be responsible for the excellent electrochemical performance featuring a low OER onset at ∼550 mVSCE and high current density in alkaline condition. Unlike traditional cobalt-based spinel oxides (Co3O4, NiCo2O4) and phosphate (Co-Pi, Co(PO3)2) electrocatalysts, with proper energy band alignment for light-assisted water oxidation, cobalt potassium phosphate hydrate also exhibits robust visible-light response, generating a photocurrent density of ∼200 μA cm-2 at 0.7 VSCE. This catalyst could thus be considered as a promising candidate to perform photoelectrochemical water splitting.

Westerly Winds and the Southern Ocean CO2 Sink Since the Last Glacial-Interglacial Transition

NASA Astrophysics Data System (ADS)

Hodgson, D. A.; Saunders, K. M.; Roberts, S. J.; Perren, B.; Butz, C.; Sime, L. C.; Davies, S. J.; Grosjean, M.

2017-12-01

The capacity of the Southern Ocean carbon sink is partly controlled by the Southern Hemisphere westerly winds (SHW) and sea ice. These regulate the upwelling of dissolved carbon-rich deep water to Antarctic surface waters, determine the surface area for air-sea gas exchange and therefore modulate the net uptake of atmospheric CO2. Some models have proposed that strengthened SHW will result in a weakening of the Southern Ocean CO2 sink. If these models are correct, then one would expect that reconstructions of changes in SHW intensity on centennial to millennial timescales would show clear links with Antarctic ice core and Southern Ocean marine geological records of atmospheric CO2, temperature and sea ice. Here, we present a 12,300 year reconstruction of past wind strength based on three independent proxies that track the changing inputs of sea salt aerosols and minerogenic particles into lake sediments on sub-Antarctic Macquarie Island. The proxies are consistent in showing that periods of high wind intensity corresponded with the increase in CO2 across the late Last Glacial-Interglacial Transition and in the last 7,000 years, suggesting that the winds have contributed to the long term outgassing of CO2 from the ocean during these periods.

Carbonate system parameters and anthropogenic CO2 in the North Aegean Sea during October 2013

NASA Astrophysics Data System (ADS)

Krasakopoulou, E.; Souvermezoglou, E.; Giannoudi, L.; Goyet, C.

2017-10-01

Data of AT (total alkalinity) and CT (total inorganic carbon) collected during October 2013, on a N-S transect crossing the North of Lemnos basin allowed to identify the peculiarities of the CO2 system in the North Aegean Sea and estimate the anthropogenic CO2 (CANT) concentrations. Extremely high concentrations of AT and CT were recorded in the upper layer of the North Aegean reflecting the high loads of AT and CT by the brackish BSW (Black Sea Water) outflowing through the Dardanelles strait and by the rivers runoff. Both AT and CT exhibit strong negative linear correlation with salinity in the upper layer (0-20 m). Investigation of the AT-S relationship along with the salinity adjustment of AT revealed excess alkalinity throughout the water column in relation to the surface waters implying a possible occurrence of non-carbonate alkalinity inputs as well as of other processes that take place probably over the extended shelves and contribute to the alkalinity surplus. The intermediate layer occupied by the Modified Levantine Intermediate Water (MLIW) mass exhibits the lowest CT and AT concentrations, while rather elevated AT and CT concentrations characterize the North Aegean Deep Water (NAgDW) mass filling the deep layer of the North of Lemnos basin linked to previous dense water formation episodes. High anthropogenic CO2 content was detected at intermediate and deep layers of the North Aegean reflecting the effective transportation of the absorbed atmospheric CO2 from the surface to the deeper waters via the dense water formation episodes. The MLIW layer is more affected by the penetration of CANT than the NAgDW that fills the deep part of the basin. The observed variability of CANT distribution reflects the influence of the intensity of dense water formation events, of the different θ/S properties of the newly formed dense waters as well as of the diverse submarine pathways followed by the cascading dense waters. The invasion of CANT has lead to more acidic conditions and to lower saturation degree of calcium carbonate in relation to the preindustrial era. The findings of this study provide baseline information about the carbonate system properties of the North Aegean and highlight its active role in sequestering and storing anthropogenic CO2.

North Polar Surfaces of the Uranian Moons: Coated with CO2 Frost?

NASA Astrophysics Data System (ADS)

Cartwright, Richard; Emery, Joshua; Rivkin, Andy; Trilling, David; Pinilla-Alonso, Noemi

2014-12-01

We propose to investigate the near-surface composition of the Uranian moons Ariel, Umbriel, Titania, and Oberon by using the Infrared Array Camera (IRAC) onboard the Spitzer Space Telescope. Previous IRAC observations of these objects in Program 71 (2003 - 2005) indicate that the surfaces of their southern hemispheres are dominated by pure water ice (sub-observer latitudes 7 - 18 degree S). The observations we propose here are of these objects' now observable northern hemispheres (sub-observer latitudes 25 - 33 degree N). Unlike the Program 71 observations, which collected data near the end of southern summer when any seasonal CO2 frost would have migrated to the winter hemisphere, we are proposing to observe these moons at the beginning of northern summer when seasonal CO2 frost should still be present. Therefore, the 2015 - 2016 Cycle 11 opportunity window represents an ideal time frame to search for seasonal CO2 frost on these objects.

The relative influence of H2O and CO2 on the primitive surface conditions and evolution of rocky planets

NASA Astrophysics Data System (ADS)

Salvador, A.; Massol, H.; Davaille, A.; Marcq, E.; Sarda, P.; Chassefière, E.

2017-07-01

How the volatile content influences the primordial surface conditions of terrestrial planets and, thus, their future geodynamic evolution is an important question to answer. We simulate the secular convective cooling of a 1-D magma ocean (MO) in interaction with its outgassed atmosphere. The heat transfer in the atmosphere is computed either using the grey approximation or using a k-correlated method. We vary the initial CO2 and H2O contents (respectively from 0.1 × 10-2 to 14 × 10-2 wt % and from 0.03 to 1.4 times the Earth Ocean current mass) and the solar distance—from 0.63 to 1.30 AU. A first rapid cooling stage, where efficient MO cooling and degassing take place, producing the atmosphere, is followed by a second quasi steady state where the heat flux balance is dominated by the solar flux. The end of the rapid cooling stage (ERCS) is reached when the mantle heat flux becomes negligible compared to the absorbed solar flux. The resulting surface conditions at ERCS, including water ocean's formation, strongly depend both on the initial volatile content and solar distance D. For D > DC, the "critical distance," the volatile content controls water condensation and a new scaling law is derived for the water condensation limit. Although today's Venus is located beyond DC due to its high albedo, its high CO2/H2O ratio prevents any water ocean formation. Depending on the formation time of its cloud cover and resulting albedo, only 0.3 Earth ocean mass might be sufficient to form a water ocean on early Venus.

Saturn's satellites: Potential for organic chemistry

NASA Astrophysics Data System (ADS)

Delitsky, M. L.; Lane, A. L.; Henry-Riyad, H.; Tidwell, T. T.

2003-05-01

The surfaces of the Saturnian satellites are subjected to irradiation from solar wind ions, photons, and magnetospheric ions and electrons. This bombardment will transform the chemical nature of the surfaces. At present, only water ice has been detected on their surfaces. Further studies by the Cassini spacecraft may reveal other molecules. If CO2 ice is found there, a whole panoply of new species may be detected. As nitrogen ions in the magnetosphere are thought to be an important species bombarding the satellites, Delitsky and Lane (2002) outlined the nitrogen oxides chemistry that may result from implantation of N+ into the water ice surfaces. Sittler et al (2002) showed that N+ ions originating from Titan will be enriched in the magnetospheric ion population as they move inwards towards Saturn, making the nitrogen oxides chemistry more likely. If CO2 is present, a complicated C-H-N-O chemistry may result from deposition of the N+ into a H2O/CO2 mixed ice, including nitriles, isocyanates, polymers, and amino acids. The combination of H2O/CO2 upon irradiation may also yield a complex mixture of hydrocarbons, esters, alcohols, organic acids and ketones. Possible chemical pathways and computations of their energetics will be presented. -Ref:- 1. Delitsky and Lane, Saturn's inner satellites: Ice chemistry and magnetosphere effects, JGR (Planets), Nov 2002, 3-1;; 2. Sittler et al., Energetic nitrogen ions within the inner magnetosphere of Saturn, Fall AGU meeting, Dec 2002, abstracts, pg F858, P21B-0379

Effects of climate change on surface-water photochemistry: a review.

PubMed

De Laurentiis, Elisa; Minella, Marco; Maurino, Valter; Minero, Claudio; Vione, Davide

2014-10-01

Information concerning the link between surface-water photochemistry and climate is presently very scarce as only a few studies have been dedicated to the subject. On the basis of the limited knowledge that is currently available, the present inferences can be made as follows: (1) Warming can cause enhanced leaching of ionic solutes from the catchments to surface waters, including cations and more biologically labile anions such as sulphate. Preferential sulphate biodegradation followed by removal as organic sulphides in sediment could increase alkalinity, favouring the generation of the carbonate radical, CO3 (·-). However, this phenomenon would be easily offset by fluctuations of the dissolved organic carbon (DOC), which is strongly anticorrelated with CO3 (·-). Therefore, obtaining insight into DOC evolution is a key issue in understanding the link between photochemistry and climate. (2) Climate change could exacerbate water scarcity in the dry season in some regions. Fluctuations in the water column could deeply alter photochemistry that is usually favoured in shallower waters. However, the way water is lost would strongly affect the prevailing photoinduced processes. Water outflow without important changes in solute concentration would mostly favour reactions induced by the hydroxyl and carbonate radicals (·OH and CO3 (·-)). In contrast, evaporative concentration would enhance reactions mediated by singlet oxygen ((1)O2) and by the triplet states of chromophoric dissolved organic matter ((3)CDOM*). (3) In a warmer climate, the summer stratification period of lakes would last longer, thereby enhancing photochemical reactions in the epilimnion but at the same time keeping the hypolimnion water in the dark for longer periods.

C4 grasses prosper as carbon dioxide eliminates desiccation in warmed semi-arid grassland.

PubMed

Morgan, Jack A; LeCain, Daniel R; Pendall, Elise; Blumenthal, Dana M; Kimball, Bruce A; Carrillo, Yolima; Williams, David G; Heisler-White, Jana; Dijkstra, Feike A; West, Mark

2011-08-03

Global warming is predicted to induce desiccation in many world regions through increases in evaporative demand. Rising CO(2) may counter that trend by improving plant water-use efficiency. However, it is not clear how important this CO(2)-enhanced water use efficiency might be in offsetting warming-induced desiccation because higher CO(2) also leads to higher plant biomass, and therefore greater transpirational surface. Furthermore, although warming is predicted to favour warm-season, C(4) grasses, rising CO(2) should favour C(3), or cool-season plants. Here we show in a semi-arid grassland that elevated CO(2) can completely reverse the desiccating effects of moderate warming. Although enrichment of air to 600 p.p.m.v. CO(2) increased soil water content (SWC), 1.5/3.0 °C day/night warming resulted in desiccation, such that combined CO(2) enrichment and warming had no effect on SWC relative to control plots. As predicted, elevated CO(2) favoured C(3) grasses and enhanced stand productivity, whereas warming favoured C(4) grasses. Combined warming and CO(2) enrichment stimulated above-ground growth of C(4) grasses in 2 of 3 years when soil moisture most limited plant productivity. The results indicate that in a warmer, CO(2)-enriched world, both SWC and productivity in semi-arid grasslands may be higher than previously expected.

Histologic comparison of the CO2 laser and Nd:YAG with and without water/air surface cooling on tooth root structure

NASA Astrophysics Data System (ADS)

Cobb, Charles M.; Spencer, Paulette; McCollum, Mark H.

1995-05-01

Specimens consisted of 18 extracted single rooted teeth unaffected by periodontal disease. After debriding roots, specimens were randomly divided into 4 treatment groups and subjected to a single pass, at varying energy densities, of a CO2, Nd:YAG, and Nd:YAG with air/water surface cooling (Nd:YAG-C). The rate of exposure was controlled at 4 mm/sec. Approximate energy densities were: CO2, 138, 206, 275, and 344 J/cm2; Nd:YAG, 114, 171, 229, and 286 J/cm2; Nd:YAG-C, 286, 343, 514, and 571 J/cm2. The CO2 laser was used both in continuous and pulsed beam modes (20 Hz, 0.01 sec pulse length and 0.8 mm dia spot size) whereas the Nd:YAG and Nd:YAG-C were preset at 50 Hz, 0.08 sec pulse length and 0.6 mm dia spot size. Specimen examination by SEM revealed, for all lasers, a direct correlation between increasing energy densities and depth of tissue ablation and width of tissue damage. However, to achieve the same relative dept of tissue ablation, the Nd:YAG-C required higher energy densities than either the CO2 or Nd:YAG lasers. The Nd:YAG-C generated a cavitation with sharply defined margins. Furthermore, regardless of energy density, and in contrast with other laser types, areas treated with the Nd:YAG-C did not exhibit collateral zones of heat damaged surface tissue.

Arsenic mobilization in shallow aquifers due to CO 2 intrusion from storage reservoirs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xiao, Ting; Dai, Zhenxue; Viswanathan, Hari S.

We developed an integrated framework of combined batch experiments and reactive transport simulations to quantify water-rock-CO 2 interactions and arsenic (As) mobilization responses to CO 2 and/or saline water leakage into USDWs. Experimental and simulation results suggest that when CO 2 is introduced, pH drops immediately that initiates release of As from clay minerals. Calcite dissolution can increase pH slightly and cause As re-adsorption. Thus, the mineralogy of the USDW is ultimately a determining factor of arsenic fate and transport. Salient results suggest that: (1) As desorption/adsorption from/onto clay minerals is the major reaction controlling its mobilization, and clay mineralsmore » could mitigate As mobilization with surface complexation reactions; (2) dissolution of available calcite plays a critical role in buffering pH; (3) high salinity in general hinders As release from minerals; and (4) the magnitude and quantitative uncertainty of As mobilization are predicated on the values of reaction rates and surface area of calcite, adsorption surface areas and equilibrium constants of clay minerals, and cation exchange capacity. Results of this study are intended to improve ability to quantify risks associated with potential leakage of reservoir fluids into shallow aquifers, in particular the possible environmental impacts of As mobilization at carbon sequestration sites.« less

Arsenic mobilization in shallow aquifers due to CO 2 intrusion from storage reservoirs

DOE PAGES

Xiao, Ting; Dai, Zhenxue; Viswanathan, Hari S.; ...

2017-06-05

We developed an integrated framework of combined batch experiments and reactive transport simulations to quantify water-rock-CO 2 interactions and arsenic (As) mobilization responses to CO 2 and/or saline water leakage into USDWs. Experimental and simulation results suggest that when CO 2 is introduced, pH drops immediately that initiates release of As from clay minerals. Calcite dissolution can increase pH slightly and cause As re-adsorption. Thus, the mineralogy of the USDW is ultimately a determining factor of arsenic fate and transport. Salient results suggest that: (1) As desorption/adsorption from/onto clay minerals is the major reaction controlling its mobilization, and clay mineralsmore » could mitigate As mobilization with surface complexation reactions; (2) dissolution of available calcite plays a critical role in buffering pH; (3) high salinity in general hinders As release from minerals; and (4) the magnitude and quantitative uncertainty of As mobilization are predicated on the values of reaction rates and surface area of calcite, adsorption surface areas and equilibrium constants of clay minerals, and cation exchange capacity. Results of this study are intended to improve ability to quantify risks associated with potential leakage of reservoir fluids into shallow aquifers, in particular the possible environmental impacts of As mobilization at carbon sequestration sites.« less

Spectral induced polarization of the three-phase system CO2 - brine - sand under reservoir conditions

NASA Astrophysics Data System (ADS)

Börner, Jana H.; Herdegen, Volker; Repke, Jens-Uwe; Spitzer, Klaus

2017-01-01

The spectral complex conductivity of a water-bearing sand during interaction with carbon dioxide (CO2) is influenced by multiple, simultaneous processes. These processes include partial saturation due to the replacement of conductive pore water with CO2 and chemical interaction of the reactive CO2 with the bulk fluid and the grain-water interface. We present a laboratory study on the spectral induced polarization of water-bearing sands during exposure to and flow-through by CO2. Conductivity spectra were measured successfully at pressures up to 30 MPa and 80 °C during active flow and at steady-state conditions concentrating on the frequency range between 0.0014 and 100 Hz. The frequency range between 0.1 and 100 Hz turned out to be most indicative for potential monitoring applications. The presented data show that the impact of CO2 on the electrolytic conductivity may be covered by a model for pore-water conductivity, which depends on salinity, pressure and temperature and has been derived from earlier investigations of the pore-water phase. The new data covering the three-phase system CO2-brine-sand further show that chemical interaction causes a reduction of surface conductivity by almost 20 per cent, which could be related to the low pH-value in the acidic environment due to CO2 dissolution and the dissociation of carbonic acid. The quantification of the total CO2 effect may be used as a correction during monitoring of a sequestration in terms of saturation. We show that this leads to a correct reconstruction of fluid saturation from electrical measurements. In addition, an indicator for changes of the inner surface area, which is related to mineral dissolution or precipitation processes, can be computed from the imaginary part of conductivity. The low frequency range between 0.0014 and 0.1 Hz shows additional characteristics, which deviate from the behaviour at higher frequencies. A Debye decomposition approach is applied to isolate the feature dominating the data at low frequencies. We conclude from our study that electrical conductivity is not only a highly sensitive indicator for CO2 saturation in pore space. When it is measured in its full spectral and complex form it contains additional information on the chemical state of the system, which holds the potential of getting access to both saturation and interface properties with one monitoring method.

Enhanced selectivity for the hydrolysis of block copoly(2-oxazoline)s in ethanol-water resulting in linear poly(ethylene imine) copolymers.

PubMed

van Kuringen, Huub P C; de la Rosa, Victor R; Fijten, Martin W M; Heuts, Johan P A; Hoogenboom, Richard

2012-05-14

The ability of merging the properties of poly(2-oxazoline)s and poly(ethylene imine) is of high interest for various biomedical applications, including gene delivery, biosensors, and switchable surfaces and nanoparticles. In the present research, a methodology for the controlled and selective hydrolysis of (co)poly(2-oxazoline)s is developed in an ethanol-water solvent mixture, opening the path toward a wide range of block poly(2-oxazoline-co-ethylene imine) (POx-PEI) copolymers with tunable properties. The unexpected influence of the selected ethanol-water binary solvent mixture on the hydrolysis kinetics and selectivity is highlighted in the pursue of well-defined POx-PEI block copolymers. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Near-infrared spectra of the Martian surface: Reading between the lines

NASA Technical Reports Server (NTRS)

Crisp, D.; Bell, J. F., III

1993-01-01

Moderate-resolution near-infrared (NIR) spectra of Mars have been widely used in studies of the Martian surface because many candidate surface materials have distinctive absorption features at these wavelengths. Recent advances in NIR detector technology and instrumentation have also encouraged studies in this spectral region. The use of moderate spectral resolution has often been justified for NIR surface observations because the spectral features produced by most surface materials are relatively broad, and easily discriminated at this resolution. In spite of this, NIR spectra of Mars are usually very difficult to interpret quantitatively. One problem is that NIR surface absorption features are often only a few percent deep, requiring observations with great signal-to-noise ratios. A more significant problem is that gases in the Martian atmosphere contribute numerous absorption features at these wavelengths. Ground-based observers must also contend with variable absorption by several gases in the Earth's atmosphere (H2O, CO2, O3, N2O, CH4, O2). The strong CO2 bands near 1.4, 1.6, 2.0, 2.7, 4.3, and 4.8 micrometers largely preclude the analysis of surface spectral features at these wavelengths. Martian atmospheric water vapor also contributes significant absorption near 1.33, 1.88, and 2.7 micrometers, but water vapor in the Earth's atmosphere poses a much larger problem to ground-based studies of these spectral regions. The third most important NIR absorber in the Martian atmosphere is CO. This gas absorbs most strongly in the relatively-transparent spectral windows near 4.6 and 2.3 micrometers. It also produces 1-10 percent absorption in the solar spectrum at these NIR wavelengths. This solar CO absorption cannot be adequately removed by dividing the Martian spectrum by that of a star, as is commonly done to calibrate ground-based spectroscopic observations, because most stars do not have identical amounts of CO absorption in their spectra. Here, we describe tow effective methods for eliminating contamination of Martian surface spectra by absorption in the solar, terrestrial, and Martian atmospheres. Both methods involve the use of very-high-resolution spectra that completely resolve the narrow atmospheric absorption lines.

Stable carbon isotope cycling in mobile coastal muds of Amapá, Brazil

NASA Astrophysics Data System (ADS)

Zhu, Zhongbin; Aller, Robert C.; Mak, John

2002-10-01

Approximately 10% of the sediment delivered by the Amazon River moves northwest along the coast of Amapá, Brazil, initiating the Guianas mobile mud belt. Amapá coastal muds generally have a two-layer transport structure and are characterized by highly non-steady-state sedimentation. Isotopic compositions of pore water ∑CO 2 and solid phase C org demonstrate that remineralization in the surficial mobile zone (˜0.3-1 m thick) is dominated by terrestrial sources at sites in proximity to the mangrove fringe (˜1-2 m water depth), and marine (plus possible carbonate dissolution) sources further offshore (˜21 km, ˜7 m depth). The net δ13C of ∑CO 2 produced and C org remineralized is ˜-26‰ and -25.9‰, respectively inshore, and ˜-14‰ and -18.6‰, respectively offshore (compared to average terrestrial and marine C org end members of -28‰ and -20‰). Efficient remineralization in the suboxic mobile zone lowers particle surface loading of C org from ˜0.35 mg C m -2 in the Amazon delta topset to ˜0.13-0.16 along Amapá. Sequential, temperature-dependent extractions were used to operationally fractionate inorganic C pools. Authigenic carbonates, mostly siderite and mixed Ca, Mg, Fe, Mn-carbonates, dominate sediment inorganic C (˜50-200 μmol g -1). The mass weighted δ13C of carbonates, ˜-15‰ to -19‰, is relatively restricted in range compared to pore water ∑CO 2, implying most precipitation in the reactive mobile surface sediments. Periodic mixing with bottom seawater and/or dissolution of biogenic carbonates in the surficial layer shift δ13C values of pore water to heavier values than C org reactant sources. At one offshore site (˜7 m), about 22% of pore water ∑CO 2 has undergone reduction during methanogenesis below the mobile surface zone, extracting ∑CO 2 with δ13C˜-90‰ and leaving a residual δ13C˜-0.37‰. Diagenetic processes in the suboxic mobile mud zone dominate C remineralization and storage along the coast of Amapá.

Effective Permeability Change in Wellbore Cement with Carbon Dioxide Reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Um, Wooyong; Jung, Hun Bok; Martin, Paul F.

2011-11-01

Portland cement, a common sealing material for wellbores for geological carbon sequestration was reacted with CO{sub 2} in supercritical, gaseous, and aqueous phases at various pressure and temperature conditions to simulate cement-CO{sub 2} reaction along the wellbore from carbon injection depth to the near-surface. Hydrated Portland cement columns (14 mm diameter x 90 mm length; water-to-cement ratio = 0.33) including additives such as steel coupons and Wallula basalt fragments were reacted with CO{sub 2} in the wet supercritical (the top half) and dissolved (the bottom half) phases under carbon sequestration condition with high pressure (10 MPa) and temperature (50 C)more » for 5 months, while small-sized hydrated Portland cement columns (7 mm diameter x 20 mm length; water-to-cement ratio = 0.38) were reacted with CO{sub 2} in dissolved phase at high pressure (10 MPa) and temperature (50 C) for 1 month or with wet CO{sub 2} in gaseous phase at low pressure (0.2 MPa) and temperature (20 C) for 3 months. XMT images reveal that the cement reacted with CO{sub 2} saturated groundwater had degradation depth of {approx}1 mm for 1 month and {approx}3.5 mm for 5 month, whereas the degradation was minor with cement exposure to supercritical CO{sub 2}. SEM-EDS analysis showed that the carbonated cement was comprised of three distinct zones; the innermost less degraded zone with Ca atom % > C atom %, the inner degraded zone with Ca atom % {approx} C atom % due to precipitation of calcite, the outer degraded zone with C atom % > Ca atom % due to dissolution of calcite and C-S-H, as well as adsorption of carbon to cement matrix. The outer degraded zone of carbonated cement was porous and fractured because of dissolution-dominated reaction by carbonic acid exposure, which resulted in the increase in BJH pore volume and BET surface area. In contrast, cement-wet CO{sub 2}(g) reaction at low P (0.2 MPa)-T (20 C) conditions for 1 to 3 months was dominated by precipitation of micron-sized calcite on the outside surface of cement, which resulted in the decrease in BJH pore volume and BET surface area. Cement carbonation and pore structure change are significantly dependent on pressure and temperature conditions as well as the phase of CO{sub 2}, which controls the balance between precipitation and dissolution in cement matrix. Geochemical modeling result suggests that ratio of solid (cement)-to-solution (carbonated water) has a significant effect on cement carbonation, thus the cement-CO{sub 2} reaction experiment needs to be conducted under realistic conditions representing the in-situ wellbore environment of carbon sequestration field site. Total porosity and air permeability for a duplicate cement column with water-to-cement ratio of 0.38 measured after oven-drying by Core Laboratories using Boyle's Law technique and steady-state method were 31% and 0.576 mD. A novel method to measure the effective liquid permeability of a cement column using X-ray micro-tomography images after injection of pressurized KI (potassium iodide) is under development by PNNL. Preliminary results indicate the permeability of a cement column with water-to-cement ratio of 0.38 is 4-8 mD. PNNL will apply the method to understand the effective permeability change of Portland cement by CO{sub 2}(g) reaction under a variety of pressure and temperature conditions to develop a more reliable well-bore leakage risk model.« less

Atmospheric carbon dioxide and chlorofluoromethanes - Combined effects on stratospheric ozone, temperature, and surface temperature

NASA Technical Reports Server (NTRS)

Callis, L. B.; Natarajan, M.

1981-01-01

The effects of combined CO2 and CFCl3 and CF2Cl2 time-dependent scenarios on atmospheric O3 and temperature are described; the steady-state levels of O3 and surface temperature, to which the chlorofluoromethane scenario tends in the presence of twice and four time ambient CO2, are examined; and surface temperature changes, caused by the combined effects, are established. A description of the model and of the experiments is presented. Results indicate that (1) the total ozone time history is significantly different from that due to the chlorofluoromethane alone; (2) a local ozone minimum occurs in the upper stratosphere about 45 years from the present with a subsequent ozone increase, then decline; and (3) steady-state solutions indicate that tropospheric temperature and water vapor increases, associated with increased infrared opacity, cause significant changes in tropospheric ozone levels for 2 x CO2 and 4 x CO2, without the addition of chlorofluoromethanes.

Characterization and Modeling Of Microbial Carbon Metabolism In Thawing Permafrost

NASA Astrophysics Data System (ADS)

Graham, D. E.; Phelps, T. J.; Xu, X.; Carroll, S.; Jagadamma, S.; Shakya, M.; Thornton, P. E.; Elias, D. A.

2012-12-01

Increased annual temperatures in the Arctic are warming the surface and subsurface, resulting in thawing permafrost. Thawing exposes large pools of buried organic carbon to microbial degradation, increasing greenhouse gas generation and emission. Most global-scale land-surface models lack depth-dependent representations of carbon conversion and GHG transport; therefore they do not adequately describe permafrost thawing or microbial mineralization processes. The current work was performed to determine how permafrost thawing at moderately elevated temperatures and anoxic conditions would affect CO2 and CH4 generation, while parameterizing depth-dependent GHG production processes with respect to temperature and pH in biogeochemical models. These enhancements will improve the accuracy of GHG emission predictions and identify key biochemical and geochemical processes for further refinement. Three core samples were obtained from discontinuous permafrost terrain in Fairbanks, AK with a mean annual temperature of -3.3 °C. Each core was sectioned into surface/near surface (0-0.8 m), active layer (0.8-1.6 m), and permafrost (1.6-2.2 m) horizons, which were homogenized for physico-chemical characterization and microcosm construction. Surface samples had low pH values (6.0), low water content (18% by weight), low organic carbon (0.8%), and high C:N ratio (43). Active layer samples had higher pH values (6.4), higher water content (34%), more organic carbon (1.4%) and a lower C:N ratio (24). Permafrost samples had the highest pH (6.5), highest water content (46%), high organic carbon (2.5%) and the lowest C:N ratio (19). Most organic carbon was quantified as labile or intermediate pool versus stable pool in each sample, and all samples had low amounts of carbonate. Surface layer microcosms, containing 20 g sediment in septum-sealed vials, were incubated under oxic conditions, while similar active and permafrost layer samples were anoxic. These microcosms were incubated at -2, +3, or +5 °C for 6 months. The pH decreased in all samples (5.5 to 5.9). The proportions of carbon in labile and intermediate turnover pools from permafrost samples decreased during incubation, while microbial biomass carbon increased in all cases. Microcosm samples and original core material were analyzed by 16S rDNA pyrosequencing and showed increased populations of bacteria that ferment simple and complex carbohydrates, as well as acidophilic bacteria. Microbial diversity declined in permafrost samples. Concentrations of CO2 and CH4 were measured monthly by gas chromatography. CO2 production was highest in the surface/near surface incubations (4-14%) while CH4 was undetectable. Active layer sediments produced considerably less CO2 (0.2-0.7%) but CH4 was detected up to 0.25%. Concentrations of CO2 found in the deep permafrost incubations were comparable to those in the active layer, while CH4 was considerably higher ranging from 0.2-0.6%. Overall, the CO2 generation rate (0.02-0.12 μmol/g/month) was roughly 50 times that of methanogenesis (0.002-0.007 μmol/g/month). GHG levels peaked after 4 months, and the decreasing pH suggested that organic acid accumulation could control GHG biogenesis. Surprisingly, increasing temperature and water content did not necessarily increase GHG emission rates or proportions of CO2 and CH4.

A large CO2 sink enhanced by eutrophication in a tropical coastal embayment (Guanabara Bay, Rio de Janeiro, Brazil)

NASA Astrophysics Data System (ADS)

Cotovicz, L. C., Jr.; Knoppers, B. A.; Brandini, N.; Costa Santos, S. J.; Abril, G.

2015-03-01

In contrast to its small surface area, the coastal zone plays a disproportionate role in the global carbon cycle. Carbon production, transformation, emission and burial rates at the land-ocean interface are still poorly known, especially in tropical regions. Surface water pCO2 and ancillary parameters were monitored during nine field campaigns between April 2013 and April 2014 in Guanabara Bay, a tropical eutrophic to hypertrophic semi-enclosed estuarine embayment surrounded by the city of Rio de Janeiro, SE-Brazil. Water pCO2 varied between 22 and 3715 ppmv in the Bay showing spatial, diurnal and seasonal trends that mirrored those of dissolved oxygen (DO) and Chlorophyll a (Chl a). Marked pCO2 undersaturation was prevalent in the shallow, confined and thermally stratified waters of the upper bay, whereas pCO2 oversaturation was restricted to sites close to the small river mouths and small sewage channels, which covered only 10% of the bay's area. Substantial daily variations in pCO2 (up to 395 ppmv between dawn and dusk) were also registered and could be integrated temporally and spatially for the establishment of net diurnal, seasonal and annual CO2 fluxes. In contrast to other estuaries worldwide, Guanabara Bay behaved as a net sink of atmospheric CO2, a property enhanced by the concomitant effects of strong radiation intensity, thermal stratification, and high availability of nutrients, which promotes phytoplankton development and net autotrophy. In the inner part of the bay, the calculated annual CO2 sink (-19.6 mol C m2 yr-1) matched the organic carbon burial in the sediments reported in the literature. The carbon sink and autotrophy of Guanabara Bay was driven by planktonic primary production promoted by eutrophication, and by its typology of marine embayment lacking the classical extended estuarine mixing zone, in contrast to river-dominated estuarine systems, which are generally net heterotrophic and CO2 emitters. Our results show that global CO2 budgetary assertions still lack information on tropical estuarine embayments and lagoons, which are affected by thermal stratification and eutrophication and behave specifically with respect to atmospheric CO2.

Numerical Simulation of the Water Cycle Change Over the 20th Century

NASA Technical Reports Server (NTRS)

Bosilovich, Michael G.; Schubert, Siegfried D.

2003-01-01

We have used numerical models to test the impact of the change in Sea Surface Temperatures (SSTs) and carbon dioxide (CO2) concentration on the global circulation, particularly focusing on the hydrologic cycle, namely the global cycling of water and continental recycling of water. We have run four numerical simulations using mean annual SST from the early part of the 20th century (1900-1920) and the later part (1980-2000). In addition, we vary the CO2 concentrations for these periods as well. The duration of the simulations is 15 years, and the spatial resolution is 2 degrees. We use passive tracers to study the geographical sources of water. Surface evaporation from predetermined continental and oceanic regions provides the source of water for each passive tracer. In this way, we compute the percent of precipitation of each region over the globe. This can also be used to estimate precipitation recycling. In addition, we are using the passive tracers to independently compute the global cycling of water (compared to the traditional, Q/P calculation).

Carbon dioxide induced bubble formation in a CH4-CO2-H2O ternary system: a molecular dynamics simulation study.

PubMed

Sujith, K S; Ramachandran, C N

2016-02-07

The extraction of methane from its hydrates using carbon dioxide involves the decomposition of the hydrate resulting in a CH4-CO2-H2O ternary solution. Using classical molecular dynamics simulations, we investigate the evolution of dissolved gas molecules in the ternary system at different concentrations of CO2. Various compositions considered in the present study resemble the solution formed during the decomposition of methane hydrates at the initial stages of the extraction process. We find that the presence of CO2 aids the formation of CH4 bubbles by causing its early nucleation. Elucidation of the composition of the bubble revealed that in ternary solutions with high concentration of CO2, mixed gas bubbles composed of CO2 and CH4 are formed. To understand the role of CO2 in the nucleation of CH4 bubbles, the structure of the bubble formed was analyzed, which revealed that there is an accumulation of CO2 at the interface of the bubble and the surrounding water. The aggregation of CO2 at the bubble-water interface occurs predominantly when the concentration of CO2 is high. Radial distribution function for the CH4-CO2 pair indicates that there is an increasingly favorable direct contact between dissolved CH4 and CO2 molecules in the bubble-water interface. It is also observed that the presence of CO2 at the interface results in the decrease in surface tension. Thus, CO2 leads to greater stability of the bubble-water interface thereby bringing down the critical size of the bubble nuclei. The results suggest that a rise in concentration of CO2 helps in the removal of dissolved CH4 thereby preventing the accumulation of methane in the liquid phase. Thus, the presence of CO2 is predicted to assist the decomposition of methane hydrates in the initial stages of the replacement process.

Processes affecting the stable isotope composition of calcite during precipitation on the surface of stalagmites: Laboratory experiments investigating the isotope exchange between DIC in the solution layer on top of a speleothem and the CO2 of the cave atmosphere

NASA Astrophysics Data System (ADS)

Dreybrodt, Wolfgang; Hansen, Maximilian; Scholz, Denis

2016-02-01

We present a theoretical derivation of the exchange time, τex, needed to establish isotopic equilibrium between atmospheric CO2 in a cave and HCO3- dissolved in a thin water film covering the surface of a speleothem. The result is τex = τredex · [HCO3-]/ (KH · pCO2cave) , where τredex depends on the depth, a, of the water film and on temperature. [HCO3-] is the concentration of bicarbonate, pCO2cave the partial pressure of CO2, and KH is Henry's constant. To test the theory we prepared stagnant or flowing thin films of a NaHCO3 solution and exposed them at 20 °C to an CO2 containing atmosphere of pCO2 500, 12,500, or 25,000 ppmV and defined isotope composition. The δ13C and δ18O values of the DIC in the solution were measured as a function of the exposure time. For stagnant films with depths between 0.06 and 0.2 cm the δ13C values exhibit an exponential approach towards isotope equilibrium with the atmospheric CO2 with exchange time, τex. The δ18O values first evolve towards isotopic equilibrium with atmospheric CO2, reach a minimum value and then drift away from the isotopic equilibrium with atmospheric CO2 approaching a steady state caused by isotopic exchange of oxygen with water. The experimental findings are in satisfactory agreement with the theoretical predictions. To further investigate isotope evolution in cave analogue conditions, a water film containing 5 mmol/L of NaHCO3 with a depth of 0.013 cm flowing down an inclined borosilicate glass plate was exposed to an atmosphere with pCO2 = 500 ppmV at a temperature of 20 °C. The δ13C and δ18O values were measured as a function of flow (exposure) time, t. The isotope compositions in the DIC of the water film decrease linear in time by δDIC (t) =δDIC (0) - (δDIC (0) -δDIC (∞)) · t /τex where δDIC (0) is the initial isotope composition of dissolved inorganic carbon (DIC) in the water film and δDIC (∞) its final value. From these data an exchange time τex of ca. 7000 s was obtained, in satisfactory agreement with the theoretical predictions. The exchange times can be calculated by τex = τredex · [HCO3-]/ (KH · pCO2cave), where τredex is given by the theory as function of temperature and the depth, a, of the water film. This way it is possible to obtain exchange times for various conditions of stalagmite growth as they occur in caves.

Estimating surface pCO2 in the northern Gulf of Mexico: Which remote sensing model to use?

NASA Astrophysics Data System (ADS)

Chen, Shuangling; Hu, Chuanmin; Cai, Wei-Jun; Yang, Bo

2017-12-01

Various approaches and models have been proposed to remotely estimate surface pCO2 in the ocean, with variable performance as they were designed for different environments. Among these, a recently developed mechanistic semi-analytical approach (MeSAA) has shown its advantage for its explicit inclusion of physical and biological forcing in the model, yet its general applicability is unknown. Here, with extensive in situ measurements of surface pCO2, the MeSAA, originally developed for the summertime East China Sea, was tested in the northern Gulf of Mexico (GOM) where river plumes dominate water's biogeochemical properties during summer. Specifically, the MeSAA-predicted surface pCO2 was estimated by combining the dominating effects of thermodynamics, river-ocean mixing and biological activities on surface pCO2. Firstly, effects of thermodynamics and river-ocean mixing (pCO2@Hmixing) were estimated with a two-endmember mixing model, assuming conservative mixing. Secondly, pCO2 variations caused by biological activities (ΔpCO2@bio) was determined through an empirical relationship between sea surface temperature (SST)-normalized pCO2 and MODIS (Moderate Resolution Imaging Spectroradiometer) 8-day composite chlorophyll concentration (CHL). The MeSAA-modeled pCO2 (sum of pCO2@Hmixing and ΔpCO2@bio) was compared with the field-measured pCO2. The Root Mean Square Error (RMSE) was 22.94 μatm (5.91%), with coefficient of determination (R2) of 0.25, mean bias (MB) of - 0.23 μatm and mean ratio (MR) of 1.001, for pCO2 ranging between 316 and 452 μatm. To improve the model performance, a locally tuned MeSAA was developed through the use of a locally tuned ΔpCO2@bio term. A multi-variate empirical regression model was also developed using the same dataset. Both the locally tuned MeSAA and the regression models showed improved performance comparing to the original MeSAA, with R2 of 0.78 and 0.84, RMSE of 12.36 μatm (3.14%) and 10.66 μatm (2.68%), MB of 0.00 μatm and - 0.10 μatm, MR of 1.001 and 1.000, respectively. A sensitivity analysis was conducted to study the uncertainties in the predicted pCO2 as a result of the uncertainties in the input variables of each model. Although the MeSAA was more sensitive to variations in SST and CHL than in sea surface salinity (SSS), and the locally tuned MeSAA and the empirical regression models were more sensitive to changes in SST and SSS than in CHL, generally for these three models the bias induced by the uncertainties in the empirically derived parameters (river endmember total alkalinity (TA) and dissolved inorganic carbon (DIC), biological coefficient of the MeSAA and locally tuned MeSAA models) and environmental variables (SST, SSS, CHL) was within or close to the uncertainty of each model. While all these three models showed that surface pCO2 was positively correlated to SST, the MeSAA showed negative correlation between surface pCO2 and SSS and CHL but the locally tuned MeSAA and the empirical regression showed the opposite. These results suggest that the locally tuned MeSAA worked better in the river-dominated northern GOM than the original MeSAA, with slightly worse statistics but more meaningful physical and biogeochemical interpretations than the empirical regression model. Because data from abnormal upwelling were not used to train the models, they are not applicable for waters with strong upwelling, yet the empirical regression approach showed ability to be further tuned to adapt to such cases.

Iron Resources and Oceanic Nutrients - Advancement of Global Environment Simulations (ironages)

NASA Astrophysics Data System (ADS)

de Baar, H. J. W.; Ironages Team

Iron limits productivity in 40 percent of the oceans, and is a co-limitation in the re- maining 60 percent of surface waters. Moreover the paradigm of a single factor limit- ing plankton blooms, is presently giving way to co-limitation by light, and the nutri- ents N, P, Si, and Fe. Primary production, export into the deep sea, and CO2 uptake from the atmosphere together form the 'biological pump' in Ocean Biogeochemi- cal Climate Models (OBCM's). Thus far OBCM's assume just one limiting nutrient (P) and one universal phytoplankton species, for deriving C budgets and CO2 ex- change with the atmosphere. New realistic OBCM's are being developed in IRON- AGES for budgeting and air/sea exchanges of both CO2 and DMS, implementing (1) co-limitation by 4 nutrients of 5 major taxonomic classes of phytoplankton in a nested plankton ecosystem model, (ii) DMS(P) pathways, (iii) global iron cycling, (iv) chem- ical forms of iron and (v) iron supply in surface waters from above by aerosols and from below out of reducing margin sediments. IRONAGES is a consortium of 12 Eu- ropean institutes coordinated by the Royal NIOZ.

The Role of Plate Tectonic-Climate Coupling and Exposed Land Area in the Development of Habitable Climates on Rocky Planets

NASA Astrophysics Data System (ADS)

Foley, Bradford J.

2015-10-01

The long-term carbon cycle is vital for maintaining liquid water oceans on rocky planets due to the negative climate feedbacks involved in silicate weathering. Plate tectonics plays a crucial role in driving the long-term carbon cycle because it is responsible for CO2 degassing at ridges and arcs, the return of CO2 to the mantle through subduction, and supplying fresh, weatherable rock to the surface via uplift and orogeny. However, the presence of plate tectonics itself may depend on climate according to recent geodynamical studies showing that cool surface temperatures are important for maintaining vigorous plate tectonics. Using a simple carbon cycle model, I show that the negative climate feedbacks inherent in the long-term carbon cycle are uninhibited by climate's effect on plate tectonics. Furthermore, initial atmospheric CO2 conditions do not impact the final climate state reached when the carbon cycle comes to equilibrium, as long as liquid water is present and silicate weathering can occur. Thus an initially hot, CO2 rich atmosphere does not prevent the development of a temperate climate and plate tectonics on a planet. However, globally supply limited weathering does prevent the development of temperate climates on planets with small subaerial land areas and large total CO2 budgets because supply limited weathering lacks stabilizing climate feedbacks. Planets in the supply limited regime may become inhospitable for life and could experience significant water loss. Supply limited weathering is less likely on plate tectonic planets because plate tectonics promotes high erosion rates and thus a greater supply of bedrock to the surface.

Oxidation of ammonia and methane in an alkaline, saline lake

USGS Publications Warehouse

Joye, S.B.; Connell, T.L.; Miller, L.G.; Oremland, R.S.; Jellison, R.S.

1999-01-01

The oxidation of ammonia (NH3) and methane (CH4) was investigated in an alkaline saline lake, Mono Lake, California (U.S.A.). Ammonia oxidation was examined in April and July 1995 by comparing dark 14CO2 fixation rates in the presence or absence of methyl fluoride (MeF), an inhibitor of NH3 oxidation. Ammonia oxidizer-mediated dark 14CO2 fixation rates were similar in surface (5-7 m) and oxycline (11-15 m) waters, ranging between 70-340 and 89-186 nM d-1, respectively, or 1-7% of primary production by phytoplankton. Ammonia oxidation rates ranged between 580-2,830 nM d-1 in surface waters and 732-1,548 nM d-1 in oxycline waters. Methane oxidation was examined using a 14CH4 tracer technique in July 1994, April 1995, and July 1995. Methane oxidation rates were consistently higher in July, and rates in oxycline and anaerobic bottom waters (0.5-37 and 7-48 nM d-1, respectively) were 10-fold higher than those in aerobic surface waters (0.04-3.8 nM d-1). The majority of CH4 oxidation, in terms of integrated activity, occurred within anoxic bottom waters. Water column oxidation reduced the potential lake-atmosphere CH4 flux by a factor of two to three. Measured oxidation rates and water column concentrations were used to estimate the biological turnover times of NH3 and CH4. The NH3 pool turns over rapidly, on time scales of 0.8 d in surface waters and 10 d within the oxycline, while CH4 is cycled on 103-d time scales in surface waters and 102-d time scales within oxycline and bottom waters. Our data suggest an important role for NH3 oxidation in alkaline, saline lakes since the process converts volatile NH3 to soluble NO2-, thereby reducing loss via lake-atmosphere exchange and maintaining nitrogen in a form that is readily available to phytoplankton.

Carbon Cycle Model of a Hawaiian Barrier Reef under Rising Ocean Acidification and Temperature Conditions of the Anthropocene

NASA Astrophysics Data System (ADS)

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

2015-12-01

A CO2-carbonic acid system biogeochemical box model (CRESCAM, Coral Reef and Sediment Carbonate Model) of the barrier reef flat in Kaneohe Bay, Hawai'i was developed to determine how increasing temperature and dissolved inorganic carbon (DIC) content of open ocean source waters, resulting from rising anthropogenic CO2 emissions and ocean acidification, affect the CaCO3budget of coral reef ecosystems. CRESCAM consists of 17 reservoirs and 59 fluxes, including a surface water column domain, a two-layer permeable sediment domain, and a coral framework domain. Physical, chemical, and biological processes such as advection, carbonate precipitation/dissolution, and net ecosystem production and calcification were modeled. The initial model parameters were constrained by experimental and field data from previous coral reef studies, mostly in Kaneohe Bay over the past 50 years. The field studies include data collected by our research group for both the water column and sediment-porewater system.The model system, initially in a quasi-steady state condition estimated for the early 21st century, was perturbed using future projections to the year 2100 of the Anthropocene of atmospheric CO2 ­concentrations, temperature, and source water DIC. These perturbations were derived from the most recent (2013) IPCC's Representative Concentration Pathway (RCP) scenarios, which predict CO2 atmospheric concentrations and temperature anomalies out to 2100. A series of model case studies were also performed whereby one or more parameters (e.g., coral calcification response to declining surface water pH) were altered to investigate potential future outcomes. Our model simulations predict that although the Kaneohe Bay barrier reef will likely see a significant decline in NEC over the coming century, it is unlikely to reach a state of net erosion - a result contrary to several global coral reef model projections. In addition, we show that depending on the future response of NEP and NEC to OA and rising temperatures, the surface waters could switch from being a present-day source of CO2 to the atmosphere to a future sink. This ecosystem specific model can be applied to any reef system where data are available to constrain the initial model state and is a powerful tool for examining future changes in coral reef carbon budgets.

An examination of Mars' north seasonal polar cap using MGS: Composition and infrared radiation balance

NASA Astrophysics Data System (ADS)

Hansen, Gary B.

2013-08-01

A detailed analysis of data from one revolution of the Mars Global Surveyor (MGS) is presented. Approximately 80% of this revolution observes the mid-winter northern seasonal polar cap, which covers the surface to <60°N, and which is predominantly within polar night. The surface composition and temperature are determined through analysis of 6-50 μm infrared spectra from the Thermal Emission Spectrometer (TES). The infrared radiative balance, which is the entire heat balance in the polar night except for small subsurface and atmospheric advection terms, is calculated for the surface and atmospheric column. The primary constituent, CO2 ice, also dominates the infrared spectral properties by variations in its grain size and by admixtures of dust and water ice, which cause large variations in the 20-50 μm emissivity. This is modified by incomplete areal coverage, and clouds or hazes. This quantitative analysis reveals CO2 grain radii ranging from ˜100 μm in isolated areas, to 1-5 mm in more widespread regions. The water ice content varies from none to about one part per thousand by mass, with a clear increase towards the periphery of the polar cap. The dust content is typically a few parts per thousand by mass, but is as much as an order of magnitude less abundant in "cold spot" regions, where the low emissivity of pure CO2 ice is revealed. This is the first quantitative analysis of thermal spectra of the seasonal polar cap and the first to estimate water ice content. Our models show that the cold spots represent cleaner, dust-free ice rather than finer grained ice than the background. Our guess is that the dust in cold spots is hidden in the center of the CO2 frost particles rather than not present. The fringes of the cap have more dust and water ice, and become patchy, with warmer water snow filling the gaps on the night side, and warmer bare soil on the day side. A low optical depth (<1 in the visible) water ice atmospheric haze is apparent on the night side, and appears with smaller optical depth on the day side. The infrared radiative balance at the surface is typically 20-25 W m-2 in the central polar cap, with ˜25% dips in the regions of dust-free CO2. The atmospheric radiative terms are typically 1-3 W m-2.

Gas exchange and CO2 flux in the tropical Atlantic Ocean determined from Rn-222 and pCO2 measurements

NASA Technical Reports Server (NTRS)

Smethie, W. M., Jr.; Takahashi, T.; Chipman, D. W.; Ledwell, J. R.

1985-01-01

The piston velocity for the tropical Atlantic Ocean has been determined from 29 radon profiles measured during the TTO Tropical Atlantic Study. By combining these data with the pCO2 data measured in the surface water and air samples, the net flux of CO2 across the sea-air interface has been calculated for the tropical Atlantic. The dependence of the piston velocity on wind speed is discussed, and possible causes for the high sea-to-air CO2 flux observed in the equatorial zone are examined.

Physical and biological forcing of mesoscale variability in the carbonate system of the Ross Sea (Antarctica) during summer 2014

NASA Astrophysics Data System (ADS)

Rivaro, Paola; Ianni, Carmela; Langone, Leonardo; Ori, Carlo; Aulicino, Giuseppe; Cotroneo, Yuri; Saggiomo, Maria; Mangoni, Olga

2017-02-01

Water samples (0-200 m) were collected in a coastal area of the Ross Sea in January 2014 to evaluate the physical and biological forcing on the carbonate system at the mesoscale (distance between stations of 5-10 km). Remote sensing supported the determination of the sampling strategy and helped positioning each sampling station. Total alkalinity, pH, dissolved oxygen, phytoplankton pigments and composition were investigated in combination with measurements of temperature, salinity and current speed. Total inorganic carbon, sea water CO2 partial pressure and the saturation state (Ω) for calcite and aragonite were calculated from the measured total alkalinity and pH. In addition, continuous measurements of atmospheric CO2 concentration were completed. LADCP measurements revealed the presence of a significant change in current speed and direction that corresponded to a clearly defined front characterized by gradients in both temperature and salinity. Phytoplankton biomass was relatively high at all stations and the highest values of chlorophyll-a were found between 20 to 50 m, with the dominant taxonomic group being haptophyceae. The carbonate system properties in surface waters exhibited mesoscale variability with a horizontal length scale of about 10 km. Sea-ice melt, through the input of low salinity water, results in a dilution of the total alkalinity and inorganic carbon, but our observations suggest that phytoplankton activity was the major forcing of the distribution of the carbonate system variables. Higher CO3-, Ω and pH in the surface layer were found where the highest values of chlorophyll-a were observed. The calculated ΔpCO2 pattern follows both MODIS data and in situ chlorophyll-a measurements, and the estimated CO2 fluxes ranged from -0.5 ± 0.4 to -31.0 ± 6.4 mmol m- 2 d- 1. The large range observed in the fluxes is due to both the spatial variability of sea water pCO2 and to the episodic winds experienced.

Minor constituents in the Martian atmosphere from the ISM/Phobos experiment

NASA Astrophysics Data System (ADS)

Rosenqvist, J.; Drossart, P.; Combes, M.; Encrenaz, T.; Lellouch, E.; Bibring, J. P.; Erard, S.; Langevin, Y.; Chassefière, E.

1992-08-01

Global Martian atmospheric results derived from the infrared-imaging spectrometer ISM flown aboard the Phobos 2 Soviet space-craft are presented. Over low altitude regions the expected CO mixing ratio of (8 ± 3) × 10 -4 is measured. Variations of the 2.35-μm feature are inconsistent with this value over the Great Martian Volcanoes. If the 2.35-μm band is entirely attributable to carbon monoxide, the CO mixing ratio is typically depleted by a factor of 3 over these high altitude areas. Orography should play a major role in the existence of this CO "hole." If, however, these spectral variations at 2.35 μm are due to the surface composition, the fraction of the surface covered by the responsible mineral must smoothly decrease as the surface elevation decreases. This phenomenon implies a strong interaction between the surface and the atmosphere for the Great Martian Volcanoes. Diurnal behavior and latitudinal variations of water vapor are globally consistent with Viking measurements. During the Phobos observations, the water vapor amounts over the bright equatorial regions range around 11 pr-μm during the day. These amounts are slightly larger than those inferred from 1976 to 1979. The lack of global dust storms during 1988-1989 could explain the enhancement of H 2O in the atmosphere.

Amino-functionalized surface modification of polyacrylonitrile hollow fiber-supported polydimethylsiloxane membranes

NASA Astrophysics Data System (ADS)

Hu, Leiqing; Cheng, Jun; Li, Yannan; Liu, Jianzhong; Zhou, Junhu; Cen, Kefa

2017-08-01

This study aimed to improve surface polarity of polydimethylsiloxane (PDMS) membranes and provide surface active sites which were easy to react with other chemicals. 3-Aminopropyltriethoxysilane (APTES) containing an amino group was introduced into a PDMS membrane by crosslinking to prepare polyacrylonitrile hollow fiber-supported PDMS membranes with an amino-functionalized surface. Fourier transform infrared and X-ray photoelectron spectroscopic analyses proved the existence of APTES and its amino group in the PDMS membrane. The concentration of N atoms on the PDMS membrane surface reached ∼6% when the mass ratio of APTES/PDMS oligomer in the PDMS coating solution was increased to 4/3. The water contact angle decreased from ∼114° to ∼87.5°, indicating the improved surface polarization of the PDMS membrane. The density and swelling degree of the PDMS membrane decreased and increased, respectively, with increasing APTES content in PDMS. This phenomenon increased CO2 permeability and decreased CO2/H2 selectivity, CO2/CH4 selectivity, and CO2/N2 selectivity. When the mass ratio of APTES/PDMS oligomer was increased from 0 to 4/3, the CO2 permeation rate of the hollow fiber-supported PDMS membranes initially decreased from ∼2370 GPU to ∼860 GPU and then increased to ∼2000 GPU due to the change in coating solution viscosity.

Toward the minimum inner edge distance of the habitable zone

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zsom, Andras; Seager, Sara; De Wit, Julien

2013-12-01

We explore the minimum distance from a host star where an exoplanet could potentially be habitable in order not to discard close-in rocky exoplanets for follow-up observations. We find that the inner edge of the Habitable Zone for hot desert worlds can be as close as 0.38 AU around a solar-like star, if the greenhouse effect is reduced (∼1% relative humidity) and the surface albedo is increased. We consider a wide range of atmospheric and planetary parameters such as the mixing ratios of greenhouse gases (water vapor and CO{sub 2}), surface albedo, pressure, and gravity. Intermediate surface pressure (∼1-10 bars)more » is necessary to limit water loss and to simultaneously sustain an active water cycle. We additionally find that the water loss timescale is influenced by the atmospheric CO{sub 2} level, because it indirectly influences the stratospheric water mixing ratio. If the CO{sub 2} mixing ratio of dry planets at the inner edge is smaller than 10{sup –4}, the water loss timescale is ∼1 billion years, which is considered here too short for life to evolve. We also show that the expected transmission spectra of hot desert worlds are similar to an Earth-like planet. Therefore, an instrument designed to identify biosignature gases in an Earth-like atmosphere can also identify similarly abundant gases in the atmospheres of dry planets. Our inner edge limit is closer to the host star than previous estimates. As a consequence, the occurrence rate of potentially habitable planets is larger than previously thought.« less

Modeling Silicate Weathering for Elevated CO2 and Temperature

NASA Astrophysics Data System (ADS)

Bolton, E. W.

2016-12-01

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

Fast Atmosphere-Ocean Model Runs with Large Changes in CO2

NASA Technical Reports Server (NTRS)

Russell, Gary L.; Lacis, Andrew A.; Rind, David H.; Colose, Christopher; Opstbaum, Roger F.

2013-01-01

How does climate sensitivity vary with the magnitude of climate forcing? This question was investigated with the use of a modified coupled atmosphere-ocean model, whose stability was improved so that the model would accommodate large radiative forcings yet be fast enough to reach rapid equilibrium. Experiments were performed in which atmospheric CO2 was multiplied by powers of 2, from 1/64 to 256 times the 1950 value. From 8 to 32 times, the 1950 CO2, climate sensitivity for doubling CO2 reaches 8 C due to increases in water vapor absorption and cloud top height and to reductions in low level cloud cover. As CO2 amount increases further, sensitivity drops as cloud cover and planetary albedo stabilize. No water vapor-induced runaway greenhouse caused by increased CO2 was found for the range of CO2 examined. With CO2 at or below 1/8 of the 1950 value, runaway sea ice does occur as the planet cascades to a snowball Earth climate with fully ice covered oceans and global mean surface temperatures near 30 C.

Response of anaerobic carbon cycling to water table manipulation in an Alaskan rich fen

USGS Publications Warehouse

Kane, E.S.; Chivers, M.R.; Turetsky, M.R.; Treat, C.C.; Petersen, D.G.; Waldrop, M.; Harden, J.W.; McGuire, A.D.

2013-01-01

To test the effects of altered hydrology on organic soil decomposition, we investigated CO2 and CH4 production potential of rich-fen peat (mean surface pH = 6.3) collected from a field water table manipulation experiment including control, raised and lowered water table treatments. Mean anaerobic CO2 production potential at 10 cm depth (14.1 ± 0.9 μmol C g−1 d−1) was as high as aerobic CO2 production potential (10.6 ± 1.5 μmol C g−1 d−1), while CH4 production was low (mean of 7.8 ± 1.5 nmol C g−1 d−1). Denitrification enzyme activity indicated a very high denitrification potential (197 ± 23 μg N g−1 d−1), but net NO-3 reduction suggested this was a relatively minor pathway for anaerobic CO2 production. Abundances of denitrifier genes (nirK and nosZ) did not change across water table treatments. SO2-4 reduction also did not appear to be an important pathway for anaerobic CO2 production. The net accumulation of acetate and formate as decomposition end products in the raised water table treatment suggested that fermentation was a significant pathway for carbon mineralization, even in the presence of NO-3. Dissolved organic carbon (DOC) concentrations were the strongest predictors of potential anaerobic and aerobic CO2 production. Across all water table treatments, the CO2:CH4 ratio increased with initial DOC leachate concentrations. While the field water table treatment did not have a significant effect on mean CO2 or CH4 production potential, the CO2:CH4 ratio was highest in shallow peat incubations from the drained treatment. These data suggest that with continued drying or with a more variable water table, anaerobic CO2 production may be favored over CH4 production in this rich fen. Future research examining the potential for dissolved organic substances to facilitate anaerobic respiration, or alternative redox processes that limit the effectiveness of organic acids as substrates in anaerobic metabolism, would help explain additional uncertainty concerning carbon mineralization in this system.

Supercritical CO2 drying of poly(methyl methacrylate) photoresist for deep x-ray lithography: a brief note

NASA Astrophysics Data System (ADS)

Shukla, Rahul; Abhinandan, Lala; Sharma, Shivdutt

2017-07-01

Poly(methyl methacrylate) (PMMA) is an extensively used positive photoresist for deep x-ray lithography. The post-development release of the microstructures of PMMA becomes very critical for high aspect ratio fragile and freestanding microstructures. Release of high aspect ratio comb-drive microstructure of PMMA made by one-step x-ray lithography (OXL) is studied. The effect of low-surface tension Isopropyl alcohol (IPA) over water is investigated for release of the high aspect ratio microstructures using conventional and supercritical (SC) CO2 drying. The results of conventional drying are also compared for the samples released or dried in both in-house developed and commercial SC CO2 dryer. It is found that in all cases the microstructures of PMMA are permanently deformed and damaged while using SC CO2 for drying. For free-standing high aspect ratio microstructures of PMMA made by OXL, it is advised to use low-surface tension IPA over DI water. However, this brings a limitation on the design of the microstructure.

Distributions and Relationships of CO2, O2, and Dimethylsulfide in the Changjiang (Yangtze) Estuary and Its Adjacent Waters in Summer

NASA Astrophysics Data System (ADS)

Wu, Xi; Tan, Tingting; Liu, Chunying; Li, Tie; Liu, Xiaoshou; Yang, Guipeng

2018-04-01

The distributions and relationships of O2, CO2, and dimethylsulfide (DMS) in the Changjiang (Yangtze) Estuary and its adjacent waters were investigated in June 2014. In surface water, mean O2 saturation level, partial pressure of CO2 (pCO2), and DMS concentrations (and ranges) were 110% (89%-167%), 374 μatm (91-640 μatm), and 8.53 nmol L-1 (1.10-27.50 nmol L-1), respectively. The sea-to-air fluxes (and ranges) of DMS and CO2 were 8.24 μmol m-2 d-1 (0.26-62.77 μmol m-2 d-1), and -4.7 mmol m-2 d-1 (-110.8-31.7 mmol m-2 d-1), respectively. Dissolved O2 was oversaturated, DMS concentrations were relatively high, and this region served as a sink of atmospheric CO2. The pCO2 was significantly and negatively correlated with the O2 saturation level, while the DMS concentration showed different positive relationships with the O2 saturation level in different water masses. In vertical profiles, a hypoxic zone existed below 20 m at a longitude of 123°E. The stratification of temperature and salinity caused by the Taiwan Warm Current suppressed seawater exchange between upper and lower layers, resulting in the formation of a hypoxic zone. Oxidative decomposition of organic detritus carried by the Changjiang River Diluted Water (CRDW) consumed abundant O2 and produced additional CO2. The DMS concentrations decreased because of low phytoplankton biomass in the hypoxic zone. Strong correlations appeared between the O2 saturation level, pCO2 and DMS concentrations in vertical profiles. Our results strongly suggested that CRDW played an important role in the distributions and relationships of O2, CO2, and DMS.

Future ocean hypercapnia driven by anthropogenic amplification of the natural CO2 cycle.

PubMed

McNeil, Ben I; Sasse, Tristan P

2016-01-21

High carbon dioxide (CO2) concentrations in sea-water (ocean hypercapnia) can induce neurological, physiological and behavioural deficiencies in marine animals. Prediction of the onset and evolution of hypercapnia in the ocean requires a good understanding of annual variations in oceanic CO2 concentration, but there is a lack of relevant global observational data. Here we identify global ocean patterns of monthly variability in carbon concentration using observations that allow us to examine the evolution of surface-ocean CO2 levels over the entire annual cycle under increasing atmospheric CO2 concentrations. We predict that the present-day amplitude of the natural oscillations in oceanic CO2 concentration will be amplified by up to tenfold in some regions by 2100, if atmospheric CO2 concentrations continue to rise throughout this century (according to the RCP8.5 scenario of the Intergovernmental Panel on Climate Change). The findings from our data are broadly consistent with projections from Earth system climate models. Our predicted amplification of the annual CO2 cycle displays distinct global patterns that may expose major fisheries in the Southern, Pacific and North Atlantic oceans to hypercapnia many decades earlier than is expected from average atmospheric CO2 concentrations. We suggest that these ocean 'CO2 hotspots' evolve as a combination of the strong seasonal dynamics of CO2 concentration and the long-term effective storage of anthropogenic CO2 in the oceans that lowers the buffer capacity in these regions, causing a nonlinear amplification of CO2 concentration over the annual cycle. The onset of ocean hypercapnia (when the partial pressure of CO2 in sea-water exceeds 1,000 micro-atmospheres) is forecast for atmospheric CO2 concentrations that exceed 650 parts per million, with hypercapnia expected in up to half the surface ocean by 2100, assuming a high-emissions scenario (RCP8.5). Such extensive ocean hypercapnia has detrimental implications for fisheries during the twenty-first century.

Future ocean hypercapnia driven by anthropogenic amplification of the natural CO2 cycle

NASA Astrophysics Data System (ADS)

McNeil, Ben I.; Sasse, Tristan P.

2016-01-01

High carbon dioxide (CO2) concentrations in sea-water (ocean hypercapnia) can induce neurological, physiological and behavioural deficiencies in marine animals. Prediction of the onset and evolution of hypercapnia in the ocean requires a good understanding of annual variations in oceanic CO2 concentration, but there is a lack of relevant global observational data. Here we identify global ocean patterns of monthly variability in carbon concentration using observations that allow us to examine the evolution of surface-ocean CO2 levels over the entire annual cycle under increasing atmospheric CO2 concentrations. We predict that the present-day amplitude of the natural oscillations in oceanic CO2 concentration will be amplified by up to tenfold in some regions by 2100, if atmospheric CO2 concentrations continue to rise throughout this century (according to the RCP8.5 scenario of the Intergovernmental Panel on Climate Change). The findings from our data are broadly consistent with projections from Earth system climate models. Our predicted amplification of the annual CO2 cycle displays distinct global patterns that may expose major fisheries in the Southern, Pacific and North Atlantic oceans to hypercapnia many decades earlier than is expected from average atmospheric CO2 concentrations. We suggest that these ocean ‘CO2 hotspots’ evolve as a combination of the strong seasonal dynamics of CO2 concentration and the long-term effective storage of anthropogenic CO2 in the oceans that lowers the buffer capacity in these regions, causing a nonlinear amplification of CO2 concentration over the annual cycle. The onset of ocean hypercapnia (when the partial pressure of CO2 in sea-water exceeds 1,000 micro-atmospheres) is forecast for atmospheric CO2 concentrations that exceed 650 parts per million, with hypercapnia expected in up to half the surface ocean by 2100, assuming a high-emissions scenario (RCP8.5). Such extensive ocean hypercapnia has detrimental implications for fisheries during the twenty-first century.

Contribution of the biological crust to the soil CO2 efflux in a Mediterranean ecosystem

NASA Astrophysics Data System (ADS)

Morillas, Lourdes; Bellucco, Veronica; Lo Cascio, Mauro; Marras, Serena; Spano, Donatella; Mereu, Simone

2016-04-01

Lately, the important role of the soil biological crust (hereafter biocrust) in Mediterranean ecosystems is emerging from a multitude of articles. It is becoming apparent that the biocrust has an important role in regulating ecosystem functions and that it interacts with the woody and herbaceous vegetation to a degree depending on the availability of water among other factors. Here we present the first results of a wider project and focus on the contribution of the biocrust to soil CO2 efflux, and on how the respiration of the biocrust responds to soil water content and temperature. A manipulative experiment was performed in a Mediterranean shrubland ecosystem in Sardinia (Italy) to assess the contribution of the bicocrust to soil CO2 efflux and to identify the main environmental drivers of the CO2 efflux in this ecosystem. For 19 months,in situ soil CO2 efflux was measured over three different surfaces: soil deprived of biocrust (hereafter Soil), biocrust (hereafter BC) and intact soil (hereafter Soil+BC). For these surfaces, three different approaches were used to investigate the dependency of CO2 efflux on soil temperature and soil water content, e.g. a simple linear regression, a multi-linear equation, and a modified version of the most common used Lloyd and Taylor model (Lloyd and Taylor, 1994). Results showed that CO2 effluxes emitted by Soil, BC and Soil+BC were differently driven by soil moisture and temperature: BC respiration was mainly controlled by soil moisture at 5 cm depth, whereas both soil temperature and water content at 20 cm depth determined Soil CO2 efflux. Soil temperature and water content at 5 cm depth drove Soil+BC respiration. We also found that biocrust can contribute substantially (up to 60%) to the total soil respiration depending on its moisture content. This contribution persists even in periods in which deeper soil layers are inactive, as small water pulses can activate lichens, mosses and cyanobacteria associated to the biocrust as well as the metabolism of carbon in soils, while deeper soil layers remain dormant. The important differences observed in CO2 efflux between Soil and Soil+BC suggest that projections on carbon budgets may underestimate soil CO2 efflux in spatially heterogeneous Mediterranean areas. Thus, our results highlight the relevance of accounting for the biocrust contribution to soil respiration and its responses to environmental drivers. The ongoing and planned activities to understand the full complexity of all factors determining respiration in water limited environments are briefly discussed. Lloyd, J., Taylor, J. A., 1994. On the temperature dependence of soil respiration. Funct. Ecol. 8, 315-323.

Extraction of CO2 from air samples for isotopic analysis and limits to ultra high precision delta18O determination in CO2 gas.

PubMed

Werner, R A; Rothe, M; Brand, W A

2001-01-01

The determination of delta18O values in CO2 at a precision level of +/-0.02 per thousand (delta-notation) has always been a challenging, if not impossible, analytical task. Here, we demonstrate that beyond the usually assumed major cause of uncertainty - water contamination - there are other, hitherto underestimated sources of contamination and processes which can alter the oxygen isotope composition of CO2. Active surfaces in the preparation line with which CO2 comes into contact, as well as traces of air in the sample, can alter the apparent delta18O value both temporarily and permanently. We investigated the effects of different surface materials including electropolished stainless steel, Duran glass, gold and quartz, the latter both untreated and silanized. CO2 frozen with liquid nitrogen showed a transient alteration of the 18O/16O ratio on all surfaces tested. The time to recover from the alteration as well as the size of the alteration varied with surface type. Quartz that had been ultrasonically cleaned for several hours with high purity water (0.05 microS) exhibited the smallest effect on the measured oxygen isotopic composition of CO2 before and after freezing. However, quartz proved to be mechanically unstable with time when subjected to repeated large temperature changes during operation. After several days of operation the gas released from the freezing step contained progressively increasing trace amounts of O2 probably originating from inclusions within the quartz, which precludes the use of quartz for cryogenically trapping CO2. Stainless steel or gold proved to be suitable materials after proper pre-treatment. To ensure a high trapping efficiency of CO2 from a flow of gas, a cold trap design was chosen comprising a thin wall 1/4" outer tube and a 1/8" inner tube, made respectively from electropolished stainless steel and gold. Due to a considerable 18O specific isotope effect during the release of CO2 from the cold surface, the thawing time had to be as long as 20 min for high precision delta18O measurements. The presence of traces of air in almost all CO2 gases that we analyzed was another major source of error. Nitrogen and oxygen in the ion source of our mass spectrometer (MAT 252, Finnigan MAT, Bremen, Germany) give rise to the production of NO2 at the hot tungsten filament. NO2+ is isobaric with C16O18O+ (m/z 46) and interferes with the delta18O measurement. Trace amounts of air are present in CO2 extracted cryogenically from air at -196 degrees C. This air, trapped at the cold surface, cannot be pumped away quantitatively. The amount of air present depends on the surface structure and, hence, the alteration of the measured delta18O value varies with the surface conditions. For automated high precision measurement of the isotopic composition of CO2 of air samples stored in glass flasks an extraction interface ('BGC-AirTrap') was developed which allows 18 analyses (including standards) per day to be made. For our reference CO2-in-air, stored in high pressure cylinders, the long term (>9 months) single sample precision was 0.012 per thousand for delta13C and 0.019 per thousand for delta18O. Copyright 2001 John Wiley & Sons, Ltd.

Factors Controlling Diffusive CO2 Transport and Production in the Cedarburg Bog, Saukville, Wisconsin

NASA Astrophysics Data System (ADS)

Joynt, E.; Grundl, T.; Han, W. S.; Gulbranson, E. L.

2016-12-01

Wetlands are vital components of the carbon cycle containing an estimated 20-30% of the global soil carbon store. The Cedarburg Bog of southeastern Wisconsin contains multiple wetland types, including the southernmost string bog found in North America. Carbon dioxide (CO2) behavior in wetland systems respond to multiple interdependent variables that are collectively not well understood. Modeling CO2 behavior in wetland environments requires a detailed representation of these variables. In 2014 a LI-COR 8100A automated soil gas flux system was installed in the string bog, measuring CO2 concentration and flux. Groundwater data, soil temperature, and weather data (temperature, pressure, precipitation, etc.) were included to reveal correlations between soil CO2 flux/concentration and external forces. In 2015 field data were complemented with soil moisture data and depth profiles of pore water chemistry and stable carbon isotopes from peat and soil gas to discern source and evolution of CO2 at depth. Initial gaseous δ13C(CO2) average -18‰ and deplete overnight suggesting increasing microbial metabolic efficiency. δ13C soil microbial biomass measure roughly -21‰ to -22‰. LI-COR data show diurnal and seasonal trends; CO2 concentration builds overnight while flux increases during the day. CO2 flux magnitude and CO2 concentration range peak in mid-summer, but frequency of increased CO2 flux events varies seasonally each year. Flux averages 7.55 mgCO2/min-m2 during the day but reaches 530 mgCO2/min-m2. Increased atmospheric and soil temperatures and decreasing atmospheric pressure prelude increasing CO2 flux intensity, though correlation strengths vary. Water level may influence CO2 flux, but observations suggest a mobile peat surface with the water table. 2016 imagery from trail cameras will determine extent of peat/well casing movement with water level changes. Further interpretation of data trends will utilize HYDRUS-1D to quantify relationships under changing environmental conditions.

Predicting the response of the Amazon rainforest to persistent drought conditions under current and future climates: a major challenge for global land surface models

NASA Astrophysics Data System (ADS)

Joetzjer, E.; Delire, C.; Douville, H.; Ciais, P.; Decharme, B.; Fisher, R.; Christoffersen, B.; Calvet, J. C.; da Costa, A. C. L.; Ferreira, L. V.; Meir, P.

2014-08-01

While a majority of Global Climate Models project dryer and longer dry seasons over the Amazon under higher CO2 levels, large uncertainties surround the response of vegetation to persistent droughts in both present-day and future climates. We propose a detailed evaluation of the ability of the ISBACC Land Surface Model to capture drought effects on both water and carbon budgets, comparing fluxes and stocks at two recent ThroughFall Exclusion (TFE) experiments performed in the Amazon. We also explore the model sensitivity to different Water Stress Function (WSF) and to an idealized increase in CO2 concentration and/or temperature. In spite of a reasonable soil moisture simulation, ISBACC struggles to correctly simulate the vegetation response to TFE whose amplitude and timing is highly sensitive to the WSF. Under higher CO2 concentration, the increased Water Use Efficiency (WUE) mitigates the ISBACC's sensitivity to drought. While one of the proposed WSF formulation improves the response of most ISBACC fluxes, except respiration, a parameterization of drought-induced tree mortality is missing for an accurate estimate of the vegetation response. Also, a better mechanistic understanding of the forest responses to drought under a warmer climate and higher CO2 concentration is clearly needed.

Sunlight Controls Water Column Processing of Carbon in Arctic Freshwaters

NASA Astrophysics Data System (ADS)

Cory, R. M.; Ward, C. P.; Crump, B. C.; Kling, G. W.

2014-12-01

Carbon (C) in thawing permafrost soils may have global impacts on climate change, yet controls on its processing and fate are poorly understood. The dominant fate of dissolved organic C (DOC) released from soils to inland waters is either complete oxidation to CO2 or partial oxidation and river export to oceans. Both processes are most often attributed to bacterial respiration, but we recently showed that photochemical oxidation exceeds rates of respiration and accounts for 70-95% of total DOC processed in the water column of arctic lakes and rivers. While the overall dominance of photochemical processing in streams and lakes remained, the fate of DOC varied consistently by water type. In small streams DOC was mainly mineralized by sunlight to CO2, while in lakes the main fate of DOC was partial photo-oxidation. Large rivers were intermediate between these end members, and photo-mineralization to CO2 was about equal to or less than partial photo-oxidation. We suggest this pattern is a result of light-exposure history, where DOC leached from soils into headwater streams has little prior light exposure and is labile to complete photo-oxidation, but as light exposure increases moving downstream and into lakes with longer residence times the DOC photo-lability declines. Thus as easily photo-mineralized moieties are removed, DOC fate shifts toward partial photo-oxidation and downstream export in rivers and lakes. At the basin scale, photochemical processing of DOC is about one third of the total CO2 released from surface waters, and is thus an important, newly measured component of the Arctic C budget. We also suggest that these photochemical transformations of DOC will occur in any shallow surface water, and could be important for better understanding inland water carbon cycling.

Assessment of mechanical rock alteration caused by CO 2 -water mixtures using indentation and scratch experiments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sun, Yuhao; Aman, Michael; Espinoza, D. Nicolas

CO2 injection into geological formations disturbs the geochemical equilibrium between water and minerals. Thus, some mineral phases are prone to dissolution and precipitation with ensuing changes of petrophysical and geomechanical properties of the host formations. Chemically-assisted degradation of mechanical properties can endanger the structural integrity of the storage formation and must be carefully studied and considered to guarantee safe long-term trapping. Few experimental data sets involving CO2 alteration and mechanical testing of rock samples are available since these experiments are length, expensive, and require specialized equipment and personnel. Autoclave experiments are easier to perform and control but result in amore » limited 'skin depth' of chemically-altered zone near the surface of the sample. This article presents the validation of micro-indentation and micro-scratch tests as efficient tools to assess the alteration of mechanical properties of rocks geochemically altered by CO2-water mixtures. Results from tests on sandstone and siltstone from Crystal Geyser, Utah naturally altered by CO2-acidified water show that mechanical parameters measured with indentation (indentation hardness, Young's modulus and contact creep compliance rate) and scratching (scratch hardness and fracture toughness) consistently indicated weakening of the rock after CO2-induced alteration. Decreases of measured parameters vary from 14% to 87%. Experimental results and analyses show that micromechanical tests are potentially quick and reliable tools to determine the change of mechanical properties of rocks subject to exposure to CO2-acidified water, particularly in well-controlled autoclave experiments. Measured parameters are not intended to provide inputs for coupled reservoir simulation with geomechanics but rather to inform the execution of larger scale tests investigating the susceptibility of rock facies to chemical alteration by CO2-water mixtures. Recognizing this susceptibility of rock facies of CO2 geological storage target formations is critical to controlling undesired emergent behavior associated with CO2 sequestration.« less

Widespread potential for microbial MTBE degradation in surface-water sediments

USGS Publications Warehouse

Bradley, P.M.; Landmeyer, J.E.; Chapelle, F.H.

2001-01-01

Microorganisms indigenous to stream and lake bed sediments, collected from 11 sites throughout the United States, demonstrated significant mineralization of the fuel oxygenate, methyl-tert-butyl ether (MTBE). Mineralization of [U-14C]MTBE to 14CO2 ranged from 15 to 66% over 50 days and did not differ significantly between sediments collected from MTBE contaminated sites and from sites with no history of MTBE exposure. This result suggests that even the microbial communities indigenous to newly contaminated surface water systems will exhibit some innate ability to attenuate MTBE under aerobic conditions. The magnitude of MTBE mineralization was related to the sediment grain size distribution. A pronounced, inverse correlation (p < 0.001; r2 = 0.73) was observed between the final recovery of 14CO2 and the percentage content of silt and clay sized grains (grain diameter < 0.125 mm). The results of this study indicate that the microorganisms that inhabit the bed sediments of streams and lakes can degrade MTBE efficiently and that this capability is widespread in the environment. Thus aerobic bed sediment microbial processes may provide a significant environmental sink for MTBE in surface water systems throughout the United States and may contribute to the reported transience of MTBE in some surface waters.

Relationship between Water and Carbon Utilization under Different Straw Mulching and Plant Density of Summer Maize in North China Plain

NASA Astrophysics Data System (ADS)

Liu, Quanru; Du, Shoujian; Yin, Honglian; Wang, Juan

2018-03-01

To explore the relationship between water and carbon utilization and key factors to keep high water use efficiency (WUE), a 2-yr experiment was conduct by covering 0 and 0.6 kg m-2 straw to the surface of soil with plant densities of 1.0 × 105, 7.5 × 104, and 5.5 × 104 plants ha-1 in North China Plain during summer maize growing seasons of the 2012 and 2013. Results showed that straw mulching not only increased grain yield (GY), WUE, and carbon efficient ratio (CER) but also inhibited CO2 emission significantly. WUE positively correlated with CER, GY and negative correlated with evapotranspiration (ET) and CO2 emission. CER had the larger direct effect on WUE compared with ET and CO2 emission. The results indicate that straw mulching management in summer maize growing seasons could make sense for inhibiting CO2 emission.

Superheated water pretreatment combined with CO2 activation/regeneration of the exhausted activated carbon used in the treatment of industrial wastewater.

PubMed

Xiao, Jin; Yu, Bailie; Zhong, Qifan; Yuan, Jie; Yao, Zhen; Zhang, Liuyun

2017-10-01

This paper examines a novel method of regenerating saturated activated carbon after adsorption of complex phenolic, polycyclic aromatic hydrocarbons with low energy consumption by using superheated water pretreatment combined with CO 2 activation. The effects of the temperature of the superheated water, liquid-solid ratio, soaking time, activation temperature, activation time, and CO 2 flow rate of regeneration and adsorption of coal-powdered activated carbon (CPAC) were studied. The results show that the adsorption capacity of iodine values on CPAC recovers to 102.25% of the fresh activated carbon, and the recovery rate is 79.8% under optimal experimental conditions. The adsorption model and adsorption kinetics of methylene blue on regenerated activated carbon (RAC) showed that the adsorption process was in accordance with the Langmuir model and the pseudo-second-order kinetics model. Furthermore, the internal diffusion process was the main controlling step. The surface properties, Brunauer-Emmett-Teller (BET) surface area, and pore size distribution were characterized by Fourier transform infrared spectroscopy (FT-IR) and BET, which show that the RAC possesses more oxygen-containing functional groups with a specific surface area of 763.39 m 2 g -1 and a total pore volume of 0.3039 cm 3 g -1 . Micropores account for 79.8% and mesopores account for 20.2%.

A strong CO2 sink enhanced by eutrophication in a tropical coastal embayment (Guanabara Bay, Rio de Janeiro, Brazil)

NASA Astrophysics Data System (ADS)

Cotovicz, L. C., Jr.; Knoppers, B. A.; Brandini, N.; Costa Santos, S. J.; Abril, G.

2015-10-01

In contrast to its small surface area, the coastal zone plays a disproportionate role in the global carbon cycle. Carbon production, transformation, emission and burial rates at the land-ocean interface are significant at the global scale but still poorly known, especially in tropical regions. Surface water pCO2 and ancillary parameters were monitored during nine field campaigns between April 2013 and April 2014 in Guanabara Bay, a tropical eutrophic to hypertrophic semi-enclosed estuarine embayment surrounded by the city of Rio de Janeiro, southeast Brazil. Water pCO2 varied between 22 and 3715 ppmv in the bay, showing spatial, diurnal and seasonal trends that mirrored those of dissolved oxygen (DO) and chlorophyll a (Chl a). Marked pCO2 undersaturation was prevalent in the shallow, confined and thermally stratified waters of the upper bay, whereas pCO2 oversaturation was restricted to sites close to the small river mouths and small sewage channels, which covered only 10 % of the bay's area. Substantial daily variations in pCO2 (up to 395 ppmv between dawn and dusk) were also registered and could be integrated temporally and spatially for the establishment of net diurnal, seasonal and annual CO2 fluxes. In contrast to other estuaries worldwide, Guanabara Bay behaved as a net sink of atmospheric CO2, a property enhanced by the concomitant effects of strong radiation intensity, thermal stratification, and high availability of nutrients, which promotes phytoplankton development and net autotrophy. The calculated CO2 fluxes for Guanabara Bay ranged between -9.6 and -18.3 mol C m-2 yr-1, of the same order of magnitude as the organic carbon burial and organic carbon inputs from the watershed. The positive and high net community production (52.1 mol C m-2 yr-1) confirms the high carbon production in the bay. This autotrophic metabolism is apparently enhanced by eutrophication. Our results show that global CO2 budgetary assertions still lack information on tropical, marine-dominated estuarine systems, which are affected by thermal stratification and eutrophication and behave specifically with respect to atmospheric CO2.

Insights into Silicate Carbonation Processes in Water-Bearing Supercritical CO2 Fluids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miller, Quin RS; Thompson, Christopher J.; Loring, John S.

2013-07-01

Long-term geologic storage of carbon dioxide (CO2) is considered an integral part to moderating CO2 concentrations in the atmosphere and subsequently minimizing effects of global climate change. Although subsurface injection of CO2 is common place in certain industries, deployment at the scale required for emission reduction is unprecedented and therefore requires a high degree of predictability. Accurately modeling geochemical processes in the subsurface requires experimental derived data for mineral reactions occurring between the CO2, water, and rocks. Most work in this area has focused on aqueous-dominated systems in which dissolved CO2 reacts to form crystalline carbonate minerals. Comparatively little laboratorymore » research has been conducted on reactions occurring between minerals in the host rock and the wet supercritical fluid phase. In this work, we studied the carbonation of wollastonite [CaSiO3] exposed to variably hydrated supercritical CO2 (scCO2) at a range of temperatures (50, 55 and 70 °C) and pressures (90,120 and 160 bar) that simulate conditions in geologic repositories. Mineral transformation reactions were followed by three novel in situ high pressure techniques, including x-ray diffraction that tracked the rate and extents of wollastonite conversion to calcite. Increased dissolved water concentrations in the supercritical CO2 resulted in increased silicate carbonation approaching ~50 wt. %. Development of thin water films on the mineral surface were directly observed with infrared spectroscopy and determined to be critical for facilitating carbonation processes. Even in extreme low water conditions, magic angle spinning nuclear magnetic resonance detected formation of Q3 [Si(OSi)3OH] and Q4 [Si(OSi)4] amorphous silica species. Unlike the thick (<10 μm) passivating silica layers observed in the fully water saturated scCO2 experiments, images obtained from a focused ion beam sectioned sample indicted these coatings were chemically wollastonite but structurally amorphous. In addition, evidence of an intermediate hydrated amorphous calcium carbonate forming under these conditions further emphasize the importance of understanding geochemical processes occurring in water bearing scCO2 fluids.« less

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

PubMed

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

2013-01-01

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

CO2 greenhouse in the early martian atmosphere: SO2 inhibits condensation

NASA Technical Reports Server (NTRS)

Yung, Y. L.; Nair, H.; Gerstell, M. F.

1997-01-01

Many investigators of the early martian climate have suggested that a dense carbon dioxide atmosphere was present and warmed the surface above the melting point of water (J.B. Pollack, J.F. Kasting, S.M. Richardson, and K. Poliakoff 1987. Icarus 71, 203-224). However, J.F. Kasting (1991. Icarus 94, 1-13) pointed out that previous thermal models of the primitive martian atmosphere had not considered the condensation of CO2. When this effect was incorporated, Kasting found that CO2 by itself is inadequate to warm the surface. SO2 absorbs strongly in the near UV region of the solar spectrum. While a small amount of SO2 may have a negligible effect by itself on the surface temperature, it may have significantly warmed the middle atmosphere of early Mars, much as ozone warms the terrestrial stratosphere today. If this region is kept warm enough to inhibit the condensation of CO2, then CO2 remains a viable greenhouse gas. Our preliminary radiative modeling shows that the addition of 0.1 ppmv of SO2 in a 2 bar CO2 atmosphere raises the temperature of the middle atmosphere by approximately 10 degrees, so that the upper atmosphere in a 1 D model remains above the condensation temperature of CO2. In addition, this amount of SO2 in the atmosphere provides an effective UV shield for a hypothetical biosphere on the martian surface.

Review of the inorganic geochemistry of peats and peatland waters

NASA Astrophysics Data System (ADS)

Shotyk, William

1988-06-01

The major floristic and geochemical differences between bogs, fens, and swamps are summarized, and the most common peat types described. This is followed by a critical, historical review of the literature. The methods used to measure the pH of peatland (mire) waters are examined, and the pH range of various peatland types is reported. In addition, horizontal and vertical pH variations are illustrated, and factors affecting the pH of these waters reviewed. The cause of the low pH of surface waters of Sphagnum bogs (approximately pH 4) is critically investigated, and the relative importance of dissolved CO 2 and other inorganic acids, and organic acids to the low pH is assessed. Cation exchange on the surfaces of Sphagnum mosses is found to be a relatively unimportant acidification mechanism, but important to the chemical ecology of the plants. The redox chemistry of mire waters is described in terms of the geochemistry of such redox indicators as O 2, CO 2, CH 4, CO, H 2, H 2S, SO 42-, native Cu, and siderite (FeCO 3). Published studies of Eh in peatlands are cited, and the problems of Eh measurement and interpretation are explored. The chemical composition of mire waters (major and trace metals, and nonmetallic species) is examined, and factors affecting their composition reported. The abundance and distribution of mineral matter in peats is described, and the occurrence and formation of minerals of Fe (pyrite and other sulphides, siderite, vivianite), Cu (chalcopyrite, native Cu, covellite) and Zn (smithsonite and wurtzite) investigated. The abundance and distribution of major elements (Si, Al, Na, K, Mg, Ca) and trace metals (Ni, V, Cr, Fe, Mn, Cu, U, Zn, Pb) is described, and factors affecting their solubility examined.

Comparative carbon cycle dynamics of the present and last interglacial

NASA Astrophysics Data System (ADS)

Brovkin, Victor; Brücher, Tim; Kleinen, Thomas; Zaehle, Sönke; Joos, Fortunat; Roth, Raphael; Spahni, Renato; Schmitt, Jochen; Fischer, Hubertus; Leuenberger, Markus; Stone, Emma J.; Ridgwell, Andy; Chappellaz, Jérôme; Kehrwald, Natalie; Barbante, Carlo; Blunier, Thomas; Dahl Jensen, Dorthe

2016-04-01

Changes in temperature and carbon dioxide during glacial cycles recorded in Antarctic ice cores are tightly coupled. However, this relationship does not hold for interglacials. While climate cooled towards the end of both the last (Eemian) and present (Holocene) interglacials, CO2 remained stable during the Eemian while rising in the Holocene. We identify and review twelve biogeochemical mechanisms of terrestrial (vegetation dynamics and CO2 fertilization, land use, wildfire, accumulation of peat, changes in permafrost carbon, subaerial volcanic outgassing) and marine origin (changes in sea surface temperature, carbonate compensation to deglaciation and terrestrial biosphere regrowth, shallow-water carbonate sedimentation, changes in the soft tissue pump, and methane hydrates), which potentially may have contributed to the CO2 dynamics during interglacials but which remain not well quantified. We use three Earth System Models (ESMs) of intermediate complexity to compare effects of selected mechanisms on the interglacial CO2 and δ13CO2 changes, focusing on those with substantial potential impacts: namely carbonate sedimentation in shallow waters, peat growth, and (in the case of the Holocene) human land use. A set of specified carbon cycle forcings could qualitatively explain atmospheric CO2 dynamics from 8 ka BP to the pre-industrial. However, when applied to Eemian boundary conditions from 126 to 115 ka BP, the same set of forcings led to disagreement with the observed direction of CO2 changes after 122 ka BP. This failure to simulate late-Eemian CO2 dynamics could be a result of the imposed forcings such as prescribed CaCO3 accumulation and/or an incorrect response of simulated terrestrial carbon to the surface cooling at the end of the interglacial. These experiments also reveal that key natural processes of interglacial CO2 dynamics - shallow water CaCO3 accumulation, peat and permafrost carbon dynamics - are not well represented in the current ESMs. Global-scale modeling of these long-term carbon cycle components started only in the last decade, and uncertainty in parameterization of these mechanisms is a main limitation in the successful modeling of interglacial CO2 dynamics.

UV-Resistant and Thermally Stable Superhydrophobic CeO2 Nanotubes with High Water Adhesion.

PubMed

Li, Xue-Ping; Sun, Ya-Li; Xu, Yao-Yi; Chao, Zi-Sheng

2018-06-03

A novel type of sticky superhydrophobic cerium dioxide (CeO 2 ) nanotube material is prepared by hydrothermal treatment without any chemical modification. A water droplet on the material surface shows a static water contact angle of about 157° but the water droplet is pinned on the material surface even when the material surface is turned upside down. Interestingly, the as-prepared CeO 2 nanotube material displays durable superhydrophobicity and enhanced adhesion to water under ultraviolet (UV) light irradiation. Importantly, this change in water adhesion can be reversed by heat treatment to restore the original adhesive value of 20 µL. Further, the maximum volume of the water droplet adhered on the material surface of CeO 2 nanotubes can be regulated without loss of superhydrophobicity during the heating treatment/UV-irradiation cycling. Meanwhile, the superhydrophobic CeO 2 nanotube material shows remarkable thermal stability even at temperatures as high as 450 °C, long-term durability in chemical environment, and air-storage and good resistance to oily contaminant. Finally, the potential application in no-loss water transportation of this sticky superhydrophobic CeO 2 material is demonstrated. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Respiratory fluxes in a Canary Islands pine forest.

PubMed

Wieser, Gerhard; Gruber, Andreas; Bahn, Michael; Catalá, Enrique; Carrillo, Estefanía; Jiménez, Maria Soledad; Morales, Domingo

2009-03-01

We estimated component and whole-ecosystem CO(2) efflux (R(ECO)) in a Pinus canariensis Chr. Sm. ex DC stand in Tenerife, Canary Islands, an ecotone with strong seasonal changes in soil water availability. From November 2006 to February 2008, we measured foliage, stem and soil CO(2) efflux by chamber techniques. Site-specific CO(2) efflux models obtained from these chamber measurements were then combined with half-hourly measurements of canopy, stem and soil temperature as well as soil water potential, leaf and stem surface area data for scaling up component-specific CO(2) efflux to R(ECO). Integrated over an entire year, R(ECO) was 938 g of C m(-2) in 2007 and comprised the following component fluxes: 77% from soil, 11% from stems and 12% from foliage. Whole-ecosystem CO(2) efflux varied markedly throughout the year. During the cold and wet season, R(ECO) generally followed the seasonal trends in temperature, and during the warm and dry summer, however, R(ECO) was significantly reduced because of limited soil water availability in the main rooting horizon.

CO2 adsorption on diatomaceous earth modified with cetyltrimethylammonium bromide and functionalized with tetraethylenepentamine: Optimization and kinetics.

PubMed

Pornaroonthama, Phuwadej; Thouchprasitchai, Nutthavich; Pongstabodee, Sangobtip

2015-07-01

The carbon dioxide (CO2) adsorbent diatomaceous earth (DE) was modified with cetyltrimethylammonium bromide (CTAB) and functionalized with varying levels of tetraethylenepentamine (TEPA). The CO2 absorption at atmospheric pressure was optimized by varying the TEPA-loading level (0-40% (w/w)), operating temperature (40-80 °C) and water vapor concentration (0-16% (v/v)) in a 10% (v/v) CO2 feed stream in helium balance using a full 2(3) factorial design. The TEPA/CTAB-DE adsorbents were characterized by X-ray diffractometry, Fourier transform infrared spectrometry and thermogravimetric analyses. The CO2 adsorption capacity increased as each of these three factors increased. The TEPA loading level-water concentration interaction had a positive influence on the CO2 adsorption while the operating temperature-water concentration interaction was antagonistic. The optimal condition for CO2 adsorption on 40%TEPA/CTAB-DE, evaluated via a factorial design response surface method (RSM), was a temperature of 58-68 °C and a water vapor concentration of 9.5-14% (v/v), with a maximum CO2 adsorption capacity of 149.4 mg g(-1) at 63.5 °C and 12% (v/v) water vapor concentration in the feed. Validation and sensitivity tests revealed that the estimated CO2 adsorption capacity was within ±4% of the experimental values, suggesting that the RSM model was satisfied and acceptable. From three kinetic models (pseudo-first-order, pseudo-second-order model and Avrami's equation), assessed using an error function (Err) and the coefficient of determination (R(2)), Avrami's equation was the most appropriate to describe the kinetics of CO2 adsorption on the 40%TEPA/CTAB-DE adsorbent and suggested that more than one reaction pathway occurred in the CO2 adsorption. Copyright © 2015 Elsevier Ltd. All rights reserved.

Response to CO2 Transient Increase in the GISS Coupled Model: Regional Coolings in a Warming Climate

NASA Technical Reports Server (NTRS)

Russell, Gary L.; Rind, David

1999-01-01

The (GISS) Goddard Institute for Space Studies coupled atmosphere-ocean model is used to investigate the effect of increased atmospheric CO2 by comparing a compounded 1 percent CO2 increase experiment with a control simulation. After 70 years of integration, the global surface air temperature in the 1 percent CO2 experiment is 1.43 C warmer. In spite of this global warming, there are two distinct regions, the northern Atlantic Ocean and the southern Pacific Ocean, where the surface air temperature is up to 4 C cooler. This situation is maintained by two positive feedbacks: a local effect on convection in the South Pacific and a non-local impact on the meridional circulation in the North Atlantic. The poleward transport of latent energy and dry static energy by the atmosphere is greater in the 1 percent CO2 experiment, caused by warming and therefore increased water vapor and greater greenhouse capacity at lower latitudes. The larger atmospheric transports tend to reduce upward vertical fluxes of heat and moisture from the ocean surface at high latitudes, which has the effect of stabilizing the ocean, reducing both convection and the thermohaline circulation. With less convection, less warm water is brought up from below, and with a reduced North Atlantic thermohaline circulation (by 30 percent at time of CO2 doubling), the poleward energy transport by the oceans decreases. The colder water then leads to further reductions in evaporation, decreases of salinity at high latitudes, continued stabilization of the ocean, and maintenance of reduced convection and meridional overturning. Although sea ice decreases globally, it increases in the cooling regions which reduces the overall climate sensitivity; its effect is most pronounced in the Southern Hemisphere. Tropical warming has been observed over the past several decades; if modeling studies such as this and others which have produced similar effects are valid, these processes may already be beginning.

Variation in the carbon cycle of the Sevastopol Bay (Black Sea)

NASA Astrophysics Data System (ADS)

Orekhova, N. A.; Konovalov, S. K.

2018-01-01

Continuous increase in CO2 inventory in the ocean results in dramatic changes in marine biogeochemistry, e.g. acidification. That is why temporal and spatial variabilities in atmospheric pCO2 and dissolved inorganic carbon, including CO2, pH and alkalinity in water, as well as organic and inorganic carbon in bottom sediments have to be studied together making possible to resolve the key features of the carbon cycle transformation. A 30% increase of pCO2 in the Sevastopol Bay for 2008 - 2016 evidences changes in the DIC components ratios and a significant decrease in the ability to absorb atmospheric CO2 by surface waters. High organic carbon content in the bottom sediments and predominance of organic carbon production in the biological pump at inner parts of the bay reveal ongoing transformation of the carbon cycle. This has negative consequences for recreation, social and economic potentials of the Sevastopol region.

Solar Spectrum Photocatalytic Conversion of CO2 and Water Vapor Into Hydrocarbons Using TiO2 Nanoparticle Membranes

NASA Astrophysics Data System (ADS)

Rani, Sanju; Bao, Ningzhong; Roy, Somnath C.

2014-01-01

A viable option for recycling carbon dioxide is through the sunlight-powered photocatalytic conversion of CO2 and water vapor into hydrocarbon fuels over highly active nanocatalysts. With photocatalytic CO2 reduction sunlight, a renewable energy source as durable as the sun, is used to drive the catalytic reaction with the resultant fuel products compatible with the current hydrocarbon-based energy infrastructure. The use of co-catalyst (Cu, Pt)-sensitized TiO2 nanoparticle wafers in the photocatalytic conversion of CO2 and water vapor to hydrocarbon fuels, with optimal humidity levels and exposure times established. We also attempted to increase product formation by sputtering both co-catalysts on the nanoparticle wafer's surface, with the resulting product rates significantly higher than that of either the Cu or Pt coated samples. When the TiO2 nanoparticle wafers are used in a flow-through membrane implementation we find a significant increase in product rates of formation, including methane, hydrogen, and carbon monoxide. We believe that nanocatalyst-based flow-through membranes are a viable route for achieving large-scale and low cost photocatalytic solar fuel production.

Methane and CO2 Adsorption Capacities of Kerogen in the Eagle Ford Shale from Molecular Simulation.

PubMed

Psarras, Peter; Holmes, Randall; Vishal, Vikram; Wilcox, Jennifer

2017-08-15

Over the past decade, the United States has become a world leader in natural gas production, thanks in part to a large-fold increase in recovery from unconventional resources, i.e., shale rock and tight oil reservoirs. In an attempt to help mitigate climate change, these depleted formations are being considered for their long-term CO 2 storage potential. Because of the variability in mineral and structural composition from one formation to the next (even within the same region), it is imperative to understand the adsorption behavior of CH 4 and CO 2 in the context of specific conditions and pore surface chemistry, i.e., relative total organic content (TOC), clay, and surface functionality. This study examines two Eagle Ford shale samples, both recovered from shale that was extracted at depths of approximately 3800 m and having low clay content (i.e., less than 5%) and similar mineral compositions but distinct TOCs (i.e., 2% and 5%, respectively). Experimentally validated models of kerogen were used to the estimate CH 4 and CO 2 adsorption capacities. The pore size distributions modeled were derived from low-pressure adsorption isotherm data using CO 2 and N 2 as probe gases for micropores and mesopores, respectively. Given the presence of water in these natural systems, the role of surface chemistry on modeled kerogen pore surfaces was investigated. Several functional groups associated with surface-dissociated water were considered. Pressure conditions from 10 to 50 bar were investigated using grand canonical Monte Carlo simulations along with typical outgassing temperatures used in many shale characterization and adsorption studies (i.e., 60 and 250 °C). Both CO 2 and N 2 were used as probe gases to determine the total pore volume available for gas adsorption spanning pore diameters ranging from 0.3 to 30 nm. The impacts of surface chemistry, outgassing temperature, and the inclusion of nanopores with diameters of less than 1.5 nm were determined for applications of CH 4 and CO 2 storage from samples of the gas-producing region of the Eagle Ford Shale. At 50 bar and temperatures of 60 and 250 °C, CH 4 adsorption increased across all surface chemistries considered by 60% and 2-fold, respectively. In the case of CO 2 , the surface chemistry played a role at both 10 and 50 bar. For instance, at temperatures of 60 and 250 °C, CO 2 adsorption increased across all surface chemistries by 6-fold and just over 2-fold, respectively. It was also found that at both 10 and 50 bar, if too low an outgassing temperature is used, this may lead to a 2-fold underestimation of gas in place. Finally, neglecting to include pores with diameters of less than 1.5 nm has the potential to underestimate pore volume by up to 28%. Taking into consideration these aspects of kerogen and shale characterization in general will lead to improvements in estimating the CH 4 and CO 2 storage potential of gas shales.

Effects of water vapor pretreatment time and reaction temperature on CO(2) capture characteristics of a sodium-based solid sorbent in a bubbling fluidized-bed reactor.

PubMed

Seo, Yongwon; Jo, Sung-Ho; Ryu, Chong Kul; Yi, Chang-Keun

2007-10-01

CO(2) capture from flue gas using a sodium-based solid sorbent was investigated in a bubbling fluidized-bed reactor. Carbonation and regeneration temperature on CO(2) removal was determined. The extent of the chemical reactivity after carbonation or regeneration was characterized via (13)C NMR. In addition, the physical properties of the sorbent such as pore size, pore volume, and surface area after carbonation or regeneration were measured by gas adsorption method (BET). With water vapor pretreatment, near complete CO(2) removal was initially achieved and maintained for about 1-2min at 50 degrees C with 2s gas residence time, while without proper water vapor pretreatment CO(2) removal abruptly decreased from the beginning. Carbonation was effective at the lower temperature over the 50-70 degrees C temperature range, while regeneration more effective at the higher temperature over the 135-300 degrees C temperature range. To maintain the initial 90% CO(2) removal, it would be necessary to keep the regeneration temperature higher than about 135 degrees C. The results obtained in this study can be used as basic data for designing and operating a large scale CO(2) capture process with two fluidized-bed reactors.

CO2 emissions from a temperate drowned river valley estuary adjacent to an emerging megacity (Sydney Harbour)

NASA Astrophysics Data System (ADS)

Tanner, E. L.; Mulhearn, P. J.; Eyre, B. D.

2017-06-01

The Sydney Harbour Estuary is a large drowned river valley adjacent to Sydney, a large urban metropolis on track to become a megacity; estimated to reach a population of 10 million by 2100. Monthly underway surveys of surface water pCO2 were undertaken along the main channel and tributaries, from January to December 2013. pCO2 showed substantial spatio-temporal variability in the narrow high residence time upper and mid sections of the estuary, with values reaching a maximum of 5650 μatm in the upper reaches and as low as 173 μatm in the mid estuary section, dominated by respiration and photosynthesis respectively. The large lower estuary displayed less variability in pCO2 with values ranging from 343 to 544 μatm controlled mainly by tidal pumping and temperature. Air-water CO2 emissions reached a maximum of 181 mmol C m-2 d-1 during spring in the eutrophic upper estuary. After a summer high rainfall event nutrient-stimulated biological pumping promoted a large uptake of CO2 transitioning the Sydney Harbour Estuary into a CO2 sink with a maximum uptake of rate of -10.6 mmol C m-2 d-1 in the mid-section of the estuary. Annually the Sydney Harbour Estuary was heterotrophic and a weak source of CO2 with an air-water emission rate of 1.2-5 mmol C m-2 d-1 (0.4-1.8 mol C m-2 y-1) resulting in a total carbon emission of around 930 tonnes per annum. CO2 emissions (weighted m3 s-1 of discharge per km2 of estuary surface area) from Sydney Harbour were an order of magnitude lower than other temperate large tectonic deltas, lagoons and engineered systems of China, India, Taiwan and Europe but were similar to other natural drowned river valley systems in the USA. Discharge per unit area appears to be a good predictor of CO2 emissions from estuaries of a similar climate and geomorphic class.

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

NASA Astrophysics Data System (ADS)

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

2015-04-01

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

A Reactive Transport Model for Marcellus Shale Weathering

NASA Astrophysics Data System (ADS)

Li, L.; Heidari, P.; Jin, L.; Williams, J.; Brantley, S.

2017-12-01

Shale formations account for 25% of the land surface globally. One of the most productive shale-gas formations is the Marcellus, a black shale that is rich in organic matter and pyrite. As a first step toward understanding how Marcellus shale interacts with water, we developed a reactive transport model to simulate shale weathering under ambient temperature and pressure conditions, constrained by soil chemistry and water data. The simulation was carried out for 10,000 years, assuming bedrock weathering and soil genesis began right after the last glacial maximum. Results indicate weathering was initiated by pyrite dissolution for the first 1,000 years, leading to low pH and enhanced dissolution of chlorite and precipitation of iron hydroxides. After pyrite depletion, chlorite dissolved slowly, primarily facilitated by the presence of CO2 and organic acids, forming vermiculite as a secondary mineral. A sensitivity analysis indicated that the most important controls on weathering include the presence of reactive gases (CO2 and O2), specific surface area, and flow velocity of infiltrating meteoric water. The soil chemistry and mineralogy data could not be reproduced without including the reactive gases. For example, pyrite remained in the soil even after 10,000 years if O2 was not continuously present in the soil column; likewise, chlorite remained abundant and porosity remained small with the presence of soil CO2. The field observations were only simulated successfully when the specific surface areas of the reactive minerals were 1-3 orders of magnitude smaller than surface area values measured for powdered minerals, reflecting the lack of accessibility of fluids to mineral surfaces and potential surface coating. An increase in the water infiltration rate enhanced weathering by removing dissolution products and maintaining far-from-equilibrium conditions. We conclude that availability of reactive surface area and transport of H2O and gases are the most important factors affecting chemical weathering of the Marcellus shale in the shallow subsurface. This study documents the utility of reactive transport modeling for complex subsurface processes. Such modelling could be extended to understand interactions between injected fluids and Marcellus shale gas reservoirs at higher temperature and pressure.

H2O on Pt(111): structure and stability of the first wetting layer

NASA Astrophysics Data System (ADS)

Standop, Sebastian; Morgenstern, Markus; Michely, Thomas; Busse, Carsten

2012-03-01

We study the structure and stability of the first water layer on Pt(111) by variable-temperature scanning tunneling microscopy. We find that a high Pt step edge density considerably increases the long-range order of the equilibrium \\sqrt{37}\\times \\sqrt{37}{R25.3}°- and \\sqrt{39}\\times \\sqrt{39}{R16.1}°-superstructures, presumably due to the capability of step edges to trap residual adsorbates from the surface. Passivating the step edges with CO or preparing a flat metal surface leads to the formation of disordered structures, which still show the same structural elements as the ordered ones. Coadsorption of Xe and CO proves that the water layer covers the metal surface completely. Moreover, we determine the two-dimensional crystal structure of Xe on top of the chemisorbed water layer which exhibits an Xe-Xe distance close to the one in bulk Xe and a rotation angle of 90° between the close-packed directions of Xe and the close-packed directions of the underlying water layer. CO is shown to replace H2O on the Pt(111) surface as has been deduced previously. In addition, we demonstrate that tunneling of electrons into the antibonding state or from the bonding state of H2O leads to dissociation of the molecules and a corresponding reordering of the adlayer into a \\sqrt{3}\\times \\sqrt{3}{R30}°-structure. Finally, a so far not understood restructuring of the adlayer by an increased tunneling current has been observed.

Solar geoengineering, atmospheric water vapor transport, and land plants

NASA Astrophysics Data System (ADS)

Caldeira, Ken; Cao, Long

2015-04-01

This work, using the GeoMIP database supplemented by additional simulations, discusses how solar geoengineering, as projected by the climate models, affects temperature and the hydrological cycle, and how this in turn is related to projected changes in net primary productivity (NPP). Solar geoengineering simulations typically exhibit reduced precipitation. Solar geoengineering reduces precipitation because solar geoengineering reduces evaporation. Evaporation precedes precipitation, and, globally, evaporation equals precipitation. CO2 tends to reduce evaporation through two main mechanisms: (1) CO2 tends to stabilize the atmosphere especially over the ocean, leading to a moister atmospheric boundary layer over the ocean. This moistening of the boundary layer suppresses evaporation. (2) CO2 tends to diminish evapotranspiration, at least in most land-surface models, because higher atmospheric CO2 concentrations allow leaves to close their stomata and avoid water loss. In most high-CO2 simulations, these effects of CO2 which tend to suppress evaporation are masked by the tendency of CO2-warming effect to increase evaporation. In a geoengineering simulation, with the warming effect of CO2 largely offset by the solar geoengineering, the evaporation suppressing characteristics of CO2 are no longer masked and are clearly exhibited. Decreased precipitation in solar geoengineering simulations is a bit like ocean acidification - an effect of high CO2 concentrations that is not offset by solar geoengineering. Locally, precipitation ultimately either evaporates (much of that through the leaves of plants) or runs off through groundwater to streams and rivers. On long time scales, runoff equals precipitation minus evaporation, and thus, water runoff generated at a location is equal to the net atmospheric transport of water to that location. Runoff typically occurs where there is substantial soil moisture, at least seasonally. Locations where there is enough water to maintain runoff are typically locations where there is sufficient water to maintain plant growth. This work aims at: (i) Identifying the geographical distribution of sensitivity of modeled-NPP to changes in CO2, temperature, and various parameters related to the hydrological cycle; (ii) Geographically partitioning changes in modeled-NPP to changes in CO2, temperature, and hydrological variables (and a non-linear interaction term).

Greenhouse models of Venus' high surface temperature, as constrained by Pioneer Venus measurements

NASA Technical Reports Server (NTRS)

Pollack, J. B.; Toon, O. B.; Boese, R.

1980-01-01

Recent measurements conducted from the Pioneer Venus probes and orbiter have provided a significantly improved definition of the solar net flux profile, the gaseous composition, temperature structure, and cloud properties of Venus' lower atmosphere. Using these data, we have carried out a series of one-dimensional radiative-convective equilibrium calculations to determine the viability of the greenhouse model of Venus' high surface temperature and to assess the chief contributors to the greenhouse effect. New sources of infrared opacity include the permitted transitions of SO2, CO, and HCl as well as opacity due to several pressure-induced transitions of CO2. We find that the observed surface temperature and lapse rate structure of the lower atmosphere can be reproduced quite closely with a greenhouse model that contains the water vapor abundance reported by the Venera spectrophotometer experiment. Thus the greenhouse effect can account for essentially all of Venus' high surface temperature. The prime sources of infrared opacity are, in order of importance, CO2, H2O, cloud particles, and SO2, with CO and HCl playing very minor roles.

The impact of water management practices and associated methane emissions on subtropical pasture greenhouse gas budgets and ecosystem service payments

NASA Astrophysics Data System (ADS)

Chamberlain, S.; Groffman, P. M.; Boughton, E.; Gomez-Casanovas, N.; DeLucia, E. H.; Bernacchi, C.; Sparks, J. P.

2016-12-01

Pastures are an extensive land cover type, however patterns in pasture greenhouse gas (GHG) exchange vary widely depending on climate and land management. Understanding this variation is important, as pastures may be a net GHG source or sink depending on these factors. We quantified carbon dioxide (CO2) and methane (CH4) fluxes from subtropical pastures in south Florida for three years using eddy covariance, and estimated annual budgets of CO2, CH4, and GHG equivalent emissions. We also explored the influence of water retention practices on pasture GHG budgets by combining data from a multi-year pasture water retention experiment with CH4 flux data from our eddy covariance tower to 1) estimate the influence of water retention on surface soil flooding, and 2) estimate the influence of extended surface soil flooding on CH4 emissions. These findings were then used to assess the impact of CH4 emissions on stakeholder payments for water retention services in a carbon market framework. The pastures were net CO2 sinks sequestering up to 163 ± 54 g CO2-C m-2 yr-1, but were also strong CH4 sources emitting up to 23.5 ± 2.1 g CH4-C m-2 yr-1. Accounting for the global warming potential of CH4, the pastures were strong GHG sources emitting up to 584 ± 78 g CO2 eq. m-2 yr-1. Our analysis suggests CH4 emissions due to increased flooding from water management practices is a small component of the pasture GHG budget, and water retention likely contributes 2-11% of pasture GHG emissions. These emissions could reduce water retention payments by up to 12% if stakeholders were required to pay for current GHG emissions in a carbon market. It would require at least 93.7 kg CH4-C emissions per acre-foot water storage for carbon market costs to exceed water retention payments, and this scenario is highly unlikely as we estimate current practices are responsible for 11.3 ± 7.2 kg CH4-C emissions per acre-foot of water storage. Our results demonstrate that water retention practices aimed at reducing nutrient loading to the Everglades are likely responsible for only a minor increase in pasture GHG emissions and would have a small economic consequence in a carbon market.

Preparation of enhanced hydrophobic poly(L-lactide-co-ɛ-caprolactone) films surface and its blood compatibility

NASA Astrophysics Data System (ADS)

Kim, Seung Il; Lim, Jin Ik; Jung, Youngmee; Mun, Cho Hay; Kim, Ji Heung; Kim, Soo Hyun

2013-07-01

Hydrophobicity-enhanced poly(L-lactide-co-ɛ-caprolactone) (PLCL) (50:50) films were cast by using the solvent-nonsolvent casting method. PLCL (50:50) was synthesized by the well-known random copolymerization process and confirmed by 1H NMR analysis. The molecular weight of the synthesized PLCL was measured by gel permeation chromatography (GPC). Number-average (Mn), weight-average (Mw) molecular weights and polydispersity (Mw/Mn) were 7 × 104, 1.2 × 105, and 1.7, respectively. PLCL films were cast in vacuum condition with various nonsolvents and nonsolvent ratios. Tetrahydrofuran (THF) was used as the solvent and three different alcohols were used as the nonsolvent: methanol, ethanol, and isopropyl alcohol (IPA). Surface hydrophobicity was confirmed by water contact angle. The water contact angle was increased from 81° ± 2° to 107° ± 2°. Water contact angle was influenced by surface porosity and topography. The prepared film surfaces were characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The change of crystalline property was characterized by X-ray diffraction (XRD). Platelet adhesion tests on the modified PLCL film surfaces were evaluated by platelet-rich plasma (PRP). The modified film surface exhibited enhanced hydrophobicity and reduced platelet adhesion ratio depending on the surface topography. One of the candidate products proposed as a potential blood compatible material showed a markedly reduced platelet adhesion property.

Agricultural peat lands; towards a greenhouse gas sink - a synthesis of a Dutch landscape study

NASA Astrophysics Data System (ADS)

Schrier-Uijl, A. P.; Kroon, P. S.; Hendriks, D. M. D.; Hensen, A.; Van Huissteden, J. C.; Leffelaar, P. A.; Berendse, F.; Veenendaal, E. M.

2013-06-01

It is generally known that managed, drained peatlands act as carbon sources. In this study we examined how mitigation through the reduction of management and through rewetting may affect the greenhouse gas (GHG) emission and the carbon balance of intensively managed, drained, agricultural peatlands. Carbon and GHG balances were determined for three peatlands in the western part of the Netherlands from 2005 to 2008 by considering spatial and temporal variability of emissions (CO2, CH4 and N2O). One area (Oukoop) is an intensively managed grass-on-peatland, including a dairy farm, with the ground water level at an average annual depth of 0.55 m below the soil surface. The second area (Stein) is an extensively managed grass-on-peatland, formerly intensively managed, with a dynamic ground water level at an average annual depth of 0.45 m below the soil surface. The third area is an (since 1998) rewetted former agricultural peatland (Horstermeer), close to Oukoop and Stein, with the average annual ground water level at a depth of 0.2 m below the soil surface. During the measurement campaigns we found that both agriculturally managed sites acted as carbon and GHG sources but the rewetted agricultural peatland acted as a carbon and GHG sink. The terrestrial GHG source strength was 1.4 kg CO2-eq m-2 yr-1 for the intensively managed area and 1.0 kg CO2-eq m-2 yr-1 for the extensively managed area; the unmanaged area acted as a GHG sink of 0.7 kg CO2-eq m-2 yr-1. Water bodies contributed significantly to the terrestrial GHG balance because of a high release of CH4 and the loss of DOC only played a minor role. Adding the farm-based CO2 and CH4 emissions increased the source strength for the managed sites to 2.7 kg CO2-eq m-2 yr-1 for Oukoop and 2.1 kg CO2-eq m-2 yr-1 for Stein. Shifting from intensively managed to extensively managed grass-on-peat reduced GHG emissions mainly because N2O emission and farm-based CH4 emissions decreased. Overall, this study suggests that managed peatlands are large sources of GHG and carbon, but, if appropriate measures are taken they can be turned back into GHG and carbon sinks within 15 yr of abandonment and rewetting.

Synthesis of CO2/N2-triggered reversible stability-controllable poly(2-(diethylamino)ethyl methacrylate)-grafted-AuNPs by surface-initiated atom transfer radical polymerization.

PubMed

Kitayama, Yukiya; Takeuchi, Toshifumi

2014-10-28

CO2/N2-triggered stability-controllable gold nanoparticles (AuNPs) grafted with poly(2-(diethylamino)ethyl methacrylate) (PDEAEMA) layers (PDEAEMA-g-AuNPs) were synthesized by the surface-initiated atom transfer radical polymerization of DEAEMA with AuNPs bearing the bis[2-(2-bromoisobutyryloxy)undecyl] layer (grafting from method). Extension of the PDEAEMA chain length increased the stability of the PDEAEMA-g-AuNPs in CO2-bubbled water because of the electrosteric repulsion of the protonated PDEAEMA layer. The chain-length-dependent stability of PDEAEMA-g-AuNPs was confirmed by DLS and UV-vis spectra by using the localized surface plasmon resonance property of the AuNPs, where the extinction wavelength was shifted toward shorter wavelength with increasing PDEAEMA chain length. The reversible stability change with the gas stimuli of CO2/N2 was also successfully demonstrated. Finally, the transfer across the immiscible interface between water and organic solvent was successfully demonstrated by N2-triggered insolubilization of PDEAEMA layer on AuNPs in the aqueous phase, leading to the successful collection of AuNPs using organic solvent from the aqueous phase. Our "grafting from" method of reversible stability-controllable AuNPs can be applied to develop advanced materials such as reusable optical AuNP-based nanosensors because the molecular recognition layer can be constructed by two-step polymerization.

Radiative and Physiological Effects of Increased CO2: How Does This Interaction Affect Climate?

NASA Technical Reports Server (NTRS)

Bounoua, Lahouari

2011-01-01

Several climate models indicate that in a 2xCO2 environment, temperature and precipitation would increase and runoff would increase faster than precipitation. These models, however, did not allow the vegetation to increase its leaf density as a response to the physiological effects of increased CO2 and consequent changes in climate. Other assessments included these interactions but did not account for the vegetation downregulation to reduce plant's photosynthetic activity and as such resulted in a weak vegetation negative response. When we combine these interactions in climate simulations with 2xCO2, the associated increase in precipitation contributes primarily to increase evapotranspiration rather than surface runoff, consistent with observations, and results in an additional cooling effect not fully accounted for in previous 2xCO2 simulations. By accelerating the water cycle, this feedback slows but does not alleviate the projected warming, reducing the land surface warming by 0.6 C. Compared to previous studies, these results imply that long term negative feedback from CO2-induced increases in vegetation density could reduce temperature following a stabilization of CO2 concentration.

An evolutionary attractor model for sapwood cross section in relation to leaf area.

PubMed

Westoby, Mark; Cornwell, William K; Falster, Daniel S

2012-06-21

Sapwood cross-sectional area per unit leaf area (SA:LA) is an influential trait that plants coordinate with physical environment and with other traits. We develop theory for SA:LA and also for root surface area per leaf area (RA:LA) on the premise that plants maximizing the surplus of revenue over costs should have competitive advantage. SA:LA is predicted to increase in water-relations environments that reduce photosynthetic revenue, including low soil water potential, high water vapor pressure deficit (VPD), and low atmospheric CO(2). Because sapwood has costs, SA:LA adjustment does not completely offset difficult water relations. Where sapwood costs are large, as in tall plants, optimal SA:LA may actually decline with (say) high VPD. Large soil-to-root resistance caps the benefits that can be obtained from increasing SA:LA. Where a plant can adjust water-absorbing surface area of root per leaf area (RA:LA) as well as SA:LA, optimal RA:SA is not affected by VPD, CO(2) or plant height. If selection favours increased height more so than increased revenue-minus-cost, then height is predicted to rise substantially under improved water-relations environments such as high-CO(2) atmospheres. Evolutionary-attractor theory for SA:LA and RA:LA complements models that take whole-plant conductivity per leaf area as a parameter. Copyright © 2012 Elsevier Ltd. All rights reserved.

The response of inorganic carbon distributions and dynamics to upwelling-favorable winds on the northern Gulf of Mexico during summer

NASA Astrophysics Data System (ADS)

Huang, W.-J.; Cai, W.-J.; Wang, Y.; Hu, X.; Chen, B.; Lohrenz, S. E.; Chakraborty, S.; He, R.; Brandes, J.; Hopkinson, C. S.

2015-12-01

Upwelling-favorable winds and an offshore-distributed Mississippi and Atchafalaya River plume trajectory were observed in summer 2009 in contrast to the mean conditions from 2002 to 2010 (upwelling-unfavorable winds and an alongshore river plume trajectory), a set of conditions which was also observed in summer 2007. The responses of dissolved inorganic carbon (DIC) distributions and dynamics to upwelling-favorable winds are studied by comparing the contrasting conditions between summer 2009 and summer 2007 on the northern Gulf of Mexico. Patterns of surface water partial pressure of CO2 (pCO2), DIC, δ13C in DIC, and total alkalinity (TA) determined in July 2009 and August 2007 were strongly related to river plume trajectories, and differed between the two summers. The slope of the relationship between dissolved oxygen (DO) and DIC in summer 2007 was comparable to the Redfield O/C ratio of 1.3, which was attributed to respiration of organic matter in the bottom water. The slope of the DO and DIC relationship and δ13CDIC values in bottom waters during July 2009 were clearly affected by mixing since their salinities were <35. A three end-member mixing model was used to remove mixing effects in (1) δ13CDIC, to estimate the organic source of respiration, and (2) in DIC concentrations, to calculate DIC removal and release. δ13CDIC results in both summers were consistent with an apparent release of DIC in hypoxic waters (DO less than 2 mg L-1) associated with respiration of surface organic matter. The area-weighted surface DIC removal (i.e., biological production) was lower in 2009 than in 2007 on the shelf, as the plume was distributed offshore. The release of DIC in bottom waters was higher over the shelf in 2009 and was surmised to be related to stronger mixing, which was favorable for the DO supply for respiration. Overall, surface waters on the continental shelf in the region of study in July 2009 acted as a weak CO2 source to the atmosphere, but a weak CO2 sink in August 2007. We contend that the inorganic carbon distribution and concentrations on the shelf were related to regional wind forcing, through its influence on the distribution of coastal currents and plume trajectories and their subsequent impact on biogeochemical processes.

CO Diffusion and Desorption Kinetics in CO2 Ices

NASA Astrophysics Data System (ADS)

Cooke, Ilsa R.; Öberg, Karin I.; Fayolle, Edith C.; Peeler, Zoe; Bergner, Jennifer B.

2018-01-01

The diffusion of species in icy dust grain mantles is a fundamental process that shapes the chemistry of interstellar regions; yet, measurements of diffusion in interstellar ice analogs are scarce. Here we present measurements of CO diffusion into CO2 ice at low temperatures (T = 11–23 K) using CO2 longitudinal optical phonon modes to monitor the level of mixing of initially layered ices. We model the diffusion kinetics using Fick’s second law and find that the temperature-dependent diffusion coefficients are well fit by an Arrhenius equation, giving a diffusion barrier of 300 ± 40 K. The low barrier along with the diffusion kinetics through isotopically labeled layers suggest that CO diffuses through CO2 along pore surfaces rather than through bulk diffusion. In complementary experiments, we measure the desorption energy of CO from CO2 ices deposited at 11–50 K by temperature programmed desorption and find that the desorption barrier ranges from 1240 ± 90 K to 1410 ± 70 K depending on the CO2 deposition temperature and resultant ice porosity. The measured CO–CO2 desorption barriers demonstrate that CO binds equally well to CO2 and H2O ices when both are compact. The CO–CO2 diffusion–desorption barrier ratio ranges from 0.21 to 0.24 dependent on the binding environment during diffusion. The diffusion–desorption ratio is consistent with the above hypothesis that the observed diffusion is a surface process and adds to previous experimental evidence on diffusion in water ice that suggests surface diffusion is important to the mobility of molecules within interstellar ices.

Mars: A Planet with a Dynamic Climate System

NASA Technical Reports Server (NTRS)

Haberle, Robert M.

2013-01-01

Mars is a well-observed planet. Since the 1960s orbiters, landers, rovers, and earth-based telescopic observations show that its climate system is dynamic. Its dynamic nature, largely the result of atmosphere-surface interactions, is most obvious in the seasonal cycles of dust, water, and carbon dioxide that define the planet's climate system. These cycles are linked through the global circulation and MGS, Odyssey, Phoenix, MER, Mars Express, MRO, and now MSL have continuously observed them at Mars for the past 16 years. Their observations show that while the seasonal cycles are largely annually repeatable, there are interannual variations. Planet-encircling dust storms, for example, are quasi-triennial and originate over a broader range of seasons and locations than previously thought. Water moves from pole-to-pole each year in a largely, but not precisely, repeatable pattern that suggests but does not demand non-polar surface reservoirs. And the seasonal CO2 polar caps grow and retreat in a very predictable way with only minor deviations from year-to-year in spite of significant differences in atmospheric dust content. These behaviors suggest a complicated but robust coupled system in which these cycles interact to produce the greatest interannual variability in the dust cycle and least variability in the CO2 cycle. The nature of these interactions is the subject of ongoing research, but clouds, both water ice and CO2 ice, now appear to play a bigger role than believed at the end of the 20th century. There may also be some long-term trends in these cycles as there is evidence from imaging data, for example, that the south polar residual cap may not be stable on decadal to centennial time scales. On even longer time scales, the discovery of as much as 5 mb global equivalent of buried CO2 ice near the south pole, the detection of vast quantities of subsurface water ice at very shallow depths in midlatitudes of both hemispheres, and the presence of remnant glacial features at almost all latitudes, strongly suggests the possibility of significant climate change associated with orbital variations. Some of the major questions these data raise concern how closed the seasonal cycles are and which reservoirs are gaining or loosing, the cause of the large interannual variability of the dust cycle and how it couples to the water and CO2 cycles, and the mechanisms for the origin of past glacial activity and the emplacement and removal of subsurface ice. While many of these questions can be addressed with continued research based on existing data, new observations focused on atmosphere surface-interactions would provide valuable constraints on how dust, water, and CO2 move between the surface and atmosphere.

On the habitability of a stagnant-lid Earth

NASA Astrophysics Data System (ADS)

Tosi, Nicola; Stracke, Barbara; Godolt, Mareike; Ruedas, Thomas; Grenfell, John Lee; Höning, Dennis; Nikolaou, Athanasia; Plesa, Ana-Catalina; Breuer, Doris; Spohn, Tilman

2016-04-01

Whether plate tectonics is a recurrent feature of terrestrial bodies orbiting other stars or is unique to the Earth is unknown. The stagnant-lid may rather be the most common tectonic mode through which terrestrial bodies operate. Here we model the thermal history of the mantle, the outgassing evolution of H2O and CO2, and the resulting climate of a hypothetical planet with the same mass, radius, and composition as the Earth, but lacking plate tectonics. We employ a 1-D model of parameterized stagnant-lid convection to simulate the evolution of melt generation, crust production, and volatile extraction over a timespan of 4.5 Gyr, focusing on the effects of three key mantle parameters: the initial temperature, which controls the overall volume of partial melt produced; the initial water content, which affects the mantle rheology and solidus temperature; and the oxygen fugacity, which is employed in a model of redox melting to determine the amount of carbon stored in partial melts. We assume that the planet lost its primordial atmosphere and use the H2O and CO2 outgassed from the interior to build up a secondary atmosphere over time. Furthermore, we assume that the planet may possess an Earth-like ocean. We calculate the atmospheric pressure based on the solubility of H2O and CO2 in basaltic magmas at the evolving surface pressure conditions. We then employ a 1-D radiative-convective, cloud-free stationary atmospheric model to calculate the resulting atmospheric temperature, pressure and water content, and the corresponding boundaries of the habitable zone (HZ) accounting for the evolution of the Sun's luminosity with time but neglecting escape processes. The interior evolution is characterized by a large initial production of partial melt accompanied by the formation of crust that rapidly grows until its thickness matches that of the stagnant lid so that the convecting sublithospheric mantle prevents further crustal growth. Even for initial water concentrations in excess of thousands of ppm, the high solubility of water in surface magmas limits the maximal partial pressure of atmospheric H2O to a few tens of bars, which places de facto an upper bound on the amount of water that can be delivered to the surface and atmosphere from the interior. The relatively low solubility of CO2 causes instead most of the carbon contained in surface melts to be outgassed. As a consequence, the partial pressure of atmospheric CO2 is largely controlled by the redox state of the mantle, with values that range from a few up to tens of bars for oxygen fugacities between the iron-wüstite buffer and one log-unit above it. At 1 AU and for most cases, liquid water on the surface is possible, hence the planets considered would be regarded as habitable although the atmospheric temperature may be well above the temperature limits for terrestrial life. The inner edge of the HZ depends on the amount of outgassed H2O and is located further away from the star if no initial water ocean is assumed. The outer edge of the HZ is controlled by the amount of outgassed CO2, hence by the assumed redox state of the mantle and its initial temperature.

New Class of Amphiphiles Designed for Use in Water-in-Supercritical CO2 Microemulsions.

PubMed

Sagisaka, Masanobu; Ogiwara, Shunsuke; Ono, Shinji; James, Craig; Yoshizawa, Atsushi; Mohamed, Azmi; Rogers, Sarah E; Heenan, Richard K; Yan, Ci; Peach, Jocelyn Alice; Eastoe, Julian

2016-11-29

Water-in-supercritical CO 2 microemulsions formed using the hybrid F-H surfactant sodium 1-oxo-1-[4-(perfluorohexyl)phenyl]hexane-2-sulfonate, FC6-HC4, have recently been shown to have the highest water-solubilizing power ever reported. FC6-HC4 demonstrated the ability to outperform not only other surfactants but also other FCm-HCn analogues containing different fluorocarbon and hydrocarbon chain lengths (Sagisaka, M. et al. Langmuir 2015, 31, 7479-7487). With the aim of clarifying the key structural features of this surfactant, this study examined the phase behavior and water/supercritical CO 2 aggregate formation of 1-oxo-1-[4-(perfluorohexyl)phenyl]hexane (Nohead FC6-HC4), which is an FC6-HC4 analogue but now, interestingly, without the sulfonate headgroup. Surprisingly, Nohead FC6-HC4, which would not normally be identified as a classic surfactant, yielded transparent single-phase W/CO 2 microemulsions with polar cores able to solubilize a water-soluble dye, even at pressures and temperatures so low as to approach the critical point of CO 2 (e.g., ∼100 bar at 35 °C). High-pressure small-angle scattering (SANS) measurements revealed the transparent phases to consist of ellipsoidal nanodroplets of water. The morphology of these droplets was shown to be dependent on the pressure, Nohead FC6-HC4 concentration, and water-to-surfactant molar ratio. Despite having almost the same structure as Nohead FC6-HC4, analogues containing both shorter and longer hydrocarbons were unable to form W/CO 2 microemulsion droplets. This shows the importance of the role of the hydrocarbon chain in the stabilization of W/CO 2 microemulsions. A detailed examination of the mechanism of Nohead FC6-HC4 adsorption onto the water surface suggests that the hexanoyl group protrudes into the aqueous core, allowing for association between the carbonyl group and water.

Desorption Kinetics of Ar, Kr, Xe, N2, O2, CO, Methane, Ethane, and Propane from Graphene and Amorphous Solid Water Surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, R. Scott; May, Robert A.; Kay, Bruce D.

2016-03-03

The desorption kinetics for Ar, Kr, Xe, N2, O2, CO, methane, ethane, and propane from grapheme covered Pt(111) and amorphous solid water (ASW) surfaces are investigated using temperature programmed desorption (TPD). The TPD spectra for all of the adsorbates from graphene have well-resolved first, second, third, and multi- layer desorption peaks. The alignment of the leading edges is consistent the zero-order desorption for all of the adsorbates. An Arrhenius analysis is used to obtain desorption energies and prefactors for desorption from graphene for all of the adsorbates. In contrast, the leading desorption edges for the adsorbates from ASW do notmore » align (for coverages < 2 ML). The non-alignment of TPD leading edges suggests that there are multiple desorption binding sites on the ASW surface. Inversion analysis is used to obtain the coverage dependent desorption energies and prefactors for desorption from ASW for all of the adsorbates.« less

Desorption Kinetics of Ar, Kr, Xe, N2, O2, CO, Methane, Ethane, and Propane from Graphene and Amorphous Solid Water Surfaces.

PubMed

Smith, R Scott; May, R Alan; Kay, Bruce D

2016-03-03

The desorption kinetics for Ar, Kr, Xe, N2, O2, CO, methane, ethane, and propane from graphene-covered Pt(111) and amorphous solid water (ASW) surfaces are investigated using temperature-programmed desorption (TPD). The TPD spectra for all of the adsorbates from graphene have well-resolved first, second, third, and multilayer desorption peaks. The alignment of the leading edges is consistent the zero-order desorption for all of the adsorbates. An Arrhenius analysis is used to obtain desorption energies and prefactors for desorption from graphene for all of the adsorbates. In contrast, the leading desorption edges for the adsorbates from ASW do not align (for coverages < 2 ML). The nonalignment of TPD leading edges suggests that there are multiple desorption binding sites on the ASW surface. Inversion analysis is used to obtain the coverage dependent desorption energies and prefactors for desorption from ASW for all of the adsorbates.

Reaction of silanes in supercritical CO2 with TiO2 and Al2O3.

PubMed

Gu, Wei; Tripp, Carl P

2006-06-20

Infrared spectroscopy was used to investigate the reaction of silanes with TiO2 and Al2O3 using supercritical CO2 (Sc-CO2) as a solvent. It was found that contact of Sc-CO2 with TiO2 leads to partial removal of the water layer and to the formation of carbonate, bicarbonate, and carboxylate species on the surface. Although these carbonate species are weakly bound to the TiO2 surface and can be removed by a N2 purge, they poison the surface, resulting in a lower level of reaction of silanes with TiO2. Specifically, the amount of hexamethyldisilazane adsorbed on TiO2 is about 10% of the value obtained when the reaction is performed from the gas phase. This is not unique to TiO2, as the formation of carbonate species also occurs upon contact of Al2O3 with Sc-CO2 and this leads to a lower level of reaction with hexamethyldisilazane. This is in contrast to reactions of silanes on SiO2 where Sc-CO2 has several advantages over conventional gaseous or nonaqueous methods. As a result, caution needs to be applied when using Sc-CO2 as a solvent for silanization reactions on oxides other than SiO2.

The fabrication of visible light responsive Ag-SiO2 co-doped TiO2 thin films by the sol-gel method

NASA Astrophysics Data System (ADS)

Dam Le, Duy; Dung Dang, Thi My; Thang Chau, Vinh; Chien Dang, Mau

2010-03-01

In this study we have successfully deposited Ag-SiO2 co-doped TiO2 thin films on glass substrates by the sol-gel method. After being coated by a dip coating method, the film was transparent, smooth and had strong adhesion on the glass surface. The deposited film was characterized by x-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), ultraviolet-visible spectroscopy (UV-Vis), a scanning electron microscope (SEM) and atomic force microscope (AFM) to investigate its crystallization, transmittance and surface structure. The antifogging ability is explained by the contact angle of water on the surface of the glass substrates under visible-light. The obtained results show that Ag-SiO2 co-doped TiO2 film has potential applications for self cleaning and anti-bacterial ceramic tiles.

Warming Early Mars by Impact Degassing of Reduced Greenhouse Gases

NASA Technical Reports Server (NTRS)

Haberle, R. M.; Zahnle, K.; Barlow, N. G.

2018-01-01

Reducing greenhouse gases are once again the latest trend in finding solutions to the early Mars climate dilemma. In its current form collision induced absorptions (CIA) involving H2 and/or CH4 provide enough extra greenhouse power in a predominately CO2 atmosphere to raise global mean surface temperatures to the melting point of water provided the atmosphere is thick enough and the reduced gases are abundant enough. Surface pressures must be at least 500 mb and H2 and/or CH4 concentrations must be at or above the several percent level for CIA to be effective. Atmospheres with 1-2 bars of CO2 and 2- 10% H2 can sustain surface environments favorable for liquid water. Smaller concentrations of H2 are sufficient if CH4 is also present. If thick CO2 atmospheres with percent level concentrations of reduced gases are the solution to the faint young Sun paradox for Mars, then plausible mechanisms must be found to generate and sustain the gases. Possible sources of reducing gases include volcanic outgassing, serpentinization, and impact delivery; sinks include photolyis, oxidation, and escape to space. The viability of the reduced greenhouse hypothesis depends, therefore, on the strength of these sources and sinks. In this paper we focus on impact delivered reduced gases.

Potential for iron oxides to control metal releases in CO2 sequestration scenarios

USGS Publications Warehouse

Berger, P.M.; Roy, W.R.

2011-01-01

The potential for the release of metals into groundwater following the injection of carbon dioxide (CO2) into the subsurface during carbon sequestration projects remains an open research question. Changing the chemical composition of even the relatively deep formation brines during CO2 injection and storage may be of concern because of the recognized risks associated with the limited potential for leakage of CO2-impacted brine to the surface. Geochemical modeling allows for proactive evaluation of site geochemistry before CO2 injection takes place to predict whether the release of metals from iron oxides may occur in the reservoir. Geochemical modeling can also help evaluate potential changes in shallow aquifers were CO2 leakage to occur near the surface. In this study, we created three batch-reaction models that simulate chemical changes in groundwater resulting from the introduction of CO2 at two carbon sequestration sites operated by the Midwest Geological Sequestration Consortium (MGSC). In each of these models, we input the chemical composition of groundwater samples into React??, and equilibrated them with selected mineral phases and CO 2 at reservoir pressure and temperature. The model then simulated the kinetic reactions with other mineral phases over a period of up to 100 years. For two of the simulations, the water was also at equilibrium with iron oxide surface complexes. The first model simulated a recently completed enhanced oil recovery (EOR) project in south-central Illinois in which the MGSC injected into, and then produced CO2, from a sandstone oil reservoir. The MGSC afterwards periodically measured the brine chemistry from several wells in the reservoir for approximately two years. The sandstone contains a relatively small amount of iron oxide, and the batch simulation for the injection process showed detectable changes in several aqueous species that were attributable to changes in surface complexation sites. After using the batch reaction configuration to match measured geochemical changes due to CO2 injection, we modeled potential changes in groundwater chemistry at the Illinois Basin - Decatur Project (IBDP) site in Decatur, Illinois, USA. At the IBDP, the MGSC will inject 1 million tonnes of CO2 over the course of three years at a depth of about 2 km below the surface into the Mt. Simon Formation. Sections of the Mt. Simon Formation contain up to 10 percent iron oxide, and therefore surface complexes on iron oxides should play a major role in controlling brine chemistry. The batch simulation of this system showed a significant decrease in pH after the injection of CO2 with corresponding changes in brine chemistry resulting from both mineral precipitation/dissolution reactions and changes in the chemistry on iron oxide surfaces. To ensure the safety of shallow drinking water sources, there are several shallow monitoring wells at the IBDP that the MGSC samples regularly to determine baseline chemical concentrations. Knowing what geochemical parameters are most sensitive to CO2 disturbances allows us to focus monitoring efforts. Modeling a major influx of CO2 into the shallow groundwater allowed us to determine that were an introduction of CO2 to occur, the only immediate effect will be dolomite dissolution and calcite precipitation. ?? 2011 Published by Elsevier Ltd.

Spatial and temporal characterization of trace elements and nutrients in the Rawal Lake Reservoir, Pakistan using multivariate analysis techniques.

PubMed

Malik, Riffat Naseem; Nadeem, Muhammad

2011-12-01

Rawal Lake Reservoir is renowned for its ecological significance and is the sole source of drinking water of the third largest city of Pakistan. However, fish kill in recent years and anthropogenic impacts from human-related activities in its catchment area have resulted in deterioration of its surface water quality. This study aims to characterize spatial and temporal variations in surface water quality, identify contaminant sources, and compare their levels with quality guidelines. Surface water samples were collected from 10 sites and analyzed for 27 physicochemical parameters for a period of 2 years on a seasonal basis. Concentration of metals in surface water in pre-monsoon were in the order: Fe > Mg > Ca > Mn > Zn > Ni > Cr > Cu > Co > Pb, whereas in post-monsoon, the order of elemental concentrations was: Ca > Mg > Na > Fe > K > Zn > Cr > Li > Pb > Co > Ni > Cu > Mn > Cd. Metals (Ni, Fe, Zn, and Ca), pH, electrical conductivity (EC), dissolved oxygen (DO), chemical oxygen demand (COD), and nutrients (PO (4) (3-) , NO(3)-N, and SO (4) (2-) ) were measured higher in pre-monsoon, whereas concentration of Cu, Mn, Cr, Co, Pb, Cd, K, Na, Mg, Li, Cl(-), and NH(4)-N were recorded higher in post-monsoon. Results highlighted serious metal pollution of surface water. Mean concentration of Zn, Cd, Ni, Cu, Fe, Cr, and Pb in both seasons and Mn in post-monsoon were well above the permissible level of surface water quality criteria. Results stress the dire need to reduce heavy-metal input into the lake basin and suggest that heavy-metal contamination should be considered as an integral part of future planning and management strategies for restoration of water quality of the lake reservoir.

Seasonal and spatial variations in surface pCO2 and air-sea CO2 flux in the Chesapeake Bay

NASA Astrophysics Data System (ADS)

Cai, W. J.; Chen, B.

2017-12-01

Bay-wide observations of surface water partial pressure of carbon dioxide (pCO2) were conducted in May, June, August, and October 2016 to study the spatial and seasonal variations in surface pCO2 and to estimate air-sea CO2 flux in the Chesapeake Bay. Overall, high surface pCO2 in the upper-bay decreased downstream rapidly below the atmospheric value near the bay bridge in the mid-bay and then increased slightly to the lower-bay where pCO2 approached the atmospheric level. Over the course of a year, pCO2 was higher than 1000 µatm in the upper bay and the highest pCO2 (2500 µatm) was observed in August. Significant biologically-induced pCO2 undersaturation was observed at the upper part of the mid-bay in August with pCO2 as low as 50 µatm and oversaturated DO% of 200%. In addition to biological control, vertical mixing and upwelling controlled by wind direction and tidal stage played an important role in controlling surface pCO2 in the mid-bay as is evidenced by co-occurrence of high pCO2 with low temperature and low oxygen or high salinity from the subsurface. These physical processes occurred regularly and in short time scale of hours, suggesting they must be considered in the assessment of annual air-sea CO2 flux. Seasonally, the upper-bay acted as a source for atmospheric CO2 over the course of a year. The boundary of upper and mid bay transited from a CO2 source to a sink from May to August and was a source again in October due to strong biological production in summer. In contrast, the mid-bay represented as a CO2 source with large temporal variation due to dynamic hydrographic settings. The lower-bay transited from a weak sink in May to equilibrated with the atmosphere from June to August, while became a source again in October. Moreover, the CO2 flux could be reversed very quickly under episodic severe weather events. Thus further research, including the influence of severe weather and subsequent bloom, is needed to get better understanding of the carbon cycling in the Chesapeake Bay.

One-pot synthesis of ternary Ag₂CO₃/Ag/AgCl photocatalyst in natural geothermal water with enhanced photocatalytic activity under visible light irradiation.

PubMed

Yao, Xiaxi; Liu, Xiaoheng

2014-09-15

Geothermal water is a clean, cheap and renewable resource and it is widely distributed all over the world. In this work, ternary Ag2CO3/Ag/AgCl photocatalyst has been successfully synthesized via a one-pot precipitation method in natural geothermal water at room temperature, wherein the geothermal water serves as the source of chlorine and carbonate. The results suggest that the Ag/AgCl nanoparticles are anchored on the surface of Ag2CO3 and Ag2CO3/Ag/AgCl composite shows strong absorption ability in the visible light region. The evaluation of the photocatalytic activity indicates that the as-synthesized Ag2CO3/Ag/AgCl photocatalyst exhibits higher photocatalytic performance for the degradation of methylene blue (MB) aqueous solution under visible light irradiation than one-component (Ag2CO3), two-component (Ag/AgCl, Ag2CO3/AgCl) and the mechanical mixture of Ag2CO3 and Ag/AgCl. The trapping experiments confirmed that holes (h(+)) and (•)O2(-) were the two main active species in the photocatalytic process. Finally, a possible Z-scheme photocatalytic mechanism of the charge transfer was proposed for the enhanced photocatalytic performance. This work may open up new insights into the application of cheap geothermal water resources in the word and provide new opportunities for facile fabrication of Ag/AgCl-based photocatalysts. Copyright © 2014 Elsevier B.V. All rights reserved.

Effect of redox conditions on MTBE biodegradation in surface water Sediments

USGS Publications Warehouse

Bradley, P.M.; Chapelle, F.H.; Landmeyer, J.E.

2001-01-01

Microbial degradation of methyl tert-butyl ether (MTBE) was observed in surface water-sediment microcosms under anaerobic conditions. The efficiency and products of anaerobic MTBE biodegradation were dependent on the predominant terminal electron-accepting conditions. In the presence of substantial methanogenic activity, MTBE biodegradation was nominal and involved reduction of MTBE to the toxic product, tert-butyl alcohol (TBA). In the absence of significant methanogenic activity, accumulation of [14C]TBA generally decreased, and mineralization of [U-14C]MTBE to 14CO2 generally increased as the oxidative potential of the predominant terminal electron acceptor increased in the order of SO4, Fe(III), Mn(IV) < NO3 < O2. Microbial mineralization of MTBE to CO2 under Mn(IV)or SO4-reducing conditions has not been reported previously. The results of this study indicate that microorganisms inhabiting the sediments of streams and lakes can degrade MTBE effectively under a range of anaerobic terminal electron-accepting conditions. Thus, anaerobic bed sediment microbial processes may provide a significant environmental sink for MTBE in surface water systems throughout the United States.

Rain events decrease boreal peatland net CO2 uptake through reduced light availability.

PubMed

Nijp, Jelmer J; Limpens, Juul; Metselaar, Klaas; Peichl, Matthias; Nilsson, Mats B; van der Zee, Sjoerd E A T M; Berendse, Frank

2015-06-01

Boreal peatlands store large amounts of carbon, reflecting their important role in the global carbon cycle. The short-term exchange and the long-term storage of atmospheric carbon dioxide (CO2 ) in these ecosystems are closely associated with the permanently wet surface conditions and are susceptible to drought. Especially, the single most important peat forming plant genus, Sphagnum, depends heavily on surface wetness for its primary production. Changes in rainfall patterns are expected to affect surface wetness, but how this transient rewetting affects net ecosystem exchange of CO2 (NEE) remains unknown. This study explores how the timing and characteristics of rain events during photosynthetic active periods, that is daytime, affect peatland NEE and whether rain event associated changes in environmental conditions modify this response (e.g. water table, radiation, vapour pressure deficit, temperature). We analysed an 11-year time series of half-hourly eddy covariance and meteorological measurements from Degerö Stormyr, a boreal peatland in northern Sweden. Our results show that daytime rain events systematically decreased the sink strength of peatlands for atmospheric CO2 . The decrease was best explained by rain associated reduction in light, rather than by rain characteristics or drought length. An average daytime growing season rain event reduced net ecosystem CO2 uptake by 0.23-0.54 gC m(-2) . On an annual basis, this reduction of net CO2 uptake corresponds to 24% of the annual net CO2 uptake (NEE) of the study site, equivalent to a 4.4% reduction of gross primary production (GPP) during the growing season. We conclude that reduced light availability associated with rain events is more important in explaining the NEE response to rain events than rain characteristics and changes in water availability. This suggests that peatland CO2 uptake is highly sensitive to changes in cloud cover formation and to altered rainfall regimes, a process hitherto largely ignored. © 2015 John Wiley & Sons Ltd.

Warming Early Mars With CH4

NASA Astrophysics Data System (ADS)

Justh, H. L.; Kasting, J. F.

2002-12-01

The nature of the ancient climate of Mars remains one of the fundamental unresolved problems in martian research. While the present environment is hostile to life, images from the Mariner, Viking and Mars Global Surveyor missions, have shown geologic features on the martian surface that seem to indicate an earlier period of hydrologic activity. The fact that ancient valley networks and degraded craters have been seen on the martian surface indicates that the early martian climate may have been more Earth-like, with a warmer surface temperature. The presence of liquid water would require a greenhouse effect much larger than needed at present, as the solar constant, S0, was 25% lower 3.8 billion years ago when the channels are thought to have formed (1,2). Previous calculations have shown that gaseous CO2 and H2O alone could not have warmed the martian surface to the temperature needed to account for the presence of liquid water (3). It has been hypothesized that a CO2-H2O atmosphere could keep early Mars warm if it was filled with CO2 ice clouds in the upper martian troposphere (4). Obtaining mean martian surface temperatures above 273 K would require nearly 100% cloud cover, a condition that is unrealistic for condensation clouds on early Mars. Any reduction in cloud cover makes it difficult to achieve warm martian surface temperatures except at high pressures and CO2 clouds could cool the martian surface if they were low and optically thick (5). CO2 and CH4 have been suggested as important greenhouse gases on the early Earth. Our research focuses on the effects of increased concentrations of atmospheric greenhouse gases on the surface temperature of early Mars, with emphasis on the reduced greenhouse gas, CH4. To investigate the possible warming effect of CH4, we modified a one-dimensional, radiative-convective climate model used in previous studies of the early martian climate (5). New cloud-free temperature profiles for various surface pressures and CH4 mixing ratios will be presented. This use of climate modeling is important since it is the fundamental way that the magnitude of possible geochemical and biological CH4 sources can be related to predicted CH4 concentrations in the early martian atmosphere. References: 1) Gough, D. O. Solar Physics 74, 21-34 (1981). 2) Carr, M. H. Water on Mars (1996). 3) Kasting, J. F. Icarus 94, 1-13 (1991). 4) Forget, F., and Pierrehumbert R. T. Science 278, 1273-1276 (1997). 5) Mischna, M. A., Kasting J. F., Pavlov A., and Freedman R. Icarus 145, 546-554 (2000).

Cassini finds an oxygen-carbon dioxide atmosphere at Saturn's icy moon Rhea.

PubMed

Teolis, B D; Jones, G H; Miles, P F; Tokar, R L; Magee, B A; Waite, J H; Roussos, E; Young, D T; Crary, F J; Coates, A J; Johnson, R E; Tseng, W-L; Baragiola, R A

2010-12-24

The flyby measurements of the Cassini spacecraft at Saturn's moon Rhea reveal a tenuous oxygen (O(2))-carbon dioxide (CO(2)) atmosphere. The atmosphere appears to be sustained by chemical decomposition of the surface water ice under irradiation from Saturn's magnetospheric plasma. This in situ detection of an oxidizing atmosphere is consistent with remote observations of other icy bodies, such as Jupiter's moons Europa and Ganymede, and suggestive of a reservoir of radiolytic O(2) locked within Rhea's ice. The presence of CO(2) suggests radiolysis reactions between surface oxidants and organics or sputtering and/or outgassing of CO(2) endogenic to Rhea's ice. Observations of outflowing positive and negative ions give evidence for pickup ionization as a major atmospheric loss mechanism.

Study of the influence of the supersaturation coefficient on scaling rate using the pre-calcified surface of a quartz crystal microbalance.

PubMed

Cheap-Charpentier, Hélène; Horner, Olivier; Lédion, Jean; Perrot, Hubert

2018-05-29

Scale deposition is a common issue in industrial plants, which creates technical problems, i.e. reduction of heat transfer, decrease of flow rate due to an obstruction of pipes. Therefore, the development of some appropriate methods based on well suitable in situ sensors to evaluate and predict the scaling propensity of water is a major concern in current research. This would be a good strategy for the optimization of anti-scaling treatments. In this study, scaling tests were carried out using a sensitive sensor, which has been developed using a quartz crystal microbalance with a pre-calcified electrode surface (SQCM). This technique allowed studying the influence of the supersaturation on the scaling rate. The set-up was tested with different water samples which were brought to a given supersaturation coefficient by degassing the dissolved CO 2 . The prediction of the scaling propensity of water was then possible through the relationship between the scaling rate on a pre-calcified surface and the supersaturation coefficient. In addition, the kinetics of CaCO 3 deposit on the pre-calcified SQCM surface was found to be slower for natural water than for synthetic water (same calcium concentration). Furthermore, the activation energy for scale deposit, in synthetic water, was found to be 22 kJ.mol -1 , which may be related to the diffusion of ions and/or CaCO 3 nuclei in solution. Copyright © 2018 Elsevier Ltd. All rights reserved.

Exposed water ice discovered near the south pole of Mars

USGS Publications Warehouse

Titus, T.N.; Kieffer, H.H.; Christensen, P.R.

2003-01-01

The Mars Odyssey Thermal Emission Imaging System (THEMIS) has discovered water ice exposed near the edge of Mars' southern perennial polar cap. The surface H2O ice was first observed by THEMIS as a region that was cooler than expected for dry soil at that latitude during the summer season. Diurnal and seasonal temperature trends derived from Mars Global Surveyor Thermal Emission Spectrometer observations indicate that there is H2O ice at the surface. Viking observations, and the few other relevant THEMIS observations, indicate that surface H2O ice may be widespread around and under the perennial CO2 cap.

Ethylene Glycol Adsorption and Reaction over CeOX(111) Thin Films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mullins, David R; Chen, Tsung-Liang

2011-01-01

This study reports the interaction of ethylene glycol with well-ordered CeO{sub x}(111) thin film surfaces. Ethylene glycol initially adsorbs on fully oxidized CeO{sub 2}(111) and reduced CeO{sub 2-x}(111) through the formation of one C-O-Ce bond and then forms a second alkoxy bond after annealing. On fully oxidized CeO{sub 2}(111) both recombination of ethylene glycol and water desorption occur at low temperature leaving stable -OCH{sub 2}CH{sub 2}O- (ethylenedioxy) intermediates and oxygen vacancies on the surface. This ethylenedioxy intermediate goes through C-C bond scission to produce formate species which then react to produce CO and CO{sub 2}. The formation of water resultsmore » in the reduction of the ceria. On a reduced CeO{sub 2-x}(111) surface the reaction selectivity shifts toward a dehydration process. The ethylenedioxy intermediate decomposes by breaking a C-O bond and converts into an enolate species. Similar to the reaction of acetaldehyde on reduced CeO{sub 2-x}(111), the enolate reacts to produce acetaldehyde, acetylene, and ethylene. The loss of O from ethylene glycol leads to a small amount of oxidation of the reduced ceria.« less

Ethylene Glycol Adsorption and Reaction over CeOX(111) Thin Films

DOE Office of Scientific and Technical Information (OSTI.GOV)

T Chen; D Mullins

2011-12-31

This study reports the interaction of ethylene glycol with well-ordered CeO{sub x}(111) thin film surfaces. Ethylene glycol initially adsorbs on fully oxidized CeO{sub 2}(111) and reduced CeO{sub 2-x}(111) through the formation of one C-O-Ce bond and then forms a second alkoxy bond after annealing. On fully oxidized CeO{sub 2}(111) both recombination of ethylene glycol and water desorption occur at low temperature leaving stable -OCH{sub 2}CH{sub 2}O- (ethylenedioxy) intermediates and oxygen vacancies on the surface. This ethylenedioxy intermediate goes through C-C bond scission to produce formate species which then react to produce CO and CO{sub 2}. The formation of water resultsmore » in the reduction of the ceria. On a reduced CeO{sub 2-x}(111) surface the reaction selectivity shifts toward a dehydration process. The ethylenedioxy intermediate decomposes by breaking a C-O bond and converts into an enolate species. Similar to the reaction of acetaldehyde on reduced CeO{sub 2-x}(111), the enolate reacts to produce acetaldehyde, acetylene, and ethylene. The loss of O from ethylene glycol leads to a small amount of oxidation of the reduced ceria.« less

Diffuse CO2 fluxes from Santiago and Congro volcanic lakes (São Miguel, Azores archipelago)

NASA Astrophysics Data System (ADS)

Andrade, César; Cruz, José; Viveiros, Fátima; Branco, Rafael

2017-04-01

Diffuse CO2 degassing occurring in Santiago and Congro lakes, both located in depressions associated to maars from São Miguel Island (Azores, Portugal), was studied through detailed flux measurements. Four sampling campaigns were developed between 2013 and 2016 in each water body, split by the cold and wet seasons. São Miguel has an area of 744.6 km2, being the largest island of the archipelago. The geology of the island is dominated by three quiescent central volcanoes (Sete Cidades, Fogo and Furnas), linked by volcanic fissural zones (Picos and Congro Fissural Volcanic systems). The oldest volcanic systems of the island are located in its eastern part (Povoação-Nordeste). Santiago lake, with a surface area of 0.26 km2 and a depth of 30.5 m, is located inside a maar crater in the Sete Cidades volcano at an altitude of 355 m. The watershed of the lake has an area of 0.97 km2 and a surface flow estimated as 1.54x10 m3/a. A total of 1612 CO2 flux measurements using the accumulation chamber method were made at Santiago lake, 253 in the first campaign (November 2013), and 462, 475 and 422 in the three other campaigns, respectively, in April 2014, September 2016 and December 2016. The total CO2 flux estimated for this lake varies between 0.4 t d-1 and 0.59 t d-1, for the surveys performed, respectively, in November 2013 and September 2016; higher CO2 outputs of 1.57 and 5.87 t d-1 were calculated for the surveys carried out in April 2014 and December 2016. These higher CO2 emissions were associated with a period without water column stratification. Similarly to Santiago lake, Congro lake is located inside a maar, in the Congro Fissural Volcanic system, and has a surface area of 0.04 km2 with 18.5 m depth and a storage of about 2.4x105 m3/a. The lake, located at an altitude of 420 m, is fed by a watershed with an area of 0.33 km2 and a runoff estimated as about 8x104 m3/a. In Congro lake a total of 713 CO2 flux measurements were performed during four surveys from November 2013 to February 2016. The CO2 flux output was estimated as ranging between 0.06 t d-1 and 0.31 t d-1; the lower CO2 emission occurred in July 2015 and should reflect the stratification of the water column that prevents the CO2 flux release at the lake surface. Considering both volcanic lakes, the mean CO2 emissions, standardized per area, in the cold season were ˜14.9 t km-2 d-1 and ˜7.1 t km-2 d-1, respectively, for Santiago and Congro lakes. During summer period, CO2 emissions were lower in both lakes (˜1.9 t km-2 d-1 and ˜4.1 t km-2 d-1 for Santiago and Congro, correspondingly), what is explained by the lake stratification. Due to the organic processes that occur in the lakes, the CO2 emission is mostly associated to a biogenic origin, but a volcanic influence cannot be excluded and further research using carbon isotopic data is crucial to discriminate the CO2 sources. Key words: volcanic lakes, CO2 flux, maars, São Miguel Island

Low temperature-pressure batch experiments and field push-pull tests: Assessing potential effects of an unintended CO2 release from CCUS projects on groundwater chemistry

NASA Astrophysics Data System (ADS)

Mickler, P. J.; Yang, C.; Lu, J.; Reedy, R. C.; Scanlon, B. R.

2012-12-01

Carbon Capture Utilization and Storage projects (CCUS), where CO2 is captured at point sources such as power stations and compressed into a supercritical liquid for underground storage, has been proposed to reduce atmospheric CO2 and mitigate global climate change. Problems may arise from CO2 releases along discreet pathways such as abandoned wells and faults, upwards and into near surface groundwater. Migrating CO2 may inversely impact fresh water resources by increasing mineral solubility and dissolution rates and mobilizing harmful trace elements including As and Pb. This study addresses the impacts on fresh water resources through a combination of laboratory batch experiments, where aquifer sediment are reacted in their corresponding groundwater in 100% CO2 environments, and field push-pull tests where groundwater is equilibrated with 100% CO2, reacted in-situ in the groundwater system, and pulled out for analyses. Batch experiments were performed on aquifer material from carbonate dominated, mixed carbonate/silicalstic, and siliclastic dominated systems. A mixed silicalstic/carbonate system was chosen for the field based push-pull test. Batch experiment results suggest carbonate dissolution increased the concentration of Ca, Mg, Sr, Ba, Mn, U and HCO3- in groundwater. In systems with significant carbonate content, dissolution continued until carbonate saturation was achieved at approximately 1000 hr. Silicate dissolution increased the conc. of Si, K Ni and Co, but at much lower rates than carbonate dissolution. The elements As, Mo, V, Zn, Se and Cd generally show similar behavior where concentrations initially increase but soon drop to levels at or below the background concentrations (~48 hours). A Push-Pull test on one aquifer system produced similar geochemical behavior but observed reaction rates are higher in batch experiments relative to push-pull tests. Release of CO2 from CCUS sites into overlying aquifer systems may adversely impact groundwater quality primarily through carbonate dissolution which releases Ca and elements that substitute for Ca in crystal lattices. Silicate weathering releases primarily Si and K at lower rates. Chemical changes with the addition of CO2 may initially mobilize As, Mo, V, Zn, Se and Cd but these elements become immobile in the lowered pH water and sorb onto aquifer minerals. A combined laboratory batch experiment and field push-pull test in fresh water aquifers overlying CCUS projects will best characterize the response of the aquifer to increased pCO2. The long experimental duration of the batch experiments may allow reactions to reach equilibrium however; reaction rates may be artificially high due to increased mineral surface areas. Field based push-pull tests offer a more realistic water rock ratio and test a much larger volume of aquifer material but the test must be shorter in duration because the high pCO2 water is subject to mixing with low pCO2 background water and migration away from the test well with groundwater flow. A comparison of the two methods best characterizes the potential effects on groundwater chemistry

The effects of ecological restoration on CO2 fluxes from a climatically marginal upland blanket bog

NASA Astrophysics Data System (ADS)

Dixon, Simon; Qassim, Suzane; Rowson, James; Worrall, Fred; Evans, Martin

2013-04-01

A legacy of gully incision, deposition of industrially-derived aerial pollutants, inappropriate management and wildfire has left large expanses of the topographic Bleaklow Plateau (Peak District National Park, England, UK) bare of vegetation and susceptible to massive erosion of the peat soils. The consequence of such degradation has been to decrease the capacity of the peatland on the plateau to provide important ecosystem services including; loss of net C sink function, discolouration of surface waters, mobilisation to surface waters of stored heavy metals and infilling of upland reservoirs with peat-derived sediment. In response to on-going and worsening degradation a programme of ecological restoration has been undertaken. Restoration methods include: seeding with a lawn grass mix; liming; fertilisation; slope stabilisation; and gully blocking. This talk will present data from a five-year, observational-study of CO2 fluxes from eight sites, with four sites sampling different restoration treatments and four sampling bare and least disturbed areas. The results of the analysis reveal that sites with revegetation alongside slope stabilisation were most productive and were the largest net (daylight hours) sinks of CO2. Unrestored, bare sites, while having relatively low gross fluxes of CO2 were the largest net sources of CO2. Revegetation without slope stabilisation took longer (~18 months) to show an impact on CO2 flux in comparison to the sites with slope stabilisation. Binary logistic regression indicated that a ten centimetre increase in water table depth decreases the odds of observing a net CO2 sink, on a given site, by up to 30%. Sites with slope stabilisation were between 5-8x more likely to be net CO2 sinks than the bare sites. Sites without slope stabilisation were only 2-2.3x more likely to be net CO2 sinks compared to the bare sites. The most important conclusion of this research is that revegetation appears to be effective at increasing the likelihood of net CO2 behaviour on degraded, climatically marginal blanket peat, with revegetation alongside slope stabilisation having the greatest impact.

Effects of sulfate ligand on uranyl carbonato surface species on ferrihydrite surfaces.

PubMed

Arai, Yuji; Fuller, C C

2012-01-01

Understanding uranium (U) sorption processes in permeable reactive barriers (PRB) are critical in modeling reactive transport for evaluating PRB performance at the Fry Canyon demonstration site in Utah, USA. To gain insight into the U sequestration mechanism in the amorphous ferric oxyhydroxide (AFO)-coated gravel PRB, U(VI) sorption processes on ferrihydrite surfaces were studied in 0.01 M Na(2)SO(4) solutions to simulate the major chemical composition of U-contaminated groundwater (i.e., [SO(4)(2-)] ~13 mM L(-1)) at the site. Uranyl sorption was greater at pH 7.5 than that at pH 4 in both air- and 2% pCO(2)-equilibrated systems. While there were negligible effects of sulfate ligands on the pH-dependent U(VI) sorption (<24 h) in both systems, X-ray absorption spectroscopy (XAS) analysis showed sulfate ligand associated U(VI) surface species at the ferrihydrite-water interface. In air-equilibrated systems, binary and mono-sulfate U(VI) ternary surface species co-existed at pH 5.43. At pH 6.55-7.83, a mixture of mono-sulfate and bis-carbonato U(VI) ternary surface species became more important. At 2% pCO(2), there was no contribution of sulfate ligands on the U(VI) ternary surface species. Instead, a mixture of bis-carbonato inner-sphere (38%) and tris-carbonato outer-sphere U(VI) ternary surface species (62%) was found at pH 7.62. The study suggests that the competitive ligand (bicarbonate and sulfate) coordination on U(VI) surface species might be important in evaluating the U solid-state speciation in the AFO PRB at the study site where pCO(2) fluctuates between 1 and 2 pCO(2)%. Copyright © 2011 Elsevier Inc. All rights reserved.

Kinetics, Thermodynamics and Modelling of Amido Black Dye Photodegradation in Water Using Co/TiO2 Nanoparticles.

PubMed

Ali, Imran; M L Alharbi, Omar; A Alothman, Zeid; Badjah, Ahmad Yacine

2018-05-16

Titanium oxide nanoparticles were doped with copper and characterized by XRD, FT-IR, TEM and SEM. The surface morphology was spherical with 15-26 nm as particle size. The doped titanium oxide (Co/TiO 2 ) nanomaterial was used for photodegradation of amido black dye in water. The maximum photodegradation of amido black obtained was 90%. The values of free energy, and enthalpy were negative, indicating spontaneous photodegradation of amido black dye. The photodegradation of amido black dye obeyed first order kinetic model. The photodegradation mechanism of amido black involved adsorption of the dye on the surface of cobalt doped titanium oxide and its degradation under UV radiation. The electron (e - ) and hole (h + ) pairs are generated by Co/TiO 2 , which consequently generated superoxide oxygen anion and hydroxyl free radical. These species degraded amido black dye. The reported method is fast, effective and economic, which may be utilized to remove amido black in water. The doped TiO 2 catalyst was quite stable and can be used up to 5 cycles. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

Isotopic analysis for degradation diagnosis of calcite matrix in mortar.

PubMed

Dotsika, E; Psomiadis, D; Poutoukis, D; Raco, B; Gamaletsos, P

2009-12-01

Mortar that was used in building as well as in conservation and restoration works of wall paintings have been analysed isotopically (delta(13)C and delta(18)O) in order to evaluate the setting environments and secondary processes, to distinguish the structural components used and to determine the exact causes that incurred the degradation phenomena. The material undergoes weathering and decay on a large proportion of its surface and in depth, due to the infiltration of water through the structural blocks. Mineralogical analysis indicated signs of sulphation and dissolution/recrystallisation processes taking place on the material, whereas stable isotopes provided information relative to the origin of the CO(2) and water during calcite formation and degradation processes. Isotopic change of the initial delta(13)C and delta(18)O in carbonate matrix was caused by alteration of the primary source of CO(2) and H(2)O in mortar over time, particularly by recrystallisation of calcite with porewater, evaporated or re-condensed water, and CO(2) from various sources of atmospheric and biogenic origin. Human influence (surface treatment) and biological growth (e.g. fungus) are major exogenic processes which may alter delta(18)O and delta(13)C in lime mortar.

Early Mars: A Warm Wet Niche for Life

NASA Technical Reports Server (NTRS)

Gibson, Everett K.; McKay, David S.; Thomas-Keprta, Kathie L.; Clemett, Simon J.

2010-01-01

Exploration of Mars has begun to unveil the history of the planet. Combinations of remote sensing, in situ compositional measurements and photographic observations have shown Mars had a dynamic and active geologic evolution. Mars geologic evolution had conditions that were suitable for supporting life. A habitable planet must have water, carbon and energy sources along with a dynamic geologic past. Mars meets all of these requirements. The first 600 Ma of Martian history were ripe for life to develop because of the abundance of: (i) Water-as shown by carved canyons and oceans or lakes with the early presence of near surface water shown by precipitated carbonates in ALH84001, well-dated at approx.3.9 Ga, (ii) Energy from the original accretional processes, a molten core which generated a strong magnetic field leaving a permanent record in the early crust, active volcanism continuing throughout Martian history, and continuing impact processes, (iii) Carbon, water and a likely thicker atmosphere from extensive volcanic outgassing (i.e. H2O, CO2, CH4, CO, O2, N2, H2S, SO2, etc.) and (iv) crustal tectonics as revealed by faulting and possible plate movement reflected by the magnetic patterns in the crust [1]. The question arises: "Why would life not develop from these favorable conditions on Mars in its first 600 Ma?" During this period, environmental near-surface conditions on Mars were more favorable to life than at any later time. Standing bodies of water, precipitation and flowing surface water, and possibly abundant hydrothermal energy would favor the formation of early life. (Even if life developed elsewhere on Earth, Venus, or on other bodies-it was transported to Mars where surface conditions were suitable for life to evolve)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fernandez, Carlos A.; Nune, Satish K.; Annapureddy, Harsha V.

Metal-organic frameworks (MOFs) have proved to be very attractive for applications including gas storage, separation, sensing and catalysis. In particular, CO2 separation from flue gas in post-combustion processes is one of the main focuses of research among the scientific community. One of the major issues that are preventing the successful commercialization of these novel materials (e.g., MgDOBDC and NiDOBDC) is their high affinity towards water that not only compromises gas sorption capacity but also the chemical stability. In this paper, we demonstrate a novel post-synthesis modification approach to modify MOFs towards increasing hydrophobic behavior and chemical stability against moisture withoutmore » compromising CO2 sorption capacity. Our approach consists of incorporating hydrophobic moieties on the external surface of the MOFs via physical adsorption. The rationale behind this concept is to increase the surface hydrophobicity in the porous materials without the need of introducing bulky functionalities inside the pore which compromises the sorption capacity toward other gases. This allows MOF interaction/sorption of CO2 molecules comparable to unmodified MOFs. We herein report preliminary results on three routinely studied MOF materials [MIL-101(Cr), MgDOBDC and NiDOBDC] demonstrating that the polymer-modified MOFs retain CO2 sorption capacity while reducing the water adsorption up to three times, respect to the un-modified materials, via an equilibrium effect. Furthermore, the water stability of the polymer-functionalized MOFs is significantly higher than the water stability of the bare material. Molecular dynamic simulations demonstrated that this equilibrium effect implies a fundamental and permanent change in the water sorption capacity of MOFs. This approach can also be employed to render moisture stability and selectivity to MOFs that find applications in gas separations, catalysis and sensing where water plays a critical role in compromising MOF performance and recyclability.« less

The CO2 Flux and the Chemistry of the Crater lake in 2013-2015 Evidence for the Enhanced Activity of El Chichon volcano, Mexico.

NASA Astrophysics Data System (ADS)

Taran, Y.; Jácome Paz, M. P.; Inguaggiato, S.; Collard, N.

2015-12-01

During 2013-2015, four CO2 flux surveys were performed in the El Chichon crater both, from the lake surface and from the soil of the crater. The chemistry of the lake water, as well as its physical parameters (surface area, depth, temperature) were also determined. The CO2 flux in 2014-2015 compared to the 2007-2008 data (Mazot et al., 2011, BV, 73: 423-441) increased almost one order of magnitude (from ~ 140 ton d-1 in 2008 to ~ 840 ton d-1 in 2014). During the last two years the lake became the largest for the whole time of observations with the maximum surface area more than 18 ha covering completely the NE fumarolic field and all thermal springs feeding the lake with mineralized water. Despite the maximum volume of the lake it was characterized in 2015 by the highest since 2007 chloride content (~2500 ppm) and temperature (34°C). A large degassing spot in the middle of the lake for the first time was observed in April 2015 with more than 10,000 g m-2 d-1 of the CO2 flux. These observations evidence that the volcano-hydrothermal system of El Chichon volcano came into a new stage of activity associated most probably with changes in the magmatic activity at depth.

Synthesis of FeCoB amorphous nanoparticles and application in ferrofluids

NASA Astrophysics Data System (ADS)

Zhao, Shuchun; Bian, Xiufang; Yang, Chuncheng; Yu, Mengchun; Wang, Tianqi

2018-03-01

Magnetic FeCoB amorphous nanoparticles were successfully synthesized by borohydride reduction in water/n-hexane (W/He) microemulsions. The as-prepared FeCoB alloys are amorphous and spherical nanoparticles with an average particle size about 10.7 nm, compared to FeCoB alloys with an average particle size about 304.2 nm which were synthesized by a conventional aqua-solution method. Furthermore, three kinds of FeCoB ferrofluids (FFs) were prepared by dispersing FeCoB particles into W/He microemulsion, water and silicone oil respectively. Results show that the W/He-based FeCoB FFs are superparamagnetic with saturation magnetization (Ms) reaching to 12.4 emu/g. Besides, compared to water-based and silicone oil-based FFs, W/He-based FeCoB FFs exhibit high stability, with magnetic weights decreasing slightly even under the magnetic field intensity of H = 210 mT. In the W/He-based FeCoB FFs, interfacial tensions of water phase and oil phase are supposed to prevent the agglomeration and sedimentation of FeCoB nanoparticles dispersed in different water droplets of the microemulsion, compared to the current stabilizing method of directly modifying the surface of particles.

Exploring the influence of surface waves in the carbon dioxide transfer velocity between the ocean and atmosphere in the coastal region

NASA Astrophysics Data System (ADS)

Ocampo-Torres, Francisco Javier; Francisco Herrera, Carlos; Gutiérrez-Loza, Lucía; Osuna, Pedro

2016-04-01

Field measurements have been carried out in order to better understand the possible influence of ocean surface waves in the transfer of carbon dioxide between the ocean and atmosphere in the coastal zone. The CO2 fluxes are being analysed and results are shown in a contribution by Gutiérrez-Loza et al., in this session. Here we try to highlight the findings regarding the transfer velocity (kCO2) once we have incorporated direct measurements of carbon dioxide concentration in the water side. In this study direct measurements of CO2 fluxes were obtained with an eddy covariance tower located in the shoreline equipped with an infrared open-path gas analyzer (LI-7500, LI-COR) and a sonic anemometer (R3-100 Professional Anemometer, Gill Instruments), both at about 13 m above the mean sea level, and sampling at 20 Hz. For some period of time simultaneous information of waves was recorded with a sampling rate of 2 Hz using an Acoustic Doppler Current Profiler (Workhorse Sentinel, Teledyne RD Instruments) at 10 m depth and 350 m away from the tower. Besides, recently the concentration of CO2 in water has also been recorded making use of a SAMI-CO2 instrument. A subtle effect of the wave field is detected in the estimated kCO2. Looking into details of the surface currents being detected very near the air-sea interface through an ADPC, a certain association can be found with the gas transfer velocity. Furthermore, some of the possible effects of breaking wave induced turbulence in the coastal zone is to be addressed. This work represents a RugDiSMar Project (CONACYT 155793) contribution. The support from CB-2011-01-168173 CONACYT project is greatly acknowledged.

Quantifying the magnitude and spatiotemporal variation of aquatic CO2 fluxes in a sub-tropical karst catchment, Southwest China

NASA Astrophysics Data System (ADS)

Ding, Hu; Waldron, Susan; Newton, Jason; Garnett, Mark H.

2017-04-01

The role played by rivers in regional and global C budgets is receiving increasing attention. A large portion of the carbon transported via inland waters is returned to the atmosphere by carbon dioxide evasion from rivers and lakes. Karst landscapes represent an important C store on land, and are also considered to play an important role in climate regulation by consuming atmospheric CO2 during chemical weathering. However, we cannot be certain how effective this sink is if we do not know how efficiently the rivers draining karst landscapes remobilise weathered C to the atmosphere as CO2. pCO2 in karst waters is generally greater than atmospheric equilibrium, indicating that there can be a net CO2 efflux to the atmosphere. However, measurement confirming this and quantifying flux rates has been rarely conducted. Using a floating chamber method, in 2016 we directly measured CO2 fluxes from spatially distributed freshwaters (springs, sinkholes, streams and reservoirs/ponds) in the Houzhai Catchment, a karst region in SW China. Fluxes ranged from -0.5 to +267.4 μmol CO2 m-2s-1, and most sites showed seasonal variations with higher CO2 efflux rates in the wet (April - September) than dry season (October - March). There was a significant positive relationship between CO2 efflux and flow velocity, indicating that hydraulic controls on CO2 efflux from flowing water are important, while for water with little movement (sinkholes and reservoirs/ponds), pCO2 appears a more important control on efflux rates. Conditions similar to this study area may exist in many sub-tropical rivers that drain karst landscapes in South China. These waters are rich in DIC which can be an order of magnitude greater than some non-karst catchments. The large DIC pool has the potential to be a considerable source of free CO2 to the atmosphere. Considering that carbonate lithology covers a significant part of the Earth's surface, CO2 evasion in fluvial water from these regions is expected to contribute notably to the annual carbon dioxide release from global freshwater systems, thus must be better represented in global spatial analyses of CO2 evasion. This research advances this need.

The concurrent use of novel soil surface microclimate measurements to evaluate CO2 pulses in biocrusted interspaces in a cool desert ecosystem

USGS Publications Warehouse

Tucker, Colin; McHugh, Theresa A.; Howell, Armin; Gill, Richard; Weber, Bettina; Belnap, Jayne; Grote, Ed; Reed, Sasha C.

2017-01-01

Carbon cycling associated with biological soil crusts, which occupy interspaces between vascular plants in drylands globally, may be an important part of the coupled climate-carbon cycle of the Earth system. A major challenge to understanding CO2 fluxes in these systems is that much of the biotic and biogeochemical activity occurs in the upper few mm of the soil surface layer (i.e., the ‘mantle of fertility’), which exhibits highly dynamic and difficult to measure temperature and moisture fluctuations. Here, we report a multi-sensor approach to simultaneously measuring temperature and moisture of this biocrust surface layer (0–2 mm), and the deeper soil profile, concurrent with automated measurement of surface soil CO2effluxes. Our results illuminate robust relationships between biocrust water content and field CO2 pulses that have previously been difficult to detect and explain. All observed CO2 pulses over the measurement period corresponded to surface wetting events, including when the wetting events did not penetrate into the soil below the biocrust layer (0–2 mm). The variability of temperature and moisture of the biocrust surface layer was much greater than even in the 0–5 cm layer of the soil beneath the biocrust, or deeper in the soil profile. We therefore suggest that coupling surface measurements of biocrust moisture and temperature to automated CO2flux measurements may greatly improve our understanding of the climatic sensitivity of carbon cycling in biocrusted interspaces in our study region, and that this method may be globally relevant and applicable.

The Carbon Isotopic Record of The C37:2 Alkenone In Sediments From The Equatorial and South Atlantic: Last Glacial Maximum (lgm) Vs. Holocene

NASA Astrophysics Data System (ADS)

Benthien, A.; Schulte, S.; Andersen, N.; Müller, P. J.; Schneider, R. R.

The carbon isotopic signal of the C37-alkenone, a taxon-specific biomarker for hap- tophyte algae, has been used in various paleoceanographic studies as a proxy for an- cient surface water CO2 concentration ([CO2aq]). However, a number of recent cul- ture, field and sediment studies imply that the carbon isotopic fractionation (ep) of alkenones is controlled predominantly by physiological processes and environmental factors other than the ambient CO2 concentration (i.e., growth rate, nutrient availabil- ity, light intensity, active carbon uptake, bicarbonate utilisation). The environmental conditions controlling phytoplankton growth are likely to vary strongly with oceano- graphic setting. Culture experiments can not perfectly recreate natural growth con- ditions and physical processes which affect the carbon isotopic signal in the field and its preservation in the sediment. Consequently, the use of the carbon isotopic record of alkenones as a reliable paleoceonographic proxy also requires sediment- based studies covering a broad range of different oceanic regimes for the past and modern ocean. Here, we present the first basin-wide comparison of alkenone ep val- ues from sediments of the Last Glacial Maximum (LGM) and the latest Holocene. Different oceanographic regions from the equatorial and South Atlantic Ocean were examined. Generally, alkenone ep is lower during the LGM compared to the Holocene. Considering present understanding of LGM-Holocene changes in surface water condi- tions, the observed glacial/interglacial difference in ep indicates that different effects controlled the isotopic fractionation in alkenone-producing algae depending on the regional setting. In upwelling regions, the variations in ep probably reflect a glacial increase in haptophyte productivity controlled by the availability of surface water nu- trient concentrations. By contrast, in oligotrophic areas slightly lower nutrient content was available during LGM. Here, the observed ep difference can be explained partly with an assumed glacial decrease in surface water [CO2aq]. However, it can not be ruled out that changes in haptophyte productivity also affected the ep signal to some extent. This study clearly demonstrates that a reliable reconstruction of [CO2aq] on the basis of the isotopic composition of alkenones is not feasible without a detailed 1 knowledge of ancient haptophyte growth conditions. 2

Porosity and thermal collapse measurements of H2O, CH3OH, CO2, and H2O:CO2 ices.

PubMed

Isokoski, K; Bossa, J-B; Triemstra, T; Linnartz, H

2014-02-28

The majority of astronomical and laboratory based studies of interstellar ices have been focusing on ice constituents. Ice structure is a much less studied topic. Particularly the amount of porosity is an ongoing point of discussion. A porous ice offers more surface area than a compact ice, for reactions that are fully surface driven. In this paper we discuss the amount of compaction for four different ices--H2O, CH3OH, CO2 and mixed H2O : CO2 = 2 : 1--upon heating over an astronomically relevant temperature regime. Laser interference and Fourier transform infrared spectroscopy are used to confirm that for amorphous solid water the full signal loss of dangling OH bonds is not a proof for full compaction. These data are compared with the first compaction results for pure CH3OH, pure CO2 and mixed H2O : CO2 = 2 : 1 ice. Here we find that thermal segregation benefits from a higher degree of porosity.

Preparation and characterization of magnetic allylamine modified graphene oxide-poly(vinyl acetate-co-divinylbenzene) nanocomposite for vortex assisted magnetic solid phase extraction of some metal ions.

PubMed

Khan, Mansoor; Yilmaz, Erkan; Sevinc, Basak; Sahmetlioglu, Ertugrul; Shah, Jasmin; Jan, Muhammad Rasul; Soylak, Mustafa

2016-01-01

Magnetic allylamine modified graphene oxide-poly(vinyl acetate-co-divinylbenzene) (MGO-DVB-VA) was synthesized and used for magnetic solid phase extraction of Pb(II), Cd(II), Cu(II), Ni(II) and Co(II) prior to their determination by flame atomic absorption spectroscopy. The adsorbent surface functional group was characterized by using FT-IR and Raman spectroscopy. XRD pattern was used to determine the layers of GO. Surface morphology and elemental composition of the adsorbent were evaluated by using SEM and EDX analysis. Various parameters, effecting adsorption efficiency like initial solution pH, adsorbent dose, type and volume of eluent, volume of sample and diverse ions effects were optimized. The preconcentration factor (PF) is 40 for all the metals and the limits of detection for Pb, Cd, Cu, Ni and Co are in the range of 0.37-2.39 µg L(-1) and relative standard deviation below 3.1%. The method was validated by using the method for certified reference materials (Tobacco Leaves (INCT-OBTL-5), Tomato Leaves (1573a), Certified Water (SPS-ww2) and Certified Water (TMDA 64-2)). The method was successfully applied for natural water and food samples. Copyright © 2015 Elsevier B.V. All rights reserved.

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

PubMed

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

2016-07-19

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

Short-lived radium isotopes on the Scotian Shelf: Unique distribution and tracers of cross-shelf CO2 and nutrient transport

NASA Astrophysics Data System (ADS)

Burt, William; Thomas, Helmuth

2013-04-01

Radium (Ra) isotopes have become a common tool for investigating mixing rates on continental shelves, and more recently have been used to quantify the release of dissolved compounds enriched in pore-waters into the water column. We present results from Ra sampling of the Scotian Shelf region of the Canadian northwestern Atlantic Ocean, which reveal cross-shelf Ra distributions that are unique compared to other coastal regions. We explain the observations of lower 224Ra activities near the coast, relatively high activities at large distances offshore (>100km), and gradients in both offshore and onshore directions by inferring the regional geomorphology, as well as shelf bathymetry and circulation patterns. Ra gradients are used to calculate individual estimates of eddy diffusion in both the cross-shelf (KX) and vertical (KZ) directions using 1-D eddy diffusion models. Enhanced vertical mixing above offshore banks allows for Ra enrichments in offshore surface waters, while horizontal dispersion of this bank-related signal can transport Ra off the shelf break in surface waters, and towards the shore beneath the surface mixed layer. Similar onshore gradients in CO2 and nutrient species combined with Ra-derived KX values can yield onshore carbon and nutrient fluxes in subsurface waters, which in turn supply the CO2 outgassing from the Scotian Shelf. Our results thus provide constraints for cross-shelf transports of carbon and nutrients on the Scotian Shelf in order to guide mass balance or model based budget approaches in future studies.

Initial Net CO2 Uptake Responses and Root Growth for a CAM Community Placed in a Closed Environment

PubMed Central

NOBEL, PARK S.; BOBICH, EDWARD G.

2002-01-01

To help understand carbon balance between shoots and developing roots, 41 bare‐root crassulacean acid metabolism (CAM) plants native to the Sonoran Desert were studied in a glass‐panelled sealable room at day/night air temperatures of 25/15 °C. Net CO2 uptake by the community of Agave schottii, Carnegia gigantea, Cylindropuntia versicolor, Ferocactus wislizenii and Opuntia engelmannii occurred 3 weeks after watering. At 4 weeks, the net CO2 uptake rate measured for south‐east‐facing younger parts of the shoots averaged 1·94 µmol m–2 s–1 at night, considerably higher than the community‐level nocturnal net CO2 uptake averaged over the total shoot surface, primarily reflecting the influences of surface orientation on radiation interception (predicted net CO2 uptake is twice as high for south‐east‐facing surfaces compared with all compass directions). Estimated growth plus maintenance respiration of the roots averaged 0·10 µmol m–2 s–1 over the 13‐week period, when the community had a net carbon gain from the atmosphere of 4 mol C while the structural C incorporated into the roots was 23 mol. Thus, these five CAM species diverted all net C uptake over the 13‐week period plus some existing shoot C to newly developing roots. Only after sufficient roots develop to support shoot water and nutrient requirements will the plant community have net above‐ground biomass gains. PMID:12466099

Soil Water Balance and Vegetation Dynamics in two Contrasting Water-limited Mediterranean Ecosystems on Sardinia, Italy

NASA Astrophysics Data System (ADS)

Montaldo, N.; Albertson, J. D.; Corona, R.

2011-12-01

Water limited conditions strongly impacts soil and vegetation dynamics in Mediterranean regions, which are commonly heterogeneous ecosystems, characterized by inter-annual rainfall variability, topography variability and contrasting plant functional types (PFTs) competing for water use. Mediterranean regions are characterized by two main ecosystems, grassland and woodland, which for both natural and anthropogenic causes can grow in soils with different characteristics, highly impacting water resources. Water resources and forestal planning need a deep understanding of the dynamics between PFTs, soil and atmosphere and their impacts on water and CO2 distributions of these two main ecosystems. The first step is the monitoring of land surface fluxes, soil moisture, and vegetation dynamics of the two contrasting ecosystems. Moreover, due to the large percentage of soils with low depth (< 50 cm), and due to the quick hydrologic answer to atmospheric forcing in these soils, there is also the need to understand the impact of the soil depth in the vegetation dynamics, and make measurements in these types of soils. Sardinia island is a very interesting and representative region of Mediterranean ecosystems. It is low urbanized, and is not irrigated, except some plan areas close to the main cities where main agricultural activities are concentrated. The case study sites are within the Flumendosa river basin on Sardinia. Two sites, both in the Flumendosa river and with similar height a.s.l., are investigated. The distance between the sites is around 4 km but the first is a typically grass site located on an alluvial plan valley with a soil depth more than 2m, while the second site is a patchy mixture of Mediterranean vegetation types Oaks, creepers of the wild olive trees and C3 herbaceous species and the soil thickness varies from 15-40 cm, bounded from below by a rocky layer of basalt, partially fractured. In both sites land-surface fluxes and CO2 fluxes are estimated by eddy correlation technique based micrometeorological towers. Soil moisture profiles were also continuously estimated using water content reflectometers and gravimetric method, and periodically leaf area index PFTs are estimated during the Spring-Summer 2005. The following objectives are addressed:1) pointing out the dynamics of land surface fluxes, soil moisture, CO2 and vegetation cover for two contrasting water-limited ecosystems; 2) assess the impact of the soil depth and type on the CO2 and water balance dynamics. For reaching the objectives an ecohydrologic model is also successfully used and applied to the case studies. It couples a vegetation dynamic model, which computes the change in biomass over time for the PFTs, and a 3-component (bare soil, grass and woody vegetation) land surface model.

Radiolytic Model for Chemical Composition of Europa's Atmosphere and Surface

NASA Technical Reports Server (NTRS)

Cooper, John F.

2004-01-01

The overall objective of the present effort is to produce models for major and selected minor components of Europa s neutral atmosphere in 1-D versus altitude and in 2-D versus altitude and longitude or latitude. A 3-D model versus all three coordinates (alt, long, lat) will be studied but development on this is at present limited by computing facilities available to the investigation team. In this first year we have focused on 1-D modeling with Co-I Valery Shematovich s Direct Simulation Monte Carlo (DSMC) code for water group species (H2O, O2, O, OH) and on 2-D with Co-I Mau Wong's version of a similar code for O2, O, CO, CO2, and Na. Surface source rates of H2O and O2 from sputtering and radiolysis are used in the 1-D model, while observations for CO2 at the Europa surface and Na detected in a neutral cloud ejected from Europa are used, along with the O2 sputtering rate, to constrain source rates in the 2-D version. With these separate approaches we are investigating a range of processes important to eventual implementation of a comprehensive 3-D atmospheric model which could be used to understand present observations and develop science requirements for future observations, e.g. from Earth and in Europa orbit. Within the second year we expect to merge the full water group calculations into the 2-D version of the DSMC code which can then be extended to 3-D, pending availability of computing resources. Another important goal in the second year would be the inclusion of sulk and its more volatile oxides (SO, SO2).

Whole water column distribution and carbon isotopic composition of bulk particulate organic carbon, cholesterol and brassicasterol from the Cape Basin to the northern Weddell Gyre in the Southern Ocean

NASA Astrophysics Data System (ADS)

Cavagna, A.-J.; Dehairs, F.; Woule-Ebongué, V.; Bouillon, S.; Planchon, F.; Delille, B.; Bouloubassi, I.

2012-02-01

The combination of concentrations and δ13C signatures of Particulate Organic Carbon (POC) and sterols provides a powerful approach to study ecological and environmental changes both in the modern and ancient ocean, but its application has so far been restricted to the surface area. We applied this tool to study the biogeochemical changes in the modern ocean water column during the BONUS-GoodHope survey (Feb-Mar 2008) from Cape Basin to the northern part of the Weddell Gyre. Cholesterol and brassicasterol were chosen as ideal biomarkers of the heterotrophic and autotrophic carbon pools, respectively, because of their ubiquitous and relatively refractory nature. We document depth distributions of concentrations (relative to bulk POC) and δ13C signatures of cholesterol and brassicasterol from the Cape Basin to the northern Weddell Gyre combined with CO2 aq. surface concentration variation. While relationships between surface water CO2 aq. and δ13C of bulk POC and biomarkers have been previously established for surface waters, our data show that these remain valid in deeper waters, suggesting that δ13C signatures of certain biomarkers could be developed as proxies for surface water CO2 aq. Our data suggest a key role of zooplankton fecal aggregates in carbon export for this part of the Southern Ocean. We observed a general increase in sterol δ13C signatures with depth, which is likely related to a combination of particle size effects, selective feeding on larger cells by zooplankton, and growth rate related effects Additionally, in the southern part of the transect south of the Polar Front (PF), the release of sea-ice algae is hypothesized to influence the isotopic signature of sterols in the open ocean. Overall, combined use of δ13C and concentrations measurements of both bulk organic C and specific sterol markers throughout the water column shows the promising potential of analyzing δ13C signatures of individual marine sterols to explore the recent history of plankton and the fate of organic matter in the SO.

Altitude controls carbon dioxide in boreal lakes

NASA Astrophysics Data System (ADS)

Bhattacharya, Atreyee

2012-09-01

Organic matter present in lakes, derived either from land-based sources—such as plants, soil, and sediments—or from in situ processes—such as degrading detritus in the water—could be important in the global carbon cycle, and possibly a significant source of the atmospheric carbon dioxide (CO2) budget. The partial pressure of CO2 in surface waters (pCO2) drives the escape of CO2 to the atmosphere. Hence, scientists have long suspected that the relationship between pCO2 and the dissolved organic matter (DOC) in lake waters refects the relative contribution of the environment and in situ processes to the high-latitude carbon budget. Combining measurements of DOC and pCO2 from nearly 200 lakes across Quebec, Canada, with an additional 13 lake-based studies from temperate regions across the northern hemisphere, Lapierre and del Giorgio suggest that on a regional scale the A variety of lakes dominate the boreal landscape of Quebec, Canada. elevation of lakes is one of the strongest controls on the relationship between DOC and pCO2 in boreal lakes.

The Dye Sensitized Photoelectrosynthesis Cell (DSPEC) for Solar Water Splitting and CO2 Reduction

NASA Astrophysics Data System (ADS)

Meyer, Thomas; Alibabaei, Leila; Sherman, Benjamin; Sheridan, Matthew; Ashford, Dennis; Lapides, Alex; Brennaman, Kyle; Nayak, Animesh; Roy, Subhangi; Wee, Kyung-Ryang; Gish, Melissa; Meyer, Jerry; Papanikolas, John

The dye-sensitized photoelectrosynthesis cell (DSPEC) integrates molecular level light absorption and catalysis with the bandgap properties of stable oxide materials such as TiO2 and NiO. Excitation of surface-bound chromophores leads to excited state formation and rapid electron or hole injection into the conduction or valence bands of n or p-type oxides. Addition of thin layers of TiO2 or NiO on the surfaces of mesoscopic, nanoparticle films of semiconductor or transparent conducting oxides to give core/shell structures provides a basis for accumulating multiple redox equivalents at catalysts for water oxidation or CO2 reduction. UNC EFRC Center for Solar Fuels, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0001011.

Effects of sulfate ligand on uranyl carbonato surface species on ferrihydrite surfaces

USGS Publications Warehouse

Arai, Yuji; Fuller, C.C.

2012-01-01

Understanding uranium (U) sorption processes in permeable reactive barriers (PRB) are critical in modeling reactive transport for evaluating PRB performance at the Fry Canyon demonstration site in Utah, USA. To gain insight into the U sequestration mechanism in the amorphous ferric oxyhydroxide (AFO)-coated gravel PRB, U(VI) sorption processes on ferrihydrite surfaces were studied in 0.01 M Na2SO4 solutions to simulate the major chemical composition of U-contaminatedgroundwater (i.e., [SO42-]~13 mM L-1) at the site. Uranyl sorption was greater at pH 7.5 than that at pH 4 in both air- and 2% pCO2-equilibrated systems. While there were negligible effects of sulfate ligands on the pH-dependent U(VI) sorption (<24 h) in both systems, X-ray absorption spectroscopy (XAS) analysis showed sulfate ligand associated U(VI) surface species at the ferrihydrite–water interface. In air-equilibrated systems, binary and mono-sulfate U(VI) ternary surface species co-existed at pH 5.43. At pH 6.55–7.83, a mixture of mono-sulfate and bis-carbonato U(VI) ternary surface species became more important. At 2% pCO2, there was no contribution of sulfate ligands on the U(VI) ternary surface species. Instead, a mixture of bis-carbonato inner-sphere (38%) and tris-carbonato outer-sphere U(VI) ternary surface species (62%) was found at pH 7.62. The study suggests that the competitive ligand (bicarbonate and sulfate) coordination on U(VI) surface species might be important in evaluating the U solid-state speciation in the AFO PRB at the study site where pCO2 fluctuates between 1 and 2 pCO2%.

The relative influence of H2O and CO2 on the primitive surface conditions of Venus

NASA Astrophysics Data System (ADS)

Salvador, A.; Massol, H.; Davaille, A.; Marcq, E.; Sarda, P.; Chassefiere, E.

2017-12-01

How the volatile content influences the primordial surface conditions of terrestrial planets and, thus, their future geodynamic evolution is an important question to answer. We simulate the secular convective cooling of a 1-D magma ocean (MO) in interaction with its outgassed atmosphere. A first rapid cooling stage, where efficient MO cooling and degassing take place, producing the atmosphere, is followed by a second quasi steady state where the heat flux balance is dominated by the solar flux. The end ofthe rapid cooling stage (ERCS) is reached when the mantle heat flux becomes negligible compared tothe absorbed solar flux. Varying the initial CO2 and H2O contents and the solar distance, we showed that the resulting surface conditions at ERCS strongly depend on these parameters and that water ocean's formation obeys simple scaling laws.Although today's Venus is located beyond the inner edge of the habitable zone due to its high albedo, its high CO2/H2O ratio prevents any water ocean formation.We already showed that depending on the formation time of its cloudcover and resulting albedo, only 0.3 Earth ocean mass might be sufficient to form a water ocean onearly Venus. Here we investigate more precisely these results by taking into account the effect of shortwave radiation on the radiative budget by computing the feedbacks between atmospheric composition and incident stellar flux instead of using a prescribed albedo value.

Thermal effects on electronic properties of CO/Pt(111) in water.

PubMed

Duan, Sai; Xu, Xin; Luo, Yi; Hermansson, Kersti; Tian, Zhong-Qun

2013-08-28

Structure and adsorption energy of carbon monoxide molecules adsorbed on the Pt(111) surfaces with various CO coverages in water as well as work function of the whole systems at room temperature of 298 K were studied by means of a hybrid method that combines classical molecular dynamics and density functional theory. We found that when the coverage of CO is around half monolayer, i.e. 50%, there is no obvious peak of the oxygen density profile appearing in the first water layer. This result reveals that, in this case, the external force applied to water molecules from the CO/Pt(111) surface almost vanishes as a result of the competitive adsorption between CO and water molecules on the Pt(111) surface. This coverage is also the critical point of the wetting/non-wetting conditions for the CO/Pt(111) surface. Averaged work function and adsorption energy from current simulations are consistent with those of previous studies, which show that thermal average is required for direct comparisons between theoretical predictions and experimental measurements. Meanwhile, the statistical behaviors of work function and adsorption energy at room temperature have also been calculated. The standard errors of the calculated work function for the water-CO/Pt(111) interfaces are around 0.6 eV at all CO coverages, while the standard error decreases from 1.29 to 0.05 eV as the CO coverage increases from 4% to 100% for the calculated adsorption energy. Moreover, the critical points for these electronic properties are the same as those for the wetting/non-wetting conditions. These findings provide a better understanding about the interfacial structure under specific adsorption conditions, which can have important applications on the structure of electric double layers and therefore offer a useful perspective for the design of the electrochemical catalysts.

Cobalt Oxide Nanoclusters on Rutile Titania as Bifunctional Units for Water Oxidation Catalysis and Visible Light Absorption: Understanding the Structure-Activity Relationship.

PubMed

Maeda, Kazuhiko; Ishimaki, Koki; Okazaki, Megumi; Kanazawa, Tomoki; Lu, Daling; Nozawa, Shunsuke; Kato, Hideki; Kakihana, Masato

2017-02-22

The structure of cobalt oxide (CoO x ) nanoparticles dispersed on rutile TiO 2 (R-TiO 2 ) was characterized by X-ray diffraction, UV-vis-NIR diffuse reflectance spectroscopy, high-resolution transmission electron microscopy, X-ray absorption fine-structure spectroscopy, and X-ray photoelectron spectroscopy. The CoO x nanoparticles were loaded onto R-TiO 2 by an impregnation method from an aqueous solution containing Co(NO 3 ) 2 ·6H 2 O followed by heating in air. Modification of the R-TiO 2 with 2.0 wt % Co followed by heating at 423 K for 1 h resulted in the highest photocatalytic activity with good reproducibility. Structural analyses revealed that the activity of this photocatalyst depended strongly on the generation of Co 3 O 4 nanoclusters with an optimal distribution. These nanoclusters are thought to interact with the R-TiO 2 surface, resulting in visible light absorption and active sites for water oxidation.

Warming and Carbon Dioxide Enrichment Alter Plant Production and Ecosystem gas Exchange in a Semi-Arid Grassland Through Direct Responses to Global Change Factors and Indirect Effects on Water Relations

NASA Astrophysics Data System (ADS)

Morgan, J. A.; Pendall, E.; Williams, D. G.; Bachman, S.; Dijkstra, F. A.; Lecain, D. R.; Follett, R.

2007-12-01

The Prairie Heating and CO2 Enrichment (PHACE) experiment was initiated in Spring, 2007 to evaluate the combined effects of warming and elevated CO2 on a northern mixed-grass prairie. Thirty 3-m diameter circular experimental plots were installed in Spring, 2006 at the USDA-ARS High Plains Grasslands Research Station, just west of Cheyenne, WY, USA. Twenty plots were assigned to a two-level factorial combination of two CO2 concentrations (present ambient, 380 ppmV; and elevated, 600 ppmV), and two levels of temperature (present ambient; and elevated temperature, 1.5/3.0 C warmer day/night), with five replications for each treatment. Five of the ten remaining plots were subjected to either frequent, small water additions throughout the growing season, and the other five to a deep watering once or twice during the growing season. The watering treatments were imposed to simulate hypothesized water savings in the CO2-enriched plots, and to contrast the influence of variable water dynamics on ecosystem processes. Carbon dioxide enrichment of the ten CO2- enriched plots is accomplished with Free Air CO2 Enrichment (FACE) technology and occurs during daylight hours of the mid-April - October growing season. Warming is done year-round with circularly-arranged ceramic heater arrays positioned above the ring perimeters, and with temperature feed-backs to control day/night canopy surface temperatures. Carbon dioxide enrichment began in Spring, 2006, and warming was added in Spring, 2007. Results from the first year of CO2 enrichment (2006) confirmed earlier reports that CO2 increases productivity in semi-arid grasslands (21% increase in peak seasonal above ground biomass for plants grown under elevated CO2 compared to non-enriched controls), and that the response was related to CO2- induced water savings. Growth at elevated CO2 reduced leaf carbon isotope discrimination and N concentrations in plants compared to results obtained in control plots, but the magnitude of changes were highly species specific. Ecosystem-level gas exchange measurements indicated that interactions between watering and CO2 enrichment increased C cycling over a range of soil moisture conditions, although watering had a greater relative impact on C fluxes than CO2 enrichment. Results from the combined warming and CO2 enrichment experiment in 2007 indicate soil fluxes of CO2 increased with elevated CO2 and warming, but decreased with warming later in the year compared to un-heated controls. Soil CH4 uptake was enhanced by elevated CO2 but reduced by warming, particularly later in the year. Soil fluxes of N2O were unaffected by treatment. These preliminary results indicate potentially strong feedbacks between carbon cycling and warming are mediated by ecosystem processes in this semiarid rangeland.

Mathematical modeling of synthesis gas fueled electrochemistry and transport including H2/CO co-oxidation and surface diffusion in solid oxide fuel cell

NASA Astrophysics Data System (ADS)

Bao, Cheng; Jiang, Zeyi; Zhang, Xinxin

2015-10-01

Fuel flexibility is a significant advantage of solid oxide fuel cell (SOFC). A comprehensive macroscopic framework is proposed for synthesis gas (syngas) fueled electrochemistry and transport in SOFC anode with two main novelties, i.e. analytical H2/CO electrochemical co-oxidation, and correction of gas species concentration at triple phase boundary considering competitive absorption and surface diffusion. Staring from analytical approximation of the decoupled charge and mass transfer, we present analytical solutions of two defined variables, i.e. hydrogen current fraction and enhancement factor. Giving explicit answer (rather than case-by-case numerical calculation) on how many percent of the current output contributed by H2 or CO and on how great the water gas shift reaction plays role on, this approach establishes at the first time an adaptive superposition mechanism of H2-fuel and CO-fuel electrochemistry for syngas fuel. Based on the diffusion equivalent circuit model, assuming series-connected resistances of surface diffusion and bulk diffusion, the model predicts well at high fuel utilization by keeping fixed porosity/tortuosity ratio. The model has been validated by experimental polarization behaviors in a wide range of operation on a button cell for H2-H2O-CO-CO2-N2 fuel systems. The framework could be helpful to narrow the gap between macro-scale and meso-scale SOFC modeling.

Evasion of CO2 from streams - the dominant component of the carbon export through the aquatic conduit in a boreal landscape.

PubMed

Wallin, Marcus B; Grabs, Thomas; Buffam, Ishi; Laudon, Hjalmar; Agren, Ånneli; Öquist, Mats G; Bishop, Kevin

2013-03-01

Evasion of gaseous carbon (C) from streams is often poorly quantified in landscape C budgets. Even though the potential importance of the capillary network of streams as C conduits across the land-water-atmosphere interfaces is sometimes mentioned, low-order streams are often left out of budget estimates due to being poorly characterized in terms of gas exchange and even areal surface coverage. We show that evasion of C is greater than all the total dissolved C (both organic and inorganic) exported downstream in the waters of a boreal landscape. In this study evasion of carbon dioxide (CO2 ) from running waters within a 67 km(2) boreal catchment was studied. During a 4 year period (2006-2009) 13 streams were sampled on 104 different occasions for dissolved inorganic carbon (DIC) and dissolved organic carbon (DOC). From a locally determined model of gas exchange properties, we estimated the daily CO2 evasion with a high-resolution (5 × 5 m) grid-based stream evasion model comprising the entire ~100 km stream network. Despite the low areal coverage of stream surface, the evasion of CO2 from the stream network constituted 53% (5.0 (±1.8) g C m(-2)  yr(-1) ) of the entire stream C flux (9.6 (±2.4) g C m(-2)  yr(-1) ) (lateral as DIC, DOC, and vertical as CO2 ). In addition, 72% of the total CO2 loss took place already in the first- and second-order streams. This study demonstrates the importance of including CO2 evasion from low-order boreal streams into landscape C budgets as it more than doubled the magnitude of the aquatic conduit for C from this landscape. Neglecting this term will consequently result in an overestimation of the terrestrial C sink strength in the boreal landscape. © 2012 Blackwell Publishing Ltd.

Assessing the Internal Consistency of the Marine Carbon Dioxide System at High Latitudes: The Labrador Sea AR7W Line Study Case

NASA Astrophysics Data System (ADS)

Raimondi, L.; Azetsu-Scott, K.; Wallace, D.

2016-02-01

This work assesses the internal consistency of ocean carbon dioxide through the comparison of discrete measurements and calculated values of four analytical parameters of the inorganic carbon system: Total Alkalinity (TA), Dissolved Inorganic Carbon (DIC), pH and Partial Pressure of CO2 (pCO2). The study is based on 486 seawater samples analyzed for TA, DIC and pH and 86 samples for pCO2 collected during the 2014 Cruise along the AR7W line in Labrador Sea. The internal consistency has been assessed using all combinations of input parameters and eight sets of thermodynamic constants (K1, K2) in calculating each parameter through the CO2SYS software. Residuals of each parameter have been calculated as the differences between measured and calculated values (reported as ΔTA, ΔDIC, ΔpH and ΔpCO2). Although differences between the selected sets of constants were observed, the largest were obtained using different pairs of input parameters. As expected the couple pH-pCO2 produced to poorest results, suggesting that measurements of either TA or DIC are needed to define the carbonate system accurately and precisely. To identify signature of organic alkalinity we isolated the residuals in the bloom area. Therefore only ΔTA from surface waters (0-30 m) along the Greenland side of the basin were selected. The residuals showed that no measured value was higher than calculations and therefore we could not observe presence of organic bases in the shallower water column. The internal consistency in characteristic water masses of Labrador Sea (Denmark Strait Overflow Water, North East Atlantic Deep Water, Newly-ventilated Labrador Sea Water, Greenland and Labrador Shelf waters) will also be discussed.

Interfacial Energy Transfer during Gamma Radiolysis of Water on the Surface of ZrO2 and Some Other Oxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Petrik, Nikolay G.; Alexandrov, Alexandr B.; Vall, Andrey I.

Effect of oxide interface on 60Co gamma radiolysis of water molecules was studied. Based on the molecular hydrogen yield when compared with that from the radiolysis of pure gas-phase water, all tested oxides can be classified into three groups: (i) inhibitors - MnO2, Co3O4, CuO and Fe2O3; (ii) oxides with H2 yields, which are similar to or slightly greater than radiolysis of pure gas-phase water - MgO, CaO, SrO, BaO, ZnO, CdO, Cu2O, NiO, Cr2O3, Al2O3, CeO2, SiO2, TiO2, Nb2O5 and WO3; (iii) promoters - Ga2O3, Y2O3, La2O3, Nd2O3, Sm2O3, Eu2O3, Gd2O3, Yb2O3, Er2O3, HfO2, and ZrO2. H2O radiolysis enhancementmore » for ZrO2 and other promoters is result of effective energy transfer at the oxide/water interface, presumably due to migration of excitons to the surface and their resonant coupling with the H2O adsorption complex. Plot''effective H2 yield vs. band-gap (Eg) energy'' shows a maximum near 5 eV.« less

The Impact of CO2-Driven Vegetation Changes on Wildfire Risk

NASA Astrophysics Data System (ADS)

Skinner, C. B.; Poulsen, C. J.

2017-12-01

While wildfires are a key component of natural ecological restoration and succession, they also pose tremendous risks to human life, health, and property. Wildfire frequency is expected to increase in many regions as the radiative effects of elevated CO2 drive warmer surface air temperatures, earlier spring snow melt, and more frequent meteorological drought. However, high CO2 concentrations will also directly impact vegetation growth and physiology, potentially altering wildfire characteristics through changes in fuel amount and surface hydrology. Depending on the biome and time of year, these vegetation-driven responses may mitigate or enhance radiative-driven wildfire changes. In this study, we use a suite of earth system models from the Coupled Model Intercomparison Project 5 with active biogeophysics and biogeochemistry to understand how the vegetation response to high CO2 (CO2 quadrupling) contributes to future changes in wildfire risk across the globe. Across the models, projected CO2 fertilization enhances aboveground biomass (about a 30% leaf area index (LAI) increase averaged across the globe) during the spring and summer months, increasing the availability of wildfire fuel across all biomes. Despite greater LAI, models robustly project widespread reductions in summer season transpiration (about -15% averaged across the globe) in response to reduced stomatal conductance from CO2 physiological forcing. Reduced transpiration warms summer season near surface temperatures and lowers relative humidity across vegetated regions of the mid-to-high latitudes, heightening the risk of wildfire occurrence. However, as transpiration goes down in response to greater plant water use efficiency, a larger fraction of soil water remains in the soil, potentially halting the spread of wildfires in some regions. Given the myriad ways in which the vegetation response to CO2 may alter wildfire risk, and the robustness of the responses across models, an explicit simulation of the wildfire response to CO2-driven vegetation change with the Community Earth System Model will be presented. The results suggest that many atmosphere-centric statistical wildfire metrics do not capture the many processes that will shape future wildfire risk in a high CO2 world and highlight the need for process-based fire modeling.

Dynamics of photogenerated holes in surface modified α-Fe2O3 photoanodes for solar water splitting

PubMed Central

Barroso, Monica; Mesa, Camilo A.; Pendlebury, Stephanie R.; Cowan, Alexander J.; Hisatomi, Takashi; Sivula, Kevin; Grätzel, Michael; Klug, David R.; Durrant, James R.

2012-01-01

This paper addresses the origin of the decrease in the external electrical bias required for water photoelectrolysis with hematite photoanodes, observed following surface treatments of such electrodes. We consider two alternative surface modifications: a cobalt oxo/hydroxo-based (CoOx) overlayer, reported previously to function as an efficient water oxidation electrocatalyst, and a Ga2O3 overlayer, reported to passivate hematite surface states. Transient absorption studies of these composite electrodes under applied bias showed that the cathodic shift of the photocurrent onset observed after each of the surface modifications is accompanied by a similar cathodic shift of the appearance of long-lived hematite photoholes, due to a retardation of electron/hole recombination. The origin of the slower electron/hole recombination is assigned primarily to enhanced electron depletion in the Fe2O3 for a given applied bias. PMID:22802673

Soil Water Balance and Vegetation Dynamics in two Water-limited Mediterranean Ecosystem on Sardinia under past and future climate change

NASA Astrophysics Data System (ADS)

Corona, R.; Montaldo, N.; Albertson, J. D.

2016-12-01

Water limited conditions strongly impacts soil and vegetation dynamics in Mediterranean regions, which are commonly heterogeneous ecosystems, characterized by inter-annual rainfall variability, topography variability and contrasting plant functional types (PFTs) competing for water use. Historical human influences (e.g., deforestation, urbanization) further altered these ecosystems. Sardinia island is a representative region of Mediterranean ecosystems. It is low urbanized except some plan areas close to the main cities where main agricultural activities are concentrated. Two contrasting case study sites are within the Flumendosa river basin (1700 km2). The first site is a typical grassland on an alluvial plan valley (soil depth > 2m) while the second is a patchy mixture of Mediterranean vegetation species (mainly wild olive trees and C3 herbaceous) that grow in a soil bounded from below by a rocky layer of basalt, partially fractured (soil depth 15 - 40 cm). In both sites land-surface fluxes and CO2 fluxes are estimated by the eddy correlation technique while soil moisture was continuously estimated with water content reflectometers, and periodically leaf area index (LAI) was estimated. The following objectives are addressed:1) pointing out the dynamics of land surface fluxes, soil moisture, CO2 and vegetation cover for two contrasting water-limited ecosystems; 2) assess the impact of the soil depth and type on the CO2 and water balance dynamics; 3) evaluate the impact of past and future climate change scenarios on the two contrasting ecosystems. For reaching the objectives an ecohydrologic model that couples a vegetation dynamic model (VDM), and a 3-component (bare soil, grass and woody vegetation) land surface model (LSM) has been used. Historical meteorological data are available from 1922 and hydro-meteorological scenarios are then generated using a weather generator. The VDM-LSM model predict soil water balance and vegetation dynamics for the generated hydrometeorological scenarios in the two contrasting ecosystems. Results demonstrate that vegetation dynamics are influenced by the inter-annual variability of atmospheric forcing, with vegetation density changing significantly according to seasonal rainfall amount. At the same time the vegetation dynamics affect the soil water balance.

TiO2@PEI-Grafted-MWCNTs Hybrids Nanocomposites Catalysts for CO2 Photoreduction

PubMed Central

Falcicchio, Aurelia; Fracassi, Francesco; Margiotta, Valerio; Moliterni, Anna

2018-01-01

Anatase (TiO2) and multiwalled carbon nanotubes bearing polyethylenimine (PEI) anchored on their surface were hybridized in different proportions according to a sol-gel method. The resulting nanocomposites (TiO2@PEI-MWCNTs), characterized by BET, XRD, XPS, SEM, and UV techniques, were found efficient catalysts for CO2 photoreduction into formic and acetic acids in water suspension and under visible light irradiation. PEI-grafted nanotubes co-catalysts are believed to act as CO2 activators by forming a carbamate intermediate allowing to accomplish the first example in the literature of polyamines/nanotubes/TiO2 mediated CO2 photoreduction to carboxylic acids. PMID:29461484

Carbonates, surfates, phosphates, nitrates, and organic materials: Their association in a Martian meteorite

NASA Technical Reports Server (NTRS)

Wright, I. P.; Grady, M. M.; Pillinger, C. T.

1993-01-01

The debate concerning the evolution of CO2 on Mars continues. It would appear that in order to explain the valley networks and other relict fluvial landforms it is necessary to accept that liquid water was once present at the surface of Mars. This in turn requires, at some point in the planet's history, a higher surface temperature than exists today, proposition explained traditionally by an early dense CO2, atmosphere. However, there are a number of problems with this notion: for instance, CO2 alone is not an efficient greenhouse gas because of its tendency to form clouds. Moreover, if there was an early dense CO2 atmosphere, it is necessary to explain where the elemental constituents now reside. There are two possibilities for the latter, namely loss to outer space of atmospheric CO2 or the formation of vast carbonate deposits. While some models of atmospheric loss predict that up to 0.4 bar of CO2 could be removed from the Martian surface, this is still not enough to account for the original atmospheric inventory, usually considered to have been in the range of 1-5 bar. Thus, most models of the evolution of the Martian surface require removal of CO2 from the atmosphere and into carbonate deposits. However, as yet, the evidence for the existence of carbonates on Mars is fairly scant. This is an issue that would have been resolved by results obtained from Mars Observer.

Geochemistry of mineral waters and associated gases of the Sakhalin Island (Far East of Russia)

NASA Astrophysics Data System (ADS)

Chelnokov, George A.; Bragin, Ivan V.; Kharitonova, Natalia A.

2018-04-01

Isotopic and chemical data on the mineral water, mud volcanoes fluid and associated gases from the biggest Russian island Sakhalin, together with previous stable isotope data (d18O, dD, 13C), allow elucidation of their origin and general evolution. The water fluid circulation is mainly related to marine environment inducing three distinct types: Na-HCO3-Cl alkali carbonate groundwaters, Na-Cl-HCO3 highly evolved saline and Na-Cl mature groundwaters, indicating different evolution. Chemical evolution of groundwater on Sakhalin Island demonstrated cation exchange and salinization as dominant evolutionary pathways. Isotopic composition of groundwaters varies from meteoric to metamorphic waters. These metamorphic waters consist of water hydration from the clay and seawater are traced in fluids of Yuzhno-Sakhalin mud volcano despite modification by mixing with meteoric waters and water-rock interaction processes. Fault systems that define the areas of highly mineralized water circulation appear to play a major role in the CO2 migration to the surface and CH4 generation. The δ13C(CO2) values have pointed that gas phase in high-pCO2 waters mostly consists of mantle-derived CO2. The carbon isotope signature of methane δ13C(CH4) and δD(CH4) indicates its distinct origin which is specified by tectonics. Methane manifestation in the south of the Sakhalin Island is mainly related to thermogenic reservoirs as they are more often dislocate by tectonics, and crossed by active and permeable faults. The sources of biogenous methane in the north of Sakhalin Island is related to younger and shallower reservoirs, and less affected by tectonic processes. The determinations of 222Rn have allowed observing that maximal radon flux is associated with high pCO2 waters.

Airborne Lidar measurements of Atmospheric CO2 Column Absorption and Line Shapes from 3-11 km altitudes

NASA Astrophysics Data System (ADS)

Abshire, J. B.; Riris, H.; Allan, G. R.; Weaver, C.; Mao, J.; Hasselbrack, W.

2009-04-01

Accurate measurements of tropospheric CO2 abundances with global-coverage are needed to quantify processes that regulate CO2 exchange with the land and oceans. The 2007 Decadal Survey for Earth Science by the US National Research Council recommended a space-based CO2 measuring mission called ASCENDS. We have been developing a technique for the remote measurement of tropospheric CO2 concentrations from aircraft and as a candidate for the ASCENDS mission. It uses the 1570-nm CO2 band and a dual channel laser absorption spectrometer (ie DIAL used in altimeter mode). It uses several tunable laser transmitters allowing simultaneous measurement of the absorption from a CO2 absorption line in the 1570 nm band, O2 extinction in the oxygen A-band, and surface height and aerosol backscatter in the same path. It directs the narrow co-aligned laser beams toward nadir, and measures the energy of the laser echoes reflected from land and water surfaces. During the measurement, the lasers are stepped in wavelength across the CO2 line and an O2 line (near 765 nm) at a ~ 1 kHz rate. The receiver uses a telescope and photon counting detectors, and measures the background light and energies of the laser echoes from the surface along with scattering from any aerosols in the path. The gas extinction and column densities for the CO2 and O2 gases are estimated from the ratio of the on- and off- line signals via the DIAL technique. We use pulsed laser signals and time gating to isolate the laser echo signals from the surface, and to reject photons scattered from thin clouds and aerosols in the path. Previously we had constructed breadboard versions of our CO2 and O2 sensors, using tunable diode lasers, fiber laser amplifiers and 20 cm diameter telescopes. We have used them to make measurements of gas absorptions over 0.2, 0.4 and 1.3 km long outdoor paths. We also have also calculated several characteristics of the technique for space and have performed an initial space mission accommodation study. During 2008 we reconfigured our lidar for airborne use and made measurements of atmospheric CO2 absorption in the nadir column from the aircraft to the surface during 5 flights. The airborne lidar sweeps the laser wavelength across the CO2 line in either 10 or 20 steps per measurement. The line scan rate is ~ 1 KHz and the laser pulse widths are 1 usec. The time resolved laser backscatter is collected by the telescope and detected by a photomultiplier and recorded by a photon counting timing system. We installed our lidar on the NASA Glenn Lear-25 aircraft in October and first made measurements using the 1571.4 nm CO2 absorption line while flying in northern Ohio. We made laser backscatter and absorption measurements over a variety of land surface types, water surfaces and through thin clouds, broken clouds and to cloud tops. Strong laser signals were observed at altitudes from 2.5 to 11 km on two flights. We completed three additional flights during December 2008 and gathered over 6 hours of atmospheric CO2 column measurements using the 1572.02 and 1572.33 nm CO2 lines. Airborne CO2 line shape and absorption measurements were made while flying at 3-11 km altitudes over southwestern Ohio. Subsequently two flights were made from Ponca City OK, just east of the US Department of Energy's (DOE) ARM site. We made 4 hours of airborne measurements in square patterns around the ARM site at altitudes from 3-8 km. The increased CO2 line absorptions at higher altitudes were evident in all flights. The December flights were also coordinated with DOE investigators who flew an in-situ CO2 sensor on a Cessna aircraft inside the CO2 sounder's flight pattern. These yielded two height resolved profiles of CO2 concentrations from 5 km to the surface, which are being analyzed with radiosonde measurements for comparisons. More details of the flights, measurements and their analysis will be described in the presentation.

[Effect of water-nitrogen coupling on photosynthesis and ultrastructure of cucumber leaves under CO2 enrichment].

PubMed

Cui, Qing Qing; Dong, Yan Hong; Li, Man; Zhang, Wen Dong; Liu, Bin Bin; Ai, Xi Zhen; Bi, Huan Gai; Li, Qing Ming

2017-04-18

Using split plot and then-split plot design, effects of water-nitrogen coupling on photosynthesis and ultrastructure of cucumber (Cucumis sativus) (Jinyou No.35) under CO 2 enrichment were investigated. The main plot had two CO 2 concentrations: ambient CO 2 concentration (400 μmol·mol -1 , A) and doubled CO 2 concentration (800±20 μmol·mol -1 , E). The split plot had two treatments: no drought stress (95% of field capacity, W) and drought stress (75% of field capacity, D). The then-split plot contained low nitrogen treatment (450 kg·hm -2 , N 1 ) and high nitrogen treatment (900 kg·hm -2 , N 2 ). The results showed that under the condition of drought and high nitrogen, increasing CO 2 enhanced the cucumber plant height, and no matter what kinds of water treatment, CO 2 enrichment increased the leaf area significantly under high nitrogen. Under the condition of normal irrigation, the photosynthetic rate, stomatal conductance and transpiration rate of high nitrogen treatment were higher than low nitrogen treatment, while it was under the drought condition. Elevated CO 2 enhanced the water use efficiency of cucumber leaf which increased with increasing nitrogen application rate. Under drought stress, cucumber adaxial surface porosity density was increased, and the CO 2 enrichment and high nitrogen significantly reduced the stomatal density. Increasing nitrogen application improved the number of chloroplast, and reduced that of starch grains. Drought stress decreased the number of chloroplast, but tended to promote the number of starch grains. Drought stress increased the chloroplast length and width, and the size of the starch grains, while high nitrogen reduced the length and width of the chloroplast and starch grains. CO 2 enrichment and high nitrogen increased grana thickness and layers (except ADN 2 ), and the slice layer of EDN 2 was significantly higher than that of ADN 2 . In conclusion, CO 2 enrichment and suitable water and nitrogen could promote the development of chloroplast thylakoid membrane system, significantly increase the thickness of grana and the number of grana lamella, and effectively improve the chloroplast structure of cucumber, which would benefit the photosynthesis of cucumber plants and ability to utilize CO 2 and water and nitrogen.

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

PubMed

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 (< 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 the wide range of carbonate chemistry conditions organisms may currently experience in this and similar coastal ecosystems.

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

PubMed Central

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 (< 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 the wide range of carbonate chemistry conditions organisms may currently experience in this and similar coastal ecosystems. PMID:24586915

CO2 induced growth response in a diatom dominated phytoplankton community from SW Bay of Bengal coastal water

NASA Astrophysics Data System (ADS)

Biswas, Haimanti; Shaik, Aziz Ur Rahman; Bandyopadhyay, Debasmita; Chowdhury, Neha

2017-11-01

The ongoing increase in surface seawater CO2 level could potentially impact phytoplankton primary production in coastal waters; however, CO2 sensitivity studies on tropical coastal phytoplankton assemblages are rare. The present study investigated the interactive impacts of variable CO2 level, light and zinc (Zn) addition on the diatom dominated phytoplankton assemblages from the western coastal Bay of Bengal. Increased CO2 supply enhanced particulate organic matter (POC) production; a concomitant depletion in δ13CPOM values at elevated CO2 suggested increased CO2 diffusive influx inside the cell. Trace amount of Zn added under low CO2 level accelerated growth probably by accelerating Zn-Carbonic Anhydrase activity which helps in converting bicarbonate ion to CO2. Almost identical values of δ13CPOM in the low CO2 treated cells grown with and without Zn indicated a low discrimination between 13C and 12C probably due to bicarbonate uptake. These evidences collectively indicated the existence of the carbon concentration mechanisms (CCMs) at low CO2. A minimum growth rate was observed at low CO2 and light limited condition indicating light dependence of CCMs activity. Upon the increase of light and CO2 level, growth response was maximum. The cells grown in the low CO2 levels showed higher light stress (higher values of both diatoxanthin index and the ratio of photo-protective to light-harvesting pigments) that was alleviated by both increasing CO2 supply and Zn addition (probably by efficient light energy utilization in presence of adequate CO2). This is likely that the diatom dominated phytoplankton communities benefited from the increasing CO2 supply and thus may enhance primary production in response to any further increase in coastal water CO2 levels and can have large biogeochemical consequences in the study area.