Near surface stoichiometry in UO 2: A density functional theory study

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

Yu, Jianguo; Valderrama, Billy; Henderson, Hunter B.

2015-08-01

The mechanisms of oxygen stoichiometry variation in UO 2 at different temperature and oxygen partial pressure are important for understanding the dynamics of microstructure in these crystals. However, very limited experimental studies have been performed to understand the atomic structure of UO 2 near surface and defect effects of near surface on stoichiometry in which the system can exchange atoms with the external reservoir. In this study, the near (110) surface relaxation and stoichiometry in UO 2 have been studied with density functional theory (DFT) calculations. On the basis of the point-defect model (PDM), a general expression for the nearmore » surface stoichiometric variation is derived by using DFT total-energy calculations and atomistic thermodynamics, in an attempt to pin down the mechanisms of oxygen exchange between the gas environment and defected UO 2. By using the derived expression, it is observed that, under poor oxygen conditions, the stoichiometry of near surface is switched from hyperstoichiometric at 300 K with a depth around 3 nm to near-stoichiometric at 1000 K and hypostoichiometric at 2000 K. Furthermore, at very poor oxygen concentrations and high temperatures, our results also suggest that the bulk of the UO 2 prefers to be hypostoichiometric, although the surface is near-stoichiometric.« less

Acetone and Water on TiO₂(110): H/D Exchange

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

Henderson, Michael A.

2005-04-12

Isotopic H/D exchange between coadsorbed acetone and water on the TiO?(110) surface was examined using temperature programmed desorption (TPD) as a function of coverage and two surface pretreatments (oxidation and reduction). Coadsorbed acetone and water interact repulsively on reduced TiO?(110) based on results from the companion paper to this study, with water exerting a greater influence in destabilizing acetone and acetone having only a nominal influence on water. Despite the repulsive interaction between these coadsorbates, about 0.02 ML of a 1 ML d6-acetone on the reduced surface exhibits H/D exchange with coadsorbed water, with the exchange occurring exclusively in themore » high temperature region of the d?-acetone TPD spectrum at {approx}340 K. The effect was confirmed with combinations of d?-acetone and D?O. The extent of exchange decreased on the reduced surface with water coverages above {approx}0.3 ML due to the ability of water to displace coadsorbed acetone from first layer sites to the multilayer. In contrast, the extent of exchange increased by a factor of 3 when the surface was pre-oxidized prior to coadsorption. In this case, there was no evidence for the negative influence of high water coverages on the extent of H/D exchange. Comparison of the TPD spectra from the exchange products (either d?- or d?-acetone depending on the coadsorption pairing) suggests that, in addition to the 340 K exchange process seen on the reduced surface, a second exchange process was observed on the oxidized surface at {approx}390 K. In both cases (oxidized and reduced), desorption of the H/D exchange products appeared to be reaction limited and to involve the influence of OH/OD groups (or water formed during recombinative desorption of OH/OD groups) instead of molecularly adsorbed water. The 340 K exchange process is assigned to reaction at step sites and the 390 K exchange process is attributed to the influence of oxygen adatoms deposited during surface oxidation. The H/D exchange mechanism likely involves an enolate or propenol surface intermediate formed transiently during the desorption of oxygen-stabilized acetone molecules.« less

Scaling laws for oxygen transport across the space-filling system of respiratory membranes in the human lung

NASA Astrophysics Data System (ADS)

Hou, Chen

Space-filling fractal surfaces play a fundamental role in how organisms function at various levels and in how structure determines function at different levels. In this thesis, we develop a quantitative theory of oxygen transport to and across the surface of the highly branched, space-filling system of alveoli, the fundamental gas exchange unit (acinar airways), in the human lung. Oxygen transport in the acinar airways is by diffusion, and we treat the two steps---diffusion through the branched airways, and transfer across the alveolar membranes---as a stationary diffusion-reaction problem, taking into account that there may be steep concentration gradients between the entrance and remote alveoli (screening). We develop a renormalization treatment of this screening effect and derive an analytic formula for the oxygen current across the cumulative alveolar membrane surface, modeled as a fractal, space-filling surface. The formula predicts the current from a minimum of morphological data of the acinus and appropriate values of the transport parameters, through a number of power laws (scaling laws). We find that the lung at rest operates near the borderline between partial screening and no screening; that it switches to no screening under exercise; and that the computed currents agree with measured values within experimental uncertainties. From an analysis of the computed current as a function of membrane permeability, we find that the space-filling structure of the gas exchanger is simultaneously optimal with respect to five criteria. The exchanger (i) generates a maximum oxygen current at minimum permeability; (ii) 'wastes' a minimum of surface area; (iii) maintains a minimum residence time of oxygen in the acinar airways; (iv) has a maximum fault tolerance to loss of permeability; and (v) generates a maximum current increase when switching from rest to exercise.

Surface monofunctionalized polymethyl pentene hollow fiber membranes by plasma treatment and hemocompatibility modification for membrane oxygenators

NASA Astrophysics Data System (ADS)

Huang, Xin; Wang, Weiping; Zheng, Zhi; Fan, Wenling; Mao, Chun; Shi, Jialiang; Li, Lei

2016-01-01

The hemocompatibility of polymethyl pentene (PMP) hollow fiber membranes (HFMs) was improved through surface modification for membrane oxygenator applications. The modification was performed stepwise with the following: (1) oxygen plasma treatment, (2) functionalization of monosort hydroxyl groups through NaBH4 reduction, and (3) grafting 2-methacryloyloxyethyl phosphorylcholine (MPC) or heparin. SEM, ATR-FTIR, and XPS analyses were conducted to confirm successful grafting during the modification. The hemocompatibility of PMP HFMs was analyzed and compared through protein adsorption, platelet adhesion, and coagulation tests. Pure CO2 and O2 permeation rates, as well as in vitro gas exchange rates, were determined to evaluate the mass transfer properties of PMP HFMs. SEM results showed that different nanofibril topographies were introduced on the HFM surface. ATR-FTIR and XPS spectra indicated the presence of functionalization of monosort hydroxyl group and the grafting of MPC and heparin. Hemocompatibility evaluation results showed that the modified PMP HFMs presented optimal hemocompatibility compared with pristine HFMs. Gas permeation results revealed that gas permeation flux increased in the modified HFMs because of dense surface etching during the plasma treatment. The results of in vitro gas exchange rates showed that all modified PMP HFMs presented decreased gas exchange rates because of potential surface fluid wetting. The proposed strategy exhibits a potential for fabricating membrane oxygenators for biomedical applications to prevent coagulation formation and alter plasma-induced surface topology and composition.

Sorption of Molecular Oxygen by Metal-Ion Exchanger Nanocomposites

NASA Astrophysics Data System (ADS)

Krysanov, V. A.; Plotnikova, N. V.; Kravchenko, T. A.

2018-03-01

Kinetic features are studied of the chemisorption and reduction of molecular oxygen from water by metal-ion exchanger nanocomposites that differ in the nature of the dispersed metal and state of oxidation. In the Pd < Ag < Cu series, the increasing chemical activity of metal nanoparticles raises the degree of oxygen sorption due to its chemisorption and subsequent reduction, while the role of the molecular chemisorption stage increases in the Cu < Ag < Pd series. Metal particles or their oxides are shown to act as adsorption sites on the surface and in the pores of the ion-exchanger matrix; the equilibrium sorption coefficient for oxygen dissolved in water ranges from 20 to 50, depending on the nature and oxidation state of the metal component.

Degradation of oxygen reduction reaction kinetics in porous La0.6Sr0.4Co0.2Fe0.8O3-δ cathodes due to aging-induced changes in surface chemistry

NASA Astrophysics Data System (ADS)

Baqué, Laura C.; Soldati, Analía L.; Teixeira-Neto, Erico; Troiani, Horacio E.; Schreiber, Anja; Serquis, Adriana C.

2017-01-01

The modification of surface composition after long-term operation is one of the most reported degradation mechanisms of (La,Sr)(Co,Fe)O3-δ (LSCFO) cathodes for Solid Oxide Fuel Cells (SOFCs). Nevertheless, its effect on the oxygen reduction reaction kinetics of porous LSCFO cathodes has not been yet reliably established. In this work, La- and Sr-enrichment at the LSCFO surface of porous cathodes has been induced after 50 h aging at 800 °C under air. Such cation redistribution can extend up to ∼400 nm depth under the LSCFO surface as detected by high resolution Scanning Transmission Electron Microscopy-Energy Dispersive Spectroscopy maps acquired inside the cathode pores. The observed surface chemical changes hamper the oxygen surface exchange reaction at the LSCFO/gas interface. Accordingly, a suitable Electrochemical Impedance Spectroscopy analysis revealed that the oxygen ion conductivity remains practically unaltered during the aging treatment while the oxygen surface exchange resistance increases up to 1.8 times. As a result, the cathode impedance response deteriorates within the 10-0.1 Hz frequency range during the aging treatment, resulting in a total cathode area specific resistance increase of 150%. The methodology adopted has demonstrated to be very valuable for studying the degradation of SOFC cathodes produced by the modification of surface composition.

A multiscale model of placental oxygen exchange: The effect of villous tree structure on exchange efficiency.

PubMed

Lin, Mabelle; Mauroy, Benjamin; James, Joanna L; Tawhai, Merryn H; Clark, Alys R

2016-11-07

The placenta is critical to fetal health during pregnancy as it supplies oxygen and nutrients to maintain life. It has a complex structure, and alterations to this structure across spatial scales are associated with several pregnancy complications, including intrauterine growth restriction (IUGR). The relationship between placental structure and its efficiency as an oxygen exchanger is not well understood in normal or pathological pregnancies. Here we present a computational framework that predicts oxygen transport in the placenta which accounts for blood and oxygen transport in the space around a placental functional unit (the villous tree). The model includes the well-defined branching structure of the largest villous tree branches, as well as a smoothed representation of the small terminal villi that comprise the placenta's gas exchange interfaces. The model demonstrates that oxygen exchange is sensitive to villous tree geometry, including the villous branch length and volume, which are seen to change in IUGR. This is because, to be an efficient exchanger, the architecture of the villous tree must provide a balance between maximising the surface area available for exchange, and the opposing condition of allowing sufficient maternal blood flow to penetrate into the space surrounding the tree. The model also predicts an optimum oxygen exchange when the branch angle is 24 °, as villous branches and TBs are spread out sufficiently to channel maternal blood flow deep into the placental tissue for oxygen exchange without being shunted directly into the DVs. Without concurrent change in the branch length and angles, the model predicts that the number of branching generations has a small influence on oxygen exchange. The modelling framework is presented in 2D for simplicity but is extendible to 3D or to incorporate the high-resolution imaging data that is currently evolving to better quantify placental structure. Copyright © 2016 Elsevier Ltd. All rights reserved.

Oxygen mobility in CeO{sub 2} and Ce{sub x}Zr({sub 1-x})O{sub 2} compounds: Study by CO transient oxidation and {sup 18}O/{sup 16}O isotopic exchange

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

Madier, Y.; Descorme, C.; Govic, A.M. Le

Cerium-zirconium mixed oxides (Ce{sub x}Zr{sub 1{minus}x}O{sub 2}), precalcined at 900 C in dry air, were supplied by Rhodia Terres Rares as monophasic solid solutions. Introduction of some zirconium atoms in the ceria lattice by isomorphous substitution clearly influences the final properties of these materials as long as the cubic structure of ceria is maintained. Modifications in oxygen storage capacity (OSC measurements), redox properties (CO TPR), and oxygen exchange processes (TPIE) were studied. Ce{sub 0.63}Zr{sub 0.37}O{sub 2} was shown to have the most promising properties with the largest OSC at 400 C and the highest reactivity in O{sub 2} exchange. Allmore » mixed oxides are able to exchange very large amounts of oxygen compared to ceria, implying the participation of bulk oxygen. Furthermore, on Ce{sub x}Zr{sub (1{minus}x)}O{sub 2} samples, oxygen is predominantly exchanged via a multiple heteroexchange mechanism involving surface dioxygen species as superoxides or peroxides.« less

Surface analysis of mixed-conducting ferrite membranes by the conversion-electron Mössbauer spectroscopy

NASA Astrophysics Data System (ADS)

Waerenborgh, J. C.; Tsipis, E. V.; Yaremchenko, A. A.; Kharton, V. V.

2011-09-01

Conversion-electron Mössbauer spectroscopy analysis of iron surface states in the dense ceramic membranes made of 57Fe-enriched SrFe 0.7Al 0.3O 3- δ perovskite, shows no traces of reductive decomposition or carbide formation in the interfacial layers after operation under air/CH 4 gradient at 1173 K, within the limits of experimental uncertainty. The predominant trivalent state of iron cations at the membrane permeate-side surface exposed to flowing dry methane provides evidence of the kinetic stabilization mechanism, which is only possible due to slow oxygen-exchange kinetics and enables long-term operation of the ferrite-based ceramic reactors for natural gas conversion. At the membrane feed-side surface exposed to air, the fractions of Fe 4+ and Fe 3+ are close to those in the powder equilibrated at atmospheric oxygen pressure, suggesting that the exchange limitations to oxygen transport are essentially localized at the partially reduced surface.

The importance of perivitelline fluid convection to oxygen uptake of Pseudophryne bibronii eggs.

PubMed

Mueller, Casey A; Seymour, Roger S

2011-01-01

The ciliated epithelium of amphibian embryos produces a current within the perivitelline fluid of the egg that is important in the convective transfer of oxygen to the embryo's surface. The effects of convection on oxygen uptake and the immediate oxygen environment of the embryo were investigated in Pseudophryne bibronii. Gelatin was injected into the eggs, setting the perivitelline fluid and preventing convective flow. Oxygen consumption rate (M(.)o₂) and the oxygen partial pressure (Po₂) of the perivitelline fluid were measured in eggs with and without this treatment. M(.)o₂ decreased in eggs without convection at Gosner stages 17-19 under normoxia. The lack of convection also shifted embryos from regulators to conformers as environmental Po₂ decreased. A strong Po₂ gradient formed within the eggs when convection was absent, demonstrating that the loss of convection is equivalent to decreasing the inner radius of the capsule, an important factor in gas exchange, by 25%. M(.)o₂ also declined in stage 26-27 embryos without cilia-driven convection, although not to the extent of younger stages, because of muscular movements and a greater skin surface area in direct contact with the inner capsule wall. This study demonstrates the importance of convective flow within the perivitelline fluid to gas exchange. Convection is especially important in the middle of embryonic development, when the perivitelline space has formed, creating a barrier to gas exchange, but the embryos have yet to develop muscular movements or have a large surface area exposed directly to the jelly capsule.

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

Jia, Y.F.; Thomas, K.M.

Various types of oxygen functional groups were introduced onto the surface of coconut shell derived activated carbon by oxidation using nitric acid. Fourier-transform infrared spectroscopy (FTIR), temperature-programmed desorption (TPD), and selective neutralization were used to characterize the surface oxygen functional groups. The oxidized carbons were also heat treated to provide a suite of carbons where the oxygen functional groups of various thermal stabilities were varied progressively. The adsorption of cadmium ions was enhanced dramatically by oxidation of the carbon. The ratio of released protons to adsorbed cadmium ions on oxidized carbon was approximately 2, indicating cation exchange was involved inmore » the process of adsorption. Na{sup +} exchange studies with the oxidized carbon gave a similar ratio. After heat treatment of the oxidized carbons to remove oxygen functional groups, the ratio of H{sup +} released to Cd{sup 2+} adsorbed and the adsorption capacity decreased significantly. Both reversible and irreversible processes were involved in cadmium ion adsorption with reversible adsorption having higher enthalpy. The irreversible adsorption resulted from cation exchange with carboxylic acid groups, whereas the reversible adsorption probably involved physisorption of the partially hydrated cadmium ion.« less

Electrical insulator assembly with oxygen permeation barrier

DOEpatents

Van Der Beck, R.R.; Bond, J.A.

1994-03-29

A high-voltage electrical insulator for electrically insulating a thermoelectric module in a spacecraft from a niobium-1% zirconium alloy wall of a heat exchanger filled with liquid lithium while providing good thermal conductivity between the heat exchanger and the thermoelectric module. The insulator has a single crystal alumina layer (SxAl[sub 2]O[sub 3], sapphire) with a niobium foil layer bonded thereto on the surface of the alumina crystal facing the heat exchanger wall, and a molybdenum layer bonded to the niobium layer to act as an oxygen permeation barrier to preclude the oxygen depleting effects of the lithium from causing undesirable niobium-aluminum intermetallic layers near the alumina-niobium interface. 3 figures.

Theoretical study of oxygen sorption and diffusion in the volume and on the surface of a γ-TiAl alloy

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

Bakulin, A. V., E-mail: bakulin@ispms.tsc.ru; Kulkova, S. E.; Hu, Q. M.

2015-02-15

The oxygen sorption on the low-index (001), (100), and (110) surfaces of a γ-TiAl alloy is studied by the pseudopotential method with the generalized gradient approximation for the exchange-correlation functional. The most preferred sites for oxygen sorption in the bulk and on the surface of the alloy are determined. The titanium-rich octahedral site is shown to be preferred for oxygen sorption in the bulk material. The effect of the oxygen concentration on the atomic and electronic structures of the stoichiometric TiAl(100) surface is studied. It is shown that, at the first stage of oxidation, oxygen prefers to form bonds withmore » titanium. The energy barriers for oxygen diffusion on the stoichiometric (100) surface and in the bulk of the material are calculated. The energy barriers are shown to depend substantially on the local environments of oxygen and to increase during diffusion from titanium-rich sites. The most possible mechanism of oxygen diffusion from the (100) surface to the bulk of the material is oxygen migration through tetrahedral sites.« less

Feasibility Analysis of Liquefying Oxygen Generated from Water Electrolysis Units on Lunar Surface

NASA Technical Reports Server (NTRS)

Jeng, Frank F.

2009-01-01

Concepts for liquefying oxygen (O2) generated from water electrolysis subsystems on the Lunar surface were explored. Concepts for O2 liquefaction units capable of generating 1.38 lb/hr (0.63 kg/hr) liquid oxygen (LOX) were developed. Heat and mass balance calculations for the liquefaction concepts were conducted. Stream properties, duties of radiators, heat exchangers and compressors for the selected concepts were calculated and compared.

Orientation-Dependent Oxygen Evolution on RuO 2 without Lattice Exchange

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

Stoerzinger, Kelsey A.; Diaz-Morales, Oscar; Kolb, Manuel

RuO2 catalysts exhibit record activities towards the oxygen evolution reaction (OER), which is crucial to enable efficient and sustainable energy storage. Here we examine the RuO2 OER kinetics on rutile (110), (100), (101), and (111) orientations, finding (100) the most active. We assess the potential involvement of lattice oxygen in the OER mechanism with online 3 electrochemical mass spectrometry, which showed no evidence of oxygen exchange on these oriented facets in acidic or basic electrolytes. Similar results were obtained for polyoriented RuO2 films and particles, in contrast to previous work, suggesting lattice oxygen is not exchanged in catalyzing OER onmore » crystalline RuO2 surfaces. This hypothesis is supported by the correlation of activity with the number of active Ru-sites calculated by DFT, where more active facets bind oxygen more weakly. This new understanding of the active sites provides a design strategy to enhance the OER activity of RuO2 nanoparticles by facet engineering.« less

Effects of Dopant Ionic Radius on Cerium Reduction in Epitaxial Cerium Oxide Thin Films

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

Yang, Nan; Orgiani, Pasquale; Di Bartolomeo, Elisabetta

The role of trivalent rare-earth dopants in ceria epitaxial films on surface ion exchange reactivity and ion conductivity has been systematically studied. Single-crystal epitaxial films with unique crystal orientation and micro-structure nature have allowed us to rule out the influence of structural defects on both transport and surface ion exchange properties. The films conductivities were larger than those reported in literature for both polycrystalline ceramic pellets and crystalline films. An increase in oxygen vacancies and Ce 3+ concentration while decreasing the dopant ionic radius from La 3+ to Yb 3+ was observed, thus explaining the measured increased activation energy andmore » enhanced surface reactivity. The more significant ability of smaller dopant ionic radius in releasing the stress strength induced by the larger Ce 3+ ionic radius allows promoting the formation of oxygen vacancies and Ce 3+, which are two precious species in determining the efficiency of ion transport and surface ion exchange processes. This can open new perspectives in designing ceria-based materials in tailoring functional properties, either ion migration or surface reactivity, by rational cation substitutions.« less

Effects of Dopant Ionic Radius on Cerium Reduction in Epitaxial Cerium Oxide Thin Films

DOE PAGES

Yang, Nan; Orgiani, Pasquale; Di Bartolomeo, Elisabetta; ...

2017-04-17

The role of trivalent rare-earth dopants in ceria epitaxial films on surface ion exchange reactivity and ion conductivity has been systematically studied. Single-crystal epitaxial films with unique crystal orientation and micro-structure nature have allowed us to rule out the influence of structural defects on both transport and surface ion exchange properties. The films conductivities were larger than those reported in literature for both polycrystalline ceramic pellets and crystalline films. An increase in oxygen vacancies and Ce 3+ concentration while decreasing the dopant ionic radius from La 3+ to Yb 3+ was observed, thus explaining the measured increased activation energy andmore » enhanced surface reactivity. The more significant ability of smaller dopant ionic radius in releasing the stress strength induced by the larger Ce 3+ ionic radius allows promoting the formation of oxygen vacancies and Ce 3+, which are two precious species in determining the efficiency of ion transport and surface ion exchange processes. This can open new perspectives in designing ceria-based materials in tailoring functional properties, either ion migration or surface reactivity, by rational cation substitutions.« less

Electrical insulator assembly with oxygen permeation barrier

DOEpatents

Van Der Beck, Roland R.; Bond, James A.

1994-01-01

A high-voltage electrical insulator (21) for electrically insulating a thermoelectric module (17) in a spacecraft from a niobium-1% zirconium alloy wall (11) of a heat exchanger (13) filled with liquid lithium (16) while providing good thermal conductivity between the heat exchanger and the thermoelectric module. The insulator (21) has a single crystal alumina layer (SxAl.sub.2 O.sub.3, sapphire) with a niobium foil layer (32) bonded thereto on the surface of the alumina crystal (26) facing the heat exchanger wall (11), and a molybdenum layer (31) bonded to the niobium layer (32) to act as an oxygen permeation barrier to preclude the oxygen depleting effects of the lithium from causing undesirable niobium-aluminum intermetallic layers near the alumina-niobium interface.

Isotope exchange in oxide-containing catalyst

NASA Technical Reports Server (NTRS)

Brown, Kenneth G. (Inventor); Upchurch, Billy T. (Inventor); Hess, Robert V. (Inventor); Miller, Irvin M. (Inventor); Schryer, David R. (Inventor); Sidney, Barry D. (Inventor); Wood, George M. (Inventor); Hoyt, Ronald F. (Inventor)

1989-01-01

A method of exchanging rare-isotope oxygen for common-isotope oxygen in the top several layers of an oxide-containing catalyst is disclosed. A sample of an oxide-containing catalyst is exposed to a flowing stream of reducing gas in an inert carrier gas at a temperature suitable for the removal of the reactive common-isotope oxygen atoms from the surface layer or layers of the catalyst without damaging the catalyst structure. The reduction temperature must be higher than any at which the catalyst will subsequently operate. Sufficient reducing gas is used to allow removal of all the reactive common-isotope oxygen atoms in the top several layers of the catalyst. The catalyst is then reoxidized with the desired rare-isotope oxygen in sufficient quantity to replace all of the common-isotope oxygen that was removed.

Oxygen surface exchange kinetics and stability of (La,Sr) 2 CoO 4±δ/La 1-xSr xMO 3-δ (M = Co and Fe) hetero-interfaces at intermediate temperatures

DOE PAGES

Lee, Dongkyu; Lee, Yueh-Lin; Hong, Wesley T.; ...

2014-11-13

Heterostructured oxide interfaces created by decorating Ruddlesden-Popper phases (A2BO4) or perovskites on perovskites have shown not only pronounced cation segregation at the interface and in the A2BO4 structure but also much enhanced kinetics for oxygen electrocatalysis at elevated temperatures. In this study, we report and compare the time-dependent surface exchange kinetics and stability of (La 0.5Sr 0.5) 2CoO 4 -decorated (LSC 214) La 0.6Sr 0.4Co 0.2Fe 0.8O 3-δ (LSCF 113) and La 0.8Sr 0.2CoO 3-δ (LSC 113) thin films. While LSC 214 decoration on LSC 113 greatly reduced the degradation in the surface exchange kinetics as a function of timemore » relative to LSC 113, LSCF 113 with LSC 214 coverage showed comparable surface exchange kinetics and stability to LSCF 113. This difference can be explained by greater surface stability of LSCF 113 than LSC 113 under testing conditions, and that LSC 214 decoration on LSC 113 reduced the decomposition of LSC 113 to form secondary phases that impedes oxygen exchange kinetics, and thus resulted in enhanced stability. This hypothesis is supported by the observations that annealing at 550 °C led to the formation of Sr-rich secondary particles on LSC 113 while no such particles were observed on LSCF 113. Density functional theory (DFT) computation provides further support, which revealed greater capacity of surface Sr segregation for LSCF 113 having SrO termination than LSC 113 having (La 0.25Sr 0.75)O termination for the experimental conditions, and lower energy gain to move Sr from LSCF 113 into LSC 214 relative to the LSC 214-LSC 113 system.« less

Plastron Respiration Using Commercial Fabrics

PubMed Central

Atherton, Shaun; Brennan, Joseph C.; Morris, Robert H.; Smith, Joshua D.E.; Hamlett, Christopher A.E.; McHale, Glen; Shirtcliffe, Neil J.; Newton, Michael I.

2014-01-01

A variety of insect and arachnid species are able to remain submerged in water indefinitely using plastron respiration. A plastron is a surface-retained film of air produced by surface morphology that acts as an oxygen-carbon dioxide exchange surface. Many highly water repellent and hydrophobic surfaces when placed in water exhibit a silvery sheen which is characteristic of a plastron. In this article, the hydrophobicity of a range of commercially available water repellent fabrics and polymer membranes is investigated, and how the surface of the materials mimics this mechanism of underwater respiration is demonstrated allowing direct extraction of oxygen from oxygenated water. The coverage of the surface with the plastron air layer was measured using confocal microscopy. A zinc/oxygen cell is used to consume oxygen within containers constructed from the different membranes, and the oxygen consumed by the cell is compared to the change in oxygen concentration as measured by an oxygen probe. By comparing the membranes to an air-tight reference sample, it was found that the membranes facilitated oxygen transfer from the water into the container, with the most successful membrane showing a 1.90:1 ratio between the cell oxygen consumption and the change in concentration within the container. PMID:28788469

Insensitivity of cerebral oxygen transport to oxygen affinity of hemoglobin-based oxygen carriers.

PubMed

Koehler, Raymond C; Fronticelli, Clara; Bucci, Enrico

2008-10-01

The cerebrovascular effects of exchange transfusion of various cell-free hemoglobins that possess different oxygen affinities are reviewed. Reducing hematocrit by transfusion of a non-oxygen-carrying solution dilates pial arterioles on the brain surface and increases cerebral blood flow to maintain a constant bulk oxygen transport to the brain. In contrast, transfusion of hemoglobins with P50 of 4-34 Torr causes constriction of pial arterioles that offsets the decrease in blood viscosity to maintain cerebral blood flow and oxygen transport. The autoregulatory constriction is dependent on synthesis of 20-HETE from arachidonic acid. This oxygen-dependent reaction is apparently enhanced by facilitated oxygen diffusion from the red cell to the endothelium arising from increased plasma oxygen solubility in the presence of low or high-affinity hemoglobin. Exchange transfusion of recombinant hemoglobin polymers with P50 of 3 and 18 Torr reduces infarct volume from experimental stroke. Cell-free hemoglobins do not require a P50 as high as red blood cell hemoglobin to facilitate oxygen delivery.

Dynamics of Gas Exchange through the Fractal Architecture of the Human Lung, Modeled as an Exactly Solvable Hierarchical Tree

NASA Astrophysics Data System (ADS)

Mayo, Michael; Pfeifer, Peter; Gheorghiu, Stefan

2008-03-01

The acinar airways lie at the periphery of the human lung and are responsible for the transfer of oxygen from air to the blood during respiration. This transfer occurs by the diffusion-reaction of oxygen over the irregular surface of the alveolar membranes lining the acinar airways. We present an exactly solvable diffusion-reaction model on a hierarchically branched tree, allowing a quantitative prediction of the oxygen current over the entire system of acinar airways responsible for the gas exchange. We discuss the effect of diffusional screening, which is strongly coupled to oxygen transport in the human lung. We show that the oxygen current is insensitive to a loss of permeability of the alveolar membranes over a wide range of permeabilities, similar to a ``constant-current source'' in an electric network. Such fault tolerance has been observed in other treatments of the gas exchange in the lung and is obtained here as a fully analytical result.

Fundamental understanding of oxygen reduction and reaction behavior and developing high performance and stable hetero-structured cathodes

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

Liu, Xingbo

2016-11-14

New unique hetero-structured cathode has been developed in this project. La 2NiO 4+δ (LNO) as a surface catalyst with interstitial oxygen defects was introduced onto the state-of-the-art (La 0.6Sr 0.4) 0.95Co 0.2Fe 0.8O 3-δ (LSCF) cathode to enhance the surface-limited ORR kinetics on SOFC cathode. Furthermore, the hetero-structured cathode surface maintains high activity under electrode polarization with much less negative effects from surface cation segregation of Sr, which is known to cause degradation issues for conventional LSCF and LSC cathodes, thus improving the cathode long-term stability. The interface chemistry distribution and oxygen transport properties have been studied to prove themore » enhancement of power out and stability of LNO-infiltrated LSCF cathode. The further investigation demonstrates that CeO 2 & La 2-xNiO 4+δ (x=0-0.2) co-infiltration is a simple and cost-effective method to improve both performance and stability of LSCF cathode by limiting nano-particles growth/delamination and further improve the surface stability. For the first time, a physical model is proposed to illustrate how unique interstitial species on hetero-structured cathode surface work to regulate the exchange rate of the incorporation reaction. Meanwhile, fundamental investigation of the surface oxygen exchange and bulk oxygen transport properties under over-potential conditions across cathode materials have been carried out in this project, which were discussed and compared to the Nernst equation that is generally applied to treat any oxide electrodes under equilibrium.« less

Net community production at Ocean Station Papa observed with nitrate and oxygen sensors on profiling floats

NASA Astrophysics Data System (ADS)

Plant, Joshua N.; Johnson, Kenneth S.; Sakamoto, Carole M.; Jannasch, Hans W.; Coletti, Luke J.; Riser, Stephen C.; Swift, Dana D.

2016-06-01

Six profiling floats equipped with nitrate and oxygen sensors were deployed at Ocean Station P in the Gulf of Alaska. The resulting six calendar years and 10 float years of nitrate and oxygen data were used to determine an average annual cycle for net community production (NCP) in the top 35 m of the water column. NCP became positive in February as soon as the mixing activity in the surface layer began to weaken, but nearly 3 months before the traditionally defined mixed layer began to shoal from its winter time maximum. NCP displayed two maxima, one toward the end of May and another in August with a summertime minimum in June corresponding to the historical peak in mesozooplankton biomass. The average annual NCP was determined to be 1.5 ± 0.6 mol C m-2 yr-1 using nitrate and 1.5 ± 0.7 mol C m-2 yr-1 using oxygen. The results from oxygen data proved to be quite sensitive to the gas exchange model used as well as the accuracy of the oxygen measurement. Gas exchange models optimized for carbon dioxide flux generally ignore transport due to gas exchange through the injection of bubbles, and these models yield NCP values that are two to three time higher than the nitrate-based estimates. If nitrate and oxygen NCP rates are assumed to be related by the Redfield model, we show that the oxygen gas exchange model can be optimized by tuning the exchange terms to reproduce the nitrate NCP annual cycle.

Oxygen Reduction Kinetics of La2-xSrxNiO 4+delta Electrodes for Solid Oxide Fuel Cells

NASA Astrophysics Data System (ADS)

Guan, Bo

In the development of intermediate temperature solid oxide fuel cell (IT-SOFC), mixed ionic-electronic conductors (MIEC) have drawn big interests due to their both ionic and electronic species transport which can enlarge the 3-dimension of the cathode network. This thesis presents an investigation of MIEC of Ruddlesden-popper (RP) phases like K2NiF4 type La2NiO4+delta (LNO)-based oxides which have interesting transport, catalytic properties and suitable thermal expansion coefficients. The motivation of this present work is to further understand the fundamental of the effect of Sr doing on the oxygen reduction reaction (ORR) kinetics of LNO cathode. Porous symmetrical cells of La2-xSrxNiO4+delta (0≤x≤0.4) were fabricated and characterized by electrochemical impedance spectroscopy (EIS) in different PO2 from temperature range of 600˜800°C. The spectra were analyzed based on the impedance model introduced by Adler et al. The rate determining steps (RDS) for ORR were proposed and the responsible reasons were discussed. The overall polarization resistances of doped samples increase with Sr level. Surface oxygen exchange and bulk ionic diffusion co-control the ORR kinetics. With high Sr content (x=0.3, 0.4), oxygen ion transfer resistance between nickelate/electrolyte is observed. However for porous symmetrical cells it is hard to associate the resistance from EIS directly to each ORR elementary processes because of the difficulty in describing the microstructure of the porous electrode. The dense electrode configuration was adopted in this thesis. By using the dense electrode, the surface area, the thickness of electrode, the interface between electrode and electrolyte and lastly the 3PB are theoretically well-defined. Through this method, there is a good chance to distinguish the contribution of surface exchange from other processes. Dense and thin electrode layers in thickness of ˜40 mum are fabricated by using a novel spray modified pressing method. Negligible bulk diffusion resistance is confirmed by parallel experiment and EIS analysis, resulting in exclusive focus on the surface process. It is ambiguously proved that Sr doping impairs the surface kinetics of lanthanum nickelates. The interstitial oxygen is suggested to be the key role when the oxygen incorporation is rat determining. For the first time, a physical model is proposed to illustrate how those interstitial species work to regulate the exchange rate of the incorporation reaction. To achieve better surface exchange ability on LNO, Mn is chosen as the doping element substituted for Ni with different levels to improve the surface kinetics because Mn is much active both for adsorption process and for incorporation process due to the high state of Mn leading to the high amount of the interstitial oxygen. Mn is found to substantially promote the surface kinetics, showing highest surface exchange coefficient (k) of 1.57x10-6cm/s at 700°C on composition of La1.8Sr0.2Ni0.9 Mn0.1O4+delta. Such value is ˜80% larger than that of the undoped sample, and is one of the highest k among the currently available R-P phase intermediate temperature (IT) cathode.

Composite oxygen transport membrane

DOEpatents

Christie, Gervase Maxwell; Lane, Jonathan A.

2014-08-05

A method of producing a composite oxygen ion membrane and a composite oxygen ion membrane in which a porous fuel oxidation layer and a dense separation layer and optionally, a porous surface exchange layer are formed on a porous support from mixtures of (Ln.sub.1-xA.sub.x).sub.wCr.sub.1-yB.sub.yO.sub.3-.delta. and a doped zirconia. In the porous fuel oxidation layer and the optional porous surface exchange layer, A is Calcium and in the dense separation layer A is not Calcium and, preferably is Strontium. Preferred materials are (La.sub.0.8Ca.sub.0.2).sub.0.95Cr.sub.0.5Mn.sub.0.5O.sub.3-.delta. for the porous fuel oxidation and optional porous surface exchange layers and (La.sub.0.8Sr.sub.0.2).sub.0.95Cr.sub.0.5Fe.sub.0.5O.sub.3-.delta. for the dense separation layer. The use of such materials allows the membrane to sintered in air and without the use of pore formers to reduce membrane manufacturing costs. The use of materials, as described herein, for forming the porous layers have application for forming any type of porous structure, such as a catalyst support.

Composite oxygen transport membrane

DOEpatents

Christie, Gervase Maxwell; Lane, Jonathan A.

2016-11-15

A method of producing a composite oxygen ion membrane and a composite oxygen ion membrane in which a porous fuel oxidation layer and a dense separation layer and optionally, a porous surface exchange layer are formed on a porous support from mixtures of (Ln.sub.1-xA.sub.x).sub.wCr.sub.1-yB.sub.yO.sub.3-.delta. and a doped zirconia. In the porous fuel oxidation layer and the optional porous surface exchange layer, A is Calcium and in the dense separation layer A is not Calcium and, preferably is Strontium. Preferred materials are (La.sub.0.8Ca.sub.0.2).sub.0.95Cr.sub.0.5Mn.sub.0.5O.sub.3-.delta. for the porous fuel oxidation and optional porous surface exchange layers and (La.sub.0.8Sr.sub.0.2).sub.0.95Cr.sub.0.5Fe.sub.0.5O.sub.3-.delta. for the dense separation layer. The use of such materials allows the membrane to sintered in air and without the use of pore formers to reduce membrane manufacturing costs. The use of materials, as described herein, for forming the porous layers have application for forming any type of porous structure, such as a catalyst support.

Insensitivity of cerebral oxygen transport to oxygen affinity of hemoglobin-based oxygen carriers

PubMed Central

Koehler, Raymond C.; Fronticelli, Clara; Bucci, Enrico

2008-01-01

The cerebrovascular effects of exchange transfusion of various cell-free hemoglobins that possess different oxygen affinities are reviewed. Reducing hematocrit by transfusion of a non-oxygen-carrying solution dilates pial arterioles on the brain surface and increases cerebral blood flow to maintain a constant bulk oxygen transport to the brain. In contrast, transfusion of hemoglobins with P50 of 4–34 Torr causes constriction of pial arterioles that offsets the decrease in blood viscosity to maintain cerebral blood flow and oxygen transport. The autoregulatory constriction is dependent on synthesis of 20-HETE from arachidonic acid. This oxygen-dependent reaction is apparently enhanced by facilitated oxygen diffusion from the red cell to the endothelium arising from increased plasma oxygen solubility in the presence of low or high-affinity hemoglobin. Exchange transfusion of recombinant hemoglobin polymers with P50 of 3 and 18 Torr reduces infarct volume from experimental stroke. Cell-free hemoglobins do not require a P50 as high as red blood cell hemoglobin to facilitate oxygen delivery. PMID:18230370

Strontium-free rare earth perovskite ferrites with fast oxygen exchange kinetics: Experiment and theory

NASA Astrophysics Data System (ADS)

Berger, Christian; Bucher, Edith; Windischbacher, Andreas; Boese, A. Daniel; Sitte, Werner

2018-03-01

The Sr-free mixed ionic electronic conducting perovskites La0.8Ca0.2FeO3-δ (LCF82) and Pr0.8Ca0.2FeO3-δ (PCF82) were synthesized via a glycine-nitrate process. Crystal structure, phase purity, and lattice constants were determined by XRD and Rietveld analysis. The oxygen exchange kinetics and the electronic conductivity were obtained from in-situ dc-conductivity relaxation experiments at 600-800 °C and 1×10-3≤pO2/bar≤0.1. Both LCF82 and PCF82 show exceptionally fast chemical surface exchange coefficients and chemical diffusion coefficients of oxygen. The oxygen nonstochiometry of LCF82 and PCF82 was determined by precision thermogravimetry. A point defect model was used to calculate the thermodynamic factors of oxygen and to estimate self-diffusion coefficients and ionic conductivities. Density Functional Theory (DFT) calculations on the crystal structure, oxygen vacancy formation as well as oxygen migration energies are in excellent agreement with the experimental values. Due to their favourable properties both LCF82 and PCF82 are of interest for applications in solid oxide fuel cell cathodes, solid oxide electrolyser cell anodes, oxygen separation membranes, catalysts, or electrochemical sensors.

A review of factors influencing the availability of dissolved oxygen to incubating salmonid embryos

NASA Astrophysics Data System (ADS)

Greig, S. M.; Sear, D. A.; Carling, P. A.

2007-01-01

Previous investigations into factors influencing incubation success of salmonid progeny have largely been limited to the development of empirical relationships between characteristics of the incubation environment and survival to emergence. It is suggested that adopting a process-based approach to assessing incubation success aids identification of the precise causes of embryonic mortalities, and provides a robust framework for developing and implementing managerial responses.Identifying oxygen availability within the incubation environment as a limiting factor, a comprehensive review of trends in embryonic respiration, and processes influencing the flux of oxygenated water through gravel riverbeds is provided. The availability of oxygen to incubating salmonid embryos is dependent on the exchange of oxygenated water with the riverbed, and the ability of the riverbed gravel medium to transport this water at a rate and concentration appropriate to support embryonic respiratory requirements. Embryonic respiratory trends indicate that oxygen consumption varies with stage of development, ambient water temperature and oxygen availability. The flux of oxygenated water through the incubation environment is controlled by a complex interaction of intragravel and extragravel processes and factors. The processes driving the exchange of channel water with gravel riverbeds include bed topography, bed permeability, and surface roughness effects. The flux of oxygenated water through riverbed gravels is controlled by gravel permeability, coupling of surface-subsurface flow and oxygen demands imposed by materials infiltrating riverbed gravels. Temporally and spatially variable inputs of groundwater can also influence the oxygen concentration of interstitial water. Copyright

Mixed ionic and electronic conducting membranes for hydrogen generation and separation

NASA Astrophysics Data System (ADS)

Cui, Hengdong

Dense mixed ionic and electronic conducting (MIEC) membranes are receiving increasing attention due to their potential for application as gas separation membranes to separate oxygen from air. The objective of this work is to study a novel, chemically-assisted separation process that utilizes oxygen-ion and electron-conducting MIECs for generating and separating hydrogen from steam. This research aims at exploring new routes and materials for high-purity hydrogen production for use in fuel cells and hydrogen-based internal combustion (IC) engines. In this approach, hydrocarbon fuel such as methane is fed to one side of the membrane, while steam is fed to the other side. The MIEC membrane separation process involves steam dissociation and oxidation of the fuel. The oxygen ions formed as a result of steam dissociation are transported across the membrane in a coupled transport process with electrons being transported in the opposite direction. Upon reaching the fuel side of the membrane, the oxygen ions oxidize the hydrocarbon. This process results in hydrogen production on the steam side of the membrane. The oxygen partial pressure gradient across the membrane is the driving force for this process. In this work, a novel, dual-phase composite MIEC membrane system comprising of rare-earth doped ceria with high oxygen ion conductivity and donor-doped strontium titanate with high electronic conductivity were investigated. The chemical diffusion coefficient and surface exchange coefficient have been measured using the electrical conductivity relaxation (ECR) technique. These two parameters control the rate of oxygen permeation across the membrane. The permeation data have been fit with a kinetic model that incorporates oxygen surface exchange on two sides of the membrane and bulk transport of oxygen through the membrane. This material has higher bulk diffusion coefficient and surface exchange reaction rate compared to other known MIEC conductors under the process conditions of interest. Over 10 mumol·cm-2·s-1 (micromoles per square cm per second) of area specific hydrogen flux has been achieved employing a membrane of this material with thickness of 0.2 mm. This flux is several orders of magnitude higher than the hydrogen generation rates reported using other MIEC materials under similar operating conditions.

Strain control of oxygen kinetics in the Ruddlesden-Popper oxide La 1.85Sr 0.15CuO 4

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

Meyer, Tricia L.; Jacobs, Ryan; Lee, Dongkyu

Oxygen defect control has long been considered an important route to functionalizing complex oxide films. However, the nature of oxygen defects in thin films is often not investigated beyond basic redox chemistry. One of the model examples for oxygen-defect studies is the layered Ruddlesden–Popper phase La 2-xSr x CuO 4-δ (LSCO), in which the superconducting transition temperature is highly sensitive to epitaxial strain. However, previous observations of strain-superconductivity coupling in LSCO thin films were mainly understood in terms of elastic contributions to mechanical buckling, with minimal consideration of kinetic or thermodynamic factors. Here, we report that the oxygen nonstoichiometry commonlymore » reported for strained cuprates is mediated by the strain-modified surface exchange kinetics, rather than reduced thermodynamic oxygen formation energies. Remarkably, tensile-strained LSCO shows nearly an order of magnitude faster oxygen exchange rate than a compressively strained film, providing a strategy for developing high-performance energy materials.« less

Strain control of oxygen kinetics in the Ruddlesden-Popper oxide La 1.85Sr 0.15CuO 4

DOE PAGES

Meyer, Tricia L.; Jacobs, Ryan; Lee, Dongkyu; ...

2018-01-08

Oxygen defect control has long been considered an important route to functionalizing complex oxide films. However, the nature of oxygen defects in thin films is often not investigated beyond basic redox chemistry. One of the model examples for oxygen-defect studies is the layered Ruddlesden–Popper phase La 2-xSr x CuO 4-δ (LSCO), in which the superconducting transition temperature is highly sensitive to epitaxial strain. However, previous observations of strain-superconductivity coupling in LSCO thin films were mainly understood in terms of elastic contributions to mechanical buckling, with minimal consideration of kinetic or thermodynamic factors. Here, we report that the oxygen nonstoichiometry commonlymore » reported for strained cuprates is mediated by the strain-modified surface exchange kinetics, rather than reduced thermodynamic oxygen formation energies. Remarkably, tensile-strained LSCO shows nearly an order of magnitude faster oxygen exchange rate than a compressively strained film, providing a strategy for developing high-performance energy materials.« less

Plastron properties of a superhydrophobic surface

NASA Astrophysics Data System (ADS)

Shirtcliffe, Neil J.; McHale, Glen; Newton, Michael I.; Perry, Carole C.; Pyatt, F. Brian

2006-09-01

Most insects and spiders drown when submerged during flooding or tidal inundation, but some are able to survive and others can remain submerged indefinitely without harm. Many achieve this by natural adaptations to their surface morphology to trap films of air, creating plastrons which fix the water-vapor interface and provide an incompressible oxygen-carbon dioxide exchange surface. Here the authors demonstrate how the surface of an extremely water-repellent foam mimics this mechanism of underwater respiration and allows direct extraction of oxygen from aerated water. The biomimetic principle demonstrated can be applied to a wide variety of man-made superhydrophobic materials.

Insights into the role of wettability in cathode catalyst layer of proton exchange membrane fuel cell; pore scale immiscible flow and transport processes

NASA Astrophysics Data System (ADS)

Fathi, H.; Raoof, A.; Mansouri, S. H.

2017-05-01

The production of liquid water in cathode catalyst layer, CCL, is a significant barrier to increase the efficiency of proton exchange membrane fuel cell. Here we present, for the first time, a direct three-dimensional pore-scale modelling to look at the complex immiscible two-phase flow in CCL. After production of the liquid water at the surface of CCL agglomerates due to the electrochemical reactions, water spatial distribution affects transport of oxygen through the CCL as well as the rate of reaction at the agglomerate surfaces. To explore the wettability effects, we apply hydrophilic and hydrophobic properties using different surface contact angles. Effective diffusivity is calculated under several water saturation levels. Results indicate larger diffusive transport values for hydrophilic domain compared to the hydrophobic media where the liquid water preferentially floods the larger pores. However, hydrophobic domain showed more available surface area and higher oxygen consumption rate at the reaction sites under various saturation levels, which is explained by the effect of wettability on pore-scale distribution of water. Hydrophobic domain, with a contact angle of 150, reveals efficient water removal where only 28% of the pore space stays saturated. This condition contributes to the enhanced available reaction surface area and oxygen diffusivity.

Exploring scaling relations for chemisorption energies on transition-metal-exchanged zeolites ZSM-22 and ZSM-5

DOE PAGES

Siahrostami, Samira; Falsig, Hanne; Beato, Pablo; ...

2016-01-12

Copper exchange on all the different T sites of ZSM-22 and ZSM-5 is considered and the chemisorption energies of dioxygen, OH, and O species are studied. We show that for different T sites the adsorption energies vary significantly. The oxygen adsorption energy on copper-exchanged zeolites is quite similar to those of the most selective catalysts for oxidation reactions, that is, Ag and Au surfaces. The chemisorption energies of oxygen, carbon-, and nitrogen-containing species on different transition metals exchanged in ZSM-22 are also investigated. The study covers three different oxidation states, that is, 1+, 2+, and 3+ for the transition-metal exchanges.more » Scaling relations are presented for the corresponding species. Lastly, chemisorption of O scales with chemisorption of OH for all three considered exchanges, whereas there are essentially rough correlations for NH 2 and N as well as CH 3 and C.« less

Synthesis and characterization of high performing Fe-N-C catalyst for oxygen reduction reaction (ORR) in Alkaline Exchange Membrane Fuel Cells

NASA Astrophysics Data System (ADS)

Hossen, Md Mosaddek; Artyushkova, Kateryna; Atanassov, Plamen; Serov, Alexey

2018-01-01

In this article, three different Fe-N-C oxygen reduction reaction (ORR) catalysts derived from different organic molecules i.e. Fe-NMG, Fe-NMP, Fe-MBZ have been synthesized, characterized by physical-chemical methods and studied in the reaction of oxygen reduction (ORR). It is found that Fe-NMG shows higher ORR performance than Fe-NMP and Fe-MBZ, by both rotating ring disk electrode (RRDE) and fuel cell tests. From characterization and surface analysis, it can be explained that the presence of higher amount of surface oxides and pyridinic nitrogen is the main reason for better performance towards ORR in alkaline media. To achieve the highest performance in alkaline exchange membrane fuel cell (AEMFC), the optimization of catalyst layer composition using various concentrations of ionomer (Tokuyama, AS4) was performed. At the optimum cathode layer configuration utilizing Fe-NMG produces the peak power density of 218 mWcm-2, which is one of the highest values presented in the open literature.

Elementary surface chemistry during CuO/Al nanolaminate-thermite synthesis: copper and oxygen deposition on aluminum (111) surfaces.

PubMed

Lanthony, Cloé; Guiltat, Mathilde; Ducéré, Jean Marie; Verdier, Agnes; Hémeryck, Anne; Djafari-Rouhani, Mehdi; Rossi, Carole; Chabal, Yves J; Estève, Alain

2014-09-10

The surface chemistry associated with the synthesis of energetic nanolaminates controls the formation of the critical interfacial layers that dominate the performances of nanothermites. For instance, the interaction of Al with CuO films or CuO with Al films needs to be understood to optimize Al/CuO nanolaminates. To that end, the chemical mechanisms occurring during early stages of molecular CuO adsorption onto crystalline Al(111) surfaces are investigated using density functional theory (DFT) calculations, leading to the systematic determination of their reaction enthalpies and associated activation energies. We show that CuO undergoes dissociative chemisorption on Al(111) surfaces, whereby the Cu and O atoms tend to separate from each other. Both Cu and O atoms form islands with different properties. Copper islanding fosters Cu insertion (via surface site exchange mechanism) into the subsurface, while oxygen islands remain stable at the surface. Above a critical local oxygen coverage, aluminum atoms are extracted from the Al surface, leading to oxygen-aluminum intermixing and the formation of aluminum oxide (γ-alumina). For Cu and O co-deposition, copper promotes oxygen-aluminum interaction by oxygen segregation and separates the resulting oxide from the Al substrate by insertion into Al and stabilization below the oxide front, preventing full mixing of Al, Cu, and O species.

Oxygen reduction on a Pt(111) catalyst in HT-PEM fuel cells by density functional theory

NASA Astrophysics Data System (ADS)

Sun, Hong; Li, Jie; Almheiri, Saif; Xiao, Jianyu

2017-08-01

The oxygen reduction reaction plays an important role in the performance of high-temperature proton exchange membrane (HT-PEM) fuel cells. In this study, a molecular dynamics model, which is based on the density functional theory and couples the system's energy, the exchange-correlation energy functional, the charge density distribution function, and the simplified Kohn-Sham equation, was developed to simulate the oxygen reduction reaction on a Pt(111) surface. Additionally, an electrochemical reaction system on the basis of a four-electron reaction mechanism was also developed for this simulation. The reaction path of the oxygen reduction reaction, the product structure of each reaction step and the system's energy were simulated. It is found that the first step reaction of the first hydrogen ion with the oxygen molecule is the controlling step of the overall reaction. Increasing the operating temperature speeds up the first step reaction rate and slightly decreases its reaction energy barrier. Our results provide insight into the working principles of HT-PEM fuel cells.

XPS of oxygen atoms on Ag(111) and Ag(110) surfaces: accurate study with SAC/SAC-CI combined with dipped adcluster model.

PubMed

Ishikawa, Atsushi; Nakatsuji, Hiroshi

2013-08-05

O1s core-electron binding energies (CEBE) of the atomic oxygens on different Ag surfaces were investigated by the symmetry adapted cluster-configuration interaction (SAC-CI) method combined with the dipped adcluster model, in which the electron exchange between bulk metal and adsorbate is taken into account properly. Electrophilic and nucleophilic oxygens (O(elec) and O(nuc)) that might be important for olefin epoxidation in a low-oxygen coverage condition were focused here. We consider the O1s CEBE as a key property to distinguish the surface oxygen states, and series of calculation was carried out by the Hartree-Fock, Density functional theory, and SAC/SAC-CI methods. The experimental information and our SAC/SAC-CI results indicate that O(elec) is the atomic oxygen adsorbed on the fcc site of Ag(111) and that O(nuc) is the one on the reconstructed added-row site of Ag(110) and that one- and two-electron transfers occur, respectively, to the O(elec) and O(nuc) adclusters from the silver surface. Copyright © 2013 Wiley Periodicals, Inc.

Investigation of the oxygen exchange mechanism on Pt|yttria stabilized zirconia at intermediate temperatures: Surface path versus bulk path

PubMed Central

Opitz, Alexander K.; Lutz, Alexander; Kubicek, Markus; Kubel, Frank; Hutter, Herbert; Fleig, Jürgen

2011-01-01

The oxygen exchange kinetics of platinum on yttria-stabilized zirconia (YSZ) was investigated by means of geometrically well-defined Pt microelectrodes. By variation of electrode size and temperature it was possible to separate two temperature regimes with different geometry dependencies of the polarization resistance. At higher temperatures (550–700 °C) an elementary step located close to the three phase boundary (TPB) with an activation energy of ∼1.6 eV was identified as rate limiting. At lower temperatures (300–400 °C) the rate limiting elementary step is related to the electrode area and exhibited a very low activation energy in the order of 0.2 eV. From these observations two parallel pathways for electrochemical oxygen exchange are concluded. The nature of these two elementary steps is discussed in terms of equivalent circuits. Two combinations of parallel rate limiting reaction steps are found to explain the observed geometry dependencies: (i) Diffusion through an impurity phase at the TPB in parallel to diffusion of oxygen through platinum – most likely along Pt grain boundaries – as area-related process. (ii) Co-limitation of oxygen diffusion along the Pt|YSZ interface and charge transfer at the interface with a short decay length of the corresponding transmission line (as TPB-related process) in parallel to oxygen diffusion through platinum. PMID:22210951

Modeling of the oxygen reduction reaction for dense LSM thin films

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

Yang, Tao; Liu, Jian; Yu, Yang

In this study, the oxygen reduction reaction mechanism is investigated using numerical methods on a dense thin (La 1-xSr x) yMnO 3±δ film deposited on a YSZ substrate. This 1-D continuum model consists of defect chemistry and elementary oxygen reduction reaction steps coupled via reaction rates. The defect chemistry model contains eight species including cation vacancies on the A- and B-sites. The oxygen vacancy is calculated by solving species transportation equations in multiphysics simulations. Due to the simple geometry of a dense thin film, the oxygen reduction reaction was reduced to three elementary steps: surface adsorption and dissociation, incorporation onmore » the surface, and charge transfer across the LSM/YSZ interface. The numerical simulations allow for calculation of the temperature- and oxygen partial pressure-dependent properties of LSM. The parameters of the model are calibrated with experimental impedance data for various oxygen partial pressures at different temperatures. The results indicate that surface adsorption and dissociation is the rate-determining step in the ORR of LSM thin films. With the fine-tuned parameters, further quantitative analysis is performed. The activation energy of the oxygen exchange reaction and the dependence of oxygen non-stoichiometry on oxygen partial pressure are also calculated and verified using the literature results.« less

Modeling of the oxygen reduction reaction for dense LSM thin films

DOE PAGES

Yang, Tao; Liu, Jian; Yu, Yang; ...

2017-10-17

In this study, the oxygen reduction reaction mechanism is investigated using numerical methods on a dense thin (La 1-xSr x) yMnO 3±δ film deposited on a YSZ substrate. This 1-D continuum model consists of defect chemistry and elementary oxygen reduction reaction steps coupled via reaction rates. The defect chemistry model contains eight species including cation vacancies on the A- and B-sites. The oxygen vacancy is calculated by solving species transportation equations in multiphysics simulations. Due to the simple geometry of a dense thin film, the oxygen reduction reaction was reduced to three elementary steps: surface adsorption and dissociation, incorporation onmore » the surface, and charge transfer across the LSM/YSZ interface. The numerical simulations allow for calculation of the temperature- and oxygen partial pressure-dependent properties of LSM. The parameters of the model are calibrated with experimental impedance data for various oxygen partial pressures at different temperatures. The results indicate that surface adsorption and dissociation is the rate-determining step in the ORR of LSM thin films. With the fine-tuned parameters, further quantitative analysis is performed. The activation energy of the oxygen exchange reaction and the dependence of oxygen non-stoichiometry on oxygen partial pressure are also calculated and verified using the literature results.« less

Composite oxygen transport membrane

DOEpatents

Lu, Zigui; Plonczak, Pawel J.; Lane, Jonathan A.

2016-11-08

A method is described of producing a composite oxygen ion membrane and a composite oxygen ion membrane in which a porous fuel oxidation layer and a dense separation layer and optionally, a porous surface exchange layer are formed on a porous support from mixtures of (Ln.sub.1-xA.sub.x).sub.wCr.sub.1-yB.sub.yO.sub.3-.delta. and a doped zirconia. Preferred materials are (La.sub.0.8Sr.sub.0.2).sub.0.95Cr.sub.0.7Fe.sub.0.3O.sub.3-.delta. for the porous fuel oxidation layer, (La.sub.0.8Sr.sub.0.2).sub.0.95Cr.sub.0.5Fe.sub.0.5O.sub.3-.delta. for the dense separation layer, and (La.sub.0.8Sr.sub.0.2).sub.0.95Cr.sub.0.3Fe.sub.0.7O.sub.3-.delta. for the porous surface exchange layer. Firing the said fuel activation and separation layers in nitrogen atmosphere unexpectedly allows the separation layer to sinter into a fully densified mass.

Laboratory Measurements of Oxygen Gas Release from Basaltic Minerals Exposed to UV- Radiation: Implications for the Viking Gas Exchange Experiments

NASA Astrophysics Data System (ADS)

Hurowitz, J. A.; Yen, A. S.

2007-12-01

The biology experiments onboard the Viking Landers determined that the Martian soils at Chryse and Utopia Planitia contain an unknown chemical compound of a highly oxidizing nature. The Gas Exchange Experiments (GEx) demonstrated that the humidification of a 1-cc Martian soil sample resulted in the production of as much as 790 nanomoles of oxygen gas. Yen et al. (2000) have provided experimental evidence that superoxide radicals can be generated on plagioclase feldspar (labradorite) grain surfaces by exposure to ultraviolet (UV) light in the presence of oxygen gas. Adsorbed superoxide radicals are thought to react readily with water vapor, and produce oxygen gas in quantities sufficient to explain the Viking GEx results. Direct evidence for the formation of oxygen gas, however, was not provided in the experiments of Yen et al (2000). Accordingly, the motivation of this study is to determine whether superoxide radicals adsorbed on labradorite surfaces are capable of producing oxygen gas upon exposure to water vapor. We have constructed an experimental apparatus that is capable of monitoring oxygen gas release from basaltic mineral powders that have been exposed to UV-radiation under Martian atmospheric pressure conditions. The apparatus consists of a stainless-steel vacuum chamber with a UV- transparent window where sample radiation exposures are performed. The vacuum chamber has multiple valved ports for injection of gases and water vapor. The vacuum chamber is connected via a precision leak valve to a quadrupole mass spectrometer, which measures changes in the composition of the headspace gases over our mineral samples. We will report on the results of our experiments, which are aimed at detecting and quantifying oxygen gas release from UV-exposed basaltic mineral samples using this new experimental facility. These results will further constrain whether superoxide ions adsorbed on mineral surfaces provide a viable explanation for the Viking GEx results, which have been of considerable controversy in the roughly three decades since the measurements were first made.

Near-ambient pressure XPS of high-temperature surface chemistry in Sr2Co2O5 thin films

DOE PAGES

Hong, Wesley T.; Stoerzinger, Kelsey; Crumlin, Ethan J.; ...

2016-02-11

Transition metal perovskite oxides are promising electrocatalysts for the oxygen reduction reaction (ORR) in fuel cells, but a lack of fundamental understanding of oxide surfaces impedes the rational design of novel catalysts with improved device efficiencies. In particular, understanding the surface chemistry of oxides is essential for controlling both catalytic activity and long-term stability. Thus, elucidating the physical nature of species on perovskite surfaces and their catalytic enhancement would generate new insights in developing oxide electrocatalysts. In this article, we perform near-ambient pressure XPS of model brownmillerite Sr 2Co 2O 5 (SCO) epitaxial thin films with different crystallographic orientations. Detailedmore » analysis of the Co 2p spectra suggests that the films lose oxygen as a function of temperature. Moreover, deconvolution of the O 1s spectra shows distinct behavior for (114)-oriented SCO films compared to (001)-oriented SCO films, where an additional bulk oxygen species is observed. These findings indicate a change to a perovskite-like oxygen chemistry that occurs more easily in (114) SCO than (001) SCO, likely due to the orientation of oxygen vacancy channels out-of-plane with respect to the film surface. This difference in surface chemistry is responsible for the anisotropy of the oxygen surface exchange coefficient of SCO and may contribute to the enhanced ORR kinetics of La 0.8Sr 0.2CoO 3-δ thin films by SCO surface particles observed previously.« less

Balancing the competing requirements of air-breathing and display behaviour during male-male interactions in Siamese fighting fish Betta splendens.

PubMed

Alton, Lesley A; Portugal, Steven J; White, Craig R

2013-02-01

Air-breathing fish of the Anabantoidei group meet their metabolic requirements for oxygen through both aerial and aquatic gas exchange. Siamese fighting fish Betta splendens are anabantoids that frequently engage in aggressive male-male interactions which cause significant increases in metabolic rate and oxygen requirements. These interactions involve opercular flaring behaviour that is thought to limit aquatic oxygen uptake, and combines with the increase in metabolic rate to cause an increase in air-breathing behaviour. Air-breathing events interrupt display behaviour and increase risk of predation, raising the question of how Siamese fighting fish manage their oxygen requirements during agonistic encounters. Using open-flow respirometry, we measured rate of oxygen consumption in displaying fish to determine if males increase oxygen uptake per breath to minimise visits to the surface, or increase their reliance on aquatic oxygen uptake. We found that the increased oxygen requirements of Siamese fighting fish during display behaviour were met by increased oxygen uptake from the air with no significant changes in aquatic oxygen uptake. The increased aerial oxygen uptake was achieved almost entirely by an increase in air-breathing frequency. We conclude that limitations imposed by the reduced gill surface area of air-breathing fish restrict the ability of Siamese fighting fish to increase aquatic uptake, and limitations of the air-breathing organ of anabantoids largely restrict their capacity to increase oxygen uptake per breath. The resulting need to increase surfacing frequency during metabolically demanding agonistic encounters has presumably contributed to the evolution of the stereotyped surfacing behaviour seen during male-male interactions, during which one of the fish will lead the other to the surface, and each will take a breath of air. Copyright © 2012. Published by Elsevier Inc.

Respiratory Mechanics and Gas Exchange: The Effect of Surfactants

NASA Astrophysics Data System (ADS)

Jbaily, Abdulrahman; Szeri, Andrew J.

2017-11-01

The purpose of the lung is to exchange gases, primarily oxygen and carbon dioxide, between the atmosphere and the circulatory system. To enable this exchange, the airways in the lungs terminate in some 300 million alveoli that provide adequate surface area for transport. During breathing, work must be done to stretch various tissues to accommodate a greater volume of gas. Considerable work must also be done to expand the liquid lining (hypophase) that coats the interior surfaces of the alveoli. This is enabled by a surface active lipo-protein complex, known as pulmonary surfactant, that modifies the surface tension at the hypophase-air interface. Surfactants also serve as physical barriers that modify the rate of gas transfer across interfaces. We develop a mathematical model to study the action of pulmonary surfactant and its determinative contributions to breathing. The model is used to explore the influence of surfactants on alveolar mechanics and on gas exchange: it relates the work of respiration at the level of the alveolus to the gas exchange rate through the changing influence of pulmonary surfactant over the breathing cycle. This work is motivated by a need to develop improved surfactant replacement therapies to treat serious medical conditions.

Morphological respiratory diffusion capacity of the lungs of ball pythons (Python regius).

PubMed

Starck, J Matthias; Aupperle, Heike; Kiefer, Ingmar; Weimer, Isabel; Krautwald-Junghanns, Maria-Elisabeth; Pees, Michael

2012-08-01

This study aims at a functional and morphological characterization of the lung of a boid snake. In particular, we were interested to see if the python's lungs are designed with excess capacity as compared to resting and working oxygen demands. Therefore, the morphological respiratory diffusion capacity of ball pythons (Python regius) was examined following a stereological, hierarchically nested approach. The volume of the respiratory exchange tissue was determined using computed tomography. Tissue compartments were quantified using stereological methods on light microscopic images. The tissue diffusion barrier for oxygen transport was characterized and measured using transmission electron micrographs. We found a significant negative correlation between body mass and the volume of respiratory tissue; the lungs of larger snakes had relatively less respiratory tissue. Therefore, mass-specific respiratory tissue was calculated to exclude effects of body mass. The volume of the lung that contains parenchyma was 11.9±5.0mm(3)g(-1). The volume fraction, i.e., the actual pulmonary exchange tissue per lung parenchyma, was 63.22±7.3%; the total respiratory surface was, on average, 0.214±0.129m(2); it was significantly negatively correlated to body mass, with larger snakes having proportionally smaller respiratory surfaces. For the air-blood barrier, a harmonic mean of 0.78±0.05μm was found, with the epithelial layer representing the thickest part of the barrier. Based on these findings, a median diffusion capacity of the tissue barrier ( [Formula: see text] ) of 0.69±0.38ml O(2)min(-1)mmHg(-1) was calculated. Based on published values for blood oxygen concentration, a total oxygen uptake capacity of 61.16mlO(2)min(-1)kg(-1) can be assumed. This value exceeds the maximum demand for oxygen in ball pythons by a factor of 12. We conclude that healthy individuals of P. regius possess a considerable spare capacity for tissue oxygen exchange. Copyright © 2012 Elsevier GmbH. All rights reserved.

Fundamental Impact of Humidity on SOFC Cathode ORR

DOE PAGES

Huang, Y. L.; Pellegrinelli, C.; Wachsman, E. D.

2015-12-17

Although solid oxide fuel cells (SOFC) have demonstrated excellent performance, the durability of SOFCs under real working conditions is still an issue for commercial deployment. In particular cathode exposure to atmospheric air contaminants, such as humidity, can result in long-term performance degradation issues. Therefore, a fundamental understanding of the interaction between water molecules and cathodes is essential to resolve this issue and further enhance cathode durability. In order to study the effects of humidity on the oxygen reduction reaction (ORR), we used in-situ 18O isotope exchange techniques to probe the exchange of water with two of themost common SOFC cathodemore » materials, (La 0.8Sr 0.2) 0.95MnO 3±δ (LSM) and La 0.6Sr 0.4Co 0.2Fe 0.8O 3-δ (LSCF). In this experiment, heavy water, D 2O (with a mass/charge ratio of m/z = 20), is used to avoid the overlapping of H 2O and the 18O 2 cracking fraction, which both provide a peak at m/z = 18. A series of temperature programmed isotope exchange measurements were performed to comprehensively study the interaction of water with the cathode surface as a function of temperature, oxygen partial pressure, and water vapor concentration. The results suggest that water and O 2 share the same surface exchange sites, leading to competitive adsorption. Our findings show that water prefers to exchange with LSCF at lower temperatures, around 300–450°C. For LSM, O 2 is more favorable than water to be adsorbed on the surface and the presence of O 2 limits water exchange. The experimental data are summarized in a Temperature-PO 2 diagram to help visualize how the exchange of water on each material depends on the operating conditions.« less

Isotopic exchange in mineral-fluid systems. IV. The crystal chemical controls on oxygen isotope exchange rates in carbonate-H 2O and layer silicate-H 2O systems

NASA Astrophysics Data System (ADS)

Cole, David R.

2000-03-01

Oxygen isotope exchange between minerals and water in systems far from chemical equilibrium is controlled largely by surface reactions such as dissolution-precipitation. In many cases, this behavior can be modeled adequately by a simple pseudo-first order rate model that accounts for changes in surface area of the solid. Previous modeling of high temperature isotope exchange data for carbonates, sulfates, and silicates indicated that within a given mineral group there appears to be a systematic relationship between rate and mineral chemistry. We tested this idea by conducting oxygen isotope exchange experiments in the systems, carbonate-H 2O and layer silicate-H 2O at 300 and 350°C, respectively. Witherite (BaCO 3), strontianite (SrCO 3) and calcite (CaCO 3) were reacted with pure H 2O for different lengths of time (271-1390 h) at 300°C and 100 bars. The layer silicates, chlorite, biotite and muscovite were reacted with H 2O for durations ranging from 132 to 3282 h at 350°C and 250 bars. A detailed survey of grain sizes and grain habits using scanning electron microscopy (SEM) indicated that grain regrowth occurred in all experiments to varying extents. Changes in the mean grain diameters were particularly significant in experiments involving withertite, strontianite and biotite. The variations in the extent of oxygen isotope exchange were measured as a function of time, and fit to a pseudo-first order rate model that accounted for the change in surface area of the solid during reaction. The isotopic rates (ln r) for the carbonate-H 2O system are -20.75 ± 0.44, -18.95 ± 0.62 and -18.51 ± 0.48 mol O m -2 s -1 for calcite, strontianite and witherite, respectively. The oxygen isotope exchange rates for layer silicate-H 2O systems are -23.99 ± 0.89, -23.14 ± 0.74 and -22.40 ± 0.66 mol O m -2 s -1 for muscovite, biotite and chlorite, respectively. The rates for the carbonate-H 2O systems increase in order from calcite to strontianite to witherite. This order clearly reflects the influence of the change in cation chemistry, i.e., Ba > Sr > Ca. A similar pattern is observed for the layer silicate-H 2O systems, where chlorite>biotite>muscovite. The link between cation chemistry and rate is more complicated in this case, but in general, the order follows a trend where Mg-Fe > K-Mg > K, with an associated increase in Si and Al, and decrease in hydroxyl. The isotopic-chemical relations suggest that oxygen isotope exchange behavior monitored experimentally in this study is the net result of bond-breaking and dissolution of the mineral, complex ion formation in solution and growth of the mineral, whose structure is controlled, in large part, by the lattice energy. We compared the rates against the electrostatic attractive lattice energies (neglecting the repulsive forces), normalized per number of cations. The correlations between rates and lattice energies are quite good for both mineral-H 2O systems. The increase in rates correlated with a decrease in the electrostatic attractive lattice energies, i.e., the greater the lattice energy required to break up the crystal, the more sluggish the rates for both chemical and isotopic exchange. By establishing an unambiguous relationship between rate, lattice energy, and ultimately temperature, we can begin to develop empirical equations useful in predicting rates of isotopic exchange for minerals for which experimental data are lacking.

Catalytic Activity and Stability of Oxides: The Role of Near-Surface Atomic Structures and Compositions.

PubMed

Feng, Zhenxing; Hong, Wesley T; Fong, Dillon D; Lee, Yueh-Lin; Yacoby, Yizhak; Morgan, Dane; Shao-Horn, Yang

2016-05-17

Electrocatalysts play an important role in catalyzing the kinetics for oxygen reduction and oxygen evolution reactions for many air-based energy storage and conversion devices, such as metal-air batteries and fuel cells. Although noble metals have been extensively used as electrocatalysts, their limited natural abundance and high costs have motivated the search for more cost-effective catalysts. Oxides are suitable candidates since they are relatively inexpensive and have shown reasonably high activity for various electrochemical reactions. However, a lack of fundamental understanding of the reaction mechanisms has been a major hurdle toward improving electrocatalytic activity. Detailed studies of the oxide surface atomic structure and chemistry (e.g., cation migration) can provide much needed insights for the design of highly efficient and stable oxide electrocatalysts. In this Account, we focus on recent advances in characterizing strontium (Sr) cation segregation and enrichment near the surface of Sr-substituted perovskite oxides under different operating conditions (e.g., high temperature, applied potential), as well as their influence on the surface oxygen exchange kinetics at elevated temperatures. We contrast Sr segregation, which is associated with Sr redistribution in the crystal lattice near the surface, with Sr enrichment, which involves Sr redistribution via the formation of secondary phases. The newly developed coherent Bragg rod analysis (COBRA) and energy-modulated differential COBRA are uniquely powerful ways of providing information about surface and interfacial cation segregation at the atomic scale for these thin film electrocatalysts. In situ ambient pressure X-ray photoelectron spectroscopy (APXPS) studies under electrochemical operating conditions give additional insights into cation migration. Direct COBRA and APXPS evidence for surface Sr segregation was found for La1-xSrxCoO3-δ and (La1-ySry)2CoO4±δ/La1-xSrxCoO3-δ oxide thin films, and the physical origin of segregation is discussed in comparison with (La1-ySry)2CoO4±δ/La1-xSrxCo0.2Fe0.8O3-δ. Sr enrichment in many electrocatalysts, such as La1-xSrxMO3-δ (M = Cr, Co, Mn, or Co and Fe) and Sm1-xSrxCoO3, has been probed using alternative techniques, including low energy ion scattering, secondary ion mass spectrometry, and X-ray fluorescence-based methods for depth-dependent, element-specific analysis. We highlight a strong connection between cation segregation and electrocatalytic properties, because cation segregation enhances oxygen transport and surface oxygen exchange kinetics. On the other hand, the formation of cation-enriched secondary phases can lead to the blocking of active sites, inhibiting oxygen exchange. With help from density functional theory, the links between cation migration, catalyst stability, and catalytic activity are provided, and the oxygen p-band center relative to the Fermi level can be identified as an activity descriptor. Based on these findings, we discuss strategies to increase a catalyst's activity while maintaining stability to design efficient, cost-effective electrocatalysts.

Modern and ancient geochemical constraints on Proterozoic atmosphere-ocean redox evolution

NASA Astrophysics Data System (ADS)

Hardisty, D. S.; Horner, T. J.; Wankel, S. D.; Lu, Z.; Lyons, T.; Nielsen, S.

2017-12-01

A detailed understanding of the spatiotemporal oxygenation of Earth's atmosphere-ocean system through the Precambrian has important implications for the environments capable of sustaining early eukaryotic life and the evolving oxidant budget of subducted sediments. Proxy records suggest an anoxic Fe-rich deep ocean through much of the Precambrian and atmospheric and surface-ocean oxygenation that started in earnest at the Paleoproterozoic Great Oxidation Event (GOE). The marine photic zone represented the initial site of oxygen production and accumulation via cyanobacteria, yet our understanding of surface-ocean oxygen contents and the extent and timing of oxygen propagation and exchange between the atmosphere and deeper ocean are limited. Here, we present an updated perspective of the constraints on atmospheric, surface-ocean, and deep-ocean oxygen contents starting at the GOE. Our research uses the iodine content of Proterozoic carbonates as a tracer of dissolved iodate in the shallow ocean, a redox-sensitive species quantitatively reduced in modern oxygen minimum zones. We supplement our understanding of the ancient record with novel experiments examining the rates of iodate production from oxygenated marine environments based on seawater incubations. Combining new data from iodine with published shallow marine (Ce anomaly, N isotopes) and atmospheric redox proxies, we provide an integrated view of the vertical redox structure of the atmosphere and ocean across the Proterozoic.

Similarity principles for the biology of pelagic animals

PubMed Central

Barenblatt, G. I.; Monin, A. S.

1983-01-01

A similarity principle is formulated according to which the statistical pattern of the pelagic population is identical in all scales sufficiently large in comparison with the molecular one. From this principle, a power law is obtained analytically for the pelagic animal biomass distribution over the animal sizes. A hypothesis is presented according to which, under fixed external conditions, the oxygen exchange intensity of an animal is governed only by its mass and density and by the specific absorbing capacity of the animal's respiratory organ. From this hypothesis a power law is obtained by the method of dimensional analysis for the exchange intensity mass dependence. The known empirical values of the exponent of this power law are interpreted as an indication that the oxygen-absorbing organs of the animals can be represented as so-called fractal surfaces. In conclusion the biological principle of the decrease in specific exchange intensity with increase in animal mass is discussed. PMID:16593327

Hemocompatibility and oxygenation performance of polysulfone membranes grafted with polyethylene glycol and heparin by plasma-induced surface modification.

PubMed

Wang, Weiping; Zheng, Zhi; Huang, Xin; Fan, Wenling; Yu, Wenkui; Zhang, Zhibing; Li, Lei; Mao, Chun

2017-10-01

Polyethylene glycol (PEG) and heparin (Hep) were grafted onto polysulfone (PSF) membrane by plasma-induced surface modification to prepare PSF-PEG-Hep membranes used for artificial lung. The effects of plasma treatment parameters, including power, gas type, gas flow rate, and treatment time, were investigated, and different PEG chains were bonded covalently onto the surface in the postplasma grafting process. Membrane surfaces were characterized by water contact angle, PEG grafting degree, attenuated total reflectance-Fourier transform infrared spectroscopy, ultraviolet-visible spectrophotometry, X-ray photoelectron spectroscopy, critical water permeability pressure, and scanning electron microscopy. Protein adsorption, platelet adhesion, and coagulation tests showed significant improvement in the hemocompatibility of PSF-PEG-Hep membranes compared to pristine PSF membrane. Gas exchange tests through PSF-PEG6000-Hep membrane showed that when the flow rate of porcine blood reached 5.0 L/min, the permeation fluxes of O 2 and CO 2 reached 192.6 and 166.9 mL/min, respectively, which were close to the gas exchange capacity of a commercial membrane oxygenator. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 105B: 1737-1746, 2017. © 2016 Wiley Periodicals, Inc.

Kinetic bottlenecks to chemical exchange rates for deep-sea animals - Part 1: Oxygen

NASA Astrophysics Data System (ADS)

Hofmann, A. F.; Peltzer, E. T.; Brewer, P. G.

2012-10-01

Ocean warming will reduce dissolved oxygen concentrations which can pose challenges to marine life. Oxygen limits are traditionally reported simply as a static concentration thresholds with no temperature, pressure or flow rate dependency. Here we treat the oceanic oxygen supply potential for heterotrophic consumption as a dynamic molecular exchange problem analogous to familiar gas exchange processes at the sea surface. A combination of the purely physico-chemical oceanic properties temperature, hydrostatic pressure, and oxygen concentration defines the ability of the ocean to supply oxygen to any given animal. This general oceanic oxygen supply potential is modulated by animal specific properties such as the diffusive boundary layer thickness to define and limit maximal oxygen supply rates. Here we combine all these properties into formal, mechanistic equations defining novel oceanic properties that subsume various relevant classical oceanographic parameters to better visualize, map, comprehend, and predict the impact of ocean deoxygenation on aerobic life. By explicitly including temperature and hydrostatic pressure into our quantities, various ocean regions ranging from the cold deep-sea to warm, coastal seas can be compared. We define purely physico-chemical quantities to describe the oceanic oxygen supply potential, but also quantities that contain organism-specific properties which in a most generalized way describe general concepts and dependencies. We apply these novel quantities to example oceanic profiles around the world and find that temperature and pressure dependencies of diffusion and partial pressure create zones of greatest physical constriction on oxygen supply typically at around 1000 m depth, which coincides with oxygen concentration minimum zones. In these zones, which comprise the bulk of the world ocean, ocean warming and deoxygenation have a clear negative effect for aerobic life. In some shallow and warm waters the enhanced diffusion and higher partial pressure due to higher temperatures might slightly overcompensate for oxygen concentration decreases due to decreases in solubility.

[Comparative study of respiratory exchanging surfaces in birds and mammals].

PubMed

Jammes, Y

1975-01-01

Anatomical studies of the respiratory apparatus of birds show evidences for a gas exchanging tubular system (parabronchi and air capillaries); these exchanging structures are entirely dissociated from the ventilatory drive acting on the air sacs. A "cross-current" gas exchanging system (perpendicular disposition of air and blood capillaries) allow a good wash-out of carbon dioxide (PaCO2 lower than PECO2). The great efficiency of this lung is allowed by its very large diffusive surface (ASa) and by the high values of lung specific oxygen diffusing capacity (DO2/ASa) and of O2 extraction coefficient in inspired air. The ventilatory pattern of birds is characterized by a greater tidal volume and a smaller respiratory frequency than in mammals of same weight. Respiratory centers of birds receive afferences from lung stretch receptors, CO2-sensitive lung receptors and arterial chemoreceptors.

Oxidative regeneration of toluene-saturated natural zeolite by gaseous ozone: the influence of zeolite chemical surface characteristics.

PubMed

Alejandro, Serguei; Valdés, Héctor; Manéro, Marie-Hélène; Zaror, Claudio A

2014-06-15

In this study, the effect of zeolite chemical surface characteristics on the oxidative regeneration of toluene saturated-zeolite samples is investigated. A Chilean natural zeolite (53% clinoptilolite, 40% mordenite and 7% quartz) was chemically modified by acid treatment with hydrochloric acid and by ion-exchange with ammonium sulphate. Thermal pre-treatments at 623 and 823K were applied and six zeolite samples with different chemical surface characteristics were generated. Chemical modification of natural zeolite followed by thermal out-gassing allows distinguishing the role of acidic surface sites on the regeneration of exhausted zeolites. An increase in Brønsted acid sites on zeolite surface is observed as a result of ammonium-exchange treatment followed by thermal treatment at 623K, thus increasing the adsorption capacity toward toluene. High ozone consumption could be associated to a high content of Lewis acid sites, since these could decompose ozone into atomic active oxygen species. Then, surface oxidation reactions could take part among adsorbed toluene at Brønsted acid sites and surface atomic oxygen species, reducing the amount of adsorbed toluene after the regenerative oxidation with ozone. Experimental results show that the presence of adsorbed oxidation by-products has a negative impact on the recovery of zeolite adsorption capacity. Copyright © 2014 Elsevier B.V. All rights reserved.

Oxygen transport in the internal xenon plasma of a dispenser hollow cathode

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

Capece, Angela M., E-mail: acapece@pppl.gov; Shepherd, Joseph E.; Polk, James E.

2014-04-21

Reactive gases such as oxygen and water vapor modify the surface morphology of BaO dispenser cathodes and degrade the electron emission properties. For vacuum cathodes operating at fixed temperature, the emission current drops rapidly when oxygen adsorbs on top of the low work function surface. Previous experiments have shown that plasma cathodes are more resistant to oxygen poisoning and can operate with O{sub 2} partial pressures one to two orders of magnitude higher than vacuum cathodes before the onset of poisoning occurs. Plasma cathodes used for electric thrusters are typically operated with xenon; however, gas phase barium, oxygen, and tungstenmore » species may be found in small concentrations. The densities of these minor species are small compared with the plasma density, and thus, their presence in the discharge does not significantly alter the xenon plasma parameters. It is important, however, to consider the transport of these minor species as they may deposit on the emitter surface and affect the electron emission properties. In this work, we present the results of a material transport model used to predict oxygen fluxes to the cathode surface by solving the species conservation equations in a cathode with a 2.25 mm diameter orifice operated at a discharge current of 15 A, a Xe flow rate of 3.7 sccm, and 100 ppm of O{sub 2}. The dominant ionization process for O{sub 2} is resonant charge exchange with xenon ions. Ba is effectively recycled in the plasma; however, BaO and O{sub 2} are not. The model shows that the oxygen flux to the surface is not diffusion-limited; therefore, the high resistance to oxygen poisoning observed in plasma cathodes likely results from surface processes not considered here.« less

SIMS study of oxygen diffusion in monoclinic HfO2

NASA Astrophysics Data System (ADS)

Mueller, Michael P.; De Souza, Roger A.

2018-01-01

The diffusion of oxygen in dense ceramics of monoclinic HfO2 was studied by means of (18O/16O) isotope exchange annealing and subsequent determination of isotope depth profiles by Secondary Ion Mass Spectrometry. Anneals were performed in the temperature range of 573 ≤T /K ≤ 973 at an oxygen partial pressure of p O2=200 mbar . All measured isotope profiles exhibited two features: the first feature, closer to the surface, was attributed mainly to slow oxygen diffusion in an impurity silicate phase; the second feature, deeper in the sample, was attributed to oxygen diffusion in bulk monoclinic HfO2 . The activation enthalpy of oxygen tracer diffusion in bulk HfO2 was found to be ΔHD∗≈0.5 eV .

Ionic Conductivity and its Role in Oxidation Reactions

NASA Astrophysics Data System (ADS)

Tamimi, Mazin Abdulla

In the field of solid oxide fuel cells (SOFCs), a substantial portion of research is focused on the ability of some oxide materials to conduct oxygen anions through their structure. For electrolytes, the benefits of improving bulk transport of ions are obvious: decrease the resistive losses of the electrolyte, and device efficiency goes up and higher power densities are possible. Even for cathode materials, better bulk ion transport leads to an increase in the oxygen exchange rate at the cathode surface, and the oxygen reduction reaction at the cathode surface is the rate limiting step for SOFC operation at intermediate temperatures (500-700ºC). As operation in this regime is a key step towards lowering the manufacturing cost and increasing the lifetime of devices, much effort is spent searching for new, more conductive materials, and analyzing existing materials to discover the structure-activity relationships that influence ionic conductivity. In the first part of this work, an overview is given of the neutron powder diffraction (NPD) techniques that are used to probe the structure of the materials in later parts. In the second part, NPD was used to analyze the structures of perovskite-type cathode materials, and show that increases in bulk conductivity led to increases in the surface oxygen exchange rate of these materials. In the final part, the methods used for SOFC cathode design were applied towards the design of oxide catalysts used for certain hydrocarbon partial oxidation reactions. The reactions studied follow the Mars van Krevelen mechanism, where oxygen atoms in the catalyst are consumed as part of the reaction and are subsequently replenished by oxygen in the gas phase. Similar to SOFC cathode operation, these processes include an oxygen reduction step, so it was hypothesized that increasing the ionic conductivity of the catalysts would improve their performance, just as it does for SOFC cathode materials. While the results are preliminary, the combination of a reference catalyst for the oxidative coupling of methane with a support with very high oxygen conductivity demonstrated a small increase in performance at low temperatures.

Thin film surface modifications of thin/tunable liquid/gas diffusion layers for high-efficiency proton exchange membrane electrolyzer cells

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

Kang, Zhenye; Mo, Jingke; Yang, Gaoqiang

We present that a proton exchange membrane electrolyzer cell (PEMEC) is one of the most promising devices for high-efficiency and low-cost energy storage and ultrahigh purity hydrogen production. As one of the critical components in PEMECs, the titanium thin/tunable LGDL (TT-LGDL) with its advantages of small thickness, planar surface, straight-through pores, and well-controlled pore morphologies, achieved superior multifunctional performance for hydrogen and oxygen production from water splitting even at low temperature. Different thin film surface treatments on the novel TT-LGDLs for enhancing the interfacial contacts and PEMEC performance were investigated both in-situ and ex-situ for the first time. Surface modifiedmore » TT-LGDLs with about 180 nm thick Au thin film yielded performance improvement (voltage reduction), from 1.6849 V with untreated TT-LGDLs to only 1.6328 V with treated TT-LGDLs at 2.0 A/cm 2 and 80°C. Furthermore, the hydrogen/oxygen production rate was increased by about 28.2% at 1.60 V and 80°C. The durability test demonstrated that the surface treated TT-LGDL has good stability as well. Finally, the gold electroplating surface treatment is a promising method for the PEMEC performance enhancement and titanium material protection even in harsh environment.« less

Thin film surface modifications of thin/tunable liquid/gas diffusion layers for high-efficiency proton exchange membrane electrolyzer cells

DOE PAGES

Kang, Zhenye; Mo, Jingke; Yang, Gaoqiang; ...

2017-09-14

We present that a proton exchange membrane electrolyzer cell (PEMEC) is one of the most promising devices for high-efficiency and low-cost energy storage and ultrahigh purity hydrogen production. As one of the critical components in PEMECs, the titanium thin/tunable LGDL (TT-LGDL) with its advantages of small thickness, planar surface, straight-through pores, and well-controlled pore morphologies, achieved superior multifunctional performance for hydrogen and oxygen production from water splitting even at low temperature. Different thin film surface treatments on the novel TT-LGDLs for enhancing the interfacial contacts and PEMEC performance were investigated both in-situ and ex-situ for the first time. Surface modifiedmore » TT-LGDLs with about 180 nm thick Au thin film yielded performance improvement (voltage reduction), from 1.6849 V with untreated TT-LGDLs to only 1.6328 V with treated TT-LGDLs at 2.0 A/cm 2 and 80°C. Furthermore, the hydrogen/oxygen production rate was increased by about 28.2% at 1.60 V and 80°C. The durability test demonstrated that the surface treated TT-LGDL has good stability as well. Finally, the gold electroplating surface treatment is a promising method for the PEMEC performance enhancement and titanium material protection even in harsh environment.« less

Oxidation of the Ru(0001) surface covered by weakly bound, ultrathin silicate films

DOE PAGES

Emmez, Emre; Anibal Boscoboinik, J.; Tenney, Samuel; ...

2015-06-30

Bilayer silicate films grown on metal substrates are weakly bound to the metal surfaces, which allows ambient gas molecules to intercalate the oxide/metal interface. In this work, we studied the interaction of oxygen with Ru(0001) supported ultrathin silicate and aluminosilicate films at elevated O 2 pressures (10 -5–10 mbar) and temperatures (450–923 K). The results show that the silicate films stay essentially intact under these conditions, and oxygen in the film does not exchange with oxygen in the ambient. O 2 molecules readily penetrate the film and dissociate on the underlying Ru surface underneath. Also, the silicate layer does howevermore » strongly passivate the Ru surface towards RuO 2(110) oxide formation that readily occurs on bare Ru(0001) under the same conditions. Lastly, the results indicate considerable spatial effects for oxidation reactions on metal surfaces in the confined space at the interface. Moreover, the aluminosilicate films completely suppress the Ru oxidation, providing some rationale for using crystalline aluminosilicates in anti-corrosion coatings.« less

Unifying theoretical framework for deciphering the oxygen reduction reaction on platinum.

PubMed

Huang, Jun; Zhang, Jianbo; Eikerling, Michael

2018-05-07

Rapid conversion of oxygen into water is crucial to the operation of polymer electrolyte fuel cells and other emerging electrochemical energy technologies. Chemisorbed oxygen species play double-edged roles in this reaction, acting as vital intermediates on one hand and site-blockers on the other. Any attempt to decipher the oxygen reduction reaction (ORR) must first relate the formation of oxygen intermediates to basic electronic and electrostatic properties of the catalytic surface, and then link it to parameters of catalyst activity. An approach that accomplishes this feat will be of great utility for catalyst materials development and predictive model formulation of electrode operation. Here, we present a theoretical framework for the multiple interrelated surface phenomena and processes involved, particularly, by incorporating the double-layer effects. It sheds light on the roles of oxygen intermediates and gives out the Tafel slope and exchange current density as continuous functions of electrode potential. Moreover, it develops the concept of a rate determining term, which should replace the concept of a rate determining step for multielectron reactions, and offers a new perspective on the volcano relation of the ORR.

Measurement of the oxygen mass transfer through the air-water interface.

PubMed

Mölder, Erik; Mashirin, Alelxei; Tenno, Toomas

2005-01-01

Gas mass transfer through the liquid-gas interface has enormous importance in various natural and industrial processes. Surfactants or insoluble compounds adsorbed onto an interface will inhibit the gas mass transfer through the liquid-gas surface. This study presents a technique for measuring the oxygen mass transfer through the air-water interface. Experimental data obtained with the measuring device were incorporated into a novel mathematical model, which allowed one to calculate diffusion conduction of liquid surface layer and oxygen mass transfer coefficient in the liquid surface layer. A special measurement cell was constructed. The most important part of the measurement cell is a chamber containing the electrochemical oxygen sensor inside it. Gas exchange between the volume of the chamber and the external environment takes place only through the investigated surface layer. Investigated liquid was deoxygenated, which triggers the oxygen mass transfer from the chamber through the liquid-air interface into the liquid phase. The decrease of oxygen concentration in the cell during time was measured. By using this data it is possible to calculate diffusional parameters of the water surface layer. Diffusion conduction of oxygen through the air-water surface layer of selected wastewaters was measured. The diffusion conduction of different wastewaters was about 3 to 6 times less than in the unpolluted water surface. It was observed that the dilution of wastewater does not have a significant impact on the oxygen diffusion conduction through the wastewater surface layer. This fact can be explained with the presence of the compounds with high surface activity in the wastewater. Surfactants achieved a maximum adsorption and, accordingly, the maximum decrease of oxygen permeability already at a very low concentration of surfactants in the solution. Oxygen mass transfer coefficient of the surface layer of the water is found to be Ds/ls = 0.13 x 10(-3) x cm/s. A simple technique for measuring oxygen diffusion parameters through the air-water solution surface has been developed. Derived equations enable the calculation of diffusion parameters of the surface layer at current conditions. These values of the parameters permit one to compare the resistances of the gas-liquid interface to oxygen mass transfer in the case of adsorption of different substances on the surface layer. This simple technique may be used for a determination of oxygen permeability of different water-solution surface layers. It enables one to measure the resistance to the oxygen permeability of all inflowing wastewater surface layers in the wastewater treatment plant, and to initiate a preliminary cleaning of this wastewater if required. Similarly, we can measure oxygen permeability of natural waterbodies. Especially in the case of pollution, it is important to know to what extent the oxygen permeability of the water surface layer has been decreased. Based on the tehnique presented in this research, fieldwork equipment will be developed.

The pumping oxygenator: design criteria and first in vitro results.

PubMed

Fiore, G B; Costantino, M L; Fumero, R; Montevecchi, F M

2000-10-01

A new project is presented, the pumping oxygenator, functionally integrating pulsatile pumping and blood oxygenation in a single device. Solid, semipermeable silicone membranes allow gas exchange and simultaneously transfer energy from pressurized gas to blood thanks to their distensibility and to inlet and outlet 1-way valves. Two small-sized (1 m2 exchange surface area) prototypes were designed, constructed, hydraulically characterized, and subjected to gas transfer evaluation tests. Blood flow rates (Q(b)) up to 1,250 ml/min were obtained with 30 mm Hg static preload and 130 mm Hg afterload with 0.7 m upstream and 2.1 m downstream 3/8 inch pipes. Physiological oxygen transfer (VO2 = 5 ml/dl, ml of transferred O2/dl of treated blood) was delivered at Q(b) < 900 ml/min, about 4 ml/dl at Q(b) = 1,250 ml/min. VO2 also was significantly increased by increasing percent systolic time. CO2 transfer decreased regularly with increasing Q(b) from VCO2 = 4.8 ml/dl at Q(b) = 400 ml/min to VCO 2 = 2.1 ml/dl at Q(b) = 1,250 ml/min. The results confirm the possibility of integrating oxygenation and pulsatile pumping. The pumping oxygenator represents a promising project deserving further improvements.

Morphological Pulmonary Diffusion Capacity for Oxygen of Burmese Pythons (Python molurus): a Comparison of Animals in Healthy Condition and with Different Pulmonary Infections.

PubMed

Starck, J M; Weimer, I; Aupperle, H; Müller, K; Marschang, R E; Kiefer, I; Pees, M

2015-11-01

A qualitative and quantitative morphological study of the pulmonary exchange capacity of healthy and diseased Burmese pythons (Python molurus) was carried out in order to test the hypothesis that the high morphological excess capacity for oxygen exchange in the lungs of these snakes is one of the reasons why pathological processes extend throughout the lung parenchyma and impair major parts of the lungs before clinical signs of respiratory disease become apparent. Twenty-four Burmese pythons (12 healthy and 12 diseased) were included in the study. A stereology-based approach was used to quantify the lung parenchyma using computed tomography. Light microscopy was used to quantify tissue compartments and the respiratory exchange surface, and transmission electron microscopy was used to measure the thickness of the diffusion barrier. The morphological diffusion capacity for oxygen of the lungs and the anatomical diffusion factor were calculated. The calculated anatomical diffusion capacity was compared with published values for oxygen consumption of healthy snakes, and the degree to which the exchange capacity can be obstructed before normal physiological function is impaired was estimated. Heterogeneous pulmonary infections result in graded morphological transformations of pulmonary parenchyma involving lymphocyte migration into the connective tissue and thickening of the septal connective tissue, increasing thickness of the diffusion barrier and increasing transformation of the pulmonary epithelium into a columnar pseudostratified or stratified epithelium. The transformed epithelium developed by hyperplasia of ciliated cells arising from the tip of the faveolar septa and by hyperplasia of type II pneumocytes. These results support the idea that the lungs have a remarkable overcapacity for oxygen consumption and that the development of pulmonary disease continuously reduces the capacity for oxygen consumption. However, due to the overcapacity of the lungs, this reduction does not result in clinical signs and disease can progress unrecognized for an extended period. Copyright © 2015 Elsevier Ltd. All rights reserved.

Oxygen-limited thermal tolerance is seen in a plastron-breathing insect and can be induced in a bimodal gas exchanger.

PubMed

Verberk, Wilco C E P; Bilton, David T

2015-07-01

Thermal tolerance has been hypothesized to result from a mismatch between oxygen supply and demand. However, the generality of this hypothesis has been challenged by studies on various animal groups, including air-breathing adult insects. Recently, comparisons across taxa have suggested that differences in gas exchange mechanisms could reconcile the discrepancies found in previous studies. Here, we test this suggestion by comparing the behaviour of related insect taxa with different gas exchange mechanisms, with and without access to air. We demonstrate oxygen-limited thermal tolerance in air-breathing adults of the plastron-exchanging water bug Aphelocheirus aestivalis. Ilyocoris cimicoides, a related, bimodal gas exchanger, did not exhibit such oxygen-limited thermal tolerance and relied increasingly on aerial gas exchange with warming. Intriguingly, however, when denied access to air, oxygen-limited thermal tolerance could also be induced in this species. Patterns in oxygen-limited thermal tolerance were found to be consistent across life-history stages in these insects, with nymphs employing the same gas exchange mechanisms as adults. These results advance our understanding of oxygen limitation at high temperatures; differences in the degree of respiratory control appear to modulate the importance of oxygen in setting tolerance limits. © 2015. Published by The Company of Biologists Ltd.

Oxygen-limited thermal tolerance is seen in a plastron-breathing insect and can be induced in a bimodal gas exchanger

PubMed Central

Verberk, Wilco C. E. P.; Bilton, David T.

2015-01-01

ABSTRACT Thermal tolerance has been hypothesized to result from a mismatch between oxygen supply and demand. However, the generality of this hypothesis has been challenged by studies on various animal groups, including air-breathing adult insects. Recently, comparisons across taxa have suggested that differences in gas exchange mechanisms could reconcile the discrepancies found in previous studies. Here, we test this suggestion by comparing the behaviour of related insect taxa with different gas exchange mechanisms, with and without access to air. We demonstrate oxygen-limited thermal tolerance in air-breathing adults of the plastron-exchanging water bug Aphelocheirus aestivalis. Ilyocoris cimicoides, a related, bimodal gas exchanger, did not exhibit such oxygen-limited thermal tolerance and relied increasingly on aerial gas exchange with warming. Intriguingly, however, when denied access to air, oxygen-limited thermal tolerance could also be induced in this species. Patterns in oxygen-limited thermal tolerance were found to be consistent across life-history stages in these insects, with nymphs employing the same gas exchange mechanisms as adults. These results advance our understanding of oxygen limitation at high temperatures; differences in the degree of respiratory control appear to modulate the importance of oxygen in setting tolerance limits. PMID:25964420

Ab initio study of perovskite type oxide materials for solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Lee, Yueh-Lin

2011-12-01

Perovskite type oxides form a family of materials of significant interest for cathodes and electrolytes of solid oxide fuel cells (SOFCs). These perovskites not only are active catalysts for surface oxygen reduction (OR) reactions but also allow incorporating the spilt oxygen monomers into their bulk, an unusual and poorly understood catalytic mechanism that couples surface and bulk properties. The OR mechanisms can be influenced strongly by defects in perovskite oxides, composition, and surface defect structures. This thesis work initiates a first step in developing a general strategy based on first-principles calculations for detailed control of oxygen vacancy content, transport rates of surface and bulk oxygen species, and surface/interfacial reaction kinetics. Ab initio density functional theory methods are used to model properties relevant for the OR reactions on SOFC cathodes. Three main research thrusts, which focus on bulk defect chemistry, surface defect structures and surface energetics, and surface catalytic properties, are carried to investigate different level of material chemistry for improved understanding of key physics/factors that govern SOFC cathode OR activity. In the study of bulk defect chemistry, an ab initio based defect model is developed for modeling defect chemistry of LaMnO 3 under SOFC conditions. The model suggests an important role for defect interactions, which are typically excluded in previous defect models. In the study of surface defect structures and surface energetics, it is shown that defect energies change dramatically (1˜2 eV lower) from bulk values near surfaces. Based on the existing bulk defect model with the calculated ab initio surface defect energetics, we predict the (001) MnO 2 surface oxygen vacancy concentration of (La0.9Sr0.1 )MnO3 is about 5˜6 order magnitude higher than that of the bulk under typical SOFC conditions. Finally, for surface catalytic properties, we show that area specific resistance, oxygen exchange rates, and key OR energetics of the SOFC cathode perovskites, can be described by a single descriptor, either the bulk O p-band or the bulk oxygen vacancy formation energy. These simple descriptors will further enable first-principles optimization/design of new SOFC cathodes.

Adsorption of oxygen on low-index surfaces of the TiAl{sub 3} alloy

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

Latyshev, A. M.; Bakulin, A. V.; Kulkova, S. E., E-mail: kulkova@ms.tsc.ru

Method of the projector augmented waves in the plane-wave basis within the generalized-gradient approximation for the exchange-correlation functional has been used to study oxygen adsorption on (001), (100), and (110) low-index surfaces of the TiAl{sub 3} alloy. It has been established that the sites that are most energetically preferred for the adsorption of oxygen are hollow (H) positions on the (001) surface and bridge (B) positions on the (110) and (100) surfaces. Structural and electronic factors that define their energy preference have been discussed. Changes in the atomic and electronic structure of subsurface layers that occur as the oxygen concentrationmore » increases to three monolayers have been analyzed. It has been shown that the formation of chemical bonds of oxygen with both components of the alloy leads to the appearance of states that are split-off from the bottoms of their valence bands, which is accompanied by the formation of a forbidden gap at the Fermi level and by a weakening of the Ti–Al metallic bonds in the alloy. On the Al-terminated (001) and (110) surfaces, the oxidation of aluminum dominates over that of titanium. On the whole, the binding energy of oxygen on the low-index surfaces with a mixed termination is higher than that at the aluminum-terminated surface. The calculation of the diffusion of oxygen in the TiAl{sub 3} alloy has shown that the lowest barriers correspond to the diffusion between tetrahedral positions in the (001) plane; the diffusion of oxygen in the [001] direction occurs through octahedral and tetrahedral positions. An increase in the concentration of aluminum in the alloy favors a reduction in the height of the energy barriers as compared to the corresponding barriers in the γ-TiAl alloy.« less

High performance methanol-oxygen fuel cell with hollow fiber electrode

NASA Technical Reports Server (NTRS)

Lawson, Daniel D. (Inventor); Ingham, John D. (Inventor)

1983-01-01

A methanol/air-oxygen fuel cell including an electrode formed by open-ended ion-exchange hollow fibers having a layer of catalyst deposited on the inner surface thereof and a first current collector in contact with the catalyst layer. A second current collector external of said fibers is provided which is immersed along with the hollow fiber electrode in an aqueous electrolyte body. Upon passage of air or oxygen through the hollow fiber electrode and introduction of methanol into the aqueous electrolyte, a steady current output is obtained. Two embodiments of the fuel cell are disclosed. In the first embodiment the second metal electrode is displaced away from the hollow fiber in the electrolyte body while in the second embodiment a spiral-wrap electrode is provided about the outer surface of the hollow fiber electrode.

Influence of persistent exchangeable oxygen on biogenic silica δ18O in deep sea cores

NASA Astrophysics Data System (ADS)

Menicucci, A. J.; Spero, H. J.

2016-12-01

The removal of exchangeable oxygen from biogenic opal prior to IRMS analysis is critical during sample preparation. Exchangeable oxygen is found in the form of hydroxyl and between defects within the amorphous silicate lattice structure. Typical analytical procedures utilize a variety of dehydroxylation methods to eliminate this exchangeable oxygen, including vacuum dehydroxylation and prefluorination. Such methods are generally considered sufficient for elimination of non-lattice bound oxygen that would obfuscate environmental oxygen isotopic signals contained within the silicate tetrahedra. δ18O data that are then empirically calibrated against modern hydrographic data, and applied down core in paleoceanographic applications. We have conducted a suite of experiments on purified marine opal samples using the new microfluorination method (Menicucci et al., 2013). Our data demonstrate that the amount of exchangeable oxygen in biogenic opal decreases as sample age/depth in core increases. These changes are not accounted for by current researchers. Further, our experimental data indicate that vacuum dehydroxylation does not eliminate all exchangeable oxygen, even after hydroxyl is undetectable. We have conducted experiments to quantify the amount of time necessary to ensure vacuum dehydroxylation has eliminated exchangeable oxygen so that opal samples are stable prior to δ18Odiatom analysis. Our experiments suggest that previously generated opal δ18O data may contain a variable down-core offset due to the presence of exchangeable, non-lattice bound oxygen sources. Our experiments indicate that diatom silica requires dehydroxylation for ≥ 44 hours at 1060oC to quantitatively remove all non-lattice bound oxygen. Further, this variable amount of exchangeable oxygen may be responsible for some of the disagreement between existing empirical calibrations based on core-top diatom frustule remains. Analysis of δ18Odiatom values after this long vacuum dehydroxylation time is necessary for quantitative comparisons of stable isotopic values across geologic time periods. Menicucci, A. J., et al. (2013). "Oxygen isotope analyses of biogenic opal and quartz using a novel microfluorination technique." Rapid Communications in Mass Spectrometry 27(16): 1873-1881

Tether System for Exchanging Payloads Between the International Space Station and the Lunar Surface

NASA Technical Reports Server (NTRS)

Hoyt, Robert P.

1998-01-01

Systems composed of several rotating and/or hanging tethers may provide a means of exchanging supplies between low Earth orbit facilities and lunar bases without requiring the use of propellant. This work develops methods for designing a tether system capable of repeatedly exchanging payloads between a LEO facility such as the International Space Station or a Space Business Park and a base on the lunar surface. In this system, a hanging tether extended upwards from the LEO facility, places a payload into a slightly elliptical orbit, where it is caught by a rotating tether in a higher elliptical orbit. This rotating tether then tosses the payload to the moon. At the moon, a long rotating "Lunavator" tether catches the payload and deposits it on the surface of the moon. By transporting an equal mass of lunar materials such as oxygen back down to the LEO facility through the tether transport system, the momentum and energy of the system is conserved, allowing frequent traffic between LEO and the lunar surface with minimal propellant requirements.

A new route of oxygen isotope exchange in the solid phase: demonstration in CuSO4.5H2O.

PubMed

Danon, Albert; Saig, Avraham; Finkelstein, Yacov; Koresh, Jacob E

2005-11-10

Temperature-programmed desorption mass spectrometry (TPD-MS) measurements on [(18)O]water-enriched copper sulfate pentahydrate (CuSO(4).5H(2)(18)O) reveal an unambiguous occurrence of efficient oxygen isotope exchange between the water of crystallization and the sulfate in its CuSO(4) solid phase. To the best of our knowledge, the occurrence of such an exchange was never observed in a solid phase. The exchange process was observed during the stepwise dehydration (50-300 degrees C) of the compound. Specifically, the exchange promptly occurs somewhere between 160 and 250 degrees C; however, the exact temperature could not be resolved conclusively. It is shown that only the fifth, sulfate-associated, anionic H(2)O molecule participates in the exchange process and that the exchange seems to occur in a preferable fashion with, at the most, one oxygen atom in SO(4). Such an exchange, occurring below 250 degrees C, questions the common conviction of unfeasible oxygen exchange under geothermic conditions. This new oxygen exchange phenomenon is not exclusive to copper sulfate but is unambiguously observed also in other sulfate- and nitrate-containing minerals.

Oxygen isotope exchange between refractory inclusion in Allende and solar nebula gas.

PubMed

Yurimoto, H; Ito, M; Nagasawa, H

1998-12-04

A calcium-aluminum-rich inclusion (CAI) from the Allende meteorite was analyzed and found to contain melilite crystals with extreme oxygen-isotope composition (approximately 5 percent oxygen-16 enrichment relative to terrestrial oxygen-16). Some of the melilite is also anomalously enriched in oxygen-16 compared with oxygen isotopes measured in other CAIs. The oxygen isotopic variation measured among the minerals (melilite, spinel, and fassaite) indicates that crystallization of the CAI started from oxygen-16-rich materials that were probably liquid droplets in the solar nebula, and oxygen isotope exchange with the surrounding oxygen-16-poor nebular gas progressed through the crystallization of the CAI. Additional oxygen isotope exchange also occurred during subsequent reheating events in the solar nebula.

Oxygen isotope exchange between refractory inclusion in allende and solar nebula Gas

PubMed

Yurimoto; Ito; Nagasawa

1998-12-04

A calcium-aluminum-rich inclusion (CAI) from the Allende meteorite was analyzed and found to contain melilite crystals with extreme oxygen-isotope compositions ( approximately 5 percent oxygen-16 enrichment relative to terrestrial oxygen-16). Some of the melilite is also anomalously enriched in oxygen-16 compared with oxygen isotopes measured in other CAIs. The oxygen isotopic variation measured among the minerals (melilite, spinel, and fassaite) indicates that crystallization of the CAI started from oxygen-16-rich materials that were probably liquid droplets in the solar nebula, and oxygen isotope exchange with the surrounding oxygen-16-poor nebular gas progressed through the crystallization of the CAI. Additional oxygen isotope exchange also occurred during subsequent reheating events in the solar nebula.

Modeling Corneal Oxygen with Scleral Gas Permeable Lens Wear.

PubMed

Compañ, Vicente; Aguilella-Arzo, Marcel; Edrington, Timothy B; Weissman, Barry A

2016-11-01

The main goal of this current work is to use an updated calculation paradigm, and updated boundary conditions, to provide theoretical guidelines to assist the clinician whose goal is to improve his or her scleral gas permeable (GP) contact lens wearing patients' anterior corneal oxygen supply. Our model uses a variable value of corneal oxygen consumption developed through Monod equations that disallows negative oxygen tensions within the stroma to predict oxygen tension at the anterior corneal surface of scleral GP contact lens wearing eyes, and to describe oxygen tension and flux profiles, for various boundary conditions, through the lens, tears, and cornea. We use several updated tissue and boundary parameters in our model. Tear exchange with GP scleral lenses is considered nonexistent in this model. The majority of current scleral GP contact lenses should produce some levels of corneal hypoxia under open eye conditions. Only lenses producing the thinnest of tear vaults should result in anterior corneal surface oxygen tensions greater than a presumed critical oxygen tension of 100 mmHg. We also find that corneal oxygen tension and flux are each more sensitive to modification in tear vault than to changes in lens oxygen permeability, within the ranges of current clinical manipulation. Our study suggests that clinicians would be prudent to prescribe scleral GP lenses manufactured from higher oxygen permeability materials and especially to fit without excessive corneal clearance.

A Hybrid Density Functional Study of Atomic Hydrogen and Oxygen Adsorptions on the (0001) Surface of Non-Magnetic DHCP Americium

NASA Astrophysics Data System (ADS)

Amdani-Moten, Shafaq; Atta-Fynn, Raymond; Ray, Asok

2010-03-01

As our group have recently shown^+, hybrid density functional theory (HDFT) which replaces a fraction (40%) of approximate DFT exchange with exact Hartree-Fock exchange yield structural, magnetic, and electronic properties for Americium-I that are in excellent agreement with experimental data. As a natural progression, ab initio calculations for atomic adsorptions on the (0001) surface of non-magnetic americium have been performed using HDFT. The americium surface is modeled by a seven-layer slab using inversion symmetry consisting of one atom per layer and non-magnetic ABAC stacking arrangement of these layers. Top, bridge, hcp and fcc chemisorption sites have been investigated with energies optimized with respect to the adatom distance from the surface. Details of the chemisorptions processes as well as comparisons of different sites will be presented. ^+ R. Atta-Fynn and A. K. Ray, Chemical Physics Letters, 482, 223-227 (2009).

STIR: Improved Electrolyte Surface Exchange via Atomically Strained Surfaces

DTIC Science & Technology

2015-09-03

at the University of Delaware. Concomitant with the experimental work, we also conducted numerical simulations of the experiments. A Poisson- Nernst ...oxygen ion lattice site results in a reaction volume and an associated Vex·ΔP term in the Arrhenius rate equation . In addition, tensile strain (i.e...simulations of the experiments. In recent work at the University of Delaware [9-13], we used finite element solution of generalized Poisson- Nernst -Planck

The ancient oxygen exosphere of Mars - Implications for atmosphere evolution

NASA Technical Reports Server (NTRS)

Zhang, M. H. G.; Luhmann, J. G.; Bougher, S. W.; Nagy, A. F.

1993-01-01

The paper considers absorption of oxygen (atoms and ions) by the surface as a mechanism for the early Martian atmosphere escape, due to the effect of high EUV flux of the ancient sun. Hot oxygen exosphere densities in ancient atmosphere and ionosphere are calculated for different EUV fluxes and the escape fluxes associated with these exposures. Using these densities, the ion production rate above the ionopause is calculated for different epochs including photoionization, charge exchange, and solar wind electron impact. It is found that, when the inferred high solar EUV fluxes of the past are taken into account, oxygen equivalent to that in several tens of meters of water, planet-wide, should have escaped Martian atmosphere to space over the last 3 Gyr.

The ancient oxygen exosphere of Mars - Implications for atmosphere evolution

NASA Astrophysics Data System (ADS)

Zhang, M. H. G.; Luhmann, J. G.; Bougher, S. W.; Nagy, A. F.

1993-06-01

The paper considers absorption of oxygen (atoms and ions) by the surface as a mechanism for the early Martian atmosphere escape, due to the effect of high EUV flux of the ancient sun. Hot oxygen exosphere densities in ancient atmosphere and ionosphere are calculated for different EUV fluxes and the escape fluxes associated with these exposures. Using these densities, the ion production rate above the ionopause is calculated for different epochs including photoionization, charge exchange, and solar wind electron impact. It is found that, when the inferred high solar EUV fluxes of the past are taken into account, oxygen equivalent to that in several tens of meters of water, planet-wide, should have escaped Martian atmosphere to space over the last 3 Gyr.

Using Argo-O2 data to examine the impact of deep-water formation events on oxygen uptake in the Labrador Sea

NASA Astrophysics Data System (ADS)

Wolf, M. K.; Hamme, R. C.; Gilbert, D.; Yashayaev, I.

2016-02-01

Deep-water formation allows the deep ocean to communicate with the atmosphere, facilitating exchanges of heat as well as important gases such as CO2 and oxygen. The Labrador Sea is the most studied location of deep convection in the North Atlantic Ocean and a strong contributor to the global thermohaline circulation. Since there are no internal sources of oxygen below the euphotic zone, deep-water formation is vital for oxygen transport to the deep ocean. Recent studies document large interannual variability in the strength and depth of convection in the Labrador Sea, from mixed layers of 100m to greater than 1000m. A weakening of this deep convection starves the deep ocean of oxygen, disrupting crucial deep sea biological processes, as well as reducing oceanic CO2 uptake and ocean circulation. We used data from the extensive Argo float network to examine these deep-water formation events in the Labrador Sea. The oxygen optodes onboard many Argo floats suffer from biases whose amplitude must be determined; therefore we investigated and applied various optode calibration methods. Using calibrated vertical profiles of oxygen, temperature, and salinity, we observed the timing, magnitude, and location of deep convection, restratification, and spring phytoplankton blooms. In addition, we used surface oxygen values along with NCEP wind speeds to calculate the air-sea oxygen flux using a range of air-sea gas exchange parameterizations. We then compared this oxygen flux to the rate of change of the measured oxygen inventory. Where the inventory and flux did not agree, we identified other oceanic processes such as biological activity or lateral advection of water masses occurring, or advection of the float itself into a new area. The large role that horizontal advection of water or the float has on oxygen uptake and cycling leads us to conclude that this data cannot be easily interpreted as a 1-D system. Oxygen exchanges with the atmosphere at a faster rate than CO2, is more affected by bubble injection, and reacts differently to temperature change. Oxygen is also produced and consumed by photosynthesis and respiration respectively at a specific ratio to CO2. These properties enable us to use oxygen as a separate constraint from carbon to determine the effect these various processes have on gas cycling, and the global ocean circulation.

A palaeotemperature curve for the Precambrian oceans based on silicon isotopes in cherts.

PubMed

Robert, François; Chaussidon, Marc

2006-10-26

The terrestrial sediment record indicates that the Earth's climate varied drastically in the Precambrian era (before 550 million years ago), ranging from surface temperatures similar to or higher than today's to global glaciation events. The most continuous record of sea surface temperatures of that time has been derived from variations in oxygen isotope ratios of cherts (siliceous sediments), but the long-term cooling of the oceans inferred from those data has been questioned because the oxygen isotope signature could have been reset through the exchange with hydrothermal fluids after deposition of the sediments. Here we show that the silicon isotopic composition of cherts more than 550 million years old shows systematic variations with age that support the earlier conclusion of long-term ocean cooling and exclude post-depositional exchange as the main source of the isotopic variations. In agreement with other lines of evidence, a model of the silicon cycle in the Precambrian era shows that the observed silicon isotope variations imply seawater temperature changes from about 70 degrees C 3,500 million years ago to about 20 degrees C 800 million years ago.

Kinetics of oxygen reduction in perovskite cathodes for solid oxide fuel cells: A combined modeling and experimental approach

NASA Astrophysics Data System (ADS)

Miara, Lincoln James

Solid oxide fuel cells (SOFCs) have the potential to replace conventional stationary power generation technologies; however, there are major obstacles to commercialization, the most problematic of which is poor cathode performance. Commercialization of SOFCs will follow when the mechanisms occurring at the cathode are more thoroughly understood and adapted for market use. The catalytic reduction of oxygen occurring in SOFC cathodes consists of many elementary steps such as gas phase diffusion, chemical and/or electrochemical reactions which lead to the adsorption and dissociation of molecular oxygen onto the cathode surface, mass transport of oxygen species along the surface and/or through the bulk of the cathode, and full reduction and incorporation of the oxygen at the cathode/electrolyte two or three phase boundary. Electrochemical impedance spectroscopy (EIS) is the main technique used to identify the occurrence of these different processes, but when this technique is used without an explicit model describing the kinetics it is difficult to unravel the interdependence of each of these processes. The purpose of this dissertation is to identify the heterogeneous reactions occurring at the cathode of an SOFC by combining experimental EIS results with mathematical models describing the time dependent behavior of the system. This analysis is performed on two different systems. In the first case, experimental EIS results from patterned half cells composed of Ca-doped lanthanum manganite (LCM)| yttria-doped ZrO2 (YSZ) are modeled to investigate the temperature and partial pressure of oxygen, pO2, dependence of oxygen adsorption/dissociation onto the LCM surface, surface diffusion of atomic oxygen, and electrochemical reduction and incorporation of the oxygen into the electrolyte in the vicinity of the triple phase boundary (TPB). This model determines the time-independent state-space equations from which the Faradaic admittance transfer function is obtained. The unknown rate constants (kad, k des, k1, k1¯ ), and parameters (Ds, Q°, n) arising from the governing equations are estimated from a combination of experiments, mathematical analysis, and numerical data analysis. In the second system, dense patterned films of cathode with composition: La0.6Sr0.4Co0.2Fe0.8O3-delta (LSCF-6428) were fabricated on Ga-doped CeO2 coated YSZ substrates. These samples were analyzed by EIS over a temperature and pO 2 range of 600--800 °C and 10-3--1.00 atm, respectively. To understand the EIS results, a 2-dimensional model was developed which accounted for surface oxygen exchange, and both surface and bulk transport of oxygen to the electrolyte interface. The results were obtained by numerically solving a stationary partial differential equation describing the oxygen vacancy distribution in the cathode. From these results, the model impedance was derived and then fitted to the experimental EIS results. From the fitting results the contributions to the impedance from each of the processes were estimated. Also, the surface exchange rate was estimated over the experimental operating conditions. Finally, the results suggest that the surface diffusion occurred by an interstitial type mechanism in this material. The cathode surface is intimately involved in most of the oxygen reduction processes; however, the surface structure and chemistry is typically treated as an extension of the bulk without consideration of the actual surface properties. Recent evidence suggests that significant changes occur to the surface during operation which in turn leads to changes in electrochemical performance. To investigate these phenomena, well-oriented thin films (250 nm in thickness) of Sr-doped lanthanum manginite (LSM) films were grown on single crystals of YSZ (111). Films which were cathodically biased with a -1 V applied dc potential were compared to control samples. The cathodic bias results in both an enhancement in electrochemical performance and a change in surface chemistry. The changes in electrochemical performance were monitored by ES, while the surface changes were tracked with a combination of soft x-ray techniques such as x-ray photoemission spectroscopy and x-ray absorption spectroscopy. The soft x-ray results indicated that the removal of surface passivating phases (i.e., SrO and MnO) are correlated with improved performance. This work demonstrates the success of estimating fundamental parameters, such as diffusivity and surface coverage, from experimental EIS results using a physically realistic model without, as is commonly done, assuming a specific rate limiting step or using an ambiguous equivalent circuit. This allows researchers to fabricate designer cathodes by selecting materials with optimal kinetic properties such as rapid oxygen dissociation and rapid oxygen transport in (or on) the cathode, independent of geometry.

Computational insights into crystal plane dependence of thermal activity of anion (C and N)-substituted titania.

PubMed

V, Sai Phani Kumar; Arya, Rahul; Deshpande, Parag A

2017-11-29

Geometry optimizations of anion (C and N) doped anatase TiO 2 were carried out by using DFT+U calculations. Various anion vacancy sites were examined to study the synergistic effects of anion doping accompanied with anion vacancy formation on lattice oxygen activation. Two non-identical crystal planes (0 0 1) and (1 0 0) were chosen for C and N substitutions. Energetically favoured N-vacancy pairs were identified on TiO 2 surfaces. Substitution of N along with anion vacancies at various sites was energetically more favoured than that of C-doping in bulk TiO 2 while the energies were comparable for surface substitutions. Bond length distributions due to the formation of differential bonds were determined. Net oxygen activation and accompanying reversible oxygen exchange capacities were compared for TiO 2-2x C x and TiO 2-3x N 2x . Substitution of C in the surface exposed (1 0 0) plane of TiO 2 resulted in 47.6% and 23.8% of bond elongation and compression, respectively, resulting in 23.8% of net oxygen activation which was higher when compared to N substitution in the (1 0 0) plane of TiO 2 resulting in a net oxygen activation of 17%.

Measures of net oxidant concentration in seawater

NASA Astrophysics Data System (ADS)

Jackson, George A.; Williams, Peter M.

1988-02-01

Dissolved oxygen deficits in the ocean have been used as a measure of the organic matter oxidized in a volume of water. Such organic matter is usually assumed to be predominantly settled particles. Using dissolved oxygen concentration in this way has two problems: first, it does not differentiate between oxidant consumed by the pool of dissolved organic matter present near the ocean surface and oxidant consumed by organic matter contained by falling particles; second, it does not account for other oxidant sources, such as nitrate, which can be as important to organic matter decay as oxygen in low-oxygen water, such as off Peru or in the Southern California submarine basins. New parameters provide better measures of the net oxidant concentration in a water parcel. One such, NetOx, is changed only by gaseous exchange with the atmosphere, exchange with the benthos, or the production or consumption of sinking particles. A simplified version of NetOx, NetOx = [O2] + 1.25[NO3-] - [TOC], where TOC (total organic carbon), the dissolved organic carbon (DOC) plus the suspended particulate organic carbon (POC), provides an index based on the usually dominant variables. Calculation of NetOx and a second property, NetOC ([O2] - [TOC]), for data from GEOSECS and ourselves in the Atlantic and Pacific oceans using property-property graphs show differences from those from oxygen deficits alone. Comparison of NetOx and NetOC concentrations at high and low latitudes of the Pacific Ocean shows the difference in surface water oxidant concentrations is even larger than the difference in oxygen concentration. Vertical particle fluxes off Peru calculated from NetOx gradients are much greater than those calculated from oxygen gradients. The potential value of NetOx and NetOC as parameters to understand particle fluxes implies that determination of TOC should be a routine part of hydrographic measurements.

In-vitro evaluation of limitations and possibilities for the future use of intracorporeal gas exchangers placed in the upper lobe position.

PubMed

Schumer, Erin; Höffler, Klaus; Kuehn, Christian; Slaughter, Mark; Haverich, Axel; Wiegmann, Bettina

2018-03-01

The lack of donor organs has led to the development of alternative "destination therapies", such as a bio-artificial lung (BA) for end-stage lung disease. Ultimately aiming at a fully implantable BA, general capabilities and limitations of different oxygenators were tested based on the model of BA positioning at the right upper lobe. Three different-sized oxygenators (neonatal, paediatric, and adult) were tested in a mock circulation loop regarding oxygenation and decarboxylation capacities for three respiratory pathologies. Blood flows were imitated by a roller pump, and respiration was imitated by a mechanical ventilator with different FiO 2 applications. Pressure drops across the oxygenators and the integrity of the gas-exchange hollow fibers were analyzed. The neonatal oxygenator proved to be insufficient regarding oxygenation and decarboxylation. Despite elevated pCO 2 levels, the paediatric and adult oxygenators delivered comparable sufficient oxygen levels, but sufficient decarboxylation across the oxygenators was ensured only at flow rates of 0.5 L min. Only the adult oxygenator indicated no significant pressure drops. For all tested conditions, gas-exchange hollow fibers remained intact. This is the first study showing the general feasibility of delivering sufficient levels of gas exchange to an intracorporeal BA via patient's breathing, without damaging gas-exchange hollow fiber membranes.

Stability of Zircon and its Isotopic Ratios in High-Temperature Fluids: Long-Term (4 months) Isotope Exchange Experiment at 850 °C and 50 MPa

NASA Astrophysics Data System (ADS)

Bindeman, Ilya N.; Schmitt, Axel K.; Lundstrom, Craig C.; Hervig, Richard L.

2018-05-01

Stability of zircon in hydrothermal fluids and vanishingly slow rates of diffusion identify zircon as a reliable recorder of its formation conditions in recent and ancient rocks. Debate, however, persists on how rapidly oxygen and key trace elements (e.g., Li, B, Pb) diffuse when zircon is exposed to hot aqueous fluids. Here, we report results of a nano- to micrometer-scale investigation of isotopic exchange using natural zircon from Mesa Falls Tuff (Yellowstone) treated with quartz-saturated, isotopically (18O, D, 7Li, and 11B) labeled water with a nominal δ18O value of +450‰ over 4 months at 850°C and 50 MPa. Frontside (crystal rim inwards) δ18O depth profiling of zircon by magnetic sector SIMS shows initially high but decreasing 18O/16O over a 130 nm non-Fickian profile, with a decay length comparable to the signal from surficial Au coating deposited onto zircon. In contrast, backside (crystal interior outwards) depth profiling on a 2-3 µm thick wafer cut and thinned from treated zircon by focused ion beam (FIB) milling lacks any significant increase in 18O/16O during penetration of the original surface layer. Near-surface time-of-flight (TOF-SIMS) frontside profiles of uncoated zircon from 4-month and 1-day-long experiments as well as untreated zircons display similar enrichments of 18O over a distance of 20 nm. All frontside 18O profiles are here interpreted as transient surface signals from nm-thick surface enrichment or contamination unrelated to diffusion. Likewise, frontside depth profiling of H, Li, and B isotopes are similar for long- and short-duration experiments. Additionally, surface U-Pb dating of zircon from the 4-month experiment returned U-Pb ages by depth profiling with 1 µm penetration that were identical to untreated samples. Frontside and backside depth-profiling thus demonstrate that diffusive 18O enrichment in the presence of H2O is much slower than predicted from experiments in Watson and Cherniak (1997). Instead, intracrystalline exchange of oxygen between fluid and zircon in wet experimental conditions with excess silica occurred over length-scales equivalent to those predicted for dry diffusion. Oxygen diffusion coefficients even under wet conditions and elevated temperatures (850 °C) are <1-3×10-23 m2/sec, underscoring a virtual lack of oxygen diffusion and an outstanding survivability of zircons

Impact of oxygen diffusion on superconductivity in YBa2Cu3O7 -δ thin films studied by positron annihilation spectroscopy

NASA Astrophysics Data System (ADS)

Reiner, M.; Gigl, T.; Jany, R.; Hammerl, G.; Hugenschmidt, C.

2018-04-01

The oxygen deficiency δ in YBa2Cu3O7 -δ (YBCO) plays a crucial role for affecting high-temperature superconductivity. We apply (coincident) Doppler broadening spectroscopy of the electron-positron annihilation line to study in situ the temperature dependence of the oxygen concentration and its depth profile in single crystalline YBCO film grown on SrTiO3 (STO) substrates. The oxygen diffusion during tempering is found to lead to a distinct depth dependence of δ , which is not accessible using x-ray diffraction. A steady state reached within a few minutes is defined by both, the oxygen exchange at the surface and at the interface to the STO substrate. Moreover, we reveal the depth-dependent critical temperature Tc in the as prepared and tempered YBCO film.

Effects of Low-Permeability Layers in the Hyporheic Zone on Oxygen Consumption Under Losing and Gaining Groundwater Flow Conditions

NASA Astrophysics Data System (ADS)

Arnon, S.; Krause, S.; Gomez-Velez, J. D.; De Falco, N.

2017-12-01

Recent studies at the watershed scale have demonstrated the dominant role that river bedforms play in driving hyporheic exchange and constraining biogeochemical processes along river corridors. At the reach and bedform scales, modeling studies have shown that sediment heterogeneity significantly modifies hyporheic flow patterns within bedforms, resulting in spatially heterogeneous biogeochemical processes. In this work, we summarize a series of flume experiments to evaluate the effect that low-permeability layers, representative of structural heterogeneity, have on hyporheic exchange and oxygen consumption in sandy streambeds. In this case, we systematically changed the geometry of the heterogeneities, the surface channel flow driving the exchange, and groundwater fluxes (gaining/losing) modulating the exchange. The flume was packed with natural sediments, which were amended with compost to minimize carbon limitations. Structural heterogeneities were represented by continuous and discontinuous layers of clay material. Flow patterns were studied using dye imaging through the side walls. Oxygen distribution in the streambed was measured using planar optodes. The experimental observations revealed that the clay layer had a significant effect on flow patterns and oxygen distribution in the streambed under neutral and losing conditions. Under gaining conditions, the aerobic zone was limited to the upper sections of the bedform and thus was less influenced by the clay layers that were located at a depth of 1-3 cm below the water-sediment interface. We are currently analyzing the results with a numerical flow and transport model to quantify the reactions rates under the different flow conditions and spatial sediment structures. Our preliminary results enable us to show the importance of the coupling between flow conditions, local heterogeneity within the streambed and oxygen consumption along bed forms and are expected to improve our ability to model the effect of stream-groundwater interactions on nutrient cycling.

Metal-air flow batteries using oxygen enriched electrolyte

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

Zheng, Jian-ping; Andrei, Petru; Shellikeri, Annadanesh

A metal air flow battery includes an electrochemical reaction unit and an oxygen exchange unit. The electrochemical reaction unit includes an anode electrode, a cathode electrode, and an ionic conductive membrane between the anode and the cathode, an anode electrolyte, and a cathode electrolyte. The oxygen exchange unit contacts the cathode electrolyte with oxygen separate from the electrochemical reaction unit. At least one pump is provided for pumping cathode electrolyte between the electrochemical reaction unit and the oxygen exchange unit. A method for producing an electrical current is also disclosed.

Metal-air flow batteries using oxygen enriched electrolyte

DOEpatents

Zheng, Jian-ping; Andrei, Petru; Shellikeri, Annadanesh; Chen, Xujie

2017-08-01

A metal air flow battery includes an electrochemical reaction unit and an oxygen exchange unit. The electrochemical reaction unit includes an anode electrode, a cathode electrode, and an ionic conductive membrane between the anode and the cathode, an anode electrolyte, and a cathode electrolyte. The oxygen exchange unit contacts the cathode electrolyte with oxygen separate from the electrochemical reaction unit. At least one pump is provided for pumping cathode electrolyte between the electrochemical reaction unit and the oxygen exchange unit. A method for producing an electrical current is also disclosed.

Steel reinforced composite silicone membranes and its integration to microfluidic oxygenators for high performance gas exchange.

PubMed

Matharoo, Harpreet; Dabaghi, Mohammadhossein; Rochow, Niels; Fusch, Gerhard; Saraei, Neda; Tauhiduzzaman, Mohammed; Veldhuis, Stephen; Brash, John; Fusch, Christoph; Selvaganapathy, P Ravi

2018-01-01

Respiratory distress syndrome (RDS) is one of the main causes of fatality in newborn infants, particularly in neonates with low birth-weight. Commercial extracorporeal oxygenators have been used for low-birth-weight neonates in neonatal intensive care units. However, these oxygenators require high blood volumes to prime. In the last decade, microfluidics oxygenators using enriched oxygen have been developed for this purpose. Some of these oxygenators use thin polydimethylsiloxane (PDMS) membranes to facilitate gas exchange between the blood flowing in the microchannels and the ambient air outside. However, PDMS is elastic and the thin membranes exhibit significant deformation and delamination under pressure which alters the architecture of the devices causing poor oxygenation or device failure. Therefore, an alternate membrane with high stability, low deformation under pressure, and high gas exchange was desired. In this paper, we present a novel composite membrane consisting of an ultra-thin stainless-steel mesh embedded in PDMS, designed specifically for a microfluidic single oxygenator unit (SOU). In comparison to homogeneous PDMS membranes, this composite membrane demonstrated high stability, low deformation under pressure, and high gas exchange. In addition, a new design for oxygenator with sloping profile and tapered inlet configuration has been introduced to achieve the same gas exchange at lower pressure drops. SOUs were tested by bovine blood to evaluate gas exchange properties. Among all tested SOUs, the flat design SOU with composite membrane has the highest oxygen exchange of 40.32 ml/min m 2 . The superior performance of the new device with composite membrane was demonstrated by constructing a lung assist device (LAD) with a low priming volume of 10 ml. The LAD was achieved by the oxygen uptake of 0.48-0.90 ml/min and the CO 2 release of 1.05-2.27 ml/min at blood flow rates ranging between 8 and 48 ml/min. This LAD was shown to increase the oxygen saturation level by 25% at the low pressure drop of 29 mm Hg. Finally, a piglet was used to test the gas exchange capacity of the LAD in vivo . The animal experiment results were in accordance with in-vitro results, which shows that the LAD is capable of providing sufficient gas exchange at a blood flow rate of ∼24 ml/min.

Understanding Groundwater and Surface Water Exchange Processes Along a Controlled Stream Using Thermal Remote Sensing and In-Situ Measurements

NASA Astrophysics Data System (ADS)

Varli, D.; Yilmaz, K. K.

2016-12-01

Effective management of water resources requires understanding and quantification of interaction between groundwater and surface water bodies. Moreover, the exchange processes have recently received increasing attention due to important influences on biogeochemical and ecological status of watersheds. In this study we investigated the exchange processes between surface water and groundwater along Kirmir stream - a controlled stream nearby Kizilcahamam, Ankara, Turkey. At the first stage, potential stream reaches where the exchange processes could occur were pinpointed using geological and geomorphological information. Then, thermal remote sensing was utilized to further narrow down the potential locations in which interaction could occur at a smaller scale. Nested piezometers were installed at identified locations to observe the variations in vertical hydraulic gradient over time. Differential discharge measurements were performed to understand the gains and losses along the stream reach. Streambed temperature measurements were taken at two different depths for a period of time using temperature loggers to calculate the vertical fluid fluxes through the streambed at various locations. Basic water quality field parameters (temperature, electrical conductivity, total dissolved solid amount, dissolved oxygen, pH and oxidation - reduction potential) were measured along the stream reach, from surface water and the piezometers as wells as from the nearby springs and wells. Chloride mass balance was performed to find the contribution of groundwater and chloride concentrations were associated with the geology of the area. This hierarchical, multi-scale methodology provided an efficient and effective way to determine the locations and the direction of groundwater and surface water exchange processes within the study area.

Hydrogen and oxygen isotope exchange reactions between clay minerals and water

USGS Publications Warehouse

O'Neil, J.R.; Kharaka, Y.K.

1976-01-01

The extent of hydrogen and oxygen isotope exchange between clay minerals and water has been measured in the temperature range 100-350?? for bomb runs of up to almost 2 years. Hydrogen isotope exchange between water and the clays was demonstrable at 100??. Exchange rates were 3-5 times greater for montmorillonite than for kaolinite or illite and this is attributed to the presence of interlayer water in the montmorillonite structure. Negligible oxygen isotope exchange occurred at these low temperatures. The great disparity in D and O18 exchange rates observed in every experiment demonstrates that hydrogen isotope exchange occurred by a mechanism of proton exchange independent of the slower process of O18 exchange. At 350?? kaolinite reacted to form pyrophyllite and diaspore. This was accompanied by essentially complete D exchange but minor O18 exchange and implies that intact structural units in the pyrophyllite were inherited from the kaolinite precursor. ?? 1976.

Fast MAS 1H NMR Study of Water Adsorption and Dissociation on the (100) Surface of Ceria Nanocubes: A Fully Hydroxylated, Hydrophobic Ceria Surface

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

Gill, Lance; Beste, Ariana; Chen, Banghao

1H nuclear magnetic resonance (NMR) spectroscopy was used to study hydroxylic surface species on ceria nanocubes, a crystalline, high-surface-area CeO 2 that presents mostly (100) facets. Water adsorption and desorption experiments in combination with fast magic angle spinning (MAS, 20–40 kHz) 1H NMR provide high-resolution 1H spectra that allow the observation of ten resonance bands (water or hydroxyl) on or under the (100) surface. Assignments were made using a combination of adsorption and temperature-programmed desorption, quantitative spin counting, deuterium exchange, spin–lattice (T 1) and spin–spin (T 2) relaxation, and DFT calculations. In air, the (100) surface exists as a fullymore » hydroxylated surface. Water adsorption and dissociation on dry ceria surfaces occur first at oxygen vacancies, but Ce 3+ centers are not required since water dissociation is barrier-less on the fully oxidized surface. Surface $-$OH functionality occurs in two resolved bands representing isolated $-$OH (1 ppm) and hydrogen-bonded $-$OH (9 ppm), the latter being dominant. Deuterium exchange of surface hydroxyls with D 2O does not occur under mild or forcing conditions. Despite large differences in the T 1 of surface hydroxyls and physisorbed water, surface hydroxyl T 1 values are independent of the presence or absence of physisorbed water, demonstrating that the protons within these two functional group pools are not in intimate contact. These observations show that, once hydroxylated, the surface $-$OH functionality preferentially forms hydrogen bonds with surface lattice oxygen, i.e., the hydroxylated (100) surface of ceria is hydrophobic. Near this surface it is energetically more favorable for physisorbed water to hydrogen bond to itself rather than to the surface. DFT calculations support this notion. Impurity Na + remaining in incompletely washed ceria nanocubes increases the surface hydrophilicity. In conclusion, sharp, low-field resonances observed in spectra of noncalcined nanocubes arise from kinetically trapped subsurface $-$OH.« less

Fast MAS 1H NMR Study of Water Adsorption and Dissociation on the (100) Surface of Ceria Nanocubes: A Fully Hydroxylated, Hydrophobic Ceria Surface

DOE PAGES

Gill, Lance; Beste, Ariana; Chen, Banghao; ...

2017-03-22

1H nuclear magnetic resonance (NMR) spectroscopy was used to study hydroxylic surface species on ceria nanocubes, a crystalline, high-surface-area CeO 2 that presents mostly (100) facets. Water adsorption and desorption experiments in combination with fast magic angle spinning (MAS, 20–40 kHz) 1H NMR provide high-resolution 1H spectra that allow the observation of ten resonance bands (water or hydroxyl) on or under the (100) surface. Assignments were made using a combination of adsorption and temperature-programmed desorption, quantitative spin counting, deuterium exchange, spin–lattice (T 1) and spin–spin (T 2) relaxation, and DFT calculations. In air, the (100) surface exists as a fullymore » hydroxylated surface. Water adsorption and dissociation on dry ceria surfaces occur first at oxygen vacancies, but Ce 3+ centers are not required since water dissociation is barrier-less on the fully oxidized surface. Surface $-$OH functionality occurs in two resolved bands representing isolated $-$OH (1 ppm) and hydrogen-bonded $-$OH (9 ppm), the latter being dominant. Deuterium exchange of surface hydroxyls with D 2O does not occur under mild or forcing conditions. Despite large differences in the T 1 of surface hydroxyls and physisorbed water, surface hydroxyl T 1 values are independent of the presence or absence of physisorbed water, demonstrating that the protons within these two functional group pools are not in intimate contact. These observations show that, once hydroxylated, the surface $-$OH functionality preferentially forms hydrogen bonds with surface lattice oxygen, i.e., the hydroxylated (100) surface of ceria is hydrophobic. Near this surface it is energetically more favorable for physisorbed water to hydrogen bond to itself rather than to the surface. DFT calculations support this notion. Impurity Na + remaining in incompletely washed ceria nanocubes increases the surface hydrophilicity. In conclusion, sharp, low-field resonances observed in spectra of noncalcined nanocubes arise from kinetically trapped subsurface $-$OH.« less

Application of an eddy correlation system for the estimation of oxygen benthic fluxes in coastal permeable sediments impacted by submarine groundwater discharge

NASA Astrophysics Data System (ADS)

Donis, D.; Janssen, F.; Böttcher, M.; McGinnis, D.; Holtappels, M.; Wenzhöfer, F.

2012-04-01

Measurements of solute exchange across the sediment-water interface are crucial for marine environment monitoring. This interface has fundamental filter functions for the mass exchange between the seafloor and the water column. Being a non-invasive technique, the eddy correlation method, is probably the most accurate measurement for benthic fluxes. It does not interfere with local hydrodynamics and integrates over large areas, showing considerable advantages compared to traditional methods, i.e., microprofiles and benthic chambers. One of the most important exchange processes across the sediment-water interface is flux of oxygen, which is a predominant control factor for the biogeochemical activity in the sediment, carbon processing and the composition of benthic communities. The eddy correlation method performs simultaneous recordings of vertical velocities and oxygen concentrations at a specific distance to the seafloor and is becoming a standard method for resolving dissolved oxygen fluxes in aquatic systems. However, data treatment and interpretation, especially in shallow environments, is still challenging. One major concern in eddy correlation studies of coastal environments is how to consider surface wave motions that can dominate the turbulence range and that may bias flux calculations. A critical part of the data treatment thus is the removal of wave biases from the vertical velocity component, by separating the wave frequency oscillations (due to a tilted or miss-aligned sensor) from those containing meaningful flux contributions. Here we present in situ benthic oxygen exchange rates as determined by an eddy correlation system (ECS) and simultaneously deployed stirred benthic chambers. The study was carried out in a coastal ecosystem of the southern Baltic Sea that was impacted by low salinity groundwater discharge (Hel peninsula, Poland). Oxygen fluxes determined with ECS compared well with results from benthic chambers. Flux data and seepage rates are discussed in the context of groundwater and their importance for benthic biogeochemical processes in shallow sandy sediments. This work was supported by 7th framework EU ITN-project SENSEnet and BONUS+ project AMBER.

Oxygen isotope exchange with quartz during pyrolysis of silver sulfate and silver nitrate.

PubMed

Schauer, Andrew J; Kunasek, Shelley A; Sofen, Eric D; Erbland, Joseph; Savarino, Joel; Johnson, Ben W; Amos, Helen M; Shaheen, Robina; Abaunza, Mariana; Jackson, Terri L; Thiemens, Mark H; Alexander, Becky

2012-09-30

Triple oxygen isotopes of sulfate and nitrate are useful metrics for the chemistry of their formation. Existing measurement methods, however, do not account for oxygen atom exchange with quartz during the thermal decomposition of sulfate. We present evidence for oxygen atom exchange, a simple modification to prevent exchange, and a correction for previous measurements. Silver sulfates and silver nitrates with excess (17)O were thermally decomposed in quartz and gold (for sulfate) and quartz and silver (for nitrate) sample containers to O(2) and byproducts in a modified Temperature Conversion/Elemental Analyzer (TC/EA). Helium carries O(2) through purification for isotope-ratio analysis of the three isotopes of oxygen in a Finnigan MAT253 isotope ratio mass spectrometer. The Δ(17)O results show clear oxygen atom exchange from non-zero (17)O-excess reference materials to zero (17)O-excess quartz cup sample containers. Quartz sample containers lower the Δ(17)O values of designer sulfate reference materials and USGS35 nitrate by 15% relative to gold or silver sample containers for quantities of 2-10 µmol O(2). Previous Δ(17)O measurements of sulfate that rely on pyrolysis in a quartz cup have been affected by oxygen exchange. These previous results can be corrected using a simple linear equation (Δ(17)O(gold) = Δ(17)O(quartz) * 1.14 + 0.06). Future pyrolysis of silver sulfate should be conducted in gold capsules or corrected to data obtained from gold capsules to avoid obtaining oxygen isotope exchange-affected data. Copyright © 2012 John Wiley & Sons, Ltd.

Effect of mineral surface properties (alumina, kaolinite) on the sorptive fractionation mechanisms of soil fulvic acids: Molecular-scale ESI-MS studies

NASA Astrophysics Data System (ADS)

Fleury, Guillaume; Del Nero, Mirella; Barillon, Rémi

2017-01-01

We addressed the effects of mineral surface properties (kaolinite versus Al-oxide) on the sorption-driven fractionation of a soil fulvic acid (FA) at acidic pH, mainly by means of ESI(-)-FTMS analysis of initial and supernatant solutions of FA sorption batch experiments. The MS data provided clear molecular-scale evidence of distinct mechanisms and molecular parameters controlling the FA fractionation upon its sorption on clay and oxide surfaces, respectively. Identification of sorbing and not-sorbing FA compounds in kaolinite-solution systems revealed a weak fractionation among members of sbnd CO2 series of aliphatics or not-condensed aromatics (NCAs) at pH 3.8, and almost no sorption of poorly-oxygenated polycyclic aromatic compounds (PACs) and NCAs. This first molecular-scale description of a FA fractionation in a clay-solution system suggests that H-bonding with low affinity sites (aluminol/silanol) on the basal planes of the clay particles is the main mechanism of sorption. Due to the predominance of such weak and poorly-selective mechanism, the sorption of aliphatic and NCA molecules bearing oxygenated functionalities was prevented at pH 5, due to dissolved Al competing successfully for their coordination. In contrast, a strong FA fractionation was observed onto alumina, with a preferential retention of PACs and highly-oxygenated aliphatics and NCAs. The major part of the poorly oxygenated aliphatics was left in solution. The sorption degree of NCAs and aliphatics was strongly correlated with molecular acidity. For PACs and poorly-oxygenated NCAs, the sorption was driven by reactions of surface ligand exchange (for the most oxygenated compounds) or by hydrophobic interactions (for the least oxygenated compounds).

Optimal villi density for maximal oxygen uptake in the human placenta.

PubMed

Serov, A S; Salafia, C M; Brownbill, P; Grebenkov, D S; Filoche, M

2015-01-07

We present a stream-tube model of oxygen exchange inside a human placenta functional unit (a placentone). The effect of villi density on oxygen transfer efficiency is assessed by numerically solving the diffusion-convection equation in a 2D+1D geometry for a wide range of villi densities. For each set of physiological parameters, we observe the existence of an optimal villi density providing a maximal oxygen uptake as a trade-off between the incoming oxygen flow and the absorbing villus surface. The predicted optimal villi density 0.47±0.06 is compatible to previous experimental measurements. Several other ways to experimentally validate the model are also proposed. The proposed stream-tube model can serve as a basis for analyzing the efficiency of human placentas, detecting possible pathologies and diagnosing placental health risks for newborns by using routine histology sections collected after birth. Copyright © 2014 Elsevier Ltd. All rights reserved.

Thermal and Electrical Stability of Sr 0.9Y 0.1CoO 2.5+δ as a Promising Cathode for Intermediate-Temperature Solid Oxide Fuel Cells

DOE PAGES

Jiang, Long; Wang, Jie; Xiong, Xiaolei; ...

2016-01-21

Here, the present study reports thermal and electrical properties of Sr 1-xYxCoO 2.5+δ (x = 0–0.40) as a promising cathode for intermediatetemperature solid oxide fuel cells. The results show that x = 0.10 is the best composition possessing a single primitive cubic perovskite structure, stable conductivity and the lowest polarization resistance. Thermogravimetric analysis indicates an oxygen intake from RT to ~375°C, above which oxygen loss occurs. The oxygen gain-loss behavior corresponds well with the conductivity increase-decrease trending, reflecting that oxygen-nonstoichiometry controls the hole-concentration (or oxidation-state of Co-ions). Electrochemical impedance spectroscopy analysis further reveals that the overall ORR polarization consists ofmore » a faster charge-transfer and a slower surface oxygen exchange.« less

Thermal and Electrical Stability of Sr 0.9Y 0.1CoO 2.5+δ as a Promising Cathode for Intermediate-Temperature Solid Oxide Fuel Cells

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

Jiang, Long; Wang, Jie; Xiong, Xiaolei

Here, the present study reports thermal and electrical properties of Sr 1-xYxCoO 2.5+δ (x = 0–0.40) as a promising cathode for intermediatetemperature solid oxide fuel cells. The results show that x = 0.10 is the best composition possessing a single primitive cubic perovskite structure, stable conductivity and the lowest polarization resistance. Thermogravimetric analysis indicates an oxygen intake from RT to ~375°C, above which oxygen loss occurs. The oxygen gain-loss behavior corresponds well with the conductivity increase-decrease trending, reflecting that oxygen-nonstoichiometry controls the hole-concentration (or oxidation-state of Co-ions). Electrochemical impedance spectroscopy analysis further reveals that the overall ORR polarization consists ofmore » a faster charge-transfer and a slower surface oxygen exchange.« less

Microwave plasma induced surface modification of diamond-like carbon films

NASA Astrophysics Data System (ADS)

Rao Polaki, Shyamala; Kumar, Niranjan; Gopala Krishna, Nanda; Madapu, Kishore; Kamruddin, Mohamed; Dash, Sitaram; Tyagi, Ashok Kumar

2017-12-01

Tailoring the surface of diamond-like carbon (DLC) film is technically relevant for altering the physical and chemical properties, desirable for useful applications. A physically smooth and sp3 dominated DLC film with tetrahedral coordination was prepared by plasma-enhanced chemical vapor deposition technique. The surface of the DLC film was exposed to hydrogen, oxygen and nitrogen plasma for physical and chemical modifications. The surface modification was based on the concept of adsorption-desorption of plasma species and surface entities of films. Energetic chemical species of microwave plasma are adsorbed, leading to desorbtion of the surface carbon atoms due to energy and momentum exchange. The interaction of such reactive species with DLC films enhanced the roughness, surface defects and dangling bonds of carbon atoms. Adsorbed hydrogen, oxygen and nitrogen formed a covalent network while saturating the dangling carbon bonds around the tetrahedral sp3 valency. The modified surface chemical affinity depends upon the charge carriers and electron covalency of the adsorbed atoms. The contact angle of chemically reconstructed surface increases when a water droplet interacts either through hydrogen or van dear Waals bonding. These weak interactions influenced the wetting property of the DLC surface to a great extent.

Acetone Chemistry on Oxidized and Reduced TiO 2(110)

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

Henderson, Michael A

2004-12-09

The chemistry of acetone on the oxidized and reduced surfaces of TiO 2(110) was examined using temperature programmed desorption (TPD) and high resolution electron energy loss spectroscopy (HREELS). The reduced surface was prepared with about 7% oxygen vacancy sites by annealing in ultrahigh vacuum (UHV) at 850 K, and the oxidized surface was prepared by exposure of the reduced surface to molecular oxygen at 95 K followed by heating the surface to a variety of temperatures between 200 and 500 K. Acetone adsorbs molecularly on the reduced surface with no evidence for either decomposition or preferential binding at vacancy sites.more » Based on HREELS, the majority of acetone molecules adsorbed in an η¹ configuration at Ti⁴⁺ sites through interaction of lone pair electrons on the carbonyl oxygen atom. Repulsive acetone-acetone interactions shift the desorption peak from 345 K at low coverage to 175 K as the first layer saturates with a coverage of ~ 1 ML. In contrast, about 7% of the acetone adlayer decomposes when the surface is pretreated with molecular oxygen. Acetate is among the detected decomposition products, but only comprises about 1/3rd of the amount of acetone decomposed and its yield depends on the temperature at which the O₂ exposed surface was preheated to prior to acetone adsorption. Aside from the small level of irreversible decomposition, about 0.25 ML of acetone is stabilized to 375 K by coadsorbed oxygen. These acetone species exhibit an HREELS spectrum unlike that of η¹-acetone or of any other species proposed to exist from the interaction of acetone with TiO₂ powders. Based on the presence of extensive ¹⁶O/¹⁸O exchange between acetone and coadsorbed oxygen in the 375 K acetone TPD state, it is proposed that a polymeric form of acetone forms on the TiO₂(110) surface through nucleophilic attack of oxygen on the carbonyl carbon atom of acetone, and is propagated to neighboring η¹-acetone molecules. This process is initiated at temperatures as low as 135 K based on HREELS. Although the dominant thermal pathway of this surface species is to liberate acetone in UHV, it may be a key intermediate in acetone thermal and photolytic chemistry on TiO₂ surfaces.« less

Kinetics of oxygen interstitial injection and lattice exchange in rutile TiO{sub 2}

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

Gorai, Prashun; Hollister, Alice G.; Pangan-Okimoto, Kristine

2014-05-12

The existence of a facile surface pathway for generation of O interstitials (O{sub i}) in rutile that can facilitate annihilation of O undesirable vacancies has been demonstrated recently. Through isotopic self-diffusion experiments, the present work determines a value of approximately 1.8 eV for the activation energy of O{sub i} injection from TiO{sub 2} (110). The mean path length for O{sub i} diffusion decreases by nearly an order of magnitude upon adsorption of 0.1 monolayer of sulfur. Sulfur apparently inhibits the surface annihilation rate of Ti interstitials, lowering their bulk concentration and the corresponding catalytic effect they seem to exert upon O{submore » i} exchange with the lattice.« less

Polymer Electrolyte Membranes for Water Photo-Electrolysis

PubMed Central

Aricò, Antonino S.; Girolamo, Mariarita; Siracusano, Stefania; Sebastian, David; Baglio, Vincenzo; Schuster, Michael

2017-01-01

Water-fed photo-electrolysis cells equipped with perfluorosulfonic acid (Nafion® 115) and quaternary ammonium-based (Fumatech® FAA3) ion exchange membranes as separator for hydrogen and oxygen evolution reactions were investigated. Protonic or anionic ionomer dispersions were deposited on the electrodes to extend the interface with the electrolyte. The photo-anode consisted of a large band-gap Ti-oxide semiconductor. The effect of membrane characteristics on the photo-electrochemical conversion of solar energy was investigated for photo-voltage-driven electrolysis cells. Photo-electrolysis cells were also studied for operation under electrical bias-assisted mode. The pH of the membrane/ionomer had a paramount effect on the photo-electrolytic conversion. The anionic membrane showed enhanced performance compared to the Nafion®-based cell when just TiO2 anatase was used as photo-anode. This was associated with better oxygen evolution kinetics in alkaline conditions compared to acidic environment. However, oxygen evolution kinetics in acidic conditions were significantly enhanced by using a Ti sub-oxide as surface promoter in order to facilitate the adsorption of OH species as precursors of oxygen evolution. However, the same surface promoter appeared to inhibit oxygen evolution in an alkaline environment probably as a consequence of the strong adsorption of OH species on the surface under such conditions. These results show that a proper combination of photo-anode and polymer electrolyte membrane is essential to maximize photo-electrolytic conversion. PMID:28468242

Polymer Electrolyte Membranes for Water Photo-Electrolysis.

PubMed

Aricò, Antonino S; Girolamo, Mariarita; Siracusano, Stefania; Sebastian, David; Baglio, Vincenzo; Schuster, Michael

2017-04-29

Water-fed photo-electrolysis cells equipped with perfluorosulfonic acid (Nafion ® 115) and quaternary ammonium-based (Fumatech ® FAA3) ion exchange membranes as separator for hydrogen and oxygen evolution reactions were investigated. Protonic or anionic ionomer dispersions were deposited on the electrodes to extend the interface with the electrolyte. The photo-anode consisted of a large band-gap Ti-oxide semiconductor. The effect of membrane characteristics on the photo-electrochemical conversion of solar energy was investigated for photo-voltage-driven electrolysis cells. Photo-electrolysis cells were also studied for operation under electrical bias-assisted mode. The pH of the membrane/ionomer had a paramount effect on the photo-electrolytic conversion. The anionic membrane showed enhanced performance compared to the Nafion ® -based cell when just TiO₂ anatase was used as photo-anode. This was associated with better oxygen evolution kinetics in alkaline conditions compared to acidic environment. However, oxygen evolution kinetics in acidic conditions were significantly enhanced by using a Ti sub-oxide as surface promoter in order to facilitate the adsorption of OH species as precursors of oxygen evolution. However, the same surface promoter appeared to inhibit oxygen evolution in an alkaline environment probably as a consequence of the strong adsorption of OH species on the surface under such conditions. These results show that a proper combination of photo-anode and polymer electrolyte membrane is essential to maximize photo-electrolytic conversion.

Biochar production method and composition therefrom

DOEpatents

Lee, James W; Buchanan, III, Archibald C; Evans, Barbara R; Kidder, Michelle K

2014-04-29

The invention is directed to a method for producing an oxygenated biochar material possessing a cation-exchanging property, wherein a biochar source is reacted with one or more oxygenating compounds in such a manner that the biochar source homogeneously acquires oxygen-containing cation-exchanging groups in an incomplete combustion process. The invention is also directed to oxygenated biochar compositions and soil formulations containing the oxygenated biochar material.

Biochar production method and composition therefrom

DOEpatents

Lee, James W.; Buchanan, III, Archibald C.; Evans, Barbara R.; Kidder, Michelle K.

2013-03-19

The invention is directed to a method for producing an oxygenated biochar material possessing a cation-exchanging property, wherein a biochar source is reacted with one or more oxygenating compounds in such a manner that the biochar source homogeneously acquires oxygen-containing cation-exchanging groups in an incomplete combustion process. The invention is also directed to oxygenated biochar compositions and soil formulations containing the oxygenated biochar material.

Estimating oxygen diffusive conductances of gas-exchange systems: A stereological approach illustrated with the human placenta.

PubMed

Mayhew, Terry M

2014-01-01

For many organisms, respiratory gas exchange is a vital activity and different types of gas-exchange apparatus have evolved to meet individual needs. They include not only skin, gills, tracheal systems and lungs but also transient structures such as the chorioallantois of avian eggs and the placenta of eutherian mammals. The ability of these structures to allow passage of oxygen by passive diffusion can be expressed as a diffusive conductance (units: cm(3) O2 min(-1) kPa(-1)). Occasionally, the ability to estimate diffusive conductance by physiological techniques is compromised by the difficulty of obtaining O2 partial pressures on opposite sides of the tissue interface between the delivery medium (air, water, blood) and uptake medium (usually blood). An alternative strategy is to estimate a morphometric diffusive conductance by combining stereological estimates of key structural quantities (volumes, surface areas, membrane thicknesses) with complementary physicochemical data (O2-haemoglobin chemical reaction rates and Krogh's permeability coefficients). This approach has proved valuable in a variety of comparative studies on respiratory organs from diverse species. The underlying principles were formulated in pioneering studies on the pulmonary lung but are illustrated here by taking the human placenta as the gas exchanger. Copyright © 2012 Elsevier GmbH. All rights reserved.

In vitro performance testing of a pediatric oxygenator with an integrated pulsatile pump.

PubMed

Borchardt, Ralf; Schlanstein, Peter; Mager, Ilona; Arens, Jutta; Schmitz-Rode, Thomas; Steinseifer, Ulrich

2012-01-01

For different lung and heart diseases (e.g., acute respiratory distress syndrome, congenital heart failure, and cardiomyopathy) extracorporeal membrane oxygenation is a well-established therapy, particularly in the field of neonatal and pediatric medicine. To reduce the priming volume of the extracorporeal circuit, different components can be combined. In this study, an oval-shaped oxygenator (called ExMeTrA) with integrated pulsatile pump was tested in vitro using porcine blood. A feasibility study regarding the performance of collapsing and expanding silicone tubes within an oxygenator fiber bundle as a pulsatile pump was previously completed with successful results. The findings of this study improve upon the previous feasibility results, particularly in terms of gas exchange and filling volume. Five modules were manufactured in sizes of 20 ± 2.2 ml (priming volume) with fiber surface areas of 0.24 ± 0.027 m(2) and an analytically calculated volume pumping capacity of 692 ± 75 ml/min. The modules were made of polymethylpentene fibers with dense outer layer to permit long-term applications. The gas exchange rates at a gas/blood flow ratio of 2:1 were between 64 and 72.7 ml(O)(2)/l(blood) and between 62.5 and 81.5 ml/l(blood), depending on the blood flow. The individual module's pumping capacity ranged from 200-500 ml/min thus providing room for further improvements. In order to enhance the pumping capacity while maintaining sufficient gas exchange rates future optimization, adjustments will be made to the inlet and outlet geometries.

Stable Isotope Characteristics of Jarosite: The Acidic Aqueous History of Mars

NASA Technical Reports Server (NTRS)

Earl, Lyndsey D.

2005-01-01

The Mars Rover Opportunity found jarosite (Na(+) or K(+))Fe3SO4(OH)6 at the Meridiani Planum site. This mineral forms from the evaporation of an aqueous acidic sulfate brine. Oxygen isotope compositions may characterize formation conditions but subsequent isotope exchange may have occurred between the sulfate and hydroxide of jarosite and water. The rate of oxygen isotope exchange depends on the acidity and temperature of the brine, but it has not been investigated in detail. We performed laboratory experiments to determine the rate of oxygen isotope exchange under varying acidities and temperatures to learn more about this process. Barium sulfate samples were precipitated weekly from acidic sodium sulfate brines. The oxygen isotope composition of the precipitated sulfate was obtained using a Finnigan MAT253 Isotope Ratio Mass-Spectrometer. The results show that water was trapped in barium sulfate during precipitation. Trapped water may exchange with sulfate when exposed to high temperatures, thus changing the isotope composition of sulfate and the observed fractionation factor of oxygen isotope exchange between sulfate and water. The results of our research will contribute to the understanding of oxygen isotope exchange rates between water and sulfate under acidic conditions and provide experimental knowledge for the dehydration of barium sulfate samples.

High surface area synthesis, electrochemical activity, and stability of tungsten carbide supported Pt during oxygen reduction in proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Chhina, H.; Campbell, S.; Kesler, O.

The oxidation of carbon catalyst supports to carbon dioxide gas leads to degradation in catalyst performance over time in proton exchange membrane fuel cells (PEMFCs). The electrochemical stability of Pt supported on tungsten carbide has been evaluated on a carbon-based gas diffusion layer (GDL) at 80 °C and compared to that of HiSpec 4000™ Pt/Vulcan XC-72R in 0.5 M H 2SO 4. Due to other electrochemical processes occurring on the GDL, detailed studies were also performed on a gold mesh substrate. The oxygen reduction reaction (ORR) activity was measured both before and after accelerated oxidation cycles between +0.6 V and +1.8 V vs. RHE. Tafel plots show that the ORR activity remained high even after accelerated oxidation tests for Pt/tungsten carbide, while the ORR activity was extremely poor after accelerated oxidation tests for HiSpec 4000™. In order to make high surface area tungsten carbide, three synthesis routes were investigated. Magnetron sputtering of tungsten on carbon was found to be the most promising route, but needs further optimization.

OXYGEN 18 EXCHANGE REACTIONS OF ALDEHYDES AND KETONES

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

Byrn, Marianne; Calvin, Melvin

1965-12-01

Using infra-red spectroscopy, the equilibrium exchange times have been determined for a series of ketones, aromatic aldehydes, and {beta}-ketoesters reacting with oxygen 18 enriched water. These exchange times have been evaluated in terms of steric and electronic considerations, and applied to a discussion of the exchange times of chlorophylls a and b and chlorophyll derivatives.

In situ investigation on ultrafast oxygen evolution reactions of water splitting in proton exchange membrane electrolyzer cells

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

Mo, Jingke; Kang, Zhenye; Yang, Gaoqiang

We present that the oxygen evolution reaction (OER) is a half reaction in electrochemical devices, including low-temperature water electrolysis, which is considered as one of the most promising methods to generate hydrogen/oxygen for the storage of energy. It is affected by many factors, and its mechanism is still not completely understood. A proton exchange membrane electrolyzer cell (PEMEC) with optical access to the surface of anode catalyst layer (CL) coupled with a distinguished high-speed and micro-scale visualization system (HMVS) was developed to in situ investigate OERs. It was revealed in real time that OERs only occur on the anode CLmore » adjacent to liquid/gas diffusion layer (LGDL). The CL electrical conductivity plays a crucial role in OERs on CLs. The large in-plane electrical resistance of CLs becomes a threshold of OERs over the entire CL, and causes a lot of catalyst waste in the middle of LGDL pores. Moreover, the oxygen bubble nucleation, growth, and detachment and the effect of current density on those processes were also characterized. Here, this study proposes a new approach for better understanding the mechanisms of OERs and optimizing the design and fabrication of membrane electrode assemblies.« less

In situ investigation on ultrafast oxygen evolution reactions of water splitting in proton exchange membrane electrolyzer cells

DOE PAGES

Mo, Jingke; Kang, Zhenye; Yang, Gaoqiang; ...

2017-08-25

We present that the oxygen evolution reaction (OER) is a half reaction in electrochemical devices, including low-temperature water electrolysis, which is considered as one of the most promising methods to generate hydrogen/oxygen for the storage of energy. It is affected by many factors, and its mechanism is still not completely understood. A proton exchange membrane electrolyzer cell (PEMEC) with optical access to the surface of anode catalyst layer (CL) coupled with a distinguished high-speed and micro-scale visualization system (HMVS) was developed to in situ investigate OERs. It was revealed in real time that OERs only occur on the anode CLmore » adjacent to liquid/gas diffusion layer (LGDL). The CL electrical conductivity plays a crucial role in OERs on CLs. The large in-plane electrical resistance of CLs becomes a threshold of OERs over the entire CL, and causes a lot of catalyst waste in the middle of LGDL pores. Moreover, the oxygen bubble nucleation, growth, and detachment and the effect of current density on those processes were also characterized. Here, this study proposes a new approach for better understanding the mechanisms of OERs and optimizing the design and fabrication of membrane electrode assemblies.« less

Ultrasound-mediated oxygen delivery from chitosan nanobubbles.

PubMed

Cavalli, Roberta; Bisazza, Agnese; Rolfo, Alessandro; Balbis, Sonia; Madonnaripa, Daniele; Caniggia, Isabella; Guiot, Caterina

2009-08-13

Ultrasound (US) energy combined with gas-filled microbubbles has been used for several years in medical imaging. This study investigated the ability of oxygen-loaded chitosan bubbles to exchange oxygen in the presence or in the absence of US. Oxygen delivery is enhanced by sonication and both frequency and time duration of US affected the exchange kinetics.

Volume to Surface Area Ratios of Foraminifera over the Phanerozoic

NASA Astrophysics Data System (ADS)

Cheung, K.; Gomez, D.; Guo, D.; Jost, A.; Payne, J.

2010-12-01

Although there have been numerous studies regarding the issue of the volume to surface area ratio, no study has been extensive enough to include over 35000 species of foraminifera. The Stanford Paleobiology lab undertook the enormous task of extracting from the Catalogue of Foraminifera, by Ellis and Messina, all relevant data of the foraminifera, such as the three dimensions of the organism, the magnification, and the time period in which the organism existed. For the purpose of calculating the volume and surface area, the foraminifera were generalized as ellipsoids. It is known that the surface area of foraminifera represents where the exchange between the interior body and exterior environment of the foraminifera occurs. The volume of the foraminifera indicates the physical needs of the foraminifera. With more volume in foraminifera, more body functions are occurring and more exterior resources are needed to sustain those bodily functions. Thus with a larger volume to surface area ratio, foraminifera are disadvantaged because they must use more effort in order to acquire adequate resources to fulfill their biological needs. So, the hypothesis is that when there is an increase in oxygen (a vital exterior resource of the foraminifera), the average volume to surface area ratio would be greater because the abundance of oxygen allows foraminifera to work with greater ease in maintaining an exterior resource that they cannot survive without. To prove or refute this assertion, graphs were generated in this study; the graphs indeed suggested that there is a correlation between the volume to surface area ratios and oxygen levels, illustrating that it is plausible that oxygen is a limiting factor of the volume to surface area ratio in foraminifera.

New electrocatalysts for unitized regenerative fuel cell: Pt-Ir alloy deposited on the proton exchange membrane surface by impregnation-reduction method.

PubMed

Wan, Chieh-Hao; Wu, Chun-Lin; Lin, Meng-Tsun; Shih, Chihhsiong

2010-07-01

In this paper, a modified technique to prepare Pt-Ir catalyst layer on the proton exchange membrane (PEM) surface using the impregnation-reduction (IR) method is proposed to improve the electrocatalytic activity as well as the life cycle of the bifunctional oxygen electrode (BOE). The resulted electrocatalysts were characterized by the Scanning Electron Microscopy (SEM), X-ray Diffraction (XRD), Electron Probe Micro-Analysis (EPMA), and Transmission Electron Microscope (TEM). The electrocatalytic properties of the Pt-Ir layer on PEM surface for the oxygen reduction and water oxidation reactions as well as the life cycle of MEA were investigated. Experimental results showed that the Ir particles were dispersed densely in the platinum layer through the modified IR technique. The atomic ratio of Pt over Ir elements was 9:1, and the resulted thickness of the obtained Pt-Ir catalyst layer was about 1.0 microm. The Pt-Ir catalyst layer was composed of Pt layer doped with Ir nano-particles comprising nano Pt-Ir alloy phase. The large surface area of Ir core with Pt shell particles and the presence of nano Pt-Ir alloy phase led to a higher electrocatalytic activity of BOE. Due to the good binding between the Nafion membrane and the Pt-Ir alloy catalyst, as well as the composite structure of the resulted Pt-Ir, the life cycle of Unitized Regenerative Fuel Cell (URFC) is improved through this novel BOE.

The role of water exchange between a stream channel and its hyporheic zone in nitrogen cycling at the terrestrial-aquatic interface

USGS Publications Warehouse

Triska, F.J.; Duff, J.H.; Avanzino, R.J.

1993-01-01

The subsurface riparian zone was examined as an ecotone with two interfaces. Inland is a terrestrial boundary, where transport of water and dissolved solutes is toward the channel and controlled by watershed hydrology. Streamside is an aquatic boundary, where exchange of surface water and dissolved solutes is bi-directional and flux is strongly influenced by channel hydraulics. Streamside, bi-directional exchange of water was qualitatively defined using biologically conservative tracers in a third order stream. In several experiments, penetration of surface water extended 18 m inland. Travel time of water from the channel to bankside sediments was highly variable. Subsurface chemical gradients were indirectly related to the travel time. Sites with long travel times tended to be low in nitrate and DO (dissolved oxygen) but high in ammonium and DOC (dissolved organic carbon). Sites with short travel times tended to be high in nitrate and DO but low in ammonium and DOC. Ammonium concentration of interstitial water also was influenced by sorption-desorption processes that involved clay minerals in hyporheic sediments. Denitrification potential in subsurface sediments increased with distance from the channel, and was limited by nitrate at inland sites and by DO in the channel sediments. Conversely, nitrification potential decreased with distance from the channel, and was limited by DO at inland sites and by ammonium at channel locations. Advection of water and dissolved oxygen away from the channel resulted in an oxidized subsurface habitat equivalent to that previously defined as the hyporheic zone. The hyporheic zone is viewed as stream habitat because of its high proportion of surface water and the occurrence of channel organisms. Beyond the channel's hydrologic exchange zone, interstitial water is often chemically reduced. Interstitial water that has not previously entered the channel, groundwater, is viewed as a terrestrial component of the riparian ecotone. Thus, surface water habitats may extend under riparian vegetation, and terrestrial groundwater habitats may be found beneath the stream channel. ?? 1993 Kluwer Academic Publishers.

Cuticular gas exchange by Antarctic sea spiders.

PubMed

Lane, Steven J; Moran, Amy L; Shishido, Caitlin M; Tobalske, Bret W; Woods, H Arthur

2018-04-25

Many marine organisms and life stages lack specialized respiratory structures, like gills, and rely instead on cutaneous respiration, which they facilitate by having thin integuments. This respiratory mode may limit body size, especially if the integument also functions in support or locomotion. Pycnogonids, or sea spiders, are marine arthropods that lack gills and rely on cutaneous respiration but still grow to large sizes. Their cuticle contains pores, which may play a role in gas exchange. Here, we examined alternative paths of gas exchange in sea spiders: (1) oxygen diffuses across pores in the cuticle, a common mechanism in terrestrial eggshells, (2) oxygen diffuses directly across the cuticle, a common mechanism in small aquatic insects, or (3) oxygen diffuses across both pores and cuticle. We examined these possibilities by modeling diffusive oxygen fluxes across all pores in the body of sea spiders and asking whether those fluxes differed from measured metabolic rates. We estimated fluxes across pores using Fick's law parameterized with measurements of pore morphology and oxygen gradients. Modeled oxygen fluxes through pores closely matched oxygen consumption across a range of body sizes, which means the pores facilitate oxygen diffusion. Furthermore, pore volume scaled hypermetrically with body size, which helps larger species facilitate greater diffusive oxygen fluxes across their cuticle. This likely presents a functional trade-off between gas exchange and structural support, in which the cuticle must be thick enough to prevent buckling due to external forces but porous enough to allow sufficient gas exchange. © 2018. Published by The Company of Biologists Ltd.

Numerical modeling of fluid and oxygen exchanges through microcirculation for the assessment of microcirculation alterations caused by type 2 diabetes.

PubMed

Tang, Yuanliang; He, Ying

2018-05-01

Type 2 diabetes mellitus (DM2) is frequently accompanied by microcirculation complications, including structural and functional alterations, which may have serious effects on substance exchanges between blood and interstitial tissue and the health of organs. In this paper, we aim to study the influence of microcirculation alterations in DM2 patients on fluid and oxygen exchanges through a model analysis. A fluid flow and oxygen transport model were developed by considering the interplay between blood in capillary network and interstitial tissue. The two regions were separately represented by 1D network model and 3D volume model, and the immersed boundary method (IBM) was adopted to solve fluid and mass transfer between these two regions. By using the model, the steady flow field and the distributions of oxygen in capillary network and surrounding tissue were firstly simulated. In the interstitial volume, fluid pressure and oxygen tension decreased with the increase of distance from the network; in the network, oxygen tension in blood plasma dropped from 100 mm Hg at the entrance to about 40 mm Hg at the exit. We further tested several structural and functional disorders related to diabetic pathological conditions. Simulated results show that the impaired connectivity of the network could result in poor robustness in maintaining blood flow and perfused surface; under high fluid permeability conditions of capillary walls, the pressure gradient was much larger around the capillary bed, and this alteration led to a saturation level of the interstitial pressure when lymphatic flow drainage can't work effectively; the variations in network connectivity and permeability of capillary wall also had unfavorable influence on oxygen distributions in interstitial tissue. In addition, when the oxygen releasing capacity of hemoglobin was confined by glycosylated hemoglobin (HbA1) in the case of diabetes, the plasma could not be complemented with adequate oxygen and thus the hypoxic tissue range will be extended. This study illustrates that when microcirculation disturbances, including the structure of capillary network, the wall osmosis property and the capacity of blood binding oxygen occur in DM2, some negative impacts are raised on microvascular hemodynamics and metabolism circumstance of interstitial tissue. Copyright © 2018 Elsevier Inc. All rights reserved.

Processes for washing a spent ion exchange bed and for treating biomass-derived pyrolysis oil, and apparatuses for treating biomass-derived pyrolysis oil

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

Baird, Lance Awender; Brandvold, Timothy A.

Processes and apparatuses for washing a spent ion exchange bed and for treating biomass-derived pyrolysis oil are provided herein. An exemplary process for washing a spent ion exchange bed employed in purification of biomass-derived pyrolysis oil includes the step of providing a ion-depleted pyrolysis oil stream having an original oxygen content. The ion-depleted pyrolysis oil stream is partially hydrotreated to reduce the oxygen content thereof, thereby producing a partially hydrotreated pyrolysis oil stream having a residual oxygen content that is less than the original oxygen content. At least a portion of the partially hydrotreated pyrolysis oil stream is passed throughmore » the spent ion exchange bed. Water is passed through the spent ion exchange bed after passing at least the portion of the partially hydrotreated pyrolysis oil stream therethrough.« less

Interaction of oxygen with ZrC(001) and VC(001): Photoemission and first-principles studies

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

Rodriguez, J.A.; Liu, P.; Gomes, J.

2005-08-15

High-resolution photoemission and first-principles density-functional calculations were used to study the interaction of oxygen with ZrC(001) and VC(001) surfaces. Atomic oxygen is present on the carbide substrates after small doses of O{sub 2} at room temperature. At 500 K, the oxidation of the surfaces is fast and clear features for ZrO{sub x} or VO{sub x} are seen in the O(1s), Zr(3d), and V(2p{sub 3/2}) core levels spectra, with an increase in the metal/carbon ratio of the samples. A big positive shift (1.3-1.6 eV) was detected for the C 1s core level in O/ZrC(001), indicating the existence of strong O{r_reversible}C ormore » C{r_reversible}C interactions. A phenomenon corroborated by the results of first-principles calculations, which show a CZrZr hollow as the most stable site for the adsorption of O. Furthermore, the calculations also show that a C{r_reversible}O exchange is exothermic on ZrC(001), and the displaced C atoms bond to CZrZr sites. In the O/ZrC(001) interface, the surface C atoms play a major role in determining the behavior of the system. In contrast, the adsorption of oxygen induces very minor changes in the C(1s) spectrum of VC(001). The O{r_reversible}V interactions are stronger than the O{r_reversible}Zr interactions, and O{r_reversible}C interactions do not play a dominant role in the O/VC(001) interface. In this system, C{r_reversible}O exchange is endothermic. VC(001) has a larger density of metal d states near the Fermi level than ZrC(001), but the rate of oxidation of VC(001) is slower. Therefore the O/ZrC(001) and O/VC(001) systems illustrate two different types of pathways for the oxidation of carbide surfaces.« less

Oxygen in the deep-sea: The challenge of maintaining uptake rates in a changing ocean

NASA Astrophysics Data System (ADS)

Hofmann, A. F.; Peltzer, E. T.; Brewer, P. G.

2011-12-01

Although focused on recently, ocean acidification is not the only effect of anthropogenic CO2 emissions on the ocean. Ocean warming will reduce dissolved oxygen concentrations and at the hypoxic limit for a given species this can pose challenges to marine life. The limit is traditionally reported simply as the static mass concentration property [O2]; here we treat it as a dynamic gas exchange problem for the animal analogous to gas exchange at the sea surface. The diffusive limit and its relationship to water velocity is critical for the earliest stages of marine life (eggs, embryos), but the effect is present for all animals at all stages of life. We calculate the external limiting O2 conditions for several representative metabolic rates and their relationship to flow of the bulk fluid under different environmental conditions. Ocean O2 concentrations decline by ≈ 14 μmol kg-1 for a 2 °C rise in temperature. At standard 1000 m depth conditions in the Pacific, flow over the surface would have to increase by ≈ 60% from 2.0 to 3.2 cm s-1 to compensate for this change. The functions derived allow new calculations of depth profiles of limiting O2 concentrations, as well as maximal diffusively sustainable metabolic oxygen consumption rates at various places around the world. Our treatment shows that there is a large variability in the global ocean in terms of facilitating aerobic life. This variability is greater than the variability of the oxygen concentration alone. It becomes clear that temperature and pressure dependencies of diffusion and partial pressure create a region typically around 1000 m depth where a maximal [O2] is needed to sustain a given metabolic rate. This zone of greatest physical constriction on the diffusive transport in the boundary layer is broadly consistent with the oxygen minimum zone, i.e., the zone of least oxygen concentration supply, resulting in a pronounced minimum of maximal diffusively sustainable metabolic oxygen consumption rates. This least-favorable zone for aerobic respiration is bound to expand with further ocean warming.

Vortical ciliary flows actively enhance mass transport in reef corals.

PubMed

Shapiro, Orr H; Fernandez, Vicente I; Garren, Melissa; Guasto, Jeffrey S; Debaillon-Vesque, François P; Kramarsky-Winter, Esti; Vardi, Assaf; Stocker, Roman

2014-09-16

The exchange of nutrients and dissolved gasses between corals and their environment is a critical determinant of the growth of coral colonies and the productivity of coral reefs. To date, this exchange has been assumed to be limited by molecular diffusion through an unstirred boundary layer extending 1-2 mm from the coral surface, with corals relying solely on external flow to overcome this limitation. Here, we present direct microscopic evidence that, instead, corals can actively enhance mass transport through strong vortical flows driven by motile epidermal cilia covering their entire surface. Ciliary beating produces quasi-steady arrays of counterrotating vortices that vigorously stir a layer of water extending up to 2 mm from the coral surface. We show that, under low ambient flow velocities, these vortices, rather than molecular diffusion, control the exchange of nutrients and oxygen between the coral and its environment, enhancing mass transfer rates by up to 400%. This ability of corals to stir their boundary layer changes the way that we perceive the microenvironment of coral surfaces, revealing an active mechanism complementing the passive enhancement of transport by ambient flow. These findings extend our understanding of mass transport processes in reef corals and may shed new light on the evolutionary success of corals and coral reefs.

Universal model for water costs of gas exchange by animals and plants

PubMed Central

Woods, H. Arthur; Smith, Jennifer N.

2010-01-01

For terrestrial animals and plants, a fundamental cost of living is water vapor lost to the atmosphere during exchange of metabolic gases. Here, by bringing together previously developed models for specific taxa, we integrate properties common to all terrestrial gas exchangers into a universal model of water loss. The model predicts that water loss scales to gas exchange with an exponent of 1 and that the amount of water lost per unit of gas exchanged depends on several factors: the surface temperature of the respiratory system near the outside of the organism, the gas consumed (oxygen or carbon dioxide), the steepness of the gradients for gas and vapor, and the transport mode (convective or diffusive). Model predictions were largely confirmed by data on 202 species in five taxa—insects, birds, bird eggs, mammals, and plants—spanning nine orders of magnitude in rate of gas exchange. Discrepancies between model predictions and data seemed to arise from biologically interesting violations of model assumptions, which emphasizes how poorly we understand gas exchange in some taxa. The universal model provides a unified conceptual framework for analyzing exchange-associated water losses across taxa with radically different metabolic and exchange systems. PMID:20404161

Universal model for water costs of gas exchange by animals and plants.

PubMed

Woods, H Arthur; Smith, Jennifer N

2010-05-04

For terrestrial animals and plants, a fundamental cost of living is water vapor lost to the atmosphere during exchange of metabolic gases. Here, by bringing together previously developed models for specific taxa, we integrate properties common to all terrestrial gas exchangers into a universal model of water loss. The model predicts that water loss scales to gas exchange with an exponent of 1 and that the amount of water lost per unit of gas exchanged depends on several factors: the surface temperature of the respiratory system near the outside of the organism, the gas consumed (oxygen or carbon dioxide), the steepness of the gradients for gas and vapor, and the transport mode (convective or diffusive). Model predictions were largely confirmed by data on 202 species in five taxa--insects, birds, bird eggs, mammals, and plants--spanning nine orders of magnitude in rate of gas exchange. Discrepancies between model predictions and data seemed to arise from biologically interesting violations of model assumptions, which emphasizes how poorly we understand gas exchange in some taxa. The universal model provides a unified conceptual framework for analyzing exchange-associated water losses across taxa with radically different metabolic and exchange systems.

The pressure dependence of oxygen-isotope-exchange rates between solution and apical oxygens on the UO 2(OH) 4 2- ion

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

Harley, Steven J.; Ohlin, C. Andre; Johnson, Rene L.

2011-04-06

The pressure dependence of isotope exchange rate was determined for apical oxygen atoms in the UO 2(OH) 4 2-(aq) ion. The results can be interpreted to indicate an associative character of the reaction.

The role of horizontal exchanges on ventilation of the benthic boundary layer on the Black Sea shelf

NASA Astrophysics Data System (ADS)

Shapiro, Georgy; Wobus, Fred

2010-05-01

The state of the benthic component of the shelf ecosystem is strongly influenced by availability of dissolved oxygen. The chemical structure of the Black Sea waters is largely determined by the location and the strength of the pycnocline. Due to similarity in the mechanisms of vertical exchanges the oxycline and the chemocline occur at the same depth intervals as the halocline and pycnocline (Özsoy and Ünlüata, 1997). As the data for dissolved oxygen on the shelf is relatively sparse we assume that much abundant data on physical parameters (temperature and salinity) can be used as proxy in determining the location of the oxycline and hence the spatial extent of near-bottom waters depleted in oxygen. When the waters of the benthic boundary layers below the pycnocline are ‘locked' i.e. unable to mix vertically with surface then the biological pump and supply of oxygen are suppressed. However, the locked water can, in principle, move ‘horizontally', predominantly along the constant density levels and get ventilated via isopycnal exchanges. The isopycnals in the Black Sea have generally a dome-like structure, so that the isopycnal movements across the shelf break can ventilate bottom shelf waters with water masses from upper parts of the water column in the deep sea. We use the intra- and inter-annual variations in the near-bottom temperature as indicators for variability of physical conditions in the benthic boundary layer on the shelf. The physical reason for this is that interannual variations in the near-bottom temperature are directly related with the volume of cold waters (Ivanov et al., 2000) which are formed on the shelf and then exported into the deep sea, so that variations in temperature may indicate changes in the intensity of horizontal exchanges. In this paper we identified areas on the Black Sea margin where bottom waters can not be mixed vertically (‘locked' waters) during the winter months and locations to which the locked waters can move ‘horizontally'. The potential energy approach was used to identify the spatial and temporal variability of the areas and volumes occupied by the locked waters. This approach allows to assess a relative strength of the ability of locked waters to mix vertically with oxygen rich surface waters as compared to ‘horizontal' exchanges with the deep sea along isopycnic surfaces. Analysis of interannual variability of temperature showed that the period 1965-1983 was a warm period when the ‘summer' season ( May to November) temperatures of the benthic waters were higher than the average; to the contrary the period 1983-2001 (i.e. up to end of available data sets) was a cold period. Correlations between various time series of hydrographical and meteorological parameters were calculated to establish the relative importance of vertical versus horizontal exchanges in ventilation of the locked water masses. A low correlation (R=0.24) was obtained between the variation of the winter sea surface temperature on the shelf and the ‘summer' temperatures of locked waters. A higher correlation (R=0.56) was found between the summer temperatures of the Cold Intermediate Waters below the seasonal pycnocline in the deep sea (density range sigma-theta= 14.2-14.8) and the ‘summer' temperatures of the ‘locked' waters in the benthic boundary layer on the shelf. Analysis shows that the isopycnic exchanges with the deep sea are more important for ventilation of the benthic boundary layer on the shelf than winter convection on the shelf itself. This work was made possible via support from EU FP6 SESAME and EU FP7 MyOcean projects and NERC PhD studentship. References Özsoy, E. and Ünlüata, Ü., 1997. Oceanography of the Black Sea: a review of some recent results. Earth-Sci. Rev., 42(4): 231-272. Ivanov, L.I., Belokopytov, V.N., Özsoy, E. and Samodurov, A., 2000. Ventilation of the Black Sea pycnocline on seasonal and interannual time scales. Mediterr. Mar. Sci., 1/2: 61-74.

A novel electrochemical ion exchange system and its application in water treatment.

PubMed

Li, Yansheng; Li, Yongbin; Liu, Zhigang; Wu, Tao; Tian, Ying

2011-06-01

A novel electrochemical ion exchange system with porous cylinder electrodes is proposed for treatment of wastewater. This system can be used for desalination without the costly ion-exchange membrane and extra chemical reagents. Since the electrodes are completely uniform and no ion-exchange membrane was used in this system, it can be operated by switching anodes and cathodes flexibly for eliminating the scaling on the surface of electrodes. The strong base ion-exchange resin grains placed among the anode and cathode have played as supporting electrolyte, which is capable for the treatment of wastewater with low conductivity. The concentrated and neutralized anolyte containing chlorine is effective for disinfection and contaminants removal. Under the experimental conditions, the removal percentage of total dissolved salts was 83% and the removal percentage of chemical oxygen demand was 92% without consumption of extra chemical reagents. Copyright © 2011 The Research Centre for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

Oxygen Isotope Signatures of Biogenic Manganese(III/IV) Oxides

NASA Astrophysics Data System (ADS)

Sutherland, K. M.; Hansel, C. M.; Wankel, S. D.

2015-12-01

Manganese (Mn) oxide minerals are pervasive throughout a number of surface earth environments as rock varnishes, ferromanganese nodules, crusts around deep-sea vents, and cave deposits among many other marine, freshwater, and terrestrial deposits. Mn(III,IV) oxides are also among the strongest sorbents and oxidants in surface earth environments and are crucial to understanding the fate of organic matter in sedimentary environments. The precipitation of Mn oxide minerals proceeds via both abiotic and biotic oxidation pathways, the latter due to the indirect or direct activity of Mn(II)- oxidizing microorganisms, including bacteria and fungi. Although the precipitation of Mn oxides is believed to be primarily controlled by Mn(II)-oxidizing organisms in most surface earth environments, confirmation of this generally held notion has remained illusive and limits our understanding of their formation on Earth and beyond (e.g., Mars). Previous work provided evidence that O atom incorporation by specific Mn oxidation pathways may exhibit unique and predictable isotopic fractionation. In this study, we expand upon this evidence by measuring the oxygen isotope signature of several biogenic and abiogenic Mn oxide minerals synthesized under a range of oxygen-18 labeled water. These results allow us to determine the relative amount oxygen atoms derived from water and molecular oxygen that are incorporated in the oxide and shed light on corresponding isotope fractionation factors. Additionally, we show that, once precipitated, Mn oxide isotope signatures are robust with respect to aqueous oxygen isotope exchange. The study provides a foundation on which to study and interpret Mn oxides in natural environments and determine which environmental controls may govern Mn(II) oxidation.

Fungal oxygen exchange between denitrification intermediates and water.

PubMed

Rohe, Lena; Anderson, Traute-Heidi; Braker, Gesche; Flessa, Heinz; Giesemann, Anette; Wrage-Mönnig, Nicole; Well, Reinhard

2014-02-28

Fungi can contribute greatly to N2O production from denitrification. Therefore, it is important to quantify the isotopic signature of fungal N2O. The isotopic composition of N2O can be used to identify and analyze the processes of N2O production and N2O reduction. In contrast to bacteria, information about the oxygen exchange between denitrification intermediates and water during fungal denitrification is lacking, impeding the explanatory power of stable isotope methods. Six fungal species were anaerobically incubated with the electron acceptors nitrate or nitrite and (18)O-labeled water to determine the oxygen exchange between denitrification intermediates and water. After seven days of incubation, gas samples were analyzed for N2O isotopologues by isotope ratio mass spectrometry. All the fungal species produced N2O. N2O production was greater when nitrite was the sole electron acceptor (129 to 6558 nmol N2O g dw(-1)  h(-1)) than when nitrate was the electron acceptor (6 to 47 nmol N2O g dw(-1)  h(-1)). Oxygen exchange was complete with nitrate as electron acceptor in one of five fungi and with nitrite in two of six fungi. Oxygen exchange of the other fungi varied (41 to 89% with nitrite and 11 to 61% with nitrate). This is the first report on oxygen exchange with water during fungal denitrification. The exchange appears to be within the range previously reported for bacterial denitrification. This adds to the difficulty of differentiating N2O producing processes based on the origin of N2O-O. However, the large oxygen exchange repeatedly observed for bacteria and now also fungi could lead to less variability in the δ(18)O values of N2O from soils, which could facilitate the assessment of the extent of N2O reduction. Copyright © 2013 John Wiley & Sons, Ltd.

Deep drilling at the Siljan Ring impact structure: oxygen-isotope geochemistry of granite

USGS Publications Warehouse

Komor, S.C.; Valley, J.W.

1990-01-01

The Siljan Ring is a 362-Ma-old impact structure formed in 1700-Ma-old I-type granites. A 6.8-km-deep borehole provides a vertical profile through granites and isolated horizontal diabase sills. Fluid-inclusion thermometry, and oxygen-isotope compositions of vein quartz, granite, diabase, impact melt, and pseudotachylite, reveal a complex history of fluid activity in the Siljan Ring, much of which can be related to the meteorite impact. In granites from the deep borehole, ??18O values of matrix quartz increase with depth from near 8.0 at the surface to 9.5??? at 5760 m depth. In contrast, feldspar ??18O values decrease with depth from near 10 at the surface to 7.1??? at 5760 m, forming a pattern opposite to the one defined by quartz isotopic compositions. Values of ??18O for surface granites outside the impact structure are distinct from those in near-surface samples from the deep borehole. In the deep borehole, feldspar coloration varies from brick-red at the surface to white at 5760 m, and the abundances of crack-healing calcite and other secondary minerals decrease over the same interval. Superimposed on the overall decrease in alteration intensity with depth are localized fracture zones at 4662, 5415, and 6044 m depth that contain altered granites, and which provided pathways for deep penetration of surface water. The antithetic variation of quartz and feldspar ??18O values, which can be correlated with mineralogical evidence of alteration, provides evidence for interaction between rocks and impact-heated fluids (100-300?? C) in the upper 2 km of the pluton. Penetration of water to depths below 2 km was restricted by a general decrease in impact-fracturing with depth, and by a 60-m-thick diabase sill at 1500 m depth that may have been an aquitard. At depths below 4 km in the pluton, where water/rock ratios were low, oxygen isotopic compositions preserve evidence for limited high-temperature (>500?? C) exchange between alkali feldspar and fluids. The high-temperature exchange may have been a post-impact event involving impact-heated fluids, or a post-magmatic event. ?? 1990 Springer-Verlag.

Double perovskite cathodes for proton-conducting ceramic fuel cells: are they triple mixed ionic electronic conductors?

NASA Astrophysics Data System (ADS)

Téllez Lozano, Helena; Druce, John; Cooper, Samuel J.; Kilner, John A.

2017-12-01

18O and 2H diffusion has been investigated at a temperature of 300 °C in the double perovskite material PrBaCo2O5+δ (PBCO) in flowing air containing 200 mbar of 2H216O. Secondary ion mass spectrometry (SIMS) depth profiling of exchanged ceramics has shown PBCO still retains significant oxygen diffusivity ( 1.3 × 10-11 cm2s-1) at this temperature and that the presence of water (2H216O), gives rise to an enhancement of the surface exchange rate over that in pure oxygen by a factor of 3. The 2H distribution, as inferred from the 2H216O- SIMS signal, shows an apparent depth profile which could be interpreted as 2H diffusion. However, examination of the 3-D distribution of the signal shows it to be nonhomogeneous and probably related to the presence of hydrated layers in the interior walls of pores and is not due to proton diffusion. This suggests that PBCO acts mainly as an oxygen ion mixed conductor when used in PCFC devices, although the presence of a small amount of protonic conductivity cannot be discounted in these materials.

Lung assist device technology with physiologic blood flow developed on a tissue engineered scaffold platform.

PubMed

Hoganson, David M; Pryor, Howard I; Bassett, Erik K; Spool, Ira D; Vacanti, Joseph P

2011-02-21

There is no technology available to support failing lung function for patients outside the hospital. An implantable lung assist device would augment lung function as a bridge to transplant or possible destination therapy. Utilizing biomimetic design principles, a microfluidic vascular network was developed for blood inflow from the pulmonary artery and blood return to the left atrium. Computational fluid dynamics analysis was used to optimize blood flow within the vascular network. A micro milled variable depth mold with 3D features was created to achieve both physiologic blood flow and shear stress. Gas exchange occurs across a thin silicone membrane between the vascular network and adjacent alveolar chamber with flowing oxygen. The device had a surface area of 23.1 cm(2) and respiratory membrane thickness of 8.7 ± 1.2 μm. Carbon dioxide transfer within the device was 156 ml min(-1) m(-2) and the oxygen transfer was 34 ml min(-1) m(-2). A lung assist device based on tissue engineering architecture achieves gas exchange comparable to hollow fiber oxygenators yet does so while maintaining physiologic blood flow. This device may be scaled up to create an implantable ambulatory lung assist device.

Simulation of annual biogeochemical cycles of nutrient balance, phytoplankton bloom(s), and DO in Puget Sound using an unstructured grid model

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

Khangaonkar, Tarang; Sackmann, Brandon; Long, Wen

2012-08-14

Nutrient pollution from rivers, nonpoint source runoff, and nearly 100 wastewater discharges is a potential threat to the ecological health of Puget Sound with evidence of hypoxia in some basins. However, the relative contributions of loads entering Puget Sound from natural and anthropogenic sources, and the effects of exchange flow from the Pacific Ocean are not well understood. Development of a quantitative model of Puget Sound is thus presented to help improve our understanding of the annual biogeochemical cycles in this system using the unstructured grid Finite-Volume Coastal Ocean Model framework and the Integrated Compartment Model (CE-QUAL-ICM) water quality kinetics.more » Results based on 2006 data show that phytoplankton growth and die-off, succession between two species of algae, nutrient dynamics, and dissolved oxygen in Puget Sound are strongly tied to seasonal variation of temperature, solar radiation, and the annual exchange and flushing induced by upwelled Pacific Ocean waters. Concentrations in the mixed outflow surface layer occupying approximately 5–20 m of the upper water column show strong effects of eutrophication from natural and anthropogenic sources, spring and summer algae blooms, accompanied by depleted nutrients but high dissolved oxygen levels. The bottom layer reflects dissolved oxygen and nutrient concentrations of upwelled Pacific Ocean water modulated by mixing with biologically active surface outflow in the Strait of Juan de Fuca prior to entering Puget Sound over the Admiralty Inlet. The effect of reflux mixing at the Admiralty Inlet sill resulting in lower nutrient and higher dissolved oxygen levels in bottom waters of Puget Sound than the incoming upwelled Pacific Ocean water is reproduced. Finally, by late winter, with the reduction in algal activity, water column constituents of interest, were renewed and the system appeared to reset with cooler temperature, higher nutrient, and higher dissolved oxygen waters from the Pacific Ocean.« less

Aspects of bimodal gas exchange in the bowfin, Amia calva L. (actinopterygii: amiiformes).

PubMed

Randall, D J; Cameron, J N; Daxboeck, C; Smatresk, N

1981-03-01

The bowfin, Amia calva is a facultative air breathing fish which uses its respiratory swimbladder to augment oxygen uptake in normoxia at 30 degrees C. It does not die however, when denied access to the surface at this temperature. The bladder RQ is 0.21 while the gill RQ is 1.61 and thus most of the CO2 is excreted into the water across the gills. In aquatic hypoxia some of the oxygen taken up via the swimbladder is lost to the water across the gills. However CO2 excretion across the gills is maintained at the same rate as that found in normoxia.

The Pressure Dependence of Oxygen Isotope Exchange Rates Between Solution and Apical Oxygen Atoms on the [UO2(OH)4]2- Ion

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

Harley, Steven J.; Ohlin, C. André; Johnson, Rene L.

2011-04-06

Under pressure: The pressure dependence of isotope exchange rate was determined for apical oxygen atoms in the [UO2(OH)4]2-(aq) ion (see picture). The results can be interpreted to indicate an associative character of the reaction.

Sickling of red blood cells through rapid oxygen exchange in microfluidic drops.

PubMed

Abbyad, Paul; Tharaux, Pierre-Louis; Martin, Jean-Louis; Baroud, Charles N; Alexandrou, Antigoni

2010-10-07

We have developed a microfluidic approach to study the sickling of red blood cells associated with sickle cell anemia by rapidly varying the oxygen partial pressure within flowing microdroplets. By using the perfluorinated carrier oil as a sink or source of oxygen, the oxygen level within the water droplets quickly equilibrates through exchange with the surrounding oil. This provides control over the oxygen partial pressure within an aqueous drop ranging from 1 kPa to ambient partial pressure, i.e. 21 kPa. The dynamics of the oxygen exchange is characterized through fluorescence lifetime measurements of a ruthenium compound dissolved in the aqueous phase. The gas exchange is shown to occur primarily during and directly after droplet formation, in 0.1 to 0.5 s depending on the droplet diameter and speed. The controlled deoxygenation is used to trigger the polymerization of hemoglobin within sickle red blood cells, encapsulated in drops. This process is observed using polarization microscopy, which yields a robust criterion to detect polymerization based on transmitted light intensity through crossed polarizers.

Ab initio Potential-Energy Surfaces and Electron-Spin-Exchange Cross Sections for H-O2 Interactions

NASA Technical Reports Server (NTRS)

Stallcop, James R.; Partridge, Harry; Levin, Eugene

1996-01-01

Accurate quartet- and doublet-state potential-energy surfaces for the interaction of a hydrogen atom and an oxygen molecule in their ground states have been determined from an ab initio calculation using large-basis sets and the internally contracted multireference configuration interaction method. These potential surfaces have been used to calculate the H-O2 electron-spin-exchange cross section; the square root of the cross section (in a(sub 0)), not taking into account inelastic effects, can be obtained approximately from the expressions 2.390E(sup -1/6) and 5.266-0.708 log10(E) at low and high collision energies E (in E(sub h)), respectively. These functional forms, as well as the oscillatory structure of the cross section found at high energies, are expected from the nature of the interaction energy. The mean cross section (the cross section averaged over a Maxwellian velocity distribution) agrees reasonably well with the results of measurements.

The interplanetary exchange of photosynthesis.

PubMed

Cockell, Charles S

2008-02-01

Panspermia, the transfer of organisms from one planet to another, either through interplanetary or interstellar space, remains speculation. However, its potential can be experimentally tested. Conceptually, it is island biogeography on an interplanetary or interstellar scale. Of special interest is the possibility of the transfer of oxygenic photosynthesis between one planet and another, as it can initiate large scale biospheric productivity. Photosynthetic organisms, which must live near the surface of rocks, can be shown experimentally to be subject to destruction during atmospheric transit. Many of them grow as vegetative cells, which are shown experimentally to be susceptible to destruction by shock during impact ejection, although the effectiveness of this dispersal filter can be shown to be mitigated by the characteristics of the cells and their local environment. Collectively these, and other, experiments reveal the particular barriers to the cross-inoculation of photosynthesis. If oxygen biosignatures are eventually found in the atmospheres of extrasolar planets, understanding the potential for the interplanetary exchange of photosynthesis will aid in their interpretation.

Membrane oxygenator heat exchanger failure detected by unique blood gas findings.

PubMed

Hawkins, Justin L

2014-03-01

Failure of components integrated into the cardiopulmonary bypass circuit, although rare, can bring about catastrophic results. One of these components is the heat exchanger of the membrane oxygenator. In this compartment, unsterile water from the heater cooler device is separated from the sterile blood by stainless steel, aluminum, or by polyurethane. These areas are glued or welded to keep the two compartments separate, maintaining sterility of the blood. Although quality control testing is performed by the manufacturer at the factory level, transport presents the real possibility for damage. Because of this, each manufacturer has included in the instructions for use a testing procedure for testing the integrity of the heat exchanger component. Water is circulated through the heat exchanger before priming and a visible check is made of the oxygenator bundle to check for leaks. If none are apparent, then priming of the oxygenator is performed. In this particular case, this procedure was not useful in detecting communication between the water and blood chambers of the oxygenator.

Impact of transient stream flow on water exchange and reactions in the hyporheic zone of an in-stream gravel bar

NASA Astrophysics Data System (ADS)

Trauth, Nico; Schmidt, Christian; Fleckenstein, Jan H.

2015-04-01

Groundwater-surface water exchange is an important process that can facilitate the degradation of critical substances like nitrogen-species and contaminants, supporting a healthy status of the aquatic ecosystem. In our study, we simulate water exchange, solute transport and reactions within a natural in-stream gravel bar using a coupled surface and subsurface numerical model. Stream water flow is simulated by computational fluid dynamics software that provides hydraulic head distributions at the streambed, which are used as an upper boundary condition for a groundwater model. In the groundwater model water exchange, solute transport, aerobic respiration and denitrification in the subsurface are simulated. Ambient groundwater flow is introduced by lateral upstream and downstream hydraulic head boundaries that generate neutral, losing or gaining stream conditions. Stream water transports dissolved oxygen, organic carbon (as the dominant electron donor) and nitrate into the subsurface, whereas an additional nitrate source exists in the ambient groundwater. Scenarios of stream flow events varying in duration and stream stage are simulated and compared with steady state scenarios with respect to water fluxes, residence times and the solute turn-over rates. Results show, that water exchange and solute turn-over rates highly depend on the interplay between event characteristics and ambient groundwater levels. For scenarios, where the stream flow event shifts the hydraulic system to a net-neutral hydraulic gradient between the average stream stage and the ambient groundwater level (minimal exchange between ground- and surface water), solute consumption is higher, compared to the steady losing or gaining case. In contrast, events that induce strong losing conditions lead to a lower potential of solute consumption.

Size-related bioconcentration kinetics of hydrophobic chemicals in fish

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

Sijm, D.T.H.M.; Linde, A. van der

1994-12-31

Uptake and elimination of hydrophobic chemicals by fish can be regarded as passive diffusive transport processes. Diffusion coefficients, lipid/water partitioning, diffusion pathlenghts, concentration gradients and surface exchange areas are key parameters describing this bioconcentration distribution process. In the present study two of these parameters were studied: the influence of lipid/water partitioning was studied by using hydrophobic chemicals of different hydrophobicity, and the surface exchange area by using different sizes of fish. By using one species of fish it was assumed that all other parameters were kept constant. Seven age classes of fish were exposed to a series of hydrophobic, formore » five days, which was followed by a deputation phase lasting up to 6 months. Bioconcentration parameters, such as uptake and elimination rate constants, and bioconcentration factors were determined. Uptake of the hydrophobic compounds was compared to that of oxygen. Uptake and elimination rates were compared to weight and estimated (gill) exchange areas. The role of weight and its implications for extrapolations of bioconcentration parameters to other species and sizes will be discussed.« less

Fine-tuning the Wall Thickness of Ordered Mesoporous Graphene by Exploiting Ligand Exchange of Colloidal Nanocrystals

NASA Astrophysics Data System (ADS)

Han, Dandan; Yan, Yancui; Wei, Jishi; Wang, Biwei; Li, Tongtao; Guo, Guannan; Yang, Dong; Xie, Songhai; Dong, Angang

2017-12-01

Because of their unique physical properties, three-dimensional (3D) graphene has attracted enormous attention over the past years. However, it is still a challenge to precisely control the layer thickness of 3D graphene. Here, we report a novel strategy to rationally adjust the wall thickness of ordered mesoporous graphene (OMG). By taking advantage of ligand exchange capability of colloidal Fe3O4 nanocrystals, we are able to fine-tune the wall thickness of OMG from 2 to 6 layers of graphene by tailoring the hydrocarbon ligands attached to the nanocrystal surface. When evaluated as electrocatalyst for oxygen reduction reaction upon S and N doping, the 4-layer OMG is found to show better catalytic performance compared with its 2- and 6-layer counterparts, which we attribute to the enhanced exposure of active sites resulting from its ultrathin wall thickness and high surface area.

Capacity and mechanisms of ammonium and cadmium sorption on different wetland-plant derived biochars.

PubMed

Cui, Xiaoqiang; Hao, Hulin; Zhang, Changkuan; He, Zhenli; Yang, Xiaoe

2016-01-01

The objective of this study was to investigate the relationship between Cd(2+)/NH4(+) sorption and physicochemical properties of biochars produced from different wetland plants. Biochars from six species of wetland plants (i.e., Canna indica, Pennisetum purpureum Schum, Thalia dealbata, Zizania caduciflora, Phragmites australis and Vetiveria zizanioides) were obtained at 500°C and characterized, and their sorption for ammonium and cadmium was determined. There were significant differences in elemental composition, functional groups and specific surface area among the biochars derived from different wetland plant species. Sorption of ammonium and cadmium on the biochars could be described by a pseudo second order kinetic model, and the simple Langmuir model fits the isotherm data better than the Freundlich or Temkin model. The C. indica derived biochar had the largest sorption capacity for NH4(+) and Cd(2+), with a maximum sorption of 13.35 and 125.8mgg(-1), respectively. P. purpureum Schum derived biochar had a similar maximum sorption (119.3mgg(-1)) for Cd(2+). Ammonium sorption was mainly controlled by cation exchange, surface complexation with oxygen-containing functional groups and the formation of magnesium ammonium phosphate compounds, whereas for Cd(2+) sorption, the formation of cadmium phosphate precipitates, cation exchange and binding to oxygen-containing groups were the major possible mechanisms. In addition, the sorption of ammonium and cadmium was not affected by surface area and microporosity of the biochars. Copyright © 2015 Elsevier B.V. All rights reserved.

N-type Cu2O doped activated carbon as catalyst for improving power generation of air cathode microbial fuel cells.

PubMed

Zhang, Xi; Li, Kexun; Yan, Pengyu; Liu, Ziqi; Pu, Liangtao

2015-01-01

A novel n-type Cu2O doped activated carbon (AC) air cathode (Cu/AC) was developed as an alternative to Pt electrode for oxygen reduction in microbial fuel cells (MFCs). The maximum power density of MFCs using this novel air cathode was as high as 1390±76mWm(-2), almost 59% higher than the bare AC air cathode. Specifically, the resistance including total resistance and charge transfer resistance significantly decreased comparing to the control. Tafel curve also showed the faster electro-transfer kinetics of Cu/AC with exchange current density of 1.03×10(-3)Acm(-2), which was 69% higher than the control. Ribbon-like Cu2O was deposited on the surface of AC with the mesopore surface area increasing. Cubic Cu2O crystals exclusively expose (111) planes with the interplanar crystal spacing of 2.48Å, which was the dominate active sites for oxygen reduction reaction (ORR). N-type Cu2O with oxygen vacancies played crucial roles in electrochemical catalytic activity. Copyright © 2015 Elsevier Ltd. All rights reserved.

VQS (vapor-quasiliquid-solid, vapor-quasisolid-solid) mechanism presents a unified foundation for the syntheses of nanotubes, primarily carbon nanotubes

NASA Astrophysics Data System (ADS)

Mohammad, S. Noor

2017-09-01

Nanotubes are synthesized almost entirely by metal-catalyst-free and metal-catalyst-mediated non-eutectic mechanism(s). An investigation has been carried out to understand the basics of this mechanism. Various possible chemical and physical processes involved in nanotube synthesis have been researched. Various components and attributes of nanotube synthesis have been evaluated. Phase transitions, alloy formation, porosity, carrier transport and the fundamentals underlying them have been examined. Nanoparticle surfaces conducive to nanotube synthesis have been examined. The role of surface treatment, which includes oxidation, oxygenation, acid treatment, plasma treatment, water treatment, sputtering, etc in creating such surfaces, has been investigated. The role of surface treatment and phase transitions as functions of temperature, pressure, ambient, contaminants, surface amorphicity, etc in creating diffusion paths for the diffusion of growth species for supersaturation and nucleation has been explored. Interdiffusion of catalyst and source materials, and hence exchange of materials, on the nanoparticle surface, have been elucidated. This exchange of materials on catalyst surface appears to add a new dimension to the synthesis kinetics. Integrated together, they reveal a general mechanism for probably all metal-catalyst-free and metal-catalyst-mediated non-eutectic nanotube synthesis. Available experiments strongly support the proposed mechanism; they suggest that this mechanism has a broad appeal.

Exchange interactions in transition metal oxides: the role of oxygen spin polarization.

PubMed

Logemann, R; Rudenko, A N; Katsnelson, M I; Kirilyuk, A

2017-08-23

Magnetism of transition metal (TM) oxides is usually described in terms of the Heisenberg model, with orientation-independent interactions between the spins. However, the applicability of such a model is not fully justified for TM oxides because spin polarization of oxygen is usually ignored. In the conventional model based on the Anderson principle, oxygen effects are considered as a property of the TM ion and only TM interactions are relevant. Here, we perform a systematic comparison between two approaches for spin polarization on oxygen in typical TM oxides. To this end, we calculate the exchange interactions in NiO, MnO and hematite (Fe 2 O 3 ) for different magnetic configurations using the magnetic force theorem. We consider the full spin Hamiltonian including oxygen sites, and also derive an effective model where the spin polarization on oxygen renormalizes the exchange interactions between TM sites. Surprisingly, the exchange interactions in NiO depend on the magnetic state if spin polarization on oxygen is neglected, resulting in non-Heisenberg behavior. In contrast, the inclusion of spin polarization in NiO makes the Heisenberg model more applicable. Just the opposite, MnO behaves as a Heisenberg magnet when oxygen spin polarization is neglected, but shows strong non-Heisenberg effects when spin polarization on oxygen is included. In hematite, both models result in non-Heisenberg behavior. The general applicability of the magnetic force theorem as well as the Heisenberg model to TM oxides is discussed.

Percolation Magnetism in Ferroelectric Nanoparticles

NASA Astrophysics Data System (ADS)

Golovina, Iryna S.; Lemishko, Serhii V.; Morozovska, Anna N.

2017-06-01

Nanoparticles of potassium tantalate (KTaO3) and potassium niobate (KNbO3) were synthesized by oxidation of metallic tantalum in molten potassium nitrate with the addition of potassium hydroxide. Magnetization curves obtained on these ferroelectric nanoparticles exhibit a weak ferromagnetism, while these compounds are nonmagnetic in a bulk. The experimental data are used as a start point for theoretical calculations. We consider a microscopic mechanism that leads to the emerging of a ferromagnetic ordering in ferroelectric nanoparticles. Our approach is based on the percolation of magnetic polarons assuming the dominant role of the oxygen vacancies. It describes the formation of surface magnetic polarons, in which an exchange interaction between electrons trapped in oxygen vacancies is mediated by magnetic impurity Fe3+ ions. The dependences of percolation radius on concentration of the oxygen vacancies and magnetic defects are determined in the framework of percolation theory.

Conclusions and Recommendations Regarding the Deep Sea Hybrid Power Systems Initial Study

DTIC Science & Technology

2010-06-01

proton-exchange membrane fuel cells ( PEMFC ) powered with hydrogen and oxygen, similar to that used on proven subsurface vessels; (2) fuel-cells...AND STORAGE OPTIONS CONSIDERED FOR INITIAL STUDY NO. NOMENCLATURE DESCRIPTION 1 PWR Nuclear Reactor + Battery 2 FC1 PEMFC + Line for surface O2...Wellhead Gas + Reformer + Battery 3 FC2 PEMFC + Stored O2 + Wellhead Gas + Reformer + Battery 4 SV1 PEMFC + Submersible Vehicle for O2 Transport

Hydrologic and geochemical effects on oxygen uptake in bottom sediments of an effluent-dominated river

USGS Publications Warehouse

McMahon, P.B.; Tindall, J.A.; Collins, J.A.; Lull, K.J.; Nuttle, J.R.

1995-01-01

More than 95% of the water in the South Platte River downstream from the largest wastewater treatment plant serving the metropolitan Denver, Colorado, area consists of treated effluent during some periods of low flow. Fluctuations in effluent-discharge rates caused daily changes in river stage that promoted exchange of water between the river and bottom sediments. Groundwater discharge measurements indicated fluxes of water across the sediment-water interface as high as 18 m3 s−1 km−1. Laboratory experiments indicated that downward movement of surface water through bottom sediments at velocities comparable to those measured in the field (median rate ≈0.005 cm s−1) substantially increased dissolved oxygen uptake rates in bottom sediments (maximum rate 212 ± 10 μmol O2 L−1 h−1) compared with rates obtained when no vertical advective flux was generated (maximum rate 25 ± 8.8 μmol O2 L−1 h−1). Additions of dissolved ammonium to surface waters generally increased dissolved oxygen uptake rates relative to rates measured in experiments without ammonium. However, the magnitude of the advective flux through bottom sediments had a greater effect on dissolved oxygen uptake rates than did the availability of ammonium. Results from this study indicated that efforts to improve dissolved oxygen dynamics in effluent-dominated rivers might include stabilizing daily fluctuations in river stage.

Influence of Microstructure and Surface Activation of Dual-Phase Membrane Ce 0.8 Gd 0.2 O 2-δ -FeCo 2 O 4 on Oxygen Permeation

DOE PAGES

Ramasamy, Madhumidha; Baumann, Stefan; Palisaitis, Justinas; ...

2015-09-24

In dual-phase oxygen transport membranes we noticed that there is fast-growing interest in research for oxyfuel combustion process application. One such potential candidate is CGO-FCO (60wt% Ce 0.8Gd 0.2O 2-δ-40wt% FeCo 2O4) identified to provide good oxygen permeation flux with substantial stability in harsh atmosphere. Dense CGO-FCO membranes of 1mm thickness were fabricated by sintering dry pellets pressed from powders synthesized by one-pot method (modified Pechini process) at 1200 degrees C for 10h. Microstructure analysis indicates presence of a third orthorhombic perovskite phase in the sintered composite. We also identified that the spinel phase tends to form an oxygen deficientmore » phase at the grain boundary of spinel and CGO phases. Surface exchange limitation of the membranes was overcome by La 0.6Sr 0.4Co 0.2Fe 0.8O 3-δ (LSCF) porous layer coating over the composite. Moreover, the oxygen permeation flux of the CGO-FCO screen printed with a porous layer of 10mthick LSCF is 0.11mL/cm 2 per minute at 850 degrees C with argon as sweep and air as feed gas at the rates of 50 and 250mL/min.« less

Metabolism estimates in small boreal lakes: the importance of accounting for vertical fluxes of oxygen

NASA Astrophysics Data System (ADS)

Klaus, M.; MacIntyre, S.; Hotchkiss, E. R.; Bergström, A. K.; Karlsson, J.

2015-12-01

Lake metabolism models based on the diel oxygen technique often assume that oxygen dynamics are mainly controlled by metabolic processes, only accounting for wind-driven atmospheric gas exchange. However, oxygen dynamics can also be affected by abiotic mass fluxes across oxygen gradients within lakes and atmospheric gas exchange driven by convection. Here, we quantify how much vertical fluxes of oxygen modify epilimnetic metabolism estimates for three pairs of small Swedish boreal lakes, one of each fertilized with nitrate, with dissolved organic carbon (DOC) concentrations of 7 to 22 mg l-1. Oxygen concentrations were measured every 10 min at 50 cm depth and biweekly across depths profiles during one full open water period. Based on additional two weeks of ten-minute oxygen profiling we calculated vertical fluxes of oxygen using equations for atmospheric gas exchange caused by wind shear (F1) and convection (F2), and lake-internal gas exchange caused by diffusion and mixed layer deepening (F3). We ran three inverse Bayesian models to estimate daily metabolism: (M1) accounting for F1, (M2) accounting for F1 and F2, and (M3) accounting for F1 and F3. Initial results suggest that gross primary production (GPP), ecosystem respiration (ER) and net ecosystem production (NEP) ranged from 0.1 to 0.2, -0.3 to -0.5 and -0.2 to -0.4 g C m-2 d-1, respectively. GPP and R were higher in fertilized lakes and at the lower end of previous worldwide estimates. Accounting for convection-driven gas exchange increased ER estimates by 10-40% (M2 vs. M1). This bias increased with DOC concentration but was not affected by fertilization. Including lake-internal vertical oxygen fluxes changed GPP and ER estimates by up to ±40% (M3 vs. M1), with inconsistent trends along the DOC-gradient. We conclude that vertical fluxes of oxygen can significantly affect diel oxygen dynamics in oligotrophic humic systems and should therefore be included in metabolism models applied to small boreal lakes.

High porewater exchange in a mangrove-dominated estuary revealed from short-lived radium isotopes

NASA Astrophysics Data System (ADS)

Sadat-Noori, Mahmood; Santos, Isaac R.; Tait, Douglas R.; Reading, Michael J.; Sanders, Christian J.

2017-10-01

We hypothesise that mangroves play an important role in groundwater exchange processes in sub-tropical and tropical estuarine waters. To investigate this, multiple high resolution time series measurements of radium across a tidal estuary (Coffs Creek, NSW, Australia) were performed as well as a spatial survey in both bottom and surface layers. Results from the spatial survey revealed increasing radium concentrations in parts of the estuary surrounded by mangroves. The average radium concentration in estuary areas lined with mangroves was 2.5 times higher than the average concentration at the mouth of the estuary and 6.5-fold higher than upstream freshwater areas. Additionally, the area enriched in radium coincided with low dissolved oxygen concentrations, implying that porewater exchange may drive anoxia. A radium mass balance model based on 223Ra and 224Ra isotopes at different sections of the estuary confirmed higher porewater exchange rates from areas fringed with mangrove vegetation. Estimated porewater exchange rates were 27.8 ± 5.3 and 13.6 ± 2.1 cm d-1 (0.8 ± 0.1 and 0.4 ± 0.1 m3 s-1) based on 223Ra and 224Ra isotopes, respectively. The average saline porewater exchange was ∼ 10-fold larger than the upstream surface freshwater inputs to the estuary. We suggest that mangrove environments within subtropical estuaries are hotspots for porewater exchange due to the complex belowground structure of crab burrows and the effect of tidal pumping. Because porewater exchange releases carbon and nitrogen from coastal sediments, development and modification of mangrove areas in subtropical estuaries have a significant effect on coastal biogeochemical cycles.

Lunar and Planetary Science XXXV: Special Session: Oxygen in the Solar System, II

NASA Technical Reports Server (NTRS)

2004-01-01

The Special Session: Oxygen in the Solar System, II, included the following reports:Evolution of Oxygen Isotopes in the Solar Nebula; Disequilibrium Melting of Refractory Inclusions: A Mechanism for High-Temperature Oxygen; Isotope Exchange in the Solar Nebula; Oxygen Isotopic Compositions of the Al-rich Chondrules in the CR Carbonaceous Chondrites: Evidence for a Genetic Link to Ca-Al-rich Inclusions and for Oxygen Isotope Exchange During Chondrule Melting; Nebular Formation of Fayalitic Olivine: Ineffectiveness of Dust Enrichment; Water in Terrestrial Planets: Always an Oxidant?; Oxygen Barometry of Basaltic Glasses Based on Vanadium Valence Determination Using Synchrotron MicroXANES; A New Oxygen Barometer for Solar System Basaltic Glasses Based on Vanadium Valence; The Relationship Between Clinopyroxene Fe3+ Content and Oxygen Fugacity ; and Olivine-Silicate Melt Partitioning of Iridium.

Double perovskite cathodes for proton-conducting ceramic fuel cells: are they triple mixed ionic electronic conductors?

PubMed Central

Téllez Lozano, Helena; Druce, John; Cooper, Samuel J.; Kilner, John A.

2017-01-01

Abstract 18O and 2H diffusion has been investigated at a temperature of 300 °C in the double perovskite material PrBaCo2O5+δ (PBCO) in flowing air containing 200 mbar of 2H2 16O. Secondary ion mass spectrometry (SIMS) depth profiling of exchanged ceramics has shown PBCO still retains significant oxygen diffusivity (~1.3 × 10−11 cm2s−1) at this temperature and that the presence of water (2H2 16O), gives rise to an enhancement of the surface exchange rate over that in pure oxygen by a factor of ~3. The 2H distribution, as inferred from the 2H2 16O− SIMS signal, shows an apparent depth profile which could be interpreted as 2H diffusion. However, examination of the 3-D distribution of the signal shows it to be nonhomogeneous and probably related to the presence of hydrated layers in the interior walls of pores and is not due to proton diffusion. This suggests that PBCO acts mainly as an oxygen ion mixed conductor when used in PCFC devices, although the presence of a small amount of protonic conductivity cannot be discounted in these materials. PMID:29383047

Oxygen isotope ratios of PO4: An inorganic indicator of enzymatic activity and P metabolism and a new biomarker in the search for life

PubMed Central

Blake, Ruth E.; Alt, Jeffrey C.; Martini, Anna M.

2001-01-01

The distinctive relations between biological activity and isotopic effect recorded in biomarkers (e.g., carbon and sulfur isotope ratios) have allowed scientists to suggest that life originated on this planet nearly 3.8 billion years ago. The existence of life on other planets may be similarly identified by geochemical biomarkers, including the oxygen isotope ratio of phosphate (δ18Op) presented here. At low near-surface temperatures, the exchange of oxygen isotopes between phosphate and water requires enzymatic catalysis. Because enzymes are indicative of cellular activity, the demonstration of enzyme-catalyzed PO4–H2O exchange is indicative of the presence of life. Results of laboratory experiments are presented that clearly show that δ18OP values of inorganic phosphate can be used to detect enzymatic activity and microbial metabolism of phosphate. Applications of δ18Op as a biomarker are presented for two Earth environments relevant to the search for extraterrestrial life: a shallow groundwater reservoir and a marine hydrothermal vent system. With the development of in situ analytical techniques and future planned sample return strategies, δ18Op may provide an important biosignature of the presence of life in extraterrestrial systems such as that on Mars. PMID:11226207

Oxygen isotope ratios of PO4: an inorganic indicator of enzymatic activity and P metabolism and a new biomarker in the search for life.

PubMed

Blake, R E; Alt, J C; Martini, A M

2001-02-27

The distinctive relations between biological activity and isotopic effect recorded in biomarkers (e.g., carbon and sulfur isotope ratios) have allowed scientists to suggest that life originated on this planet nearly 3.8 billion years ago. The existence of life on other planets may be similarly identified by geochemical biomarkers, including the oxygen isotope ratio of phosphate (delta(18)O(p)) presented here. At low near-surface temperatures, the exchange of oxygen isotopes between phosphate and water requires enzymatic catalysis. Because enzymes are indicative of cellular activity, the demonstration of enzyme-catalyzed PO(4)-H(2)O exchange is indicative of the presence of life. Results of laboratory experiments are presented that clearly show that delta(18)O(P) values of inorganic phosphate can be used to detect enzymatic activity and microbial metabolism of phosphate. Applications of delta(18)O(p) as a biomarker are presented for two Earth environments relevant to the search for extraterrestrial life: a shallow groundwater reservoir and a marine hydrothermal vent system. With the development of in situ analytical techniques and future planned sample return strategies, delta(18)O(p) may provide an important biosignature of the presence of life in extraterrestrial systems such as that on Mars.

Organic and inorganic molecules as probes of mineral surfaces (Invited)

NASA Astrophysics Data System (ADS)

Sverjensky, D. A.

2010-12-01

Although the multi-site nature of mineral surfaces is to be expected based on the underlying crystal structure, definitive evidence of the need to use more than one site in modelling proton surface charge or adsorption of a single adsorbate at the mineral-water interface is lacking. Instead, a single-site approach affords a practical way of averaging over all possible crystal planes and sites in a powdered mineral sample. Extensive analysis of published proton surface charge and adsorption of metals on oxide mineral surfaces can be undertaken with a single site density for each mineral based on tritium exchange or estimation from averages of the site densities of likely exposed surfaces. Even in systems with competing metals (e.g. Cu and Pb on hematite), the same site density as used for proton surface charge can be employed depending on the reaction stoichiometry. All of this indicates that protons and metals can bind to a great variety of sites with the same overall site density. However, simple oxyanions such as carbonate, sulfate, selenate, arsenate and arsenite require a much lower site density for a given mineral. For example, on goethite these oxyanions utilize a site density that correlates with the BET surface area of the goethite. In this way, the oxyanions can be thought of as selectively probing the available sites on the mineral. The correlation probably arises because goethites with different BET surface areas have different proportions of singly and multiply-bonded oxygens, and only the singly-bonded oxygens are useful for inner-sphere surface complexation by the ligand exchange mechanism. Small organic molecules behave in a remarkably similar way. For example, adsorption of oxalate on goethite, and aspartate, glutamate, dihydroxyphenylalanine, lysine and arginine on rutile are all consistent with a much smaller site density than those required for metals such as calcium or neodymium. Overall, these results suggest that both inorganic oxyanions and organic molecules containing carboxylate functional groups serve as much more sensitive probes of the surface structures of minerals than do protons or metals.

Surface modified stainless steels for PEM fuel cell bipolar plates

DOEpatents

Brady, Michael P [Oak Ridge, TN; Wang, Heli [Littleton, CO; Turner, John A [Littleton, CO

2007-07-24

A nitridation treated stainless steel article (such as a bipolar plate for a proton exchange membrane fuel cell) having lower interfacial contact electrical resistance and better corrosion resistance than an untreated stainless steel article is disclosed. The treated stainless steel article has a surface layer including nitrogen-modified chromium-base oxide and precipitates of chromium nitride formed during nitridation wherein oxygen is present in the surface layer at a greater concentration than nitrogen. The surface layer may further include precipitates of titanium nitride and/or aluminum oxide. The surface layer in the treated article is chemically heterogeneous surface rather than a uniform or semi-uniform surface layer exclusively rich in chromium, titanium or aluminum. The precipitates of titanium nitride and/or aluminum oxide are formed by the nitriding treatment wherein titanium and/or aluminum in the stainless steel are segregated to the surface layer in forms that exhibit a low contact resistance and good corrosion resistance.

STS-84 oxygen generator for Mir on display at SPACEHAB

NASA Technical Reports Server (NTRS)

1997-01-01

Representatives of RSC Energia in Russia and other onlookers in the SPACEHAB Payload Processing Facility examine an oxygen generator which the Space Shuttle Atlantis will carry to the Russian Mir Space Station on Mission STS-84. Sergei Romanov, second from right in the white shirt, is the spokesperson for generator manufacturer RSC Energia. The nearly 300-pound generator will be strapped down on the inside surface of a SPACEHAB Double Module for the trip to Mir. It will replace one of two Mir units that have been malfunctioning recently. The generator functions by electrolysis, which separates water into its oxygen and hydrogen components. The hydrogen is vented and the oxygen is used for breathing by the Mir crew. The generator is 4.2 feet in length and 1.4 feet in diameter. STS-84, which is planned to include a Mir crew exchange of astronaut C. Michael Foale for Jerry M. Linenger, is targeted for a May 15 liftoff. It will be the sixth Shuttle-Mir docking.

Therapeutic Plasma Exchange in Critically Ill Children Requiring Intensive Care.

PubMed

Cortina, Gerard; McRae, Rosemary; Chiletti, Roberto; Butt, Warwick

2018-02-01

To characterize the clinical indications, procedural safety, and outcome of critically ill children requiring therapeutic plasma exchange. Retrospective observational study based on a prospective registry. Tertiary and quaternary referral 30-bed PICU. Forty-eight critically ill children who received therapeutic plasma exchange during an 8-year period (2007-2014) were included in the study. Therapeutic plasma exchange. A total of 48 patients underwent 244 therapeutic plasma exchange sessions. Of those, therapeutic plasma exchange was performed as sole procedure in 193 (79%), in combination with continuous renal replacement therapy in 40 (16.4%) and additional extracorporeal membrane oxygenation in 11 (4.6%) sessions. The most common admission diagnoses were hematologic disorders (30%), solid organ transplantation (20%), neurologic disorders (20%), and rheumatologic disorders (15%). Complications associated with the procedure occurred in 50 (21.2%) therapeutic plasma exchange sessions. Overall, patient survival from ICU was 82%. Although patients requiring therapeutic plasma exchange alone (n = 31; 64%) had a survival rate of 97%, those with additional continuous renal replacement therapy (n = 13; 27%) and extracorporeal membrane oxygenation (n = 4; 8%) had survival rates of 69% and 50%, respectively. Factors associated with increased mortality were lower Pediatric Index of Mortality 2 score, need for mechanical ventilation, higher number of failed organs, and longer ICU stay. Our results indicate that, in specialized centers, therapeutic plasma exchange can be performed relatively safely in critically ill children, alone or in combination with continuous renal replacement therapy and extracorporeal membrane oxygenation. Outcome in children requiring therapeutic plasma exchange alone is excellent. However, survival decreases with the number of failed organs and the need for continuous renal replacement therapy and extracorporeal membrane oxygenation.

Analyzing the dependence of oxygen incorporation current density on overpotential and oxygen partial pressure in mixed conducting oxide electrodes.

PubMed

Guan, Zixuan; Chen, Di; Chueh, William C

2017-08-30

The oxygen incorporation reaction, which involves the transformation of an oxygen gas molecule to two lattice oxygen ions in a mixed ionic and electronic conducting solid, is a ubiquitous and fundamental reaction in solid-state electrochemistry. To understand the reaction pathway and to identify the rate-determining step, near-equilibrium measurements have been employed to quantify the exchange coefficients as a function of oxygen partial pressure and temperature. However, because the exchange coefficient contains contributions from both forward and reverse reaction rate constants and depends on both oxygen partial pressure and oxygen fugacity in the solid, unique and definitive mechanistic assessment has been challenging. In this work, we derive a current density equation as a function of both oxygen partial pressure and overpotential, and consider both near and far from equilibrium limits. Rather than considering specific reaction pathways, we generalize the multi-step oxygen incorporation reaction into the rate-determining step, preceding and following quasi-equilibrium steps, and consider the number of oxygen ions and electrons involved in each. By evaluating the dependence of current density on oxygen partial pressure and overpotential separately, one obtains the reaction orders for oxygen gas molecules and for solid-state species in the electrode. We simulated the oxygen incorporation current density-overpotential curves for praseodymium-doped ceria for various candidate rate-determining steps. This work highlights a promising method for studying the exchange kinetics far away from equilibrium.

The mechanism of oxygen isotopic fractionation during fungal denitrification - A pure culture study

NASA Astrophysics Data System (ADS)

Wrage-Moennig, Nicole; Rohe, Lena; Anderson, Traute-Heidi; Braker, Gesche; Flessa, Heinz; Giesemann, Annette; Lewicka-Szczebak, Dominika; Well, Reinhard

2014-05-01

Nitrous oxide (N2O) from soil denitrification originates from bacteria and - to an unknown extent - also from fungi. During fungal denitrification, oxygen (O) exchange takes place between H2O and intermediates of the denitrification process as in bacterial exchange[1,2]. However, information about enzymes involved in fungal O exchanges and the associated fractionation effects is lacking. The objectives of this study were to estimate the O fractionation and O exchange during the fungal denitrifying steps using a conceptual model[2] adapted from concepts for bacterial denitrification[3], implementing controls of O exchange proposed by Aerssens, et al.[4] and using fractionation models by Snider et al.[5] Six different pure fungal cultures (five Hypocreales, one Sordariales) known to be capable of denitrification were incubated under anaerobic conditions, either with nitrite or nitrate. Gas samples were analyzed for N2O concentration and its isotopic signatures (SP, average δ15N, δ18O). To investigate O exchange, both treatments were also established with 18O-labelled water as a tracer in the medium. The Hypocreales strains showed O exchange mainly at NO2- reductase (Nir) with NO2- as electron acceptor and no additional O exchange at NO3- reductase (Nar) with NO3- as electron acceptor. The only Hypocreales species having higher O exchange with NO3- than with NO2- also showed O exchange at Nar. The Sordariales species tested seems capable of O exchange at NO reductase (Nor) additionally to O exchange at Nir with NO2-. The data will help to better interpret stable isotope values of N2O from soils. .[1] D. M. Kool, N. Wrage, O. Oenema, J. Dolfing, J. W. Van Groenigen. Oxygen exchange between (de)nitrification intermediates and H2O and its implications for source determination of NO?3- and N2O: a review. Rapid Commun. Mass Spec. 2007, 21, 3569. [2] L. Rohe, T.-H. Anderson, B. Braker, H. Flessa, A. Giesemann, N. Wrage-Mönnig, R. Well. Fungal Oxygen Exchange between Denitrification Intermediates and Water. Rapid Commun. Mass Spec. 2014, 28, 377. [3] K. L. Casciotti, J. K. Böhlke, M. R. McIlvin, S. J. Mroczkowski, J. E. Hannon. Oxygen Isotopes in Nitrite: Analysis, Calibration, and Equilibration. Anal. Chem. 2007, 79, 2427. [4] E. Aerssens, J. M. Tiedje, B. A. Averill. Isotope Labeling Studies on the Mechanisms of N-bond Formation in Denitrification J. Biol. Chem. 1986, 261, 9652. [5] D. M. Snider, J. J. Venkiteswaran, S. L. Schiff, J. Spoelstra. Deciphering the oxygen isotope composition of nitrous oxide produced by nitrification. Glob. Change Biol. 2012, 18, 356.

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

McNicol, Gavin

Wetlands cover only a small fraction of the Earth’s land surface, but have a disproportionately large influence on global climate. Low oxygen conditions in wetland soils slows down decomposition, leading to net carbon dioxide sequestration over long timescales, while also favoring the production of redox sensitive gases such as nitrous oxide and methane. Freshwater marshes in particular sustain large exchanges of greenhouse gases under temperate or tropical climates and favorable nutrient regimes, yet have rarely been studied, leading to poor constraints on the magnitude of marsh gas sources, and the biogeochemical drivers of flux variability. The Sacramento-San Joaquin Delta inmore » California was once a great expanse of tidal and freshwater marshes but underwent drainage for agriculture during the last two centuries. The resulting landscape is unsustainable with extreme rates of land subsidence and oxidation of peat soils lowering the surface elevation of much of the Delta below sea level. Wetland restoration has been proposed as a means to slow further subsidence and rebuild peat however the balance of greenhouse gas exchange in these novel ecosystems is still poorly described. In this dissertation I first explore oxygen availability as a control on the composition and magnitude of greenhouse gas emissions from drained wetland soils. In two separate experiments I quantify both the temporal dynamics of greenhouse gas emission and the kinetic sensitivity of gas production to a wide range of oxygen concentrations. This work demonstrated the very high sensitivity of carbon dioxide, methane, and nitrous oxide production to oxygen availability, in carbon rich wetland soils. I also found the temporal dynamics of gas production to follow a sequence predicted by thermodynamics and observed spatially in other soil or sediment systems. In the latter part of my dissertation I conduct two field studies to quantify greenhouse gas exchange and understand the carbon sources for decomposition in a 1 km2 restored wetland in the Sacramento Delta. By coupling flux measurements at multiple-scales with remote sensing imagery I showed that large methane emissions produce an overall climate warming effect from the wetland for the next several centuries, despite relatively high productivity. I also used radiocarbon analyses of wetland sediment carbon dioxide and methane to show that both bulk peat and recently fixed carbon contribute to decomposition in the wetland, and that their relative importance is regulated by proximity to, and the phenological cycles of, emergent vegetation.« less

Tidal controls on riverbed denitrification along a tidal freshwater zone

NASA Astrophysics Data System (ADS)

Knights, Deon; Sawyer, Audrey H.; Barnes, Rebecca T.; Musial, Cole T.; Bray, Samuel

2017-01-01

In coastal rivers, tidal pumping enhances the exchange of oxygen-rich river water across the sediment-water interface, controlling nitrogen cycling in riverbed sediment. We developed a one-dimensional, fluid flow and solute transport model that quantifies the influence of tidal pumping on nitrate removal and applied it to the tidal freshwater zone (TFZ) of White Clay Creek (Delaware, USA). In field observations and models, both oxygenated river water and anoxic groundwater deliver nitrate to carbon-rich riverbed sediment. A zone of nitrate removal forms beneath the aerobic interval, which expands and contracts over daily timescales due to tidal pumping. At high tide when oxygen-rich river water infiltrates into the bed, denitrification rates decrease by 25% relative to low tide. In the absence of tidal pumping, our model predicts that the aerobic zone would be thinner, and denitrification rates would increase by 10%. As tidal amplitude increases toward the coast, nitrate removal rates should decrease due to enhanced oxygen exchange across the sediment-water interface, based on sensitivity analysis. Denitrification hot spots in TFZs are more likely to occur in less permeable sediment under lower tidal ranges and higher rates of ambient groundwater discharge. Our models suggest that tidal pumping is not efficient at removing surface water nitrate but can remove up to 81% of nitrate from discharging groundwater in the TFZ of White Clay Creek. Given the high population densities of coastal watersheds, the reactive riverbeds of TFZs play a critical role in mitigating new nitrogen loads to coasts.

Comparative Study of Chromium(VI) Removal from Simulated Industrial Wastewater with Ion Exchange Resins

NASA Astrophysics Data System (ADS)

Li, Xiaofan; Shi, Shaoyuan; Cao, Hongbin; Li, Yuping; Xu, Dongyao

2018-06-01

Ion exchange process is an alternative technique for removal of heavy metal ions from industrial wastewater. The main aim of this paper is to evaluate the performance of different ion exchange resins in removing Cr(VI) from wastewater. The effects of resin types and dosage, initial pH were examined systemically. The results showed that the performance of different resins had obvious difference for the removal of the Cr(VI) ions, in which the type of functional groups of the resin was the main factor. The SEM images indicated that the micro-morphology of resins before and after adsorption of the Cr(VI) presented a little difference. The EDS analysis showed that the adsorbed Cr(VI) was uniformly distributed at the surface of the resins with formation of oxygen-containing groups. The adsorption isotherms and kinetics of Cr(VI) by the different resins are also discussed.

Cobalt sulfide aerogel prepared by anion exchange method with enhanced pseudocapacitive and water oxidation performances.

PubMed

Gao, Qiuyue; Shi, Zhenyu; Xue, Kaiming; Ye, Ziran; Hong, Zhanglian; Yu, Xinyao; Zhi, Mingjia

2018-05-25

This work introduces the anion exchange method into the sol-gel process for the first time to prepare a metal sulfide aerogel. A porous Co 9 S 8 aerogel with a high surface area (274.2 m 2 g -1 ) and large pore volume (0.87 cm 3 g -1 ) has been successfully prepared by exchanging cobalt citrate wet gel in thioacetamide and subsequently drying in supercritical ethanol. Such a Co 9 S 8 aerogel shows enhanced supercapacitive performance and catalytic activity toward oxygen evolution reaction (OER) compared to its oxide aerogel counterpart. High specific capacitance (950 F g -1 at 1 A g -1 ), good rate capability (74.3% capacitance retention from 1 to 20 A g -1 ) and low onset overpotential for OER (220 mV) were observed. The results demonstrated here have implications in preparing various sulfide chalcogels.

Cobalt sulfide aerogel prepared by anion exchange method with enhanced pseudocapacitive and water oxidation performances

NASA Astrophysics Data System (ADS)

Gao, Qiuyue; Shi, Zhenyu; Xue, Kaiming; Ye, Ziran; Hong, Zhanglian; Yu, Xinyao; Zhi, Mingjia

2018-05-01

This work introduces the anion exchange method into the sol-gel process for the first time to prepare a metal sulfide aerogel. A porous Co9S8 aerogel with a high surface area (274.2 m2 g‑1) and large pore volume (0.87 cm3 g‑1) has been successfully prepared by exchanging cobalt citrate wet gel in thioacetamide and subsequently drying in supercritical ethanol. Such a Co9S8 aerogel shows enhanced supercapacitive performance and catalytic activity toward oxygen evolution reaction (OER) compared to its oxide aerogel counterpart. High specific capacitance (950 F g‑1 at 1 A g‑1), good rate capability (74.3% capacitance retention from 1 to 20 A g‑1) and low onset overpotential for OER (220 mV) were observed. The results demonstrated here have implications in preparing various sulfide chalcogels.

Controllable positive exchange bias via redox-driven oxygen migration

DOE PAGES

Gilbert, Dustin A.; Olamit, Justin; Dumas, Randy K.; ...

2016-03-21

We report that ionic transport in metal/oxide heterostructures offers a highly effective means to tailor material properties via modification of the interfacial characteristics. However, direct observation of ionic motion under buried interfaces and demonstration of its correlation with physical properties has been challenging. Using the strong oxygen affinity of gadolinium, we design a model system of Gd xFe 1-x/NiCoO bilayer films, where the oxygen migration is observed and manifested in a controlled positive exchange bias over a relatively small cooling field range. The exchange bias characteristics are shown to be the result of an interfacial layer of elemental nickel andmore » cobalt, a few nanometres in thickness, whose moments are larger than expected from uncompensated NiCoO moments. This interface layer is attributed to a redox-driven oxygen migration from NiCoO to the gadolinium, during growth or soon after. Ultimately, these results demonstrate an effective path to tailoring the interfacial characteristics and interlayer exchange coupling in metal/oxide heterostructures.« less

Numerical modeling of the fetal blood flow in the placental circulatory system

NASA Astrophysics Data System (ADS)

Shannon, Alexander; Gallucci, Sergio; Mirbod, Parisa

2015-11-01

The placenta is a unique organ of exchange between the growing fetus and the mother. It incorporates almost all functions of the adult body, acting as the fetal lung, digestive and immune systems, to mention a few. The exchange of oxygen and nutrients takes place at the surface of the villous tree. Using an idealized geometry of the fetal villous trees in the mouse placenta, in this study we performed 3D computational analysis of the unsteady fetal blood flow, gas, and nutrient transport over the chorionic plate. The fetal blood was treated as an incompressible Newtonian fluid, and the oxygen and nutrient were treated as a passive scalar dissolved in blood plasma. The flow was laminar, and a commercial CFD code (COMSOL Multiphysics) has been used for the simulation. COMSOL has been selected because it is multi-physics FEM software that allows for the seamless coupling of different physics represented by partial differential equations. The results clearly illustrate that the specific branching pattern and the in-plane curvature of the fetal villous trees affect the delivery of blood, gas and nutrient transport to the whole placenta.

Synchrotron-Based In Situ Characterization of Carbon-Supported Platinum and Platinum Monolayer Electrocatalysts

DOE PAGES

Sasaki, Kotaro; Marinkovic, Nebojsa; Isaacs, Hugh S.; ...

2015-11-17

Understanding oxidation/dissolution mechanisms of Pt is critical in designing durable catalysts for the oxygen reduction reaction (ORR), but exact mechanisms remain unclear. Our present work explores the oxidation/dissolution of Pt and Pt monolayer (ML) electrocatalysts over a wide range of applied potentials using cells that facilitate in situ measurements by combining X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) measurements. Furthermore, the X-ray absorption near edge structure (XANES) measurement demonstrated that Pt nanoparticle surfaces were oxidized from metallic Pt to α-PtO 2-type oxide during the potential sweep from 0.41 to 1.5 V, and the transition state of O or OHmore » adsorption on Pt and the onset of the place exchange process were revealed by the delta mu (Δμ) method. Only the top layers of Pt nanoparticles were oxidized, while the inner Pt atoms remained intact. At a higher potential over 1.9 V, α-PtO 2-type surface oxides dissolve due to local acidification caused by the oxygen evolution reaction and carbon corrosion. Pt oxidation of Pt ML on the Pd nanoparticle electrocatalyst is considerably hampered compared with the Pt/C catalyst, presumably because preferential Pd oxidation proceeds at the defects in Pt MLs up to 0.91 V and through O penetrated through the Pt MLs by the place exchange process above 1.11 V.« less

Seasonal and interannual variability of dissolved oxygen around the Balearic Islands from hydrographic data

NASA Astrophysics Data System (ADS)

Balbín, R.; López-Jurado, J. L.; Aparicio-González, A.; Serra, M.

2014-10-01

Oceanographic data obtained between 2001 and 2011 by the Spanish Institute of Oceanography (IEO, Spain) have been used to characterise the spatial distribution and the temporal variability of the dissolved oxygen around the Balearic Islands (Mediterranean Sea). The study area includes most of the Western Mediterranean Sea, from the Alboran Sea to Cape Creus, at the border between France and Spain. Dissolved oxygen (DO) at the water surface is found to be in a state of equilibrium exchange with the atmosphere. In the spring and summer a subsurface oxygen supersaturation is observed due to the biological activity, above the subsurface fluorescence maximum. Minimum observed values of dissolved oxygen are related to the Levantine Intermediate Waters (LIW). An unusual minimum of dissolved oxygen concentrations was also recorded in the Alboran Sea Oxygen Minimum Zone. The Western Mediterranean Deep Waters (WMDW) and the Western Intermediate Waters (WIW) show higher values of dissolved oxygen than the Levantine Intermediate Waters due to their more recent formation. Using these dissolved oxygen concentrations it is possible to show that the Western Intermediate Waters move southwards across the Ibiza Channel and the deep water circulates around the Balearic Islands. It has also been possible to characterise the seasonal evolution of the different water masses and their dissolved oxygen content in a station in the Algerian sub-basin.

DNA combing on low-pressure oxygen plasma modified polysilsesquioxane substrates for single-molecule studies

PubMed Central

Sriram, K. K.; Chang, Chun-Ling; Rajesh Kumar, U.; Chou, Chia-Fu

2014-01-01

Molecular combing and flow-induced stretching are the most commonly used methods to immobilize and stretch DNA molecules. While both approaches require functionalization steps for the substrate surface and the molecules, conventionally the former does not take advantage of, as the latter, the versatility of microfluidics regarding robustness, buffer exchange capability, and molecule manipulation using external forces for single molecule studies. Here, we demonstrate a simple one-step combing process involving only low-pressure oxygen (O2) plasma modified polysilsesquioxane (PSQ) polymer layer to facilitate both room temperature microfluidic device bonding and immobilization of stretched single DNA molecules without molecular functionalization step. Atomic force microscopy and Kelvin probe force microscopy experiments revealed a significant increase in surface roughness and surface potential on low-pressure O2 plasma treated PSQ, in contrast to that with high-pressure O2 plasma treatment, which are proposed to be responsible for enabling effective DNA immobilization. We further demonstrate the use of our platform to observe DNA-RNA polymerase complexes and cancer drug cisplatin induced DNA condensation using wide-field fluorescence imaging. PMID:25332730

Description of a flow optimized oxygenator with integrated pulsatile pump.

PubMed

Borchardt, Ralf; Schlanstein, Peter; Arens, Jutta; Graefe, Roland; Schreiber, Fabian; Schmitz-Rode, Thomas; Steinseifer, Ulrich

2010-11-01

Extracorporeal membrane oxygenation (ECMO) is a well-established therapy for several lung and heart diseases in the field of neonatal and pediatric medicine (e.g., acute respiratory distress syndrome, congenital heart failure, cardiomyopathy). Current ECMO systems are typically composed of an oxygenator and a separate nonpulsatile blood pump. An oxygenator with an integrated pulsatile blood pump for small infant ECMO was developed, and this novel concept was tested regarding functionality and gas exchange rate. Pulsating silicone tubes (STs) were driven by air pressure and placed inside the cylindrical fiber bundle of an oxygenator to be used as a pump module. The findings of this study confirm that pumping blood with STs is a viable option for the future. The maximum gas exchange rate for oxygen is 48mL/min/L(blood) at a medium blood flow rate of about 300mL/min. Future design steps were identified to optimize the flow field through the fiber bundle to achieve a higher gas exchange rate. First, the packing density of the hollow-fiber bundle was lower than commercial oxygenators due to the manual manufacturing. By increasing this packing density, the gas exchange rate would increase accordingly. Second, distribution plates for a more uniform blood flow can be placed at the inlet and outlet of the oxygenator. Third, the hollow-fiber membranes can be individually placed to ensure equal distances between the surrounding hollow fibers. © 2010, Copyright the Authors. Artificial Organs © 2010, International Center for Artificial Organs and Transplantation and Wiley Periodicals, Inc.

pH matters: The influence of the catalyst ink on the oxygen reduction activity determined in thin film rotating disk electrode measurements

NASA Astrophysics Data System (ADS)

Inaba, Masanori; Quinson, Jonathan; Arenz, Matthias

2017-06-01

We investigated the influence of the ink properties of proton exchange membrane fuel cell (PEMFC) catalysts on the oxygen reduction reaction (ORR) activity determined in thin film rotating disk electrode (TF-RDE) measurements. It was found that the adaption of a previously reported ink recipe to home-made catalysts does not lead to satisfying results, although reported work could be reproduced using commercial catalyst samples. It is demonstrated that the pH of the catalyst ink, which has not been addressed in previous TF-RDE studies, is an important parameter that needs to be carefully controlled to determine the intrinsic ORR activity of high surface area catalysts.

Isotope shift of the 590-cm-1 Raman feature in underdoped Bi2Sr2CaCu2O8+δ

NASA Astrophysics Data System (ADS)

Hewitt, K. C.; Wang, N. L.; Irwin, J. C.; Pooke, D. M.; Pantoja, A. E.; Trodahl, H. J.

1999-10-01

Raman-scattering studies have been performed on underdoped Bi2Sr2CaCu2O8+δ. In single crystals underdoped by oxygen removal, a 590-cm-1 peak is observed in the B1g spectrum. The feature is observed to soften in frequency by 3.8% with isotopic exchange of 16O by 18O. In contrast, the 590-cm-1 peak is not observed in crystals underdoped by Y substitution which suggests that it is a vibrational mode activated by oxygen deficency. We have also found that underdoping leads to a depletion of low-energy spectral weight from regions of the Fermi surface located near the Brillouin-zone axes.

Mixing-dependent Reactions in the Hyporheic Zone: Laboratory and Numerical Experiments

NASA Astrophysics Data System (ADS)

Santizo, K. Y.; Eastes, L. A.; Hester, E. T.; Widdowson, M.

2017-12-01

The hyporheic zone is the surface water-groundwater interface surrounding the river's perimeter. Prior research demonstrates the ability of the hyporheic zone to attenuate pollutants when surface water cycles through reactive sediments (non-mixing-dependent reactions). However, the colocation of both surface and ground water within hyporheic sediments also allows mixing-dependent reactions that require mixing of reactants from these two water sources. Recent modeling studies show these mixing zones can be small under steady state homogeneous conditions, but do not validate those results in the laboratory or explore the range of hydrological characteristics that control the extent of mixing. Our objective was to simulate the mixing zone, quantify its thickness, and probe its hydrological controls using a "mix" of laboratory and numerical experiments. For the lab experiments, a hyporheic zone was simulated in a sand mesocosm, and a mixing-dependent abiotic reaction of sodium sulfite and dissolved oxygen was induced. Oxygen concentration response and oxygen consumption were visualized via planar optodes. Sulfate production by the mixing-dependent reaction was measured by fluid samples and a spectrophometer. Key hydrologic controls varied in the mesocosm included head gradient driving hyporheic exchange and hydraulic conductivity/heterogeneity. Results show a clear mixing area, sulfate production, and oxygen gradient. Mixing zone length (hyporheic flow cell size) and thickness both increase with the driving head gradient. For the numerical experiments, transient surface water boundary conditions were implemented together with heterogeneity of hydraulic conductivity. Results indicate that both fluctuating boundary conditions and heterogeneity increase mixing-dependent reaction. The hyporheic zone is deemed an attenuation hotspot by multiple studies, but here we demonstrate its potential for mixing-dependent reactions and the influence of important hydrological parameters.

Scanning tunneling microscopy image simulation of the rutile (110) TiO2 surface with hybrid functionals and the localized basis set approach

NASA Astrophysics Data System (ADS)

Di Valentin, Cristiana

2007-10-01

In this work we present a simplified procedure to use hybrid functionals and localized atomic basis sets to simulate scanning tunneling microscopy (STM) images of stoichiometric, reduced and hydroxylated rutile (110) TiO2 surface. For the two defective systems it is necessary to introduce some exact Hartree-Fock exchange in the exchange functional in order to correctly describe the details of the electronic structure. Results are compared to the standard density functional theory and planewave basis set approach. Both methods have advantages and drawbacks that are analyzed in detail. In particular, for the localized basis set approach, it is necessary to introduce a number of Gaussian function in the vacuum region above the surface in order to correctly describe the exponential decay of the integrated local density of states from the surface. In the planewave periodic approach, a thick vacuum region is required to achieve correct results. Simulated STM images are obtained for both the reduced and hydroxylated surface which nicely compare with experimental findings. A direct comparison of the two defects as displayed in the simulated STM images indicates that the OH groups should appear brighter than oxygen vacancies in perfect agreement with the experimental STM data.

Low Temperature Propane Oxidation over Co 3O 4 based Nano-array Catalysts. Ni Dopant Effect, Reaction Mechanism and Structural Stability

DOE PAGES

Ren, Zheng; Wu, Zili; Gao, Puxian; ...

2015-06-09

Low temperature propane oxidation has been achieved by Co 3O 4-based nano-array catalysts featuring low catalytic materials loading. The Ni doping into the Co 3O 4 lattice has led to enhanced reaction kinetics at low temperature by promoting the surface lattice oxygen activity. In situ DRIFTS investigation in tandem with isotopic oxygen exchange reveals that the propane oxidation proceeds via Mars-van Krevelen mechanism where surface lattice oxygen acts as the active site whereas O 2 in the reaction feed does not directly participate in CO 2 formation. The Ni doping promotes the formation of less stable carbonates on the surfacemore » to facilitate the CO 2 desorption. The thermal stability of Ni doped Co 3O 4 decreases with increased Ni concentration while catalytic activity increases. A balance between enhanced activity and compromised thermal stability shall be considered in the Ni doped Co 3O 4 nano-array catalysts for low temperature hydrocarbon oxidation. This study provides useful and timely guidance for rational catalyst design toward low temperature catalytic oxidation.« less

Macro- and microscopic properties of strontium doped indium oxide

NASA Astrophysics Data System (ADS)

Nikolaenko, Y. M.; Kuzovlev, Y. E.; Medvedev, Y. V.; Mezin, N. I.; Fasel, C.; Gurlo, A.; Schlicker, L.; Bayer, T. J. M.; Genenko, Y. A.

2014-07-01

Solid state synthesis and physical mechanisms of electrical conductivity variation in polycrystalline, strontium doped indium oxide In2O3:(SrO)x were investigated for materials with different doping levels at different temperatures (T = 20-300 °C) and ambient atmosphere content including humidity and low pressure. Gas sensing ability of these compounds as well as the sample resistance appeared to increase by 4 and 8 orders of the magnitude, respectively, with the doping level increase from zero up to x = 10%. The conductance variation due to doping is explained by two mechanisms: acceptor-like electrical activity of Sr as a point defect and appearance of an additional phase of SrIn2O4. An unusual property of high level (x = 10%) doped samples is a possibility of extraordinarily large and fast oxygen exchange with ambient atmosphere at not very high temperatures (100-200 °C). This peculiarity is explained by friable structure of crystallite surface. Friable structure provides relatively fast transition of samples from high to low resistive state at the expense of high conductance of the near surface layer of the grains. Microscopic study of the electro-diffusion process at the surface of oxygen deficient samples allowed estimation of the diffusion coefficient of oxygen vacancies in the friable surface layer at room temperature as 3 × 10-13 cm2/s, which is by one order of the magnitude smaller than that known for amorphous indium oxide films.

Temperature influences on water permeability and chlorpyrifos uptake in aquatic insects with differing respiratory strategies.

PubMed

Buchwalter, David B; Jenkins, Jeffrey J; Curtis, Lawrence R

2003-11-01

Aquatic insects have evolved diverse respiratory strategies that range from breathing atmospheric air to breathing dissolved oxygen. These strategies result in vast morphological differences among taxa in terms of exchange epithelial surface areas that are in direct contact with the surrounding water that, in turn, affect physiological processes. This paper examines the effects of acute temperature shifts on water permeability and chlorpyrifos uptake in aquatic insects with different respiratory strategies. While considerable differences existed in water permeability among the species tested, acute temperature shifts raised water influx rates similarly in air-breathing and gill-bearing taxa. This contrasts significantly with temperature-shift effects on chlorpyrifos uptake. Temperature shifts of 4.5 degrees C increased 14C-chlorpyrifos accumulation rates in the gill-bearing mayfly Cinygma sp. and in the air-breathing hemipteran Sigara washingtonensis. However, the temperature-induced increase in 14C-chlorpyrifos uptake after 8 h of exposure was 2.75-fold higher in Cinygma than in Sigara. Uptake of 14C-chlorpyrifos was uniformly higher in Cinygma than in Sigara in all experiments. These findings suggest that organisms with relatively large exchange epithelial surface areas are potentially more vulnerable to both osmoregulatory distress as well as contaminant accumulation. Temperature increases appear more likely to impact organisms that have relatively large exchange epithelial surface areas, both as an individual stressor and in combination with additional stressors such as contaminants.

Temperature influences on water permeability and chlorpyrifos uptake in aquatic insects with differing respiratory strategies

USGS Publications Warehouse

Buchwalter, D.B.; Jenkins, J.J.; Curtis, L.R.

2003-01-01

Aquatic insects have evolved diverse respiratory strategies that range from breathing atmospheric air to breathing dissolved oxygen. These strategies result in vast morphological differences among taxa in terms of exchange epithelial surface areas that are in direct contact with the surrounding water that, in turn, affect physiological processes. This paper examines the effects of acute temperature shifts on water permeability and chlorpyrifos uptake in aquatic insects with different respiratory strategies. While considerable differences existed in water permeability among the species tested, acute temperature shifts raised water influx rates similarly in air-breathing and gill-bearing taxa. This contrasts significantly with temperature-shift effects on chlorpyrifos uptake. Temperature shifts of 4.5??C increased 14C-chlorpyrifos accumulation rates in the gill-bearing mayfly Cinygma sp. and in the air-breathing hemipteran Sigara washingtonensis. However, the temperature-induced increase in 14C-chlorpyrifos uptake after 8 h of exposure was 2.75-fold higher in Cinygma than in Sigara. Uptake of 14C-chlorpyrifos was uniformly higher in Cinygma than in Sigara in all experiments. These findings suggest that organisms with relatively large exchange epithelial surface areas are potentially more vulnerable to both osmoregulatory distress as well as contaminant accumulation. Temperature increases appear more likely to impact organisms that have relatively large exchange epithelial surface areas, both as an individual stressor and in combination with additional stressors such as contaminants.

Phosphate oxygen isotope ratios as a tracer for sources and cycling of phosphate in North San Francisco Bay, California

USGS Publications Warehouse

McLaughlin, K.; Kendall, C.; Silva, S.R.; Young, M.; Paytan, A.

2006-01-01

A seasonal analysis assesing variations in the oxygen isotopic composition of dissolved inorganic phosphate (DIP) was conducted in the San Francisco Bay estuarine system, California. Isotopic fractionation of oxygen in DIP (exchange of oxygen between phosphate and environmental water) at surface water temperatures occurs only as a result of enzyme-mediated, biological reactions. Accordingly, if phospate demand is low relative to input and phosphate is not heavily cycled in the ecosystem, the oxygen isotopic composition of DIP (?? 18Op) will reflect the isotopic composition of the source of phosphate to the system. Such is the case for the North San Francisco Bay, an anthropogenically impacted estuary with high surface water phosphate concentrations. Variability in the ?? 18Op in the bay is primarily controlled by mixing of water masses with different ??18Op signatures. The ??18Op values range from 11.4??? at the Sacramento River to 20.1??? at the Golden Gate. Deviations from the two-component mixing model for the North Bay reflect additional, local sources of phosphate to the estuary that vary seasonally. Most notably, deviations from the mixing model occur at the confluence of a major river into the bay during periods of high river discharge and near wastewater treatment outlets. These data suggest that ??18Op can be an effective tool for identifying P point sources and understanding phosphate dynamics in estuarine systems. Copyright 2006 by the American Geophysical Union.

Oxygen isotope fractionation between analcime and water - An experimental study

NASA Technical Reports Server (NTRS)

Karlsson, Haraldur R.; Clayton, Robert N.

1990-01-01

The oxygen isotope fractionation between analcime and water is studied to test the feasibility of using zeolites as low-temperature thermometers. The fractionation of oxygen isotopes between natural analcime and water is determined at 300, 350, and 400 C, and at fluid pressures ranging from 1.5 to 5.0 kbar. Also, isotope ratios for the analcime framework, the channel water, and bulk water are obtained. The results suggest that the channel water is depleted in O-18 relative to bulk water by a constant value of about 5 percent, nearly independent of temperature. The analcime-water fractionation curve is presented, showing that the exchange has little effect on grain morphology and does not involve recrystallization. The exchange is faster than any other observed for a silicate. The exchange rates suggest that zeolites in active high-temperature geothermal areas are in oxygen isotopic equilibrium with ambient fluids. It is concluded that calibrated zeolites may be excellent low-temperature oxygen isotope geothermometers.

Synergism between airborne singlet oxygen and a trisubstituted olefin sulfonate for the inactivation of bacteria.

PubMed

Choudhury, Rajib; Greer, Alexander

2014-04-01

The reactivity of a trisubstituted alkene surfactant (8-methylnon-7-ene-1 sulfonate, 1) to airborne singlet oxygen in a solution containing E. coli was examined. Surfactant 1 was prepared by a Strecker-type reaction of 9-bromo-2-methylnon-2-ene with sodium sulfite. Submicellar concentrations of 1 were used that reacted with singlet oxygen by an "ene" reaction to yield two hydroperoxides (7-hydroperoxy-8-methylnon-8-ene-1 sulfonate and (E)-8-hydroperoxy-8-methylnon-6-ene-1 sulfonate) in a 4:1 ratio. Exchanging the H2O solution for D2O where the lifetime of solution-phase singlet oxygen increases by 20-fold led to an ∼2-fold increase in the yield of hydroperoxides pointing to surface activity of singlet oxygen with the surfactant in a partially solvated state. In this airborne singlet oxygen reaction, E. coli inactivation was monitored in the presence and absence of 1 and by a LIVE/DEAD cell permeabilization assay. It was shown that the surfactant has low dark toxicity with respect to the bacteria, but in the presence of airborne singlet oxygen, it produces a synergistic enhancement of the bacterial inactivation. How the ene-derived surfactant hydroperoxides can provoke (1)O2 toxicity and be of general utility is discussed.

The long-term carbon cycle, fossil fuels and atmospheric composition.

PubMed

Berner, Robert A

2003-11-20

The long-term carbon cycle operates over millions of years and involves the exchange of carbon between rocks and the Earth's surface. There are many complex feedback pathways between carbon burial, nutrient cycling, atmospheric carbon dioxide and oxygen, and climate. New calculations of carbon fluxes during the Phanerozoic eon (the past 550 million years) illustrate how the long-term carbon cycle has affected the burial of organic matter and fossil-fuel formation, as well as the evolution of atmospheric composition.

Synthesis of Fe nanoparticles on polyaniline covered carbon nanotubes for oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Hu, Tian-Hang; Yin, Zhong-Shu; Guo, Jian-Wei; Wang, Cheng

2014-12-01

Fe nanoparticles immobilized on polyaniline-covered carbon nanotube (CNT) surfaces (Fe NPs-PANI/CNT) are prepared by reducing FeCl3 in the mixing solution of aniline and CNT. Significantly, the structure of such composites can be effectively optimized by pretreating FeCl3 with sodium citrate (CA). In the absence of CNTs, we found these two routes have large differences in reduction behaviors and different PANI states with varied conductivities. Therefore, the self-assembly mechanism in the preparation is proposed and the controlled self-assembly manner in the pretreating route is disclosed. Under acid condition, both catalysts demonstrate high oxygen reduction reaction (ORR) activity with four-electron pathway, and high electrochemical durability, revealing a promising application in the proton exchange membrane fuel cells. However, the high Tafel slopes relating to the surface red-ox couple and porous conductivity are still the main obstacles to improve their ORR dynamic, and more efforts on these aspects are needed to drive non-noble catalyst application in future.

Application of green chemistry techniques to prepare electrocatalysts for direct methanol fuel cells.

PubMed

Shimizu, Kenichi; Wang, Joanna S; Wai, Chien M

2010-03-25

A series of green techniques for synthesizing carbon nanotube-supported platinum nanoparticles and their high electrocatalytic activity toward methanol fuel cell applications are reported. The techniques utilize either the supercritical fluid carbon dioxide or water as a medium for depositing platinum nanoparticles on surfaces of multiwalled or single-walled carbon nanotubes. The catalytic properties of the carbon nanotubes-supported Pt nanoparticle catalysts prepared by four different techniques are compared for anodic oxidation of methanol and cathodic reduction of oxygen using cyclic voltammetry. One technique using galvanic exchange of Pt(2+) in water with zerovalent iron present on the surfaces of as-grown single-walled carbon nanotubes produces a Pt catalyst that shows an unusually high catalytic activity for reduction of oxygen but a negligible activity for oxidation of methanol. This fuel-selective catalyst may have a unique application as a cathode catalyst in methanol fuel cells to alleviate the problems caused by crossover of methanol through the polymer electrolyte membrane.

Two band model for the cuprates

NASA Astrophysics Data System (ADS)

Liu, Shiu; White, Steven

2009-03-01

We use a numerical canonical transformation approach to derive an effective two-band model for the hole-doped cuprates, which keeps both oxygen and copper orbitals but removes double occupancy from each. A similar model was considered previously by Frenkel, Gooding, Shraiman, and Siggia (PRB 41, number 1, page 350). We compare the numerically derived model with previously obtained analytical results. In addition to the usual hopping terms between oxygens tpp and Cu-Cu exchange terms Jdd, the model also includes a strong copper-oxygen exchange interaction Jpd and a Kondo-like spin-flip oxygen-oxygen hopping term Kpdp. We use the density matrix renormalization group to study the charge, spin, and pairing properties of the derived model on ladder systems.

21 CFR 870.4350 - Cardiopulmonary bypass oxygenator.

Code of Federal Regulations, 2010 CFR

2010-04-01

... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Cardiopulmonary bypass oxygenator. 870.4350... bypass oxygenator. (a) Identification. A cardiopulmonary bypass oxygenator is a device used to exchange... the FDA guidance document entitled “Guidance for Cardiopulmonary Bypass Oxygenators 510(k) Submissions...

21 CFR 870.4350 - Cardiopulmonary bypass oxygenator.

Code of Federal Regulations, 2011 CFR

2011-04-01

... 21 Food and Drugs 8 2011-04-01 2011-04-01 false Cardiopulmonary bypass oxygenator. 870.4350... bypass oxygenator. (a) Identification. A cardiopulmonary bypass oxygenator is a device used to exchange... the FDA guidance document entitled “Guidance for Cardiopulmonary Bypass Oxygenators 510(k) Submissions...

Imaging oxygen distribution in marine sediments. The importance of bioturbation and sediment heterogeneity.

PubMed

Pischedda, L; Poggiale, J C; Cuny, P; Gilbert, F

2008-06-01

The influence of sediment oxygen heterogeneity, due to bioturbation, on diffusive oxygen flux was investigated. Laboratory experiments were carried out with 3 macrobenthic species presenting different bioturbation behaviour patterns: the polychaetes Nereis diversicolor and Nereis virens, both constructing ventilated galleries in the sediment column, and the gastropod Cyclope neritea, a burrowing species which does not build any structure. Oxygen two-dimensional distribution in sediments was quantified by means of the optical planar optode technique. Diffusive oxygen fluxes (mean and integrated) and a variability index were calculated on the captured oxygen images. All species increased sediment oxygen heterogeneity compared to the controls without animals. This was particularly noticeable with the polychaetes because of the construction of more or less complex burrows. Integrated diffusive oxygen flux increased with oxygen heterogeneity due to the production of interface available for solute exchanges between overlying water and sediments. This work shows that sediment heterogeneity is an important feature of the control of oxygen exchanges at the sediment-water interface.

Water exchange in manganese-based water-oxidizing catalysts in photosynthetic systems: from the water-oxidizing complex in photosystem II to nano-sized manganese oxides.

PubMed

Najafpour, Mohammad Mahdi; Isaloo, Mohsen Abbasi; Eaton-Rye, Julian J; Tomo, Tatsuya; Nishihara, Hiroshi; Satoh, Kimiyuki; Carpentier, Robert; Shen, Jian-Ren; Allakhverdiev, Suleyman I

2014-09-01

The water-oxidizing complex (WOC), also known as the oxygen-evolving complex (OEC), of photosystem II in oxygenic photosynthetic organisms efficiently catalyzes water oxidation. It is, therefore, responsible for the presence of oxygen in the Earth's atmosphere. The WOC is a manganese-calcium (Mn₄CaO₅(H₂O)₄) cluster housed in a protein complex. In this review, we focus on water exchange chemistry of metal hydrates and discuss the mechanisms and factors affecting this chemical process. Further, water exchange rates for both the biological cofactor and synthetic manganese water splitting are discussed. The importance of fully unveiling the water exchange mechanism to understand the chemistry of water oxidation is also emphasized here. This article is part of a special issue entitled: photosynthesis research for sustainability: keys to produce clean energy. Copyright © 2014 Elsevier B.V. All rights reserved.

Zhamanshin astrobleme provides evidence for carbonaceous chondrite and post-impact exchange between ejecta and Earth's atmosphere.

PubMed

Magna, Tomáš; Žák, Karel; Pack, Andreas; Moynier, Frédéric; Mougel, Bérengère; Peters, Stefan; Skála, Roman; Jonášová, Šárka; Mizera, Jiří; Řanda, Zdeněk

2017-08-09

Chemical fingerprints of impacts are usually compromised by extreme conditions in the impact plume, and the contribution of projectile matter to impactites does not often exceed a fraction of per cent. Here we use chromium and oxygen isotopes to identify the impactor and impact-plume processes for Zhamanshin astrobleme, Kazakhstan. ε 54 Cr values up to 1.54 in irghizites, part of the fallback ejecta, represent the 54 Cr-rich extremity of the Solar System range and suggest a CI-like chondrite impactor. Δ 17 O values as low as -0.22‰ in irghizites, however, are incompatible with a CI-like impactor. We suggest that the observed 17 O depletion in irghizites relative to the terrestrial range is caused by partial isotope exchange with atmospheric oxygen (Δ 17 O = -0.47‰) following material ejection. In contrast, combined Δ 17 O-ε 54 Cr data for central European tektites (distal ejecta) fall into the terrestrial range and neither impactor fingerprint nor oxygen isotope exchange with the atmosphere are indicated.Identifying the original impactor from craters remains challenging. Here, the authors use chromium and oxygen isotopes to indicate that the Zhamanshin astrobleme impactor was a carbonaceous chrondrite by demonstrating that depleted 17O values are due to exchange with atmospheric oxygen.

Gas Transfer in Cellularized Collagen-Membrane Gas Exchange Devices.

PubMed

Lo, Justin H; Bassett, Erik K; Penson, Elliot J N; Hoganson, David M; Vacanti, Joseph P

2015-08-01

Chronic lower respiratory disease is highly prevalent in the United States, and there remains a need for alternatives to lung transplant for patients who progress to end-stage lung disease. Portable or implantable gas oxygenators based on microfluidic technologies can address this need, provided they operate both efficiently and biocompatibly. Incorporating biomimetic materials into such devices can help replicate native gas exchange function and additionally support cellular components. In this work, we have developed microfluidic devices that enable blood gas exchange across ultra-thin collagen membranes (as thin as 2 μm). Endothelial, stromal, and parenchymal cells readily adhere to these membranes, and long-term culture with cellular components results in remodeling, reflected by reduced membrane thickness. Functionally, acellular collagen-membrane lung devices can mediate effective gas exchange up to ∼288 mL/min/m(2) of oxygen and ∼685 mL/min/m(2) of carbon dioxide, approaching the gas exchange efficiency noted in the native lung. Testing several configurations of lung devices to explore various physical parameters of the device design, we concluded that thinner membranes and longer gas exchange distances result in improved hemoglobin saturation and increases in pO2. However, in the design space tested, these effects are relatively small compared to the improvement in overall oxygen and carbon dioxide transfer by increasing the blood flow rate. Finally, devices cultured with endothelial and parenchymal cells achieved similar gas exchange rates compared with acellular devices. Biomimetic blood oxygenator design opens the possibility of creating portable or implantable microfluidic devices that achieve efficient gas transfer while also maintaining physiologic conditions.

Letter: Observation of the 16O/18O exchange during electrospray ionization.

PubMed

Kostyukevich, Yury; Kononikhin, Alexey; Popov, Igor; Nikolaev, Eugene

2015-01-01

Isotopic exchange approach coupled to high-resolution mass spectrometry has become the power analytical approach for a wide range of analytical and bioanalyticall applications. Considerable efforts have been dedicated to developing fast exchange techniques directly in the ionization source. But all such methods are limited to the hydrogen/deuterium exchange approaches. In this paper we demonstrate that certain types of oxygen atoms can also be exchanged for (18)O on the time scale of the ionization process. Using HIO(3) and NaIO(4) and by infusing the heavy water H(2)(18)O in the ESI source we have demonstrated that it is possible to obtain a high level of oxygen exchange. It was observed that the rate of this exchange depends to a large extent on the temperature of the desolvating capillary of the mass spectrometer. Several other species, such as peptides, oligonucleotides and low weight organic molecules, were subjected to in-ESI (16)O/(18)O exchange but the exchange was not observed.

Perfluorocarbon-associated gas exchange in normal and acid-injured large sheep.

PubMed

Hernan, L J; Fuhrman, B P; Kaiser, R E; Penfil, S; Foley, C; Papo, M C; Leach, C L

1996-03-01

We hypothesized that a) perfluorocarbon-associated gas exchange could be accomplished in normal large sheep; b) the determinants of gas exchange would be similar during perfluorocarbon-associated gas exchange and conventional gas ventilation; c)in large animals with lung injury, perfluorocarbon-associated gas exchange could be used to enhance gas exchange without adverse effects on hemodynamics; and d) the large animal with lung injury could be supported with an FIO2 of <1.0 during perfluorocarbon-associated gas exchange. Prospective, observational animal study and prospective randomized, controlled animal study. An animal laboratory in a university setting. Thirty adult ewes. Five normal ewes (61.0 +/- 4.0 kg) underwent perfluorocarbon-associated gas exchange to ascertain the effects of tidal volume, end-inspiratory pressure, and positive end-expiratory pressure (PEEP) on oxygenation. Respiratory rate, tidal volume, and minute ventilation were studied to determine their effects on CO2 clearance. Sheep, weighing 58.9 +/- 8.3 kg, had lung injury induced by instilling 2 mL/kg of 0.05 Normal hydrochloric acid into the trachea. Five minutes after injury, PEEP was increased to 10 cm H2O. Ten minutes after injury, sheep with Pao2 values of <100 torr (<13.3 kPa) were randomized to continue gas ventilation (control, n=9) or to institute perfluorocarbon-associated gas exchange (n=9) by instilling 1.6 L of unoxygenated perflubron into the trachea and resuming gas ventilation. Blood gas and hemodynamic measurements were obtained throughout the 4-hr study. Both tidal volume and end-inspiratory pressure influenced oxygenation in normal sheep during perfluorocarbon-associated gas exchange. Minute ventilation determined CO2 clearance during perfluorocarbon-associated gas exchange in normal sheep. After acid aspiration lung injury, perfluorocarbon-associated gas exchange increased PaO2 and reduced intrapulmonary shunt fraction. Hypoxia and intrapulmonary shunting were unabated after injury in control animals. Hemodynamics were not influenced by the institution of perfluorocarbon-associated gas exchange. Tidal volume and end-inspiratory pressure directly influence oxygenation during perfluorocarbon-associated gas exchange in large animals. Minute ventilation influences clearance of CO2. In adult sheep with acid aspiration lung injury, perfluorocarbon-associated gas exchange at an FIO2 of <1.0 supports oxygenation and improves intrapulmonary shunting, without adverse hemodynamic effects, when compared with conventional gas ventilation.

High-Pressure Oxygen Generation for Outpost EVA

NASA Technical Reports Server (NTRS)

Jeng, Frank; Conger, Bruce; Anderson, Molly

2008-01-01

Low Lunar Orbit (LLO) poses unique thermal challenges for the orbiting space craft, particularly regarding the performance of the radiators. The emitted infrared (IR) heat flux from the lunar surface varies drastically from the light side to the dark side of the moon. Due to the extremely high incident IR flux, especially at low beta angles, a radiator is oftentimes unable to reject the vehicle heat load throughout the entire lunar orbit. One solution to this problem is to implement Phase Change Material (PCM) Heat Exchangers. PCM Heat Exchangers act as a "thermal capacitor, storing thermal energy when the radiator is unable to reject the required heat load. The stored energy is then removed from the PCM heat exchanger when the environment is more benign. Because they do not use an expendable resource, such as the feed water used by sublimators and evaporators, PCM Heat Exchangers are ideal for long duration Low Lunar Orbit missions. The Advanced Thermal Control project at JSC is completing a PCM heat exchanger life test to determine whether further technology development is warranted. The life test is being conducted on four nPentadecane, carbon filament heat exchangers. Fluid loop performance, repeatability, and measurement of performance degradation over 2500 meltfreeze cycles will be performed and reported in the current document.

A New, Noninvasive Method of Measuring Impaired Pulmonary Gas Exchange in Lung Disease: An Outpatient Study.

PubMed

West, John B; Crouch, Daniel R; Fine, Janelle M; Makadia, Dipen; Wang, Daniel L; Prisk, G Kim

2018-02-13

It would be valuable to have a noninvasive method of measuring impaired pulmonary gas exchange in patients with lung disease and thus reduce the need for repeated arterial punctures. This study reports the results of using a new test in a group of outpatients attending a pulmonary clinic. Inspired and expired partial pressure of oxygen (PO 2 ) and Pco 2 are continually measured by small, rapidly responding analyzers. The arterial PO 2 is calculated from the oximeter blood oxygen saturation level and the oxygen dissociation curve. The PO 2 difference between the end-tidal gas and the calculated arterial value is called the oxygen deficit. Studies on 17 patients with a variety of pulmonary diseases are reported. The mean ± SE oxygen deficit was 48.7 ± 3.1 mm Hg. This finding can be contrasted with a mean oxygen deficit of 4.0 ± 0.88 mm Hg in a group of 31 normal subjects who were previously studied (P < .0001). The analysis emphasizes the value of measuring the composition of alveolar gas in determining ventilation-perfusion ratio inequality. This factor is largely ignored in the classic index of impaired pulmonary gas exchange using the ideal alveolar PO 2 to calculate the alveolar-arterial oxygen gradient. The results previously reported in normal subjects and the present studies suggest that this new noninvasive test will be valuable in assessing abnormal gas exchange in the clinical setting. Copyright © 2018 American College of Chest Physicians. Published by Elsevier Inc. All rights reserved.

Role of oxygen defects on the magnetic properties of ultra-small Sn1-xFexO2 nanoparticles

NASA Astrophysics Data System (ADS)

Dodge, Kelsey; Chess, Jordan; Eixenberger, Josh; Alanko, Gordon; Hanna, Charles B.; Punnoose, Alex

2013-05-01

Although the role of oxygen defects in the magnetism of metal oxide semiconductors has been widely discussed, it is been difficult to directly measure the oxygen defect concentration of samples to verify this. This work demonstrates a direct correlation between the photocatalytic activity of Sn1-xFexO2 nanoparticles and their magnetic properties. For this, a series of ˜2.6 nm sized, well characterized, single-phase Sn1-xFexO2 crystallites with x = 0-0.20 were synthesized using tin acetate, urea, and appropriate amounts of iron acetate. X-ray photoelectron spectroscopy confirmed the concentration and 3+ oxidation state of the doped Fe ions. The maximum magnetic moment/Fe ion, μ, of 1.6 × 10-4 μB observed for the 0.1% Fe doped sample is smaller than the expected spin-only contribution from either high or low spin Fe3+ ions, and μ decreases with increasing Fe concentration. This behavior cannot be explained by the existing models of magnetic exchange. Photocatalytic studies of pure and Fe-doped SnO2 were used to understand the roles of doped Fe3+ ions and of the oxygen vacancies and defects. The photocatalytic rate constant k also showed an increase when SnO2 nanoparticles were doped with low concentrations of Fe3+, reaching a maximum at 0.1% Fe, followed by a rapid decrease of k for further increase in Fe%. Fe doping presumably increases the concentration of oxygen vacancies, and both Fe3+ ions and oxygen vacancies act as electron acceptors to reduce e--h+ recombination and promote transfer of electrons (and/or holes) to the nanoparticle surface, where they participate in redox reactions. This electron transfer from the Fe3+ ions to local defect density of states at the nanoparticle surface could develop a magnetic moment at the surface states and leads to spontaneous ferromagnetic ordering of the surface shell under favorable conditions. However, at higher doping levels, the same Fe3+ ions might act as recombination centers causing a decrease of both k and magnetic moment μ.

Long-Term (4 mo) Oxygen Isotope Exchange Experiment between Zircon and Hydrothermal Fluid

NASA Astrophysics Data System (ADS)

Bindeman, I. N.; Schmitt, A. K.; Lundstrom, C.; Golledge, S.

2013-12-01

Knowing oxygen diffusivity in zircon has several critical applications: 1) establishing zircon stability and solubility in hot silica-saturated hydrothermal solutions; 2) deriving metamorphic and magmatic heating timescales from intra-crystal oxygen isotopic gradients; 3) assessing the survivability of oxygen isotopic signatures in Hadean zircons. We report results of a microanalytical investigation of an isotope exchange experiment using a cold-seal pressure apparatus at 850°C and 500 MPa over 4 months duration. Natural zircon, quartz and rutile were sealed with a silica-rich solution doped with 18-O, D, 7-Li and 10-B in a gold capsule. The diffusion length-scales were examined by depth profiling using time-of-flight (TOF) and high-sensitivity dynamic secondary ionization mass spectrometry (SIMS). Starting materials had distinct and homogeneous δ18O: zircon from Mesa Falls tuff of Yellowstone (+3.6‰), rutile from Karelia (-29‰), Bishop Tuff Quartz (+8.4‰), and δ18O doped water (+400‰). Starting material zircon showed invariant 18O/16O during depth profiling. After the 4 month experiment, rutile crystal surfaces displayed etching (100's of nm), while zircon exteriors lacked visible change. Quartz was completely dissolved and reprecipitated in a minor residue. Rutile developed ~2 μm long Fickian diffusion profiles largely consistent with the wet diffusion coefficients for rutile previously reported [1]. Surface U-Pb dating of zircon detected no significant Pb loss from the outermost ~300 nm of the crystal face and returned identical core-face ages. We performed δ18O depth profiling of zircon in two directions. First, forward profiles (crystal rim inwards) by dynamic SIMS (no surface treatment besides Au-coating; Cs+ beam of 20 kV impact energy) showed initially high and decreasing 18O/16O over ~130 nm; TOF-SIMS forward profiles using a 2 kV Cs+ sputter beam and 25 kV Bi3+ primary ions on uncoated zircon surfaces (cleaned for 2 min with HF) yielded decreasing 18O/16O over a similar length scale. These profile lengths are largely consistent with wet diffusion coefficient for zircon reported by [2]. In contrast, back-side depth profiling was conducted by dynamic SIMS on a 1 μm thick wafer cut from the zircon by FIB. No significant elevation in 18O/16O was detected when the surface layer was penetrated, consistent with dry diffusion coefficients of [2]. The results suggest that nm-scale SIMS surface analysis of isotope ratios is challenging. We are investigating if they can be critically affected by knock-on effects and/or continuous mixing of a very thin enriched surface layer during depth profiling in our and previous experiments. [1] Moore et al., 1998, Am. Min. 83, 700-711 [2] Watson and Cherniak, 1997, EPSL 148, 537-544

The effect of sustained hypoxia on the cardio-respiratory response of bowfin Amia calva: implications for changes in the oxygen transport system.

PubMed

Porteus, C S; Wright, P A; Milsom, W K

2014-03-01

This study examined mechanisms underlying cardio-respiratory acclimation to moderate sustained hypoxia (6.0 kPa for 7 days at 22° C) in the bowfin Amia calva, a facultative air-breathing fish. This level of hypoxia is slightly below the critical oxygen tension (pcrit ) of A. calva denied access to air (mean ± s.e. = 9.3 ± 1.0 kPa). Before exposure to sustained hypoxia, A. calva with access to air increased air-breathing frequency on exposure to acute progressive hypoxia while A. calva without access to air increased gill-breathing frequency. Exposure to sustained hypoxia increased the gill ventilation response to acute progressive hypoxia in A. calva without access to air, regardless of whether they had access to air or not during the sustained hypoxia. Additionally, there was a decrease in Hb-O2 binding affinity in these fish. This suggests that, in A. calva, acclimation to hypoxia elicits changes that increase oxygen delivery to the gas exchange surface for oxygen uptake and reduce haemoglobin affinity to enhance oxygen delivery to the tissues. © 2013 The Fisheries Society of the British Isles.

The effect of different oxygen exchange layers on TaO x based RRAM devices

NASA Astrophysics Data System (ADS)

Alamgir, Zahiruddin; Holt, Joshua; Beckmann, Karsten; Cady, Nathaniel C.

2018-01-01

In this work, we investigated the effect of the oxygen exchange layer (OEL) on the resistive switching properties of TaO x based memory cells. It was found that the forming voltage, SET-RESET voltage, R off, R on and retention properties are strongly correlated with the oxygen scavenging ability of the OEL, and the resulting oxygen vacancy formation ability of this layer. Higher forming voltage was observed for OELs having lower electronegativity/lower Gibbs free energy for oxide formation, and devices fabricated with these OELs exhibited an increased memory window, when using similar SET-RESET voltage range.

Redox Sorption of Oxygen Dissolved in Water on Copper Nanoparticles in an Ion Exchange Matrix

NASA Astrophysics Data System (ADS)

Vakhnin, D. D.; Pridorogina, V. E.; Polyanskii, L. N.; Kravchenko, T. A.; Gorshkov, V. S.

2018-01-01

The redox sorption of molecular oxygen from water by a thin granular layer of a copper-ion exchanger nanocomposite in the currentless mode and under cathodic polarization is studied. The speed of propagation of the boundaries of the chemical reaction of stepwise oxidation of copper nanoparticles under the conditions of polarization slows considerably. At the same time, the amount of electrochemically regenerated copper from the resulting oxides that is capable of interacting with oxygen again grows. The stationarity of the redox sorption of oxygen is due to the equality of the rates of oxidation and reduction of the metallic component of the composite.

Void space inside the developing seed of Brassica napus and the modelling of its function

PubMed Central

Verboven, Pieter; Herremans, Els; Borisjuk, Ljudmilla; Helfen, Lukas; Ho, Quang Tri; Tschiersch, Henning; Fuchs, Johannes; Nicolaï, Bart M; Rolletschek, Hardy

2013-01-01

The developing seed essentially relies on external oxygen to fuel aerobic respiration, but it is currently unknown how oxygen diffuses into and within the seed, which structural pathways are used and what finally limits gas exchange. By applying synchrotron X-ray computed tomography to developing oilseed rape seeds we uncovered void spaces, and analysed their three-dimensional assembly. Both the testa and the hypocotyl are well endowed with void space, but in the cotyledons, spaces were small and poorly inter-connected. In silico modelling revealed a three orders of magnitude range in oxygen diffusivity from tissue to tissue, and identified major barriers to gas exchange. The oxygen pool stored in the voids is consumed about once per minute. The function of the void space was related to the tissue-specific distribution of storage oils, storage protein and starch, as well as oxygen, water, sugars, amino acids and the level of respiratory activity, analysed using a combination of magnetic resonance imaging, specific oxygen sensors, laser micro-dissection, biochemical and histological methods. We conclude that the size and inter-connectivity of void spaces are major determinants of gas exchange potential, and locally affect the respiratory activity of a developing seed. PMID:23692271

Effects of a flood pulse on exchange flows along a sinuous stream

NASA Astrophysics Data System (ADS)

Käser, D.; Brunner, P.; Renard, P.; Perrochet, P.; Schirmer, M.; Hunkeler, D.

2012-04-01

Flood pulses are important events for river ecosystems: they create hydrological interactions at the terrestrial/aquatic interface that fuel biological productivity and shape the hyporheic-riparian habitats. For example, floods promote faunal activity and decomposition by increasing the supply of oxygenated water in downwelling areas, while the following recession periods tend to provide stable thermal conditions favoured by fish or insects in areas of groundwater upwelling. This 3-D modelling study investigates the effect of stream stage transience (with events characterised by their intensity and duration) on hydrological exchanges between the surface and the near-stream subsurface. It evaluates, in particular, its effect on streams of varying sinuosity by quantifying the dynamic response of: (1) subsurface flow paths, (2) the exchange pattern at the sediment-water interface, and (3) integrative measures such as total exchange flux and total storage. Understanding geomorphological controls on groundwater/surface water interactions is attractive because topography is generally better constrained than subsurface parameters, and can be used in data-poor situations. The numerical model represents a hypothetical alluvial plain limited by impervious bedrock on all four sides, and in which the channel meanders according to the sine-generated curve of Langbein and Leopold (1966). As the model (HydroGeoSphere) couples surface and subsurface flow, the stream stage transience is imposed by a fluctuating head at the channel inlet. Preliminary results show that a simple rectangular flood pulse in an idealised sinuous stream without additional complexity can generate multiple flow direction reversals at a single point in the channel. The initial conditions of the groundwater table, the channel sinuosity and the time characteristics of the flood pulse all control exchange flow features in different ways. Results are also compared with 'bank storage' analytical solutions that typically assume a straight channel. The discussion covers an evaluation of this work with respect to previous studies that considered the influence of sinuosity on interfacial exchange flows. It addresses the issue of steady vs. transient exchanges, which is of uppermost importance at the operational scale of river restoration schemes. Langbein WB, Leopold LB. 1966. River meanders - theory of minimum variance. U.S. Geol. Surv. Prof. Pap. 422-H: 15 p.

Synthesis of finely divided molybdenum sulfide nanoparticles in propylene carbonate solution

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

Afanasiev, Pavel, E-mail: pavel.afanasiev@ircelyon.univ-lyon1.fr

2014-05-01

Molybdenum sulfide nanoparticles have been prepared from the reflux solution reaction involving ammonium heptamolybdate and elemental sulfur in propylene carbonate. Addition to the reaction mixture of starch as a natural capping agent leads to lesser agglomeration and smaller size of the particles. Nanoparticles of MoS{sub x} (x≈4) of 10–30 nm size are highly divided and form stable colloidal suspensions in organic solvents. Mo K edge EXAFS of the amorphous materials shows rapid exchange of oxygen to sulfur in the molybdenum coordination sphere during the solution reaction. Thermal treatment of the amorphous sulfides MoS{sub x} under nitrogen or hydrogen flow atmore » 400 °C allows obtaining mesoporous MoS{sub 2} materials with very high pore volume and specific surface area, up to 0.45 cm{sup 3}/g and 190 m{sup 2}/g, respectively. The new materials show good potential for the application as unsupported hydrotreating catalysts. - Graphical abstract: Solution reaction in propylene carbonate allows preparing weakly agglomerated molybdenum sulfide with particle size 20 nm and advantageous catalytic properties. - Highlights: • Solution reaction in propylene carbonate yields MoS{sub x} particles near 20 nm size. • Addition of starch as capping agent reduces particles size and hinder agglomeration. • EXAFS at Mo K edge shows rapid oxygen to sulfur exchange in the solution. • Thermal treatment leads to MoS{sub 2} with very high porosity and surface area.« less

Three-dimensional graphene networks as a new substrate for immobilization of laccase and dopamine and its application in glucose/O2 biofuel cell.

PubMed

Zhang, Yijia; Chu, Mi; Yang, Lu; Tan, Yueming; Deng, Wenfang; Ma, Ming; Su, Xiaoli; Xie, Qingji

2014-08-13

We report here three-dimensional graphene networks (3D-GNs) as a novel substrate for the immobilization of laccase (Lac) and dopamine (DA) and its application in glucose/O2 biofuel cell. 3D-GNs were synthesized with an Ni(2+)-exchange/KOH activation combination method using a 732-type sulfonic acid ion-exchange resin as the carbon precursor. The 3D-GNs exhibited an interconnected network structure and a high specific surface area. DA was noncovalently functionalized on the surface of 3D-GNs with 3,4,9,10-perylene tetracarboxylic acid (PTCA) as a bridge and used as a novel immobilized mediating system for Lac-based bioelectrocatalytic reduction of oxygen. The 3D-GNs-PTCA-DA nanocomposite modified glassy carbon electrode (GCE) showed stable and well-defined redox current peaks for the catechol/o-quinone redox couple. Due to the mediated electron transfer by the 3D-GNs-PTCA-DA nanocomposite, the Nafion/Lac/3D-GNs-PTCA-DA/GCE exhibited high catalytic activity for oxygen reduction. The 3D-GNs are proven to be a better substrate for Lac and its mediator immobilization than 2D graphene nanosheets (2D-GNs) due to the interconnected network structure and high specific surface area of 3D-GNs. A glucose/O2 fuel cell using Nafion/Lac/3D-GNs-PTCA-DA/GCE as the cathode and Nafion/glucose oxidase/ferrocence/3D-GNs/GCE as the anode can output a maximum power density of 112 μW cm(-2) and a short-circuit current density of 0.96 mA cm(-2). This work may be helpful for exploiting the popular 3D-GNs as an efficient electrode material for many other biotechnology applications.

Identifying and Quantifying Chemical Forms of Sediment-Bound Ferrous Iron.

NASA Astrophysics Data System (ADS)

Kohler, M.; Kent, D. B.; Bekins, B. A.; Cozzarelli, I.; Ng, G. H. C.

2015-12-01

Aqueous Fe(II) produced by dissimilatory iron reduction comprises only a small fraction of total biogenic Fe(II) within an aquifer. Most biogenic Fe(II) is bound to sediments on ion exchange sites; as surface complexes and, possibly, surface precipitates; or incorporated into solid phases (e.g., siderite, magnetite). Different chemical forms of sediment-bound Fe(II) have different reactivities (e.g., with dissolved oxygen) and their formation or destruction by sorption/desorption and precipitation/dissolution is coupled to different solutes (e.g., major cations, H+, carbonate). We are quantifying chemical forms of sediment-bound Fe(II) using previously published extractions, novel extractions, and experimental studies (e.g., Fe isotopic exchange). Sediments are from Bemidji, Minnesota, where biodegradation of hydrocarbons from a burst oil pipeline has driven extensive dissimilatory Fe(III) reduction, and sites potentially impacted by unconventional oil and gas development. Generally, minimal Fe(II) was mobilized from ion exchange sites (batch desorption with MgCl2 and repeated desorption with NH4Cl). A < 2mm sediment fraction from the iron-reducing zone at Bemidji had 1.8umol/g Fe(II) as surface complexes or carbonate phases (sodium acetate at pH 5) of which ca. 13% was present as surface complexes (FerroZine extractions). Total bioavailable Fe(III) and biogenic Fe(II) (HCl extractions) was 40-50 umole/g on both background and iron-reducing zone sediments . Approximately half of the HCl-extractable Fe from Fe-reducing zone sediments was Fe(II) whereas 12 - 15% of Fe extracted from background sediments was present as Fe(II). One-third to one-half of the total biogenic Fe(II) extracted from sediments collected from a Montana prairie pothole located downgradient from a produced-water disposal pit was present as surface-complexed Fe(II).

Pilot study of oxygen transport rate of banked red blood cells.

PubMed

Buchwald, H; Menchaca, H J; Michalek, V N; Rudser, K D; Rohde, T D; O'Dea, T; Connett, J E; Gorlin, J

2009-01-01

Dynamic oximetry provides a new way to assess the effect of blood storage on the oxygen transport rate (OTR). In dynamic oximetry, the rate at which oxyhemoglobin becomes deoxyhemoglobin is measured optically, thereby, indirectly measuring the rate at which oxygen leaves the red blood cell (RBC) making it available for transfer to tissues. Extending the physiologic diffusion time in an in vitro apparatus, consisting of a diffusion system and gas exchanger capable of controlling the surface area and the time of exposure for oxygenation and deoxygenation, makes OTR measurement feasible. Eight normal blood donor units, collected in adenine, dextrose, sorbitol, sodium chloride and mannitol , were stored for 8 weeks under standard conditions and serially sampled for OTR. We report that the OTR at the time of blood bank donation appears to be singular for each donor, that the interdonor differences are maintained over time, and that the individual OTR increased 1.72-fold (95% CI 1.51, 1.95) over 8 weeks, adjusting for sex, age and plasma cholesterol level. Oxygen transport rate increases during storage; blood units with similar haemoglobin content may have significant differences in OTR. Studies examining blood parameters at the time of donation and blood storage on patient outcomes should consider measuring OTR, as it may contribute to differences in observed efficacy of tissue oxygenation.

Platinum group metal-free electrocatalysts: Effects of synthesis on structure and performance in proton-exchange membrane fuel cell cathodes

NASA Astrophysics Data System (ADS)

Workman, Michael J.; Dzara, Michael; Ngo, Chilan; Pylypenko, Svitlana; Serov, Alexey; McKinney, Sam; Gordon, Jonathan; Atanassov, Plamen; Artyushkova, Kateryna

2017-04-01

Development of platinum group metal free catalysts for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs) requires understanding of the interactions between surface chemistry and performance, both of which are strongly dependent on synthesis conditions. To elucidate these complex relationships, a set of Fe-N-C catalysts derived from the same set of precursor materials is fabricated by varying several key synthetic parameters under controlled conditions. The results of physicochemical characterization are presented and compared with the results of rotating disk electrode (RDE) analysis and fuel cell testing. We find that electrochemical performance is strongly correlated with three key properties related to catalyst composition: concentrations of 1) atomically dispersed Fe species, 2) species in which N is bound to Fe, and 3) surface oxides. Not only are these factors related to performance, these types of chemical species are shown to correlate with each other. This study provides evidence supporting the role of iron coordinated with nitrogen as an active species for the ORR, and offers synthetic pathways to increase the density of atomically dispersed iron species and surface oxides for optimum performance.

Hadean Oceanography: Experimental Constraints on the Development of the Terrestrial Hydrosphere and the Origin of Life on Earth

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

Ryerson, F J

The oxygen isotopic compositions of the world's oldest mineral grains, zircon, have recently been used to infer the compositions of the rocks from which they crystallized. The results appear to require a source that had once experienced isotopic fractionation between clay minerals and liquid water, thereby implying the presence of liquid water at the Earth's surface prior to 4.4 billion years ago, less than 2 million years after accretion. This observation has important implications for the development of the Earth's continental crust. The inferred composition of the zircon source rock is directly dependent upon the oxygen isotopic fractionation between zirconmore » and melt, and zircon and water. These fractionation factors have not been determined experimentally, however, constituting the weak link in this argument. A series of experiments to measure these fractionation factors has been conducted. The experiments consist of finely powdered quartz, a polished single crystal of zircon and isotopically-enriched or isotopically normal water to provide a range of isotopic compositions. The experiments will be run until quartz is in isotopic equilibrium with water. Zircon was expected to partially equilibrate producing an oxygen isotopic diffusion profile perpendicular to the surface. Ion probe spot analysis of quartz and depth profiling of zircon will determine the bulk and surface isotopic compositions of the phases, respectively. The well-known quartz-water isotopic fractionation factors can be used to calculate the oxygen isotopic composition of the fluid, and with the zircon surface composition, the zircon-water fractionation factor. Run at temperatures up to 1000 C for as long as 500 hours have not produced diffusion profiles longer than 50 nm. The steep isotopic gradient at the samples surface precludes use of the diffusion profile for estimation on the surface isotopic composition. The short profiles may be the result of surface dissolution, although such dissolution cannot be resolved in SEM images. The sluggish nature of diffusion in zircon may require that fractionation factors be determined by direct hydrothermal synthesis of zircon rather than by mineral-fluid exchange.« less

Three dimensional metal/N-doped nanoplate carbon catalysts for oxygen reduction, the reason for using a layered nanoreactor.

PubMed

Yeganeh Ghotbi, Mohammad; Javanmard, Arash; Soleimani, Hassan

2018-02-21

A layered nanoreactor (zinc hydroxide gallate/nitrate nanohybrid) has been designed as a nano-vessel to confine the gallate/nitrate reaction inside zinc hydroxide layers for production of metal/nitrogen-doped carbon catalysts. Metals (Fe 2+ , Co 2+ and Ni 2+ ) doped and bare zinc hydroxide nitrates (ZHN) were synthesized as the α-phase hydroxide hosts. By an incomplete ion-exchange process, nitrate anions between the layers of the hosts were then partially replaced by the gallate anions to produce the layered nanoreactors. Under heat-treatment, the reaction between the remaining un-exchanged nitrate anions and the organic moiety inside the basal spacing of each nanohybrid plate resulted in obtaining highly porous 3D metal/nitrogen-doped carbon nanosheets. These catalysts were then used as extremely efficient electrocatalysts for catalyzing oxygen reduction reaction (ORR). This study is intended to show the way to get maximum electrocatalytic activity of the metal/N-doped carbon catalysts toward the ORR. This exceptionally high ORR performance originates from the increased available surface, the best pore size range and the uniform distribution of the active sites in the produced catalysts, all provided by the use of new idea of the layered nanoreactor.

Adsorption of Cr(III) on ozonised activated carbon. Importance of Cpi-cation interactions.

PubMed

Rivera-Utrilla, J; Sánchez-Polo, M

2003-08-01

The adsorption of Cr(III) in aqueous solution was investigated on a series of ozonised activated carbons, analysing the effect of oxygenated surface groups on the adsorption process. A study was carried out to determine the adsorption isotherms and the influence of the pH on the adsorption of this metal. The adsorption capacity and affinity of the adsorbent for Cr(III) increased with the increase in oxygenated acid groups on the surface of the activated carbon. These findings imply that electrostatic-type interactions predominate in the adsorption process, although the adsorption of Cr(III) on the original (basic) carbon indicates that other forces also participate in the adsorption process. Thus, the ionic exchange of protons in the -Cpi-H3O(+) interaction for Cr(III) accounts for the adsorption of cationic species in basic carbons with positive charge density. Study of the influence of pH on the adsorption of Cr(III) showed that, in each system, the maximum adsorption occurred when the charge of the carbon surface was opposite that of the species of Cr(III) present at the pH of the experiment. These results confirmed that electrostatic interactions predominate in the adsorption process.

Photoregenerative I⁻/I₃⁻ couple as a liquid cathode for proton exchange membrane fuel cell.

PubMed

Liu, Zhen; Wang, Yadong; Ai, Xinping; Tu, Wenmao; Pan, Mu

2014-10-28

A photoassisted oxygen reduction reaction (ORR) through I(-)/I3(-) redox couple was investigated for proton exchange membrane (PEM) fuel cell cathode reaction. The I(-)/I3(-)-based liquid cathode was used to replace conventional oxygen cathode, and its discharge product I(-) was regenerated to I3(-) by photocatalytic oxidation with the participation of oxygen. This new and innovative approach may provide a strategy to eliminate the usage of challenging ORR electrocatalysts, resulting in an avenue for developing low-cost and high-efficiency PEM fuel cells.

La and Al co-doped CaMnO3 perovskite oxides: From interplay of surface properties to anion exchange membrane fuel cell performance

NASA Astrophysics Data System (ADS)

Dzara, Michael J.; Christ, Jason M.; Joghee, Prabhuram; Ngo, Chilan; Cadigan, Christopher A.; Bender, Guido; Richards, Ryan M.; O'Hayre, Ryan; Pylypenko, Svitlana

2018-01-01

This work reports the first account of perovskite oxide and carbon composite oxygen reduction reaction (ORR) catalysts integrated into anion exchange membrane fuel cells (AEMFCs). Perovskite oxides with a theoretical stoichiometry of Ca0.9La0.1Al0.1Mn0.9O3-δ are synthesized by an aerogel method and calcined at various temperatures, resulting in a set of materials with varied surface chemistry and surface area. Material composition is evaluated by X-ray diffraction, energy dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy. The perovskite oxide calcined at 800 °C shows the importance of balance between surface area, purity of the perovskite phase, and surface composition, resulting in the highest ORR mass activity when evaluated in rotating disk electrodes. Integration of this catalyst into AEMFCs reveals that the best AEMFC performance is obtained when using composites with 30:70 perovskite oxide:carbon composition. Doubling the loading leads to an increase in the power density from 30 to 76 mW cm-2. The AEMFC prepared with a composite based on perovskite oxide and N-carbon achieves a power density of 44 mW cm-2, demonstrating an ∼50% increase when compared to the highest performing composite with undoped carbon at the same loading.

The role of mounds in promoting water-exchange in the egg-tending burrows of monogamous goby, Valenciennea longipinnis (Lay et Bennett).

PubMed

Takegaki; Nakazono

2000-10-25

Valenciennea longipinnis spawns monogamously in a burrow. After spawning, the paired female constructs a conspicuous mound on the burrow by carrying and piling up substratum-derived materials while the male tends eggs in the burrow until hatching occurs. In this study, the mounds of V. longipinnis were tested in the field to confirm their function of promoting water-exchange in the burrow, and their ecological role was examined in relation to egg care by the male. The mound of V.longipinnis promoted water-exchange in the burrow, contributing to the provision of external oxygenated sea water into the burrow. Therefore, dissolved oxygen (DO) concentrations in the burrow with a mound were significantly higher than those without a mound. Although male egg-tending behaviour (e.g., fanning) may also promote water-exchange in the burrow, the water-exchange appeared to depend mainly on the hydrodynamic effect. Removals of the mound and paired female on the day of spawning led to high rates of egg-desertion by males. Since the frequency and time of fanning increase with a decrease of DO concentration in the burrow, the egg-desertion may result from an increased parental cost to males due to the decrease of water-exchange without a mound. This was supported by the fact that the DO concentrations on the day after mound removal were significantly lower in the egg-deserted burrows (measured before desertions) than in burrows not deserted by the male. Moreover, removals of paired females only also led to higher desertion rates. After removal of the female, the mound gradually collapsed by wave action and other factors, and the surface of the mound was covered with planktonic materials. Such a mound of poor quality may provide little water-exchange, which may lead to the egg-desertion by males. These results indicated that mound maintenance by females during the egg-tending period has an important role in the success of parental care by males.

The effect of surface-groundwater interaction on dissolved organic carbon transformation

NASA Astrophysics Data System (ADS)

De Falco, Natalie; Boano, Fulvio; Arnon, Shai

2014-05-01

The preservation and improvement of water quality in streams is a challenging task, limited by our partial understanding of the coupling between biogeochemical and hydrological processes occurring in stream ecosystems. High potential for biogeochemical activity is found in the hyporheic zone, the saturated sediments where surface water and ground water mixes and degradation activities occur. The aim of the study was to quantifythe effect of losing and gaining flow conditions on the degradation of dissolved organic carbon (DOC). Experiments were conducted in a recirculating flume that is equipped with a drainage system that enables the control on losing and gaining fluxes. The degradation of DOC under losing and gaining conditions was studied by spiking the water with benzoic acid and monitoring the decrease in DOC concentration in the bulk water over time using an online UV/Vis spectrophotometer. In addition, the spatial and temporal change in oxygen concentrations within the benthic biofilm was measured using a Clark-type oxygen microelectrode. Preliminary results showed that DOC degradation rate was faster under higher overlying water velocity, due to enhanced delivery of DOC to the biofilm. Under both gaining and losing conditions, the DOC degradation was slower than under neutral condition, probably as a consequence of the reduction of the hyporheic exchange zone. Series of oxygen profiles under losing conditions showed a complete depletion of oxygen within the first 3 millimeters of sediment. In contrast, oxygen profiles under gaining condition showed a incomplete consumption of oxygen (usually within 1 mm), followed by an increase in the concentration of oxygen deeper in the sediments due to the upward flow of oxygenated groundwater. The results suggest that the size of the active aerobic region within the hyporheic zone is changing dynamically with the flow conditions. The effect of flow conditions on redox zonation in the hyporheic zone is expected to affect a myriad of important reactions and ecological processes and should be incorporated on future models.

KSC-97pc654

NASA Image and Video Library

1997-04-16

Representatives of RSC Energia in Russia and other onlookers in the SPACEHAB Payload Processing Facility examine an oxygen generator which the Space Shuttle Atlantis will carry to the Russian Mir Space Station on Mission STS-84. Sergei Romanov, second from right in the white shirt, is the spokesperson for generator manufacturer RSC Energia. The nearly 300-pound generator will be strapped down on the inside surface of a SPACEHAB Double Module for the trip to Mir. It will replace one of two Mir units that have been malfunctioning recently. The generator functions by electrolysis, which separates water into its oxygen and hydrogen components. The hydrogen is vented and the oxygen is used for breathing by the Mir crew. The generator is 4.2 feet in length and 1.4 feet in diameter. STS-84, which is planned to include a Mir crew exchange of astronaut C. Michael Foale for Jerry M. Linenger, is targeted for a May 15 liftoff. It will be the sixth Shuttle-Mir docking

Role of hemoglobin and capillarization for oxygen delivery and extraction in muscular exercise.

PubMed

Saltin, B; Kiens, B; Savard, G; Pedersen, P K

1986-01-01

Through the years the role of the various links in the transport of oxygen in the human body has been discussed extensively, and especially whether one of these links could be singled out as limiting oxygen uptake during exercise. In his thesis work Lars Hermansen dealt with several of these variables related to oxygen transport and uptake. Two of these were the hemoglobin concentration of the blood (Hb) and skeletal muscle capillarization. These are the focus of this article. It can be demonstrated that variation in arterial oxygen content due to different Hb concentrations is fully compensated for at the level of the muscle, i.e. the amount of oxygen delivered to contracting muscles is adjusted by a variation in the blood flow so that it is the same regardless of Hb concentration in the range of 118-172 g X l-1. At the systemic level, with a large fraction of the muscle exercising, this causes an increase in submaximal heart rate and a lowering in maximal oxygen uptake in people with low as compared to normal or high Hb concentration. The primary significance of an enlarged capillary network in the muscle does not appear to be for accommodating a larger flow, but rather to allow for a long enough mean transit time and large enough surface area for optimal exchange of gases, substrates and metabolites.

Finite Element Model of Oxygen Transport for the Design of Geometrically Complex Microfluidic Devices Used in Biological Studies

PubMed Central

Fraser, Graham M.; Goldman, Daniel; Ellis, Christopher G.

2016-01-01

Red blood cells play a crucial role in the local regulation of oxygen supply in the microcirculation through the oxygen dependent release of ATP. Since red blood cells serve as an oxygen sensor for the circulatory system, the dynamics of ATP release determine the effectiveness of red blood cells to relate the oxygen levels to the vessels. Previous work has focused on the feasibility of developing a microfluidic system to measure the dynamics of ATP release. The objective was to determine if a steep oxygen gradient could be developed in the channel to cause a rapid decrease in hemoglobin oxygen saturation in order to measure the corresponding levels of ATP released from the red blood cells. In the present study, oxygen transport simulations were used to optimize the geometric design parameters for a similar system which is easier to fabricate. The system is composed of a microfluidic device stacked on top of a large, gas impermeable flow channel with a hole to allow gas exchange. The microfluidic device is fabricated using soft lithography in polydimethyl-siloxane, an oxygen permeable material. Our objective is twofold: (1) optimize the parameters of our system and (2) develop a method to assess the oxygen distribution in complex 3D microfluidic device geometries. 3D simulations of oxygen transport were performed to simulate oxygen distribution throughout the device. The simulations demonstrate that microfluidic device geometry plays a critical role in molecule exchange, for instance, changing the orientation of the short wide microfluidic channel results in a 97.17% increase in oxygen exchange. Since microfluidic devices have become a more prominent tool in biological studies, understanding the transport of oxygen and other biological molecules in microfluidic devices is critical for maintaining a physiologically relevant environment. We have also demonstrated a method to assess oxygen levels in geometrically complex microfluidic devices. PMID:27829071

Finite Element Model of Oxygen Transport for the Design of Geometrically Complex Microfluidic Devices Used in Biological Studies.

PubMed

Sové, Richard J; Fraser, Graham M; Goldman, Daniel; Ellis, Christopher G

2016-01-01

Red blood cells play a crucial role in the local regulation of oxygen supply in the microcirculation through the oxygen dependent release of ATP. Since red blood cells serve as an oxygen sensor for the circulatory system, the dynamics of ATP release determine the effectiveness of red blood cells to relate the oxygen levels to the vessels. Previous work has focused on the feasibility of developing a microfluidic system to measure the dynamics of ATP release. The objective was to determine if a steep oxygen gradient could be developed in the channel to cause a rapid decrease in hemoglobin oxygen saturation in order to measure the corresponding levels of ATP released from the red blood cells. In the present study, oxygen transport simulations were used to optimize the geometric design parameters for a similar system which is easier to fabricate. The system is composed of a microfluidic device stacked on top of a large, gas impermeable flow channel with a hole to allow gas exchange. The microfluidic device is fabricated using soft lithography in polydimethyl-siloxane, an oxygen permeable material. Our objective is twofold: (1) optimize the parameters of our system and (2) develop a method to assess the oxygen distribution in complex 3D microfluidic device geometries. 3D simulations of oxygen transport were performed to simulate oxygen distribution throughout the device. The simulations demonstrate that microfluidic device geometry plays a critical role in molecule exchange, for instance, changing the orientation of the short wide microfluidic channel results in a 97.17% increase in oxygen exchange. Since microfluidic devices have become a more prominent tool in biological studies, understanding the transport of oxygen and other biological molecules in microfluidic devices is critical for maintaining a physiologically relevant environment. We have also demonstrated a method to assess oxygen levels in geometrically complex microfluidic devices.

Influence of water on clumped-isotope bond reordering kinetics in calcite

NASA Astrophysics Data System (ADS)

Brenner, Dana C.; Passey, Benjamin H.; Stolper, Daniel A.

2018-03-01

Oxygen self-diffusion in calcite and many other minerals is considerably faster under wet conditions relative to dry conditions. Here we investigate whether this "water effect" also holds true for solid-state isotope exchange reactions that alter the abundance of carbonate groups with multiple rare isotopes ('clumped' isotope groups) via the process of solid-state bond reordering. We present clumped-isotope reordering rates for optical calcite heated under wet, high-pressure (100 MPa) conditions. We observe only modest increases in reordering rates under such conditions compared with rates for the same material reacted in dry CO2 under low-pressure conditions. Activation energies under wet, high-pressure conditions are indistinguishable from those for dry, low-pressure conditions, while rate constants are resolvably higher (up to ∼3 times) for wet, high-pressure relative to dry, low-pressure conditions in most of our interpretations of experimental results. This contrasts with the water effect for oxygen self-diffusion in calcite, which is associated with lower activation energies, and diffusion coefficients that are ≥103 times higher compared with dry (pure CO2) conditions in the temperature range of this study (385-450 °C). The water effect for clumped-isotopes leads to calculated apparent equilibrium temperatures ("blocking temperatures") for typical geological cooling rates that are only a few degrees higher than those for dry conditions, while O self-diffusion blocking temperatures in calcite grains are ∼150-200 °C lower in wet conditions compared with dry conditions. Since clumped-isotope reordering is a distributed process that occurs throughout the mineral volume, our clumped-isotope results support the suggestion of Labotka et al. (2011) that the water effect in calcite does not involve major changes in bulk (volume) diffusivity, but rather is primarily a surface phenomenon that facilitates oxygen exchange between the calcite surface and external fluids. We explore the mechanism(s) by which clumped isotope reordering rates may be modestly increased under wet, high-pressure conditions, including changes in defect concentrations in the near surface environment due to reactions at the water-mineral interface, and lattice deformation resulting from pressurization of samples.

Insights into Acetone Photochemistry on Rutile TiO2(110). 1. Off-Normal CH3 Ejection from Acetone Diolate.

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

Petrik, Nikolay G.; Henderson, Michael A.; Kimmel, Gregory A.

2015-06-04

Thermal- and photon-stimulated reactions of acetone co-adsorbed with oxygen on rutile TiO2(110) surface are studied with infrared reflection-adsorption spectroscopy (IRAS) combined with temperature programmed desorption and angle-resolved photon stimulated desorption. IRAS results show that n2-acetone diolate ((CH3)2COO) is produced via thermally-activated reactions between the chemisorbed oxygen with co-adsorbed acetone. Formation of acetone diolate is also consistent with 18O / 16O isotopic exchange experiments. During UV irradiation at 30 K, CH3 radicals are ejected from the acetone diolate with a distribution that is peaked at .-. +- 66 degrees from the surface normal along the azimuth (i.e. perpendicular to the rowsmore » of bridging oxygen and Ti5c ions). This distribution is also consistent with the orientation of the C–CH3 bonds in the n2-acetone diolate on TiO2(110). The acetone diolate peaks disappear from the IRAS spectra after UV irradiation and new peaks are observed and associated with n2-acetate. The data presented here demonstrate direct signatures of the proposed earlier 2-step mechanism for acetone photooxidation on TiO2(110)« less

'water splitting' by titanium exchanged zeolite A. Technical report

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

Kuznicki, S.M.; Eyring, E.M.

1978-09-01

Visually detectable and chromatographically and mass spectrally identified hydrogen gas evolves from titanium (III) exchanged zeolite A immersed in water and illuminated with visible light. Titanium(III) exchanged zeolite X and zeolite Y do not produce this reaction. A photochemically produced, oxygenated titanium free radical (detected by electron spin resonance) not previously described is the species in the zeolite that reduces protons to molecular hydrogen. The other product of this reduction step is a nonradical, oxygenated titanium species of probable empirical formula TiO4. Heating the spent oxygenated titanium containing zeolite A under vacuum at 375 C restores over fifty percent ofmore » the free radical. Unlike previously reported systems, heating does not restore the original aquotitanium(III) species in the zeolite. Thus a means other than heating must be found to achieve a closed photochemical cycle that harnesses visible solar energy in the production of molecular hydrogen. The titanium exchanged zeolite A does, however, lend itself to a thermolysis of water previously described by Kasai and Bishop. (Author)« less

Automatable Measurement of Gas Exchange Rate in Streams: Oxygen-Carbon Method

NASA Astrophysics Data System (ADS)

Pennington, R.; Haggerty, R.; Argerich, A.; Wondzell, S. M.

2015-12-01

Gas exchange rates between streams and the atmosphere are critically important to measurement of in-stream ecologic processes, as well as fate and transport of hazardous pollutants such as mercury and PCBs. Methods to estimate gas exchange rates include empirical relations to hydraulics, and direct injection of a tracer gas such as propane or SF6. Empirical relations are inconsistent and inaccurate, particularly for lower order, high-roughness streams. Gas injections are labor-intensive, and measured gas exchange rates are difficult to extrapolate in time since they change with discharge and stream geometry. We propose a novel method for calculation of gas exchange rates utilizing O2, pCO2, pH, and temperature data. Measurements, which can be automated using data loggers and probes, are made on the upstream and downstream end of the study reach. Gas exchange rates are then calculated from a solution to the transport equations for oxygen and dissolved inorganic carbon. Field tests in steep, low order, high roughness streams of the HJ Andrews Experimental Forest indicate the method to be viable along stream reaches with high downstream gas concentration gradients and high rates of gas transfer velocity. Automated and continuous collection of oxygen and carbonate chemistry data is increasingly common, thus the method may be used to estimate gas exchange rates through time, and is well suited for interactivity with databases.

Mechanisms of Exchange Reactions of Primary and Secondary Alkyl Iodides with Elementary Iodine

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

Bujake, John E.; Pratt, M. W. T.; Noyes, Richard M.

1961-04-01

Several primary and secondary alkyl iodides exchange thermally with I/ sup 131/ in hexachlorobutadiene between 130 and 200 deg . If the solutions are saturated with oxygen at one atmosphere, rates of exchange fit the kinetic expression k/sub b/STARI! STAl/sub 2/!1/2. Degassed solutions always exchange faster than oxygen saturated ones, but methyl, ethyl, and n-propyl iodides show the same kinetics as with oxygen. Exchange rates of degassed isopropyl and neopentyl iodides also show contributions from a k/sub a/STARI! term. Exchange in degassed ethylene dichloride is 3 to 4 times as fast as in degassed hexachlorobutadiene. Activation energies for k/sub b/more » are usually about 27 to 31 kcal/mole. Effects of substitution on alpha carbon are illustrated by the rate sequence methyl < ethyl < i-propyl = sec-butyl. Effects of substitution on beta carbon are illustrated by the rate sequence ethyl < npropyl>> neopentyl. Since the rates of exchange of methyl, ethyl, and i-propyl iodides vary in the opposite direction from the sequence for bimolecular nucleophilic substitution, the explanation proposed suggests that for nucleophilic substitution the effect of added methyl groups on an alpha carbon is a steric hindrance to solvation by solvent dipoles rather than a steric hindrance to the group attacking the carbon atom itself.« less

Catalytic Oxidation of Methane into Methanol over Copper-Exchanged Zeolites with Oxygen at Low Temperature

PubMed Central

2016-01-01

The direct catalytic conversion of methane to liquid oxygenated compounds, such as methanol or dimethyl ether, at low temperature using molecular oxygen is a grand challenge in C–H activation that has never been met with synthetic, heterogeneous catalysts. We report the first demonstration of direct, catalytic oxidation of methane into methanol with molecular oxygen over copper-exchanged zeolites at low reaction temperatures (483–498 K). Reaction kinetics studies show sustained catalytic activity and high selectivity for a variety of commercially available zeolite topologies under mild conditions (e.g., 483 K and atmospheric pressure). Transient and steady state measurements with isotopically labeled molecules confirm catalytic turnover. The catalytic rates and apparent activation energies are affected by the zeolite topology, with caged-based zeolites (e.g., Cu-SSZ-13) showing the highest rates. Although the reaction rates are low, the discovery of catalytic sites in copper-exchanged zeolites will accelerate the development of strategies to directly oxidize methane into methanol under mild conditions. PMID:27413787

Sulfidation behavior of ZnFe2O4 roasted with pyrite: Sulfur inducing and sulfur-oxygen interface exchange mechanism

NASA Astrophysics Data System (ADS)

Min, Xiaobo; Zhou, Bosheng; Ke, Yong; Chai, Liyuan; Xue, Ke; Zhang, Chun; Zhao, Zongwen; Shen, Chen

2016-05-01

The sulfidation roasting behavior was analyzed in detail to reveal the reaction mechanism. Information about the sulfidation reaction, including phase transformation, ionic migration behavior and morphological change, were obtained by XRD, 57Fe Mossbauer spectroscopy, XPS and SEM analysis. The results showed that the sulfidation of zinc ferrite is a process of sulfur inducing and sulfur-oxygen interface exchange. This process can be divided into six stages: decomposition of FeS2, formation of the oxygen-deficient environment, migration of O2- induced by S2(g), formation of ZnFe2O4-δ, migration of Fe2+ accompanied by the precipitation of ZnO, and the sulfur-oxygen interface exchange reaction. The sulfidation products were zinc blende, wurtzite, magnetite and a fraction of zinc-bearing magnetite. These findings can provide theoretical support for controlling the process during which the recovery of Zn and Fe is achieved through the combined flotation-magnetic separation process.

The Synthesis, Structures, and Chemical Properties of Macrocyclic Ligands Covalently Bonded into Layered Arrays

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

Clearfield, Abraham

2014-11-01

In this part of the proposal we have concentrated on the surface functionalization of α-zirconium phosphate of composition Zr(O3POH)2•H2O. It is a layered compound that can be prepared as particles as small as 30 nm to single crystals in the range of cm. This compound is an ion exchanger with a capacity of 6.64 meq per gram. It finds use as a catalyst, proton conductor, sensors, biosensors, in kidney dialysis and drug delivery. By functionalizing the surface additional uses are contemplated as will be described. The layers consist of the metal, with 4+ charge, that is positioned slightly above andmore » below the mean layer plane and bridged by three of the four phosphate oxygens. The remaining POH groups point into the interlayer space creating double rows of POH groups but single arrays on the surface layers. The surface groups are reactive and we were able to bond silanes, isocyanates, epoxides, acrylates ` and phosphates to the surface POH groups. The layers are easily exfoliated or filled with ions by ion exchange or molecules by intercalation reactions. Highlights of our work include, in addition to direct functionalization of the surfaces, replacement of the protons on the surface with ions of different charge. This allows us to bond phosphates, biophosphates, phosphonic acids and alcohols to the surface. By variation of the ion charge of the ions that replace the surface protons, different surface structures are obtained. We have already shown that polymer fillers, catalysts and Janus particles may be prepared. The combination of surface functionalization with the ability to insert molecules and ions between the layers allow for a rich development of numerous useful other applications as well as nano-surface chemistry.« less

State of gas exchange in recumbent and orthostatic positions and under physical load in healthy persons of varying age, sex and body build

NASA Technical Reports Server (NTRS)

Glezer, G. A.; Charyyev, M.; Zilbert, N. L.

1980-01-01

Age effect on gas exchange was studied in the recumbent and orthostatic positions and under physical load. In the case of the older age group and for normal as compared with hypersthenic persons, oxygen consumption during rest and during moderate physical overload diminishes. When the vertical position is assumed oxygen consumption in persons of various age groups is distinctly increased, particularly in the elderly group. There is a reduction in the amount of oxygen consumption, oxygen pulse, recovery coefficient, and work efficiency under moderate overload. In persons over 50, physical labor induces a large oxygen requirement and a sharp rise in the level of lactic acid and the blood's lactate/pyruvate ratio. No distinct difference was noted in the amount of oxygen consumed during rest and during physical overload in men and women of the same physical development and age.

Heterojunction-Assisted Co3 S4 @Co3 O4 Core-Shell Octahedrons for Supercapacitors and Both Oxygen and Carbon Dioxide Reduction Reactions.

PubMed

Yan, Yibo; Li, Kaixin; Chen, Xiaoping; Yang, Yanhui; Lee, Jong-Min

2017-12-01

Expedition of electron transfer efficiency and optimization of surface reactant adsorption products desorption processes are two main challenges for developing non-noble catalysts in the oxygen reduction reaction (ORR) and CO 2 reduction reaction (CRR). A heterojunction prototype on Co 3 S 4 @Co 3 O 4 core-shell octahedron structure is established via hydrothermal lattice anion exchange protocol to implement the electroreduction of oxygen and carbon dioxide with high performance. The synergistic bifunctional catalyst consists of p-type Co 3 O 4 core and n-type Co 3 S 4 shell, which afford high surface electron density along with high capacitance without sacrificing mechanical robustness. A four electron ORR process, identical to the Pt catalyzed ORR, is validated using the core-shell octahedron catalyst. The synergistic interaction between cobalt sulfide and cobalt oxide bicatalyst reduces the activation energy to convert CO 2 into adsorbed intermediates and hereby enables CRR to run at a low overpotential, with formate as the highly selective main product at a high faraday efficiency of 85.3%. The remarkable performance can be ascribed to the synergistic coupling effect of the structured co-catalysts; heterojunction structure expedites the electron transfer efficiency and optimizes surface reactant adsorption product desorption processes, which also provide theoretical and pragmatic guideline for catalyst development and mechanism explorations. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fuel cell technology for lunar surface operations

NASA Technical Reports Server (NTRS)

Deronck, Henry J.

1992-01-01

Hydrogen-oxygen fuel cells have been shown, in several NASA and contractor studies, to be an enabling technology for providing electrical power for lunar bases, outposts, and vehicles. The fuel cell, in conjunction with similar electrolysis cells, comprises a closed regenerative energy storage system, commonly referred to as a regenerative fuel cell (RFC). For stationary applications, energy densities of 1,000 watt-hours per kilograms an order of magnitude over the best rechargeable batteries, have been projected. In this RFC, the coupled fuel cell and electrolyzer act as an ultra-light battery. Electrical energy from solar arrays 'charges' the system by electrolyzing water into hydrogen and oxygen. When an electrical load is applied, the fuel cell reacts the hydrogen and oxygen to 'discharge' usable power. Several concepts for utilizing RFC's, with varying degrees of integration, have been proposed, including both primary and backup roles. For mobile power needs, such as rovers, an effective configuration may be to have only the fuel cell located on the vehicle, and to use a central electrolysis 'gas station'. Two fuel cell technologies are prime candidates for lunar power system concepts: alkaline electrolyte and proton exchange membrane. Alkaline fuel cells have been developed to a mature production power unit in NASA's Space Shuttle Orbiter. Recent advances in materials offer to significantly improve durability to the level needed for extended lunar operations. Proton exchange membrane fuel cells are receiving considerable support for hydrospace and terrestrial transportation applications. This technology promises durability, simplicity, and flexibility.

Dynamics of oxygen and carbon dioxide in rhizospheres of Lobelia dortmanna - a planar optode study of belowground gas exchange between plants and sediment.

PubMed

Lenzewski, Nikola; Mueller, Peter; Meier, Robert Johannes; Liebsch, Gregor; Jensen, Kai; Koop-Jakobsen, Ketil

2018-04-01

Root-mediated CO 2 uptake, O 2 release and their effects on O 2 and CO 2 dynamics in the rhizosphere of Lobelia dortmanna were investigated. Novel planar optode technology, imaging CO 2 and O 2 distribution around single roots, provided insights into the spatiotemporal patterns of gas exchange between roots, sediment and microbial community. In light, O 2 release and CO 2 uptake were pronounced, resulting in a distinct oxygenated zone (radius: c. 3 mm) and a CO 2 -depleted zone (radius: c. 2 mm) around roots. Simultaneously, however, microbial CO 2 production was stimulated within a larger zone around the roots (radius: c. 10 mm). This gave rise to a distinct pattern with a CO 2 minimum at the root surface and a CO 2 maximum c. 2 mm away from the root. In darkness, CO 2 uptake ceased, and the CO 2 -depleted zone disappeared within 2 h. By contrast, the oxygenated root zone remained even after 8 h, but diminished markedly over time. A tight coupling between photosynthetic processes and the spatiotemporal dynamics of O 2 and CO 2 in the rhizosphere of Lobelia was demonstrated, and we suggest that O 2 -induced stimulation of the microbial community in the sediment increases the supply of inorganic carbon for photosynthesis by building up a CO 2 reservoir in the rhizosphere. © 2018 The Authors. New Phytologist © 2018 New Phytologist Trust.

Fuel cell technology for lunar surface operations

NASA Astrophysics Data System (ADS)

Deronck, Henry J.

1992-02-01

Hydrogen-oxygen fuel cells have been shown, in several NASA and contractor studies, to be an enabling technology for providing electrical power for lunar bases, outposts, and vehicles. The fuel cell, in conjunction with similar electrolysis cells, comprises a closed regenerative energy storage system, commonly referred to as a regenerative fuel cell (RFC). For stationary applications, energy densities of 1,000 watt-hours per kilograms an order of magnitude over the best rechargeable batteries, have been projected. In this RFC, the coupled fuel cell and electrolyzer act as an ultra-light battery. Electrical energy from solar arrays 'charges' the system by electrolyzing water into hydrogen and oxygen. When an electrical load is applied, the fuel cell reacts the hydrogen and oxygen to 'discharge' usable power. Several concepts for utilizing RFC's, with varying degrees of integration, have been proposed, including both primary and backup roles. For mobile power needs, such as rovers, an effective configuration may be to have only the fuel cell located on the vehicle, and to use a central electrolysis 'gas station'. Two fuel cell technologies are prime candidates for lunar power system concepts: alkaline electrolyte and proton exchange membrane. Alkaline fuel cells have been developed to a mature production power unit in NASA's Space Shuttle Orbiter. Recent advances in materials offer to significantly improve durability to the level needed for extended lunar operations. Proton exchange membrane fuel cells are receiving considerable support for hydrospace and terrestrial transportation applications. This technology promises durability, simplicity, and flexibility.

Reverse Estuarine Circulation Due to Local and Remote Wind Forcing, Enhanced by the Presence of Along-Coast Estuaries

NASA Astrophysics Data System (ADS)

Giddings, S. N.; MacCready, P.

2017-12-01

Estuarine exchange flow governs the interaction between oceans and estuaries and thus plays a large role in their biogeochemical processes. This study investigates the variability in estuarine exchange flow due to offshore oceanic conditions including upwelling/downwelling, and the presence of a river plume offshore (from a neighboring estuary). We address these processes via numerical simulations at the mouth of the Salish Sea, a large estuarine system in the Northeast Pacific. An analysis of the Total Exchange Flow indicates that during the upwelling season, the exchange flow is fairly consistent in magnitude and oriented in a positive (into the estuary at depth and out at the surface) direction. However, during periods of downwelling favorable winds, the exchange flow shows significantly more variability including multiple reversals, consistent with observations, and surface intrusions of the Columbia River plume which originates 250 km to the south. Numerical along-strait momentum budgets show that the exchange flow is forced dominantly by the pressure gradients, particularly the baroclinic. The pressure gradient is modified by Coriolis and sometimes advection, highlighting the importance of geostrophy and local adjustments. In experiments conducted without the offshore river plume, reversals still occur but are weaker, and the baroclinic pressure gradient plays a reduced role. These results suggest that estuaries along strong upwelling coastlines should experience significant modulation in the exchange flow during upwelling versus downwelling conditions. Additionally, they highlight the importance of nearby estuaries impacting one-another, not only in terms of connectivity, but also altering the exchange flow.