Science.gov

Sample records for water oxidation cycle

  1. A hybrid water-splitting cycle using copper sulfate and mixed copper oxides

    NASA Technical Reports Server (NTRS)

    Schreiber, J. D.; Remick, R. J.; Foh, S. E.; Mazumder, M. M.

    1980-01-01

    The Institute of Gas Technology has derived and developed a hybrid thermochemical water-splitting cycle based on mixed copper oxides and copper sulfate. Similar to other metal oxide-metal sulfate cycles that use a metal oxide to 'concentrate' electrolytically produced sulfuric acid, this cycle offers the advantage of producing oxygen (to be vented) and sulfur dioxide (to be recycled) in separate steps, thereby eliminating the need of another step to separate these gases. The conceptual process flow-sheet efficiency of the cycle promises to exceed 50%. It has been completely demonstrated in the laboratory with recycled materials. Research in the electrochemical oxidation of sulfur dioxide to produce sulfuric acid and hydrogen performed at IGT indicates that the cell performance goals of 200 mA/sq cm at 0.5 V will be attainable using relatively inexpensive electrode materials.

  2. Low-temperature, manganese oxide-based, thermochemical water splitting cycle

    PubMed Central

    Xu, Bingjun; Bhawe, Yashodhan; Davis, Mark E.

    2012-01-01

    Thermochemical cycles that split water into stoichiometric amounts of hydrogen and oxygen below 1,000 °C, and do not involve toxic or corrosive intermediates, are highly desirable because they can convert heat into chemical energy in the form of hydrogen. We report a manganese-based thermochemical cycle with a highest operating temperature of 850 °C that is completely recyclable and does not involve toxic or corrosive components. The thermochemical cycle utilizes redox reactions of Mn(II)/Mn(III) oxides. The shuttling of Na+ into and out of the manganese oxides in the hydrogen and oxygen evolution steps, respectively, provides the key thermodynamic driving forces and allows for the cycle to be closed at temperatures below 1,000 °C. The production of hydrogen and oxygen is fully reproducible for at least five cycles. PMID:22647608

  3. Use of oxides in thermochemical water-splitting cycles for solar heat sources. Copper oxides

    SciTech Connect

    Jones, W.M.; Bowman, M.G.

    1984-01-01

    Several oxides can be decomposed to oxygen and a lower oxide at temperatures that might be feasible with a solar heat source. Heat might be directly transmitted to the solid through an air window, rather than quartz, with release of oxygen to the atmosphere. The cycle utilizing CuO, I/sub 2/, and Mg (OH)/sub 2/ is similar to the previous Co/sub 3/O/sub 4/ - CoO cycle. We are concentrating on the reformation of CuO. At 448 K the rate is favorable; for example, the yield rises about linearly with time to 92% at 1.17 h and more slowly thereafter. The only difficulty is the formation of CuI as a metastable intermediate. The oxidation of CuI is thermodynamically very favorable, but its rate limits completion. Excess Mg(OH)/sub 2/ appears to increase the rate but not to the point where IO/sub 3//sup -/ oxidation of CuI competes with oxidation of Cu/sub 2/O. Nevertheless, the batch runs suggest that about 98% of the maximum possible MgI/sub 2/ could be formed. Cuprous iodide complexes formed in the concentrated MgI/sub 2/ may give the necessary improvement by providing a solution path for their oxidation by iodate. Work of others pertaining to the cycle is briefly discussed.

  4. Water-oxidation catalysis by manganese in a geochemical-like cycle

    NASA Astrophysics Data System (ADS)

    Hocking, Rosalie K.; Brimblecombe, Robin; Chang, Lan-Yun; Singh, Archana; Cheah, Mun Hon; Glover, Chris; Casey, William H.; Spiccia, Leone

    2011-06-01

    Water oxidation in all oxygenic photosynthetic organisms is catalysed by the Mn4CaO4 cluster of Photosystem II. This cluster has inspired the development of synthetic manganese catalysts for solar energy production. A photoelectrochemical device, made by impregnating a synthetic tetranuclear-manganese cluster into a Nafion matrix, has been shown to achieve efficient water oxidation catalysis. We report here in situ X-ray absorption spectroscopy and transmission electron microscopy studies that demonstrate that this cluster dissociates into Mn(II) compounds in the Nafion, which are then reoxidized to form dispersed nanoparticles of a disordered Mn(III/IV)-oxide phase. Cycling between the photoreduced product and this mineral-like solid is responsible for the observed photochemical water-oxidation catalysis. The original manganese cluster serves only as a precursor to the catalytically active material. The behaviour of Mn in Nafion therefore parallels its broader biogeochemistry, which is also dominated by cycles of oxidation into solid Mn(III/IV) oxides followed by photoreduction to Mn2+.

  5. Optimal design of solid oxide fuel cell, ammonia-water single effect absorption cycle and Rankine steam cycle hybrid system

    NASA Astrophysics Data System (ADS)

    Mehrpooya, Mehdi; Dehghani, Hossein; Ali Moosavian, S. M.

    2016-02-01

    A combined system containing solid oxide fuel cell-gas turbine power plant, Rankine steam cycle and ammonia-water absorption refrigeration system is introduced and analyzed. In this process, power, heat and cooling are produced. Energy and exergy analyses along with the economic factors are used to distinguish optimum operating point of the system. The developed electrochemical model of the fuel cell is validated with experimental results. Thermodynamic package and main parameters of the absorption refrigeration system are validated. The power output of the system is 500 kW. An optimization problem is defined in order to finding the optimal operating point. Decision variables are current density, temperature of the exhaust gases from the boiler, steam turbine pressure (high and medium), generator temperature and consumed cooling water. Results indicate that electrical efficiency of the combined system is 62.4% (LHV). Produced refrigeration (at -10 °C) and heat recovery are 101 kW and 22.1 kW respectively. Investment cost for the combined system (without absorption cycle) is about 2917 kW-1.

  6. Interactions between nitrogen cycling and methane oxidation in the pelagic waters of the Gulf of Mexico.

    NASA Astrophysics Data System (ADS)

    Joye, S. B.; Weber, S.; Battles, J.; Montoya, J. P.

    2014-12-01

    Methane is an important greenhouse gas that plays a critical role in climate variation. Although a variety of marine methane sources and sinks have been identified, key aspects of the fate of methane in the ocean remain poorly constrained. At cold seeps in the Gulf of Mexico and elsewhere, methane is introduced into the overlying water column via fluid escape from the seabed. We quantified the fate of methane in the water column overlying seafloor cold seeps, in a brine basin, and at several control sites. Our goals were to determine the factors that regulated methane consumption and assimilation and to explore how these controlling factors varied among and between sites. In particular, we examined the impact of nitrogen availability on methane oxidation and studied the ability of methane oxidizing bacteria to fix molecular nitrogen. Methane oxidation rates were highest in the methane rich bottom waters of natural hydrocabron seeps. At these sites, inorganic nitrogen addition stimulated methane oxidation in laboratory experiments. In vitro shipboard experiments revealed that rates of methane oxidation and nitrogen fixation were correlated strongly, suggesting that nitrogen fixation may have been mediated by methanotrophic bacteria. The highest rates of methane oxidation and nitrogen fixation were observed in the deepwater above at natural hydrocarbon seeps. Rates of methane oxidation were substantial along the chemocline of a brine basin but in these ammonium-rich brines, addition of inorganic nitrogen had little impact on methane oxidation suggesting that methanotrophy in these waters were not nitrogen limited. Control sites exhibited the lowest methane concentrations and methane oxidation rates but even these waters exhibited substantial potential for methane oxidation when methane and inorganic nitrogen concentrations were increased. Together, these data suggest that the availability of inorganic nitrogen plays a critical role in regulating methane oxidation in pelagic ocean waters. Some methanotrophs may obtain a competitive advantage in nitrogen-limited oceanic environments by fixing molecular nitrogen. The importance of such "methano-diazotrophy" on a global scale warrants further investigation.

  7. Redox cycle stability of mixed oxides used for hydrogen generation in the cyclic water gas shift process

    SciTech Connect

    Datta, Pradyot

    2013-10-15

    Graphical abstract: - Highlights: • Fe{sub 2}O{sub 3} modified with CaO, SiO{sub 2} and Al{sub 2}O{sub 3} was studied in cyclic water gas shift reactor. • For the first time stability of such oxides were tested for 100 redox cycles. • Optimally added oxides significantly improved the activity and the stability of Fe{sub 2}O{sub 3}. • Increased stability was attributed to the impediment of neck formation. - Abstract: Repeated cycles of the reduction of Fe{sub 3}O{sub 4} with reductive gas, e.g. hydrogen and subsequent oxidation of the reduced iron material with water vapor can be harnessed as a process for the production of pure hydrogen. The redox behavior of iron oxide modified with various amounts of SiO{sub 2}, CaO and Al{sub 2}O{sub 3} was investigated in the present study. The total amount of the additional metal oxides was always below 15 wt%. The samples were prepared by co-precipitation using urea hydrolysis method. The influence of various metal oxides on the hydrogen production capacity and the material stability was studied in detail in terms of temperature-programmed reduction (TPR), X-ray diffraction (XRD), scanning electron microscopy (SEM) and BET analysis. Furthermore, the activity and the stability of the samples were tested in repeated reduction with diluted H{sub 2} and re-oxidation cycles with H{sub 2}O. The results indicate that combination of several oxides as promoter increases the stability of the iron oxide material by mitigating the sintering process. The positive influence of the oxides in stabilizing the iron oxide material is attributed to the impediment of neck formation responsible for sintering.

  8. Dissociation of manganese(III) oxide as part of a thermochemical water splitting cycle

    NASA Astrophysics Data System (ADS)

    Francis, Todd Michael

    A three-step thermochemical cycle to produce renewable hydrogen was proposed, which utilizes manganese(III) oxide and thermal energy to produce hydrogen. Most work on the cycle has focused on the hydrogen generating and product recovery steps with little work on the dissociation. It is essential to understand the dissociation because the feasibility of the cycle is based on this reaction having a high conversion. Because of the importance of the reduction step, this reaction has been selected as the topic of this dissertation. Additionally, because the dispersion of Mn2O3 particles into an Aerosol Flow Reactor (AFR) is important, feeding concepts were developed as well. Two powder feeding systems were developed: a Spinning Wheel Feeder (SWF) and a Fluidized Bed Feeder (FBF). Results of statistical particle size distribution studies indicated that the FBF was the better choice to disperse Mn2O3 powder. Additionally, results in an AFR demonstrated that the FBF was able to produce higher dissociation conversions. A study in a Thermogravimetric Analyzer (TGA) indicated multiple mechanisms were controlling Mn2O3 dissociation. The first half reaction of the dissociation was calculated to be controlled by an Avrami-Erofeev mechanism and had an activation energy of 106.4+/-1.9 kJ/mol. The second half reaction had a duel mechanism utilizing an Avrami-Erofeev and Order of Reaction (OOR) mechanism. The mechanisms had activation energies of 251.2+/-6.5 and 110.7+/-24.6 kJ/mol respectively. Mn2O3 dissociation investigations were done in an AFR. They revealed oxygen is a significant factor and to effectively control the dissociation with temperature and gas flow rate, the oxygen concentration must be below 0.25%. Experimental runs that had oxygen concentrations less than 0.25% were used to calculate reaction rate constants. The Avrami-Erofeev mechanisms were combined into a single mechanism. Rate constants for the Avrami-Erofeev and OOR mechanisms were 1.8E7+/-1.3E7 and 5.6E3+/-4.1E3 s -1 respectively. The results of a CFD model compared favorably with what was observed experimentally. A heavy feed concentration case predicted this as well. When the gas flow rate was higher the r-velocity was concluded to transport the more reacted powder near the wall to the center of the reactor, leading to higher conversions for the high gas flow rate.

  9. Global water cycle

    NASA Technical Reports Server (NTRS)

    Robertson, Franklin; Goodman, Steven J.; Christy, John R.; Fitzjarrald, Daniel E.; Chou, Shi-Hung; Crosson, William; Wang, Shouping; Ramirez, Jorge

    1993-01-01

    This research is the MSFC component of a joint MSFC/Pennsylvania State University Eos Interdisciplinary Investigation on the global water cycle extension across the earth sciences. The primary long-term objective of this investigation is to determine the scope and interactions of the global water cycle with all components of the Earth system and to understand how it stimulates and regulates change on both global and regional scales. Significant accomplishments in the past year are presented and include the following: (1) water vapor variability; (2) multi-phase water analysis; (3) global modeling; and (4) optimal precipitation and stream flow analysis and hydrologic processes.

  10. Global water cycle

    NASA Technical Reports Server (NTRS)

    Robertson, Franklin R.; Christy, John R.; Goodman, Steven J.; Miller, Tim L.; Fitzjarrald, Dan; Lapenta, Bill; Wang, Shouping

    1991-01-01

    The primary objective is to determine the scope and interactions of the global water cycle with all components of the Earth system and to understand how it stimulates and regulates changes on both global and regional scales. The following subject areas are covered: (1) water vapor variability; (2) multi-phase water analysis; (3) diabatic heating; (4) MSU (Microwave Sounding Unit) temperature analysis; (5) Optimal precipitation and streamflow analysis; (6) CCM (Community Climate Model) hydrological cycle; (7) CCM1 climate sensitivity to lower boundary forcing; and (8) mesoscale modeling of atmosphere/surface interaction.

  11. GEOSS Water Cycle Integrator

    NASA Astrophysics Data System (ADS)

    Koike, T.; Lawford, R. G.; Cripe, D.

    2012-12-01

    It is critically important to recognize and co-manage the fundamental linkages across the water-dependent domains; land use, including deforestation; ecosystem services; and food-, energy- and health-securities. Sharing coordinated, comprehensive and sustained observations and information for sound decision-making is a first step; however, to take full advantage of these opportunities, we need to develop an effective collaboration mechanism for working together across different disciplines, sectors and agencies, and thereby gain a holistic view of the continuity between environmentally sustainable development, climate change adaptation and enhanced resilience. To promote effective multi-sectoral, interdisciplinary collaboration based on coordinated and integrated efforts, the Global Earth Observation System of Systems (GEOSS) is now developing a "GEOSS Water Cycle Integrator (WCI)", which integrates "Earth observations", "modeling", "data and information", "management systems" and "education systems". GEOSS/WCI sets up "work benches" by which partners can share data, information and applications in an interoperable way, exchange knowledge and experiences, deepen mutual understanding and work together effectively to ultimately respond to issues of both mitigation and adaptation. (A work bench is a virtual geographical or phenomenological space where experts and managers collaborate to use information to address a problem within that space). GEOSS/WCI enhances the coordination of efforts to strengthen individual, institutional and infrastructure capacities, especially for effective interdisciplinary coordination and integration. GEO has established the GEOSS Asian Water Cycle Initiative (AWCI) and GEOSS African Water Cycle Coordination Initiative (AfWCCI). Through regional, inter-disciplinary, multi-sectoral integration and inter-agency coordination in Asia and Africa, GEOSS/WCI is now leading to effective actions and public awareness in support of water security and sustainable development.

  12. GEOSS Water Cycle Integrator

    NASA Astrophysics Data System (ADS)

    Koike, Toshio; Lawford, Richard; Cripe, Douglas

    2013-04-01

    It is critically important to recognize and co-manage the fundamental linkages across the water-dependent domains; land use, including deforestation; ecosystem services; and food-, energy- and health-securities. Sharing coordinated, comprehensive and sustained observations and information for sound decision-making is a first step; however, to take full advantage of these opportunities, we need to develop an effective collaboration mechanism for working together across different disciplines, sectors and agencies, and thereby gain a holistic view of the continuity between environmentally sustainable development, climate change adaptation and enhanced resilience. To promote effective multi-sectoral, interdisciplinary collaboration based on coordinated and integrated efforts, the intergovernmental Group on Earth Observations (GEO) is implementing the Global Earth Observation System of Systems (GEOSS). A component of GEOSS now under development is the "GEOSS Water Cycle Integrator (WCI)", which integrates Earth observations, modeling, data and information, management systems and education systems. GEOSS/WCI sets up "work benches" by which partners can share data, information and applications in an interoperable way, exchange knowledge and experiences, deepen mutual understanding and work together effectively to ultimately respond to issues of both mitigation and adaptation. (A work bench is a virtual geographical or phenomenological space where experts and managers collaborate to use information to address a problem within that space). GEOSS/WCI enhances the coordination of efforts to strengthen individual, institutional and infrastructure capacities, especially for effective interdisciplinary coordination and integration. GEO has established the GEOSS Asian Water Cycle Initiative (AWCI) and GEOSS African Water Cycle Coordination Initiative (AfWCCI). Through regional, inter-disciplinary, multi-sectoral integration and inter-agency coordination in Asia and Africa, GEOSS/WCI is now leading to effective actions and public awareness in support of water security and sustainable development.

  13. Studies of thermochemical water-splitting cycles

    NASA Technical Reports Server (NTRS)

    Remick, R. J.; Foh, S. E.

    1980-01-01

    Higher temperatures and more isothermal heat profiles of solar heat sources are developed. The metal oxide metal sulfate class of cycles were suited for solar heat sources. Electrochemical oxidation of SO2 and thermochemical reactions are presented. Electrolytic oxidation of sulfur dioxide in dilute sulfuric acid solutions were appropriate for metal oxide metal sulfate cycles. The cell voltage at workable current densities required for the oxidation of SO2 was critical to the efficient operation of any metal oxide metal sulfate cycle. A sulfur dioxide depolarized electrolysis cell for the splitting of water via optimization of the anode reaction is discussed. Sulfuric acid concentrations of 30 to 35 weight percent are preferred. Platinized platinum or smooth platinum gave the best anode kinetics at a given potential of the five materials examined.

  14. Behavior of oxide scales on 2. 25Cr-1Mo steel during thermal cycling. II. Scales grown in water vapor

    SciTech Connect

    Christl, W.; Rahmel, A.; Schuetze, M.

    1989-02-01

    The acoustic emission (AE) technique has been applied to identify scale cracking during thermal cycling of tubes of 2.25Cr-1Mo steel. The scale morphology and failure mode were investigated by light and electron optical method. The scale formed at 600/degree/C in water vapor consists of an outer magnetite and an inner, chromium-containing spinel layer. Cooling leads to tensile stresses in the scale that cause macro- and microcrack formation in the scale. At constant-cycle parameters, a characteristic set of crack length and crack density is established. Changes in the cycle parameters also change the crack length and crack density. The experimental results can be described by a model developed by Hasselmann assuming a large number of noninteracting microcracks in a ceramic plate.

  15. The water cycle for kids

    USGS Publications Warehouse

    Neno, Stephanie; Morgan, Jim; Zonolli, Gabriele; Perlman, Howard; Gonthier, Gerard

    2013-01-01

    The U.S. Geological Survey (USGS) and the Food and Agriculture Organization of the United Nations (FAO) have created a water-cycle diagram for use in elementary and middle schools. The diagram is available in many languages. This diagram is part of the USGS's Water Science School, in which the water cycle is described in detail.

  16. Nitrogen cycling. Rapid nitrous oxide cycling in the suboxic ocean.

    PubMed

    Babbin, Andrew R; Bianchi, Daniele; Jayakumar, Amal; Ward, Bess B

    2015-06-01

    Nitrous oxide (N2O) is a powerful greenhouse gas and a major cause of stratospheric ozone depletion, yet its sources and sinks remain poorly quantified in the oceans. We used isotope tracers to directly measure N2O reduction rates in the eastern tropical North Pacific. Because of incomplete denitrification, N2O cycling rates are an order of magnitude higher than predicted by current models in suboxic regions, and the spatial distribution suggests strong dependence on both organic carbon and dissolved oxygen concentrations. Furthermore, N2O turnover is 20 times higher than the net atmospheric efflux. The rapid rate of this cycling coupled to an expected expansion of suboxic ocean waters implies future increases in N2O emissions. PMID:26045434

  17. The Mars water cycle

    NASA Technical Reports Server (NTRS)

    Davies, D. W.

    1981-01-01

    A model has been developed to test the hypothesis that the observed seasonal and latitudinal distribution of water on Mars is controlled by the sublimation and condensation of surface ice deposits in the Arctic and Antarctic, and the meridional transport of water vapor. Besides reproducing the observed water vapor distribution, the model correctly reproduces the presence of a large permanent ice cap in the Arctic and not in the Antarctic. No permanent ice reservoirs are predicted in the temperate or equatorial zones. Wintertime ice deposits in the Arctic are shown to be the source of the large water vapor abundances observed in the Arctic summertime, and the moderate water vapor abundances in the northern temperate region. Model calculations suggest that a year without dust storms results in very little change in the water vapor distribution. The current water distribution appears to be the equilibrium distribution for present atmospheric conditions.

  18. The NEWS Water Cycle Climatology

    NASA Technical Reports Server (NTRS)

    Rodell, Matthew; Beaudoing, Hiroko Kato; L'Ecuyer, Tristan; William, Olson

    2012-01-01

    NASA's Energy and Water Cycle Study (NEWS) program fosters collaborative research towards improved quantification and prediction of water and energy cycle consequences of climate change. In order to measure change, it is first necessary to describe current conditions. The goal of the first phase of the NEWS Water and Energy Cycle Climatology project was to develop "state of the global water cycle" and "state of the global energy cycle" assessments based on data from modern ground and space based observing systems and data integrating models. The project was a multi-institutional collaboration with more than 20 active contributors. This presentation will describe the results of the water cycle component of the first phase of the project, which include seasonal (monthly) climatologies of water fluxes over land, ocean, and atmosphere at continental and ocean basin scales. The requirement of closure of the water budget (i.e., mass conservation) at various scales was exploited to constrain the flux estimates via an optimization approach that will also be described. Further, error assessments were included with the input datasets, and we examine these in relation to inferred uncertainty in the optimized flux estimates in order to gauge our current ability to close the water budget within an expected uncertainty range.

  19. Biological water oxidation.

    PubMed

    Cox, Nicholas; Pantazis, Dimitrios A; Neese, Frank; Lubitz, Wolfgang

    2013-07-16

    Photosystem II (PSII), a multisubunit pigment-protein supercomplex found in cyanobacteria, algae, and plants, catalyzes a unique reaction in nature: the light-driven oxidation of water. Remarkable recent advances in the structural analysis of PSII now give a detailed picture of the static supercomplex on the molecular level. These data provide a solid foundation for future functional studies, in particular the mechanism of water oxidation and oxygen release. The catalytic core of the PSII is a tetramanganese-calcium cluster (Mn₄O₅Ca), commonly referred to as the oxygen-evolving complex (OEC). The function of the OEC rests on its ability to cycle through five metastable states (Si, i = 0-4), transiently storing four oxidizing equivalents, and in so doing, facilitates the four electron water splitting reaction. While the latest crystallographic model of PSII gives an atomic picture of the OEC, the exact connectivity within the inorganic core and the S-state(s) that the X-ray model represents remain uncertain. In this Account, we describe our joint experimental and theoretical efforts to eliminate these ambiguities by combining the X-ray data with spectroscopic constraints and introducing computational modeling. We are developing quantum chemical methods to predict electron paramagnetic resonance (EPR) parameters for transition metal clusters, especially focusing on spin-projection approaches combined with density functional theory (DFT) calculations. We aim to resolve the geometric and electronic structures of all S-states, correlating their structural features with spectroscopic observations to elucidate reactivity. The sequence of manganese oxidations and concomitant charge compensation events via proton transfer allow us to rationalize the multielectron S-state cycle. EPR spectroscopy combined with theoretical calculations provides a unique window into the tetramangenese complex, in particular its protonation states and metal ligand sphere evolution, far beyond the scope of static techniques such as X-ray crystallography. This approach has led, for example, to a detailed understanding of the EPR signals in the S₂-state of the OEC in terms of two interconvertible, isoenergetic structures. These two structures differ in their valence distribution and spin multiplicity, which has important consequences for substrate binding and may explain its low barrier exchange with solvent water. New experimental techniques and innovative sample preparations are beginning to unravel the complex sequence of substrate uptake/inclusion, which is coupled to proton release. The introduction of specific site perturbations, such as replacing Ca²⁺ with Sr²⁺, provides discrete information about the ligand environment of the individual Mn ions. In this way, we have identified a potential open coordination site for one Mn center, which may serve as a substrate binding site in the higher S-states, such as S₃ and S₄. In addition, we can now monitor the binding of the substrate water in the lower S-states (S₁ and S₂) using new EPR-detected NMR spectroscopies. These studies provided the first evidence that one of the substrates is subsumed into the complex itself and forms an oxo-bridge between two Mn ions. This result places important new restrictions on the mechanism of O-O bond formation. These new insights from nature's water splitting catalyst provide important criteria for the rational design of bioinspired synthetic catalysts. PMID:23506074

  20. Copper-catalyzed hydroquinone oxidation and associated redox cycling of copper under conditions typical of natural saline waters.

    PubMed

    Yuan, Xiu; Pham, A Ninh; Miller, Christopher J; Waite, T David

    2013-08-01

    A detailed kinetic model has been developed to describe the oxidation of Cu(I) by O2 and the reduction of Cu(II) by 1,4-hydroquinone (H2Q) in the presence of O2 in 0.7 M NaCl solution over a pH range of 6.5-8.0. The reaction between Cu(I) and O2 is shown to be the most important pathway in the overall oxidation of Cu(I), with the rate constant for this oxidation process increasing with an increasing pH. In 0.7 M NaCl solutions, Cu(II) is capable of catalyzing the oxidation of H2Q in the presence of O2 with the monoanion, HQ(-), the kinetically active hydroquinone form, reducing Cu(II) with an intrinsic rate constant of (5.0 ± 0.4) × 10(7) M(-1) s(-1). Acting as a chain-propagating species, the deprotonated semiquinone radical (SQ(•) (-)) generated from both the one-electron oxidation of H2Q and the one-electron reduction of 1,4-benzoquinone (BQ) also reacts rapidly with Cu(II) and Cu(I), with the same rate constant of (2.0 ± 0.5) × 10(7) M(-1) s(-1). In addition to its role in reformation of Cu(II) via continuous oxidation of Cu(I), O2 rapidly removes SQ(•) (-), resulting in the generation of O2(•) (-). Agreement between half-cell reduction potentials of different redox couples provides confirmation of the veracity of the proposed model describing the interactions of copper and quinone species in circumneutral pH saline solutions. PMID:23796190

  1. Water Cycling &the GPM Mission

    NASA Astrophysics Data System (ADS)

    Smith, E. A.

    2003-04-01

    The GPM mission is currently planned for start in the late'07 - early'08 time frame. Its main scientific goal is to help answer pressing scientific problems arising within the context of global and regional water cycles. These problems cut across a hierarchy of scales and include climate-water cycle interactions, techniques for improving weather and climate predictions, and better methods for combining observed precipitation with hydrometeorological prediction models for applications to hazardous flood-producing storms, seasonal flood/draught conditions, and fresh water resource assessments. The GPM mission will expand the scope of precipitation measurement through the use of a constellation of some 9 satellites, one of which will be an advanced TRMM-like "core" satellite carrying a dual-frequency Ku-Ka band precipitation radar and an advanced, multifrequency passive microwave radiometer with vertical-horizontal polarization discrimination. The other constellation members will include new dedicated satellites and co-existing operational/research satellites carrying similar (but not identical) passive microwave radiometers. The goal of the constellation is to achieve 3-hour sampling at any spot on the globe - continuously. The constellation's orbit architecture will consist of a mix of sun-synchronous and non-sun-synchronous satellites with the "core" satellite providing measurements of cloud-precipitation microphysical processes plus calibration-quality rainrates to be used with the other retrieval information to ensure bias-free constellation coverage. GPM is organized internationally, involving existing, pending, projected, and under-study partnerships which will link NASA and NOAA in the US, NASDA in Japan, ESA in Europe, ISRO in India, CNES in France, and possibly ASI in Italy, KARI in South Korea, CSA in Canada, and AEB in Brazil. Additionally, the program is actively pursuing agreements with other international collaborators and domestic scientific agencies and institutions, as well as participation by individual scientists from academia, government, and the private sector to fulfill mission goals and to pave the way for what ultimately is expected to become an internationally-organized operational global precipitation observing system. Notably, the broad societal applications of GPM are reflected in the United Nation's identification of this mission as a foremost candidate for its Peaceful Uses of Space Program. An overview of the GPM mission design is given, followed by an explanation of its scientific agenda as an outgrowth of making improvements in rain retrieval accuracy, microphysics dexterity, sampling frequency, and global coverage. All of these improvements offer new means to observe variability in precipitation and water cycle fluxes, to improve water budget closure at regional and global scales, and to leverage these improvements in achieving improved predictability of weather, climate, and hydrometeorology. Specifically, the scientific agenda of GPM has been designed to leverage the measurement improvements to improve prognostic model performance, particularly quantitative precipitation forecasting and its linked phenomena at short, intermediate, and extended time scales. The talk addresses how GPM measurements will enable more accurate satellite-based calculations of the water cycle relative to where things stand today (two examples will be provided), and how such measurements can be used to evaluate accelerations and decelerations in regional and global water cycle processes and thus improve our understanding of water-driven climatic shifts. These improvements become possible by using more accurate, more microphysically-centric, more frequent, and fully global precipitation observations to achieve better water budget closure and to provide more realistic forcing and assessment of prediction models.

  2. Molecular water oxidation catalyst

    DOEpatents

    Gratzel, Michael; Munavalli, Shekhar; Pern, Fu-Jann; Frank, Arthur J.

    1993-01-01

    A dimeric composition of the formula: ##STR1## wherein L', L", L'", and L"" are each a bidentate ligand having at least one functional substituent, the ligand selected from bipyridine, phenanthroline, 2-phenylpyridine, bipyrimidine, and bipyrazyl and the functional substituent selected from carboxylic acid, ester, amide, halogenide, anhydride, acyl ketone, alkyl ketone, acid chloride, sulfonic acid, phosphonic acid, and nitro and nitroso groups. An electrochemical oxidation process for the production of the above functionally substituted bidentate ligand diaqua oxo-bridged ruthenium dimers and their use as water oxidation catalysts is described.

  3. Solid oxide fuel cell combined cycles

    SciTech Connect

    Bevc, F.P.; Lundberg, W.L.; Bachovchin, D.M.

    1996-12-31

    The integration of the solid oxide fuel cell and combustion turbine technologies can result in combined-cycle power plants, fueled with natural gas, that have high efficiencies and clean gaseous emissions. Results of a study are presented in which conceptual designs were developed for 3 power plants based upon such an integration, and ranging in rating from 3 to 10 MW net ac. The plant cycles are described and characteristics of key components summarized. Also, plant design-point efficiency estimates are presented as well as values of other plant performance parameters.

  4. The Water Cycle in Volusia County

    USGS Publications Warehouse

    German, Edward R.

    2009-01-01

    Earth's water is always in motion. The water cycle, also known as the hydrologic cycle, describes the continuous movement of water on, above, and below the Earth's surface. This fact sheet provides information about how much water moves into and out of Volusia County, and where it is stored. It also illustrates the seasonal variation in water quantity and movement using data from some of the hydrologic data collection sites in or near Volusia County, Florida.

  5. Creative Writing and the Water Cycle.

    ERIC Educational Resources Information Center

    Young, Rich; Virmani, Jyotika; Kusek, Kristen M.

    2001-01-01

    Uses the story "The Life of a Drop of Water" to initiate a creative writing activity and teach about the water cycle. Attempts to stimulate students' understanding of a scientific concept by using their imaginations. (YDS)

  6. Water Cycle Missions for the Next Decade

    NASA Astrophysics Data System (ADS)

    Houser, P. R.

    2013-12-01

    The global water cycle describes the circulation of water as a vital and dynamic substance in its liquid, solid, and vapor phases as it moves through the atmosphere, oceans and land. Life in its many forms exists because of water, and modern civilization depends on learning how to live within the constraints imposed by the availability of water. The scientific challenge posed by the need to observe the global water cycle is to integrate in situ and space-borne observations to quantify the key water-cycle state variables and fluxes. The vision to address that challenge is a series of Earth observation missions that will measure the states, stocks, flows, and residence times of water on regional to global scales followed by a series of coordinated missions that will address the processes, on a global scale, that underlie variability and changes in water in all its three phases. The accompanying societal challenge is to foster the improved use of water data and information as a basis for enlightened management of water resources, to protect life and property from effects of extremes in the water cycle. A major change in thinking about water science that goes beyond its physics to include its role in ecosystems and society is also required. Better water-cycle observations, especially on the continental and global scales, will be essential. Water-cycle predictions need to be readily available globally to reduce loss of life and property caused by water-related natural hazards. Building on the 2007 Earth Science Decadal Survey, NASA's Plan for a Climate-Centric Architecture for Earth Observations and Applications from Space , and the 2012 Chapman Conference on Remote Sensing of the Terrestrial Water Cycle, a workshop was held in April 2013 to gather wisdom and determine how to prepare for the next generation of water cycle missions in support of the second Earth Science Decadal Survey. This talk will present the outcomes of the workshop including the intersection between science questions, technology readiness and satellite design optimization. A series of next-generation water cycle mission working groups were proposed and white papers, designed to identify capacity gaps and inform NASA were developed. The workshop identified several visions for the next decade of water cycle satellite observations, and developed a roadmap and action plan for developing the foundation for these missions. Achieving this outcome will result in optimized community investments and better functionality of these future missions, and will help to foster broader range of scientists and professionals engaged in water cycle observation planning and development around the country, and the world.

  7. Water Cycle. K-6 Science Curriculum.

    ERIC Educational Resources Information Center

    Blueford, J. R.; And Others

    Water Cycle is one of the units of a K-6 unified science curriculum program. The unit consists of four organizing sub-themes: (1) atmosphere (highlighting the processes of evaporation, condensation, convection, wind movement and air pollution); (2) water (examining the properties of liquids, water distribution, use, and quality, and the water

  8. Water oxidation: High five iron

    NASA Astrophysics Data System (ADS)

    Lloret-Fillol, Julio; Costas, Miquel

    2016-03-01

    The oxidation of water is essential to the sustainable production of fuels using sunlight or electricity, but designing active, stable and earth-abundant catalysts for the reaction is challenging. Now, a complex containing five iron atoms is shown to efficiently oxidize water by mimicking key features of the oxygen-evolving complex in green plants.

  9. Biomimetic Water-Oxidation Catalysts: Manganese Oxides.

    PubMed

    Kurz, Philipp

    2016-01-01

    The catalytic oxidation of water to molecular oxygen is a key process for the production of solar fuels. Inspired by the biological manganese-based active site for this reaction in the enzyme Photosystem II, researchers have made impressive progress in the last decades regarding the development of synthetic manganese catalysts for water oxidation. For this, it has been especially fruitful to explore the many different types of known manganese oxides MnOx. This chapter first offers an overview of the structural, thermodynamic, and mechanistic aspects of water-oxidation catalysis by MnOx. The different test systems used for catalytic studies are then presented together with general reactivity trends. As a result, it has been possible to identify layered, mixed Mn (III/IV)-oxides as an especially promising class of bio-inspired catalysts and an attempt is made to give structure-based reasons for the good performances of these materials. In the outlook, the challenges of catalyst screenings (and hence the identification of a "best MnOx catalyst") are discussed. There is a great variety of reaction conditions which might be relevant for the application of manganese oxide catalysts in technological solar fuel-producing devices, and thus catalyst improvements are currently still addressing a very large parameter space. Nonetheless, detailed knowledge about the biological catalyst and a solid experimental basis concerning the syntheses and water-oxidation reactivities of MnOx materials have been established in the last decade and thus this research field is well positioned to make important contributions to solar fuel research in the future. PMID:25980320

  10. Water Cycle. K-6 Science Curriculum.

    ERIC Educational Resources Information Center

    Blueford, J. R.; And Others

    Water Cycle is one of the units of a K-6 unified science curriculum program. The unit consists of four organizing sub-themes: (1) atmosphere (highlighting the processes of evaporation, condensation, convection, wind movement and air pollution); (2) water (examining the properties of liquids, water distribution, use, and quality, and the water…

  11. Integrated urban water cycle management: the UrbanCycle model.

    PubMed

    Hardy, M J; Kuczera, G; Coombes, P J

    2005-01-01

    Integrated urban water cycle management presents a new framework in which solutions to the provision of urban water services can be sought. It enables new and innovative solutions currently constrained by the existing urban water paradigm to be implemented. This paper introduces the UrbanCycle model. The model is being developed in response to the growing and changing needs of the water management sector and in light of the need for tools to evaluate integrated watercycle management approaches. The key concepts underpinning the UrbanCycle model are the adoption of continuous simulation, hierarchical network modelling, and the careful management of computational complexity. The paper reports on the integration of modelling capabilities across the allotment, and subdivision scales, enabling the interactions between these scales to be explored. A case study illustrates the impacts of various mitigation measures possible under an integrated water management framework. The temporal distribution of runoff into ephemeral streams from a residential allotment in Western Sydney is evaluated and linked to the geomorphic and ecological regimes in receiving waters. PMID:16445168

  12. Observing the Global Water Cycle from Space

    NASA Technical Reports Server (NTRS)

    Hildebrand, P. H.

    2004-01-01

    This paper presents an approach to measuring all major components of the water cycle from space. Key elements of the global water cycle are discussed in terms of the storage of water-in the ocean, air, cloud and precipitation, in soil, ground water, snow and ice, and in lakes and rivers, and in terms of the global fluxes of water between these reservoirs. Approaches to measuring or otherwise evaluating the global water cycle are presented, and the limitations on known accuracy for many components of the water cycle are discussed, as are the characteristic spatial and temporal scales of the different water cycle components. Using these observational requirements for a global water cycle observing system, an approach to measuring the global water cycle from space is developed. The capabilities of various active and passive microwave instruments are discussed, as is the potential of supporting measurements from other sources. Examples of space observational systems, including TRMM/GPM precipitation measurement, cloud radars, soil moisture, sea surface salinity, temperature and humidity profiling, other measurement approaches and assimilation of the microwave and other data into interpretative computer models are discussed to develop the observational possibilities. The selection of orbits is then addressed, for orbit selection and antenna size/beamwidth considerations determine the sampling characteristics for satellite measurement systems. These considerations dictate a particular set of measurement possibilities, which are then matched to the observational sampling requirements based on the science. The results define a network of satellite instrumentation systems, many in low Earth orbit, a few in geostationary orbit, and all tied together through a sampling network that feeds the observations into a data-assimilative computer model.

  13. Observing the Global Water Cycle from Space

    NASA Technical Reports Server (NTRS)

    Hildebrand, Peter H.; Houser, Paul; Schlosser, C. Adam

    2003-01-01

    This paper presents an approach to measuring all major components of the water cycle from space. The goal of the paper is to explore the concept of using a sensor-web of satellites to observe the global water cycle. The details of the required measurements and observation systems are therefore only an initial approach and will undergo future refinement, as their details will be highly important. Key elements include observation and evaluation of all components of the water cycle in terms of the storage of water-in the ocean, air, cloud and precipitation, in soil, ground water, snow and ice, and in lakes and rivers-and in terms of the global fluxes of water between these reservoirs. For each component of the water cycle that must be observed, the appropriate temporal and spatial scales of measurement are estimated, along with the some of the frequencies that have been used for active and passive microwave observations of the quantities. The suggested types of microwave observations are based on the heritage for such measurements, and some aspects of the recent heritage of these measurement algorithms are listed. The observational requirements are based on present observational systems, as modified by expectations for future needs. Approaches to the development of space systems for measuring the global water cycle can be based on these observational requirements.

  14. ENGINEERING BULLETIN: SUPERCRITICAL WATER OXIDATION

    EPA Science Inventory

    This engineering bulletin presents a description and status of supercritical water oxidation technology, a summary of recent performance tests, and the current applicability of this emerging technology. This information is provided to assist remedial project managers, contractors...

  15. Global water cycle and solar activity variations

    NASA Astrophysics Data System (ADS)

    Al-Tameemi, Muthanna A.; Chukin, Vladimir V.

    2016-05-01

    The water cycle is the most active and most important component in the circulation of global mass and energy in the Earth system. Furthermore, water cycle parameters such as evaporation, precipitation, and precipitable water vapour play a major role in global climate change. In this work, we attempt to determine the impact of solar activity on the global water cycle by analyzing the global monthly values of precipitable water vapour, precipitation, and the Solar Modulation Potential in 1983-2008. The first object of this study was to calculate global evaporation for the period 1983-2008. For this purpose, we determined the water cycle rate from satellite data, and precipitation/evaporation relationship from 10 years of Planet Simulator model data. The second object of our study was to investigate the relationship between the Solar Modulation Potential (solar activity index) and the evaporation for the period 1983-2008. The results showed that there is a relationship between the solar modulation potential and the evaporation values for the period of study. Therefore, we can assume that the solar activity has an impact on the global water cycle.

  16. Fast water oxidation using iron.

    PubMed

    Ellis, W Chadwick; McDaniel, Neal D; Bernhard, Stefan; Collins, Terrence J

    2010-08-18

    Photolysis of water, a long-studied strategy for storing solar energy, involves two half-reactions: the reduction of protons to dihydrogen and the oxidation of water to dioxygen. Proton reduction is well-understood, with catalysts achieving quantum yields of 34% when driven by visible light. Water oxidation, on the other hand, is much less advanced, typically involving expensive metal centers and rarely working in conjunction with a photochemically powered system. Before further progress can be made in the field of water splitting, significant developments in the catalysis of oxygen evolution are needed. Herein we present an iron-centered tetraamido macrocyclic ligand (Fe-TAML) that efficiently catalyzes the oxidative conversion of water to dioxygen. When the catalyst is combined in unbuffered solution with ceric ammonium nitrate, its turnover frequency exceeds 1.3 s(-1). Real-time UV-vis and oxygen monitoring of the active complex give insights into the reaction and decay kinetics. PMID:20698652

  17. The NASA Energy and Water cycle Study

    NASA Astrophysics Data System (ADS)

    Houser, P. R.; Entin, J. K.; Schiffer, R. A.; Belvedere, D. R.

    2010-12-01

    In 2003 NASA established the NASA Energy and Water-cycle Study (NEWS), whose long-term grand challenge is to document and enable improved, observationally based, predictions of water and energy cycle consequences of Earth system variability and change. Over the past two years, the NEWS team has been working on how to refine its approach to science integration . To this end, NEWS has created four working groups that identify integration needs and make the needed connections to partner and coordinate with water & energy cycle research and application activities going on at other organizations within NASA, nationally, and internationally. The four groups are: (1) Drought & Flood Extremes- including water and energy aspects of abrupt climate change, (2) Evaporation & Latent Heating - including both land and ocean, (3) Water and Energy Cycle Climatology - to exploit and influence evolving observing systems, and (4) Modeling & Water Cycle Prediction - foster interaction with the global modeling community. The first phase of NEWS focuses on the first coordinated attempt to describe the complete global energy and water cycle using existing and forthcoming satellite and ground based observations, and laying the foundation for essential NEWS developments in model representations of atmospheric energy and water exchange processes. This comprehensive energy and water data analysis program must exploit crucial datasets, some still requiring complete re-processing, and new satellite measurements. These data products will then be evaluated for accuracy and consistency, in part by using them in the first diagnosis of the weather-scale (space and time) variations of the global energy and water cycle over the past one-two decades. The primary objective is to ensure that results of this analysis effort serve as a recognized data basis to compare with corresponding climate statistics produced by existing climate models, quantify systematic deficiencies, and identify needed improvements. The data records to be produced through these efforts are mandatory for developing and validating models that meet NEWS scientific requirements. At the same time, NEWS implementation calls for the development of radically new model representations of energy and water exchange processes that resolve significant process scales and spatial variability in ground boundary conditions. Such process-resolving models may be first constructed as independent stand-alone modules that can be tested against ad hoc field measurements and systematic observations at selected experimental sites. At a later stage, the codes may be simplified through statistical sampling of process-scale variables or otherwise reduced to generate integrated fluxes representative of each grid-element in a climate model. Finally, the implementation plan calls for broad exploration of potential new observing techniques concerning all aspects of the energy and water cycle, and initiating relevant technical feasibility and scientific benefit studies.

  18. The seasonal cycle of water on Mars

    NASA Technical Reports Server (NTRS)

    Jakosky, B. M.

    1985-01-01

    A review of the behavior of water in the Mars atmosphere and subsurface is appropriate now that data from the Mariner and Viking spacecraft have been analyzed and discussed for several years following completion of those missions. Observations and analyses pertinent to the seasonal cycle of water vapor in the atmosphere of Mars are reviewed, with attention toward transport of water and the seasonal exchange of water between the atmosphere and various non-atmospheric reservoirs. Possible seasonally-accessible sources and sinks for water include water ice on or within the seasonal and residual polar caps; surface or subsurface ice in the high-latitude regions of the planet; adsorbed or chemically-bound water within the near-surface regolith; or surface or subsurface liquid water. The stability of water within each of these reservoirs is discussed, as are the mechanisms for driving exchange of the water with the atmosphere and the timescales for exchange. Specific conclusions are reached about the distribution of water and the viability of each mechanism as a seasonal reservoir. Discussion is also included of the behavior of water on longer timescales, driven by the variations in solar forcing due to the quasi-periodic variations of the orbital obliquity. Finally, specific suggestions are made for future observations from spacecraft which would further define or constrain the seasonal cycle of water.

  19. Rapid nitrous oxide cycling in the suboxic ocean

    NASA Astrophysics Data System (ADS)

    Babbin, Andrew R.; Bianchi, Daniele; Jayakumar, Amal; Ward, Bess B.

    2015-06-01

    Nitrous oxide (N2O) is a powerful greenhouse gas and a major cause of stratospheric ozone depletion, yet its sources and sinks remain poorly quantified in the oceans. We used isotope tracers to directly measure N2O reduction rates in the eastern tropical North Pacific. Because of incomplete denitrification, N2O cycling rates are an order of magnitude higher than predicted by current models in suboxic regions, and the spatial distribution suggests strong dependence on both organic carbon and dissolved oxygen concentrations. Furthermore, N2O turnover is 20 times higher than the net atmospheric efflux. The rapid rate of this cycling coupled to an expected expansion of suboxic ocean waters implies future increases in N2O emissions.

  20. Modern Estimates of Global Water Cycle Fluxes

    NASA Astrophysics Data System (ADS)

    Rodell, M.; Beaudoing, H. K.; L'Ecuyer, T. S.; Olson, W. S.

    2014-12-01

    The goal of the first phase of the NASA Energy and Water Cycle Study (NEWS) Water and Energy Cycle Climatology project was to develop "state of the global water cycle" and "state of the global energy cycle" assessments based on data from modern ground and space based observing systems and data integrating models. Here we describe results of the water cycle assessment, including mean annual and monthly fluxes over continents and ocean basins during the first decade of the millennium. To the extent possible, the water flux estimates are based on (1) satellite measurements and (2) data-integrating models. A careful accounting of uncertainty in each flux was applied within a routine that enforced multiple water and energy budget constraints simultaneously in a variational framework, in order to produce objectively-determined, optimized estimates. Simultaneous closure of the water and energy budgets caused the ocean evaporation and precipitation terms to increase by about 10% and 5% relative to the original estimates, mainly because the energy budget required turbulent heat fluxes to be substantially larger in order to balance net radiation. In the majority of cases, the observed annual, surface and atmospheric water budgets over the continents and oceans close with much less than 10% residual. Observed residuals and optimized uncertainty estimates are considerably larger for monthly surface and atmospheric water budget closure, often nearing or exceeding 20% in North America, Eurasia, Australia and neighboring islands, and the Arctic and South Atlantic Oceans. The residuals in South America and Africa tend to be smaller, possibly because cold land processes are a non-issue. Fluxes are poorly observed over the Arctic Ocean, certain seas, Antarctica, and the Australasian and Indonesian Islands, leading to reliance on atmospheric analysis estimates. Other details of the study and future directions will be discussed.

  1. Geothermal Water Use: Life Cycle Water Consumption, Water Resource Assessment, and Water Policy Framework

    DOE Data Explorer

    Schroeder, Jenna N.

    2014-06-10

    This report examines life cycle water consumption for various geothermal technologies to better understand factors that affect water consumption across the life cycle (e.g., power plant cooling, belowground fluid losses) and to assess the potential water challenges that future geothermal power generation projects may face. Previous reports in this series quantified the life cycle freshwater requirements of geothermal power-generating systems, explored operational and environmental concerns related to the geochemical composition of geothermal fluids, and assessed future water demand by geothermal power plants according to growth projections for the industry. This report seeks to extend those analyses by including EGS flash, both as part of the life cycle analysis and water resource assessment. A regional water resource assessment based upon the life cycle results is also presented. Finally, the legal framework of water with respect to geothermal resources in the states with active geothermal development is also analyzed.

  2. An updated view of global water cycling

    NASA Astrophysics Data System (ADS)

    Houser, P. R.; Schlosser, A.; Lehr, J.

    2009-04-01

    Unprecedented new observation capacities combined with revolutions in modeling, we are poised to make huge advances in water cycle assessment, understanding, and prediction. To realize this goal, we must develop a discipline of prediction and verification through the integration of water and energy cycle observations and models, and to verify model predictions against observed phenomena to ensure that research delivers reliable improvements in prediction skill. Accomplishing these goals will require, in part, an accurate accounting of the key reservoirs and fluxes associated with the global water and energy cycle, including their spatial and temporal variability, through integration of all necessary observations and research tools. A brief history of the lineage of the conventional water balance and a summary accounting of all major parameters of the water balance using highly respected secondary sources will be presented. Principally, recently published peer reviewed papers reporting results of original work involving direct measurements and new data generated by high-tech devices (e.g. satellite / airborne instruments, supercomputers, geophysical tools) will be employed. This work lends credence to the conventional water balance ideas, but also reveals anachronistic scientific concepts/models, questionable underlying data, longstanding oversights and outright errors in the water balance.

  3. Global Changes of the Water Cycle Intensity

    NASA Technical Reports Server (NTRS)

    Bosilovich, Michael G.; Schubert, Siegfried D.; Walker, Gregory K.

    2003-01-01

    In this study, we evaluate numerical simulations of the twentieth century climate, focusing on the changes in the intensity of the global water cycle. A new diagnostic of atmospheric water vapor cycling rate is developed and employed, that relies on constituent tracers predicted at the model time step. This diagnostic is compared to a simplified traditional calculation of cycling rate, based on monthly averages of precipitation and total water content. The mean sensitivity of both diagnostics to variations in climate forcing is comparable. However, the new diagnostic produces systematically larger values and more variability than the traditional average approach. Climate simulations were performed using SSTs of the early (1902-1921) and late (1979- 1998) twentieth century along with the appropriate C02 forcing. In general, the increase of global precipitation with the increases in SST that occurred between the early and late twentieth century is small. However, an increase of atmospheric temperature leads to a systematic increase in total precipitable water. As a result, the residence time of water in the atmosphere increased, indicating a reduction of the global cycling rate. This result was explored further using a number of 50-year climate simulations from different models forced with observed SST. The anomalies and trends in the cycling rate and hydrologic variables of different GCMs are remarkably similar. The global annual anomalies of precipitation show a significant upward trend related to the upward trend of surface temperature, during the latter half of the twentieth century. While this implies an increase in the hydrologic cycle intensity, a concomitant increase of total precipitable water again leads to a decrease in the calculated global cycling rate. An analysis of the land/sea differences shows that the simulated precipitation over land has a decreasing trend while the oceanic precipitation has an upward trend consistent with previous studies and the available observations. The decreasing continental trend in precipitation is located primarily over tropical land regions, with some other regions, such as North America experiencing an increasing trend. Precipitation trends are diagnosed further using the water tracers to delineate the precipitation that occurs because of continental evaporation, as opposed to oceanic evaporation. These diagnostics show that over global land areas, the recycling of continental moisture is decreasing in time. However, the recycling changes are not spatially uniform so that some regions, most notably over the United States, experience continental recycling of water that increases in time.

  4. Children's Views about the Water Cycle.

    ERIC Educational Resources Information Center

    Bar, Varda

    1989-01-01

    Israeli children's (kindergarten to grade nine) explanations about the water cycle are described. Reports the children's views about the source of clouds and the mechanism of rainfall. It was concluded that understanding evaporation is a necessary condition for explaining a mechanism of rain containing the ideas of condensation and heaviness. (YP)

  5. Solar High Temperature Water-Splitting Cycle with Quantum Boost

    SciTech Connect

    Taylor, Robin; Davenport, Roger; Talbot, Jan; Herz, Richard; Genders, David; Symons, Peter; Brown, Lloyd

    2014-04-25

    A sulfur family chemical cycle having ammonia as the working fluid and reagent was developed as a cost-effective and efficient hydrogen production technology based on a solar thermochemical water-splitting cycle. The sulfur ammonia (SA) cycle is a renewable and sustainable process that is unique in that it is an all-fluid cycle (i.e., with no solids handling). It uses a moderate temperature solar plant with the solar receiver operating at 800°C. All electricity needed is generated internally from recovered heat. The plant would operate continuously with low cost storage and it is a good potential solar thermochemical hydrogen production cycle for reaching the DOE cost goals. Two approaches were considered for the hydrogen production step of the SA cycle: (1) photocatalytic, and (2) electrolytic oxidation of ammonium sulfite to ammonium sulfate in aqueous solutions. Also, two sub-cycles were evaluated for the oxygen evolution side of the SA cycle: (1) zinc sulfate/zinc oxide, and (2) potassium sulfate/potassium pyrosulfate. The laboratory testing and optimization of all the process steps for each version of the SA cycle were proven in the laboratory or have been fully demonstrated by others, but further optimization is still possible and needed. The solar configuration evolved to a 50 MW(thermal) central receiver system with a North heliostat field, a cavity receiver, and NaCl molten salt storage to allow continuous operation. The H2A economic model was used to optimize and trade-off SA cycle configurations. Parametric studies of chemical plant performance have indicated process efficiencies of ~20%. Although the current process efficiency is technically acceptable, an increased efficiency is needed if the DOE cost targets are to be reached. There are two interrelated areas in which there is the potential for significant efficiency improvements: electrolysis cell voltage and excessive water vaporization. Methods to significantly reduce water evaporation are proposed for future activities. Electrolysis membranes that permit higher temperatures and lower voltages are attainable. The oxygen half cycle will need further development and improvement.

  6. Multi-cycle boiling water reactor fuel cycle optimization

    SciTech Connect

    Ottinger, K.; Maldonado, G.I.

    2013-07-01

    In this work a new computer code, BWROPT (Boiling Water Reactor Optimization), is presented. BWROPT uses the Parallel Simulated Annealing (PSA) algorithm to solve the out-of-core optimization problem coupled with an in-core optimization that determines the optimum fuel loading pattern. However it uses a Haling power profile for the depletion instead of optimizing the operating strategy. The result of this optimization is the optimum new fuel inventory and the core loading pattern for the first cycle considered in the optimization. Several changes were made to the optimization algorithm with respect to other nuclear fuel cycle optimization codes that use PSA. Instead of using constant sampling probabilities for the solution perturbation types throughout the optimization as is usually done in PSA optimizations the sampling probabilities are varied to get a better solution and/or decrease runtime. The new fuel types available for use can be sorted into an array based on any number of parameters so that each parameter can be incremented or decremented, which allows for more precise fuel type selection compared to random sampling. Also, the results are sorted by the new fuel inventory of the first cycle for ease of comparing alternative solutions. (authors)

  7. Bioelectrochemical oxidation of water.

    PubMed

    Pita, Marcos; Mate, Diana M; Gonzalez-Perez, David; Shleev, Sergey; Fernandez, Victor M; Alcalde, Miguel; De Lacey, Antonio L

    2014-04-23

    The electrolysis of water provides a link between electrical energy and hydrogen, a high energy density fuel and a versatile energy carrier, but the process is very expensive. Indeed, the main challenge is to reduce energy consumption for large-scale applications using efficient renewable catalysts that can be produced at low cost. Here we present for the first time that laccase can catalyze electrooxidation of H2O to molecular oxygen. Native and laboratory-evolved laccases immobilized onto electrodes serve as bioelectrocatalytic systems with low overpotential and a high O2 evolution ratio against H2O2 production during H2O electrolysis. Our results open new research ground on H2O splitting, as they overcome serious practical limitations associated with artificial electrocatalysts currently used for O2 evolution. PMID:24725275

  8. Does GRACE see the water cycle 'intensifying'?

    NASA Astrophysics Data System (ADS)

    Eicker, Annette; Kusche, Jürgen; Forootan, Ehsan; Springer, Anne; Schumacher, Maike; Ohlwein, Christian

    2014-05-01

    Several researchers have postulated that, under a changing climate due to anthropogenic forcing, an intensification of the water cycle is already under way (Huntington, 2006). This is usually related to increases in hydrological fluxes such as precipitation (P), evapotranspiration (E), and river discharge (R). It is under debate, however, whether such observed or reconstructed flux changes are real and on what scales. Large-scale increase or decrease of the flux deficit (P-E) would lead to acceleration or deceleration of water storage anomalies possibly visible in GRACE time series, when discharge variability is small or properly accounted for. We investigate to what extent such accelerations, which are indeed found in maps of global gridded GRACE water storage anomalies, can be explained using output fields derived from global and regional atmospheric (re-)analyses and from hydrological models. We find this analysis challenging, since the GRACE time series is short and dominated by ENSO-type natural variability. Observed accelerations strongly depend on the analysis time frame, and may be explained to a large percentage by natural variability, thus masking a possible anthropogenically driven intensification of the terrestrial water cycle. This motivates us to apply statistical decomposition techniques in order to identify modes of natural variabilities and to remove them from the GRACE time series prior to the estimation of accelerations. Huntington T.G. (2006): Evidence for intensification of the global water cycle: Review and synthesis. J. Hydrology, 319:83-95

  9. Following the Water Cycle to Sustainability

    NASA Astrophysics Data System (ADS)

    Lutz, T. M.

    2012-12-01

    For scientists, modeling the connections among the parts of complex, dynamic systems is crucial. Doing so lets us understand emergent phenomena such as ecosystem behavior and climate patterns that could not otherwise be predicted. Emergent phenomena can typically only be understood or appreciated when we stand "outside" the system. When scientists take such an outsiders view of earth's systems they can propose many ways that human activities modify the climate system (e.g., increasing or reducing GHG emissions). But what should we do to achieve a sustainable future? Sustainability is an emergent property that arises at the level of the planetary management system, of which the scientific establishment is just a part. We are "insiders" and it is impossible to completely envision the conditions for sustainability or to plan for it. The crises in our atmosphere, biosphere, oceans, and in the natural and energy resource sectors are based in science and do call for urgent changes in science education. But education that focuses solely on science to meet the challenges of sustainability may be as likely to harm humanity's long-term prospects as to improve them. I present activities and teaching strategies that I use in general education classes at West Chester University, a comprehensive institution of roughly 14,000 undergraduates. The overarching concept is to extend "modeling the connections" to the sustainability level and to train students to think outside the system. To make the ideas more accessible, I have the students become sensors at their particular point in the web of connections that constitute the planetary management system. I ask them to evaluate their connection in three domains proposed by John Ehrenfeld (Sustainability by Design, Yale University Press, 2008): sense of place in the natural world; sense of responsibility for our actions, and sense of what it is to be a human being. I have them analyze their sense of connection with reference to a systems learning model based on feedback and limits to perception. I focus on a part of the course that builds on connections that start in the hydrosphere and that includes some basic experiential learning about the water cycle and students' reliance on it. We measure and visualize aspects of the water cycle in nearby areas of campus (designated as an outdoor classroom and demonstration garden). The evapotranspiration flow is used to introduce notions of what can happen when flows are not sensed (e.g., invisible to us). Students use an online water footprint calculator to discover how large their water reliance is, particularly through energy generation, food consumption and food waste; and how far their water reach extends (virtual water trade). They consider the ethical implications of their water use in a world in which it is becoming a more rare resource and in some cases a valued commodity. They learn about non-utilitarian values of water based on an activity on the values of nature. They look at local, community-based efforts to improve water quality and to re-localize water dependence. A reading from Aldo Leopold puts the water cycle in a historical and cultural perspective. The water cycle is strongly interwoven with natural and human energy systems, the climate system, the carbon cycle, nutrient cycles, the rock cycle, and serves as a starting point to reach many other topics.

  10. The artificial water cycle: emergy analysis of waste water treatment.

    PubMed

    Bastianoni, Simone; Fugaro, Laura; Principi, Ilaria; Rosini, Marco

    2003-04-01

    The artificial water cycle can be divided into the phases of water capture from the environment, potabilisation, distribution, waste water collection, waste water treatment and discharge back into the environment. The terminal phase of this cycle, from waste water collection to discharge into the environment, was assessed by emergy analysis. Emergy is the quantity of solar energy needed directly or indirectly to provide a product or energy flow in a given process. The emergy flow attributed to a process is therefore an index of the past and present environmental cost to support it. Six municipalities on the western side of the province of Bologna were analysed. Waste water collection is managed by the municipal councils and treatment is carried out in plants managed by a service company. Waste water collection was analysed by compiling a mass balance of the sewer system serving the six municipalities, including construction materials and sand for laying the pipelines. Emergy analysis of the water treatment plants was also carried out. The results show that the great quantity of emergy required to treat a gram of water is largely due to input of non renewable fossil fuels. As found in our previous analysis of the first part of the cycle, treatment is likewise characterised by high expenditure of non renewable resources, indicating a correlation with energy flows. PMID:12817633

  11. The DOE Water Cycle Pilot Study

    SciTech Connect

    Miller, N.L.; King, A.W.; Miller, M.A.; Springer, E.P.; Wesely, M.L.; Bashford, K.E.; Conrad, M.E.; Costigan, K.; Foster, P.N.; Gibbs, H.K.; Jin, J.; Klazura, J.; Lesht, B.M.; Machavaram, M.V.; Pan, F.; Song, J.; Troyan, D.; Washington-Allen, R.A.

    2003-09-20

    A Department of Energy (DOE) multi-laboratory Water Cycle Pilot Study (WCPS) investigated components of the local water budget at the Walnut River Watershed in Kansas to study the relative importance of various processes and to determine the feasibility of observational water budget closure. An extensive database of local meteorological time series and land surface characteristics was compiled. Numerical simulations of water budget components were generated and, to the extent possible, validated for three nested domains within the Southern Great Plains; the DOE Atmospheric Radiation Measurement/Cloud Atmospheric Radiation Testbed (ARM/CART), the Walnut River Watershed (WRW), and the Whitewater Watershed (WW), Kansas A 2-month Intensive Observation Period (IOP) was conducted to gather detailed observations relevant to specific details of the water budget, including fine-scale precipitation, streamflow, and soil moisture measurements not made routinely by other programs. Event and season al water isotope (delta 18O, delta D) sampling in rainwater, streams, soils, lakes, and wells provided a means of tracing sources and sinks within and external to the WW, WRW, and the ARM/CART domains. The WCPS measured changes in leaf area index for several vegetation types, deep groundwater variations at two wells, and meteorological variables at a number of sites in the WRW. Additional activities of the WCPS include code development toward a regional climate model with water isotope processes, soil moisture transect measurements, and water level measurements in ground water wells.

  12. Futile cycling increases sensitivity toward oxidative stress in Escherichia coli

    PubMed Central

    Adolfsen, Kristin J.; Brynildsen, Mark P.

    2015-01-01

    Reactive oxygen species (ROS) are toxic molecules utilized by the immune system to combat invading pathogens. Recent evidence suggests that inefficiencies in ATP production or usage can lead to increased endogenous ROS production and sensitivity to oxidative stress in bacteria. With this as inspiration, and knowledge that ATP is required for a number of DNA repair mechanisms, we hypothesized that futile cycling would be an effective way to increase sensitivity to oxidative stress. We developed a mixed integer linear optimization framework to identify experimentally-tractable futile cycles, and confirmed metabolic modeling predictions that futile cycling depresses growth rate, and increases both O2 consumption and ROS production per biomass generated. Further, intracellular ATP was decreased and sensitivity to oxidative stress increased in all actively cycling strains compared to their catalytically inactive controls. This research establishes a fundamental connection between ATP metabolism, endogenous ROS production, and tolerance toward oxidative stress in bacteria. PMID:25732623

  13. Transpiration in the Global Water Cycle

    NASA Astrophysics Data System (ADS)

    Schlesinger, W. H.; Jasechko, S.

    2014-12-01

    A compilation of 81 studies that have partitioned evapotranspiration (ET) into its components—transpiration (T) and evaporation (E)—at the ecosystem scale indicates that T accounts for 61% (±15% s.d.) of ET and returns approximately 39±10% of incident precipitation (P) to the atmosphere, creating a dominant force in the global water cycle. T as a proportion of ET is highest in tropical rainforests (70±14 %) and lowest in steppes, shrublands and deserts (51±15%), but there is no relationship of T/ET versus P across all available data (R2 = 0.01). Changes to transpiration due to increasing CO2 concentrations, land use changes, shifting ecozones and climate warming are expected to have significant impacts upon runoff and groundwater recharge, reflecting human impacts on the global biogeochemical cycle of water.

  14. Carbon footprint estimation of municipal water cycle

    NASA Astrophysics Data System (ADS)

    Bakhshi, Ali A.

    2009-11-01

    This research investigates the embodied energy associated with water use. A geographic information system (GIS) was tested using data from Loudoun County, Virginia. The objective of this study is to estimate the embodied energy and carbon emission levels associated with water service at a geographical location and to improve for sustainability planning. Factors that affect the carbon footprint were investigated and the use of a GIS based model as a sustainability planning framework was evaluated. The carbon footprint metric is a useful tool for prediction and measurement of a system's sustainable performance over its expected life cycle. Two metrics were calculated: tons of carbon dioxide per year to represent the contribution to global warming and watt-hrs per gallon to show the embodied energy associated with water consumption. The water delivery to the building, removal of wastewater from the building and associated treatment of water and wastewater create a sizable carbon footprint; often the energy attributed to this water service is the greatest end use of electrical energy. The embodied energy in water depends on topographical characteristics of the area's local water supply, the efficiency of the treatment systems, and the efficiency of the pumping stations. The questions answered by this research are: What is the impact of demand side sustainable water practices on the embodied energy as represented by a comprehensive carbon footprint? What are the major energy consuming elements attributed to the system? What is a viable and visually identifiable tool to estimate the carbon footprint attributed to those Greenhouse Gas (GHG) producing elements? What is the embodied energy and emission associated with water use delivered to a building? Benefits to be derived from a standardized GIS applied carbon footprint estimation approach include: (1) Improved environmental and economic information for the developers, water and wastewater processing and municipal planners; (2) Improved energy use reporting and conservation planning; (3) Establishment of a benchmark for GHG emissions attributed to the water and wastewater industry; (4) Ability to quantify relative impacts of building design options using carbon emission equivalents. The GIS based model was applied to the Dulles South and Brambelton regions in Loudoun County, Virginia. The GIS revealed the customer's embodied energy to be in the range of 4.41MWh/Mgal to 8.0 MWh/Mgal. The customer's carbon footprint is between 0.008 and18.0 Tons of CO2 for year 2008. The results of this study contributed to development of a standardized approach to estimate the GHG impact of a total water cycle, and provided a viable GIS tool resulting in visual maps as a decision support. It also showed the use of derived empirical formulas in predication of GHG impact for end users in a specific geographical area. The embodied energy in delivered water can be estimated using the devised model and be considered by the building sustainability ranking programs such as the USGBC LEED rating system. KEYWORDS. Water Life Cycle, Embodied Energy, Global Warming Potential, Energy Intensity, Energy Intensity Matrix, Emission Intensity, Emission Coefficient, Carbon Dioxide Emission, Water and Wastewater, Collection, Treatment and Distribution, Carbon Footprint, Topography, Municipality, Environmental Indicator, ArcGIS, LEED, GHG, ESI, LCA, LCEA, LCI, Sustainability, End Use, Potable Water

  15. Water Cycle Multimission Observation Strategy (WACMOS)

    NASA Astrophysics Data System (ADS)

    Su, Z.

    2009-04-01

    To understand the role of the terrestrial hydrosphere-biosphere in Earth's climate system it is essential to be able to measure from space hydroclimatic variables, such as radiation, precipitation, evapotranspiration, soil moisture, clouds, water vapour, surface water and runoff, vegetation state, albedo and surface temperature, etc. Such measurements are required to further increase our understanding of the global climate and its variability, both spatially and temporally. Additionally, such observations advance our understanding of the coupling between terrestrial and atmospheric branches of the water cycle, and how this coupling may influence climate variability and predictability. To enhance the prediction of variations in the global water cycle, based on improved understanding of hydrological processes and its close linkage with the energy cycle and its sustained monitoring capability, is a key contribution to mitigation of water-related damages and sustainable human development. In many cases, the combination of space-based and high-resolution in situ data provides the essential information for effectively addressing water management issues (GEOSS 10-Year Implementation Plan - REFERENCE DOCUMENT, GEO 203-1). Recently the European Space Agency (ESA) has initiated, in its Support to Science Element programme, the Water Cycle Multimission Observation Strategy (WACMOS). WACMOS contributes to above described international efforts by supporting scientists in ESA member countries to develop and validate novel and improved multi-mission based products, and to enhance currently available global water datasets, so as to maximize the use of ESA data. In this context, the short term objectives of the project include: • Develop and validate a Product Portfolio of novel and/or improved multi-mission based geoinformation datasets at global and regional scales contributing to the objectives of the GEWEX program. WACMOS is focused on four Thematic Priorities described below and identified in close collaboration with GEWEX. This includes: 1. Evapotranspiration based on the synergic use of MERIS, AATSR and MODIS data; 2. First multi-decadal (30+ years) multi-mission soil moisture data set based on the synergic use of soil measurements derived from scatterometer data (from ERS-1/2 and METOP) and passive (SMMR, SSM/I, TMI, AMSR-E) microwave observations; 3. Water vapour measurements based on the combination of SEVIRI and IASI observations at 25Km resolution and SEVIRI and MERIS at 1Km resolution. 4. Enhanced cloud and precipitation products based on the synergic use of MSG, GOME(2) and SCIAMACHY data. • Explore ways to facilitate the integration of the final Product Portfolio into models through data assimilation processes at different scales (e.g., run-off, water balance, flood risk, drought, climate) and demonstrating its value for science and applications; • Consolidate a Scientific Roadmap to advance towards establishing long-term coherent multi-source data records in support of GEWEX and other user communities.

  16. Oxidative elemental cycling under the low O2 Eoarchean atmosphere

    NASA Astrophysics Data System (ADS)

    Frei, Robert; Crowe, Sean A.; Bau, Michael; Polat, Ali; Fowle, David A.; Døssing, Lasse N.

    2016-02-01

    The Great Oxidation Event signals the first large-scale oxygenation of the atmosphere roughly 2.4 Gyr ago. Geochemical signals diagnostic of oxidative weathering, however, extend as far back as 3.3-2.9 Gyr ago. 3.8-3.7 Gyr old rocks from Isua, Greenland stand as a deep time outpost, recording information on Earth’s earliest surface chemistry and the low oxygen primordial biosphere. Here we find fractionated Cr isotopes, relative to the igneous silicate Earth reservoir, in metamorphosed banded iron formations (BIFs) from Isua that indicate oxidative Cr cycling 3.8-3.7 Gyr ago. Elevated U/Th ratios in these BIFs relative to the contemporary crust, also signal oxidative mobilization of U. We suggest that reactive oxygen species were present in the Eoarchean surface environment, under a very low oxygen atmosphere, inducing oxidative elemental cycling during the deposition of the Isua BIFs and possibly supporting early aerobic biology.

  17. Oxidative elemental cycling under the low O2 Eoarchean atmosphere.

    PubMed

    Frei, Robert; Crowe, Sean A; Bau, Michael; Polat, Ali; Fowle, David A; Døssing, Lasse N

    2016-01-01

    The Great Oxidation Event signals the first large-scale oxygenation of the atmosphere roughly 2.4 Gyr ago. Geochemical signals diagnostic of oxidative weathering, however, extend as far back as 3.3-2.9 Gyr ago. 3.8-3.7 Gyr old rocks from Isua, Greenland stand as a deep time outpost, recording information on Earth's earliest surface chemistry and the low oxygen primordial biosphere. Here we find fractionated Cr isotopes, relative to the igneous silicate Earth reservoir, in metamorphosed banded iron formations (BIFs) from Isua that indicate oxidative Cr cycling 3.8-3.7 Gyr ago. Elevated U/Th ratios in these BIFs relative to the contemporary crust, also signal oxidative mobilization of U. We suggest that reactive oxygen species were present in the Eoarchean surface environment, under a very low oxygen atmosphere, inducing oxidative elemental cycling during the deposition of the Isua BIFs and possibly supporting early aerobic biology. PMID:26864443

  18. Fe-Oxides in Water Remediation Technologies

    NASA Astrophysics Data System (ADS)

    Vaclavikova, M.; Stefusova, K.; Gallios, G. P.

    Water is essential for life, a strategic resource for every country and population. Its availability and sanitary safety is highly connected with the health and economic status of a population. The burden of disease due to polluted water is a major public health problem throughout the world. Many pollutants in water streams have been identified as toxic and harmful to the environment and human health, and among them arsenic, mercury and cadmium are considered those with the highest priority. Iron is the fourth most abundant element in the Earth's crust, and reactions involving iron play a major role in the environmental cycling of a range of important contaminants. Our earlier research has shown that Fe oxides/oxyhydroxides are particularly effective adsorbents of a range of contaminants (toxic metals), due to their high (reactive) specific surface area. It has been proven that Fe is particularly effective in As removal as a chemical bond is created on Fe surface and As is stabilised and can be safely deposited. Removal of contaminants from waste streams through precipitation with (hydrous) ferric oxides is an established methodology in a number of industrial processes (high density sludge systems for arsenic control in effluents from the mining industry, and in the treatment of textile dye effluent).

  19. EDITORIAL: The global atmospheric water cycle

    NASA Astrophysics Data System (ADS)

    Bengtsson, Lennart

    2010-06-01

    Water vapour plays a key role in the Earth's energy balance. Almost 50% of the absorbed solar radiation at the surface is used to cool the surface, through evaporation, and warm the atmosphere, through release of latent heat. Latent heat is the single largest factor in warming the atmosphere and in transporting heat from low to high latitudes. Water vapour is also the dominant greenhouse gas and contributes to a warming of the climate system by some 24°C (Kondratev 1972). However, water vapour is a passive component in the troposphere as it is uniquely determined by temperature and should therefore be seen as a part of the climate feedback system. In this short overview, we will first describe the water on planet Earth and the role of the hydrological cycle: the way water vapour is transported between oceans and continents and the return of water via rivers to the oceans. Generally water vapour is well observed and analysed; however, there are considerable obstacles to observing precipitation, in particular over the oceans. The response of the hydrological cycle to global warming is far reaching. Because different physical processes control the change in water vapour and evaporation/precipitation, this leads to a more extreme distribution of precipitation making, in general, wet areas wetter and dry areas dryer. Another consequence is a transition towards more intense precipitation. It is to be expected that the changes in the hydrological cycle as a consequence of climate warming may be more severe that the temperature changes. Water on planet Earth The total amount of available water on the Earth amounts to some 1.5 x 109 km3. The dominant part of this, 1.4 x 109 km3, resides in the oceans. About 29 x 106 km3 are locked up in land ice and glaciers and some 15 x 106 km3 are estimated to exist as groundwater. If all land ice and glaciers were to melt the sea level would rise some 80 m (Baumgartner and Reichel 1975). 13 x 103 km3 of water vapour are found in the atmosphere corresponding to a global average of 26 kg m-2 or 26 mm m-2 of water for each column of air on the surface of the Earth. There are large geographical differences such as between low and high latitudes. Figure 1 shows an estimate of the global water exchange between ocean and land, an annual average in units of 103 km3 (Baumgartner and Reichel 1975). An updated version can be found in Trenberth et al 2007 (their figure 1) showing broadly similar results. There is a net transport of some 38 units from ocean to land with about the same amount returning by the rivers to the ocean. However the amount of precipitation over the continents is almost three times as high, indicating a considerable recirculation of water over land. As shown by Trenberth et al (2007) the recirculation has a marked annual cycle as well as having large variations between continents. The recirculation is larger during the summer and for tropical land areas. The hydrological cycle of the world's oceans interacts differently with that of the continents. Most of the water from the Pacific Ocean recirculates between different parts of the Pacific itself, as and there is little net transport towards land. The pattern of water exchange between ocean and land is different in the Atlantic and Indian Oceans. Two thirds of the total net transport of water towards the continents comes from the Atlantic Ocean, with the rest essentially from the Indian Ocean. Most of the continental water for North and South America, Europe and Africa emanates from the Atlantic and is also returned to the Atlantic by the rivers. Figure 1 Figure 1. The global water cycle following Baumgartner and Reichel (1975). Annual values are in units of 103 km3 year-1. There is widespread evaporation (maximum some 2 m year-1) on each side of the inter-tropical convergence zone (ITCZ), transporting water vapour into the ITCZ and into the storm tracks of high latitudes. Conversely, in regions of net evaporation ocean salinity is increasing, leading to increased ocean vertical mixing. In the ITCZ and in the extra-tropical storm tracks ocean salinity is decreasing due to high precipitation thus reducing ocean vertical mixing. This means that moisture convergence in the atmosphere is compensated for by moisture divergence (salinity convergence) and vice versa in the oceans, which can be seen as a counterpart to the atmospheric circulation (Webster 1994). Atmospheric water vapour is measured both from space and from in situ observations and analysed in detail both by the operational weather services and through different re-analysis programs (e.g. Uppala et al 2005, Onogi et al 2007). However, while data for atmospheric water vapour are generally well observed we are much less comfortable with observations of precipitation. Precipitation has a large variance on small time and space scales and current observing systems cannot sample this sufficiently. This is especially the case over ocean areas where measurements from ships are notoriously poor as the collection of precipitation is strongly influenced by wind, including the local wind effect caused by the movements of the ship itself. Different proxy methods have been developed using space and rain gauge data and combining these with model data. The most commonly used are the NOAA Climate Prediction Centre Merged Analysis of Precipitation (CMAP; Xie and Arkin 1997) and the Global Precipitation Climatology Project (GPCP; Adler et al 2003). GPCP consists of combined satellite and in situ precipitation measurements and provides global coverage of monthly averages. As with most climate data sets, great caution should be exercised in trying to identify trends in precipitation (e.g. Allan and Soden 2007). In addition to the severe sampling problems we also have to identify the effect caused by ongoing changes in the global observing systems. Hagemann et al (2006) has undertaken a study using the ECHAM5 model (Roeckner et al 2003, 2006) where they compared the hydrological cycle over 20 years using 11 different model versions having resolutions from T21/L19 (spectral transform model until wave number 21 and with 19 vertical levels) to T156/L31. There is a minor increase in global precipitation with resolution by some 7% (between T21/L19 and T156/L31) with a systematic increase of large-scale precipitation and reduced convective precipitation with resolution. There is generally good agreement between model results and CMAP and GPCP over land but the modelled precipitation is larger over the oceans by some 70 x 103 km3 year-1 on average. Whether this implies that the model overestimates precipitation over oceans cannot be concluded as it might equally well imply that the CMAP and GPCP underestimate. Another way of evaluating the hydrological cycle is to measure the river outflow and compare this with the net water flux of the river catchments. A detailed study has been conducted for the different sub-regions of the Baltic Sea covering some 10 years with excellent agreement between observed river outflow and calculations of the atmospheric water cycle from a limited area model (figure 2; D Jacob 2001, private communication). This suggests that, when reliable river outflow data exist, this is an alternative way to validate the model-generated atmospheric hydrological cycle for a larger scale area. Figure 2 Figure 2. Model simulation of the water balance of the Baltic Sea (1979-1988). Units in km3 year-1. (Courtesy D Jacob (2001) Max-Planck-Institute for Meteorology, Hamburg.) The estimated total river run off agrees broadly with measured data (Raschke et al (2001). The net outflow from the Baltic Sea is close to various estimates (e.g. Omstedt and Rutgersson 2000). Net water vapour inflow into the region is calculated under the assumption of long-term water balance. Water vapour as a greenhouse gas Water vapour is the dominant greenhouse gas and accounts for around 75% of the total greenhouse effect on Earth (Kondratev 1972). Water vapour in the atmosphere is strongly controlled by the atmospheric circulation. If, for example, we follow a trajectory of water vapour in the atmosphere it shows that it undergoes a complex series of vertical and horizontal motions that can include several events of condensation. At any given time the saturation mixing ratio is determined by the temperature of the latest event of condensation. For this reason it follows that the mixing ratio will increase with temperature broadly following the Clausius-Clapeyron relation (Pierrehumbert et al 2007). The residence time of water vapour in the atmosphere is about a week, as compared with the very long residence time of the greenhouse gases, in particular CO2which includes multi-centennial time scales. Water vapour is, of course, continuously replenished by evaporation from the oceans and the land surfaces but is nevertheless regulated by temperature. In that sense, water vapour should be seen as a part of the response of the climate system to external forcing. Such a change in climate forcing can be due to changes in the concentration of the more persistent greenhouse gases such as CO2. Alternatively it can be due to changes in solar radiation, or to aerosols from volcanic eruptions or due to anthropogenic emissions. The absorption bands in the water vapour spectra are close to saturation, similar to those of CO2, with the absorption mainly occurring in the wings of the spectral bands. The total effect on the radiation balance can be approximated by a logarithmic function of the mixing ratio. This is how the effect of atmospheric water vapour is included in the code for the calculation of long-wave radiation in weather and climate models. In contrast to the well-mixed greenhouse gases, water vapour varies strongly in the atmosphere and this on a small scale in both time and space. The reason is strong vertical motion of different signs that implies sharp gradients in the moisture field. Climate models that have coarse resolution have difficulties in representing sharp gradients and generally underestimate the strong outgoing long-wave radiation (OLR) in dry air. Because of the logarithmic function of the mixing ratio this implies an underestimation of OLR. Hagemann et al (2006) noted a decrease of OLR in clear sky by 7 W m-2 by reducing the horizontal spectral resolution from T159 to T21. Furthermore a correct vertical distribution of water vapour is essential as water vapour in the upper troposphere is proportionately more important. All indications are that water vapour constitutes a positive feedback but the strength of the feedback is debated. Observational as well as modelling studies (Held and Soden 2006, Semenov and Bengtsson 2002) suggest that the relative humidity is broadly maintained and water vapour closely follows the Clausius-Clapeyron relation. The feedback effect cannot be determined from observational studies but can be estimated from models through bypassing the part of the long-wave radiation code that calculates the effect of increasing water vapour (Hall and Manabe 1999). They showed that water vapour increases the effect of a doubling of the CO2concentration from 1.05°C to 3.38°C, suggesting a clear positive feedback from water vapour. However, a more recent analysis by Soden and Held (2006) give an amplification factor of 1.9 to 3.2 by water vapour alone, yet much of this spread is due to different changes in lapse rate; when water vapour and lapse rate are considered together the amplification of warming by these feedbacks is around 1.3 to 1.6 (Randell et al 2007, figure 8.14 and footnote). How will precipitation change in a warmer climate? Observational studies, as well as numerical models, show that water vapour in the atmosphere closely follows temperature in agreement with the Clausius-Clapeyron relation. That means that an increase in temperature by 1°C in the lower troposphere implies an increase in the vertical profile of water vapour by 6-7%. However, the increase in the hydrological cycle (global mean precipitation and evaporation) as obtained from model integration is limited to some 1-2% (Held and Soden 2006). This is because atmospheric water vapour is determined from atmospheric circulation in a warmer climate while global precipitation is constrained by evaporation from the surface. This in turn is a consequence of the radiation imbalance at the surface as well as being influenced by surface winds, stability of the boundary layer and the absorption of short-wave radiation in the atmosphere. According to Takahashi (2009) the change of the sum of latent heat flux and short-wave absorption at the surface by temperature is broadly controlled by the long-wave flux above the boundary layer that is well understood and modelled. It may therefore be considered unlikely that models can be wrong by factors of several 100%. Rather it is more likely that models might even overestimate the latent heat flux due to an underestimation of the absorption of short-wave radiation in the atmosphere as line-by-line integration suggests a larger absorption by water vapour than what is used in climate models (Takahashi 2009). The fact that water vapour is increasing faster than precipitation has far-reaching consequences (Held and Soden 2006). Because the increase in the strength of the global atmospheric hydrological cycle is constrained by small changes in latent heat flux (Richter and Xie 2008), it cannot keep up with the rapid increase in atmospheric water vapour. This implies that the residence time of water vapour in the atmosphere is increasing; that means that the exchange of mass between the boundary layer must decrease and, since much of this exchange occurs in moist convection in the Tropics, the convective mass flux must consequently decrease. This result is perhaps counterintuitive to some of the ideas that flourish in the climate change debate where it is implicitly assumed that the atmosphere will in some sense become more energetic as it warms. But, in fact, the average vertical exchange of mass between the boundary layer and the free atmosphere must imply a slowing down of the large-scale atmospheric circulation. To what extent this will affect tropical cyclones is not clear but it has been suggested (Bengtsson et al 2007) that this could be the reason for the reduced number of tropical cyclones in a warmer climate. The fact that the increase in water vapour follows the Clausius-Clapeyron relation has a number of other important consequences including the poleward transport of water vapour and the pattern of evaporation-precipitation (E-P). The (E-P) gradient increases proportionally to the lower tropospheric water vapour (Held and Soden 2006), implying that wet regions get wetter and dry regions drier. This result is of key importance for understanding how future patterns of precipitation might change in a warmer climate. This includes more precipitation in the ITCZ and in the middle- and high-latitude storm tracks and alternatively less precipitation in mid-latitudes including the Mediterranean region, California and Texas, southern Africa and southern Australia. Changes in extreme precipitation The distribution of precipitation as a function of time is mostly represented by a gamma function, since a comparatively large part of the total precipitation at a given place occurs during short time intervals (Juras 1994). The reason is that in most precipitation situations small-scale convective systems develop with large vertical motions that generate intense precipitation. As described by Bengtsson (2001 and references therein), convective processes are embedded in practically all precipitation systems including warm front conditions at high latitudes during the cold season. Intense precipitation dominates, in particular, convectively driven storms such as tropical cyclones. It is during such events that enormous amounts of precipitation have been measured including cases with some 1000 mm precipitation or more in less than 12 hours (http://en.wiki pedia.org/wiki/List_of_weather_records#Rain). The most severe damages to society are related to intense precipitation occurring on time scales from hours to a couple of days. A most important question is, consequently: what may happen to intense precipitation in a warmer climate? Model experiments (Bengtsson et al 2009) for a warmer climate show a marked increase in extreme precipitation. In the storm track region there are increases in extreme 6 hr precipitation of 40-50% (at the 99 percentile or higher). As there is a much smaller increase in the average precipitation, this means that the whole spectrum of precipitation changes (Semenov and Bengtsson 2002). As the climate warming so far has been rather modest and only about some 25% compared to the experiment used by Bengtsson et al (2009), we expect it will be difficult to observe such changes in the time spectrum of precipitation. However, there are some signals from natural variability, e.g. Allan and Soden (2008). Furthermore, this will require persistent high-quality observations over a very long period of time. Karl and Knight (1998) have examined the precipitation at the 90th percentile or higher for an area over central USA and noted an increase that was found to broadly agree with the modelling result by Semenov and Bengtsson (2002, their figure 4(a)). The large increase in extreme precipitation suggested from models is likely to have serious consequences. The change in the time distribution of precipitation intensity will radically reduce the probability of the return of extreme events. Using the same model experiment as the one by Semenov and Bengtsson it was found that the 50-year return flow in the Yangtse river calculated from model results representative for the present climate was changed to a 5-year return flow for a climate that might be expected at the end of this century using the IPCC A1B (moderate) scenario (Voss et al 2002). If such changes occur the consequences will be severe, requiring urgent enhancements of flood protection systems. Tropical cyclones are driven by organized convection that in turn will become more intensive as the amount of available water vapour is increasing in a warmer climate. This has been found to occur but will require a high horizontal resolution (Bengtsson et al 2007, Oouchi et al 2006). Bengtsson et al (2007) found when using a global model at T319 resolution (around 40 km grid distance) that intense storms of category 3 or higher increased from 12 to 17 year-1 overall for the Northern Hemisphere, while the total number of tropical cyclones decreased. Similar results were obtained by Oouchi et al (2006) and Binder et al (2010) in a recent study of Atlantic hurricanes. Binder et al used a two-step downscaling of individual storms to better describe the detailed hurricane structure. So in general it seems that the large increase in water vapour in a warmer climate might not only change the structure of precipitation events but also the statistical distribution of weather systems driven by release of latent heat in a similar way. This is very important, as damages are broadly proportional to the third power of the wind speed. Discussion Water vapour is of fundamental importance for the climate system. The transport of water from the surface of the Earth cools the surface and warms the atmosphere with an average of around 80 W m-2. Water vapour flux is a key mechanism in transporting energy between low and high latitudes. The atmospheric water cycle is important for the ocean circulation. In areas of net evaporation, salinity is, increasing resulting in convection in the upper ocean. The opposite occurs in areas of net precipitation. Water vapour is the dominant greenhouse gas but it is controlled by temperature and in that respect it is part of the climate response or feedback system. All indications are that water vapour constitutes a positive feedback on climate, but the strength of the feedback is model sensitive. This is mostly due to different patterns of low/high-latitude temperature and resulting lapse rate changes since the combined water vapour lapse rate feedback is fairly robust. Water vapour is increasing rapidly in a warmer climate but theory and models suggest that global precipitation might be increasing much more slowly. This has a number of important consequences for the hydrological cycle in a warmer climate, namely that areas with high precipitation rates today will have increased precipitation rates and areas with low precipitation will have reduced rates, making the hydrological cycle more extreme. The increase in water vapour in a warmer climate is expected to lead to more intense precipitation and this is actually simulated by models. In the same way latent-heat-driven weather systems such as tropical cyclones are likely to be more intense in a warmer climate. This is also simulated by high-resolution climate models that at the same time show an overall reduction in the total number of tropical cyclones. References Adler R F et al 2003 The version 2 Global Precipitation Climatology Project (GPCP) monthly precipitation analysis (1979-present) J. Hydrometeorol. 4 1147-67 Allan R P and Soden B J 2007 Geophys. Res. Lett. 34 L18705 Allan R P and Soden B J 2008 Science 321 1481-4 Baumgartner A and Reichel E 1975 The World Water Balance (New York: Elsevier) Bengtsson L 2001 Numerical modelling of the energy and water cycle of the Baltic Sea Meteorol. Atmos. Phys. 77 9-17 Bengtsson L, Hodges K I, Esch M, Keenlyside N, Kornblueh L, Luo J-J and Yamagata T 2007 How may tropical cyclones change in a warmer climate? Tellus A 59 539-61 Bengtsson L, Hodges K I and Keenlyside N 2009 Will extra-tropical storms intensify in a warmer climate? J. Climate 22 2276-301 Binder M A, Knutson T R, Tuleya R E, Sirutis J J, Vecchi G A, Garner S T and Held I M 2010 Science 327 454-8 Hagemann S, Arpe K and Roeckner E 2006 Evaluation of the hydrological cycle in the ECHAM5 model J. Climate 19 3810-27 Hall A and Manabe S 1999 The role of water vapor feedback in unperturbed climate variability and global warming J. Climate 12 2327-46 Held I M and Soden B J 2006 Robust responses of the hydrological cycle to global warming J. Climate 19 5686-99 Juras J 1994 Some common features of probability distribution for precipitation Theor. Appl. Climatol. 49 69-76 Karl T R and Knight R W 1998 Secular trends of precipitation amount, frequency, and intensity in the United States Bull. Am. Meteorol. Soc. 79 231-41 Kondratev K Ya 1972 Radiation Processes in the Atmosphere (Geneva: World Meteorological Organization) Omstedt A and Rutgersson A 2000 Closing the water cycle of the Baltic Sea Meteorol. Z. 9 57-66 Onogi K et al 2007 The JRA-25 reanalysis J. Meteorol. Soc. Japan 85 369-432 Oouchi K et al 2006 Tropical cyclone climatology in a global-warming climate as simulated in a 20 km-mesh global atmospheric model: frequency and wind intensity analysis J. Meteorol. Soc. Japan 84 259-76 Pierrehumbert R T, Brogniez H and Roca R 2007 On the relative humidity of the Earth's atmosphere The Global Circulation of the Atmosphere ed T Schneider and A H Sobel (Princeton, NJ: Princeton University Press) pp 143-85 Randell D A et al 2007 Climate models and their evaluation Climate Change 2007: The Physical Science Basis ed S Solomon et al (Cambridge: Cambridge University Press) pp 591-662 Raschke E et al 2001 The Baltic Sea Experiment (BALTEX): a european contribution to the investigation of the energy and water cycle over a large drainage basin Bull. Am. Meteorol. Soc. 82 2389-413 Richter I and Xie S 2008 Muted precipitation increase in global warming simulations: a surface evaporation perspective J. Geophys. Res. 113 D24118 Roeckner E et al 2003 The atmospheric general circulation model ECHAM5. Part I: Model description Report 349 Max Planck Institute for Meteorology 127 pp (available from MPI for Meteorology, Bundesstr. 53, 20146 Hamburg, Germany) Roeckner E et al 2006 Sensitivity of simulated climate to horizontal and vertical resolution in the ECHAM5 atmosphere model J. Climate 19 3771-91 Rubel F and Hantel M 2001 BALTEX precipitation analysis: results from the BRIDGE preparation phase Phys. Chem. Earth B: Hydrol. Ocean. Atmos. 26 397-401 Semenov V and Bengtsson L 2002 Secular trends in daily precipitation characteristics: greenhouse gas simulation with a coupled AOGCM Clim. Dyn. 19 123-40 Soden B and Held I 2006 An assessment of climate feedbacks in coupled ocean-atmosphere models J. Climate 19 3354-60 Takahashi K 2009 Radiative constraints on the hydrological cycle in an idealized radiative-convective equilibrium model J. Atmos. Sci 66 77-91 Trenberth K E et al 2007 Estimate of the global water budget and its annual cycle using observational and model data J. Hydrometeorol. 8 758-69 Uppala S M et al 2005 The ERA-40 reanalysis Q. J. R. Meteorol. Soc. 131 2961-3012 Voss R, May W and Roeckner E 2002 Enhanced resolution modelling study on anthropogenic climate change: changes in extremes of the hydrological cycle Int. J. Climatol. 22 755-77 Webster P J 1994 The role of hydrological processes in ocean-atmosphere interactions Rev. Geophys. 32 427-76 Xie P and Arkin P A 1997 Global precipitation: a 17-year monthly analysis based on gauge observations, satellite estimates and numerical model outputs Bull. Am. Meteorol. Soc. 78 2539-58

  20. The Passive Microwave Water Cycle (PMWC) Product: Closing the Water Cycle Using a Constellation of Satellites

    NASA Astrophysics Data System (ADS)

    Hilburn, K.; Wentz, F.

    2007-12-01

    We have developed a water cycle product as part of the NASA Energy and Water Cycle Study (NEWS). The purpose of the product is to integrate passive microwave retrievals from a variety of different sensors on different satellites including SSMI (F08, F10, F11, F13, F14, and F15), SSMIS (F16 and F17), AMSR (Aqua and Midori-II), TMI on TRMM, WindSat, and eventually AMSU (NOAA-15 and NOAA-16). The water cycle over a particular location averaged over a time scale of one month is given by: E-P=WVTD; where E is evaporation, P is precipitation, and WVTD is water vapor transport divergence. The new and unique feature of our product is that we make use of the large quantity of accurately intercalibrated water vapor and wind observations in order to estimate WVTD. As part of developing this product we have evaluated our new intercalibrated microwave rain rates, developed a procedure for estimating evaporation, and developed a procedure for estimating water vapor transport and its divergence. The Version-01 Passive Microwave Water Cycle (PMWC) dataset will contain maps of evaporation, precipitation, water vapor transport, water vapor transport divergence, and water vapor. Uncertainty estimates for each parameter will also be supplied. Currently, the product is a 20-year (1987-2007), 0.25-degree, monthly average product over the global oceans. One of our principle motivations is to obtain estimates of the uncertainty in "direct" physically-based retrievals of precipitation. Direct physically-based rain retrievals are subject to large uncertainties that are hard to quantify, such as horizontal inhomogeneity (beamfilling), cloud and rain water partitioning, rain column height and the rain vertical profile, drop size distribution, and the effects of frozen hydrometeors. By using the balanced water cycle, we can estimate precipitation uncertainties in P by estimating uncertainties in E and WVTD. Estimating uncertainties in E can be done with a straight-forward classical uncertainty analysis. Uncertainties in WVTD can easily be estimated using on-orbit simulation experiments with model data. In addition to uncertainty estimates, we also note that estimating precipitation through balancing the water cycle provides a new and independent estimate of precipitation. The errors with this technique are independent from the errors in passive microwave, active microwave, and infrared precipitation retrievals. This will be of great value as we enter the Global Precipitation Measurement (GPM) era. Moreover, consistency among hydrological parameters (evaporation, precipitation, water vapor transport divergence) and especially their trends provides indirect validation of the retrievals. Currently, we have evaluated trends in our evaporation, precipitation, and water vapor datasets on a global average basis. We find water vapor trends of 7 Percent/degree as the world warms - consistent with the Clausius-Clapeyron (C-C) relationship and with climate models. We also find that our evaporation and precipitation measurements both increase at close to the C-C rate. This is in contrast with climate models that predict a muted response of precipitation to global warming with rates between 1 to 3 Percent/degree. These water cycle relationships will be discussed in terms of their implications for the global energy balance.

  1. Terrestrial nitrous oxide cycles and atmospheric effects

    NASA Technical Reports Server (NTRS)

    Whitten, R. C.; Lawless, J. G.; Banin, A.

    1984-01-01

    The basic processes that cause N2O emission from soils are briefly discussed, and the rate of the processes is shown to vary widely in space and time, depending on soil, climate, and agrotechnical conditions. Although significant amounts of N2O are indeed emitted from the land, the complexity of the soil processes involved and the wide variation of measured rates still prevents the quantitative evaluation, global budgeting, and reliable prediction of atmospheric N2O. Increased atmospheric N2O abundance increases the levels of odd-nitrogen in the stratosphere, which, in turn, decreases the stratospheric ozone density via a catalytic cycle. Using appropriate atmospheric models and current chemical kinetic data, it has been found that the dependence of ozone reduction on N2O increase is nearly linear; a simulated doubling of N2O leads to a predicted decrease of about 14 percent in total ozone column density. A 10 percent increase in N2O yields a predicted increase in nonmelanoma skin cancer of several percent, and a possible raising of surface temperature of 0.03 K.

  2. Highly efficient 6-stroke engine cycle with water injection

    SciTech Connect

    Szybist, James P; Conklin, James C

    2012-10-23

    A six-stroke engine cycle having improved efficiency. Heat is recovered from the engine combustion gases by using a 6-stroke engine cycle in which combustion gases are partially vented proximate the bottom-dead-center position of the fourth stroke cycle, and water is injected proximate the top-dead-center position of the fourth stroke cycle.

  3. Chromium cycling in soils and water: links, gaps, and methods.

    PubMed Central

    Bartlett, R J

    1991-01-01

    The major links in the cycling of chromium in soils and in natural waters are between chromium(III) and chromium (VI). Between the larger links are lesser links involving processes of mobilization and oxidation of CrIII and reduction of CrVI. The gaps are mainly in our understanding of the factors that control these processes. If soluble CrIII is added to an "average" soil, a portion of it will become immediately oxidized by manganese oxides to CrVI. The rest of the CrIII may remain reduced for long periods of time, even in the presence of electron-accepting manganese oxides. However, this less available CrIII can be mobilized by low molecular weight organic complexers and then oxidized where redox conditions are optimal. Usually part of any CrVI added to a soil or sediment will be reduced instantly, especially under acid conditions. On the other hand, high concentrations of polluting CrVI may quickly exhaust the readily available reducing power of the matrix material and excess CrVI, the thermodynamically stable form in air, may persist for years in soils or lagoons without reduction. Cleanup of chromium pollution must involve the surrounding of both CrIII and CrVI with excesses of slowly available reducing substances and sealing them permanently from inputs of atmospheric oxygen. Monitoring the effectiveness of the measures is mandatory, but fortunately the chemical testing for CrVI in soil and water is simple and problem free compared with most colorimetric determinations. PMID:1935847

  4. Earth's changing energy and water cycles

    NASA Astrophysics Data System (ADS)

    Trenberth, K. E.; Fasullo, J. T.

    2008-12-01

    A new assessment of the flows of energy through the climate system and its changes over time will be presented. It features an imbalance at the top-of-atmosphere owing to an enhanced greenhouse effect that produces global warming. Most of the surplus energy trapped at TOA increases ocean heat content. Large upward surface thermal radiation is offset by back radiation from greenhouse gases and clouds in the atmosphere. At the surface, the net losses of energy are greatest through evaporation, followed by net radiation, while sensible heat losses are much smaller. The budget highlights the vital role of the hydrological cycle and its response as a consequence of climate change. Nonetheless, net changes in total surface evaporation are fairly modest and a much larger percentage change occurs in the water-holding capacity as atmospheric temperatures increase (7 percent per C). Consequences include increased water vapor in the atmosphere, which projects nonlinearly onto convective instability, and the intensification of severe precipitation - changes that are now observable. Moreover the disparity between modestly enhanced evaporation and increases in the heaviest rains implies a decreased frequency of precipitation. Combined with elevated surface temperatures, drought probability is therefore enhanced.

  5. The cycling and oxidation pathways of organic carbon in a shallow estuary along the Texas Gulf Coast

    SciTech Connect

    Warnken, Kent W.; Santschi, Peter H.; Roberts, Kimberly A.; Gill, Gary A.

    2007-08-08

    The cycling and oxidation pathways of organic carbon were investigated at a single shallow water estuarine site in Trinity Bay, Texas, the uppermost lobe of Galveston Bay, during November 2000. Radio-isotopes were used to estimate sediment mixing and accumulation rates, and benthic chamber and pore water measurements were used to determine sediment-water exchange fluxes of oxygen, nutrients and metals, and infer carbon oxidation rates.

  6. Alternating electron and proton transfer steps in photosynthetic water oxidation.

    PubMed

    Klauss, André; Haumann, Michael; Dau, Holger

    2012-10-01

    Water oxidation by cyanobacteria, algae, and plants is pivotal in oxygenic photosynthesis, the process that powers life on Earth, and is the paradigm for engineering solar fuel-production systems. Each complete reaction cycle of photosynthetic water oxidation requires the removal of four electrons and four protons from the catalytic site, a manganese-calcium complex and its protein environment in photosystem II. In time-resolved photothermal beam deflection experiments, we monitored apparent volume changes of the photosystem II protein associated with charge creation by light-induced electron transfer (contraction) and charge-compensating proton relocation (expansion). Two previously invisible proton removal steps were detected, thereby filling two gaps in the basic reaction-cycle model of photosynthetic water oxidation. In the S(2) → S(3) transition of the classical S-state cycle, an intermediate is formed by deprotonation clearly before electron transfer to the oxidant (Y Z OX). The rate-determining elementary step (τ, approximately 30 µs at 20 °C) in the long-distance proton relocation toward the protein-water interface is characterized by a high activation energy (E(a) = 0.46 ± 0.05 eV) and strong H/D kinetic isotope effect (approximately 6). The characteristics of a proton transfer step during the S(0) → S(1) transition are similar (τ, approximately 100 µs; E(a) = 0.34 ± 0.08 eV; kinetic isotope effect, approximately 3); however, the proton removal from the Mn complex proceeds after electron transfer to . By discovery of the transient formation of two further intermediate states in the reaction cycle of photosynthetic water oxidation, a temporal sequence of strictly alternating removal of electrons and protons from the catalytic site is established. PMID:22988080

  7. Alternating electron and proton transfer steps in photosynthetic water oxidation

    PubMed Central

    Klauss, André; Haumann, Michael; Dau, Holger

    2012-01-01

    Water oxidation by cyanobacteria, algae, and plants is pivotal in oxygenic photosynthesis, the process that powers life on Earth, and is the paradigm for engineering solar fuel–production systems. Each complete reaction cycle of photosynthetic water oxidation requires the removal of four electrons and four protons from the catalytic site, a manganese–calcium complex and its protein environment in photosystem II. In time-resolved photothermal beam deflection experiments, we monitored apparent volume changes of the photosystem II protein associated with charge creation by light-induced electron transfer (contraction) and charge-compensating proton relocation (expansion). Two previously invisible proton removal steps were detected, thereby filling two gaps in the basic reaction-cycle model of photosynthetic water oxidation. In the S2 → S3 transition of the classical S-state cycle, an intermediate is formed by deprotonation clearly before electron transfer to the oxidant (). The rate-determining elementary step (τ, approximately 30 µs at 20 °C) in the long-distance proton relocation toward the protein–water interface is characterized by a high activation energy (Ea = 0.46 ± 0.05 eV) and strong H/D kinetic isotope effect (approximately 6). The characteristics of a proton transfer step during the S0 → S1 transition are similar (τ, approximately 100 µs; Ea = 0.34 ± 0.08 eV; kinetic isotope effect, approximately 3); however, the proton removal from the Mn complex proceeds after electron transfer to . By discovery of the transient formation of two further intermediate states in the reaction cycle of photosynthetic water oxidation, a temporal sequence of strictly alternating removal of electrons and protons from the catalytic site is established. PMID:22988080

  8. The Water Cycle of La Plata Basin

    NASA Astrophysics Data System (ADS)

    Berbery, E. H.; Collini, E. A.; Barros, V.; Pyle, M.

    2004-05-01

    The regional economies in subtropical South America hinge on vital water resources, which are significantly affected by climate variability. The subtropical region encompasses La Plata basin (LPB), recently endorsed as a GEWEX Continental Scale Experiment. This presentation describes a transferability experiment by which methodologies developed for data rich regions (e.g., the Mississippi basin) can be applied to data sparse regions of the world, and in particular to the La Plata basin. The mesoscale regional model employed for this activity is an adaptation to South America of NCEP's Eta model. Here, the short term forecasts for the period April 2001-October 2003 are employed to estimate the water cycle of the La Plata basin. During the period covered by this study there is a remarkable agreement between observed and forecast precipitation (both are 3.1 mm/day) despite some regional differences. A cautious assessment will include further evaluation of the uncertainties in both the model and the observed estimates. There is a slight imbalance (~ -0.28 mm/day) between P-E and moisture flux convergence partly due to not including the local changes of atmospheric water content in the computation. Nevertheless, this term is expected to be small, and indeed even if the water balance can be estimated with an uncertainty of about 0.3 mm/day, by itself this is a promising result for future activities. Still, the ultimate verification of the reliability of the model estimates is by comparison of P-E or MFC with river discharge. The long term river discharge is equivalent to 0.61 mm/day, which is very close to the MFC (0.60 mm/day). If river discharge values are representative of the more recent period covered by the model products, then the model produces a correct value for MFC and in turn it suggests that the model overestimates evaporation by about 0.2-0.3 mm/day in the annual average. The previous results are encouraging in our efforts to bridge the gap resulting from scarce observations; currently, we are employing the Eta model for seasonal simulations over South America, in particular to assess the effect of lower boundary conditions on the precipitation processes affecting La Plata basin as a first step toward studies of seasonal predictability. Results indicate that the model is stable and does not drift to an unknown climate.

  9. Biological water oxidation: lessons from nature.

    PubMed

    Najafpour, Mohammad Mahdi; Moghaddam, Atefeh Nemati; Allakhverdiev, Suleyman I; Govindjee

    2012-08-01

    Hydrogen production by water splitting may be an appealing solution for future energy needs. To evolve hydrogen efficiently in a sustainable manner, it is necessary first to synthesize what we may call a 'super catalyst' for water oxidation, which is the more challenging half reaction of water splitting. An efficient system for water oxidation exists in the water oxidizing complex in cyanobacteria, algae and plants; further, recently published data on the Manganese-calcium cluster have provided details on the mechanism and structure of the water oxidizing complex. Here, we have briefly reviewed the characteristics of the natural system from the standpoint of what we could learn from it to produce an efficient artificial system. In short, to design an efficient water oxidizing complex for artificial photosynthesis, we must learn and use wisely the knowledge about water oxidation and the water oxidizing complex in the natural system. This article is part of a Special Issue entitled: Photosynthesis Research for Sustainability: from Natural to Artificial. PMID:22507946

  10. Nitrous oxide in coastal waters

    SciTech Connect

    Bange, H.W.; Rapsomanikis, S.; Andreae, M.O.

    1996-03-01

    Measurements of dissolved and atmospheric nitrous oxide (N{sub 2}O) are presented for three coastal environments: (1) the central North Sea, (2) the German Bight, and (3) the Gironde estuary. The contribution of coastal regions to the oceanic emissions of atmospheric N{sub 2}O were also determined. N{sub 2}O was measured with a gas chromatograph equipped with an electron capture detector and analyzed. The surface waters of the central North Sea and the German bight were found to be near equilibrium with the overlying atmosphere, while the mean saturation in the Gironde estuary was 132%. Mean saturations in coastal regions without estuaries or upwelling phenomena were only slightly higher than in the open ocean. When estuaries and regions with upwelling are included, however, approximately 60% of the oceanic N{sub 2}O flux is attributable to coastal regions. A review of published data indicated that previous studies have seriously underestimated N{sub 2}O sea-to-air flux from coastal regions. 69 refs., 8 figs., 4 tabs.

  11. Oxidative elemental cycling under the low O2 Eoarchean atmosphere

    PubMed Central

    Frei, Robert; Crowe, Sean A.; Bau, Michael; Polat, Ali; Fowle, David A.; Døssing, Lasse N.

    2016-01-01

    The Great Oxidation Event signals the first large-scale oxygenation of the atmosphere roughly 2.4 Gyr ago. Geochemical signals diagnostic of oxidative weathering, however, extend as far back as 3.3–2.9 Gyr ago. 3.8–3.7 Gyr old rocks from Isua, Greenland stand as a deep time outpost, recording information on Earth’s earliest surface chemistry and the low oxygen primordial biosphere. Here we find fractionated Cr isotopes, relative to the igneous silicate Earth reservoir, in metamorphosed banded iron formations (BIFs) from Isua that indicate oxidative Cr cycling 3.8–3.7 Gyr ago. Elevated U/Th ratios in these BIFs relative to the contemporary crust, also signal oxidative mobilization of U. We suggest that reactive oxygen species were present in the Eoarchean surface environment, under a very low oxygen atmosphere, inducing oxidative elemental cycling during the deposition of the Isua BIFs and possibly supporting early aerobic biology. PMID:26864443

  12. Connecting the oxidation of soot to its redox cycling abilities

    PubMed Central

    Antiñolo, María; Willis, Megan D.; Zhou, Shouming; Abbatt, Jonathan P.D.

    2015-01-01

    Although it is known that soot particles are emitted in large quantities to the atmosphere, our understanding of their environmental effects is limited by our knowledge of how their composition is subsequently altered through atmospheric processing. Here we present an on-line mass spectrometric study of the changing chemical composition of hydrocarbon soot particles as they are oxidized by gas-phase ozone, and we show that the surface-mediated loss rates of adsorbed polycyclic aromatic hydrocarbons in soot are directly connected to a significant increase in the particle redox cycling abilities. With redox cycling implicated as an oxidative stress mechanism that arises after inhalation of atmospheric particles, this work draws a quantitative connection between the detailed heterogeneous chemistry occurring on atmospheric particles and a potential toxic mechanism attributable to that aerosol. PMID:25873384

  13. Connecting the oxidation of soot to its redox cycling abilities

    NASA Astrophysics Data System (ADS)

    Antiñolo, María; Willis, Megan D.; Zhou, Shouming; Abbatt, Jonathan P. D.

    2015-04-01

    Although it is known that soot particles are emitted in large quantities to the atmosphere, our understanding of their environmental effects is limited by our knowledge of how their composition is subsequently altered through atmospheric processing. Here we present an on-line mass spectrometric study of the changing chemical composition of hydrocarbon soot particles as they are oxidized by gas-phase ozone, and we show that the surface-mediated loss rates of adsorbed polycyclic aromatic hydrocarbons in soot are directly connected to a significant increase in the particle redox cycling abilities. With redox cycling implicated as an oxidative stress mechanism that arises after inhalation of atmospheric particles, this work draws a quantitative connection between the detailed heterogeneous chemistry occurring on atmospheric particles and a potential toxic mechanism attributable to that aerosol.

  14. Successful treatment with supercritical water oxidation

    SciTech Connect

    Jensen, R.

    1994-06-01

    Supercritical Water Oxidation (SCWO) operates in a totally enclosed system. It uses water at high temperatures and high pressure to chemically change wastes. Oily substances become soluble and complex hydrocarbons are converted into water and carbon dioxide. Research and development on SCWO is described.

  15. Modified Graphene Oxide for Long Cycle Sodium-Ion Batteries

    NASA Astrophysics Data System (ADS)

    Shareef, Muhamed; Gunn, Harrison; Voigt, Victoria; Singh, Gurpreet

    Hummer's process was modified to produce gram levels of 2-dimensional nanosheets of graphene oxide (GO) with varying degree of exfoliation and chemical functionalization. This was achieved by varying the weight ratios and reaction times of oxidizing agents used in the process. Based on Raman and Fourier transform infra red spectroscopy we show that potassium permanganate (KMnO4) is the key oxidizing agent while sodium nitrate (NaNO3) and sulfuric acid (H2SO4) play minor role during the exfoliation of graphite. Tested as working electrode in sodium-ion half-cell, the GO nanosheets produced using this optimized approach showed high rate capability and exceptionally high energy density of ~500 mAh/g for up to at least 100 cycles, which is among the highest reported for sodium/graphite electrodes. The average Coulombic efficiency was approximately 99 %. NSF Grant No. 1454151.

  16. A Satellite View of Global Water and Energy Cycling

    NASA Astrophysics Data System (ADS)

    Houser, P. R.

    2012-12-01

    The global water cycle describes liquid, solid and vapor water dynamics as it moves through the atmosphere, oceans and land. Life exists because of water, and civilization depends on adapting to the constraints imposed by water availability. The carbon, water and energy cycles are strongly interdependent - energy is moved through evaporation and condensation, and photosynthesis is closely related to transpiration. There are significant knowledge gaps about water storage, fluxes and dynamics - we currently do not really know how much water is stored in snowpacks, groundwater or reservoirs. The view from space offers a vision for water science advancement. This vision includes observation, understanding, and prediction advancements that will improve water management and to inform water-related infrastructure that planning to provide for human needs and to protect the natural environment. The water cycle science challenge is to deploy a series of coordinated earth observation satellites, and to integrate in situ and space-borne observations to quantify the key water-cycle state variables and fluxes. The accompanying societal challenge is to integrate this information along with water cycle physics, and ecosystems and societal considerations as a basis for enlightened water resource management and to protect life and property from effects of water cycle extremes. Better regional to global scale water-cycle observations and predictions need to be readily available to reduce loss of life and property caused by water-related hazards. To this end, the NASA Energy and Water cycle Study (NEWS) has been documenting the satellite view of the water cycle with a goal of enabling improved, observationally based, predictions of water and energy cycle consequences of Earth system variability and change. NEWS has fostered broad interdisciplinary collaborations to study experimental and operational satellite observations and has developed analysis tools for characterizing air/sea fluxes, ocean circulation, atmospheric states, radiative balances, land surface states, sub-surface hydrology, snow and ice. This presentation will feature an overview of recent progress towards this challenge, and lay out the plan for coordination with complementary international efforts.

  17. Manganese Compounds as Water-Oxidizing Catalysts: From the Natural Water-Oxidizing Complex to Nanosized Manganese Oxide Structures.

    PubMed

    Najafpour, Mohammad Mahdi; Renger, Gernot; Hołyńska, Małgorzata; Moghaddam, Atefeh Nemati; Aro, Eva-Mari; Carpentier, Robert; Nishihara, Hiroshi; Eaton-Rye, Julian J; Shen, Jian-Ren; Allakhverdiev, Suleyman I

    2016-03-01

    All cyanobacteria, algae, and plants use a similar water-oxidizing catalyst for water oxidation. This catalyst is housed in Photosystem II, a membrane-protein complex that functions as a light-driven water oxidase in oxygenic photosynthesis. Water oxidation is also an important reaction in artificial photosynthesis because it has the potential to provide cheap electrons from water for hydrogen production or for the reduction of carbon dioxide on an industrial scale. The water-oxidizing complex of Photosystem II is a Mn-Ca cluster that oxidizes water with a low overpotential and high turnover frequency number of up to 25-90 molecules of O2 released per second. In this Review, we discuss the atomic structure of the Mn-Ca cluster of the Photosystem II water-oxidizing complex from the viewpoint that the underlying mechanism can be informative when designing artificial water-oxidizing catalysts. This is followed by consideration of functional Mn-based model complexes for water oxidation and the issue of Mn complexes decomposing to Mn oxide. We then provide a detailed assessment of the chemistry of Mn oxides by considering how their bulk and nanoscale properties contribute to their effectiveness as water-oxidizing catalysts. PMID:26812090

  18. Nitrogen oxide cycle regulates nitric oxide levels and bacterial cell signaling.

    PubMed

    Sasaki, Yasuyuki; Oguchi, Haruka; Kobayashi, Takuya; Kusama, Shinichiro; Sugiura, Ryo; Moriya, Kenta; Hirata, Takuya; Yukioka, Yuriya; Takaya, Naoki; Yajima, Shunsuke; Ito, Shinsaku; Okada, Kiyoshi; Ohsawa, Kanju; Ikeda, Haruo; Takano, Hideaki; Ueda, Kenji; Shoun, Hirofumi

    2016-01-01

    Nitric oxide (NO) signaling controls various metabolic pathways in bacteria and higher eukaryotes. Cellular enzymes synthesize and detoxify NO; however, a mechanism that controls its cellular homeostasis has not been identified. Here, we found a nitrogen oxide cycle involving nitrate reductase (Nar) and the NO dioxygenase flavohemoglobin (Fhb), that facilitate inter-conversion of nitrate, nitrite, and NO in the actinobacterium Streptomyces coelicolor. This cycle regulates cellular NO levels, bacterial antibiotic production, and morphological differentiation. NO down-regulates Nar and up-regulates Fhb gene expression via the NO-dependent transcriptional factors DevSR and NsrR, respectively, which are involved in the auto-regulation mechanism of intracellular NO levels. Nitrite generated by the NO cycles induces gene expression in neighboring cells, indicating an additional role of the cycle as a producer of a transmittable inter-cellular communication molecule. PMID:26912114

  19. Nitrogen oxide cycle regulates nitric oxide levels and bacterial cell signaling

    PubMed Central

    Sasaki, Yasuyuki; Oguchi, Haruka; Kobayashi, Takuya; Kusama, Shinichiro; Sugiura, Ryo; Moriya, Kenta; Hirata, Takuya; Yukioka, Yuriya; Takaya, Naoki; Yajima, Shunsuke; Ito, Shinsaku; Okada, Kiyoshi; Ohsawa, Kanju; Ikeda, Haruo; Takano, Hideaki; Ueda, Kenji; Shoun, Hirofumi

    2016-01-01

    Nitric oxide (NO) signaling controls various metabolic pathways in bacteria and higher eukaryotes. Cellular enzymes synthesize and detoxify NO; however, a mechanism that controls its cellular homeostasis has not been identified. Here, we found a nitrogen oxide cycle involving nitrate reductase (Nar) and the NO dioxygenase flavohemoglobin (Fhb), that facilitate inter-conversion of nitrate, nitrite, and NO in the actinobacterium Streptomyces coelicolor. This cycle regulates cellular NO levels, bacterial antibiotic production, and morphological differentiation. NO down-regulates Nar and up-regulates Fhb gene expression via the NO-dependent transcriptional factors DevSR and NsrR, respectively, which are involved in the auto-regulation mechanism of intracellular NO levels. Nitrite generated by the NO cycles induces gene expression in neighboring cells, indicating an additional role of the cycle as a producer of a transmittable inter-cellular communication molecule. PMID:26912114

  20. Surface-oxidized carbon black as a catalyst for the water oxidation and alcohol oxidation reactions.

    PubMed

    Suryanto, Bryan H R; Zhao, Chuan

    2016-05-11

    Carbon black (CB) is popularly used as a catalyst support for metal/metal oxide nanoparticles due to its large surface area, excellent conductivity and stability. Herein, we show that surface oxidized CB itself, after acidic treatment and electrochemical oxidation, exhibits significant catalytic activity for the electrochemical oxidation of water and alcohols. PMID:27097802

  1. The resorption cycle using ammonia and water

    SciTech Connect

    Pande, M.; Herold, K.E.

    1996-11-01

    The term resorption originates in the German literature and refers to the concept of replacing a condenser/expansion value/evaporator in a refrigeration or heat pump cycle with a solution circuit. The solution circuit typically includes a desorber, an absorber, a solution pump, and a solution heat exchanger. The absorber takes the place of the condenser and the desorber takes the place of the evaporator. In contrast to the usual condenser-evaporator arrangement, the presence of the additional solution circuit in the resorption cycle implies that the processes in the components at all four corners of the cycle are partial phase-change processes. The resorption concept provides an additional degree of freedom in the cycle design and application. By allowing the solution loop concentrations to vary, it is possible to adjust the component temperatures and pressures to the application of interest. The solution loop flow rate also can be easily varied to allow effective capacity control. These advantages are obtained with some additional complexity in hardware and some resultant loss of performance due to additional internal irreversibilities. However, the temperature glide that exists in the resorption cycle components provides an opportunity for improved thermodynamic performance through temperature matching with an application. For certain applications, these trade-offs are quite beneficial.

  2. Water Interaction with Iron Oxides.

    PubMed

    Dementyev, Petr; Dostert, Karl-Heinz; Ivars-Barceló, Francisco; O'Brien, Casey P; Mirabella, Francesca; Schauermann, Swetlana; Li, Xiaoke; Paier, Joachim; Sauer, Joachim; Freund, Hans-Joachim

    2015-11-16

    We present a mechanistic study on the interaction of water with a well-defined model Fe3 O4 (111) surface that was investigated by a combination of direct calorimetric measurements of adsorption energies, infrared vibrational spectroscopy, and calculations bases on density functional theory (DFT). We show that the adsorption energy of water (101 kJ mol(-1) ) is considerably higher than all previously reported values obtained by indirect desorption-based methods. By employing (18) O-labeled water molecules and an Fe3 O4 substrate, we proved that the generally accepted simple model of water dissociation to form two individual OH groups per water molecule is not correct. DFT calculations suggest formation of a dimer, which consists of one water molecule dissociated into two OH groups and another non-dissociated water molecule creating a thermodynamically very stable dimer-like complex. PMID:26457889

  3. Ammonia/water absorption cycles with relatively high generator temperatures

    NASA Astrophysics Data System (ADS)

    Johnston, A. M.

    1980-01-01

    It is shown that the performance of single-state ammonia/water absorption cycles (COPs up to 0.8) is appreciably superior to that of commercial single-state water/lithium bromide appliances (COPs up to 0.72), with ammonia/water cycles having the additional advantage of satisfactory operation with air cooling and in refrigeration and heat pump modes, if high-temperature collectors, such as evacuated tubular collectors, are available. In particular, the improved performance of the two-stage cycle should permit improvement in overall steady-state system performance when used in conjunction with evacuated tubular collectors.

  4. Towards an Integrated Global Water Cycle Observations (IGWCO) Strategy

    NASA Astrophysics Data System (ADS)

    Lawford, R. G.

    2004-12-01

    The Integrated Global Observing Strategy Partnership (IGOS-P), which consists of space agencies (represented by the Committee on Earth Observing Satellites) and international programs, adopted water as a priority in 2001. Subsequently, in November 2003, it adopted a Global Water Cycle Observations theme report and now is planning follow-on activities. The Integrated Global Water Cycle Observing (IGWCO) strategy provides an international framework for guiding decisions on priorities and strategies regarding water cycle observations for: a) monitoring climate variability and change; b) effective water management and sustainable development of the world's water resources; c) societal applications for resource development and environmental management; d) specification of initial conditions for weather and climate forecasts, and e) research directed at priority water cycle questions. It also promotes strategies that facilitate the processing, archiving and distribution of water cycle data and products. The IGWCO report contains a number of recommendations aimed at improving water cycle observations and products and supporting the further development of the theme. Since November 2003, a number of steps have been taken to develop a plan for implementing the theme. This implementation plan has identified activities and studies related to the Coordinated Enhanced Observing Period (CEOP), the Global Water System Project (GWSP), and the development of integrated precipitation and soil moisture products. Other activities under consideration involve building the capacity of developing countries to make measurements and analyze global water cycle variables thereby strengthening their ability to manage national water resources. The purpose of this presentation is to inform the scientific community of these activities and to solicit advice and assistance in the implementation of the strategy.

  5. Relationships between Cycling Hypoxia, HIF-1, Angiogenesis and Oxidative Stress

    PubMed Central

    Dewhirst, Mark W.

    2009-01-01

    This Failla Lecture focused on the inter-relationships between tumor angiogenesis, HIF-1 expression and radiotherapy responses. A common thread that bonds all of these factors together is microenvironmental stress caused by reactive oxygen and nitrogen species formed during tumor growth and angiogenesis or in response to cytotoxic treatment. In this review we focus on one aspect of the crossroad between oxidative stress and angiogenesis, namely cycling hypoxia. Understanding of the relative importance of this feature of the tumor microenvironment has recently expanded; it influences tumor biology in ways that are separate from chronic hypoxia. Cycling hypoxia can influence angiogenesis, treatment responses and metastatic behavior. It represents an important and relatively less well understood feature of tumor biology that requires additional research. PMID:19929412

  6. Analysis of oxidative stress during the menstrual cycle

    PubMed Central

    2013-01-01

    Background Few data concerning the oxidative stress (OS) in plasma during the entire menstrual cycle of eumenorrheic women are available. Methods OS was assessed in 20 healthy volunteers during the phase of the menstrual cycle by determining the plasmatic hydroperoxides levels (d-ROMs test). The assessment was performed every three days, starting from the first day (t1) up the end of the menstrual phase (t27). Concomitantly, the estrogen (E2) and progestin (P4) levels were determined at the same time intervals. Results From a base value (t1) of 284 +/− 38.0 CARR.U., which is essentially within the normal range (<300 Carratelli units or CARR.U.), the OS levels progressively increased to 378 +/− 115 CARR.U. at t15, and then slightly decreased over the subsequent time but with average values >300 CARR.U. Analysis of the E2 levels showed that the maximum OS values were noticed near the estrogen peak, while remaining above the base levels, and then decreased during the progestin phase until returning to normal at the end of the menstrual cycle. Conclusions It may concludes that the healthy women go into OS for 2/3 of the menstrual cycle. PMID:23915183

  7. Presence of Ammonia-oxidizing Archaea and Their Influence on Nitrogen Cycling in Ilica Bay, Turkey

    NASA Astrophysics Data System (ADS)

    Gulecal, Y.; Temel, M.

    2011-12-01

    Recenlty, the processes of anaerobic ammonium oxidation (anammox), and ammonia oxidation within the domain Archaea, have been recognized as two new links in the global nitrogen cycle. The distribution and ubiquity of marine Archaea an important role in global carbon and nitrogen cycling (Ingalls et al., 2006; Leininger et al., 2006; Wuchter et al.,2006a). However, our knowledge on archaeal distribution in aquatic ecosystem was largely confined to the extreme environments for a long time until DeLong (1992, 1998) revealed the ubiquity of archaea in common marine environments. Despite the great progress, more efforts need to be given to the study of archaeal diversity in the vast oceans and of the variations in the ecological environment from coastal to oceanic waters (Massana et al.,2000). Our studying area which Ilica Bay in Izmir (Turkey) has a lot of thermal springs. The aim of study was to investigate the presence of ammonia-oxidizing Archaea and their roles of nitrogen cycling in marine enviroments.We have not only used the geochemical analyses but also genetic tools. This study will supply knowledge for marine nitrogen cycling to understanding very well, in addition how Archea genes players in the process of anammox in shallow coastal marine environments.

  8. Plans and Activities for NASA's Global Water Cycle Research

    NASA Astrophysics Data System (ADS)

    Schlosser, C. A.

    2002-05-01

    Strictly speaking, the water (or hydrologic) cycle is by definition a global phenomenon. To observe, analyze, characterize, understand, and predict its structure and variations requires a coordinated, global effort of observations as well as global prediction systems which can assimilate and predict key fluxes and quantities. The National Aeronautics and Space Administration (NASA) has the unique capability of space-based experimental and research measurements that observe the Earth's system as well as core modelling activities to exploit these space-based observations for assimilation in diagnostic studies and initialization in weather and climate predictions. A summary of NASA's current water-cycle activities and implementation plans will be presented. Currently, NASA's Global Water and Energy Cycle and Terrestrial Hydrology (formally known as the Land Surface Hydrology) Programs are the key funding sources which support relevant scientific research. These programs not only fund individual scientists, but also support large-scale field missions (for example the Cold Land Processes Experiment, CLPX, and the Soil Moisture Experiment, SMEx) which are critical for calibration/validation of space instruments and retrievals as well as gaining fundamental understanding of local-scale processes which comprise the global system. In addition, a new initiative for Water and Energy cycle Research (WatER) is being formulated which responds to the recent charge of USGCRP and NRC scientific panels calling for focused and prioritized research plans that serve to make significant strides in our understanding and prediction of the global water cycle. Following NASA's unique vocation, the WatER initative sets priorities for science/research support for key observable quantities of the water cycle (precipitation and surface wetness) whose instrument technology is tactable and scientfic end-returns not only benefit water-cycle predictions, but also serve to benefit other critical cross-cutting themes (such as the carbon cycle).

  9. Nitrous oxide cycling in the water column and sediments of the oxygen minimum zone, eastern subtropical North Pacific, Southern California, and Northern Mexico (23°N-34°N)

    NASA Astrophysics Data System (ADS)

    Townsend-Small, Amy; Prokopenko, Maria G.; Berelson, William M.

    2014-05-01

    Identifying sources and sinks of N2O can illuminate N cycling processes in marine systems, particularly where changes in dissolved O2 can lead to changes in N cycling pathways (i.e., nitrification versus denitrification). We measured N2O and NO3- concentration and their stable isotope ratios (δ15N and δ18O) in the water column and sediments of the oxygen minimum zone in the nearshore eastern subtropical North Pacific (23°N-34°N). Atmospheric efflux of N2O ranged from 2.2 to 17.9 μmol m-2 d-1 or about 2-20 times higher than in oxygenated regions of the North Pacific. Surface waters were a source of 15N-depleted and 18O-enriched N2O to the atmosphere, indicating a bacterial, not archaeal, nitrification N2O source. Stable isotopes indicated that nitrification in both surface and intermediate waters (˜0-200 m) was the major source of N2O in this study area, with denitrification acting as a small N2O sink in strongly O2-depleted waters. Denitrification had a larger impact on observed patterns of N2O and NO3- concentrations and isotope ratios in the southern oxygen minimum zone. Sediments were generally neutral or a weak sink for N2O, with only one site (Soledad basin) showing a positive efflux of +3.5 ± 1.0 μmol N2O-N m-2 d-1. Sediment fluxes of N2O at all sites were several orders of magnitude smaller than fluxes of dinitrogen, nitrate, and ammonium measured in previous studies and did not appear to impact water column N2O concentrations. N2O was less than 0.1% of the N2 efflux from sedimentary denitrification.

  10. Homogeneous and heterogenized iridium water oxidation catalysts

    NASA Astrophysics Data System (ADS)

    Macchioni, Alceo

    2014-10-01

    The development of an efficient catalyst for the oxidative splitting of water into molecular oxygen, protons and electrons is of key importance for producing solar fuels through artificial photosynthesis. We are facing the problem by means of a rational approach aimed at understanding how catalytic performance may be optimized by the knowledge of the reaction mechanism of water oxidation and the fate of the catalytic site under the inevitably harsh oxidative conditions. For the purposes of our study we selected iridium water oxidation catalysts, exhibiting remarkable performance (TOF > 5 s-1 and TON > 20000). In particular, we recently focused our attention on [Cp*Ir(N,O)X] (N,O = 2-pyridincarboxylate; X = Cl or NO3) and [IrCl(Hedta)]Na water oxidation catalysts. The former exhibited a remarkable TOF whereas the latter showed a very high TON. Furthermore, [IrCl(Hedta)]Na was heterogenized onto TiO2 taking advantage of the presence of a dandling -COOH functionality. The heterogenized catalyst maintained approximately the same catalytic activity of the homogeneous analogous with the advantage that could be reused many times. Mechanistic studies were performed in order to shed some light on the rate-determining step and the transformation of catalysts when exposed to "oxidative stress". It was found that the last oxidative step, preceding oxygen liberation, is the rate-determining step when a small excess of sacrificial oxidant is used. In addition, several intermediates of the oxidative transformation of the catalyst were intercepted and characterized by NMR, X-Ray diffractometry and ESI-MS.

  11. Supercritical Water Oxidation Data Acquisition Testing

    SciTech Connect

    K. M. Garcia

    1996-08-01

    Supercritical Water Oxidation (SCWO) is a high pressure oxidation process that blends air, water, and organic waste material in an oxidizer in which where the temperature and pressure in the oxidizer are maintained above the critical point of water. Supercritical water mixed with hydrocarbons, which would be insoluble at subcritical conditions, forms a homogeneous phase which possesses properties associated with both a gas and a liquid. Hydrocarbons in contact with oxygen and SCW are readily oxidized. These properties of SCW make it an attractive means for the destruction of waste streams containing organic materials. SCWO technology holds great promise for treating mixed wastes in an environmentally safe and efficient manner. In the spring of 1994 the U.S. Department of Energy (DOE) initiated a Supercritical Water Oxidation Data Acquisition Testing (SCWODAT) program. The SCWODAT program provided further information and operational data on the effectiveness of treating both simulated mixed waste and typical Navy hazardous waste using the SCWO technology. The program concentrated on the acquisition of data through pilot plant testing. The Phase I DOE testing used a simulated waste stream that contained a complex machine cutting oil and metals, that acted as surrogates for radionuclides. The Phase II Navy testing included pilot testing using hazardous waste materials to demonstrate the effectiveness of the SCWO technology. The SCWODAT program demonstrated that the SCWO process oxidized the simulated waste stream containing complex machine cutting oil, selected by DOE as representative of one of the most difficult of the organic waste streams for which SCWO had been applied. The simulated waste stream with surrogate metals in solution was oxidized, with a high destruction efficiency, on the order of 99.97%, in both the neutralized and unneutralized modes of operation.

  12. Modeling Nitrogen Cycle at the Surface-Subsurface Water Interface

    NASA Astrophysics Data System (ADS)

    Marzadri, A.; Tonina, D.; Bellin, A.

    2011-12-01

    Anthropogenic activities, primarily food and energy production, have altered the global nitrogen cycle, increasing reactive dissolved inorganic nitrogen, Nr, chiefly ammonium NH4+ and nitrate NO3-, availability in many streams worldwide. Increased Nr promotes biological activity often with negative consequences such as water body eutrophication and emission of nitrous oxide gas, N2O, an important greenhouse gas as a by-product of denitrification. The hyporheic zone may play an important role in processing Nr and returning it to the atmosphere. Here, we present a process-based three-dimensional semi-analytical model, which couples hyporheic hydraulics with biogeochemical reactions and transport equations. Transport is solved by means of particle tracking with negligible local dispersion and biogeochemical reactions modeled by linearized Monod's kinetics with temperature dependant reaction rate coefficients. Comparison of measured and predicted N2O emissions from 7 natural stream shows a good match. We apply our model to gravel bed rivers with alternate bar morphology to investigate the role of hyporheic hydraulic, depth of alluvium, relative availability of stream concentration of NO3- and NH4+ and water temperature on nitrogen gradients within the sediment. Our model shows complex concentration dynamics, which depend on hyporheic residence time distribution and consequently on streambed morphology, within the hyporheic zone. Nitrogen gas emissions from the hyporheic zone increase with alluvium depth in large low-gradient streams but not in small steep streams. On the other hand, hyporheic water temperature influences nitrification/denitrification processes mainly in small-steep than large low-gradient streams, because of the long residence times, which offset the slow reaction rates induced by low temperatures in the latter stream. The overall conclusion of our analysis is that river morphology has a major impact on biogeochemical processes such as nitrification and denitrification with a direct impact on the stream nutrient removal and transport.

  13. Electric field cycling behavior of ferroelectric hafnium oxide.

    PubMed

    Schenk, Tony; Schroeder, Uwe; Pešić, Milan; Popovici, Mihaela; Pershin, Yuriy V; Mikolajick, Thomas

    2014-11-26

    HfO2 based ferroelectrics are lead-free, simple binary oxides with nonperovskite structure and low permittivity. They just recently started attracting attention of theoretical groups in the fields of ferroelectric memories and electrostatic supercapacitors. A modified approach of harmonic analysis is introduced for temperature-dependent studies of the field cycling behavior and the underlying defect mechanisms. Activation energies for wake-up and fatigue are extracted. Notably, all values are about 100 meV, which is 1 order of magnitude lower than for conventional ferroelectrics like lead zirconate titanate (PZT). This difference is mainly atttributed to the one to two orders of magnitude higher electric fields used for cycling and to the different surface to volume ratios between the 10 nm thin films in this study and the bulk samples of former measurements or simulations. Moreover, a new, analog-like split-up effect of switching peaks by field cycling is discovered and is explained by a network model based on memcapacitive behavior as a result of defect redistribution. PMID:25365475

  14. Supercritical water oxidation - Microgravity solids separation

    NASA Technical Reports Server (NTRS)

    Killilea, William R.; Hong, Glenn T.; Swallow, Kathleen C.; Thomason, Terry B.

    1988-01-01

    This paper discusses the application of supercritical water oxidation (SCWO) waste treatment and water recycling technology to the problem of waste disposal in-long term manned space missions. As inorganic constituents present in the waste are not soluble in supercritical water, they must be removed from the organic-free supercritical fluid reactor effluent. Supercritical water reactor/solids separator designs capable of removing precipitated solids from the process' supercritical fluid in zero- and low- gravity environments are developed and evaluated. Preliminary experiments are then conducted to test the concepts. Feed materials for the experiments are urine, feces, and wipes with the addition of reverse osmosis brine, the rejected portion of processed hygiene water. The solid properties and their influence on the design of several oxidation-reactor/solids-separator configurations under study are presented.

  15. Earth observation Water Cycle Multi-Mission Observation Strategy (WACMOS)

    NASA Astrophysics Data System (ADS)

    Su, Z.; Dorigo, W.; Fernández-Prieto, D.; van Helvoirt, M.; Hungershoefer, K.; de Jeu, R.; Parinussa, R.; Timmermans, J.; Roebeling, R.; Schröder, M.; Schulz, J.; van der Tol, C.; Stammes, P.; Wagner, W.; Wang, L.; Wang, P.; Wolters, E.

    2010-10-01

    Observing and monitoring the different components of the global water cycle and their dynamics are essential steps to understand the climate of the Earth, forecast the weather, predict natural disasters like floods and droughts, and improve water resources management. Earth observation technology is a unique tool to provide a global understanding of many of the essential variables governing the water cycle and monitor their evolution over time from global to basin scales. In the coming years an increasing number of Earth observation missions will provide an unprecedented capacity to quantify several of these variables on a routine basis. In this context, the European Space Agency (ESA), in collaboration with the Global Energy and Water Cycle Experiment (GEWEX) of the World Climate Research Program (WCRP), launched the Water Cycle Multi-Mission Observation Strategy (WACMOS) project in 2009. The project aims at developing and validating a novel set of geo-information products relevant to the water cycle covering the following thematic areas: evapotranspiration, soil moisture, cloud characterization and water vapour. The generation of these products is based on a number of innovative techniques and methods aiming at exploiting the synergies of different types of Earth observation data available today to the science community. This paper provides an overview of the major findings of the project with the ultimate goal of demonstrating the potential of innovative multi-mission based strategies to improve current observations by maximizing the synergistic use of the different types of information provided by the currently available observation systems.

  16. Ceramic coating system or water oxidation environments

    DOEpatents

    Hong, Glenn T.

    1996-01-01

    A process for water oxidation of combustible materials in which during at least a part of the oxidation corrosive material is present and makes contact with at least a portion of the apparatus over a contact area on the apparatus. At least a portion of the contact surface area comprises titanium dioxide coated onto a titanium metal substrate. Such ceramic composites have been found to be highly resistant to environments encountered in the process of supercritical water oxidation. Such environments typically contain greater than 50 mole percent water, together with oxygen, carbon dioxide, and a wide range of acids, bases, and salts. Pressures are typically about 27.5 to about 1000 bar while temperatures range as high as 700.degree. C. The ceramic composites are also resistant to degradation mechanisms caused by thermal stresses.

  17. A self-improved water-oxidation catalyst: is one site really enough?

    PubMed

    López, Isidoro; Ertem, Mehmed Z; Maji, Somnath; Benet-Buchholz, Jordi; Keidel, Anke; Kuhlmann, Uwe; Hildebrandt, Peter; Cramer, Christopher J; Batista, Victor S; Llobet, Antoni

    2014-01-01

    The homogeneous catalysis of water oxidation by transition-metal complexes has experienced spectacular development over the last five years. Practical energy-conversion schemes, however, require robust catalysts with large turnover frequencies. Herein we introduce a new oxidatively rugged and powerful dinuclear water-oxidation catalyst that is generated by self-assembly from a mononuclear catalyst during the catalytic process. Our kinetic and DFT computational analysis shows that two interconnected catalytic cycles coexist while the mononuclear system is slowly and irreversibly converted into the more stable dinuclear system: an extremely robust water-oxidation catalyst that does not decompose over extended periods of time. PMID:24259487

  18. Emerging Contaminants in the Drinking Water Cycle.

    EPA Science Inventory

    In the past decade, the scientific community and general public have become increasingly aware of the potential for the presence of unregulated, and generally unmonitored contaminants, found at low concentrations (sub-g/L) in surface, ground and drinking water. The most common...

  19. Toward a hydro-political water cycle: virtual water,hydrology and international political economy

    NASA Astrophysics Data System (ADS)

    Greco, Francesca

    2014-05-01

    At the light of global food trade, no water cycle can be considered "closed" under a political point of view. While the hydrological cycle is a circular closed environment, if we open up our perspectives to social sciences, we will demonstrate how, thanks to virtual water, it is today possible to elaborate how much water 'enters or leave' any water body under the form crop-export, in terms of " water used for the production of agri-food products'. This new 'hydro-political cycle' will be discussed at the light of different theoretical perspectives: food trade theories, hydrology, international water law, socio-economic metabolism, material flow analysis.

  20. Life cycle water footprints of nonfood biomass fuels in China.

    PubMed

    Zhang, Tingting; Xie, Xiaomin; Huang, Zhen

    2014-04-01

    This study presented life cycle water footprints (WFs) of biofuels from biomass in China based on the resource distribution, climate conditions, soil conditions and crop growing characteristics. Life cycle WFs including blue, green and gray water were evaluated for the selected fuel pathways. Geographical differences of water requirements were revealed to be different by locations. The results indicated that water irrigation requirements were significantly different from crop to crop, ranging from 2-293, 78-137, and 17-621 m(3)/ha, for sweet sorghum, cassava, and Jatropha curcas L., respectively. Four biofuel pathways were selected on this basis to analyze the life cycle WF: cassava based bioethanol in Guangxi, sweet sorghum based bioethanol in Northeast China, Jatropha curcal L. based biodiesel in Yunnan and microalgae based biodiesel in Hainan. The life cycle WFs of bioethanol from cassava and sweet sorghum were 3708, and 17?156 m(3) per ton of bioethanol, respectively, whereas for biodiesel produced from Jatropha curcas L. and microalgae, they were 5787, and 31?361 m(3) per ton of biodiesel, respectively. The crop growing stage was the main contributor to the whole life cycle of each pathway. Compared to blue and green water, gray water was significant due to the use of fertilizer during the growing of biomass. From the perspective of the WF, cassava based bioethanol in Guangxi and Jatropha based biodiesel in Yunnan were suitable for promotion, whereas the promotion for microalage based biodiesel in Hainan required improvement on technology. PMID:24400620

  1. Massive swings in the marine N cycle during the Great Oxidation Event

    NASA Astrophysics Data System (ADS)

    Zerkle, A.; Poulton, S.; Newton, R.; Claire, M.; Bekker, A.

    2012-12-01

    Nitrogen isotope values preserved in sedimentary organic matter show a general increase sometime between 2.5 and 2.1 Ga (e.g., Beaumont and Robert, 1999), coincident with the initial rise of O2 in the Earth's atmosphere (the Great Oxidation Event; Holland, 2002). This shift is commonly interpreted to represent a major change in the global N cycle related to oxygenation of Earth's surficial environments. Despite the invoked connection between δ15N values and the GOE, high resolution studies of N isotopes across this critical time interval are lacking. Here we present δ15N data for kerogens from the ~2.32 Ga Rooihoogte and Timeball Hill formations, South Africa. These sediments were deposited during the GOE, when the disappearance of S-isotope mass-independent fractionation first indicates O2 levels consistently greater than 10-5 times present atmospheric level (e.g., Bekker et al., 2004). We interpret these data in the context of paleoredox indicators for ocean chemistry (Fe speciation analysis), further allowing us to explore changes in the N cycle under evolving environmental conditions. Our data show unusually 15N-depleted values (down to -13‰) at the bottom of the stratigraphic succession, in sediments deposited under a water column with dynamic redox conditions that fluctuated between oxic, ferruginous, and sulfidic states (possibly related to a shifting chemocline). The δ15N values increase dramatically (up to +14‰) across the boundary between the Rooihoogte and Timeball Hill formations, before settling to near modern values (+6‰) in sediments that were deposited under persistently oxygenated waters. We suggest that this record reflects the permanent onset of the oxidative N cycle (nitrification), which would have produced sufficient oxidized N compounds to establish denitrification and anammox as the dominant controls on δ15N values of marine organic matter. We also estimate the N fluxes required to produce this record using a global marine nitrogen cycle model.

  2. The Global Water Cycle Geochemistry, and Environment

    NASA Astrophysics Data System (ADS)

    Bricker, Owen P.

    In the preface the authors state, as reasons for producing this book, the need for an appropriate undergraduate-level text on water chemistry and the desire to provide broader coverage of atmospheric and environmental chemistry than is found in other existing books on this topic. They have attempted to write a book that could be understood by almost anyone with an elementarv knowledge of science, yet could still serve as a source of geochemical and environmental data for researchers in a variety of fields. The authors have succeeded admirably in achieving these difficult goals.

  3. What regulates the annual cycle of stratospheric water vapor?

    NASA Astrophysics Data System (ADS)

    Jucker, Martin; Gerber, Edwin

    2015-04-01

    Stratospheric water vapor is a potent greenhouse gas and active chemical tracer. Most of the stratosphere is well below saturation due to freeze drying at the tropical cold point -- the coldest region of the lower stratosphere where most air enters the middle atmosphere. The leading mode of variability of the tropical cold point is an annual cycle, despite the semi-annual cycle of radiative forcing in the tropics. This causes the stratospheric water vapor mixing ratio to follow a similar annual cycle, even remotely from the entry point, the so-called tape recorder. We develop an idealized GCM to investigate the origin of the annual cycle in the tropical cold point, with a particular focus on the interaction between dynamics and radiation. By varying the surface conditions of the model, we first show that planetary scale asymmetries in the midlatitude troposphere drive the annual cycle in the cold point. Both large scale topography and land sea contrast are important, influencing synoptic and planetary scale wave forcing. We then probe the impact of water vapor on the stratospheric circulation by comparing fully interactive integrations of the model to companion integrations where the coupling between the circulation and water vapor is disconnected. Our findings have implications in estimating the impacts of stratospheric water vapor feedbacks on decadal time scales and sensitivities to climate change.

  4. Nitric oxide cycle in mammals and the cyclicity principle.

    PubMed

    Reutov, V P

    2002-03-01

    This paper continues a series of reports considering nitric oxide (NO) and its cyclic conversions in mammals. Numerous facts are summarized with the goal of developing a general concept that would allow the statement of the multiple effects of NO on various systems of living organisms in the form of a short and comprehensive law. The current state of biological aspects of NO research is analyzed in term of elucidation of possible role of these studies in the system of biological sciences. The general concept is based on a notion on cyclic conversions of NO and its metabolites. NO cycles in living organisms and nitrogen turnover in the biosphere and also the Bethe nitrogen-carbon cycle in star matter are considered. A hypothesis that the cyclic organization of processes in living organisms and the biosphere reflects the evolution of life is proposed: the development of physiological functions and metabolism are suggested to be closely related to space and evolution of the Earth as a planet of the Solar System. PMID:11970729

  5. Supercritical water oxidation of landfill leachate

    SciTech Connect

    Wang Shuzhong; Guo Yang; Chen Chongming; Zhang Jie; Gong Yanmeng; Wang Yuzhen

    2011-09-15

    Highlights: > Thermal analysis of NH{sub 3} in supercritical water oxidation reaction. > Research on the catalytic reaction of landfill leachate by using response surface method. > Kinetic research of supercritical water oxidation of NH{sub 3} with and without MnO{sub 2} catalyst. - Abstract: In this paper, ammonia as an important ingredient in landfill leachate was mainly studied. Based on Peng-Robinson formulations and Gibbs free energy minimization method, the estimation of equilibrium composition and thermodynamic analysis for supercritical water oxidation of ammonia (SCWO) was made. As equilibrium is reached, ammonia could be totally oxidized in SCW. N{sub 2} is the main product, and the formation of NO{sub 2} and NO could be neglected. The investigation on SCWO of landfill leachate was conducted in a batch reactor at temperature of 380-500 deg. C, reaction time of 50-300 s and pressure of 25 MPa. The effect of reaction parameters such as oxidant equivalent ratio, reaction time and temperature were investigated. The results showed that COD and NH{sub 3} conversion improved as temperature, reaction time and oxygen excess increased. Compared to organics, NH{sub 3} is a refractory compound in supercritical water. The conversion of COD and NH{sub 3} were higher in the presence of MnO{sub 2} than that without catalyst. The interaction between reaction temperature and time was analyzed by using response surface method (RSM) and the results showed that its influence on the NH{sub 3} conversion was relatively insignificant in the case without catalyst. A global power-law rate expression was regressed from experimental data to estimate the reaction rate of NH{sub 3}. The activation energy with and without catalyst for NH{sub 3} oxidation were 107.07 {+-} 8.57 kJ/mol and 83.22 {+-} 15.62 kJ/mol, respectively.

  6. Microbial iron oxidation in the Arctic tundra and its implications for biogeochemical cycling.

    PubMed

    Emerson, David; Scott, Jarrod J; Benes, Joshua; Bowden, William B

    2015-12-01

    The role that neutrophilic iron-oxidizing bacteria play in the Arctic tundra is unknown. This study surveyed chemosynthetic iron-oxidizing communities at the North Slope of Alaska near Toolik Field Station (TFS) at Toolik Lake (lat 68.63, long -149.60). Microbial iron mats were common in submerged habitats with stationary or slowly flowing water, and their greatest areal extent is in coating plant stems and sediments in wet sedge meadows. Some Fe-oxidizing bacteria (FeOB) produce easily recognized sheath or stalk morphotypes that were present and dominant in all the mats we observed. The cool water temperatures (9 to 11°C) and reduced pH (5.0 to 6.6) at all sites kinetically favor microbial iron oxidation. A microbial survey of five sites based on 16S rRNA genes found a predominance of Proteobacteria, with Betaproteobacteria and members of the family Comamonadaceae being the most prevalent operational taxonomic units (OTUs). In relative abundance, clades of lithotrophic FeOB composed 5 to 10% of the communities. OTUs related to cyanobacteria and chloroplasts accounted for 3 to 25% of the communities. Oxygen profiles showed evidence for oxygenic photosynthesis at the surface of some mats, indicating the coexistence of photosynthetic and FeOB populations. The relative abundance of OTUs belonging to putative Fe-reducing bacteria (FeRB) averaged around 11% in the sampled iron mats. Mats incubated anaerobically with 10 mM acetate rapidly initiated Fe reduction, indicating that active iron cycling is likely. The prevalence of iron mats on the tundra might impact the carbon cycle through lithoautotrophic chemosynthesis, anaerobic respiration of organic carbon coupled to iron reduction, and the suppression of methanogenesis, and it potentially influences phosphorus dynamics through the adsorption of phosphorus to iron oxides. PMID:26386054

  7. Dual-Templated Cobalt Oxide for Photochemical Water Oxidation.

    PubMed

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

    2016-02-01

    Mesoporous Co3 O4 was prepared using a dual templating approach whereby mesopores inside SiO2 nanospheres, as well as the void spaces between the nanospheres, were used as templates. The effect of calcination temperature on the crystallinity, morphology, and textural parameters of the Co3 O4 replica was investigated. The catalytic activity of Co3 O4 for photochemical water oxidation in a [Ru(bpy)3 ](2+) [S2 O8 ](2-) system was evaluated. The Co3 O4 replica calcined at the lowest temperature (150 °C) exhibited the best performance as a result of the unique nanostructure and high surface area arising from the dual templating. The performance of Co3 O4 with highest surface area was further examined in electrochemical water oxidation. Superior activity over high temperature counterpart and decent stability was observed. Furthermore, CoO with identical morphology was prepared from Co3 O4 using an ethanol reduction method and a higher turnover-frequency number for photochemical water oxidation was obtained. PMID:26404798

  8. Hydrogen Peroxide Cycling in Acidic Geothermal Environments and Potential Implications for Oxidative Stress

    NASA Astrophysics Data System (ADS)

    Mesle, M.; Beam, J.; Jay, Z.; Bodle, B.; Bogenschutz, E.; Inskeep, W.

    2014-12-01

    Hydrogen peroxide (H2O2) may be produced in natural waters via photochemical reactions between dissolved oxygen, organic carbon and light. Other reactive oxygen species (ROS) such as superoxide and hydroxyl radicals are potentially formed in environments with high concentrations of ferrous iron (Fe(II), ~10-100 μM) by reaction between H2O2 and Fe(II) (i.e., Fenton chemistry). Thermophilic archaea and bacteria inhabiting acidic iron-oxide mats have defense mechanisms against both extracellular and intracellular peroxide, such as peroxiredoxins (which can degrade H2O2) and against other ROS, such as superoxide dismutases. Biological cycling of H2O2 is not well understood in geothermal ecosystems, and geochemical measurements combined with molecular investigations will contribute to our understanding of microbial response to oxidative stress. We measured H2O2 and other dissolved compounds (Fe(II), Fe(III), H2S, O2), as well as photon flux, pH and temperature, over time in surface geothermal waters of several acidic springs in Norris Geyser Basin, Yellowstone National Park, WY (Beowulf Spring and One Hundred Spring Plain). Iron-oxide mats were sampled in Beowulf Spring for on-going analysis of metatranscriptomes and RT-qPCR assays of specific stress-response gene transcription (e.g., superoxide dismutases, peroxiredoxins, thioredoxins, and peroxidases). In situ analyses show that H2O2 concentrations are lowest in the source waters of sulfidic systems (ca. 1 μM), and increase by two-fold in oxygenated waters corresponding to Fe(III)-oxide mat formation (ca. 2 - 3 μM). Channel transects confirm increases in H2O2 as a function of oxygenation (distance). The temporal dynamics of H2O2, O2, Fe(II), and H2S in Beowulf geothermal waters were also measured during a diel cycle, and increases in H2O2 were observed during peak photon flux. These results suggest that photochemical reactions may contribute to changes in H2O2. We hypothesize that increases in H2O2 and O2 concentrations in iron-oxidizing habitats will induce higher transcription rates of genes responsible for H2O2 degradation and O2 respiration. Subsequent measurements of additional ROS and analysis of transcript data will provide broader insight on the interactions and metabolic response within iron mat communities under oxidative stress.

  9. Method of removing oxidized contaminants from water

    DOEpatents

    Amonette, James E.; Fruchter, Jonathan S.; Gorby, Yuri A.; Cole, Charles R.; Cantrell, Kirk J.; Kaplan, Daniel I.

    1998-01-01

    The present invention is a method for removing oxidized contaminant(s) from water. More specifically, the invention has the steps of contacting water containing the oxidized contaminant(s) with a layered aluminosilicate having Fe(II). The aluminosilicate may contain naturally occurring Fe(II), or the Fe(II) may be produced by reducing Fe(III) that is initially present. Reduction may be either by exposure to a chemical or biological reductant. Contacting the water containing oxidized contaminant(s) may be by (1) injection of Fe(II)-containing layered aluminosilicate, via a well, into a saturated zone where it is likely to intercept the contaminated water; (2) injection of contaminated water into a vessel containing the Fe(II)-bearing layered aluminosilicate; and (3) first reducing Fe(III) in the layered aluminosilicate to Fe(II) by injection of a biological or chemical reductant, into an aquifer or vessel having sufficient Fe(III)-bearing aluminosilicate to produce the necessary Fe(II).

  10. Method of removing oxidized contaminants from water

    DOEpatents

    Amonette, J.E.; Fruchter, J.S.; Gorby, Y.A.; Cole, C.R.; Cantrell, K.J.; Kaplan, D.I.

    1998-07-21

    The present invention is a method for removing oxidized contaminant(s) from water. More specifically, the invention has the steps of contacting water containing the oxidized contaminant(s) with a layered aluminosilicate having Fe(II). The aluminosilicate may contain naturally occurring Fe(II), or the Fe(II) may be produced by reducing Fe(III) that is initially present. Reduction may be either by exposure to a chemical or biological reductant. Contacting the water containing oxidized contaminant(s) may be by (1) injection of Fe(II)-containing layered aluminosilicate, via a well, into a saturated zone where it is likely to intercept the contaminated water; (2) injection of contaminated water into a vessel containing the Fe(II)-bearing layered aluminosilicate; and (3) first reducing Fe(III) in the layered aluminosilicate to Fe(II) by injection of a biological or chemical reductant, into an aquifer or vessel having sufficient Fe(III)-bearing aluminosilicate to produce the necessary Fe(II). 8 figs.

  11. Water Clustering on Nanostructured Iron Oxide Films

    SciTech Connect

    Merte, L. R.; Bechstein, Ralf; Peng, Guowen; Rieboldt, Felix; Farberow, Carrie A.; Zeuthen, Helene; Knudsen, Jan; Laegsgaard, E.; Wendt, Stefen; Mavrikakis, Manos; Besenbacher, Fleming

    2014-06-30

    The adhesion of water to solid surfaces is characterized by the tendency to balance competing molecule–molecule and molecule–surface interactions. Hydroxyl groups form strong hydrogen bonds to water molecules and are known to substantially influence the wetting behaviour of oxide surfaces, but it is not well-understood how these hydroxyl groups and their distribution on a surface affect the molecular-scale structure at the interface. Here we report a study of water clustering on a moire´-structured iron oxide thin film with a controlled density of hydroxyl groups. While large amorphous monolayer islands form on the are film, the hydroxylated iron oxide film acts as a hydrophilic nanotemplate, causing the formation of a regular array of ice-like hexameric nanoclusters. The formation of this ordered phase is localized at the nanometre scale; with increasing water coverage, ordered and amorphous water are found to coexist at adjacent hydroxylated and hydroxyl-free domains of the moire´ structure.

  12. OXIDATION-REDUCTION POTENTIAL MEASUREMENTS OF IMPORTANT OXIDANTS IN DRINKING WATER

    EPA Science Inventory

    Oxidation-reduction (redox) reactions are important in drinking water treatment and distribution. Oxidation-reduction potential (ORP) measurements of water reflect the tendency of major constituents in the water to accept or lose electrons. Although ORP measurements are valuable...

  13. DIURNAL CYCLE OF PRECIPITABLE WATER VAPOR OVER SPAIN

    SciTech Connect

    Ortiz de Galisteo, J. P.; Cachorro, V. E.; Toledano, C.; Torres, B.; Laulainen, Nels S.; Bennouna, Yasmine; de Frutos, A. M.

    2011-05-20

    Despite the importance of the diurnal cycle of precipitable water vapor (PWV), its knowledge is very limited due to the lack of data with sufficient temporal resolution. Currently, from GPS receivers, PWV can be obtained with high temporal resolution in all weather conditions for all hours of the day. In this study we have calculated the diurnal cycle of PWV for ten GPS stations over Spain. The minimum value is reached approximately at the same time at all the stations, ~0400-0500 UTC, whereas the maximum is reached in the second half of the day, but with a larger dispersion of its occurrence between stations. The amplitude of the cycle ranges between 0.72 mm and 1.78 mm. The highest values are recorded at the stations on the Mediterranean coast, with a doubling of the values of the stations on the Atlantic coast or inland. The amplitude of the PWV cycle, relative to the annual mean value, ranges between 8.8 % on the Mediterranean coast and 3.6 % on the Atlantic coast. Two distinctly different seasonal diurnal cycles have been identified, one in winter and other in summer, with spring and autumn being only transition states. The winter cycle is quite similar at all locations, whereas in summer, local effects are felt strongly, making the diurnal cycle quite different between stations. The amplitude of the summer cycle is 1.69 mm, it is almost double the winter one (0.93 mm). Analogous to the annual cycles, the seasonal cycles of the different stations are more similar during the night and early morning hours than during the afternoon. The observed features of the PWV diurnal cycle are explained in a qualitative way on the basis of the air temperature, the transport of moisture by local winds, and the turbulent vertical mixing.

  14. Nature and Stability of the Martian Seasonal Water Cycle

    NASA Astrophysics Data System (ADS)

    Richardson, M. I.; Wilson, R. J.

    2001-12-01

    Which components control the contemporary water cycle and what is the nature of the control mechanisms? These questions are at the heart of understanding how the Martian exchangeable water budget adjusts to perturbations and changes in the climate system. Analysis of a water cycle model embedded in the GFDL Mars GCM provides a paradigm for the water cycle as a feedback system, providing information on the important control points and response times. Much information on this system derives from monitoring the evolution towards steady state--one that resembles the observed water vapour and ice cloud distributions. The most important exchange balance in the system is that between the northern polar atmosphere and the rest of the planet. As the major net source for water, the northern residual water ice cap is active during summer, in the window of time between the sublimation and recondensation of the seasonal CO2 cap. At this time, water is exported from the northern polar atmosphere at a rate determined by the mixing capacity of the atmosphere and the amount of water held in the polar atmosphere. The latter is determined by the cap surface temperature. During the remainder of the year, water is returned to the pole. This return flux is determined by the atmospheric mixing capacity and the amount of water vapour held in the tropical and winter extratropical atmosphere. Steady-state is achieved when these fluxes balance. For a given climate state (and a roughly repeatable annual cycle of mixing), the outflux and influx of polar water are controlled by separate variables. Holding the cap temperature constant, the outflux will remain constant. Any perturbation to the global water budget will result in a change in the return flux that tends to oppose the sense of the perturbation--the perturbation will be damped. In the same way, a change in cap temperature (e.g. associated with a change in albedo) will result in changed water outflow. Again, this will tend to change the non-polar water vapour budget and hence the polar water influx so as to develop a new steady-state. It is important to note that only in this case is the steady-state global humidity changed: a given cap temperature and seasonal cycle of mixing capacity specifies a bulk steady-state atmospheric humidity. In all cases, the regolith acts as a damper on the system and adjusts to the global water distribution dictated ultimately by the northern cap. The model also suggests fast adjustment times, on order decades. A number of factors can affect atmospheric mixing capacity. As climate forcing factors change (associated with obliquity or greenhouse gas loading) the mixing capacity will change--an area for future study. The current mixing capacity of the atmosphere is also different from one that would obtain without atmospheric water condensation and sedimentation. Model clouds play important roles in returning water to the residual ice cap in northern summer, and significantly altering interhemispheric transport from that which would occur without clouds. As with previous studies, the southern polar cap acts as a permanent sink for water. The model and resulting paradigm for the water cycle can be used in very preliminary studies of past climate states. Forcing the model with an obliquity of 45 deg., the seasonal water ice caps become significantly more extended, reaching into the summer hemisphere. In fact, the seasonal caps "overlap" in the northern tropics, generating a year-round surface ice belt. Much work remains to be done in understanding water ice transport and exchange processes before models of paleoclimate can be of widespread utility--of which analysis of data from MGS and future missions will be key.

  15. Supercritical water oxidation of ammonium picrate

    SciTech Connect

    LaJeunesse, C.A.; Mills, B.E.; Brown, B.G.

    1994-11-01

    This study demonstrates the feasibility of using supercritical water oxidation to destroy ammonium picrate. Analyses of reactor effluent composition at various temperatures, residence times, and oxidant concentrations were used to design an improved reactor configuration for achieving destruction with minimum corrosion. The engineering evaluation reactor, a room-sized laboratory scale reactor, was reconfigured to incorporate this design change. Destruction of ammonium picrate with minimized corrosion was demonstrated on this reconfigured reactor. Factors that must be considered in scaling up to pilot plant size are discussed.

  16. NASA's Earth Science Enterprise's Water and Energy Cycle Focus Area

    NASA Astrophysics Data System (ADS)

    Entin, J. K.

    2004-05-01

    Understanding the Water and Energy cycles is critical towards improving our understanding of climate change, as well as the consequences of climate change. In addition, using results from water and energy cycle research can help improve water resource management, agricultural efficiency, disaster management, and public health. To address this, NASA's Earth Science Enterprise (ESE) has an end-to-end Water and Energy Cycle Focus Area, which along with the ESE's other five focus areas will help NASA answer key Earth Science questions. In an effort to build upon the pre-existing discipline programs, which focus on precipitation, radiation sciences, and terrestrial hydrology, NASA has begun planning efforts to create an implementation plan for integrative research to improve our understanding of the water and energy cycles. The basics of this planning process and the core aspects of the implementation plan will be discussed. Roadmaps will also be used to show the future direction for the entire focus area. Included in the discussion, will be aspects of the end-to-end nature of the Focus Area that encompass current and potential actives to extend research results to operational agencies to enable improved performance of policy and management decision support systems.

  17. The impact of electrogenic sulfide oxidation on elemental cycling and solute fluxes in coastal sediment

    NASA Astrophysics Data System (ADS)

    Rao, Alexandra M. F.; Malkin, Sairah Y.; Hidalgo-Martinez, Silvia; Meysman, Filip J. R.

    2016-01-01

    Filamentous sulfide oxidizing cable bacteria are capable of linking the oxidation of free sulfide in deep anoxic layers of marine sediments to the reduction of oxygen or nitrate in surface sediments by conducting electrons over centimeter-scale distances. Previous studies have shown that this newly discovered microbial process, referred to as electrogenic sulfide oxidation (e-SOx), may alter elemental cycling in sediments, but the nature and rates of the resulting biogeochemical transformations and their influence on benthic-pelagic coupling remain largely unknown. Here we quantify changes in sediment geochemistry and solute fluxes at the sediment-water interface as e-SOx develops and declines over time in laboratory incubations of organic-rich sediments from a seasonally hypoxic coastal basin (Marine Lake Grevelingen, The Netherlands). Our results show that e-SOx enhanced sediment O2 consumption and acidified subsurface sediment, resulting in the dissolution of calcium carbonate and iron sulfide minerals in deeper sediment horizons and the associated accumulation of dissolved iron, manganese, and calcium in porewater. Remobilized Fe diffusing upward was reoxidized at the sediment-water interface, producing an amorphous Fe oxide crust, while dissolved Fe diffusing downward was reprecipitated in the form of FeS as it encountered the free sulfide horizon. The development of e-SOx enhanced the diffusive release of dissolved Mn at the sediment-water interface, capped the phosphate efflux, generated a buildup of organic matter in surface sediments, and strongly stimulated the release of alkalinity from the sediment. About 75% of this alkalinity production was associated with net CaCO3 dissolution, while the remaining 25% was attributed to a pumping mechanism that transfers alkalinity from anodic H2S oxidation (an alkalinity sink) in deeper sediments to cathodic O2 reduction (an alkalinity source) near the sediment-water interface. The resulting sediment alkalinity efflux buffers the release of dissolved inorganic carbon at the sediment-water interface, and may therefore counteract the influence of benthic respiration on coastal ocean pH. Overall, our results demonstrate that e-SOx development strongly affects the biogeochemical cycles of C, P, Ca, Fe, Mn, and S in coastal sediments.

  18. Land surface water cycles observed with satellite sensors

    NASA Technical Reports Server (NTRS)

    Nghiem, Son V.; Njoku, E. G.; Brakenridge, G. R.; Kim, Y.

    2005-01-01

    Acceleration of the global water cycle may lead to increased global precipitation, faster evaporation and a consequent exacerbation of hydrologic extreme. In the U.S. national assessment of the potential consequences of climate variability and change, two GCMs (CGCM1 and HadCM2) show a large increase in precipitation in the future over the southwestern U.S. particularly during winter (Felzer and Heard, 1999). Increased precipitation potentially has important impacts on agricultural and water use in the southeast U.S. (Hatch et al., 1999) and in the central Great Plains (Nielsen, 1997). A hurricane model predicts a 40% precipitation increase for severe hurricanes affecting southeastern Florida, which provokes substantially greater flooding that could negate most of the benefits of present water-management practices in this basin (Gutowski et al., 1994). Thus, it is important to observe the hydroclimate on a continuous longterm basis to address the question of increased precipitation in the enhanced water cycle.

  19. Geographical features of global water cycle during warm geological epochs

    SciTech Connect

    Georgiadi, A.G.

    1996-12-31

    The impact of global warming on the water cycle can be extremely complex and diverse. The goal of the investigation was to estimate the geographic features of the mean annual water budget of the world during climatic optimums of the Holocene and the Eemian interglacial periods. These geological epochs could be used as analogs of climatic warming on 1 degree, centigrade and 2 degrees, centigrade. The author used the results of climatic reconstructions based on a simplified version of a GCM.

  20. Biotransformations utilizing β-oxidation cycle reactions in the synthesis of natural compounds and medicines.

    PubMed

    Swizdor, Alina; Panek, Anna; Milecka-Tronina, Natalia; Kołek, Teresa

    2012-01-01

    β-Oxidation cycle reactions, which are key stages in the metabolism of fatty acids in eucaryotic cells and in processes with a significant role in the degradation of acids used by microbes as a carbon source, have also found application in biotransformations. One of the major advantages of biotransformations based on the β-oxidation cycle is the possibility to transform a substrate in a series of reactions catalyzed by a number of enzymes. It allows the use of sterols as a substrate base in the production of natural steroid compounds and their analogues. This route also leads to biologically active compounds of therapeutic significance. Transformations of natural substrates via β-oxidation are the core part of the synthetic routes of natural flavors used as food additives. Stereoselectivity of the enzymes catalyzing the stages of dehydrogenation and addition of a water molecule to the double bond also finds application in the synthesis of chiral biologically active compounds, including medicines. Recent advances in genetic, metabolic engineering, methods for the enhancement of bioprocess productivity and the selectivity of target reactions are also described. PMID:23443116

  1. Biotransformations Utilizing β-Oxidation Cycle Reactions in the Synthesis of Natural Compounds and Medicines

    PubMed Central

    Œwizdor, Alina; Panek, Anna; Milecka-Tronina, Natalia; Kołek, Teresa

    2012-01-01

    β-Oxidation cycle reactions, which are key stages in the metabolism of fatty acids in eucaryotic cells and in processes with a significant role in the degradation of acids used by microbes as a carbon source, have also found application in biotransformations. One of the major advantages of biotransformations based on the β-oxidation cycle is the possibility to transform a substrate in a series of reactions catalyzed by a number of enzymes. It allows the use of sterols as a substrate base in the production of natural steroid compounds and their analogues. This route also leads to biologically active compounds of therapeutic significance. Transformations of natural substrates via β-oxidation are the core part of the synthetic routes of natural flavors used as food additives. Stereoselectivity of the enzymes catalyzing the stages of dehydrogenation and addition of a water molecule to the double bond also finds application in the synthesis of chiral biologically active compounds, including medicines. Recent advances in genetic, metabolic engineering, methods for the enhancement of bioprocess productivity and the selectivity of target reactions are also described. PMID:23443116

  2. The effect of widespread early aerobic marine ecosystems on methane cycling and the Great Oxidation

    NASA Astrophysics Data System (ADS)

    Daines, Stuart J.; Lenton, Timothy M.

    2016-01-01

    The balance of evidence suggests that oxygenic photosynthesis had evolved by 3.0-2.7 Ga, several hundred million years prior to the Great Oxidation ≈2.4 Ga. Previous work has shown that if oxygenic photosynthesis spread globally prior to the Great Oxidation, this could have supported widespread aerobic ecosystems in the surface ocean, without oxidising the atmosphere. Here we use a suite of models to explore the implications for carbon cycling and the Great Oxidation. We find that recycling of oxygen and carbon within early aerobic marine ecosystems would have restricted the balanced fluxes of methane and oxygen escaping from the ocean, lowering the atmospheric concentration of methane in the Great Oxidation transition and its aftermath. This in turn would have minimised any bi-stability of atmospheric oxygen, by weakening a stabilising feedback on oxygen from hydrogen escape to space. The result would have been a more reversible and probably episodic rise of oxygen at the Great Oxidation transition, consistent with existing geochemical evidence. The resulting drop in methane levels to ≈10 ppm is consistent with climate cooling at the time but adds to the puzzle of what kept the rest of the Proterozoic warm. A key test of the scenario of abundant methanotrophy in oxygen oases before the Great Oxidation is its predicted effects on the organic carbon isotope (δ13Corg) record. Our open ocean general circulation model predicts δC13org ≈ - 30 to -45‰ consistent with most data from 2.65 to 2.45 Ga. However, values of δC13org ≈ - 50 ‰ require an extreme scenario such as concentrated methanotroph production where shelf-slope upwelling of methane-rich water met oxic shelf water.

  3. Greenlighting photoelectrochemical oxidation of water by iron oxide.

    PubMed

    Kim, Dong Wook; Riha, Shannon C; DeMarco, Erica J; Martinson, Alex B F; Farha, Omar K; Hupp, Joseph T

    2014-12-23

    Hematite (α-Fe2O3) is one of just a few candidate electrode materials that possess all of the following photocatalyst-essential properties for scalable application to water oxidation: excellent stability, earth-abundance, suitability positive valence-band-edge energy, and significant visible light absorptivity. Despite these merits, hematite's modest oxygen evolution reaction kinetics and its poor efficiency in delivering photogenerated holes, especially holes generated by green photons, to the electrode/solution interface, render it ineffective as a practical water-splitting catalyst. Here we show that hole delivery and catalytic utilization can be substantially improved through Ti alloying, provided that the alloyed material is present in ultrathin-thin-film form. Notably, the effects are most pronounced for charges photogenerated by photons with energy comparable to the band gap for excitation of Fe(3d)→Fe(3d) transitions (i.e., green photons). Additionally, at the optimum Ti substitution level the lifetimes of surface-localized holes, competent for water oxidation, are extended. Together these changes explain an overall improvement in photoelectrochemical performance, especially enhanced internal quantum efficiencies, observed upon Ti(IV) incorporation. PMID:25414974

  4. A Seamless Framework for Global Water Cycle Monitoring and Prediction

    NASA Astrophysics Data System (ADS)

    Sheffield, J.; Wood, E. F.; Chaney, N.; Fisher, C. K.; Caylor, K. K.

    2013-12-01

    The Global Earth Observation System of Systems (GEOSS) Water Strategy ('From Observations to Decisions') recognizes that 'water is essential for ensuring food and energy security, for facilitating poverty reduction and health security, and for the maintenance of ecosystems and biodiversity', and that water cycle data and observations are critical for improved water management and water security - especially in less developed regions. The GEOSS Water Strategy has articulated a number of goals for improved water management, including flood and drought preparedness, that include: (i) facilitating the use of Earth Observations for water cycle observations; (ii) facilitating the acquisition, processing, and distribution of data products needed for effective management; (iii) providing expertise, information systems, and datasets to the global, regional, and national water communities. There are several challenges that must be met to advance our capability to provide near real-time water cycle monitoring, early warning of hydrological hazards (floods and droughts) and risk assessment under climate change, regionally and globally. Current approaches to monitoring and predicting hydrological hazards are limited in many parts of the world, and especially in developing countries where national capacity is limited and monitoring networks are inadequate. This presentation describes the development of a seamless monitoring and prediction framework at all time scales that allows for consistent assessment of water variability from historic to current conditions, and from seasonal and decadal predictions to climate change projections. At the center of the framework is an experimental, global water cycle monitoring and seasonal forecast system that has evolved out of regional and continental systems for the US and Africa. The system is based on land surface hydrological modeling that is driven by satellite remote sensing precipitation to predict current hydrological conditions, flood potential and the state of drought. Seasonal climate model forecasts are downscaled and bias-corrected to drive the land surface model to provide hydrological forecasts and drought products out 6-9 months. The system relies on historic reconstructions of water variability over the 20th century, which forms the background climatology to which current conditions can be assessed. Future changes in water availability and drought risk are quantified based on bias-corrected and downscaled climate model projections that are used to drive the land surface models. For regions with lack of on-the-ground data we are field-testing low-cost environmental sensors and along with new satellite products for terrestrial hydrology and vegetation, integrating these into the system for improved monitoring and prediction. We provide an overview of the system and some examples of real-world applications to flood and drought events, with a focus on Africa.

  5. INTRODUCTION: Anticipated changes in the global atmospheric water cycle

    NASA Astrophysics Data System (ADS)

    Allan, Richard P.; Liepert, Beate G.

    2010-06-01

    The atmospheric branch of the water cycle, although containing just a tiny fraction of the Earth's total water reserves, presents a crucial interface between the physical climate (such as large-scale rainfall patterns) and the ecosystems upon which human societies ultimately depend. Because of the central importance of water in the Earth system, the question of how the water cycle is changing, and how it may alter in future as a result of anthropogenic changes, present one of the greatest challenges of this century. The recent Intergovernmental Panel on Climate Change report on Climate Change and Water (Bates et al 2008) highlighted the increasingly strong evidence of change in the global water cycle and associated environmental consequences. It is of critical importance to climate prediction and adaptation strategies that key processes in the atmospheric water cycle are precisely understood and determined, from evaporation at the surface of the ocean, transport by the atmosphere, condensation as cloud and eventual precipitation, and run-off through rivers following interaction with the land surface, sub-surface, ice, snow and vegetation. The purpose of this special focus issue of Environmental Research Letters on anticipated changes in the global atmospheric water cycle is to consolidate the recent substantial advances in understanding past, present and future changes in the global water cycle through evidence built upon theoretical understanding, backed up by observations and borne out by climate model simulations. Thermodynamic rises in water vapour provide a central constraint, as discussed in a guest editorial by Bengtsson (2010). Theoretical implications of the Clausius-Clapeyron equation are presented by O'Gorman and Muller (2010) and with reference to a simple model (Sherwood 2010) while observed humidity changes confirm these anticipated responses at the land and ocean surface (Willett et al 2008). Rises in low-level moisture are thought to fuel an intensification of precipitation (O'Gorman and Schneider 2009) and analysis of observed and simulated changes in extreme rainfall for Europe (Lenderink and van Mijgaard 2008) and over tropical oceans by Allan et al (2010) appear to corroborate this. Radiative absorption by water vapour (Previdi 2010, Stephens and Ellis 2008) also provides a thermodynamic feedback on the water cycle, and explains why climate model projections of global precipitation and evaporation of around 1-3% K-1 are muted with respect to the expected 7% K-1 increases in low-level moisture. Climate models achieve dynamical responses through reductions in strength of the Walker circulation (Vecchi et al 2006) and small yet systematic changes in the atmospheric boundary layer over the ocean that modify evaporation (Richter and Xie 2008). A further consequence is anticipated sub-tropical drying (Neelin et al 2006, Chou et al 2007); Allan et al (2010) confirm a decline in dry sub-tropical precipitation while the wet regions become wetter both in model simulations and satellite-based observations. Discrepancies between observed and climate model simulated hydrological response to warming (Wentz et al 2007, Yu and Weller 2007) are of immediate concern in understanding and predicting future responses. Over decadal time-scales it is important to establish whether such discrepancies relate to the observing system, climate modeling deficiencies, or are a statistical artifact of the brevity of the satellite records (Liepert and Previdi 2009). Techniques for extracting information on century-scale changes in precipitation are emerging (Smith et al 2009) but are also subject to severe limitations. Past decadal-scale changes in the water cycle may be further influenced by regionally and temporally varying forcings and resulting feedbacks which must be represented realistically by models (Andrews et al 2009). The radiative impact of aerosols and their indirect effects on clouds and precipitation (Liepert et al 2004) provide an important example. Understanding surface solar 'dimming' and 'brightening' trends in the context of past and current changes in the water cycle are discussed in a guest editorial by Wild and Liepert (2010). The key roles anthropogenic aerosols can play on a regional scale are discussed by Lau et al (2010) through their study of the regional impact of absorbing aerosols on warming and snow melt over the Himalayas. The overarching goal of climate prediction is to provide reliable, probabilistic estimates of future changes. Relating hydrological responses back to a sound physical basis, the motivation for this special focus issue, is paramount in building confidence in anticipated changes, especially in the global water cycle. We are grateful to the reviewers and the journal editorial board for making this focus issue possible. Focus on Anticipated Changes in the Global Atmospheric Water Cycle Contents Editorials The global atmospheric water cycle Lennart Bengtsson The Earth radiation balance as driver of the global hydrological cycle Martin Wild and Beate Liepert Letters Enhanced surface warming and accelerated snow melt in the Himalayas and Tibetan Plateau induced by absorbing aerosols William K M Lau, Maeng-Ki Kim, Kyu-Myong Kim and Woo-Seop Lee Current changes in tropical precipitation Richard P Allan, Brian J Soden, Viju O John, William Ingram and Peter Good Direct versus indirect effects of tropospheric humidity changes on the hydrologic cycle S C Sherwood How closely do changes in surface and column water vapor follow Clausius-Clapeyron scaling in climate change simulations? P A O'Gorman and C J Muller Linking increases in hourly precipitation extremes to atmospheric temperature and moisture changes Geert Lenderink and Erik van Meijgaard Are climate-related changes to the character of global-mean precipitation predictable? Graeme L Stephens and Yongxiang Hu A comparison of large scale changes in surface humidity over land in observations and CMIP3 general circulation models Katharine M Willett, Philip D Jones, Peter W Thorne and Nathan P Gillett Radiative feedbacks on global precipitation Michael Previdi The transient response of global-mean precipitation to increasing carbon dioxide levels Timothy Andrews and Piers M Forster The observed sensitivity of the global hydrological cycle to changes in surface temperature Phillip A Arkin, Thomas M Smith, Mathew R P Sapiano and John Janowiak Precipitation changes within dynamical regimes in a perturbed climate Jonny Williams and Mark A Ringer

  6. PHOTOREACTIONS IN SURFACE WATERS AND THEIR ROLE IN BIOGEOCHEMICAL CYCLES

    EPA Science Inventory

    During the past decade significant interest has developed in the influence of photochemical reactions on biogeochemical cycles in surface waters of lakes and the sea. A major portion of recent research on these photoreactions has focused on the colored component of dissolved org...

  7. Multimodal Science Teachers' Discourse in Modeling the Water Cycle

    ERIC Educational Resources Information Center

    Marquez, Conxita; Izquierdo, Merce; Espinet, Mariona

    2006-01-01

    The paper presents an intensive study of a micro-event aiming at the characterization of teacher's discourse from a multimodal communication perspective in a secondary school science classroom dealing with the topic of "water cycle." The research addresses the following questions: (a) What communicative modes are used by the teacher?, (b) what

  8. Multimodal Science Teachers' Discourse in Modeling the Water Cycle

    ERIC Educational Resources Information Center

    Marquez, Conxita; Izquierdo, Merce; Espinet, Mariona

    2006-01-01

    The paper presents an intensive study of a micro-event aiming at the characterization of teacher's discourse from a multimodal communication perspective in a secondary school science classroom dealing with the topic of "water cycle." The research addresses the following questions: (a) What communicative modes are used by the teacher?, (b) what…

  9. Membranes and the water cycle: challenges and opportunities

    NASA Astrophysics Data System (ADS)

    Fane, A. G.

    2011-09-01

    Membrane technology for the water cycle has been around for about 50 years and is taking an increasingly important role in the provision of safe water supply and treatment and reuse of wastewater. It is timely to examine the challenges and the future of the technology. The challenges are both technical and socio-political and they provide the drivers for new developments. This paper summarizes the status of membranes in the water industry and discusses the major challenges and possible responses that will determine the possible futures.

  10. Potential for Observing the Global Water Cycle from Space

    NASA Astrophysics Data System (ADS)

    Lettenmaier, D. P.

    2003-12-01

    The fundamental challenge in observing the global water cycle is to understand where the water is, and where it is moving. Of course, the answer to the "where is it?" question is "mostly in the oceans and ice sheets", but when one considers relative mobility, the focus becomes somewhat different. From the standpoint of the land surface, moisture stored in the atmosphere, and especially that released from the atmosphere as precipitation and returned to it as evapotranspiration, are the largest fluxes over most of the globe. Runoff and streamflow, although usually a somewhat smaller fraction of precipitation than ET, are critically important, as they are the source of or contribute directly to much of the water available for human use. Water stored in the subsurface, especially as soil moisture, controls vegetation moisture stress, and hence ET under many conditions. Soil moisture "antecedent conditions" are well known to affect storm runoff production as well. Furthermore, groundwater and variations therein are important both for human use, and through interactions with soil moisture and streamflow, depending on the particular conditions. Current estimates of the terms in the global water cycle are based primarily on in situ observations. For instance, over land, most estimates of precipitation are primarily gage-based. The same is true of streamflow. ET is measured directly only at a relatively small number of sites; large area estimates are primarily based either on the difference between precipitation and runoff (ignoring storage change in the long-term mean) or atmospheric budget analyses. Soil moisture, groundwater, and snow storage (except glaciers) are generally not well enough measured to provide quantitative estimates, except through use of models. Of the major terms on the land surface branch of the global water cycle, most terms (precipitation, streamflow, soil moisture, and snow water storage) are more or less directly observable from space, albeit at different (and sometimes incompatible) time and space scales. ET is observable only somewhat indirectly, as is groundwater storage. Space-based observation of many, if not most, terms in the global water cycle has considerable advantages, and poses a number of challenges as well. A major advantage of space-based observation is the potential for a truly global observing strategy, free from logistical complications of in situ observations. On the other hand, some terms are not easily observable, if at all. The potential and challenges of a true space-based global water cycle observing system are discussed, with particular focus on the land surface, but considering other aspects of global moisture storage and flux as well.

  11. Enhanced Oxidation Catalysts for Water Reclamation

    NASA Technical Reports Server (NTRS)

    Jolly, Clifford D.

    1999-01-01

    This effort seeks to develop and test high-performance, long operating life, physically stable catalysts for use in spacecraft water reclamation systems. The primary goals are to a) reduce the quantity of expendable water filters used to purify water aboard spacecraft, b) to extend the life of the oxidation catalysts used for eliminating organic contaminants in the water reclamation systems, and c) reduce the weight/volume of the catalytic oxidation systems (e.g. VRA) used. This effort is targeted toward later space station utilization and will consist of developing flight-qualifiable catalysts and long-term ground tests of the catalyst prior to their utilization in flight. Fixed -bed catalytic reactors containing 5% platinum on granular activated carbon have been subjected to long-term dynamic column tests to measure catalyst stability vs throughput. The data generated so far indicate that an order of magnitude improvement can be obtained with the treated catalysts vs the control catalyst, at only a minor loss (approx 10%) in the initial catalytic activity.

  12. Projections of Water-Cycle Change: Uncertainty and Utility.

    NASA Astrophysics Data System (ADS)

    Gutowski, W. J.

    2012-12-01

    Climate models have proven to be invaluable tools to developing scenarios of possible future water resources. However, hydrologic simulation involves complex interactions among many processes, including precipitation, evapotranspiration, infiltration, freezing, and thawing, among others. Furthermore, the modeling of these processes and their interactions remains imperfect. Nonetheless, despite these challenges, some broad features of future water availability have emerged consistently across generations of climate models and future scenarios. One can understand these features on the basis of some fairly simple physical principles, but is this understanding useful? Is the climate community producing the information needed to address future water needs by a growing population? This talk will present perspectives on global and regional water cycles seen in ensemble simulation programs such as the Coupled Model Intercomparison Program (CMIP) for global models and the North American Regional Climate Change Assessment Program (NARCCAP) for regional models. The talk will consider global and regional models as sources of consistency and differences in their projections of climate change, through their representation of physical processes in the water cycle. The talk will also consider how water utilities previously have used climate information and what requirements this imposes on climate simulation. Finally, the talk will explore the question of how well typical diagnoses evaluate climate simulations on the basis of water resource needs, especially those for formulating management, planning and policy decisions.

  13. Use of Copper Oxide Nanoparticles for the Oxidative Degradation of Persistent Organic Water Pollutants

    NASA Astrophysics Data System (ADS)

    Dror, I.; Ben Moshe, T.; Berkowitz, B.

    2008-12-01

    The continuous release of persistent organic chemicals such as pesticides, halogenated organic solvents, PAHs, and PCBs to the subsurface environment is an unfortunate reality. These compounds are recognized as toxic, and often carcinogenic and/or mutagenic, and they thus require highly efficient treatment procedures in aqueous systems. The current study presents an oxidation process, to decontaminate polluted water, using nanosized copper oxide particles as the catalyst and hydrogen peroxide as the oxidation agent. The process shows complete and rapid degradation of a wide range of organic contaminants under ambient pressure and temperature. In contrast, control runs that measured the degradation through exposure to hydrogen peroxide only or copper oxide nanoparticles only showed less than 10% reduction in contaminant concentration, as compared to the complete degradation achieved when particles and oxidation agent were used. Lack of exposure to light and the method of mixing seem to have no influence on the reaction rate or products. The reaction was found to proceed effectively in the range pH 3-8.5, and much slower at pH 10. Testing various concentrations of oxidation agent, an optimum point was found, with an increase above this concentration resulting in a reduced reaction rate. Moreover, measurements of reaction kinetics demonstrated a conversion from exponential decay of a contaminant, typical of a first-order reaction, to a linear decrease in contaminant concentration which is typical of a pseudo-zero-order reaction. This behavior indicates that upon increase in oxidation agent concentration, a different reaction pathway which is independent of the contaminant concentration becomes the prevailing process. The copper oxide nanoparticles were characterized before and after the reaction, and also shown to retain reactivity for several cycles after refreshing the contaminant solution and adding more hydrogen peroxide.

  14. Water oxidation reaction in natural and artificial photosynthetic systems

    SciTech Connect

    Yano, Junko; Yachandra, Vittal

    2013-12-10

    Understanding the structure and mechanism of water oxidation catalysts is an essential component for developing artificial photosynthetic devices. In the natural water oxidation catalyst, the geometric and electronic structure of its inorganic core, the Mn{sub 4}CaO{sub 5} cluster, has been studied by spectroscopic and diffraction measurements. In inorganic systems, metal oxides seem to be good candidates for water oxidation catalysts. Understanding the reaction mechanism in both natural and oxide-based catalysts will helpin further developing efficient and robust water oxidation catalysts.

  15. Is Blood Lactate Removal During Water Immersed Cycling Faster than During Cycling on Land?

    PubMed Central

    Masi, Fabrízio Di; De Souza Vale, Rodrigo Gomes; Dantas, Estélio Henrique Martin; Barreto, Ana Cristina Lopes; Novaes, Jefferson da Silva; Reis, Victor M.

    2007-01-01

    The aim of the present study was to compare lactate removal during active recovery performed during cycling in water immersion (CW) and during cycling on land (CL), after a similar exercise bout in male adults. Eleven healthy and physically active men, aged between 20 and 26 years old participated in the experiment. Before the experimental tests, the ventilatory threshold of the subjects was determined. Each subject completed the experimental tests twice, with one week separating the two periods of experiment. The subjects exercised on the treadmill during 6 min at a speed 10% above the speed corresponding to their ventilatory threshold. Subsequently, the subjects recovered from the exercise bout either on a stationary bike (CL) or on a aquatic-specific bike (CW). On the subsequent week the subjects performed the same protocol but with a different recovery condition. Recovery condition assignment for the first test was counterbalanced (six subjects started with one condition and five with the other). Capillary blood samples were collected after each test and during the recovery period (at 3, 6, 9 and 15 minutes) and blood lactate was measured. The blood lactate values during CW were lower than during CL and significant differences were observed at the 6th minute (p ≤ 0.05) and at the 15th minute of recovery (p ≤ 0.05). Therefore, we may conclude that active recovery using cycling in water immersion may be more efficient than cycling on land for blood lactate removal. Key pointsPrevious studies have found positive effects of half liquid environment on blood lactate removal.However, few studies have compared lactate removal in half liquid and in dry land conditions with the use of stationary bikes.We have compared the lactate removal during active recovery on half-liquid cycling and active recovery on dry land cycling after a similar exercise bout in male adults.The blood lactate values during the recovery were lower after half-liquid cycling when compared with dry land cycling and significant differences were observed at the 6th minute and at the 15th minute of recovery.We may conclude that active recovery using half-liquid cycling may be more efficient than dry land cycling for blood lactate removal. PMID:24149328

  16. Intense nitrogen cycling in permeable intertidal sediment revealed by a nitrous oxide hot spot

    NASA Astrophysics Data System (ADS)

    Schutte, Charles A.; Joye, Samantha B.; Wilson, Alicia M.; Evans, Tyler; Moore, Willard S.; Casciotti, Karen

    2015-10-01

    Approximately 40% of the total global rate of nitrogen fixation is the result of human activities, and most of this anthropogenic nitrogen is used to fertilize agricultural fields. Approximately 23% of the applied agricultural nitrogen is delivered to the coastal zone, often reducing water quality and driving eutrophication. Nitrogen cycling in coastal sediments can mitigate eutrophication by removing bioavailable nitrogen. However, some of these processes generate nitrous oxide, a potent greenhouse gas, as a by-product. Here we report the discovery of a nitrous oxide production hot spot in shallow barrier island sands. Nitrous oxide concentrations, production and consumption rates, vertical diffusion fluxes, and flux to the atmosphere were measured across triplicate depth profiles. Using a mass balance approach, rates of net nitrous oxide production were estimated to be 40 µmol m-2 d-1. This production was driven by a hot spot of nitrate consumption that removed bioavailable nitrogen from the coastal environment at a rate of 10 mmol m-2 d-1, a rate that is comparable with the highest rates of denitrification reported for coastal sediments.

  17. Solar Cycle comparison of Nitric Oxide in the lower thermosphere

    NASA Astrophysics Data System (ADS)

    Carstens, P. L.; Bailey, S. M.; Thurairajah, B.; Yonker, J. D.; Venkataramani, K.; Russell, J. M.; Hervig, M. E.

    2013-12-01

    Nitric oxide (NO) is a key minor constituent in the lower thermosphere. Of particular importance is its role in the energy balance in that altitude region. NO is produced through the reaction of excited atomic nitrogen with molecular oxygen. Thus, its production is very sensitive to those energy sources able to break the strong molecular nitrogen bond. These include solar soft X-rays and precipitating energetic particles. NO emits efficiently in the infrared and is an important cooling mechanism in the lower thermosphere. The abundance of NO is thus both a direct response to recent energy deposition as well as a key mechanism by which the upper atmosphere releases that energy. The concentration of NO should show a close relation to solar energy input. In this poster, we analyze the NO observations from the Solar Occultation for Ice Experiment (SOFIE) instrument. The SOFIE instrument was launched on-board the Aeronomy of Ice in the Mesosphere (AIM) satellite on April 25, 2007. It is currently in its sixth year of operation. SOFIE is a 16 channel differential absorption radiometer using the solar occultation technique to measure ice and environmental properties at a range of altitudes, and in particular the mesopause region. One of the constituents measured by SOFIE is NO in the mesosphere and lower thermosphere to about 130 km. The AIM orbit and the solar occultation technique confine observations to latitudes of 65 to 85 degrees in each hemisphere and varying with season. Here, we present the SOFIE observations and discuss its relationship with current levels of solar X-ray irradiance. We will further estimate the change in NO concentration (mixing ratios and densities) for the previous and current solar minimum. The statistics for this change will be presented for northern, equatorial and southern latitudes. We take the period of Jul 2008 - Jun 2009 to represent the current solar minimum between the solar cycles 23 and 24 and the period of Jan - Dec 1996 to represent the previous solar minimum between the solar cycles 22 and 23 following Jian et al 2010. We will use the data from HALOE (Halogen Occultation Experiment instrument), ACE (Atmospheric Chemistry Experiment) and SOFIE for our analysis. We will also discuss the factors influencing the changes seen in our analysis. We show no significant change in the concentration of NO at the equator, but a significant change at higher latitudes.

  18. Increasing water cycle extremes in California and in relation to ENSO cycle under global warming

    NASA Astrophysics Data System (ADS)

    Yoon, Jin-Ho; Wang, S.-Y. Simon; Gillies, Robert R.; Kravitz, Ben; Hipps, Lawrence; Rasch, Philip J.

    2015-10-01

    Since the winter of 2013-2014, California has experienced its most severe drought in recorded history, causing statewide water stress, severe economic loss and an extraordinary increase in wildfires. Identifying the effects of global warming on regional water cycle extremes, such as the ongoing drought in California, remains a challenge. Here we analyse large-ensemble and multi-model simulations that project the future of water cycle extremes in California as well as to understand those associations that pertain to changing climate oscillations under global warming. Both intense drought and excessive flooding are projected to increase by at least 50% towards the end of the twenty-first century; this projected increase in water cycle extremes is associated with a strengthened relation to El Niño and the Southern Oscillation (ENSO)--in particular, extreme El Niño and La Niña events that modulate California's climate not only through its warm and cold phases but also its precursor patterns.

  19. Increasing water cycle extremes in California and in relation to ENSO cycle under global warming.

    PubMed

    Yoon, Jin-Ho; Wang, S-Y Simon; Gillies, Robert R; Kravitz, Ben; Hipps, Lawrence; Rasch, Philip J

    2015-01-01

    Since the winter of 2013-2014, California has experienced its most severe drought in recorded history, causing statewide water stress, severe economic loss and an extraordinary increase in wildfires. Identifying the effects of global warming on regional water cycle extremes, such as the ongoing drought in California, remains a challenge. Here we analyse large-ensemble and multi-model simulations that project the future of water cycle extremes in California as well as to understand those associations that pertain to changing climate oscillations under global warming. Both intense drought and excessive flooding are projected to increase by at least 50% towards the end of the twenty-first century; this projected increase in water cycle extremes is associated with a strengthened relation to El Niño and the Southern Oscillation (ENSO)--in particular, extreme El Niño and La Niña events that modulate California's climate not only through its warm and cold phases but also its precursor patterns. PMID:26487088

  20. Increasing water cycle extremes in California and in relation to ENSO cycle under global warming

    PubMed Central

    Yoon, Jin-Ho; Wang, S-Y Simon; Gillies, Robert R.; Kravitz, Ben; Hipps, Lawrence; Rasch, Philip J.

    2015-01-01

    Since the winter of 2013–2014, California has experienced its most severe drought in recorded history, causing statewide water stress, severe economic loss and an extraordinary increase in wildfires. Identifying the effects of global warming on regional water cycle extremes, such as the ongoing drought in California, remains a challenge. Here we analyse large-ensemble and multi-model simulations that project the future of water cycle extremes in California as well as to understand those associations that pertain to changing climate oscillations under global warming. Both intense drought and excessive flooding are projected to increase by at least 50% towards the end of the twenty-first century; this projected increase in water cycle extremes is associated with a strengthened relation to El Niño and the Southern Oscillation (ENSO)—in particular, extreme El Niño and La Niña events that modulate California's climate not only through its warm and cold phases but also its precursor patterns. PMID:26487088

  1. The effects of deep water cycling on planetary thermal evolution

    NASA Astrophysics Data System (ADS)

    Sandu, Constantin; Lenardic, Adrian; McGovern, Patrick

    2011-12-01

    We use a parameterized convection model to investigate the effects of deep water cycling on the thermal evolution of an Earth-like planet. The model incorporates two water reservoirs, a surface and an interior mantle reservoir. Exchange between the two is calculated using a mantle convection parameterization that allows for temperature- and water-dependent mantle viscosity together with internally self-consistent degassing and regassing parameterizations. The balance between degassing and regassing depends on the average spreading rate of tectonic plates, the amount of water partitioned into melt, the thickness of a mantle melt zone, and of a hydrated layer at the top of subducting plates. Degassing scales with melt zone thickness such that an early period of extensive melting would create a drier and more viscous mantle, shifting the solidus line in a direction that would reduce the melt zone thickness and the rate of mantle heat loss. Coupling a hydrated zone thickness-dependent regassing factor to the model, to mimic water delivery to the mantle via a serpentinized layer, allows for the potential of a reversing point where the overall water flow direction switches from degassing to regassing as the mantle cools. The water effect on viscosity creates a negative feedback that tends to regulate the final amount of water in the mantle so it is not strongly dependent on the initial amount of planetary water. The final amount of water in the surface reservoir is then determined by this feedback effect together with the initial water budget of the entire planet. This implies that if the initial water budget of a planet can be estimated, from planetary formation models, then the volume of surface water can be used to estimate the volume of water in the mantle of an Earth-like planet. Applying this methodology to the Earth leads to predictions for water concentration in the Earth's mantle that are in line with geochemical and petrological constraints.

  2. Effects of land use change and water reuse options on urban water cycle.

    PubMed

    Lee, Jiho; Pak, Gijung; Yoo, Chulsang; Kim, Sangdan; Yoon, Jaeyoung

    2010-01-01

    The aim of this article was to study the effects of land use change and water reuse options on an urban water cycle. A water cycle analysis was performed on the Goonja drainage basin, located in metropolitan Seoul, using the Aquacycle model. The chronological effects of urbanization were first assessed for the land uses of the Goonja drainage basin from 1975 to 2005, where the ratio of impervious areas ranged from 43% to 84%. Progressive urbanization was identified as leading to a decrease in evapotranspiration (29%), an increase in surface runoff (41%) and a decrease in groundwater recharge (74%), indicating a serious distortion of the water cycle. From a subsequent analysis of the water reuse options, such as rainwater use and wastewater reuse, it is concluded that wastewater reuse seemed to have an advantage over rainwater use for providing a consistent water supply throughout the year for a country like Korea, where the rainy season is concentrated during the summer monsoon. PMID:20923107

  3. Changes in continental Europe water cycle in a changing climate

    NASA Astrophysics Data System (ADS)

    Rouholahnejad, Elham; Schirmer, Mario; Abbaspour, Karim

    2015-04-01

    Changes in atmospheric water vapor content provide strong evidence that the water cycle is already responding to a warming climate. According to IPCC's last report on Climate Change (AR5), the water cycle is expected to intensify in a warmer climate as the atmosphere can hold more water vapor. This changes the frequency of precipitation extremes, increases evaporation and dry periods, and effects the water redistribution in land. This process is represented by most global climate models (GCMs) by increased summer dryness and winter wetness over large areas of continental mid to high latitudes in the Northern Hemisphere, associated with a reduction in water availability at continental scale. Observing changes in precipitation and evaporation directly and at continental scale is difficult, because most of the exchange of fresh water between the atmosphere and the surface happens the oceans. Long term precipitation records are available only from over the land and there are no measurement of evaporation or redistribution of precipitation over the land area. On the other hand, understanding the extent of climate change effects on various components of the water cycle is of strategic importance for public, private sectors, and policy makers when it comes to fresh water management. In order to better understand the extent of climate change impacts on water resources of continental Europe, we developed a distributed hydrological model of Europe at high spatial and temporal resolution using the Soil and Water Assessment Tool (SWAT). The hydrological model was calibrated for 1970 to 2006 using daily observation of streamflow and nitrate loads from 360 gauging stations across Europe. A vegetation growth routine was added to the model to better simulate evapotranspiration. The model results were calibrated with available agricultural crop yield data from other sources. As of future climate scenarios, we used the ISI-MIP project results which provides bias-corrected climate data from the GCMs participating in the CMIP5 at 0.5° x 0.5° resolution. Data cover the time period from 1901 to 2099, i.e. the historical period, and future projections for all Representative Concentration Pathways (RCP2.6, RCP 4.5, RCP 6.0, and RCP 8.5). We used four different models output (GFDL, HADGEMES, MIROC, and IPSL) for all RCPs for near (2006-2035) and far (3065-2099) future. Multi-model ensembles (16 scenarios) are then used to study the potential impacts of future climate change on fresh water availability across Europe.

  4. Supercritical water oxidation of products of human metabolism

    NASA Technical Reports Server (NTRS)

    Tester, Jefferson W.; Orge A. achelling, Richard K. ADTHOMASSON; Orge A. achelling, Richard K. ADTHOMASSON

    1986-01-01

    Although the efficient destruction of organic material was demonstrated in the supercritical water oxidation process, the reaction kinetics and mechanisms are unknown. The kinetics and mechanisms of carbon monoxide and ammonia oxidation in and reaction with supercritical water were studied experimentally. Experimental oxidation of urine and feces in a microprocessor controlled system was performed. A minaturized supercritical water oxidation process for space applications was design, including preliminary mass and energy balances, power, space and weight requirements.

  5. Water Cycling in the North Polar Region of Mars

    NASA Technical Reports Server (NTRS)

    Tamppari, L. K.; Smith, M. D.; Bass, D. S.

    2003-01-01

    To date, there has been no comprehensive study to understand the partitioning of water into vapor and ice clouds, and the associated effects of dust and surface temperature in the north polar region. Ascertaining the degree to which water is transported out of the cap region versus within the cap region will give much needed insight into the overall story of water cycling on a seasonal basis. In particular, understanding the mechanism for the polar cap surface albedo changes would go along way in comprehending the sources and sinks of water in the northern polar region. We approach this problem by examining Thermal Emission Spectrometer (TES) atmospheric and surface data acquired in the northern summer season and comparing it to Viking data when possible. Because the TES instrument spans the absorption bands of water vapor, water ice, dust, and measures surface temperature, all three aerosols and surface temperature can be retrieved simultaneously. This presentation will show our latest results on the water vapor, water-ice clouds seasonal and spatial distributions, as well as surface temperatures and dust distribution which may lend insight into where the water is going.

  6. Diurnal Cycles in Water Quality Across the Periodic Table

    NASA Astrophysics Data System (ADS)

    Kirchner, J. W.

    2013-12-01

    Diurnal cycles in water quality can provide important clues to the processes that regulate aquatic chemistry, but they often are masked by longer-term, larger-amplitude variability, making their detection and quantification difficult. Here I outline several methods that can detect diurnal cycles even when they are massively obscured by statistically ill-behaved noise. I demonstrate these methods using high-frequency water quality data from the Plylimon catchment in mid-Wales (Neal et al., 2013; Kirchner and Neal, 2013). Several aspects combine to make the Plynlimon data set unique worldwide. Collected at 7-hour intervals, the Plynlimon data set is much more densely sampled than typical long-term weekly or monthly water quality data. This 7-hour sampling was also continued for two years, much longer than typical intensive sampling campaigns, and the resulting time series encompass a wide range of climatic and hydrological conditions. Furthermore, each sample was analyzed for a wide range of solutes with diverse sources in the natural environment. However, the 7-hour sampling frequency is both coarse and irregular in comparison to diurnal cycles, making their detection and quantification difficult. Nonetheless, the methods outlined here enable detection of statistically significant diurnal cycles in over 30 solutes at Plynlimon, including alkali metals (Li, Na, K, Rb, and Cs), alkaline earths (Be, Mg, Ca, Sr, and Ba), transition metals (Al, Ti, Mn, Fe, Co, Ni, Zn, Mo, Cd, and Pb), nonmetals (B, NO3, Si, As, and Se), lanthanides and actinides (La, Ce, Pr, and U), as well as total dissolved nitrogen (TDN), dissolved organic carbon (DOC), Gran alkalinity, pH, and electrical conductivity. These solutes span every row of the periodic table, and more than six orders of magnitude in concentration. Many of these diurnal cycles are subtle, representing only a few percent, at most, of the total variance in the concentration time series. Nonetheless they are diagnostically useful, because their amplitude and phase contain important clues to the mechanisms controlling these solutes in streamwater. Examples of these cycles and their likely origins will be discussed. Neal, C., B. Reynolds, J. W. Kirchner, P. Rowland, D. Norris, D. Sleep, A. Lawlor, C. Woods, S. Thacker, H. Guyatt, C. Vincent, K. Lehto, S. Grant, J. Williams, M. Neal, H. Wickham, S. Harman, and L. Armstrong. 2013. High-frequency precipitation and stream water quality time series from Plynlimon, Wales: an openly accessible data resource spanning the periodic table. Hydrological Processes 27:2531-2539. Kirchner, J. W., and C. Neal. 2013. Universal fractal scaling in stream chemistry and its implications for solute transport and water quality trend detection. Proceedings of the National Academy of Sciences of the United States of America 110:12213-12218.

  7. Enhancing water cycle measurements for future hydrologic research

    USGS Publications Warehouse

    Loescher, H.W.; Jacobs, J.M.; Wendroth, O.; Robinson, D.A.; Poulos, G.S.; McGuire, K.; Reed, P.; Mohanty, B.P.; Shanley, J.B.; Krajewski, W.

    2007-01-01

    The Consortium of Universities for the Advancement of Hydrologic Sciences, Inc., established the Hydrologic Measurement Facility to transform watershed-scale hydrologic research by facilitating access to advanced instrumentation and expertise that would not otherwise be available to individual investigators. We outline a committee-based process that determined which suites of instrumentation best fit the needs of the hydrological science community and a proposed mechanism for the governance and distribution of these sensors. Here, we also focus on how these proposed suites of instrumentation can be used to address key scientific challenges, including scaling water cycle science in time and space, broadening the scope of individual subdisciplines of water cycle science, and developing mechanistic linkages among these subdisciplines and spatio-temporal scales. ?? 2007 American Meteorological Society.

  8. Solar Metal Sulfate-Ammonia Based Thermochemical Water Splitting Cycle for Hydrogen Production

    NASA Technical Reports Server (NTRS)

    Huang, Cunping (Inventor); T-Raissi, Ali (Inventor); Muradov, Nazim (Inventor)

    2014-01-01

    Two classes of hybrid/thermochemical water splitting processes for the production of hydrogen and oxygen have been proposed based on (1) metal sulfate-ammonia cycles (2) metal pyrosulfate-ammonia cycles. Methods and systems for a metal sulfate MSO.sub.4--NH3 cycle for producing H2 and O2 from a closed system including feeding an aqueous (NH3)(4)SO3 solution into a photoctalytic reactor to oxidize the aqueous (NH3)(4)SO3 into aqueous (NH3)(2)SO4 and reduce water to hydrogen, mixing the resulting aqueous (NH3)(2)SO4 with metal oxide (e.g. ZnO) to form a slurry, heating the slurry of aqueous (NH4)(2)SO4 and ZnO(s) in the low temperature reactor to produce a gaseous mixture of NH3 and H2O and solid ZnSO4(s), heating solid ZnSO4 at a high temperature reactor to produce a gaseous mixture of SO2 and O2 and solid product ZnO, mixing the gaseous mixture of SO2 and O2 with an NH3 and H2O stream in an absorber to form aqueous (NH4)(2)SO3 solution and separate O2 for aqueous solution, recycling the resultant solution back to the photoreactor and sending ZnO to mix with aqueous (NH4)(2)SO4 solution to close the water splitting cycle wherein gaseous H2 and O2 are the only products output from the closed ZnSO4--NH3 cycle.

  9. Water cycles in closed ecological systems: effects of atmospheric pressure

    NASA Technical Reports Server (NTRS)

    Rygalov, Vadim Y.; Fowler, Philip A.; Metz, Joannah M.; Wheeler, Raymond M.; Bucklin, Ray A.; Sager, J. C. (Principal Investigator)

    2002-01-01

    In bioregenerative life support systems that use plants to generate food and oxygen, the largest mass flux between the plants and their surrounding environment will be water. This water cycle is a consequence of the continuous change of state (evaporation-condensation) from liquid to gas through the process of transpiration and the need to transfer heat (cool) and dehumidify the plant growth chamber. Evapotranspiration rates for full plant canopies can range from 1 to 10 L m-2 d-1 (1 to 10 mm m-2 d-1), with the rates depending primarily on the vapor pressure deficit (VPD) between the leaves and the air inside the plant growth chamber. VPD in turn is dependent on the air temperature, leaf temperature, and current value of relative humidity (RH). Concepts for developing closed plant growth systems, such as greenhouses for Mars, have been discussed for many years and the feasibility of such systems will depend on the overall system costs and reliability. One approach for reducing system costs would be to reduce the operating pressure within the greenhouse to reduce structural mass and gas leakage. But managing plant growth environments at low pressures (e.g., controlling humidity and heat exchange) may be difficult, and the effects of low-pressure environments on plant growth and system water cycling need further study. We present experimental evidence to show that water saturation pressures in air under isothermal conditions are only slightly affected by total pressure, but the overall water flux from evaporating surfaces can increase as pressure decreases. Mathematical models describing these observations are presented, along with discussion of the importance for considering "water cycles" in closed bioregenerative life support systems.

  10. Effects of the Fabrication Process and Thermal Cycling on the Oxidation of Zirconium-Niobium Pressure Tubes

    NASA Astrophysics Data System (ADS)

    Nam, Cheol

    2009-12-01

    Pressure tubes made of Zr-2.5%Nb alloy are used to contain fuels and coolant in CANDU nuclear power reactors The pressure tube oxidizes during reactor operation and hydrogen ingress through the oxide grown on the tube limits its lifetime. Little attention was paid to the intermediate tube manufacturing processes in enhancing the oxidation resistance. In addition, the oxide grown on the tube experiences various thermal cycles depending on the reactor shutdown and startup cycles. To address these two aspects and to better understand the oxidation process of the Zr-2.5Nb tube, research was conducted in two parts: (i) effects of tube fabrication on oxidation behavior, and (ii) thermal cycling behaviors of oxides grown on a pressure tube. In the first part, the optimum manufacturing process was pursued to improve the corrosion resistance of Zr-2.5Nb tubes. Experimental micro-tubes were fabricated with various manufacturing routes in the stages of billet preparation, hot extrusion and cold drawing. These were oxidized in air at 400°C and 500°C, and in an autoclave at 360°C lithiated water. Microstructure and texture of the tubes and oxides were characterized with X-ray diffraction, scanning electron microscope and optical microscope. Special emphasis was given to examinations of the metal/oxide interface structures. A correlation between the manufacturing process and oxidation resistance was investigated in terms of tube microstructure and the metal/oxide interface structure. As a result, it was consistently observed that uniform interface structures were formed on the tubes which had a fine distribution of secondary phases. These microstructures were found to be beneficial in enhancing the oxidation resistance as opposed to the tubes that had coarse and continuous beta-Zr phases. Based on these observations, a schematic model of the oxidation process was proposed with respect to the oxidation resistance under oxidizing temperatures of 360°C, 400°C and 500°C. In the second part, the oxides grown on a standard Zr-2.5Nb pressure tube were analyzed by X-ray diffraction peak broadening and line shift. Crystallite size, t-ZrO2 fraction and residual stress of the zirconium oxides were investigated upon several thermal cycles at DeltaT range of 500°C--750°C. The oxide residual stresses measured by the sin2psi method were always compressive around 2 GPa. Different stress-states were noticed with the oxides grown on different sections of pressure tube. The compressive stress was released when the oxide was thermally cycled at the highest DeltaT of 750°C. Discussion was given to the effects of anisotropic nature of thermal expansion coefficients and crystallographic texture on the stress-state of Zr oxides.

  11. Hydrogen production by water decomposition using a combined electrolytic-thermochemical cycle

    NASA Technical Reports Server (NTRS)

    Farbman, G. H.; Brecher, L. E.

    1976-01-01

    A proposed dual-purpose power plant generating nuclear power to provide energy for driving a water decomposition system is described. The entire system, dubbed Sulfur Cycle Water Decomposition System, works on sulfur compounds (sulfuric acid feedstock, sulfur oxides) in a hybrid electrolytic-thermochemical cycle; performance superior to either all-electrolysis systems or presently known all-thermochemical systems is claimed. The 3345 MW(th) graphite-moderated helium-cooled reactor (VHTR - Very High Temperature Reactor) generates both high-temperature heat and electric power for the process; the gas stream at core exit is heated to 1850 F. Reactor operation is described and reactor innards are illustrated. A cost assessment for on-stream performance in the 1990's is optimistic.

  12. Supercritical water oxidation technology for DWPF

    SciTech Connect

    Carter, J.T.; Gentilucci, J.A.

    1992-02-07

    At the request of Mr. H.L. Brandt and others in the Savannah River Field Office High Level Waste Division office, DWPF, and SRL personnel have reviewed two potential applications for supercritical water oxidation technology in DWPF. The first application would replace the current hydrolysis process by destroying the organic fractions of the precipitated cesium / potassium tetraphenylborate slurry. The second application pertains to liquid benzene destruction. After a thorough evaluation the first application is not recommended. The second is ready to be tested if needed.

  13. Water Vapor Tracers as Diagnostics of the Regional Hydrologic Cycle

    NASA Technical Reports Server (NTRS)

    Bosilovich, Michael G.; Schubert, Siegfried; Einaudi, Franco (Technical Monitor)

    2001-01-01

    Numerous studies suggest that local feedback of evaporation on precipitation, or recycling, is a significant source of water for precipitation. Quantitative results on the exact amount of recycling have been difficult to obtain in view of the inherent limitations of diagnostic recycling calculations. The current study describes a calculation of the amount of local and remote sources of water for precipitation, based on the implementation of passive constituent tracers of water vapor (termed water vapor tracers, WVT) in a general circulation model. In this case, the major limitation on the accuracy of the recycling estimates is the veracity of the numerically simulated hydrological cycle, though we note that this approach can also be implemented within the context of a data assimilation system. In this approach, each WVT is associated with an evaporative source region, and tracks the water until it precipitates from the atmosphere. By assuming that the regional water is well mixed with water from other sources, the physical processes that act on the WVT are determined in proportion to those that act on the model's prognostic water vapor. In this way, the local and remote sources of water for precipitation can be computed within the model simulation, and can be validated against the model's prognostic water vapor. Furthermore, estimates of precipitation recycling can be compared with bulk diagnostic approaches. As a demonstration of the method, the regional hydrologic cycles for North America and India are evaluated for six summers (June, July and August) of model simulation. More than 50% of the precipitation in the Midwestern United States came from continental regional tracers, and the local source was the largest of the regional tracers (14%). The Gulf of Mexico and Atlantic 2 regions contributed 18% of the water for Midwestern precipitation, but further analysis suggests that the greater region of the Tropical Atlantic Ocean may also contribute significantly. In general, most North American land regions showed a positive correlation between evaporation and recycling ratio (except the Southeast United States) and negative correlations of recycling ratio with precipitation and moisture transport (except the Southwestern United States). The Midwestern local source is positively correlated with local evaporation, but it is not correlated with water vapor transport. This is contrary to bulk diagnostic estimates of precipitation recycling. In India, the local source of precipitation is a small percentage of the precipitation owing to the dominance of the atmospheric transport of oceanic water. The southern Indian Ocean provides a key source of water for both the Indian continent and the Sahelian region.

  14. DIRECT-CYCLE, BOILING-WATER NUCLEAR REACTOR

    DOEpatents

    Harrer, J.M.; Fromm, L.W. Jr.; Kolba, V.M.

    1962-08-14

    A direct-cycle boiling-water nuclear reactor is described that employs a closed vessel and a plurality of fuel assemblies, each comprising an outer tube closed at its lower end, an inner tube, fuel rods in the space between the tubes and within the inner tube. A body of water lying within the pressure vessel and outside the fuel assemblies is converted to saturated steam, which enters each fuel assembly at the top and is converted to superheated steam in the fuel assembly while it is passing therethrough first downward through the space between the inner and outer tubes of the fuel assembly and then upward through the inner tube. (AEC)

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

    PubMed

    Weber, Carolyn F; King, Gary M

    2009-12-01

    Water availability oscillates dramatically on young volcanic deposits, and may control the distribution and activity of microbes during early stages of biological succession. Carbon monoxide (CO)-oxidizing bacteria are among the pioneering colonists on volcanic deposits and are subjected to these water stresses. We report here the effects of water potential on CO-oxidizing bacteria in unvegetated (bare) and vegetated (canopy) sites on a 1959 volcanic deposit on Kilauea Volcano (Hawai'i). Time course measurements of water potential showed that average water potentials in the surface layer (0-1 cm) of canopy soil remained between -0.1 and 0 MPa, whereas dramatic diurnal oscillations (for example, between -60 and 0 MPa) occur in bare site surface cinders. During a moderate drying event in situ (-1.7 to 0 MPa), atmospheric CO consumption by intact bare site cores decreased 2.7-fold. For bare and canopy surface samples, maximum potential CO oxidation rates decreased 40 and 60%, respectively, when water potentials were lowered from 0 to -1.5 MPa in the laboratory. These observations indicated that CO oxidation is moderately sensitive to changes in water potential. Additional analyses showed that CO oxidation resumes within a few hours of rehydration, even after desiccation at -150 MPa for 63 days. Samples from both sites exposed to multiple cycles of drying and rewetting (-80 to 0 MPa), lost significant activity after the first cycle, but not after subsequent cycles. Similar responses of CO oxidation in both sites suggested that active CO-oxidizing communities in bare and canopy sites do not express differential adaptations to water stress. PMID:19641536

  16. Climate change and the water cycle in newly irrigated areas.

    PubMed

    Abrahão, Raphael; García-Garizábal, Iker; Merchán, Daniel; Causapé, Jesús

    2015-02-01

    Climate change is affecting agriculture doubly: evapotranspiration is increasing due to increments in temperature while the availability of water resources is decreasing. Furthermore, irrigated areas are expanding worldwide. In this study, the dynamics of climate change impacts on the water cycle of a newly irrigated watershed are studied through the calculation of soil water balances. The study area was a 752-ha watershed located on the left side of the Ebro river valley, in Northeast Spain. The soil water balance procedures were carried out throughout 1827 consecutive days (5 years) of hydrological and agronomical monitoring in the study area. Daily data from two agroclimatic stations were used as well. Evaluation of the impact of climate change on the water cycle considered the creation of two future climate scenarios for comparison: 2070 decade with climate change and 2070 decade without climate change. The main indicators studied were precipitation, irrigation, reference evapotranspiration, actual evapotranspiration, drainage from the watershed, and irrigation losses. The aridity index was also applied. The results represent a baseline scenario in which adaptation measures may be included and tested to reduce the impacts of climate change in the studied area and other similar areas. PMID:25626569

  17. Containment system for supercritical water oxidation reactor

    DOEpatents

    Chastagner, Philippe

    1994-01-01

    A system for containment of a supercritical water oxidation reactor in the event of a rupture of the reactor. The system includes a containment for housing the reaction vessel and a communicating chamber for holding a volume of coolant, such as water. The coolant is recirculated and sprayed to entrain and cool any reactants that might have escaped from the reaction vessel. Baffles at the entrance to the chamber prevent the sprayed coolant from contacting the reaction vessel. An impact-absorbing layer is positioned between the vessel and the containment to at least partially absorb momentum of any fragments propelled by the rupturing vessel. Remote, quick-disconnecting fittings exterior to the containment, in cooperation with shut-off valves, enable the vessel to be isolated and the system safely taken off-line. Normally-closed orifices throughout the containment and chamber enable decontamination of interior surfaces when necessary.

  18. Containment system for supercritical water oxidation reactor

    DOEpatents

    Chastagner, P.

    1994-07-05

    A system is described for containment of a supercritical water oxidation reactor in the event of a rupture of the reactor. The system includes a containment for housing the reaction vessel and a communicating chamber for holding a volume of coolant, such as water. The coolant is recirculated and sprayed to entrain and cool any reactants that might have escaped from the reaction vessel. Baffles at the entrance to the chamber prevent the sprayed coolant from contacting the reaction vessel. An impact-absorbing layer is positioned between the vessel and the containment to at least partially absorb momentum of any fragments propelled by the rupturing vessel. Remote, quick-disconnecting fittings exterior to the containment, in cooperation with shut-off valves, enable the vessel to be isolated and the system safely taken off-line. Normally-closed orifices throughout the containment and chamber enable decontamination of interior surfaces when necessary. 2 figures.

  19. Uranium oxidation: Characterization of oxides formed by reaction with water by infrared and sorption analyses

    NASA Astrophysics Data System (ADS)

    Fuller, E. L.; Smyrl, N. R.; Condon, J. B.; Eager, M. H.

    1984-04-01

    Three different uranium oxide samples have been characterized with respect to the different preparation techniques. The results show that the water reaction with uranium metal occurs cyclically forming laminar layers of oxide which spall off due to the strain at the oxide/metal interface. Single laminae are released if liquid water is present due to the prizing penetration at the reaction zone. The rate of reaction of water with uranium is directly proportional to the amount of adsorbed water on the oxide product. Rapid transport is effected through the open hydrous oxide product. Dehydration of the hydrous oxide irreversibly forms a more inert oxide which cannot be rehydrated to the degree that prevails in the original hydrous product of uranium oxidation with water. Inert gas sorption analyses and diffuse reflectance infrared studies combined with electron microscopy prove valuable in defining the chemistry and morphology of the oxidic products and hydrated intermediates.

  20. HIV-1 gp120 and morphine induced oxidative stress: role in cell cycle regulation

    PubMed Central

    Samikkannu, Thangavel; Ranjith, Deepa; Rao, Kurapati V. K.; Atluri, Venkata S. R.; Pimentel, Emely; El-Hage, Nazira; Nair, Madhavan P. N.

    2015-01-01

    HIV infection and illicit drugs are known to induce oxidative stress and linked with severity of viral replication, disease progression, impaired cell cycle regulation and neurodegeneration. Studies have shown that morphine accelerates HIV infection and disease progression mediated by Reactive oxygen species (ROS). Oxidative stress impact redox balance and ROS production affect cell cycle regulation. However, the role of morphine in HIV associated acceleration of oxidative stress and its link to cell cycle regulation and neurodegeneration has not been elucidated. The aim of present study is to elucidate the mechanism of oxidative stress induced glutathione synthases (GSS), super oxide dismutase (SOD), and glutathione peroxidase (GPx) impact cell cycle regulated protein cyclin-dependent kinase 1, cell division cycle 2 (CDK-1/CDC-2), cyclin B, and cell division cycle 25C (CDC-25C) influencing neuronal dysfunction by morphine co-morbidity with HIV-1 gp120. It was observed that redox imbalance inhibited the GSS, GPx and increased SOD which, subsequently inhibited CDK-1/CDC-2 whereas cyclin B and CDC-25C significantly up regulated in HIV-1 gp120 with morphine compared to either HIV-1 gp120 or morphine treated alone in human microglial cell line. These results suggest that HIV positive morphine users have increased levels of oxidative stress and effect of cell cycle machinery, which may cause the HIV infection and disease progression. PMID:26157430

  1. Life-cycle testing of receiving waters with Ceriodaphnia dubia

    SciTech Connect

    Stewart, A.J.; Beane, B.K.

    1995-12-31

    Seven-day tests with Ceriodaphnia are commonly used to estimate the toxicity of effluents or receiving waters, but may yield no toxicity outcomes even when pollutants are present (a possible type II error). The authors conducted two sets of full life-cycle tests with C. dubia to (1) see if tests with longer exposure periods revealed evidence for toxicity that might not be evident from shorter tests, and (2) determine the relative importance of water quality versus food as factors influencing C. dubia reproduction. In the first set of tests, daphnids were reared in diluted mineral water (control), water from a stream impacted by coal fly-ash, or water from a mercury-contaminated retention basin. The second set of tests used water from the retention basin only, but this water was either filtered or not filtered, and food was either added or not added. C. dubia survival and reproduction did not differ much among the three waters in the first set of tests. However, both parameters were strongly affected by the filtering and food-addition treatments in the second set of tests. Thus, C. dubia seems to be moderately insensitive to general water-quality factors, but quite sensitive to food-related parameters. Regression analysis showed that the predictability of life-time reproduction of C. dubia from 7-day test results was low in five of six cases. The increase in predictability as a function of test duration also differed among water types (first set of tests), and among treatments (second set of tests). Thus, 7-day tests with C. dubia may be used to quantify water-quality problems, but it may not be possible to reliably extrapolate the results of such tests to longer time scales.

  2. Life-cycle testing of receiving waters with Ceriodaphnia dubia

    SciTech Connect

    Stewart, A.J.; Konetsky, B.K.

    1996-12-31

    Seven-day tests with Ceriodaphnia dubia are commonly used to estimate toxicity of effluents or receiving waters but can sometimes yield {open_quotes}no toxicity{close_quotes} outcomes even if pollutants are present. We conducted two sets of full life-cycle tests with C. dubia to (1) see if tests with longer exposure periods would reveal evidence for toxicity that might not be evident from 7-day tests, and (2) determine the relative importance of water quality versus food as factors influencing C. dubia reproduction. In the first set of tests, C. dubia was reared in diluted mineral water (negative control), water from a stream impacted by coal fly-ash, or water from a retention basin containing sediments contaminated with mercury, other metals and polychlorinated biphenyls. The second set of tests used water from the retention basin only, but this water was either filtered or not filtered, and food was either added or not added, prior to testing. C. dubia survival and reproduction did not differ much among the three water types in the first set of tests, but these two parameters were strongly affected by the filtering and food-addition treatments in the second set of tests. Thus, C. dubia appeared to be relatively insensitive to general water-quality factors, but quite sensitive to food-related factors. Regression analyses showed that the predictability of life-time reproduction by C. dubia from the results of 7-day tests was very low (R{sup 2}< 0.35) in five of the six experiments. The increase in predictability as a function of test duration also differed among water types in the first set of tests, and among treatments in the second set of tests. Thus, 7-day tests with C. dubia may be used to quantify water-quality problems, but it may not be possible to reliably extrapolate the results of these tests to longer time scales.

  3. Photoassisted oxidation of oil films on water

    SciTech Connect

    Heller, A.; Brock, J.R.

    1990-10-01

    The objective of the project is to develop a method for the solar assisted oxidation of oil slicks. A semiconducting photocatalyst, titanium dioxide, is used. Upon absorbing a photon, an electron-hole pair is generated in the TiO{sub 2} microcrystal. The electron reacts with surface-adsorbed oxygen, reducing it to hydrogen peroxide; the hole directly oxidizes adsorbed organic compounds. Titanium dioxide is denser than either oil or seawater; the density of its anatase phase is 3.8 and that of its rutile phase is 4.3. In order to keep the titanium dioxide at the air/oil interface, it is attached to a low density, floating material. The particles of the latter are sufficiently small to make the system economical. Specifically, the photocatalyst particles are attached to inexpensive hollow glass microbeads of about 100{mu}m diameter. Those areas of the microbeads that are not covered by photocatalyst are made oleophilic, so that the microbeads will follow the oil slick and not migrate to either the air/water or the water/oil interface.

  4. Influence of localized plasticity on oxidation behaviour of austenitic stainless steels under primary water reactor

    NASA Astrophysics Data System (ADS)

    Ciss, Sarata; Laffont, Lydia; Lafont, Marie-Christine; Tanguy, Benoit; Andrieu, Eric

    2013-02-01

    The sensitivity of precipitation-strengthened A286 austenitic stainless steel to stress corrosion cracking was studied by means of slow-strain-rate tests. First, alloy cold working by low cycle fatigue (LCF) was investigated. Fatigue tests under plastic strain control were performed at different strain levels (??p/2 = 0.2%, 0.5%, 0.8% and 2%) to establish correlations between stress softening and the deformation microstructure resulting from the LCF tests. Deformed microstructures were identified through TEM investigations. The interaction between oxidation and localized deformation bands was also studied and it resulted that localized deformation bands are not preferential oxide growth channels. The pre-cycling of the alloy did not modify its oxidation behaviour. However, intergranular oxidation in the subsurface under the oxide layer formed after exposure to PWR primary water was shown.

  5. Electrochemical water oxidation with carbon-grafted iridium complexes.

    PubMed

    deKrafft, Kathryn E; Wang, Cheng; Xie, Zhigang; Su, Xin; Hinds, Bruce J; Lin, Wenbin

    2012-02-01

    Hydrogen production from water splitting provides a potential solution to storing harvested solar energy in chemical fuels, but this process requires active and robust catalysts that can oxidize water to provide a source of electrons for proton reduction. Here we report the direct, covalent grafting of molecular Ir complexes onto carbon electrodes, with up to a monolayer coverage. Carbon-grafted Ir complexes electrochemically oxidize water with a turnover frequency of up to 3.3 s(-1) and a turnover number of 644 during the first hour. Electrochemical water oxidation with grafted catalysts gave enhanced rates and stability compared to chemically driven water oxidation with the corresponding molecular catalysts. This strategy provides a way to systematically evaluate catalysts under tunable conditions, potentially providing new insights into electrochemical water oxidation processes and water oxidation catalyst design. PMID:22292527

  6. Raman Spectroscopy Applied to Mars Water Cycle Studies

    NASA Astrophysics Data System (ADS)

    Nikolakakos, G.; Whiteway, J. A.

    2014-12-01

    One of the key findings during the Phoenix and Mars Science Laboratory landed Mars missions has been the detection of perchlorate, a highly deliquescent salt. Perchlorates are of great interest on Mars due to their high affinity for water vapour as well as their ability to greatly depress the freezing point of water when in solution. This has intriguing biological implications as resulting brines could potentially provide a habitable environment for living organisms. Additionally, it has been speculated that these salts may play a significant role in influencing the hydrological cycle on Mars. In order to experimentally study brine formation on Mars and assess the feasibility of a future landed detection tool, a stand-off Raman spectroscopy instrument and environmental simulation chamber have been developed at York University. A sample of magnesium perchlorate has been subjected to the water vapour pressure, background pressure and temperatures found at polar Martian latitudes. Results indicate that at a water vapour pressure of ~20 Pa, Raman spectroscopy is able to detect the onset of brine formation and provide an estimate of the quantity of water taken up by the sample. At the lower water vapour pressures typically found on Mars ( ~1 Pa), it appears that slower dynamics inhibit the onset of water uptake over relevant time scales. The experimental setup and current results will be presented.

  7. The NASA Energy and Water Cycle Extreme (NEWSE) Integration Project

    NASA Technical Reports Server (NTRS)

    House, P. R.; Lapenta, W.; Schiffer, R.

    2008-01-01

    Skillful predictions of water and energy cycle extremes (flood and drought) are elusive. To better understand the mechanisms responsible for water and energy extremes, and to make decisive progress in predicting these extremes, the collaborative NASA Energy and Water cycle Extremes (NEWSE) Integration Project, is studying these extremes in the U.S. Southern Great Plains (SGP) during 2006-2007, including their relationships with continental and global scale processes, and assessment of their predictability on multiple space and time scales. It is our hypothesis that an integrative analysis of observed extremes which reflects the current understanding of the role of SST and soil moisture variability influences on atmospheric heating and forcing of planetary waves, incorporating recently available global and regional hydro- meteorological datasets (i.e., precipitation, water vapor, clouds, etc.) in conjunction with advances in data assimilation, can lead to new insights into the factors that lead to persistent drought and flooding. We will show initial results of this project, whose goals are to provide an improved definition, attribution and prediction on sub-seasonal to interannual time scales, improved understanding of the mechanisms of decadal drought and its predictability, including the impacts of SST variability and deep soil moisture variability, and improved monitoring/attributions, with transition to applications; a bridging of the gap between hydrological forecasts and stakeholders (utilization of probabilistic forecasts, education, forecast interpretation for different sectors, assessment of uncertainties for different sectors, etc.).

  8. eWaterCycle: A global operational hydrological forecasting model

    NASA Astrophysics Data System (ADS)

    van de Giesen, Nick; Bierkens, Marc; Donchyts, Gennadii; Drost, Niels; Hut, Rolf; Sutanudjaja, Edwin

    2015-04-01

    Development of an operational hyper-resolution hydrological global model is a central goal of the eWaterCycle project (www.ewatercycle.org). This operational model includes ensemble forecasts (14 days) to predict water related stress around the globe. Assimilation of near-real time satellite data is part of the intended product that will be launched at EGU 2015. The challenges come from several directions. First, there are challenges that are mainly computer science oriented but have direct practical hydrological implications. For example, we aim to make use as much as possible of existing standards and open-source software. For example, different parts of our system are coupled through the Basic Model Interface (BMI) developed in the framework of the Community Surface Dynamics Modeling System (CSDMS). The PCR-GLOBWB model, built by Utrecht University, is the basic hydrological model that is the engine of the eWaterCycle project. Re-engineering of parts of the software was needed for it to run efficiently in a High Performance Computing (HPC) environment, and to be able to interface using BMI, and run on multiple compute nodes in parallel. The final aim is to have a spatial resolution of 1km x 1km, which is currently 10 x 10km. This high resolution is computationally not too demanding but very memory intensive. The memory bottleneck becomes especially apparent for data assimilation, for which we use OpenDA. OpenDa allows for different data assimilation techniques without the need to build these from scratch. We have developed a BMI adaptor for OpenDA, allowing OpenDA to use any BMI compatible model. To circumvent memory shortages which would result from standard applications of the Ensemble Kalman Filter, we have developed a variant that does not need to keep all ensemble members in working memory. At EGU, we will present this variant and how it fits well in HPC environments. An important step in the eWaterCycle project was the coupling between the hydrological and hydrodynamic models. The hydrological model will run operationally for the whole globe. Once special situations are predicted, such as floods, navigation hindrances, or water shortages, a detailed local hydraulic model will start to predict the exact local consequences. In Vienna, we will show for the first time the operational global eWaterCycle model, including high resolution forecasts, our new data assimilation technique, and coupled hydrological/hydraulic models.

  9. Using NASA Products of the Water Cycle for Improved Water Resources Management

    NASA Astrophysics Data System (ADS)

    Toll, D. L.; Doorn, B.; Engman, E. T.; Lawford, R. G.

    2010-12-01

    NASA Water Resources works within the Earth sciences and GEO community to leverage investments of space-based observation and modeling results including components of the hydrologic cycle into water resources management decision support tools for the goal towards the sustainable use of water. These Earth science hydrologic related observations and modeling products provide a huge volume of valuable data in both near-real-time and extended back nearly 50 years. Observations of this type enable assessment of numerous water resources management issues including water scarcity, extreme events of drought and floods, and water quality. Examples of water cycle estimates make towards the contributions to the water management community include snow cover and snowpack, soil moisture, evapotranspiration, precipitation, streamflow and ground water. The availability of water is also contingent on the quality of water and hence water quality is an important part of NASA Water Resources. Water quality activities include both nonpoint source (agriculture land use, ecosystem disturbances, impervious surfaces, etc.) and direct remote sensing ( i.e., turbidity, algae, aquatic vegetation, temperature, etc.). . The NASA Water Resources Program organizes its projects under five functional themes: 1) stream-flow and flood forecasting; 2) water consumptive use and irrigation (includes evapotranspiration); 3) drought; 4) water quality; and 5) climate impacts on water resources. Currently NASA Water Resources is supporting 21 funded projects with 11 additional projects being concluded. To maximize the use of NASA water cycle measurements end to projects are supported with strong links with decision support systems. The NASA Water Resources Program works closely with other government agencies NOAA, USDA-FAS, USGS, AFWA, USAID, universities, and non-profit, international, and private sector organizations. International water cycle applications include: 1) Famine Early Warning System Network (FEWSNET) being expanded for famine relief to many developing nations of the world using a NASA Land Data Assimilation System (LDAS); 2) Air Force Weather Agency (AFWA) global hydrology mapping program that extends their global hydrology to much finer resolutions through use of an optimized LDAS; 3) 'SERVIR' a visualization and monitoring center of Earth science information in Central America and East Africa with plans for additional locations in developing countries of the world; 4) installing NASA Water Information System Platforms (WISPs) strategically located throughout the Middle East and North Africa (MENA) in partnerships with USAID and the World Bank; and 5) Latin American capacity building efforts within GEO.

  10. Oxidation with air by ascorbate-driven quinone redox cycling.

    PubMed

    Silveira-Dorta, Gastn; Monzn, Diego M; Crisstomo, Fernando P; Martn, Toms; Martn, Vctor S; Carrillo, Romen

    2015-04-25

    Transition metal-free oxidation with air at room temperature has been achieved by simply using ascorbate (vitamin C) and catalytic amounts of menadione (vitamin K3). A combination of the mentioned vitamins transforms atmospheric oxygen into hydrogen peroxide, which is able to oxidize arylboronic acids and other chemical moieties. PMID:25805569

  11. Nitrogen cycling following The Great Oxidation Event, evidence from the Paleoproterozoic of Fennoscandia.

    NASA Astrophysics Data System (ADS)

    Junium, C. K.; Kump, L.; Arthur, M. A.; Melezhik, V.; Lepland, A.; Members of the FAR-DEEP Drilling Team

    2011-12-01

    The Fennoscandia Arctic Russia - Drilling Early Earth Project (FAR-DEEP) recovered core materials spanning the early Paleoproterozoic of Arctic Russia under the auspices of the International Continental Scientific Drilling Program. Here we present N and C isotopic data documenting N and C cycle dynamics during this critical interval of Earth history. Additionally, we will discuss the challenges of nitrogen isotope studies in such ancient sediments and the methods that we have utilized to test the fidelity of our nitrogen isotope data. Nitrogen isotope studies in very ancient sedimentary rocks, like those recovered by the FAR-DEEP are plagued by the concerns of diagenetic and metamorphic overprinting. Nitrogen is often present in very low concentrations and in a variety of inorganic phases that may or may not be derived from the ambient organic matter. For these reasons, bulk sediment δ15N data can be at best, ambiguous. To overcome these issues we have utilized kerogens for δ15N and δ13C analyses. The large difference between bulk and kerogen δ15N data demonstrates that inorganic N is anomalously 15N-enriched, by up to 7% and bulk δ15N values substantially overestimate the magnitude of the 15N variability in the Onega Basin (OB) sediments. Metasomatic processes during basinal magamatic activity resulted in the addition of 15N-enriched inorganic-N. Authigenic K-bearing micas are common in intervals where bulk δ15N values are 15N-enriched, suggesting that secondary mineral phases have retained 15N-enriched ammonia generated during metsomatism. The FAR-DEEP drilling team has documented an anomalously large, and rapid δ13C shift of -17% in carbonates and organic matter of the Zhaoneskaya Formation (ZF) of the OB following the extended period of 13Ccarb-enrichment know as the Lomagundi-Jatuli event. The isotopic shift in reduced carbon has also been recognized in the Franceville Formation of Gabon, termed here as "Shunga-Francevillian" anomaly, and may reflect the global oxidation of organic matter buried during the buildup of atmospheric oxygen in response to Lomagundi-Jatuli carbon burial. The dynamic response of the nitrogen cycle in the ZF is consistent with increased availability of O2 in the water column and is similar to the response documented in Archean sequences. Kerogen δ15N values are below 2%, most likely reflecting a biological N2-fixation source for nutrient-nitrogen with little influence from denitrification. δ13C values increase from -26% to -19% signaling a transient increase in the burial of organic carbon and net production of O2. Transition from a largely anoxic OB water column to one that was oxidized in its surface waters would have allowed for redox cycling of nitrogen and accompanying 15N-enrichment. Thus, the observed δ15N increase of 5% reflects an expansion in denitrification and associated reactions and oxidation of the OB water column under elevated atmospheric O2. At the end of the precipitous decrease in δ13C values δ15N values return pre-excursion values of ~+2%. This drop in δ13C and δ15N suggests a return to less oxidizing conditions in the OB following drawdown of atmospheric O2 during organic matter oxidation.

  12. Microbial As(III) Oxidation in Water Treatment Plant Filters

    EPA Science Inventory

    Arsenic exists in two oxidation states in water - arsenite [As(III)] and arsenate [As(V)]. As(III) is relatively mobile in water and difficult to remove by arsenic-removal treatment processes. Source waters that contain As(III) must add a strong oxidant such as free chlorine or p...

  13. Specific features of aluminum nanoparticle water and wet air oxidation

    NASA Astrophysics Data System (ADS)

    Lozhkomoev, Aleksandr S.; Glazkova, Elena A.; Svarovskaya, Natalia V.; Bakina, Olga V.; Kazantsev, Sergey O.; Lerner, Marat I.

    2015-10-01

    The oxidation processes of the electrically exploded aluminum nanopowders in water and in wet air are examined in the paper. The morphology of the intermediate reaction products of aluminum oxidation has been studied using the transmission electron microscopy. It was shown that the aluminum nanopowder water oxidation causes the formation of the hollow spheres with mesoporous boehmite nanosheets coating. The wedge-like bayerite particles are formed during aluminum nanopowder wet air oxidation.

  14. Cycling endurance of silicon{endash}oxide{endash}nitride{endash}oxide{endash}silicon nonvolatile memory stacks prepared with nitrided SiO{sub 2}/Si(100) interfaces

    SciTech Connect

    Habermehl, S.; Nasby, R.D.; Rightley, M.J.

    1999-08-01

    The effects of nitrided SiO{sub 2}/Si(100) interfaces upon cycling endurance in silicon{endash}oxide{endash}nitride{endash}oxide{endash}silicon (SONOS) nonvolatile memory transistors are investigated. Analysis of metal{endash}oxide{endash}silicon field-effect transistor subthreshold characteristics indicate cycling degradation to be a manifestation of interface trap generation at the tunnel oxide/silicon interface. After 10{sup 6} write/erase cycles, SONOS film stacks prepared with nitrided tunnel oxides exhibit enhanced cycling endurance over stacks prepared with non-nitrided tunnel oxides. If the capping oxide is formed by steam oxidation, rather than by deposition, SONOS stacks prepared with non-nitrided tunnel oxides exhibit endurance characteristics similar to stacks with nitrided tunnel oxides. For this case, a mechanism for latent nitridation of the tunnel oxide/silicon interface is proposed. {copyright} {ital 1999 American Institute of Physics.}

  15. Water Vapor Tracers as Diagnostics of the Regional Hydrologic Cycle

    NASA Technical Reports Server (NTRS)

    Bosilovich, Michael G.; Schubert, Siegfried D.; Einaudi, Franco (Technical Monitor)

    2001-01-01

    Numerous studies suggest that local feedback of surface evaporation on precipitation, or recycling, is a significant source of water for precipitation. Quantitative results on the exact amount of recycling have been difficult to obtain in view of the inherent limitations of diagnostic recycling calculations. The current study describes a calculation of the amount of local and remote geographic sources of surface evaporation for precipitation, based on the implementation of three-dimensional constituent tracers of regional water vapor sources (termed water vapor tracers, WVT) in a general circulation model. The major limitation on the accuracy of the recycling estimates is the veracity of the numerically simulated hydrological cycle, though we note that this approach can also be implemented within the context of a data assimilation system. In the WVT approach, each tracer is associated with an evaporative source region for a prognostic three-dimensional variable that represents a partial amount of the total atmospheric water vapor. The physical processes that act on a WVT are determined in proportion to those that act on the model's prognostic water vapor. In this way, the local and remote sources of water for precipitation can be predicted within the model simulation, and can be validated against the model's prognostic water vapor. As a demonstration of the method, the regional hydrologic cycles for North America and India are evaluated for six summers (June, July and August) of model simulation. More than 50% of the precipitation in the Midwestern United States came from continental regional sources, and the local source was the largest of the regional tracers (14%). The Gulf of Mexico and Atlantic regions contributed 18% of the water for Midwestern precipitation, but further analysis suggests that the greater region of the Tropical Atlantic Ocean may also contribute significantly. In most North American continental regions, the local source of precipitation is correlated with total precipitation. There is a general positive correlation between local evaporation and local precipitation, but it can be weaker because large evaporation can occur when precipitation is inhibited. In India, the local source of precipitation is a small percentage of the precipitation owing to the dominance of the atmospheric transport of oceanic water. The southern Indian Ocean provides a key source of water for both the Indian continent and the Sahelian region.

  16. Tracking evolution of urban biogeochemical cycles: salinization of fresh water

    NASA Astrophysics Data System (ADS)

    Kaushal, S.; McDowell, W. H.; Wollheim, W. M.; Duan, S.; Gorman, J. K.; Haq, S.; Hohman, S.; Smith, R. M.; Mayer, P. M.

    2014-12-01

    The built environment often changes quickly in response to human activities, thus contributing to an evolution of stream chemistry over time. Depending upon development and management strategies, these changes can result in pulses and/or long-term trends. Here, we explore patterns of evolving salinization of fresh water over time, and we evaluate the potential water quality implications of fresh water salinization. We show that there has been global salinization of freshwater across urbanizing landscapes over a century. We also show that human-accelerated weathering in watersheds and river alkalinization can further influence regional rates of salinization (in addition to anthropogenic sources such as road salts, sewage leaks, etc.). Finally, we investigate how salinization of fresh water can impact stream sediment fluxes of carbon, nutrients, and sulfate in watersheds across a land use gradient at the Baltimore Long-Term Ecological Research (LTER) site. The impacts of salinization on mobilization and uptake of carbon, nutrients, and sulfate in streams warrant further consideration in water quality management strategies. Overall, we propose that salinization can be a "universal tracer" of watershed urbanization globally with major regional consequences for drinking water and evolution of biogeochemical cycles in freshwater ecosystems.

  17. Increasing water cycle extremes in California and relation to ENSO cycle under global warming

    DOE PAGESBeta

    Yoon, Jin -Ho; Wang, S. -Y. Simon; Gillies, Robert R.; Kravitz, Benjamin S.; Hipps, Lawrence; Rasch, Philip J.

    2015-10-21

    California has experienced its most severe drought in recorded history since the winter of 2013-2014. The long duration of drought has stressed statewide water resources and the economy, while fueling an extraordinary increase in wildfires. The effects of global warming on the regional climate include a hotter and drier climate, as well as earlier snowmelt, both of which exacerbate drought conditions. However, connections between a changing climate and how climate oscillations modulate regional water cycle extremes are not well understood. Here we analyze large-ensemble simulations of future climate change in California using the Community Earth System Model version 1 (CESM1)more » and multiple climate models participating in the Coupled Model Intercomparison Project Phase 5 (CMIP5). Both intense drought and excessive flooding are projected to increase by at least 50% toward the end of the 21st century. Furthermore, the projected increase in water cycle extremes is associated with tighter relation to El Niño and Southern Oscillation (ENSO), particularly extreme El Niño and La Niña events, which modulates California’s climate not only through its warm and cold phases, but also ENSO’s precursor patterns.« less

  18. Increasing water cycle extremes in California and relation to ENSO cycle under global warming

    SciTech Connect

    Yoon, Jin -Ho; Wang, S. -Y. Simon; Gillies, Robert R.; Kravitz, Benjamin S.; Hipps, Lawrence; Rasch, Philip J.

    2015-10-21

    California has experienced its most severe drought in recorded history since the winter of 2013-2014. The long duration of drought has stressed statewide water resources and the economy, while fueling an extraordinary increase in wildfires. The effects of global warming on the regional climate include a hotter and drier climate, as well as earlier snowmelt, both of which exacerbate drought conditions. However, connections between a changing climate and how climate oscillations modulate regional water cycle extremes are not well understood. Here we analyze large-ensemble simulations of future climate change in California using the Community Earth System Model version 1 (CESM1) and multiple climate models participating in the Coupled Model Intercomparison Project Phase 5 (CMIP5). Both intense drought and excessive flooding are projected to increase by at least 50% toward the end of the 21st century. Furthermore, the projected increase in water cycle extremes is associated with tighter relation to El Niño and Southern Oscillation (ENSO), particularly extreme El Niño and La Niña events, which modulates California’s climate not only through its warm and cold phases, but also ENSO’s precursor patterns.

  19. Increasing water cycle extremes in California and relation to ENSO cycle under global warming

    SciTech Connect

    Yoon, Jin-Ho; Wang, S-Y; Gillies, Robert R.; Kravitz, Benjamin S.; Hipps, Lawrence; Rasch, Philip J.

    2015-10-21

    California has experienced its most severe drought in recorded history since the winter of 2013-2014. The long duration of drought has stressed statewide water resources and the economy, while fueling an extraordinary increase in wildfires. The effects of global warming on the regional climate include a hotter and drier climate, as well as earlier snowmelt, both of which exacerbate drought conditions. However, connections between a changing climate and how climate oscillations modulate regional water cycle extremes are not well understood. Here we analyze large-ensemble simulations of future climate change in California using the Community Earth System Model version 1 (CESM1) and multiple climate models participating in the Coupled Model Intercomparison Project Phase 5 (CMIP5). Both intense drought and excessive flooding are projected to increase by at least 50% toward the end of the 21st century. The projected increase in water cycle extremes is associated with tighter relation to El Niño and Southern Oscillation (ENSO), particularly extreme El Niño and La Niña events, which modulates California’s climate not only through its warm and cold phases, but also ENSO’s precursor patterns.

  20. Supercritical Water Reactor Cycle for Medium Power Applications

    SciTech Connect

    BD Middleton; J Buongiorno

    2007-04-25

    Scoping studies for a power conversion system based on a direct-cycle supercritical water reactor have been conducted. The electric power range of interest is 5-30 MWe with a design point of 20 MWe. The overall design objective is to develop a system that has minimized physical size and performs satisfactorily over a broad range of operating conditions. The design constraints are as follows: Net cycle thermal efficiency {ge}20%; Steam turbine outlet quality {ge}90%; and Pumping power {le}2500 kW (at nominal conditions). Three basic cycle configurations were analyzed. Listed in order of increased plant complexity, they are: (1) Simple supercritical Rankine cycle; (2) All-supercritical Brayton cycle; and (3) Supercritical Rankine cycle with feedwater preheating. The sensitivity of these three configurations to various parameters, such as reactor exit temperature, reactor pressure, condenser pressure, etc., was assessed. The Thermoflex software package was used for this task. The results are as follows: (a) The simple supercritical Rankine cycle offers the greatest hardware simplification, but its high reactor temperature rise and reactor outlet temperature may pose serious problems from the viewpoint of thermal stresses, stability and materials in the core. (b) The all-supercritical Brayton cycle is not a contender, due to its poor thermal efficiency. (c) The supercritical Rankine cycle with feedwater preheating affords acceptable thermal efficiency with lower reactor temperature rise and outlet temperature. (d) The use of a moisture separator improves the performance of the supercritical Rankine cycle with feedwater preheating and allows for a further reduction of the reactor outlet temperature, thus it was selected for the next step. Preliminary engineering design of the supercritical Rankine cycle with feedwater preheating and moisture separation was performed. All major components including the turbine, feedwater heater, feedwater pump, condenser, condenser pump and pipes were modeled with realistic assumptions using the PEACE module of Thermoflex. A three-dimensional layout of the plant was also generated with the SolidEdge software. The results of the engineering design are as follows: (i) The cycle achieves a net thermal efficiency of 24.13% with 350/460 C reactor inlet/outlet temperatures, {approx}250 bar reactor pressure and 0.75 bar condenser pressure. The steam quality at the turbine outlet is 90% and the total electric consumption of the pumps is about 2500 kWe at nominal conditions. (ii) The overall size of the plant is attractively compact and can be further reduced if a printed-circuit-heat-exchanger (vs shell-and-tube) design is used for the feedwater heater, which is currently the largest component by far. Finally, an analysis of the plant performance at off-nominal conditions has revealed good robustness of the design in handling large changes of thermal power and seawater temperature.

  1. Diurnal cycles in water quality across the periodic table

    NASA Astrophysics Data System (ADS)

    Kirchner, James

    2014-05-01

    Diurnal cycles in water quality can provide important clues to the processes that regulate aquatic chemistry, but they often are masked by longer-term, larger-amplitude variability, making their detection and quantification difficult. Here I outline methods that can detect diurnal cycles even when they are massively obscured by statistically ill-behaved noise. I demonstrate these methods using high-frequency water quality data from the Plylimon catchment in mid-Wales (Neal et al., 2013; Kirchner and Neal, 2013). Several aspects combine to make the Plynlimon data set unique worldwide. Collected at 7-hour intervals, the Plynlimon data set is much more densely sampled than typical long-term weekly or monthly water quality data. This 7-hour sampling was also continued for two years, much longer than typical intensive sampling campaigns, and the resulting time series encompass a wide range of climatic and hydrological conditions. Furthermore, each sample was analyzed for a wide range of solutes with diverse sources in the natural environment. However, the 7-hour sampling frequency is both coarse and irregular in comparison to diurnal cycles, making their detection and quantification difficult. Nonetheless, the methods outlined here enable detection of statistically significant diurnal cycles in over 30 solutes at Plynlimon, including alkali metals (Li, Na, K, Rb, and Cs), alkaline earths (Be, Mg, Ca, Sr, and Ba), transition metals (Al, Ti, Mn, Fe, Co, Ni, Zn, Mo, Cd, and Pb), nonmetals (B, NO3, Si, As, and Se), lanthanides and actinides (La, Ce, Pr, and U), as well as total dissolved nitrogen (TDN), dissolved organic carbon (DOC), Gran alkalinity, pH, and electrical conductivity. These solutes span every row of the periodic table, and more than six orders of magnitude in concentration. Many of these diurnal cycles are subtle, representing only a few percent, at most, of the total variance in the concentration time series. Nonetheless they are diagnostically useful, because their amplitude and phase contain important clues to the mechanisms controlling these solutes in streamwater. The amplitudes of these cycles vary seasonally, and from wet to dry conditions; the phases are typically much more consistent over time. Under low-flow conditions, the diurnal cycle phases of different elements vary systematically with their electronic structure, as reflected in their placement in the periodic table. Potential mechanisms for this surprising pattern will be discussed. Neal, C., B. Reynolds, J. W. Kirchner, P. Rowland, D. Norris, D. Sleep, A. Lawlor, C. Woods, S. Thacker, H. Guyatt, C. Vincent, K. Lehto, S. Grant, J. Williams, M. Neal, H. Wickham, S. Harman, and L. Armstrong. 2013. High-frequency precipitation and stream water quality time series from Plynlimon, Wales: an openly accessible data resource spanning the periodic table. Hydrological Processes 27:2531-2539. Kirchner, J. W., and C. Neal. 2013. Universal fractal scaling in stream chemistry and its implications for solute transport and water quality trend detection. Proceedings of the National Academy of Sciences of the United States of America 110:12213-12218.

  2. Change in Water Cycle- Important Issue on Climate Earth System

    NASA Astrophysics Data System (ADS)

    Singh, Pratik

    Change in Water Cycle- Important Issue on Climate Earth System PRATIK KUMAR SINGH1 1BALDEVRAM MIRDHA INSTITUTE OF TECHNOLOGY,JAIPUR (RAJASTHAN) ,INDIA Water is everywhere on Earth and is the only known substance that can naturally exist as a gas, liquid, and solid within the relatively small range of air temperatures and pressures found at the Earth's surface.Changes in the hydrological cycle as a consequence of climate and land use drivers are expected to play a central role in governing a vast range of environmental impacts.Earth's climate will undergo changes in response to natural variability, including solar variability, and to increasing concentrations of green house gases and aerosols.Further more, agreement is widespread that these changes may profoundly affect atmospheric water vapor concentrations, clouds and precipitation patterns.As we know that ,a warmer climate, directly leading to increased evaporation, may well accelerate the hydrological cycle, resulting in an increase in the amount of moisture circulating through the atmosphere.The Changing Water Cycle programmer will develop an integrated, quantitative understanding of the changes taking place in the global water cycle, involving all components of the earth system, improving predictions for the next few decades of regional precipitation, evapotranspiration, soil moisture, hydrological storage and fluxes.The hydrological cycle involves evaporation, transpiration, condensation, precipitation, and runoff. NASA's Aqua satellite will monitor many aspects of the role of water in the Earth's systems, and will do so at spatial and temporal scales appropriate to foster a more detailed understanding of each of the processes that contribute to the hydrological cycle. These data and the analyses of them will nurture the development and refinement of hydrological process models and a corresponding improvement in regional and global climate models, with a direct anticipated benefit of more accurate weather and climate forecasts. Aqua is a major mission of the Earth Observing System (EOS), an international program centered in NASA's Earth Science Enterprise to study the Earth in detail from the unique vantage point of space. Focused on key measurements identified by a consensus of U.S. and international scientists, EOS is further enabling studies of the complex interactions amongst the Earth's land, ocean, air, ice and biological systems. Aqua's contributions to monitoring water in the Earth's environment will involve all six of Aqua's instruments: the Atmospheric Infrared Sounder (AIRS), the Advanced Microwave Sounding Unit (AMSU), the Humidity Sounder for Brazil (HSB), the Advanced Microwave Scanning Radiometer- Earth Observing System (AMSR-E), the Moderate Resolution Imaging Spectroradiometer (MODIS), and Clouds and the Earth's Radiant Energy System (CERES). Frozen water in the oceans, in the form of sea ice, will be examined with both AMSR-E and MODIS data, the former allowing routine monitoring of sea ice at a coarse resolution and the latter providing greater spatial resolution but only under cloud-free conditions. Sea ice can insulate the underlying liquid water against heat loss to the often frigid overlying polar atmosphere and also reflects sunlight that would otherwise be available to warm the ocean. AMSR-E measurements will allow the routine derivation of sea ice concentrations in both polar regions, through taking advantage of the marked contrast in microwave emissions of sea ice and liquid water. This will continue, with improved resolution and accuracy, a 22-year satellite record of changes in the extent of polar ice. MODIS, with its finer resolution, will permit the identification of individual ice flows, when unobscured by clouds. AMSR-E and MODIS will also provide monitoring, the AIRS/AMSU/HSB combination will provide more-accurate space-based measurements of atmospheric temperature and water vapor than have ever been obtained before, with the highest vertical resolution to date as well. Since water vapor is the Earth's primary greenhouse gas and contributes significantly to uncertainties in projections of future global warming, it is critical to understand how it varies in the Earth system. We should concern for these drastic changes and should protect it. Keywords-Hydrological cycle,Climate models,Aqua’s instruments

  3. [Fundamental studies in oxidation reduction in relation to water photolysis

    SciTech Connect

    Hurst, J.K.

    1992-01-01

    Objectives were to understand 3 elementary processes central to developing membrane-based integrated chemical systems for water photolysis: role of interfaces in charge separation/recombination reactions, pathways for transmembrane charge separation, and mechanisms of water oxidation catalyzed by transition metal coordination complexes. Research during this period is arranged under the headings transmembrane oxidation-reduction mechanisms, optically gated transmembrane redox, and mechanisms of water oxidation catalysis. Viologens are involved.

  4. Nanostructured transition metal oxides useful for water oxidation catalysis

    DOEpatents

    Frei, Heinz M; Jiao, Feng

    2013-12-24

    The present invention provides for a composition comprising a nanostructured transition metal oxide capable of oxidizing two H.sub.2O molecules to obtain four protons. In some embodiments of the invention, the composition further comprises a porous matrix wherein the nanocluster of the transition metal oxide is embedded on and/or in the porous matrix.

  5. Boosting water oxidation layer-by-layer.

    PubMed

    Hidalgo-Acosta, Jonnathan C; Scanlon, Micheál D; Méndez, Manuel A; Amstutz, Véronique; Vrubel, Heron; Opallo, Marcin; Girault, Hubert H

    2016-04-01

    Electrocatalysis of water oxidation was achieved using fluorinated tin oxide (FTO) electrodes modified with layer-by-layer deposited films consisting of bilayers of negatively charged citrate-stabilized IrO2 NPs and positively charged poly(diallyldimethylammonium chloride) (PDDA) polymer. The IrO2 NP surface coverage can be fine-tuned by controlling the number of bilayers. The IrO2 NP films were amorphous, with the NPs therein being well-dispersed and retaining their as-synthesized shape and sizes. UV/vis spectroscopic and spectro-electrochemical studies confirmed that the total surface coverage and electrochemically addressable surface coverage of IrO2 NPs increased linearly with the number of bilayers up to 10 bilayers. The voltammetry of the modified electrode was that of hydrous iridium oxide films (HIROFs) with an observed super-Nernstian pH response of the Ir(iii)/Ir(iv) and Ir(iv)-Ir(iv)/Ir(iv)-Ir(v) redox transitions and Nernstian shift of the oxygen evolution onset potential. The overpotential of the oxygen evolution reaction (OER) was essentially pH independent, varying only from 0.22 V to 0.28 V (at a current density of 0.1 mA cm(-2)), moving from acidic to alkaline conditions. Bulk electrolysis experiments revealed that the IrO2/PDDA films were stable and adherent under acidic and neutral conditions but degraded in alkaline solutions. Oxygen was evolved with Faradaic efficiencies approaching 100% under acidic (pH 1) and neutral (pH 7) conditions, and 88% in alkaline solutions (pH 13). This layer-by-layer approach forms the basis of future large-scale OER electrode development using ink-jet printing technology. PMID:26977761

  6. Electrochemical oxidation of perfluorinated compounds in water.

    PubMed

    Niu, Junfeng; Li, Yang; Shang, Enxiang; Xu, Zesheng; Liu, Jinzi

    2016-03-01

    Perfluorinated compounds (PFCs) are persistent and refractory organic pollutants that have been detected in various environmental matrices and municipal wastewater. Electrochemical oxidation (EO) is a promising remediation technique for wastewater contaminated with PFCs. A number of recent studies have demonstrated that the "non-active" anodes, including boron-doped diamond, tin oxide, and lead dioxide, are effective in PFCs elimination in wastewater due to their high oxygen evolution potential. Many researchers have conducted experiments to investigate the optimal conditions (i.e., potential, current density, pH value, plate distance, initial PFCs concentration, electrolyte, and other factors) for PFCs elimination to obtain the maximal elimination efficiency and current efficiency. The EO mechanism and pathways of PFCs have been clearly elucidated, which undergo electron transfer, Kolbe decarboxylation or desulfonation, hydrolysis, and radical reaction. In addition, the safety evaluation and energy consumption evaluation of the EO technology have also been summarized to decrease toxic ion release from electrode and reduce the cost of this technique. Although the ultrasonication and hydrothermal techniques combined with the EO process can improve the removal efficiency and current efficiency significantly, these coupled techniques have not been commercialized and applied in industrial wastewater treatment. Finally, key challenges facing EO technology are listed and the directions for further research are pointed out (such as combination with other techniques, treatment for natural waters contaminated by low levels of PFCs, and reactor design). PMID:26745381

  7. A learning process of water cycle as complex system

    NASA Astrophysics Data System (ADS)

    Schertzer, D.; Deroubaix, J. F.; Tchiguirinskaia, I.; Tassin, B.; Thevenot, D.

    2009-04-01

    Water cycle is a very good example of a complex geosystem which has many societal impacts and drivers. A permanent and ubiquitous question is how to increase public awareness and understanding of its extreme behaviours, as well as of the related uncertainties. For instance, CEREVE is highly solicited to help the general public, particularly the youth, and the local politicians to get better acquainted with the new water culture in general and with flood risks in particular, in the nearby county Val-de-Marne. Since 2001, May is the month of the "Festival de l'Oh"(which sounds like "Festival de l'Eau", i.e. the water festival co-organized by the county council and city of Paris. "Oh » at the same time partly displays the chemical composition of water and is an exclamation for atonishment). This festival starts with the Scientific Days of Environment that involve researchers and students of the county, as well as collaborators of all around the world. This conference is open to the public who can be informed from the latest research developments, in particular with the help of some general synthesis and panel discussions. On the other hand, (young) researchers can present their own works to a large public. This conference is followed by a Professional Forum where students, heads of water public services or private operators can meet. In the framework of the water festival preparation, there are several water forums for the secondary schools. All along the year, there are regular pedagogical activities for secondary schools, in particular in the framework of Water Houses scattered across the county. We will discuss the importance to better evaluate the effective impact of these pedagogical events on the public awareness and understanding, and to make the learning process more adaptive and interactive, as well as to better address the underlying fundamental problems, e.g. the present limitations of current modelling and data processing.

  8. A Hydrological Perspective to Advance Understanding of the Water Cycle

    NASA Astrophysics Data System (ADS)

    Berghuijs, W.

    2014-12-01

    In principle hydrologists are scientists that study relationships within the water cycle. Yet, current technology makes it tempting for hydrology students to lose their "hydrological perspective" and become instead full-time computer programmers or statisticians. I assert that students should ensure their hydrological perspective thrives, notwithstanding the importance and possibilities of current technology. This perspective is necessary to advance the science of hydrology. As other hydrologists have pondered similar views before, I make no claims of originality here. I just hope that in presenting my perspective on this issue I may spark the interest of other early career hydrologists.

  9. GEWEX - The Global Energy and Water Cycle Experiment

    NASA Technical Reports Server (NTRS)

    Chahine, Moustafa T.

    1992-01-01

    GEWEX, which is part of the World Climate Research Program, has as its goal an order-of-magnitude improvement in the ability to model global precipitation and evaporation and furnish an accurate assessment of the sensitivity of atmospheric radiation and clouds. Attention will also be given to the response of the hydrological cycle and water resources to climate change. GEWEX employs a single program to coordinate all aspects of climatology from model development to the deployment and operation of observational systems. GEWEX will operate over the next two decades.

  10. A Strategy for Integrated Water Cycle Observations from Space

    NASA Astrophysics Data System (ADS)

    Wood, E. F.; Houser, P. R.

    2005-12-01

    The coupling of land surface hydrologic processes to atmospheric processes over a range of spatial and temporal scales is needed for understanding how atmosphere-land surface interactions operate and feed back onto the regional and larger scale climate system. An integral component of NASA's Global Water and Energy Cycle (GWEC) program and the World Climate Research is whether knowledge of land surface hydrologic states results in improved weather and short-term climate predictions. The inherent research strategy for NASA/GWEC and WCRP/GEWEX for investigating this is through the merging (assimilation) of remotely sensed observations of the surface hydrospheric state with process-based, terrestrial water and energy balance models. NASA assumes that remote sensing observations using current (TRMM, Terra, and Aqua) and planned (e.g. Global Precipitation Mission, HYDROS for surface soil moisture and freeze-thaw state, and possibly snow and surface water) platforms will provide sufficient estimates of surface hydrologic state variables. The extent to which this assumption can be realized remains an open question. The unmet needs facing the community in fully exploiting space-borne observations include: (i) having sufficiently accurate retrieval of physical surface states, including validation programs that can estimate retrieval error characteristics; (ii) overcoming satellite sensor programs that primarily focus on a single physical parameter; and (iii) having consistency between satellite observations and land surface models in terms of consistency in the retrieved variables as they relate to the spatial and temporal variability of the terrestrial hydrosphere. This presentation will offer a new vision for water cycle observation and modeling that has, at its core, the concept of integrated observations as opposed to isolated observations, and consistency between models and observations. By integrated observations, we mean the simultaneous retrieval of related water cycle variables from a single satellite platform with sensors for multiple frequencies, combining passive and active sensors, and perhaps lidar. By consistency between observations and models, we mean the satellite observations be processed and utilized in an integrated manner with water cycle models. By recognizing that there are fast and slow components to the hydrosphere, an observational strategy can be developed that combines sensors in either Geostationary Earth Obit (GEO) for the fast components or Low Earth (polar) Orbit (LEO) for the slow components. The talk will present the challenges that need to be addressed and a roadmap for this vision. The challenges in developing an integrated observation strategy include innovative sensor and antennae technology, including the identification and selection of frequencies and sensors to meet the needs of water cycle research. For the modeling component, the challenge is in developing computational solutions that extract the maximum information from the integrated observations. This includes both retrieval algorithms that better relate model variables to satellite measurements and land models that more effectively reflect and describe the retrieved variables.

  11. The Martian Water Cycle Based on 3-D Modeling

    NASA Technical Reports Server (NTRS)

    Houben, H.; Haberle, R. M.; Joshi, M. M.

    1999-01-01

    Understanding the distribution of Martian water is a major goal of the Mars Surveyor program. However, until the bulk of the data from the nominal missions of TES, PMIRR, GRS, MVACS, and the DS2 probes are available, we are bound to be in a state where much of our knowledge of the seasonal behavior of water is based on theoretical modeling. We therefore summarize the results of this modeling at the present time. The most complete calculations come from a somewhat simplified treatment of the Martian climate system which is capable of simulating many decades of weather. More elaborate meteorological models are now being applied to study of the problem. The results show a high degree of consistency with observations of aspects of the Martian water cycle made by Viking MAWD, a large number of ground-based measurements of atmospheric column water vapor, studies of Martian frosts, and the widespread occurrence of water ice clouds. Additional information is contained in the original extended abstract.

  12. A general circulation model study of the Mars water cycle

    NASA Astrophysics Data System (ADS)

    Richardson, Mark Ian

    1999-10-01

    This study has focused on the development and application of the first fully three-dimensional model of the current Mars water cycle. Previous models of the water cycle have suggested the importance of transport processes in determining the observed variations in atmospheric water [Jakosky and Haberle (1992)]. This work addresses questions regarding the relative importance of water reservoirs, transport of water, control of global average vapour amounts, and the importance of clouds. The results of this work show that model transport out of the northern polar region during summer occurs primarily in surface forced, zonally asymmetric currents. Significantly more hemispheric transport is predicted than expected with zonal average models. Transport capacity is higher for south to north flow during southern summer than for north to south flow in northern summer. Houben et al. (1997) suggested that a model without regolith would ``flood'' with vapour. Our model does riot show this behaviour, thus the regolith may not provide sole control over global vapour amounts. The mechanism of ``equilibration'' for the model without regolith pivots on an annual average vapour flux balance across the northern high-latitude/polar latitude boundary. However, as there is always net loss to the south polar cold tap the ``equilibrium'' is only approximate. Simulations suggest that an exposed southern water cap would be unstable with respect to the northern cap. Comparison with zonal-average vapour data suggests that the residual cap provides <= 40% of the vapour observed to accrue after L S = 80. Simulations employing seasonal ice show improved ``fits,'' but additional (regolith) sources are needed. As suggested by Kahn (1990), agreement with data requires cloud ice precipitation. Precipitation allows water to be removed from a cold atmosphere more rapidly than diffusion of ice or vapour. Simulations also suggest that cloud formation may reduce interhemispheric water transport [Clancy et al. (1996)]. The model evolution of zonal-average vapour distributions is in rough agreement with data. Cloudiness is generally overpredicted, likely due to defects in the cloud microphysics scheme. The spatial distribution of clouds compare reasonably well with the limited observations, however errors do occur in the tropics and winter hemisphere. These likely result from errors in the vertical wind field and local scale vapour transport. Differences between the true and model topography and surface temperatures are the most likely causes. Detailed modeling of vapour transport will require very close attention to the surface prescription.

  13. In Situ Electrochemical Oxidation Tuning of Transition Metal Disulfides to Oxides for Enhanced Water Oxidation

    PubMed Central

    2015-01-01

    The development of catalysts with earth-abundant elements for efficient oxygen evolution reactions is of paramount significance for clean and sustainable energy storage and conversion devices. Our group demonstrated recently that the electrochemical tuning of catalysts via lithium insertion and extraction has emerged as a powerful approach to improve catalytic activity. Here we report a novel in situ electrochemical oxidation tuning approach to develop a series of binary, ternary, and quaternary transition metal (e.g., Co, Ni, Fe) oxides from their corresponding sulfides as highly active catalysts for much enhanced water oxidation. The electrochemically tuned cobalt–nickel–iron oxides grown directly on the three-dimensional carbon fiber electrodes exhibit a low overpotential of 232 mV at current density of 10 mA cm–2, small Tafel slope of 37.6 mV dec–1, and exceptional long-term stability of electrolysis for over 100 h in 1 M KOH alkaline medium, superior to most non-noble oxygen evolution catalysts reported so far. The materials evolution associated with the electrochemical oxidation tuning is systematically investigated by various characterizations, manifesting that the improved activities are attributed to the significant grain size reduction and increase of surface area and electroactive sites. This work provides a promising strategy to develop electrocatalysts for large-scale water-splitting systems and many other applications. PMID:27162978

  14. Water footprint of European cars: potential impacts of water consumption along automobile life cycles.

    PubMed

    Berger, Markus; Warsen, Jens; Krinke, Stephan; Bach, Vanessa; Finkbeiner, Matthias

    2012-04-01

    Due to global increase of freshwater scarcity, knowledge about water consumption in product life cycles is important. This study analyzes water consumption and the resulting impacts of Volkswagen's car models Polo, Golf, and Passat and represents the first application of impact-oriented water footprint methods on complex industrial products. Freshwater consumption throughout the cars' life cycles is allocated to material groups and assigned to countries according to import mix shares or location of production sites. Based on these regionalized water inventories, consequences for human health, ecosystems, and resources are determined by using recently developed impact assessment methods. Water consumption along the life cycles of the three cars ranges from 52 to 83 m(3)/car, of which more than 95% is consumed in the production phase, mainly resulting from producing iron, steel, precious metals, and polymers. Results show that water consumption takes place in 43 countries worldwide and that only 10% is consumed directly at Volkswagen's production sites. Although impacts on health tend to be dominated by water consumption in South Africa and Mozambique, resulting from the production of precious metals and aluminum, consequences for ecosystems and resources are mainly caused by water consumption of material production in Europe. PMID:22390631

  15. Homogeneous and Heterogeneous Photocatalytic Water Oxidation by Persulfate.

    PubMed

    Fukuzumi, Shunichi; Jung, Jieun; Yamada, Yusuke; Kojima, Takahiko; Nam, Wonwoo

    2016-04-20

    Photocatalytic water oxidation by persulfate (Na2 S2 O8 ) with [Ru(bpy)3 ](2+) (bpy=2,2'-bipyridine) as a photocatalyst provides a standard protocol to study the catalytic reactivity of water oxidation catalysts. The yield of evolved oxygen per persulfate is regarded as a good index for the catalytic reactivity because the oxidation of bpy of [Ru(bpy)3 ](2+) and organic ligands of catalysts competes with the catalytic water oxidation. A variety of metal complexes act as catalysts in the photocatalytic water oxidation by persulfate with [Ru(bpy)3 ](2+) as a photocatalyst. Herein, the catalytic mechanisms are discussed for homogeneous water oxidation catalysis. Some metal complexes are converted to metal oxide or hydroxide nanoparticles during the photocatalytic water oxidation by persulfate, acting as precursors for the actual catalysts. The catalytic reactivity of various metal oxides is compared based on the yield of evolved oxygen and turnover frequency. A heteropolynuclear cyanide complex is the best catalyst reported so far for the photocatalytic water oxidation by persulfate and [Ru(bpy)3 ](2+) , affording 100 % yield of O2 per persulfate. PMID:26889913

  16. Water cycle of a seasonally dry tropical forest (Southern Vietnam)

    NASA Astrophysics Data System (ADS)

    Kuricheva, O. A.; Avilov, V. C.; Dinh, Duy Ba; Kurbatova, J. A.

    2015-12-01

    How does the activity of the ecosystem of monsoon tropical forest decrease during the dry season of more than 4 months? To answer this question, the dynamics of evapotranspiration is analyzed in the national park of Cát Tiên (Southern Vietnam) using continuous eddy covariance and meteorological dataset for 2012-2013. A comparison of evapotranspiration between Cát Tiên and 21 sites in different tropical forests over the world is performed. It is shown that the abundance of resources of energy and moisture in the annual cycle, as well as the storage of water from the rainy season allows monsoon ecosystem to implement the proactive vegetation during the dry season and make specificity of ecosystem energy and water fluxes in Cát Tiên forest similar to the rainforests.

  17. Arsenic cycling within the water column of a small lake receiving contaminated ground-water discharge

    SciTech Connect

    Ford, Robert G.; Wilkin, Richard T.; Hernandez, Gina

    2008-09-18

    The fate of arsenic discharged from contaminated ground water to a small, shallow lake at a hazardous waste site was examined to understand the role of iron (hydr)oxide precipitation-dissolution processes within the water column. Field and laboratory observations indicate that arsenic solubility was controlled, in part, by the extent of ferrous iron oxidation-precipitation and arsenic sorption occurring near the lake chemocline. Laboratory experiments were conducted using site-derived water to assess the impact of these coupled processes on the removal of dissolved arsenic from the water column. The measured concentration of organic carbon from epilimnetic and hypolimnetic water sampled from the lake was approximately 1.3 mM and 17.0 mM, respectively. Experiments conducted with these samples along with synthetic controls containing no organic carbon demonstrated that observed rates of formation and crystallinity of the precipitated iron (hydr)oxide were dependent on the concentration of organic carbon in the lake water. Increasing dissolved organic matter concentration did not significantly interfere with ferrous iron oxidation, but inhibited iron (hydr)oxide precipitation and subsequent sorption of arsenic. For experiments using water sampled from the lake hypolimnion there was a strong relationship between the fraction of precipitated iron and the fraction of sorbed arsenic. Laboratory- and field-derived iron (hydr)oxide precipitates were characterized to evaluate mineralogy and arsenic distribution. In-situ suspended solids and precipitates formed in laboratory experiments using hypolimnetic water were identified as poorly crystalline 2-line ferrihydrite. These solids were readily dissolved in the presence of dithionite indicating that elevated dissolved iron and arsenic observed in the hypolimnion resulted, in part, from in-situ reductive dissolution of settling 2-line ferrihydrite near the sediment-water interface. These observations support the contention that the levels of dissolved arsenic observed in the shallow lake can be attributed to ground-water discharge and internal recycling of arsenic within the water column. The efficiency of the process resulting in iron (hydr)oxide precipitation and arsenic sorption limits the downgradient export of arsenic derived from ground-water discharge.

  18. Does GRACE see the terrestrial water cycle "intensifying"?

    NASA Astrophysics Data System (ADS)

    Eicker, Annette; Forootan, Ehsan; Springer, Anne; Longuevergne, Laurent; Kusche, Jürgen

    2016-01-01

    Several researchers have postulated that, under a changing climate due to anthropogenic forcing, an intensification of the water cycle is already under way. This is usually related to increases in hydrological fluxes as precipitation (P), evapotranspiration (E), and river discharge (R). It is under debate, however, whether such observed or reconstructed flux changes are real and on what scales. Large-scale increase or decrease of the flux deficit (P-E-R), i.e., flux changes that do not compensate, would lead to acceleration or deceleration of water storage anomalies potentially visible in Gravity Recovery and Climate Experiment (GRACE) data. In agreement with earlier studies, we do find such accelerations in global maps of gridded GRACE water storage anomalies over 2003-2012. However, these have been generally associated with interannual and decadal climate variability. Yet we show that even after carefully isolating and removing the contribution of El Niño that partially masks long-term changes, using a new method, accelerations of up to 12 mm/yr2 remain in regions such as Australia, Turkey, and Northern India. We repeat our analysis with flux fields from two global atmospheric reanalyses that include land surface models (ERA-Interim and MERRA-Land). While agreeing well with GRACE on shorter time scales, they fall short in displaying long-term trends corresponding to GRACE accelerations. We hypothesize that this may be due to time-varying biases in the reanalysis fluxes as noticed in other studies. We conclude that even though its data record is short, GRACE provides new information that should be used to constrain future reanalyses toward a better representation of long-term water cycle evolution.

  19. Supercritical water oxidation: An engineering update

    SciTech Connect

    Gloyna, E.F. . Environmental Health Engineering); Lixiong Li . Supercritical Water Oxidation Separations Research Program)

    1993-01-01

    This paper reviews the need for innovative treatment technologies and describes a wastewater treatment system capable of completely destroying toxic organic substances and biological sludges. The basic concepts of supercritical water oxidation (SCWO), associated engineering research, and technology development are examined. During the last few years a growing body of SCWO knowledge has been assembled. A number of universities, federal agencies, and private companies have participated in both engineering research and technology development. In general, engineering research has focused upon reaction kinetics and mechanisms, salt formation and solubility, mass and heat transfer, transformation product identification, catalysis, corrosion, and additive impacts. As research progressed technology development has directed its attention to materials of construction, reactor design, heat exchange and recuperative heat recovery, solid-liquid separation, gas-liquid separation, control systems, emuent handling, ash disposal, safety requirements, and process integration. SCWO technology relies on the unique properties of supercritical water to create an excellent reaction medium. The system is capable of operating as a totally enclosed facility, providing complete destruction, and meeting all regulatory emuent requirements. As such, this new technology is an environmentally attractive option. Because of favorable treatability, safety, and economic considerations a growing number private and governmental entities are currently involved in the development of more effective SCWO facilities.

  20. Exploring causes of interannual variability in the seasonal cycles of tropospheric nitrous oxide

    NASA Astrophysics Data System (ADS)

    Nevison, C. D.; Dlugokencky, E.; Dutton, G.; Elkins, J. W.; Fraser, P.; Hall, B.; Krummel, P. B.; Langenfelds, R. L.; O'Doherty, S.; Prinn, R. G.; Steele, L. P.; Weiss, R. F.

    2011-04-01

    Seasonal cycles in the mixing ratios of tropospheric nitrous oxide (N2O) are derived by detrending long-term measurements made at sites across four global surface monitoring networks. The detrended monthly data display large interannual variability, which at some sites challenges the concept of a "mean" seasonal cycle. In the Northern Hemisphere, correlations between polar winter lower stratospheric temperature and detrended N2O data, around the month of the seasonal minimum, provide empirical evidence for a stratospheric influence, which varies in strength from year to year and can explain much of the interannual variability in the surface seasonal cycle. Even at sites where a strong, competing, regional N2O source exists, such as from coastal upwelling at Trinidad Head, California, the stratospheric influence must be understood to interpret the biogeochemical signal in monthly mean data. In the Southern Hemisphere, detrended surface N2O monthly means are correlated with polar spring lower stratospheric temperature in months preceding the N2O minimum, providing empirical evidence for a coherent stratospheric influence in that hemisphere as well, in contrast to some recent atmospheric chemical transport model (ACTM) results. Correlations between the phasing of the surface N2O seasonal cycle in both hemispheres and both polar lower stratospheric temperature and polar vortex break-up date provide additional support for a stratospheric influence. The correlations discussed above are generally more evident in high-frequency in situ data than in data from weekly flask samples. Furthermore, the interannual variability in the N2O seasonal cycle is not always correlated among in situ and flask networks that share common sites, nor do the mean seasonal amplitudes always agree. The importance of abiotic influences such as the stratospheric influx and tropospheric transport on N2O seasonal cycles suggests that, at sites remote from local sources, surface N2O mixing ratio data by themselves are unlikely to provide information about seasonality in surface sources, e.g., for atmospheric inversions, unless the ACTMs employed in the inversions accurately account for these influences. An additional abioitc influence is the seasonal ingassing and outgassing of cooling and warming surface waters, which creates a thermal signal in tropospheric N2O that is of particular importance in the extratropical Southern Hemisphere, where it competes with the biological ocean source signal.

  1. RELATIONSHIPS BETWEEN OXIDATION-REDUCTION POTENTIAL, OXIDANT, AND PH IN DRINKING WATER

    EPA Science Inventory

    Oxidation and reduction (redox) reactions are very important in drinking water. Oxidation-reduction potential (ORP) measurements reflect the redox state of water. Redox measurements are not widely made by drinking water utilities in part because they are not well understood. The ...

  2. RELATIONSHIPS BETWEEN OXIDATION-REDUCTION, OXIDANT, AND PH IN DRINKING WATER

    EPA Science Inventory

    Oxidation and reduction (redox) reactions are very important in drinking water. Oxidation-reduction potential (ORP) measurements reflect the redox state of water. Redox measurements are not widely made by drinking water utilities in part because they are not well understood. The ...

  3. Solid Oxide Fuel Cell/Gas Turbine Hybrid Cycle Technology for Auxiliary Aerospace Power

    NASA Technical Reports Server (NTRS)

    Steffen, Christopher J., Jr.; Freeh, Joshua E.; Larosiliere, Louis M.

    2005-01-01

    A notional 440 kW auxiliary power unit has been developed for 300 passenger commercial transport aircraft in 2015AD. A hybrid engine using solid-oxide fuel cell stacks and a gas turbine bottoming cycle has been considered. Steady-state performance analysis during cruise operation has been presented. Trades between performance efficiency and system mass were conducted with system specific energy as the discriminator. Fuel cell performance was examined with an area specific resistance. The ratio of fuel cell versus turbine power was explored through variable fuel utilization. Area specific resistance, fuel utilization, and mission length had interacting effects upon system specific energy. During cruise operation, the simple cycle fuel cell/gas turbine hybrid was not able to outperform current turbine-driven generators for system specific energy, despite a significant improvement in system efficiency. This was due in part to the increased mass of the hybrid engine, and the increased water flow required for on-board fuel reformation. Two planar, anode-supported cell design concepts were considered. Designs that seek to minimize the metallic interconnect layer mass were seen to have a large effect upon the system mass estimates.

  4. Community of Practice Applications from WaterNet: The NASA Water Cycle Solutions Network

    NASA Astrophysics Data System (ADS)

    Matthews, D.; Brilly, M.; Gregoric, G.; Polajnar, J.; Houser, P.; Rodell, M.; Lehning, M.

    2009-04-01

    WaterNet is a new international network of researchers, stakeholders, and end-users of remote sensing tools that will benefit the water resources management community. It addresses a means for enhancing the social and economic developments of nations by increased use of practical research products from the terrestrial water cycle for making informed decisions. This paper provides a summary of the Water Cycle Community of Practice (CoP) plans and examples of Land Surface Model (LSM) applications for extreme events - floods, droughts, and heavy snowstorms in Europe. It discusses the concept of NASA's solutions networks focusing on the WaterNet. It invites EGU teams to join our WaterNet network. The NASA Water cycle Solutions Network's goal is to improve and optimize the sustained ability of water cycle researchers, stakeholders, organizations and networks to interact, identify, harness, and extend NASA research results to augment decision support tools and meet national needs. Our team is developing WaterNet by engaging relevant NASA water cycle research and community-of-practice organizations, to develop what we term an "actionable database" that can be used to communicate and connect NASA Water cycle research Results (NWRs) towards the improvement of water-related Decision Support Tools (DSTs). Recognizing that the European Commission and European Space Agency have also developed many related research products (EWRs), we seek to learn about these and network with the EU teams to include their information in the WaterNet actionable data base. Recognizing the many existing highly valuable water-related science and application networks in the US and EU, we focus the balance of our efforts on enabling their interoperability - facilitating access and communications among decision-makers and scientists. We present results of our initial focus on identification, collection, and analysis of the two end points, these being the NWRs and EWRs and water related DSTs. We discuss strategies to connect these two end points via innovative communication strategies, improved user access to NASA resources, improved water cycle research community appreciation for user DST requirements, improved policymaker, management and stakeholder knowledge of NASA and EU research and application products, and improved identification of pathways for progress. Extreme event analysis and prediction is important to water managers, emergency managers-civil defense and local law enforcement, and the public. The paper presents examples from the extreme flash flood event of 18 September 2007 which cost over 200 M Euro in damages to roads, homes, and other infrastructure in the mountains west of Ljubljana. Results from NASA's Global Land Data Assimilation System - Land Surface Model show the precipitation, runoff, and soil moisture simulated in this extreme local flood event highlighting the limitations of coarse grid ¼ degree grid and 1 km grid spacing models. Drought simulations over Southeastern Europe also provide examples of model capabilities for drought management decision-making focusing on soil moisture, soil temperature, and precipitation simulations from GLDAS. Extreme snowfall events also pose a serious problem for emergency managers, ski industry and transportation managers. An example of GLDAS simulations of a heavy snow event in the Alps shows the capabilities of GLDAS, and contrasts results from the SLF snow and avalanche research. We seek to build on existing partnerships with EU scientific teams that represent a cross-section of individual and networked NWRs, EWRs and DSTs from government, private, and academic domains, that will enable us to quickly establish an operational solutions network, entrain more partner nodes and networks, and move WaterNet toward self-sustainability in the US and EU. EU projects like AWARE, and the flood and drought forecasting research efforts (DMCSEE) and GMES projects are potential projects that may directly benefit from this WaterNet networking. Specific goals and objectives, methods of communication, and process to join the WaterNet Community of Practice are discussed.

  5. Anticipated SWOT Observations of Human Impacts on the Water Cycle

    NASA Astrophysics Data System (ADS)

    Clark, E.; Andreadis, K.; Moller, D.; Lettenmaier, D. P.

    2012-12-01

    The impoundment of water behind dams alters the timing and magnitude of the discharge of rivers to the ocean, and hence sea level, as well as evaporation from the global land areas, and, through irrigation, the storage of water on land in the soil column. The impact of these effects on the global hydrologic cycle globally is difficult to estimate given currently available (and shared) observations of temporally varying reservoir storage. The upcoming joint U.S.-France Surface Water and Ocean Topography (SWOT) mission* will measure terrestrial surface water storage dynamics with unprecedented global coverage for managed reservoirs, as well as natural lakes and rivers. Previous studies have investigated SWOT's potential ability to measure storage change for some lakes; however, because reservoirs are typically located in flooded river valleys, they tend to be more elongate than the high latitude lakes that have been studied, and have more complex shorelines (and hence a longer land-water boundary). Furthermore, for reservoirs in mountainous regions, SWOT observations will be prone to topographic layover effects. Finally, the temporal variability of water levels in reservoirs is determined by management goals (i.e., hydropower, flood control, irrigation, supply, recreation), rather than climate, as in the case of natural lakes. We report an investigation of the potential accuracy of SWOT observations of storage change over selected managed reservoirs in the United States. First, we developed a time series of water height maps over each reservoir by combining available bathymetry data with observations of reservoir storage. We then simulated realistic SWOT observations of water level over these water bodies, given the planned SWOT orbital parameters, anticipated noise, and topographic layover errors. We also simulated a realistic tropospheric delay, modeled from daily MERRA reanalysis data. From these synthetic observations, we estimate the number of overpasses needed to construct accurate area-elevation-volume curves. We discuss the accuracy of absolute volume estimated from an extrapolation of the smoothed elevation-volume relationship, as well as the accuracy of the directly observed storage change. SWOT performs better in terms of storage change accuracy over large reservoirs with regular boundaries and relatively flat topography. In addition, we assess the ability of SWOT's planned sampling schedule to reconstruct the variability in storage change for U.S. reservoirs as a function of their storage capacity. Estimates of absolute storage are most accurate for reservoirs that experience the most water level variation during the anticipated SWOT sampling period. *The SWOT mission has not been formally approved by NASA. The decision to proceed with the mission will not occur until the completion of the National Environmental Policy Act (NEPA) process. Material in this paper related to SWOT is for information purposes only.

  6. Carbon cycle. Sunlight controls water column processing of carbon in arctic fresh waters.

    PubMed

    Cory, Rose M; Ward, Collin P; Crump, Byron C; Kling, George W

    2014-08-22

    Carbon in thawing permafrost soils may have global impacts on climate change; however, the factors that control its processing and fate are poorly understood. The dominant fate of dissolved organic carbon (DOC) released from soils to inland waters is either complete oxidation to CO2 or partial oxidation and river export to oceans. Although both processes are most often attributed to bacterial respiration, we found that photochemical oxidation exceeds rates of respiration and accounts for 70 to 95% of total DOC processed in the water column of arctic lakes and rivers. At the basin scale, photochemical processing of DOC is about one-third of the total CO2 released from surface waters and is thus an important component of the arctic carbon budget. PMID:25146289

  7. Potential Seasonal Predictability of Water Cycle in Observations and Reanalysis

    NASA Astrophysics Data System (ADS)

    Feng, X.; Houser, P.

    2012-12-01

    Identification of predictability of water cycle variability is crucial for climate prediction, water resources availability, ecosystem management and hazard mitigation. An analysis that can assess the potential skill in seasonal prediction was proposed by the authors, named as analysis of covariance (ANOCOVA). This method tests whether interannual variability of seasonal means exceeds that due to weather noise under the null hypothesis that seasonal means are identical every year. It has the advantage of taking into account autocorrelation structure in the daily time series but also accounting for the uncertainty of the estimated parameters in the significance test. During the past several years, multiple reanalysis datasets have become available for studying climate variability and understanding climate system. We are motivated to compare the potential predictability of water cycle variation from different reanalysis datasets against observations using the newly proposed ANOCOVA method. The selected eight reanalyses include the National Centers for Environmental Prediction-National Center for Atmospheric Research (NCEP/NCAR) 40-year Reanalysis Project (NNRP), the National Centers for Environmental Prediction-Department of Energy (NCEP/DOE) Reanalysis Project (NDRP), the European Centre for Medium-Range Weather Forecasts (ECMWF) 40-year Reanalysis, The Japan Meteorological Agency 25-year Reanalysis Project (JRA25), the ECMWF) Interim Reanalysis (ERAINT), the NCEP Climate Forecast System Reanalysis (CFSR), the National Aeronautics and Space Administration (NASA) Modern-Era Retrospective Analysis for Research and Applications (MERRA), and the National Oceanic and Atmospheric Administration-Cooperative Institute for Research in Environmental Sciences (NOAA/CIRES) 20th Century Reanalysis Version 2 (20CR). For key water cycle components, precipitation and evaporation, all reanalyses consistently show high fraction of predictable variance in the tropics, low predictability over the extratropics, more potential predictability over the ocean than land, and a stronger seasonal variation in potential predictability over land than ocean. The substantial differences are observed especially over the extropical areas where boundary-forced signal is not as significant as in tropics. We further evaluate the accuracy of reanalysis in estimating seasonal predictability over several selected regions, where rain gauge measurement or land surface data assimilation product is available and accurate, to gain insight on the strength and weakness of reanalysis products.

  8. Failure and life cycle evaluation of watering valves.

    PubMed

    Gonzalez, David M; Graciano, Sandy J; Karlstad, John; Leblanc, Mathias; Clark, Tom; Holmes, Scott; Reuter, Jon D

    2011-09-01

    Automated watering systems provide a reliable source of ad libitum water to animal cages. Our facility uses an automated water delivery system to support approximately 95% of the housed population (approximately 14,000 mouse cages). Drinking valve failure rates from 2002 through 2006 never exceeded the manufacturer standard of 0.1% total failure, based on monthly cage census and the number of floods. In 2007, we noted an increase in both flooding and cases of clinical dehydration in our mouse population. Using manufacturer's specifications for a water flow rate of 25 to 50 mL/min, we initiated a wide-scale screening of all valves used. During a 4-mo period, approximately 17,000 valves were assessed, of which 2200 failed according to scoring criteria (12.9% overall; 7.2% low flow; 1.6% no flow; 4.1% leaky). Factors leading to valve failures included residual metal shavings, silicone flash, introduced debris or bedding, and (most common) distortion of the autoclave-rated internal diaphragm and O-ring. Further evaluation revealed that despite normal autoclave conditions of heat, pressure, and steam, an extreme negative vacuum pull caused the valves' internal silicone components (diaphragm and O-ring) to become distorted and water-permeable. Normal flow rate often returned after a 'drying out' period, but components then reabsorbed water while on the animal rack or during subsequent autoclave cycles to revert to a variable flow condition. On the basis of our findings, we recalibrated autoclaves and initiated a preventative maintenance program to mitigate the risk of future valve failure. PMID:22330720

  9. Failure and Life Cycle Evaluation of Watering Valves

    PubMed Central

    Gonzalez, David M; Graciano, Sandy J; Karlstad, John; Leblanc, Mathias; Clark, Tom; Holmes, Scott; Reuter, Jon D

    2011-01-01

    Automated watering systems provide a reliable source of ad libitum water to animal cages. Our facility uses an automated water delivery system to support approximately 95% of the housed population (approximately 14,000 mouse cages). Drinking valve failure rates from 2002 through 2006 never exceeded the manufacturer standard of 0.1% total failure, based on monthly cage census and the number of floods. In 2007, we noted an increase in both flooding and cases of clinical dehydration in our mouse population. Using manufacturer's specifications for a water flow rate of 25 to 50 mL/min, we initiated a wide-scale screening of all valves used. During a 4-mo period, approximately 17,000 valves were assessed, of which 2200 failed according to scoring criteria (12.9% overall; 7.2% low flow; 1.6% no flow; 4.1% leaky). Factors leading to valve failures included residual metal shavings, silicone flash, introduced debris or bedding, and (most common) distortion of the autoclave-rated internal diaphragm and O-ring. Further evaluation revealed that despite normal autoclave conditions of heat, pressure, and steam, an extreme negative vacuum pull caused the valves’ internal silicone components (diaphragm and O-ring) to become distorted and water-permeable. Normal flow rate often returned after a ‘drying out’ period, but components then reabsorbed water while on the animal rack or during subsequent autoclave cycles to revert to a variable flow condition. On the basis of our findings, we recalibrated autoclaves and initiated a preventative maintenance program to mitigate the risk of future valve failure. PMID:22330720

  10. The Urban Water Cycle and how it Modulates the Microclimate and the Energy Cycle

    NASA Astrophysics Data System (ADS)

    Bou-Zeid, E.; Wang, Z.; Ramamurthy, P.; Li, D.; Sun, T.; Smith, J. A.

    2012-12-01

    Urbanization is the land-use modification with the largest and most manifest impacts on hydrologic storage and fluxes. This perturbation of the water cycle also has considerable ramifications on the surface energy budget and the microclimatology in built terrain: reducing the potential for water storage and subsequent evaporation reduces the fraction of incoming radiative energy dissipated through surface evaporation, and consequently increases the sensible heating of the urban atmosphere and solid surfaces (buildings, roads, …). However, the complexity of the involved physical processes and their interactions have so far been oversimplified, leading to considerable biases in model output when compared to observations. Using novel sensing techniques that include wireless sensor networks, this study seeks to build a better understanding of the Urban Water Cycle. Our findings indicate that "impervious surfaces" in urban area are not really impervious and not always dry. The role of evaporation from gravel-covered roofs and from concrete, brick, stone and asphalt surfaces can be considerable, leading to lower sensible heating. In addition, the different thermal properties of the various urban materials lead to extreme spatial heterogeneity in surface conditions that is much higher than over natural terrain. Building on this understanding, an improved urban canopy model is developed that includes much better representation of surface heterogeneity and of hydrological and thermal storage and transport processes, including analytical solutions of the heat equation and numerical solutions of the Richards equation in the urban surface. The model development will be detailed and applications focusing on the role of evaporation in mitigating summer building cooling needs and urban heat island effects will be presented.

  11. Rapid thermal cycling of metal-supported solid oxide fuel cellmembranes

    SciTech Connect

    Matus, Yuriy B.; De Jonghe, Lutgard C.; Jacobson, Craig P.; Visco, Steven J.

    2004-01-02

    Solid oxide fuel cell (SOFC) membranes were developed in which zirconia-based electrolyte thin films were supported by a composite metal/ceramic electrode, and were subjected to rapid thermal cycling between 200 and 800 C. The effects of this cycling on membrane performance were evaluated. The membranes, not yet optimized for performance, showed a peak power density of 350mW/cm2at 900 C in laboratory-sized SOFCs that was not affected by the thermal cycling. This resistance to cycling degradation is attributed to the close matching of thermal expansion coefficient of the cermet support electrode with that of the zirconia electrolyte.

  12. Semiconductor photocatalysts for water oxidation: current status and challenges.

    PubMed

    Yang, Lingling; Zhou, Han; Fan, Tongxiang; Zhang, Di

    2014-04-21

    Artificial photosynthesis is a highly-promising strategy to convert solar energy into hydrogen energy for the relief of the global energy crisis. Water oxidation is the bottleneck for its kinetic and energetic complexity in the further enhancement of the overall efficiency of the artificial photosystem. Developing efficient and cost-effective photocatalysts for water oxidation is a growing desire, and semiconductor photocatalysts have recently attracted more attention due to their stability and simplicity. This article reviews the recent advancement of semiconductor photocatalysts with a focus on the relationship between material optimization and water oxidation efficiency. A brief introduction to artificial photosynthesis and water oxidation is given first, followed by an explanation of the basic rules and mechanisms of semiconductor particulate photocatalysts for water oxidation as theoretical references for discussions of componential, surface structure, and crystal structure modification. O2-evolving photocatalysts in Z-scheme systems are also introduced to demonstrate practical applications of water oxidation photocatalysts in artificial photosystems. The final part proposes some challenges based on the dynamics and energetics of photoholes which are fundamental to the enhancement of water oxidation efficiency, as well as on the simulation of natural water oxidation that will be a trend in future research. PMID:24599528

  13. Investigation of Iron Oxide Morphology in a Cyclic Redox Water Splitting Process for Hydrogen Generation

    SciTech Connect

    Bobek, MM; Stehle, RC; Hahn, DW

    2012-10-23

    A solar fuels generation research program is focused on hydrogen production by means of reactive metal water splitting in a cyclic iron-based redox process. Iron-based oxides are explored as an intermediary reactive material to dissociate water molecules at significantly reduced thermal energies. With a goal of studying the resulting oxide chemistry and morphology, chemical assistance via CO is used to complete the redox cycle. In order to exploit the unique characteristics of highly reactive materials at the solar reactor scale, a monolithic laboratory scale reactor has been designed to explore the redox cycle at temperatures ranging from 675 to 875 K. Using high resolution scanning electron microscope (SEM) and electron dispersive X-ray spectroscopy (EDS), the oxide morphology and the oxide state are quantified, including spatial distributions. These images show the change of the oxide layers directly after oxidation and after reduction. The findings show a significant non-stoichiometric O/Fe gradient in the atomic ratio following oxidation, which is consistent with a previous kinetics model, and a relatively constant, non-stoichiometric O/Fe atomic ratio following reduction.

  14. Reservoir in Global Water Cycle: Macro Scale Hydrologic Modeling for Water Management

    NASA Astrophysics Data System (ADS)

    Zhou, T.; Nijssen, B.; Haddeland, I.; Gao, H.; Lettenmaier, D. P.

    2014-12-01

    Man-made reservoirs play a key role in the terrestrial water system. They support purposes, such as irrigation, hydropower generation, and flood control, which can substantially change water fluxes at the land surface and redistribute the storage of surface water in space and time. Although most developed countries have sophisticated observing systems for many variables in the natural surface water cycle, long-term and consistent records that focus on water management and human impacts on the global water cycle are much more limited, and most land surface models ignore water management activities. We describe a continental-scale model of reservoir storage, which is combined with a soil moisture deficit-based irrigation scheme within the Variable Infiltration Capacity (VIC) macro-scale hydrological model to simulate the effects of water management in the major river basins of the world. The model is forced with merged NCEP/NCAR and satellite meteorological data at a spatial resolution of 0.25 degrees latitude-longitude, for the period 1948 to 2010. A total of 167 of the largest reservoirs in the world with a total storage capacity around 3900 km3 (nearly 60% of the global total reservoir storage) are simulated. We successfully predict the monthly reservoir storage time series for most of a set of 23 global reservoirs for which observed storage is available either via in situ or satellite remote sensing measurements. We evaluate, on a continental and global basis, the magnitude of inter-seasonal and inter-annual reservoir storage variations in comparison with other terms in the land surface water cycle, including Snow Water Equivalent (SWE) and soil moisture.

  15. Oxidative stress-induced DNA damage and cell cycle regulation in B65 dopaminergic cell line.

    PubMed

    Pizarro, Javier G; Folch, Jaume; Vazquez De la Torre, Aurelio; Verdaguer, Ester; Junyent, Felix; Jordán, Joaquín; Pallàs, Mercè; Camins, Antoni

    2009-10-01

    Reactive oxygen species and oxidative stress are associated with neuronal cell death in many neurodegenerative conditions. However, the exact molecular mechanisms triggered by oxidative stress in neurodegeneration are still unclear. This study used the B65 rat neuroblastoma cell line as a model to study the molecular events that occur after H(2)O(2) treatment. Treatment of B65 cells with H(2)O(2) rapidly up-regulated the DNA damage pathway involved in double-strand breakage. Subsequently, proteins involved in p53 regulation, such as sirtuin 1 and STAT1, were modified. In addition, H(2)O(2) treatment altered the pattern of cell cycle protein expression. Specifically, a decrease was found in the expression of cyclin D1, cdk4 and surprisingly the levels of cyclin A and the retinoblastoma protein phosphorylated at ser780 were increased. Furthermore, this study shows that pre-treatment of B65 cells with 50 microM trolox confers almost total protection against apoptotic cell death and restores the cell cycle. Likewise, the increase in retinoblastoma phosphorylation was attenuated by KU-55993, a selective ATM inhibitor, and also by trolox. These observations indicate that DNA damage and oxidative stress are responsible for cell cycle regulation. In summary, this study describes the molecular mechanisms involved in cell cycle alterations induced by oxidative stress in B65 cells. These findings highlight the relevance of ATM in the regulation of cell cycle after oxidative stress. PMID:19657808

  16. Exploring the limits of the terrestrial fresh water cycle

    NASA Astrophysics Data System (ADS)

    van der Ent, Ruud; Wang-Erlandsson, Lan; Keys, Patrick; Savenije, Hubert

    2014-05-01

    Precipitation is the ultimate source of life on this planet: it makes our crops grow, provides drinking water, feeds rivers and replenishes groundwater aquifers. Climate modelling studies estimate changes in precipitation due to increased greenhouse gas emissions and climate impact studies use those estimates as input to their (hydrological) models to predict future water availability and societal impact. However, humans also significantly alter the land surface by, for example, deforestation and irrigation, which is not frequently taken into account in our climate studies. Here, we present an overview of several papers in the field of moisture recycling, published by our group, that show the extent to which terrestrial evaporation influences terrestrial precipitation. It is found that 38% of the terrestrial precipitation originates from terrestrial evaporation and that 58% of all terrestrial evaporation recycles, and return again as terrestrial precipitation. Knowing this, it is clear that evaporation is not necessary a loss to the hydrological cycle. We show that in some cases even transpiration during the dry season can act as a moisture source for a distant region. To assess the vulnerability of a region to local and remote land use changes we propose the concept of the precipitationshed, which maps out a region's precipitation sources. Our results are useful in mapping out possible land use change threats, but also opportunities to safeguard our water resources in the Anthropocene.

  17. Diverse arsenic- and iron-cycling microbial communities in arsenic-contaminated aquifers used for drinking water in Bangladesh.

    PubMed

    Hassan, Zahid; Sultana, Munawar; van Breukelen, Boris M; Khan, Sirajul I; Röling, Wilfred F M

    2015-04-01

    Subsurface removal of arsenic by injection with oxygenated groundwater has been proposed as a viable technology for obtaining 'safe' drinking water in Bangladesh. While the oxidation of ferrous iron to solid ferric iron minerals, to which arsenic adsorbs, is assumed to be driven by abiotic reactions, metal-cycling microorganisms may potentially affect arsenic removal. A cultivation-independent survey covering 24 drinking water wells in several geographical regions in Bangladesh was conducted to obtain information on microbial community structure and diversity in general, and on specific functional groups capable of the oxidation or reduction of arsenic or iron. Each functional group, targeted by either group-specific 16S rRNA or functional gene amplification, occurred in at least 79% of investigated samples. Putative arsenate reducers and iron-oxidizing Gallionellaceae were present at low diversity, while more variation in potentially arsenite-oxidizing microorganisms and iron-reducing Desulfuromonadales was revealed within and between samples. Relations between community composition on the one hand and hydrochemistry on the other hand were in general not evident, apart from an impact of salinity on iron-cycling microorganisms. Our data suggest widespread potential for a positive contribution of arsenite and iron oxidizers to arsenic removal upon injection with oxygenated water, but also indicate a potential risk for arsenic re-mobilization by anaerobic arsenate and iron reducers once injection is halted. PMID:25778510

  18. Multimodal science teachers' discourse in modeling the water cycle

    NASA Astrophysics Data System (ADS)

    Márquez, Conxita; Izquierdo, Mercè; Espinet, Mariona

    2006-03-01

    The paper presents an intensive study of a micro-event aiming at the characterization of teacher's discourse from a multimodal communication perspective in a secondary school science classroom dealing with the topic of water cycle. The research addresses the following questions: (a) What communicative modes are used by the teacher?, (b) what role do the different communicative modes play within teacher's discourse?, and (c) what are the relationships among communicative modes being used by the teacher? Theoretical framework is developed based on three strands: multimodal communication, science teaching and learning as modeling, and social semotics and Halliday's functional grammar. An analytic scheme guiding teachers' discourse analysis is presented and results discussed. Implications for science teacher education are drawn that would contribute to the improvement of science teacher education.

  19. Our Environment in Hot Water: Comparing Water Heaters, A Life Cycle Approach Comparing Tank and Tankless Water Heaters in California

    SciTech Connect

    Lu, Alison; McMahon, James; Masanet, Eric; Lutz, Jim

    2008-08-13

    Residential water heating is a large source of energy use in California homes. This project took a life cycle approach to comparing tank and tankless water heaters in Northern and Southern California. Information about the life cycle phases was calculated using the European Union�s Methodology study for EcoDesign of Energy-using Products (MEEUP) and the National Renewable Energy Laboratory�s Life Cycle Inventory (NREL LCI) database. In a unit-to-unit comparison, it was found that tankless water heaters would lessen impacts of water heating by reducing annual energy use by 2800 MJ/year (16% compared to tank), and reducing global warming emissions by 175 kg CO2 eqv./year (18% reduction). Overall, the production and combustion of natural gas in the use phase had the largest impact. Total waste, VOCs, PAHs, particulate matter, and heavy-metals-to-air categories were also affected relatively strongly by manufacturing processes. It was estimated that tankless water heater users would have to use 10 more gallons of hot water a day (an increased usage of approximately 20%) to have the same impact as tank water heaters. The project results suggest that if a higher percentage of Californians used tankless water heaters, environmental impacts caused by water heating would be smaller.

  20. The NASA Energy and Water cycle Extreme (NEWSE) Integration Project

    NASA Astrophysics Data System (ADS)

    Houser, P. R.; Lapenta, W.; Schiffer, R.

    2008-05-01

    Skillful predictions of water and energy cycle extremes (flood and drought) are elusive. To better understand the mechanisms responsible for water and energy extremes, and to make decisive progress in predicting these extremes, the collaborative NASA Energy and Water cycle Extremes (NEWSE) Integration Project, is studying these extremes in the U.S. Southern Great Plains (SGP) during 2006-2007, including their relationships with continental and global scale processes, and assessment of their predictability on multiple space and time scales. It is our hypothesis that an integrative analysis of observed extremes which reflects the current understanding of the role of SST and soil moisture variability influences on atmospheric heating and forcing of planetary waves, incorporating recently available global and regional hydro- meteorological datasets (i.e., precipitation, water vapor, clouds, etc.) in conjunction with advances in data assimilation, can lead to new insights into the factors that lead to persistent drought and flooding. We will show initial results of this project, whose goals are toprovide an improved definition, attribution and prediction on sub-seasonal to interannual time scales, improved understanding of the mechanisms of decadal drought and its predictability, including the impacts of SST variability and deep soil moisture variability, and improved monitoring/attributions, with transition to applications; a bridging of the gap between hydrological forecasts and stakeholders (utilization of probabilistic forecasts, education, forecast interpretation for different sectors, assessment of uncertainties for different sectors, etc.). *The NEWSE Team is: Romanou, Anastasiam, Columbia U.; Brian Soden, U. Miami; William Lapenta, NASA- MSFC; Megan Larko, CREW; Bing Lin, NASA-LaRC; Christa Peters-Lidard, NASA-GSFC; Xiquan Dong, U. North Dakota; Debbie Belvedere, CREW; Mathew Sapiano, U. Maryland; Duane Waliser, NASA-JPL; Eni Njoku, NASA/JPL; Eric Fetzer, NASA-JPL; Eyal Amitai, NASA-GSFC; Xiaogang Gao, U. California, Irvine; George Huffman, NASA-GSFC & SSAI; Jared Entin, NASA; Joseph Santanello, NASA-GSFC; John Roads, UCSD; W. Timothy Liu, NASA-JPL; Lixin Lu, Colorado State U.; Zhengzhao Luo, Colorado State U.; Michael Bosilovich, NASA-GSFC; Michael Jasinski, NASA-GSFC; William Olson, NASA-GSFC & UMBC-GEST; Pete Robertson, NASA-MSFC; Phil Arkin, U. Maryland; Paul Houser, CREW & GMU; Ralph Ferraro, NOAA; Pete Robertson, NASA-MSFC; Robert Schiffer; UMBC-GEST; Sujay Kumar, NASA-GSFC; Joseph A. Santanello, NASA-GSFC; Tristan L'Ecuyer, Colorado State U.; Wei-Kuo Tao; NASA-GSFC; Xia Feng; George Mason U.

  1. ARSENIC CYCLING WITHIN THE WATER COLUMN OF A SMALL LAKE RECEIVING CONTAMINATED GROUND WATER DISCHARGE

    EPA Science Inventory

    The fate of arsenic discharged from contaminated ground water to a small, shallow lake at a hazardous waste site is controlled, in part, by the rate of ferrous iron oxidation-precipitation and arsenic sorption occurring near the lake chemocline. Laboratory experiments were condu...

  2. Polyoxometalate water oxidation catalysts and methods of use thereof

    DOEpatents

    Hill, Craig L.; Gueletii, Yurii V.; Musaev, Djamaladdin G.; Yin, Qiushi; Botar, Bogdan

    2014-09-02

    Homogeneous water oxidation catalysts (WOCs) for the oxidation of water to produce hydrogen ions and oxygen, and methods of making and using thereof are described herein. In a preferred embodiment, the WOC is a polyoxometalate WOC which is hydrolytically stable, oxidatively stable, and thermally stable. The WOC oxidized waters in the presence of an oxidant. The oxidant can be generated photochemically, using light, such as sunlight, or electrochemically using a positively biased electrode. The hydrogen ions are subsequently reduced to form hydrogen gas, for example, using a hydrogen evolution catalyst (HEC). The hydrogen gas can be used as a fuel in combustion reactions and/or in hydrogen fuel cells. The catalysts described herein exhibit higher turn over numbers, faster turn over frequencies, and/or higher oxygen yields than prior art catalysts.

  3. A new method to assess oxidative stress in ART cycles.

    PubMed

    Di Rosa, Alessandra; Albani, Elena; Morenghi, Emanuela; Iommiello, Valeria Maria; Levi Setti, Paolo Emanuele

    2016-03-01

    The role of oxidative stress (OS) in female reproduction is an understudied area for investigation. The aim of the study was to assess reactive oxygen species (ROS) levels both in follicular fluid (FF) and in serum samples of women undergoing IVF and to relate them to clinical outcomes. A total of 56 women were enrolled. From each patient a sample of serum and FF were collected at oocyte retrieval day and analyzed for OS, by measuring a class of reactive oxygen metabolites (ROMs) (dROMs test) and for biological anti-oxidant potential levels (BAP test). The data analyzed in serum and in FF were related to pregnancy outcomes. There was no significant relationship between d-ROMs and BAP levels in serum or FF GROUP A and B and the clinical parameters of prognosis of women: age, number of oocytes retrieved number of oocytes methaphase II, FSH, fertilization rate and cleavage rate, number of embryos transferred and embryo score. There was a positive association between systemic levels of OS measured in serum GROUP A and pregnancy outcomes (p = 0.007) suggesting that the evaluation of OS in FF needs more investigation about markers in follicular microenvironment in order to predict IVF success. PMID:26608547

  4. Strongly improved electrochemical cycling durability by adding iridium to electrochromic nickel oxide films.

    PubMed

    Wen, Rui-Tao; Niklasson, Gunnar A; Granqvist, Claes G

    2015-05-13

    Anodically colored nickel oxide (NiO) thin films are of much interest as counter electrodes in tungsten oxide based electrochromic devices such as "smart windows" for energy-efficient buildings. However, NiO films are prone to suffering severe charge density degradation upon prolonged electrochemical cycling, which can lead to insufficient device lifetime. Therefore, a means to improve the durability of NiO-based films is an important challenge at present. Here we report that the incorporation of a modest amount of iridium into NiO films [Ir/(Ir + Ni) = 7.6 atom %] leads to remarkable durability, exceeding 10000 cycles in a lithium-conducting electrolyte, along with significantly improved optical modulation during extended cycling. Structure characterization showed that the face-centered-cubic-type NiO structure remained after iridium addition. Moreover, the crystallinity of these films was enhanced upon electrochemical cycling. PMID:25919917

  5. A Review of RedOx Cycling of Solid Oxide Fuel Cells Anode

    PubMed Central

    Faes, Antonin; Hessler-Wyser, Aïcha; Zryd, Amédée; Van Herle, Jan

    2012-01-01

    Solid oxide fuel cells are able to convert fuels, including hydrocarbons, to electricity with an unbeatable efficiency even for small systems. One of the main limitations for long-term utilization is the reduction-oxidation cycling (RedOx cycles) of the nickel-based anodes. This paper will review the effects and parameters influencing RedOx cycles of the Ni-ceramic anode. Second, solutions for RedOx instability are reviewed in the patent and open scientific literature. The solutions are described from the point of view of the system, stack design, cell design, new materials and microstructure optimization. Finally, a brief synthesis on RedOx cycling of Ni-based anode supports for standard and optimized microstructures is depicted. PMID:24958298

  6. Advanced oxidation degradation kinetics as a function of ultraviolet LED duty cycle.

    PubMed

    Duckworth, Kelsey; Spencer, Michael; Bates, Christopher; Miller, Michael E; Almquist, Catherine; Grimaila, Michael; Magnuson, Matthew; Willison, Stuart; Phillips, Rebecca; Racz, LeeAnn

    2015-01-01

    Ultraviolet (UV) light emitting diodes (LEDs) may be a viable option as a UV light source for advanced oxidation processes (AOPs) utilizing photocatalysts or oxidizing agents such as hydrogen peroxide. The effect of UV-LED duty cycle, expressed as the percentage of time the LED is powered, was investigated in an AOP with hydrogen peroxide, using methylene blue (MB) to assess contaminant degradation. The UV-LED AOP degraded the MB at all duty cycles. However, adsorption of MB onto the LED emitting surface caused a linear decline in reactor performance over time. With regard to the effect of duty cycle, the observed rate constant of MB degradation, after being adjusted to account for the duty cycle, was greater for 5 and 10% duty cycles than higher duty cycles, providing a value approximately 160% higher at 5% duty cycle than continuous operation. This increase in adjusted rate constant at low duty cycles, as well as contaminant fouling of the LED surface, may impact design and operational considerations for pulsed UV-LED AOP systems. PMID:25945855

  7. NEWS Climatology Project: The State of the Water Cycle at Continental to Global Scales

    NASA Technical Reports Server (NTRS)

    Rodell, Matthew; LEcuyer, Tristan; Beaudoing, Hiroko Kato; Olson, Bill

    2011-01-01

    NASA's Energy and Water Cycle Study (NEWS) program fosters collaborative research towards improved quantification and prediction of water and energy cycle consequences of climate change. In order to measure change, it is first necessary to describe current conditions. The goal of the NEWS Water and Energy Cycle Climatology project is to develop "state of the global water cycle" and "state of the global energy cycle" assessments based on data from modern ground and space based observing systems and data integrating models. The project is a multiinstitutional collaboration with more than 20 active contributors. This presentation will describe results of the first stage of the water budget analysis, whose goal was to characterize the current state of the water cycle on mean monthly, continental scales. We examine our success in closing the water budget within the expected uncertainty range and the effects of forcing budget closure as a method for refining individual flux estimates.

  8. Iron oxidation kinetics and phosphorus immobilization at the groundwater-surface water interface

    NASA Astrophysics Data System (ADS)

    van der Grift, Bas; Rozemeijer, Joachim; Griffioen, Jasper; van der Velde, Ype

    2014-05-01

    Eutrophication of freshwater environments following diffuse nutrient loads is a widely recognized water quality problem in catchments. Fluxes of non-point P sources to surface waters originate from surface runoff and flow from soil water and groundwater into surface water. The availability of P in surface waters is controlled strongly by biogeochemical nutrient cycling processes at the soil-water interface. The mechanisms and rates of the iron oxidation process with associated binding of phosphate during exfiltration of anaerobic Fe(II) bearing groundwater are among the key unknowns in P retention processes in surface waters in delta areas where the shallow groundwater is typically pH-neutral to slightly acid, anoxic, iron-rich. We developed an experimental field set-up to study the dynamics in Fe(II) oxidation and mechanisms of P immobilization at the groundwater-surface water interface in an agricultural experimental catchment of a small lowland river. We physically separated tube drain effluent from groundwater discharge before it entered a ditch in an agricultural field. The exfiltrating groundwater was captured in in-stream reservoirs constructed in the ditch. Through continuous discharge measurements and weekly water quality sampling of groundwater, tube drain water, exfiltrated groundwater, and ditch water, we quantified Fe(II) oxidation kinetics and P immobilization processes across the seasons. This study showed that seasonal changes in climatic conditions affect the Fe(II) oxidation process. In winter time the dissolved iron concentrations in the in-stream reservoirs reached the levels of the anaerobic groundwater. In summer time, the dissolved iron concentrations of the water in the reservoirs are low, indicating that dissolved Fe(II) is completely oxidized prior to inflow into the reservoirs. Higher discharges, lower temperatures and lower pH of the exfiltrated groundwater in winter compared to summer shifts the location of the redox transition zone, with Fe(II) oxidation taking place in the soil surrounding the ditch during summer and in the surface water during winter. The dynamics in Fe(II) oxidation did not affect the dissolved P concentrations. The dissolved P concentrations of the in-stream reservoirs water were an order of magnitude lower than observed in the groundwater and have no seasonal trend. Our data showed preferential binding of P during initial stage of the Fe(II) oxidation process, indicating the formation of Fe(III)-phosphate precipitates. The formation of Fe(III)-phosphates at the groundwater-surface water interface is an important geochemical mechanism in the transformation of dissolved phosphate to particulate phosphate and therefore a major control on the P retention in natural waters that drain anaerobic aquifers.

  9. The cycling and oxidation pathways of organic carbon in a shallow estuary along the Texas Gulf Coast

    NASA Astrophysics Data System (ADS)

    Warnken, Kent W.; Santschi, Peter H.; Roberts, Kimberly A.; Gill, Gary A.

    2008-01-01

    The cycling and oxidation pathways of organic carbon were investigated at a single shallow water estuarine site in Trinity Bay, Texas, the uppermost lobe of Galveston Bay, during November 2000. Radio-isotopes were used to estimate sediment mixing and accumulation rates, and benthic chamber and pore water measurements were used to determine sediment-water exchange fluxes of oxygen, nutrients and metals, and infer carbon oxidation rates. Using 7Be and 234Th XS, the sediment-mixing coefficient ( Db) was 4.3 ± 1.8 cm 2 y -1, a value that lies at the lower limit for marine environments, indicating that mixing was not important in these sediments at this time. Sediment accumulation rates ( Sa), estimated using 137Cs and 210Pb XS, were 0.16 ± 0.02 g cm -2 y -1. The supply rate of organic carbon to the sediment-water interface was 30 ± 3.9 mmol C m -2 d -1, of which ˜10% or 2.9 ± 0.44 mmol C m -2 d -1was lost from the system through burial below the 1-cm thick surface mixed layer. Measured fluxes of O 2 were 26 ± 3.8 mmol m -2 d -1 and equated to a carbon oxidation rate of 20 ± 3.3 mmol C m -2 d -1, which is an upper limit due to the potential for oxidation of additional reduced species. Using organic carbon gradients in the surface mixed layer, carbon oxidation was estimated at 2.6 ± 1.1 mmol C m -2 d -1. Independent estimates made using pore water concentration gradients of ammonium and C:N stoichiometry, equaled 2.8 ± 0.46 mmol C m -2 d -1. The flux of DOC out of the sediments (DOC efflux) was 5.6 ± 1.3 mmol C m -2 d -1. In general, while mass balance was achieved indicating the sediments were at steady state during this time, changes in environmental conditions within the bay and the surrounding area, mean this conclusion might not always hold. These results show that the majority of carbon oxidation occurred at the sediment-water interface, via O 2 reduction. This likely results from the high frequency of sediment resuspension events combined with the shallow sediment mixing zone, leaving anaerobic oxidants responsible for only ˜10-15% of the carbon oxidized in these sediments.

  10. Unexpected Voltage Fade in LMR-NMC Oxides Cycled below the “Activation” Plateau

    SciTech Connect

    Li, Yan; Bareno, Javier; Bettge, Martin; Abraham, Daniel P

    2015-01-01

    A common feature of lithium-excess layered oxides, nominally of composition xLi2MnO3•(1-x)LiMO2 (M = transition metal) is a high-voltage plateau (~4.5 V vs. Li/Li+) in their capacity-voltage profile during the first delithiation cycle. This plateau is believed to result from activation of the Li2MnO3 component, which makes additional lithium available for electrochemical cycling. However, oxides cycled beyond this activation plateau are known to display voltage fade which is a continuous reduction in their equilibrium potential. In this article we show that these oxides display gradual voltage fade even on electrochemical cycling in voltage ranges well below the activation plateau. The average fade is ~0.08 mV-cycle-1 for Li1.2Ni0.15Mn0.55Co0.1O2 vs. Li cells after 20 cycles in the 2–4.1 V range at 55°C; a ~54 mV voltage hysteresis, expressed as the difference in average cell voltage between charge and discharge cycles, is also observed. The voltage fade results from a gradual accumulation of local spinel environments in the crystal structure. Some of these spinel sites result from lithium deficiencies during oxide synthesis and are likely to be at the particle surfaces; other sites result from the migration of transition metal atoms in the partially-delithiated LiMO2 component into the lithium planes during electrochemical cycling. The observed rate of voltage fade depends on a combination of factors that includes the phase equilibrium between the layered and spinel components and the kinetics of transition metal migration.

  11. Ice haze, snow, and the Mars water cycle

    NASA Technical Reports Server (NTRS)

    Kahn, Ralph

    1990-01-01

    Light curves and extinction profiles derived from Martian limb observations are used to constrain the atmospheric temperature structure in regions of the atmosphere with thin haze and to analyze the haze particle properties and atmospheric eddy mixing. Temperature between 170 and 190 K are obtained for three cases at levels in the atmosphere ranging from 20 to 50 km. Eddy diffusion coefficients around 100,000 sq cm/s, typical of a nonconvecting atmosphere, are derived in the haze regions at times when the atmosphere is relatively clear of dust. This parameter apparently changes by more than three orders of magnitude with season and local conditions. The derived particle size parameter varies systematically by more than an order of magnitude with condensation level, in such a way that the characteristic fall time is always about one Martian day. Ice hazes provide a mechanism for scavenging water vapor in the thin Mars atmosphere and may play a key role in the seasonal cycle of water on Mars.

  12. Global operational hydrological forecasts through eWaterCycle

    NASA Astrophysics Data System (ADS)

    van de Giesen, Nick; Bierkens, Marc; Donchyts, Gennadii; Drost, Niels; Hut, Rolf; Sutanudjaja, Edwin

    2015-04-01

    Central goal of the eWaterCycle project (www.ewatercycle.org) is the development of an operational hyper-resolution hydrological global model. This model is able to produce 14 day ensemble forecasts based on a hydrological model and operational weather data (presently NOAA's Global Ensemble Forecast System). Special attention is paid to prediction of situations in which water related issues are relevant, such as floods, droughts, navigation, hydropower generation, and irrigation stress. Near-real time satellite data will be assimilated in the hydrological simulations, which is a feature that will be presented for the first time at EGU 2015. First, we address challenges that are mainly computer science oriented but have direct practical hydrological implications. An important feature in this is the use of existing standards and open-source software to the maximum extent possible. For example, we use the Community Surface Dynamics Modeling System (CSDMS) approach to coupling models (Basic Model Interface (BMI)). The hydrological model underlying the project is PCR-GLOBWB, built by Utrecht University. This is the motor behind the predictions and state estimations. Parts of PCR-GLOBWB have been re-engineered to facilitate running it in a High Performance Computing (HPC) environment, run parallel on multiple nodes, as well as to use BMI. Hydrological models are not very CPU intensive compared to, say, atmospheric models. They are, however, memory hungry due to the localized processes and associated effective parameters. To accommodate this memory need, especially in an ensemble setting, a variation on the traditional Ensemble Kalman Filter was developed that needs much less on-chip memory. Due to the operational nature, the coupling of the hydrological model with hydraulic models is very important. The idea is not to run detailed hydraulic routing schemes over the complete globe but to have on-demand simulation prepared off-line with respect to topography and parameterizations. This allows for very detailed simulations at hectare to meter scales, where and when this is needed. At EGU 2015, the operational global eWaterCycle model will be presented for the first time, including forecasts at high resolution, the innovative data assimilation approach, and on-demand coupling with hydraulic models.

  13. Heat-sterilized silver oxide-zinc cells: Cycle life studies

    NASA Technical Reports Server (NTRS)

    Arms, J. T.

    1973-01-01

    A JPL study was conducted to evaluate the cell design parameters that contribute to the cycle life of sealed, heat-sterilized silver oxide-zinc cells. Test cells having a rated capacity of 4.2 A-h were fabricated using zinc oxide electrodes prepared by the sintered Teflon process. Two separator variations were evaluated, one having acrylic acid and the other methacrylic acid grafted to irradiated polyethylene film. Significant results of this study include the following: (1) cycle life in excess of 300 cycles was attained; (2) a zinc oxide/silver stoichiometric ratio of 1.5 resulted in greater cycle life than a ratio of 1.1, and similar cycle life to cells having a ratio of 2; (3) cells having methacrylic acid grafted separators suffered somewhat less in capacity loss due to zinc electrode shape change than cells having acrylic acid type; (4) use of acrylic acid grafted separators was slightly superior to the methacrylic acid type in respect to silver penetration; and (5) the inclusion of a layer of potassium titanate paper adjacent to the zinc electrodes resulted in cells that achieved higher cycle life before any of the group failed than that reached by cells of any other construction.

  14. A pentanuclear iron catalyst designed for water oxidation

    NASA Astrophysics Data System (ADS)

    Okamura, Masaya; Kondo, Mio; Kuga, Reiko; Kurashige, Yuki; Yanai, Takeshi; Hayami, Shinya; Praneeth, Vijayendran K. K.; Yoshida, Masaki; Yoneda, Ko; Kawata, Satoshi; Masaoka, Shigeyuki

    2016-02-01

    Although the oxidation of water is efficiently catalysed by the oxygen-evolving complex in photosystem II (refs 1 and 2), it remains one of the main bottlenecks when aiming for synthetic chemical fuel production powered by sunlight or electricity. Consequently, the development of active and stable water oxidation catalysts is crucial, with heterogeneous systems considered more suitable for practical use and their homogeneous counterparts more suitable for targeted, molecular-level design guided by mechanistic understanding. Research into the mechanism of water oxidation has resulted in a range of synthetic molecular catalysts, yet there remains much interest in systems that use abundant, inexpensive and environmentally benign metals such as iron (the most abundant transition metal in the Earth’s crust and found in natural and synthetic oxidation catalysts). Water oxidation catalysts based on mononuclear iron complexes have been explored, but they often deactivate rapidly and exhibit relatively low activities. Here we report a pentanuclear iron complex that efficiently and robustly catalyses water oxidation with a turnover frequency of 1,900 per second, which is about three orders of magnitude larger than that of other iron-based catalysts. Electrochemical analysis confirms the redox flexibility of the system, characterized by six different oxidation states between FeII5 and FeIII5; the FeIII5 state is active for oxidizing water. Quantum chemistry calculations indicate that the presence of adjacent active sites facilitates O-O bond formation with a reaction barrier of less than ten kilocalories per mole. Although the need for a high overpotential and the inability to operate in water-rich solutions limit the practicality of the present system, our findings clearly indicate that efficient water oxidation catalysts based on iron complexes can be created by ensuring that the system has redox flexibility and contains adjacent water-activation sites.

  15. A pentanuclear iron catalyst designed for water oxidation.

    PubMed

    Okamura, Masaya; Kondo, Mio; Kuga, Reiko; Kurashige, Yuki; Yanai, Takeshi; Hayami, Shinya; Praneeth, Vijayendran K K; Yoshida, Masaki; Yoneda, Ko; Kawata, Satoshi; Masaoka, Shigeyuki

    2016-02-25

    Although the oxidation of water is efficiently catalysed by the oxygen-evolving complex in photosystem II (refs 1 and 2), it remains one of the main bottlenecks when aiming for synthetic chemical fuel production powered by sunlight or electricity. Consequently, the development of active and stable water oxidation catalysts is crucial, with heterogeneous systems considered more suitable for practical use and their homogeneous counterparts more suitable for targeted, molecular-level design guided by mechanistic understanding. Research into the mechanism of water oxidation has resulted in a range of synthetic molecular catalysts, yet there remains much interest in systems that use abundant, inexpensive and environmentally benign metals such as iron (the most abundant transition metal in the Earth's crust and found in natural and synthetic oxidation catalysts). Water oxidation catalysts based on mononuclear iron complexes have been explored, but they often deactivate rapidly and exhibit relatively low activities. Here we report a pentanuclear iron complex that efficiently and robustly catalyses water oxidation with a turnover frequency of 1,900 per second, which is about three orders of magnitude larger than that of other iron-based catalysts. Electrochemical analysis confirms the redox flexibility of the system, characterized by six different oxidation states between Fe(II)5 and Fe(III)5; the Fe(III)5 state is active for oxidizing water. Quantum chemistry calculations indicate that the presence of adjacent active sites facilitates O-O bond formation with a reaction barrier of less than ten kilocalories per mole. Although the need for a high overpotential and the inability to operate in water-rich solutions limit the practicality of the present system, our findings clearly indicate that efficient water oxidation catalysts based on iron complexes can be created by ensuring that the system has redox flexibility and contains adjacent water-activation sites. PMID:26863188

  16. Promoting Photochemical Water Oxidation with Metallic Band Structures.

    PubMed

    Liu, Hongfei; Moré, René; Grundmann, Henrik; Cui, Chunhua; Erni, Rolf; Patzke, Greta R

    2016-02-10

    The development of economic water oxidation catalysts is a key step toward large-scale water splitting. However, their current exploration remains empirical to a large extent. Elucidating the correlations between electronic properties and catalytic activity is crucial for deriving general and straightforward catalyst design principles. Herein, strongly correlated electronic systems with abundant and easily tunable electronic properties, namely La1-xSrxBO3 perovskites and La2-xSrxBO4 layered perovskites (B = Fe, Co, Ni, or Mn), were employed as model systems to identify favorable electronic structures for water oxidation. We established a direct correlation between the enhancement of catalytic activity and the insulator to metal transition through tuning the electronic properties of the target perovskite families via the La(3+)/Sr(2+) ratio. Their improved photochemical water oxidation performance was clearly linked to the increasingly metallic character. These electronic structure-activity relations provide a promising guideline for constructing efficient water oxidation catalysts. PMID:26771537

  17. Shedding "Dark" on the Oxidation of Dissolved Organic Matter by Hydroxyl Radical in Arctic Soils and Surface Waters

    NASA Astrophysics Data System (ADS)

    Cory, R. M.; Page, S. E.; Kling, G. W.; McNeill, K.; Sander, M.; Harrold, K. H.

    2014-12-01

    Hydroxyl radical (•OH) is a very reactive and unselective oxidant produced ubiquitously by photochemical reactions of dissolved organic matter (DOM) or iron in sunlit surface waters. Once formed, •OH can oxidize DOM to produce CO2 or low molecular weight compounds that bacteria convert to CO2, thereby contributing to the mineralization of DOM in inland waters. This role of •OH in aquatic carbon cycling was thought to be limited to sunlit waters, but we recently demonstrated that •OH is also formed in the dark by a sunlight-independent pathway. We show that •OH is formed in soil and surface waters of the Alaskan Arctic during the oxidation of reduced DOM and ferrous iron. Across a gradient of soil waters from dry upland to wet lowland habitats, •OH formation rates increased with increasing concentrations of DOM and reduced iron, with highest •OH formation observed at oxic-anoxic boundaries in soil and surface waters. Comparison of measured vs. expected electron release from reduced moieties suggested that both DOM and iron contributed to •OH formation. At landscape scales, DOM oxidation to CO2 by dark •OH pathway may be as important to carbon cycling as bacterial oxidation of DOM in arctic surface waters, and is likely much more important than photochemical oxidation of DOM by •OH in sunlit surface waters of the Arctic.

  18. Capacity and cycle-life of batteries using bismuth-bearing oxide

    NASA Astrophysics Data System (ADS)

    Lam, L. T.; Haigh, N. P.; Lim, O. V.; Rand, D. A. J.; Manders, J. E.

    An examination is made of the capacity performance of lead-acid positive electrodes which are prepared from bismuth (Bi)-bearing oxide. This oxide is produced from Pasminco VRLA Refined™ lead which contains 0.05 wt.% Bi. For comparison, benchmark tests are performed on electrodes made from oxide with virtually no bismuth (<0.005 wt.%). The change in capacity is investigated by means of a purpose-built `compression cell'. With this design, the positive active-material is constrained under the action of a desirable, constant force during charge-discharge cycling. In general, the capacity increases with the compressive force. Importantly, the use of Bi-bearing oxide yields higher initial capacity and then a significantly faster rise in capacity to the full value with subsequent cycling. Commercial VRLA batteries made with Bi-bearing oxide exhibit a lower rate of self-discharge than those fabricated with conventional factory oxide. In addition, Bi-bearing batteries provide good cycle-life under the International Electrotechnical Commission (IEC) test.

  19. Photosynthetic water oxidation: insights from manganese model chemistry.

    PubMed

    Young, Karin J; Brennan, Bradley J; Tagore, Ranitendranath; Brudvig, Gary W

    2015-03-17

    Catalysts for light-driven water oxidation are a critical component for development of solar fuels technology. The multielectron redox chemistry required for this process has been successfully deployed on a global scale in natural photosynthesis by green plants and cyanobacteria using photosystem II (PSII). PSII employs a conserved, cuboidal Mn4CaOX cluster called the O2-evolving complex (OEC) that offers inspiration for artificial O2-evolution catalysts. In this Account, we describe our work on manganese model chemistry relevant to PSII, particularly the functional model [Mn(III/IV)2(terpy)2(μ-O)2(OH2)2](NO3)3 complex (terpy = 2,2';6',2″-terpyridine), a mixed-valent di-μ-oxo Mn dimer with two terminal aqua ligands. In the presence of oxo-donor oxidants such as HSO5(-), this complex evolves O2 by two pathways, one of which incorporates solvent water in an O-O bond-forming reaction. Deactivation pathways of this catalyst include comproportionation to form an inactive Mn(IV)Mn(IV) dimer and also degradation to MnO2, a consequence of ligand loss when the oxidation state of the complex is reduced to labile Mn(II) upon release of O2. The catalyst's versatility has been shown by its continued catalytic activity after direct binding to the semiconductor titanium dioxide. In addition, after binding to the surface of TiO2 via a chromophoric linker, the catalyst can be oxidized by a photoinduced electron-transfer mechanism, mimicking the natural PSII process. Model oxomanganese complexes have also aided in interpreting biophysical and computational studies on PSII. In particular, the μ-oxo exchange rates of the Mn-terpy dimer have been instrumental in establishing that the time scale for μ-oxo exchange of high-valent oxomanganese complexes with terminal water ligands is slower than O2 evolution in the natural photosynthetic system. Furthermore, computational studies on the Mn-terpy dimer and the OEC point to similar Mn(IV)-oxyl intermediates in the O-O bond-forming mechanism. Comparison between the OEC and the Mn-terpy dimer indicates that challenges remain in the development of synthetic Mn water-oxidation catalysts. These include redox leveling to couple multielectron reactions with one-electron steps, avoiding labile Mn(II) species during the catalytic cycle, and protecting the catalyst active site from undesired side reactions. As the first example of a functional manganese O2-evolution catalyst, the Mn-terpy dimer exemplifies the interrelatedness of biomimetic chemistry with biophysical studies. The design of functional model complexes enriches the study of the natural photosynthetic system, while biology continues to provide inspiration for artificial photosynthetic technologies to meet global energy demand. PMID:25730258

  20. Coal Conversion Wastewater Treatment by Catalytic Oxidation in Supercritical Water

    SciTech Connect

    Savage, P.E.

    1997-08-25

    In previous reports, we showed that CARULITE 150 from Carus Chemical Company was so effective with oxidation of phenol in supercritical water (SCW) that the results we obtained were likely influenced by internal mass-transfer resistance. We also reported that oxidation of phenol over MnO{sub 2} powder in SCW improved the conversions of both phenol and total organic carbon (TOC) relative to non-catalytic oxidation while the catalytic oxidation kinetics was free from mass-transfer limitation. In this report we continued the investigation of oxidation over the MnO{sub 2} powder in SCW.

  1. Supercritical water fuel cleaning for improved combined cycle performance

    SciTech Connect

    Tolman, R.; Timpe, R.C.; Parkinson, W.J.

    1998-07-01

    A revolutionary hydrothermal heat recovery steam generator (HRSG) is being developed by a federal, state university and industry partnership to produce clean fuels for gas turbines. The patented hydrothermal HRSG will accept solutions and emulsions without corrosion and deposition on heat transfer surfaces. An advanced continuous-flow pilot plant is being designed to test the HRSG over a wide range of operating conditions, including the supercritical conditions of water, above 221 bar (3205 psia) and 374 C (705 F). Water at these conditions can be used to clean emulsions of crude oil, composted refuse derived fuel, coal fines, and coal water fuels. Data shows that fuel nitrogen will be converted to nitrogen gas. Inorganic materials, such as sulfur, chlorine, alkali metals, ash, vanadium and other metals can be separated and removed for recycle or disposal. Carbon can be sequestered in char for decreased carbon dioxide emissions and activated for use as an adsorbent. Combining the new HRSG with a special condensing turbine and a modern gas turbine promises to increase power output, efficiency, availability and reliability in a new Vapor Transmission Cycle (VTC). The condensing turbine reduces the pressure of steam and fuel vapor to the gas turbine combustor inlet pressure, driving a generator and high-pressure feed pump. The condensing turbine reduces the temperature for final removal of contaminants while maintaining combustibility of the vapor for high turbine inlet temperature. Water is condensed for recycling to the process, eliminating water treatment costs and effluents. An Engineering Study is being prepared at the University of North Dakota Energy and Environmental Research Center (EERC). An Aspen Technology, Inc. computer-based process simulation model has been prepared in collaboration with a consultant from the Los Alamos National Laboratory and EERC. The process simulation model includes materials and energy balances that simulate commercial-scale operations for system optimization, using test data. Preliminary bench-scale test data at subcritical conditions for lignite, refuse derived fuel, and tire rubber are presented, including yield data incorporated in the process model. The model has been used to compare the VTC to commercially available technologies. These results are presented, with conclusions affecting the design of the pilot plant.

  2. Infiltrated Phlogopite Micas with Superior Thermal Cycle Stability as Compressive Seals for Solid Oxide Fuel Cells

    SciTech Connect

    Chou, Y S.; Stevenson, Jeffry W.

    2005-03-01

    Thermal cycle stability is one of the most stringent requirements for sealants in solid oxide fuel cell stacks. The sealants have to survive several hundreds to thousands of thermal cycles during lifetime operation in stationary and transportation applications. Recently, researchers at the Pacific Northwest National Laboratory have developed a novel method to infiltrate the mica flakes with a wetting or liquid forming material such that the leak path will be reduced from 3-D to 2-D and achieve good thermal cycle stability with low leak rates.

  3. TRMM and Its Connection to the Global Water Cycle

    NASA Technical Reports Server (NTRS)

    Kummerow, Christian; Hong, Ye

    1999-01-01

    The importance of quantitative knowledge of tropical rainfall, its associated latent heating and variability is summarized in the context of the global hydrologic cycle. Much of the tropics is covered by oceans. What land exists, is covered largely by rainforests that are only thinly populated. The only way to adequately measure the global tropical rainfall for climate and general circulation models is from space. The TRMM orbit is inclined 35' leading to good sampling in the tropics and a rapid precession to study the diurnal cycle of precipitation. The precipitation instrument complement consists of the first rain radar to be flown in space (PR), a multi-channel passive microwave sensor (TMI) and a five-channel VIS/IR (VIRS) sensor. The precipitation radar operates at a frequency of 13.6 GHz. The swath width is 220 km, with a horizontal resolution of 4 km and the vertical resolution of 250 in. The minimum detectable signal from the precipitation radar has been measured at 17 dBZ. The TMI instrument is designed similar to the SSM/I with two important changes. The 22.235 GHz water vapor absorption channel of the SSM/I was moved to 21.3 GHz in order to avoid saturation in the tropics and 10.7 GHz V&H polarized channels were added to expand the dynamic range of rainfall estimates. The resolution of the TMI varies from 4.6 km at 85 GHz to 36 km at 10.7 GHz. The visible and infrared sensor (VIRS) measures radiation at 0.63, 1.6, 3.75, 10.8 and 12.0 microns. The spatial resolution of all five VIRS channels is 2 km at nadir. In addition to the three primary rainfall instruments, TRMM will also carry a Lightning Imaging Sensor (LIS) and a Clouds and the Earth's Radiant Energy System (CERES) instrument.

  4. Nitric oxide alleviates aluminum-induced oxidative damage through regulating the ascorbate-glutathione cycle in roots of wheat.

    PubMed

    Sun, Chengliang; Liu, Lijuan; Yu, Yan; Liu, Wenjing; Lu, Lingli; Jin, Chongwei; Lin, Xianyong

    2015-06-01

    The possible association with nitric oxide (NO) and ascorbate-glutathione (AsA-GSH) cycle in regulating aluminum (Al) tolerance of wheat (Triticum aestivum L.) was investigated using two genotypes with different Al resistance. Exposure to Al inhibited root elongation, and triggered lipid peroxidation and oxidation of AsA to dehydroascorbate and GSH to glutathione disulfide in wheat roots. Exogenous NO significantly increased endogenous NO levels, and subsequently alleviated Al-induced inhibition of root elongation and oxidation of AsA and GSH to maintain the redox molecules in the reduced form in both wheat genotypes. Under Al stress, significantly increased activities and gene transcriptional levels of ascorbate peroxidase, glutathione reductase, and dehydroascorbate reductase, were observed in the root tips of the Al-tolerant genotype Jian-864. Nitric oxide application enhanced the activity and gene transcriptional level of these enzymes in both wheat genotypes. γ-Glutamylcysteine synthetase was not significantly affected by Al or NO, but NO treatments increased the activity of glutathione peroxidase and glutathione S-transferase to a greater extent than the Al-treated wheat seedlings. Proline was significantly decreased by Al, while it was not affected by NO. These results clearly suggest that NO protects wheat root against Al-induced oxidative stress, possibly through its regulation of the AsA-GSH cycle. PMID:25319364

  5. Combinations of solid oxide fuel cell and several enhanced gas turbine cycles

    NASA Astrophysics Data System (ADS)

    Kuchonthara, Prapan; Bhattacharya, Sankar; Tsutsumi, Atsushi

    Combined power generation systems with combinations of solid oxide fuel cell (SOFC) and various enhanced gas turbine (GT) cycles were evaluated. In the GT part, steam injected gas turbine (STIG) cycle, GT/steam turbine (ST) combined cycle, and humid air turbine (HAT) cycle were considered. Moreover, additional recuperation was considered by means of air preheating (APH) in the STIG cycle. Effects of operating turbine inlet temperature (TIT) and pressure ratio (PR) on overall system performance were assessed. Although the SOFC-HAT system shows the lowest specific work output compared to other systems, its highest thermal efficiency presents a significant advantage. Furthermore, at high TITs and PRs the SOFC-HAT system gives the best performance in terms of both thermal efficiency and specific work. Results indicate that energy recuperative features in the HAT promote the positive effect of increasing TIT by means of enhancing GT efficiency, leading to the improvement in thermal efficiency of the overall system.

  6. Evaluation of Physicochemical Deterioration and Lipid Oxidation of Beef Muscle Affected by Freeze-thaw Cycles

    PubMed Central

    Rahman, M. H.; Hossain, M. M.; Rahman, S. M. E.; Amin, M. R.; Oh, Deog-Hwan

    2015-01-01

    This study was performed to explore the deterioration of physicochemical quality of beef hind limb during frozen storage at −20℃, affected by repeated freeze-thaw cycles. The effects of three successive freeze-thaw cycles on beef hind limb were investigated comparing with unfrozen beef muscle for 80 d by keeping at −20±1℃. The freeze-thaw cycles were subjected to three thawing methods and carried out to select the best one on the basis of deterioration of physicochemical properties of beef. As the number of repeated freeze-thaw cycles increased, drip loss decreased and water holding capacity (WHC) increased (p<0.05) till two cycles and then decreased. Cooking loss increased in cycle one and three but decreased in cycle two. Moreover, drip loss, WHC and cooking loss affected (p<0.05) by thawing methods within the cycles. However, pH value decreased (p<0.05), but peroxide value (p<0.05), free fatty acids value (p<0.05) and TBARS value increased (p<0.05) significantly as the number of repeated freeze-thaw cycles increased. Moreover, significant (p<0.05) interactive effects were found among the thawing methods and repeated cycles. As a result, freeze-thaw cycles affected the physicochemical quality of beef muscle, causing the degradation of its quality. PMID:26877637

  7. Metal-Free Oxidation of Primary Amines to Nitriles through Coupled Catalytic Cycles.

    PubMed

    Lambert, Kyle M; Bobbitt, James M; Eldirany, Sherif A; Kissane, Liam E; Sheridan, Rose K; Stempel, Zachary D; Sternberg, Francis H; Bailey, William F

    2016-04-01

    Synergism among several intertwined catalytic cycles allows for selective, room temperature oxidation of primary amines to the corresponding nitriles in 85-98 % isolated yield. This metal-free, scalable, operationally simple method employs a catalytic quantity of 4-acetamido-TEMPO (ACT; TEMPO=2,2,6,6-tetramethylpiperidine N-oxide) radical and the inexpensive, environmentally benign triple salt oxone as the terminal oxidant under mild conditions. Simple filtration of the reaction mixture through silica gel affords pure nitrile products. PMID:26868873

  8. A molecular catalyst for water oxidation that binds to metal oxide surfaces

    PubMed Central

    Sheehan, Stafford W.; Thomsen, Julianne M.; Hintermair, Ulrich; Crabtree, Robert H.; Brudvig, Gary W.; Schmuttenmaer, Charles A.

    2015-01-01

    Molecular catalysts are known for their high activity and tunability, but their solubility and limited stability often restrict their use in practical applications. Here we describe how a molecular iridium catalyst for water oxidation directly and robustly binds to oxide surfaces without the need for any external stimulus or additional linking groups. On conductive electrode surfaces, this heterogenized molecular catalyst oxidizes water with low overpotential, high turnover frequency and minimal degradation. Spectroscopic and electrochemical studies show that it does not decompose into iridium oxide, thus preserving its molecular identity, and that it is capable of sustaining high activity towards water oxidation with stability comparable to state-of-the-art bulk metal oxide catalysts. PMID:25757425

  9. Fouling Study of Silicon Oxide Pores Exposed to Tap Water

    SciTech Connect

    Nilsson, J.; Bourcier, W.L.; Lee, J.R.I.; Letant, S.E.; /LLNL, Livermore

    2007-07-12

    We report on the fouling of Focused Ion Beam (FIB)-fabricated silicon oxide nanopores after exposure to tap water for two weeks. Pore clogging was monitored by Scanning Electron Microscopy (SEM) on both bare silicon oxide and chemically functionalized nanopores. While fouling occurred on hydrophilic silicon oxide pore walls, the hydrophobic nature of alkane chains prevented clogging on the chemically functionalized pore walls. These results have implications for nanopore sensing platform design.

  10. Cadmium Oxide Nanostructures in Water; Synthesis, Characterizations & Optical Properties

    NASA Astrophysics Data System (ADS)

    Singh, S. C.; Swarnkar, R. K.; Gopal, R.

    2009-06-01

    Cadmium oxide nanoparticles are synthesized by pulsed laser ablation of cadmium metal in double distilled water, which are found stable for 24 hours. The sample is characterized by using UV-VIS absorption, scanning electron microscopy, thermo gravimetric analysis, differential thermal analysis, X-ray diffraction and fourier transform infrared techniques. XRD pattern shows that as synthesized nanopowder has maximum amount of the Cadmium hydroxide rather than its oxide, which converts into Cadmium oxide after annealing at 350° C.

  11. Roles of surface water areas for water and solute cycle in Hanoi city, Viet Nam

    NASA Astrophysics Data System (ADS)

    Hayashi, Takeshi; Kuroda, Keisuke; Do Thuan, An; Tran Thi Viet, Nga; Takizawa, Satoshi

    2013-04-01

    Hanoi city, the capital of Viet Nam, has developed beside the Red river. Recent rapid urbanization of this city has reduced a large number of natural water areas such as lakes, ponds and canals not only in the central area but the suburban area. Contrary, the urbanization has increased artificial water areas such as pond for fish cultivation and landscaping. On the other hand, the urbanization has induced the inflow of waste water from households and various kinds of factories to these water areas because of delay of sewerage system development. Inflow of the waste water has induced eutrophication and pollution of these water areas. Also, there is a possibility of groundwater pollution by infiltration of polluted surface water. However, the role of these water areas for water cycle and solute transport is not clarified. Therefore, this study focuses on the interaction between surface water areas and groundwater in Hanoi city to evaluate appropriate land development and groundwater resource management. We are carrying out three approaches: a) understanding of geochemical characteristics of surface water and groundwater, b) monitoring of water levels of pond and groundwater, c) sampling of soil and pond sediment. Correlation between d18O and dD of precipitation (after GNIP), the Red River (after GNIR) and the water samples of this study showed that the groundwater is composed of precipitation, the Red River and surface water that has evaporation process. Contribution of the surface water with evaporation process was widely found in the study area. As for groundwater monitoring, the Holocene aquifers at two sites were in unconfined condition in dry season and the groundwater levels in the aquifer continued to increase through rainy season. The results of isotopic analysis and groundwater level monitoring showed that the surface water areas are one of the major groundwater sources. On the other hand, concentrations of dissolved Arsenic (filtered by 0.45um) in the pore water of the pond sediments were much higher than the pond water and closed to that of groundwater. Also, other metal elements showed the same trend. This result suggested that Arsenic and other metal elements recharged to these ponds is probably adsorbed and removed by sediments (including organic matters). That is, pond sediment plays an important role for solute transport as a filter of Arsenic and metal elements. The results of this study strongly suggest that the natural and artificial surface water areas have important roles for water cycle and solute transport in Hanoi city. Although the number of the natural water areas is decreasing, dredging of artificial water areas increases the infiltration from the surface to aquifers. Therefore, qualitative and quantitative preservation of the surface water areas is important for conservation of groundwater environment and contribute to sustainable groundwater management in Hanoi city.

  12. Supercritical water oxidation data acquisition testing. Final report, Volume I

    SciTech Connect

    1996-11-01

    This report discusses the phase one testing of a data acquisition system for a supercritical water waste oxidation system. The system is designed to destroy a wide range of organic materials in mixed wastes. The design and testing of the MODAR Oxidizer is discussed. An analysis of the optimized runs is included.

  13. Subcritical and supercritical water oxidation of CELSS model wastes.

    PubMed

    Takahashi, Y; Wydeven, T; Koo, C

    1989-01-01

    Controlled-Ecological-Life-Support-System (CELSS) model wastes were wet-oxidized at temperatures from 250 to 500 degrees C, i.e., below and above the critical point of water (374 degrees C and 218 kg/cm2 or 21.4 MPa). A solution of ammonium hydroxide and acetic acid and a slurry of human urine, feces, and wipes were used as model wastes. Almost all of the organic matter in the model wastes was oxidized in the temperature range from 400 to 500 degrees C, i.e., above the critical conditions for water. In contrast, only a small portion of the organic matter was oxidized at subcritical conditions. Although the extent of nitrogen oxidation to nitrous oxide (N2O) and/or nitrogen gas (N2) increased with reaction temperature, most of the nitrogen was retained in solution as ammonia near 400 degrees C. This important finding suggests that most of the nitrogen in the waste feed can be retained in solution as ammonia during oxidation at low supercritical temperatures and be subsequently used as a nitrogen source for plants in a CELSS while at the same time organic matter is almost completely oxidized to carbon dioxide and water. It was also found in this study the Hastelloy C-276 alloy reactor corroded during waste oxidation. The rate of corrosion was lower above than below the critical temperature for water. PMID:11537396

  14. Molecular water oxidation mechanisms followed by transition metals: state of the art.

    PubMed

    Sala, Xavier; Maji, Somnath; Bofill, Roger; García-Antón, Jordi; Escriche, Lluís; Llobet, Antoni

    2014-02-18

    One clean alternative to fossil fuels would be to split water using sunlight. However, to achieve this goal, researchers still need to fully understand and control several key chemical reactions. One of them is the catalytic oxidation of water to molecular oxygen, which also occurs at the oxygen evolving center of photosystem II in green plants and algae. Despite its importance for biology and renewable energy, the mechanism of this reaction is not fully understood. Transition metal water oxidation catalysts in homogeneous media offer a superb platform for researchers to investigate and extract the crucial information to describe the different steps involved in this complex reaction accurately. The mechanistic information extracted at a molecular level allows researchers to understand both the factors that govern this reaction and the ones that derail the system to cause decomposition. As a result, rugged and efficient water oxidation catalysts with potential technological applications can be developed. In this Account, we discuss the current mechanistic understanding of the water oxidation reaction catalyzed by transition metals in the homogeneous phase, based on work developed in our laboratories and complemented by research from other groups. Rather than reviewing all of the catalysts described to date, we focus systematically on the several key elements and their rationale from molecules studied in homogeneous media. We organize these catalysts based on how the crucial oxygen-oxygen bond step takes place, whether via a water nucleophilic attack or via the interaction of two M-O units, rather than based on the nuclearity of the water oxidation catalysts. Furthermore we have used DFT methodology to characterize key intermediates and transition states. The combination of both theory and experiments has allowed us to get a complete view of the water oxidation cycle for the different catalysts studied. Finally, we also describe the various deactivation pathways for these catalysts. PMID:24328498

  15. Plumbing the global carbon cycle: Integrating inland waters into the terrestrial carbon budget

    USGS Publications Warehouse

    Cole, J.J.; Prairie, Y.T.; Caraco, N.F.; McDowell, W.H.; Tranvik, L.J.; Striegl, R.G.; Duarte, C.M.; Kortelainen, P.; Downing, J.A.; Middelburg, J.J.; Melack, J.

    2007-01-01

    Because freshwater covers such a small fraction of the Earth's surface area, inland freshwater ecosystems (particularly lakes, rivers, and reservoirs) have rarely been considered as potentially important quantitative components of the carbon cycle at either global or regional scales. By taking published estimates of gas exchange, sediment accumulation, and carbon transport for a variety of aquatic systems, we have constructed a budget for the role of inland water ecosystems in the global carbon cycle. Our analysis conservatively estimates that inland waters annually receive, from a combination of background and anthropogenically altered sources, on the order of 1.9 Pg C y-1 from the terrestrial landscape, of which about 0.2 is buried in aquatic sediments, at least 0.8 (possibly much more) is returned to the atmosphere as gas exchange while the remaining 0.9 Pg y-1 is delivered to the oceans, roughly equally as inorganic and organic carbon. Thus, roughly twice as much C enters inland aquatic systems from land as is exported from land to the sea. Over prolonged time net carbon fluxes in aquatic systems tend to be greater per unit area than in much of the surrounding land. Although their area is small, these freshwater aquatic systems can affect regional C balances. Further, the inclusion of inland, freshwater ecosystems provides useful insight about the storage, oxidation and transport of terrestrial C, and may warrant a revision of how the modern net C sink on land is described. ?? 2007 Springer Science+Business Media, LLC.

  16. The diel cycle of water vapor in west Greenland

    NASA Astrophysics Data System (ADS)

    Kopec, B. G.; Lauder, A. M.; Posmentier, E. S.; Feng, X.

    2014-08-01

    We present a study of the dynamics of small-scale (~100 km) atmospheric circulation in west Greenland which is dominated by interactions of marine and continental air masses. Water vapor concentration and isotopic ratios measured continuously over a 25 day period in Kangerlussuaq, Greenland were used to monitor the convergence of easterly katabatic winds and westerly sea breezes that form a front between the dry, isotopically depleted, glacial air mass and the moist, isotopically enriched, marine air mass. During the latter 16 days of the measurement period, an interval with no large-scale synoptic interference, the inland penetration of the sea breeze controlled the largest day-to-day humidity and vapor isotopic variations. Kangerlussuaq experienced sea breezes in the afternoon on 9 days, consistent with the long-term average of such occurrences on 56% of days in July and August. The inland position of the sea breeze front is controlled by the katabatic wind strength, which is stronger during times of reduced cloud coverage and/or higher-pressure gradient between the coast and the Greenland ice sheet. The position and movement of the front will likely respond to changes in the general atmospheric circulation and regional radiation balance resulting from global warming, which will, in turn, impact the local hydrological cycle and ecosystem processes.

  17. Selective Electrochemical Generation of Hydrogen Peroxide from Water Oxidation.

    PubMed

    Viswanathan, Venkatasubramanian; Hansen, Heine A; Nørskov, Jens K

    2015-11-01

    Water is a life-giving source, fundamental to human existence, yet over a billion people lack access to clean drinking water. The present techniques for water treatment such as piped, treated water rely on time and resource intensive centralized solutions. In this work, we propose a decentralized device concept that can utilize sunlight to split water into hydrogen and hydrogen peroxide. The hydrogen peroxide can oxidize organics while the hydrogen bubbles out. In enabling this device, we require an electrocatalyst that can oxidize water while suppressing the thermodynamically favored oxygen evolution and form hydrogen peroxide. Using density functional theory calculations, we show that the free energy of adsorbed OH* can be used to determine selectivity trends between the 2e(-) water oxidation to H2O2 and the 4e(-) oxidation to O2. We show that materials which bind oxygen intermediates sufficiently weakly, such as SnO2, can activate hydrogen peroxide evolution. We present a rational design principle for the selectivity in electrochemical water oxidation and identify new material candidates that could perform H2O2 evolution selectively. PMID:26538037

  18. Process for treating effluent from a supercritical water oxidation reactor

    DOEpatents

    Barnes, Charles M.; Shapiro, Carolyn

    1997-01-01

    A method for treating a gaseous effluent from a supercritical water oxidation reactor containing entrained solids is provided comprising the steps of expanding the gas/solids effluent from a first to a second lower pressure at a temperature at which no liquid condenses; separating the solids from the gas effluent; neutralizing the effluent to remove any acid gases; condensing the effluent; and retaining the purified effluent to the supercritical water oxidation reactor.

  19. Process for treating effluent from a supercritical water oxidation reactor

    DOEpatents

    Barnes, C.M.; Shapiro, C.

    1997-11-25

    A method for treating a gaseous effluent from a supercritical water oxidation reactor containing entrained solids is provided comprising the steps of expanding the gas/solids effluent from a first to a second lower pressure at a temperature at which no liquid condenses; separating the solids from the gas effluent; neutralizing the effluent to remove any acid gases; condensing the effluent; and retaining the purified effluent to the supercritical water oxidation reactor. 6 figs.

  20. The chemical state of fission products in oxide fuels at different stages of the nuclear fuel cycle

    SciTech Connect

    Kleykamp, H.

    1988-03-01

    A survey of work at the Kernforschungszentrum Karlsruhe is presented on the chemical state of selected fission products that are relevant in the fuel cycle of light water reactor (LWR) and fast breeder reactor fuels. The influence of fuel type and irradiation progress on the composition of the Mo-Tc-Ru-Rh-Pd fission product alloys precipitated in the oxide matrix is examined using the respective multicomponent phase diagrams. The kinetics of dissolution of these phases in nitric acid at the reprocessing stage is discussed. Composition and structure of the residues, and the reprecipitation phenomena from highly active waste (HAW), are elucidated. A second metamorphosis of the fission products is recognized during the vitrification process. The formation of Ru(Rh) oxide and Pd(Rh, U, Te) alloys in simulated vitrified HAW concentrate and in HAW concentrate from the reprocessing of irradiated LWR fuels in interpreted on the basis of heterogeneous equilibria.

  1. Donor-Flexible Nitrogen Ligands for Efficient Iridium-Catalyzed Water Oxidation Catalysis.

    PubMed

    Navarro, Miquel; Li, Mo; Müller-Bunz, Helge; Bernhard, Stefan; Albrecht, Martin

    2016-05-10

    A pyridylideneamide ligand with variable donor properties owing to a pronounced zwitterionic and a neutral diene-type resonance structure was used as a dynamic ligand at a Cp* iridium center to facilitate water oxidation catalysis, a reaction that requires the stabilization of a variety of different iridium oxidation states and that is key for developing an efficient solar fuel device. The ligand imparts high activity (nearly three-fold increase of turnover frequency compared to benchmark systems), and exceptionally high turnover numbers, which indicate a robust catalytic cycle and little catalyst degradation. PMID:26919306

  2. Species, Abundance and Function of Ammonia-oxidizing Archaea in Inland Waters across China

    PubMed Central

    Zhou, Leiliu; Wang, Shanyun; Zou, Yuxuan; Xia, Chao; Zhu, Guibing

    2015-01-01

    Ammonia oxidation is the first step in nitrification and was thought to be performed solely by specialized bacteria. The discovery of ammonia-oxidizing archaea (AOA) changed this view. We examined the large scale and spatio-temporal occurrence, abundance and role of AOA throughout Chinese inland waters (n = 28). Molecular survey showed that AOA was ubiquitous in inland waters. The existence of AOA in extreme acidic, alkaline, hot, cold, eutrophic and oligotrophic environments expanded the tolerance limits of AOA, especially their known temperature tolerance to −25 °C, and substrate load to 42.04 mM. There were spatio-temporal divergences of AOA community structure in inland waters, and the diversity of AOA in inland water ecosystems was high with 34 observed species-level operational taxonomic units (OTUs; based on a 15% cutoff) distributed widely in group I.1b, I.1a, and I.1a-associated. The abundance of AOA was quite high (8.5 × 104 to 8.5 × 109 copies g−1), and AOA outnumbered ammonia-oxidizing bacteria (AOB) in the inland waters where little human activities were involved. On the whole AOB predominate the ammonia oxidation rate over AOA in inland water ecosystems, and AOA play an indispensable role in global nitrogen cycle considering that AOA occupy a broader habitat range than AOB, especially in extreme environments. PMID:26522086

  3. Species, Abundance and Function of Ammonia-oxidizing Archaea in Inland Waters across China

    NASA Astrophysics Data System (ADS)

    Zhou, Leiliu; Wang, Shanyun; Zou, Yuxuan; Xia, Chao; Zhu, Guibing

    2015-11-01

    Ammonia oxidation is the first step in nitrification and was thought to be performed solely by specialized bacteria. The discovery of ammonia-oxidizing archaea (AOA) changed this view. We examined the large scale and spatio-temporal occurrence, abundance and role of AOA throughout Chinese inland waters (n = 28). Molecular survey showed that AOA was ubiquitous in inland waters. The existence of AOA in extreme acidic, alkaline, hot, cold, eutrophic and oligotrophic environments expanded the tolerance limits of AOA, especially their known temperature tolerance to -25 °C, and substrate load to 42.04 mM. There were spatio-temporal divergences of AOA community structure in inland waters, and the diversity of AOA in inland water ecosystems was high with 34 observed species-level operational taxonomic units (OTUs; based on a 15% cutoff) distributed widely in group I.1b, I.1a, and I.1a-associated. The abundance of AOA was quite high (8.5 × 104 to 8.5 × 109 copies g-1), and AOA outnumbered ammonia-oxidizing bacteria (AOB) in the inland waters where little human activities were involved. On the whole AOB predominate the ammonia oxidation rate over AOA in inland water ecosystems, and AOA play an indispensable role in global nitrogen cycle considering that AOA occupy a broader habitat range than AOB, especially in extreme environments.

  4. Species, Abundance and Function of Ammonia-oxidizing Archaea in Inland Waters across China.

    PubMed

    Zhou, Leiliu; Wang, Shanyun; Zou, Yuxuan; Xia, Chao; Zhu, Guibing

    2015-01-01

    Ammonia oxidation is the first step in nitrification and was thought to be performed solely by specialized bacteria. The discovery of ammonia-oxidizing archaea (AOA) changed this view. We examined the large scale and spatio-temporal occurrence, abundance and role of AOA throughout Chinese inland waters (n = 28). Molecular survey showed that AOA was ubiquitous in inland waters. The existence of AOA in extreme acidic, alkaline, hot, cold, eutrophic and oligotrophic environments expanded the tolerance limits of AOA, especially their known temperature tolerance to -25 °C, and substrate load to 42.04 mM. There were spatio-temporal divergences of AOA community structure in inland waters, and the diversity of AOA in inland water ecosystems was high with 34 observed species-level operational taxonomic units (OTUs; based on a 15% cutoff) distributed widely in group I.1b, I.1a, and I.1a-associated. The abundance of AOA was quite high (8.5 × 10(4) to 8.5 × 10(9) copies g(-1)), and AOA outnumbered ammonia-oxidizing bacteria (AOB) in the inland waters where little human activities were involved. On the whole AOB predominate the ammonia oxidation rate over AOA in inland water ecosystems, and AOA play an indispensable role in global nitrogen cycle considering that AOA occupy a broader habitat range than AOB, especially in extreme environments. PMID:26522086

  5. Stoichiometry of Reducing Equivalents and Splitting of Water in the Citric Acid Cycle.

    ERIC Educational Resources Information Center

    Madeira, Vitor M. C.

    1988-01-01

    Presents a solution to the problem of finding the source of extra reducing equivalents, and accomplishing the stoichiometry of glucose oxidation reactions. Discusses the citric acid cycle and glycolysis. (CW)

  6. Kinetics of plastoquinol oxidation by the Q-cycle in leaves.

    PubMed

    Laisk, Agu; Oja, Vello; Eichelmann, Hillar

    2016-06-01

    Electrochromic shift measurements confirmed that the Q-cycle operated in sunflower leaves. The slow temporarily increasing post-pulse phase was recorded, when ATP synthase was inactivated in the dark and plastoquinol (PQH2) oxidation was initiated by a short pulse of far-red light (FRL). During illumination by red light, the Q-cycle-supported proton arrival at the lumen and departure via ATP synthase were simultaneous, precluding extreme build-up of the membrane potential. To investigate the kinetics of the Q-cycle, less than one PQH2 per cytochrome b6f (Cyt b6f) were reduced by illuminating the leaf with strong light pulses or single-turnover Xe flashes. The post-pulse rate of oxidation of these PQH2 molecules was recorded via the rate of reduction of plastocyanin (PC(+)) and P700(+), monitored at 810 and 950nm. The PSII-reduced PQH2 molecules were oxidized with multi-phase overall kinetics, τd=1, τp=5.6 and τs=16 ms (22 °C). We conclude that τd characterizes PSII processes and diffusion, τp is the bifurcated oxidation of the primary quinol and τs is the Q-cycle-involving reduction of the secondary quinol at the n-site, its transport to the p-site, and bifurcated oxidation there. The extraordinary slow kinetics of the Q-cycle may be related to the still unsolved mechanism of the "photosynthetic control." PMID:27056771

  7. Dissolved N2/Ar Ratios in Sedimentary Pore Waters: A New Twist in Marine Nitrogen Cycle

    NASA Astrophysics Data System (ADS)

    Berelson, W.; Prokopenko, M. G.; Sigman, D. M.; Hammond, D.

    2008-12-01

    The nitrogen cycle is comprised predominantly of biologically mediated pathways, leading to a series of negative feedbacks that stabilize the cycle. Sedimentary denitrification, the major sink in the nitrogen budget, is regulated by the rate of organic carbon rain to the sea floor, as well as oxygen concentrations in overlying bottom waters. The sensitivity of sedimentary denitrification as a negative feedback can be expressed as a ratio between total denitrification (including nitrification sub-cycle) rates integrated over depth (fluxes) and fluxes of remineralized organic carbon out of the sediments, Ndenitr/Coxid_total. We have investigated benthic nitrogen cycling in three, semi-enclosed basins of the California Borderlands: Santa Monica, San Pedro and Santa Barbara located in the regime of seasonal coastal upwelling. Deep water in these basins is separated from the open ocean by sills of various depths, contributing to the low [O2], <1 to10 uM. In this study, we developed a method to sample pore waters for dissolved gas analysis. Ratios between O2, Ar and N2 were determined on extracted pore waters with 1) offline cryogenic extraction and subsequent analysis on Finnigan Delta Plus IRMS with 8 collectors; 2) Membrane Inlet Mass Spectrometery (MIMS). Vertical profiles of pore water N2/Ar in the three basins indicate N2 production at depth horizons which exceed by a factor of 5 to 20 the depth of nitrate penetration supported solely by diffusive flux. At depths of maximum subsurface N2 production, we discovered large pools of intracellular nitrate. The relationship between δ15N and δ18O of nitrate are consistent with the activity of a membrane-bound nitrate reductase affecting the measured isotopic composition of the nitrate pool (Granger et al., 2008, in press). In addition, increases in δ15N of pore water NH4 at this depth suggests that at least some of the nitrate might be used for anaerobic ammonium oxidation. Our model estimates up to 25 % of the measured total nitrate flux into the sediments must be transported by non-diffusive processes to support the subsurface N2 production rate. We hypothesize that nitrate is transported to depth by motile microorganisms, bacteria or protists, for use in yet to be identified reactions with sulfide, dissolved metals or organic matter. We propose that the non-local transport of nitrate also sustains the population of Anammox performing bacteria, living in close association with nitrate transporting organisms and contributing to the subsurface N2 production. This process presents yet another pathway for nitrate losses from the oceans, increasing sensitivity of sedimentary denitrification as a stabilizing feedback in the nitrogen cycle, as the conversion of transported nitrate to N2 may not be directly linked to oxidation of the organic carbon.

  8. Thaumarchaeal ammonium oxidation and evidence for a nitrogen cycle in a subsurface radioactive thermal spring in the Austrian Central Alps.

    PubMed

    Gerbl, Friedrich W; Weidler, Gerhard W; Wanek, Wolfgang; Erhardt, Angelika; Stan-Lotter, Helga

    2014-01-01

    Previous studies had suggested the presence of ammonium oxidizing Thaumarchaeota as well as nitrite oxidizing Bacteria in the subsurface spring called Franz Josef Quelle (FJQ), a slightly radioactive thermal mineral spring with a temperature of 43.6-47°C near the alpine village of Bad Gastein, Austria. The microbiological consortium of the FJQ was investigated for its utilization of nitrogen compounds and the putative presence of a subsurface nitrogen cycle. Microcosm experiments made with samples from the spring water, containing planktonic microorganisms, or from biofilms, were used in this study. Three slightly different media, enriched with vitamins and trace elements, and two incubation temperatures (30 and 40°C, respectively) were employed. Under aerobic conditions, high rates of conversion of ammonium to nitrite, as well as nitrite to nitrate were measured. Under oxygen-limited conditions nitrate was converted to gaseous compounds. Stable isotope probing with (15)NH4Cl or ((15)NH4)2SO4as sole energy sources revealed incorporation of (15)N into community DNA. Genomic DNA as well as RNA were extracted from all microcosms. The following genes or fragments of genes were successfully amplified, cloned and sequenced by standard PCR from DNA extracts: Ammonia monooxygenase subunit A (amoA), nitrite oxidoreductase subunits A and B (nxrA and nxrB), nitrate reductase (narG), nitrite reductase (nirS), nitric oxide reductases (cnorB and qnorB), nitrous oxide reductase (nosZ). Reverse transcription of extracted total RNA and real-time PCR suggested the expression of each of those genes. Nitrogen fixation (as probed with nifH and nifD) was not detected. However, a geological origin of NH(+) 4 in the water of the FJQ cannot be excluded, considering the silicate, granite and gneiss containing environment. The data suggested the operation of a nitrogen cycle in the subsurface environment of the FJQ. PMID:24904540

  9. Thaumarchaeal ammonium oxidation and evidence for a nitrogen cycle in a subsurface radioactive thermal spring in the Austrian Central Alps

    PubMed Central

    Gerbl, Friedrich W.; Weidler, Gerhard W.; Wanek, Wolfgang; Erhardt, Angelika; Stan-Lotter, Helga

    2014-01-01

    Previous studies had suggested the presence of ammonium oxidizing Thaumarchaeota as well as nitrite oxidizing Bacteria in the subsurface spring called Franz Josef Quelle (FJQ), a slightly radioactive thermal mineral spring with a temperature of 43.6–47°C near the alpine village of Bad Gastein, Austria. The microbiological consortium of the FJQ was investigated for its utilization of nitrogen compounds and the putative presence of a subsurface nitrogen cycle. Microcosm experiments made with samples from the spring water, containing planktonic microorganisms, or from biofilms, were used in this study. Three slightly different media, enriched with vitamins and trace elements, and two incubation temperatures (30 and 40°C, respectively) were employed. Under aerobic conditions, high rates of conversion of ammonium to nitrite, as well as nitrite to nitrate were measured. Under oxygen-limited conditions nitrate was converted to gaseous compounds. Stable isotope probing with 15NH4Cl or (15NH4)2SO4as sole energy sources revealed incorporation of 15N into community DNA. Genomic DNA as well as RNA were extracted from all microcosms. The following genes or fragments of genes were successfully amplified, cloned and sequenced by standard PCR from DNA extracts: Ammonia monooxygenase subunit A (amoA), nitrite oxidoreductase subunits A and B (nxrA and nxrB), nitrate reductase (narG), nitrite reductase (nirS), nitric oxide reductases (cnorB and qnorB), nitrous oxide reductase (nosZ). Reverse transcription of extracted total RNA and real-time PCR suggested the expression of each of those genes. Nitrogen fixation (as probed with nifH and nifD) was not detected. However, a geological origin of NH+4 in the water of the FJQ cannot be excluded, considering the silicate, granite and gneiss containing environment. The data suggested the operation of a nitrogen cycle in the subsurface environment of the FJQ. PMID:24904540

  10. A method for determining the oxidation state of uranium in natural waters

    NASA Astrophysics Data System (ADS)

    Anderson, Robert F.

    1984-06-01

    Uranium exhibits radically different geochemical properties in its two oxidation states. Hexavalent uranium is quite soluble, especially when complexed by carbonate ions in alkaline solutions. Tetravalent uranium, by contrast, is very insoluble, and it would be expected to be rapidly removed from natural waters either by precipitation of a mineral phase such as UO 2(s) or by adsorption to solid surfaces. It is important to know the oxidation state in which uranium will occur under specified conditions of Eh and pH as this relates both to processes forming economically valuable uranium deposits and to the mobility of uranium released to the environment during various stages of the nuclear fuel cycle. In this work, yield monitors in each oxidation state [ 232U(IV)], 236U(VI)] are added to water samples, and uranium oxidation states are separated by a NdF 3 coprecipitation in which only the U(IV) is carried. The precipitate is removed by filtration. Subsequently, TiCl 3 is added to reduce U(IV) and the NdF 3 coprecipitation is repeated. A similar method is widely used for separating oxidation states of plutonium. Results from a meromictic lake (Fayetteville Green Lake, Syracuse, New York, USA) and from an anoxic marine basin (Cariaco Trench, Venezuela) where total H 2S concentrations in the bottom waters reach 1 mM 1 -1 and 50 μM 1 -1 respectively show that in both cases the dissolved uranium is present in its oxidized form.

  11. Emerging contaminants of public health significance as water quality indicator compounds in the urban water cycle.

    PubMed

    Pal, Amrita; He, Yiliang; Jekel, Martin; Reinhard, Martin; Gin, Karina Yew-Hoong

    2014-10-01

    The contamination of the urban water cycle (UWC) with a wide array of emerging organic compounds (EOCs) increases with urbanization and population density. To produce drinking water from the UWC requires close examination of their sources, occurrence, pathways, and health effects and the efficacy of wastewater treatment and natural attenuation processes that may occur in surface water bodies and groundwater. This paper researches in details the structure of the UWC and investigates the routes by which the water cycle is increasingly contaminated with compounds generated from various anthropogenic activities. Along with a thorough survey of chemicals representing compound classes such as hormones, antibiotics, surfactants, endocrine disruptors, human and veterinary pharmaceuticals, X-ray contrast media, pesticides and metabolites, disinfection-by-products, algal toxins and taste-and-odor compounds, this paper provides a comprehensive and holistic review of the occurrence, fate, transport and potential health impact of the emerging organic contaminants of the UWC. This study also illustrates the widespread distribution of the emerging organic contaminants in the different aortas of the ecosystem and focuses on future research needs. PMID:24972248

  12. Potential Seasonal Predictability of the Global Water Cycle

    NASA Astrophysics Data System (ADS)

    Feng, X.; DelSole, T. M.; Houser, P. R.

    2011-12-01

    The potential predictability of seasonal means of water cycle components, specifically precipitation and evaporation, are estimated using recently developed methods based on Analysis of Covariance (ANOCOVA) and the bootstrap, and the previous methods proposed by Katz (KZ), Shukla-Gutzler (SG) and Madden (MN). The ANOCOVA method has the advantage of not only taking into account autocorrelation structure in the daily time series but also accounting for the uncertainty of the estimated parameters in the significance test. This method tests whether interannual variability of seasonal means exceeds that due to weather noise under the null hypothesis that seasonal means are identical every year. The second method is based on the bootstrap technique that makes few assumptions about physical process, model structure and underlying distribution. The essence of the bootstrap is to randomly resample the daily time series to build up an empirical distribution of the variance of seasonal means under the null hypothesis that seasonal mean is independent of year. The predictability of the observed precipitation estimated by ANOCOVA, the bootstrap and KZ reveals similar spatial distribution patterns: large fraction of predictable variance (FPV) in tropics and low FPV over extatropics where interannual variability is not significantly distinguished from the weather noise. There are more regions identified potentially predictable in December-January-February (DJF) and March-April-May (MAM) than in June-July-August (JJA) and September-October-November (SON). The ANOCOVA method exhibits the highest predictability of the three methods and is close to the bootstrap, while KZ shows the smallest FPV due to the dominance of noise. Seasonal evaporation over global land from ANOCOVA, bootstrap, SG and MN indicates that high predictability occurs predominately over tropical and southern mid-latitude land areas, and modest predictability occurs over North America and Europe. The potential predictability of evaporation also exhibits a prominent seasonal cycle with JJA and SON having the most predictable area. The bootstrap suggests that 58% of land is potentially predictable, the largest predictable area of the four methods. The ANOCOVA method also has larger FPV than SG and MN, while it generally produces estimates similar to those of the bootstrap. The predictable area suggested by MN barely exceeds 30% of the globe, the smallest area of predictable estimated among all the four methods.

  13. TRMM and Its Connection to the Global Water Cycle

    NASA Technical Reports Server (NTRS)

    Kummerow, Chiristian

    1999-01-01

    The importance of quantitative knowledge of tropical rainfall, its associated latent heating and variability is summarized in the context of the global hydrologic cycle. Much of the tropics is covered by oceans. What land exists, is covered largely by rainforests that are only thinly populated. The only way to adequately measure the global tropical rainfall for climate and general circulation models is from space. The TRMM orbit is inclined 35 degrees leading to good sampling in the tropics and a rapid precession to study the diurnal cycle of precipitation. The precipitation instrument complement consists of the first rain radar to be flown in space (PR), a multi-channel passive microwave sensor (TMI) and a five-channel VIS/IR (VIRS) sensor. The precipitation radar operates at a frequency of 13.6 GHz. The swath width is 220 km, with a horizontal resolution of 4 km and the vertical resolution of 250 m. The minimum detectable signal from the precipitation radar has been measured at 17 dBZ. The TMI instrument is designed similar to the SSM/I with two important changes. The 22.235 GHz water vapor absorption channel of the SSM/I was moved to 21.3 GHz in order to avoid saturation in the tropics and 10.7 GHz V&H polarized channels were added to expand the dynamic range of rainfall estimates. The resolution of the TMI varies from 4.6 km at 85 GHz to 36 km at 10.7 GHz. The visible and infrared sensor (VIRS) measures radiation at 0.63, 1.6, 3.75, 10.8 and 12.0 microns. The spatial resolution of all five VIRS channels is 2 km at nadir. In addition to the three primary rainfall instruments, TRMM will also carry a Lightning Imaging Sensor (LIS) and a Clouds and the Earth's Radiant Energy System (CERES) instrument. This presentation will focus primarily on the advances in our understanding of tropical rain systems needed to interpret the TRMM data. Global averages, as well as case studies from TRMM radar (PR), the TRMM Microwave Imager (TMI) and Visible and Infrared Sensor (VIRS) will be presented. Comparisons and contrasts among the different sensors will be drawn. Results will also be compared to previous rainfall climatologies generated from the SSM/I instrument. In particular this paper will focus on the synergy between the TRMM radar and passive microwave radiometer and what we have learned from is synergy.

  14. TRMM and its Connection to the Global Water Cycle

    NASA Technical Reports Server (NTRS)

    Kummerow, Christian; Hong, Ye

    1999-01-01

    The importance of quantitative knowledge of tropical rainfall, its associated latent heating and variability is summarized in the context of the global hydrologic cycle. Much of the tropics is covered by oceans. What land exists, is covered largely by rainforests that are only thinly populated. The only way to adequately measure the global tropical rainfall for climate and general circulation models is from space. The Tropical Rainfall Measuring Mission (TRMM) orbit is inclined 35 degrees leading to good sampling in the tropics and a rapid precession to study the diurnal cycle of precipitation. The precipitation instrument complement consists of the first rain radar to be flown in space (PR), a multi-channel passive microwave sensor (TMI) and a five-channel VIS/IR (VIRS) sensor. The precipitation radar operates at a frequency of 13.6 GHz. The swath width is 220 km, with a horizontal resolution of 4 km and the vertical resolution of 250 m. The minimum detectable signal from the precipitation radar has been measured at - 17 dBZ. The TMI instrument is designed similar to the SSM/I with two important changes. The 22.235 GHz water vapor absorption channel of the SSM/I was moved to 21.3 GHz in order to avoid saturation in the tropics and 10.7 GHz V&H polarized channels were added to expand the dynamic range of rainfall estimates. The resolution of the TMI varies from 4.6 km at 85 GHz to 36 km at 10.7 GHz. The visible and infrared sensor (VIRS) measures radiation at 0.63, 1.6, 3.75, 10.8 and 12.0 microns. The spatial resolution of all five VIRS channels is 2 km at nadir. In addition to the three primary rainfall instruments, TRMM will also carry a Lightning Imaging Sensor (LIS) and a Clouds and the Earth's Radiant Energy System (CERES) instrument. This presentation will focus primarily on the advances in our understanding of tropical rain systems needed to interpret the TRMM data. Global averages, as well as case studies from TRMM radar (PR), the TRMM Microwave Imager (TMI) and Visible and Infrared Sensor (VIRS) will be presented. Comparisons and contrasts among the different sensors will be drawn. Results will also be compared to previous rainfall climatologies generated from the SSM/I instrument. In particular this paper will focus on the synergy between the TRMM radar and passive microwave radiometer and what we have learned from its synergy.

  15. Using MGS TES Data to Understand Water Cycling in Mars' North Polar Region

    NASA Technical Reports Server (NTRS)

    Tamppari, L. K.; Hale, A. S.; Bass, D. S.; Smith, M. D.

    2003-01-01

    The Martian water cycle is one of the three annual cycles on Mars, dust and CO2 being the other two. Despite the fact that detailed spacecraft data, including global and annual coverage in a variety of wavelengths, have been taken of Mars spanning more than 25 years, there are many outstanding questions regarding the water cycle. There is very little exposed water on Mars today, in either the atmosphere or on the surface although there is geological evidence of catastrophic flooding and continuously running water in past epochs in Mars' history as well as recent (within about 10,000 years ago) evidence for running water in the form of gullies. While there is little water in the atmosphere, water- ice clouds do form and produce seasonal clouds caused by general circulation and by storms. These clouds may in turn be controlling the cycling of the water within the general circulation.

  16. The Use of Water Vapor as a Refrigerant: Impact of Cycle Modifications on Commercial Viability

    SciTech Connect

    Brandon F. Lachner, Jr.; Gregory F. Nellis; Douglas T. Reindl

    2004-08-30

    This project investigated the economic viability of using water as the refrigerant in a 1000-ton chiller application. The most attractive water cycle configuration was found to be a flash-intercooled, two-stage cycle using centrifugal compressors and direct contact heat exchangers. Component level models were developed that could be used to predict the size and performance of the compressors and heat exchangers in this cycle as well as in a baseline, R-134a refrigeration cycle consistent with chillers in use today. A survey of several chiller manufacturers provided information that was used to validate and refine these component models. The component models were integrated into cycle models that were subsequently used to investigate the life-cycle costs of both an R-134a and water refrigeration cycle. It was found that the first cost associated with the water as a refrigerant cycle greatly exceeded the savings in operating costs associated with its somewhat higher COP. Therefore, the water refrigeration cycle is not an economically attractive option to today's R-134a refrigeration system. There are a number of other issues, most notably the requirements associated with purging non-condensable gases that accumulate in a direct contact heat exchanger, which will further reduce the economic viability of the water cycle.

  17. Succession of Internal Sulfur Cycles and Sulfur-Oxidizing Bacterial Communities in Microaerophilic Wastewater Biofilms

    PubMed Central

    Okabe, Satoshi; Ito, Tsukasa; Sugita, Kenichi; Satoh, Hisashi

    2005-01-01

    The succession of sulfur-oxidizing bacterial (SOB) community structure and the complex internal sulfur cycle occurring in wastewater biofilms growing under microaerophilic conditions was analyzed by using a polyphasic approach that employed 16S rRNA gene-cloning analysis combined with fluorescence in situ hybridization, microelectrode measurements, and standard batch and reactor experiments. A complete sulfur cycle was established via S0 accumulation within 80 days in the biofilms in replicate. This development was generally split into two phases, (i) a sulfur-accumulating phase and (ii) a sulfate-producing phase. In the first phase (until about 40 days), since the sulfide production rate (sulfate-reducing activity) exceeded the maximum sulfide-oxidizing capacity of SOB in the biofilms, H2S was only partially oxidized to S0 by mainly Thiomicrospira denitirificans with NO3− as an electron acceptor, leading to significant accumulation of S0 in the biofilms. In the second phase, the SOB populations developed further and diversified with time. In particular, S0 accumulation promoted the growth of a novel strain, strain SO07, which predominantly carried out the oxidation of S0 to SO42− under oxic conditions, and Thiothrix sp. strain CT3. In situ hybridization analysis revealed that the dense populations of Thiothrix (ca. 109 cells cm−3) and strain SO07 (ca. 108 cells cm−3) were found at the sulfur-rich surface (100 μm), while the population of Thiomicrospira denitirificans was distributed throughout the biofilms with a density of ca. 107 to 108 cells cm−3. Microelectrode measurements revealed that active sulfide-oxidizing zones overlapped the spatial distributions of different phylogenetic SOB groups in the biofilms. As a consequence, the sulfide-oxidizing capacities of the biofilms became high enough to completely oxidize all H2S produced by SRB to SO42− in the second phase, indicating establishment of the complete sulfur cycle in the biofilms. PMID:15870342

  18. Trace element cycling through iron oxide minerals during redox-driven dynamic recrystallization

    SciTech Connect

    Frierdich, Andrew J.; Luo, Yun; Catalano, Jeffrey G.

    2011-11-17

    Microbially driven iron redox cycling in soil and sedimentary systems, including during diagenesis and fluid migration, may activate secondary abiotic reactions between aqueous Fe(II) and solid Fe(III) oxides. These reactions catalyze dynamic recrystallization of iron oxide minerals through localized and simultaneous oxidative adsorption of Fe(II) and reductive dissolution of Fe(III). Redox-active trace elements undergo speciation changes during this process, but the impact redox-driven recrystallization has on redox-inactive trace elements associated with iron oxides is uncertain. Here we demonstrate that Ni is cycled through the minerals goethite and hematite during redox-driven recrystallization. X-ray absorption spectroscopy demonstrates that during this process adsorbed Ni becomes progressively incorporated into the minerals. Kinetic studies using batch reactors containing aqueous Fe(II) and Ni preincorporated into iron oxides display substantial release of Ni to solution. We conclude that iron oxide recrystallization activated by aqueous Fe(II) induces cycling of Ni through the mineral structure, with adsorbed Ni overgrown in regions of Fe(II) oxidative adsorption and incorporated Ni released in regions of reductive dissolution of structural Fe(III). The redistribution of Ni among the mineral bulk, mineral surface, and aqueous solution appears to be thermodynamically controlled and catalyzed by Fe(II). Our work suggests that important proxies for ocean composition on the early Earth may be invalid, identifies new processes controlling micronutrient availability in soil, sedimentary, and aquatic ecosystems, and points toward a mechanism for trace element mobilization during diagenesis and enrichment in geologic fluids.

  19. Copper as a robust and transparent electrocatalyst for water oxidation.

    PubMed

    Du, Jialei; Chen, Zuofeng; Ye, Shengrong; Wiley, Benjamin J; Meyer, Thomas J

    2015-02-01

    Copper metal is in theory a viable oxidative electrocatalyst based on surface oxidation to Cu(III) and/or Cu(IV) , but its use in water oxidation has been impeded by anodic corrosion. The in situ formation of an efficient interfacial oxygen-evolving Cu catalyst from Cu(II) in concentrated carbonate solutions is presented. The catalyst necessitates use of dissolved Cu(II) and accesses the higher oxidation states prior to decompostion to form an active surface film, which is limited by solution conditions. This observation and restriction led to the exploration of ways to use surface-protected Cu metal as a robust electrocatalyst for water oxidation. Formation of a compact film of CuO on Cu surface prevents anodic corrosion and results in sustained catalytic water oxidation. The Cu/CuO surface stabilization was also applied to Cu nanowire films, which are transparent and flexible electrocatalysts for water oxidation and are an attractive alternative to ITO-supported catalysts for photoelectrochemical applications. PMID:25581365

  20. Anomalous dielectric relaxation of water confined in graphite oxide

    NASA Astrophysics Data System (ADS)

    Yu, Ji; Tian, Yuchen; Gu, Min; Tang, Tong B.

    2015-09-01

    Nonmonotonic thermal dependence of dielectric relaxation of water has been observed in hydrated graphite oxide (GO). Graphite oxide prepared via Hummers method then imbued with specific water contents were characterized, with 13C and 1H nuclear magnetic resonance spectroscopies, X-ray photoelectron spectroscopy, ambient- and variable-temperature X-ray diffractometries, as well as thermogravimetric analysis. Pressed pellets provided with either conducting or blocking electrodes yielded dielectric loss, which was shown to originate from dielectric relaxation of the confined water. Three relaxation processes were observed in impedance spectroscopy. Our previous work has identified two different types of water in GO, namely, intercalated water and water in inter-grain voids. P1 expresses the reorientation of water confined inside inter-grain voids, and P2, the rotation of intercalated water molecules confined in interlayers. The present work reveals a new process P3, which also relates to intercalated water. It slows down with temperature, and this apparent anomaly is explained by the decrease in water content and consequent narrowing of interlayer spacing in graphite oxide, as confirmed by characterization techniques. The present study should contribute to our understanding of surface water dynamics.

  1. Developing and Testing Water Cycle Intensification Indicator (WCI) over the United States

    NASA Astrophysics Data System (ADS)

    Feng, X.; Houser, P. R.

    2014-12-01

    Is the water cycle intensifying in response to global warming due to temperature-driven changes in atmospheric water holding capacity? To address this question, we are developing and testing Water Cycle Intensification Indicator (WCI) to quantify the current and future change in the strength of the water cycle across the conterminous U.S. in support of the National Climate Assessment (NCA). The WCI consists of a suite of primary water cycle trend and extreme composites that are spatially- and temporally-scalable for summarizing how the climate changes results in stronger or more extreme water cycling over the nation. We calculated trend and extreme in water cycle components using NASA-produced data and modeling products. Six water cycle variables are chosen, including precipitation, evaporation, runoff, moisture convergence flux, terrestrial storage and water vapor. Our preliminary results showed that the strength of water cycle depends on specific regions and variables, even different datasets. For instance, precipitation from MERRA-Land offline simulation is consistent with the CPC unified precipitation dataset in showing positive trend over the northeastern, northwestern and west north central, but negative trend over the western and central regions. However, negative trends are observed in MERRA-land over the southern Texas and some parts of the southern coast, contrary to the positive trend revealed by the unified dataset in the same area. Next, we are going to integrate and combine the trends and extremes of these water cycle components to develop a suite of climate indicators to monitor the changes of water cycle as result of climate change. These indicators will be implemented and tested over the nation for further optimization. Moreover, we will also be developing innovative WCI visualization, documentation and distribution methods to disseminate WCI products to the public and stakeholders.

  2. Room-Temperature Oxidation of Formaldehyde by Layered Manganese Oxide: Effect of Water.

    PubMed

    Wang, Jinlong; Zhang, Pengyi; Li, Jinge; Jiang, Chuanjia; Yunus, Rizwangul; Kim, Jeonghyun

    2015-10-20

    Layered manganese oxide, i.e., birnessite was prepared via the reaction of potassium permanganate with ammonium oxalate. The water content in the birnessite was adjusted by drying/calcining the samples at various temperatures (30 °C, 100 °C, 200 °C, 300 °C, and 500 °C). Thermogravimetry-mass spectroscopy showed three types of water released from birnessite, which can be ascribed to physically adsorbed H2O, interlayer H2O and hydroxyl, respectively. The activity of birnessite for formaldehyde oxidation was positively associated with its water content, i.e., the higher the water content, the better activity it has. In-situ DRIFTS and step scanning XRD analysis indicate that adsorbed formaldehyde, which is promoted by bonded water via hydrogen bonding, is transformed into formate and carbonate with the consumption of hydroxyl and bonded water. Both bonded water and water in air can compensate the consumed hydroxyl groups to sustain the mineralization of formaldehyde at room temperature. In addition, water in air stimulates the desorption of carbonate via water competitive adsorption, and accordingly the birnessite recovers its activity. This investigation elucidated the role of water in oxidizing formaldehyde by layered manganese oxides at room temperature, which may be helpful for the development of more efficient materials. PMID:26426569

  3. Rare earth element partitioning between hydrous ferric oxides and acid mine water during iron oxidation

    USGS Publications Warehouse

    Verplanck, P.L.; Nordstrom, D.K.; Taylor, H.E.; Kimball, B.A.

    2004-01-01

    Ferrous iron rapidly oxidizes to Fe (III) and precipitates as hydrous Fe (III) oxides in acid mine waters. This study examines the effect of Fe precipitation on the rare earth element (REE) geochemistry of acid mine waters to determine the pH range over which REEs behave conservatively and the range over which attenuation and fractionation occur. Two field studies were designed to investigate REE attenuation during Fe oxidation in acidic, alpine surface waters. To complement these field studies, a suite of six acid mine waters with a pH range from 1.6 to 6.1 were collected and allowed to oxidize in the laboratory at ambient conditions to determine the partitioning of REEs during Fe oxidation and precipitation. Results from field experiments document that even with substantial Fe oxidation, the REEs remain dissolved in acid, sulfate waters with pH below 5.1. Between pH 5.1 and 6.6 the REEs partitioned to the solid phases in the water column, and heavy REEs were preferentially removed compared to light REEs. Laboratory experiments corroborated field data with the most solid-phase partitioning occurring in the waters with the highest pH. ?? 2004 Elsevier Ltd. All rights reserved.

  4. Carbon for engineering of a water-oxidizing catalyst.

    PubMed

    Najafpour, Mohammad Mahdi; Salimi, Saeideh

    2015-12-28

    Herein we report that the reaction of KMnO4 with cobalt nanoparticles coated with multiple graphene layers forms a promising catalyst toward water oxidation. The compound was characterized by scanning electron microscopy, energy-dispersive spectroscopy, high resolution transmission electron microscopy, X-ray diffraction, electronic spectroscopy, Fourier transform infrared spectroscopy, and atomic absorption spectroscopy. In addition to the Mn oxide-based characteristics of the catalyst, it is a conductive, self-healing, recycling, highly dispersible, magnetically separable, environmentally friendly, and nano-sized catalyst for water oxidation. The turnover frequency for the catalyst toward water oxidation is 0.1 and 0.05 (mmol O2 per mol Mn s) in the presence of cerium(iv) ammonium nitrate and photo-produced Ru(bpy)3(3+). PMID:26586131

  5. Rate Law Analysis of Water Oxidation on a Hematite Surface

    PubMed Central

    2015-01-01

    Water oxidation is a key chemical reaction, central to both biological photosynthesis and artificial solar fuel synthesis strategies. Despite recent progress on the structure of the natural catalytic site, and on inorganic catalyst function, determining the mechanistic details of this multiredox reaction remains a significant challenge. We report herein a rate law analysis of the order of water oxidation as a function of surface hole density on a hematite photoanode employing photoinduced absorption spectroscopy. Our study reveals a transition from a slow, first order reaction at low accumulated hole density to a faster, third order mechanism once the surface hole density is sufficient to enable the oxidation of nearest neighbor metal atoms. This study thus provides direct evidence for the multihole catalysis of water oxidation by hematite, and demonstrates the hole accumulation level required to achieve this, leading to key insights both for reaction mechanism and strategies to enhance function. PMID:25936408

  6. Supercritical water fuel cleaning for improved combined cycle performance

    SciTech Connect

    Tolman, R.; Timpe, R.C.; Parkinson, W.J.

    1998-04-01

    New limits on greenhouse gases, dioxin and mercury emissions are forcing electric power producers worldwide to seek new technologies to prevent pollution. Conventional coal-fired steam power plants operate at less than 40% efficiency, while circulating fluid bed incinerators operate at less than 30%, and mass-burn incinerators produce power at less than 20% efficiency. These plants can produce 4 to 6 times as much carbon dioxide and other emissions as modem natural gas-fired combined cycle gas turbine systems. These systems operate at over 50% efficiency and can be installed in less than half the time and at less than half the capital costs of conventional coal-fired plants and incinerators. The US Energy Information Administration predicts that US coal used for electricity will increase 20% to 21 quadrillion Btu`s per year by 2015. In the developing world, coal used for electricity is expected to increase by 128% to 38 quadrillion Btu`s. Without significant improvements in fuel use, there will be a 68% increase in emissions by 2015. A revolutionary hydrothermal heat recovery steam generator (HRSG) is being developed by a federal, state university and industry partnership to produce clean fuels for gas turbines. The patented hydrothermal HRSG will accept solutions and emulsions without corrosion and deposition on heat transfer surfaces. An advanced continuous-flow pilot plant is being designed to test the HRSG over a wide range of operating conditions, including the supercritical conditions of water, above 221 bar (3205 psia) and 374 C (705 F).

  7. THE FORMATION OF PB(IV) OXIDES IN CHLORINATED WATER

    EPA Science Inventory

    Recent research has shown that Pb(IV) oxides can play an important geochemical role in drinking water distribution systems. The basis of most guidance for lead control in drinking water, however, presumes that Pb(II) solids control lead solubility. Therefore, it is important that...

  8. A supramolecular ruthenium macrocycle with high catalytic activity for water oxidation that mechanistically mimics photosystem II.

    PubMed

    Schulze, Marcus; Kunz, Valentin; Frischmann, Peter D; Würthner, Frank

    2016-06-01

    Mimicking the ingenuity of nature and exploiting the billions of years over which natural selection has developed numerous effective biochemical conversions is one of the most successful strategies in a chemist's toolbox. However, an inability to replicate the elegance and efficiency of the oxygen-evolving complex of photosystem II (OEC-PSII) in its oxidation of water into O2 is a significant bottleneck in the development of a closed-loop sustainable energy cycle. Here, we present an artificial metallosupramolecular macrocycle that gathers three Ru(bda) centres (bda = 2,2'-bipyridine-6,6'-dicarboxylic acid) that catalyses water oxidation. The macrocyclic architecture accelerates the rate of water oxidation via a water nucleophilic attack mechanism, similar to the mechanism exhibited by OEC-PSII, and reaches remarkable catalytic turnover frequencies >100 s(-1). Photo-driven water oxidation yields outstanding activity, even in the nM concentration regime, with a turnover number of >1,255 and turnover frequency of >13.1 s(-1). PMID:27219702

  9. Perceptions of the Water Cycle among Primary School Children in Botswana.

    ERIC Educational Resources Information Center

    Taiwo, A. A.; Motswiri, M. J.; Masene, R.

    1999-01-01

    Describes qualitative and quantitative methods used to elucidate the nature of the perception of the water cycle held by Botswana primary-grade pupils in three different geographic areas. Concludes that the students' perception of the water cycle was positively influenced by schooling but negatively impacted upon, to some extent, by the untutored

  10. Perceptions of the Water Cycle among Primary School Children in Botswana.

    ERIC Educational Resources Information Center

    Taiwo, A. A.; Motswiri, M. J.; Masene, R.

    1999-01-01

    Describes qualitative and quantitative methods used to elucidate the nature of the perception of the water cycle held by Botswana primary-grade pupils in three different geographic areas. Concludes that the students' perception of the water cycle was positively influenced by schooling but negatively impacted upon, to some extent, by the untutored…

  11. Cycling-Induced Changes in the Entropy Profiles of Lithium Cobalt Oxide Electrodes

    SciTech Connect

    Hudak, N. S.; Davis, L. E.; Nagasubramanian, G.

    2014-12-09

    Entropy profiles of lithium cobalt oxide (LiCoO2) electrodes were measured at various stages in the cycle life to examine performance degradation and cycling-induced changes, or lack thereof, in thermodynamics. LiCoO2 electrodes were cycled at C/2 rate in half-cells (vs. lithium anodes) up to 20 cycles or C/5 rate in full cells (vs. MCMB anodes) up to 500 cycles. The electrodes were then subjected to entropy measurements (∂E/∂T, where E is open-circuit potential and T is temperature) in half-cells at regular intervals over the approximate range 0.5 ≤ x ≤ 1 in LixCoO2. Despite significant losses in capacity upon cycling, neither cycling rate resulted in any change to the overall shape of the entropy profile relative to an uncycled electrode, indicating retention of the basic LiCoO2 structure, lithium insertion mechanism, and thermodynamics. This confirms that cycling-induced performance degradation in LiCoO2 electrodes is primarily caused by kinetic barriers that increase with cycling. In the case of electrodes cycled at C/5, there was a subtle, quantitative, and gradual change in the entropy profile in the narrow potential range of the hexagonal-to-monoclinic phase transition. The observed change is indicative of a decrease in the intralayer lithium ordering that occurs at these potentials, and it demonstrates that a cyclinginduced structural disorder accompanies the kinetic degradation mechanisms.

  12. Cycling-Induced Changes in the Entropy Profiles of Lithium Cobalt Oxide Electrodes

    DOE PAGESBeta

    Hudak, N. S.; Davis, L. E.; Nagasubramanian, G.

    2014-12-09

    Entropy profiles of lithium cobalt oxide (LiCoO2) electrodes were measured at various stages in the cycle life to examine performance degradation and cycling-induced changes, or lack thereof, in thermodynamics. LiCoO2 electrodes were cycled at C/2 rate in half-cells (vs. lithium anodes) up to 20 cycles or C/5 rate in full cells (vs. MCMB anodes) up to 500 cycles. The electrodes were then subjected to entropy measurements (∂E/∂T, where E is open-circuit potential and T is temperature) in half-cells at regular intervals over the approximate range 0.5 ≤ x ≤ 1 in LixCoO2. Despite significant losses in capacity upon cycling, neithermore » cycling rate resulted in any change to the overall shape of the entropy profile relative to an uncycled electrode, indicating retention of the basic LiCoO2 structure, lithium insertion mechanism, and thermodynamics. This confirms that cycling-induced performance degradation in LiCoO2 electrodes is primarily caused by kinetic barriers that increase with cycling. In the case of electrodes cycled at C/5, there was a subtle, quantitative, and gradual change in the entropy profile in the narrow potential range of the hexagonal-to-monoclinic phase transition. The observed change is indicative of a decrease in the intralayer lithium ordering that occurs at these potentials, and it demonstrates that a cyclinginduced structural disorder accompanies the kinetic degradation mechanisms.« less

  13. Light-driven water oxidation for solar fuels

    PubMed Central

    Young, Karin J.; Martini, Lauren A.; Milot, Rebecca L.; III, Robert C. Snoeberger; Batista, Victor S.; Schmuttenmaer, Charles A.; Crabtree, Robert H.; Brudvig, Gary W.

    2014-01-01

    Light-driven water oxidation is an essential step for conversion of sunlight into storable chemical fuels. Fujishima and Honda reported the first example of photoelectrochemical water oxidation in 1972. In their system, TiO2 was irradiated with ultraviolet light, producing oxygen at the anode and hydrogen at a platinum cathode. Inspired by this system, more recent work has focused on functionalizing nanoporous TiO2 or other semiconductor surfaces with molecular adsorbates, including chromophores and catalysts that absorb visible light and generate electricity (i.e., dye-sensitized solar cells) or trigger water oxidation at low overpotentials (i.e., photocatalytic cells). The physics involved in harnessing multiple photochemical events for multielectron reactions, as required in the four-electron water oxidation process, has been the subject of much experimental and computational study. In spite of significant advances with regard to individual components, the development of highly efficient photocatalytic cells for solar water splitting remains an outstanding challenge. This article reviews recent progress in the field with emphasis on water-oxidation photoanodes inspired by the design of functionalized thin film semiconductors of typical dye-sensitized solar cells. PMID:25364029

  14. Silicon and tungsten oxide nanostructures for water splitting

    NASA Astrophysics Data System (ADS)

    Reyes Gil, Karla R.; Spurgeon, Joshua M.; Lewis, Nathan S.

    2009-08-01

    Inorganic semiconductors are promising materials for driving photoelectrochemical water-splitting reactions. However, there is not a single semiconductor material that can sustain the unassisted splitting of water into H2 and O2. Instead, we are developing a three part cell design where individual catalysts for water reduction and oxidation will be attached to the ends of a membrane. The job of splitting water is therefore divided into separate reduction and oxidation reactions, and each catalyst can be optimized independently for a single reaction. Silicon might be suitable to drive the water reduction. Inexpensive highly ordered Si wire arrays were grown on a single crystal wafer and transferred into a transparent, flexible polymer matrix. In this array, light would be absorbed along the longer axial dimension while the resulting electrons or holes would be collected along the much shorter radial dimension in a massively parallel array resembling carpet fibers on a microscale, hence the term "solar carpet". Tungsten oxide is a good candidate to drive the water oxidation. Self-organized porous tungsten oxide was successfully synthesized on the tungsten foil by anodization. This sponge-like structure absorbs light efficiently due to its high surface area; hence we called it "solar sponge".

  15. Surface treatment of hematite photoanodes with zinc acetate for water oxidation.

    PubMed

    Xi, Lifei; Bassi, Prince Saurabh; Chiam, Sing Yang; Mak, Wai Fatt; Tran, Phong D; Barber, James; Chye Loo, Joachim Say; Wong, Lydia Helena

    2012-08-01

    A simple and inexpensive method to form a hematite photoanode for efficient water oxidation is reported. A very thin ZnO overlayer was deposited on top of a thin film of hematite and found, compared with non-treated hematite, to increase the photocurrent and reduce the onset potential for generating oxygen from water. After 3 cycles of ZnAc treatment, the photocurrent increased more than 40% to 1.08 mA cm(-2) at 0.23 V vs. Ag/AgCl and onset potential for water oxidation shifted by -170 mV. It is proposed that the ZnO overlayer changes the flat band potential of hematite and reduces the surface defects. PMID:22688799

  16. The Mars water cycle at other epochs: History of the polar caps and layered terrain

    NASA Technical Reports Server (NTRS)

    Jakosky, Bruce M.; Henderson, Bradley G.; Mellon, Michael T.

    1992-01-01

    The atmospheric water cycle at the present epoch involves summertime sublimation of water from the north polar cap, transport of water through the atmosphere, and condensation on one or both winter CO2 caps. Exchange with the regolith is important seasonally, but the water content of the atmosphere appears to be controlled by the polar caps. The net annual transport through the atmosphere, integrated over long timescales, must be the driving force behind the long-term evolution of the polar caps; clearly, this feeds back into the evolution of the layered terrain. We have investigated the behavior of the seasonal water cycle and the net integrated behavior at the pole for the last 10 exp 7 years. Our model of the water cycle includes the solar input, CO2 condensation and sublimation, and summertime water sublimation through the seasonal cycles, and incorporates the long-term variations in the orbital elements describing the Martian orbit.

  17. Investigating the First-Cycle Irreversibility of Lithium Metal Oxide Cathodes for Li Batteries

    SciTech Connect

    Kang,S.; Yoon , W.; Nam, K.; Yang, X.; Abraham, D.

    2008-01-01

    Layered lithium metal oxide cathodes typically exhibit irreversibility during the first cycle in lithium cells when cycled in conventional voltage ranges (e.g., 3-4.3 V vs. Li+/Li). In this work, we have studied the first-cycle irreversibility of lithium cells containing various layered cathode materials using galvanostatic cycling and in situ synchrotron X-ray diffraction. When cycled between 3.0 and 4.3 V vs. Li+/Li, the cells containing LiCoO2, LiNi0.8Co0.15Al0.05O2, and Li1.048(Ni1/3Co1/3Mn1/3)0.952O2 as cathodes showed initial coulombic efficiencies of 98.0, 87.0, and 88.6%, respectively, at relatively slow current (8 mA/g). However, the 'lost capacity' could be completely recovered by discharging the cells to low voltages (<2 V vs Li+/Li). During this deep discharge, the same cells exhibited voltage plateaus at 1.17, 1.81, and 1.47 V, respectively, which is believed to be associated with formation of a Li2MO2-like phase (M = Ni, Co, Mn) on the oxide particle surface due to very sluggish lithium diffusion in LieMO2 with {var_epsilon}{yields} 1 (i.e., near the end of discharge). The voltage relaxation curve and in situ X-ray diffraction patterns, obtained from a Li/Li1.048(Ni1/3Co1/3Mn1/3)0.952O2 cell, showed that the oxide cathode reversibly returned to its original state [i.e., Li1.048(Ni1/3Co1/3Mn1/3)0.952O2] during relaxation following the deep discharge to achieve 100% cycle efficiency.

  18. Patterns, structures and regulations of domestic water cycle systems in China

    NASA Astrophysics Data System (ADS)

    Chu, Junying; Wang, Hao; Wang, Jianhua; Qin, Dayong

    2010-05-01

    Domestic water cycle systems serving as one critical component of artificial water cycle at the catchment's scale, is so closely related to public healthy, human rights and social-economic development, and has gained the highest priority in strategic water resource and municipal infrastructure planning. In this paper, three basic patterns of domestic water cycle systems are identified and analyzed, including rural domestic water system (i.e. primary level), urban domestic water system (i.e. intermediate level) and metropolitan domestic water system (i.e. senior level), with different "abstract-transport-consume-discharge" mechanisms and micro-components of water consumption (such as drinking, cooking, toilet flushing, showering or cleaning). The rural domestic water system is general simple with three basic "abstract-consume-discharge" mechanisms and micro-components of basic water consumption such as drinking, cooking, washing and sanitation. The urban domestic water system has relative complex mechanisms of "abstract-supply-consume-treatment-discharge" and more micro-components of water consumption such as bath, dishwashing or car washing. The metropolitan domestic water system (i.e. senior level) has the most complex mechanisms by considering internal water reuse, external wastewater reclamation, and nutrient recycling processes. The detailed structures for different water cycle pattern are presented from the aspects of water quantity, wastewater quality and nutrients flow. With the speed up of urbanization and development of social-economy in China, those three basic patterns are interacting, transforming and upgrading. According to the past experiences and current situations, urban domestic water system (i.e. intermediate level) is the dominant pattern based on indicator of system number or system scale. The metropolitan domestic water system (i.e. senior level) is the idealized model for the future development and management. Current domestic water system management efforts typically fail in China, because the approach is generally narrowly-focused and fragmented. This paper put forward a total-process control framework following the water and pollutants (or nutrients) flows along the dualistic domestic water cycle process. Five key objectives of domestic water cycle system regulation are identified including water use safety, water use equity, water saving, wastewater reduction and nutrient recycling. Comprehensive regulatory framework regarding administrative, economic, technical and social measures is recommended to promote sustainable domestic water usage and demand management. Considering the relatively low affordability in rural area, economic measures should be mainly applied in urban domestic water systems and metropolitan domestic water systems. Engineering or technological measures which are suitable to the three domestic water cycle systems are discussed respectively.

  19. A Bioinspired Molecular Polyoxometalate Catalyst with Two Cobalt(II) Oxide Cores for Photocatalytic Water Oxidation.

    PubMed

    Wei, Jie; Feng, Yingying; Zhou, Panpan; Liu, Yan; Xu, Jingyin; Xiang, Rui; Ding, Yong; Zhao, Chongchao; Fan, Linyuan; Hu, Changwen

    2015-08-24

    To overcome the bottleneck of water splitting, the exploration of efficient, selective, and stable water oxidation catalysts (WOCs) is crucial. We report an all-inorganic, oxidatively and hydrolytically stable WOC based on a polyoxometalate [(A-α-SiW9 O34)2Co8(OH)6(H2O)2(CO3)3](16-) (Co8 POM). As a cobalt(II)-based cubane water oxidation catalyst, Co8POM embeds double Co(II)4O3 cores. The self-assembled catalyst is similar to the oxygen evolving complex (OEC) of photosystem II (PS II). Using [Ru(bpy)3](2+) as a photosensitizer and persulfate as a sacrificial electron acceptor, Co8POM exhibits excellent water oxidation activity with a turnover number (TON) of 1436, currently the highest among bioinspired catalysts with a cubical core, and a high initial turnover frequency (TOF). Investigation by several spectroscopy, spectrometry, and other techniques confirm that Co8POM is a stable and efficient catalyst for visible light-driven water oxidation. The results offer a useful insight into the design of water oxidation catalysts. PMID:26130568

  20. Nano-sized manganese oxides as biomimetic catalysts for water oxidation in artificial photosynthesis: a review

    PubMed Central

    Najafpour, Mohammad Mahdi; Rahimi, Fahimeh; Aro, Eva-Mari; Lee, Choon-Hwan; Allakhverdiev, Suleyman I.

    2012-01-01

    There has been a tremendous surge in research on the synthesis of various metal compounds aimed at simulating the water-oxidizing complex (WOC) of photosystem II (PSII). This is crucial because the water oxidation half reaction is overwhelmingly rate-limiting and needs high over-voltage (approx. 1 V), which results in low conversion efficiencies when working at current densities required for hydrogen production via water splitting. Particular attention has been given to the manganese compounds not only because manganese has been used by nature to oxidize water but also because manganese is cheap and environmentally friendly. The manganese–calcium cluster in PSII has a dimension of about approximately 0.5 nm. Thus, nano-sized manganese compounds might be good structural and functional models for the cluster. As in the nanometre-size of the synthetic models, most of the active sites are at the surface, these compounds could be more efficient catalysts than micrometre (or bigger) particles. In this paper, we focus on nano-sized manganese oxides as functional and structural models of the WOC of PSII for hydrogen production via water splitting and review nano-sized manganese oxides used in water oxidation by some research groups. PMID:22809849

  1. Photoassisted oxidation of oil films on water

    SciTech Connect

    Heller, A.; Brock, J.R.

    1991-08-01

    The objective of the project is to develop TiO{sub 2}-based photocatalysts for the solar assisted oxidative dissolution of oil slicks. In a TiO{sub 2} crystal, absorption of a photon generates an electron-hole pair. The electron reacts with surface-adsorbed oxygen, reducing it to hydrogen peroxide; the hole directly oxidizes adsorbed organic compounds, usually via an intermediate OH radical. Since the density of TiO{sub 2} (3.8g/cc for anatase, 4.3 g/cc for rutile) is greater than that of either oil or seawater, TiO{sub 2} crystals are attached to inexpensive, engineered hollow glass microspheres to ensure flotation on the oil slick surface. Portions of the microsphere surface not covered by TiO{sub 2} are made oleophilic so that the microbeads will be preferentially attracted to the oil-air interface.

  2. Oxidation of aluminum particles in the presence of water.

    PubMed

    Schoenitz, Mirko; Chen, Chi-Mon; Dreizin, Edward L

    2009-04-16

    Oxidation of spherical aluminum powder was investigated in mixed argon-oxygen-steam atmospheres by thermogravimetric measurements at heating rates between 1 and 20 K/min and up to 1100 degrees C. The observed oxidation behavior in the presence of steam differs markedly from oxidation in dry oxygen. Oxidation in steam is complete near 1000 degrees C vs 1500 degrees C in dry oxygen. Furthermore, in steam, a stepwise weight change is observed at the melting point of aluminum, while no such step can be distinguished in dry oxygen. The complete oxidation observed at a lower temperature in steam as compared to dry oxygen is explained by the stabilization of the gamma polymorph of the surface oxide in the presence of water so that a denser and slower growing alpha-alumina does not form until higher temperatures. Experiments in mixed oxygen/steam oxidizers showed that the size of the oxidation step observed upon aluminum melting only correlates with the concentration of steam in the atmosphere. This may be interpreted as the effect of transient porosity, the degree of which is controlled by the steam concentration, or the surface oxide stressed by the expanding melting metal core may behave as a semipermeable membrane where hydrous species have significantly higher diffusion rates than oxygen. A clear distinction cannot be drawn, and further research is warranted. Preliminary results on isoconversion processing of the oxidation kinetics are presented. PMID:19309144

  3. Caffeinated nitric oxide-releasing lozenge improves cycling time trial performance.

    PubMed

    Lee, J; Kim, H T; Solares, G J; Kim, K; Ding, Z; Ivy, J L

    2015-02-01

    Boosting nitric oxide production during exercise by various means has been found to improve exercise performance. We investigated the effects of a nitric oxide releasing lozenge with added caffeine (70 mg) on oxygen consumption during steady-state exercise and cycling time trial performance using a double-blinded randomized, crossover experimental design. 15 moderately trained cyclists (7 females and 8 males) were randomly assigned to ingest the caffeinated nitric oxide lozenge or placebo 5 min before exercise. Oxygen consumption and blood lactate were assessed at rest and at 50%, 65% and 75% maximal oxygen consumption. Exercise performance was assessed by time to complete a simulated 20.15 km cycling time-trial course. No significant treatment effects for oxygen consumption or blood lactate at rest or during steady-state exercise were observed. However, time-trial performance was improved by 2.1% (p<0.01) when participants consumed the nitric oxide lozenge (2,424±69 s) compared to placebo (2,476±78 s) and without a significant difference in rating of perceived exertion. These results suggest that acute supplementation with a caffeinated nitric oxide releasing lozenge may be a practical and effective means of improving aerobic exercise performance. PMID:25285468

  4. One-electron activation of water oxidation catalysis.

    PubMed

    Tamaki, Yusuke; Vannucci, Aaron K; Dares, Christopher J; Binstead, Robert A; Meyer, Thomas J

    2014-05-14

    Rapid water oxidation catalysis is observed following electrochemical oxidation of [Ru(II)(tpy)(bpz)(OH)](+) to [Ru(V)(tpy)(bpz)(O)](3+) in basic solutions with added buffers. Under these conditions, water oxidation is dominated by base-assisted Atom Proton Transfer (APT) and direct reaction with OH(-). More importantly, we report here that the Ru(IV)═O(2+) form of the catalyst, produced by 1e(-) oxidation of [Ru(II)(tpy)(bpz)(OH2)](2+) to Ru(III) followed by disproportionation to [Ru(IV)(tpy)(bpz)(O)](2+) and [Ru(II)(tpy)(bpz)(OH2)](2+), is also a competent water oxidation catalyst. The rate of water oxidation by [Ru(IV)(tpy)(bpz)(O)](2+) is greatly accelerated with added PO4(3-) with a turnover frequency of 5.4 s(-1) reached at pH 11.6 with 1 M PO4(3-) at an overpotential of only 180 mV. PMID:24758154

  5. [Oxidative metabolism of funicular tissue. II. Determination of the activity of certain Krebs cycle enzymes].

    PubMed

    Brachet, E

    1975-01-01

    Previous experiments have suggested that a partial metabolic block might restrain the oxidative metabolism of the cord tissue between the decarboxylation of pyruvate and the oxidation of succinate. Some of the dehydrogenases of the Kreb's cycle were assayed on acetone powders prepared from human cords. Isocitrate dehydrogenases (both NAD and NADP-specific) have much lower activities than the alpha-ketoglutarate- and malate dehydrogenases; a partial block might be located at this level. Moreover, the malic enzyme has a rather high activity, and might play a significant role by regenerating NADPH in a tissue where other sources of this coenzyme are practically absent. PMID:2373

  6. Electric behavior of interlayer water in graphene oxide films

    NASA Astrophysics Data System (ADS)

    Smirnov, V. A.; Vasil'ev, V. P.; Denisov, N. N.; Baskakova, Yu. V.; Dubovitskii, V. A.

    2016-03-01

    Current-voltage characteristics of graphene oxide (GO) films were explored in water vapor as a function of film water content. It has been found that the films under study may contain free and bound water that can be completely eliminated in vacuum. A new phenomenon - a decrease in current with time at a constant voltage - was revealed. This was associated with elimination of water in the absence of electrochemical processes. The theoretical model was suggested to rationalize the behavior of water diffusivity in the process of electroconductivity.

  7. Sonochemical water splitting in the presence of powdered metal oxides.

    PubMed

    Morosini, Vincent; Chave, Tony; Virot, Matthieu; Moisy, Philippe; Nikitenko, Sergey I

    2016-03-01

    Kinetics of hydrogen formation was explored as a new chemical dosimeter allowing probing the sonochemical activity of argon-saturated water in the presence of micro- and nano-sized metal oxide particles exhibiting catalytic properties (ThO2, ZrO2, and TiO2). It was shown that the conventional sonochemical dosimeter based on H2O2 formation is hardly applicable in such systems due to catalytic degradation of H2O2 at oxide surface. The study of H2 generation revealed that at low-frequency ultrasound (20 kHz) the sonochemical water splitting is greatly improved for all studied metal oxides. The highest efficiency is observed for relatively large micrometric particles of ThO2 which is assigned to ultrasonically-driven particle fragmentation accompanied by mechanochemical water molecule splitting. The nanosized metal oxides do not exhibit particle size reduction under ultrasonic treatment but nevertheless yield higher quantities of H2. The enhancement of sonochemical water splitting in this case is most probably resulting from better bubble nucleation in heterogeneous systems. At high-frequency ultrasound (362 kHz), the effect of metal oxide particles results in a combination of nucleation and ultrasound attenuation. In contrast to 20 kHz, micrometric particles slowdown the sonolysis of water at 362 kHz due to stronger attenuation of ultrasonic waves while smaller particles show a relatively weak and various directional effects. PMID:26558997

  8. GEWEX: The Global Energy and Water Cycle Experiment

    NASA Technical Reports Server (NTRS)

    Chahine, M.; Vane, D.

    1994-01-01

    GEWEX is one of the world's largest global change research programs. Its purpose is to observe and understand the hydrological cycle and energy fluxes in the atmosphere, at land surfaces and in the upper oceans.

  9. Towards a Global Water Cycle Theme within the Integrated Global Observing Strategy (IGOS) Framework

    NASA Astrophysics Data System (ADS)

    Lawford, R. G.

    2004-05-01

    Over the past three years a number of scientists, international programs and national agencies have been working towards the establishment of a water cycle theme within the IGOS-Partnership. The current theme definition provides a framework for guiding decisions regarding priorities and strategies for the enhancement of water cycle observations in support of 1) monitoring climate variability and change, 2) effective macroscale water management and sustainable development of the world's water resources, 3) local societal applications for resource development and environmental management, 4) initialization of prediction models, and 5) priority water cycle science questions. Based on a review of the needs, adequacy, and priorities for water cycle observations outlined in a theme report, the theme was adopted by IGOS-P in November 2003. After briefly tracing the contributions of observations in the development of civilization, this presentation will provide an overview of the assessments of water cycle observations from the theme report and discusses recommended priorities for the enhancement and integration of water-related observational systems. The steps being taken to implement this theme will also be described. The talk concludes with a possible vision for new approaches to water resources management through broad acceptance of the principles of this theme and the development of the requisite water cycle science.

  10. Nitrous Oxide Cycling in the Eastern Tropical South Pacific as Inferred from Isotopic and Isotopomeric Data.

    NASA Astrophysics Data System (ADS)

    Vedamati, J.; Chang, B. X.; Peters, B. D.; Forbes, M. S.; Mordy, C.; Warner, M. J.; Devol, A.; Ward, B. B.; Casciotti, K. L.

    2014-12-01

    Marine sources of nitrous oxide (N2O), an important greenhouse gas, account for up to 25% of global emissions, out of which 25-75% originates from oxygen minimum zones (OMZs). The Eastern Tropical South Pacific (ETSP) OMZ is characterized by low to undetectable oxygen concentrations within the water column and is known to be a region of intense N2O cycling. However, the balance of processes regulating N2O production and emissions is still uncertain. The isotopic composition of dissolved N2O is a tracer of its production, transport, and consumption processes in the ocean. Here we use concentration, isotopic and isotopomeric measurements of dissolved N2O collected during cruise NBP1305 to the ETSP in 2013 to examine the processes affecting the distribution of N2O throughout the water column. Dissolved N2O concentrations ranged between 42-65 nmol/L at the edges of the oxycline while ranging between 6 -20 nmol/L at the core of the OMZ. The nitrogen and oxygen isotopic composition of dissolved N2O (reported as δ15N vs air N2 and δ18O vs VSMOW in units of ‰, respectively) displayed maxima coincident with the OMZ core. δ15N of N2O ranged between 14 - 22‰, δ18O of N2O ranged between 68 - 100‰ while site preference of N2O ranged between 39 - 60‰ at the OMZ core. Based on the T-S plot and N2O concentration profiles, there appears to be a strong correlation between N2O and water mass features within the OMZ. Thus, the differences in δ15N and δ18O of N2O along the north- south transect within the OMZ core may be related to differences in N2O production-consumption mechanisms along with N2O transport. Within the OMZ, the δ18O: δ15N relationship is also much lower than the 2.5:1 ratio expected for N2O consumption via denitrification, leading us to believe that both production and consumption processes are likely to be at play.

  11. eWaterCycle: A high resolution global hydrological model

    NASA Astrophysics Data System (ADS)

    van de Giesen, Nick; Bierkens, Marc; Drost, Niels; Hut, Rolf; Sutanudjaja, Edwin

    2014-05-01

    In 2013, the eWaterCycle project was started, which has the ambitious goal to run a high resolution global hydrological model. Starting point was the PCR-GLOBWB built by Utrecht University. The software behind this model will partially be re-engineered in order to enable to run it in a High Performance Computing (HPC) environment. The aim is to have a spatial resolution of 1km x 1km. The idea is also to run the model in real-time and forecasting mode, using data assimilation. An on-demand hydraulic model will be available for detailed flow and flood forecasting in support of navigation and disaster management. The project faces a set of scientific challenges. First, to enable the model to run in a HPC environment, model runs were analyzed to examine on which parts of the program most CPU time was spent. These parts were re-coded in Open MPI to allow for parallel processing. Different parallelization strategies are thinkable. In our case, it was decided to use watershed logic as a first step to distribute the analysis. There is rather limited recent experience with HPC in hydrology and there is much to be learned and adjusted, both on the hydrological modeling side and the computer science side. For example, an interesting early observation was that hydrological models are, due to their localized parameterization, much more memory intensive than models of sister-disciplines such as meteorology and oceanography. Because it would be deadly to have to swap information between CPU and hard drive, memory management becomes crucial. A standard Ensemble Kalman Filter (enKF) would, for example, have excessive memory demands. To circumvent these problems, an alternative to the enKF was developed that produces equivalent results. This presentation shows the most recent results from the model, including a 5km x 5km simulation and a proof of concept for the new data assimilation approach. Finally, some early ideas about financial sustainability of an operational global hydrological model are presented.

  12. Visible-Light-Driven Water Oxidation by a Molecular Manganese Vanadium Oxide Cluster.

    PubMed

    Schwarz, Benjamin; Forster, Johannes; Goetz, McKenna K; Yücel, Duygu; Berger, Claudia; Jacob, Timo; Streb, Carsten

    2016-05-17

    Photosynthetic water oxidation in plants occurs at an inorganic calcium manganese oxo cluster, which is known as the oxygen evolving complex (OEC), in photosystem II. Herein, we report a synthetic OEC model based on a molecular manganese vanadium oxide cluster, [Mn4 V4 O17 (OAc)3 ](3-) . The compound is based on a [Mn4 O4 ](6+) cubane core, which catalyzes the homogeneous, visible-light-driven oxidation of water to molecular oxygen and is stabilized by a tripodal [V4 O13 ](6-) polyoxovanadate and three acetate ligands. When combined with the photosensitizer [Ru(bpy)3 ](2+) and the oxidant persulfate, visible-light-driven water oxidation with turnover numbers of approximately 1150 and turnover frequencies of about 1.75 s(-1) is observed. Electrochemical, mass-spectrometric, and spectroscopic studies provide insight into the cluster stability and reactivity. This compound could serve as a model for the molecular structure and reactivity of the OEC and for heterogeneous metal oxide water-oxidation catalysts. PMID:27062440

  13. Cobalt, nickel/iron, and titanium oxide electrodes for water oxidation

    NASA Astrophysics Data System (ADS)

    Selloni, Annabella

    2014-03-01

    Water splitting on metal oxide surfaces has attracted enormous interest for more than forty years. While a great deal of work has focused on titanium dioxide (TiO2) , recently cobalt and mixed Ni-Fe oxides have also emerged as promising electrocatalysts for water oxidation due to their low cost and high activity. In this talk I shall discuss various aspects of water oxidation on cobalt (hydro-)oxides, pure and mixed nickel and iron (hydro-)oxides, and TiO2\\ surfaces. Using DFT +U calculations, I shall examine the composition and structure of cobalt and Ni-Fe oxides under electrochemical conditions, and present studies of the oxygen evolution reaction (OER) on the relevant stable compounds. I shall also present hybrid functional calculations of the first proton-coupled-electron transfer at the water/TiO2 interface in the presence of a photoexcited hole. Our results provide evidence that the proton and electron transfers are not concerted but rather represent two sequential processes. They also suggest that the OER is faster at higher pH, as indeed observed experimentally. This work was supported by DoE-BES, Division of Chemical Sciences, Geosciences and Biosciences under Award DE-FG02-12ER16286.

  14. Water Oxidation and Oxygen Monitoring by Cobalt-Modified Fluorine-Doped Tin Oxide Electrodes

    SciTech Connect

    Kent, CA; Concepcion, JJ; Dares, CJ; Torelli, DA; Rieth, AJ; Miller, AS; Hoertz, PG; Meyer, TJ

    2013-06-12

    Electrocatalytic water oxidation occurs at fluoride-doped tin oxide (FTO) electrodes that have been surface-modified by addition of Co(II). On the basis of X-ray photoelectron spectroscopy and transmission electron microscopy measurements, the active surface site appears to be a single site or small-molecule assembly bound as Co(II), with no evidence for cobalt oxide film or cluster formation. On the basis of cyclic voltammetry measurements, surface-bound Co(II) undergoes a pH-dependent 1e(-)/1H(+) oxidation to Co(III), which is followed by pH-dependent catalytic water oxidation. O-2 reduction at FTO occurs at -0.33 V vs NHE, allowing for in situ detection of oxygen as it is formed by water oxidation on the surface. Controlled-potential electrolysis at 1.61 V vs NHE at pH 7.2 resulted in sustained water oxidation catalysis at a current density of 0.16 mA/cm(2) with 29 000 turnovers per site over an electrolysis period of 2 h. The turnover frequency for oxygen production per Co site was 4 s(-1) at an overpotential of 800 mV at pH 7.2. Initial experiments with Co(II) on a mesoporous, high-surface-area nanoFTO electrode increased the current density by a factor of similar to 5

  15. Photocatalytic Water Oxidation over Metal Oxide Nanosheets Having a Three-Layer Perovskite Structure.

    PubMed

    Oshima, Takayoshi; Eguchi, Miharu; Maeda, Kazuhiko

    2016-02-01

    Metal oxide nanosheets having a three-layer perovskite structure were studied as photocatalysts for water oxidation in the presence of IO3 (-) as a reversible electron acceptor. This work examined the effects of the lateral dimensions and composition of the nanosheets as well as metal oxide co-catalysts deposited on the restacked nanosheets. Depositing metal oxides capable of promoting reduction reactions on the nanosheets were found to promote the water oxidation activity. In contrast, the lateral dimensions and the degree of crystallinity of the nanosheets had little effect on the activity. Experimental results demonstrated that the reduction of IO3 (-) is the rate-limiting step in this reaction and that nanosheets with less distorted structures are advantageous with regard to increasing both light absorption and the mobility of photoexcited charge carriers. PMID:26733314

  16. Proton and hydrogen currents in photosynthetic water oxidation.

    PubMed

    Tommos, C; Babcock, G T

    2000-05-12

    The photosynthetic processes that lead to water oxidation involve an evolution in time from photon dynamics to photochemically-driven electron transfer to coupled electron/proton chemistry. The redox-active tyrosine, Y(Z), is the component at which the proton currents necessary for water oxidation are switched on. The thermodynamic and kinetic implications of this function for Y(Z) are discussed. These considerations also provide insight into the related roles of Y(Z) in preserving the high photochemical quantum efficiency in Photosystem II (PSII) and of conserving the highly oxidizing conditions generated by the photochemistry in the PSII reaction center. The oxidation of Y(Z) by P(680)(+) can be described well by a treatment that invokes proton coupling within the context of non-adiabatic electron transfer. The reduction of Y(.)(Z), however, appears to proceed by an adiabatic process that may have hydrogen-atom transfer character. PMID:10812034

  17. Water electrolyte promoted oxidation of functional thiol groups.

    PubMed

    Lauwers, K; Breynaert, E; Rombouts, I; Delcour, J A; Kirschhock, C E A

    2016-04-15

    The formation of disulfide bonds is of the utmost importance for a wide range of food products with gluten or globular proteins as functional agents. Here, the impact of mineral electrolyte composition of aqueous solutions on thiol oxidation kinetics was studied, using glutathione (GSH) and cysteine (CYS) as model systems. Interestingly, the oxidation rate of both compounds into their corresponding disulfides was significantly higher in common tap water than in ultrapure water. The systematic study of different electrolyte components showed that especially CaCl2 improved the oxidation rate of GSH. However, this effect was not observed for CYS, which indicated a strong impact of the local chemical environment on thiol oxidation kinetics. PMID:26675862

  18. A biomimetic copper water oxidation catalyst with low overpotential.

    PubMed

    Zhang, Teng; Wang, Cheng; Liu, Shubin; Wang, Jin-Liang; Lin, Wenbin

    2014-01-01

    Simply mixing a Cu(II) salt and 6,6'-dihydroxy-2,2'-bipyridine (H2L) in a basic aqueous solution afforded a highly active water oxidation catalyst (WOC). Cyclic voltammetry of the solution at pH = 12-14 shows irreversible catalytic current with an onset potential of ~0.8 V versus NHE. Catalytic oxygen evolution takes place in controlled potential electrolysis at a relatively low overpotential of 640 mV. Experimental and computational studies suggest that the L ligand participates in electron transfer processes to facilitate the oxidation of the Cu center to lead to an active WOC with low overpotential, akin to the use of the tyrosine radical by Photosystem II to oxidize the CaMn4 center for water oxidation. PMID:24325734

  19. Atomic layer-deposited tunnel oxide stabilizes silicon photoanodes for water oxidation

    NASA Astrophysics Data System (ADS)

    Chen, Yi Wei; Prange, Jonathan D.; Dhnen, Simon; Park, Yohan; Gunji, Marika; Chidsey, Christopher E. D.; McIntyre, Paul C.

    2011-07-01

    A leading approach for large-scale electrochemical energy production with minimal global-warming gas emission is to use a renewable source of electricity, such as solar energy, to oxidize water, providing the abundant source of electrons needed in fuel synthesis. We report corrosion-resistant, nanocomposite anodes for the oxidation of water required to produce renewable fuels. Silicon, an earth-abundant element and an efficient photovoltaic material, is protected by atomic layer deposition (ALD) of a highly uniform, 2?nm thick layer of titanium dioxide (TiO2) and then coated with an optically transmitting layer of a known catalyst (3?nm iridium). Photoelectrochemical water oxidation was observed to occur below the reversible potential whereas dark electrochemical water oxidation was found to have low-to-moderate overpotentials at all pH values, resulting in an inferred photovoltage of ~550?mV. Water oxidation is sustained at these anodes for many hours in harsh pH and oxidative environments whereas comparable silicon anodes without the TiO2 coating quickly fail. The desirable electrochemical efficiency and corrosion resistance of these anodes is made possible by the low electron-tunnelling resistance (<0.006???cm2 for p+-Si) and uniform thickness of atomic-layer deposited TiO2.

  20. Methane oxidation coupled to oxygenic photosynthesis in anoxic waters.

    PubMed

    Milucka, Jana; Kirf, Mathias; Lu, Lu; Krupke, Andreas; Lam, Phyllis; Littmann, Sten; Kuypers, Marcel M M; Schubert, Carsten J

    2015-09-01

    Freshwater lakes represent large methane sources that, in contrast to the Ocean, significantly contribute to non-anthropogenic methane emissions to the atmosphere. Particularly mixed lakes are major methane emitters, while permanently and seasonally stratified lakes with anoxic bottom waters are often characterized by strongly reduced methane emissions. The causes for this reduced methane flux from anoxic lake waters are not fully understood. Here we identified the microorganisms and processes responsible for the near complete consumption of methane in the anoxic waters of a permanently stratified lake, Lago di Cadagno. Interestingly, known anaerobic methanotrophs could not be detected in these waters. Instead, we found abundant gamma-proteobacterial aerobic methane-oxidizing bacteria active in the anoxic waters. In vitro incubations revealed that, among all the tested potential electron acceptors, only the addition of oxygen enhanced the rates of methane oxidation. An equally pronounced stimulation was also observed when the anoxic water samples were incubated in the light. Our combined results from molecular, biogeochemical and single-cell analyses indicate that methane removal at the anoxic chemocline of Lago di Cadagno is due to true aerobic oxidation of methane fuelled by in situ oxygen production by photosynthetic algae. A similar mechanism could be active in seasonally stratified lakes and marine basins such as the Black Sea, where light penetrates to the anoxic chemocline. Given the widespread occurrence of seasonally stratified anoxic lakes, aerobic methane oxidation coupled to oxygenic photosynthesis might have an important but so far neglected role in methane emissions from lakes. PMID:25679533

  1. Sirt3 promotes the urea cycle and fatty acid oxidation during dietary restriction

    PubMed Central

    Hallows, William C.; Yu, Wei; Smith, Brian C.; Devries, Mark K.; Ellinger, James J.; Someya, Shinichi; Shortreed, Michael R.; Prolla, Tomas; Markley, John L.; Smith, Lloyd M.; Zhao, Shimin; Guan, Kun-Liang; Denu, John M.

    2011-01-01

    Summary Emerging evidence suggests that protein acetylation is a broad-ranging regulatory mechanism. Here we utilize acetyl-peptide arrays and metabolomic analyses to identify substrates of mitochondrial deacetylase Sirt3. We identified ornithine transcarbamoylase (OTC) from the urea cycle, and enzymes involved in β-oxidation. Metabolomic analyses of fasted mice lacking Sirt3 (sirt3−/−) revealed alterations in β-oxidation and the urea cycle. Biochemical analysis demonstrated that Sirt3 directly deacetylates OTC and stimulates its activity. Mice under caloric restriction (CR) increased Sirt3 protein levels, leading to deacetylation and stimulation of OTC activity. In contrast, sirt3−/− mice failed to deacetylate OTC in response to CR. Inability to stimulate OTC under CR led to a failure to reduce orotic acid levels, a known outcome of OTC deficiency. Thus, Sirt3 directly regulates OTC activity and promotes the urea cycle during CR, and the results suggest that under low energy input, Sirt3 modulates mitochondria by promoting amino-acid catabolism and β-oxidation. PMID:21255725

  2. Oxidation behavior of a ferritic stainless steel Crofer22 APU with thermal cycling

    NASA Astrophysics Data System (ADS)

    Song, MyoungYoup; Duong, Anh T.; Mumm, Daniel R.

    2013-01-01

    Crofer22 APU specimens were prepared by grinding with grit 80 and 120 SiC grinding papers and were thermally cycled. The variation in oxidation behavior with thermal cycling was then investigated. Observation of microstructure, measurement of area specific resistance (ASR), analysis of the atomic percentages of the elements by EDX, and XRD analysis were performed. XRD patterns showed that the (Cr, Mn)3O4 spinel phase grew on the surface of the Crofer22 APU samples ground with grit 120. For the samples ground with grit 80, the ASR increased as the number of thermal cycles increased. Plots of ln (ASR/T) vs. 1/T for the samples ground with grit 80 after n = 4, 20 and 40 exhibited good linearity, and the apparent activation energies were between 63.7 kJ/mole and 76.3 kJ/mole.

  3. Interdisciplinary research in global biogeochemical cycling Nitrous oxide in terrestrial ecosystems

    NASA Technical Reports Server (NTRS)

    Norman, S. D.; Peterson, D. L.

    1984-01-01

    NASA has begun an interdisciplinary research program to investigate various aspects of Global Biology and Global Habitability. An important element selected for the study of global phenomena is related to biogeochemical cycling. The studies involve a collaboration with recognized scientists in the areas of plant physiology, microbiology, nutrient cycling theory, and related areas. Selected subjects of study include nitrogen cycling dynamics in terrestrial ecosystems with special attention to biosphere/atmosphere interactions, and an identification of sensitive response variables which can be used in ecosystem models based on parameters derived from remotely sensed variables. A description is provided of the progress and findings over the past two years. Attention is given to the characteristics of nitrous oxide emissions, the approach followed in the investigations, the selection of study sites, radiometric measurements, and research in Sequoia.

  4. Subcritical and supercritical water oxidation of CELSS model wastes

    NASA Technical Reports Server (NTRS)

    Takahashi, Y.; Wydeven, T.; Koo, C.

    1989-01-01

    A mixture of ammonium hydroxide with acetic acid and a slurry of human feces, urine, and wipes were used as CELSS model wastes to be wet-oxidized at temperatures from 250 to 500 C, i.e. below and above the critical point of water (374 C and 218 kg/sq cm or 21.4 MPa). The effects of oxidation temperature ( 250-500 C) and residence time (0-120 mn) on carbon and nitrogen and on metal corrosion from the reactor material were studied. Almost all of the organic matter in the model wastes was oxidized in the temperature range from 400 to 500 C, above the critical conditions for water. In contrast, only a small portion of the organic matter was oxidized at subcritical conditions. A substantial amount of nitrogen remained in solution in the form of ammonia at temperatures ranging from 350 to 450 C suggesting that, around 400 C, organic carbon is completely oxidized and most of the nitrogen is retained in solution. The Hastelloy C-276 alloy reactor corroded during subcritical and supercritical water oxidation.

  5. NASA Contributions to Improve Understanding of Extreme Events in the Global Energy and Water Cycle

    NASA Technical Reports Server (NTRS)

    Lapenta, William M.

    2008-01-01

    The U.S. Climate Change Science Program (CCSP) has established the water cycle goals of the Nation's climate change program. Accomplishing these goals will require, in part, an accurate accounting of the key reservoirs and fluxes associated with the global water and energy cycle, including their spatial and temporal variability. through integration of all necessary observations and research tools, To this end, in conjunction with NASA's Earth science research strategy, the overarching long-term NASA Energy and Water Cycle Study (NEWS) grand challenge can he summarized as documenting and enabling improved, observationally based, predictions of water and energy cycle consequences of Earth system variability and change. This challenge requires documenting and predicting trends in the rate of the Earth's water and energy cycling that corresponds to climate change and changes in the frequency and intensity of naturally occurring related meteorological and hydrologic events, which may vary as climate may vary in the future. The cycling of water and energy has obvious and significant implications for the health and prosperity of our society. The importance of documenting and predicting water and energy cycle variations and extremes is necessary to accomplish this benefit to society.

  6. Study of nickel electrode oxidation as a function of 80% depth of discharge cycling

    SciTech Connect

    Pickett, D.F. Jr.; Scoles, D.L.; Johnson, Z.W.; Hayden, J.W.; Pennington, R.D.

    1997-12-31

    Oxidation of nickel sinter used in nickel oxide electrodes in aerospace nickel cadmium cells leads to hydrogen gassing and the potential for cell rupture. The oxidation is directly related to loss of overcharge protection built into the cell during manufacturing. In nickel hydrogen cells, excessive oxidation of the nickel sinter can eventually lead to a burst before leak situation and is a potential source of failure. It is well known that nickel cadmium cells having nylon separators contribute to loss of overcharge via a hydrolysis reaction of the nylon in the potassium hydroxide electrolyte environment in the cell. The hydrolysis reaction produces lower chain organics which are oxidized by the positive electrode and oxygen. Oxidation of the organics diminishes the overcharge protection. With introduction of the Super NiCd{trademark} and the Magnum{trademark} nickel cadmium cells the nylon hydrolysis reaction is eliminated, but any reducing agent in the cell such as nickel or an organic additive can contribute to loss of overcharge protection. The present effort describes chemical analyses made to evaluate the extent of overcharge protection loss in nickel cadmium cells which do not have nylon hydrolysis, and quantifies the amount of hydrogen buildup in nickel hydrogen cells which are subjected to 80% depth of discharge cycling with and without the presence of cadmium in the positive electrode.

  7. Oxidation and Volatilization of Silica-Formers in Water Vapor

    NASA Technical Reports Server (NTRS)

    Opila, E. J.; Gray, Hugh R. (Technical Monitor)

    2002-01-01

    At high temperatures SiC and Si3N4 react with water vapor to form a silica scale. Silica scales also react with water vapor to form a volatile Si(OH)4 species. These simultaneous reactions, one forming silica and the other removing silica, are described by paralinear kinetics. A steady state, in which these reactions occur at the same rate, is eventually achieved, After steady state is achieved, the oxide found on the surface is a constant thickness and recession of the underlying material occurs at a linear rate. The steady state oxide thickness, the time to achieve steady state, and the steady state recession rate can all be described in terms of the rate constants for the oxidation and volatilization reactions. In addition, the oxide thickness, the time to achieve steady state, and the recession rate can also be determined from parameters that describe a water vapor-containing environment. Accordingly, maps have been developed to show these steady state conditions as a function of reaction rate constants, pressure, and gas velocity. These maps can be used to predict the behavior of silica formers in water-vapor containing environments such as combustion environments. Finally, these maps are used to explore the limits of the paralinear oxidation model for SiC and Si3N4

  8. Supercritical water oxidation - Concept analysis for evolutionary Space Station application

    NASA Technical Reports Server (NTRS)

    Hall, John B., Jr.; Brewer, Dana A.

    1986-01-01

    The ability of a supercritical water oxidation (SCWO) concept to reduce the number of processes needed in an evolutionary Space Station design's Environmental Control and Life Support System (ECLSS), while reducing resupply requirements and enhancing the integration of separate ECLSS functions into a single Supercritical Water Oxidation process, is evaluated. While not feasible for an initial operational capability Space Station, the SCWO's application to the evolutionary Space Station configuration would aid the integration of eight ECLSS functions into a single one, thereby significantly reducing program costs.

  9. Aircraft water vapor measurements utilizing an aluminum oxide hygrometer

    NASA Technical Reports Server (NTRS)

    Hilsenrath, E.

    1974-01-01

    A hygrometer for water vapor measurements from an aircraft was developed. An aluminum oxide hygrometer mounted in an aircraft Rosemount air temperature scoop was flown on the NASA Convair 990 and on a USAF B-57 aircraft. Water vapor measurements from the Convair 990 were conducted up to 40,000 ft with penetration into the stratosphere. Good agreement was obtained with simultaneously flown remote sounders of water vapor. During transcontinental flights the hygrometer demonstrated adequate response to measure the natural variability of water vapor near the tropopause. Rapid response was demonstrated in pursuit of the jet wake of an F-104 at 35,000 ft.

  10. Aircraft water vapor measurements utilizing an aluminum oxide hygrometer

    NASA Technical Reports Server (NTRS)

    Hilsenrath, E.

    1973-01-01

    A hygrometer for water vapor measurements from an aircraft has been developed. An aluminum oxide hygrometer mounted in an aircraft Rosemount air temperature scoop was flown on NASA and USAF aircraft. Water vapor measurements were conducted up to 40,000 feet with penetration into the stratosphere. Good agreement was obtained with simultaneously flown remote sounders of water vapor. During transcontinental flights the hygrometer demonstrated adequate response to measure the natural variability of water vapor near the tropopause. Rapid response was demonstrated in pursuit of the jet wake of an F-104 at 35,000 feet.

  11. Climate Change and Expected Impacts on the Global Water Cycle

    NASA Technical Reports Server (NTRS)

    Rind, David; Hansen, James E. (Technical Monitor)

    2002-01-01

    How the elements of the global hydrologic cycle may respond to climate change is reviewed, first from a discussion of the physical sensitivity of these elements to changes in temperature, and then from a comparison of observations of hydrologic changes over the past 100 million years. Observations of current changes in the hydrologic cycle are then compared with projected future changes given the prospect of global warming. It is shown that some of the projections come close to matching the estimated hydrologic changes that occurred long ago when the earth was very warm.

  12. Coordination tuning of cobalt phosphates towards efficient water oxidation catalyst

    PubMed Central

    Kim, Hyunah; Park, Jimin; Park, Inchul; Jin, Kyoungsuk; Jerng, Sung Eun; Kim, Sun Hee; Nam, Ki Tae; Kang, Kisuk

    2015-01-01

    The development of efficient and stable water oxidation catalysts is necessary for the realization of practically viable water-splitting systems. Although extensive studies have focused on the metal-oxide catalysts, the effect of metal coordination on the catalytic ability remains still elusive. Here we select four cobalt-based phosphate catalysts with various cobalt- and phosphate-group coordination as a platform to better understand the catalytic activity of cobalt-based materials. Although they exhibit various catalytic activities and stabilities during water oxidation, Na2CoP2O7 with distorted cobalt tetrahedral geometry shows high activity comparable to that of amorphous cobalt phosphate under neutral conditions, along with high structural stability. First-principles calculations suggest that the surface reorganization by the pyrophosphate ligand induces a highly distorted tetrahedral geometry, where water molecules can favourably bind, resulting in a low overpotential (∼0.42 eV). Our findings emphasize the importance of local cobalt coordination in the catalysis and suggest the possible effect of polyanions on the water oxidation chemistry. PMID:26365091

  13. Bacterial Oxidation of Iron in Olivine: Implications for the Subsurface Biosphere, Global Chemical Cycles, and Life on Mars

    NASA Astrophysics Data System (ADS)

    Fisk, M. R.; Popa, R.; Smith, A. R.; Popa, R.; Boone, J.

    2011-12-01

    We isolated 21 species of bacteria from subseafloor and terrestrial basalt environments and which thrive on olivine at neutral pH. Cell numbers increase four to five orders of magnitude over three weeks in media where the only metabolic energy comes from the oxidation of Fe(II) in olivine. The subseafloor bacteria were isolated from a borehole on the flank of Juan de Fuca Ridge in the northeast Pacific basin where the temperature ranged from 4 up to 64 °C over four years. Terrestrial isolates originated from the basalt-ice boundary in a lava tube on the flank of Newberry Caldera in the Cascades of Oregon. The borehole water was either seawater or seawater plus subseafloor formation water and the lava tube ice was frozen meteoric or ground water. Although microorganisms capable of oxidizing iron for growth are known, microbes that oxidize iron from silicate minerals at neutral pH have not previously been cultured. The 21 species in this study are the first neutrophilic, iron-oxidizing bacteria (nFeOB) to be isolated and cultured that grow on olivine. These nFeOB are primary producers and we believe that they are a widespread component of the subsurface biosphere. In addition to their ability use iron from olivine, these microbes assimilate carbon from bicarbonate in solution and can grow when oxygen pressures are low. They also use nitrate as an alternative electron acceptor to oxygen in anaerobiosis. Since basalt is the most common rock in the Earth's crust and iron is the fourth most abundant element in the crust, we believe nFeOB are likely to be a significant portion of the subsurface biosphere. They are likely to affect, and perhaps in some environments control, the weathering rate of olivine and possibly of pyroxene and basalt glass. Olivine is a component of Mars's surface and it is present on other rocky bodies in the solar system. The ability of these bacteria to use Fe(II) from olivine, to assimilate carbon, to grow at low temperature, and to use low levels of oxygen and nitrate as oxidants would allow them to survive below the surface of Mars. These cultured organisms, which are the first known to oxidize iron from olivine at neutral pH, may be a major component of the subsurface biosphere, may affect global chemical cycles of elements in basalt, and could potentially, live in the Martian subsurface.

  14. Increasing thermal oxidizer capacity with water cooling

    SciTech Connect

    Alford, G.N.; Sudnick, J.J.

    1997-06-01

    Title III of the Clean Air Act Amendments of 1990, as well as state air regulations, require substantial reductions of volatile organic compounds (VOCs) and hazardous air pollutants (HAPs). Industrial facilities affected by these mandated reductions have several options available to comply with the new requirements. These include: process and operational modifications; changes in raw materials; installation of new air pollution control equipment; and modification of existing air pollution control equipment. The focus here will be on some of the process, mechanical and operational changes that need to be considered when modifying existing control equipment. A chemical manufacturer operates a number of processes that generate streams containing VOC and HAP emissions. Stream 1 is from a drying operation and is composed predominantly of air with small amounts of organics. The flow rate is constant, although there may be some variation in the organic concentrations in the stream. Stream 2 is a reactor vent of mostly organics with some nitrogen generated by the reactor purge. This stream is intermittent, having a flow duration of between five and 15 minutes. Stream 3 also is a reactor vent, composed primarily of organics with some nitrogen from the reactor purge. The constituent profile of each stream is given. The three streams are controlled by a thermal oxidizer system. The facility`s plans to add reactor capacity which will create a fourth vent stream. Like streams 2 and 3, this additional stream will consist primarily of organics with some purge nitrogen.

  15. Exfoliation Propensity of Oxide Scale in Heat Exchangers Used for Supercritical CO2 Power Cycles

    SciTech Connect

    Sabau, Adrian S; Shingledecker, John P.; Kung, Steve; Wright, Ian G.; Nash, Jim

    2016-01-01

    Supercritical CO2 (sCO2) Brayton cycle systems offer the possibility of improved efficiency in future fossil energy power generation plants operating at temperatures of 650 C and above. As there are few data on the oxidation/corrosion behavior of structural alloys in sCO2 at these temperatures, modeling to predict the propensity for oxide exfoliation is not well developed, thus hindering materials selection for these novel cycles. The ultimate goal of this effort is to provide needed data on scale exfoliation behavior in sCO2 for confident alloy selection. To date, a model developed by ORNL and EPRI for the exfoliation of oxide scales formed on boiler tubes in high-temperature, high-pressure steam has proven useful for managing exfoliation in conventional steam plants. A major input provided by the model is the ability to predict the likelihood of scale failure and loss based on understanding of the evolution of the oxide morphologies and the conditions that result in susceptibility to exfoliation. This paper describes initial steps taken to extend the existing model for exfoliation of steam-side oxide scales to sCO2 conditions. The main differences between high-temperature, high-pressure steam and sCO2 that impact the model involve (i) significant geometrical differences in the heat exchangers, ranging from standard pressurized tubes seen typically in steam-producing boilers to designs for sCO2 that employ variously-curved thin walls to create shaped flow paths for extended heat transfer area and small channel cross-sections to promote thermal convection and support pressure loads; (ii) changed operating characteristics with sCO2 due to the differences in physical and thermal properties compared to steam; and (iii) possible modification of the scale morphologies, hence properties that influence exfoliation behavior, due to reaction with carbon species from sCO2. The numerical simulations conducted were based on an assumed sCO2 operating schedule and several generic heat exchanger channel shapes and cross-sectional areas. Implications for the evolution of stresses in the oxide scales formed on sCO2 heat exchangers, and ensuing critical oxide thicknesses for exfoliation, were derived and compared with expectations for an equivalent conventional tubular heat exchanger in a steam cycle (for a given alloy).

  16. Visible light water splitting using dye-sensitized oxide semiconductors.

    PubMed

    Youngblood, W Justin; Lee, Seung-Hyun Anna; Maeda, Kazuhiko; Mallouk, Thomas E

    2009-12-21

    Researchers are intensively investigating photochemical water splitting as a means of converting solar to chemical energy in the form of fuels. Hydrogen is a key solar fuel because it can be used directly in combustion engines or fuel cells, or combined catalytically with CO(2) to make carbon containing fuels. Different approaches to solar water splitting include semiconductor particles as photocatalysts and photoelectrodes, molecular donor-acceptor systems linked to catalysts for hydrogen and oxygen evolution, and photovoltaic cells coupled directly or indirectly to electrocatalysts. Despite several decades of research, solar hydrogen generation is efficient only in systems that use expensive photovoltaic cells to power water electrolysis. Direct photocatalytic water splitting is a challenging problem because the reaction is thermodynamically uphill. Light absorption results in the formation of energetic charge-separated states in both molecular donor-acceptor systems and semiconductor particles. Unfortunately, energetically favorable charge recombination reactions tend to be much faster than the slow multielectron processes of water oxidation and reduction. Consequently, visible light water splitting has only recently been achieved in semiconductor-based photocatalytic systems and remains an inefficient process. This Account describes our approach to two problems in solar water splitting: the organization of molecules into assemblies that promote long-lived charge separation, and catalysis of the electrolysis reactions, in particular the four-electron oxidation of water. The building blocks of our artificial photosynthetic systems are wide band gap semiconductor particles, photosensitizer and electron relay molecules, and nanoparticle catalysts. We intercalate layered metal oxide semiconductors with metal nanoparticles. These intercalation compounds, when sensitized with [Ru(bpy)(3)](2+) derivatives, catalyze the photoproduction of hydrogen from sacrificial electron donors (EDTA(2-)) or non-sacrificial donors (I(-)). Through exfoliation of layered metal oxide semiconductors, we construct multilayer electron donor-acceptor thin films or sensitized colloids in which individual nanosheets mediate light-driven electron transfer reactions. When sensitizer molecules are "wired" to IrO(2).nH(2)O nanoparticles, a dye-sensitized TiO(2) electrode becomes the photoanode of a water-splitting photoelectrochemical cell. Although this system is an interesting proof-of-concept, the performance of these cells is still poor (approximately 1% quantum yield) and the dye photodegrades rapidly. We can understand the quantum efficiency and degradation in terms of competing kinetic pathways for water oxidation, back electron transfer, and decomposition of the oxidized dye molecules. Laser flash photolysis experiments allow us to measure these competing rates and, in principle, to improve the performance of the cell by changing the architecture of the electron transfer chain. PMID:19905000

  17. Mercury cycling in surface water, pore water and sediments of Mugu Lagoon, CA, USA.

    PubMed

    Rothenberg, Sarah E; Ambrose, Richard F; Jay, Jennifer A

    2008-07-01

    Mugu Lagoon is an estuary in southern California, listed as impaired for mercury. In 2005, we examined mercury cycling at ten sites within at most four habitats. In surface water (unfiltered and filtered) and pore water, the concentration of total mercury was correlated with methylmercury levels (R2=0.29, 0.26, 0.27, respectively, p<0.05), in contrast to sediments, where organic matter and reduced iron levels were most correlated with methylmercury content (R2=0.37, 0.26, respectively, p<0.05). Interestingly, levels for percent methylmercury of total mercury in sediments were higher than typical values for estuarine sediments (average 5.4%, range 0.024-38%, n=59), while pore water methylmercury Kd values were also high (average 3.1, range 2.0-4.2l kg(-1), n=39), and the estimated methylmercury flux from sediments was low (average 1.7, range 0.14-5.3ng m(-2) day(-1), n=19). Mercury levels in predatory fish tissue at Mugu are >0.3ppm, suggesting biogeochemical controls on methylmercury mobility do not completely mitigate methylmercury uptake through the food web. PMID:18342417

  18. Assembly of the water-oxidizing complex in photosystem II.

    PubMed

    Becker, Kristin; Cormann, Kai U; Nowaczyk, Marc M

    2011-01-01

    The efficient incorporation and assembly of calcium, chloride and manganese followed by photoactivation of the water-oxidizing complex (WOC) is a prerequisite for the unique water-splitting activity of photosystem II. This minireview summarizes the recent results on incorporation and storage of the inorganic cofactors, photoactivation of the WOC and assembly of the protein environment at the donor site of PSII in cyanobacteria with a special focus on the role of the Psb27 protein. PMID:21382728

  19. Vibrational properties of water retained in graphene oxide

    NASA Astrophysics Data System (ADS)

    Drużbicki, Kacper; Natkaniec, Ireneusz

    2014-04-01

    Vibrational properties of water molecules retained in the interlayer space of graphene oxide were studied by combining inelastic neutron scattering spectroscopy with density functional theory calculations. The credibility of Lerf-Klinowski model in the description of the amplitude weighted vibrational density of states has been successfully examined. The solid-state plane-wave DFT computations have delivered satisfying qualitative interpretation of the INS spectrum, which was found to be mainly driven by the vibrational dynamics of the retained water.

  20. K562 cells display different vulnerability to H₂O₂ induced oxidative stress in differing cell cycle phases.

    PubMed

    Akcakaya, Handan; Dal, Fulya; Tok, Sabiha; Cinar, Suzan-Adin; Nurten, Rustem

    2015-02-01

    Oxidative stress can be defined as the increase of oxidizing agents like reactive oxygen and nitrogen species, or the imbalance between the antioxidative defense mechanism and oxidants. Cell cycle checkpoint response can be defined as the arrest of the cell cycle functioning after damaging chemical exposure. This temporary arrest may be a period of time given to the cells to repair the DNA damage before entering the cycle again and completing mitosis. In order to determine the effects of oxidative stress on several cell cycle phases, human erytroleukemia cell line (K562) was synchronized with mimosine and genistein, and cell cycle analysis carried out. Synchronized cells were exposed to oxidative stress with hydrogen peroxide (H2O2) at several concentrations and different times. Changes on mitochondria membrane potential (ΔΨm) of K562 cells were analyzed in G1, S, and G2 /M using Rhodamine 123 (Rho 123). To determine apoptosis and necrosis, stressed cells were stained with Annexin V (AnnV) and propidium iodide (PI) for flow cytometry. Changes were observed in the ΔΨm of synchronized and asynchronized cells that were exposed to oxidative stress. Synchronized cells in S phase proved resistant to the effects of oxidative stress and synchronized cells at G2 /M phase were sensitive to the effects of H2O2 -induced oxidative stress at 500 μM and above. PMID:25181960

  1. Coupling carbon dioxide reduction with water oxidation in nanoscale photocatalytic assemblies.

    PubMed

    Kim, Wooyul; McClure, Beth Anne; Edri, Eran; Frei, Heinz

    2016-06-01

    The reduction of carbon dioxide by water with sunlight in an artificial system offers an opportunity for utilizing non-arable land for generating renewable transportation fuels to replace fossil resources. Because of the very large scale required for the impact on fuel consumption, the scalability of artificial photosystems is of key importance. Closing the photosynthetic cycle of carbon dioxide reduction and water oxidation on the nanoscale addresses major barriers for scalability as well as high efficiency, such as resistance losses inherent to ion transport over macroscale distances, loss of charge and other efficiency degrading processes, or excessive need for the balance of system components, to mention a few. For the conversion of carbon dioxide to six-electron or even more highly reduced liquid fuel products, introduction of a proton conducting, gas impermeable separation membrane is critical. This article reviews recent progress in the development of light absorber-catalyst assemblies for the reduction and oxidation half reactions with focus on well defined polynuclear structures, and on novel approaches for optimizing electron transfer among the molecular or nanoparticulate components. Studies by time-resolved optical and infrared spectroscopy for the understanding of charge transfer processes between the chromophore and the catalyst, and of the mechanism of water oxidation at metal oxide nanocatalysts through direct observation of surface reaction intermediates are discussed. All-inorganic polynuclear units for reducing carbon dioxide by water at the nanoscale are introduced, and progress towards core-shell nanotube assemblies for completing the photosynthetic cycle under membrane separation is described. PMID:27121982

  2. Efficient and sustained photoelectrochemical water oxidation by cobalt oxide/silicon photoanodes with nanotextured interfaces.

    PubMed

    Yang, Jinhui; Walczak, Karl; Anzenberg, Eitan; Toma, Francesca M; Yuan, Guangbi; Beeman, Jeffrey; Schwartzberg, Adam; Lin, Yongjing; Hettick, Mark; Javey, Ali; Ager, Joel W; Yano, Junko; Frei, Heinz; Sharp, Ian D

    2014-04-30

    Plasma-enhanced atomic layer deposition of cobalt oxide onto nanotextured p(+)n-Si devices enables efficient photoelectrochemical water oxidation and effective protection of Si from corrosion at high pH (pH 13.6). A photocurrent density of 17 mA/cm(2) at 1.23 V vs RHE, saturation current density of 30 mA/cm(2), and photovoltage greater than 600 mV were achieved under simulated solar illumination. Sustained photoelectrochemical water oxidation was observed with no detectable degradation after 24 h. Enhanced performance of the nanotextured structure, compared to planar Si, is attributed to a reduced silicon oxide thickness that provides more intimate interfacial contact between the light absorber and catalyst. This work highlights a general approach to improve the performance and stability of Si photoelectrodes by engineering the catalyst/semiconductor interface. PMID:24720554

  3. Mobility of Water on Oxide Surfaces Studied by QENS

    SciTech Connect

    Mamontov, Eugene

    2007-01-01

    Although neutron scattering is often considered a bulk probe, we demonstrate that the mobility of surface water on oxide nano-powders can be investigated using quasielastic neutron scattering. We discuss how the reduced number of hydrogen bonds per water molecule associated with surface confinement leads to a qualitative modification of single-particle translational dynamics compared to bulk water. The mobility of surface water in zirconium oxide with two hydration layers present is discussed in detail. The outer hydration layer exhibits translational dynamics on the time scale of tens of picoseconds, and thus can be studied using time-of-flight neutron spectrometry. The translational dynamics of the inner hydration layer in the range of hundreds of picoseconds can be assessed with backscattering neutron spectrometry. Interestingly, despite being slower by two orders of magnitude, the translational motion of the molecules of the inner hydration layer may share more common traits with bulk water compared to the motion of the outer hydration layer, the dynamics of which is slower than that of bulk water by just one order of magnitude. Similar to bulk water, the temperature dependence of the residence time for the water molecules of the inner hydration layer is non-Arrhenius, and can be described by a Vogel-Fulcher-Tammann (VFT) law. On the other hand, the molecules of the outer hydration layer demonstrate Arrhenius-type temperature dependence indicative of thermally activated surface jump diffusion. Our recent study of surface water on cerium oxide, which exhibits faster dynamics compared to water on zirconium oxide, has ventured into the low-temperature region (down to 200 K). Below 215 K, we have found a deviation from the VFT temperature dependence for the residence time indicative of a surprise "fragile"-to-"strong" transition in the surface water. While "fragile"-to-"strong" transition has been predicted in supercooled bulk water, there has been no prediction of such a transition in surface water. We discuss the links between our results and recent work on hydration water in carbon nanotubes and proteins.

  4. Oxidation of Carbon Fibers in Water Vapor Studied

    NASA Technical Reports Server (NTRS)

    Opila, Elizabeth J.

    2003-01-01

    T-300 carbon fibers (BP Amoco Chemicals, Greenville, SC) are a common reinforcement for silicon carbide composite materials, and carbon-fiber-reinforced silicon carbide composites (C/SiC) are proposed for use in space propulsion applications. It has been shown that the time to failure for C/SiC in stressed oxidation tests is directly correlated with the fiber oxidation rate (ref. 1). To date, most of the testing of these fibers and composites has been conducted in oxygen or air environments; however, many components for space propulsion, such as turbopumps, combustors, and thrusters, are expected to operate in hydrogen and water vapor (H2/H2O) environments with very low oxygen contents. The oxidation rate of carbon fibers in conditions representative of space propulsion environments is, therefore, critical for predicting component lifetimes for real applications. This report describes experimental results that demonstrate that, under some conditions, lower oxidation rates of carbon fibers are observed in water vapor and H2/H2O environments than are found in oxygen or air. At the NASA Glenn Research Center, the weight loss of the fibers was studied as a function of water pressure, temperature, and gas velocity. The rate of carbon fiber oxidation was determined, and the reaction mechanism was identified.

  5. Impact of ocean acidification on benthic and water column ammonia oxidation

    NASA Astrophysics Data System (ADS)

    Kitidis, Vassilis; Laverock, Bonnie; McNeill, Louise C.; Beesley, Amanda; Cummings, Denise; Tait, Karen; Osborn, Mark A.; Widdicombe, Stephen

    2011-11-01

    Ammonia oxidation is a key microbial process within the marine N-cycle. Sediment and water column samples from two contrasting sites in the English Channel (mud and sand) were incubated (up to 14 weeks) in CO2-acidified seawater ranging from pH 8.0 to pH 6.1. Additional observations were made off the island of Ischia (Mediterranean Sea), a natural analogue site, where long-term thermogenic CO2 ebullition occurs (from pH 8.2 to pH 7.6). Water column ammonia oxidation rates in English Channel samples decreased under low pH with near-complete inhibition at pH 6.5. Water column Ischia samples showed a similar though not statistically significant trend. However, sediment ammonia oxidation rates at all three locations were not affected by reduced pH. These observations may be explained by buffering within sediments or low-pH adaptation of the microbial ammonia oxidizing communities. Our observations have implications for modeling the future impact of ocean acidification on marine ecosystems.

  6. Alternatives to the 'water oxidation pathway' of biological ozone formation.

    PubMed

    Onyango, Arnold N

    2016-01-01

    Recent studies have shown that ozone (O3) is endogenously generated in living tissues, where it makes both positive and negative physiological contributions. A pathway for the formation of both O3 and hydrogen peroxide (H2O2) was previously proposed, beginning with the antibody or amino acid-catalyzed oxidation of water by singlet oxygen ((1)O2) to form hydrogen trioxide (H2O3) as a key intermediate. A key pillar of this hypothesis is that some of the H2O2 molecules incorporate water-derived oxygen atoms. However, H2O3 decomposes extremely readily in water to form (1)O2 and water, rather than O3 and H2O2. This article highlights key literature indicating that the oxidation of organic molecules such as the amino acids methionine, tryptophan, histidine, and cysteine by (1)O2 is involved in ozone formation. Based on this, an alternative hypothesis for ozone formation is developed involving a further reaction of singlet oxygen with various oxidized organic intermediates. H2O2 having water-derived oxygen atoms is subsequently formed during ozone decomposition in water by known reactions. PMID:26855676

  7. The Global Enery and Water Cycle Experiment Science Strategy

    NASA Technical Reports Server (NTRS)

    Chahine, M. T.

    1997-01-01

    The distribution of water in the atmosphere and at the surface of the Earth is the most influential factor regulating our environment, not only because water is essential for life but also because through phase transitions it is the main energy source that control clouds and radiation and drives the global circulation of the atmosphere.

  8. Effects of tempol and redox-cycling nitroxides in models of oxidative stress

    PubMed Central

    Wilcox, Christopher S.

    2010-01-01

    Tempol is a redox cycling nitroxide that promotes the metabolism of many reactive oxygen species (ROS) and improves nitric oxide bioavailability. It has been studied extensively in animal models of oxidative stress. Tempol has been shown to preserve mitochondria against oxidative damage and improve tissue oxygenation. Tempol improved insulin responsiveness in models of diabetes mellitus and improved the dyslipidemia, reduced the weight gain and prevented diastolic dysfunction and heart failure in fat-fed models of the metabolic syndrome. Tempol protected many organs, including the heart and brain, from ischemia/reperfusion damage. Tempol prevented podocyte damage, glomerulosclerosis, proteinuria and progressive loss of renal function in models of salt and mineralocorticosteroid excess. It reduced brain or spinal cord damage after ischemia or trauma and exerted a spinal analgesic action. Tempol improved survival in several models of shock. It protected normal cells from radiation while maintaining radiation sensitivity of tumor cells. Its paradoxical pro-oxidant action in tumor cells accounted for a reduction in spontaneous tumor formation. Tempol was effective in some models of neurodegeneration. Thus, tempol has been effective in preventing several of the adverse consequences of oxidative stress and inflammation that underlie radiation damage and many of the diseases associated with aging. Indeed, tempol given from birth prolonged the life span of normal mice. However, presently tempol has been used only in human subjects as a topical agent to prevent radiation-induced alopecia. PMID:20153367

  9. The urban harvest approach as framework and planning tool for improved water and resource cycles.

    PubMed

    Leusbrock, I; Nanninga, T A; Lieberg, K; Agudelo-Vera, C M; Keesman, K J; Zeeman, G; Rijnaarts, H H M

    2015-01-01

    Water and resource availability in sufficient quantity and quality for anthropogenic needs represents one of the main challenges in the coming decades. To prepare for upcoming challenges such as increased urbanization and climate change related consequences, innovative and improved resource management concepts are indispensable. In recent years we have developed and applied the urban harvest approach (UHA). The UHA aims to model and quantify the urban water cycle on different temporal and spatial scales. This approach allowed us to quantify the impact of the implementation of water saving measures and new water treatment concepts in cities. In this paper we will introduce the UHA and its application for urban water cycles. Furthermore, we will show first results for an extension to energy cycles and highlight future research items (e.g. nutrients, water-energy-nexus). PMID:26360761

  10. Methane concentrations and oxidation in nearshore waters of the Lena River Delta

    NASA Astrophysics Data System (ADS)

    Joye, S. B.; Samarkin, V.; Shakhova, N. E.; Semiletov, I. P.

    2014-12-01

    The Arctic is warming dramatically, with potentially catastrophic impacts on climate change through rapid mobilization of labile carbon reservoirs sequestered presently in permafrost. Increasingly, Arctic feedbacks are recognized as key contributors to climate change, including cycles associated with the powerful greenhouse gas methane, whose atmospheric concentration has more than doubled since the pre-industrial epoch. Sustained methane release to the atmosphere from thawing Arctic permafrost and delivery to the coastal ocean through groundwater or riverine discharge or expulsion from the seabed is a positive and likely highly significant feedback to climate warming. Microbially-mediated methane oxidation provides a key sink and effective biofilter that can limit methane fluxes from coastal environments to the atmosphere. We examined methane dynamics on the East Siberian Arctic Shelf by determining concentrations and oxidation rates at a series of stations near the Lena River Delta and moving offshore. Methane concentrations and oxidation rates were highly elevated in and near the river mouth compared to offshore waters, except when the offshore waters were impacted by seabed methane seepage. The regulation of methane oxidation in Arctic waters appears two-fold: first, rates are strongly related to methane availability and second, in the presence of methane, nutrient availability strongly regulates methane consumption. Along the Lena river delta, elevated concentrations of both nutrients and methane create ideal conditions to support high rates of pelagic methanotrophy. Offshore, where nutrient concentrations are lower and more limiting, methane oxidation rates are considerably lower. These data suggest that, at present, nearshore waters are fairly efficient methane sinks while in offshore waters, pelagic methanotrophy is inefficient, allowing methane to escape to the atmosphere.

  11. Electrosynthesis of Biomimetic Manganese-Calcium Oxides for Water Oxidation Catalysis-Atomic Structure and Functionality.

    PubMed

    González-Flores, Diego; Zaharieva, Ivelina; Heidkamp, Jonathan; Chernev, Petko; Martínez-Moreno, Elías; Pasquini, Chiara; Mohammadi, Mohammad Reza; Klingan, Katharina; Gernet, Ulrich; Fischer, Anna; Dau, Holger

    2016-02-01

    Water-oxidizing calcium-manganese oxides, which mimic the inorganic core of the biological catalyst, were synthesized and structurally characterized by X-ray absorption spectroscopy at the manganese and calcium K edges. The amorphous, birnesite-type oxides are obtained through a simple protocol that involves electrodeposition followed by active-site creation through annealing at moderate temperatures. Calcium ions are inessential, but tune the electrocatalytic properties. For increasing calcium/manganese molar ratios, both Tafel slopes and exchange current densities decrease gradually, resulting in optimal catalytic performance at calcium/manganese molar ratios of close to 10 %. Tracking UV/Vis absorption changes during electrochemical operation suggests that inactive oxides reach their highest, all-Mn(IV) oxidation state at comparably low electrode potentials. The ability to undergo redox transitions and the presence of a minor fraction of Mn(III) ions at catalytic potentials is identified as a prerequisite for catalytic activity. PMID:26692571

  12. SUPERCRITICAL WATER OXIDATION MODEL DEVELOPMENT FOR SELECTED EPA PRIORITY POLLUTANTS

    EPA Science Inventory

    Supercritical Water Oxidation (SCWO) evaluated for five compounds: acetic acid, 2,4-dichlorophenol, pentachlorophenol, pyridine, 2,4-dichlorophenoxyacetic acid (methyl ester). inetic models were developed for acetic acid, 2,4-dichlorophenol, and pyridine. he test compounds were e...

  13. Electrophotolysis oxidation system for measurement of organic concentration in water

    NASA Technical Reports Server (NTRS)

    Winkler, H. E. (Inventor)

    1981-01-01

    Methods and apparatus for determining organic carbon in aqueous solution are described. The method comprises subjecting the aqueous solution to electrolysis, for generating oxygen from water, and simultaneously to ultraviolet radiation, for oxidation of substantially all organic carbon to carbon dioxide. The carbon dioxide is measured and the value is related to the concentration of organic carbon in the aqueous solution.

  14. An Overview of the NASA Energy and Water cycle Study (NEWS) and the North American Water Program (NAWP)

    NASA Astrophysics Data System (ADS)

    Houser, P. R.

    2014-12-01

    NEWS: 10 years ago, NASA established the NASA Energy and Water-cycle Study (NEWS), whose long-term grand challenge is to document and enable improved, observationally based, predictions of water and energy cycle consequences of Earth system variability and change. The NEWS program builds upon existing NASA-supported basic research in atmospheric physics and dynamics, radiation, climate modeling, and terrestrial hydrology. While these NASA programs fund research activities that address individual aspects of the global energy and water cycles, they are not specifically designed to generate a coordinated result. NEWS developed the first coordinated attempt to describe the complete global energy and water cycle using existing and forthcoming satellite and ground based observations, and laying the foundation for essential NEWS developments in model representations of atmospheric energy and water exchange processes. This comprehensive energy and water data analysis program exploited crucial datasets, some requiring complete re-processing, and new satellite measurements. NAWP: Dramatically changing climates has had an indelible impact on North America's water crisis. To decisively address these challenges, we recommend that NAWP coalesce an interdisciplinary, international and interagency effort to make significant contributions to continental- to decision-scale hydroclimate science and solutions. By entraining, integrating and coordinating the vast array of interdisciplinary observational and prediction resources available, NAWP will significantly advance skill in predicting, assessing and managing variability and changes in North American water resources. We adopt three challenges to organize NAWP efforts. The first deals with developing a scientific basis and tools for mitigating and adapting to changes in the water supply-demand balance. The second challenge is benchmarking; to use incomplete and uncertain observations to assess water storage and quality dynamics, and to characterize the information content of water cycle predictions in a way that allows for model improvement. The final challenge is to establish clear pathways to inform water managers, practitioners and decision makers about newly developed tools, observations and research results.

  15. Examining Language To Capture Scientific Understandings: The Case of the Water Cycle.

    ERIC Educational Resources Information Center

    Varelas, Maria; Pappas, Christine; Barry, Anne; O'Neill, Amy

    2001-01-01

    Presents units that address states of matter and changes of states of matter linked with the water cycle and integrates literacy and science. Discusses the language in science books. Lists characteristics of good science inquiry units. (Contains 11 references.) (ASK)

  16. Reduced Water Density in a Poly(ethylene oxide) Brush

    SciTech Connect

    Lee, Hoyoung; Kim, Dae Hwan; Park, Hae-Woong; Mahynski, Nathan A.; Kim, Kyungil; Meron, Mati; Lin, Binhua; Won, You-Yeon

    2012-09-05

    A model poly(ethylene oxide) (PEO) brush system, prepared by spreading a poly(ethylene oxide)-poly(n-butyl acrylate) (PEO-PnBA) amphiphilic diblock copolymer onto an air-water interface, was investigated under various grafting density conditions by using the X-ray reflectivity (XR) technique. The overall electron density profiles of the PEO-PnBA monolayer in the direction normal to the air-water interface were determined from the XR data. From this analysis, it was found that inside of the PEO brush, the water density is significantly lower than that of bulk water, in particular, in the region close to the PnBA-water interface. Separate XR measurements with a PnBA homopolymer monolayer confirm that the reduced water density within the PEO-PnBA monolayer is not due to unfavorable contacts between the PnBA surface and water. The above result, therefore, lends support to the notion that PEO chains provide a hydrophobic environment for the surrounding water molecules when they exist as polymer brush chains.

  17. Destruction of energetic materials by supercritical water oxidation

    SciTech Connect

    Beulow, S.J.; Dyer, R.B.; Harradine, D.M.; Robinson, J.M.; Oldenborg, R.C.; Funk, K.A.; McInroy, R.E.; Sanchez, J.A.; Spontarelli, T.

    1993-10-01

    Supercritical water oxidation is a relatively low-temperature process that can give high destruction efficiencies for a variety of hazardous chemical wastes. Results are presented examining the destruction of high explosives and propellants in supercritical water and the use of low temperature, low pressure hydrolysis as a pretreatment process. Reactions of cyclotrimethylene trinitramine (RDX), cyclotetramethylene tetranitramine (HMX), nitroguanidine (NQ), pentaerythritol tetranitrate (PETN), and 2,4,6-trinitrotoluene (TNT) are examined in a flow reactor operated at temperatures between 400{degrees}C and 650{degrees}C. Explosives are introduced into the reactor at concentrations below the solubility limits. For each of the compounds, over 99.9% is destroyed in less than 30 seconds at temperatures above 600{degrees}C. The reactions produce primarily N{sub 2}, N{sub 2}O,CO{sub 2}, and some nitrate and nitrite ions. The distribution of reaction products depends on reactor pressure, temperature, and oxidizer concentration. Kinetics studies of the reactions of nitrate and nitrite ions with various reducing reagents in supercritical water show that they can be rapidly and completely destroyed at temperatures above 525{degrees}C. The use of slurries and hydrolysis to introduce high concentrations of explosives into a supercritical water reactor is examined. For some compounds the rate of reaction depends on particle size. The hydrolysis of explosives at low temperatures (<100{degrees}C) and low pressures (<1 atm) under basic conditions produces water soluble, non-explosive products which are easily destroyed by supercritical water oxidation. Large pieces of explosives (13 cm diameter) have been successfully hydrolyzed. The rate, extent, and products of the hydrolysis depend on the type and concentration of base. Results from the base hydrolysis of triple base propellant M31A1E1 and the subsequent supercritical water oxidation of the hydrolysis products are presented.

  18. Priority organic pollutants in the urban water cycle (Toulouse, France).

    PubMed

    Sablayrolles, C; Breton, A; Vialle, C; Vignoles, C; Montréjaud-Vignoles, M

    2011-01-01

    Application of the European Water Framework Directive requires Member States to have better understanding of the quality of surface waters in order to improve knowledge of priority pollutants. Xenobiotics in urban receiving waters are an emerging concern. This study proposes a screening campaign of nine molecular species of xenobiotics in a separated sewer system. Five sites were investigated over one year in Toulouse (France) using quantitative monitoring. For each sample, polycyclic aromatic hydrocarbons, polychlorinated biphenyls, nonylphenols, diethelhexylphthalate, linear alkylbenzene sulphonates, methyl tert-butylether, total hydrocarbons, estradiol and ethinylestradiol were analysed. Ground, rain and roof collected water concentrations are similar to treated wastewater levels. Run-off water was the most polluted of the five types investigated, discharged into the aquatic environment. The wastewater treatment plant reduced xenobiotic concentrations by 66% before discharge into the environment. Regarding environmental quality standards, observed concentrations in waters were in compliance with standards. The results show that xenobiotic concentrations are variable over time and space in all urban water compartments. PMID:22097031

  19. Surfactant-mediated electrodeposition of a water-oxidizing manganese oxide.

    PubMed

    Osowiecki, Wojciech T; Sheehan, Stafford W; Young, Karin J; Durrell, Alec C; Mercado, Brandon Q; Brudvig, Gary W

    2015-10-14

    Splitting water into hydrogen and oxygen is one of the most promising ways of storing energy from intermittent, renewable sources in the future. Toward this goal, development of inexpensive, stable, and non-toxic catalysts for water oxidation is crucial. We report that the electrodeposition of manganese oxide in the presence of sodium dodecyl sulfate (SDS) produces a material that is highly active for electrocatalytic water oxidation at pH near 7 and remains stable for over 24 hours of sustained electrolysis. Clark electrode measurements demonstrate more than 95% Faradaic efficiency for oxygen evolution after an initial charging period. We found that catalytic performance was optimized in films prepared by electrodeposition using a precursor solution containing moderate concentration of substrates, namely 25 mM Mn(2+) and 25 mM SDS. Microstructure and elemental analyses revealed that the deposited material, a mixed-phase manganese oxide, is structurally similar to materials used for electrochemical capacitors and batteries, drawing a parallel between highly studied cathode materials for rechargeable batteries and heterogeneous catalysts for water oxidation. PMID:26350519

  20. New Ir Bis-Carbonyl Precursor for Water Oxidation Catalysis.

    PubMed

    Huang, Daria L; Beltrán-Suito, Rodrigo; Thomsen, Julianne M; Hashmi, Sara M; Materna, Kelly L; Sheehan, Stafford W; Mercado, Brandon Q; Brudvig, Gary W; Crabtree, Robert H

    2016-03-01

    This paper introduces Ir(I)(CO)2(pyalc) (pyalc = (2-pyridyl)-2-propanoate) as an atom-efficient precursor for Ir-based homogeneous oxidation catalysis. This compound was chosen to simplify analysis of the water oxidation catalyst species formed by the previously reported Cp*Ir(III)(pyalc)OH water oxidation precatalyst. Here, we present a comparative study on the chemical and catalytic properties of these two precursors. Previous studies show that oxidative activation of Cp*Ir-based precursors with NaIO4 results in formation of a blue Ir(IV) species. This activation is concomitant with the loss of the placeholder Cp* ligand which oxidatively degrades to form acetic acid, iodate, and other obligatory byproducts. The activation process requires substantial amounts of primary oxidant, and the degradation products complicate analysis of the resulting Ir(IV) species. The species formed from oxidation of the Ir(CO)2(pyalc) precursor, on the other hand, lacks these degradation products (the CO ligands are easily lost upon oxidation) which allows for more detailed examination of the resulting Ir(pyalc) active species both catalytically and spectroscopically, although complete structural analysis is still elusive. Once Ir(CO)2(pyalc) is activated, the system requires acetic acid or acetate to prevent the formation of nanoparticles. Investigation of the activated bis-carbonyl complex also suggests several Ir(pyalc) isomers may exist in solution. By (1)H NMR, activated Ir(CO)2(pyalc) has fewer isomers than activated Cp*Ir complexes, allowing for advanced characterization. Future research in this direction is expected to contribute to a better structural understanding of the active species. A diol crystallization agent was needed for the structure determination of 3. PMID:26901517

  1. An analysis of hydrogen production via closed-cycle schemes. [thermochemical processings from water

    NASA Technical Reports Server (NTRS)

    Chao, R. E.; Cox, K. E.

    1975-01-01

    A thermodynamic analysis and state-of-the-art review of three basic schemes for production of hydrogen from water: electrolysis, thermal water-splitting, and multi-step thermochemical closed cycles is presented. Criteria for work-saving thermochemical closed-cycle processes are established, and several schemes are reviewed in light of such criteria. An economic analysis is also presented in the context of energy costs.

  2. Effects of microbial redox cycling of iron on cast iron pipe corrosion in drinking water distribution systems.

    PubMed

    Wang, Haibo; Hu, Chun; Zhang, Lili; Li, Xiaoxiao; Zhang, Yu; Yang, Min

    2014-11-15

    Bacterial characteristics in corrosion products and their effect on the formation of dense corrosion scales on cast iron coupons were studied in drinking water, with sterile water acting as a reference. The corrosion process and corrosion scales were characterized by electrochemical and physico-chemical measurements. The results indicated that the corrosion was more rapidly inhibited and iron release was lower due to formation of more dense protective corrosion scales in drinking water than in sterile water. The microbial community and denitrifying functional genes were analyzed by pyrosequencing and quantitative polymerase chain reactions (qPCR), respectively. Principal component analysis (PCA) showed that the bacteria in corrosion products played an important role in the corrosion process in drinking water. Nitrate-reducing bacteria (NRB) Acidovorax and Hydrogenophaga enhanced iron corrosion before 6 days. After 20 days, the dominant bacteria became NRB Dechloromonas (40.08%) with the protective corrosion layer formation. The Dechloromonas exhibited the stronger corrosion inhibition by inducing the redox cycling of iron, to enhance the precipitation of iron oxides and formation of Fe3O4. Subsequently, other minor bacteria appeared in the corrosion scales, including iron-respiring bacteria and Rhizobium which captured iron by the produced siderophores, having a weaker corrosion-inhibition effect. Therefore, the microbially-driven redox cycling of iron with associated microbial capture of iron caused more compact corrosion scales formation and lower iron release. PMID:25150521

  3. Life cycle water use for electricity generation: a review and harmonization of literature estimates

    NASA Astrophysics Data System (ADS)

    Meldrum, J.; Nettles-Anderson, S.; Heath, G.; Macknick, J.

    2013-03-01

    This article provides consolidated estimates of water withdrawal and water consumption for the full life cycle of selected electricity generating technologies, which includes component manufacturing, fuel acquisition, processing, and transport, and power plant operation and decommissioning. Estimates were gathered through a broad search of publicly available sources, screened for quality and relevance, and harmonized for methodological differences. Published estimates vary substantially, due in part to differences in production pathways, in defined boundaries, and in performance parameters. Despite limitations to available data, we find that: water used for cooling of thermoelectric power plants dominates the life cycle water use in most cases; the coal, natural gas, and nuclear fuel cycles require substantial water per megawatt-hour in most cases; and, a substantial proportion of life cycle water use per megawatt-hour is required for the manufacturing and construction of concentrating solar, geothermal, photovoltaic, and wind power facilities. On the basis of the best available evidence for the evaluated technologies, total life cycle water use appears lowest for electricity generated by photovoltaics and wind, and highest for thermoelectric generation technologies. This report provides the foundation for conducting water use impact assessments of the power sector while also identifying gaps in data that could guide future research.

  4. The Water Cycle from Space: Use of Satellite Data in Land Surface Hydrology and Water Resource Management

    NASA Technical Reports Server (NTRS)

    Laymon, Charles; Blankenship, Clay; Khan, Maudood; Limaye, Ashutosh; Hornbuckle, Brian; Rowlandson, Tracy

    2010-01-01

    This slide presentation reviews how our understanding of the water cycle is enhanced by our use of satellite data, and how this informs land surface hydrology and water resource management. It reviews how NASA's current and future satellite missions will provide Earth system data of unprecedented breadth, accuracy and utility for hydrologic analysis.

  5. Water-Mediated Proton Hopping on an Iron Oxide Surface

    SciTech Connect

    Merte, L. R.; Peng, Guowen; Bechstein, Ralf; Rieboldt, Felix; Farberow, Carrie A.; Grabow, Lars C.; Kudernatsch, Wilhelmine; Wendt, Stefen; Laegsgaard, E.; Mavrikakis, Manos; Besenbacher, Fleming

    2012-05-18

    The diffusion of hydrogen atoms across solid oxide surfaces is often assumed to be accelerated by the presence of water molecules. Here we present a high-resolution, high-speed scanning tunneling microscopy (STM) study of the diffusion of H atoms on an FeO thin film. STM movies directly reveal a water-mediated hydrogen diffusion mechanism on the oxide surface at temperatures between 100 and 300 kelvin. Density functional theory calculations and isotope-exchange experiments confirm the STM observations, and a proton-transfer mechanism that proceeds via an H3O+-like transition state is revealed. This mechanism differs from that observed previously for rutile TiO2(110), where water dissociation is a key step in proton diffusion.

  6. Water-mediated proton hopping on an iron oxide surface.

    PubMed

    Merte, Lindsay R; Peng, Guowen; Bechstein, Ralf; Rieboldt, Felix; Farberow, Carrie A; Grabow, Lars C; Kudernatsch, Wilhelmine; Wendt, Stefan; Lægsgaard, Erik; Mavrikakis, Manos; Besenbacher, Flemming

    2012-05-18

    The diffusion of hydrogen atoms across solid oxide surfaces is often assumed to be accelerated by the presence of water molecules. Here we present a high-resolution, high-speed scanning tunneling microscopy (STM) study of the diffusion of H atoms on an FeO thin film. STM movies directly reveal a water-mediated hydrogen diffusion mechanism on the oxide surface at temperatures between 100 and 300 kelvin. Density functional theory calculations and isotope-exchange experiments confirm the STM observations, and a proton-transfer mechanism that proceeds via an H(3)O(+)-like transition state is revealed. This mechanism differs from that observed previously for rutile TiO(2)(110), where water dissociation is a key step in proton diffusion. PMID:22605771

  7. Advances in Understanding Global Water Cycle with Advent of Global Precipitation Measurement (GPM) Mission

    NASA Technical Reports Server (NTRS)

    Smith, Eric A.; Starr, David (Technical Monitor)

    2002-01-01

    Within this decade the internationally organized Global Precipitation Measurement (GPM) Mission will take an important step in creating a global precipitation observing system from space. One perspective for understanding the nature of GPM is that it will be a hierarchical system of datastreams beginning with very high caliber combined dual frequency radar/passive microwave (PMW) rain-radiometer retrievals, to high caliber PMW rain-radiometer only retrievals, and then on to blends of the former datastreams with additional lower-caliber PMW-based and IR-based rain retrievals. Within the context of the now emerging global water & energy cycle (GWEC) programs of a number of research agencies throughout the world, GPM serves as a centerpiece space mission for improving our understanding of the global water cycle from a global measurement perspective. One of the salient problems within our current understanding of the global water and energy cycle is determining whether a change in the rate of the water cycle is accompanying changes in climate, e.g., climate warming. As there are a number of ways in which to define a rate-change of the global water cycle, it is not entirely clear as to what constitutes such a determination. This paper presents an overview of the GPM Mission and how its observations can be used within the framework of the oceanic and continental water budget equations to determine whether a given perturbation in precipitation is indicative of an actual rate change in the global water cycle, consistent with required responses in water storage and/or water flux transport processes, or whether it is the natural variability of a fixed rate cycle.

  8. Advances In Understanding Global Water Cycle With Advent of GPM Mission

    NASA Technical Reports Server (NTRS)

    Smith, Eric A.

    2002-01-01

    During the coming decade, the internationally organized Global Precipitation Measurement (GPM) Mission will take an important step in creating a global precipitation observing system from space based on an international fleet of satellites operated as a constellation. One perspective for understanding the nature of GPM is that it will be a hierarchical system of datastreams beginning with very high caliber combined dual frequency radar/passive microwave (PMW) rain-radiometer retrievals, to high caliber PMW rain-radiometer only retrievals, and then on to blends of the former datastreams with additional lower-caliber PMW-based and IR-based rain retrievals. Within the context of the now emerging global water & energy cycle (GWEC) programs of a number of research agencies throughout the world, GPM serves as a centerpiece space mission for improving our understanding of the Earth's water cycle from a global measurement perspective and on down to regional scales and below. One of the salient problems within our current understanding of the global water and energy cycle is determining whether a change in the rate of the water cycle is accompanying changes in climate, e.g., climate warming. As there are a number of ways in which to define a rate-change of the global water cycle, it is not entirely clear as to what constitutes such a determination. This paper first presents an overview of the GPM Mission and how its overriding scientific objectives for climate, weather, and hydrology flow from the anticipated improvements that are being planned for the constellation-based measuring system. Next, the paper shows how the GPM observations can be used within the framework of the oceanic and continental water budget equations to determine whether a given perturbation in precipitation is indicative of an actual rate change in the water cycle, consistent with required responses in water storage and/or water flux transport processes, or whether it is simply part of the natural variability of a fixed rate cycle.

  9. Role of mechanical loads in inducing in-cycle tensile stress in thermally grown oxide

    SciTech Connect

    Diaz, R.; Jansz, M.; Mossaddad, M.; Raghavan, S.; Okasinski, J.S.; Almer, J.D.; Perez, H.P.; Imbrie, P.

    2012-01-01

    Experimental in situ synchrotron x-ray diffraction results tracking the strain behavior of the various layers during a cycle, under thermo-mechanical conditions are presented in this work. The quantitative strain measurements here show that the thermally grown oxide briefly experiences in-plane tensile stress ({sigma}{sub 22} = +36.4 MPa) with increased mechanical loading during ramp-up in the thermal cycle. These findings are the first in situ experimental observations of these strains under thermo-mechanical conditions, envisaged to serve as a catalyst for crack initiation. The depth resolved measurements of strain taken during applied thermal and mechanical load in this work are a significant step towards achieving realistic testing conditions.

  10. Biochemical predetermination of the NO synthase and nitrite reductase components of the nitric oxide cycle.

    PubMed

    Reutov, V P

    1999-05-01

    This review presents some aspects of a concept of cellular evolution bearing a relationship to nitrate--nitrite respiration, the endosymbiosis theory, and the origin of NO synthase and nitrite reductase activity in heme-containing proteins. Analysis of structural and functional unity of the NO synthase and nitrite reductase systems suggests that these systems did not arise without any relation to evolutionarily ancient energetic systems of cells. The use of symmetry principles reveals commonalities among many electron transport chains which in the language of physics is called "invariance". This work also comparatively analyzes the nitric oxide cycle and the known nitrogen cycle. The ideas about evolution of the NO synthase and nitrite reductase systems developed here are clearly compatible with the endosymbiotic theory and the hypothesis that nitrate--nitrite respiration was a precursor of oxygen-dependent respiration. PMID:10381613

  11. Concept for a small, colocated fuel cycle facility for oxide breeder fuels

    SciTech Connect

    Burch, W.D.; Stradley, J.G.; Lerch, R.E.

    1987-01-01

    As part of a United States Department of Energy (USDOE) program to examine innovative liquid-metal reactor (LMR) system designs over the past three years, the Oak Ridge National Laboratory (ORNL) and the Westinghouse Hanford Company (WHC) collaborated on studies of mixed oxide fuel cycle options. A principal effort was an advanced concept for a small integrated fuel cycle colocated with a 1300-MW(e) reactor station. The study provided a scoping design and a basis on which to proceed with implementation of such a facility if future plans so dictate. The facility integrated reprocessing, waste management, and refabrication functions in a single facility of nominal 35-t/year capacity utilizing the latest technology developed in fabrication programs at WHC and in reprocessing at ORNL. The concept was based on many years of work at both sites and extensive design studies of prior years.

  12. Concept for a small, colocated fuel cycle facility for oxide breeder fuels

    SciTech Connect

    Burch, W.D.; Lerch, R.E.; Stradley, J.G.

    1987-01-01

    As part of a United States Department of Energy (USDOE) program to examine innovative liquid-metal reactor (LMR) system designs over the past three years, the Oak Ridge National Laboratory (ORNL) and the Westinghouse Hanford Company (WHC) collaborated on studies of mixed oxide fuel cycle options. A principal effort was an advanced concept for a small integrated fuel cycle colocated with a 1300-MW(e) reactor station. The study provided a scoping design, capital and operating cost estimates, and a basis on which to proceed with implementation of such a facility if future plans so dictate. The facility integrated reprocessing, waste management, and refabrication functions in a single facility of nominal 35-t/year capacity utilizing the latest technology developed in fabrication programs at WHC and in reprocessing at ORNL. The concept was based on many years of work at both sites and extensive design studies of prior years.

  13. Kinetics of the catalytic oxidation of phenol over manganese oxide in supercritical water

    SciTech Connect

    Oshima, Yoshito; Tomita, Kengo; Koda, Seiichiro

    1999-11-01

    A kinetic analysis was made for the phenol disappearance rate in catalytic oxidation of phenol over MnO{sub 2} in supercritical water at a fixed temperature of 425 C and pressures between 22.7 and 27.2 MPa. The nonsupported MnO{sub 2} catalyst possessed a strong activity for promoting phenol oxidation, though the overall reaction rate was appreciably influenced by internal mass-transfer resistance. From the kinetic analysis on the reaction rate of the phenol disappearance, the global rate expression of the surface reaction was obtained, where the reaction orders with respect to phenol, oxygen, and water were almost unity, 0.7, and {minus}2.0, respectively. A Langmuir-type mechanism, in which phenol and oxygen adsorbed on the catalytic sites and water adsorbed on the same site to inhibit the phenol and oxygen adsorption, was proposed to explain the reaction orders for phenol, oxygen, and water.

  14. Light-harvesting photocatalysis for water oxidation using mesoporous organosilica.

    PubMed

    Takeda, Hiroyuki; Ohashi, Masataka; Goto, Yasutomo; Ohsuna, Tetsu; Tani, Takao; Inagaki, Shinji

    2014-07-14

    An organic-based photocatalysis system for water oxidation, with visible-light harvesting antennae, was constructed using periodic mesoporous organosilica (PMO). PMO containing acridone groups in the framework (Acd-PMO), a visible-light harvesting antenna, was supported with [Ru(II)(bpy)3(2+)] complex (bpy = 2,2'-bipyridyl) coupled with iridium oxide (IrO(x)) particles in the mesochannels as photosensitizer and catalyst, respectively. Acd-PMO absorbed visible light and funneled the light energy into the Ru complex in the mesochannels through excitation energy transfer. The excited state of Ru complex is oxidatively quenched by a sacrificial oxidant (Na2S2O8) to form Ru(3+) species. The Ru(3+) species extracts an electron from IrO(x) to oxidize water for oxygen production. The reaction quantum yield was 0.34 %, which was improved to 0.68 or 1.2 % by the modifications of PMO. A unique sequence of reactions mimicking natural photosystem II, 1) light-harvesting, 2) charge separation, and 3) oxygen generation, were realized for the first time by using the light-harvesting PMO. PMID:24890840

  15. Global Energy and Water Cycle Experiment (GEWEX) and the Continental-scale International Project (GCIP)

    NASA Technical Reports Server (NTRS)

    Vane, Deborah

    1993-01-01

    A discussion of the objectives of the Global Energy and Water Cycle Experiment (GEWEX) and the Continental-scale International Project (GCIP) is presented in vugraph form. The objectives of GEWEX are as follows: determine the hydrological cycle by global measurements; model the global hydrological cycle; improve observations and data assimilation; and predict response to environmental change. The objectives of GCIP are as follows: determine the time/space variability of the hydrological cycle over a continental-scale region; develop macro-scale hydrologic models that are coupled to atmospheric models; develop information retrieval schemes; and support regional climate change impact assessment.

  16. Evaluation on Efficiency of CO2 Heat Pump Cycle for Hot Water Supply

    NASA Astrophysics Data System (ADS)

    Saikawa, Michiyuki; Hashimoto, Katsumi

    In Japan, it is very effective for saving energy to develop highly efficient heat pumps for hot water supply. On the other hand, heat pumps with "natural working fluids" are being developed eagerly for environmental protection. After surveying the status of R&D relating to heat pumps with natural working f1uids, CRIEPI focused on a CO2 heat pump and started a basic study on it. We calculated COP of CO2 heat pump cycle for hot water supply and studied the characteristics of the cycle. We verified that CO2 cycle had unique characteristics and achieved higher COP than those of conventional working fluids.

  17. Teaching the Krebs Cycle.

    ERIC Educational Resources Information Center

    Akeroyd, F. Michael

    1983-01-01

    Outlines a simple but rigorous treatment of the Krebs Cycle suitable for A-level Biology students. The importance of the addition of water molecules in various stages of the cycle is stressed as well as the removal of hydrogen atoms by the oxidizing enzymes. (JN)

  18. Passive regulation of soil biogeochemical cycling by root water transport

    NASA Astrophysics Data System (ADS)

    Quijano, Juan C.; Kumar, Praveen; Drewry, Darren T.

    2013-06-01

    Surface and subsurface moisture dynamics are strongly influenced by the ability of vegetation to take up and redistribute soil moisture using hydraulic redistribution (HR). These dynamics in turn affect soil biogeochemical cycling through controls on decomposition and mineralization rates and ion transport. The goal of this study is to explore this coupling between HR and biogeochemistry using a numerical model. We examine decomposition and mineralization of organic matter and analyze whether differences in decomposition rates induced by HR influence the long-term storage of carbon in the soil and the movement of nitrate (NO 3-) and ammonium (NH 4+) in the rhizosphere. These dynamics are studied in a framework that incorporates the interaction between multiple plant species. The net effect of HR on decomposition is controlled by a trade-off between the resultant moisture and temperature states. This trade-off is conditioned by the availability of fine roots near the surface, and it impacts the long-term storage and vertical distribution of carbon in the soil. HR also impacts the transport and uptake of ions from the soil. It reduces the leaching of nitrate considerably, and, therefore facilitates the uptake of nitrate by vegetation roots. Furthermore, the magnitude and patterns of the feedbacks induced by HR are also influenced by the presence of different plant species that coexist. These results suggest that the alteration of soil moisture by plants through associated processes such as HR can have considerable impact on the below-ground biogeochemical cycling of carbon and nitrogen.

  19. Anthropogenic impacts on the global water cycle - a multi model approach.

    NASA Astrophysics Data System (ADS)

    Ludwig, F.; haddeland, I.; Biemans, H.; Clark, D.; Fransen, W.; Voss, F.; Floerke, M.; Heinke, J.; Hagemann, S.; Hanasakki, N.; Gerten, D.; Kabat, P.

    2012-04-01

    Humans activities have a large impact on the global water cycle. Through the building of dams and irrigation schemes large amounts of water are diverted from river systems. Through the emission of greenhouse gases causing global warming, also the rainfall and evaporation patterns are changed across the globe. It is, however, still difficult to quantify current and future impacts on the global water cycle due to limited data availability, model imperfections and large uncertainties in climate change projections. To partly overcome these limitations we used a multi-model approach to study anthropogenic impacts on the global water cycle. Four different global hydrological models (H08, VIC, WaterGAP and LPJml) were forced with an historical climate dataset (Watch Forcing Data) and bias corrected output of three different global climate models (Echam, IPSL and CNRM) using two emission scenarios (A2 and B1). In addition the LPJml model was also run with two different land use change scenarios. Combining the water availability simulations with the water demand scenarios developed within the Watch project we also analyzed current and future water scarcity. The analyses show that current human impacts and on the water cycle are especially high in Central Asia, parts of Europe, the Southwestern US and the Murray-Darling Basin in Australia. The model comparison of agricultural water use and demand showed that the differences in total global agricultural demand and water use were relatively smaller than the differences in simulated water availability. All models showed agricultural water extractions are high in South and East Asia in particular in Northern India and Pakistan and in Northeast China. The most important spatial differences between the different models was observed for Northern China where H08 showed much higher water demands than VIC. Future analyses showed that climate change impacts on the global water cycle are potentially high especially in the semi-arid regions. Although there were considerable differences in the four hydrological models in general all models predicted the same direction of change. In conclusion the analyses showed that both under the B1 and the A2 scenarios the percentage of agricultural water demand than cannot be fulfilled by surface and ground-water will increase. Water shortages will be much higher under the A2 than under the B1 scenario. In conclusion using a multi model approach gives a more robust quantification of possible future anthropogenic impacts on the global water cycle.

  20. Intramolecular Proton Transfer Boosts Water Oxidation Catalyzed by a Ru Complex.

    PubMed

    Matheu, Roc; Ertem, Mehmed Z; Benet-Buchholz, Jordi; Coronado, Eugenio; Batista, Victor S; Sala, Xavier; Llobet, Antoni

    2015-08-26

    We introduce a new family of complexes with the general formula [Ru(n)(tda)(py)2](m+) (n = 2, m = 0, 1; n = 3, m = 1, 2(+); n = 4, m = 2, 3(2+)), with tda(2-) being [2,2':6',2″-terpyridine]-6,6″-dicarboxylate, including complex [Ru(IV)(OH)(tda-κ-N(3)O)(py)2](+), 4H(+), which we find to be an impressive water oxidation catalyst, formed by hydroxo coordination to 3(2+) under basic conditions. The complexes are synthesized, isolated, and thoroughly characterized by analytical, spectroscopic (UV-vis, nuclear magnetic resonance, electron paramagnetic resonance), computational, and electrochemical techniques (cyclic voltammetry, differential pulse voltammetry, coulometry), including solid-state monocrystal X-ray diffraction analysis. In oxidation state IV, the Ru center is seven-coordinated and diamagnetic, whereas in oxidation state II, the complex has an unbonded dangling carboxylate and is six-coordinated while still diamagnetic. With oxidation state III, the coordination number is halfway between the coordination of oxidation states II and IV. Species generated in situ have also been characterized by spectroscopic, computational, and electrochemical techniques, together with the related species derived from a different degree of protonation and oxidation states. 4H(+) can be generated potentiometrically, or voltammetrically, from 3(2+), and both coexist in solution. While complex 3(2+) is not catalytically active, the catalytic performance of complex 4H(+) is characterized by the foot of the wave analysis, giving an impressive turnover frequency record of 8000 s(-1) at pH 7.0 and 50 000 s(-1) at pH 10.0. Density functional theory calculations provide a complete description of the water oxidation catalytic cycle of 4H(+), manifesting the key functional role of the dangling carboxylate in lowering the activation free energies that lead to O-O bond formation. PMID:26226390

  1. Intramolecular proton transfer boosts water oxidation catalyzed by a Ru complex

    DOE PAGESBeta

    Matheu, Roc; Ertem, Mehmed Z.; Benet-Buchholz, J.; Coronado, Eugenio; Batista, Victor S.; Sala, Xavier; Llobet, Antoni

    2015-07-30

    We introduce a new family of complexes with the general formula [Run(tda)(py)2]m+ (n = 2, m = 0, 1; n = 3, m = 1, 2+; n = 4, m = 2, 32+), with tda2– being [2,2':6',2"-terpyridine]-6,6"-dicarboxylate, including complex [RuIV(OH)(tda-κ-N3O)(py)2]+, 4H+, which we find to be an impressive water oxidation catalyst, formed by hydroxo coordination to 32+ under basic conditions. The complexes are synthesized, isolated, and thoroughly characterized by analytical, spectroscopic (UV–vis, nuclear magnetic resonance, electron paramagnetic resonance), computational, and electrochemical techniques (cyclic voltammetry, differential pulse voltammetry, coulometry), including solid-state monocrystal X-ray diffraction analysis. In oxidation state IV, the Rumore » center is seven-coordinated and diamagnetic, whereas in oxidation state II, the complex has an unbonded dangling carboxylate and is six-coordinated while still diamagnetic. With oxidation state III, the coordination number is halfway between the coordination of oxidation states II and IV. Species generated in situ have also been characterized by spectroscopic, computational, and electrochemical techniques, together with the related species derived from a different degree of protonation and oxidation states. 4H+ can be generated potentiometrically, or voltammetrically, from 32+, and both coexist in solution. While complex 32+ is not catalytically active, the catalytic performance of complex 4H+ is characterized by the foot of the wave analysis, giving an impressive turnover frequency record of 8000 s–1 at pH 7.0 and 50,000 s–1 at pH 10.0. Density functional theory calculations provide a complete description of the water oxidation catalytic cycle of 4H+, manifesting the key functional role of the dangling carboxylate in lowering the activation free energies that lead to O–O bond formation.« less

  2. Development of a Life Cycle Inventory of Water Consumption Associated with the Production of Transportation Fuels

    SciTech Connect

    Lampert, David J.; Cai, Hao; Wang, Zhichao; Keisman, Jennifer; Wu, May; Han, Jeongwoo; Dunn, Jennifer; Sullivan, John L.; Elgowainy, Amgad; Wang, Michael; Keisman, Jennifer

    2015-10-01

    The production of all forms of energy consumes water. To meet increased energy demands, it is essential to quantify the amount of water consumed in the production of different forms of energy. By analyzing the water consumed in different technologies, it is possible to identify areas for improvement in water conservation and reduce water stress in energy-producing regions. The transportation sector is a major consumer of energy in the United States. Because of the relationships between water and energy, the sustainability of transportation is tied to management of water resources. Assessment of water consumption throughout the life cycle of a fuel is necessary to understand its water resource implications. To perform a comparative life cycle assessment of transportation fuels, it is necessary first to develop an inventory of the water consumed in each process in each production supply chain. The Greenhouse Gases, Regulated Emissions, and Energy Use in Transportation (GREET) model is an analytical tool that can used to estimate the full life-cycle environmental impacts of various transportation fuel pathways from wells to wheels. GREET is currently being expanded to include water consumption as a sustainability metric. The purpose of this report was to document data sources and methodologies to estimate water consumption factors (WCF) for the various transportation fuel pathways in GREET. WCFs reflect the quantity of freshwater directly consumed per unit production for various production processes in GREET. These factors do not include consumption of precipitation or low-quality water (e.g., seawater) and reflect only water that is consumed (i.e., not returned to the source from which it was withdrawn). The data in the report can be combined with GREET to compare the life cycle water consumption for different transportation fuels.

  3. Paleoecology of cool-water, subtidal cycles in mid-cenozoic limestones, Eucla Platform, Southern Australia

    SciTech Connect

    James, N.P.; Bone, Y.

    1994-10-01

    The open-shelf, subtidal, bryozoan-rich Abrakurrie Limestone beneath the Nullarbor Plain (Eucla Platform) is cyclic at the meter-scale. Best developed cycles are asymmetric and comprise three distinct parts with a capping hardground. The basal part (A) is a thin, coarse, grainstone or rudstone that is rich in robust bryosoan and epifaunal echinoid fragments and pecten bivalves, reflecting growth and accumulation in generally high energy, hard bottom environments. The middle part (B), intepreted as a low-energy, sub-swellbase accumulation, is a burrowed to planar cross-laminated fine grainstone or packstone with a low diversity, delicate-branching bryozoan assemblage and little else except scattered infaunal echinoids and pectens. The upper part (C) is a burrowed, abundantly fossilferous (bryozoan, bivalve, echinoid) rudstone or floatstone. Upward increases in the numbers and diversity of Mg-calcite and aragonitic cheilostome bryozoans (especially erect rigid, flat robust branching and nodular/arborescent types), gastropods, infaunal bivalves, and infaunal echinoids points to a high-energy environment. Sediments at the top of C are variably cemented by inclusion-rich marine cement (now calcite) that formed a hardground which was subsequently physically and biologically eroded and stained by iron oxides during a period of non-deposition. Sediments from the next overlying cycle succeed cements in uppermost intergranular pores and fill open crustacean burrows. Variably developed cyclicity is interpreted, on the basis of comparable Holocene cool-water shelf sediments, to reflect deposition in generally sub-photic environments that ranged from just below swell base (B) upwards towards the zone of wave abrasion (A and C). Hardgrounds (H) formed when the seafloor was within the zone of wave abrasion. Shallowing and deepening of these critical interfaces was controlled by fluctuating sea level and/or climatic change. 55 refs., 12 figs.

  4. Ferrates: greener oxidants with multimodal action in water treatment technologies.

    PubMed

    Sharma, Virender K; Zboril, Radek; Varma, Rajender S

    2015-02-17

    CONSPECTUS: One of the biggest challenges for humanity in the 21st century is easy access to purified and potable water. The presence of pathogens and toxins in water causes more than two million deaths annually, mostly among children under the age of five. Identifying and deploying effective and sustainable water treatment technologies is critical to meet the urgent need for clean water globally. Among the various agents used in the purification and treatment of water, iron-based materials have garnered particular attention in view of their special attributes such as their earth-abundant and environmentally friendly nature. In recent years, higher-valent tetraoxy iron(VI) (Fe(VI)O4(2-), Fe(VI)), commonly termed, ferrate, is being explored for a broad portfolio of applications, including a greener oxidant in synthetic organic transformations, a water oxidation catalyst, and an efficient agent for abatement of pollutants in water. The use of Fe(VI) as an oxidant/disinfectant and further utilization of the ensuing iron(III) oxides/hydroxide as coagulants are other additional attributes of ferrate for water treatment. This multimodal action and environmentally benign character of Fe(VI) are key advantages over other commonly used oxidants (e.g., chlorine, chlorine dioxide, permanganate, hydrogen peroxide, and ozone). This Account discusses current state-of-the-art applications of Fe(VI) and the associated unique chemistry of these high-valence states of iron. The main focus centers around the description and salient properties of ferrate species involving various electron transfer and oxygen-atom transfer pathways in terms of presently accepted mechanisms. The mechanisms derive the number of electron equivalents per Fe(VI) (i.e., oxidation capacity) in treating various contaminants. The role of pH in the kinetics of the reactions and in determining the removal efficiency of pollutants is highlighted; the rates of competing reactions of Fe(VI) with itself, water, and the contaminants, which are highly pH dependent, determine the optimum pH range of maximum efficacy. The main emphasis of this account is placed on cases where various modes of ferrate action are utilized, including the treatment of nitrogen- and sulfur-containing waste products, antibiotics, viruses, bacteria, arsenic, and heavy metals. For example, the oxidative degradation of N- and S-bearing contaminants by Fe(VI) yields either Fe(II) or Fe(III) via the intermediacy of Fe(IV) and Fe(V) species, respectively (e.g., Fe(VI) → Fe(IV) → Fe(II) and Fe(VI) → Fe(V) → Fe(III)). Oxidative transformations of antibiotics such as trimethoprim by Fe(VI) generate products with no residual antibiotic activity. Disinfection and inactivation of bacteria and viruses can easily be achieved by Fe(VI). Advanced applications involve the use of ferrate for the degradation of cyanobacteria and microcystin originating from algal blooms and for covalently embedding arsenic and heavy metals into the structure of formed magnetic iron(III) oxides, therefore preventing their leaching. Applications of state-of-the-art analytical techniques, namely, in situ Mössbauer spectroscopy, rapid-freeze electron paramagnetic resonance, nuclear forward scattering of synchrotron radiation, and mass spectrometry will enhance the mechanistic understanding of ferrate species. This will make it possible to unlock the true potential of ferrates for degrading emerging toxins and pollutants, and in the sustainable production and use of nanomaterials in an energy-conserving environment. PMID:25668700

  5. The role of water in resistive switching in graphene oxide

    SciTech Connect

    Rogala, M.; Kowalczyk, P. J.; Dabrowski, P.; Wlasny, I.; Kozlowski, W.; Busiakiewicz, A.; Pawlowski, S.; Dobinski, G.; Smolny, M.; Klusek, Z.; Lipinska, L.; Kozinski, R.; Librant, K.; Jagiello, J.; Grodecki, K.; Baranowski, J. M.; Szot, K.

    2015-06-29

    The resistive switching processes are investigated at the nano-scale in graphene oxide. The modification of the material resistivity is driven by the electrical stimulation with the tip of atomic force microscope. The presence of water in the atmosphere surrounding graphene oxide is found to be a necessary condition for the occurrence of the switching effect. In consequence, the switching is related to an electrochemical reduction. Presented results suggest that by changing the humidity level the in-plane resolution of data storage process can be controlled. These findings are essential when discussing the concept of graphene based resistive random access memories.

  6. The role of water in resistive switching in graphene oxide

    NASA Astrophysics Data System (ADS)

    Rogala, M.; Kowalczyk, P. J.; Dabrowski, P.; Wlasny, I.; Kozlowski, W.; Busiakiewicz, A.; Pawlowski, S.; Dobinski, G.; Smolny, M.; Karaduman, I.; Lipinska, L.; Kozinski, R.; Librant, K.; Jagiello, J.; Grodecki, K.; Baranowski, J. M.; Szot, K.; Klusek, Z.

    2015-06-01

    The resistive switching processes are investigated at the nano-scale in graphene oxide. The modification of the material resistivity is driven by the electrical stimulation with the tip of atomic force microscope. The presence of water in the atmosphere surrounding graphene oxide is found to be a necessary condition for the occurrence of the switching effect. In consequence, the switching is related to an electrochemical reduction. Presented results suggest that by changing the humidity level the in-plane resolution of data storage process can be controlled. These findings are essential when discussing the concept of graphene based resistive random access memories.

  7. Paralinear Oxidation of CVD SiC in Water Vapor

    NASA Technical Reports Server (NTRS)

    Opila, Elizabeth J.; Hann, Raiford E., Jr.

    1997-01-01

    The oxidation kinetics of CVD SiC were monitored by thermogravimetric analysis (TGA) in a 50% H2O/50% O2 gas mixture flowing at 4.4 cm/s for temperatures between 1200 and 1400 C. Paralinear weight change kinetics were observed as the water vapor oxidized the SiC and simultaneously volatilized the silica scale. The long-term degradation rate of SiC is determined by the volatility of the silica scale. Rapid SiC surface recession rates were estimated from these data for actual aircraft engine combustor conditions.

  8. Oxide-carbon composites and porous oxides prepared via water-swellable polymer networks

    SciTech Connect

    Ruckenstein, E.; Hong, L.

    1996-02-01

    Water-swellable polymer networks (WSPN) were employed as media for lodging metal nitrate salts or partially hydrolyzed tetraethyl orthosilicate (TEOS), which are precursors for inorganic oxides. The loading achieved either via the polymerization of a suitable monomer and a cross-linker in an aqueous solution of the precursor or, in the case of TEOS, via the simultaneous polymerization of both monomers. The pyrolysis of the precursor loaded network under N{sub 2} flow generated interpenetrating networks of carbon and metal oxide. The combustion of the composite in air removed the carbon network and a porous metal oxide framework remained. On the basis of the methodology, a coating layer of C-SiO{sub 2} composite was generated on a carbon-fiber, and a porous powders of SiO{sub 2}, ZrO{sub 2}, MgO, and CuO-ZnO-Al{sub 2}O{sub 3} oxide(s) were synthesized. It was found that the specific surface area of the oxides is affected by the nature of the WSPN. Two methodologies which lead to particles were developed. In one of them, sedimentation polymerization, large particles of about 1 mm size were obtained. In the other one, which starts from an emulsion of a water solution in an organic liquid (toluene, cyclohexane), micrometer size particles were prepared. 16 refs., 10 figs., 6 tabs.

  9. Transtion metal oxides for solar water splitting devices

    NASA Astrophysics Data System (ADS)

    Smith, Adam M.

    Although the terrestrial flux of solar energy is enough to support human endeavors, storage of solar energy remains a significant challenge to large-scale implementation of solar energy production. One route to energy storage involves the capture and conversion of sunlight to chemical species such as molecular hydrogen and oxygen via water splitting devices. The oxygen evolution half-reaction particularly suffers from large kinetic overpotentials. Additionally, a photoactive material that exhibits stability in oxidizing conditions present during oxygen evolution represents a unique challenge for devices. These concerns can be potentially addressed with a metal oxide photoanode coupled with efficient water oxidation electrocatalysts. Despite decades of research, structure-composition to property relationships are still needed for the design of metal oxide oxygen evolution materials. This dissertation investigates transition metal oxide materials for the oxygen evolution portion of water splitting devices. Chapter I introduces key challenges for solar driven water splitting. Chapter II elucidates the growth mechanism of tungsten oxide (WOX) nanowires (NWs), a proposed photoanode material for water splitting. Key findings include (1) a planar defect-driven pseudo-one-dimensional growth mechanism and (2) morphological control through the supersaturation of vapor precursors. Result 1 is significant as it illustrates that common vapor-phase syntheses of WOX NWs depend on the formation of planar defects through NWs, which necessitates reconsideration of WOX as a photoanode. Chapter III presents work towards (1) single crystal WOX synthesis and characterization and (2) WOX NW device fabrication. Chapter IV makes use of the key result that WOX NWs are defect rich and therefore conductive in order to utilize them as a catalyst scaffold for oxygen evolution in acidic media. Work towards utilizing NW scaffolds include key results such as stability under anodic potentials and strongly acidic conditions used for oxygen evolution. Chapter V includes work characterizing nickel oxide/oxyhydroxide oxygen evolution catalysts at near-neutral pH. Key findings include (1) previous reports of anodic conditioning resulting in greater catalytic activity are actually due to incidental incorporation of iron impurities from solution and (2) through intentional iron incorporation via electrochemical co-deposition, catalytic activity is increased ~50-fold over Fe-free catalysts. This dissertation contains previously published coauthored material.

  10. An evaluation of China's water cycle in the MetUM-GC2 coupled model

    NASA Astrophysics Data System (ADS)

    Rodriguez, Jose; Marzin, Charline

    2015-04-01

    There is a general consensus in climate projections that the global hydrological cycle is likely to experience significant changes in the future, in response to increased concentrations of greenhouse gases. At the regional scale, model simulations show large variations in the predictions of changes in the components of the water cycle. Increasing confidence in regional prediction of the water cycle is at the top of the NWP and climate research agenda, requiring a comprehensive evaluation of the physical processes which may play an important role. Here we present preliminary results of an evaluation of the capacity of the MetUM-GC2 coupled model to reproduce the characteristics of the water cycle in the region of China. Using water budget techniques in the atmospheric and terrestrial branches we test the water cycle components and the model's ability to replicate the climatological annual cycle and its interannual variability. Recent drought and flood events are evaluated and various metrics are employed to compare the role played by the atmospheric general circulation including the boreal summer and winter monsoon regimes and soil moisture feedback in model and observations.

  11. An electrochemical approach to graphene oxide coated sulfur for long cycle life

    NASA Astrophysics Data System (ADS)

    Moon, Joonhee; Park, Jungjin; Jeon, Cheolho; Lee, Jouhahn; Jo, Insu; Yu, Seung-Ho; Cho, Sung-Pyo; Sung, Yung-Eun; Hong, Byung Hee

    2015-07-01

    Owing to the possibilities of achieving high theoretical energy density and gravimetric capacity, sulfur has been considered as a promising cathode material for rechargeable lithium batteries. However, sulfur shows rapid capacity fading due to the irreversible loss of soluble polysulfides and the decrease in active sites needed for conducting agents. Furthermore, the low electrical conductivity of sulfur hampers the full utilization of active materials. Here we report that graphene oxide coated sulfur composites (GO-S/CB) exhibit improved electrochemical stability as well as enhanced rate performance, evidenced by various electrochemical analyses. The cyclic voltammetry and the galvanostatic cycling analysis revealed that the GO plays key roles in homogenizing the nanocomposite structures of the electrodes, in improving the electrochemical contact, and in minimizing the loss of soluble polysulfide intermediates. An electrochemical impedance spectroscopy analysis also confirms the enhanced structural stability of the GO-S/CB composites after battery operation. As a result, the GO-S/CB exhibited excellent cycle stability and specific capacity as high as ~723.7 mA h g-1 even after 100 cycles at 0.5 C.Owing to the possibilities of achieving high theoretical energy density and gravimetric capacity, sulfur has been considered as a promising cathode material for rechargeable lithium batteries. However, sulfur shows rapid capacity fading due to the irreversible loss of soluble polysulfides and the decrease in active sites needed for conducting agents. Furthermore, the low electrical conductivity of sulfur hampers the full utilization of active materials. Here we report that graphene oxide coated sulfur composites (GO-S/CB) exhibit improved electrochemical stability as well as enhanced rate performance, evidenced by various electrochemical analyses. The cyclic voltammetry and the galvanostatic cycling analysis revealed that the GO plays key roles in homogenizing the nanocomposite structures of the electrodes, in improving the electrochemical contact, and in minimizing the loss of soluble polysulfide intermediates. An electrochemical impedance spectroscopy analysis also confirms the enhanced structural stability of the GO-S/CB composites after battery operation. As a result, the GO-S/CB exhibited excellent cycle stability and specific capacity as high as ~723.7 mA h g-1 even after 100 cycles at 0.5 C. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr01951f

  12. Earth Science (A Process Approach), Section 1: The Water Cycle.

    ERIC Educational Resources Information Center

    Campbell, K. C.; And Others

    Included is a collection of earth science laboratory activities, which may provide the junior or senior high school science teacher with ideas for activities in his program. The included 48 experiments are grouped into these areas: properties of matter; evaporation; atmospheric moisture and condensation; precipitation; moving water, subsurface…

  13. Emerging Contaminants in the Drinking Water Cycle - MCEARD

    EPA Science Inventory

    In the past decade, the scientific community and general public have become increasingly aware of the potential for the presence of unregulated, and generally unmonitored contaminants, found at low concentrations (sub-?g/L) in surface, ground and drinking water. The most common...

  14. EMERGING CONTAMINANTS IN THE WATER CYCLE: FATE AND TRANSPORT

    EPA Science Inventory

    In the past decade, the scientific community and general public have become increasingly aware of the potential for the presence of unregulated, and generally unmonitored contaminants, found at low concentrations in surface, ground and drinking water. The most common pathway for...

  15. Emerging Contaminants in the Drinking Water Cycle - MCEARD

    EPA Science Inventory

    In the past decade, the scientific community and general public have become increasingly aware of the potential for the presence of unregulated, and generally unmonitored contaminants, found at low concentrations (sub-g/L) in surface, ground and drinking water. The most common...

  16. MULTIPLE SPACEBORNE WATER CYCLE OBSERVATIONS WOULD AID MODELING

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Land data assimilation systems (LDAS) are designed to provide continental-scale estimates of surface moisture and temperature states - and water and energy flux exchanges with the atmosphere - by propagating land surface models using observations of micrometeorological forcing data (e.g. surface pre...

  17. Stability of Supported Platinum Sulfuric Acid Decomposition Catalysts for use in Thermochemical Water Splitting Cycles

    SciTech Connect

    Daniel M. Ginosar; Lucia M. Petkovic; Anne W. Glenn; Kyle C. Burch

    2007-03-01

    The activity and stability of several metal oxide supported platinum catalysts were explored for the sulfuric acid decomposition reaction. The acid decomposition reaction is common to several sulfur based thermochemical water splitting cycles. Reactions were carried out using a feed of concentrated liquid sulfuric acid (96 wt%) at atmospheric pressure at temperatures between 800 and 850 °C and a weight hour space velocity of 52 g acid/g catalyst/hr. Reactions were run at these high space velocities such that variations in kinetics were not masked by surplus catalyst. The influence of exposure to reaction conditions was explored for three catalysts; 0.1-0.2 wt% Pt supported on alumina, zirconia and titania. The higher surface area Pt/Al2O3 and Pt/ZrO2 catalysts were found to have the highest activity but deactivated rapidly. A low surface area Pt/TiO2 catalyst was found to have good stability in short term tests, but slowly lost activity for over 200 hours of continuous operation.

  18. Improving the performance of ammonia-water absorption cycles using salt additives and membranes

    SciTech Connect

    Ibrahim, O.M.; Barnett, S.M.; Balamuru, V.G.

    1997-12-31

    This paper proposes a new design of an ammonia-water absorption refrigeration cycle for low-temperature heat sources such as solar energy and waste heat. The proposed cycle uses a salt additive to shift the chemical equilibrium toward more effective separation of ammonia molecules from aqueous solution (i.e., salting out). Since salt additives can affect all aspects of the absorption cycle, membranes have been chosen to control the flow of ions in the cycle and limit their effects to the generation side. This paper describes an absorption cycle that uses membrane separation processes, such as reverse osmosis, dialysis, and electrodialysis. To optimize the performance of the cycle, however, the membranes and salts must be carefully chosen.

  19. Carbon and Water Cycles in a New Zealand Peat Bog

    NASA Astrophysics Data System (ADS)

    Campbell, D.; Smith, J.

    2001-12-01

    Peat soils represent globally significant stores of carbon and an understanding of carbon exchange processes between peat wetland ecosystems and the atmosphere is important for understanding the effects of, and impacts upon, global climate change. Eddy covariance measurements of CO2, water vapour and energy fluxes were made during 1999 and 2000 at a remnant oligotrophic raised peat bog in North Island, New Zealand. The bog's hydrology has been modified by drainage of surrounding agricultural land, so that the water table is relatively deep compared to that of unmodified bogs in the region. Vegetation is dominated by two indigenous species of rush-like vascular plants belonging to the Southern hemisphere family Restionaceae. Maximum daytime CO2 fluxes were commonly -9 {μ }mol m-2 s-1 and averaged -1.3 {μ }mol m-2 s-1 over the 24-hour period in summertime. The ecosystem was a sink of atmospheric carbon for most of the year, with wintertime characterised by 12--15 weeks of carbon neutrality or slight carbon loss. Average carbon uptake by the ecosystem was 196 gC m-2 yr-1 for the two-year period. Modelling suggests that the key factor determining inter-annual variability of the carbon budget is seasonal soil temperature, whereas ecosystem respiration is relatively insensitive to the position of the lowered water table. The bog vegetation acts as a major control over water vapour loss and energy partitioning favors sensible heat production with mean summertime Bowen ratios of approximately 2.0. Water use efficiency was highest in the morning, indicating that the vegetation maximizes CO2 assimilation while the saturation vapour pressure deficit and transpiration rates are low. The dense canopy structure also restricts penetration of solar radiation to the peat surface, which minimizes evaporation and soil respiration.

  20. Open Cycle OTEC System with Fresh Water Product

    NASA Astrophysics Data System (ADS)

    Amano, Masatugu; Tanaka, Tadayosi

    An open-cycle ocean thermal energy conversion (OC-OTEC) system is one of energy conversion methods to generate electricity from ocean thermal energy. For OC-OTEC system, steam evaporated from the surface seawater due to flash evaporation drives the turbine. At that time, dissolved gas such as air is introduced into the low-pressure system (OC-OTEC system) as the non-condensable gas, which degrades the performance of condensation heat transfer. In this paper, a small scale OC-OTEC experimental unit experimentally investigates the effect of non-condensable gas on the heat transfer performance in a condenser. The experimental results are discussed in comparison with theoretical estimation by Sparrow-Lin method. It is shown that the condensation is occupied by heat and mass transfer near a condensation surface and that the condensation efficiency is affected by exhaust quantity of non-condensable gas at relative high concentration ratio of condensable gas.

  1. Pt/TiO2 (Rutile) Catalysts for Sulfuric Acid Decomposition in Sulfur-Based Thermochemical Water-Splitting Cycles

    SciTech Connect

    L. M. Petkovic; D. M. Ginosar; H. W. Rollins; K. C. Burch; P. J. Pinhero; H. H. Farrell

    2008-04-01

    Thermochemical cycles consist of a series of chemical reactions to produce hydrogen from water at lower temperatures than by direct thermal decomposition. All the sulfur-based cycles for water splitting employ the sulfuric acid decomposition reaction. This work reports the studies performed on platinum supported on titania (rutile) catalysts to investigate the causes of catalyst deactivation under sulfuric acid decomposition reaction conditions. Samples of 1 wt% Pt/TiO2 (rutile) catalysts were submitted to flowing concentrated sulfuric acid at 1123 K and atmospheric pressure for different times on stream (TOS) between 0 and 548 h. Post-operation analyses of the spent catalyst samples showed that Pt oxidation and sintering occurred under reaction conditions and some Pt was lost by volatilization. Pt loss rate was higher at initial times but total loss appeared to be independent of the gaseous environment. Catalyst activity showed an initial decrease that lasted for about 66 h, followed by a slight recovery of activity between 66 and 102 h TOS, and a period of slower deactivation after 102 h TOS. Catalyst sulfation did not seem to be detrimental to catalyst activity and the activity profile suggested that a complex dynamical situation involving platinum sintering, volatilization, and oxidation, along with TiO2 morphological changes affected catalyst activity in a non-monotonic way.

  2. Photochemical route for accessing amorphous metal oxide materials for water oxidation catalysis.

    PubMed

    Smith, Rodney D L; Prévot, Mathieu S; Fagan, Randal D; Zhang, Zhipan; Sedach, Pavel A; Siu, Man Kit Jack; Trudel, Simon; Berlinguette, Curtis P

    2013-04-01

    Large-scale electrolysis of water for hydrogen generation requires better catalysts to lower the kinetic barriers associated with the oxygen evolution reaction (OER). Although most OER catalysts are based on crystalline mixed-metal oxides, high activities can also be achieved with amorphous phases. Methods for producing amorphous materials, however, are not typically amenable to mixed-metal compositions. We demonstrate that a low-temperature process, photochemical metal-organic deposition, can produce amorphous (mixed) metal oxide films for OER catalysis. The films contain a homogeneous distribution of metals with compositions that can be accurately controlled. The catalytic properties of amorphous iron oxide prepared with this technique are superior to those of hematite, whereas the catalytic properties of a-Fe(100-y-z)Co(y)Ni(z)O(x) are comparable to those of noble metal oxide catalysts currently used in commercial electrolyzers. PMID:23539180

  3. [Nitrogen and water cycling of typical cropland in the North China Plain].

    PubMed

    Pei, Hong-wei; Shen, Yan-jun; Liu, Chang-ming

    2015-01-01

    Intensive fertilization and irrigation associated increasing grain production has led to serious groundwater depletion and soil/water pollution in the North China Plain (NCP). Intensive agriculture changes the initial mass and energy balance, and also results in huge risks to the water/soil resources and food security regionally. Based on the research reports on the nitrogen cycle and water cycle in typical cropland (winter wheat and summer corn) in the NCP during the past 20 years, and the meteorological data, field experiments and surveys, we calculated the nitrogen cycle and water-cycle for this typical cropland. Annual total nitrogen input were 632 kg N . hm-2, including 523 kg N . hm-2 from commercial fertilizer, 74 kg N . hm-2 from manure, 23 kg N . hm-2 from atmosphere, and 12 kg N . hm-2 from irrigation. All of annual outputs summed to 532 kg N . hm-2 including 289 kg N . hm-2 for crop, 77 kg N . hm-2 staying in soil profile, leaching 104 kg N . hm-2, 52 kg N . hm-2 for ammonia volatilization, 10 kg N . hm-2 loss in nitrification and denitrification. Uncertainties of the individual cases and the summary process lead to the unbalance of nitrogen. For the dominant parts of the field water cycle, annual precipitation was 557 mm, irrigation was 340 mm, while 762 mm was for evapotranspiration and 135 mm was for deep percolation. Considering uncertainties in the nitrogen and water cycles, coupled experiments based on multi-disciplines would be useful for understanding mechanisms for nitrogen and water transfer processes in the soil-plant-atmosphere-continuum (SPAC) , and the interaction between nitrogen and water, as well as determining the critical threshold values for sustainability of soil and water resources in the NCP. PMID:25985681

  4. Advances in Global Water Cycle Science Made Possible by Global Precipitation Mission (GPM)

    NASA Technical Reports Server (NTRS)

    Smith, Eric A.; Starr, David OC. (Technical Monitor)

    2001-01-01

    Within this decade the internationally sponsored Global Precipitation Mission (GPM) will take an important step in creating a global precipitation observing system from space. One perspective for understanding the nature of GPM is that it will be a hierarchical system of datastreams from very high caliber combined dual frequency radar/passive microwave (PMW) rain-radiometer retrievals, to high caliber PMW rain-radiometer only retrievals, and on to blends of the former datastreams with other less-high caliber PMW-based and IR-based rain retrievals. Within the context of NASA's role in global water cycle science and its own Global Water & Energy Cycle (GWEC) program, GPM is the centerpiece mission for improving our understanding of the global water cycle from a space-based measurement perspective. One of the salient problems within our current understanding of the global water and energy cycle is determining whether a change in the rate of the water cycle is accompanying changes in global temperature. As there are a number of ways in which to define a rate-change of the global water cycle, it is not entirely clear as to what constitutes such a determination, This paper presents an overview of the Global Precipitation Mission and how its datasets can be used in a set of quantitative tests within the framework of the oceanic and continental water budget equations to determine comprehensively whether substantive rate changes do accompany perturbations in global temperatures and how such rate changes manifest themselves in both water storage and water flux transport processes.

  5. Seasonal and diurnal cycles of liquid water in snow

    NASA Astrophysics Data System (ADS)

    Heilig, Achim; Mitterer, Christoph; Schmid, Lino; Marshall, Hans-Peter; Schweizer, Jürg; Okorn, Robert; Eisen, Olaf

    2014-05-01

    The combination of upward-looking ground-penetrating radar (upGPR), automatic weather station (AWS) and lysimeter allows for continuous monitoring of bulk volumetric liquid water content (θw) within the snowpack and direct comparison with measurements of the corresponding outflow. The AWS data can be utilized to calculate energy fluxes between atmosphere and snowpack at the location of the station. While combining all data sets, we were able to quantify diurnal and seasonal changes in residual water content and relate modeled energy fluxes to water outflow. Since upGPR is a non-destructive monitoring technique, it is possible to continuously observe the snowpack and results are not biased through spatial variability of pit locations. Data analysis conducted for three consecutive years at the flat test site Weissfluhjoch, Davos, Switzerland showed that diurnal θw variations never exceeded 2%. Without regard to days with new snow accumulation or refreezing, the diurnal patterns in θw were very similar, with always daily peaks in the late afternoon (at about 17:00h) at the site. Although θw values varied during a day up to 2%, the gradients during the season were very small. In 2012, for the whole melting period (>100 days), increases in θw from day to day were 0.4% liquid water content on average. After the snowpack has become isothermal, positive energy fluxes result in outflow and increase the residual water content (θr). Our data showed that as long as potential melt - calculated for the determined energy fluxes - was exceeding measured outflow, θr values were increasing but only until reaching a certain threshold. For all three years, the thresholds were similar at about θr=4-5%. Only shortly before full ablation, these thresholds were surpassed. In two sloped test sites (about 22 degree slope angle) in Boise, Idaho, USA and above Davos, we installed upGPR systems as well. AWS data and energy-flux calculations for both slopes were extrapolated for the respective aspect and slope angle. Our data showed that snow stratigraphy highly influences θr in slopes. As long as e.g. crusts ponded the vertical water flow, residual θw of the whole snowpack was fairly low (

  6. Exploring water cycle dynamics through sampling multitude stable water isotope pools in a small developed landscape of Germany

    NASA Astrophysics Data System (ADS)

    Orlowski, N.; Kraft, P.; Breuer, L.

    2015-02-01

    Conducting a dual stable water isotope (δ2H and δ18O) study in the developed landscape of the Schwingbach catchment (Germany) helped to unravel connectivity and disconnectivity between the different water cycle components. The two-year weekly to biweekly measurements of precipitation, stream, and groundwater isotopes revealed that surface and groundwater are decoupled from the annual precipitation cycle but showed bidirectional interactions between each other. Seasonal variations based on temperature effects were observed in the precipitation signal but neither reflected in stream nor in groundwater isotopic signatures. Apparently, snowmelt played a fundamental role for groundwater recharge explaining the observed differences to precipitation δ-values. A spatially distributed snapshot sampling of soil water isotopes in two soil depths at 52 sampling points across different land uses (arable land, forest, and grassland) revealed that top soil isotopic signatures were similar to the precipitation input signal. Preferential water flow paths occurred under forested soils explaining the isotopic similarities between top and subsoil isotopic signatures. Due to human-impacted agricultural land use (tilling and compression) of arable and grassland soils, water delivery to the deeper soil layers was reduced, resulting in significant different isotopic signatures. However, the land use influence smoothed out with depth and soil water approached groundwater δ-values. Seasonally tracing stable water isotopes through soil profiles showed that the influence of new percolating soil water decreased with depth as no remarkable seasonality in soil isotopic signatures was obvious at depth > 0.9 m and constant values were observed through space and time. Little variation in individual isotope time series of stream and groundwater restricted the use of classical isotope hydrology techniques e.g. mean transit time estimation or hydrograph separation. Still, tracing stable water isotopes through the water cycle was valuable for determining interactions between different water cycle components and gaining catchment specific process understanding in a developed, human-impacted landscape.

  7. Economic Input-Output Life Cycle Assessment of Water Reuse Strategies in Residential Buildings

    EPA Science Inventory

    This paper evaluates the environmental sustainability and economic feasibility of four water reuse designs through economic input-output life cycle assessments (EIO-LCA) and benefit/cost analyses. The water reuse designs include: 1. Simple Greywater Reuse System for Landscape Ir...

  8. SHORTER MENSTRUAL CYCLES ASSOCIATED WITH CHLORINATION BY-PRODUCTS IN DRINKING WATER

    EPA Science Inventory

    Shorter Menstrual Cycles Associated with Chlorination by-Products in Drinking Water.
    Gayle Windham, Kirsten Waller, Meredith Anderson, Laura Fenster, Pauline Mendola, Shanna Swan. California Department of Health Services.

    In previous studies of tap water consumption we...

  9. Thermochemical hydrogen production via a cycle using barium and sulfur - Reaction between barium sulfide and water

    NASA Technical Reports Server (NTRS)

    Ota, K.; Conger, W. L.

    1977-01-01

    The reaction between barium sulfide and water, a reaction found in several sulfur based thermochemical cycles, was investigated kinetically at 653-866 C. Gaseous products were hydrogen and hydrogen sulfide. The rate determining step for hydrogen formation was a surface reaction between barium sulfide and water. An expression was derived for the rate of hydrogen formation.

  10. Water-induced thermogenesis and fat oxidation: a reassessment

    PubMed Central

    Charrière, N; Miles-Chan, J L; Montani, J-P; Dulloo, A G

    2015-01-01

    Background/Objectives: Drinking large amounts of water is often recommended for weight control. Whether water intake stimulates energy and fat metabolism is, however, controversial with some studies reporting that drinking half a litre or more of water increases resting energy expenditure (REE) by 10–30% and decreases respiratory quotient (RQ), whereas others report no significant changes in REE or RQ. The aim here was to reassess the concept of water-induced thermogenesis and fat oxidation in humans, with particular focus on interindividual variability in REE and RQ responses, comparison with a time-control Sham drink, and on the potential impact of gender, body composition and abdominal adiposity. Subjects/Methods: REE and RQ were measured in healthy young adults (n=27; body mass index range: 18.5–33.9 kg m−2), by ventilated hood indirect calorimetry for at least 30 min before and 130 min after ingesting 500 ml of purified (distilled) water at 21–22 °C or after Sham drinking, in a randomized cross-over design. Body composition and abdominal fat were assessed by bioimpedance techniques. Results: Drinking 500 ml of distilled water led to marginal increases in REE (<3% above baseline), independently of gender, but which were not significantly different from Sham drinking. RQ was found to fall after the water drink, independently of gender, but it also diminished to a similar extent in response to sham drinking. Interindividual variability in REE and RQ responses was not associated with body fatness, central adiposity or fat-free mass. Conclusions: This study conducted in young men and women varying widely in adiposity, comparing the ingestion of distilled water to Sham drinking, suggests that ingestion of purified water per se does not result in the stimulation of thermogenesis or fat oxidation. PMID:26690288

  11. The catalytic role of water in CO oxidation

    NASA Astrophysics Data System (ADS)

    Gong, Xue-Qing; Hu, P.; Raval, R.

    2003-09-01

    Water, one of the most popular species in our planet, can play a catalytic role in many reactions, including reactions in heterogeneous catalysis. In a recent experimental work, Bergeld, Kasemo, and Chakarov demonstrated that water is able to promote CO oxidation under low temperatures (˜200 K). In this study, we choose CO oxidation on Pt(111) in the presence of water as a model system to address the catalytic role of water for surface reactions in general using density functional theory. Many elementary steps possibly involved in the CO oxidation on Pt(111) at low temperatures have been investigated. We find the following. First, in the presence of water, the CO oxidation barrier is reduced to 0.33 eV (without water the barrier is 0.80 eV). This barrier reduction is mainly due to the H-bonding between the H in the H2O and the O at the transition state (TS), which stabilizes the TS. Second, CO can readily react with OH with a barrier of 0.44 eV, while COOH dissociation to produce CO2 is not easy (the barrier is 1.02 eV). Third, in the H2O+OH mixed phase, CO can be easily converted into CO2. It occurs through two steps: CO reacts with OH, forming COOH; and COOH transfers the H to a nearby H2O and, at the same time, an H in the H2O transfers to a OH, leading to CO2 formation. The reaction barrier of this process is 0.60 eV under CO coverage of 1/6 ML and 0.33 eV under CO coverage of 1/3 ML. The mechanism of CO oxidation at low temperatures is discussed. On the basis of our calculations, we propose that the water promotion effect can in general be divided into two classes: (i) By H-bonding between the H of H2O and an electron negative species such as the O in the reaction of CO+O+H2O→CO2+H2O, H2O can stabilize the TS of the reaction and hence reduce the barrier. (ii) H2O first dissociates into H and OH and then OH or H participates directly in the reaction to induce new reaction mechanism with more favorable routes, in which OH or H can act as an intermediate.

  12. [Environment effects of algae-caused black spots: impacts on Fe-Mn-S cycles in water-sediment interface].

    PubMed

    Liu, Guo-Feng; He, Jun; Fan, Cheng-Xin; Zhang, Lei; Shen, Qiu-Shi; Zhong, Ji-Cheng; Yan, Shao-Hua

    2010-11-01

    The driving effects of algal cells settlement in the water-sediment interface on Fe, Mn, S biogeochemistry in laboratory through static cultivation device. Results showed that dissolved oxygen would be exhausted by algae cells in 50 min after the cyanobacteria cells settled to the sediment surface. Soon the water-sediment interface formed the severe anoxia and Fe-Mn oxides and sulfides were deoxidized quickly in the strong reducing environment. The Fe2+, Mn2+ content in interface increased to the summit at the 4th day and their concentrations were 4.40 mg/L and 2.35 mg/L, respectively. When it comes to the end of the experiment, the Fe2+ content had a little reduction and Mn2+ reduced quickly, their concentrations were 3.37 mg/L and 0.97 mg/L at the end of experiment. However, S2- concentration in interface reached the highest at the 2nd day and its content was 0.63 mg/L, and its concentration was only 0.12 mg/L at the end since it has been reduced. The ORP was--150 mV in the sediment surface and indicated that the sediment environment was a strong reducing environment. Phenomenon of algal cells induced black spots in water bodies was the main driving factors on Fe/Mn oxides and sulfides biogeochemistry cycle, and also the extreme anoxia environment would have great harm on the water body's ecology. PMID:21250447

  13. Development and Validation of Water Vapor Tracers as Diagnostics for the Atmospheric Hydrologic Cycle

    NASA Technical Reports Server (NTRS)

    Bosilovich, Michael G.; Schubert, Siegfried D.; Einaudi, Franco (Technical Monitor)

    2000-01-01

    Understanding of the local and remote sources of water vapor can be a valuable diagnostic in understanding the regional atmospheric hydrologic cycle. In the present study, we have implemented passive tracers as prognostic variables to follow water vapor evaporated in predetermined regions until the water tracer precipitates. The formulation of the sources and sinks of tracer water is generally proportional to the prognostic water vapor variable. Because all water has been accounted for in tracers, the water vapor variable provides the validation of the tracer water and the formulation of the sources and sinks. The tracers have been implemented in a GEOS General Circulation Model (GCM) simulation consisting of several summer periods to determine the source regions of precipitation for the United States and India. The recycling of water and interannual variability of the sources of water will be examined. Potential uses in GCM sensitivity studies, predictability studies and data assimilation will be discussed.

  14. Water displacements in the Pacific and the genesis of El Nino cycles

    SciTech Connect

    Wyrtki, K.

    1985-07-20

    Sea level observations are used to estimate the amounts of warm water exchanged during the 1982 to 1983 El Nino event, indicating an eastward flux of about 40 x 10/sup 6/ m/sup 3/ s/sup -1/. At the end of El Nino the equatorial Pacific is depleted of warm water which is lost toward higher latitudes. The duration of a complete El Nino cycle is determined by the time required for the slow accumulation of warm water in the western Pacific. The cycle constitutes an energy relaxation of the ocean-atmosphere system.

  15. TCA cycle inactivation in Staphylococcus aureus alters nitric oxide production in RAW 264.7 cells.

    PubMed

    Massilamany, Chandirasegaran; Gangaplara, Arunakumar; Gardner, Donald J; Musser, James M; Steffen, David; Somerville, Greg A; Reddy, Jay

    2011-09-01

    Inactivation of the Staphylococcus aureus tricarboxylic acid (TCA) cycle delays the resolution of cutaneous ulcers in a mouse soft tissue infection model. In this study, it was observed that cutaneous lesions in mice infected with wild-type or isogenic aconitase mutant S. aureus strains contained comparable inflammatory infiltrates, suggesting the delayed resolution was independent of the recruitment of immune cells. These observations led us to hypothesize that staphylococcal metabolism can modulate the host immune response. Using an in vitro model system involving RAW 264.7 cells, the authors observed that cells cultured with S. aureus aconitase mutant strains produced significantly lower amounts of nitric oxide (NO(•)) and an inducible nitric oxide synthase as compared to those cells exposed to wild-type bacteria. Despite the decrease in NO(•) synthesis, the expression of antigen-presentation and costimulatory molecules was similar in cells cultured with wild-type and those cultured with aconitase mutant bacteria. The data suggest that staphylococci can evade innate immune responses and potentially enhance their ability to survive in infected hosts by altering their metabolism. This may also explain the occurrence of TCA cycle mutants in clinical S. aureus isolates. PMID:21519920

  16. Potential roles of anaerobic ammonium and methane oxidation in the nitrogen cycle of wetland ecosystems.

    PubMed

    Zhu, Guibing; Jetten, Mike S M; Kuschk, Peter; Ettwig, Katharina F; Yin, Chengqing

    2010-04-01

    Anaerobic ammonium oxidation (anammox) and anaerobic methane oxidation (ANME coupled to denitrification) with nitrite as electron acceptor are two of the most recent discoveries in the microbial nitrogen cycle. Currently the anammox process has been relatively well investigated in a number of natural and man-made ecosystems, while ANME coupled to denitrification has only been observed in a limited number of freshwater ecosystems. The ubiquitous presence of anammox bacteria in marine ecosystems has changed our knowledge of the global nitrogen cycle. Up to 50% of N(2) production in marine sediments and oxygen-depleted zones may be attributed to anammox bacteria. However, there are only few indications of anammox in natural and constructed freshwater wetlands. In this paper, the potential role of anammox and denitrifying methanotrophic bacteria in natural and artificial wetlands is discussed in relation to global warming. The focus of the review is to explore and analyze if suitable environmental conditions exist for anammox and denitrifying methanotrophic bacteria in nitrogen-rich freshwater wetlands. PMID:20195861

  17. Global atmospheric cycle of mercury: a model study on the impact of oxidation mechanisms.

    PubMed

    De Simone, F; Gencarelli, C N; Hedgecock, I M; Pirrone, N

    2014-03-01

    Mercury (Hg) is a global pollutant since its predominant atmospheric form, elemental Hg, reacts relatively slowly with the more abundant atmospheric oxidants. Comprehensive knowledge on the details of the atmospheric Hg cycle is still lacking, and in particular, there is some uncertainty regarding the atmospherically relevant reduction-oxidation reactions of mercury and its compounds. ECHMERIT is a global online chemical transport model, based on the ECHAM5 global circulation model, with a highly customisable chemistry mechanism designed to facilitate the investigation of both aqueous- and gas-phase atmospheric mercury chemistry. An improved version of the model which includes a new oceanic emission routine has been developed. Results of multiyear model simulations with full atmospheric chemistry have been used to examine the how changes to chemical mechanisms influence the model's ability to reproduce measured Hg concentrations and deposition flux patterns. The results have also been compared to simple fixed-lifetime tracer simulations to constrain the possible range of atmospheric mercury redox rates. The model provides a new and unique picture of the global cycle of mercury, in that it is online and includes a full atmospheric chemistry module. PMID:24424480

  18. Life cycle assessments of urban water systems: a comparative analysis of selected peer-reviewed literature.

    PubMed

    Loubet, Philippe; Roux, Philippe; Loiseau, Eleonore; Bellon-Maurel, Veronique

    2014-12-15

    Water is a growing concern in cities, and its sustainable management is very complex. Life cycle assessment (LCA) has been increasingly used to assess the environmental impacts of water technologies during the last 20 years. This review aims at compiling all LCA papers related to water technologies, out of which 18 LCA studies deals with whole urban water systems (UWS). A focus is carried out on these 18 case studies which are analyzed according to criteria derived from the four phases of LCA international standards. The results show that whereas the case studies share a common goal, i.e., providing quantitative information to policy makers on the environmental impacts of urban water systems and their forecasting scenarios, they are based on different scopes, resulting in the selection of different functional units and system boundaries. A quantitative comparison of life cycle inventory and life cycle impact assessment data is provided, and the results are discussed. It shows the superiority of information offered by multi-criteria approaches for decision making compared to that derived from mono-criterion. From this review, recommendations on the way to conduct the environmental assessment of urban water systems are given, e.g., the need to provide consistent mass balances in terms of emissions and water flows. Remaining challenges for urban water system LCAs are identified, such as a better consideration of water users and resources and the inclusion of recent LCA developments (territorial approaches and water-related impacts). PMID:25282088

  19. Oxidation kinetics of antibiotics during water treatment with potassium permanganate.

    PubMed

    Hu, Lanhua; Martin, Heather M; Strathmann, Timothy J

    2010-08-15

    The ubiquitous occurrence of antibiotics in aquatic environments raises concerns about potential adverse effects on aquatic ecology and human health, including the promotion of increased antibiotic resistance. This study examined the oxidation of three widely detected antibiotics (ciprofloxacin, lincomycin, and trimethoprim) by potassium permanganate [KMnO(4); Mn(VII)]. Reaction kinetics were described by second-order rate laws, with apparent second-order rate constants (k(2)) at pH 7 and 25 degrees C in the order of 0.61 +/- 0.02 M(-1) s(-1) (ciprofloxacin) < 1.6 +/- 0.1 M(-1) s(-1) (trimethoprim) < 3.6 +/- 0.1 M(-1) s(-1) (lincomycin). Arrhenius temperature dependence was observed with apparent activation energies (E(a)) ranging from 49 kJ mol(-1) (trimethoprim) to 68 kJ mol(-1) (lincomycin). Rates of lincomycin and trimethoprim oxidation exhibited marked pH dependences, whereas pH had only a small effect on rates of ciprofloxacin oxidation. The effects of pH were quantitatively described by considering parallel reactions between KMnO(4) and individual acid-base species of the target antibiotics. Predictions from a kinetic model that included temperature, KMnO(4) dosage, pH, and source water oxidant demand as input parameters agreed reasonably well with measurements of trimethoprim and lincomycin oxidation in six drinking water utility sources. Although Mn(VII) reactivity with the antibiotics was lower than that reported for ozone and free chlorine, its high selectivity and stability suggests a promising oxidant for treating sensitive micropollutants in organic-rich matrices (e.g., wastewater). PMID:20704243

  20. Water Sorption and Gamma Radiolysis Studies for Uranium Oxides

    SciTech Connect

    Icenhour, A.S.

    2002-02-27

    During the development of a standard for the safe, long-term storage of {sup 233}U-containing materials, several areas were identified that needed additional experimental studies. These studies were related to the perceived potential for the radiolytic generation of large pressures or explosive concentrations of gases in storage containers. This report documents the results of studies on the sorption of water by various uranium oxides and on the gamma radiolysis of uranium oxides containing various amounts of sorbed moisture. In all of the experiments, {sup 238}U was used as a surrogate for the {sup 233}U. For the water sorption experiments, uranium oxide samples were prepared and exposed to known levels of humidity to establish the water uptake rate. Subsequently, the amount of water removed was studied by heating samples in a oven at fixed temperatures and by thermogravimetric analysis (TGA)/differential thermal analysis (DTA). It was demonstrated that heating at 650 C adequately removes all moisture from the samples. Uranium-238 oxides were irradiated in a {sup 60}Co source and in the high-gamma-radiation fields provided by spent nuclear fuel elements of the High Flux Isotope Reactor. For hydrated samples of UO{sub 3}, H{sub 2} was the primary gas produced; but the total gas pressure increase reached steady value of about 10 psi. This production appears to be a function of the dose and the amount of water present. Oxygen in the hydrated UO{sub 3} sample atmosphere was typically depleted, and no significant pressure rise was observed. Heat treatment of the UO{sub 3} {center_dot} xH{sub 2}O at 650 C would result in conversion to U{sub 3}O{sub 8} and eliminate the H{sub 2} production. For all of the U{sub 3}O{sub 8} samples loaded in air and irradiated with gamma radiation, a pressure decrease was seen and little, if any, H{sub 2} was produced--even for samples with up to 9 wt % moisture content. Hence, these results demonstrated that the efforts to remove trace moisture from U{sub 3}O{sub 8} are not necessary to avoid pressurization of stored uranium oxides caused by gamma-induced radiolysis. In fact, this system can tolerate several percent of sorbed moisture--most of which can be easily removed by heating to only 150 C. To complete the picture of the radiolytic response of uranium oxides that have sorbed moisture, alpha radiolysis experiments have been initiated.

  1. Response of the water-water cycle to the change in photorespiration in tobacco.

    PubMed

    Huang, Wei; Yang, Ying-Jie; Hu, Hong; Zhang, Shi-Bao

    2016-04-01

    Photosynthetic electron transport produces ATP and NADPH, which are used by the primary metabolism. The production and consumption of ATP and NADPH must be balanced to maintain steady-state rates of CO2 assimilation and photorespiration. It has been indicated that the water-water cycle (WWC) is indispensable for driving photosynthesis via increasing ATP/NADPH production. However, the relationship between the WWC and photorespiration is little known. We tested the hypothesis that the WWC responds to change in photorespiration by balancing ATP/NADPH ratio. Measurements of gas exchange and chlorophyll fluorescence were conducted in tobacco plants supplied with high (HN-plants) or low nitrogen concentration (LN-plants). The WWC was activated under high light but not low light in both HN-plants and LN-plants. HN-plants had significantly higher capacities of the WWC and photorespiration than LN-plants. Under high light, the relative high WWC activation in HN-plants was accompanied with relative low levels of NPQ compared LN-plants, suggesting that the main role of the WWC under high light was to favor ATP synthesis but not to activate NPQ. Interestingly, the activation of WWC was positively correlated to the electron flow devoted to RuBP oxygenation, indicating that the WWC plays an important role in energy balancing when photorespiration is high. We conclude that the WWC is an important flexible mechanism to optimize the stoichiometry of the ATP/NADPH ratio responding to change in photorespiration. Furthermore, HN-plants enhance the WWC activity to maintain higher rates of CO2 assimilation and photorespiration. PMID:26896885

  2. Ground Water Sampling at ISCO Sites - Residual Oxidant Impact on Sample Quality and Sample Preservation Guideline

    EPA Science Inventory

    In-situ chemical oxidation (ISCO) involves the delivery of a chemical oxidant into the subsurface where oxidative reactions transform ground water contaminants into less toxic or harmless byproducts. Due to oxidant persistence, ground water samples collected at hazardous waste si...

  3. Breakdown of fast water transport in graphene oxides.

    PubMed

    Wei, Ning; Peng, Xinsheng; Xu, Zhiping

    2014-01-01

    Fast slip flow was identified for water inside the interlayer gallery between graphene layers or carbon nanotubes. We report here that this significant flow rate enhancement (over two orders) breaks down with the presence of chemical functionalization and relaxation of nanoconfinement in graphene oxides. Molecular dynamics simulation results show that hydrodynamics applies in this circumstance, even at length scales down to nanometers. However, corrections to the slip boundary condition and apparent viscosity of nanoconfined flow must be included to make quantitative predictions. These results were discussed with the structural characteristics of liquid water and hydrogen-bond networks. PMID:24580178

  4. Breakdown of fast water transport in graphene oxides

    NASA Astrophysics Data System (ADS)

    Wei, Ning; Peng, Xinsheng; Xu, Zhiping

    2014-01-01

    Fast slip flow was identified for water inside the interlayer gallery between graphene layers or carbon nanotubes. We report here that this significant flow rate enhancement (over two orders) breaks down with the presence of chemical functionalization and relaxation of nanoconfinement in graphene oxides. Molecular dynamics simulation results show that hydrodynamics applies in this circumstance, even at length scales down to nanometers. However, corrections to the slip boundary condition and apparent viscosity of nanoconfined flow must be included to make quantitative predictions. These results were discussed with the structural characteristics of liquid water and hydrogen-bond networks.

  5. Conversion of hazardous materials using supercritical water oxidation

    DOEpatents

    Rofer, Cheryl K.; Buelow, Steven J.; Dyer, Richard B.; Wander, Joseph D.

    1992-01-01

    A process for destruction of hazardous materials in a medium of supercritical water without the addition of an oxidant material. The harzardous material is converted to simple compounds which are relatively benign or easily treatable to yield materials which can be discharged into the environment. Treatment agents may be added to the reactants in order to bind certain materials, such as chlorine, in the form of salts or to otherwise facilitate the destruction reactions.

  6. Destruction of representative submarine food waste using supercritical water oxidation.

    PubMed

    Chen, Shiying; Qu, Xuan; Zhang, Rong; Bi, Jicheng

    2015-03-01

    In this study, 13 types of organic materials were oxidized using H2O2 in a continuous flow reactor under the condition of supercritical water. The effect of the operational parameters on the conversion of total organic carbon (TOC) and total nitrogen (TN) was investigated, and the resulting quality of treated water was analyzed. It was found that these materials were easily oxidized with a TOC conversion achieving 99% at temperature of 460 °C and TN conversion reaching 94% at temperature of 500 °C. Rice decomposition was rapid, with TOC and TN decomposition rates of 99% obtained within residence of 100 s at temperature of 460 °C. At temperature of 460 °C, pressure of 24 MPa, residence time of 100 s, and excess oxygen of 100%, the quality of treated water attained levels commensurate with China's Standards for Drinking Water Quality. Reaction rate equation parameters were obtained by fitting the experimental data to the differential equation obtained using the Runge-Kutta algorithm. The decrease of the TOC in water samples exhibited reaction orders of 0.95 for the TOC concentration and 0.628 for the oxygen concentration. The activation energy was 83.018 kJ/mol. PMID:25315932

  7. Water Lubrication of Stainless Steel using Reduced Graphene Oxide Coating

    PubMed Central

    Kim, Hae-Jin; Kim, Dae-Eun

    2015-01-01

    Lubrication of mechanical systems using water instead of conventional oil lubricants is extremely attractive from the view of resource conservation and environmental protection. However, insufficient film thickness of water due to low viscosity and chemical reaction of water with metallic materials have been a great obstacle in utilization of water as an effective lubricant. Herein, the friction between a 440 C stainless steel (SS) ball and a 440 C stainless steel (SS) plate in water lubrication could be reduced by as much as 6-times by coating the ball with reduced graphene oxide (rGO). The friction coefficient with rGO coated ball in water lubrication was comparable to the value obtained with the uncoated ball in oil lubrication. Moreover, the wear rate of the SS plate slid against the rGO coated ball in water lubrication was 3-times lower than that of the SS plate slid against the uncoated ball in oil lubrication. These results clearly demonstrated that water can be effectively utilized as a lubricant instead of oil to lower the friction and wear of SS components by coating one side with rGO. Implementation of this technology in mechanical systems is expected to aid in significant reduction of environmental pollution caused by the extensive use of oil lubricants. PMID:26593645

  8. Water Lubrication of Stainless Steel using Reduced Graphene Oxide Coating

    NASA Astrophysics Data System (ADS)

    Kim, Hae-Jin; Kim, Dae-Eun

    2015-11-01

    Lubrication of mechanical systems using water instead of conventional oil lubricants is extremely attractive from the view of resource conservation and environmental protection. However, insufficient film thickness of water due to low viscosity and chemical reaction of water with metallic materials have been a great obstacle in utilization of water as an effective lubricant. Herein, the friction between a 440 C stainless steel (SS) ball and a 440 C stainless steel (SS) plate in water lubrication could be reduced by as much as 6-times by coating the ball with reduced graphene oxide (rGO). The friction coefficient with rGO coated ball in water lubrication was comparable to the value obtained with the uncoated ball in oil lubrication. Moreover, the wear rate of the SS plate slid against the rGO coated ball in water lubrication was 3-times lower than that of the SS plate slid against the uncoated ball in oil lubrication. These results clearly demonstrated that water can be effectively utilized as a lubricant instead of oil to lower the friction and wear of SS components by coating one side with rGO. Implementation of this technology in mechanical systems is expected to aid in significant reduction of environmental pollution caused by the extensive use of oil lubricants.

  9. Oxidation kinetics of Fe(II) in sea water

    SciTech Connect

    Millero, F.J.; Sotolongo, S.; Izaguirre, M.

    1987-04-01

    The oxidation of Fe(II) has been studied as a function of pH (5 to 9), temperature (5 to 45/sup 0/C), and salinity (0 to 35). The pseudo-first-order rate constant, k/sub 1/, in water and sea water was found to be a second degree function of pH over the pH range of 7.5 to 8.5 at 5/sup 0/C and 6.0 to 8.0 at 25/sup 0/C. The overall rate constant (k) was determined from 5 to 45/sup 0/C and S = 0 to 35. The results have been fit to an equation of the form with a standard error = 0.09. The energy of activation for the overall rate constant in water and sea water was 29 +/- 2 kJ mol/sup -1/. The equations are provided with this paper. The values of the rate constant for pure water (k/sub 0/) are in good agreement with literature data. The half times for sea water from some previous studies at a pH = 8.0 were slower than the authors results for Gulf Stream waters. Measurements on Biscayne Bay waters also yield slower half times apparently due to the presence of organic ligands that can complex Fe(II).

  10. Water Lubrication of Stainless Steel using Reduced Graphene Oxide Coating.

    PubMed

    Kim, Hae-Jin; Kim, Dae-Eun

    2015-01-01

    Lubrication of mechanical systems using water instead of conventional oil lubricants is extremely attractive from the view of resource conservation and environmental protection. However, insufficient film thickness of water due to low viscosity and chemical reaction of water with metallic materials have been a great obstacle in utilization of water as an effective lubricant. Herein, the friction between a 440 C stainless steel (SS) ball and a 440 C stainless steel (SS) plate in water lubrication could be reduced by as much as 6-times by coating the ball with reduced graphene oxide (rGO). The friction coefficient with rGO coated ball in water lubrication was comparable to the value obtained with the uncoated ball in oil lubrication. Moreover, the wear rate of the SS plate slid against the rGO coated ball in water lubrication was 3-times lower than that of the SS plate slid against the uncoated ball in oil lubrication. These results clearly demonstrated that water can be effectively utilized as a lubricant instead of oil to lower the friction and wear of SS components by coating one side with rGO. Implementation of this technology in mechanical systems is expected to aid in significant reduction of environmental pollution caused by the extensive use of oil lubricants. PMID:26593645

  11. Tunable water desalination across Graphene Oxide Framework membranes

    SciTech Connect

    Nicolai, Adrien; Sumpter, Bobby G; Meunier, V.

    2014-01-01

    The performance of graphene oxide framework (GOF) membranes for water desalination is assessed using classical molecular dynamics (MD) simulations. The coupling between water permeability and salt rejection GOF membranes is studied as a function of linker concentration n, thickness h and applied pressure DP. The simulations reveal that water permeability in GOF-(n,h) membranes can be tuned from 5 (n = 32 and h = 6.5 nm) to 400 L/cm2/day/MPa (n = 64 and h = 2.5 nm) and follows the law Cnh an . For a given pore size (n = 16 or 32), water permeability of GOF membranes increases when the pore spacing decreases, whereas for a given pore spacing (n = 32 or 64), water permeability increases by up to two orders of magnitude when the pore size increases. Furthermore, for linker concentrations n 32, the high water permeability corresponds to a 100% salt rejection, elevating this type of GOF membrane as an ideal candidate for water desalination. Compared to experimental performance of reverse osmosis membranes, our calculations suggest that under the same conditions of applied pressure and characteristics of membranes (DP 10 MPa and h 100 nm), one can expect a perfect salt rejection coupled to a water permeability two orders of magnitude higher than existing technologies, i.e., from a few cL/cm2/day/MPa to a few L/cm2/day/MPa.

  12. Amavadin and Homologues as Mediators of Water Oxidation.

    PubMed

    Domarus, Magdalena; Kuznetsov, Maxim L; Marçalo, Joaquim; Pombeiro, Armando J L; da Silva, José Armando L

    2016-01-01

    The vanadium(IV) N-hydroxyiminodicarboxylate complexes [V(HIDPA)2 ](2-) and [V(HIDA)2 ](2-) , close models of the amavadin (a natural product from Amanita fungi lacking the V=O group but exhibiting a rare NO-bound oxyiminate moiety), are shown to be the first recognized complexes of the early transition metals (up to periodic Group 7) that mediate the oxidation of water. The reactions were analyzed by visible spectrophotometry, mass spectrometry, and measurement of evolved dioxygen using Ce(4+) as sacrificial oxidant. A mechanism proposed on the basis of DFT calculations involves the reversible oxidation to the mononuclear V(V) -{ON˙<} center, where the redox active oxyimino group plays a key role and metal oxidation state variation is only one unit. The more similar model of the metallobiomolecule, [V(HIDPA)2 ](2-) , displays a lower oxidation rate than [V(HIDA)2 ](2-) but does not undergo appreciable degradation, in contrast to the latter. PMID:26663718

  13. Photoassembly of the Water-Oxidizing Complex in Photosystem II

    PubMed Central

    Dasgupta, Jyotishman; Ananyev, Gennady M; Dismukes, G. Charles

    2008-01-01

    The light-driven steps in the biogenesis and repair of the inorganic core comprising the O2-evolving center of oxygenic photosynthesis (photosystem II water-oxidation complex, PSII-WOC) are reviewed. These steps, known collectively as photoactivation, involve the photoassembly of the free inorganic cofactors to the cofactor-depleted PSII-(apo-WOC) driven by light and produce the active O2-evolving core comprised of Mn4CaOxCly. We focus on the functional role of the inorganic components as seen through the competition with non-native cofactors (“inorganic mutants”) on water oxidation activity, the rate of the photoassembly reaction, and on structural insights gained from EPR spectroscopy of trapped intermediates formed in the initial steps of the assembly reaction. A chemical mechanism for the initial steps in photoactivation is given that is based on these data. Photoactivation experiments offer the powerful insights gained from replacement of the native cofactors, which together with the recent X-ray structural data for the resting holoenzyme provide a deeper understanding of the chemistry of water oxidation. We also review some new directions in research that photoactivation studies have inspired that look at the evolutionary history of this remarkable catalyst. PMID:19190725

  14. A soluble copper-bipyridine water-oxidation electrocatalyst

    NASA Astrophysics Data System (ADS)

    Barnett, Shoshanna M.; Goldberg, Karen I.; Mayer, James M.

    2012-06-01

    The oxidation of water to O2 is a key challenge in the production of chemical fuels from electricity. Although several catalysts have been developed for this reaction, substantial challenges remain towards the ultimate goal of an efficient, inexpensive and robust electrocatalyst. Reported here is the first copper-based catalyst for electrolytic water oxidation. Copper-bipyridine-hydroxo complexes rapidly form in situ from simple commercially available copper salts and bipyridine at high pH. Cyclic voltammetry of these solutions at pH 11.8-13.3 shows large, irreversible currents, indicative of catalysis. The production of O2 is demonstrated both electrochemically and with a fluorescence probe. Catalysis occurs at about 750 mV overpotential. Electrochemical, electron paramagnetic resonance and other studies indicate that the catalyst is a soluble molecular species, that the dominant species in the catalytically active solutions is (2,2‧-bipyridine)Cu(OH)2 and that this is among the most rapid homogeneous water-oxidation catalysts, with a turnover frequency of ~100 s-1.

  15. ESA's STSE WACMOS Project: Towards a Water Cycle Multimission Observation Strategy

    NASA Astrophysics Data System (ADS)

    Fernández Prieto, Diego; Su, Bob

    2010-05-01

    Understanding the role of the global water cycle in the Earth system it is essential to be able to measure from space hydro-climatic variables, such as radiation, precipitation, evapotranspiration, soil moisture, clouds, water vapour, surface water and runoff, vegetation state, albedo and surface temperature, etc. Such measurements are required to further increase not only our understanding of the different components of the water cycle and its variability, both spatially and temporally, but also to characterise the processes and interactions between the terrestrial and atmospheric branches of the water cycle, and how this coupling may influence climate variability and predictability. Moreover, enhancing the observational capacity and the model capabilities to predict in a reliable manner the variations in the global water cycle will be a key contribution to the improvement of water governance, the mitigation of water-related damages and the sustainable human development. In the last few years, EO has demonstrated the capacity to provide reliable measurements over oceans, land and atmosphere representing an unique tool for scientist to observe and monitor the earth system. Now, the earth observation panorama is getting into a new era where the increasing number of missions and sensors available for scientific and operational applications, besides the advances in computer science, modelling and data assimilation, open unprecedented opportunities to enhance human capacities to observe, understand and predict the water cycle and its variability in time. However, in order to fully exploit this increasing potential and bring this newly available capacity to practical operational levels, significant scientific efforts are required in order to: • Develop novel and enhanced geo-physical products exploiting available synergies among different observational system; • Consolidate the development of consistent long-term data sets integrating different EO systems in a synergic manner; • Develop robust methodologies to integrate and assimilate space observations and in situ measurements into advance coupled models being able to describe biophysical processes and interactions between ocean, land and atmosphere describing the water cycle and hydrological processes; In this context, the European Space Agency (ESA) in collaboration with the Global Energy and Water Experiment (GEWEX) of the World Climate Research Program (WCRP) launched the project Water Cycle Multi-mission Observation Strategy (WACMOS) early in 2009. The project, funded under the ESA's Support To Science Element, address the first of the above objectives. In particular, the project objective is twofold: • On the one hand, developing and validating a Product Portfolio of novel geo-information products responding to the GEWEX scientific priorities and exploiting the synergic capabilities between ESA EO data and other non-ESA missions. • Exploring and assessing different methodologies to exploit in a synergic manner different observations towards the development of long-term consistent datasets of key (essential) variables describing the water cycle. In this context, WACMOS is focused on four components of the above cycle that are also thematic priorities identified in close collaboration with the GEWEX scientific community: Evapotranspiration, soil moisture, clouds and water vapour. The product portfolio comprises: 1) AATSR-MERIS based evapotranspiration modelling approach; 2) Merged passive and active microwave first multi-decade soil moisture data set; 3) Novel MSG SEVIRI-SCIAMACHY cloud products and 4) Synergic SEVIRI-IASI and SEVIRI-MERIS water vapour products. In this paper, the methodologies and preliminary results of WACMOS are introduced. In the next phase of the project, consolidated methods, data products and validation results will be generated, so that a global water cycle product of evapotranpiration, soil moisture, clouds and water vapour with quantified uncertainties can be produced for climate research and water resources management uses.

  16. COAL CONVERSION WASTEWATER TREATMENT BY CATALYTIC OXIDATION IN SUPERCRITICAL WATER

    SciTech Connect

    Phillip E. Savage

    1999-10-18

    Wastewaters from coal-conversion processes contain phenolic compounds in appreciable concentrations. These compounds need to be removed so that the water can be discharged or re-used. Catalytic oxidation in supercritical water is one potential means of treating coal-conversion wastewaters, and this project examined the reactions of phenol over different heterogeneous oxidation catalysts in supercritical water. More specifically, we examined the oxidation of phenol over a commercial catalyst and over bulk MnO{sub 2}, bulk TiO{sub 2}, and CuO supported on Al{sub 2} O{sub 3}. We used phenol as the model pollutant because it is ubiquitous in coal-conversion wastewaters and there is a large database for non-catalytic supercritical water oxidation (SCWO) with which we can contrast results from catalytic SCWO. The overall objective of this research project is to obtain the reaction engineering information required to evaluate the utility of catalytic supercritical water oxidation for treating wastes arising from coal conversion processes. All four materials were active for catalytic supercritical water oxidation. Indeed, all four materials produced phenol conversions and CO{sub 2} yields in excess of those obtained from purely homogeneous, uncatalyzed oxidation reactions. The commercial catalyst was so active that we could not reliably measure reaction rates that were not limited by pore diffusion. Therefore, we performed experiments with bulk transition metal oxides. The bulk MnO{sub 2} and TiO{sub 2} catalysts enhance both the phenol disappearance and CO{sub 2} formation rates during SCWO. MnO{sub 2} does not affect the selectivity to CO{sub 2}, or to the phenol dimers at a given phenol conversion. However, the selectivities to CO{sub 2} are increased and the selectivities to phenol dimers are decreased in the presence of TiO{sub 2} , which are desirable trends for a catalytic SCWO process. The role of the catalyst appears to be accelerating the rate of formation of phenoxy radicals, which then react in the fluid phase by the same mechanism operative for non-catalytic SCWO of phenol. The rates of phenol disappearance and CO{sub 2} formation are sensitive to the phenol and O{sub 2} concentrations, but independent of the water density. Power-law rate expressions were developed to correlate the catalytic kinetics. The catalytic kinetics were also consistent with a Langmuir-Hinshelwood rate law derived from a dual-site mechanism comprising the following steps: reversible adsorption of phenol on one type of catalytic site, reversible dissociative adsorption of oxygen on a different type of site, and irreversible, rate-determining surface reaction between adsorbed phenol and adsorbed oxygen.

  17. Coal conversion wastewater treatment by catalytic oxidation in supercritical water

    SciTech Connect

    Phillip E. Savage

    1999-10-20

    Wastewaters from coal-conversion processes contain phenolic compounds in appreciable concentrations. These compounds need to be removed so that the water can be discharged or re-used. Catalytic oxidation in supercritical water is one potential means of treating coal-conversion wastewaters, and this project examined the reactions of phenol over different heterogeneous oxidation catalysts in supercritical water. More specifically, the authors examined the oxidation of phenol over a commercial catalyst and over bulk MnO{sub 2}, bulk TiO{sub 2}, and CuO supported on Al{sub 2}O{sub 3}. They used phenol as the model pollutant because it is ubiquitous in coal-conversion wastewaters and there is a large database for non-catalytic supercritical water oxidation (SCWO) with which they can contrast results from catalytic SCWO. The overall objective of this research project is to obtain the reaction engineering information required to evaluate the utility of catalytic supercritical water oxidation for treating wastes arising from coal conversion processes. All four materials were active for catalytic supercritical water oxidation. Indeed, all four materials produced phenol conversions and CO{sub 2} yields in excess of those obtained from purely homogeneous, uncatalyzed oxidation reactions. The commercial catalyst was so active that the authors could not reliably measure reaction rates that were not limited by pore diffusion. Therefore, they performed experiments with bulk transition metal oxides. The bulk MnO{sub 2} and TiO{sub 2} catalysts enhance both the phenol disappearance and CO{sub 2} formation rates during SCWO. MnO{sub 2} does not affect the selectivity to CO{sub 2}, or to the phenol dimers at a given phenol conversion. However, the selectivities to CO{sub 2} are increased and the selectivities to phenol dimers are decreased in the presence of TiO{sub 2}, which are desirable trends for a catalytic SCWO process. The role of the catalyst appears to be accelerating the rate of formation of phenoxy radicals, which then react in the fluid phase by the same mechanism operative for non-catalytic SCWO of phenol. The rates of phenol disappearance and CO{sub 2} formation are sensitive to the phenol and O{sub 2} concentrations, but independent of the water density. Power-law rate expressions were developed to correlate the catalytic kinetics. The catalytic kinetics were also consistent with a Langmuir-Hinshelwood rate law derived from a dual-site mechanism comprising the following steps: reversible adsorption of phenol on one type of catalytic site, reversible dissociative adsorption of oxygen on a different type of site, and irreversible, rate-determining surface reaction between adsorbed phenol and adsorbed oxygen.

  18. Lipid oxidation in minced beef meat with added Krebs cycle substrates to stabilise colour.

    PubMed

    Yi, G; Grabež, V; Bjelanovic, M; Slinde, E; Olsen, K; Langsrud, O; Phung, V T; Haug, A; Oostindjer, M; Egelandsdal, B

    2015-11-15

    Krebs cycle substrates (KCS) can stabilise the colour of packaged meat by oxygen reduction. This study tested whether this reduction releases reactive oxygen species that may lead to lipid oxidation in minced meat under two different storage conditions. KCS combinations of succinate and glutamate increased peroxide forming potential (PFP, 1.18-1.32 mmol peroxides/kg mince) and thiobarbituric acid reactive substances (TBARS, 0.30-0.38 mg malondialdehyde (MDA) equivalents/kg mince) under low oxygen storage conditions. Both succinate and glutamate were metabolised. Moreover, under high oxygen (75%) storage conditions, KCS combinations of glutamate, citrate and malate increased PFP (from 1.22 to 1.29 mmol peroxides/kg) and TBARS (from 0.37 to 0.40 mg MDA equivalents/kg mince). Only glutamate was metabolised. The KCS combinations that were added to stabilise colour were metabolised during storage, and acted as pro-oxidants that promoted lipid oxidation in both high and low oxygen conditions. PMID:25977064

  19. Biostimulation of Iron Reduction and Subsequent Oxidation of Sediment Containing Fe-silicates and Fe-oxides: Effect of Redox Cycling on Fe(III) Bioreduction

    SciTech Connect

    Komlos, John; Kukkadapu, Ravi K.; Zachara, John M.; Jaffe, Peter R.

    2007-07-01

    Microbial reduction of iron has been shown to be important in the transformation and remediation of contaminated sediments. Re-oxidation of microbially reduced iron may occur in sediments that experience oxidation-reduction cycling and can thus impact the extent of contaminant remediation. The purpose of this research was to quantify iron oxidation in a flow-through column filled with biologically-reduced sediment and to compare the iron phases in the re-oxidized sediment to both the pristine and biologically-reduced sediment. The sediment contained both Fe(III)-oxides (primarily goethite) and silicate Fe (illite/vermiculite) and was biologically reduced in phosphate buffered (PB) medium during a 497 day column experiment with acetate supplied as the electron donor. Long-term iron reduction resulted in partial reduction of silicate Fe(III) without any goethite reduction, based on Mössbauer spectroscopy measurements. This reduced sediment was treated with an oxygenated PB solution in a flow-through column resulting in the oxidation of 38% of the biogenic Fe(II). Additional batch experiments showed that the Fe(III) in the oxidized sediment was more quickly reduced compared to the pristine sediment, indicating that oxidation of the sediment not only regenerated Fe(III) but also enhanced iron reduction compared to the pristine sediment. Oxidation-reduction cycling may be a viable method to extend iron-reducing conditions during in-situ bioremediation.

  20. Artificial photosynthesis: from nanosecond electron transfer to catalytic water oxidation.

    PubMed

    Kärkäs, Markus D; Johnston, Eric V; Verho, Oscar; Akermark, Björn

    2014-01-21

    Human society faces a fundamental challenge as energy consumption is projected to increase due to population and economic growth as fossil fuel resources decrease. Therefore the transition to alternative and sustainable energy sources is of the utmost importance. The conversion of solar energy into chemical energy, by splitting H2O to generate molecular O2 and H2, could contribute to solving the global energy problem. Developing such a system will require the combination of several complicated processes, such as light-harvesting, charge separation, electron transfer, H2O oxidation, and reduction of the generated protons. The primary processes of charge separation and catalysis, which occur in the natural photosynthetic machinery, provide us with an excellent blueprint for the design of such systems. This Account describes our efforts to construct supramolecular assemblies capable of carrying out photoinduced electron transfer and to develop artificial water oxidation catalysts (WOCs). Early work in our group focused on linking a ruthenium chromophore to a manganese-based oxidation catalyst. When we incorporated a tyrosine unit into these supramolecular assemblies, we could observe fast intramolecular electron transfer from the manganese centers, via the tyrosine moiety, to the photooxidized ruthenium center, which clearly resembles the processes occurring in the natural system. Although we demonstrated multi-electron transfer in our artificial systems, the bottleneck proved to be the stability of the WOCs. Researchers have developed a number of WOCs, but the majority can only catalyze H2O oxidation in the presence of strong oxidants such as Ce(IV), which is difficult to generate photochemically. By contrast, illumination of ruthenium(II) photosensitizers in the presence of a sacrificial acceptor generates [Ru(bpy)3](3+)-type oxidants. Their oxidation potentials are significantly lower than that of Ce(IV), but our group recently showed that incorporating negatively charged groups into the ligand backbone could decrease the oxidation potential of the catalysts and, at the same time, decrease the potential for H2O oxidation. This permitted us to develop both ruthenium- and manganese-based WOCs that can operate under neutral conditions, driven by the mild oxida