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

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

    2012-06-12

    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.

  3. 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

  4. 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.

  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. 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.

  7. The global water cycle

    NASA Astrophysics Data System (ADS)

    Oki, Taikan; Entekhabi, Dara; Harrold, Timothy Ives

    The global water cycle consists of the oceans, water in the atmosphere, and water in the landscape. The cycle is closed by the fluxes between these reservoirs. Although the amounts of water in the atmosphere and river channels are relatively small, the fluxes are high, and this water plays a critical role in society, which is dependent on water as a renewable resource. On a global scale, the meridional component of river runoff is shown to be about 10% of the corresponding atmospheric and oceanic meridional fluxes. Artificial storages and water withdrawals for irrigation have significant impacts on river runoff and hence on the overall global water cycle. Fully coupled atmosphere-land-river-ocean models of the world's climate are essential to assess the future water resources and scarcities in relation to climate change. An assessment of future water scarcity suggests that water shortages will worsen, with a very significant increase in water stress in Africa. The impact of population growth on water stress is shown to be higher than that of climate change. The virtual water trade, which should be taken into account when discussing the global water cycle and water scarcity, is also considered. The movement of virtual water from North America, Oceania, and Europe to the Middle East, North West Africa, and East Asia represents significant global savings of water. The anticipated world water crisis widens the opportunities for the study of the global water cycle to contribute to the development of sustainability within society and to the solution of practical social problems.

  8. 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.

  9. 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.

  10. 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

  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

  12. 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.

  13. 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.

  14. Subcritical and supercritical water oxidation of organic, wet wastes for carbon cycling in regenerative life support systems

    NASA Astrophysics Data System (ADS)

    Ronsse, Frederik; Lasseur, Christophe; Rebeyre, Pierre; Clauwaert, Peter; Luther, Amanda; Rabaey, Korneel; Zhang, Dong Dong; López Barreiro, Diego; Prins, Wolter; Brilman, Wim

    2016-07-01

    For long-term human spaceflight missions, one of the major requirements is the regenerative life support system which has to be capable of recycling carbon, nutrients and water from both solid and liquid wastes generated by the crew and by the local production of food through living organisms (higher plants, fungi, algae, bacteria, …). The European Space Agency's Life Support System, envisioned by the MELiSSA project, consists of a 5 compartment artificial ecosystem, in which the waste receiving compartment (so-called compartment I or briefly 'CI') is based on thermophilic fermentation. However, as the waste generated by the crew compartment and food production compartment contain typical plant fibres (lignin, cellulose and hemicellulose), these recalcitrant fibres end up largely unaffected in the digestate (sludge) generated in the C-I compartment. Therefore, the C-I compartment has to be supplemented with a so-called fibre degradation unit (in short, FDU) for further oxidation or degradation of said plant fibres. A potential solution to degrading these plant fibres and other recalcitrant organics is their oxidation, by means of subcritical or supercritical water, into reusable CO2 while retaining the nutrients in an organic-free liquid effluent. By taking advantage of the altered physicochemical properties of water above or near its critical point (647 K, 22.1 MPa) - including increased solubility of non-polar compounds and oxygen, ion product and diffusivity - process conditions can be created for rapid oxidation of C into CO2. In this research, the oxidizer is provided as a hydrogen peroxide solution which, at elevated temperature, will dissociated into O2. The purpose of this study is to identify ideal process conditions which (a) ensure complete oxidation of carbon, (b) retaining the nutrients other than C in the liquid effluent and (c) require as little oxidizer as possible. Experiments were conducted on a continuous, tubular heated reactor and on batch

  15. 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

  16. 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.

  17. 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.

  18. The NEWS Water Cycle Climatology

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

    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. The Water Cycle Solutions Network

    NASA Astrophysics Data System (ADS)

    Houser, P.; Belvedere, D.; Imam, B.; Schiffer, R.; Schlosser, C.; Gupta, H.; Welty, C.; Vörösmarty, C.; Matthews, D.; Lawford, R.

    2006-12-01

    The goal of the Water cycle Solutions Network is to improve and optimize the sustained ability of water cycle researchers, stakeholders, organizations and networks to interact, identify, harness, and extend research results to augment decision support tools and meet national needs. WaterNet will engage relevant NASA water cycle research resources and community-of-practice organizations, to develop what we term an "actionable database" that can be used to communicate and connect water cycle research results (WCRs) towards the improvement of water-related Decision Support Tools (DSTs). An actionable database includes enough sufficient knowledge about its nodes and their heritage so that connections between these nodes are identifiable and robust. Recognizing the many existing highly valuable water-related science and application networks, we will focus the balance of our efforts on enabling their interoperability in a solutions network context. We will initially focus on identification, collection, and analysis of the two end points, these being the WCRs and water related DSTs. We will then develop strategies to connect these two end points via innovative communication strategies, improved user access to NASA resources, improved water cycle research community appreciation for DST requirements, improved policymaker, management and stakeholder knowledge of NASA research and application products, and improved identification of pathways for progress. Finally, we will develop relevant benchmarking and metrics, to understand the network's characteristics, to optimize its performance, and to establish sustainability. The WaterNet will deliver numerous pre-evaluation reports that will identify the pathways for improving the collective ability of the water cycle community to routinely harness WCRs that address crosscutting water cycle challenges.

  20. 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

  1. Hydroquinone-Mediated Redox Cycling of Iron and Concomitant Oxidation of Hydroquinone in Oxic Waters under Acidic Conditions: Comparison with Iron-Natural Organic Matter Interactions.

    PubMed

    Jiang, Chao; Garg, Shikha; Waite, T David

    2015-12-15

    Interactions of 1,4-hydroquinone with soluble iron species over a pH range of 3-5 in the air-saturated and partially deoxygenated solution are examined here. Our results show that 1,4-hydroquinone reduces Fe(III) in acidic conditions, generating semiquinone radicals (Q(•-)) that can oxidize Fe(II) back to Fe(III). The oxidation rate of Fe(II) by Q(•-)increases with increase in pH due to the speciation change of Q(•-) with its deprotonated form (Q(•-)) oxidizing Fe(II) more rapidly than the protonated form (HQ(•)). Although the oxygenation of Fe(II) is negligible at pH < 5, O2 still plays an important role in iron redox transformation by rapidly oxidizing Q(•-) to form benzoquinone (Q). A kinetic model is developed to describe the transformation of quinone and iron under all experimental conditions. The results obtained here are compared with those obtained in our previous studies of iron-Suwannee River fulvic acid (SRFA) interactions in acidic solutions and support the hypothesis that hydroquinone moieties can reduce Fe(III) in natural waters. However, the semiquinone radicals generated in pure hydroquinone solution are rapidly oxidized by dioxygen, while the semiquinone radicals generated in SRFA solution are resistant to oxidation by dioxygen, with the result that steady-state semiquinone concentrations in SRFA solutions are 2-3 orders of magnitude greater than in solutions of 1,4-hydroquinone. As a result, semiquinone moieties in SRFA play a much more important role in iron redox transformations than is the case in solutions of simple quinones such as 1,4-hydroquinone. This difference in the steady-state concentration of semiquinone species has a dramatic effect on the cycling of iron between the +II and +III oxidation states, with iron turnover frequencies in solutions containing SRFA being 10-20 times higher than those observed in solutions of 1,4-hydroquinone.

  2. Water oxidation: Intermediate identification

    NASA Astrophysics Data System (ADS)

    Cowan, Alexander J.

    2016-08-01

    The slow kinetics of light-driven water oxidation on haematite is an important factor limiting the material's efficiency. Now, an intermediate of the water-splitting reaction has been identified offering hope that the full mechanism will soon be resolved.

  3. Nonaqueous Catalytic Water Oxidation

    SciTech Connect

    Chen, Zuofeng; Concepcion, Javier J.; Luo, Hanlin; Hull, Jonathan F.; Paul, Amit; Meyer, Thomas J.

    2010-11-23

    The complex [Ru(Mebimpy)(bpy)(OH2)]2+ [Mebimpy = 2,6-bis(1-methylbenzimidazol-2-yl)pyridine; bpy = 2,2'-bipyridine] and its 4,4'-(PO3H2CH2)2bpy derivative on oxide electrodes are water oxidation catalysts in propylene carbonate and 2,2,2-trifluoroethanol (TFE) to which water has been added as a limiting reagent. The rate of water oxidation is greatly enhanced relative to that with water as the solvent and occurs by a pathway that is first-order in H2O; an additional pathway that is first-order in acetate appears when TFE is used as the solvent.

  4. 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

  5. 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.

  6. 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.

  7. Modelling the Krebs cycle and oxidative phosphorylation.

    PubMed

    Korla, Kalyani; Mitra, Chanchal K

    2014-01-01

    The Krebs cycle and oxidative phosphorylation are the two most important sets of reactions in a eukaryotic cell that meet the major part of the total energy demands of a cell. In this paper, we present a computer simulation of the coupled reactions using open source tools for simulation. We also show that it is possible to model the Krebs cycle with a simple black box with a few inputs and outputs. However, the kinetics of the internal processes has been modelled using numerical tools. We also show that the Krebs cycle and oxidative phosphorylation together can be combined in a similar fashion - a black box with a few inputs and outputs. The Octave script is flexible and customisable for any chosen set-up for this model. In several cases, we had no explicit idea of the underlying reaction mechanism and the rate determining steps involved, and we have used the stoichiometric equations that can be easily changed as and when more detailed information is obtained. The script includes the feedback regulation of the various enzymes of the Krebs cycle. For the electron transport chain, the pH gradient across the membrane is an essential regulator of the kinetics and this has been modelled empirically but fully consistent with experimental results. The initial conditions can be very easily changed and the simulation is potentially very useful in a number of cases of clinical importance.

  8. 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.

  9. 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)

  10. 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

  11. 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…

  12. 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.

  13. 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.

  14. 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.

  15. Inorganic chemistry: Deconstructing water oxidation

    NASA Astrophysics Data System (ADS)

    Cook, Sarah A.; Borovik, A. S.

    2013-04-01

    During photosynthesis, the oxygen-evolving complex oxidizes water to produce molecular oxygen. Now, a possible role for the calcium ion in this complex has been proposed based on the electrochemical properties of a series of synthetic heterometallic clusters.

  16. 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.

  17. 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.

  18. WaterNet: The NASA Water Cycle Solutions Network

    NASA Astrophysics Data System (ADS)

    Houser, P. R.; Belvedere, D. R.; Pozzi, W. H.; Imam, B.; Schiffer, R.; Lawford, R.; Schlosser, C. A.; Gupta, H.; Welty, C.; Vorosmarty, C.; Matthews, D.

    2007-12-01

    Water is essential to life and directly impacts and constrains society's welfare, progress, and sustainable growth, and is continuously being transformed by climate change, erosion, pollution, and engineering practices. The water cycle is a critical resource for industry, agriculture, natural ecosystems, fisheries, aquaculture, hydroelectric power, recreation, and water supply, and is central to drought, flood, transportation-aviation, and disease hazards. It is therefore a national priority to use advancements in scientific observations and knowledge to develop solutions to the water challenges faced by society. NASA's unique role is to use its view from space to improve water and energy cycle monitoring and prediction. NASA has collected substantial water cycle information and knowledge that must be transitioned to develop solutions for all twelve National Priority Application (NPA) areas. NASA cannot achieve this goal alone -it must establish collaborations and interoperability with existing networks and nodes of research organizations, operational agencies, science communities, and private industry. Therefore, WaterNet: The NASA Water Cycle Solutions Network 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. WaterNet is a catalyst for discovery and sharing of creative solutions to water problems. It serves as a creative, discovery process that is the entry-path for a research-to-solutions systems engineering NASA framework, with the end result to ultimately improve decision support.

  19. 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.

  20. Global Hydrological Cycles and World Water Resources

    NASA Astrophysics Data System (ADS)

    Oki, Taikan; Kanae, Shinjiro

    2006-08-01

    Water is a naturally circulating resource that is constantly recharged. Therefore, even though the stocks of water in natural and artificial reservoirs are helpful to increase the available water resources for human society, the flow of water should be the main focus in water resources assessments. The climate system puts an upper limit on the circulation rate of available renewable freshwater resources (RFWR). Although current global withdrawals are well below the upper limit, more than two billion people live in highly water-stressed areas because of the uneven distribution of RFWR in time and space. Climate change is expected to accelerate water cycles and thereby increase the available RFWR. This would slow down the increase of people living under water stress; however, changes in seasonal patterns and increasing probability of extreme events may offset this effect. Reducing current vulnerability will be the first step to prepare for such anticipated changes.

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

    SciTech Connect

    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. 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

  3. 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)

  4. The Martian North Polar Summer Water Cycle

    NASA Astrophysics Data System (ADS)

    Brown, A. J.; Calvin, W. M.; Becerra, P.; Byrne, S.

    2016-09-01

    We report on the summer water cycle of the north polar cap and identify regions and times across the cap when the cap is in 'net deposition' and 'net sublimation' modes. This may help us to determine regions of the cap that are currently stable.

  5. 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)

  6. 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

  7. WaterNet: The NASA Water Cycle Solutions Network

    NASA Astrophysics Data System (ADS)

    Belvedere, D. R.; Houser, P. R.; Imam, B.; Schiffer, R.; Schlosser, C. A.; Gupta, H. V.; Welty, C.; Vorosmarty, C.; Matthews, D.; Lawford, R.

    2006-05-01

    The water cycle is continuously being transformed by climate change, erosion, pollution, salinization, and engineering practices, and is central to drought, flood, and disease hazards. Therefore, it is a national priority is to use advancements in scientific observations and knowledge to develop solutions to society's water challenges. NASA's unique role in this national priority is to exploit its unique view from space to improve water and energy cycle monitoring and prediction. As such, NASA's Earth science programs have collected substantial water cycle information and knowledge that must be integrated and shared to develop solutions in all twelve national priority application areas. However, NASA alone cannot achieve the ultimate goal of improved operational environmental assessments, predictions and applications and therefore must establish collaborations and interoperability with existing networks and nodes of research organizations, operational agencies, the scientific community, and private industry. Therefore, we propose to develop WaterNet: The NASA Water Cycle Solutions Network whose 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. We will develop WaterNet by engaging relevant NASA water and energy cycle resources and community-of-practice organizations to develop what we term an "actionable database" that can be used to communicate and connect NASA Water and energy cycle focus area research Results (NWRs) towards the improvement of water-related Decision Support Tools (DSTs). Recognizing the many existing highly valuable water-related science and application networks, we will focus a balance of our efforts to enable their interoperability in a solutions network context. We will initially focus on identifying, collecting information about, and analyzing the

  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. 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

  10. Following the Water Cycle to Sustainability

    NASA Astrophysics Data System (ADS)

    Lutz, T. M.

    2012-12-01

    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.

  11. 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

  12. 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.

  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. Uranium oxidation: characterization of oxides formed by reaction with water

    SciTech Connect

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

    1983-04-27

    Three different uranium oxide samples have been characterized with respect to the different preparation techniques. 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. 27 figures.

  15. 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

  16. A rapid-temperature-cycling apparatus for oxidation testing

    SciTech Connect

    Cabrera, A.L.; Kirner, J.F. )

    1991-06-01

    An oxidation test with rapid temperature cycling was developed to evaluate small coated parts. The samples in the form of wire or foils are resistively heated with a high-current AC power supply, allowing fast heating and cooling of the samples. Fast temperature cycling of the samples permits to complete more than 100 cycles in one day. A variety of steels coated with silicon diffusion coatings were tested and the results compared with oxidation via traditional thermal cycling. The test accurately predicts enhanced performance for siliconized 1010 steel, an increase by a factor of three for the life of siliconized 302 stainless steel, and an inadequate siliconized coating for 410 stainless steel. Details of the rapid temperature cycling apparatus as well as testing of the coated steels are described in the paper.

  17. 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

  18. 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

  19. 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.

  20. 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

    2016-02-11

    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.

  1. Isotopes in the Arctic atmospheric water cycle

    NASA Astrophysics Data System (ADS)

    Bonne, Jean-Louis; Werner, Martin; Meyer, Hanno; Kipfstuhl, Sepp; Rabe, Benjamin; Behrens, Melanie; Schönicke, Lutz; Steen Larsen, Hans Christian; Masson-Delmotte, Valérie

    2016-04-01

    The ISO-ARC project aims at documenting the Arctic atmospheric hydrological cycle, by assessing the imprint of the marine boundary conditions (e.g. temperature variations, circulation changes, or meltwater input) to the isotopic composition of the atmospheric water cycle (H218O and HDO) with a focus on North Atlantic and Arctic oceans. For this purpose, two continuous monitoring water vapour stable isotopes cavity ring-down spectrometers have been installed in July 2015: on-board the Polarstern research vessel and in the Siberian Lena delta Samoylov research station (N 72° 22', E 126° 29'). The Polarstern measurements cover the summer 2015 Arctic campaign from July to mid-October, including six weeks in the Fram Strait region in July- August, followed by a campaign reaching the North Pole and a transect from the Norwegian Sea to the North Sea. These vapour observations are completed by water isotopic measurements in samples from the surface ocean water for Polarstern and from precipitation in Samoylov and Tiksi (120 km south-east of the station). A custom-made designed automatic calibration system has been implemented in a comparable manner for both vapour instruments, based on the injection of different liquid water standards, which are completely vaporised in dry air at high temperature. Subsequent humidity level can be adjusted from 2000 to at least 30000 ppm. For a better resilience, an independent calibration system has been added on the Samoylov instrument, allowing measurements of one standard at humidity levels ranging from 2000 to 15000 ppm: dry air is introduced in a tank containing a large amount of liquid water standard, undergoing evaporation under a controlled environment. The measurement protocol includes an automatic calibration every 25 hours. First instrument characterisation experiments depict a significant isotope-humidity effect at low humidity, dependant on the isotopic composition of the standard. For ambient air, our first isotope

  2. 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).

  3. Martian north polar cap summer water cycle

    NASA Astrophysics Data System (ADS)

    Brown, Adrian J.; Calvin, Wendy M.; Becerra, Patricio; Byrne, Shane

    2016-10-01

    A key outstanding question in Martian science is "are the polar caps gaining or losing mass and what are the implications for past, current and future climate?" To address this question, we use observations from the Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) of the north polar cap during late summer for multiple Martian years, to monitor the summertime water cycle in order to place quantitative limits on the amount of water ice deposited and sublimed in late summer. We establish here for the first time the summer cycle of water ice absorption band signatures on the north polar cap. We show that in a key region in the interior of the north polar cap, the absorption band depths grow until Ls = 120, when they begin to shrink, until they are obscured at the end of summer by the north polar hood. This behavior is transferable over the entire north polar cap, where in late summer regions 'flip' from being net sublimating into net condensation mode. This transition or 'mode flip' happens earlier for regions closer to the pole, and later for regions close to the periphery of the cap. The observations and calculations presented herein estimate that on average a water ice layer ∼70 microns thick is deposited during the Ls = 135-164 period. This is far larger than the results of deposition on the south pole during summer, where an average layer 0.6-6 microns deep has been estimated by Brown et al. (2014) Earth Planet. Sci. Lett., 406, 102-109.

  4. 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.

  5. Oxidation phenomena in water treeing. Final report

    SciTech Connect

    Noirhomme, B.; Bulinski, A.T.; Bamji, S.S.; Crine, J.P.; Densley, R.J.

    1993-08-01

    An investigation of oxidation of cross-linked polyethylene (XLPE) insulation determined that it is only one parameter influencing water treeing and not necessarily the controlling or major one. Oxygen presence during water treeing influences water tree propagation more than water tree initiation. Very high levels of oxidation, to the extent that dielectric losses increase, were found to retard water tree growth. 1. The investigative team sought oxidation in many service-aged cables via diagnostic techniques including FTIR; oxidation in the water tree stem and branches, and outside the water trees of adjacent insulation, was studied. 2. XLPE insulation was intentionally oxidized via thermal treatment, and water tree growth under controlled degrees of oxidation was studied. 3. Water trees were grown in an inert (nitrogen) environment to determine the influence of oxygen on water tree initiation and propagation. Field-aged cables studied do not reveal any excess degree of oxidation inside water trees relative to nontreed regions (carbonyl, carboxylate) via the diagnostics employed. Oxygen presence does not influence water tree initiation; however, water tree propagation was enhanced by the presence of oxygen (versus nitrogen) and ionic impurities; tree length was reduced in the presence of nitrogen. Preoxidation of XLPE insulation does not enhance water tree growth (initiation/propagation). Very high levels of preoxidation, induced thermally, lead to fewer and shorter water trees; very heavy preoxidation treatment (higher than seen in service) causes an increase in dielectric losses and reduces tree growth.

  6. 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.

  7. 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.

  8. 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

  9. 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.

  10. 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

  11. Iridium oxide-polymer nanocomposite electrode materials for water oxidation.

    PubMed

    Lattach, Youssef; Rivera, Juan Francisco; Bamine, Tahya; Deronzier, Alain; Moutet, Jean-Claude

    2014-08-13

    Nanocomposite anode materials for water oxidation have been readily synthesized by electrodeposition of iridium oxide nanoparticles into poly(pyrrole-alkylammonium) films, previously deposited onto carbon electrodes by oxidative electropolymerization of a pyrrole-alkylammonium monomer. The nanocomposite films were characterized by electrochemistry, transmission electron microscopy, and atomic force microscopy. They showed an efficient electrocatalytic activity toward the oxygen evolution reaction. Data from Tafel plots have demonstrated that the catalytic activity of the iridium oxide nanoparticles is maintained following their inclusion in the polymer matrix. Bulk electrolysis of water at carbon foam modified electrodes have shown that the iridium oxide-polymer composite presents a higher catalytic activity and a better operational stability than regular oxide films.

  12. 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.

  13. 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.

  14. 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.

  15. 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

  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

  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. 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

  19. 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.

  20. 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

  1. 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.

  2. Thermodynamic properties of ammonia-water mixtures for power cycles

    SciTech Connect

    Thorin, E. |; Dejfors, C.; Svedberg, G.

    1998-03-01

    Power cycles with ammonia-water mixtures as working fluids have been shown to reach higher thermal efficiencies than the traditional steam turbine (Rankine) cycle with water as the working fluid. Different correlations for the thermodynamic properties of ammonia-water mixtures have been used in studies of ammonia-water mixture cycles described in the literature. Four of these correlations are compared in this paper. The differences in thermal efficiencies for a bottoming Kalina cycle when these four property correlations are used are in the range 0.5 to 3.3%. The properties for saturated liquid and vapor according to three of the correlations and available experimental data are also compared at high pressures and temperatures [up to 20 MPa and 337 C (610 K)]. The difference in saturation temperature for the different correlations is up to 20%, and the difference in saturation enthalpy is as high as 100% when the pressure is 20 MPa.

  3. Short-term Fe cycling during Fe(II) oxidation: exploring joint oxidation and precipitation with a combinatorial system.

    PubMed

    Burns, Justina M; Craig, Preston S; Shaw, Timothy J; Ferry, John L

    2011-04-01

    The net oxidation of Fe(II)aq by dioxygen initiates a suite of reactions including the oxidation of multiple Fe(II) complexes, generation of secondary oxidants, Fe(III) reduction, and precipitation of insoluble products. This work reports application of a multifactorial strategy to describe the oxidation of Fe(II) under conditions that correspond to those found where Fe(II)-rich groundwaters mix rapidly with overlying oxygenated waters. Response surfaces were constructed describing the relationship of the net oxidation process with mixtures of the common ligands chloride (Cl-), bromide (Br-), total carbonate (CO3(2-)), Fe(II), and Suwannee River natural organic matter (SRNOM) at pH 8.00. Response surfaces were generated in the presence and absence of added phosphate, representing conditional end members corresponding to geographical locations where Fe(III) precipitation is respectively forced and unconstrained. Comparison of net Fe(II) oxidation rates in the presence and absence of phosphate then enabled resolution of the relative contributions of Fe(II) oxidation and Fe(III) reduction to the overall process. The differences between the two surfaces demonstrated the importance of Fe(II) regeneration on the rapid (min) time scale during net oxidation. The minimum Fe(II) concentration necessary to initiate measurable cycling is reported. The presence of reactive oxygen species was evaluated through the use of probes added to the center point condition of the experimental matrix. Analysis of the statistical significance of the Fe(II)-factor relationships demonstrated that over the conditional scale of the experiments complexation of Fe(II) by the selected ligands did not correlate to the experimental outcome.

  4. 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.

  5. 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.

  6. Tunable water desalination across Graphene Oxide Frameworks

    NASA Astrophysics Data System (ADS)

    Nicolai, Adrien; Meunier, Vincent

    2014-03-01

    ``Water, water, everywhere, nor any drop to drink.'' wrote Samuel Taylor Coleridge in 1798. Today's scientific advances in water desalination promise to change the second part of the sentence into ``and every drop to drink,'' by transforming sea water into fresh water and quench the thirst of 1.2B people facing shortages of water. To achieve this, the design of nanoporous materials with high water permeability and coupled with high salt rejection capacity is crucial. Graphene Oxide Frameworks (GOF) materials are a class of porous materials consisting of layers of graphene oxide sheets interconnected by linear boronic acid linkers. Water desalination across GOF is studied using classical Molecular Dynamics simulations. We used quantum mechanically obtained boron-related force field parameters to study the diffusion of water molecules inside bulk GOF. Properties, such as the self-diffusion coefficient of water molecules increases linearly with linker concentration n. Further, the desalination performance of GOF membranes reveals that the water permeability of GOF is several orders of magnitude higher than conventional membranes and an high water permeability can be coupled with a 100% efficiency of salt rejection by choosing the appropriate concentration n and thickness h.

  7. Thermodynamic limitations of photosynthetic water oxidation at high proton concentrations.

    PubMed

    Zaharieva, Ivelina; Wichmann, Jörg M; Dau, Holger

    2011-05-20

    In oxygenic photosynthesis, solar energy drives the oxidation of water catalyzed by a Mn(4)Ca complex bound to the proteins of Photosystem II. Four protons are released during one turnover of the water oxidation cycle (S-state cycle), implying thermodynamic limitations at low pH. For proton concentrations ranging from 1 nm (pH 9) to 1 mm (pH 3), we have characterized the low-pH limitations using a new experimental approach: a specific pH-jump protocol combined with time-resolved measurement of the delayed chlorophyll fluorescence after nanosecond flash excitation. Effective pK values were determined for low-pH inhibition of the light-induced S-state transitions: pK(1)=3.3 ± 0.3, pK(2)=3.5 ± 0.2, and pK(3)≈pK(4)=4.6 ± 0.2. Alkaline inhibition was not observed. An extension of the classical Kok model facilitated assignment of these four pK values to specific deprotonation steps in the reaction cycle. Our results provide important support to the extended S-state cycle model and criteria needed for assessment of quantum chemical calculations of the mechanism of water oxidation. They also imply that, in intact organisms, the pH in the lumen compartment can hardly drop below 5, thereby limiting the ΔpH contribution to the driving force of ATP synthesis. PMID:21464129

  8. 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.

  9. 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.

  10. Coastal water column ammonium and nitrite oxidation are decoupled in summer

    NASA Astrophysics Data System (ADS)

    Heiss, Elise M.; Fulweiler, Robinson W.

    2016-09-01

    Water column nitrification is a key process in the nitrogen cycle as it links reduced and oxidized forms of nitrogen and also provides the substrate (nitrate) needed for reactive nitrogen removal by denitrification. We measured potential water column ammonium and nitrite oxidation rates at four sites along an estuary to continental shelf gradient over two summers. In most cases, nitrite oxidation rates outpaced ammonium oxidation rates. Overall, ammonium and nitrite oxidation rates were higher outside of the estuary, and this trend was primarily driven by higher oxidation rates in deeper waters. Additionally, both ammonium and nitrite oxidation rates were impacted by different in situ variables. Ammonium oxidation rates throughout the water column as a whole were most positively correlated to depth and salinity and negatively correlated to dissolved oxygen and light. In contrast, nitrite oxidation rates throughout the water column were negatively correlated with light and pH. Multivariate regression analysis revealed that while both surface (<20 m) and deep (>20 m) ammonium oxidation rates were most strongly predicted by depth and light, surface rates were also regulated by salinity and deep rates by temperature. Surface (<20 m) nitrite oxidation rates were best explained by [H+] (i.e. pH) alone, while salinity, [H+], temperature, and depth all played a role in predicting deep (>20 m) nitrite oxidation rates. These results support the growing body of evidence that ammonium oxidation and nitrite oxidation are not always coupled, should be measured separately, and are influenced by different environmental conditions.

  11. 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...

  12. Micropollutant loads in the urban water cycle.

    PubMed

    Musolff, Andreas; Leschik, Sebastian; Reinstorf, Frido; Strauch, Gerhard; Schirmer, Mario

    2010-07-01

    The assessment of micropollutants in the urban aquatic environment is a challenging task since both the water balance and the contaminant concentrations are characterized by a pronounced variability in time and space. In this study the water balance of a central European urban drainage catchment is quantified for a period of one year. On the basis of a concentration monitoring of several micropollutants, a contaminant mass balance for the study area's wastewater, surface water, and groundwater is derived. The release of micropollutants from the catchment was mainly driven by the discharge of the wastewater treatment plant. However, combined sewer overflows (CSO) released significant loads of caffeine, bisphenol A, and technical 4-nonylphenol. Since an estimated fraction of 9.9-13.0% of the wastewater's dry weather flow was lost as sewer leakages to the groundwater, considerable loads of bisphenol A and technical 4-nonylphenol were also released by the groundwater pathway. The different temporal dynamics of release loads by CSO as an intermittent source and groundwater as well as treated wastewater as continuous pathways may induce acute as well as chronic effects on the receiving aquatic ecosystem. This study points out the importance of the pollution pathway CSO and groundwater for the contamination assessments of urban water resources.

  13. 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

  14. 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

  15. Seasonal cycles of mitochondrial ADP sensitivity and oxidative capacities in trout oxidative muscle.

    PubMed

    Guderley, H; St Pierre, J

    1999-10-01

    Mitochondria from red myotomal muscle of rainbow trout, Oncorhynchus mykiss, showed seasonal cycles of their maximal rates of substrate oxidation (nmol.min-1 mg-1 mitochondrial protein) and their apparent ADP affinity (Kmapp), as well as in the thermal sensitivity of these properties. Increases in the maximal capacity of pyruvate oxidation were sufficient to compensate for seasonal changes in temperature, except during the winter months when rates at habitat temperature were depressed relative to other periods. The ADP affinity of isolated mitochondria was highest during cold months. Thus, the Kmapp for ADP at habitat temperature showed less seasonal variation than the ADP Kmapp at a given temperature. A loss in ADP affinity with decreasing temperature occurred through much of the year, and only was definitively suppressed in December and July. Both the ADP affinity and the maximal oxidative capacities of muscle mitochondria seem to be regulated parameters. PMID:10595316

  16. 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.

  17. Microbial Iron Oxidation in the Arctic Tundra and Its Implications for Biogeochemical Cycling

    PubMed Central

    Scott, Jarrod J.; Benes, Joshua; Bowden, William B.

    2015-01-01

    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

  18. 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.

  19. 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

  20. Modeling and remote sensing of human induced water cycle change

    NASA Astrophysics Data System (ADS)

    Pokhrel, Yadu N.

    2016-04-01

    The global water cycle has been profoundly affected by human land-water management especially during the last century. Since the changes in water cycle can affect the functioning of a wide range of biophysical and biogeochemical processes of the Earth system, it is essential to account for human land-water management in land surface models (LSMs) which are used for water resources assessment and to simulate the land surface hydrologic processes within Earth system models (ESMs). During the last two decades, noteworthy progress has been made in modeling human impacts on the water cycle but sufficient advancements have not yet been made, especially in representing human factors in large-scale LSMs toward integrating them into ESMs. In this study, an integrated modeling framework of continental-scale water cycle, with explicit representation of climate and human induced forces (e.g., irrigation, groundwater pumping) is developed and used to reconstruct the observed water cycle changes in the past and to attribute the observed changes to climatic and human factors. The new model builds upon two different previously developed models: a global LSM called the Human Impacts and GroundWater in the MATSIRO (HiGW-MAT) and a high-resolution regional groundwater model called the LEAF-Hydro-Flood. The model is used to retro-simulate the hydrologic stores and fluxes in close dialogue with in-situ and GRACE satellite based observations at a wide range of river basin scales around the world, with a particular focus on the changes in groundwater dynamics in northwest India, Pakistan, and the High Plains and Central Valley aquifers in the US.

  1. Dynamic Kinetics of Nitrogen Cycle in Groundwater-Surface Water Interaction Zone at Hanford Site

    NASA Astrophysics Data System (ADS)

    Liu, Y.; Liu, C.; Liu, Y.; Xu, F.; Yan, A.; Shi, L.; Zachara, J. M.; Gao, Y.; Qian, W.; Nelson, W.; Fredrickson, J.; Zhong, L.; Thompson, C.

    2015-12-01

    Nitrogen cycle carried out by microbes is an important geobiological process that has global implications for carbon and nitrogen cycling and climate change. This presentation describes a study of nitrogen cycle in groundwater-surface water interaction zone (GSIZ) at the US Department of Energy's Hanford Site. Groundwater at Hanford sites has long been documented with nitrate contamination. Nearby Columbia River stage changes of up to 3 m every day because of daily discharge fluctuation from upstream Priest Rapids Dam; resulting an exchange of groundwater and surface water in a short time period. Yet, nitrogen cycle in the GSIZ at Hanford Site remains unclear. Column studies have been used to identify nitrogen metabolism pathways and investigate kinetics of nitrogen cycle in groundwater saturated zone, surface water saturated zone, and GSIZ. Functional gene and protein abundances were determined by qPCR and PRISM-SRM (high-pressure, high-resolution separations coupled with intelligent selection and multiplexing for sensitive selected reaction monitoring) to identify key enzymatic reactions and metabolic pathways of nitrogen cycle. The results showed that dissimilatory nitrate reduction to ammonium (DNRA) competed with denitrification under anaerobic conditions, reducing 30% of NO3- to NH4+, a cation strongly retained on the sediments. As dissolved oxygen intruded the anaerobic zone with river water, NH4+ was oxidized to NO3-, increasing the mobility of NO3-. Multiplicative Monod models were established to describe nitrogen cycle in columns fed with O2 depleted synthetic groundwater and O2 saturated synthetic river water, respectively. The two models were then coupled to predict the dynamic kinetics of nitrogen cycle in GSIZ.

  2. 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.

  3. Incomplete Denitrification Causes Rapid Nitrous Oxide Cycling in the Oceanic Oxygen Minimum Zones

    NASA Astrophysics Data System (ADS)

    Babbin, A. R.; Ward, B. B.; Stocker, R.

    2015-12-01

    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.

  4. 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...

  5. 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

  6. 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.

  7. 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).

  8. Water clustering on nanostructured iron oxide films

    NASA Astrophysics Data System (ADS)

    Merte, Lindsay R.; Bechstein, Ralf; Peng, Guowen; Rieboldt, Felix; Farberow, Carrie A.; Zeuthen, Helene; Knudsen, Jan; Lægsgaard, Erik; Wendt, Stefan; Mavrikakis, Manos; Besenbacher, Flemming

    2014-06-01

    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 moiré-structured iron oxide thin film with a controlled density of hydroxyl groups. While large amorphous monolayer islands form on the bare 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 moiré structure.

  9. 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.

  10. 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

  11. 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

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

    PubMed

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

    2012-12-05

    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.

  13. 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.

  14. 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.

  15. Nano-sized layered Mn oxides as promising and biomimetic water oxidizing catalysts for water splitting in artificial photosynthetic systems.

    PubMed

    Najafpour, Mohammad Mahdi; Heidari, Sima; Amini, Emad; Khatamian, Masoumeh; Carpentier, Robert; Allakhverdiev, Suleyman I

    2014-04-01

    One challenge in artificial photosynthetic systems is the development of artificial model compounds to oxidize water. The water-oxidizing complex of Photosystem II which is responsible for biological water oxidation contains a cluster of four Mn ions bridged by five oxygen atoms. Layered Mn oxides as efficient, stable, low cost, environmentally friendly and easy to use, synthesize, and manufacture compounds could be considered as functional and structural models for the site. Because of the related structure of these Mn oxides and the catalytic centre of the active site of the water oxidizing complex of Photosystem II, the study of layered Mn oxides may also help to understand more about the mechanism of water oxidation by the natural site. This review provides an overview of the current status of layered Mn oxides in artificial photosynthesis and discuss the sophisticated design strategies for Mn oxides as water oxidizing catalysts.

  16. 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.

  17. 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.

  18. Super critical water oxidation on energetic materials

    SciTech Connect

    Sanchez, J.A.

    1993-01-01

    Supercritical water oxidation (SCWO) is an innovative process for the destruction of hazardous wastes that occurs above the critical temperature and pressure of water. In this paper we present results for the oxidation of simple organic wastes and the destruction of explosives. We have tested a 50 gal./day mobile tubular reactor using both acetone and hexane as surrogate aqueous wastes in reaction with excess oxygen. For acetone, our results indicate that the fuel and oxidant can be conveniently premixed before heating and the acetone effectively destroyed (>99.999%). By contrast, hexane, and likely other insoluble flammable organics must be separately preheated to above the critical temperature of water to avoid detonation. With regards to the treatment of explosives, we have demonstrated detection-sensitivity-limited destruction (typically >99.9%) of five explosives, HMX, RDX, TNT, NQ, and PETN, in a smaller scale SCWO reactor. Two alternative methods of increasing processing throughput for explosives, which have very low solubility in water at room temperature, were also investigated. They are the use of slurries and the SCWO postprocessing of the products of explosives hydrolyzed in low-temperature, basic solutions.

  19. Tracer Cycles and Water Ages in Heterogeneous Catchments and Aquifers

    NASA Astrophysics Data System (ADS)

    Kirchner, J. W.; Jasechko, S.

    2015-12-01

    Estimates of catchment mean transit times are often based on seasonal cycles of stable isotope tracers in precipitation and streamflow. In many cases these transit time estimates are derived directly from sine-wave fitting to the observed seasonal isotope cycles. Broadly similar results are also obtained from time-domain convolutions or explicit tracer modeling, because here too the dominant tracer signal that these techniques seek to match is the seasonal isotopic cycle. Here I use simple benchmark tests to show that estimates of mean transit times based on seasonal tracer cycles will typically be wrong by several hundred percent, when applied to catchments with realistic degrees of spatial heterogeneity. This aggregation bias arises from the strong nonlinearity in the relationship between tracer cycle amplitude and mean travel time. A similar bias arises in estimates of mean transit times in nonstationary catchments. Since typical real-world catchments are both spatially heterogeneous and nonstationary, this analysis poses a fundamental challenge to tracer-based estimates of mean transit times. I propose an alternative storage metric, the fraction of "young water" in streamflow, defined as the fraction of runoff with transit times of less than roughly 0.2 years. I show that young water fractions are virtually free of aggregation bias; that is, they can be accurately estimated from tracer cycles in highly heterogeneous mixtures of subcatchments with strongly contrasting transit time distributions. They can also be reliably estimated in strongly nonstationary catchments. Young water fractions can be estimated separately for individual flow regimes, allowing direct determination of how shifts in hydraulic regime alter the fraction of water reaching the stream by fast flowpaths. One can also estimate the chemical composition of idealized "young water" and "old water" end-members, using relationships between young water fractions and solute concentrations across

  20. Photolytic water oxidation catalyzed by a molecular carbene iridium complex.

    PubMed

    Petronilho, Ana; Rahman, Mahfujur; Woods, James A; Al-Sayyed, Haris; Müller-Bunz, Helge; Don MacElroy, J M; Bernhard, Stefan; Albrecht, Martin

    2012-11-14

    The complex IrCl(2)(Cp*)(trz) (trz = triazolylidene), 2, was prepared from readily available 1,3-dimethyl-4-phenyl-1,2,3-triazolium salt. Under basic conditions, the C-bound phenyl group readily cyclometalates, while under acidic conditions, cyclometalation is reversed. The sensitivity of the C(aryl)-Ir bond but not the C(trz)-Ir bond towards acidolysis provided a basis for using 2 as a catalyst in Ce(IV)-mediated water oxidation. The catalytic activity is characterized by a robust catalytic cycle, affording excellent turnover numbers (TON > 20,000). Under cerium-free conditions and in the presence of hematite as a photoelectrode, light-induced activity was observed. The photoelectrochemical reaction is strongly pH-dependent, which requires pH adjustments when running multiple cycle experiments to regenerate the catalytic activity. Analogous chelating complexes display better stability and higher catalytic activity than the monodentate complex 2.

  1. The water-oxidation complex in photosynthesis

    PubMed Central

    Sauer, Kenneth; Yachandra, Vittal K.

    2014-01-01

    Studies of the photosynthetic water-oxidation complex of photosystem II (PS II) using spectroscopic techniques have characterized not only important structural features, but also changes that occur in oxidation state of the Mn4 cluster and in its internal organization during the accumulation of oxidizing equivalents leading to O2 formation. Combining this spectroscopic information with that from the recently published relatively low-resolution X-ray diffraction studies, we have succeeded in limiting the range of likely cluster arrangements. This evidence strongly supports several options proposed earlier by DeRose et al. [J. Am. Chem. Soc. 116 (1994) 5239] and these can be further narrowed using compatibility with electron paramagnetic resonance (EPR) data. PMID:15100026

  2. 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

  3. 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

  4. Scientific Models Help Students Understand the Water Cycle

    ERIC Educational Resources Information Center

    Forbes, Cory; Vo, Tina; Zangori, Laura; Schwarz, Christina

    2015-01-01

    The water cycle is a large, complex system that encompasses ideas across the K-12 science curriculum. By the time students leave fifth grade, they should understand "that a system is a group of related parts that make up a whole and can carry out functions its individual parts cannot" and be able to describe both components and processes…

  5. 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…

  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. 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

  8. Coupled reductive and oxidative sulfur cycling in the phototrophic plate of a meromictic lake.

    PubMed

    Hamilton, T L; Bovee, R J; Thiel, V; Sattin, S R; Mohr, W; Schaperdoth, I; Vogl, K; Gilhooly, W P; Lyons, T W; Tomsho, L P; Schuster, S C; Overmann, J; Bryant, D A; Pearson, A; Macalady, J L

    2014-09-01

    Mahoney Lake represents an extreme meromictic model system and is a valuable site for examining the organisms and processes that sustain photic zone euxinia (PZE). A single population of purple sulfur bacteria (PSB) living in a dense phototrophic plate in the chemocline is responsible for most of the primary production in Mahoney Lake. Here, we present metagenomic data from this phototrophic plate--including the genome of the major PSB, as obtained from both a highly enriched culture and from the metagenomic data--as well as evidence for multiple other taxa that contribute to the oxidative sulfur cycle and to sulfate reduction. The planktonic PSB is a member of the Chromatiaceae, here renamed Thiohalocapsa sp. strain ML1. It produces the carotenoid okenone, yet its closest relatives are benthic PSB isolates, a finding that may complicate the use of okenone (okenane) as a biomarker for ancient PZE. Favorable thermodynamics for non-phototrophic sulfide oxidation and sulfate reduction reactions also occur in the plate, and a suite of organisms capable of oxidizing and reducing sulfur is apparent in the metagenome. Fluctuating supplies of both reduced carbon and reduced sulfur to the chemocline may partly account for the diversity of both autotrophic and heterotrophic species. Collectively, the data demonstrate the physiological potential for maintaining complex sulfur and carbon cycles in an anoxic water column, driven by the input of exogenous organic matter. This is consistent with suggestions that high levels of oxygenic primary production maintain episodes of PZE in Earth's history and that such communities should support a diversity of sulfur cycle reactions.

  9. [The presence of medications in the water cycle].

    PubMed

    van der Hoek, Jan Peter; van Alphen, Jacques; Kaas, Reinoutje; van der Oost, Ron

    2013-01-01

    Medications and radiographic contrast dyes are sometimes detected in surface waters, ground water and drinking water; these have proven detrimental effects on organisms living in such waters The concentration of medications found in drinking water is at least a thousand times below their minimum therapeutic dosages. In humans, the long-term effects of daily exposure to low dosages of medications and 'mixture toxicity' is not known; based on the concentrations and substance toxicity, it is presumed that the risk is nil.. Physicians can play their part in controlling the problem of medications becoming part of the water cycle by taking this into account when prescribing medications. Users can make a difference by handling their medications with care and by returning all unused portions to the pharmacy. The pharmaceutical industry can also do its part by taking degradability, options for removal and the environmental effects of medications into account during their stages of development.

  10. The water and energy cycles in an upcoming NASA reanalysis

    NASA Astrophysics Data System (ADS)

    Chen, J.; Bosilovich, M. G.

    2008-05-01

    Global water and energy cycles are tightly related and critical components of the Earth climate system. In current assimilation systems, model output is only locally constrained by available observations, which are always uncompleted and contaminated by random error and biases. Thus the global water and energy balances are good yet high standard indicators of the performance of an assimilation system. In this study, we use several independent observed datasets to evaluate the water and energy cycles in an upcoming NASA global reanalysis, the Modern Era Retrospective-analysis for Research and Applications (MERRA) based on NASA GEOS-5 data assimilation system. The observed datasets include CERES ERBE-like TOA radiation fluxes, GPCP precipitation, CMAP precipitation etc. Comparison with other reanalyses will also be given.

  11. 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

  12. 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

  13. 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

    2015-10-21

    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.

  14. 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

  15. 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.

  16. 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.

  17. 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.

  18. 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

  19. Water pulses and biogeochemical cycles in arid and semiarid ecosystems.

    PubMed

    Austin, Amy T; Yahdjian, Laura; Stark, John M; Belnap, Jayne; Porporato, Amilcare; Norton, Urszula; Ravetta, Damián A; Schaeffer, Sean M

    2004-10-01

    The episodic nature of water availability in arid and semiarid ecosystems has significant consequences on belowground carbon and nutrient cycling. Pulsed water events directly control belowground processes through soil wet-dry cycles. Rapid soil microbial response to incident moisture availability often results in almost instantaneous C and N mineralization, followed by shifts in C/N of microbially available substrate, and an offset in the balance between nutrient immobilization and mineralization. Nitrogen inputs from biological soil crusts are also highly sensitive to pulsed rain events, and nitrogen losses, particularly gaseous losses due to denitrification and nitrate leaching, are tightly linked to pulses of water availability. The magnitude of the effect of water pulses on carbon and nutrient pools, however, depends on the distribution of resource availability and soil organisms, both of which are strongly affected by the spatial and temporal heterogeneity of vegetation cover, topographic position and soil texture. The 'inverse texture hypothesis' for net primary production in water-limited ecosystems suggests that coarse-textured soils have higher NPP than fine-textured soils in very arid zones due to reduced evaporative losses, while NPP is greater in fine-textured soils in higher rainfall ecosystems due to increased water-holding capacity. With respect to belowground processes, fine-textured soils tend to have higher water-holding capacity and labile C and N pools than coarse-textured soils, and often show a much greater flush of N mineralization. The result of the interaction of texture and pulsed rainfall events suggests a corollary hypothesis for nutrient turnover in arid and semiarid ecosystems with a linear increase of N mineralization in coarse-textured soils, but a saturating response for fine-textured soils due to the importance of soil C and N pools. Seasonal distribution of water pulses can lead to the accumulation of mineral N in the dry season

  20. 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

  1. An engineered polypeptide around nano-sized manganese-calcium oxide: copying plants for water oxidation.

    PubMed

    Najafpour, Mohammad Mahdi; Ghobadi, Mohadeseh Zarei; Sarvi, Bahram; Haghighi, Behzad

    2015-09-14

    Synthesis of new efficient catalysts inspired by Nature is a key goal in the production of clean fuel. Different compounds based on manganese oxide have been investigated in order to find their water-oxidation activity. Herein, we introduce a novel engineered polypeptide containing tyrosine around nano-sized manganese-calcium oxide, which was shown to be a highly active catalyst toward water oxidation at low overpotential (240 mV), with high turnover frequency of 1.5 × 10(-2) s(-1) at pH = 6.3 in the Mn(III)/Mn(IV) oxidation range. The compound is a novel structural and efficient functional model for the water-oxidizing complex in Photosystem II. A new proposed clever strategy used by Nature in water oxidation is also discussed. The new model of the water-oxidizing complex opens a new perspective for synthesis of efficient water-oxidation catalysts.

  2. An engineered polypeptide around nano-sized manganese-calcium oxide: copying plants for water oxidation.

    PubMed

    Najafpour, Mohammad Mahdi; Ghobadi, Mohadeseh Zarei; Sarvi, Bahram; Haghighi, Behzad

    2015-09-14

    Synthesis of new efficient catalysts inspired by Nature is a key goal in the production of clean fuel. Different compounds based on manganese oxide have been investigated in order to find their water-oxidation activity. Herein, we introduce a novel engineered polypeptide containing tyrosine around nano-sized manganese-calcium oxide, which was shown to be a highly active catalyst toward water oxidation at low overpotential (240 mV), with high turnover frequency of 1.5 × 10(-2) s(-1) at pH = 6.3 in the Mn(III)/Mn(IV) oxidation range. The compound is a novel structural and efficient functional model for the water-oxidizing complex in Photosystem II. A new proposed clever strategy used by Nature in water oxidation is also discussed. The new model of the water-oxidizing complex opens a new perspective for synthesis of efficient water-oxidation catalysts. PMID:26017548

  3. 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.

  4. 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.

  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

  7. Water defluoridation by aluminium oxide-manganese oxide composite material.

    PubMed

    Alemu, Sheta; Mulugeta, Eyobel; Zewge, Feleke; Chandravanshi, Bhagwan Singh

    2014-08-01

    In this study, aluminium oxide-manganese oxide (AOMO) composite material was synthesized, characterized, and tested for fluoride removal in batch experiments. AOMO was prepared from manganese(II) chloride and aluminium hydroxide. The surface area of AOMO was found to be 30.7m2/g and its specific density was determined as 2.78 g/cm3. Detailed investigation of the adsorbent by inductively coupled plasma-optical emission spectrometry, inductively coupled plasma-mass spectrometry, and ion chromatography (for sulphate only) showed that it is composed of Al, Mn, SO4, and Na as major components and Fe, Si, Ca, and Mg as minor components. Thermogravimetric analysis was used to study the thermal behaviour of AOMO. X-ray diffraction analysis showed that the adsorbent is poorly crystalline. The point of zero charge was determined as 9.54. Batch experiments (by varying the proportion of MnO, adsorbent dose, contact time, initial F concentration, and raw water pH) showed that fluoride removal efficiency ofAOMO varied significantly with percentage of MnO with an optimum value of about I11% of manganese oxide in the adsorbent. The optimum dose of the adsorbent was 4 g/L which corresponds to the equilibrium adsorption capacity of 4.8 mg F-/g. Both the removal efficiency and adsorption capacity showed an increasing trend with an increase in initial fluoride concentration of the water. The pH for optimum fluoride removal was found to be in the range between 5 and 7. The adsorption data were analysed using the Freundlich, Langmuir, and Dubinirn-Radushkevich models. The minimum adsorption capacity obtained from the non-linear Freundlich isotherm model was 4.94 mg F-/g and the maximum capacity from the Langmuir isotherm method was 19.2mg F-/g. The experimental data of fluoride adsorption on AOMO fitted well to the Freundlich isotherm model. Kinetic studies showed that the adsorption is well described by a non-linear pseudo-second-order reaction model with an average rate constant of 3

  8. New Capabilities for Studies Using Isotopes in the Water Cycle

    NASA Astrophysics Data System (ADS)

    Aggarwal, Pradeep K.; Alduchov, Oleg; Araguás, Luis Araguás; Dogramaci, Shawan; Katzlberger, Gernot; Kriz, Karel; Kulkarni, Kshitij M.; Kurttas, Türker; Newman, Brent D.; Pucher, Alexander

    2007-12-01

    The characterization and quantification of hydrological fluxes within components of the water cycle and across interfaces (e.g., atmosphere/land surface, aquifer/river, soil/plant) are critical for assessing and managing water resources and for understanding the impacts of climate change and variability on the hydrological cycle. Stable isotopes of oxygen and hydrogen, and radioactive isotopes such as tritium and carbon-14, provide unique insights into hydrological and climatic processes at local, regional, and global scales, including the role of groundwater in rivers and lakes, groundwater recharge rates, and sources and recycling rates of atmospheric moisture [Aggarwal et al., 2005; Gat, 1996; Kendall and McDonnell, 1998]. Isotopes also provide critical insights into understanding feedbacks and interactions between physical and biological processes (e.g., ecohydrology).

  9. 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.

  10. 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.

  11. 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.

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

    PubMed

    Rygalov, Vadim Y; Fowler, Philip A; Metz, Joannah M; Wheeler, Raymond M; Bucklin, Ray A

    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.

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

    PubMed

    Rygalov, Vadim Y; Fowler, Philip A; Metz, Joannah M; Wheeler, Raymond M; Bucklin, Ray A

    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. PMID:12481804

  14. 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

  15. 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.

  16. 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.

  17. WaterNet: The NASA water cycle solutions network - Danubian regional applications

    NASA Astrophysics Data System (ADS)

    Matthews, Dave; Brilly, Mitja; Kobold, Mira; Zagar, Mark; Houser, Paul

    2008-11-01

    WaterNet is a new international network of researchers, stakeholders, and end-users of remote sensing tools that will benefit the water resources management community. This paper provides an overview and it discusses the concept of solutions networks focusing on the WaterNet. It invites Danubian research and applications 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 will develop WaterNet by engaging relevant NASA water cycle research resources 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 Water 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 and Community of Practice. WaterNet will then develop strategies to connect researchers and decision-makers via innovative communication strategies, improved user access to NASA and EU - Danubian resources, improved water cycle research community appreciation for user requirements, improved policymaker, management and stakeholder knowledge of research and application products, and improved identification of pathways for progress. Finally, WaterNet will develop relevant benchmarking and metrics, to understand the network's characteristics, to optimize its performance, and to establish sustainability. This paper provides examples of several NASA products based on remote sensing and land data assimilation systems that integrate remotely sensed and in

  18. 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.

  19. 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.

  20. 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 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.

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

    NASA Astrophysics Data System (ADS)

    Cissé, 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 (Δɛp/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.

  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. Activities of Tricarboxylic Acid Cycle Enzymes, Glyoxylate Cycle Enzymes, and Fructose Diphosphatase in Bakers' Yeast During Adaptation to Acetate Oxidation

    PubMed Central

    Gosling, J. P.; Duggan, P. F.

    1971-01-01

    Bakers' yeast oxidizes acetate at a high rate only after an adaptation period during which the capacity of the glyoxylate cycle is found to increase. There was apparently no necessity for the activity of acetyl-coenzyme A synthetase, the capacity of the tricarboxylic acid cycle, or the concentrations of the cytochromes to increase for this adaptation to occur. Elevation of fructose 1,6 diphosphatase occurred only when acetate oxidation was nearly maximal. Cycloheximide almost completely inhibited adaptation as well as increases in the activities of isocitrate lyase and aconitate hydratase, the only enzymes assayed. p-Fluorophenylalanine was partially effective and chloramphenicol did not inhibit at all. The presence of ammonium, which considerably delayed adaptation of the yeast to acetate oxidation, inhibited the increases in the activities of the glyoxylate cycle enzymes to different degrees, demonstrating noncoordinate control of these enzymes. Under the various conditions, the only enzyme activity increase consistently related to the rising oxygen uptake rate was that of isocitrate lyase which apparently limited the activity of the cycle. PMID:5557595

  4. 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.).

  5. 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.

  6. 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.

  7. 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

  8. 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

  9. 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.

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

    DOE PAGES

    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

  11. The effect of different metal ions between nanolayers of manganese oxide on water oxidation.

    PubMed

    Najafpour, Mohammad Mahdi; Isaloo, Mohsen Abbasi; Ghobadi, Mohadeseh Zarei; Amini, Emad; Haghighi, Behzad

    2014-12-01

    Here, we used a strategy to answer to the question that whether Ca(II) ion is specific for water oxidation or not? In the procedure, first we synthesized layered Mn oxides with K(I) between layers and then replaced K(I) by Ca(II), K(I), Mg(II), La(III) or Ni(II). We proposed that Ca(II), K(I), Mg(II), La(III) and Ni(II), between layers are important to form efficient water-oxidizing catalyst, but not specific in water oxidation. However, Cu(II) ions decrease water-oxidizing activity of layered Mn oxides. The result is important to find critical factors in water oxidation by low-cost and environmentally friendly nanolayered Mn oxides.

  12. 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

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

    SciTech Connect

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

    2015-10-27

    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. 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.

  15. 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...

  16. 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

  17. 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.

  18. 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

  19. Water Cycle at Gale Crater Through MSL REMS Observations

    NASA Astrophysics Data System (ADS)

    Harri, Ari-Matti; Genzer, Maria; Kemppinen, Osku; Gomez-Elvira, Javier; McConnochie, Timothy; Savijarvi, Hannu; Polkko, Jouni; de la Torre-Juarez, Manuel; Newman, Claire; Martinez, German; Paton, Mark; Martin-Torres, Javier; Haberle, Robert; Vazquez, Luis; Renno, Nilton; Makinen, Terhi; Schmidt, Walter; Siili, Tero

    2016-04-01

    The Mars Science laboratory (MSL) has been successfully operating at the Gale crater since early August 2012 and provided a wealth of extremely valuable data. That includes atmospheric observations by the REMS (Rover Environmental Monitoring Station) comprising instrumentation for the observation of atmospheric pressure, temperature of the air, ground temperature, wind speed and direction, relative humidity (REMS-H), and UV measurements. The REMS-H device is based on polymeric capacitive humidity sensors developed by Vaisala Inc. and it makes use of transducer electronics section placed in the vicinity of the three (3) humidity sensor heads. The humidity device is mounted on the REMS boom providing ventilation with the ambient atmosphere through a filter protecting the device from airborne dust. We focus on describing the first annual water cycle at the Martian surface using the improved REMS-H calibration for the period of almost two Martian years. The characteristics of the Martian water cycle with the relative humidity, mixing ratio and partial water pressure will be discussed. The results will be constrained through comparison with independent indirect observations and through modeling efforts.

  20. 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

  1. 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.

  2. Reversal of the β-oxidation cycle in Saccharomyces cerevisiae for production of fuels and chemicals.

    PubMed

    Lian, Jiazhang; Zhao, Huimin

    2015-03-20

    Functionally reversing the β-oxidation cycle represents an efficient and versatile strategy for synthesis of a wide variety of fuels and chemicals. However, due to the compartmentalization of cellular metabolisms, reversing the β-oxidation cycle in eukaryotic systems remains elusive. Here, we report the first successful reversal of the β-oxidation cycle in Saccharomyces cerevisiae, an important cell factory for large-scale production of fuels and chemicals. After extensive gene cloning and enzyme activity assays, a reversed β-oxidation pathway was functionally constructed in the yeast cytosol, which led to the synthesis of n-butanol, medium-chain fatty acids (MCFAs), and medium-chain fatty acid ethyl esters (MCFAEEs). The resultant recombinant strain provides a new broadly applicable platform for synthesis of fuels and chemicals in S. cerevisiae.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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).

  9. 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

  10. Water oxidation by amorphous cobalt-based oxides: volume activity and proton transfer to electrolyte bases.

    PubMed

    Klingan, Katharina; Ringleb, Franziska; Zaharieva, Ivelina; Heidkamp, Jonathan; Chernev, Petko; Gonzalez-Flores, Diego; Risch, Marcel; Fischer, Anna; Dau, Holger

    2014-05-01

    Water oxidation in the neutral pH regime catalyzed by amorphous transition-metal oxides is of high interest in energy science. Crucial determinants of electrocatalytic activity were investigated for a cobalt-based oxide film electrodeposited at various thicknesses on inert electrodes. For water oxidation at low current densities, the turnover frequency (TOF) per cobalt ion of the bulk material stayed fully constant for variation of the thickness of the oxide film by a factor of 100 (from about 15 nm to 1.5 μm). Thickness variation changed neither the nanostructure of the outer film surface nor the atomic structure of the oxide catalyst significantly. These findings imply catalytic activity of the bulk hydrated oxide material. Nonclassical dependence on pH was observed. For buffered electrolytes with pKa values of the buffer base ranging from 4.7 (acetate) to 10.3 (hydrogen carbonate), the catalytic activity reflected the protonation state of the buffer base in the electrolyte solution directly and not the intrinsic catalytic properties of the oxide itself. It is proposed that catalysis of water oxidation occurs within the bulk hydrated oxide film at the margins of cobalt oxide fragments of molecular dimensions. At high current densities, the availability of a proton-accepting base at the catalyst-electrolyte interface controls the rate of water oxidation. The reported findings may be of general relevance for water oxidation catalyzed at moderate pH by amorphous transition-metal oxides.

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

    PubMed

    Chen, Wei; Wang, Haotian; Li, Yuzhang; Liu, Yayuan; Sun, Jie; Lee, Sanghan; Lee, Jang-Soo; Cui, Yi

    2015-08-26

    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

  12. 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

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

    PubMed

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

    2014-09-01

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

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

    PubMed

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

    2014-09-01

    The water-oxidizing complex (WOC), also known as the oxygen-evolving complex (OEC), of photosystem II in oxygenic photosynthetic organisms efficiently catalyzes water oxidation. It is, therefore, responsible for the presence of oxygen in the Earth's atmosphere. The WOC is a manganese-calcium (Mn₄CaO₅(H₂O)₄) cluster housed in a protein complex. In this review, we focus on water exchange chemistry of metal hydrates and discuss the mechanisms and factors affecting this chemical process. Further, water exchange rates for both the biological cofactor and synthetic manganese water splitting are discussed. The importance of fully unveiling the water exchange mechanism to understand the chemistry of water oxidation is also emphasized here. This article is part of a special issue entitled: photosynthesis research for sustainability: keys to produce clean energy. PMID:24685431

  15. 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.

  16. Long cycle life lithium ion battery with lithium nickel cobalt manganese oxide (NCM) cathode

    NASA Astrophysics Data System (ADS)

    Liu, Shuang; Xiong, L.; He, C.

    2014-09-01

    Lithium ion batteries with lithium nickel cobalt manganese oxide (NCM) cathode were characterized by extensive cycling (>2000 cycles), discharge rate test, hybrid pulse power characterization test (HPPC), and electrochemical impedance spectroscopy (EIS). The crystal structure, morphology and particle size of cathode materials were characterized by X-ray diffraction and scanning electron microscopy (SEM). It was demonstrated that the rate performance and cycle life of battery are closely related to the cathode material composition and electrode design. With proper selection of cathode composition and electrode design, the lithium ion battery cell achieved close to 3500 cycles with 85% capacity retention at 1C current.

  17. 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.

  18. 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

  19. 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.

  20. Influences of Vegetation Phenological Shifts on Water and Energy Cycle

    NASA Astrophysics Data System (ADS)

    Xu, X.; Riley, W. J.; Koven, C. D.

    2015-12-01

    Remote sensed vegetation indices and field measurements have demonstrated that climate change has influenced vegetation phenology. The phenological changes are expressed in shifts in the timing of spring vegetation activity and the length of the active growing season. According to NDVI data from NOAA and GIMMS, the length of the active growing season north of 45°N has extended by 12 days due to 8 days advancement in spring and 4 days prolongation in autumn between July 1981 and June 1991. The same NDVI dataset from July 1981 to December 1999 has shown the growing season increased by 18 days in Eurasia and 12 days in North America. Phenology regulates vegetation interactions with climate by influencing the energy, water and carbon cycles. Here, we use observations and the Community Land Model 4.5 (CLM4.5) in offline mode and coupled with CESM to evaluate influences of shifts in phenology on energy and water budget and partitioning and on interactions with the atmosphere. Satellite retrieved leaf area index (LAI) is used to prescribe shifts in vegetation phenology in CLM4.5. We find that phenological advancement of 12 days over the past few decades can result in monthly mean changes of (-5-7 Wm-2) in latent heat and (-5-9Wm-2) in sensible heat balance over wide regions. We will discuss (1) the capability of current climate models to predict the impacts of phenological shifts on climate change, (2) seasonal to annual changes in energy and water cycles in response to phenological shifts, (3) the spatial heterogeneity in phenological-induced energy and water partitioning in different plant functional types across regions and continents, and (4) phenology and plant-climate interactions in changing climate.

  1. 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

  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. 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 ...

  4. Life cycle assessment for sustainable metropolitan water systems planning.

    PubMed

    Lundie, Sven; Peters, Gregory M; Beavis, Paul C

    2004-07-01

    Life Cycle Assessment (LCA) is useful as an information tool for the examination of alternative future scenarios for strategic planning. Developing a life cycle assessment for a large water and wastewater system involves making methodological decisions about the level of detail which is retained through different stages of the process. In this article we discuss a methodology tailored to strategic planning needs which retains a high degree of model segmentation in order to enhance modeling of a large, complex system. This is illustrated by a case study of Sydney Water, which is Australia's largest water service provider. A prospective LCA was carried out to examine the potential environmental impacts of Sydney Water's total operations in the year 2021. To our knowledge this is the first study to create an LCA model of an integrated water and wastewater system with this degree of complexity. A "base case" system model was constructed to represent current operating assets as augmented and upgraded to 2021. The base case results provided a basis for the comparison of alternative future scenarios and for conclusions to be drawn regarding potential environmental improvements. The scenarios can be roughly classified in two categories: (1) options which improve the environmental performance across all impact categories and (2) options which improve one indicator and worsen others. Overall environmental improvements are achieved in all categories by the scenarios examining increased demand management, energy efficiency, energy generation, and additional energy recovery from biosolids. The scenarios which examined desalination of seawater and the upgrades of major coastal sewage treatment plants to secondary and tertiary treatment produced an improvement in one environmental indicator but deteriorations in all the other impact categories, indicating the environmental tradeoffs within the system. The desalination scenario produced a significant increase in greenhouse gas

  5. Operation of the Oxide Washer for Water-Washing Solubles out of Impure Pu Oxide

    SciTech Connect

    Dodson, K E; Close, W L; Krikorian, O H; Summers III, H V

    2006-01-30

    An evaluation has been made for using the Oxide Washer to wash water-soluble materials out of impure Pu oxide. It is found that multiple washes are needed to reduce the water-soluble materials to very low levels in the impure Pu oxides. The removal of the wash water from the Oxide Washer is accompanied by particulates of the impure Pu oxide, which subsequently need to be filtered out. In spite of the additional filtration needed, the overall level of manpower required for processing is still only about one third of that for an all-manual operation.

  6. 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.

  7. 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

  8. 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

  9. 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.

  10. 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

  11. Life cycle assessment of nuclear-based hydrogen production via thermochemical water splitting using a copper-chlorine (Cu-Cl) cycle

    NASA Astrophysics Data System (ADS)

    Ozbilen, Ahmet Ziyaettin

    The energy carrier hydrogen is expected to solve some energy challenges. Since its oxidation does not emit greenhouse gases (GHGs), its use does not contribute to climate change, provided that it is derived from clean energy sources. Thermochemical water splitting using a Cu-Cl cycle, linked with a nuclear super-critical water cooled reactor (SCWR), which is being considered as a Generation IV nuclear reactor, is a promising option for hydrogen production. In this thesis, a comparative environmental study is reported of the three-, four- and five-step Cu-Cl thermochemical water splitting cycles with various other hydrogen production methods. The investigation uses life cycle assessment (LCA), which is an analytical tool to identify and quantify environmentally critical phases during the life cycle of a system or a product and/or to evaluate and decrease the overall environmental impact of the system or product. The LCA results for the hydrogen production processes indicate that the four-step Cu-Cl cycle has lower environmental impacts than the three- and five-step Cu-Cl cycles due to its lower thermal energy requirement. Parametric studies show that acidification potentials (APs) and global warming potentials (GWPs) for the four-step Cu-Cl cycle can be reduced from 0.0031 to 0.0028 kg SO2-eq and from 0.63 to 0.55 kg CO2-eq, respectively, if the lifetime of the system increases from 10 to 100 years. Moreover, the comparative study shows that the nuclear-based S-I and the four-step Cu-Cl cycles are the most environmentally benign hydrogen production methods in terms of AP and GWP. GWPs of the S-I and the four-step Cu-Cl cycles are 0.412 and 0.559 kg CO2-eq for reference case which has a lifetime of 60 years. Also, the corresponding APs of these cycles are 0.00241 and 0.00284 kg SO2-eq. It is also found that an increase in hydrogen plant efficiency from 0.36 to 0.65 decreases the GWP from 0.902 to 0.412 kg CO 2-eq and the AP from 0.00459 to 0.00209 kg SO2-eq for the

  12. 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

  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. Tricarboxylic acid cycle intermediate pool size: functional importance for oxidative metabolism in exercising human skeletal muscle.

    PubMed

    Bowtell, Joanna L; Marwood, Simon; Bruce, Mark; Constantin-Teodosiu, Dumitru; Greenhaff, Paul L

    2007-01-01

    The tricarboxylic acid (TCA) cycle is the major final common pathway for oxidation of carbohydrates, lipids and some amino acids, which produces reducing equivalents in the form of nicotinamide adenine dinucleotide and flavin adenine dinucleotide that result in production of large amounts of adenosine triphosphate (ATP) via oxidative phosphorylation. Although regulated primarily by the products of ATP hydrolysis, in particular adenosine diphosphate, the rate of delivery of reducing equivalents to the electron transport chain is also a potential regulatory step of oxidative phosphorylation. The TCA cycle is responsible for the generation of approximately 67% of all reducing equivalents per molecule of glucose, hence factors that influence TCA cycle flux will be of critical importance for oxidative phosphorylation. TCA cycle flux is dependent upon the supply of acetyl units, activation of the three non-equilibrium reactions within the TCA cycle, and it has been suggested that an increase in the total concentration of the TCA cycle intermediates (TCAi) is also necessary to augment and maintain TCA cycle flux during exercise. This article reviews the evidence of the functional importance of the TCAi pool size for oxidative metabolism in exercising human skeletal muscle. In parallel with increased oxidative metabolism and TCA cycle flux during exercise, there is an exercise intensity-dependent 4- to 5-fold increase in the concentration of the TCAi. TCAi concentration reaches a peak after 10-15 minutes of exercise, and thereafter tends to decline. This seems to support the suggestion that the concentration of TCAi may be of functional importance for oxidative phosphorylation. However, researchers have been able to induce dissociations between TCAi pool size and oxidative energy provision using a variety of nutritional, pharmacological and exercise interventions. Brief periods of endurance training (5 days or 7 weeks) have been found to result in reduced TCAi pool

  15. Tricarboxylic acid cycle intermediate pool size: functional importance for oxidative metabolism in exercising human skeletal muscle.

    PubMed

    Bowtell, Joanna L; Marwood, Simon; Bruce, Mark; Constantin-Teodosiu, Dumitru; Greenhaff, Paul L

    2007-01-01

    The tricarboxylic acid (TCA) cycle is the major final common pathway for oxidation of carbohydrates, lipids and some amino acids, which produces reducing equivalents in the form of nicotinamide adenine dinucleotide and flavin adenine dinucleotide that result in production of large amounts of adenosine triphosphate (ATP) via oxidative phosphorylation. Although regulated primarily by the products of ATP hydrolysis, in particular adenosine diphosphate, the rate of delivery of reducing equivalents to the electron transport chain is also a potential regulatory step of oxidative phosphorylation. The TCA cycle is responsible for the generation of approximately 67% of all reducing equivalents per molecule of glucose, hence factors that influence TCA cycle flux will be of critical importance for oxidative phosphorylation. TCA cycle flux is dependent upon the supply of acetyl units, activation of the three non-equilibrium reactions within the TCA cycle, and it has been suggested that an increase in the total concentration of the TCA cycle intermediates (TCAi) is also necessary to augment and maintain TCA cycle flux during exercise. This article reviews the evidence of the functional importance of the TCAi pool size for oxidative metabolism in exercising human skeletal muscle. In parallel with increased oxidative metabolism and TCA cycle flux during exercise, there is an exercise intensity-dependent 4- to 5-fold increase in the concentration of the TCAi. TCAi concentration reaches a peak after 10-15 minutes of exercise, and thereafter tends to decline. This seems to support the suggestion that the concentration of TCAi may be of functional importance for oxidative phosphorylation. However, researchers have been able to induce dissociations between TCAi pool size and oxidative energy provision using a variety of nutritional, pharmacological and exercise interventions. Brief periods of endurance training (5 days or 7 weeks) have been found to result in reduced TCAi pool

  16. The Global Water System Project: Integrative Studies of the Water Cycle (invited)

    NASA Astrophysics Data System (ADS)

    Vorosmarty, C. J.; Lettenmaier, D.; Naiman, R.; Lawford, R.

    2004-05-01

    The water cycle figures prominently in the study of global change. In addition to greenhouse warming and concerns about an accelerated hydrologic cycle, several other anthropogenic factors interact with the water system to produce potentially global-scale effects. Prominent among these are widespread land cover change, urbanization, reservoir construction, irrigated agriculture, destruction of aquatic habitat, and pollution. A rich history of research at the local scale demonstrates the clear impact of such factors on the environment. Evidence now shows that humans are rapidly embedding themselves in the basic character of the water cycle over much broader domains. The collective significance of such a transformation of a basic element of the Earth system remains fundamentally unknown. This presentation summarizes a new project launched as part of the Earth System Science Partnership (ESSP) of the Global Environmental Change Programs (Diversitas, IGBP, IHDP, WCRP) that will study these water cycle changes. The aim of the GWSP is to catalyze our understanding of the dynamics of water in the Earth system, the unique role that humans play in the hydrologic cycle and reciprocal interactions between the biogeophysical and human components of the coupled system. A major emphasis will be on interactions, feedbacks, and thresholds, necessitating a balanced consideration of all factors at play-- physical, chemical, biological, and societal. The GWSP is the product of contributions made by a broad cross-section of the water science and assessment community, with more than 150 contributors to a series of planning meetings, science scoping documents, and a recent Open Science Conference (October 2003; Portsmouth, NH). This paper reviews the scientific rationale for the initiative, presents the Project's key science questions, and describes the emerging agenda for study. Contributions from the North American science community will be reviewed.

  17. Fifty Years of Water Cycle Change expressed in Ocean Salinity

    NASA Astrophysics Data System (ADS)

    Durack, P. J.; Wijffels, S.

    2010-12-01

    Using over 1.6 million profiles of salinity, potential temperature and density from historical archives and Argo, we derive the global field of linear change for ocean state properties over the period 1950-2008, taking care to minimise aliasing associated with seasonal and El Nino Southern Oscillation modes. We find large, robust and spatially coherent multi-decadal linear trends in ocean surface salinities. Increases are found in evaporation-dominated regions and freshening in precipitation-dominated regions. The spatial patterns of surface change strongly resemble the climatological mean surface salinity field, consistent with an amplification of the global water cycle. A robust amplification of the mean salinity pattern of 8% (to 200m depth) is found globally and 5-9% is found in each of the 3 key ocean basins. 20th century runs from the CMIP3 model suite support the relationship between amplified patterns of freshwater flux driving an amplified pattern of ocean surface salinity only in models that warm substantially. Models with volcanic aerosols show a diminished warming response and a corresponding weak response in ocean surface salinity change, which implies dampened changes to the global water cycle. The warming response represented in realistic (when compared to observations) 20th century simulations appear quite similar in their broad zonal patterns to those of the projected 21st century simulations, these projected runs being strongly forced by greenhouse gases. This pattern amplification is mostly absent from 20th century simulations which include volcanic forcing. While we confirm that global mean precipitation only weakly change with surface warming (2-3% K-1), the pattern amplification rate in both the freshwater flux and ocean salinity fields indicate larger responses. Our new observed salinity estimates suggest a change of between 8-16% K-1, close to, or greater than, the theoretical response described by the Clausius-Clapeyron relation. The

  18. Effect of operational cycle time length on nitrogen removal in an alternating oxidation ditch system.

    PubMed

    Mantziaras, I D; Stamou, A; Katsiri, A

    2011-06-01

    This paper refers to nitrogen removal optimization of an alternating oxidation ditch system through the use of a mathematical model and pilot testing. The pilot system where measurements have been made has a total volume of 120 m(3) and consists of two ditches operating in four phases during one cycle and performs carbon oxidation, nitrification, denitrification and settling. The mathematical model consists of one-dimensional mass balance (convection-dispersion) equations based on the IAWPRC ASM 1 model. After the calibration and verification of the model, simulation system performance was made. Optimization is achieved by testing operational cycles and phases with different time lengths. The limits of EU directive 91/271 for nitrogen removal have been used for comparison. The findings show that operational cycles with smaller time lengths can achieve higher nitrogen removals and that an "equilibrium" between phase time percentages in the whole cycle, for a given inflow, must be achieved.

  19. 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

  20. 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

  1. 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

  2. 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.

  3. 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

  4. 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.

  5. 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.

  6. [Effects of different iron oxides on methane emission in paddy soil as related to drying/wetting cycles].

    PubMed

    Zhang, Tian-Jiao; Tang, Jia; Zhuang, Li; Xiong, Ge-Sheng; Liu, Zhi; Zhou, Shun-Gui

    2014-03-01

    This study investigated the effects of iron oxides with different crystallinities, ferrihydrite (SF) and hematite (SH), on the methane emission in paddy soil of South China under different water conditions, alternative drying/wetting cycles (DW) and continuous flooding (CF). The rates of methane emission, methane production potential and concentrations of Fe(II) and Fe(III) were determined. Results showed that compared with CF, the average methane emission rate was greatly inhibited by DW over 61%, and the addition of iron oxides reduced methane emission rates by 53%. Under the circumstance of DW and iron oxides addition, the combined inhibition effect on the average methane emission (65%-94%) and methane production potential (57%-93%) was significantly higher than the single effect caused by DW or iron oxides. Interestingly, DW coupling poorly crystalline ferrihydrite (SF-DW, 94%) posed a more significantly inhibitory effect on the methane emission than coupling crystalline hematite (SH-DW, 65%). Statistical analysis showed that there was a significantly negative correlation between the Fe(III) concentrations and the methane emission rates (R2 = -0.98, P < 0.01). Experimental results showed that DW facilitated the cyclic regeneration of Fe(III), and the Fe(III)/Fe(II) cycle in poorly crystalline ferrihydrite was more susceptible to DW than hematite. This study suggested that alternative drying/wetting cycles can remarkably enhance the inhibitory effect of iron oxides on methane emission from paddy soil, and the coupled suppression effect of DW and poorly crystalline ferrihydrite is more obvious than the coupled effect of DW and crystalline hematite.

  7. Climatically induced sedimentary cycles in Pliocene deep-water carbonates

    SciTech Connect

    Gardulski, A.F. )

    1991-03-01

    Two DSDP sites (86 and 94) on the Campeche ramp in the southern Gulf of Mexico penetrated more than 100 m of Pliocene pelagic ooze. The ooze is primarily carbonate, with a much smaller volcanic ash component than occurs in some Pleistocene sediments at these sites. Cores recovered from these holes display variations in carbonate mineralogy as well as total carbonate and sand abundances that are correlated with the oxygen isotope stratigraphy. Diagenetic loss of Mg-calcite is complete by the base of the Pleistocene, but aragonite, especially high-Sr aragonite forming algal needles that were transported off the shelf to the slope, persists through upper Pliocene cores. Variations in oxygen isotope ratios in planktonic foraminifera occur throughout the Pliocene, although the amplitude of those cycles is smaller than for the Pleistocene, with its more dramatic glacial-interglacial contrasts. As in overlying Pleistocene slope sediments, cooler intervals correspond with greater abundances of aragonite in the upper Pliocene section, reflecting a shift of the shallow, productive shelf seaward across the ramp surface during times of relatively low sea level. However, the aragonite abundances in the Pliocene are reduced on average compared to the Pleistocene. This difference is due in part to diagenetic loss, but also it likely reflects the overall higher sea level that apparently characterized Pliocene oceans, trapping more algal aragonite landward. Although sea level and climatic fluctuations were indeed less extreme in the Pliocene, they were still sufficient to generate sedimentary cycles in deep-water carbonates.

  8. Life Cycle Assesment of Daugavgriva Waste Water Treatment Plant

    NASA Astrophysics Data System (ADS)

    Romagnoli, F.; Sampaio, F.; Blumberga, D.

    2009-01-01

    This paper presents the assessment of the environmental impacts caused by the treatment of Riga's waste water in the Daugavgriva plant with biogas energy cogeneration through the life cycle assessment (LCA). The LCA seems to be a good tool to assess and evaluate the most serious environmental impacts of a facility The results showed clearly that the impact category contributing the most to the total impact -eutrophicationcomes from the wastewater treatment stage. Climate change also seems to be a relevant impact coming from the wastewater treatment stage and the main contributor to the Climate change is N2O. The main environmental benefits, in terms of the percentages of the total impact, associated to the use of biogas instead of any other fossil fuel in the cogeneration plant are equal to: 3,11% for abiotic depletation, 1,48% for climate change, 0,51% for acidification and 0,12% for eutrophication.

  9. 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.

  10. 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

  11. Water cycle observations in forest watersheds of Cambodia

    NASA Astrophysics Data System (ADS)

    Shimizu, A.; Tamai, K.; Kabeya, N.; Shimizu, T.; Iida, S. I.

    2015-12-01

    The Lower Mekong River flows through Cambodia, where forests cover ~60% of the country and are believed to have a marked effect on the water cycle. These tropical seasonal forests in the Cambodian flat lands are very precious in the Indochinese Peninsula as few forests of this type remain. However, few hydrological observations have been conducted in these areas. In Cambodia, deciduous and evergreen forests make up 42% and 33% of the total forest area, respectively. We established experimental watersheds both in deciduous and evergreen forests containing meteorological observation towers in Cambodia and collected various observational data since 2003 (O'Krieng, deciduous forest watershed including a 30-m-high observation tower, 2,245 km2; Stung Chinit, evergreen forest watershed including a 60-m-high observation tower, 3,700 km2 including three small watersheds). The basic data from these sites included various kinds of information related to the composition of vegetation, soil characteristics, etc. Hydrologic data was collected and linked to the above data; the main hydrologic research results follow. The water budget for each watershed was determined using an observational rainfall and runoff dataset. The evapotranspiration rate in an evergreen forest was obtained using various observational methods including the Bowen energy-balance ratio and the bandpass eddy covariance method. The annual evapotranspiration of evergreen forests, estimated using the Bowen energy-balance ratio method and water balance, was about 1100-1200 mm, corresponding to 70-80% of annual rainfall. While considering the importance of the presence of evergreen forest, we conducted sap flow measurements to analyze the transpiration process that maintains water uptake through root systems that reach to depths exceeding 8 m. Characteristics of the evaporation from the forest floor that form an important element of the evaporation system were estimated in both evergreen and deciduous forests.

  12. 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...

  13. 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.

  14. 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.

  15. 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.

  16. 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.

  17. [Stable Isotope Characteristics in Different Water Bodies in Changsha and Implications for the Water Cycle].

    PubMed

    Li, Guang; Zhang, Xin-ping; Zhang, Li-feng; Wang, Yue-feng; Deng, Xiao-jun; Yang, Liu; Lei, Chao-gui

    2015-06-01

    Analysis of the variation characteristics of different water bodies is the basis of applying isotopic tracer technique in regional water cycle research. Based on the samples of atmospheric precipitation, surface water (river water) and groundwater (spring water and well water) in Changsha from January 2012 to December 2013, the study analyzed the variation characteristics of δD and δ(18)O in different water bodies. The results showed that the values of D and 18O in precipitation of Changsha showed obvious seasonal variation because of the seasonal difference of the water vapor source, and it showed significant negative correlation between δ(18)O in precipitation and some meteorological factors such as the temperature and the amount, the local meteoric water line revealed the climatic characteristic of humid and rainy in Changsha; the fluctuation of 8D and 80 in surface water was more moderate than those in precipitation, and the seasonal variation of stable isotope value showed lagging characteristic compared with that in precipitation, the difference of river water line (RWL) indicated that the main supply sources of surface water were changing in different seasons; the fluctuation of δD and δ(18)O in groundwater was the least, the variation ranges and mean values of δD and δ(18)O in spring water and well water were very close, it showed that there were some hydraulic connections in the two water bodies, the values of δD and δ(18)O in groundwater were constantly lower during drought months, this phenomenon might have a certain relationship with the increasing absorbency of tree roots from groundwater. The results of the study have certain guiding significance for rational utilization of water resources in the region. PMID:26387312

  18. 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

  19. 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

  20. 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.

  1. Water cycle at Gale crater through MSL/REMS observations

    NASA Astrophysics Data System (ADS)

    Harri, Ari-Matti; Genzer, Maria; Kemppinen, Osku; Gomez-Elvira, Javier; Savijärvi, Hannu; McConnochie, Tim; De la Torre, Manuel; Haberle, Robert; Polkko, Jouni; Paton, Mark; Richardson, Mark I.; Newman, Claire E.; Siili, Tero; Makinen, Terhi

    2016-10-01

    The Mars Science laboratory (MSL) has been successfully operating at the Gale crater since early August 2012 and has provided a wealth of extremely valuable data. That includes atmospheric observations by the REMS instrument performing atmospheric pressure, temperature of the air, ground temperature, wind speed and direction, relative humidity (REMS-H), and UV measurements.The REMS-H relative humidity device is based on polymeric capacitive humidity sensors developed by Vaisala Inc. and it makes use of three (3) humidity sensor heads. The humidity device is mounted on the REMS boom providing ventilation with the ambient atmosphere through a filter protecting the device from airborne dust.The REMS-H humidity instrument has created an unprecedented data record of more than two full Martian. REMS-H measured the relative humidity and temperature at 1.6 m height for a period of 5 minutes every hour as part of the MSL/REMS instrument package. We focus on describing the annual in situ water cycle with the new REMS-H instrument calibration for the period of two Martian years. The results will be constrained through comparison with independent indirect observations and through modeling efforts.We inferred the hourly atmospheric VMR from the REMS-H observations and compared these VMR measurements with predictions of VMR from our 1D column Martian atmospheric model and regolith to investigate the local water cycle, exchange processes and the local climate in Gale Crater. The strong diurnal variation suggests there are surface-atmosphere exchange processes at Gale Crater during all seasons, which depletes moisture to the ground in the evening and nighttime and release the moisture back to the atmosphere during the daytime. On the other hand, these processes do not result in significant water deposition on the ground, because frost has not been detected in Gale Crater by any of the MSL observations. Hence, our modelling results presumably indicate that adsorption processes take

  2. 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

  3. CP12-mediated protection of Calvin-Benson cycle enzymes from oxidative stress.

    PubMed

    Marri, Lucia; Thieulin-Pardo, Gabriel; Lebrun, Régine; Puppo, Rémy; Zaffagnini, Mirko; Trost, Paolo; Gontero, Brigitte; Sparla, Francesca

    2014-02-01

    Glyceraldehyde-3-phosphate dehydrogenase (GAPDH) and phosphoribulokinase (PRK) are two energy-consuming enzymes of the Calvin-Benson cycle, whose regulation is crucial for the global balance of the photosynthetic process under different environmental conditions. In oxygen phototrophs, GAPDH and PRK regulation involves the redox-sensitive protein CP12. In the dark, oxidized chloroplast thioredoxins trigger the formation of a GAPDH/CP12/PRK complex in which both enzyme activities are down-regulated. In this report, we show that free GAPDH (A4-isoform) and PRK are also inhibited by oxidants like H2O2, GSSG and GSNO. Both in the land plant Arabidopsis thaliana and in the green microalga Chlamydomonas reinhardtii, both enzymes can be glutathionylated as shown by biotinylated-GSSG assay and MALDI-ToF mass spectrometry. CP12 is not glutathionylated but homodisulfides are formed upon oxidant treatments. In Arabidopsis but not in Chlamydomonas, the interaction between oxidized CP12 and GAPDH provides full protection from oxidative damage. In both organisms, preformed GAPDH/CP12/PRK complexes are protected from GSSG or GSNO oxidation, and in Arabidopsis also from H2O2 treatment. Overall, the results suggest that the role of CP12 in oxygen phototrophs needs to be extended beyond light/dark regulation, and include protection of enzymes belonging to Calvin-Benson cycle from oxidative stress.

  4. CP12-mediated protection of Calvin-Benson cycle enzymes from oxidative stress.

    PubMed

    Marri, Lucia; Thieulin-Pardo, Gabriel; Lebrun, Régine; Puppo, Rémy; Zaffagnini, Mirko; Trost, Paolo; Gontero, Brigitte; Sparla, Francesca

    2014-02-01

    Glyceraldehyde-3-phosphate dehydrogenase (GAPDH) and phosphoribulokinase (PRK) are two energy-consuming enzymes of the Calvin-Benson cycle, whose regulation is crucial for the global balance of the photosynthetic process under different environmental conditions. In oxygen phototrophs, GAPDH and PRK regulation involves the redox-sensitive protein CP12. In the dark, oxidized chloroplast thioredoxins trigger the formation of a GAPDH/CP12/PRK complex in which both enzyme activities are down-regulated. In this report, we show that free GAPDH (A4-isoform) and PRK are also inhibited by oxidants like H2O2, GSSG and GSNO. Both in the land plant Arabidopsis thaliana and in the green microalga Chlamydomonas reinhardtii, both enzymes can be glutathionylated as shown by biotinylated-GSSG assay and MALDI-ToF mass spectrometry. CP12 is not glutathionylated but homodisulfides are formed upon oxidant treatments. In Arabidopsis but not in Chlamydomonas, the interaction between oxidized CP12 and GAPDH provides full protection from oxidative damage. In both organisms, preformed GAPDH/CP12/PRK complexes are protected from GSSG or GSNO oxidation, and in Arabidopsis also from H2O2 treatment. Overall, the results suggest that the role of CP12 in oxygen phototrophs needs to be extended beyond light/dark regulation, and include protection of enzymes belonging to Calvin-Benson cycle from oxidative stress. PMID:24211189

  5. Microstructural characterization of the cycling behavior of electrodeposited manganese oxide supercapacitors using 3D electron tomography

    NASA Astrophysics Data System (ADS)

    Dalili, N.; Clark, M. P.; Davari, E.; Ivey, D. G.

    2016-10-01

    Manganese oxide has been investigated extensively as an electrochemical capacitor or supercapacitor electrode material. Manganese oxide is inexpensive to fabricate and exhibits relatively high capacitance values, i.e., in excess of 200 F g-1 in many cases; the actual value depends very much on the fabrication method and test conditions. The cycling behavior of Mn oxide, fabricated using anodic electrodeposition, is investigated using slice and view techniques, via a dual scanning electron microscope (SEM) and focused ion beam (FIB) instrument to generate three-dimensional (3D) images, coupled with electrochemical characterization. The initial as-fabricated electrode has a rod-like appearance, with a fine-scale, sheet-like morphology within the rods. The rod-like structure remains after cycling, but there are significant morphological changes. These include partial dissolution of Mn oxide followed by redeposition of Mn oxide in regions close to the substrate. The redeposited material has a finer morphology than the original as-fabricated Mn oxide. The Mn oxide coverage is also better near the substrate. These effects result in an increase in the specific capacitance.

  6. 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.

  7. 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 La(1-x)Sr(x)BO3 perovskites and La(2-x)Sr(x)BO4 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.

  8. Manganese-oxidizing and -reducing microorganisms isolated from biofilms in chlorinated drinking water systems.

    PubMed

    Cerrato, José M; Falkinham, Joseph O; Dietrich, Andrea M; Knocke, William R; McKinney, Chad W; Pruden, Amy

    2010-07-01

    The interaction of chemical, physical and biological factors that affect the fate, transport and redox cycling of manganese in engineered drinking water systems is not clearly understood. This research investigated the presence of Mn-oxidizing and -reducing bacteria in conventional water treatment plants exposed to different levels of chlorine. Mn(II)-oxidizing and Mn(IV)-reducing bacteria, principally Bacillus spp., were isolated from biofilm samples recovered from four separate drinking water systems. Rates of Mn-oxidation and -reduction for selected individual isolates were represented by pseudo-first-order kinetics. Pseudo-first-order rate constants were obtained for Mn-oxidation (range: 0.106-0.659 days(-1)), aerobic Mn-reduction (range: 0.036-0.152 days(-1)), and anaerobic Mn-reduction (range: 0.024-0.052 days(-1)). The results indicate that microbial-catalyzed Mn-oxidation and -reduction (aerobic and anaerobic) can take place simultaneously in aqueous environments exposed to considerable oxygen and chlorine levels and thus affect Mn-release and -deposition in drinking water systems. This has important implications for Mn-management strategies, which typically assume Mn-reduction is not possible in the presence of chlorine and oxidizing conditions.

  9. Highly efficient and robust molecular ruthenium catalysts for water oxidation.

    PubMed

    Duan, Lele; Araujo, Carlos Moyses; Ahlquist, Mårten S G; Sun, Licheng

    2012-09-25

    Water oxidation catalysts are essential components of light-driven water splitting systems, which could convert water to H(2) driven by solar radiation (H(2)O + hν → 1/2O(2) + H(2)). The oxidation of water (H(2)O → 1/2O(2) + 2H(+) + 2e(-)) provides protons and electrons for the production of dihydrogen (2H(+) + 2e(-) → H(2)), a clean-burning and high-capacity energy carrier. One of the obstacles now is the lack of effective and robust water oxidation catalysts. Aiming at developing robust molecular Ru-bda (H(2)bda = 2,2'-bipyridine-6,6'-dicarboxylic acid) water oxidation catalysts, we carried out density functional theory studies, correlated the robustness of catalysts against hydration with the highest occupied molecular orbital levels of a set of ligands, and successfully directed the synthesis of robust Ru-bda water oxidation catalysts. A series of mononuclear ruthenium complexes [Ru(bda)L(2)] (L = pyridazine, pyrimidine, and phthalazine) were subsequently synthesized and shown to effectively catalyze Ce(IV)-driven [Ce(IV) = Ce(NH(4))(2)(NO(3))(6)] water oxidation with high oxygen production rates up to 286 s(-1) and high turnover numbers up to 55,400.

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

    PubMed

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

    2015-03-17

    -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.

  11. 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.

  12. 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.

  13. Structural rearrangements and reaction intermediates in a di-Mn water oxidation catalyst.

    PubMed

    Vallés-Pardo, J L; de Groot, H J M; Buda, F

    2012-11-28

    By using first-principles molecular dynamics simulations combined with metadynamics to simulate rare events we analyse competing reaction coordinates for a di-Mn water oxidation catalyst ([(bis(imino)pyridine)(H(2)O)Mn(IV)(μ-O)(2)Mn(V)(O)(bis(imino)pyridine)](3+)). The catalytic water oxidation cycle of the complex is examined by addressing the thermodynamic accessibility of the hydroperoxo species that is considered a critical and rate-limiting intermediate. To achieve this, hybrid quantum-mechanics/molecular-mechanics (QM/MM) and full QM simulations have been performed for an explicit treatment of the water environment that plays an active role in the reaction processes. Starting from a likely active species for the O-O bond formation, we observe that during the water approach to the oxo ligand a facile structural rearrangement of the complex takes place, leading to the opening of one μ-O bridge and the release of a water ligand, and resulting in two pentacoordinated Mn centers. This complex appears weakly active in the water oxidation process, since a concerted reaction is required to establish a Mn-OOH hydroperoxo intermediate. The slow kinetics of a concerted reaction can allow other processes, including linear degradation of the catalyst, to take precedence over catalytic water oxidation.

  14. Simultaneous production of desalinated water and power using a hybrid-cycle OTEC plant

    SciTech Connect

    Panchal, C.B.; Bell, K.J.

    1987-05-01

    A systems study for simultaneous production of desalinated water and electric power using the hybrid-cycle OTEC system was carried out. The hybrid cycle is a combination of open and closed-cycle OTEC systems. A 10 MWe shore-based hybrid-cycle OTEC plant is discussed and corresponding operating parameters are presented. Design and plant operating criteria for adjusting the ratio of water production to power generation are described and their effects on the total system were evaluated. The systems study showed technical advantages of the hybrid-cycle power system as compared to other leading OTEC systems for simultaneous production of desalinated water and electric power generation.

  15. Oxidation behavior of Incoloy 800 under simulated supercritical water conditions

    NASA Astrophysics Data System (ADS)

    Fulger, M.; Ohai, D.; Mihalache, M.; Pantiru, M.; Malinovschi, V.

    2009-03-01

    For a correct design of supercritical water-cooled reactor (SCWR) components, data regarding the behavior of candidate materials in supercritical water are necessary. Corrosion has been identified as a critical problem because the high temperature and the oxidative nature of supercritical water may accelerate the corrosion kinetics. The goal of this paper is to investigate the oxidation behavior of Incoloy 800 exposed in autoclaves under supercritical water conditions for up to 1440 h. The exposure conditions (thermal deaerated water, temperatures of 723, 773, 823 and 873 K and a pressure of 25 MPa) have been selected as relevant for a supercritical power plant concept. To investigate the structural changes of the oxide films, X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectrometry (EDX) and electrochemical impedance spectroscopy (EIS) analyses were used. Results show changes in the oxides chemical composition, microstructure and thickness versus testing conditions (pressure, temperature and time). The oxide films are composed of two layers: an outer layer enriched in Fe oxide and an inner layer enriched in Cr and Ni oxides corresponding to small cavities supposedly due to internal oxidation.

  16. 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.

  17. 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 (PQH(2)) 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 PQH(2) per cytochrome b(6)f (Cyt b(6)f) 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 950 nm. The PSII-reduced PQH(2) molecules were oxidized with multi-phase overall kinetics, τ(d)=1, τ(p)=5.6 and τ(s)=16 ms (22 °C). We conclude that τ(d) characterizes PSII processes and diffusion, τ(p) is the bifurcated oxidation of the primary quinol and τ(s) 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

  18. The oxidation of H 2S in Black Sea waters

    NASA Astrophysics Data System (ADS)

    Millero, Frank J.

    The oxidation of H 2S with oxygen was measured in Black Sea waters at 25°C. The measurements were made on mixtures of deep waters and surface waters. The oxidation rates were found to be 10 times faster than the rates for surface seawater (Black Sea and Gulf Stream) with added H 2S. Since the rates were the same for filtered (0.2 μm) and unfiltered waters, the increase in the rates appears to be abiotic and caused by solutes dissolved in the deep waters. Laboratory measurements indicate that dissolved Fe 2+ is the likely cause of the rate increase. The oxidation of Fe(II) yields particulate Fe(III) that can catalyse the oxidation and also oxidize H 2S. Preliminary measurements of the rates of oxidation of SO 32- and S 2O 32- in oxygenated deep Black Sea waters are also presented. These measurements indicate that particulate Fe(III) also may accelerate the rates of oxidation of SO 32-.

  19. Highly efficient binuclear ruthenium catalyst for water oxidation.

    PubMed

    Sander, Anett C; Maji, Somnath; Francàs, Laia; Böhnisch, Torben; Dechert, Sebastian; Llobet, Antoni; Meyer, Franc

    2015-05-22

    Water splitting is one of the key steps in the conversion of sunlight into a usable renewable energy carrier such as dihydrogen or more complex chemical fuels. Developing rugged and highly efficient catalysts for the oxidative part of water splitting, the water oxidation reaction generating dioxygen, is a major challenge in the field. Herein, we introduce a new, and rationally designed, pyrazolate-based diruthenium complex with the highest activity in water oxidation catalysis for binuclear systems reported to date. Single-crystal X-ray diffraction showed favorable preorganization of the metal ions, well suited for binding two water molecules at a distance adequate for OO bond formation; redox titrations as well as spectroelectrochemistry allowed characterization of the system in several oxidation states. Low oxidation potentials reflect the trianionic character of the elaborate compartmental pyrazolate ligand furnished with peripheral carboxylate groups. Water oxidation has been mediated both by a chemical oxidant (Ce(IV) )-by means of manometry and a Clark electrode for monitoring the dioxygen production-and electrochemically with impressive activities.

  20. 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

  1. 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

  2. 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

  3. 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.

  4. Unification of catalytic water oxidation and oxygen reduction reactions: amorphous beat crystalline cobalt iron oxides.

    PubMed

    Indra, Arindam; Menezes, Prashanth W; Sahraie, Nastaran Ranjbar; Bergmann, Arno; Das, Chittaranjan; Tallarida, Massimo; Schmeißer, Dieter; Strasser, Peter; Driess, Matthias

    2014-12-17

    Catalytic water splitting to hydrogen and oxygen is considered as one of the convenient routes for the sustainable energy conversion. Bifunctional catalysts for the electrocatalytic oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) are pivotal for the energy conversion and storage, and alternatively, the photochemical water oxidation in biomimetic fashion is also considered as the most useful way to convert solar energy into chemical energy. Here we present a facile solvothermal route to control the synthesis of amorphous and crystalline cobalt iron oxides by controlling the crystallinity of the materials with changing solvent and reaction time and further utilize these materials as multifunctional catalysts for the unification of photochemical and electrochemical water oxidation as well as for the oxygen reduction reaction. Notably, the amorphous cobalt iron oxide produces superior catalytic activity over the crystalline one under photochemical and electrochemical water oxidation and oxygen reduction conditions.

  5. Multiple Observation Types Jointly Constrain Terrestrial Carbon and Water Cycles

    NASA Astrophysics Data System (ADS)

    Raupach, M. R.; Haverd, V.; Briggs, P. R.; Canadell, J.; Davis, S. J.; Isaac, P. R.; Law, R.; Meyer, M.; Peters, G. P.; Pickett Heaps, C.; Roxburgh, S. H.; Sherman, B.; van Gorsel, E.; Viscarra Rossel, R.; Wang, Z.

    2012-12-01

    Information about the carbon cycle potentially constrains the water cycle, and vice versa. This paper explores the utility of multiple observation sets to constrain carbon and water fluxes and stores in a land surface model, and a resulting determination of the Australian terrestrial carbon budget. Observations include streamflow from 416 gauged catchments, measurements of evapotranspiration (ET) and net ecosystem production (NEP) from 12 eddy-flux sites, litterfall data, and data on carbon pools. The model is a version of CABLE (the Community Atmosphere-Biosphere-Land Exchange model), coupled with CASAcnp (a biogeochemical model) and SLI (Soil-Litter-Iso, a soil hydrology model including liquid and vapour water fluxes and the effects of litter). By projecting observation-prediction residuals onto model uncertainty, we find that eddy flux measurements provide a significantly tighter constraint on Australian continental net primary production (NPP) than the other data types. However, simultaneous constraint by multiple data types is important for mitigating bias from any single type. Results emerging from the multiply-constrained model are as follows (with all values applying over 1990-2011 and all ranges denoting ±1 standard error): (1) on the Australian continent, a predominantly semi-arid region, over half (0.64±0.05) of the water loss through ET occurs through soil evaporation and bypasses plants entirely; (2) mean Australian NPP is 2200±400 TgC/y, making the NPP/precipitation ratio about the same for Australia as the global land average; (3) annually cyclic ("grassy") vegetation and persistent ("woody") vegetation respectively account for 0.56±0.14 and 0.43±0.14 of NPP across Australia; (4) the average interannual variability of Australia's NEP (±180 TgC/y) is larger than Australia's total anthropogenic greenhouse gas emissions in 2011 (149 TgCeq/y), and is dominated by variability in desert and savannah regions. The mean carbon budget over 1990

  6. 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, Pirkko; 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.

  7. 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.

  8. 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.

  9. 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)

  10. 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.

  11. 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.

  12. Sensitivity Analysis of Reprocessing Cooling Times on Light Water Reactor and Sodium Fast Reactor Fuel Cycles

    SciTech Connect

    R. M. Ferrer; S. Bays; M. Pope

    2008-04-01

    The purpose of this study is to quantify the effects of variations of the Light Water Reactor (LWR) Spent Nuclear Fuel (SNF) and fast reactor reprocessing cooling time on a Sodium Fast Reactor (SFR) assuming a single-tier fuel cycle scenario. The results from this study show the effects of different cooling times on the SFR’s transuranic (TRU) conversion ratio (CR) and transuranic fuel enrichment. Also, the decay heat, gamma heat and neutron emission of the SFR’s fresh fuel charge were evaluated. A 1000 MWth commercial-scale SFR design was selected as the baseline in this study. Both metal and oxide CR=0.50 SFR designs are investigated.

  13. 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.

  14. Ni-based heterogeneous catalyst from a designed molecular precursor for the efficient electrochemical water oxidation.

    PubMed

    Kuznetsov, Denis A; Konev, Dmitry V; Komarova, Natal'ya S; Ionov, Andrey M; Mozhchil, Rais N; Fedyanin, Ivan V

    2016-07-28

    Bimetallic Ni-Mo alkoxide was synthesized and exploited as the single-source precursor for the solution-processed deposition of the mixed-oxide layers on different conducting surfaces. Upon potential cycling in 1 M NaOH, these composites convert, in situ, into highly porous NiOx/NiOOH catalysts characterized by the high electrocatalytic activity for water oxidation under both basic (pH 13.6) and near neutral (pH 9.2) conditions. PMID:27354324

  15. 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

  16. 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.

  17. 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

  18. Catalytic water oxidation by mononuclear Ru complexes with an anionic ancillary ligand.

    PubMed

    Tong, Lianpeng; Inge, A Ken; Duan, Lele; Wang, Lei; Zou, Xiaodong; Sun, Licheng

    2013-03-01

    Mononuclear Ru-based water oxidation catalysts containing anionic ancillary ligands have shown promising catalytic efficiency and intriguing properties. However, their insolubility in water restricts a detailed mechanism investigation. In order to overcome this disadvantage, complexes [Ru(II)(bpc)(bpy)OH2](+) (1(+), bpc = 2,2'-bipyridine-6-carboxylate, bpy = 2,2'-bipyridine) and [Ru(II)(bpc)(pic)3](+) (2(+), pic = 4-picoline) were prepared and fully characterized, which features an anionic tridentate ligand and has enough solubility for spectroscopic study in water. Using Ce(IV) as an electron acceptor, both complexes are able to catalyze O2-evolving reaction with an impressive rate constant. On the basis of the electrochemical and kinetic studies, a water nucleophilic attack pathway was proposed as the dominant catalytic cycle of the catalytic water oxidation by 1(+), within which several intermediates were detected by MS. Meanwhile, an auxiliary pathway that is related to the concentration of Ce(IV) was also revealed. The effect of anionic ligand regarding catalytic water oxidation was discussed explicitly in comparison with previously reported mononuclear Ru catalysts carrying neutral tridentate ligands, for example, 2,2':6',2″-terpyridine (tpy). When 2(+) was oxidized to the trivalent state, one of its picoline ligands dissociated from the Ru center. The rate constant of picoline dissociation was evaluated from time-resolved UV-vis spectra.

  19. 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.

  20. 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

  1. 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.

  2. 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.

  3. Selective electrochemical generation of hydrogen peroxide from water oxidation

    DOE PAGES

    Viswanathan, Venkatasubramanian; Hansen, Heine A.; Norskov, Jens K.

    2015-10-08

    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, wemore » 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. Furthermore, we present a rational design principle for the selectivity in electrochemical water oxidation and identify new material candidates that could perform H2O2 evolution selectively.« less

  4. Selective electrochemical generation of hydrogen peroxide from water oxidation

    SciTech Connect

    Viswanathan, Venkatasubramanian; Hansen, Heine A.; Norskov, Jens K.

    2015-10-08

    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. Furthermore, we present a rational design principle for the selectivity in electrochemical water oxidation and identify new material candidates that could perform H2O2 evolution selectively.

  5. 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.

  6. Research on Water cycle Impact of South-to-North Water Diversion Project to Handan District Using MODCYCLE Model

    NASA Astrophysics Data System (ADS)

    Lu, Chuiyu; Bi, Xue; Qin, Dayong; Wang, Lin

    2010-05-01

    South-to-North Water Diversion Project is a huge interbasin water transfer project which is being constructed in China. The purpose of the project is to solve water scarcity crisis in North China. What is the water cycle response of local water cycle system to transferred water is an important topic which needs in-depth research. For this purpose, the article selected Handan district as the representative area of North China, and use MODCYCLE model as the simulating tool to do the study. MODCYCLE model is a half-distributed basin scale hydrologic / water cycle model developed by IWHR, its main simulating theory is similar to the world widely used SWAT model. MODCYCLE is developed by Object Oriented Programming method in C++ language and its input and output is based on database. A remarkable character of the model is that it supports parallel computing. Under multicore environment, the model's computing efficient will be dramatically enhanced. Furthermore, some important water cycle processes such as water surface-ponding on soil top, is considered in the model. Firstly during the study, the research simulated the water cycle process of Handan district in present situation by a 10 years dataset from 1998 to 2007. In this process the model's main parameters were being calibrated. Then based on the calibrated model and correspond to the water demand development predictions in the future, three different scenarios were simulated. These scenarios were set on different water use assumptions and strategies. By compare the scenario's forecast results, acknowledge of the role played by transferred water in the whole water cycle system of Handan district were figured out, as well as the water cycle evolution trends under different scenarios. The research indicated that the allocated transfer water of 0.47 billion m3 to Handan district during the coming first-stage water transfer plan of the project can only relieve the degradation rate of the water cycle system, mainly

  7. 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.

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

    DOE PAGES

    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

  9. 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

  10. 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

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. Energetic basis of catalytic activity of layered nanophase calcium manganese oxides for water oxidation.

    PubMed

    Birkner, Nancy; Nayeri, Sara; Pashaei, Babak; Najafpour, Mohammad Mahdi; Casey, William H; Navrotsky, Alexandra

    2013-05-28

    Previous measurements show that calcium manganese oxide nanoparticles are better water oxidation catalysts than binary manganese oxides (Mn3O4, Mn2O3, and MnO2). The probable reasons for such enhancement involve a combination of factors: The calcium manganese oxide materials have a layered structure with considerable thermodynamic stability and a high surface area, their low surface energy suggests relatively loose binding of H2O on the internal and external surfaces, and they possess mixed-valent manganese with internal oxidation enthalpy independent of the Mn(3+)/Mn(4+) ratio and much smaller in magnitude than the Mn2O3-MnO2 couple. These factors enhance catalytic ability by providing easy access for solutes and water to active sites and facile electron transfer between manganese in different oxidation states.

  17. 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.

  18. 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

  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. 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.

  1. The Effects of Radiatively Active Water Ice Clouds on the Martian Global Seasonal Water Cycle

    NASA Astrophysics Data System (ADS)

    Haberle, Robert M.; Montmessin, F.; Kahre, M. A.; Hollingsworth, J. L.; Schaeffer, J.; de Brouchoven de Bergeyck, A.; Wilson, J.

    2010-10-01

    Recently, Mars General Circulation Models (MGCM) have begun implementing cloud microphysics packages to better account for their role in the water cycle. Here, we discuss the importance of their radiative effects. For the past several years we have been implementing and testing a state-of-the-art cloud microphysics package into the NASA/Ames MGCM. This package accounts for the nucleation, growth, transport, and settling of a size distribution water ice cloud particles in a self-consistent fashion. The model also has flags to activate their solar and infrared radiative effects, which depend on the size and dust content of the ice particles. We have performed two simulations of the global water cycle on Mars: one in which the clouds are radiatively inert, and one in which they are radiatively active. We find that the thermal structure of the atmosphere in the radiatively active cloud run compares better with MGS TES and MRO MCS data. However, the water cycle dries out considerably with radiatively active clouds. There are several reasons for this but the main reason appears to be related to a cooling of the North Polar Residual Cap (NPRC) in the model that is brought about by the reflective nature of the clouds that develop in the lower atmosphere immediately above the NPRC. These clouds increase the planetary albedo at these latitudes and reduce the solar flux at the surface, which is not sufficiently compensated for by an increase in downward infrared emission. Our conclusion at this point, based upon comparison with MRO MCS and MARCI data, is that the model is overpredicting the cloud fields in the vicinity of the NPRC.

  2. Anomalous dielectric relaxation of water confined in graphite oxide

    SciTech Connect

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

    2015-09-28

    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 {sup 13}C and {sup 1}H 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. P{sub 1} expresses the reorientation of water confined inside inter-grain voids, and P{sub 2}, the rotation of intercalated water molecules confined in interlayers. The present work reveals a new process P{sub 3}, 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.

  3. 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.

  4. 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

  5. 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…

  6. Cyanamide route to calcium-manganese oxide foams for water oxidation.

    PubMed

    Baktash, Elham; Zaharieva, Ivelina; Schröder, Marc; Goebel, Caren; Dau, Holger; Thomas, Arne

    2013-12-28

    In nature, photosynthetic water oxidation is efficiently catalysed at a protein-bound μ-oxido Mn4Ca cluster. This cluster consists of earth abundant, non-toxic elements and serves as a paragon for development of synthetic catalysts. In this study we developed porous calcium-manganese oxides with a unique foam-like nanostructure prepared via a facile and robust synthetic route using cyanamide as a porogen. A series of such oxide foams annealed at different temperatures was characterized by TEM, SEM, XRD, N2 physisorption, and X-ray absorption spectroscopy (XAS) in order to correlate crystallinity, atomic structure, surface area and oxidation state of the materials with catalytic activity. Some of the resulting Ca-Mn oxides show high activity as catalysts for water oxidation in the presence of cerium(iv) ammonium nitrate as a non-oxo transfer oxidant. An amorphous calcium-manganese-oxide foam with 130 m(2) g(-1) surface area and Mn oxidation state of +3.6 was identified to be most active; its activity is superior to previously reported Ca-Mn oxides. At the atomic level, this material shares structural motifs with the biological paragon as revealed by dual-edge XAS at the Mn and Ca K-edge. Rather than nanostructure and surface area, the atomic structure of the Ca-Mn oxide and the extent of structural order appear to be crucial determinants of catalytic activity. Fully disordered low-valent Mn materials as well as high-valent but crystalline Mn-Ca oxides are unreactive. Highly disordered variants of layered manganese oxide with Ca and water molecules interfacing layer fragments are most reactive. PMID:24091767

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

    NASA Astrophysics Data System (ADS)

    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.

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

    NASA Astrophysics Data System (ADS)

    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.

  9. 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).

  10. 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.

  11. 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...

  12. Efficient water oxidation catalyzed by mononuclear ruthenium(II) complexes incorporating Schiff base ligands.

    PubMed

    Li, Ting-Ting; Chen, Yong; Li, Fu-Min; Zhao, Wei-Liang; Wang, Chuan-Jun; Lv, Xiao-Jun; Xu, Quan-Qing; Fu, Wen-Fu

    2014-06-23

    Four new charge-neutral ruthenium(II) complexes containing dianionic Schiff base and isoquinoline or 4-picoline ligands were synthesized and characterized by NMR and ESI-MS spectroscopies, elemental analysis, and X-ray diffraction. The complexes exhibited excellent chemical water oxidation activity and high stability under acidic conditions (pH 1.0) using (NH4)2Ce(NO3)6 as a sacrificial electron acceptor. The high catalytic activities of these complexes for water oxidation were sustained for more than 10 h at low concentrations. High turnover numbers of up to 3200 were achieved. A water nucleophilic attack mechanism was proposed. A Ru(V)=O intermediate was detected during the catalytic cycle by high-resolution mass spectrometry.

  13. Gas engine bottoming cycles with ammonia-water mixtures as working fluid

    SciTech Connect

    Jonsson, M.; Thorin, E.; Svedberg, G.

    1999-07-01

    Gas engines and diesel engines can be used for power generation in small-scale industrial and utility power plants. A bottoming cycle recovering heat from the exhaust gas, charge air, jacket water and lubrication oil can increase the power output of a gas or diesel engine power plant. The current study investigates ammonia-water power cycles as bottoming cycles to natural gas fired gas engines. The engines used in the calculations are 16V25SG and 18V34SG from Wartsila NSD. The configurations of the bottoming processes have been changed in order to achieve better temperature matching in the heat exchangers. The ammonia-water cycles have been compared to a simple Rankine steam cycle. All cycles have been optimized to give maximum power output. The ammonia-water bottoming cycles generate 18--54% more power than a simple Rankine steam cycle. An economic estimation of the bottoming cycles shows that the extra equipment needed for an ammonia-water cycle may be justified by the extra amount of power generated.

  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. 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

  16. 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

  17. Microbial cycling, oxidative weathering, and the triple oxygen isotope consequences for marine sulfate

    NASA Astrophysics Data System (ADS)

    Johnston, D. T.; Cowie, B.; Turchyn, A. V.; Antler, G.; Gill, B. C.; Berelson, W.

    2015-12-01

    Microorganisms are responsible for most geochemical sulfur cycling in the ocean. On both modern and geological time scales, stable isotope ratios often serve as a mechanism to track conspicuous or coupled microbial processes, which in turn inform burial fluxes. The most common example of this approach is the use of sulfur isotopes in sulfate and sulfide (both aqueous and in mineral form) to track everything from rates of microbial processes through to the presence/absence of certain metabolic processes in a given environment. The use of oxygen isotope ratios in sulfate has developed in a similar fashion, providing complementary information to that of sulfur isotopes. Through our current work, we will extend the application of oxygen isotopes to include the trace stable oxygen isotope, 17O. These data are facilitated by a new laser F2 fluorination technique running at Harvard, and accompanied by the calibration of a suite of common sulfate standards. At first blush, 16O - 17O - 18O systematics should carry mass-dependent microbial fractionations with process-specific mass laws that are resolvable at the level of our analytical precision. We look to calibrate these biogeochemical effects through the integrated picture captured in marine pore water sulfate profiles, where the 18O/16O is known to evolve. In compliment, riverine sulfate (the sulfate input to the ocean) is an oxidative weathering product and is posited to carry a memory effect of tropospheric O2. Interestingly, the 17O/16O of that O2 carries a mass-independent signal reflecting the balance between stratospheric reactions and Earth surface biospheric fluxes. Through this presentation, we look to calibrate the controls on the balance between biospheric and atmospheric contributions to the marine sulfate reservoir. This is enabled by a series of isotope mass-balance models and with the ultimate goal of developing the geological triple oxygen isotope records of sulfate as a new environmental proxy for paleo

  18. 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.

  19. 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

  20. Nanostructured manganese oxides as highly active water oxidation catalysts: a boost from manganese precursor chemistry.

    PubMed

    Menezes, Prashanth W; Indra, Arindam; Littlewood, Patrick; Schwarze, Michael; Göbel, Caren; Schomäcker, Reinhard; Driess, Matthias

    2014-08-01

    We present a facile synthesis of bioinspired manganese oxides for chemical and photocatalytic water oxidation, starting from a reliable and versatile manganese(II) oxalate single-source precursor (SSP) accessible through an inverse micellar molecular approach. Strikingly, thermal decomposition of the latter precursor in various environments (air, nitrogen, and vacuum) led to the three different mineral phases of bixbyite (Mn2 O3 ), hausmannite (Mn3 O4 ), and manganosite (MnO). Initial chemical water oxidation experiments using ceric ammonium nitrate (CAN) gave the maximum catalytic activity for Mn2 O3 and MnO whereas Mn3 O4 had a limited activity. The substantial increase in the catalytic activity of MnO in chemical water oxidation was demonstrated by the fact that a phase transformation occurs at the surface from nanocrystalline MnO into an amorphous MnOx (1oxidizing agent. Photocatalytic water oxidation in the presence of [Ru(bpy)3 ](2+) (bpy=2,2'-bipyridine) as a sensitizer and peroxodisulfate as an electron acceptor was carried out for all three manganese oxides including the newly formed amorphous MnOx . Both Mn2 O3 and the amorphous MnOx exhibit tremendous enhancement in oxygen evolution during photocatalysis and are much higher in comparison to so far known bioinspired manganese oxides and calcium-manganese oxides. Also, for the first time, a new approach for the representation of activities of water oxidation catalysts has been proposed by determining the amount of accessible manganese centers. PMID:25044528

  1. Nanostructured manganese oxides as highly active water oxidation catalysts: a boost from manganese precursor chemistry.

    PubMed

    Menezes, Prashanth W; Indra, Arindam; Littlewood, Patrick; Schwarze, Michael; Göbel, Caren; Schomäcker, Reinhard; Driess, Matthias

    2014-08-01

    We present a facile synthesis of bioinspired manganese oxides for chemical and photocatalytic water oxidation, starting from a reliable and versatile manganese(II) oxalate single-source precursor (SSP) accessible through an inverse micellar molecular approach. Strikingly, thermal decomposition of the latter precursor in various environments (air, nitrogen, and vacuum) led to the three different mineral phases of bixbyite (Mn2 O3 ), hausmannite (Mn3 O4 ), and manganosite (MnO). Initial chemical water oxidation experiments using ceric ammonium nitrate (CAN) gave the maximum catalytic activity for Mn2 O3 and MnO whereas Mn3 O4 had a limited activity. The substantial increase in the catalytic activity of MnO in chemical water oxidation was demonstrated by the fact that a phase transformation occurs at the surface from nanocrystalline MnO into an amorphous MnOx (1oxidizing agent. Photocatalytic water oxidation in the presence of [Ru(bpy)3 ](2+) (bpy=2,2'-bipyridine) as a sensitizer and peroxodisulfate as an electron acceptor was carried out for all three manganese oxides including the newly formed amorphous MnOx . Both Mn2 O3 and the amorphous MnOx exhibit tremendous enhancement in oxygen evolution during photocatalysis and are much higher in comparison to so far known bioinspired manganese oxides and calcium-manganese oxides. Also, for the first time, a new approach for the representation of activities of water oxidation catalysts has been proposed by determining the amount of accessible manganese centers.

  2. [Bacterial anaerobic ammonia oxidation (Anammox) in the marine nitrogen cycle--a review].

    PubMed

    Hong, Yiguo; Li, Meng; Gu, Jidong

    2009-03-01

    Anaerobic ammonium oxidation (Anammox) is a microbial oxidation process of ammonium, with nitrite as the electron acceptor and dinitrogen gas as the main product, and is performed by a clade of deeply branched Planctomycetes, which possess an intracytoplasmic membrane-bounded organelle, the anammoxosome, for the Anammox process. The wide distribution of Anammox bacteria in different natural environments has been greatly modified the traditional view of biogeochemical cycling of nitrogen, in which microbial denitrifier is considered as the only organism to respire nitrate and nitrite to produce nitric and nitrous oxides, and eventually nitrogen gas. More evidences indicate that Anammox is responsible for the production of more than 50% of oceanic N2 and plays an important role in global nitrogen cycling. Moreover, due to the close relationship between nitrogen and carbon cycling, it is anticipated that Anammox process might also affect the concentration of CO2 in the atmosphere, and influence the global climate change. In addition, the simultaneous transformation of nitrite and ammonium in wastewater treatment by Anammox would allow a 90% reduction in operational costs and provide a much more effective biotechnological process for wastewater treatment.

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

    NASA Astrophysics Data System (ADS)

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

    2012-07-01

    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.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. Electronic supplementary information (ESI) available: Experimental details, characterizations and supporting figures. See DOI: 10.1039/c2nr30862b

  4. Life cycle sustainability of solid oxide fuel cells: From methodological aspects to system implications

    NASA Astrophysics Data System (ADS)

    Mehmeti, Andi; McPhail, Stephen J.; Pumiglia, Davide; Carlini, Maurizio

    2016-09-01

    This study reviews the status of life cycle assessment (LCA) of Solid Oxide Fuel Cells (SOFCs) and methodological aspects, communicates SOFC environmental performance, and compares the environmental performance with competing power production technologies using a life cycle perspective. Results indicate that power generation using SOFCs can make a significant contribution to the aspired-to greener energy future. Despite superior environmental performance, empirical studies indicate that economic performance is predominantly the highest-ranked criterion in the decision making process. Future LCA studies should attempt to employ comprehensive dynamic multi-criteria environmental impact analysis coupled with economic aspects, to allow a robust comparison of results. A methodology framework is proposed to achieve simultaneously ambitious socio-economic and environmental objectives considering all life cycle stages and their impacts.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. [Distribution of Aerobic Ammonia-Oxidizing Microorganisms in Sediments from Adjacent Waters of Rushan Bay].

    PubMed

    He, Hui; Zhen, Yu; Mi, Tie-zhu; Zhang, Yu; Fu, Lu-lu; Yu, Zhi-gang

    2015-11-01

    Nitrogen cycle is a key process in material circulation of marine ecosystem, which plays an important role in maintaining ecological balance. The ammonia oxidation process promoted by aerobic ammonia-oxidizing microorganism (AOM) is a rate-limiting step of nitrification. Real-time quantitative polymerase chain reaction (qPCR ), along with the determination of potential nitrification rates (PNR) was carried out in this study to understand the distribution of AOM in sediments of adjacent waters of Rushan Bay in August, 2014. The results indicated that the abundance of total ammonia-oxidizing bacteria (AOB) was always greater than that of total ammonia-oxidizing archaea (AOA) in the three sampling stations; the ratio of active AOB to total AOB was less than 1%, while no active AOA was detected in this study; the PNR significantly decreased after adding ampicillin which could inhibit the activity of AOB (P < 0.05). It was speculated that AOB might play a more important role in the ammonia oxidation in sediments of adjacent waters of Rushan Bay in August, 2014. Dissolved oxygen concentrations, temperature and ammonium concentrations played a significant role in distribution of AOM in sediments of adjacent waters of Rushan Bay.

  10. 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.

  11. 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

  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.

  13. 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

  14. 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

  15. 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.

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

    PubMed

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

    2011-06-19

    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 (TiO(2)) 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 TiO(2) coating quickly fail. The desirable electrochemical efficiency and corrosion resistance of these anodes is made possible by the low electron-tunnelling resistance (<0.006 Ω cm(2) for p(+)-Si) and uniform thickness of atomic-layer deposited TiO(2).

  17. 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

  18. Seasonal variations of gene expression biomarkers in Mytilus galloprovincialis cultured populations: temperature, oxidative stress and reproductive cycle as major modulators.

    PubMed

    Jarque, Sergio; Prats, Eva; Olivares, Alba; Casado, Marta; Ramón, Montserrat; Piña, Benjamin

    2014-11-15

    The blue mussel Mytilus galloprovincialis has been used as monitoring organism in many biomonitoring programs because of its broad distribution in South European sea waters and its physiological characteristics. Different pollution-stress biomarkers, including gene expression biomarkers, have been developed to determine its physiological response to the presence of different pollutants. However, the existing information about basal expression profiles is very limited, as very few biomarker-based studies were designed to reflect the natural seasonal variations. In the present study, we analyzed the natural expression patterns of several genes commonly used in biomonitoring, namely ferritin, metallothionein, cytochrome P450, glutathione S-transferase, heat shock protein and the kinase responsive to stress KRS, during an annual life cycle. Analysis of mantle-gonad samples of cultured populations of M. galloprovincialis from the Delta del Ebro (North East Spain) showed natural seasonal variability of these biomarkers, pointing to temperature and oxidative stress as major abiotic modulators. In turn, the reproductive cycle, a process that can be tracked by VCLM7 expression, and known to be influenced by temperature, seems to be the major biotic factor involved in seasonality. Our results illustrate the influence of environmental factors in the physiology of mussels through their annual cycle, a crucial information for the correct interpretation of responses under stress conditions.

  19. 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

  20. Methane oxidation coupled to oxygenic photosynthesis in anoxic waters

    PubMed Central

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

    2015-01-01

    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. 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.

  2. 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

  3. [The modification of nitric oxide production by exogenous substrates of Krebs cycle during acute hypoxia].

    PubMed

    Kurhaliuk, N M; Kotsiuruba, A V; Sahach, V F

    2005-01-01

    Hypoxia causes the disruption of mitochondria electron respiratory chain, production of active oxygen forms and the unoxidative protection. In experiments on Wistar rats the influence of sodium succinate (50 mg/kg) and 6-ketoglutarate (200 mg/kg) on NO2-, NO3-, urea and polyamines contents in blood and liver under acute hypoxia (7% O2 in N2, 30 min) was investigated. Nitrite and nitrate content decreased in erythrocytes and liver but not in plasma under acute hypoxia. The exogenous succinate (SK) stimulated production of nitric oxide in erythrocytes and liver while 6-ketoglutarate (KG) only in liver. The switch from more intensive SK oxidation that reveals adrenomimetic influence and causes the synthesis and release of NO from erythrocyte, to less intensive KG correlates with well-known decrease of tissue respiration under the activation of the cholinergic system due to urea cycle activation particularly in liver. The activation of the SK oxidation takes place mainly under the different stress conditions and causes NO production in the blood cells. These conditions of the intensive and fast action under acute hypoxia are accompanied on the one hand by the increase of oxygen input ratio and on the other hand by activation of the free radical oxidation. The protective effect of the natural Krebs cycle intermediates--SK and KG in particular, is related to the regulation of NO synthesis and its metabolism in the main organs. These results proved the existence not only metabolite control of NO system by Krebs cycle intermediates, but the existence of the systemic mechanism for the support of the functional state of mitochondria under hypoxia.

  4. Doping-Promoted Solar Water Oxidation on Hematite Photoanodes.

    PubMed

    Zhang, Yuchao; Ji, Hongwei; Ma, Wanhong; Chen, Chuncheng; Song, Wenjing; Zhao, Jincai

    2016-01-01

    As one of the most promising materials for solar water oxidation, hematite has attracted intense research interest for four decades. Despite their desirable optical band gap, stability and other attractive features, there are great challenges for the implementation of hematite-based photoelectrochemical cells. In particular, the extremely low electron mobility leads to severe energy loss by electron hole recombination. Elemental doping, i.e., replacing lattice iron with foreign atoms, has been shown to be a practical solution. Here we review the significant progresses in metal and non-metal element doping-promoted hematite solar water oxidation, focusing on the role of dopants in adjusting carrier density, charge collection efficiency and surface water oxidation kinetics. The advantages and salient features of the different doping categories are compared and discussed. PMID:27376262

  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. 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.

  7. Morphological variation of multiwall carbon nanotubes in supercritical water oxidation

    NASA Astrophysics Data System (ADS)

    Chang, Jia-Yaw; Lo, Bertrand; Jeng, Meili; Tzing, Shin-Hwa; Ling, Yong-Chien

    2004-09-01

    Multiwall carbon nanotubes (MWNTs) with different morphology were prepared using supercritical water (SCW) oxidation and investigated by transmission electron microscope (TEM) and electron energy-loss spectroscopy (EELS). TEM results indicate that the peeling and sharpening of MWNTs are influenced by the etching process in SCW oxidation, of which oxidation time and amount of oxygen used is crucial. A simplified etching model is proposed, which indicates that the difference of mean etching rate between two adjoining blocks causes the morphological variation of MWNTs. The EELS results show change in characteristic energy-loss peaks as a function of total shell numbers along longitudinal axis of individual peeled tube.

  8. 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.

  9. 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

  10. Sensitivity of the global water cycle to the water-holding capacity of land

    SciTech Connect

    Milly, P.C.D.; Dunne, K.A. )

    1994-04-01

    The sensitivity of the global water cycle to the water-holding capacity of the plant-root zone of continental soils is estimated by simulations using a mathematical model of the general circulation of the atmosphere, with prescribed ocean surface temperatures and prescribed cloud. With an increase of the globally constant storage capacity, evaporation from the continents rises and runoff falls, because a high storage capacity enhances the ability of the soil to store water from periods of excess for later evaporation during periods of shortage. In addition, atmospheric feedbacks associated with higher precipitation and lower potential evaporation drive further changes in evaporation and runoff. Most changes in evaporation and runoff occur in the tropics and the northern middle-latitude rain belts. Global evaporation from land increases by 7 cm for each doubling of storage capacity. Sensitivity is negligible for capacity above 60 cm. In the tropics and in the extratropics,increased continental evaporation is split between increased continental precipitation and decreased convergence of atmospheric water vapor from ocean to land. In the tropics, this partitioning is strongly affected by induced circulation changes, which are themselves forced by changes in latent heating. In the northern middle and high latitudes, the increased continental evaporation moistens the atmosphere. This change in humidity of the atmosphere is greater above the continents than above the oceans, and the resulting reduction in the sea-land humidity gradient causes a decreased onshore transport of water vapor by transient eddies. Results here may have implications for problems in global hydrology and climate dynamics, including effects of water resource development on global precipitation, climatic control of plant rooting characteristics, climatic effects of tropical deforestation, and climate-model errors. 21 refs., 13 figs., 21 tabs.

  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. Water oxidation chemistry of a synthetic dinuclear ruthenium complex containing redox-active quinone ligands.

    PubMed

    Isobe, Hiroshi; Tanaka, Koji; Shen, Jian-Ren; Yamaguchi, Kizashi

    2014-04-21

    We investigated theoretically the catalytic mechanism of electrochemical water oxidation in aqueous solution by a dinuclear ruthenium complex containing redox-active quinone ligands, [Ru2(X)(Y)(3,6-tBu2Q)2(btpyan)](m+) [X, Y = H2O, OH, O, O2; 3,6-tBu2Q = 3,6-di-tert-butyl-1,2-benzoquinone; btpyan =1,8-bis(2,2':6',2″-terpyrid-4'-yl)anthracene] (m = 2, 3, 4) (1). The reaction involves a series of electron and proton transfers to achieve redox leveling, with intervening chemical transformations in a mesh scheme, and the entire molecular structure and motion of the catalyst 1 work together to drive the catalytic cycle for water oxidation. Two substrate water molecules can bind to 1 with simultaneous loss of one or two proton(s), which allows pH-dependent variability in the proportion of substrate-bound structures and following pathways for oxidative activation of the aqua/hydroxo ligands at low thermodynamic and kinetic costs. The resulting bis-oxo intermediates then undergo endothermic O-O radical coupling between two Ru(III)-O(•) units in an anti-coplanar conformation leading to bridged μ-peroxo or μ-superoxo intermediates. The μ-superoxo species can liberate oxygen with the necessity for the preceding binding of a water molecule, which is possible only after four-electron oxidation is completed. The magnitude of catalytic current would be limited by the inherent sluggishness of the hinge-like bending motion of the bridged μ-superoxo complex that opens up the compact, hydrophobic active site of the catalyst and thereby allows water entry under dynamic conditions. On the basis of a newly proposed mechanism, we rationalize the experimentally observed behavior of electrode kinetics with respect to potential and discuss what causes a high overpotential for water oxidation by 1.

  13. A new vicious cycle involving glutamate excitotoxicity, oxidative stress and mitochondrial dynamics.

    PubMed

    Nguyen, D; Alavi, M V; Kim, K-Y; Kang, T; Scott, R T; Noh, Y H; Lindsey, J D; Wissinger, B; Ellisman, M H; Weinreb, R N; Perkins, G A; Ju, W-K

    2011-01-01

    Glutamate excitotoxicity leads to fragmented mitochondria in neurodegenerative diseases, mediated by nitric oxide and S-nitrosylation of dynamin-related protein 1, a mitochondrial outer membrane fission protein. Optic atrophy gene 1 (OPA1) is an inner membrane protein important for mitochondrial fusion. Autosomal dominant optic atrophy (ADOA), caused by mutations in OPA1, is a neurodegenerative disease affecting mainly retinal ganglion cells (RGCs). Here, we showed that OPA1 deficiency in an ADOA model influences N-methyl-D-aspartate (NMDA) receptor expression, which is involved in glutamate excitotoxicity and oxidative stress. Opa1(enu/+) mice show a slow progressive loss of RGCs, activation of astroglia and microglia, and pronounced mitochondrial fission in optic nerve heads as found by electron tomography. Expression of NMDA receptors (NR1, 2A, and 2B) in the retina of Opa1(enu/+) mice was significantly increased as determined by western blot and immunohistochemistry. Superoxide dismutase 2 (SOD2) expression was significantly decreased, the apoptotic pathway was activated as Bax was increased, and phosphorylated Bad and BcL-xL were decreased. Our results conclusively demonstrate that not only glutamate excitotoxicity and/or oxidative stress alters mitochondrial fission/fusion, but that an imbalance in mitochondrial fission/fusion in turn leads to NMDA receptor upregulation and oxidative stress. Therefore, we propose a new vicious cycle involved in neurodegeneration that includes glutamate excitotoxicity, oxidative stress, and mitochondrial dynamics. PMID:22158479

  14. 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

  15. Electrosynthesis of highly transparent cobalt oxide water oxidation catalyst films from cobalt aminopolycarboxylate complexes.

    PubMed

    Bonke, Shannon A; Wiechen, Mathias; Hocking, Rosalie K; Fang, Xi-Ya; Lupton, David W; MacFarlane, Douglas R; Spiccia, Leone

    2015-04-24

    Efficient catalysis of water oxidation represents one of the major challenges en route to efficient sunlight-driven water splitting. Cobalt oxides (CoOx ) have been widely investigated as water oxidation catalysts, although the incorporation of these materials into photoelectrochemical devices has been hindered by a lack of transparency. Herein, the electrosynthesis of transparent CoOx catalyst films is described by utilizing cobalt(II) aminopolycarboxylate complexes as precursors to the oxide. These complexes allow control over the deposition rate and morphology to enable the production of thin, catalytic CoOx films on a conductive substrate, which can be exploited in integrated photoelectrochemical devices. Notably, under a bias of 1.0 V (vs. Ag/AgCl), the film deposited from [Co(NTA)(OH2 )2 ](-) (NTA=nitrilotriacetate) decreased the transmission by only 10 % at λ=500 nm, but still generated >80 % of the water oxidation current produced by a [Co(OH2 )6 ](2+) -derived oxide film whose transmission was only 40 % at λ=500 nm.

  16. Electrosynthesis of highly transparent cobalt oxide water oxidation catalyst films from cobalt aminopolycarboxylate complexes.

    PubMed

    Bonke, Shannon A; Wiechen, Mathias; Hocking, Rosalie K; Fang, Xi-Ya; Lupton, David W; MacFarlane, Douglas R; Spiccia, Leone

    2015-04-24

    Efficient catalysis of water oxidation represents one of the major challenges en route to efficient sunlight-driven water splitting. Cobalt oxides (CoOx ) have been widely investigated as water oxidation catalysts, although the incorporation of these materials into photoelectrochemical devices has been hindered by a lack of transparency. Herein, the electrosynthesis of transparent CoOx catalyst films is described by utilizing cobalt(II) aminopolycarboxylate complexes as precursors to the oxide. These complexes allow control over the deposition rate and morphology to enable the production of thin, catalytic CoOx films on a conductive substrate, which can be exploited in integrated photoelectrochemical devices. Notably, under a bias of 1.0 V (vs. Ag/AgCl), the film deposited from [Co(NTA)(OH2 )2 ](-) (NTA=nitrilotriacetate) decreased the transmission by only 10 % at λ=500 nm, but still generated >80 % of the water oxidation current produced by a [Co(OH2 )6 ](2+) -derived oxide film whose transmission was only 40 % at λ=500 nm. PMID:25826458

  17. Progress in base-metal water oxidation catalysis.

    PubMed

    Parent, Alexander Rene; Sakai, Ken

    2014-08-01

    This minireview provides a brief overview of the progress that has been made in developing homogeneous water oxidation catalysts based on base metals (manganese, iron, cobalt, nickel, and copper) from the 1990s to mid-2014. The impact of each contribution is analyzed, and opportunities for further improvement are noted. In addition, the relative stabilities of the base-metal catalysts that have been reported are compared to illustrate the importance of developing more robust catalytic systems by using these metals. This manuscript is intended to provide a firm foundation for researchers entering the field of water oxidation based on base metals and a useful reference for those currently involved in the field.

  18. Photocatalytic water oxidation by molecular assemblies based on cobalt catalysts.

    PubMed

    Zhou, Xu; Li, Fei; Li, Hua; Zhang, Biaobiao; Yu, Fengshou; Sun, Licheng

    2014-09-01

    Chromophore-catalyst molecular assemblies towards visible light-driven water oxidation were synthesized by covalent integration of a light-harvesting complex [Ru(bpy)3](2+) (bpy=2,2'-bipyridine) and a Co4O4 cubane water oxidation catalyst. The two components were assembled either in linear or macrocyclic configurations. In the presence of the sacrificial reagent, the Ru-Co metallocycle exhibits remarkable photocatalytic activity for oxygen evolution, which is one order of magnitude higher than that of a multicomponent system and exceeds that of a linear assembly by a factor of five, offering access to highly active photocatalyst through molecular design. PMID:25111070

  19. Water oxidation by manganese oxides, a new step towards a complete picture: simplicity is the ultimate sophistication.

    PubMed

    Najafpour, Mohammad Mahdi; Sedigh, Davood Jafarian

    2013-09-14

    We, for the first time, report that many Mn oxides (Mn3O4, α-Mn2O3, β-MnO2, CaMnO3, Ca2Mn3O8, CaMn3O6 and CaMn4O8) in the presence of cerium(IV) ammonium nitrate, in the water oxidation, convert to layered Mn oxide. This layered Mn oxide is an efficient water oxidizing catalyst.

  20. Electrical properties of porous oxides with adsorbed water

    NASA Astrophysics Data System (ADS)

    Korolev, Feodor A.; Kytin, Vladimir G.; Nosova, Ludmila; Kozlov, Sergei N.

    2005-05-01

    The impedance of porous alumina (por-Al2O3) and titanium oxide (por-TiO2) with adsorbed water has been investigated in a wide frequency range and at temperatures near the water-ice phase transition. The equivalent circuit of the investigated structures has been determined. It has been shown that water adsorption in the pores of a solid-state matrix has a great influence on its electrical properties. The characteristics of the electrical properties of experimental structures related to the water-ice phase transition have been revealed.

  1. 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.

  2. 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.

  3. 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

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

    NASA Astrophysics Data System (ADS)

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

    2015-09-01

    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.

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

    PubMed

    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

  6. Reduced graphene oxide supported titanium dioxide nanomaterials for the photocatalysis with long cycling life

    NASA Astrophysics Data System (ADS)

    Cao, Yuan-Cheng; Fu, Zhongtian; Wei, Wenjun; Zou, Linling; Mi, Tie; He, Dan; Yan, Chaolu; Liu, Xiyou; Zhu, Ying; Chen, Liuqing; Sun, Yuanjie

    2015-11-01

    The reduced Graphene Oxide (rGO) supported TiO2 (rGO@TiO2) as the photocatalyst was synthesized and evaluated. Graphene was oxided using chemical method and the AFM measurements showed that the thickness of the as-synthesized GO was 3-5 nm which indicates 4-6 layers of the resultant graphene oxide. BET surface area showed 62.4 m2/g for TiO2 and 247.3 m2/g for rGO@TiO2. Size distribution showed when the rGO ratio increases from 5% to 15% (rGO/TiO2), the resultant rGO@TiO2 samples show better size distribution in the range of 100 nm to 200 nm. Photocatalysis test showed when the exposure time increased to over 100 min, the degradation rate for rGO@TiO2 could reach to 96.4%. First order kinetics results of the rGO@TiO2 photocatalyst showed much higher degradation constant than that of the TiO2. Reproducibility test showed the rGO@TiO2 photocatalyst can keep the degradation rates at less for 25 cycles. Results showed rGO@TiO2 is a promising photocatalyst with long cycling life.

  7. Oxidative stress biomarkers in endometrial secretions: A comparison between successful and unsuccessful in vitro fertilization cycles.

    PubMed

    Rahiminejad, Mohammad Ehsan; Moaddab, Amirhossein; Ganji, Maziar; Eskandari, Nika; Yepez, Mayel; Rabiee, Soghra; Wise, Meredith; Ruano, Rodrigo; Ranjbar, Akram

    2016-08-01

    A potential role of oxidative stress has been implicated in the outcome of various steps of assisted reproductive technology (ART). In a prospective cohort study, a total of 100 patients undergoing IVF/ICSI procedure due to male factor infertility were recruited based on the inclusion criteria. In all patients, 1-2ml of endometrial secretions was aspirated prior to embryo transfer. The oxidative stress markers in endometrial secretions, including superoxide dismutase (SOD), catalase (CAT) activities, lipid peroxidation (LPO), total thiol groups (TTG), and total antioxidant power (TAP) were investigated and compared among study groups including term pregnancy, failed IVF cycle, and miscarriage. P<0.05 was considered statistically different. Of the 100 patients, 28 cases (28%) resulted in ongoing pregnancy (biochemical pregnancy followed by clinical pregnancy), 11 cases (11%) resulted in miscarriage, and 61 cases (61%), resulted in failed IVF cycle. SOD, LPO, CAT, and TAP levels in the endometrial secretions of the three groups were statistically different (P-value <0.01, <0.001, <0.001, and <0.001, respectively). TTG levels in endometrial secretion of three groups were not statistically different (P-value=0.837). Our results indicated that higher levels of antioxidants such as SOD, CAT, or TAP, and lower levels of oxidative stress markers such as LPO in the endometrial secretions were associated with successful IVF outcome. PMID:27232354

  8. Surfactant manganese complexes as models for the oxidation of water

    SciTech Connect

    Wohlgemuth, R.; Otvos, J.W.; Calvin, M.

    1984-02-01

    Surfactant manganese complexes have been studied spectroscopically and electrochemically as models for the catalysts involved in the photooxidation of water to produce oxygen. Evidence has been obtained for the participation of the suggested redox cycle Mn/sup II/ to Mn/sup III/ to Mn/sup IV/ and back to Mn/sup II/ with the evolution of oxygen.

  9. Cs(I) Cation Enhanced Cu(II) Catalysis of Water Oxidation.

    PubMed

    Zhu, Lei; Du, Jialei; Zuo, Shangshang; Chen, Zuofeng

    2016-07-18

    We report here a new catalytic water oxidation system based on Cu(II) ions and a remarkable countercation effect on the catalysis. In a concentrated fluoride solution at neutral to weakly basic pHs, simple Cu(II) salts are highly active and robust in catalyzing water oxidation homogeneously. F(-) in solution acts as a proton acceptor and an oxidatively robust ligand. F(-) coordination prevents precipitation of Cu(II) as CuF2/Cu(OH)2 and lowers potentials for accessing high-oxidation-state Cu by delocalizing the oxidative charge over F(-) ligands. Significantly, the catalytic current is greatly enhanced in a solution of CsF compared to those of KF and NaF. Although countercations are not directly involved in the catalytic redox cycle, UV-vis and (19)F nuclear magnetic resonance measurements reveal that coordination of F(-) to Cu(II) is dependent on countercations by Coulombic interaction. A less intense interaction between F(-) and well-solvated Cs(+) as compared with Na(+) and K(+) leads to a more intense coordination of F(-) to Cu(II), which accounts for the improved catalytic performance. PMID:27352033

  10. 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

  11. 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

  12. 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.

  13. 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.

  14. 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).

  15. 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.

  16. 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.

  17. 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

    2016-02-19

    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

  18. 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.

  19. 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)

  20. Treated Nanolayered Mn Oxide by Oxidizable Compounds: A Strategy To Improve the Catalytic Activity toward Water Oxidation.

    PubMed

    Mahdi Najafpour, Mohammad; Jafarian Sedigh, Davood; Maedeh Hosseini, Seyedeh; Zaharieva, Ivelina

    2016-09-01

    Herein, we investigate the effect of post-treatment of nanolayered manganese oxide by different inorganic and organic compounds. We use the fact that nanolayered manganese oxides are among the strongest naturally occurring oxidants, capable of oxidizing a wide range of organic molecules. Post-treatment of the synthetic Mn oxides with oxidizable compounds increases the cerium(IV)-driven water oxidation catalyzed by treated layered manganese oxides more than 25 times. On the basis of X-ray absorption investigations, we attribute this effect to the increased amount of manganese(III) ions. This finding can explain some puzzles in water oxidation by manganese oxides and may help to advance toward an efficient design strategy of water-oxidizing catalyst in artificial photosynthetic systems. PMID:27537432

  1. Thin-film heterostructures based on oxides of copper and zinc obtained by RF magnetron sputtering in one vacuum cycle

    NASA Astrophysics Data System (ADS)

    Afanasjev, V.; Bazhan, M.; Klimenkov, B.; Mukhin, N.; Chigirev, D.

    2016-07-01

    Investigations of formation conditions of oxide heterostructures ZnO/CuO in the same vacuum cycle using RF magnetron sputtering of powder targets of zinc and copper oxides were carried out. The optical and electrical properties of the thin film structures were studied.

  2. 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.

  3. 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...

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

    EPA Science Inventory

    The foundation for lead control in drinking water distribution systems is based on Pb(II) chemistry. In recent years, however, Pb(IV) oxides have been identified in distribution systems, suggesting that they may be important relative to predicting and controlling lead concentrat...

  5. 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

  6. 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.

  7. 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.

  8. Enhancing catalytic activity by narrowing local energy gaps--X-ray studies of a manganese water oxidation catalyst.

    PubMed

    Xiao, Jie; Khan, Munirah; Singh, Archana; Suljoti, Edlira; Spiccia, Leone; Aziz, Emad F

    2015-03-01

    Changes in the local electronic structure of the Mn 3d orbitals of a Mn catalyst derived from a dinuclear Mn(III) complex during the water oxidation cycle were investigated ex situ by X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) analyses. Detailed information about the Mn 3d orbitals, especially the local HOMO-LUMO gap on Mn sites revealed by RIXS analyses, indicated that the enhancement in catalytic activity (water oxidation) originated from the narrowing of the local HOMO-LUMO gap when electrical voltage and visible light illumination were applied simultaneously to the Mn catalytic system.

  9. 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.

  10. 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)

  11. 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.

  12. 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.

  13. Research framework of integrated simulation on bilateral interaction between water cycle and socio-economic development

    NASA Astrophysics Data System (ADS)

    Hao, C. F.; Yang, X. L.; Niu, C. W.; Jia, Y. W.

    2016-08-01

    The mechanism of bilateral interaction between natural water cycle evolution and socio-economic development has been obscured in current research due to the complexity of the hydrological process and the socio-economic system. The coupling of economic model CGE (Computable General Equilibrium) and distributed hydrological model WEP (Water and Energy transfer Processes) provides a model-based tool for research on response and feedback of water cycle and social development, as well as economic prospects under the constraint of water resources. On one hand, water policies, such as water use limitation and water price adjustment under different levels of socio-economic development, are to be evaluated by CGE model as assumed conditions and corresponding results of water demand could be put into WEP model to simulate corresponding response during the whole process of water cycle. On the other hand, variation of available water resources quantity under different scenarios simulated by WEP model may provide proper limitation for water demand in CGE model, and corresponding change of economic factors could indicate the influence of water resources constraints on socio-economic development. The research is believed to be helpful for better understanding of bilateral interaction between water and society.

  14. 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

  15. Linking Water Table Dynamics to Carbon Cycling in Artificial Soil Column Incubations

    NASA Astrophysics Data System (ADS)

    Geertje, Pronk; Adrian, Mellage; Tatjana, Milojevic; Fereidoun, Rezanezhad; Cappellen Philippe, Van

    2016-04-01

    The biogeochemistry of wetlands soils is closely tied to their hydrology. Water table fluctuations that cause flooding and drying of these systems may lead to enhanced degradation of organic matter and release of greenhouse gasses (e.g. CO2, CH4) to the atmosphere. However, predicting the influence of water table fluctuations on the biogeochemical functioning of soils requires an understanding of the interactions of soil hydrology with biogeochemical and microbial processes. To determine the effects of water table dynamics on carbon cycling, we are carrying out state-of-the-art automated soil column experiments with fully integrated monitoring of hydro-bio-geophysical process variables under both constant and oscillating water table conditions. An artificial, homogeneous mixture consisting of minerals and organic matter is used to provide a well-defined starting material. The artificial soils are composed of quartz sand, montmorillonite, goethite and humus from a forested riparian zone, from which we also extracted the microbial inoculum added to the soil mixture. The artificial soils are packed into 60 cm high, 7.5 cm wide columns. In the currently ongoing experiment, three replicate columns are incubated while keeping the water table constant water at mid-depth, while another three columns alternate between drained and saturated conditions. Micro-sensors installed at different depths below the soil surface record time-series redox potentials (Eh) varying between oxidizing (~+700 mV) and reducing (~-200 mV) conditions. Continuous O2 levels throughout the soil columns are monitored using high-resolution, luminescence-based, Multi Fiber Optode (MuFO) microsensors. Pore waters are collected periodically with MicroRhizon samplers from different depths, and analyzed for pH, EC, dissolved inorganic and organic carbon and ion/cation compositions. These measurements allow us to track the changes in pore water geochemistry and relate them to differences in carbon cycling

  16. 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

  17. 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.

  18. Oxidation of dithiocarbamates to yield N-nitrosamines by water disinfection oxidants.

    PubMed

    Padhye, Lokesh P; Kim, Jae-Hong; Huang, Ching-Hua

    2013-02-01

    Two most commonly used dithiocarbamate (DTC) pesticides, dimethyldithiocarbamate (DMDTC) and diethyldithiocarbamate (DEDTC), were examined in this study to evaluate their potential to form nitrosamines when in contact with various water disinfection oxidants. Results show that DTCs can serve as nitrosamine precursors, by release of secondary amines through hydrolysis or through reactions with oxidants. The reactions of DTCs with monochloramine and ozone were found to be particularly problematic in the risk of generating nitrosamines, though all four tested oxidants, including free chlorine and chlorine dioxide, formed nitrosamines. NDEA yield from DEDTC was lower, by different degrees, than NDMA yield from DMDTC for all four oxidants, which was attributed to the steric hindrance associated with bulkier reaction intermediate that are more difficult to be further oxidized to form nitrosamine. The yield of nitrosamines increased with the oxidant dosage for both monochloramination and ozonation of DTCs. Results for nitrosamine formation from DTCs at varying pH were found to be consistent with the pH trend of nitrosamine formation from ozonation and monochloramination of secondary amines. Kinetic study results and identification and quantification of reaction products suggest that the DTCs were not significant direct precursors of nitrosamines during monochloramination or ozonation, but rather nitrosamines formed were primarily from reaction of oxidants with the amine which may be generated either through hydrolysis or through oxidation of DTCs. PMID:23176828

  19. 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.

  20. 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.

  1. Nano-Web Cobalt Modified Silica Nanoparticles Catalysts for Water Oxidation and MB Oxidative Degradation.

    PubMed

    Wang, Li; Chen, Qiuyun; Li, Chenghao; Fang, Fang

    2016-05-01

    Dioxygen generating materials, using water as oxygen source, can be used as catalysts in hypoxic environments. Cobalt(II) modified silica (SiO2@NPCo) nanoparticles were synthesized through coordination of cobalt(II) ions with nitrogen atoms from 2-acetylpyridine modified silica (SiO2@NP). The SiO2@NPCo nanoparticles further reacted with 1,3,5-benzenetricarboxylic acids, forming porous nano-web nanoparticles (SiO2@NPCoCOOH). The synthesized SiO2@NPCoCOOH nanoparticles were demonstrated as better white LED light driven photochemical catalysts for oxidation of water than individual nanoparticles (SiO2@NPCo). Moreover, the SiO2@NPCoCOOH/water system could decrease the content of methylene blue (MB) in solution and therefore, the nanoweb cobalt(II) modified silica nanoparticles can be environmentally friendly catalysts for oxidative degradation of MB, using water as the oxygen source. PMID:27483932

  2. Nano-Web Cobalt Modified Silica Nanoparticles Catalysts for Water Oxidation and MB Oxidative Degradation.

    PubMed

    Wang, Li; Chen, Qiuyun; Li, Chenghao; Fang, Fang

    2016-05-01

    Dioxygen generating materials, using water as oxygen source, can be used as catalysts in hypoxic environments. Cobalt(II) modified silica (SiO2@NPCo) nanoparticles were synthesized through coordination of cobalt(II) ions with nitrogen atoms from 2-acetylpyridine modified silica (SiO2@NP). The SiO2@NPCo nanoparticles further reacted with 1,3,5-benzenetricarboxylic acids, forming porous nano-web nanoparticles (SiO2@NPCoCOOH). The synthesized SiO2@NPCoCOOH nanoparticles were demonstrated as better white LED light driven photochemical catalysts for oxidation of water than individual nanoparticles (SiO2@NPCo). Moreover, the SiO2@NPCoCOOH/water system could decrease the content of methylene blue (MB) in solution and therefore, the nanoweb cobalt(II) modified silica nanoparticles can be environmentally friendly catalysts for oxidative degradation of MB, using water as the oxygen source.

  3. Water-table height and microtopography control biogeochemical cycling in an Arctic coastal tundra ecosystem

    NASA Astrophysics Data System (ADS)

    Lipson, D. A.; Zona, D.; Raab, T. K.; Bozzolo, F.; Mauritz, M.; Oechel, W. C.

    2012-01-01

    production only responded to flooding in high elevation areas. Seasonal changes in the oxidation state of solid phase Fe minerals showed that net Fe reduction occurred, especially in topographically low areas. The effects of Fe reduction were also seen in the topographic patterns of pH, as protons were consumed where this process was prevalent. This suite of results can all be attributed to the effect of water table on oxygen availability: flooded conditions promote anoxia, stimulating dissolution and reduction of Fe(III), and to some extent, methanogenesis. However, two lines of evidence indicated the inhibition of methanogenesis by alternative e- acceptors such as Fe(III) and humic substances: (1) ratios of CO2:CH4 evolved from anaerobic soil incubations and dissolved in soil pore water were high; (2) CH4 concentrations were negatively correlated with the oxidation state of the soluble Fe pool in both topographically high and low areas. A second set of results could be explained by increased soil temperature in the flooding treatment, which presumably arose from the increased thermal conductivity of the soil surface: higher N mineralization rates and dissolved P concentrations were observed in flooded areas. Overall, these results could have implications for C and nutrient cycling in high Arctic areas where warming and flooding are likely consequences of climate change.

  4. 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.

  5. High temperature oxidation of molybdenum in water vapor environments

    NASA Astrophysics Data System (ADS)

    Nelson, A. T.; Sooby, E. S.; Kim, Y.-J.; Cheng, B.; Maloy, S. A.

    2014-05-01

    Molybdenum has recently gained attention as a candidate cladding material for use in light water reactors. Its excellent high temperature mechanical properties and stability under irradiation suggest that it could offer benefits to performance under a wide range of reactor conditions, but little is known about its oxidation behavior in water vapor containing atmospheres. The current study was undertaken to elucidate the oxidation behavior of molybdenum in water vapor environments to 1200 °C in order to provide an initial assessment of its feasibility as a light water reactor cladding. Initial observations indicate that at temperatures below 1000 °C, the kinetics of mass loss in water vapor would not be detrimental to cladding integrity during an off-normal event. Above 1000 °C, degradation is more rapid but remains slower than observed for optimized zirconium cladding alloys. The effect of hydrogen-water vapor and oxygen-water vapor mixtures on material loss was also explored at elevated temperatures. Parts-per-million levels of either hydrogen or oxygen will minimally impact performance, but hydrogen contents in excess of 1000 ppm were observed to limit volatilization at 1000 °C.

  6. 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

  7. Intramolecular proton transfer boosts water oxidation catalyzed by a Ru complex

    DOE PAGES

    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

  8. 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.

  9. Manganese cluster in photosynthesis: Where plants oxidize water to dioxygen

    SciTech Connect

    Yachandra, V.K.; Klein, M.P.; Sauer, K. |

    1996-11-01

    The essential involvement of manganese in photosynthetic water oxidation was implicit in the observation by Pirson in 1937 that plants and algae deprived of Mn in their growth medium lost the ability to evolve O{sub 2}. Addition of this essential element to the growth medium resulted in the restoration of water oxidation within 30 min. There is increased interest in the study of Mn in biological chemistry and dioxygen metabolism in the last two decades with the discovery of several Mn redox enzymes. The list of enzymes where Mn is required for redox activity includes a Mn superoxide dismutase, a binuclear Mn-containing catalase, a binuclear Mn-containing ribonucleotide reductase, a proposed binuclear Mn site in thiosulfate oxidase, a Mn peroxidase that is capable of oxidative degradation of lignin, and perhaps the most complex and important, the tetranuclear Mn-containing oxygen-evolving complex in photosystem II (Mn-OEC). Mn is well suited for the redox role with accessible oxidation states of II, III, and IV, and possibly V: oxidation states that have all been proposed to explain the mechanisms of the Mn redox enzymes.

  10. 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.

  11. 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

  12. 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.

  13. Water availability and cycles of drought and plenty

    NASA Astrophysics Data System (ADS)

    Mason, Peter J.

    2015-03-01

    Water availability in terms of rainfall and/or river flow tends to be analysed and predicted in probabilistic terms. That is to say historic records are analysed to produce such things as mean years and 95% wet or 95% dry years. However, there is increasing evidence to show that, on occasions, sustained periodicities appear in such records. Where this happens they can be used to supplement probabilities by better targeting which years are likely to be wet and which years are likely to be dry. The benefits in terms of planning crop yields, hydropower output, water supply and even targeting needs for famine relief are obvious. The author explores this with some examples from his own experience and that based on a talk he delivered in London on 20 February 2015 to a joint meeting of the Irrigation and Water Forum and the British Dam Society.

  14. Quantitative RT-PCR comparison of the urea and nitric oxide cycle gene transcripts in adult human tissues.

    PubMed

    Neill, Meaghan Anne; Aschner, Judy; Barr, Frederick; Summar, Marshall L

    2009-06-01

    The urea cycle and nitric oxide cycle play significant roles in complex biochemical and physiologic reactions. These cycles have distinct biochemical goals including the clearance of waste nitrogen; the production of the intermediates ornithine, citrulline, and arginine for the urea cycle; and the production of nitric oxide for the nitric oxide pathway. Despite their disparate functions, the two pathways share two enzymes, argininosuccinic acid synthase and argininosuccinic acid lyase, and a transporter, citrin. Studying the gene expression of these enzymes is paramount in understanding these complex biochemical pathways. Here, we examine the expression of genes involved in the urea cycle and the nitric oxide cycle in a panel of eleven different tissue samples obtained from individual adults without known inborn errors of metabolism. In this study, the pattern of co-expressed enzymes provides a global view of the metabolic activity of the urea and nitric oxide cycles in human tissues. Our results show that these transcripts are differentially expressed in different tissues. Using the co-expression profiles, we discovered that the combination of expression of enzyme transcripts as detected in our study, might serve to fulfill specific physiologic function(s) including urea production/nitrogen removal, arginine/citrulline production, nitric oxide production, and ornithine production. Our study reveals the importance of studying not only the expression profile of an enzyme of interest, but also studying the expression profiles of the other enzymes involved in a particular pathway so as to better understand the context of expression. The tissue patterns we observed highlight the variety of important functions of these enzymes and provides insight into the many clinical observations that result from their disruption. These results have implications for the management of urea cycle patients and raise considerations for the care of those patients receiving liver

  15. 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.

  16. DESIGN OF HYBRID POWER GENERATION CYCLES EMPLOYING AMMONIA-WATER-CARBON DIOXIDE MIXTURES

    SciTech Connect

    Ashish Gupta

    2002-06-01

    A power cycle generates electricity from the heat of combustion of fossil fuels. Its efficiency is governed by the cycle configuration, the operating parameters, and the working fluid. Typical. designs use pure water as the fluid. in the last two decades, hybrid cycles based on ammonia-water, and carbon-dioxide mixtures as the working fluid have been proposed. These cycles may improve the power generation efficiency of Rankine cycles by 15%. Improved efficiency is important for two reasons: it lowers the cost of electricity being produced, and by reducing the consumption of fossil fuels per unit power, it reduces the generation of environmental pollutants. The goal of this project is to develop a computational optimization-based method for the design and analysis of hybrid bottoming power cycles to minimize the usage of fossil fuels. The development of this methodology has been achieved by formulating this task as that of selecting the least cost power cycle design from all possible configurations. They employ a detailed thermodynamic property prediction package they have developed under a DOE-FETC grant to model working fluid mixtures. Preliminary results from this work suggest that a pure NH{sub 3} cycle outperforms steam or the expensive Kalina cycle.

  17. Anaerobic oxidation of methane in tropical and boreal soils: Ecological significance in terrestrial methane cycling

    NASA Astrophysics Data System (ADS)

    Blazewicz, Steven J.; Petersen, Dorthe G.; Waldrop, Mark P.; Firestone, Mary K.

    2012-06-01

    Anaerobic oxidation of methane (AOM) is a considerable sink for the greenhouse gas methane (CH4) in marine systems, but the importance of this process in terrestrial systems is less clear. Lowland boreal soils and wet tropical soils are two hot spots for CH4 cycling, yet AOM has been essentially uncharacterized in these systems. We investigated AOM in soils from sites in Alaska and Puerto Rico. Isotope tracers were utilized in vitro to enable the simultaneous quantification of CH4 production and consumption without use of biological inhibitors. Boreal peat soil and tropical mineral soil oxidized small but significant quantities of CH4 to CO2 under anoxic conditions (p < 0.001). Potential AOM rates were 21 ± 2 nmol gdw-1 d-1 and 2.9 ± 0.5 nmol gdw-1 d-1 for the boreal and tropical soils, respectively. The addition of terminal electron acceptors (NO3-, Fe(III), and SO42-) inhibited AOM and methanogenesis in both soils. In all incubations, CH4 production occurred simultaneously with AOM, and CH4 production rates were always greater than AOM rates. There was a strong correlation between the quantity of CH4 produced and the amount of CH4 oxidized under anoxic conditions (Alaska: r = 0.875, p < 0.0001; Puerto Rico: r = 0.817, p < 0.0001). CH4 oxidation under anoxic conditions was biological and likely mediated by methanogenic archaea. While only a small percentage of the total CH4 produced in these soils was oxidized under anoxic conditions (0.3% and 0.8% for Alaskan and Puerto Rican Soils), this process is important to understand since it could play a measurable role in controlling net CH4 flux.

  18. Reaction of catalytic oxidation by liquid water and its application to waste water purification

    SciTech Connect

    Ioffe, I.I.; Rubinskaya, E.V.

    1997-06-01

    In this paper the results of experiments and some considerations of theoretical and practical problems devoted to a new type of chemical reaction--oxidation of organic substances by liquid water with the aid of noble metal catalyst--are given. Some problems of application such as reaction to self-purification of industrial waste waters are also considered.

  19. 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

  20. 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

  1. On the Design of Oxide Films, Nanomaterials, and Heterostructures for Solar Water Oxidation Photoanodes

    NASA Astrophysics Data System (ADS)

    Kronawitter, Coleman Xaver

    Photoelectrochemistry and its associated technologies show unique potential to facilitate the large-scale production of solar fuels—those energy-rich chemicals obtained through conversion processes driven by solar energy, mimicking the photosynthetic process of green plants. The critical component of photoelectrochemical devices designed for this purpose is the semiconductor photoelectrode, which must be optically absorptive, chemically stable, and possess the required electronic band alignment with respect to the redox couple of the electrolyte to drive the relevant electrochemical reactions. After many decades of investigation, the primary technological obstacle remains the development of photoelectrode structures capable of efficient and stable conversion of light with visible frequencies, which is abundant in the solar spectrum. Metal oxides represent one of the few material classes that can be made photoactive and remain stable to perform the required functions. The unique range of functional properties of oxides, and especially the oxides of transition metals, relates to their associated diversity of cation oxidation states, cation electronic configurations, and crystal structures. In this dissertation, the use of metal oxide films, nanomaterials, and heterostructures in photoelectrodes enabling the solar-driven oxidation of water and generation of hydrogen fuel is examined. A range of transition- and post-transition-metal oxide material systems and nanoscale architectures is presented. The first chapters present results related to electrodes based on alpha-phase iron(III) oxide, a promising visible-light-active material widely investigated for this application. Studies of porous films fabricated by physical vapor deposition reveal the importance of structural quality, as determined by the deposition substrate temperature, on photoelectrochemical performance. Heterostructures with nanoscale feature dimensionality are explored and reviewed in a later chapter

  2. 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.

  3. Development of long-life-cycle tablet ceramic adsorbent for geosmin removal from water solution

    NASA Astrophysics Data System (ADS)

    Chen, Rongzhi; Xue, Qiang; Zhang, Zhenya; Sugiura, Norio; Yang, Yingnan; Li, Miao; Chen, Nan; Ying, Zhao; Lei, Zhongfang

    2011-01-01

    In this study, the tablet ceramic adsorbent (TCA), a silica/iron(III) oxide composite material, has been developed for geosmin (GSM) removal from the water solution. The physicochemical characteristics of TCA were examined with XRD, SEM, EDX and BET analyses. The sorption characteristics of GSM on TCA were investigated in a batch system. Attempts have been made to understand the adsorption kinetics, the effect of initial GSM concentration, solution pH, and reaction time. The batch experiments equilibrium data were well fitted to the Lagergren kinetic equation, which indicate the first-order nature adsorption. Over 82% of the GSM was removed by the TCA within 600 min at an initial concentration of 200 ng/L with 20 g/L of TCA dose. The batch and regeneration study indicated that the TCA is a cost-effective GSM adsorbent with sufficient mechanical strength to retain its physical integrity after long-time adsorption, and high regeneration performance for long-life-cycle application. Almost no second contamination (toxic sludge or leached iron) was observed after adsorption, and the gas resultant of thermal regeneration is harmless to atmospheric environment.

  4. 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.

  5. 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.

  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. Investigation of hair dye deposition, hair color loss, and hair damage during multiple oxidative dyeing and shampooing cycles.

    PubMed

    Zhang, Guojin; McMullen, Roger L; Kulcsar, Lidia

    2016-01-01

    Color fastness is a major concern for consumers and manufacturers of oxidative hair dye products. Hair dye loss results from multiple wash cycles in which the hair dye is dissolved by water and leaches from the hair shaft. In this study, we carried out a series of measurements to help us better understand the kinetics of the leaching process and pathways associated with its escape from the fiber. Hair dye leaching kinetics was measured by suspending hair in a dissolution apparatus and monitoring the dye concentration in solution (leached dye) with an ultraviolet-visible spectrophotometer. The physical state of dye deposited in hair fibers was evaluated by a reflectance light microscopy technique, based on image stacking, allowing enhanced depth of field imaging. The dye distribution within the fiber was monitored by infrared spectroscopic imaging of hair fiber cross sections. Damage to the ultrafine structure of the hair cuticle (surface, endocuticle, and cell membrane complex) and cortex (cell membrane complex) was determined in hair cross sections and on the hair fiber surface with atomic force microscopy. Using differential scanning calorimetry, we investigated how consecutive coloring and leaching processes affect the internal proteins of hair. Further, to probe the surface properties of hair we utilized contact angle measurements. This study was conducted on both pigmented and nonpigmented hair to gain insight into the influence of melanin on the hair dye deposition and leaching processes. Both types of hair were colored utilizing a commercial oxidative hair dye product based on pyrazole chemistry. PMID:27319056

  8. Investigation of hair dye deposition, hair color loss, and hair damage during multiple oxidative dyeing and shampooing cycles.

    PubMed

    Zhang, Guojin; McMullen, Roger L; Kulcsar, Lidia

    2016-01-01

    Color fastness is a major concern for consumers and manufacturers of oxidative hair dye products. Hair dye loss results from multiple wash cycles in which the hair dye is dissolved by water and leaches from the hair shaft. In this study, we carried out a series of measurements to help us better understand the kinetics of the leaching process and pathways associated with its escape from the fiber. Hair dye leaching kinetics was measured by suspending hair in a dissolution apparatus and monitoring the dye concentration in solution (leached dye) with an ultraviolet-visible spectrophotometer. The physical state of dye deposited in hair fibers was evaluated by a reflectance light microscopy technique, based on image stacking, allowing enhanced depth of field imaging. The dye distribution within the fiber was monitored by infrared spectroscopic imaging of hair fiber cross sections. Damage to the ultrafine structure of the hair cuticle (surface, endocuticle, and cell membrane complex) and cortex (cell membrane complex) was determined in hair cross sections and on the hair fiber surface with atomic force microscopy. Using differential scanning calorimetry, we investigated how consecutive coloring and leaching processes affect the internal proteins of hair. Further, to probe the surface properties of hair we utilized contact angle measurements. This study was conducted on both pigmented and nonpigmented hair to gain insight into the influence of melanin on the hair dye deposition and leaching processes. Both types of hair were colored utilizing a commercial oxidative hair dye product based on pyrazole chemistry.

  9. 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.

  10. 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...

  11. 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…

  12. 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.

  13. Solar-rechargeable battery based on photoelectrochemical water oxidation: Solar water battery

    PubMed Central

    Kim, Gonu; Oh, Misol; Park, Yiseul

    2016-01-01

    As an alternative to the photoelectrochemical water splitting for use in the fuel cells used to generate electrical power, this study set out to develop a solar energy rechargeable battery system based on photoelectrochemical water oxidation. We refer to this design as a “solar water battery”. The solar water battery integrates a photoelectrochemical cell and battery into a single device. It uses a water oxidation reaction to simultaneously convert and store solar energy. With the solar water battery, light striking the photoelectrode causes the water to be photo-oxidized, thus charging the battery. During the discharge process, the solar water battery reduces oxygen to water with a high coulombic efficiency (>90%) and a high average output voltage (0.6 V). Because the reduction potential of oxygen is more positive [E0 (O2/H2O) = 1.23 V vs. NHE] than common catholytes (e.g., iodide, sulfur), a high discharge voltage is produced. The solar water battery also exhibits a superior storage ability, maintaining 99% of its specific discharge capacitance after 10 h of storage, without any evidence of self-discharge. The optimization of the cell design and configuration, taking the presence of oxygen in the cell into account, was critical to achieving an efficient photocharge/discharge. PMID:27629362

  14. Solar-rechargeable battery based on photoelectrochemical water oxidation: Solar water battery

    NASA Astrophysics Data System (ADS)

    Kim, Gonu; Oh, Misol; Park, Yiseul

    2016-09-01

    As an alternative to the photoelectrochemical water splitting for use in the fuel cells used to generate electrical power, this study set out to develop a solar energy rechargeable battery system based on photoelectrochemical water oxidation. We refer to this design as a “solar water battery”. The solar water battery integrates a photoelectrochemical cell and battery into a single device. It uses a water oxidation reaction to simultaneously convert and store solar energy. With the solar water battery, light striking the photoelectrode causes the water to be photo-oxidized, thus charging the battery. During the discharge process, the solar water battery reduces oxygen to water with a high coulombic efficiency (>90%) and a high average output voltage (0.6 V). Because the reduction potential of oxygen is more positive [E0 (O2/H2O) = 1.23 V vs. NHE] than common catholytes (e.g., iodide, sulfur), a high discharge voltage is produced. The solar water battery also exhibits a superior storage ability, maintaining 99% of its specific discharge capacitance after 10 h of storage, without any evidence of self-discharge. The optimization of the cell design and configuration, taking the presence of oxygen in the cell into account, was critical to achieving an efficient photocharge/discharge.

  15. Solar-rechargeable battery based on photoelectrochemical water oxidation: Solar water battery.

    PubMed

    Kim, Gonu; Oh, Misol; Park, Yiseul

    2016-01-01

    As an alternative to the photoelectrochemical water splitting for use in the fuel cells used to generate electrical power, this study set out to develop a solar energy rechargeable battery system based on photoelectrochemical water oxidation. We refer to this design as a "solar water battery". The solar water battery integrates a photoelectrochemical cell and battery into a single device. It uses a water oxidation reaction to simultaneously convert and store solar energy. With the solar water battery, light striking the photoelectrode causes the water to be photo-oxidized, thus charging the battery. During the discharge process, the solar water battery reduces oxygen to water with a high coulombic efficiency (>90%) and a high average output voltage (0.6 V). Because the reduction potential of oxygen is more positive [E(0) (O2/H2O) = 1.23 V vs. NHE] than common catholytes (e.g., iodide, sulfur), a high discharge voltage is produced. The solar water battery also exhibits a superior storage ability, maintaining 99% of its specific discharge capacitance after 10 h of storage, without any evidence of self-discharge. The optimization of the cell design and configuration, taking the presence of oxygen in the cell into account, was critical to achieving an efficient photocharge/discharge. PMID:27629362

  16. Solar-rechargeable battery based on photoelectrochemical water oxidation: Solar water battery.

    PubMed

    Kim, Gonu; Oh, Misol; Park, Yiseul

    2016-09-15

    As an alternative to the photoelectrochemical water splitting for use in the fuel cells used to generate electrical power, this study set out to develop a solar energy rechargeable battery system based on photoelectrochemical water oxidation. We refer to this design as a "solar water battery". The solar water battery integrates a photoelectrochemical cell and battery into a single device. It uses a water oxidation reaction to simultaneously convert and store solar energy. With the solar water battery, light striking the photoelectrode causes the water to be photo-oxidized, thus charging the battery. During the discharge process, the solar water battery reduces oxygen to water with a high coulombic efficiency (>90%) and a high average output voltage (0.6 V). Because the reduction potential of oxygen is more positive [E(0) (O2/H2O) = 1.23 V vs. NHE] than common catholytes (e.g., iodide, sulfur), a high discharge voltage is produced. The solar water battery also exhibits a superior storage ability, maintaining 99% of its specific discharge capacitance after 10 h of storage, without any evidence of self-discharge. The optimization of the cell design and configuration, taking the presence of oxygen in the cell into account, was critical to achieving an efficient photocharge/discharge.

  17. Oxidation of dimethylsulfide to tetrathionate by Methylophaga thiooxidans sp. nov.: a new link in the sulfur cycle.

    PubMed

    Boden, Rich; Kelly, Donovan P; Murrell, J Colin; Schäfer, Hendrik

    2010-10-01

    A new pathway of dimethylsulfide (DMS) metabolism was identified in a novel species of Gammaproteobacteria, Methylophaga thiooxidans sp. nov., in which tetrathionate (S(4)O(6)(2-)) was the end-product of DMS oxidation. Inhibitor evidence indicated that DMS degradation was initiated by demethylation, catalysed by a corrinoid demethylase. Thiosulfate was an intermediate, which was oxidized to tetrathionate by a cytochrome-linked thiosulfate dehydrogenase. Thiosulfate oxidation was coupled to ATP synthesis, and M. thiooxidans could also use exogenous thiosulfate as an energy source during chemolithoheterotrophic growth on DMS or methanol. Cultures grown on a variety of substrates oxidized thiosulfate, indicating that thiosulfate oxidation was constitutive. The observations have relevance to interactions among sulfur-metabolizing bacteria in the marine environment. The production of tetrathionate from an organosulfur precursor is previously undocumented and represents a potential step in the biogeochemical sulfur cycle, providing a 'shunt' across the cycle.

  18. [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.

  19. 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.

  20. [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

  1. 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...

  2. 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.

  3. 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...

  4. 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.

  5. [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.

  6. The life cycle of iron Fe(III) oxide: impact of fungi and bacteria

    NASA Astrophysics Data System (ADS)

    Bonneville, Steeve

    2014-05-01

    Iron oxides are ubiquitous reactive constituents of soils, sediments and aquifers. They exhibit vast surface areas which bind a large array of trace metals, nutrients and organic molecules hence controlling their mobility/reactivity in the subsurface. In this context, understanding the "life cycle" of iron oxide in soils is paramount to many biogeochemical processes. Soils environments are notorious for their extreme heterogeneity and variability of chemical, physical conditions and biological agents at play. Here, we present studies investigating the role of two biological agents driving iron oxide dynamics in soils, root-associated fungi (mycorrhiza) and bacteria. Mycorrhiza filaments (hypha) grow preferentially around, and on the surface of nutrient-rich minerals, making mineral-fungi contact zones, hot-spots of chemical alteration in soils. However, because of the microscopic nature of hyphae (only ~ 5 µm wide for up to 1 mm long) and their tendency to strongly adhere to mineral surface, in situ observations of this interfacial micro-environment are scarce. In a microcosm, ectomycorrhiza (Paxillus involutus) was grown symbiotically with a pine tree (Pinus sylvestris) in the presence of freshly-cleaved biotite under humid, yet undersaturated, conditions typical of soils. Using spatially-resolved ion milling technique (FIB), transmission electron microscopy and spectroscopy (TEM/STEM-EDS), synchrotron based X-ray microscopy (STXM), we were able to quantify the speciation of Fe at the biotite-hypha interface. The results shows that substantial oxidation of biotite structural-Fe(II) into Fe(III) subdomains occurs at the contact zone between mycorrhiza and biotite. Once formed, iron(III) oxides can reductively dissolve under suboxic conditions via several abiotic and microbial pathways. In particular, they serve as terminal electron acceptors for the oxidation of organic matter by iron reducing bacteria. We aimed here to understand the role of Fe(III) mineral

  7. 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.

  8. Present-day Mars' water cycle: new views and blind perspectives

    NASA Astrophysics Data System (ADS)

    Montmessin, F.; Smith, M. D.; Fedorova, A.; Langevin, Y.; Mellon, M.

    2012-09-01

    Addressing recent cimate changes on Mars necessarily requires a succesful representation of present-day Mars water cycle. Decades of observations and modeling efforts have been conducted that now allow to elaborate a new, yet incomplete, picture, of the seasonal activity of water on Mars. This presentation explores the various observational and theoretical studies that have been conducted to date, and attempts to present a clear and detailed explanation of the major physical mechanisms that command the seasonal and geographical variability of present-day Mars water cycle, as inferred from the combined analysis of measurements and climate model simulations. Remaining issues and enigmae will be presented as well.

  9. Nitrogen cycling in different types of sediments from Danish waters

    SciTech Connect

    Blackburn, T.H.; Henridsen, K.

    1983-05-01

    Variations in sediment N:C ratios were correlated with water depth and season. /sup 14/NH/sub 4//sup +/ was used to measure the rates of NH/sub 4//sup +/ production (d) and incorporation into bacterial cells (i) in sediments from different stations, at different seasons. The validity of the rates d and i was indicated by the predicted correlation of d:i ratios with N:C ratios of the sediment, and the predicted N:C ratio at which net NH/sub 4//sup +/; pore water NH/sub 4//sup +/, flux of NH/sub 4//sup +/ from sediment, and flux of NH/sub 4//sup +/ into exchangeable pool. The NO/sub 3//sup -/ flux from sediment was correlated with nitrification rate and with season. Benthic infauna increased the flux of NH/sub 4//sup +/ from the sediment by 50%. The rates of transfer of nitrogen (NO/sub 3//sup -/, NH/sub 4//sup +/, N/sub 2/) from sediment to water were 44-66% of the net rates of organic nitrogen mineralization (d-i). Flux of NO/sub 3//sup -/ + NH/sub 4//sup +/ from the sediment could supply 30-82% of the nitrogen requirement of the planktonic primary producers.

  10. 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.

  11. 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

  12. 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

  13. 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).

  14. DOC-dynamics in a small headwater catchment as driven by redox fluctuations and hydrological flow paths - are DOC exports mediated by iron reduction/oxidation cycles?

    NASA Astrophysics Data System (ADS)

    Knorr, K.-H.

    2012-09-01

    Dissolved organic carbon (DOC) exports from many catchments in Europe and North-America are steadily increasing. Several studies have sought to explain this observation. As possible causes, a decrease in acid rain or sulfate deposition, concomitant reductions in ionic strength and increasing temperatures were identified. DOC often originates from riparian wetlands; but here, despite higher DOC concentrations, ionic strength in pore waters usually exceeds that in surface waters. In the catchment under study, DOC concentrations were synchronous with dissolved iron concentrations in pore and stream water. This study aims at testing the hypothesis that DOC exports are mediated by iron reduction/oxidation cycles. Following the observed hydrographs, δ18O of water, and DOC fluorescence, the wetlands were identified as main source of DOC. Antecedent biogeochemical conditions, i.e. water table levels in the wetlands, influenced the discharge patterns of nitrate, iron, and DOC during an event. The correlation of DOC with pH was positive in pore waters but negative in surface waters; it was negative for DOC with sulfate in pore waters but only weak in surface waters. The positive correlation of DOC with iron was universal for pore and surface water, though. The decline of DOC and iron concentrations in transition from anoxic wetland pore water to oxic stream water suggests a flocculation of DOC with oxidizing iron, leading to a drop in pH in the stream during high DOC fluxes. The pore water did not per se differ in pH. There is thus a need to more thoroughly consider processes of DOC mobilization in wetlands when interpreting DOC exports from catchments. The coupling of DOC with iron fluxes suggested that increased DOC exports could at least in part be caused by increasing activities in iron reduction, possibly due to increases in temperature or wetness of riparian wetlands.

  15. Conventional and Advanced Silicagel-water Adsorption Cycles Driven by Near - environmental Temperature Heat

    NASA Astrophysics Data System (ADS)

    Boelman, Elisa; B. Saha, Bidyut; Tanaka, Aiharu; Kashiwagi, Takao

    This work aims at clarifying the possible operating temperature ranges for silica gel-water adsorption refrigeration cycles driven by near-environmental temperature heat sources (between 50°C and 85°C), with relatively small regenerating temperature lifts (10 K to 65 K). A newly developed three stage advanced silica gel-water cycle, which is operational with 50°C driving heat source and 30°C cooling source is introduced and compared with a conventional single stage cycle. The cycles are evaluated in terms of cooling capacity, COP and the viability of operation with near-environmental temperature driving heat sources. The analysis is based on experimental and cycle simulation work. The results showed the advanced three stage cycle to be particularly suited for operation with low grade waste heat driving sources, since it worked with small regenerating temperature lifts (ΔTregen)of 10K to 30K. Another significant advantage of operation with small ΔTregen is the possibility to reduce irreversible heat losses from batched cycle operation. Experiments carried out on full-size machine suggested that, even with smallΔTregen, adsorber /desorber heat exchanger improvements such as higher thermal conductance and smaller heat capacitance can contribute to reduce heat losses while improving cycle performance in terms of cooling capacity and COP.

  16. 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...

  17. Triggering a Wet Climate on Mars: The Role of Outflow Channels in Martian Water Cycles

    NASA Astrophysics Data System (ADS)

    Santiago, D.; Asphaug, E. I.; Colaprete, A.

    2011-12-01

    The triggering of a robust water cycle on Mars has been hypothesized to be caused by gigantic flooding events evidenced by outflow channels. Here we use the Ames Mars General Circulation Model (MGCM) to study how these presumably abrupt eruptions of water (Carr,1996) affected the climate of Mars. We model where the water ultimately went as part of a transient hydrologic cycle. Chryse Planitia, east of Tharsis, has evidence for multiple water outflow channels. One of the largest channels is Ares Valles, which was carved by floods with estimated water volumes of order 10^5 km^2 (Andrews-Hanna, 2007 & Carr, 1996). Outflow discharge rate estimates range from 10^6 to 10^7 m^3/seconds or greater (Andrews-Hanna & Phillips, 2007, Harrison & Grimm, 2008). Studies suggest that outflow channels formed with smaller, successive floods instead of a single large flood (Wilson, et al.,2004). Warner et al. (2009) suggest up to six outflow events for the formation of Ares Valles, while estimates for another large outflow, Kasei Valles, might have been flooded by over two thousand floods with a total water volume of 5.5 x 10^5 km^3 (Harrison & Grimm, 2008). By adding water to the surface of Mars at the given outflow rate, as an expanding one-layer lake, we are able to study quantitatively how these outflow events influenced Mars climate, particularly the hydrologic cycle. In particular: Could sudden introductions of large amounts of water on the Martian surface lead to a new equilibrated water cycle? Can we tie certain fluvial surface features to transient or sustained water cycles? What are the roles of water vapor and water ice clouds to sudden changes in the water cycle on Mars? How are radiative feedbacks involved with this? What is the ultimate fate of the outflow water? This work uses the NASA Ames MGCM version 2.1 and other schemes that are part of the NASA Ames MGCM suite of tools. Various versions of the MGCM developed at Ames have been used extensively to examine dust and

  18. 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).

  19. Theoretical study of catalytic mechanism for single-site water oxidation process

    PubMed Central

    Lin, Xiangsong; Hu, Xiangqian; Concepcion, Javier J.; Chen, Zuofeng; Liu, Shubin; Meyer, Thomas J.; Yang, Weitao

    2012-01-01

    Water oxidation is a linchpin in solar fuels formation, and catalysis by single-site ruthenium complexes has generated significant interest in this area. Combining several theoretical tools, we have studied the entire catalytic cycle of water oxidation for a single-site catalyst starting with [RuII(tpy)(bpm)(OH2)]2+ (i.e., [RuII-OH2]2+; tpy is 2,2′∶6′,2′′-terpyridine and bpm is 2,2′-bypyrimidine) as a representative example of a new class of single-site catalysts. The redox potentials and pKa calculations for the first two proton-coupled electron transfers (PCETs) from [RuII-OH2]2+ to [RuIV = O]2+ and the following electron-transfer process to [RuV = O]3+ suggest that these processes can proceed readily in acidic or weakly basic conditions. The subsequent water splitting process involves two water molecules, [RuV = O]3+ to generate [RuIII-OOH]2+, and H3O+ with a low activation barrier (∼10 kcal/mol). After the key O---O bond forming step in the single-site Ru catalysis, another PECT process oxidizes [RuIII-OOH]2+ to [RuIV-OO]2+ when the pH is lower than 3.7. Two possible forms of [RuIV-OO]2+, open and closed, can exist and interconvert with a low activation barrier (< 7 kcal/mol) due to strong spin-orbital coupling effects. In Pathway 1 at pH = 1.0, oxygen release is rate-limiting with an activation barrier ∼12 kcal/mol while the electron-transfer step from [RuIV-OO]2+ to [RuV - OO]3+ becomes rate-determining at pH = 0 (Pathway 2) with Ce(IV) as oxidant. The results of these theoretical studies with atomistic details have revealed subtle details of reaction mechanisms at several stages during the catalytic cycle. This understanding is helpful in the design of new catalysts for water oxidation. PMID:22615356

  20. Supercritical water oxidation data acquisition testing. Final report, Volume II

    SciTech Connect

    1996-11-01

    Supercritical Water Oxidation (SCWO) technology holds great promise for treating mixed wastes, in an environmentally safe and efficient manner. In the spring of 1994 the US Department of Energy (DOE), Idaho Operations Office awarded Stone & Webster Engineering Corporation, of Boston Massachusetts and its sub-contractor MODAR, Inc. of Natick Massachusetts a Supercritical Water Oxidation Data Acquisition Testing (SCWODAT) program. The SCWODAT program was contracted through a Cooperative Agreement that was co-funded by the US Department of Energy and the Strategic Environmental Research and Development Program. The SCWODAT testing scope outlined by the DOE in the original Cooperative Agreement and amendments thereto was initiated in June 1994 and successfully completed in December 1995. 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 MODAR SCWO technology.

  1. Water-oxidation catalysis by synthetic manganese oxides--systematic variations of the calcium birnessite theme.

    PubMed

    Frey, Carolin E; Wiechen, Mathias; Kurz, Philipp

    2014-03-21

    Layered manganese oxides from the birnessite mineral family have been identified as promising heterogeneous compounds for water-oxidation catalysis (WOC), a key reaction for the conversion of renewable energy into storable fuels. High catalytic rates were especially observed for birnessites which contain calcium as part of their structures. With the aim to systematically improve the catalytic performance of such oxide materials, we used a flexible synthetic route to prepare three series of calcium birnessites, where we varied the calcium concentrations, the ripening times of the original precipitates and the temperature of the heat treatment following the initial synthetic steps (tempering) during the preparation process. The products were carefully analysed by a number of analytical techniques and then probed for WOC activity using the Ce(4+)-system. We find that our set of twenty closely related manganese oxides shows large, but somewhat systematic alterations in catalytic rates, indicating the importance of synthesis parameters for maximum catalytic performance. The catalyst of the series for which the highest water-oxidation rate was found is a birnessite of medium calcium content (Ca : Mn ratio 0.2 : 1) that had been subjected to a tempering temperature of 400 °C. On the basis of the detailed analysis of the results, a WOC reaction scheme for birnessites is proposed to explain the observed trends in reactivity. PMID:24225769

  2. Lindqvist Polyoxoniobate Ion-Assisted Electrodeposition of Cobalt and Nickel Water Oxidation Catalysts.

    PubMed

    Liu, YuPing; Guo, Si-Xuan; Ding, Liang; Ohlin, C André; Bond, Alan M; Zhang, Jie

    2015-08-01

    A method has been developed for the efficient electrodeposition of cobalt and nickel nanostructures with the assistance of the Lindqvist ion [Nb6O19](8-). Scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), Raman spectroscopy, inductively coupled plasma mass spectrometry (ICP-MS), inductively coupled plasma optical emission spectrometry, and a range of electrochemical techniques have been used to characterize the morphology, composition, catalytic water oxidation activity and stability of the films in alkaline solution. SEM images show that films consisting of nanoparticles with diameters of ca. 30 to 40 nm are formed after 40-50 potential cycles of deposition. Nb and Co/Ni are detected in the films by EDX. ICP-MS results show an elemental ratio of 1:1 for Co:Nb and 1:3 for Ni:Nb, respectively. Raman spectra reveal the presence of both [Nb6O19](8-) and Co(OH)2/Ni(OH)2. The films exhibit excellent stability and efficiency for electrocatalytic water oxidation in alkaline solution. Turnover frequencies of 12.9 and 13.2 s(-1) were determined by rotating ring disk electrode voltammetry at an overpotential of 480 mV for Co and Ni films, respectively. Fourier transformed large amplitude alternating current (FTAC) voltammetry reveals an additional underlying oxidation process for Co under catalytic turnover conditions, which indicates that a Co(IV) species is involved in the efficient catalytic water oxidation reactions. FTAC voltammetric data also suggest that the Ni films undergoes a clear phase transformation upon aging in aqueous 1 M NaOH and the electrogenerated higher oxidation state Ni from β-NiOOH is the more active form of the catalyst.

  3. Lindqvist Polyoxoniobate Ion-Assisted Electrodeposition of Cobalt and Nickel Water Oxidation Catalysts.

    PubMed

    Liu, YuPing; Guo, Si-Xuan; Ding, Liang; Ohlin, C André; Bond, Alan M; Zhang, Jie

    2015-08-01

    A method has been developed for the efficient electrodeposition of cobalt and nickel nanostructures with the assistance of the Lindqvist ion [Nb6O19](8-). Scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), Raman spectroscopy, inductively coupled plasma mass spectrometry (ICP-MS), inductively coupled plasma optical emission spectrometry, and a range of electrochemical techniques have been used to characterize the morphology, composition, catalytic water oxidation activity and stability of the films in alkaline solution. SEM images show that films consisting of nanoparticles with diameters of ca. 30 to 40 nm are formed after 40-50 potential cycles of deposition. Nb and Co/Ni are detected in the films by EDX. ICP-MS results show an elemental ratio of 1:1 for Co:Nb and 1:3 for Ni:Nb, respectively. Raman spectra reveal the presence of both [Nb6O19](8-) and Co(OH)2/Ni(OH)2. The films exhibit excellent stability and efficiency for electrocatalytic water oxidation in alkaline solution. Turnover frequencies of 12.9 and 13.2 s(-1) were determined by rotating ring disk electrode voltammetry at an overpotential of 480 mV for Co and Ni films, respectively. Fourier transformed large amplitude alternating current (FTAC) voltammetry reveals an additional underlying oxidation process for Co under catalytic turnover conditions, which indicates that a Co(IV) species is involved in the efficient catalytic water oxidation reactions. FTAC voltammetric data also suggest that the Ni films undergoes a clear phase transformation upon aging in aqueous 1 M NaOH and the electrogenerated higher oxidation state Ni from β-NiOOH is the more active form of the catalyst. PMID:26158219

  4. Interrelationship Between the Dust and Water Cycles in the Martian Atmosphere: Numerical Modeling Studies

    NASA Astrophysics Data System (ADS)

    Nelli, S. M.; Murphy, J. R.

    2002-05-01

    Mars' low-mass, primarily carbon dioxide atmosphere contains quantities of both water vapor and suspended dust particles. Suspended dust can have a significant impact upon the atmospheric thermal state as the dust warms and cools via absorption and emission of radiant energy. Water vapor condensing onto the dust grains will change the radiative characteristics of both. Small dust particles can potentially be carried to great altitudes and affect the temperatures there. One potential limiting factor in the vertical extent of the dust is water vapor condensation. If water vapor present in the atmosphere condenses upon a dust particle, the particle's gravitational sedimentation speed can be increased, and the likelihood of it being transported to high altitudes is diminished. Thus, water can act as a controlling mechanism with regard to the vertical extent of dust mixing. At the same time, the atmosphere's water vapor holding capacity is very strongly temperature dependent: the greater the temperature, the greater the potential water vapor mixing ratio (if a source of water or ice is available). Thus, there is a potentially significant interplay between the Martian dust and water cycles. Previous research done using computer modeling to better understand the Martian atmosphere treat the dust and the water cycles as two separate and independent processes. The existing numerical model will be improved to simulate the relationship between the Martian dust and water cycles by actually coupling the two cycles. The model will condense the water onto the dust allowing the particles radiative characteristics, fall speeds, and as a result, their vertical distribution to change. Data obtained from the Viking, Mars Pathfinder, and especially the Mars Global Surveyor missions will be used to determine the accuracy of the model results. Preliminary results will be presented at the June 2002 meeting.

  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.

  7. 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

  8. 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

    2016-01-22

    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)-{OṄ<} 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

  9. Tunable water desalination across graphene oxide framework membranes.

    PubMed

    Nicolaï, Adrien; Sumpter, Bobby G; Meunier, Vincent

    2014-05-14

    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 of GOF membranes is studied as a function of linker concentration n, thickness h and applied pressure ΔP. 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 cm(-2) day(-1) MPa(-1) (n = 64 and h = 2.5 nm) and follows a Cnh(-αn) law. 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 (ΔP ∼ 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 cm(-2) day(-1) MPa(-1) to a few L cm(-2) day(-1) MPa(-1).

  10. 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.

  11. Simulation study of water/silicon oxide interface

    NASA Astrophysics Data System (ADS)

    Lorenz, Christian; Rempe, Susan; Stevens, Mark; Grest, Gary; Tsige, Mesfin

    2006-03-01

    The interaction of water with solid surfaces plays a crucial role in many phenomena. The water-silica interface is one of the typical systems encountered in technological and natural materials. Numerous technological applications of silica were found to rely on its specific surface properties. Large scale quantum mechanics (QM) and classical molecular dynamics (MD) simulations are used to study the molecular configurations and wetting properties of water at the interface of different silicon oxide surfaces. In order to understand how the surface coverage of silanols (-SiOH) affects the wetting behavior of the silica surfaces, both crystalline ((001) α-quartz (coverage 9.6 nm-2) and (100) β-cristobalite (7.8 nm-2)) and amorphous silica (5.0 nm-2) substrates have been studied. The binding energy of the water, the number of water molecules hydrogen-bonded to the surface and the configuration of the hydrogen-bonded water molecules are determined as a function of silanol coverage from QM simulations. The number of water molecules within a monolayer and the orientation of the water molecules within the monolayer and in the bulk are determined from MD simulations. Results from two classical force fields are compared to one another and to the relevant quantities from the QM simulations. Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

  12. 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

  13. Transformation of a Cp*-iridium(III) precatalyst for water oxidation when exposed to oxidative stress.

    PubMed

    Zuccaccia, Cristiano; Bellachioma, Gianfranco; Bortolini, Olga; Bucci, Alberto; Savini, Arianna; Macchioni, Alceo

    2014-03-17

    The reaction of [Cp*Ir(bzpy)NO3 ] (1; bzpy=2-benzoylpyridine, Cp*=pentamethylcyclopentadienyl anion), a competent water-oxidation catalyst, with several oxidants (H2 O2 , NaIO4 , cerium ammonium nitrate (CAN)) was studied to intercept and characterize possible intermediates of the oxidative transformation. NMR spectroscopy and ESI-MS techniques provided evidence for the formation of many species that all had the intact Ir-bzpy moiety and a gradually more oxidized Cp* ligand. Initially, an oxygen atom is trapped in between two carbon atoms of Cp* and iridium, which gives an oxygen-Ir coordinated epoxide, whereas the remaining three carbon atoms of Cp* are involved in a η(3) interaction with iridium (2 a). Formal addition of H2 O to 2 a or H2 O2 to 1 leads to 2 b, in which a double MeCOH functionalization of Cp* is present with one MeCOH engaged in an interaction with iridium. The structure of 2 b was unambiguously determined in the solid state and in solution by X-ray single-crystal diffractometry and advanced NMR spectroscopic techniques, respectively. Further oxidation led to the opening of Cp* and transformation of the diol into a diketone with one carbonyl coordinated at the metal (2 c). A η(3) interaction between the three non-oxygenated carbons of "ex-Cp*" and iridium is also present in both 2 b and 2 c. Isolated 2 b and mixtures of 2 a-c species were tested in water-oxidation catalysis by using CAN as sacrificial oxidant. They showed substantially the same activity than 1 (turnover frequency values ranged from 9 to 14 min(-1) ). PMID:24523138

  14. Transformation of a Cp*-iridium(III) precatalyst for water oxidation when exposed to oxidative stress.

    PubMed

    Zuccaccia, Cristiano; Bellachioma, Gianfranco; Bortolini, Olga; Bucci, Alberto; Savini, Arianna; Macchioni, Alceo

    2014-03-17

    The reaction of [Cp*Ir(bzpy)NO3 ] (1; bzpy=2-benzoylpyridine, Cp*=pentamethylcyclopentadienyl anion), a competent water-oxidation catalyst, with several oxidants (H2 O2 , NaIO4 , cerium ammonium nitrate (CAN)) was studied to intercept and c