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Sample records for water oxidation tracked

  1. Enhancing hydrophilicity and water permeability of PET track-etched membranes by advanced oxidation process

    Science.gov (United States)

    Korolkov, Ilya V.; Mashentseva, Anastassiya A.; Güven, Olgun; Zdorovets, Maxim V.; Taltenov, Abzal A.

    2015-12-01

    In this study we present results on the application of advanced oxidation systems for effective and non-toxic oxidation of poly(ethylene terephthalate) track-etched membranes (PET TeMs) to improve their wettability and water transport properties. Two oxidizing systems: H2O2 under UV irradiation (H2O2/UV) and Fenton system under visible light (Fenton/H2O2/Vis) were compared. The surface of functionalized PET TeMs was characterized by using colorimetric assay, contact angle measurements and X-ray photoelectron spectroscopy (XPS). Results clearly showed that water permeability of PET TeMs treated with H2O2/UV was improved by 28 ± 5% compared with etched-only membrane, the same parameter was found to increase by 13 ± 4% in the case of Fenton/H2O2/Vis treatment. The proposed oxidation technique is very simple, environment friendly and not requiring special equipment or expensive chemicals. The surface hydrophilicity of the membranes stored for 360 days in air between paper sheets was analyzed by contact angle test, colorimetric assay to measure concentration of carboxylic groups on the surface with toluidine blue and XPS analysis. The hydrophilic properties of oxidized PET TeMs were found to be stable for a long period of time.

  2. Enthalpy changes during photosynthetic water oxidation tracked by time-resolved calorimetry using a photothermal beam deflection technique.

    Science.gov (United States)

    Krivanek, Roland; Dau, Holger; Haumann, Michael

    2008-03-01

    The energetics of the individual reaction steps in the catalytic cycle of photosynthetic water oxidation at the Mn(4)Ca complex of photosystem II (PSII) are of prime interest. We studied the electron transfer reactions in oxygen-evolving PSII membrane particles from spinach by a photothermal beam deflection technique, allowing for time-resolved calorimetry in the micro- to millisecond domain. For an ideal quantum yield of 100%, the enthalpy change, DeltaH, coupled to the formation of the radical pair Y(Z)(.+)Q(A)(-) (where Y(Z) is Tyr-161 of the D1 subunit of PSII) is estimated as -820 +/- 250 meV. For a lower quantum yield of 70%, the enthalpy change is estimated to be -400 +/- 250 meV. The observed nonthermal signal possibly is due to a contraction of the PSII protein volume (apparent DeltaV of about -13 A(3)). For the first time, the enthalpy change of the O(2)-evolving transition of the S-state cycle was monitored directly. Surprisingly, the reaction is only slightly exergonic. A value of DeltaH(S(3)-->S(0)) of -210 meV is estimated, but also an enthalpy change of zero is within the error range. A prominent nonthermal photothermal beam deflection signal (apparent DeltaV of about +42 A(3)) may reflect O(2) and proton release from the manganese complex, but also reorganization of the protein matrix.

  3. Molecular water oxidation catalysis

    CERN Document Server

    Llobet, Antoni

    2014-01-01

    Photocatalytic water splitting is a promising strategy for capturing energy from the sun by coupling light harvesting and the oxidation of water, in order to create clean hydrogen fuel. Thus a deep knowledge of the water oxidation catalysis field is essential to be able to come up with useful energy conversion devices based on sunlight and water splitting. Molecular Water Oxidation Catalysis: A Key Topic for New Sustainable Energy Conversion Schemes presents a comprehensive and state-of-the-art overview of water oxidation catalysis in homogeneous phase, describing in detail the most importan

  4. Catalytic water oxidation: Rugged water-oxidation anodes

    Science.gov (United States)

    Llobet, Antoni

    2010-10-01

    The efficient catalytic oxidation of water to dioxygen in the solid state is one of the challenges to be overcome to build sun-driven and/or electrocatalytic water-splitting devices. Now, an effective water-oxidation hybrid catalyst system has been made by attaching a ruthenium-polyoxometallate complex to a carbon nanotube.

  5. Enthalpy Changes during Photosynthetic Water Oxidation Tracked by Time-Resolved Calorimetry Using a Photothermal Beam Deflection Technique☆☆☆

    Science.gov (United States)

    Krivanek, Roland; Dau, Holger; Haumann, Michael

    2008-01-01

    The energetics of the individual reaction steps in the catalytic cycle of photosynthetic water oxidation at the Mn4Ca complex of photosystem II (PSII) are of prime interest. We studied the electron transfer reactions in oxygen-evolving PSII membrane particles from spinach by a photothermal beam deflection technique, allowing for time-resolved calorimetry in the micro- to millisecond domain. For an ideal quantum yield of 100%, the enthalpy change, ΔH, coupled to the formation of the radical pair YZ⋅+QA− (where YZ is Tyr-161 of the D1 subunit of PSII) is estimated as −820 ± 250 meV. For a lower quantum yield of 70%, the enthalpy change is estimated to be −400 ± 250 meV. The observed nonthermal signal possibly is due to a contraction of the PSII protein volume (apparent ΔV of about −13 Å3). For the first time, the enthalpy change of the O2-evolving transition of the S-state cycle was monitored directly. Surprisingly, the reaction is only slightly exergonic. A value of ΔH(S3 ⇒ S0) of −210 meV is estimated, but also an enthalpy change of zero is within the error range. A prominent nonthermal photothermal beam deflection signal (apparent ΔV of about +42 Å3) may reflect O2 and proton release from the manganese complex, but also reorganization of the protein matrix. PMID:17993488

  6. Geomorphic and biophysical factors affecting water tracks in northern Alaska

    Science.gov (United States)

    Trochim, E. D.; Jorgenson, M. T.; Prakash, A.; Kane, D. L.

    2016-03-01

    A better understanding of water movement on hillslopes in Arctic environments is necessary for evaluating the effects of climate variability. Drainage networks include a range of features that vary in transport capacity from rills to water tracks to rivers. This research focuses on describing and classifying water tracks, which are saturated linear-curvilinear stripes that act as first-order pathways for transporting water off of hillslopes into valley bottoms and streams. Multiple factor analysis was used to develop five water tracks classes based on their geomorphic, soil, and vegetation characteristics. The water track classes were then validated using conditional inference trees, to verify that the classes were repeatable. Analysis of the classes and their characteristics indicate that water tracks cover a broad spectrum of patterns and processes primarily driven by surficial geology. This research demonstrates an improved approach to quantifying water track characteristics for specific areas, which is a major step toward understanding hydrological processes and feedbacks within a region.

  7. Biomimetic Water-Oxidation Catalysts: Manganese Oxides.

    Science.gov (United States)

    Kurz, Philipp

    2016-01-01

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

  8. Tracks FAQs: What Chemicals Are In My Drinking Water?

    Centers for Disease Control (CDC) Podcasts

    2011-08-10

    In this podcast, CDC Tracking experts discuss how you can use the Tracking Network to determine what chemicals are in your drinking water. Do you have a question for our Tracking experts? Please e-mail questions to trackingsupport@cdc.gov.  Created: 8/10/2011 by National Center for Environmental Health, Division of Environmental Hazards and Health Effects, Environmental Health Tracking Branch.   Date Released: 8/10/2011.

  9. ENGINEERING BULLETIN: SUPERCRITICAL WATER OXIDATION

    Science.gov (United States)

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

  10. Tracking Energy Relaxation Within Plasmonic Metal Oxide Nanocrystals

    Science.gov (United States)

    2016-11-30

    AFRL-AFOSR-VA-TR-2016-0378 Tracking Energy Relaxation Within Plasmonic Metal Oxide Nanocrystals Sean Roberts UNIVERSITY OF TEXAS AT AUSTIN 101 EAST...UNIT NUMBER 7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES) University of Texas at Austin 105 E. 24th St. Stop A5300 Austin, TX 78712 8...within it. We have also investigated how bandgap photoexcitation can be used to manipulate the plasmon resonance of WO3-x NCs. Adding additional

  11. Source Tracking of Nitrous Oxide using A Quantum Cascade ...

    Science.gov (United States)

    Nitrous oxide is an important greenhouse gas and ozone depleting substance. Nitrification and denitrification are two major biological pathways that are responsible for soil emissions of N2O. However, source tracking of in-situ or laboratory N2O production is still challenging to soil scientists. The objective of this study was to introduce the use of a new technology, quantum cascade laser (QCL) spectroscopy, which allows for significantly improved accuracy and precision to continuously measure real-time N2O for source tracking. This data provides important emission inventory information to air quality and atmospheric chemistry models. The task demonstrated that QCL spectroscopy can measure the flux of nitrous oxide at ambient and well as elevated concentrations in real time. The fractionation of the nitrous oxide produced by microbial processing of nitrate can be measured and characterized as isotopic signatures related to the nitrifying or denitrifying state of the microbial communities. This has important implications for monitoring trace gases in the atmosphere. The data produced by this system will provide clients including the air quality and climate change communities with needed information on the sources and strengths of N2O emissions for modeling and research into mitigation strategies to reduce overall GHG emissions in agricultural systems.

  12. Development and Applications of Thallium isotopes: a new proxy tracking the extent of manganese oxide burial

    Science.gov (United States)

    Owens, J. D.; Nielsen, S.; Ostrander, C.; Peterson, L. C.; Anbar, A. D.

    2015-12-01

    Thallium (Tl) isotopes are a new and potential powerful paleoredox proxy with the possibility to track bottom water oxygen conditions based on the burial flux of manganese oxides. Thallium has a residence time of ~20 thousand years, which is long enough to render modern oxic seawater conservative with respect to concentration and isotopes. The isotopic signature of Tl in the global ocean is driven mainly by two outputs (1) adsorption onto manganese oxides and (2) low temperature oceanic crust alteration. Importantly, the isotopic inputs of Tl are all nearly the same value; thus, the isotopic composition and flux of the outputs almost exclusively set the seawater signature. For relatively short term redox events it is reasonable to assume that the dominant isotope fractionation process is associated with manganese oxide precipitation because low temperature alteration is controlled by long-term average ocean crust production rates. We present a broad range of modern samples that span several open ocean profiles combined with water column and sediment profiles from the permanently anoxic basins of the Black Sea and Cariaco Basins. The open ocean shows no variation in depth profiles that encompass most of the major water masses in the Atlantic and Southern Oceans. The anoxic basins, however, reveal Tl isotope signatures closer to their inputs, which is likely due to basinal restriction. The authigenic fraction of organic-rich sediments from the Black Sea and Cariaco Basin capture the Tl isotope value of the overlying water column, which shows that Tl isotopes could be applied as a faithful deep time redox proxy. For the first time, we will present new data showing that Tl isotopes is tracking bottom water ocean oxygenation. We are applying this isotope system to ancient samples, testing the spatial and temporal variability of ocean oxygenation coinciding with major biogeochemical events.

  13. Development of a Water Recovery System Resource Tracking Model

    Science.gov (United States)

    Chambliss, Joe; Stambaugh, Imelda; Sargusingh, Miriam; Shull, Sarah; Moore, Michael

    2015-01-01

    A simulation model has been developed to track water resources in an exploration vehicle using Regenerative Life Support (RLS) systems. The Resource Tracking Model (RTM) integrates the functions of all the vehicle components that affect the processing and recovery of water during simulated missions. The approach used in developing the RTM enables its use as part of a complete vehicle simulation for real time mission studies. Performance data for the components in the RTM is focused on water processing. The data provided to the model has been based on the most recent information available regarding the technology of the component. This paper will describe the process of defining the RLS system to be modeled, the way the modeling environment was selected, and how the model has been implemented. Results showing how the RLS components exchange water are provided in a set of test cases.

  14. Tracking Gas Phase Composition in Oil evaporation and Oxidation Experiments

    Science.gov (United States)

    Amador-Muñoz, O.; Zhang, H.; Misztal, P. K.; Worton, D.; Drozd, G.; Goldstein, A. H.

    2015-12-01

    Primary Organic Aerosol (POA) is emitted directly by anthropogenic or natural sources, whereas Secondary Organic Aerosol (SOA) is formed in the atmosphere through chemical reactions that result from conversion of more volatile species into lower volatility oxidized products and their subsequent condensation to the particulate phase. We studied SOA formation from evaporation of Macondo crude oil (MC 252) using a wind tunnel coupled to a flow tube oxidation reactor. Ozone, UV lights, and water vapor were used to make OH radicals. Organic compounds in the gas phase, both those evaporated from the wind tunnel and those formed in the flow tube oxidation experiments, were monitored using proton-transfer-reaction mass spectrometry (PTR-qMS and PTR-TOF-MS). We observed approximately 400 different species. Compounds with less than C10 were mostly evaporated in the first 5 hours when maximum SOA formation was also obtained. Hydrocarbons with carbon number (11-14) were still present in the oil after 12 h of continuous evaporation at wind speed of 2 m s-1. We will show the implications of these results for the production of SOA related to the range of evaporated chemical size and reactivity.

  15. Homogeneous and heterogenized iridium water oxidation catalysts

    Science.gov (United States)

    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.

  16. Supercritical Water Oxidation Data Acquisition Testing

    Energy Technology Data Exchange (ETDEWEB)

    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.

  17. The MEDESS-GIB database: tracking the Atlantic water inflow

    Science.gov (United States)

    García Sotillo, Marcos; Garcia-Ladona, Emilio; Orfila, Alejandro; Rodríguez-Rubio, Pablo; Cristobal Maraver, José; Conti, Daniel; Padorno, Elena; Jiménez, José Antonio; Capó, Este; Pérez, Fernando; Sayol, Juan Manuel; de los Santos, Francisco Javier; Amo, Arancha; Rietz, Ana; Troupin, Charles; Tintore, Joaquín; Álvarez-Fanjul, Enrique

    2016-03-01

    On 9 September 2014, an intensive drifter deployment was carried out in the Strait of Gibraltar. In the frame of the MEDESS-4MS Project (EU MED Program), the MEDESS-GIB experiment consisted of the deployment of 35 satellite tracked drifters, mostly of CODE-type, equipped with temperature sensor sampling at a rate of 30 min. Drifters were distributed along and on both sides of the Strait of Gibraltar. The MEDESS-GIB deployment plan was designed as to ensure quasi-synoptic spatial coverage. To this end, four boats covering an area of about 680 NM2 in 6 h were coordinated. As far as these authors know, this experiment is the most important exercise in the area in terms of number of drifters released. Collected satellite-tracked data along drifter trajectories have been quality controlled and processed to build the presented MEDESS-GIB database. This paper reports the MEDESS-GIB data set that comprises drifter trajectories, derived surface currents and in situ SST measurements collected along the buoys tracks. This series of data is available through the PANGAEA (Data Publisher for Earth and Environmental Science) repository, with the following doi:10.1594/PANGAEA.853701. Likewise, the MEDESS-GIB data will be incorporated as part of the Copernicus Marine historical products. The MEDESS-GIB data set provides a complete Lagrangian view of the surface inflow of Atlantic waters through the Strait of Gibraltar and thus, very useful data for further studies on the surface circulation patterns in the Alboran Sea, and their links with one of the most energetic Mediterranean Sea flows: the Algerian Current.

  18. Supercritical water oxidation - Microgravity solids separation

    Science.gov (United States)

    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.

  19. Iron Oxide as an Mri Contrast Agent for Cell Tracking: Supplementary Issue

    Directory of Open Access Journals (Sweden)

    Daniel J. Korchinski

    2015-01-01

    Full Text Available Iron oxide contrast agents have been combined with magnetic resonance imaging for cell tracking. In this review, we discuss coating properties and provide an overview of ex vivo and in vivo labeling of different cell types, including stem cells, red blood cells, and monocytes/macrophages. Furthermore, we provide examples of applications of cell tracking with iron contrast agents in stroke, multiple sclerosis, cancer, arteriovenous malformations, and aortic and cerebral aneurysms. Attempts at quantifying iron oxide concentrations and other vascular properties are examined. We advise on designing studies using iron contrast agents including methods for validation.

  20. Investigation and Quantification of Water Track Networks in Boreal Regions Using Remote Sensing and Geophysical Data

    Science.gov (United States)

    Mendbayar, U.; Misra, D.; Gupta, T.; Ghosh, T.

    2015-12-01

    Water tracks are the most prominent drainage pathways that route water through the soil over permafrost in the polar environment and thus play a major role in hydrology, geomorphology, and geochemistry of the polar ecosystem. Existing literature on water tracks is limited and is largely confined to tundra areas devoid of vegetation. The objective of this study is to initiate the investigation of water tracks in thickly vegetated boreal regions, many of which contain predominant engineered infrastructures. The ancillary objectives include the development of methods for mapping the distribution of water tracks in boreal regions and a preliminary analysis of the geotechnical impacts of water track interception on infrastructures. The study area is Goldstream Road in Fairbanks, Alaska. This road experiences high amounts of damage, possibly due to interception of prominent water tracks. To investigate the road damage, the Alaska Department of Transportation has collected geophysical data in 2012. We plan to create a water track distribution map around the Goldstream Road using high-spatial-and-spectral-resolution remote sensing imagery and correlate it with the geophysical data from 2012. We have collected ground data from two water tracks: one in a residence in Fairbanks and the other besides the Goldstream Road. The two tracks vary greatly in size and features. Both water tracks revealed different yet quite promising characteristics. These findings will be used to extract other water tracks from remotely sensed images of the Goldstream Road area. So far, a 2010 SPOT 5 image (2.5m x 2.5 m), an aerial orthophoto (14 cm x 14 cm) and a DEM (57 cm x 57 cm) from September 2014 have been acquired. Normalized Difference Vegetation Index (NDVI) processing was performed on the 2010 SPOT 5 image. A detailed water track database was created and water tracks are being manually digitized from the available imagery and Web Mapping Services (WMS). As a test, using FLIR, handheld

  1. Water clustering on nanostructured iron oxide films

    DEFF Research Database (Denmark)

    Merte, Lindsay Richard; Bechstein, Ralf; Peng, G.

    2014-01-01

    , 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 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...

  2. Methane oxidation in anoxic lake waters

    Science.gov (United States)

    Su, Guangyi; Zopfi, Jakob; Niemann, Helge; Lehmann, Moritz

    2017-04-01

    Freshwater habitats such as lakes are important sources of methante (CH4), however, most studies in lacustrine environments so far provided evidence for aerobic methane oxidation only, and little is known about the importance of anaerobic oxidation of CH4 (AOM) in anoxic lake waters. In marine environments, sulfate reduction coupled to AOM by archaea has been recognized as important sinks of CH4. More recently, the discorvery of anaerobic methane oxidizing denitrifying bacteria represents a novel and possible alternative AOM pathway, involving reactive nitrogen species (e.g., nitrate and nitrite) as electron acceptors in the absence of oxygen. We investigate anaerobic methane oxidation in the water column of two hydrochemically contrasting sites in Lake Lugano, Switzerland. The South Basin displays seasonal stratification, the development of a benthic nepheloid layer and anoxia during summer and fall. The North Basin is permanently stratified with anoxic conditions below 115m water depth. Both Basins accumulate seasonally (South Basin) or permanently (North Basin) large amounts of CH4 in the water column below the chemocline, providing ideal conditions for methanotrophic microorganisms. Previous work revealed a high potential for aerobic methane oxidation within the anoxic water column, but no evidence for true AOM. Here, we show depth distribution data of dissolved CH4, methane oxidation rates and nutrients at both sites. In addition, we performed high resolution phylogenetic analyses of microbial community structures and conducted radio-label incubation experiments with concentrated biomass from anoxic waters and potential alternative electron acceptor additions (nitrate, nitrite and sulfate). First results from the unamended experiments revealed maximum activity of methane oxidation below the redoxcline in both basins. While the incubation experiments neither provided clear evidence for NOx- nor sulfate-dependent AOM, the phylogenetic analysis revealed the

  3. Electrosynthesis of Biomimetic Manganese-Calcium Oxides for Water Oxidation Catalysis--Atomic Structure and Functionality.

    Science.gov (United States)

    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. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. Water Clustering on Nanostructured Iron Oxide Films

    Energy Technology Data Exchange (ETDEWEB)

    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.

  5. Water clustering on nanostructured iron oxide films

    Science.gov (United States)

    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.

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

    Science.gov (United States)

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

    2014-04-05

    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. Copyright © 2014 Elsevier B.V. All rights reserved.

  7. Tracking the morphology of fulvic acids during water uptake

    Science.gov (United States)

    Zelenay, Veronika; Krepelova, Adela; Rudich, Yinon; Huthwelker, Thomas; Ammann, Markus

    2010-05-01

    Atmospheric humic like substances (HULIS) denote a range of oxidized, polyfunctional organic aerosol components widespread in the atmosphere, which show similar extraction behaviour on exchange columns as humic substances. Stemming from oxidation of primary gas phase and particulate organics, from e.g. biomass burning events, the HULIS constitute to a major fraction of the water soluble organic aerosol components in the atmosphere. Highly oxidized organic compounds play an important role in atmospheric processes like cloud formation or modification. Important factors therein are their hygroscopic properties and their microstructure, which influences their optical properties. HULIS somewhat resemble humic substances from terrestrial and aquatic sources, which consist mainly of carboxylic, aromatic and phenolic moieties assembled into hydrogen and van der Waals bonded supermolecular structures. Hence, the Suwannee River fulvic acid (SRFA), a chemically well characterized fulvic acid obtained from the International Humic Substances Society, was used to obtain combined data on hygroscopic properties and microstructural evolution during water uptake. The measurements were performed using x-ray absorption spectroscopy (NEXAFS, near edge x-ray absorption fine structure) in combination with an x-ray microscope (STXM, scanning x-ray transmission microscope) with a spatial resolution of about 30 nm. The measurements were performed at the PolLux beamline (SLS, Paul Scherrer Institut). The NEXAFS spectroscopy provides the possibility to map important chemical functional groups of carbon (as the one mentioned above) and oxygen atoms, and also to quantify the amount of carbon and oxygen atoms. To follow the submicron structure during water uptake a new device - a microreactor - was developed for the STXM. Using this reactor, the samples could be kept in a microenvironment with controlled temperature and humidity from 0 to 95 %. The samples were deposited either as droplets with

  8. Supercritical water oxidation treatment of textile sludge.

    Science.gov (United States)

    Zhang, Jie; Wang, Shuzhong; Li, Yanhui; Lu, Jinling; Chen, Senlin; Luo, XingQi

    2017-08-01

    In this work, we studied the supercritical water oxidation (SCWO) of the textile sludge, the hydrothermal conversion of typical textile compounds and the corrosion properties of stainless steel 316. Moreover, the influence mechanisms of NaOH during these related processes were explored. The results show that decomposition efficiency for organic matter in liquid phase of the textile sludge was improved with the increment of reaction temperature or oxidation coefficient. However, the organic substance in solid phase can be oxidized completely in supercritical water. Serious coking occurred during the high pressure water at 250-450°C for the Reactive Orange 7, while at 300 and 350°C for the polyvinyl alcohol. The addition of NaOH not only accelerated the destruction of organic contaminants in the SCWO reactor, but effectively inhibited the dehydration conversion of textile compounds during the preheating process, which was favorable for the treatment system of textile sludge. The corrosion experiment results indicate that the stainless steel 316 could be competent for the body materials of the reactor and the heat exchangers. Furthermore, there was prominent enhancement of sodium hydroxide for the corrosion resistance of 316 in subcritical water. On the contrary the effect was almost none during SCWO.

  9. Greenlighting Photoelectrochemical Oxidation of Water by Iron Oxide

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-12-23

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

  10. Photocatalytic water oxidation with iron oxide hydroxide (rust) nanoparticles

    Science.gov (United States)

    Shelton, Timothy L.; Bensema, Bronwyn L.; Brune, Nicholas K.; Wong, Christopher; Yeh, Max; Osterloh, Frank E.

    2017-01-01

    Hematite has attracted considerable interest as a photoanode material for water oxidation under visible illumination. Here, we explore the limits of photocatalytic water oxidation activity with iron (III) oxide hydroxide nanocrystals and NaIO4 as a sacrificial electron acceptor (E=1.63 V NHE at pH=0.5). The sol was prepared by hydrolysis of FeCl3 in boiling 0.002-M HCl solution and confirmed to mainly consist of ß-FeO(OH) (akaganéite) particles with 5 to 15 nm diameter. From a 0.01 M aqueous NaIO4 solution, the sol evolves between 4.5 and 35.2 μmol O2 h-1, depending on pH, light intensity (>400 nm, 290 to 700 mW cm-2), ß-FeO(OH), and NaIO4 concentration. The activity increases with pH, and depends linearly on light intensity and photocatalyst amount, and it varies with sacrificial electron donor concentration. Under optimized conditions, the apparent quantum efficiency is 0.19% (at 400 nm and 460 mW cm-2), and the turnover number is 2.58 based on total ß-FeO(OH). Overall, the efficiency of the ß-FeO(OH)/NaIO4 photocatalytic system is limited by electron hole recombination and by particle aggregation over longer irradiation times (24 h). Lastly, surface photovoltage measurements on ß-FeO(OH) films on fluorine doped tin oxide substrate confirm a 2.15 eV effective band gap for the material.

  11. Electrolysis of water on (oxidized) metal surfaces

    DEFF Research Database (Denmark)

    Rossmeisl, Jan; Logadottir, Ashildur; Nørskov, Jens Kehlet

    2005-01-01

    relations are assumed to be obeyed exactly, this leads to a universal relationship between the catalytic rate and the oxygen binding energy. Finally, we conclude that for systems obeying these relations, there is a limit to how good a water splitting catalyst an oxidized metal surface can become. (c) 2005......Density functional theory calculations are used as the basis for an analysis of the electrochemical process, where by water is split to form molecular oxygen and hydrogen. We develop a method for obtaining the thermochemistry of the electrochemical water splitting process as a function of the bias...... directly from the electronic structure calculations. We consider electrodes of Pt(111) and Au(111) in detail and then discuss trends for a series of different metals. We show that the difficult step in the water splitting process is the formation of superoxy-type (OOH) species on the surface...

  12. Dark oxidation of water in soils

    Directory of Open Access Journals (Sweden)

    Siegfried Fleischer

    2013-12-01

    18O. Water is the only large-scale source of electrons for reduction of CO2 in soils, but it has not been considered as an electron donor because of the very strong oxidation system needed. A high share of soil inorganic material seems to favor the release of O2.To access the supplementary material to this article, please see Supplementary files under Article Tools online.

  13. Photocatalysis: Oxidative Processes in Water Treatment

    Directory of Open Access Journals (Sweden)

    Roman V. Prihod'ko

    2013-01-01

    Full Text Available The efficiency of various homogeneous and heterogeneous systems photocatalytic processes destructive oxidation of organic compounds of different classes is considered. It is shown that photocatalytic methods can significantly increase the speed and depth (up to complete mineralization of decomposition processes of toxicants. The use of photocatalysis (PC in the creation of low-power water treatment technologies is a promising direction in addressing environmental problems of the hydrosphere.

  14. Oxidation of Tree Oil Containing a Complex Mixture of Sesquiterpenes: Keeping Track of the Carbon

    Science.gov (United States)

    Arata, C.; Misztal, P. K.; Isaacman-VanWertz, G. A.; Yee, L.; Franklin, J. P.; O'Brien, R.; Lim, C. Y.; Massoli, P.; Lambe, A. T.; Nowak, J. B.; Onasch, T. B.; Canagaratna, M. R.; Roscioli, J. R.; Herndon, S. C.; Jayne, J. T.; Worsnop, D. R.; Su, L.; Knopf, D. A.; Kroll, J. H.; Goldstein, A. H.

    2016-12-01

    Oxidation of biogenic volatile organic compounds in the atmosphere leads to a diverse mixture of products spanning a wide range of functionalities and structures, many of which partition to the particle phase. Sesquiterpenes have large secondary organic aerosol (SOA) yields and are therefore potentially significant contributors to atmospheric OA. However, their low concentration and the low volatility of their oxidation products pose challenges for studies of product yields and oxidation mechanisms. Studies done on terpene oxidation focus on a select few representative terpenes. We performed experiments in a chamber to study oxidation products from a complex mixture of tree oil extract containing a large fraction of sesquiterpenes, with the goal of keeping track of as much of the carbon as possible. Additionally, we compare these results to the oxidation of a single sesquiterpene, β-caryophyllene. Gas phase measurements were made using a proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS), while the particle phase was monitored with an time-of-flight aerosol mass spectrometer (ToF-AMS). Together, these instruments span the wide range of volatility needed to measure the oxidation products. The high mass resolution of the PTR-ToF-MS allows for chemical formulas to be unambiguously assigned to many of the detected masses, while the high time resolution allows us to track the fast oxidation of low volatility VOCs and their subsequent transition to the particle phase. Additionally, we use selective reagent ionization with NO+ ions to provide sensitive ionization of some larger gas-phase molecules with less fragmentation, as well as some structural information.

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

    Science.gov (United States)

    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.

  16. Supercritical water oxidation of products of human metabolism

    Science.gov (United States)

    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.

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

    Science.gov (United States)

    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

  18. The mechanism of water oxidation catalyzed by nanolayered manganese oxides: New insights.

    Science.gov (United States)

    Najafpour, Mohammad Mahdi; Abbasi Isaloo, Mohsen

    2015-11-01

    Herein we consider the mechanism of water oxidation by nanolayered manganese oxide in the presence of cerium(IV) ammonium nitrate. Based on membrane-inlet mass spectrometry results, the rate of H2((18))O exchange of μ-O groups on the surface of the nanolayered Mn-K oxide, and studies on water oxidation in the presence of different ratios of acetonitrile/water we propose a mechanism for water oxidation by nanolayered Mn oxides in the presence of cerium(IV) ammonium nitrate. Copyright © 2015 Elsevier B.V. All rights reserved.

  19. Mechanism of water transport in graphene oxide laminates.

    Science.gov (United States)

    Deng, Junjiao; You, Yi; Bustamante, Heriberto; Sahajwalla, Veena; Joshi, Rakesh K

    2017-03-01

    It is understood that nano-channels of graphene oxide membranes have a water flow mechanism which is similar to the water flow inside carbon nanotube pores. The water transport mechanisms recently proposed by various researchers suggest that membranes composed of graphene oxide laminates could be regarded as an assembly of many tiny carbon nanotubes stacked together with attached functional groups as spacers.

  20. Nanostructured transition metal oxides useful for water oxidation catalysis

    Science.gov (United States)

    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.

  1. Ultrastructural characterization of mesenchymal stromal cells labeled with ultrasmall superparamagnetic iron-oxide nanoparticles for clinical tracking studies

    DEFF Research Database (Denmark)

    Hansen, Louise; Hansen, Alastair B; Mathiasen, Anders B

    2014-01-01

    tracking for years, but knowledge regarding possible cytotoxic ultrastructural changes subsequent to iron-oxide particle labeling is limited. Hence, the purpose of this study was to label MSCs with dextran-coated ultrasmall super-paramagnetic iron-oxide (USPIO) particles conjugated with the transduction......INTRODUCTION: To evaluate survival and engraftment of mesenchymal stromal cells (MSCs) in vivo, it is necessary to track implanted cells non-invasively with a method, which does not influence cellular ultrastructure and functional characteristics. Iron-oxide particles have been applied for cell...

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

    Science.gov (United States)

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

    2014-09-01

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

  3. Nanostructured manganese oxide/carbon nanotubes, graphene and graphene oxide as water-oxidizing composites in artificial photosynthesis.

    Science.gov (United States)

    Najafpour, Mohammad Mahdi; Rahimi, Fahime; Fathollahzadeh, Maryam; Haghighi, Behzad; Hołyńska, Małgorzata; Tomo, Tatsuya; Allakhverdiev, Suleyman I

    2014-07-28

    Herein, we report on nano-sized Mn oxide/carbon nanotubes, graphene and graphene oxide as water-oxidizing compounds in artificial photosynthesis. The composites are synthesized by different and simple procedures and characterized by a number of methods. The water-oxidizing activities of these composites are also considered in the presence of cerium(IV) ammonium nitrate. Some composites are efficient Mn-based catalysts with TOF (mmol O2 per mol Mn per second) ~ 2.6.

  4. Thallium Isotopes Tracking Mn-Oxide Burial - A Proxy for Deoxygenation During Oceanic Anoxic Event 2

    Science.gov (United States)

    Ostrander, C.; Owens, J. D.; Nielsen, S.

    2015-12-01

    Thallium (Tl) is proving to be a useful paleoredox proxy given that the Tl isotope composition of seawater is highly dependent on the magnitude of manganese (Mn) oxide burial in the ocean. In turn, Mn oxides require oxygen at the sediment-water interface to precipitate, linking the Tl isotope cycle to ocean oxygenation. Currently, the marine residence time of Tl is ~20kyrs and the Tl isotope composition of seawater is invariant, which suggests Tl isotopes could be a global tracer of marine Mn-oxide burial. Importantly, recent research suggests sediments deposited under a euxinic water column faithfully record the Tl isotope value of the overlying oxic water column (e.g. Black Sea and Cariaco Basin). Therefore, analysis of organic-rich black shales may prove useful in evaluating the seawater Tl isotope composition of past oceans and, hence, large-scale burial of Mn-oxides and the extent of bottom water ocean oxygenation. A logical test for this proxy is during the well-studied Cenomanian-Turonian boundary event termed Oceanic Anoxic Event 2 (OAE-2) at ~94 Ma. It is known that the global extent of anoxia and euxinia increased during this event, however, to what extent global bottom water deoxygenation occured is unconstrained. If deep water deoxygenation occurred, it would be hypothesized that Mn-oxide precipitation would decrease, resulting in a positive Tl isotope excursion during OAE-2. We have analyzed the Tl isotope composition of organic-rich black shales from Site 1258 of the Ocean Drilling Program (ODP) spanning the period before, during, and after OAE-2. Based on Fe redox proxies, the entire section is euxinic and thus no Mn-oxides are present (i.e. no local redox changes). Before the event, Tl isotope compositions are similar or slightly heavier than modern seawater values. Just prior to the onset of OAE-2, a positive shift occurs and is maintained until recovery, slightly before the termination of the event. The shift to heavier values and subsequent

  5. Water-Column Stratification Observed along an AUV-Tracked Isotherm

    Science.gov (United States)

    Zhang, Y.; Messié, M.; Ryan, J. P.; Kieft, B.; Stanway, M. J.; Hobson, B.; O'Reilly, T. C.; Raanan, B. Y.; Smith, J. M.; Chavez, F.

    2016-02-01

    Studies of marine physical, chemical and microbiological processes benefit from observing in a Lagrangian frame of reference, i.e. drifting with ambient water. Because these processes can be organized relative to specific density or temperature ranges, maintaining observing platforms within targeted environmental ranges is an important observing strategy. We have developed a novel method to enable a Tethys-class long-range autonomous underwater vehicle (AUV) (which has a propeller and a buoyancy engine) to track a target isotherm in buoyancy-controlled drift mode. In this mode, the vehicle shuts off its propeller and autonomously detects the isotherm and stays with it by actively controlling the vehicle's buoyancy. In the June 2015 CANON (Controlled, Agile, and Novel Observing Network) Experiment in Monterey Bay, California, AUV Makai tracked a target isotherm for 13 hours to study the coastal upwelling system. The tracked isotherm started from 33 m depth, shoaled to 10 m, and then deepened to 29 m. The thickness of the tracked isotherm layer (within 0.3°C error from the target temperature) increased over this duration, reflecting weakened stratification around the isotherm. During Makai's isotherm tracking, another long-range AUV, Daphne, acoustically tracked Makai on a circular yo-yo trajectory, measuring water-column profiles in Makai's vicinity. A wave glider also acoustically tracked Makai, providing sea surface measurements on the track. The presented method is a new approach for studying water-column stratification, but requires careful analysis of the temporal and spatial variations mingled in the vehicles' measurements. We will present a synthesis of the water column's stratification in relation to the upwelling conditions, based on the in situ measurements by the mobile platforms, as well as remote sensing and mooring data.

  6. Water diffusion in brain cortex closely tracks underlying neuronal activity

    National Research Council Canada - National Science Library

    Tomokazu Tsurugizawa; Luisa Ciobanu; Denis Le Bihan

    2013-01-01

    ...). Here we establish that water molecular diffusion is directly modulated by underlying neuronal activity using a rat forepaw stimulation model under different conditions of neuronal stimulation and neurovascular coupling...

  7. The role of water tracks in altering biotic and abiotic soil properties and processes in a polar desert in Antarctica

    Science.gov (United States)

    Ball, Becky A.; Levy, Joseph

    2015-02-01

    Groundwater discharge via water tracks is a largely unexplored passageway routing salts and moisture from high elevations to valley floors in the McMurdo Dry Valleys (MDV) of Antarctica. Given the influence that water tracks have on the distribution of liquid water in seasonally thawed Antarctic soils, it is surprising how little is known about their role in structuring biotic and abiotic processes this cold desert ecosystem. Particularly, it is unclear how soil biota will respond to the activation of new water tracks resulting from enhanced active layer thickening or enhanced regional snowmelt. In the MDV, water tracks are both wetter and more saline than the surrounding soils, constituting a change in soil habitat suitability for soil biology and therefore the ecological processes they carry out. To investigate the net impact that water tracks have on Dry Valley soil biology, and therefore the ecosystem processes for which they are responsible, we analyzed microbial biomass and activity in soils inside and outside of three water tracks and relate this to the physical soil characteristics. Overall, our results suggest that water tracks can significantly influence soil properties, which can further impact biological biovolume and both biotic and abiotic fluxes of CO2. However, the nature of its impact differs with water track, further suggesting that not all water tracks can be regarded the same.

  8. Supramolecular water oxidation with rubda-based catalysts

    KAUST Repository

    Richmond, Craig J.

    2014-11-05

    Extremely slow and extremely fast new water oxidation catalysts based on the Rubda (bda = 2,2′-bipyri-dine-6,6′-dicarboxylate) systems are reported with turnover frequencies in the range of 1 and 900 cycless"1, respectively. Detailed analyses of the main factors involved in the water oxidation reaction have been carried out and are based on a combination of reactivity tests, electrochemical experiments, and DFT calculations. These analyses give a convergent interpretation that generates a solid understanding of the main factors involved in the water oxidation reaction, which in turn allows the design of catalysts with very low energy barriers in all the steps involved in the water oxidation catalytic cycle. We show that for this type of system p-stacking interactions are the key factors that influence reactivity and by adequately controlling them we can generate exceptionally fast water oxidation catalysts.

  9. Water oxidation catalysts and methods of use thereof

    Energy Technology Data Exchange (ETDEWEB)

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

    2017-12-05

    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.

  10. Thin cuprous oxide films prepared by thermal oxidation of copper foils with water vapor

    Energy Technology Data Exchange (ETDEWEB)

    Liang Jianbo, E-mail: liangjienbo1980@yahoo.co.jp [Department of Frontier Materials,Nagoya Institute of Technology, Nagoya 4668555 (Japan); Kishi, Naoki; Soga, Tetsuo [Department of Frontier Materials,Nagoya Institute of Technology, Nagoya 4668555 (Japan); Jimbo, Takashi [Research Center for Nano-Device and System, Nagoya Institute of Technology, Nagoya 4668555 (Japan); Ahmed, Mohsin [Department of Frontier Materials,Nagoya Institute of Technology, Nagoya 4668555 (Japan)

    2012-01-31

    We present an improved preparation method for the growth of high quality crystals of cuprous oxide films grown by thermal oxidation of cupper foils with water vapor. This method proved to be good for preparing cuprous oxide films with high purity and large grain size. X-ray diffraction studies revealed the formation of Cu{sub 2}O films with preferred (111) orientation. The cuprous oxide diodes fabricated by the above technique have been studied using current-voltage method.

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

    Science.gov (United States)

    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. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Kinetics of zero valent iron nanoparticle oxidation in oxygenated water.

    Science.gov (United States)

    Greenlee, Lauren F; Torrey, Jessica D; Amaro, Robert L; Shaw, Justin M

    2012-12-04

    Zero valent iron (ZVI) nanoparticles are versatile in their ability to remove a wide variety of water contaminants, and ZVI-based bimetallic nanoparticles show increased reactivity above that of ZVI alone. ZVI nanoparticles degrade contaminants through the reactive species (e.g., OH*, H(2(g)), H(2)O(2)) that are produced during iron oxidation. Measurement and modeling of aqueous ZVI nanoparticle oxidation kinetics are therefore necessary to optimize nanoparticle design. Stabilized ZVI and iron-nickel nanoparticles of approximately 150 nm in diameter were synthesized through solution chemistry, and nanoparticle oxidation kinetics were determined via measured mass change using a quartz crystal microbalance (QCM). Under flowing aerated water, ZVI nanoparticles had an initial exponential growth behavior indicating surface-dominated oxidation controlled by migration of species (H(2)O and O(2)) to the surface. A region of logarithmic growth followed the exponential growth which, based on the Mott-Cabrera model of thin oxide film growth, suggests a reaction dominated by movement of species (e.g., iron cations and oxygen anions) through the oxide layer. The presence of ethanol or a nickel shell on the ZVI nanoparticles delayed the onset of iron oxidation and reduced the extent of oxidation. In oxygenated water, ZVI nanoparticles oxidized primarily to the iron oxide-hydroxide lepidocrocite.

  13. Source Tracking of Nitrous Oxide using A Quantum Cascade Laser System in the Field and Laboratory Environments

    Science.gov (United States)

    Nitrous oxide is an important greenhouse gas and ozone depleting substance. Nitrification and denitrification are two major biological pathways that are responsible for soil emissions of N2O. However, source tracking of in-situ or laboratory N2O production is still challenging to...

  14. Collecting meaningful early-time kinetic data in homogeneous catalytic water oxidation with a sacrificial oxidant.

    Science.gov (United States)

    Vickers, James W; Sumliner, Jordan M; Lv, Hongjin; Morris, Mike; Geletii, Yurii V; Hill, Craig L

    2014-06-28

    As the field of water oxidation catalysis grows, so does the sophistication of the associated experimental apparatuses. However, problems persist in studying some of the most basic aspects of catalytic water oxidation including acquisition of satisfactory early-reaction-time kinetics and rapid quantification of O2 concentration. We seek to remedy these problems and through better experimental design, elucidate mechanistic aspects of catalytic water oxidation with theory backed by experimental data. Two new methods for evaluating homogeneous water oxidation catalysts by reaction with a stoichiometric oxidant are presented which eliminate problems of incomplete fast mixing and O2 measurement response time. These methods generate early-reaction-time kinetics that have previously been unavailable.

  15. Proposed mechanisms for water oxidation by Photosystem II and nanosized manganese oxides.

    Science.gov (United States)

    Najafpour, Mohamad Mahdi; Heidari, Sima; Balaghi, S Esmael; Hołyńska, Małgorzata; Sadr, Moayad Hossaini; Soltani, Behzad; Khatamian, Maasoumeh; Larkum, Anthony W; Allakhverdiev, Suleyman I

    2017-02-01

    Plants, algae and cyanobacteria capture sunlight, extracting electrons from H2O to reduce CO2 into sugars while releasing O2 in the oxygenic photosynthetic process. Because of the important role of water oxidation in artificial photosynthesis and many solar fuel systems, understanding the structure and function of this unique biological catalyst forms a requisite research field. Herein the structure of the water-oxidizing complex and its ligand environment are described with reference to the 1.9Å resolution X-ray-derived crystallographic model of the water-oxidizing complex from the cyanobacterium Thermosynechococcus vulcanus. Proposed mechanisms for water oxidation by Photosystem II and nanosized manganese oxides are also reviewed and discussed in the paper. Copyright © 2016 Elsevier B.V. All rights reserved.

  16. Selective Electrochemical Generation of Hydrogen Peroxide from Water Oxidation

    DEFF Research Database (Denmark)

    Viswanathan, Venkatasubramanian; Hansen, Heine Anton; Nørskov, Jens K.

    2015-01-01

    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...

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

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    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.

  18. Influence of water on the anodic oxidation mechanism of ...

    African Journals Online (AJOL)

    The following successive scans showed a high decrease of the current intensity and that is due to the formation of an insulating coating layer on the electrode surface. When water is added to the non-aqueous electrolyte, a DETA oxidation wave appears on the voltammograms. That oxidation wave is observed on the ...

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

    Science.gov (United States)

    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.

  20. Mononuclear and Heterotrinuclear Ruthenium Complexes: Synthesis and Water Oxidation Activity

    OpenAIRE

    Mognon, Lorenzo

    2015-01-01

    Artificial photosynthesis constitutes an intriguing alternative to fossil fuels, and the water oxidation reaction is considered the bottleneck for the achievement of an efficient device to perform it. Extensive research has been carried out, and is still ongoing, to identify the properties and mechanisms that define a good water oxidation catalyst. Ruthenium complexes have shown to be valid candidates for this task. This work presents the synthesis and characterization of multiple mononuclear...

  1. Use of a ground-water flow model with particle tracking to evaluate ground-water vulnerability, Clark County, Washington

    Science.gov (United States)

    Snyder, D.T.; Wilkinson, J.M.; Orzol, L.L.

    1996-01-01

    A ground-water flow model was used in conjunction with particle tracking to evaluate ground-water vulnerability in Clark County, Washington. Using the particle-tracking program, particles were placed in every cell of the flow model (about 60,000 particles) and tracked backwards in time and space upgradient along flow paths to their recharge points. A new computer program was developed that interfaces the results from a particle-tracking program with a geographic information system (GIS). The GIS was used to display and analyze the particle-tracking results. Ground-water vulnerability was evaluated by selecting parts of the ground-water flow system and combining the results with ancillary information stored in the GIS to determine recharge areas, characteristics of recharge areas, downgradient impact of land use at recharge areas, and age of ground water. Maps of the recharge areas for each hydrogeologic unit illustrate the presence of local, intermediate, or regional ground-water flow systems and emphasize the three-dimensional nature of the ground-water flow system in Clark County. Maps of the recharge points for each hydrogeologic unit were overlaid with maps depicting aquifer sensitivity as determined by DRASTIC (a measure of the pollution potential of ground water, based on the intrinsic characteristics of the near-surface unsaturated and saturated zones) and recharge from on-site waste-disposal systems. A large number of recharge areas were identified, particularly in southern Clark County, that have a high aquifer sensitivity, coincide with areas of recharge from on-site waste-disposal systems, or both. Using the GIS, the characteristics of the recharge areas were related to the downgradient parts of the ground-water system that will eventually receive flow that has recharged through these areas. The aquifer sensitivity, as indicated by DRASTIC, of the recharge areas for downgradient parts of the flow system was mapped for each hydrogeologic unit. A number of

  2. A Fast Track approach to deal with the temporal dimension of crop water footprint

    Science.gov (United States)

    Tuninetti, Marta; Tamea, Stefania; Laio, Francesco; Ridolfi, Luca

    2017-07-01

    Population growth, socio-economic development and climate changes are placing increasing pressure on water resources. Crop water footprint is a key indicator in the quantification of such pressure. It is determined by crop evapotranspiration and crop yield, which can be highly variable in space and time. While the spatial variability of crop water footprint has been the objective of several investigations, the temporal variability remains poorly studied. In particular, some studies approached this issue by associating the time variability of crop water footprint only to yield changes, while considering evapotranspiration patterns as marginal. Validation of this Fast Track approach has yet to be provided. In this Letter we demonstrate its feasibility through a comprehensive validation, an assessment of its uncertainty, and an example of application. Our results show that the water footprint changes are mainly driven by yield trends, while evapotranspiration plays a minor role. The error due to considering constant evapotranspiration is three times smaller than the uncertainty of the model used to compute the crop water footprint. These results confirm the suitability of the Fast Track approach and enable a simple, yet appropriate, evaluation of time-varying crop water footprint.

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

    Science.gov (United States)

    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.

  4. Sodium periodate as a primary oxidant for water-oxidation catalysts.

    Science.gov (United States)

    Parent, Alexander R; Brewster, Timothy P; De Wolf, Wendy; Crabtree, Robert H; Brudvig, Gary W

    2012-06-04

    Sodium periodate was characterized as a primary chemical oxidant for the catalytic evolution of oxygen at neutral pH using a variety of water-oxidation catalysts. The visible spectra of solutions formed from Cp*Ir(bpy)SO(4) during oxygen-evolution catalysis were measured. NMR spectroscopy suggests that the catalyst remains molecular after several turnovers with sodium periodate. Two of our [Cp*Ir(bis-NHC)][PF(6)](2) complexes, along with other literature catalysts, such as the manganese terpyridyl dimer, Hill's cobalt polyoxometallate, and Meyer's blue dimer, were also tested for activity. Sodium periodate was found to function only for water-oxidation catalysts with low overpotentials. This specificity is attributed to the relatively low oxidizing capability of sodium periodate solutions relative to solutions of other common primary oxidants. Studying oxygen-evolution catalysis by using sodium periodate as a primary oxidant may, therefore, provide preliminary evidence that a given catalyst has a low overpotential.

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

    Science.gov (United States)

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

    2013-01-01

    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 Mn3+/Mn4+ 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. PMID:23667149

  6. Oxidation and photo-oxidation of water on TiO2 surface

    DEFF Research Database (Denmark)

    Valdes, A.; Qu, Z.W.; Kroes, G.J.

    2008-01-01

    The oxidation and photo-oxidation of water on the rutile TiO2(110) surface is investigated using density functional theory (DFT) calculations. We investigate the relative stability of different surface terminations of TiO2 interacting with H2O and analyze the overpotential needed for the electrol...

  7. Time-resolved observations of water oxidation intermediates on a cobalt oxide nanoparticle catalyst

    Science.gov (United States)

    Zhang, Miao; de Respinis, Moreno; Frei, Heinz

    2014-04-01

    In any artificial photosynthetic system, the oxidation of water to molecular oxygen provides the electrons needed for the reduction of protons or carbon dioxide to a fuel. Understanding how this four-electron reaction works in detail is important for the development of improved robust catalysts made of Earth-abundant materials, like first-row transition-metal oxides. Here, using time-resolved Fourier-transform infrared spectroscopy and under reaction conditions, we identify intermediates of water oxidation catalysed by an abundant metal-oxide catalyst, cobalt oxide (Co3O4). One intermediate is a surface superoxide (three-electron oxidation intermediate absorbing at 1,013 cm-1), whereas a second observed intermediate is attributed to an oxo Co(IV) site (one-electron oxidation intermediate absorbing at 840 cm-1). The temporal behaviour of the intermediates reveals that they belong to different catalytic sites. Knowledge of the structure and kinetics of surface intermediates will enable the design of improved metal-oxide materials for more efficient water oxidation catalysis.

  8. Dynamic Stabilization of Metal Oxide-Water Interfaces.

    Science.gov (United States)

    McBriarty, Martin E; von Rudorff, Guido Falk; Stubbs, Joanne E; Eng, Peter J; Blumberger, Jochen; Rosso, Kevin M

    2017-02-22

    The interaction of water with metal oxide surfaces plays a crucial role in the catalytic and geochemical behavior of metal oxides. In a vast majority of studies, the interfacial structure is assumed to arise from a relatively static lowest energy configuration of atoms, even at room temperature. Using hematite (α-Fe 2 O 3 ) as a model oxide, we show through a direct comparison of in situ synchrotron X-ray scattering with density functional theory-based molecular dynamics simulations that the structure of the (11̅02) termination is dynamically stabilized by picosecond water exchange. Simulations show frequent exchanges between terminal aquo groups and adsorbed water in locations and with partial residence times consistent with experimentally determined atomic sites and fractional occupancies. Frequent water exchange occurs even for an ultrathin adsorbed water film persisting on the surface under a dry atmosphere. The resulting time-averaged interfacial structure consists of a ridged lateral arrangement of adsorbed water molecules hydrogen bonded to terminal aquo groups. Surface pK a prediction based on bond valence analysis suggests that water exchange will influence the proton-transfer reactions underlying the acid/base reactivity at the interface. Our findings provide important new insights for understanding complex interfacial chemical processes at metal oxide-water interfaces.

  9. Volcano and Ship Tracks Indicate Excessive Aerosol-Induced Cloud Water Increases in a Climate Model

    Science.gov (United States)

    Toll, Velle; Christensen, Matthew; Gassó, Santiago; Bellouin, Nicolas

    2017-12-01

    Aerosol-cloud interaction is the most uncertain mechanism of anthropogenic radiative forcing of Earth's climate, and aerosol-induced cloud water changes are particularly poorly constrained in climate models. By combining satellite retrievals of volcano and ship tracks in stratocumulus clouds, we compile a unique observational data set and confirm that liquid water path (LWP) responses to aerosols are bidirectional, and on average the increases in LWP are closely compensated by the decreases. Moreover, the meteorological parameters controlling the LWP responses are strikingly similar between the volcano and ship tracks. In stark contrast to observations, there are substantial unidirectional increases in LWP in the Hadley Centre climate model, because the model accounts only for the decreased precipitation efficiency and not for the enhanced entrainment drying. If the LWP increases in the model were compensated by the decreases as the observations suggest, its indirect aerosol radiative forcing in stratocumulus regions would decrease by 45%.

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

    Science.gov (United States)

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

    2012-10-07

    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.

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

    Science.gov (United States)

    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

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

    Science.gov (United States)

    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. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Stem Cell Labeling with Superparamagnetic Iron Oxide Nanoparticles Using Focused Ultrasound and Magnetic Resonance Imaging Tracking.

    Science.gov (United States)

    Lei, Hulong; Nan, Xiang; Wang, Zhiyong; Gao, Lin; Xie, Lisi; Zou, Chao; Wan, Qian; Pan, Di; Beauchamp, Norman; Yang, Xiaoming; Matula, Thomas; Qiu, Bensheng

    2015-04-01

    Magnetosonoporation (MSP) is a relatively safe and efficient approach for instant MR stem cell labeling. In this study, the physical and magnetic properties of different formulations of synthesized superparamagnetic iron oxide nanoparticles (SPION) were characterized. Then, a "closed" MSP apparatus using focused ultrasound was designed and the feasibility of MSP stem cell labeling using focused ultrasound was validated by evaluating the proliferation, migration and differentiation of the magnetically labeled cells. Subsequently, MSP/SPION labeled neural stem cells (NSCs) were transplanted into the contralateral striatum of glioma-bearing nude mice, and their migration was monitored using magnetic resonance imaging (MRI) in vivo. The results indicated that SPION-1 with the largest size (28.43 ± 9.55 nm) had the highest T2 relaxivity (136.62 Fe mM(-1) S(-1)) and the best MRI contrast effect. Without additional transfection reagents, NSCs were labeled with SPION using focused ultrasound in vitro and the safety of MSP stem cell labeling was validated with the optimized MSP technique. Finally, confirmed by histological evaluation, pronounced signal attenuation on T2-weighted images demonstrated the intracranial tumor tropism of NSCs could be monitored non-invasively by MRI. In conclusion, MSP cell labeling using focused ultrasound is a promising technique and the "closed" device is feasible, convenient and safe for instant magnetic stem cell labeling and MRI cell tracking.

  14. Hydrothermal Synthesis of Metal Oxide Nanoparticles in Supercritical Water

    Science.gov (United States)

    Hayashi, Hiromichi; Hakuta, Yukiya

    2010-01-01

    This paper summarizes specific features of supercritical hydrothermal synthesis of metal oxide particles. Supercritical water allows control of the crystal phase, morphology, and particle size since the solvent's properties, such as density of water, can be varied with temperature and pressure, both of which can affect the supersaturation and nucleation. In this review, we describe the advantages of fine particle formation using supercritical water and describe which future tasks need to be solved. PMID:28883312

  15. Selective electrochemical generation of hydrogen peroxide from water oxidation

    CERN Document Server

    Viswanathan, Venkatasubramanian; Nørskov, Jens K

    2015-01-01

    Water is a life-giving source, fundamental to human existence, yet, over a billion people lack access to clean drinking water. 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 as a descriptor to screen for selectivity trends between the 2e$^-$ water oxidation to H$_2$O$_2$ and the 4e$^-$ oxidation to O$_2$. We show that materials that bind oxygen intermediates sufficiently weakly, such as SnO$_2$, can activate hydrogen peroxide evolution. We present a rati...

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

    Science.gov (United States)

    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. Copyright © 2015 Elsevier B.V. All rights reserved.

  17. Water Oxidation Mechanisms of Metal Oxide Catalysts by Vibrational Spectroscopy of Transient Intermediates

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Miao [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division; Univ. of California, Berkeley, CA (United States); Frei, Heinz [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Biophysics and Integrated Bioimaging Division; Univ. of California, Berkeley, CA (United States)

    2017-02-22

    Water oxidation is an essential reaction of an artificial photosystem for solar fuel generation because it provides electrons needed to reduce carbon dioxide or protons to a fuel. Earth-abundant metal oxides are among the most attractive catalytic materials for this reaction because of their robustness and scalability, but their efficiency poses a challenge. Knowledge of catalytic surface intermediates gained by vibrational spectroscopy under reaction conditions plays a key role in uncovering kinetic bottlenecks and provides a basis for catalyst design improvements. Recent dynamic infrared and Raman studies reveal the molecular identity of transient surface intermediates of water oxidation on metal oxides. In conclusion, combined with ultrafast infrared observations of how charges are delivered to active sites of the metal oxide catalyst and drive the multielectron reaction, spectroscopic advances are poised to play a key role in accelerating progress toward improved catalysts for artificial photosynthesis.

  18. Water Oxidation Mechanisms of Metal Oxide Catalysts by Vibrational Spectroscopy of Transient Intermediates

    Science.gov (United States)

    Zhang, Miao; Frei, Heinz

    2017-05-01

    Water oxidation is an essential reaction of an artificial photosystem for solar fuel generation because it provides electrons needed to reduce carbon dioxide or protons to a fuel. Earth-abundant metal oxides are among the most attractive catalytic materials for this reaction because of their robustness and scalability, but their efficiency poses a challenge. Knowledge of catalytic surface intermediates gained by vibrational spectroscopy under reaction conditions plays a key role in uncovering kinetic bottlenecks and provides a basis for catalyst design improvements. Recent dynamic infrared and Raman studies reveal the molecular identity of transient surface intermediates of water oxidation on metal oxides. Combined with ultrafast infrared observations of how charges are delivered to active sites of the metal oxide catalyst and drive the multielectron reaction, spectroscopic advances are poised to play a key role in accelerating progress toward improved catalysts for artificial photosynthesis.

  19. Nanostructured manganese oxide on silica aerogel: a new catalyst toward water oxidation.

    Science.gov (United States)

    Najafpour, Mohammad Mahdi; Salimi, Saeideh; Madadkhani, Sepideh; Hołyńska, Małgorzata; Tomo, Tatsuya; Allakhverdiev, Suleyman I

    2016-12-01

    Herein we report on the synthesis and characterization of nano-sized Mn oxide/silica aerogel with low density as a good catalyst toward water oxidation. The composite was synthesized by a simple and low-cost hydrothermal procedure. In the next step, we studied the composite in the presence of cerium(IV) ammonium nitrate and photo-produced Ru(bpy) 3(3+) as a water-oxidizing catalyst. The low-density composite is a good Mn-based catalyst with turnover frequencies of ~0.3 and 0.5 (mmol O2/(mol Mn·s)) in the presence of Ru(bpy) 3(3+) and cerium(IV) ammonium nitrate, respectively. In addition to the water-oxidizing activities of the composite under different conditions, its self-healing reaction in the presence of cerium(IV) ammonium nitrate was also studied.

  20. Sunlight-induced photochemical decay of oxidants in natural waters: implications in ballast water treatment.

    Science.gov (United States)

    Cooper, William J; Jones, Adam C; Whitehead, Robert F; Zika, Rod G

    2007-05-15

    The transport and discharge of ship ballast water has been recognized as a major vector for the introduction of invasive species. Chemical oxidants, long used in drinking water and wastewater treatment, are alternative treatment methods for the control of invasive species currently being tested for use on ships. One concern when a ballasted vessel arrives in port is the adverse effects of residual oxidant in the treated water. The most common oxidants include chlorine (HOCl/OCl-), bromine (HOBr/OBr-), ozone (03), hydrogen peroxide (H2O2), chlorine dioxide (ClO2), and monochloramine (NH2Cl). The present study was undertaken to evaluate the sunlight-mediated photochemical decomposition of these oxidants. Sunlight photodecomposition was measured at various pH using either distilled water or oligotrophic Gulf Stream water for specific oxidants. For selected oxidants, quantum yields at specific wavelengths were obtained. An environmental photochemical model, GCSOLAR, also provided predictions of the fate (sunlight photolysis half-lives) of HOCI/OCl-, HOBr/OBr-, ClO2, and NH2Cl for two different seasons at latitude 40 degrees and in water with two different concentrations of chromophoric dissolved organic matter. These data are useful in assessing the environmental fate of ballast water treatment oxidants if they were to be discharged in port.

  1. Ex-situ tracking solid oxide cell electrode microstructural evolution in a redox cycle by high resolution ptychographic nanotomography

    DEFF Research Database (Denmark)

    De Angelis, Salvatore; Jørgensen, Peter Stanley; Esposito, Vincenzo

    2017-01-01

    , the nickel and pore networks undergo major reorganization and the formation of internal voids is observed in the nickel-oxide particles after the oxidation. These observations are discussed in terms of reaction kinetics, electrode mechanical stress and the consequences of redox cycling on electrode......For solid oxide fuel and electrolysis cells, precise tracking of 3D microstructural change in the electrodes during operation is considered critical to understand the complex relationship between electrode microstructure and performance. Here, for the first time, we report a significant step...... towards this aim by visualizing a complete redox cycle in a solid oxide cell (SOC) electrode. The experiment demonstrates synchrotron-based ptychography as a method of imaging SOC electrodes, providing an unprecedented combination of 3D image quality and spatial resolution among non-destructive imaging...

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

    Science.gov (United States)

    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.

  3. Positioning the Water Oxidation Reaction Sites in Plasmonic Photocatalysts.

    Science.gov (United States)

    Wang, Shengyang; Gao, Yuying; Miao, Shu; Liu, Taifeng; Mu, Linchao; Li, Rengui; Fan, Fengtao; Li, Can

    2017-08-30

    Plasmonic photocatalysis, stemming from the effective light absorbance and confinement of surface plasmons, provides a pathway to enhance solar energy conversion. Although the plasmonic hot electrons in water reduction have been extensively studied, exactly how the plasmonic hot holes participate in the water splitting reaction has not yet been well understood. In particular, where the plasmonic hot holes participate in water oxidation is still illusive. Herein, taking Au/TiO2 as a plasmonic photocatalyst prototype, we investigated the plasmonic hot holes involved in water oxidation. The reaction sites are positioned by photodeposition together with element mapping by electron microscopy, while the distribution of holes is probed by surface photovoltage imaging with Kelvin probe force microscopy. We demonstrated that the plasmonic holes are mainly concentrated near the gold-semiconductor interface, which is further identified as the reaction site for plasmonic water oxidation. Density functional theory also corroborates these findings by revealing the promotion role of interfacial structure (Ti-O-Au) for oxygen evolution. Furthermore, the interfacial effect on plasmonic water oxidation is validated by other Au-semiconductor photocatalytic systems (Au/SrTiO3, Au/BaTiO3, etc.).

  4. Methane oxidation coupled to oxygenic photosynthesis in anoxic waters

    Science.gov (United States)

    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

  5. Effect of Magnesium Oxide Nanoparticles on Water Glass Structure

    Directory of Open Access Journals (Sweden)

    Bobrowski A.

    2012-09-01

    Full Text Available An attempt has been made to determine the effect of an addition of colloidal suspensions of the nanoparticles of magnesium oxide on the structure of water glass, which is a binder for moulding and core sands. Nanoparticles of magnesium oxide MgO in propanol and ethanol were introduced in the same mass content (5wt.% and structural changes were determined by measurement of the FT-IR absorption spectra.

  6. Destruction of Navy Hazardous Wastes by Supercritical Water Oxidation

    Science.gov (United States)

    1994-08-01

    polychlorinated byphenyls (PCBs) are "one time only" wastes generated by electrical transformer changeout. PCBs are readily destroyed by the SCWO process...sensor on the gaseous effluent discharge line generates an electrical signal that is a measure of SCWO system pressure. The measured pressure is compared...oxidation ( SCWO ) to destroy organic hazardous wastes generated by Navy industrial activities. Supercritical water oxidation is the low temperature

  7. Wet oxidation processes for water pollution remediation

    OpenAIRE

    García Molina, Verónica

    2006-01-01

    The main objective of this work was to test the efficiency of wet oxidation processes when treating several types of aqueous wastes. On one side its performance for the abatement of chloro-organic aromatic toxic pollutants, such as 4-chlorophenol and 2,4-dichlorophenol has been studied. On the other hand, wastewater from pulp and paper mills, which has been reported to be an indirect source of entry of chlorophenols in the aquatic environment, has been investigated. More in detail, it has bee...

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

    Science.gov (United States)

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

    2016-07-01

    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.

  9. Subcritical and supercritical water oxidation of CELSS model wastes

    Science.gov (United States)

    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.

  10. Dynamic Stabilization of Metal Oxide-Water Interfaces

    OpenAIRE

    McBriarty, M. E.; von Rudorff, G. F.; Stubbs, J. E.; Eng, P. J.; Blumberger, J.; Ross, K. M.

    2017-01-01

    The interaction of water with metal oxide surfaces plays a crucial role in the catalytic and geochemical behavior of metal oxides. In a vast majority of studies, the interfacial structure is assumed to arise from a relatively static lowest energy configuration of atoms, even at room temperature. Using hematite (α-Fe2O3) as a model oxide, we show through a direct comparison of in situ synchrotron X-ray scattering with density functional theory-based molecular dynamics simulations that the stru...

  11. A Case History of Tracking Water Movement Through Fracture Systems in the Barnett Shale, March 10-11, 2011

    Science.gov (United States)

    Technical Presentation Session 6: Monitoring slides to presentation by Denbury on tracking water movement through fracture systems in the Barnett shale. This includes information on micro-seismic well evaluation, well plans, and a fracture map.

  12. Electrochemical decontamination of waters by advanced oxidation

    African Journals Online (AJOL)

    a

    chronoamperometry and bulk electrolysis to give the optimization characteristics of the degradation of such a ... the degradation process is perfectly predicted by a theoretical mathematical model. HPLC and. GC-MS ... aqueous solutions by batch electrolysis in the potential region of water decomposition (2.3 V vs. SHE) in ...

  13. BACTERICIDAL ACTIVITY OF ELECTROLYZED OXIDIZING WATER ON MEAT AND POULTRY

    Directory of Open Access Journals (Sweden)

    A. Serraino

    2008-09-01

    Full Text Available Electrolyzed oxidizing water (EOW has potential application as a residue free sanitizing agent for food of animal origin. Meat and poultry were contaminated with microorganism, pathogens or not, and different types of electrolyzed oxidizing water treatement were investigated to evaluate the activity of each of these method. In detail, this study is aiming at evaluating the effectiveness of EOW in reducing microbial count, including total bacterial count, Salmonella Typhimurium, Staphylococcus aureus, Listeria monocytogenes and Escherichia coli on meat and poultry. EOW has a very strong disinfectant activity which, along with its easy and safe use, makes a good alternative to many other more widely used disinfectants.

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

    Science.gov (United States)

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

    1986-01-01

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

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

    Science.gov (United States)

    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. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Uncovering structure-activity relationships in manganese-oxide-based heterogeneous catalysts for efficient water oxidation.

    Science.gov (United States)

    Indra, Arindam; Menezes, Prashanth W; Driess, Matthias

    2015-03-01

    Artificial photosynthesis by harvesting solar light into chemical energy could solve the problems of energy conversion and storage in a sustainable way. In nature, CO2 and H2 O are transformed into carbohydrates by photosynthesis to store the solar energy in chemical bonds and water is oxidized to O2 in the oxygen-evolving center (OEC) of photosystem II (PS II). The OEC contains CaMn4 O5 cluster in which the metals are interconnected through oxido bridges. Inspired by biological systems, manganese-oxide-based catalysts have been synthesized and explored for water oxidation. Structural, functional modeling, and design of the materials have prevailed over the years to achieve an effective and stable catalyst system for water oxidation. Structural flexibility with eg(1) configuration of Mn(III) , mixed valency in manganese, and higher surface area are the main requirements to attain higher efficiency. This Minireview discusses the most recent progress in heterogeneous manganese-oxide-based catalysts for efficient chemical, photochemical, and electrochemical water oxidation as well as the structural requirements for the catalyst to perform actively. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. The structure of graphene oxide membranes in liquid water, ethanol and water-ethanol mixtures.

    Science.gov (United States)

    Talyzin, Alexandr V; Hausmaninger, Tomas; You, Shujie; Szabó, Tamás

    2014-01-07

    The structure of graphene oxide (GO) membranes was studied in situ in liquid solvents using synchrotron radiation X-ray diffraction in a broad temperature interval. GO membranes are hydrated by water similarly to precursor graphite oxide powders but intercalation of alcohols is strongly hindered, which explains why the GO membranes are permeated by water and not by ethanol. Insertion of ethanol into the membrane structure is limited to only one monolayer in the whole studied temperature range, in contrast to precursor graphite oxide powders, which are intercalated with up to two ethanol monolayers (Brodie) and four ethanol monolayers (Hummers). As a result, GO membranes demonstrate the absence of "negative thermal expansion" and phase transitions connected to insertion/de-insertion of alcohols upon temperature variations reported earlier for graphite oxide powders. Therefore, GO membranes are a distinct type of material with unique solvation properties compared to parent graphite oxides even if they are composed of the same graphene oxide flakes.

  18. Debris Flows and Water Tracks in Continental Antarctica: Water as a geomorphic agent in a hyperarid polar desert

    Science.gov (United States)

    Hauber, E.; Sassenroth, C.; De Vera, J.-P.; Schmitz, N.; Reiss, D.; Hiesinger, H.; Johnsson, A.

    2017-09-01

    Most studies using Antarctica as a Mars analogue have focused on the McMurdo Dry Valleys, which are among the coldest and driest places on Earth. However, other ice-free areas in continental Antarctica also display landforms that can inform the study of the possible geomorphic impact of water in a polar desert. Here we present a new analogue site in the interior of the Transantarctic Mountains in Northern Victoria Land. Gullies show unambiguous evidence for debris flows, and water tracks act as shallow subsurface pathways of water on top of the permafrost tale. Both processes are driven by meltwater from glacier ice and snow in an environ-ment which never experiences rainfall and in which the air temperatures probably never exceed 0°C.

  19. Biomimetic metal oxides for the extraction of nanoparticles from water.

    Science.gov (United States)

    Mallampati, Ramakrishna; Valiyaveettil, Suresh

    2013-04-21

    Contamination of nanomaterials in the environment will pose significant health risks in the future. A viable purification method is necessary to address this problem. Here we report the synthesis and application of a series of metal oxides prepared using a biological template for the removal of nanoparticles from the aqueous environment. A simple synthesis of metal oxides such as ZnO, NiO, CuO, Co3O4 and CeO2 employing eggshell membrane (ESM) as a biotemplate is reported. The morphology of the metal oxide powders was characterized using electron microscopes and the lattice structure was established using X-ray diffraction methods. Extraction of nanoparticles from water was carried out to compare the efficiency of metal oxides. NiO showed good extraction efficiency in removing gold and silver nanoparticles from spiked water samples within an hour. Easy access and enhanced stability of metal oxides makes them interesting candidates for applications in industrial effluent treatments and water purifications.

  20. Metal oxide nanostructures by a simple hot water treatment.

    Science.gov (United States)

    Saadi, Nawzat S; Hassan, Laylan B; Karabacak, Tansel

    2017-08-02

    Surfaces with metal oxide nanostructures have gained considerable interest in applications such as sensors, detectors, energy harvesting cells, and batteries. However, conventional fabrication techniques suffer from challenges that hinder wide and effective applications of such surfaces. Most of the metal oxide nanostructure synthesis methods are costly, complicated, non-scalable, environmentally hazardous, or applicable to only certain few materials. Therefore, it is crucial to develop a simple metal oxide nanostructure fabrication method that can overcome all these limitations and pave the way to the industrial application of such surfaces. Here, we demonstrate that a wide variety of metals can form metal oxide nanostructures on their surfaces after simply interacting with hot water. This method, what we call hot water treatment, offers the ability to grow metal oxide nanostructures on most of the metals in the periodic table, their compounds, or alloys by a one-step, scalable, low-cost, and eco-friendly process. In addition, our findings reveal that a "plugging" mechanism along with surface diffusion is critical in the formation of such nanostructures. This work is believed to be of importance especially for researchers working on the growth of metal oxide nanostructures and their application in functional devices.

  1. Does oxidation affect the water functionality of myofibrillar proteins?

    Science.gov (United States)

    Bertram, Hanne Christine; Kristensen, Mette; Østdal, Henrik; Baron, Caroline P; Young, Jette F; Andersen, Henrik Jørgen

    2007-03-21

    Water-binding properties of myofibrils extracted from porcine muscle, and added hemoglobin with and without exposure to H2O2, were characterized using low-field proton NMR T2 relaxometry. The effects of pH and ionic strength in the samples were investigated as pH was adjusted to 5.4, 6.2, and 7.0 and ionic strength was adjusted to 0.29, 0.46, and 0.71 M, respectively. The formation of dityrosine as a measure of oxidative protein cross-linking revealed a significant increase in dityrosine concentrations upon H2O2 activation. The formation of dityrosine was strongly pH-dependent and increased with decreasing pH. In addition, increased levels of thiobarbituric acid reactive substances were observed upon addition of H2O2, implying that lipid oxidation was enhanced, however, with a different oxidation pattern as compared to the myofibrillar proteins. Low-field NMR relaxation measurements revealed reduced T2 relaxation times upon H2O2 activation, which corresponds to reduced water-holding capacity upon oxidation. However, a direct relationship between degree of oxidation and T2 relaxation time was not observed with various pH values and ionic strengths, and further studies are needed for a complete understanding of the effect of oxidation on myofibrillar functionality.

  2. Photochemical water oxidation by crystalline polymorphs of manganese oxides: structural requirements for catalysis.

    Science.gov (United States)

    Robinson, David M; Go, Yong Bok; Mui, Michelle; Gardner, Graeme; Zhang, Zhijuan; Mastrogiovanni, Daniel; Garfunkel, Eric; Li, Jing; Greenblatt, Martha; Dismukes, G Charles

    2013-03-06

    Manganese oxides occur naturally as minerals in at least 30 different crystal structures, providing a rigorous test system to explore the significance of atomic positions on the catalytic efficiency of water oxidation. In this study, we chose to systematically compare eight synthetic oxide structures containing Mn(III) and Mn(IV) only, with particular emphasis on the five known structural polymorphs of MnO2. We have adapted literature synthesis methods to obtain pure polymorphs and validated their homogeneity and crystallinity by powder X-ray diffraction and both transmission and scanning electron microscopies. Measurement of water oxidation rate by oxygen evolution in aqueous solution was conducted with dispersed nanoparticulate manganese oxides and a standard ruthenium dye photo-oxidant system. No Ru was absorbed on the catalyst surface as observed by XPS and EDX. The post reaction atomic structure was completely preserved with no amorphization, as observed by HRTEM. Catalytic activities, normalized to surface area (BET), decrease in the series Mn2O3 > Mn3O4 ≫ λ-MnO2, where the latter is derived from spinel LiMn2O4 following partial Li(+) removal. No catalytic activity is observed from LiMn2O4 and four of the MnO2 polymorphs, in contrast to some literature reports with polydispersed manganese oxides and electro-deposited films. Catalytic activity within the eight examined Mn oxides was found exclusively for (distorted) cubic phases, Mn2O3 (bixbyite), Mn3O4 (hausmannite), and λ-MnO2 (spinel), all containing Mn(III) possessing longer Mn-O bonds between edge-sharing MnO6 octahedra. Electronically degenerate Mn(III) has antibonding electronic configuration e(g)(1) which imparts lattice distortions due to the Jahn-Teller effect that are hypothesized to contribute to structural flexibility important for catalytic turnover in water oxidation at the surface.

  3. Genetic diversity of Escherichia coli isolates in irrigation water and associated sediments: implications for source tracking.

    Science.gov (United States)

    Lu, Lingeng; Hume, Michael E; Sternes, Keith L; Pillai, Suresh D

    2004-11-01

    Identifying the sources of fecal contaminants in surface water bodies such as rivers and lakes is of significant importance for environmental quality, food safety and regulatory purposes. Current DNA library-based source tracking approaches rely on the comparison of the genetic relatedness among the fecal contaminants. The objective of this study was to determine the genetic relatedness of Escherichia coli isolated from irrigation water and associated sediments using pulse field gel electrophoresis (PFGE) and to evaluate the genetic stability of the E. coli PFGE patterns. The isolates were obtained over a 4-month period from specific locations within irrigation canals and sediments associated with the Rio Grande River along the Texas-Mexico border. Fifty E. coli isolates were genotyped using PFGE. Different E. coli genotypes were identified among samples collected in 11 different locations. Some isolates obtained over successive months showed similar genotypic patterns. In the laboratory experiment, the PFGE pattern of one E. coli strain changed during survival in irrigation water. The genetic relatedness of this strain changed from >95% to <83% over 8-week survival. These results imply that PFGE is of such extreme resolution that it may be a challenging task to rely solely on a PFGE-based source tracking DNA fingerprint library for large watersheds.

  4. Developing a program to identify and track corrosion in nuclear plant raw water systems

    Energy Technology Data Exchange (ETDEWEB)

    Spires PE, G.V. [KTA - Tator Inc., Pittsburgh, Pennsylvania (United States); Pickles PE, S.B. [Senior Engineer, Ontario Power Generation, Ontario (Canada)

    2001-07-01

    Findings derived from a comprehensive plant performance survey at Ontario Power Generation's (OPG) nuclear units convinced management that it would be prudent to expand the ongoing power piping Flow Accelerated Corrosion (FAC) induced wall thinning base-lining and tracking program to encompass the raw cooling water systems as well. Such systems are subject to a distinctly different class of pipe wall thinning (PWT) mechanisms than the FAC that degrades high-energy power piping. This paper describes the PWT corrosion assessment and tracking program that has been developed and is currently being implemented by OPG for the raw cooling water (i.e., Service Water) systems within it's nuclear generating stations. Interim databases are used prior to initial inspection rounds to catalogue the prospective locations. For each piping system being surveyed, these interim databases include physical coordinates for the candidate locations, the type and wall thickness of the components comprising each location, ranking indications and recommended NDE methodologies as a function of the anticipated corrosion mechanisms. Rationales for assessing corrosion susceptibility and ranking prospective inspection sites are expounded by way of notations built into the database. (authors)

  5. Phenol oxidation kinetics in water solution using iron(3)-oxide-based nano-catalysts.

    Science.gov (United States)

    Zelmanov, Grigory; Semiat, Raphael

    2008-08-01

    The influence of inorganic ions (HCO(3), PO(4)/HPO(4)/H(2)PO(4), Cl, SO(4), Ca, Na and Mg) on the advanced chemical oxidation process of organic compounds dissolved in water is reported here. The catalytic behavior of iron(3)-oxide-based nano-particles was investigated together with inorganic ions and hydrogen peroxide concentrations, and pH level. Phenol was chosen as a typical organic contaminant for this study as a simulating pollutant. The limiting concentrations of radical scavengers making the oxidation process inefficient were identified. The strong effect of concentration of radical scavengers HCO(3), PO(4)/HPO(4)/H(2)PO(4), the nano-catalyst and hydrogen peroxide concentrations, and pH on the phenol oxidation rate and lag time period before reaction starts was determined. It was shown that Cl, SO(4), Ca, Na and Mg ions had no significant effect on the kinetics of phenol oxidation.

  6. Oxidation of white phosphorus by peroxides in water

    Science.gov (United States)

    Abdreimova, R. R.; Akbaeva, D. N.; Polimbetova, G. S.

    2017-10-01

    A mixture of hypophosphorous, phosphorous, and phosphoric acids is formed during the anaerobic oxidation of white phosphorus by peroxides [ROOH; R = H, 3-ClC6H4CO, (CH3)3C] in water. The rate of reactions grows considerably upon adding nonpolar organic solvents. The activity series of peroxides and solvents are determined experimentally. NMR spectroscopy shows that the main product of the reaction is phosphorous acid, regardless of the nature of the peroxide and solvent. A radical mechanism of oxidation of white phosphorus by peroxides in water is proposed. It is initiated by the homolysis of peroxide with the formation of HO• radicals that are responsible for the homolytic opening of phosphoric tetrahedrons. Further oxidation and stages of the hydrolysis of intermediate phosphorus-containing compounds yield products of the reaction.

  7. SUPERCRITICAL WATER OXIDATION MODEL DEVELOPMENT FOR SELECTED EPA PRIORITY POLLUTANTS

    Science.gov (United States)

    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...

  8. New Ir Bis-Carbonyl Precursor for Water Oxidation Catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Daria L. [Department of Chemistry, Yale University, 225; Beltrán-Suito, Rodrigo [Department of Chemistry, Yale University, 225; Thomsen, Julianne M. [Department of Chemistry, Yale University, 225; Hashmi, Sara M. [Department of Chemical and Environmental; Materna, Kelly L. [Department of Chemistry, Yale University, 225; Sheehan, Stafford W. [Catalytic Innovations LLC, 70 Crandall; Mercado, Brandon Q. [Department of Chemistry, Yale University, 225; Brudvig, Gary W. [Department of Chemistry, Yale University, 225; Crabtree, Robert H. [Department of Chemistry, Yale University, 225

    2016-02-05

    This paper introduces IrI(CO)2(pyalc) (pyalc = (2-pyridyl)-2-propanoate) as an atom-efficient precursor for Ir-based homogeneous oxidation catalysis. This compound was chosen to simplify analysis of the water oxidation catalyst species formed by the previously reported Cp*IrIII(pyalc)OH water oxidation precatalyst. Here, we present a comparative study on the chemical and catalytic properties of these two precursors. Previous studies show that oxidative activation of Cp*Ir-based precursors with NaIO4 results in formation of a blue IrIV species. This activation is concomitant with the loss of the placeholder Cp* ligand which oxidatively degrades to form acetic acid, iodate, and other obligatory byproducts. The activation process requires substantial amounts of primary oxidant, and the degradation products complicate analysis of the resulting IrIV species. The species formed from oxidation of the Ir(CO)2(pyalc) precursor, on the other hand, lacks these degradation products (the CO ligands are easily lost upon oxidation) which allows for more detailed examination of the resulting Ir(pyalc) active species both catalytically and spectroscopically, although complete structural analysis is still elusive. Once Ir(CO)2(pyalc) is activated, the system requires acetic acid or acetate to prevent the formation of nanoparticles. Investigation of the activated bis-carbonyl complex also suggests several Ir(pyalc) isomers may exist in solution. By 1H NMR, activated Ir(CO)2(pyalc) has fewer isomers than activated Cp*Ir complexes, allowing for advanced characterization. Future research in this direction is expected to contribute to a better structural understanding of the active species. A diol crystallization agent was needed for the structure determination of 3.

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

    Science.gov (United States)

    Klauss, André; Haumann, Michael; Dau, Holger

    2012-10-02

    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. Copper-Intercalated Birnessite as a Water Oxidation Catalyst.

    Science.gov (United States)

    Thenuwara, Akila C; Shumlas, Samantha L; Attanayake, Nuwan H; Cerkez, Elizabeth B; McKendry, Ian G; Frazer, Laszlo; Borguet, Eric; Kang, Qing; Zdilla, Michael J; Sun, Jianwei; Strongin, Daniel R

    2015-11-24

    We report a synthetic method to increase the catalytic activity of birnessite toward water oxidation by intercalating copper in the interlayer region of the layered manganese oxide. Intercalation of copper, verified by XRD, XPS, ICP, and Raman spectroscopy, was accomplished by exposing a suspension of birnessite to a Cu(+)-bearing precursor molecule that underwent disproportionation in solution to yield Cu(0) and Cu(2+). Electrocatalytic studies showed that the Cu-modified birnessite exhibited an overpotential for water oxidation of ∼490 mV (at 10 mA/cm(2)) and a Tafel slope of 126 mV/decade compared to ∼700 mV (at 10 mA/cm(2)) and 240 mV/decade, respectively, for birnessite without copper. Impedance spectroscopy results suggested that the charge transfer resistivity of the Cu-modified sample was significantly lower than Cu-free birnessite, suggesting that Cu in the interlayer increased the conductivity of birnessite leading to an enhancement of water oxidation kinetics. Density functional theory calculations show that the intercalation of Cu(0) into a layered MnO2 model structure led to a change of the electronic properties of the material from a semiconductor to a metallic-like structure. This conclusion from computation is in general agreement with the aforementioned impedance spectroscopy results. X-ray photoelectron spectroscopy (XPS) showed that Cu(0) coexisted with Cu(2+) in the prepared Cu-modified birnessite. Control experiments using birnessite that was decorated with only Cu(2+) showed a reduction in water oxidation kinetics, further emphasizing the importance of Cu(0) for the increased activity of birnessite. The introduction of Cu(0) into the birnessite structure also increased the stability of the electrocatalyst. At a working current of 2 mA, the Cu-modified birnessite took ∼3 times longer for the overpotential for water oxdiation to increase by 100 mV compared to when Cu was not present in the birnessite.

  11. Tracking agricultural soil nitric oxide emission variations with novel isotopic measurements

    Science.gov (United States)

    Miller, D. J.; Chai, J.; Guo, F.; Overby, S.; Dell, C. J.; Karsten, H.; Hastings, M. G.

    2016-12-01

    Agricultural production systems impact the reactive nitrogen cycle via atmospheric nitrogen emissions including nitric oxide, denoted as total nitrogen oxides (NOx). NOx serve as precursors to ozone and nitrate aerosols, influencing air quality, radiative forcing, and ecosystem health. With recent declines in fuel combustion sources, soil emissions are an increasing contributor to NOx budgets. However, spatially heterogeneous, episodic soil NOx pulses are challenging to constrain and remain highly uncertain. Using a novel hourly resolution soil flux chamber-based NOx collection method, we investigate fertilizer management and climatic controls on cropland soil NOx flux and nitrogen isotopic composition (δ15N-NOx) natural abundance variations with field-based and laboratory measurements. No-till, rain-fed corn plots were sampled daily (triplicate isotope samples per treatment per day) following broadcast and shallow-disk injected dairy manure applications as part of a sustainable dairy cropping study in State College, PA (Penn State University; USDA-ARS). Injected manure plots exhibited median fluxes two times higher with larger spatial variations than that for broadcast manure. Soil emission δ15N-NOx signatures of -45 to -20 ‰ were correlated with flux magnitudes across both treatments. Median δ15N-NOx signatures for injected manure were lower with larger spatial variations (-32 ± 9 ‰) than that for broadcast manure (-24 ± 1.5 ‰). These differences are likely linked with higher NH4+ availability for nitrification with injected manure in contrast with higher NH3 volatilization and higher soil δ15N-NH4+ for broadcast manure. Although NOx fluxes were suppressed 1-2 days after heavy rainfall (>35 % water-filled pore space), δ15N-NOx remained consistent. Controlled laboratory incubation studies will also be presented quantifying links with inorganic substrate and fertilizer δ15N. Our observations suggest that agricultural soil δ15N-NOx signatures are

  12. Water-mediated proton hopping on an iron oxide surface.

    Science.gov (United States)

    Merte, Lindsay R; Peng, Guowen; Bechstein, Ralf; Rieboldt, Felix; Farberow, Carrie A; Grabow, Lars C; Kudernatsch, Wilhelmine; Wendt, Stefan; Lægsgaard, Erik; Mavrikakis, Manos; Besenbacher, Flemming

    2012-05-18

    The diffusion of hydrogen atoms across solid oxide surfaces is often assumed to be accelerated by the presence of water molecules. Here we present a high-resolution, high-speed scanning tunneling microscopy (STM) study of the diffusion of H atoms on an FeO thin film. STM movies directly reveal a water-mediated hydrogen diffusion mechanism on the oxide surface at temperatures between 100 and 300 kelvin. Density functional theory calculations and isotope-exchange experiments confirm the STM observations, and a proton-transfer mechanism that proceeds via an H(3)O(+)-like transition state is revealed. This mechanism differs from that observed previously for rutile TiO(2)(110), where water dissociation is a key step in proton diffusion.

  13. Artificial photosynthesis challenges: water oxidation at nanostructured interfaces.

    Science.gov (United States)

    Carraro, Mauro; Sartorel, Andrea; Toma, Francesca Maria; Puntoriero, Fausto; Scandola, Franco; Campagna, Sebastiano; Prato, Maurizio; Bonchio, Marcella

    2011-01-01

    Innovative oxygen evolving catalysts, taken from the pool of nanosized, water soluble, molecular metal oxides, the so-called polyoxometalates (POMs), represent an extraordinary opportunity in the field of artificial photosynthesis. These catalysts possess a highly robust, totally inorganic structure, and can provide a unique mimicry of the oxygen evolving center in photosynthetic II enzymes. As a result POMs can effect H₂O oxidation to O₂ with unprecedented efficiency. In particular, the tetra-ruthenium based POM [Ru(IV) ₄(μ-OH)₂(μ-O)₄(H₂O)₄(γ-SiW(10)O(36))₂](10-), Ru₄(POM), displays fast kinetics, electrocatalytic activity powered by carbon nanotubes and exceptionally light-driven performance. A broad perspective is presented herein by addressing the recent progress in the field of metal-oxide nano-clusters as water oxidation catalysts, including colloidal species. Moreover, the shaping of the catalyst environment plays a fundamental role by alleviating the catalyst fatigue and stabilizing competent intermediates, thus responding to what are the formidable thermodynamic and kinetic challenges of water splitting. The design of nano-interfaces with specifically tailored carbon nanostructures and/or polymeric scaffolds opens a vast scenario for tuning electron/proton transfer mechanisms. Therefore innovation is envisaged based on the molecular modification of the hybrid photocatalytic center and of its environment.

  14. Highly water-soluble multi-walled carbon nanotubes amine-functionalized by supercritical water oxidation.

    Science.gov (United States)

    Chun, Kyoung-Yong; Moon, In-Kyu; Han, Joo-Hee; Do, Seung-Hoe; Lee, Jin-Seo; Jeon, Seong-Yun

    2013-11-07

    Multi-walled carbon nanotubes (MWNTs) have been amine-functionalized by eco-friendly supercritical water oxidation. The facilely functionalized MWNTs have high solubility (~84 mg L(-1)) in water and 78% transmittance at 30-fold dilution. The Tyndall effect is also shown for several liquids.

  15. Tracking and forecasting the Nation’s water quality - Priorities and strategies for 2013-2023

    Science.gov (United States)

    Rowe, Gary L.; Gilliom, Robert J.; Woodside, Michael D.

    2013-01-01

    Water-quality issues facing the Nation are growing in number and complexity, and solutions are becoming more challenging and costly. Key factors that affect the quality of our drinking water supplies and ecosystem health include contaminants of human and natural origin in streams and groundwater; excess nutrients and sediment; alteration of natural streamflow; eutrophication of lakes, reservoirs, and coastal estuaries; and changes in surface and groundwater quality associated with changes in climate, land and water use, and management practices. Tracking and forecasting the Nation's water quality in the face of these and other pressing water-quality issues are important goals for 2013-2023, the third decade of the U.S. Geological Survey's National Water-Quality Assessment (NAWQA) program. In consultation with stakeholders and the National Research Council, a new strategic Science Plan has been developed that describes a strategy for building upon and enhancing assessment of the Nation's freshwater quality and aquatic ecosystems. The plan continues strategies that have been central to the NAWQA program's long-term success, but it also makes adjustments to the monitoring and modeling approaches NAWQA will use to address critical data and science information needs identified by stakeholders. This fact sheet describes surface-water and groundwater monitoring and modeling activities that will start in fiscal year 2013. It also provides examples of the types of data and information products planned for the next decade, including (1) restored monitoring for reliable and timely status and trend assessments, (2) maps and models that show the distribution of selected contaminants (such as atrazine, nitrate, and arsenic) in streams and aquifers, and (3) Web-based modeling tools that allow managers to evaluate how water quality may change in response to different scenarios of population growth, climate change, or land-use management.

  16. Tracking water pathways in steep hillslopes by δ18O depth profiles of soil water

    Science.gov (United States)

    Mueller, Matthias H.; Alaoui, Abdallah; Kuells, Christoph; Leistert, Hannes; Meusburger, Katrin; Stumpp, Christine; Weiler, Markus; Alewell, Christine

    2014-11-01

    Assessing temporal variations in soil water flow is important, especially at the hillslope scale, to identify mechanisms of runoff and flood generation and pathways for nutrients and pollutants in soils. While surface processes are well considered and parameterized, the assessment of subsurface processes at the hillslope scale is still challenging since measurement of hydrological pathways is connected to high efforts in time, money and personnel work. The latter might not even be possible in alpine environments with harsh winter processes. Soil water stable isotope profiles may offer a time-integrating fingerprint of subsurface water pathways. In this study, we investigated the suitability of soil water stable isotope (δ18O) depth profiles to identify water flow paths along two transects of steep subalpine hillslopes in the Swiss Alps. We applied a one-dimensional advection-dispersion model using δ18O values of precipitation (ranging from -24.7 to -2.9‰) as input data to simulate the δ18O profiles of soil water. The variability of δ18O values with depth within each soil profile and a comparison of the simulated and measured δ18O profiles were used to infer information about subsurface hydrological pathways. The temporal pattern of δ18O in precipitation was found in several profiles, ranging from -14.5 to -4.0‰. This suggests that vertical percolation plays an important role even at slope angles of up to 46°. Lateral subsurface flow and/or mixing of soil water at lower slope angles might occur in deeper soil layers and at sites near a small stream. The difference between several observed and simulated δ18O profiles revealed spatially highly variable infiltration patterns during the snowmelt periods: The δ18O value of snow (-17.7 ± 1.9‰) was absent in several measured δ18O profiles but present in the respective simulated δ18O profiles. This indicated overland flow and/or preferential flow through the soil profile during the melt period. The applied

  17. Oxidative gating of water channels (aquaporins) in corn roots.

    Science.gov (United States)

    Ye, Qing; Steudle, Ernst

    2006-04-01

    An oxidative gating of water channels (aquaporins: AQPs) was observed in roots of corn seedlings as already found for the green alga Chara corallina. In the presence of 35 mM hydrogen peroxide (H2O2)--a precursor of hydroxyl radicals (*OH)--half times of water flow (as measured with the aid of pressure probes) increased at the level of both entire roots and individual cortical cells by factors of three and nine, respectively. This indicated decreases in the hydrostatic hydraulic conductivity of roots (Lp(hr)) and of cells (Lp(h)) by the same factors. Unlike other stresses, the plant hormone abscisic acid (ABA) had no ameliorative effect either on root LP(hr) or on cell Lp(h) when AQPs were inhibited by oxidative stress. Closure of AQPs reduced the permeability of acetone by factors of two in roots and 1.5 in cells. This indicated that AQPs were not ideally selective for water but allowed the passage of the organic solute acetone. In the presence of H2O2, channel closure caused anomalous (negative) osmosis at both the root and the cell level. This was interpreted by the fact that in the case of the rapidly permeating solute acetone, channel closure caused the solute to move faster than the water and the reflection coefficient (sigma s) reversed its sign. When H2O2 was removed from the medium, the effects were reversible, again at both the root and the cell level. The results provide evidence of oxidative gating of AQPs, which leads on to inhibition of water uptake by the roots. Possible mechanisms of the oxidative gating of AQPs induced by H2O2 (*OH) are discussed.

  18. Ex-situ tracking solid oxide cell electrode microstructural evolution in a redox cycle by high resolution ptychographic nanotomography

    Science.gov (United States)

    De Angelis, Salvatore; Jørgensen, Peter Stanley; Esposito, Vincenzo; Tsai, Esther Hsiao Rho; Holler, Mirko; Kreka, Kosova; Abdellahi, Ebtisam; Bowen, Jacob R.

    2017-08-01

    For solid oxide fuel and electrolysis cells, precise tracking of 3D microstructural change in the electrodes during operation is considered critical to understand the complex relationship between electrode microstructure and performance. Here, for the first time, we report a significant step towards this aim by visualizing a complete redox cycle in a solid oxide cell (SOC) electrode. The experiment demonstrates synchrotron-based ptychography as a method of imaging SOC electrodes, providing an unprecedented combination of 3D image quality and spatial resolution among non-destructive imaging techniques. Spatially registered 3D reconstructions of the same location in the electrode clearly show the evolution of the microstructure from the pristine state to the oxidized state and to the reduced state. A complete mechanical destruction of the zirconia backbone is observed via grain boundary fracture, the nickel and pore networks undergo major reorganization and the formation of internal voids is observed in the nickel-oxide particles after the oxidation. These observations are discussed in terms of reaction kinetics, electrode mechanical stress and the consequences of redox cycling on electrode performance.

  19. Water Sorption and Gamma Radiolysis Studies for Uranium Oxides

    Energy Technology Data Exchange (ETDEWEB)

    Icenhour, A.S.

    2002-02-27

    During the development of a standard for the safe, long-term storage of {sup 233}U-containing materials, several areas were identified that needed additional experimental studies. These studies were related to the perceived potential for the radiolytic generation of large pressures or explosive concentrations of gases in storage containers. This report documents the results of studies on the sorption of water by various uranium oxides and on the gamma radiolysis of uranium oxides containing various amounts of sorbed moisture. In all of the experiments, {sup 238}U was used as a surrogate for the {sup 233}U. For the water sorption experiments, uranium oxide samples were prepared and exposed to known levels of humidity to establish the water uptake rate. Subsequently, the amount of water removed was studied by heating samples in a oven at fixed temperatures and by thermogravimetric analysis (TGA)/differential thermal analysis (DTA). It was demonstrated that heating at 650 C adequately removes all moisture from the samples. Uranium-238 oxides were irradiated in a {sup 60}Co source and in the high-gamma-radiation fields provided by spent nuclear fuel elements of the High Flux Isotope Reactor. For hydrated samples of UO{sub 3}, H{sub 2} was the primary gas produced; but the total gas pressure increase reached steady value of about 10 psi. This production appears to be a function of the dose and the amount of water present. Oxygen in the hydrated UO{sub 3} sample atmosphere was typically depleted, and no significant pressure rise was observed. Heat treatment of the UO{sub 3} {center_dot} xH{sub 2}O at 650 C would result in conversion to U{sub 3}O{sub 8} and eliminate the H{sub 2} production. For all of the U{sub 3}O{sub 8} samples loaded in air and irradiated with gamma radiation, a pressure decrease was seen and little, if any, H{sub 2} was produced--even for samples with up to 9 wt % moisture content. Hence, these results demonstrated that the efforts to remove trace

  20. Water defluoridation with activated aluminum oxide A-1

    Energy Technology Data Exchange (ETDEWEB)

    Berendeeva, V.L.; Vakhnin, I.G.; Goronovskiy, I.T.

    A column approach was used to define the actors affecting the efficiency of aluminum oxide A-1 columns in defluoridation of drinking water. The data showed that the adsorptive capacity of A-1 for the bicarbonate ion was greater than for F/sup -/ and that, therefore, the bicarbonate ion interfered with the elimination of F/sup -/. In order to increase the efficiency and adsorptivity for F/sup -/, the water pH should be adjusted to 4-5. In model systems with NaF in distilled water the adsorptive capacity for F/sup -/ was determined as 3800 g/m/sup 3/ of A-1, and for tap water containing the bicarbonate ion the adsorptivity was calculated as 900 g/m/sup 3/ of A-1. 5 references, 1 figure.

  1. Electrochemical Oxidation of PAHs in Water from Harbor Sediment Purification

    DEFF Research Database (Denmark)

    Muff, Jens; Søgaard, Erik Gydesen

    to contamination by PAH, heavy metals, TBT etc. In Denmark, contaminated harbor sediment is pumped ashore to inland lakes or upland sites where treatment of the runoff water is required before discharge to the recipient. In this study, electrochemical oxidation (EO) has been investigated as a method for treatment...... of the discharge water addressing primarily polycyclic aromatic hydrocarbons (PAHs). PAHs are by-products of incomplete combustion of organic materials with recalcitrant and strong mutagenic/carcinogenic properties, due to their benzene analogue structures. PAHs are hydrophobic compounds and their persistence...... in the environment is mainly due to their low water solubility. The experimental study was performed in laboratory scale with volumes of water from 3 to 10 L in a batch recirculation experimental setup at constant temperature with a commercial one-compartment cell of tubular design with Ti/Pt90-Ir10 anode (60 cm2...

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

    Science.gov (United States)

    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.

  3. Selenide-Based Electrocatalysts and Scaffolds for Water Oxidation Applications

    KAUST Repository

    Xia, Chuan

    2015-11-05

    Selenide-based electrocatalysts and scaffolds on carbon cloth are successfully fabricated and demonstrated for enhanced water oxidation applications. A max­imum current density of 97.5 mA cm−2 at an overpotential of a mere 300 mV and a small Tafel slope of 77 mV dec−1 are achieved, suggesting the potential of these materials to serve as advanced oxygen evolution reaction catalysts.

  4. Destruction of representative submarine food waste using supercritical water oxidation.

    Science.gov (United States)

    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.

  5. Nonstoichiometric Titanium Oxides via Pulsed Laser Ablation in Water

    Directory of Open Access Journals (Sweden)

    Chen Shuei-Yuan

    2010-01-01

    Full Text Available Abstract Titanium oxide compounds TiO,Ti2O3, and TiO2 with a considerable extent of nonstoichiometry were fabricated by pulsed laser ablation in water and characterized by X-ray/electron diffraction, X-ray photoelectron spectroscopy and electron energy loss spectroscopy. The titanium oxides were found to occur as nanoparticle aggregates with a predominant 3+ charge and amorphous microtubes when fabricated under an average power density of ca. 1 × 108W/cm2 and 1011W/cm2, respectively followed by dwelling in water. The crystalline colloidal particles have a relatively high content of Ti2+ and hence a lower minimum band gap of 3.4 eV in comparison with 5.2 eV for the amorphous state. The protonation on both crystalline and amorphous phase caused defects, mainly titanium rather than oxygen vacancies and charge and/or volume-compensating defects. The hydrophilic nature and presumably varied extent of undercoordination at the free surface of the amorphous lamellae accounts for their rolling as tubes at water/air and water/glass interfaces. The nonstoichiometric titania thus fabricated have potential optoelectronic and catalytic applications in UV–visible range and shed light on the Ti charge and phase behavior of titania-water binary in natural shock occurrence.

  6. Nonstoichiometric Titanium Oxides via Pulsed Laser Ablation in Water.

    Science.gov (United States)

    Huang, Chang-Ning; Bow, Jong-Shing; Zheng, Yuyuan; Chen, Shuei-Yuan; Ho, Newjin; Shen, Pouyan

    2010-04-13

    Titanium oxide compounds TiO,Ti2O3, and TiO2 with a considerable extent of nonstoichiometry were fabricated by pulsed laser ablation in water and characterized by X-ray/electron diffraction, X-ray photoelectron spectroscopy and electron energy loss spectroscopy. The titanium oxides were found to occur as nanoparticle aggregates with a predominant 3+ charge and amorphous microtubes when fabricated under an average power density of ca. 1 × 108W/cm2 and 1011W/cm2, respectively followed by dwelling in water. The crystalline colloidal particles have a relatively high content of Ti2+ and hence a lower minimum band gap of 3.4 eV in comparison with 5.2 eV for the amorphous state. The protonation on both crystalline and amorphous phase caused defects, mainly titanium rather than oxygen vacancies and charge and/or volume-compensating defects. The hydrophilic nature and presumably varied extent of undercoordination at the free surface of the amorphous lamellae accounts for their rolling as tubes at water/air and water/glass interfaces. The nonstoichiometric titania thus fabricated have potential optoelectronic and catalytic applications in UV-visible range and shed light on the Ti charge and phase behavior of titania-water binary in natural shock occurrence.

  7. Photoanodic Hybrid Semiconductor–Molecular Heterojunction for Solar Water Oxidation

    KAUST Repository

    Joya, Khurram Saleem

    2015-06-29

    Inorganic photo-responsive semiconducting materials have been employed in photoelectrochemical(PEC) water oxidation devicesin pursuit of solar to fuel conversion.[1]The reaction kinetics in semiconductors is limited by poor contact at the interfaces, and charge transfer is impeded by surface defects and the grain boundaries.[2]It has shown that successful surface functionalization of the photo-responsive semiconducting materials with co-catalysts can maximize the charge separation, hole delivery and its effective consumption, and enhances the efficiency and performane of the PEC based water oxidation assembly.[3]We present here unique modification of photoanodic hematite (α-Fe2O3) and bismuth vanadate (BiVO4) with molecular co-catalysts for enhanced photoelectrochemical water oxidation (Figure 1). These hybrid inorganic–organometallic heterojunctions manifest impressive cathodic shifts in the onset potentials, and the photocurrent densities have been enhanced by > 90% at all potentials relative to uncatalyzed α-Fe2O3 or BiVO4, and other catalyst-semiconductor based heterojunctions.This is a novel development in the solar to fuel conversion field, and is crucially important for designing a tandem device where light interfere very little with the catalyst layer on top of semiconducting light absorber.

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

    Science.gov (United States)

    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) ). © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. USE OF COMPOSITE DATA SETS FOR SOURCE-TRACKING ENTEROCCOCCI IN THE WATER COLUMN AND SHORELINE INTERSTITIAL WATERS ON PENSACOLA BEACH, FL

    Science.gov (United States)

    Genthner, Fred J., Joseph B. James, Diane F. Yates and Stephanie D. Friedman. Submitted. Use of Composite Data Sets for Source-Tracking Enterococci in the Water Column and Shoreline Interstitial Waters on Pensacola Beach Florida. Mar. Pollut. Bull. 33 p. (ERL,GB 1212). So...

  10. Identifying and tracking evolving water masses in optically complex aquatic environments

    Science.gov (United States)

    Palacios, Sherry L.

    Earth's climate is intimately associated with biogeochemical processes of the sea. Biological Oceanography explores mechanisms controlling carbon uptake by phytoplankton, carbon transfer through biogeochemical processes, and energy flow through ecosystems. Satellite Oceanography affords a synoptic view of the sea surface and reveals underlying physical, chemical, and biological processes. Since the advent of ocean color satellites in 1978, ocean color algorithms evolved from quantifying phytoplankton biomass to addressing more complex bio-optical and oceanographic problems: characterizing inherent optical properties of the water column, estimating primary productivity, and detecting water masses. Locating a water mass, tracking its changes, and discriminating its constituents using bio-optical algorithms are the three objectives of this dissertation. The first objective identifies the location of the Columbia River Plume (CRP) by using light absorption by chromophoric dissolved organic matter (a CDOM) as an optical proxy for salinity. It relates in situ measurements of (a CDOM to salinity using linear regression analysis, then computes "synthetic" salinity using MODIS-Aqua satellite imagery. The algorithm is robust at predicting salinity of the CRP on the Oregon and Washington shelf. The second objective identifies sub-mesoscale features within the CRP and tracks their changes in space and time. It employs k-means clustering and discriminant function analysis to identify water types from bio-optical and environmental input variables using in situ and MODIS-Aqua satellite observations. The algorithm is robust at identifying features in satellite and mooring data, consistent with measured and modeled water masses in previous work. The third objective involves development of an optical model (PHYDOTax) that discriminates phytoplankton taxa contained within an algal bloom. A hyperspectral ocean color signature-library for known phytoplankton (dinoflagellates, diatoms

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

    Science.gov (United States)

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

    2008-12-01

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

  12. Relationship of human-associated microbial source tracking markers with Enterococci in Gulf of Mexico waters.

    Science.gov (United States)

    Gordon, Katrina V; Brownell, Miriam; Wang, Shiao Y; Lepo, Joe Eugene; Mott, Joanna; Nathaniel, Rajkumar; Kilgen, Marilyn; Hellein, Kristen N; Kennedy, Elizabeth; Harwood, Valerie J

    2013-03-01

    Human and ecosystem health can be damaged by fecal contamination of recreational waters. Microbial source tracking (MST) can be used to specifically detect domestic sewage containing human waste, thereby informing both risk assessment and remediation strategies. Previously, an inter-laboratory collaboration developed standardized PCR methods for a bacterial, an archaeal, and a viral indicator of human sewage. Here we present results for two subsequent years of field testing in fresh and salt water by five laboratories across the U.S. Gulf Coast (two in Florida and one each in Mississippi, Louisiana and Texas) using common standard operating procedures (SOPs) developed previously. Culturable enterococci were enumerated by membrane filtration, and PCR was used to detect three MST markers targeting domestic sewage: human-associated Bacteroides (HF183), Methanobrevibacter smithii and human polyomaviruses BK and JC (HPyVs). Detection of sewage markers in surface waters was significantly associated with higher enterococci levels and with exceedance of the recreational water quality standard in four or three regions, respectively. Sewage markers were frequently co-detected in single samples, e.g., M. smithii and HF183 were co-detected in 81% of Louisiana samples, and HPyVs and M. smithii were co-detected in over 40% of southwest Florida and Mississippi samples. This study demonstrates the robustness and inter-laboratory transferability of these three markers for the detection of pollution from domestic sewage in the waters impacting the Gulf of Mexico over a coastal range of over 1000 miles. Copyright © 2012 Elsevier Ltd. All rights reserved.

  13. Chemical oxidation of unsymmetrical dimethylhydrazine transformation products in water

    Directory of Open Access Journals (Sweden)

    Madi Abilev

    2015-03-01

    Full Text Available Oxidation of unsymmetrical dimethylhydrazine (UDMH during a water treatment has several disadvantages including formation of stable toxic byproducts. Effectiveness of treatment methods in relation to UDMH transformation products is currently poorly studied. This work considers the effectiveness of chemical oxidants in respect to main metabolites of UDMH – 1-formyl-2,2-dimethylhydrazine, dimethylaminoacetontrile, N-nitrosodimethylamine and 1-methyl-1H-1,2,4-triazole. Experiments on chemical oxidation by Fenton's reagent, potassium permanganate and sodium nitrite were conducted. Quantitative determination was performed by HPLC. Oxidation products were identified by gas chromatography-mass spectrometry in combination with solid-phase microextraction. 1-Formyl-2,2-dimethylhydrazine was completely oxidized by Fenton's reagent with formation of formaldehyde N-formyl-N-methyl-hydrazone, 1,4-dihydro-1,4-dimethyl-5H-tetrazol-5-one by the action of potassium permanganate and N-methyl-N-nitro-methanamine in the presence of sodium nitrite. Oxidation of 1-formyl-2,2-dimethylhydrazine also resulted in formation of N-nitrosodimethylamine. Oxidation of dimethylaminoacetontrile proceeded with formation of hydroxyacetonitrile, dimethylformamide and 1,2,5-trimethylpyrrole. After 30 days, dimethylaminoacetontrile was not detected in the presence of Fenton’s reagent and potassium permanganate, but it’s concentration in samples with sodium nitrite was 77.3 mg/L. In the presence of Fenton’s reagent, potassium permanganate and sodium nitrite after 30 days, N-nitrosodimethylamine concentration decreased by 85, 80 and 50%, respectively. In control sample, N-nitrosodimethylamine concentration decreased by 50%, indicating that sodium nitrite has no effect of on N-nitrosodimethylamine concentration. Only Fenton's reagent allowed to reduce the concentration of 1-methyl-1H-1,2,4-triazole to 50% in 30 days. In the presence of other oxidants, 1-methyl-1H-1,2,4-triazole

  14. Water oxidation by manganese oxides formed from tetranuclear precursor complexes: the influence of phosphate on structure and activity.

    Science.gov (United States)

    Shevchenko, Denys; Anderlund, Magnus F; Styring, Stenbjörn; Dau, Holger; Zaharieva, Ivelina; Thapper, Anders

    2014-06-28

    Two types of manganese oxides have been prepared by hydrolysis of tetranuclear Mn(iii) complexes in the presence or absence of phosphate ions. The oxides have been characterized structurally using X-ray absorption spectroscopy and functionally by O2 evolution measurements. The structures of the oxides prepared in the absence of phosphate are dominated by di-μ-oxo bridged manganese ions that form layers with limited long-range order, consisting of edge-sharing MnO6 octahedra. The average manganese oxidation state is +3.5. The structure of these oxides is closely related to other manganese oxides reported as water oxidation catalysts. They show high oxygen evolution activity in a light-driven system containing [Ru(bpy)3](2+) and S2O8(2-) at pH 7. In contrast, the oxides formed by hydrolysis in the presence of phosphate ions contain almost no di-μ-oxo bridged manganese ions. Instead the phosphate groups are acting as bridges between the manganese ions. The average oxidation state of manganese ions is +3. This type of oxide has much lower water oxidation activity in the light-driven system. Correlations between different structural motifs and the function as a water oxidation catalyst are discussed and the lower activity in the phosphate containing oxide is linked to the absence of protonable di-μ-oxo bridges.

  15. Separation of tritiated water using graphene oxide membrane

    Energy Technology Data Exchange (ETDEWEB)

    Sevigny, Gary J. [Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Motkuri, Radha K. [Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Gotthold, David W. [Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Fifield, Leonard S. [Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Frost, Anthony P. [Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Bratton, Wesley [Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

    2015-06-28

    In future nuclear fuel reprocessing plants and possibly for nuclear power plants, the cleanup of tritiated water will be needed for hundreds of thousands of gallons of water with low activities of tritium. This cleanup concept utilizes graphene oxide laminar membranes (GOx) for the separation of low-concentration (10-3-10 µCi/g) tritiated water to create water that can be released to the environment and a much smaller waste stream with higher tritium concentrations. Graphene oxide membranes consist of hierarchically stacked, overlapping molecular layers and represent a new class of materials. A permeation rate test was performed with a 2-µm-thick cast Asbury membrane using mixed gas permeability testing with zero air (highly purified atmosphere) and with air humidified with either H2O or D2O to a nominal 50% relative humidity. The membrane permeability for both H2O and D2O was high with N2 and O2 at the system measurement limit. The membrane water permeation rate was compared to a Nafion® membrane and the GOx permeation was approximately twice as high at room temperature. The H2O vapor permeation rate was 5.9 × 102 cc/m2/min (1.2 × 10-6 g/min-cm2), which is typical for graphene oxide membranes. To demonstrate the feasibility of such isotopic water separation through GOX laminar membranes, an experimental setup was constructed to use pressure-driven separation by heating the isotopic water mixture at one side of the membrane to create steam while cooling the other side. Several membranes were tested and were prepared using different starting materials and by different pretreatment methods. The average separation result was 0.8 for deuterium and 0.6 for tritium. Higher or lower temperatures may also improve separation efficiency but neither has been tested yet. A rough estimate of cost compared to current technology was also included as an indication of potential viability of the process. The relative process costs were based on the rough size of facility to

  16. Tracking Solid Oxide Cell Microstructure Evolution by High Resolution 3D Nano-Tomography

    DEFF Research Database (Denmark)

    De Angelis, Salvatore

    Solid oxide cells (SOCs) oer great prospects for the ecient and reversible conversion of chemical to electrical energy. Therefore, they are expected to play a key role in the renewable energy landscape. However, their limited lifetime under operating conditions hinders their widespread usage...... tomography is applied. Preliminary results show rapid kinetics for the two reactions. During oxidation, void formation in metallic particles is observed. During reduction, the nickel oxide particles rst evolve to a nano-porous system of nickel crystallites and then coarsen towards dense nickel particles....

  17. Concerted hydrogen-atom abstraction in photosynthetic water oxidation.

    Science.gov (United States)

    Westphal, K L; Tommos, C; Cukier, R I; Babcock, G T

    2000-06-01

    Photosystem II evolves oxygen by using water in the unlikely role of a reductant. The absorption of sunlight by chlorophyll produces highly oxidizing equivalents that are filled with electrons stripped from water. This proton-coupled redox chemistry occurs at the oxygen-evolving complex, which contains a tetramanganese cluster, a redox-active tyrosine amino acid hydrogen-bonded to a histidine amino acid, a calcium ion and chloride. Hydrogen-atom abstraction by the tyrosyl radical from water bound to the manganese cluster is now widely held to occur in this process, at least for some of the steps in the catalytic cycle. We discuss kinetic and energetic constraints on the hydrogen-atom abstraction process.

  18. Photocatalytic polyoxometalate compositions of tungstovanadates and uses as water oxidation catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Hill, Craig L.; Gueletii, Iourii V.; Song, Jie; Lv, Hongjin; Musaev, Djamaladdin; Luo, Zhen

    2017-08-22

    This disclosure relates to photocatalytic polyoxometalate compositions of tungstovanadates and uses as water oxidation catalysts. In certain embodiments, the disclosure relates to compositions comprising water, a complex of a tetra-metal oxide cluster and VW.sub.9O.sub.34 ligands, and a photosensitizer. Typically, the metal oxide cluster is Co. In certain embodiments, the disclosure relates to electrodes and other devices comprising water oxidation catalysts disclosed herein and uses in generating fuels and electrical power from solar energy.

  19. Track structure of protons and other light ions in liquid water: applications of the LIonTrack code at the nanometer scale.

    Science.gov (United States)

    Bäckström, G; Galassi, M E; Tilly, N; Ahnesjö, A; Fernández-Varea, J M

    2013-06-01

    The LIonTrack (Light Ion Track) Monte Carlo (MC) code for the simulation of H(+), He(2+), and other light ions in liquid water is presented together with the results of a novel investigation of energy-deposition site properties from single ion tracks. The continuum distorted-wave formalism with the eikonal initial state approximation (CDW-EIS) is employed to generate the initial energy and angle of the electrons emitted in ionizing collisions of the ions with H2O molecules. The model of Dingfelder et al. ["Electron inelastic-scattering cross sections in liquid water," Radiat. Phys. Chem. 53, 1-18 (1998); "Comparisons of calculations with PARTRAC and NOREC: Transport of electrons in liquid water," Radiat. Res. 169, 584-594 (2008)] is linked to the general-purpose MC code PENELOPE/penEasy to simulate the inelastic interactions of the secondary electrons in liquid water. In this way, the extended PENELOPE/penEasy code may provide an improved description of the 3D distribution of energy deposits (EDs), making it suitable for applications at the micrometer and nanometer scales. Single-ionization cross sections calculated with the ab initio CDW-EIS formalism are compared to available experimental values, some of them reported very recently, and the theoretical electronic stopping powers are benchmarked against those recommended by the ICRU. The authors also analyze distinct aspects of the spatial patterns of EDs, such as the frequency of nearest-neighbor distances for various radiation qualities, and the variation of the mean specific energy imparted in nanoscopic targets located around the track. For 1 MeV/u particles, the C(6+) ions generate about 15 times more clusters of six EDs within an ED distance of 3 nm than H(+). On average clusters of two to three EDs for 1 MeV/u H(+) and clusters of four to five EDs for 1 MeV/u C(6+) could be expected for a modeling double strand break distance of 3.4 nm.

  20. Selection and application of microbial source tracking tools for water-quality investigations

    Science.gov (United States)

    Stoeckel, Donald M.

    2005-01-01

    Microbial source tracking (MST) is a complex process that includes many decision-making steps. Once a contamination problem has been defined, the potential user of MST tools must thoroughly consider study objectives before deciding upon a source identifier, a detection method, and an analytical approach to apply to the problem. Regardless of which MST protocol is chosen, underlying assumptions can affect the results and interpretation. It is crucial to incorporate tests of those assumptions in the study quality-control plan to help validate results and facilitate interpretation. Detailed descriptions of MST objectives, protocols, and assumptions are provided in this report to assist in selection and application of MST tools for water-quality investigations. Several case studies illustrate real-world applications of MST protocols over a range of settings, spatial scales, and types of contamination. Technical details of many available source identifiers and detection methods are included as appendixes. By use of this information, researchers should be able to formulate realistic expectations for the information that MST tools can provide and, where possible, successfully execute investigations to characterize sources of fecal contamination to resource waters.

  1. Fundamental kinetics and mechanistic pathways for oxidation reactions in supercritical water

    Science.gov (United States)

    Webley, Paul A.; Tester, Jefferson W.

    1988-01-01

    Oxidation of the products of human metabolism in supercritical water has been shown to be an efficient way to accomplish the on-board water/waste recycling in future long-term space flights. Studies of the oxidation kinetics of methane to carbon dioxide in supercritical water are presented in this paper in order to enhance the fundamental understanding of the oxidation of human waste compounds in supercritical water. It is concluded that, although the elementary reaction models remain the best hope for simulating oxidation in supercritical water, several modifications to existing mechanisms need to be made to account for the role of water in the reaction mechanism.

  2. Ground water pollution resulting from weed control of the railway tracks; Grundvandsforurening som foelge af ukrudtsbekaempelse paa jernbaneterraener

    Energy Technology Data Exchange (ETDEWEB)

    Winge, U. [Miljoe og fysisk Planlaegning, DSB (Denmark); Frederiksen, J. [Geo- og miljoeteknik, DSB Raadgivning (Denmark)

    1995-07-01

    The risk of ground water pollution exists along railway tracks where herbicides have to be applied. The Danish State Railways have used several various herbicides, now suspected of penetration (or diffusion) into the adjacent aquifers. Leaching and permeability of soil layers is examined. (EG)

  3. Microbial source tracking in shellfish harvesting waters in the Gulf of Nicoya, Costa Rica.

    Science.gov (United States)

    Symonds, E M; Young, S; Verbyla, M E; McQuaig-Ulrich, S M; Ross, E; Jiménez, J A; Harwood, V J; Breitbart, M

    2017-03-15

    Current microbial water quality monitoring is generally limited to culture-based measurements of fecal indicator bacteria (FIB). Given the many possible sources of fecal pollution within a watershed and extra-intestinal FIB reservoirs, it is important to determine source(s) of fecal pollution as a means to improve water quality and protect public health. The principal objective of this investigation was to characterize the microbial water quality of shellfish harvesting areas in the Gulf of Nicoya, Costa Rica during 2015. In order to achieve this objective, the specificity and sensitivity of 11 existing microbial source tracking (MST) PCR assays, associated with cows (BacCow), dogs (BacCan, DogBac), domestic wastewater (PMMoV), general avian (GFD), gulls (Gull2), horses (HorseBac, HoF), humans (HF183, HPyV), and pigs (PF), were evaluated using domestic wastewater and animal fecal samples collected from the region. The sensitivity of animal-associated assays ranged from 13 to 100%, while assay specificity ranged from 38 to 100%. The specificity of pepper mild mottle virus (PMMoV) and human polyomavirus (HPyV) was 100% for domestic wastewater, as compared to 94% specificity of the HF183 Bacteroidales marker. PMMoV was identified as a useful domestic wastewater-associated marker, with concentrations as high as 1.1 × 10 5 copies/ml and 100% sensitivity and specificity. Monthly surface water samples collected from four shellfish harvesting areas were analyzed using culture-based methods for Escherichia coli as well as molecular methods for FIB and a suite of MST markers, which were selected for their specificity in the region. While culturable E. coli results suggested possible fecal pollution during the monitoring period, the absence of human/domestic wastewater-associated markers and low FIB concentrations determined using molecular methods indicated sufficient microbial water quality for shellfish harvesting. This is the first study to our knowledge to test the

  4. Engineered graphite oxide materials for application in water purification.

    Science.gov (United States)

    Gao, Wei; Majumder, Mainak; Alemany, Lawrence B; Narayanan, Tharangattu N; Ibarra, Miguel A; Pradhan, Bhabendra K; Ajayan, Pulickel M

    2011-06-01

    Retaining the inherent hydrophilic character of GO (graphite-oxide) nanosheets, sp(2) domains on GO are covalently modified with thiol groups by diazonium chemistry. The surface modified GO adsorbs 6-fold higher concentration of aqueous mercuric ions than the unmodified GO. "Core-shell" adsorbent granules, readily useable in filtration columns, are synthesized by assembling aqueous GO over sand granules. The nanostructured GO-coated sand retains at least 5-fold higher concentration of heavy metal and organic dye than pure sand. The research results could open avenues for developing low-cost water purification materials for the developing economies. © 2011 American Chemical Society

  5. Tracking progress towards global drinking water and sanitation targets: A within and among country analysis.

    Science.gov (United States)

    Fuller, James A; Goldstick, Jason; Bartram, Jamie; Eisenberg, Joseph N S

    2016-01-15

    Global access to safe drinking water and sanitation has improved dramatically during the Millennium Development Goal (MDG) period. However, there is substantial heterogeneity in progress between countries and inequality within countries. We assessed countries' temporal patterns in access to drinking water and sanitation using publicly available data. We then classified countries using non-linear modeling techniques as having one of the following trajectories: 100% coverage, linear growth, linear decline, no change, saturation, acceleration, deceleration, negative acceleration, or negative deceleration. We further assessed the degree to which temporal profiles follow a sigmoidal pattern and how these patterns might vary within a given country between rural and urban settings. Among countries with more than 10 data points, between 15% and 38% showed a non-linear trajectory, depending on the indicator. Overall, countries' progress followed a sigmoidal trend, but some countries are making better progress and some worse progress than would be expected. We highlight several countries that are not on track to meet the MDG for water or sanitation, but whose access is accelerating, suggesting better performance during the coming years. Conversely, we also highlight several countries that have made sufficient progress to meet the MDG target, but in which access is decelerating. Patterns were heterogeneous and non-linearity was common. Characterization of these heterogeneous patterns will help policy makers allocate resources more effectively. For example, policy makers can identify countries that could make use of additional resources or might be in need of additional institutional capacity development to properly manage resources; this will be essential to meet the forthcoming Sustainable Development Goals. Copyright © 2015 Elsevier B.V. All rights reserved.

  6. Electro-assembly of a chromophore-catalyst bilayer for water oxidation and photocatalytic water splitting.

    Science.gov (United States)

    Ashford, Dennis L; Sherman, Benjamin D; Binstead, Robert A; Templeton, Joseph L; Meyer, Thomas J

    2015-04-13

    The use of electropolymerization to prepare electrocatalytically and photocatalytically active electrodes for water oxidation is described. Electropolymerization of the catalyst Ru(II)(bda)(4-vinylpyridine)2 (bda=2,2'-bipyridine-6,6'-dicarboxylate) on planar electrodes results in films containing semirigid polymer networks. In these films there is a change in the water oxidation mechanism compared to the solution analogue from bimolecular to single-site. Electro-assembly construction of a chromophore-catalyst structure on mesoporous, nanoparticle TiO2 films provides the basis for a dye-sensitized photoelectrosynthesis cell (DSPEC) for sustained water splitting in a pH 7 phosphate buffer solution. Photogenerated oxygen was measured in real-time by use of a two-electrode cell design. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Fecal pollution source tracking toolbox for identification, evaluation and characterization of fecal contamination in receiving urban surface waters and groundwater.

    Science.gov (United States)

    Tran, Ngoc Han; Gin, Karina Yew-Hoong; Ngo, Huu Hao

    2015-12-15

    The quality of surface waters/groundwater of a geographical region can be affected by anthropogenic activities, land use patterns and fecal pollution sources from humans and animals. Therefore, the development of an efficient fecal pollution source tracking toolbox for identifying the origin of the fecal pollution sources in surface waters/groundwater is especially helpful for improving management efforts and remediation actions of water resources in a more cost-effective and efficient manner. This review summarizes the updated knowledge on the use of fecal pollution source tracking markers for detecting, evaluating and characterizing fecal pollution sources in receiving surface waters and groundwater. The suitability of using chemical markers (i.e. fecal sterols, fluorescent whitening agents, pharmaceuticals and personal care products, and artificial sweeteners) and/or microbial markers (e.g. F+RNA coliphages, enteric viruses, and host-specific anaerobic bacterial 16S rDNA genetic markers) for tracking fecal pollution sources in receiving water bodies is discussed. In addition, this review also provides a comprehensive approach, which is based on the detection ratios (DR), detection frequencies (DF), and fate of potential microbial and chemical markers. DR and DF are considered as the key criteria for selecting appropriate markers for identifying and evaluating the impacts of fecal contamination in surface waters/groundwater. Copyright © 2015 Elsevier B.V. All rights reserved.

  8. The effect of lanthanum(III) and cerium(III) ions between layers of manganese oxide on water oxidation.

    Science.gov (United States)

    Najafpour, Mohammad Mahdi; Isaloo, Mohsen Abbasi; Hołyńska, Małgorzata; Shen, Jian-Ren; Allakhverdiev, Suleyman I; Allakhverdiev, Suleyman

    2015-12-01

    Manganese oxide structure with lanthanum(III) or cerium(III) ions between the layers was synthesized by a simple method. The ratio of Mn to Ce or La in samples was 0.00, 0.04, 0.08, 0.16, 0.32, 0.5, 0.82, or 1.62. The compounds were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction studies, and atomic absorption spectroscopy. The compounds show efficient catalytic activity of water oxidation in the presence of cerium(IV) ammonium nitrate with a turnover frequency of 1.6 mmol O2/mol Mn.s. In contrast to the water-oxidizing complex in Photosystem II, calcium(II) has no specific role to enhance the water-oxidizing activity of the layered manganese oxides and other cations can be replaced without any significant decrease in water-oxidizing activities of these layered Mn oxides. Based on this and previously reported results from oxygen evolution in the presence of H 2 (18) O, we discuss the mechanism and the important factors influencing the water-oxidizing activities of the manganese oxides.

  9. Iron oxide hydroxide nanoflower assisted removal of arsenic from water

    Energy Technology Data Exchange (ETDEWEB)

    Raul, Prasanta Kumar, E-mail: prasanta.drdo@gmail.com [Defence Research Laboratory, Post Bag No. 2, Tezpur 784001, Assam (India); Devi, Rashmi Rekha; Umlong, Iohborlang M. [Defence Research Laboratory, Post Bag No. 2, Tezpur 784001, Assam (India); Thakur, Ashim Jyoti [Department of Chemical Sciences, Tezpur University, Napaam, Tezpur 784028, Assam (India); Banerjee, Saumen; Veer, Vijay [Defence Research Laboratory, Post Bag No. 2, Tezpur 784001, Assam (India)

    2014-01-01

    Graphical abstract: Non-magnetic polycrystalline iron oxide hydroxide nanoparticle with flower like morphology is found to play as an effective adsorbent media to remove As(III) from 300 μg L{sup −1} to less than 10 μg L{sup −1} from drinking water over wide range of pH. TEM image clearly reveals that the nanoparticle looks flower like morphology with average particle size less than 20 nm. The maximum sorption capacity of the sorbent is found to be 475 μg g{sup −1} for arsenic at room temperature and the data fitted to different isotherm models indicate the heterogeneity of the adsorbent surface. The material can be regenerated up to 70% using dilute hydrochloric acid and it would be utilized for de-arsenification purposes. - Highlights: • The work includes synthesis of iron oxide hydroxide nanoflower and its applicability for the removal of arsenic from water. • The nanoparticle was characterized using modern instrumental methods like FESEM, TEM, BET, XRD, etc. • The maximum sorption capacity of the sorbent is found to be 475 μg g{sup −1} for arsenic at room temperature. • The sorption is multilayered on the heterogeneous surface of the nano adsorbent. • The mechanism of arsenic removal of IOH nanoflower follows both adsorption and ion-exchange. - Abstract: Non-magnetic polycrystalline iron oxide hydroxide nanoparticle with flower like morphology is found to play as an effective adsorbent media to remove As(III) from 300 μg L{sup −1} to less than 10 μg L{sup −1} from drinking water over wide range of pH. The nanoparticle was characterized by X-ray powder diffraction analysis (XRD), BET surface area, FTIR, FESEM and TEM images. TEM image clearly reveals flower like morphology with average particle size less than 20 nm. The nanoflower morphology is also supported by FESEM images. The maximum sorption capacity of the sorbent is found to be 475 μg g{sup −1} for arsenic and the data fitted to different isotherm models indicate the

  10. Effects of Gravity on Supercritical Water Oxidation (SCWO) Processes

    Science.gov (United States)

    Hegde, Uday; Hicks, Michael

    2013-01-01

    The effects of gravity on the fluid mechanics of supercritical water jets are being studied at NASA to develop a better understanding of flow behaviors for purposes of advancing supercritical water oxidation (SCWO) technologies for applications in reduced gravity environments. These studies provide guidance for the development of future SCWO experiments in new experimental platforms that will extend the current operational range of the DECLIC (Device for the Study of Critical Liquids and Crystallization) Facility on board the International Space Station (ISS). The hydrodynamics of supercritical fluid jets is one of the basic unit processes of a SCWO reactor. These hydrodynamics are often complicated by significant changes in the thermo-physical properties that govern flow behavior (e.g., viscosity, thermal conductivity, specific heat, compressibility, etc), particularly when fluids transition from sub-critical to supercritical conditions. Experiments were conducted in a 150 ml reactor cell under constant pressure with water injections at various flow rates. Flow configurations included supercritical jets injected into either sub-critical or supercritical water. Profound gravitational influences were observed, particularly in the transition to turbulence, for the flow conditions under study. These results will be presented and the parameters of the flow that control jet behavior will be examined and discussed.

  11. Warm Water Oxidation Verification - Scoping and Stirred Reactor Tests

    Energy Technology Data Exchange (ETDEWEB)

    Braley, Jenifer C.; Sinkov, Sergey I.; Delegard, Calvin H.; Schmidt, Andrew J.

    2011-06-15

    Scoping tests to evaluate the effects of agitation and pH adjustment on simulant sludge agglomeration and uranium metal oxidation at {approx}95 C were performed under Test Instructions(a,b) and as per sections 5.1 and 5.2 of this Test Plan prepared by AREVA. (c) The thermal testing occurred during the week of October 4-9, 2010. The results are reported here. For this testing, two uranium-containing simulant sludge types were evaluated: (1) a full uranium-containing K West (KW) container sludge simulant consisting of nine predominant sludge components; (2) a 50:50 uranium-mole basis mixture of uraninite [U(IV)] and metaschoepite [U(VI)]. This scoping study was conducted in support of the Sludge Treatment Project (STP) Phase 2 technology evaluation for the treatment and packaging of K-Basin sludge. The STP is managed by CH2M Hill Plateau Remediation Company (CHPRC) for the U.S. Department of Energy. Warm water ({approx}95 C) oxidation of sludge, followed by immobilization, has been proposed by AREVA and is one of the alternative flowsheets being considered to convert uranium metal to UO{sub 2} and eliminate H{sub 2} generation during final sludge disposition. Preliminary assessments of warm water oxidation have been conducted, and several issues have been identified that can best be evaluated through laboratory testing. The scoping evaluation documented here was specifically focused on the issue of the potential formation of high strength sludge agglomerates at the proposed 95 C process operating temperature. Prior hydrothermal tests conducted at 185 C produced significant physiochemical changes to genuine sludge, including the formation of monolithic concretions/agglomerates that exhibited shear strengths in excess of 100 kPa (Delegard et al. 2007).

  12. Ruthenium Water Oxidation Catalysts based on Pentapyridyl Ligands.

    Science.gov (United States)

    Gil-Sepulcre, Marcos; Böhler, Michael; Schilling, Mauro; Bozoglian, Fernando; Bachmann, Cyril; Scherrer, Dominik; Fox, Thomas; Spingler, Bernhard; Gimbert-Suriñach, Carolina; Alberto, Roger; Bofill, Roger; Sala, Xavier; Luber, Sandra; Richmond, Craig J; Llobet, Antoni

    2017-11-23

    Ruthenium complexes containing the pentapyridyl ligand 6,6''-(methoxy(pyridin-2-yl)methylene)di-2,2'-bipyridine (L-OMe) of general formula trans-[Ru II (X)(L-OMe-κ-N 5 )] n+ (X=Cl, n=1, trans-1 + ; X=H 2 O, n=2, trans-2 2+ ) have been isolated and characterized in solution (by NMR and UV/Vis spectroscopy) and in the solid state by XRD. Both complexes undergo a series of substitution reactions at oxidation state Ru II and Ru III when dissolved in aqueous triflic acid-trifluoroethanol solutions as monitored by UV/Vis spectroscopy, and the corresponding rate constants were determined. In particular, aqueous solutions of the Ru III -Cl complex trans-[Ru III (Cl)(L-OMe-κ-N 5 )] 2+ (trans-1 2+ ) generates a family of Ru aquo complexes, namely trans-[Ru III (H 2 O)(L-OMe-κ-N 5 )] 3+ (trans-2 3+ ), [Ru III (H 2 O) 2 (L-OMe-κ-N 4 )] 3+ (trans-3 3+ ), and [Ru III (Cl)(H 2 O)(L-OMe-κ-N 4 )] 2+ (trans-4 2+ ). Although complex trans-4 2+ is a powerful water oxidation catalyst, complex trans-2 3+ has only a moderate activity and trans-3 3+ shows no activity. A parallel study with related complexes containing the methyl-substituted ligand 6,6''-(1-pyridin-2-yl)ethane-1,1-diyl)di-2,2'-bipyridine (L-Me) was carried out. The behavior of all of these catalysts has been rationalized based on substitution kinetics, oxygen evolution kinetics, electrochemical properties, and density functional theory calculations. The best catalyst, trans-4 2+ , reaches turnover frequencies of 0.71 s -1 using Ce IV as a sacrificial oxidant, with oxidative efficiencies above 95 %. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Ultrasound-assisted advanced oxidation processes for water decontamination.

    Science.gov (United States)

    Ince, Nilsun H

    2017-04-09

    The study reflects a part of my experience in sonochemistry and ultrasound-assisted advanced oxidation processes (AOPs) acquired during the last fifteen years with my research team. The data discussed were selected from studies with azo dyes, endocrine disrupting compounds and analgesic/anti-inflammatory pharmaceuticals, which are all classified as "hazardous" or "emerging" contaminants. The research focused on their treatability by ultrasound (US) and AOPs with emphasis on the mineralization of organic carbon. Some of the highlights as pointed out in the manuscript are: i) ultrasound is capable of partially or completely oxidizing the above contaminant groups if the operating conditions are properly selected and optimized, but incapable of mineralizing them; ii) the mechanism of degradation in homogeneous solutions is OH-mediated oxidation in the bulk solution or at the bubble-liquid interface, depending on the molecular properties of the contaminant, the applied frequency and pH; iii) US-assisted AOPs such as ozonation, UV/peroxide, Fenton and UV/Fenton are substantially more effective than ultrasound alone, particularly for the mineralization process; iv) catalytic processes involving TiO2, alumina and zero-valent iron and assisted by ultrasound are promising options not only for the destruction of the parent compounds, but also for the mineralization of their oxidation byproducts. The degradation reactions in heterogeneous solutions take place mostly at the catalyst surface despite the high-water solubility of the compounds; v) sonolytic modification of the above catalysts to reduce their particle size (to nano-levels) or to decorate the surface with metallic nanoparticles increases the catalytic activity under sonolysis, photolysis and both, and improves the stability of the catalyst. Copyright © 2017 Elsevier B.V. All rights reserved.

  14. Nanostructured Titanium Oxide Film- And Membrane-Based Photocatalysis For Water Treatment

    Science.gov (United States)

    Titanium Oxide (TiO2) photocatalysis, one of the ultraviolet (UV)-based advanced oxidation technologies (AOTs) and nanotechnologies (AONs), has attracted great attention for the development of efficient water treatment and purification systems due to the effectiveness ...

  15. Benefits of neutral electrolyzed oxidizing water as a drinking water additive for broiler chickens.

    Science.gov (United States)

    Bügener, E; Kump, A Wilms-Schulze; Casteel, M; Klein, G

    2014-09-01

    In the wake of discussion about the use of drugs in food-producing farms, it seems to be more and more important to search for alternatives and supportive measures to improve health. In this field trial, the influence of electrolyzed oxidizing (EO) water on water quality, drug consumption, mortality, and performance parameters such as BW and feed conversion rate was investigated on 2 broiler farms. At each farm, 3 rearing periods were included in the study. With EO water as the water additive, the total viable cell count and the number of Escherichia coli in drinking water samples were reduced compared with the respective control group. The frequency of treatment days was represented by the number of used daily doses per population and showed lower values in EO-water-treated groups at both farms. Furthermore, the addition of EO water resulted in a lower mortality rate. In terms of analyzed performance parameters, no significant differences were determined. In this study, the use of EO water improved drinking water quality and seemed to reduce the drug use without showing negative effects on performance parameters and mortality rates. © 2014 Poultry Science Association Inc.

  16. The Effect of Oxidant and Redox Potential on Metal Corrosion in Drinking Water

    Science.gov (United States)

    Future drinking water regulatory action may require some water utilities to consider additional and/or alternative oxidation and disinfection practices. There is little known about the effect of oxidant changes on the corrosion of drinking water distribution system materials and ...

  17. Can crossover and maximal fat oxidation rate points be used equally for ergocycling and walking/running on a track?

    Science.gov (United States)

    Mendelson, M; Jinwala, K; Wuyam, B; Levy, P; Flore, P

    2012-06-01

    To verify whether exercise intensities at the crossover point (COP) and maximal lipid oxidation (Lipox(max)) can be used interchangeably regardless of exercise mode, this study compared COP, Lipox(max) and maximal fat oxidation rate (MFO) obtained during two modes of submaximal metabolic exercise tests: stationary cycling under laboratory conditions and walking/running on a track. After preliminary indirect maximal progressive tests, 15 healthy subjects randomly performed submaximal exercise tests on a stationary cycle ergometer (E) and on a track (T), during which gas exchanges and substrate oxidation rates were measured. There were no significant mean differences in COP [heart rate (HR): 149±23 beats.min(-1) (T), 145±28 beats.min(-1) (E); VO(2): 2168±896 mL.min(-1) (T), 2052±714 mL.min(-1) (E)], Lipox(max) [HR: 127±27 beats.min(-1) (T), 126±23 beats.min(-1) (E); VO(2): 1638±839 mL.min(-1) (T), 1696±656 mL.min(-1) (E)] or MFO [498.3±192.0 mg.min(-1) (T), 477.7±221.5 mg.min(-1) (E)] between the two modes of exercise. However, Bland-Altman analysis showed a clear disagreement between the two exercise modes and, in particular, a large random error [bias±random error: for COP, -3.5±53.2 beats.min(-1) (HR), -116.8±1556.4 mL.min(-1) (VO(2)); for Lipox(max), -0.4±43.3 beats.min(-1) (HR), -5.7±1286.4 mL.min(-1) (VO(2)); and for MFO, -20.6±384.9 mg.min(-1)]. This study showed that, in young, healthy, reasonably fit subjects, exercise mode can affect intensities at the COP and the Lipox(max). These results, which now have to be confirmed in patients with metabolic defects, suggest the need to perform specific tests to make individualized adaptations to physical activity outside of clinical settings. Copyright © 2012 Elsevier Masson SAS. All rights reserved.

  18. MOLECULAR TRACKING FECAL CONTAMINATION IN SURFACE WATERS: 16S RDNA VERSUS METAGENOMICS APPROACHES

    Science.gov (United States)

    Microbial source tracking methods need to be sensitive and exhibit temporal and geographic stability in order to provide meaningful data in field studies. The objective of this study was to use a combination of PCR-based methods to track cow fecal contamination in two watersheds....

  19. Remote-Sensing and Automated Water Resources Tracking: Near Real-Time Decision Support for Water Managers Facing Drought and Flood

    Science.gov (United States)

    Reiter, M. E.; Elliott, N.; Veloz, S.; Love, F.; Moody, D.; Hickey, C.; Fitzgibbon, M.; Reynolds, M.; Esralew, R.

    2016-12-01

    Innovative approaches for tracking the Earth's natural resources, especially water which is essential for all living things, are essential during a time of rapid environmental change. The Central Valley is a nexus for water resources in California, draining the Sacramento and San Joaquin River watersheds. The distribution of water throughout California and the Central Valley, while dynamic, is highly managed through an extensive regional network of canals, levees, and pumps. Water allocation and delivery is determined through a complex set of rules based on water contracts, historic priority, and other California water policies. Furthermore, urban centers, agriculture, and the environment throughout the state are already competing for water, particularly during drought. Competition for water is likely to intensify as California is projected to experience continued increases in demand due to population growth and more arid growing conditions, while also having reduced or modified water supply due to climate change. As a result, it is difficult to understand or predict how water will be used to fulfill wildlife and wetland conservation needs. A better understanding of the spatial distribution of water in near real-time can facilitate adaptation of water resource management to changing conditions on the landscape, both over the near- and long-term. The Landsat satellite mission delivers imagery every 16-days from nearly every place on the earth at a high spatial resolution. We have integrated remote sensing of satellite data, classification modeling, bioinformatics, optimization, and ecological analyses to develop an automated near real-time water resources tracking and decision-support system for the Central Valley of California. Our innovative system has applications for coordinated water management in the Central Valley to support people, places, and wildlife and is being used to understand the factors that drive variation in the distribution and abundance of water

  20. Diverse manganese(II)-oxidizing bacteria are prevalent in drinking water systems.

    Science.gov (United States)

    Marcus, Daniel N; Pinto, Ameet; Anantharaman, Karthik; Ruberg, Steven A; Kramer, Eva L; Raskin, Lutgarde; Dick, Gregory J

    2017-04-01

    Manganese (Mn) oxides are highly reactive minerals that influence the speciation, mobility, bioavailability and toxicity of a wide variety of organic and inorganic compounds. Although Mn(II)-oxidizing bacteria are known to catalyze the formation of Mn oxides, little is known about the organisms responsible for Mn oxidation in situ, especially in engineered environments. Mn(II)-oxidizing bacteria are important in drinking water systems, including in biofiltration and water distribution systems. Here, we used cultivation dependent and independent approaches to investigate Mn(II)-oxidizing bacteria in drinking water sources, a treatment plant and associated distribution system. We isolated 29 strains of Mn(II)-oxidizing bacteria and found that highly similar 16S rRNA gene sequences were present in all culture-independent datasets and dominant in the studied drinking water treatment plant. These results highlight a potentially important role for Mn(II)-oxidizing bacteria in drinking water systems, where biogenic Mn oxides may affect water quality in terms of aesthetic appearance, speciation of metals and oxidation of organic and inorganic compounds. Deciphering the ecology of these organisms and the factors that regulate their Mn(II)-oxidizing activity could yield important insights into how microbial communities influence the quality of drinking water. © 2016 Society for Applied Microbiology and John Wiley & Sons Ltd.

  1. Study of water vapour adsorption kinetics on aluminium oxide materials

    Science.gov (United States)

    Livanova, Alesya; Meshcheryakov, Evgeniy; Reshetnikov, Sergey; Kurzina, Irina

    2017-11-01

    Adsorbents on the basis of active aluminum oxide are still of demand on the adsorbent-driers market. Despite comprehensive research of alumina adsorbents, and currently is an urgent task to improve their various characteristics, and especially the task of increasing the sorption capacity. In the present work kinetics of the processes of water vapours' adsorption at room temperature on the surface of desiccant samples has been studied. It was obtained on the basis of bayerite and pseudoboehmite experimentally. The samples of pseudoboehmite modified with sodium and potassium ions were taken as study objects. The influence of an adsorbent's grain size on the kinetics of water vapours' adsorption was studied. The 0.125-0.25 mm and 0.5-1.0 mm fractions of this sample were used. It has been revealed that the saturation water vapor fine powder (0.125-0.25 mm) is almost twofold faster in comparison with the sample of fraction 0.5-1.0 mm due to the decrease in diffusion resistance in the pores of the samples when moving from the sample of larger fraction to the fine-dispersed sample. It has been established that the adsorption capacity of the pseudoboehmite samples, modified by alkaline ions, is higher by ˜40 %, than for the original samples on the basis of bayerite and pseudoboehmite.

  2. MR Tracking of Transplanted Cells With “Positive Contrast” Using Manganese Oxide Nanoparticles

    Science.gov (United States)

    Gilad, Assaf A.; Walczak, Piotr; McMahon, Michael T.; Na, Hyon Bin; Lee, Jung Hee; An, Kwangjin; Hyeon, Taegwhan; van Zijl, Peter C.M.; Bulte, Jeff W.M.

    2008-01-01

    Rat glioma cells were labeled using electroporation with either manganese oxide (MnO) or superparamagnetic iron oxide (SPIO) nanoparticles. The viability and proliferation of SPIO-labeled cells (1.9 mg Fe/ml) or cells electroporated with a low dose of MnO (100 μg Mn/ml) was not significantly different from unlabeled cells; a higher MnO dose (785 μg Mn/ml) was found to be toxic. The cellular ion content was 0.1−0.3 pg Mn/cell and 4.4 pg Fe/cell, respectively, with cellular relaxivities of 2.5−4.8 s−1 (R1) and 45−84 s−1 (R2) for MnO-labeled cells. Labeled cells (SPIO and low-dose MnO) were each transplanted in contralateral brain hemispheres of rats and imaged in vivo at 9.4T. While SPIO-labeled cells produced a strong “negative contrast” due to the increase in R2, MnO-labeled cells produced “positive contrast” with an increased R1. Simultaneous imaging of both transplants with opposite contrast offers a method for MR “double labeling” of different cell populations. PMID:18581402

  3. Supercritical water oxidation for wastewater treatment Preliminary study of urea destruction

    Science.gov (United States)

    Timberlake, S. H.; Hong, G. T.; Simson, M.; Modell, M.

    1982-01-01

    Supercritical water oxidation is being investigated as a method of treating spacecraft wastewater for recycle. In this process, oxidation is conducted in an aqueous phase maintained above the critical temperature (374 C) and pressure (215 bar) of water. Organic materials are oxidized with efficiencies greater than 99.99 percent in residence times of less than 1 minute. This paper presents preliminary results for urea destruction. Above 650 C, urea can be completely broken down to nitrogen gas, carbon dioxide and water by supercritical water oxidation, without the use of a specific catalyst.

  4. Archaea dominate ammonia oxidizers in the permian water ecosystem of midland basin.

    Science.gov (United States)

    Hong, Yiguo; Youshao, Wang; Chen, Feng

    2013-01-01

    We investigated the existence and characteristics of ammonia oxidizers in Permian water from Midland Basin. Molecular surveys targeting the amoA gene showed that only ammonia-oxidizing archaea (AOA) exist and have potential activity in this special environment. In contrast, no ammonia-oxidizing bacteria (AOB) were detected in the water. Phylogenetic analysis indicated that 72-89% of the total screened AOA clones were affiliated with those found in underground water, and 10-24% of the AOA clones were related to those found in marine water or sediments. Our results indicate AOA might be the most abundant ammonia-oxidizing microbes in this ecological niche.

  5. Supercritical water oxidation of acrylic acid production wastewater.

    Science.gov (United States)

    Gong, Y M; Wang, S Z; Tang, X Y; Xu, D H; Ma, H H

    2014-01-01

    Supercritical water oxidation (SCWO) of wastewater from an acrylic acid manufacturing plant has been studied on a continuous flow experimental system, whose reactor was made of Hastelloy C-276. Experimental conditions included a reaction temperature (T) ranging from 673 to 773K, a residence time (t) ranging from 72.7 to 339s, a constant pressure (P) of 25 MPa and a fixed oxidation coefficient (alpha) of 2.0. Experimental results indicated that reaction temperature and residence time had significant influences on the oxidation reaction, and increasing the two operation parameters could improve both degradation of chemical oxygen demand (COD) and ammonia nitrogen (NH3-N). The COD removal efficiency could reach up to 98.73% at 25 MPa, 773 K and 180.1 s, whereas the destruction efficiency of NH3-N was only 43.71%. We further carried out a kinetic analysis considering the induction period through free radical chain mechanism. It confirms that the power-law rate equation for COD removal was 345 exp(-52200/RT)[COD]1.98[O2]0.17 and for NH3-N removal was 500 exp(-64492.19/RT)[NH3-N]1.87 [O2]0.03. Moreover, the induction time formulations for COD and NH3-N were suspected to be exp(38250/RT)/173 and exp(55690/RT)/15231, respectively. Correspondingly, induction time changed from 2.22 to 5.38 s for COD and 0.38 to 1.38 s for NH3-N. Owing to the catalysis of reactor inner wall surface, more than 97% COD removal was achieved in all samples.

  6. Diffusion Limited Supercritical Water Oxidation (SCWO) in Microgravity Environments

    Science.gov (United States)

    Hicks, M. C.; Lauver, R. W.; Hegde, U. G.; Sikora, T. J.

    2006-01-01

    Tests designed to quantify the gravitational effects on thermal mixing and reactant injection in a Supercritical Water Oxidation (SCWO) reactor have recently been performed in the Zero Gravity Facility (ZGF) at NASA s Glenn Research Center. An artificial waste stream, comprising aqueous mixtures of methanol, was pressurized to approximately 250 atm and then heated to 450 C. After uniform temperatures in the reactor were verified, a controlled injection of air was initiated through a specially designed injector to simulate diffusion limited reactions typical in most continuous flow reactors. Results from a thermal mapping of the reaction zone in both 1-g and 0-g environments are compared. Additionally, results of a numerical model of the test configuration are presented to illustrate first order effects on reactant mixing and thermal transport in the absence of gravity.

  7. Adaptive re-tracking algorithm for retrieval of water level variations and wave heights from satellite altimetry data for middle-sized inland water bodies

    Science.gov (United States)

    Troitskaya, Yuliya; Lebedev, Sergey; Soustova, Irina; Rybushkina, Galina; Papko, Vladislav; Baidakov, Georgy; Panyutin, Andrey

    One of the recent applications of satellite altimetry originally designed for measurements of the sea level [1] is associated with remote investigation of the water level of inland waters: lakes, rivers, reservoirs [2-7]. The altimetry data re-tracking algorithms developed for open ocean conditions (e.g. Ocean-1,2) [1] often cannot be used in these cases, since the radar return is significantly contaminated by reflection from the land. The problem of minimization of errors in the water level retrieval for inland waters from altimetry measurements can be resolved by re-tracking satellite altimetry data. Recently, special re-tracking algorithms have been actively developed for re-processing altimetry data in the coastal zone when reflection from land strongly affects echo shapes: threshold re-tracking, The other methods of re-tracking (threshold re-tracking, beta-re-tracking, improved threshold re-tracking) were developed in [9-11]. The latest development in this field is PISTACH product [12], in which retracking bases on the classification of typical forms of telemetric waveforms in the coastal zones and inland water bodies. In this paper a novel method of regional adaptive re-tracking based on constructing a theoretical model describing the formation of telemetric waveforms by reflection from the piecewise constant model surface corresponding to the geography of the region is considered. It was proposed in [13, 14], where the algorithm for assessing water level in inland water bodies and in the coastal zone of the ocean with an error of about 10-15 cm was constructed. The algorithm includes four consecutive steps: - constructing a local piecewise model of a reflecting surface in the neighbourhood of the reservoir; - solving a direct problem by calculating the reflected waveforms within the framework of the model; - imposing restrictions and validity criteria for the algorithm based on waveform modelling; - solving the inverse problem by retrieving a tracking point

  8. Environmental assessment of supercritical water oxidation of sewage sludge

    Energy Technology Data Exchange (ETDEWEB)

    Svanstrom, Magdalena; Froling, Morgan [Department of Chemical Engineering and Environmental Science, Chalmers University of Technology, SE-412 96 Goteborg (Sweden); Modell, Michael; Peters, William A.; Tester, Jefferson [Laboratory For Energy and the Environment (LFEE), Massachusetts Institute of Technology (MIT), Building E40, 1 Amherst Street, Cambridge, MA 02139 (United States)

    2004-07-01

    Environmental aspects of using supercritical water oxidation (SCWO) to treat sewage sludge were studied using a life cycle assessment (LCA) methodology. The system studied is the first commercial scale SCWO plant for sewage sludge in the world, treating sludge from the municipal wastewater treatment facility in Harlingen, TX, USA. The environmental impacts were evaluated using three specific environmental attributes: global warming potential (GWP), photo-oxidant creation potential (POCP) and resource depletion; as well as two single point indicators: EPS2000 and EcoIndicator99. The LCA results show that for the described process, gas-fired preheating of the sludge is the major contributor to environmental impacts, and emissions from generating electricity for pumping and for oxygen production are also important. Overall, SCWO processing of undigested sewage sludge is an environmentally attractive technology, particularly when heat is recovered from the process. Energy-conserving measures and recovery of excess oxygen from the SCWO process should be considered for improving the sustainability potential.

  9. Electrochemically Reduced Water Protects Neural Cells from Oxidative Damage

    Directory of Open Access Journals (Sweden)

    Taichi Kashiwagi

    2014-01-01

    Full Text Available Aging-related neurodegenerative disorders are closely associated with mitochondrial dysfunction and oxidative stresses and their incidence tends to increase with aging. Brain is the most vulnerable to reactive species generated by a higher rate of oxygen consumption and glucose utilization compared to other organs. Electrochemically reduced water (ERW was demonstrated to scavenge reactive oxygen species (ROS in several cell types. In the present study, the protective effect of ERW against hydrogen peroxide (H2O2 and nitric oxide (NO was investigated in several rodent neuronal cell lines and primary cells. ERW was found to significantly suppress H2O2 (50–200 μM induced PC12 and SFME cell deaths. ERW scavenged intracellular ROS and exhibited a protective effect against neuronal network damage caused by 200 μM H2O2 in N1E-115 cells. ERW significantly suppressed NO-induced cytotoxicity in PC12 cells despite the fact that it did not have the ability to scavenge intracellular NO. ERW significantly suppressed both glutamate induced Ca2+ influx and the resulting cytotoxicity in primary cells. These results collectively demonstrated for the first time that ERW protects several types of neuronal cells by scavenging ROS because of the presence of hydrogen and platinum nanoparticles dissolved in ERW.

  10. Treatment of pulp mill sludges by supercritical water oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Modell, M.

    1990-07-01

    Supercritical water oxidation (SCWO) is new process that can oxidize organics very effectively at moderate temperatures (400 to 650{degree}C) and high pressure (3700 psi). It is an environmentally acceptable alternative for sludge treatment. In bench scale tests, total organic carbon (TOC) and total organic halide (TOX) reductions of 99 to 99.9% were obtained; dioxin reductions were 95 to 99.9%. A conceptual design for commercial systems has been completed and preliminary economics have been estimated. Comparisons confirm that SCWO is less costly than dewatering plus incineration for treating pulp mill sludges. SCWO can also compete effectively with dewatering plus landfilling where tipping fees exceed $35/yd{sup 3}. In some regions of the US, tipping fees are now $75/yd{sup 3} and rising steadily. In the 1995 to 2000 time frame, SCWO has a good chance of becoming the method of choice. MODEC's objective is to bring the technology to commercial availability by 1993. 10 refs., 6 figs., 19 tabs.

  11. Nitric oxide reduces oxidative damage induced by water stress in sunflower plants

    Directory of Open Access Journals (Sweden)

    Inês Cechin

    2015-06-01

    Full Text Available Drought is one of the main environmental constraints that can reduce plant yield. Nitric oxide (NO is a signal molecule involved in plant responses to several environmental stresses. The objective of this study was to investigate the cytoprotective effect of a single foliar application of 0, 1, 10 or 100 µM of the NO donor sodium nitroprusside (SNP in sunflower plants under water stress. Water stressed plants treated with 1μM SNP showed an increase in the relative water content compared with 0 μM SNP. Drought reduced the shoot dry weight but SNP applications did not result in alleviation of drought effects. Neither drought nor water stress plus SNP applications altered the content of photosynthetic pigments. Stomatal conductance was reduced by drought and this reduction was accompanied by a significant reduction in intercellular CO2 concentration and photosynthesis. Treatment with SNP did not reverse the effect of drought on the gas exchange characteristics. Drought increased the level of malondialdehyde (MDA and proline and reduced pirogalol peroxidase (PG-POD activity, but did not affect the activity of superoxide dismutase (SOD. When the water stressed plants were treated with 10 μM SNP, the activity of PG-POD and the content of proline were increased and the level of MDA was decreased. The results show that the adverse effects of water stress on sunflower plants are dependent on the external NO concentration. The action of NO may be explained by its ability to increase the levels of antioxidant compounds and the activity of ROS-scavenging enzymes.

  12. Comparative In Vitro Study on Magnetic Iron Oxide Nanoparticles for MRI Tracking of Adipose Tissue-Derived Progenitor Cells

    Science.gov (United States)

    Kasten, Annika; Grüttner, Cordula; Kühn, Jens-Peter; Bader, Rainer; Pasold, Juliane; Frerich, Bernhard

    2014-01-01

    Magnetic resonance imaging (MRI) using measurement of the transverse relaxation time (R2*) is to be considered as a promising approach for cell tracking experiments to evaluate the fate of transplanted progenitor cells and develop successful cell therapies for tissue engineering. While the relationship between core composition of nanoparticles and their MRI properties is well studied, little is known about possible effects on progenitor cells. This in vitro study aims at comparing two magnetic iron oxide nanoparticle types, single vs. multi-core nanoparticles, regarding their physico-chemical characteristics, effects on cellular behavior of adipose tissue-derived stem cells (ASC) like differentiation and proliferation as well as their detection and quantification by means of MRI. Quantification of both nanoparticle types revealed a linear correlation between labeling concentration and R2* values. However, according to core composition, different levels of labeling concentrations were needed to achieve comparable R2* values. Cell viability was not altered for all labeling concentrations, whereas the proliferation rate increased with increasing labeling concentrations. Likewise, deposition of lipid droplets as well as matrix calcification revealed to be highly dose-dependent particularly regarding multi-core nanoparticle-labeled cells. Synthesis of cartilage matrix proteins and mRNA expression of collagen type II was also highly dependent on nanoparticle labeling. In general, the differentiation potential was decreased with increasing labeling concentrations. This in vitro study provides the proof of principle for further in vivo tracking experiments of progenitor cells using nanoparticles with different core compositions but also provides striking evidence that combined testing of biological and MRI properties is advisable as improved MRI properties of multi-core nanoparticles may result in altered cell functions. PMID:25244560

  13. Oxidation of X20 in Water Vapour: The Effect of Temperature and Oxygen Partial Pressure

    DEFF Research Database (Denmark)

    Hansson, Anette Nørgaard; Montgomery, Melanie; Somers, Marcel A. J.

    2009-01-01

    The oxidation behaviour of X20 in various mixtures of water, oxygen and hydrogen was investigated at temperatures between 500 C and 700 C (time: 336 h). The samples were characterised using reflected light microscopy and scanning electron microscopy equipped with energy dispersive spectroscopy....... Double-layered oxides developed during oxidation under all conditions. The morphology of the oxide layers was strongly influenced by temperature, whereas the influence of the oxidising environment appeared to be less pronounced, as long as it contained water vapour. The inner layer consisted of converted...... M23C6 embedded in Fe–Cr spinel after oxidation at 500 and 600 C, while alternating layers of Cr-rich and Cr-poor oxide were observed after oxidation at 700 C. An internal oxidation zone developed during oxidation at 500 and 600 C, with its depth influenced by the oxidising environments. The results...

  14. Ruthenium or osmium complexes and their uses as catalysts for water oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Concepcion Corbea, Javier Jesus; Chen, Zuofeng; Jurss, Jonah Wesley; Templeton, Joseph L; Hoertz, Paul; Meyer, Thomas J

    2014-10-28

    The present invention provides ruthenium or osmium complexes and their uses as a catalyst for catalytic water oxidation. Another aspect of the invention provides an electrode and photo-electrochemical cells for electrolysis of water molecules.

  15. Ruthenium or osmium complexes and their uses as catalysts for water oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Corbea, Javier Jesus Concepcion; Chen, Zuofeng; Jurss, Jonah Wesley; Templeton, Joseph L.; Hoertz, Paul; Meyer, Thomas J.

    2013-09-03

    The present invention provides ruthenium or osmium complexes and their uses as a catalyst for catalytic water oxidation. Another aspect of the invention provides an electrode and photo-electrochemical cells for electrolysis of water molecules.

  16. Ruthenium or osmium complexes and their uses as catalysts for water oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Corbea, Javier Jesus Concepcion; Chen, Zoufeng; Jurss, Jonah Wesley; Templeton, Joseph L.; Hoertz, Paul; Meyer, Thomas J.

    2016-06-07

    The present invention provides ruthenium or osmium complexes and their uses as a catalyst for catalytic water oxidation. Another aspect of the invention provides an electrode and photo-electrochemical cells for electrolysis of water molecules.

  17. Tracking the intracellular drug release from graphene oxide using surface-enhanced Raman spectroscopy

    Science.gov (United States)

    Huang, Jie; Zong, Cheng; Shen, He; Cao, Yuhua; Ren, Bin; Zhang, Zhijun

    2013-10-01

    We have developed a graphene oxide (GO)-based nanoplatform simultaneously loaded with a chemical drug and Ag nanoparticles (NPs), and employed it to study the drug release from GO in living cells by surface-enhanced Raman spectroscopy (SERS). In our strategy, doxorubicin (DOX), a typical model anticancer drug, was loaded onto chemically prepared GO by means of π-π stacking, while the Ag NPs were covalently modified onto GO. After incubation of the DOX- and Ag NPs-loaded GO with Ca Ski cells for several hours, DOX will detach from the GO in an acidic environment due to the pH-dependent π-π interaction between DOX and GO. Real-time measurement of SERS signals of DOX using the GO loaded with Ag NPs as a SERS-active substrate allows us to monitor the process of the drug release inside the living cell. The SERS results reveal that DOX is initially released from the GO surface inside the lysosomes, then escapes into the cytoplasm, and finally enters the nucleus, while GO, the nanocarrier, remains within the cytoplasm, without entering the nucleus.We have developed a graphene oxide (GO)-based nanoplatform simultaneously loaded with a chemical drug and Ag nanoparticles (NPs), and employed it to study the drug release from GO in living cells by surface-enhanced Raman spectroscopy (SERS). In our strategy, doxorubicin (DOX), a typical model anticancer drug, was loaded onto chemically prepared GO by means of π-π stacking, while the Ag NPs were covalently modified onto GO. After incubation of the DOX- and Ag NPs-loaded GO with Ca Ski cells for several hours, DOX will detach from the GO in an acidic environment due to the pH-dependent π-π interaction between DOX and GO. Real-time measurement of SERS signals of DOX using the GO loaded with Ag NPs as a SERS-active substrate allows us to monitor the process of the drug release inside the living cell. The SERS results reveal that DOX is initially released from the GO surface inside the lysosomes, then escapes into the

  18. High-Performance Supported Iridium Oxohydroxide Water Oxidation Electrocatalysts.

    Science.gov (United States)

    Massué, Cyriac; Pfeifer, Verena; Huang, Xing; Noack, Johannes; Tarasov, Andrey; Cap, Sébastien; Schlögl, Robert

    2017-05-09

    The synthesis of a highly active and yet stable electrocatalyst for the anodic oxygen evolution reaction (OER) remains a major challenge for acidic water splitting on an industrial scale. To address this challenge, we obtained an outstanding high-performance OER catalyst by loading Ir on conductive antimony-doped tin oxide (ATO)-nanoparticles by a microwave (MW)-assisted hydrothermal route. The obtained Ir phase was identified by using XRD as amorphous (XRD-amorphous), highly hydrated IrIII/IV oxohydroxide. To identify chemical and structural features responsible for the high activity and exceptional stability under acidic OER conditions with loadings as low as 20 μgIr  cm-2 , we used stepwise thermal treatment to gradually alter the XRD-amorphous Ir phase by dehydroxylation and crystallization of IrO2 . This resulted in dramatic depletion of OER performance, indicating that the outstanding electrocatalytic properties of the MW-produced IrIII/IV oxohydroxide are prominently linked to the nature of the produced Ir phase. This finding is in contrast with the often reported stable but poor OER performance of crystalline IrO2 -based compounds produced through more classical calcination routes. Our investigation demonstrates the immense potential of Ir oxohydroxide-based OER electrocatalysts for stable high-current water electrolysis under acidic conditions. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Water Injection on Commercial Aircraft to Reduce Airport Nitrogen Oxides

    Science.gov (United States)

    Daggett, David L.; Hendricks, Robert C.; Fucke, Lars; Eames, David J. H.

    2010-01-01

    The potential nitrogen oxide (NO(x) reductions, cost savings, and performance enhancements identified in these initial studies of waterinjection technology strongly suggest that it be further pursued. The potential for engine maintenance cost savings from this system should make it very attractive to airline operators and assure its implementation. Further system tradeoff studies and engine tests are needed to answer the optimal system design question. Namely, would a low-risk combustor injection system with 70- to 90-percent NO(x) reduction be preferable, or would a low-pressure compressor (LPC) misting system with only 50-percent NO(x) reduction but larger turbine inlet temperature reductions be preferable? The low-pressure compressor injection design and operability issues identified in the report need to be addressed because they might prevent implementation of the LPC type of water-misting system. If water-injection technology challenges are overcome, any of the systems studied would offer dramatic engine NO(x) reductions at the airport. Coupling this technology with future emissions-reduction technologies, such as fuel-cell auxiliary power units will allow the aviation sector to address the serious challenges of environmental stewardship, and NO(x) emissions will no longer be an issue at airports.

  20. Preparation and Characterization of Reduced Graphene Oxide Sheets via Water-Based Exfoliation and Reduction Methods

    Directory of Open Access Journals (Sweden)

    Vorrada Loryuenyong

    2013-01-01

    Full Text Available This research studied the synthesis of graphene oxide and graphene via a low-cost manufacturing method. The process started with the chemical oxidation of commercial graphite powder into graphite oxide by modified Hummer’s method, followed by the exfoliation of graphite oxide in distilled water using the ultrasound frequency from a laboratory ultrasonic bath. Finally, the oxygen functional groups on exfoliated graphite oxide or graphene oxide were eliminated by stirring in hot distilled water at 95°C, as a replacement for highly toxic and dangerously unstable hydrazine. The results assured that stirring in hot distilled water could give the product of graphene or reduced graphene oxide. The samples were characterized by FTIR, XRD, TGA, Raman spectroscopy, SEM, and TEM methods.

  1. Enhancing Hematite Photoanode Activity for Water Oxidation by Incorporation of Reduced Graphene Oxide.

    Science.gov (United States)

    do Amaral Carminati, Saulo; Souza, Flavio L; Nogueira, Ana F

    2016-01-04

    Two effective methods to prepare reduced graphene oxide (rGO)/hematite nanostructured photoanodes and their photoelectrochemical characterization towards water splitting reactions are presented. First, graphene oxide (GO) is reduced to rGO using hydrazine in a basic solution containing tetrabutylammonium hydroxide (TBAOH), and then deposited over the nanostructured hematite photoanodes previously treated at 750 °C for 30 min. The second method follows the deposition of a paste containing a mixture of hematite nanoparticles and rGO sheets by the doctor-blade method, varying the rGO concentration. Since hematite suffers from low electron mobility, a low absorption coefficient, high recombination rates and slow reaction kinetics, the incorporation of rGO in the hematite can overcome such limitations due to graphene's exceptional properties. Using the first method, the rGO incorporation results in a photocurrent density increase from 0.56 to 0.82 mA cm(-2) at 1.23 VRHE. Our results indicate that the rGO incorporation in the hematite photoanodes shows a positive effect in the reduction of the electron-hole recombination rate. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Water Sorption and Radiolysis Studies for Neptunium Oxides

    Energy Technology Data Exchange (ETDEWEB)

    Icenhour, A.S.

    2004-02-03

    Plans are to convert the {sup 237}Np that is currently stored as a nitrate solution at the Savannah River Site to NpO{sub 2} and then ship it to the Y-12 National Security Complex in Oak Ridge for interim storage. This material will serve as feedstock for the {sup 238}Pu production program, and some will be periodically shipped to the Oak Ridge National Laboratory (ORNL) for fabrication into targets. The safe storage of this material requires an understanding of the radiolysis of moisture that is sorbed on the oxides, which, in turn, provides a basis for storage criteria (namely, moisture content). A two-component experimental program has been undertaken at ORNL to evaluate the radiolytic effects on NpO{sub 2}: (1) moisture uptake experiments and (2) radiolysis experiments using both gamma and alpha radiation. These experiments have produced two key results. First, the water uptake experiments demonstrated that the 0.5 wt % moisture limit that has been typically established for similar materials (e.g., uranium and plutonium oxides) cannot be obtained in a practical environment. In fact, the uptake in a typical environment can be expected to be at least an order of magnitude lower than the limit. The second key result is the establishment of steady-state pressure plateaus as a result of the radiolysis of sorbed moisture. These plateaus are the result of back reactions that limit the overall pressure increase and H{sub 2} production. These results clearly demonstrate that 0.5 wt % H{sub 2}O on NpO{sub 2} is safe for long-term storage--if such a moisture content could even be practically reached.

  3. Human and Animal Fecal Contamination of Community Water Sources, Stored Drinking Water and Hands in Rural India Measured with Validated Microbial Source Tracking Assays

    OpenAIRE

    Schriewer, A; Odagiri, M; Wuertz, S.; Misra, PR; Panigrahi, P.; Clasen, T; Jenkins, MW

    2015-01-01

    We examined pathways of exposure to fecal contamination of human and animal origin in 24 villages in Odisha, India. In a cross-sectional study during the monsoon season, fecal exposure via community water sources (N = 123) and in the home (N = 137) was assessed using human- and nonhuman-associated Bacteroidales microbial source tracking (MST) markers and fecal coliforms (FCs). Detection rates and marker concentrations were compared with pinpoint pathways of human fecal exposure in the public ...

  4. Sea-urchin-like iron oxide nanostructures for water treatment

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Hyun Uk, E-mail: leeho@kbsi.re.kr [Division of Materials Science, Korea Basic Science Institute, Daejeon 305-333 (Korea, Republic of); Lee, Soon Chang [Department of Fine Chemical Engineering and Applied Chemistry, Chungnam National University, Daejeon 305-764 (Korea, Republic of); Lee, Young-Chul [Department of Biological Engineering, College of Engineering, Inha University, Incheon 402-751 (Korea, Republic of); Vrtnik, Stane; Kim, Changsoo; Lee, SangGap [Division of Materials Science, Korea Basic Science Institute, Daejeon 305-333 (Korea, Republic of); Lee, Young Boo; Nam, Bora [Jeonju Center, Korea Basic Science Institute, Jeonju 561-756 (Korea, Republic of); Lee, Jae Won [Department of Energy Engineering, Dankook University, Cheonan 330-714 (Korea, Republic of); Park, So Young; Lee, Sang Moon [Division of Materials Science, Korea Basic Science Institute, Daejeon 305-333 (Korea, Republic of); Lee, Jouhahn, E-mail: jouhahn@kbsi.re.kr [Division of Materials Science, Korea Basic Science Institute, Daejeon 305-333 (Korea, Republic of)

    2013-11-15

    Highlights: • The u-MFN were synthesized via a ultrasound irradiation and/or calcinations process. • The u-MFN exhibited excellent adsorption capacities. • The u-MFN also displayed excellent adsorption of organic polluent after recycling. • The u-MFN has the potential to be used as an efficient adsorbent material. -- Abstract: To obtain adsorbents with high capacities for removing heavy metals and organic pollutants capable of quick magnetic separation, we fabricated unique sea-urchin-like magnetic iron oxide (mixed γ-Fe{sub 2}O{sub 3}/Fe{sub 3}O{sub 4} phase) nanostructures (called u-MFN) with large surface areas (94.1 m{sup 2} g{sup −1}) and strong magnetic properties (57.9 emu g{sup −1}) using a simple growth process and investigated their potential applications in water treatment. The u-MFN had excellent removal capabilities for the heavy metals As(V) (39.6 mg g{sup −1}) and Cr(VI) (35.0 mg g{sup −1}) and the organic pollutant Congo red (109.2 mg g{sup −1}). The u-MFN also displays excellent adsorption of Congo red after recycling. Because of its high adsorption capacity, fast adsorption rate, and quick magnetic separation from treated water, the u-MFN developed in the present study is expected to be an efficient magnetic adsorbent for heavy metals and organic pollutants in aqueous solutions.

  5. The mechanism change by switching the reactants from water to hydroxyl ions for electrocatalytic water oxidation: a case study of copper oxide microspheres.

    Science.gov (United States)

    Du, Xiaoqiang; Huang, Jingwei; Ding, Yong

    2017-06-06

    Developing noble metal-free water oxidation catalysts is essential for many energy conversion/storage processes (e.g., water splitting). Herein, we report a facile synthesis of CuO microspheres composed of ultrathin, single-crystal-like nanosheets via a simple solution method. The as-obtained CuO microspheres can serve as an active and stable water oxidation catalyst under electrochemical reaction conditions, owing to their unique structural features. In electrochemical water oxidation, this catalyst affords a current density of 10 mA cm-2 (a value related to practical relevance) at an overpotential of ∼0.48 V. Pure CuO was reported as a water oxidation catalyst (WOC) from near-neutral conditions to alkalescent conditions. Electrochemistry values agree with the Nernstian behavior, suggesting ne-/nH+ transfer prior to a chemical rate-determining step. Our results suggest that the delicate nanostructure can offer unique advantages for developing efficient water oxidation catalysts.

  6. Supercritical water oxidation of oil-based drill cuttings.

    Science.gov (United States)

    Chen, Zhong; Chen, Zeliang; Yin, Fengjun; Wang, Guangwei; Chen, Hongzhen; He, Chunlan; Xu, Yuanjian

    2017-06-15

    Oil-based drill cuttings (OBDC) are a typical hazardous solid waste that arises from drilling operations in oil and gas fields. The supercritical water oxidation (SCWO) of OBDC was comprehensively investigated in a batch reactor under the conditions of various oxygen coefficients (OC, 1.5-3.5), temperatures (T, 400-500°C) and reaction times (t, 0.5-10min). Preheating experiments indicated that most of the organic compounds in the initial OBDC sample were distributed within gaseous, oil, aqueous and solid phases, with no more than 9.8% of organic compounds converted into inorganic carbon. All tested variables, i.e., OC, T and t, positively affect the transformation of carbon compounds from the oil and solid phases to the aqueous phase and, ultimately, to CO 2 . Carbon monoxide is the primary stable intermediate. The total organic carbon (TOC) removal efficiency can reach up to 89.2% within 10min at 500°C. Analysis of the reaction pathways suggests both homogeneous and heterogeneous reactions exist in the reactor. The homogeneous reaction is a typical SCWO reaction that is governed by a free radical mechanism, and the heterogeneous reaction is dominated by mass transfer. The information obtained in this study is useful for further investigation and development of hydrothermal treatment procedures for OBDC. Copyright © 2017 Elsevier B.V. All rights reserved.

  7. Copper oxide--copper sulfate water-splitting cycle

    Energy Technology Data Exchange (ETDEWEB)

    Foh, S. E.; Schreiber, J. D.; Dafler, J. R.

    1978-08-01

    A hybrid copper oxide--copper sulfate thermochemical water-splitting cycle, IGT's H-5, has been demonstrated in the laboratory with recycled materials. The optimum configuration and operating conditions for the electrolytic hydrogen-producing step have not yet been defined. With cooperative funding (A.G.A./G.R.I./DOE) a conceptual flowsheet was developed for this cycle and a load-line efficiency of about 37% calculated. This figure is the result of a single iteration on the original base case flow sheet and compares well with the values calculated for other processes at this stage of development. An iterative optimization of process conditions would improve efficiency. The data required to perform an economic analysis are not yet available and the electrolysis step must be more fully defined. An attractive process efficiency, relatively few corrosive materials, and few gas-phase separations are attributes of Cycle H-5 that lead us to believe hydrogen costs (to be developed during future analyses) would be improved significantly over similar processes analyzed to date.

  8. Comparison of nano-sized Mn oxides with the Mn cluster of photosystem II as catalysts for water oxidation.

    Science.gov (United States)

    Najafpour, Mohammad Mahdi; Ghobadi, Mohadeseh Zarei; Haghighi, Behzad; Tomo, Tatsuya; Shen, Jian-Ren; Allakhverdiev, Suleyman I

    2015-02-01

    "Back to Nature" is a promising way to solve the problems that we face today, such as air pollution and shortage of energy supply based on conventional fossil fuels. A Mn cluster inside photosystem II catalyzes light-induced water-splitting leading to the generation of protons, electrons and oxygen in photosynthetic organisms, and has been considered as a good model for the synthesis of new artificial water-oxidizing catalysts. Herein, we surveyed the structural and functional details of this cluster and its surrounding environment. Then, we review the mechanistic findings concerning the cluster and compare this biological catalyst with nano-sized Mn oxides, which are among the best artificial Mn-based water-oxidizing catalysts. Copyright © 2014 Elsevier B.V. All rights reserved.

  9. The burnup dependence of light water reactor spent fuel oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Hanson, B.D.

    1998-07-01

    Over the temperature range of interest for dry storage or for placement of spent fuel in a permanent repository under the conditions now being considered, UO{sub 2} is thermodynamically unstable with respect to oxidation to higher oxides. The multiple valence states of uranium allow for the accommodation of interstitial oxygen atoms in the fuel matrix. A variety of stoichiometric and nonstoichiometric phases is therefore possible as the fuel oxidizers from UO{sub 2} to higher oxides. The oxidation of UO{sub 2} has been studied extensively for over 40 years. It has been shown that spent fuel and unirradiated UO{sub 2} oxidize via different mechanisms and at different rates. The oxidation of LWR spent fuel from UO{sub 2} to UO{sub 2.4} was studied previously and is reasonably well understood. The study presented here was initiated to determine the mechanism and rate of oxidation from UO{sub 2.4} to higher oxides. During the early stages of this work, a large variability in the oxidation behavior of samples oxidized under nearly identical conditions was found. Based on previous work on the effect of dopants on UO{sub 2} oxidation and this initial variability, it was hypothesized that the substitution of fission product and actinide impurities for uranium atoms in the spent fuel matrix was the cause of the variable oxidation behavior. Since the impurity concentration is roughly proportional to the burnup of a specimen, the oxidation behavior of spent fuel was expected to be a function of both temperature and burnup. This report (1) summarizes the previous oxidation work for both unirradiated UO{sub 2} and spent fuel (Section 2.2) and presents the theoretical basis for the burnup (i.e., impurity concentration) dependence of the rate of oxidation (Sections 2.3, 2.4, and 2.5), (2) describes the experimental approach (Section 3) and results (Section 4) for the current oxidation tests on spent fuel, and (3) establishes a simple model to determine the activation energies

  10. Disinfection of Pythium-infested recirculation water by UV-oxidation technology.

    Science.gov (United States)

    Runia, W T; Boonstra, S

    2001-01-01

    Selective disinfection against Pythium aphanidermatum in recirculation water was tested with UV-irradiation and with UV-oxidation technology with the objective to reduce the electrical energy consumption per cubic meter treated water. UV-oxidation technology is based on injection of hydrogen peroxide in recirculation water, just before passage along a UV-lamp, thus creating hydroxyl radicals. Pythium aphanidermatum was applied artificially to recirculation water from tomatoes, grown, in rockwool and coconut fibre. Other parameters in this study were pH and transmission value (T10) of the infested recirculation water. Results indicated that the recommended UV-C dose of 100 mJ/cm2 for elimination of fungal pathogens in general can be lowered in case recirculation water is infected with Pythium aphanidermatum only. When UV-oxidation technology was applied with 1 mmol hydrogen peroxide per litre recirculation water, the UV-C dose could be reduced even more in comparison with merely UV irradiation.

  11. Tracking the behavior of different size fractions of dissolved organic matter in a full-scale advanced drinking water treatment plant.

    Science.gov (United States)

    Quang, Viet Ly; Choi, Ilhwan; Hur, Jin

    2015-11-01

    In this study, five different dissolved organic matter (DOM) fractions, defined based on a size exclusion chromatography with simultaneous detection of organic carbon (OCD) and ultraviolet (UVD), were quantitatively tracked with a treatment train of coagulation/flocculation-sand filtration-ozonation-granular activated carbon (GAC) filtration in a full-scale advanced drinking water treatment plant (DWTP). Five DOM samples including raw water were taken after each treatment process in the DWTP every month over the period of three years. A higher abundance of biopolymer (BP) fraction was found in the raw water during spring and winter than in the other seasons, suggesting an influence of algal bloom and/or meltwater on DOM composition. The greater extent of removal was observed upon the coagulation/flocculation for high-molecular-weight fractions including BP and humic substances (HS) and aromatic moieties, while lower sized fractions were preferentially removed by the GAC filtration. Ozone treatment produced the fraction of low-molecular-weight neutrals probably resulting from the breakdown of double-bonded carbon structures by ozone oxidation. Coagulation/flocculation was the only process that revealed significant effects of influent DOM composition on the treatment efficiency, as revealed by a high correlation between the DOM removal rate and the relative abundance of HS for the raw water. Our study demonstrated that SEC-OCD-UVD was successful in monitoring size-based DOM composition for the advanced DWTP, providing an insight into optimizing the treatment options and the operational conditions for the removal of particular fractions within the bulk DOM.

  12. Advanced Oxidation Technology for Potable Water Disinfection Project

    Data.gov (United States)

    National Aeronautics and Space Administration — The availability of high-quality potable water is essential in crewed space missions. Closed loop water recycling systems as well as potable water holding tanks and...

  13. Importance of trivalency and the eg1 configuration in the photocatalytic oxidation of water by Mn and Co oxides

    Science.gov (United States)

    Maitra, Urmimala; Naidu, B. S.; Govindaraj, A.; Rao, C. N. R.

    2013-01-01

    Prompted by the early results on the catalytic activity of LiMn2O4 and related oxides in the photochemical oxidation of water, our detailed study of several manganese oxides has shown that trivalency of Mn is an important factor in determining the catalytic activity. Thus, Mn2O3, LaMnO3, and MgMn2O4 are found to be very good catalysts with turnover frequencies of 5 × 10−4 s−1, 4.8 × 10−4 s−1, and 0.8 ×10−4 s−1, respectively. Among the cobalt oxides, Li2Co2O4 and LaCoO3—especially the latter—exhibit excellent catalytic activity, with the turnover frequencies being 9 × 10−4 s−1 and 1.4 × 10−3 s−1, respectively. The common feature among the catalytic Mn and Co oxides is not only that Mn and Co are in the trivalent state, but Co3+ in the Co oxides is in the intermediate t2g5eg1 state whereas Mn3+ is in the t2g3eg1 state. The presence of the eg1 electron in these Mn and Co oxides is considered to play a crucial role in the photocatalytic properties of the oxides. PMID:23818589

  14. Emulsification technique affects oxidative stability of fish oil-in-water emulsions

    DEFF Research Database (Denmark)

    Horn, Anna Frisenfeldt; Nielsen, Nina Skall; Jensen, Louise Helene Søgaard

    In oil-in-water emulsions, lipid oxidation is expected to be initiated at the oil-water interface. The properties of the emulsifier used, and the structure at the interface is therefore expected to be of great importance for lipid oxidation in emulsions. Previous studies have shown that e...... of this study was to compare lipid oxidation in 10% fish oil-in-water emulsions prepared by two different kinds of high pressure homogenizers i.e. a microfluidizer and a two valve high pressure homogenizer. Emulsions were made with equal droplet sizes, and with either 1% sodium caseinate or 1% whey protein...

  15. Emulsification technique affects oxidative stability of fish oil-in-water emulsion

    DEFF Research Database (Denmark)

    Horn, Anna Frisenfeldt; Nielsen, Nina Skall; Jensen, Louise Helene Søgaard

    In oil-in-water emulsions, lipid oxidation is expected to be initiated at the oil-water interface. The properties of the emulsifier used, and the structure at the interface is therefore expected to be of great importance for lipid oxidation in emulsions. Previous studies have shown that e...... of this study was therefore to compare lipid oxidation in 10% fish oil-in-water emulsions prepared by two different kinds of high pressure homogenizers i.e. a microfluidizer and a two valve high pressure homogenizer. Emulsions were made with equal droplet sizes, and with either 1% sodium caseinate or 1% whey...

  16. Nitrogen and Oxygen Isotope Effects of Ammonia Oxidation by Thermophilic Thaumarchaeota from a Geothermal Water Stream

    Science.gov (United States)

    Sakai, Sanae; Konno, Uta; Nakahara, Nozomi; Takaki, Yoshihiro; Saito, Yumi; Imachi, Hiroyuki; Tasumi, Eiji; Makabe, Akiko; Koba, Keisuke; Takai, Ken

    2016-01-01

    ABSTRACT Ammonia oxidation regulates the balance of reduced and oxidized nitrogen pools in nature. Although ammonia-oxidizing archaea have been recently recognized to often outnumber ammonia-oxidizing bacteria in various environments, the contribution of ammonia-oxidizing archaea is still uncertain due to difficulties in the in situ quantification of ammonia oxidation activity. Nitrogen and oxygen isotope ratios of nitrite (δ15NNO2− and δ18ONO2−, respectively) are geochemical tracers for evaluating the sources and the in situ rate of nitrite turnover determined from the activities of nitrification and denitrification; however, the isotope ratios of nitrite from archaeal ammonia oxidation have been characterized only for a few marine species. We first report the isotope effects of ammonia oxidation at 70°C by thermophilic Thaumarchaeota populations composed almost entirely of “Candidatus Nitrosocaldus.” The nitrogen isotope effect of ammonia oxidation varied with ambient pH (25‰ to 32‰) and strongly suggests the oxidation of ammonia, not ammonium. The δ18O value of nitrite produced from ammonia oxidation varied with the δ18O value of water in the medium but was lower than the isotopic equilibrium value in water. Because experiments have shown that the half-life of abiotic oxygen isotope exchange between nitrite and water is longer than 33 h at 70°C and pH ≥6.6, the rate of ammonia oxidation by thermophilic Thaumarchaeota could be estimated using δ18ONO2− in geothermal environments, where the biological nitrite turnover is likely faster than 33 h. This study extended the range of application of nitrite isotopes as a geochemical clock of the ammonia oxidation activity to high-temperature environments. IMPORTANCE Because ammonia oxidation is generally the rate-limiting step in nitrification that regulates the balance of reduced and oxidized nitrogen pools in nature, it is important to understand the biological and environmental factors underlying

  17. Estimation of Oxidation Kinetics and Oxide Scale Void Position of Ferritic-Martensitic Steels in Supercritical Water

    Directory of Open Access Journals (Sweden)

    Li Sun

    2017-01-01

    Full Text Available Exfoliation of oxide scales from high-temperature heating surfaces of power boilers threatened the safety of supercritical power generating units. According to available space model, the oxidation kinetics of two ferritic-martensitic steels are developed to predict in supercritical water at 400°C, 500°C, and 600°C. The iron diffusion coefficients in magnetite and Fe-Cr spinel are extrapolated from studies of Backhaus and Töpfer. According to Fe-Cr-O ternary phase diagram, oxygen partial pressure at the steel/Fe-Cr spinel oxide interface is determined. The oxygen partial pressure at the magnetite/supercritical water interface meets the equivalent oxygen partial pressure when system equilibrium has been attained. The relative error between calculated values and experimental values is analyzed and the reasons of error are suggested. The research results show that the results of simulation at 600°C are approximately close to experimental results. The iron diffusion coefficient is discontinuous in the duplex scale of two ferritic-martensitic steels. The simulation results of thicknesses of the oxide scale on tubes (T91 of final superheater of a 600 MW supercritical boiler are compared with field measurement data and calculation results by Adrian’s method. The calculated void positions of oxide scales are in good agreement with a cross-sectional SEM image of the oxide layers.

  18. The effect of interfacial microstructure on the lipid oxidation stability of oil-in-water emulsions.

    Science.gov (United States)

    Kargar, Maryam; Spyropoulos, Fotios; Norton, Ian T

    2011-05-15

    A novel approach to reduce lipid oxidation in oil-in-water emulsions has been taken and involves the manipulation of the emulsions' interfacial microstructure. Oil-in-water emulsions stabilised by sodium caseinate (CAS), Tween 20 and silica particles were prepared and their lipid oxidation stability was assessed over a week. Lipid oxidation was monitored by measuring the concentration of primary lipid oxidation product, using the peroxide value method and secondary lipid oxidation products formation were evaluated with the p-anisidine technique. Oil-phase volume fraction and emulsifier type both play key roles in influencing the rate of lipid oxidation. Decreasing the oil fraction from 30% to 5% was found to promote lipid oxidation as a result of an increase in the amount of pro-oxidant iron per gram of oil. It was further shown that, CAS in the continuous phase reduces lipid oxidation at pH 7 due to its metal chelating ability. In addition, the results show that, emulsions stabilised with silica particles (at pH 2) inhibit lipid oxidation to a greater extent than emulsions stabilised with surfactants alone. The present study demonstrates that emulsions' physical properties such as oil-phase volume fraction, droplet size and droplet interfacial microstructure are all formulation parameters that can be used to significantly reduce the rate of lipid oxidation. Copyright © 2011 Elsevier Inc. All rights reserved.

  19. One-Dimensional Metal-Oxide Nanostructures for Solar Photocatalytic Water-Splitting

    Science.gov (United States)

    Wang, Fengyun; Song, Longfei; Zhang, Hongchao; Luo, Linqu; Wang, Dong; Tang, Jie

    2017-08-01

    Because of their unique physical and chemical properties, one-dimensional (1-D) metal-oxide nanostructures have been extensively applied in the areas of gas sensors, electrochromic devices, nanogenerators, and so on. Solar water-splitting has attracted extensive research interest because hydrogen generated from solar-driven water splitting is a clean, sustainable, and abundant energy source that not only solves the energy crisis, but also protects the environment. In this comprehensive review, the main synthesis methods, properties, and especially prominent applications in solar water splitting of 1-D metal-oxides, including titanium dioxide (TiO2), zinc oxide (ZnO), tungsten trioxide (WO3), iron oxide (Fe2O3), and copper oxide (CuO) are fully discussed.

  20. Static SIMS and XPS study of water plasma exposed tin oxide films

    Science.gov (United States)

    Tarlov, Michael J.; Evans, John F.; Newman, John G.

    1993-02-01

    Static secondary ion mass spectrometry (SIMS) and X-ray photoelectron spectroscopy (XPS) were used to examine sputter-deposited tin oxide surfaces that were air-exposed, treated in a low-power water plasma, and annealed to 825 K in vacuum. The plasma reactor was appended directly to the surface analytical system, thus sample exposure to atmosphere was avoided. Water plasma treatment of the air-exposed films results in the removal of all XPS detectable carbon contamination while leaving the surface in hydrated and hydroxylated state. The static SIMS results coupled with XPS O(1s) data indicate that H -, OH -, H 2O +, and SnOH + secondary ion intensities are sensitive to the concentration of surface hydroxyl groups and water. SnOH + yields are shown to be enhanced by the presence of molecularly adsorbed water, suggesting that water is directly involved in the formation of SnOH + species. Annealing of water plasma treated tin oxide films in vacuum results in the loss of molecularly adsorbed water and surface dehydroxylation. The secondary ion ratios of H -/O -, OH -/ O -, H 2O +/Sn +, and SnOH +/Sn + can be used to monitor the thermally induced dehydration and dehydroxylation of the tin oxide surface. In addition, changes in the oxide surface the thermally induced dehydration and dehydroxylation of the tin oxide surface. In addition, changes in the tin oxide surface electronic structure are shown to strongly modulate both relative and absolute ion yields.

  1. Radioactive Particle Tracking Technique with Concentrated {sup 68}Ga Source for Visualization of Water Flows in Digester with Vertical Impeller

    Energy Technology Data Exchange (ETDEWEB)

    Park, Jang-Guen; Moon, Jinho; Lim, Jaecheong; Jung, Sung-Hee [Korea Atomic Energy Research Institute, Daejeon (Korea, Republic of)

    2016-10-15

    It is very important to understand the dynamic behavior of mixing flow for operating digesters. Therefore, there have been incessant studies over the world to investigate hydrodynamic parameters of flows in digesters experimentally. In Korea, researchers at the Korea Atomic Energy Research Institute (KAERI) have been studying radioactive particle tracking (RPT) technique to tracks the trajectory of a single radioactive particle flowing along with flow current and then, hydrodynamics parameters are calculated based on the trajectory of particle. In this study, the RPT technique was carried out for the digester mixed by a vertical impeller to visualize water flow. In this study, the RPT technique was carried out to investigate water flows in digester mixed by vertical impeller. We used a {sup 68}Ga generator source as a radioactive particle by concentrating eluate for RPT to be independent of reactors, and that is the first attempt in the world. The reconstructed particle trajectory will be used to calculate hydrodynamics parameters to understand the dynamic behavior of flows in digester.

  2. The Manipulation of Hydrophobicity in Catalyst Design for Applications of Aerobic Alcohols Oxidation and Electrocatalytic Water Oxidation

    KAUST Repository

    Chen, Batian

    2016-05-17

    Hydrophobicity is the generalized characteristic of non-polar substances that brings about their exclusion from aqueous phases. This property, entropic in its nature, drives key self-assembly and phase separation processes in water. Protein folding, the formation of DNA double helix, the existence of lipid bilayers and the wetting properties of leaf surfaces are all due to hydrophobic interactions. Inspired by Nature, we aimed to use hydrophobicity for creating novel and improved catalytic systems. (I) A number of fluorous amphiphilic star block-copolymers containing a tris(benzyltriazolylmethyl)amine motif have been prepared. These polymers assembled into well-defined nanostructures in water, and their mode of assembly could be controlled by changing the composition of the polymer. The polymers were used for enzyme-inspired catalysis of alcohol oxidation. (II) An enzyme-inspired catalytic system based on a rationally designed multifunctional surfactant was developed. The resulting micelles feature metal-binding sites and stable free radical moieties as well as fluorous pockets that attract and preconcentrate molecular oxygen. In the presence of copper ions, the micelles effect chemoselective aerobic alcohol oxidation under ambient conditions in water, a transformation that is challenging to achieve nonenzymatically. (III) Development of a facile means of photo/electrocatalytic water splitting is one of the main barriers to establishing of a solar hydrogen economy. Of the two half-reactions involved in splitting water into O2 and H2, water oxidation presents the most challenge due to its mechanistic complexity. A practical water oxidation catalyst must be highly active, yet inexpensive and indefinitely stable under harsh oxidative conditions. Here, I shall describe the synthesis of a library of molecular water oxidation catalysts based on the Co complex of tris(2-benzimidazolylmethyl)amine, (BimH)3. A wide range of catalysts differing in their electronic properties

  3. Stable solar-driven oxidation of water by semiconducting photoanodes protected by transparent catalytic nickel oxide films

    KAUST Repository

    Sun, Ke

    2015-03-11

    Reactively sputtered nickel oxide (NiOx) films provide transparent, antireflective, electrically conductive, chemically stable coatings that also are highly active electrocatalysts for the oxidation of water to O2(g). These NiOx coatings provide protective layers on a variety of technologically important semiconducting photoanodes, including textured crystalline Si passivated by amorphous silicon, crystalline n-type cadmium telluride, and hydrogenated amorphous silicon. Under anodic operation in 1.0 M aqueous potassium hydroxide (pH 14) in the presence of simulated sunlight, the NiOx films stabilized all of these self-passivating, high-efficiency semiconducting photoelectrodes for >100 h of sustained, quantitative solar-driven oxidation of water to O2(g). © 2015, National Academy of Sciences. All rights reserved.

  4. Fundamental studies of water oxidation at model hematite electrodes prepared by atomic layer deposition

    Science.gov (United States)

    Klahr, Benjamin M.

    An increasing global demand for energy, combined with an awareness of anthropogenic climate change, has recently fueled the search for abundant, carbon neutral energy sources. The sun offers an enormous amount of energy that is practically inexhaustible and well distributed across Earth. Thus, it is an ideal source for meeting our future energy needs in a carbon neutral fashion. This work focuses on using hematite and sunlight to oxidize water, which is the rate limiting step of splitting water into the energy dense fuel, hydrogen, and the byproduct, oxygen. Hematite is abundant, absorbs a large fraction of the solar spectrum and has an appropriately placed valence band for water oxidation. However, the often cited poor bulk properties, and slow charge transfer kinetics require large applied potentials to oxidize water. Atomic layer deposition (ALD) was utilized to deposit uniform thin films of hematite on transparent conductive substrates as model electrodes to better understand the nature of the limitations in the bulk and at the surface. Comparison of the oxidation of water to the oxidation of fast redox shuttles allowed for the separation of bulk and surface processes. A combination of electrochemical impedance spectroscopy, photoelectrochemical and electrochemical measurements were employed to determine the cause of the large required applied potential. It was found that photogenerated holes initially oxidize the electrode surface under water oxidation conditions, which is attributed to the first step in water oxidation. A critical number of these surface intermediates need to be generated in order for subsequent hole-transfer steps to proceed. At low applied potentials, these intermediates are subject to recombination from the large concentration of electrons in the conduction band due to low band bending. At higher applied potentials, high band bending eliminates surface recombination and the charge collection efficiency of the electrolyte reaches unity. A

  5. Using an environmental public health tracking biomonitoring study to validate safe water restoration efforts in Florida.

    Science.gov (United States)

    Jordan, Melissa; DuClos, Chris; Kintziger, Kristina; Gray, Albert; Bonometti, Mary Ann

    2015-01-01

    Inorganic arsenic is a carcinogen when consumed over many years and is the type of arsenic that is associated with well water. Private wells in many central Florida counties have been found to contain levels of arsenic above 10 μg/L, which is the maximum contaminant level (MCL) established by the US Environmental Protection Agency. The purpose of this study was to test whether individuals living in homes with arsenic levels above the MCL who use bottled water or have a point of use (POU) filter on their main source of water in the house (eg, kitchen sink) are ingesting unsafe levels of arsenic through other unfiltered water sources in the home. Case-control study of residents with private wells above (case) and below (control) the MCL for arsenic in drinking water (10 μg/L) conducted between April and July 2013. Residents with private wells living in Hernando County, Florida, where nearly 400 unique wells of 1200 tested have been found to have elevated arsenic levels (targeted sampling). Participants with elevated water arsenic levels were referred to the Florida Safe Water Restoration Program for assistance in obtaining bottled water vouchers and/or POU filters. Creatinine-corrected total urinary arsenic levels and information on water use and consumption behaviors, dietary intake, and other possible exposure sources. Total urinary arsenic levels were similar for cases using POU filters or bottled water when compared with controls (geometric means of 7.17 and 7.19 μg/L, respectively). The current practice used by the Florida Safe Water Restoration Program of supplying POU filters or bottled water to households with arsenic levels in private wells between 10 and 50 μg/L appears to be sufficient to protect residents from arsenic exposure through tap water.

  6. The reaction of monochloramine and hydroxylamine: implications for ammonia–oxidizing bacteria in chloraminated drinking water

    Science.gov (United States)

    Drinking water chloramine use may promote ammonia–oxidizing bacteria (AOB) growth because of naturally occurring ammonia, residual ammonia remaining from chloramine formation, and ammonia released from chloramine decay and demand. A rapid chloramine residual loss is often associa...

  7. Assessment of supercritical water oxidation system testing for the Blue Grass Chemical Agent Destruction Pilot Plant

    National Research Council Canada - National Science Library

    Board on Army Science and Technology; Division on Engineering and Physical Sciences; National Research Council

    2013-01-01

    "Assessment of Supercritical Water Oxidation System Testing for the Blue Grass Chemical Agent Destruction Pilot Plant reviews and evaluates the results of the tests conducted on one of the SCWO units...

  8. Isotopic Studies of O-O Bond Formation During Water Oxidation (SISGR)

    Energy Technology Data Exchange (ETDEWEB)

    Roth, Justine P. [Johns Hopkins Univ., Baltimore, MD (United States)

    2015-03-03

    Isotopic Studies of O-O Bond Formation During Water Oxidation (SISGR) Research during the project period focused primarily on mechanisms of water oxidation by structurally defined transition metal complexes. Competitive oxygen isotope fractionation of water, mediated by oxidized precursors or reduced catalysts together with ceric, Ce(IV), ammonium nitrate in aqueous media, afforded oxygen-18 kinetic isotope effects (O-18 KIEs). Measurement, calculation, and interpretation of O-18 KIEs, described in the accompanying report has important ramifications for the production of electricity and solar hydrogen (as fuel). The catalysis division of BES has acknowledged that understanding mechanisms of transition metal catalyzed water oxidation has major ramifications, potentially leading to transformation of the global economy and natural environment in years to come. Yet, because of program restructuring and decreased availability of funds, it was recommended that the Solar Photochemistry sub-division of BES would be a more appropriate parent program for support of continued research.

  9. The emulsifying and tribological properties of modified graphene oxide in oil-in-water emulsion

    NARCIS (Netherlands)

    Wu, Yinglei; Zeng, Xiangqiong; Ren, Tianhui; de Vries, Erik G.; van der Heide, Emile

    2017-01-01

    Graphene oxide (GO) was asymmetric chemically modified with myristyltrimethylammonium bromide (TTAB) to get modified graphene oxide (MGO). This MGO was used as an emulsifier and additive in oil-in-water emulsion. The emulsifying tests showed MGO greatly improved the stability of base emulsion and

  10. Photocatalytic Oxidation in Drinking Water Treatment Using Hypochlorite and Titanium Dioxide

    NARCIS (Netherlands)

    El-Kalliny, A.S.M.

    2013-01-01

    The main focus of this thesis is to study the advanced oxidation processes (AOPs) of water pollutants via UV/hypochlorite (homogeneous AOPs), and UV solar light/TiO2 (heterogeneous AOPs) in which the highly oxidative hydroxyl radicals (•OH) are produced. These radicals are capable of destructing the

  11. Gold-Catalyzed Aerobic Oxidation of 5-Hydroxymethylfurfural in Water at Ambient Temperature

    DEFF Research Database (Denmark)

    Gorbanev, Yury; Kegnæs, Søren; Woodley, John

    2009-01-01

    The aerobic oxidation of 5-hydroxymethylfurfural, a versatile biomass-derived chemical, is examined in water with a titania-supported gold-nanoparticle catalyst at ambient temperature (30 degrees C). The selectivity of the reaction towords 2,5-furandicarboxylic acid and the intermediate oxidation...

  12. Organosilane oxidation by water catalysed by large gold nanoparticles in a membrane reactor

    NARCIS (Netherlands)

    Gitis, V.; Beerthuis, R.; Shiju, N.R.; Rothenberg, G.

    2014-01-01

    We show that gold nanoparticles catalyse the oxidation of organosilanes using water as oxidant at ambient conditions. Remarkably, monodispersions of small gold particles (3.5 nm diameter) and large ones (6-18 nm diameter) give equally good conversion rates. This is important because separating large

  13. In situ X-ray absorption spectroscopy of transition metal based water oxidation catalysts

    NARCIS (Netherlands)

    van Oversteeg, Christina H M; Doan, Hoang Q; de Groot, Frank M F; Cuk, Tanja

    2016-01-01

    X-ray absorption studies of the geometric and electronic structure of primarily heterogeneous Co, Ni, and Mn based water oxidation catalysts are reviewed. The X-ray absorption near edge and extended X-ray absorption fine structure studies of the metal K-edge, characterize the metal oxidation state,

  14. Ammonia-Oxidizing Archaea and Bacteria Differentially Contribute to Ammonia Oxidation in Sediments from Adjacent Waters of Rushan Bay, China

    Directory of Open Access Journals (Sweden)

    Hui He

    2018-02-01

    Full Text Available Ammonia oxidation plays a significant role in the nitrogen cycle in marine sediments. Ammonia-oxidizing archaea (AOA and bacteria (AOB are the key contributors to ammonia oxidation, and their relative contribution to this process is one of the most important issues related to the nitrogen cycle in the ocean. In this study, the differential contributions of AOA and AOB to ammonia oxidation in surface sediments from adjacent waters of Rushan Bay were studied based on the ammonia monooxygenase (amoA gene. Molecular biology techniques were used to analyze ammonia oxidizers’ community characteristics, and potential nitrification incubation was applied to understand the ammonia oxidizers’ community activity. The objective was to determine the community structure and activity of AOA and AOB in surface sediments from adjacent waters of Rushan Bay and to discuss the different contributions of AOA and AOB to ammonia oxidation during summer and winter seasons in the studied area. Pyrosequencing analysis revealed that the diversity of AOA was higher than that of AOB. The majority of AOA and AOB clustered into Nitrosopumilus and Nitrosospira, respectively, indicating that the Nitrosopumilus group and Nitrosospira groups may be more adaptable in studied sediments. The AOA community was closely correlated to temperature, salinity and ammonium concentration, whereas the AOB community showed a stronger correlation with temperature, chlorophyll-a content (chla and nitrite concentration. qPCR results showed that both the abundance and the transcript abundance of AOA was consistently greater than that of AOB. AOA and AOB differentially contributed to ammonia oxidation in different seasons. AOB occupied the dominant position in mediating ammonia oxidation during summer, while AOA might play a dominant role in ammonia oxidation during winter.

  15. Biological efficacy and toxic effect of emergency water disinfection process based on advanced oxidation technology.

    Science.gov (United States)

    Tian, Yiping; Yuan, Xiaoli; Xu, Shujing; Li, Rihong; Zhou, Xinying; Zhang, Zhitao

    2015-12-01

    An innovative and removable water treatment system consisted of strong electric field discharge and hydrodynamic cavitation based on advanced oxidation technologies was developed for reactive free radicals producing and waterborne pathogens eliminating in the present study. The biological efficacy and toxic effects of this advanced oxidation system were evaluated during water disinfection treatments. Bench tests were carried out with synthetic microbial-contaminated water, as well as source water in rainy season from a reservoir of Dalian city (Liaoning Province, China). Results showed that high inactivation efficiency of Escherichia coli (>5 log) could be obtained for synthetic contaminated water at a low concentration (0.5-0.7 mg L(-1)) of total oxidants in 3-10 s. The numbers of wild total bacteria (108 × 10(3) CFU mL(-1)) and total coliforms (260 × 10(2) MPN 100 mL(-1)) in source water greatly reduced to 50 and 0 CFU mL(-1) respectively after treated by the advanced oxidation system, which meet the microbiological standards of drinking water, and especially that the inactivation efficiency of total coliforms could reach 100%. Meanwhile, source water qualities were greatly improved during the disinfection processes. The values of UV254 in particular were significantly reduced (60-80%) by reactive free radicals. Moreover, the concentrations of possible disinfection by-products (formaldehyde and bromide) in treated water were lower than detection limits, indicating that there was no harmful effect on water after the treatments. These investigations are helpful for the ecotoxicological studies of advanced oxidation system in the treatments of chemical polluted water or waste water. The findings of this work suggest that the developed water treatment system is ideal in the acute phases of emergencies, which also could offer additional advantages over a wide range of applications in water pollution control.

  16. Utility of remote sensing-based surface energy balance models to track water stress in rain-fed switchgrass under dry and wet conditions

    Science.gov (United States)

    The ability of remote sensing-based surface energy balance (SEB) models to track water stress in rain-fed switchgrass has not been explored yet. In this paper, the theoretical framework of crop water stress index (CWSI) was utilized to estimate CWSI in rain-fed switchgrass (Panicum virgatum L.) usin...

  17. Application of DVC-FISH method in tracking Escherichia coli in drinking water distribution networks

    Directory of Open Access Journals (Sweden)

    L. Mezule

    2013-04-01

    Full Text Available Sporadic detection of live (viable Escherichia coli in drinking water and biofilm with molecular methods but not with standard plate counts has raised concerns about the reliability of this indicator in the surveillance of drinking water safety. The aim of this study was to determine spatial distribution of different viability forms of E. coli in a drinking water distribution system which complies with European Drinking Water Directive (98/83/EC. For two years coupons (two week old and pre-concentrated (100 times with ultrafilters water samples were collected after treatment plants and from four sites in the distribution network at several distances. The samples were analyzed for total, viable (able to divide as DVC-FISH positive and cultivable E. coli. The results showed that low numbers of E. coli enters the distribution sytem from the treatment plants and tend to accumulate in the biofilm of water distribution system. Almost all of the samples contained metabolically active E. coli in the range of 1 to 50 cells per litre or cm2 which represented approximately 53% of all E. coli detected. The amount of viable E. coli significantly increased into the network irrespective of the season. The study has shown that DVC-FISH method in combination with water pre-concentration and biofilm sampling allows to better understand the behaviour of E. coli in water distribution networks, thus, it provides new evidences for water safety control.

  18. Influence of formulation on the oxidative stability of water-in-oil emulsions.

    Science.gov (United States)

    Dridi, Wafa; Essafi, Wafa; Gargouri, Mohamed; Leal-Calderon, Fernando; Cansell, Maud

    2016-07-01

    The oxidation of water-in-oil (W/O) emulsions was investigated, emphasizing the impact of compositional parameters. The emulsions had approximately the same average droplet size and did not show any physical destabilization throughout the study. In the absence of pro-oxidant ions in the aqueous phase, lipid oxidation of the W/O emulsions was moderate at 60°C and was in the same range as that measured for the neat oils. Oxidation was significantly promoted by iron encapsulation in the aqueous phase, even at 25°C. However, iron chelation reduced the oxidation rate. Emulsions based on triglycerides rich in polyunsaturated fatty acids were more prone to oxidation, whether the aqueous phase encapsulated iron or not. The emulsions were stabilized by high- and low-molecular weight surfactants. Increased relative fractions of high molecular weight components reduced the oxidation rate when iron was present. Copyright © 2016 Elsevier Ltd. All rights reserved.

  19. Hydrothermal Synthesis of Metal Oxide Nanoparticles in Supercritical Water

    National Research Council Canada - National Science Library

    Hayashi, Hiromichi; Hakuta, Yukiya

    2010-01-01

    .... Supercritical water allows control of the crystal phase, morphology, and particle size since the solvent's properties, such as density of water, can be varied with temperature and pressure, both...

  20. Biological iron oxidation by Gallionella spp. in drinking water production under fully aerated conditions.

    Science.gov (United States)

    de Vet, W W J M; Dinkla, I J T; Rietveld, L C; van Loosdrecht, M C M

    2011-11-01

    Iron oxidation under neutral conditions (pH 6.5-8) may be a homo- or heterogeneous chemically- or a biologically-mediated process. The chemical oxidation is supposed to outpace the biological process under slightly alkaline conditions (pH 7-8). The iron oxidation kinetics and growth of Gallionella spp. - obligatory chemolithotrophic iron oxidizers - were assessed in natural, organic carbon-containing water, in continuous lab-scale reactors and full-scale groundwater trickling filters in the Netherlands. From Gallionella cell numbers determined by qPCR, balances were made for all systems. The homogeneous chemical iron oxidation occurred in accordance with the literature, but was retarded by a low water temperature (13 °C). The contribution of the heterogeneous chemical oxidation was, despite the presence of freshly formed iron oxyhydroxides, much lower than in previous studies in ultrapure water. This could be caused by the adsorption of natural organic matter (NOM) on the iron oxide surfaces. In the oxygen-saturated natural water with a pH ranging from 6.5 to 7.7, Gallionella spp. grew uninhibited and biological iron oxidation was an important, and probably the dominant, process. Gallionella growth was not even inhibited in a full-scale filter after plate aeration. From this we conclude that Gallionella spp. can grow under neutral pH and fully aerated conditions when the chemical iron oxidation is retarded by low water temperature and inhibition of the autocatalytic iron oxidation. Copyright © 2011 Elsevier Ltd. All rights reserved.

  1. Systematic tracking, visualizing, and interpreting of consumer feedback for drinking water quality.

    Science.gov (United States)

    Dietrich, Andrea M; Phetxumphou, Katherine; Gallagher, Daniel L

    2014-12-01

    Consumer feedback and complaints provide utilities with useful data about consumer perceptions of aesthetic water quality in the distribution system. This research provides a systematic approach to interpret consumer complaint water quality data provided by four water utilities that recorded consumer complaints, but did not routinely process the data. The utilities tended to write down a myriad of descriptors that were too numerous or contained a variety of spellings so that electronic "harvesting" was not possible and much manual labor was required to categorize the complaints into majors areas, such as suggested by the Drinking Water Taste and Odor Wheel or existing check-sheets. When the consumer complaint data were categorized and visualized using spider (or radar) and run-time plots, major taste, odor, and appearance patterns emerged that clarified the issue and could provide guidance to the utility on the nature and extent of the problem. A caveat is that while humans readily identify visual issues with the water, such as color, cloudiness, or rust, describing specific tastes and odors in drinking water is acknowledged to be much more difficult for humans to achieve without training. This was demonstrated with two utility groups and a group of consumers identifying the odors of orange, 2-methylisoborneol, and dimethyl trisulfide. All three groups readily and succinctly identified the familiar orange odor. The two utility groups were much more able to identify the musty odor of 2-methylisoborneol, which was likely familiar to them from their work with raw and finished water. Dimethyl trisulfide, a garlic-onion odor associated with sulfur compounds in drinking water, was the least familiar to all three groups, although the laboratory staff did best. These results indicate that utility personnel should be tolerant of consumers who can assuredly say the water is different, but cannot describe the problem. Also, it indicates that a T&O program at a utility would

  2. Fourier transform infrared difference spectroscopy for studying the molecular mechanism of photosynthetic water oxidation

    Directory of Open Access Journals (Sweden)

    Hsiu-An eChu

    2013-05-01

    Full Text Available The photosystem II reaction center mediates the light-induced transfer of electrons from water to plastoquinone, with concomitant production of O2. Water oxidation chemistry occurs in the oxygen-evolving complex (OEC, which consists of an inorganic Mn4CaO5 cluster and its surrounding protein matrix. Light-induced Fourier transform infrared (FTIR difference spectroscopy has been successfully used to study the molecular mechanism of photosynthetic water oxidation. This powerful technique has enabled the characterization of the dynamic structural changes in active water molecules, the Mn4CaO5 cluster, and its surrounding protein matrix during the catalytic cycle. This mini-review presents an overview of recent important progress in FTIR studies of the OEC and implications for revealing the molecular mechanism of photosynthetic water oxidation.

  3. Efficient electrochemical water oxidation in neutral and near-neutral systems by nanoscale silver-oxide catalyst

    KAUST Repository

    Joya, Khurram Saleem

    2016-07-19

    In electrocatalytic water splitting systems pursuing for renewable energy using sun light, developing robust, stable and easy accessible materials operating under mild chemical conditions is pivotal. We present here unique nano-particulate type silver-oxide (AgOx-NP) based robust and highly stable electrocatalyst for efficient water oxidation. The AgOx-NP is generated in situ in a HCO3–/CO2 system under benign conditions. Mircographs show that they exhibit nanoscale box type squared nano-bipyramidal configuration. The oxygen generation is initiated at low overpotential, and a sustained O2 evolution current density of > 1.1 mA cm–2 is achieved during prolonged-period water electrolysis. The AgOx-NP electrocatalyst performs exceptionally well in metal-ions free neutral or near-neutral carbonate, phosphate and borate buffers relative to recently reported Co-oxide and Ni-oxide based heterogeneous electrocatalysts, which are unstable in metal-ions free electrolyte and tend to degrade with time and lose catalytic performance during long-term experimental tests.

  4. Water transport confined in graphene oxide channels through the rarefied effect.

    Science.gov (United States)

    Chen, Bo; Jiang, Haifeng; Liu, Xiang; Hu, Xuejiao

    2018-02-21

    Understanding the mechanism of water transport inside an interlayer between graphene-based plates has tremendous value for theoretical studies and industrial applications. The fluid flow confined in nano-scaled spaces experiences a slip velocity near the wall, which is significantly different to that of bulk water. Here we propose a model combining classic hydrodynamics with kinetic theory to depict the dependency of the slip effect on the oxide concentration of valley plates. The influence of oxidized graphene on water flow is a comprehensive result of a slipped boundary, and depends on both the diffuse reflection coefficient of the wall, and the shrunken effective passageway caused by the electrostatic interactions between the oxidized surface and the water molecules. The former effect enhances the water flow, which reduces with increasing oxide concentration, while the latter effect inhibits water flow. We examine the diffuse reflection coefficient and the shrunken effective passageway at different oxide concentrations of the GO sheets by molecular dynamics simulations, and we quantitively predict the flux relationship at various concentrations. This work provides a molecular insight into transport processes of confined water and a useful guideline for the design of perfect graphene-derived membranes for desalination.

  5. Redox and electrochemical water splitting catalytic properties of hydrated metal oxide modified electrodes.

    Science.gov (United States)

    Doyle, Richard L; Godwin, Ian J; Brandon, Michael P; Lyons, Michael E G

    2013-09-07

    This paper presents a review of the redox and electrocatalytic properties of transition metal oxide electrodes, paying particular attention to the oxygen evolution reaction. Metal oxide materials may be prepared using a variety of methods, resulting in a diverse range of redox and electrocatalytic properties. Here we describe the most common synthetic routes and the important factors relevant to their preparation. The redox and electrocatalytic properties of the resulting oxide layers are ascribed to the presence of extended networks of hydrated surface bound oxymetal complexes termed surfaquo groups. This interpretation presents a possible unifying concept in water oxidation catalysis - bridging the fields of heterogeneous electrocatalysis and homogeneous molecular catalysis.

  6. Time resolved study of hydroxyl radical oxidation of oleic acid at the air-water interface

    Science.gov (United States)

    Zhang, Xinxing; Barraza, Kevin M.; Upton, Kathleen T.; Beauchamp, J. L.

    2017-09-01

    The ubiquity of oleic acid (OA) renders it a poster child for laboratory investigations of environmental oxidation chemistry. In the current study, mechanistic details of the oxidation of OA by hydroxyl radicals at the air-water interface are investigated using field-induced droplet ionization mass spectrometry (FIDI-MS). Products from OH oxidation of both unsaturated and saturated carbon atoms are identified, and mechanisms for both types of oxidation processes are proposed. Uptake of oxygen in the interfacial layer increases linearly with time, consistent with Langmuir-Hinshelwood reaction kinetics. These results provide fundamental knowledge relating to OH initiated degradation of fatty acids in atmospheric aerosols.

  7. Scalable Synthesis of Efficient Water Oxidation Catalysts: Insights into the Activity of Flame-Made Manganese Oxide Nanocrystals.

    Science.gov (United States)

    Liu, Guanyu; Hall, Jeremy; Nasiri, Noushin; Gengenbach, Thomas; Spiccia, Leone; Cheah, Mun Hon; Tricoli, Antonio

    2015-12-21

    Chemical energy storage by water splitting is a promising solution for the utilization of renewable energy in numerous currently impracticable needs, such as transportation and high temperature processing. Here, the synthesis of efficient ultra-fine Mn3O4 water oxidation catalysts with tunable specific surface area is demonstrated by a scalable one-step flame-synthesis process. The water oxidation performance of these flame-made structures is compared with pure Mn2O3 and Mn5O8, obtained by post-calcination of as-prepared Mn3O4 (115 m(2)  g(-1)), and commercial iso-structural polymorphs, probing the effect of the manganese oxidation state and synthetic route. The structural properties of the manganese oxide nanoparticles were investigated by XRD, FTIR, high-resolution TEM, and XPS. It is found that these flame-made nanostructures have substantially higher activity, reaching up to 350 % higher surface-specific turnover frequency (0.07 μmolO2  m(-2)  s(-1)) than commercial nanocrystals (0.02 μmolO2  m(-2)  s(-1)), and production of up to 0.33 mmolO2  molMn (-1)  s(-1). Electrochemical characterization confirmed the high water oxidation activity of these catalysts with an initial current density of 10 mA cm(-2) achieved with overpotentials between 0.35 and 0.50 V in 1 m NaOH electrolyte. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Iron oxidation kinetics and phosphate immobilization along the flow-path from groundwater into surface water

    Science.gov (United States)

    van der Grift, B.; Rozemeijer, J. C.; Griffioen, J.; van der Velde, Y.

    2014-06-01

    The retention of phosphorus in surface waters though co-precipitation of phosphate with Fe-oxyhydroxides during exfiltration of anaerobic Fe(II) rich groundwater is not well understood. We developed an experimental field set-up to study Fe(II) oxidation and P immobilization along the flow-path from groundwater to surface water 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. Through continuous discharge measurements and weekly water quality sampling of groundwater, tube drain water, exfiltrated groundwater, and ditch water, we investigated Fe(II) oxidation kinetics and P immobilization processes. The oxidation rate inferred from our field measurements closely agreed with the general rate law for abiotic oxidation of Fe(II) by O2. Seasonal changes in climatic conditions affected the Fe(II) oxidation process. Lower pH and lower temperatures in winter (compared to summer) resulted in low Fe oxidation rates. After exfiltration to the surface water, it took a couple of days to more than one week before complete oxidation of Fe(II) is reached. In summer time, Fe oxidation rates were much higher. The Fe concentrations in the exfiltrated groundwater were low, indicating that dissolved Fe(II) is completely oxidized prior to inflow into a ditch. While the Fe oxidation rates reduce drastically from summer to winter, P concentrations remained high in the groundwater and an order of magnitude lower in the surface water throughout the year. This study shows very fast immobilisation of dissolved P during the initial stage of the Fe(II) oxidation proces which results in P-depleted water before Fe(II) is competly depleted. This cannot be explained by surface complexation of phosphate to freshly formed Fe-oxyhydroxides but indicates the formation of Fe(III)-phosphate precipitates. The formation of Fe(III)-phosphates at redox gradients seems an

  9. Comparision of photocatalysis and photolysis processes for arsenic oxidation in water.

    Science.gov (United States)

    Fontana, Klaiani B; Lenzi, Giane G; Seára, Eriton C R; Chaves, Eduardo S

    2018-01-11

    The oxidation of As(III) to As(V) in aqueous solution was evaluated using heterogeneous photocatalysis and photolysis. The influence of TiO 2 as catalyst in different crystalline (rutile, anatase) and commercial forms was evaluated in a batch reactor and an insignificant difference was observed between them. The process by photocatalysis reached up to 97% As(III) oxidation and no significant difference was observed comparing to results obtained by photolysis. The photolysis experiments (UV radiation only), also carried out in a batch system, showed a high oxidation rate of As(III) (90% in 20min). The influence of different matrices (well water, river water and public water supply) were evaluated. Additionally, the effect of As(V) concentration, generated during the oxidation process, was studied. Continuous photolysis experiments using only UV radiation were performed, resulting in a high As(III) oxidation rate. Using a flow rate of 5mLmin -1 and an initial concentration of As(III) 200µgL -1 , gave an oxidation percentage of As(III) of up to 72%, showing a simple and economical alternative to the oxidation step of As(III) to As(V) in the treatment of water contaminated with arsenic. Copyright © 2018 Elsevier Inc. All rights reserved.

  10. Water versus DNA: new insights into proton track-structure modelling in radiobiology and radiotherapy.

    Science.gov (United States)

    Champion, C; Quinto, M A; Monti, J M; Galassi, M E; Weck, P F; Fojón, O A; Hanssen, J; Rivarola, R D

    2015-10-21

    Water is a common surrogate of DNA for modelling the charged particle-induced ionizing processes in living tissue exposed to radiations. The present study aims at scrutinizing the validity of this approximation and then revealing new insights into proton-induced energy transfers by a comparative analysis between water and realistic biological medium. In this context, a self-consistent quantum mechanical modelling of the ionization and electron capture processes is reported within the continuum distorted wave-eikonal initial state framework for both isolated water molecules and DNA components impacted by proton beams. Their respective probability of occurrence-expressed in terms of total cross sections-as well as their energetic signature (potential and kinetic) are assessed in order to clearly emphasize the differences existing between realistic building blocks of living matter and the controverted water-medium surrogate. Consequences in radiobiology and radiotherapy will be discussed in particular in view of treatment planning refinement aiming at better radiotherapy strategies.

  11. Tracking disinfection by-products and arsenic removal during various drinking water treatment trains.

    Science.gov (United States)

    Tubić, Aleksandra; Dalmacija, Bozo; Agbaba, Jasmina; Ivancev-Tumbas, Ivana; Klasnja, Mile; Dalmacija, Milena

    2010-01-01

    In the central Banat region (Northern Serbia), groundwater is used as a drinking water source. Raw water originates from a 40-80 m and 100-150 m deep layer. It contains a high amount of natural organic matter (DOC = 9.17+/-0.87 mg C/L) with a trihalomethanes formation potential of 448+/-88.2 microg/L and a haloacetic acid formation potential of 174+/-68.9 microg/L. A high amount of arsenic (86.0+/-3.4 microg/L) is also found in this water. This study used a pilot-scale system to investigate the possibilities of combining polyaluminium chloride and ferrous-chloride to remove disinfection by-products precursors and arsenic by coagulation. Two treatment trains with different pre-treatment steps were investigated (ozone vs. H2O2/O3). For the final water polishing, filtration with granulated activated carbon (GAC) was applied. Both investigated treatment lines achieved a satisfactory chemical water quality. Simulation of disinfection conditions was performed and the contents of trihalomethanes and haloacetic acids measured, to investigate whether the chemical quality of the water remained satisfactory over a 48 hour period.

  12. Heterogeneous Photo-Fenton Reaction Catalyzed by Nanosized Iron Oxides for Water Treatment

    Directory of Open Access Journals (Sweden)

    Chuan Wang

    2012-01-01

    Full Text Available Great efforts have been exerted in overcoming the drawbacks of the Fenton reaction for water treatment applications. The drawbacks include pH confinement, handling of iron sludge, slow regeneration of Fe(II, and so forth. This paper highlights the recent developments in the heterogeneous photo-Fenton reaction which utilizes nanosized iron oxides as catalyst for maximizing the activity due to the enhanced physical or chemical properties brought about by the unique structures. This paper also summarizes the fundamentals of the Fenton reaction, which determine the inherent drawbacks and associated advances, to address the advantages of iron oxides and nanosized iron oxides. Tips for applying this method in water treatment are also provided. Given that the environmental effect of nanosized iron oxides is not yet well established, rapid research growth may occur in the near future to advance this promising technology toward water treatment once it is smartly coupled with conventional technologies.

  13. Piloting water quality testing coupled with a national socioeconomic survey in Yogyakarta province, Indonesia, towards tracking of Sustainable Development Goal 6.

    Science.gov (United States)

    Cronin, Aidan A; Odagiri, Mitsunori; Arsyad, Bheta; Nuryetty, Mariet Tetty; Amannullah, Gantjang; Santoso, Hari; Darundiyah, Kristin; Nasution, Nur 'Aisyah

    2017-10-01

    There remains a pressing need for systematic water quality monitoring strategies to assess drinking water safety and to track progress towards the Sustainable Development Goals (SDG). This study incorporated water quality testing into an existing national socioeconomic survey in Yogyakarta province, Indonesia; the first such study in Indonesia in terms of SDG tracking. Multivariate regression analysis assessed the association between faecal and nitrate contamination and drinking water sources household drinking water adjusted for wealth, education level, type of water sources and type of sanitation facilities. The survey observed widespread faecal contamination in both sources for drinking water (89.2%, 95%CI: 86.9-91.5%; n=720) and household drinking water (67.1%, 95%CI: 64.1-70.1%; n=917) as measured by Escherichia coli. This was despite widespread improved drinking water source coverage (85.3%) and commonly self-reported boiling practices (82.2%). E.coli concentration levels in household drinking water were associated with wealth, education levels of a household head, and type of water source (i.e. vender water or local sources). Following the proposed SDG definition for Target 6.1 (water) and 6.2 (sanitation), the estimated proportion of households with access to safely managed drinking water and sanitation was 8.5% and 45.5%, respectively in the study areas, indicating substantial difference from improved drinking water (82.2%) and improved sanitation coverage (70.9%) as per the MDGs targets. The greatest contamination and risk factors were found in the poorest households indicating the urgent need for targeted and effective interventions here. There is suggested evidence that sub-surface leaching from on-site sanitation adversely impacts on drinking water sources, which underscores the need for further technical assistance in promoting latrine construction. Urgent action is still needed to strengthen systematic monitoring efforts towards tracking SDG Goal 6

  14. Strain-Induced Water Dissociation on Supported Ultrathin Oxide Films

    CERN Document Server

    Song, Zhenjun; Xu, Hu

    2015-01-01

    Controlling the dissociation of single water molecule on an insulating surface plays a crucial role in many catalytic reactions. In this Letter, we have identified the enhanced chemical reactivity of ultrathin MgO(100) films deposited on Mo(100) substrate that causes water dissociation. We reveal that the ability to split water on insulating surface closely depends on the lattice mismatch between ultrathin films and the underlying substrate, and substrate-induced in-plane tensile strain dramatically results in water dissociation on MgO(100). Three dissociative adsorption configurations of water with lower energy are predicted, and the structural transition going from molecular form to dissociative form is almost barrierless. Our results provide an effective avenue to achieve water dissociation at the single-molecule level and shed light on how to tune the chemical reactions of insulating surfaces by choosing the suitable substrates.

  15. Pacific and Atlantic water influence on the Beaufort Sea slope tracked by epifaunal invertebrate biogeography

    Science.gov (United States)

    Bluhm, B.

    2016-02-01

    As an interior Arctic sea with a narrow shelf and a steep slope, the US Beaufort Sea is influenced by complex vertical and horizontal domains of water masses and current regimes. The benthic invertebrates inhabiting that area form communities that reflect the long-term (year to decadal) environmental conditions and waters mass source. During six expeditions over five years, we deployed plumb-staff beam trawls to collect epifauna invertebrates at >150 locations spanning the shelf and slope to 1000 m and across the primary water masses of the region (as defined by T/S). The >250 species sampled in this effort are dominated in species richness by crustaceans and gastropods, and in abundance and biomass by echinoderms and crustaceans, with proportional variations across water depths. We find strong turnover in species and/or community composition with water depth, and moderate shifts along the west-east axis. Depth-related species/community shifts are gradual, but most pronounced around the 20 m isobaths, at the shelf break (between 100 and 200 m) and between 350 and 500 m. Inshore of 20 m, the dynamic environment (ice gouging, variable salinity) results in a species-poor community. At locations deeper than 350 m, communities increasingly include species common in the Atlantic-influenced Arctic and Atlantic-boreal regions, roughly matching the transition from Pacific-origin to Atlantic-origin waters. We conclude that benthic community distribution can delineate boundaries in hydrographic conditions that are characteristic of different water mass types that reside on the shelf and slope of the Beaufort Sea.

  16. Significant role of Mn(III) sites in e(g)(1) configuration in manganese oxide catalysts for efficient artificial water oxidation.

    Science.gov (United States)

    Indra, Arindam; Menezes, Prashanth W; Schuster, Felix; Driess, Matthias

    2015-11-01

    Development of efficient bio-inspired water oxidation system with transition metal oxide catalyst has been considered as the one of the most challenging task in the recent years. As the oxygen evolving center of photosystem II consists of Mn4CaO5 cluster, most of the water oxidation study was converged to build up manganese oxide based catalysts. Here we report the synthesis of efficient artificial water oxidation catalysts by transferring the inactive manganese monooxide (MnO) under highly oxidizing conditions with ceric ammonium nitrate (CAN) and ozone (O3). MnO was partially oxidized to form mixed-valent manganese oxide (MnOx) with CAN whereas completely oxidized to mineral phase of ε-MnO2 (Akhtenskite) upon treatment of O3 in acidic solution, which we explore first time as a water oxidation catalyst. Chemical water oxidation, as well as the photochemical water oxidation in the presence of sacrificial electron acceptor and photosensitizer with the presented catalysts were carried out that followed the trends: MnOx>MnO2>MnO. Structural and activity correlation reveals that the presence of larger extent of Mn(III) in MnOx is the responsible factor for higher activity compared to MnO2. Mn(III) species in octahedral system with eg(1) configuration furnishes and facilitates the Mn-O and Mn-Mn bond enlargement with required structural flexibility and disorder in the manganese oxide structure which indeed facilitates water oxidation. Copyright © 2014 Elsevier B.V. All rights reserved.

  17. Effect of tolvaptan on renal water and sodium excretion and blood pressure during nitric oxide inhibition

    DEFF Research Database (Denmark)

    Therwani, Safa Al; Rosenbæk, Jeppe Bakkestrøm; Mose, Frank Holden

    2017-01-01

    BACKGROUND: Tolvaptan is a selective vasopressin receptor antagonist. Nitric Oxide (NO) promotes renal water and sodium excretion, but the effect is unknown in the nephron's principal cells. In a dose-response study, we measured the effect of tolvaptan on renal handling of water and sodium and sy...

  18. Co-doped titanium oxide foam and water disinfection device

    Science.gov (United States)

    Shang, Jian-Ku; Wu, Pinggui; Xie, Rong-Cai

    2016-01-26

    A quaternary oxide foam, comprises an open-cell foam containing (a) a dopant metal, (b) a dopant nonmetal, (c) titanium, and (d) oxygen. The foam has the advantages of a high surface area and a low back pressure during dynamic flow applications. The inactivation of Escherichia coli (E. coli) was demonstrated in a simple photoreactor.

  19. Transformation of Levantine Intermediate Water tracked by MEDARGO floats in the Western Mediterranean

    Directory of Open Access Journals (Sweden)

    M. Emelianov

    2006-01-01

    Full Text Available A clustering methodology is applied to investigate the thermohaline structure of Levantine Intermediate Water (LIW in the western Mediterranean basin. Sixteen free-drifting hydrographic profilers were deployed in the framework of the MFSTEP project (MEDARGO component from September 2003. A total of 925 CTD profiles collected up to the beginning of February 2006 have been used in the analysis. The results are in good agreement with the general circulation scheme for intermediate waters in the basin and confirm the hypothesis about a "discrete-continuous" thermohaline structure of LIW.

  20. Improving the oxidation resistance of 316L stainless steel in simulated pressurized water reactor primary water by electropolishing treatment

    Energy Technology Data Exchange (ETDEWEB)

    Han, Guangdong [Institute of Materials Science, School of Materials Science and Engineering, Shanghai University, Shanghai, 200072 (China); Lu, Zhanpeng, E-mail: zplu@shu.edu.cn [Institute of Materials Science, School of Materials Science and Engineering, Shanghai University, Shanghai, 200072 (China); State Key Laboratory of Advanced Special Steels, Shanghai University, Shanghai, 200072 (China); Ru, Xiangkun; Chen, Junjie; Xiao, Qian; Tian, Yongwu [Institute of Materials Science, School of Materials Science and Engineering, Shanghai University, Shanghai, 200072 (China)

    2015-12-15

    The oxidation behavior of 316L stainless steel specimens after emery paper grounding, mechanical polishing, and electropolishing were investigated in simulated pressurized water reactor primary water at 310 °C for 120 and 500 h. Electropolishing afforded improved oxidation resistance especially during the early immersion stages. Duplex oxide films comprising a coarse Fe-rich outer layer and a fine Cr-rich inner layer formed on all specimens after 500 h of immersion. Only a compact layer was observed on the electropolished specimen after 120 h of immersion. The enrichment of chromium in the electropolished layer contributed to the passivity and protectiveness of the specimen. - Highlights: • Duplex oxide films on ground and mechanically polished specimens. • Compact oxide on electropolished specimen after 120 h immersion. • Large spinel outer layer rich in Fe and fine spinel inner layer rich in Cr. • Electropolishing improved oxidation resistance especially at the early stages. • Inhomogeneous Cr-rich inner layer with granular areas affected by surface treatment.

  1. Microbe biogeography tracks water masses in a dynamic oceanic frontal system.

    Science.gov (United States)

    Djurhuus, Anni; Boersch-Supan, Philipp H; Mikalsen, Svein-Ole; Rogers, Alex D

    2017-03-01

    Dispersal limitation, not just environmental selection, plays an important role in microbial biogeography. The distance-decay relationship is thought to be weak in habitats where dispersal is high, such as in the pelagic environment, where ocean currents facilitate microbial dispersal. Most studies of microbial community composition to date have observed little geographical heterogeneity on a regional scale (100 km). We present a study of microbial communities across a dynamic frontal zone in the southwest Indian Ocean and investigate the spatial structure of the microbes with respect to the different water masses separated by these fronts. We collected 153 samples of free-living microorganisms from five seamounts located along a gradient from subtropical to subantarctic waters and across three depth layers: (i) the sub-surface chlorophyll maximum (approx. 40 m), (ii) the bottom of the euphotic zone (approx. 200 m), and (iii) the benthic boundary layer (300-2000 m). Diversity and abundance of microbial operational taxonomic units (OTUs) were assessed by amplification and sequencing of the 16S rRNA gene on an Illumina MiSeq platform. Multivariate analyses showed that microbial communities were structured more strongly by depth than by latitude, with similar phyla occurring within each depth stratum across seamounts. The deep layer was homogeneous across the entire survey area, corresponding to the spread of Antarctic intermediate water. However, within both the sub-surface layer and the intermediate depth stratum there was evidence for OTU turnover across fronts. The microbiome of these layers appears to be divided into three distinct biological regimes corresponding to the subantarctic surface water, the convergence zone and subtropical. We show that microbial biogeography across depth and latitudinal gradients is linked to the water masses the microbes persist in, resulting in regional patterns of microbial biogeography that correspond to the regional

  2. UV/H2O2 oxidation of arsenic and terbuthylazine in drinking water.

    Science.gov (United States)

    Sorlini, S; Gialdini, F; Stefan, M

    2014-02-01

    Arsenic is a widespread contaminant in the environment. The intake of water containing high concentrations of arsenic could have serious impact on human health, such as skin and lung cancer. In the European Union, thus, also in Italy, the arsenic limit in drinking water is 10 μg L(-1). Several water remediation treatment technologies are available for arsenic removal. For some processes, the removal efficiencies can be improved after an oxidation step. Most full-scale applications are based on conventional oxidation processes for chemical micropollutant removal. However, if water contains arsenic and refractory organic contaminants, the advanced oxidation processes could be considered. The aim of this work was to investigate the effectiveness of ultraviolet (UV) radiation alone and in combination with hydrogen peroxide for the oxidation of arsenic and terbuthylazine (TBA). The experimental tests were performed in groundwater at the laboratory scale (0.1 mg L(-1) As(III) and 10 μg L(-1) TBA). Hydrogen peroxide alone (15 mg L(-1)) was ineffective on both arsenic and TBA oxidation; the 253.7-nm radiation alone did not oxidize arsenic(III), but photolyzed efficiently TBA (52 % removal yield at a UV dose of 1,200 mJ cm(-2)). The UV/H2O2 advanced oxidation (UV dose 600-2,000 mJ cm(-2), 5-15 mg L(-1) H2O2) was the most effective process for the oxidation of both arsenic and TBA, with observed oxidation efficiencies of 85 and 94 %, respectively, with 5 mg L(-1) H2O2 and a UV dose of 2,000 mJ cm(-2).

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

    Science.gov (United States)

    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. Copyright 2010 Elsevier Ltd. All rights reserved.

  4. Water dispersal of methanotrophic bacteria maintains functional methane oxidation in Sphagnum mosses

    Directory of Open Access Journals (Sweden)

    Anuliina ePutkinen

    2012-01-01

    Full Text Available It is known that Sphagnum associated methanotrophy (SAM changes in relation to the peatland water table (WT level. After drought, rising WT is able to reactivate SAM. We aimed to reveal whether this reactivation is due to activation of indigenous methane (CH4 oxidizing bacteria (MOB already present in the mosses or to MOB present in water. This was tested through two approaches: In a transplantation experiment, Sphagna lacking SAM activity were transplanted into flark water next to Sphagna oxidizing CH4. Already after 3 d, most of the transplants showed CH4 oxidation activity. Microarray showed that the MOB community compositions of the transplants and the original active mosses had become more similar within 28 d thus indicating MOB movement through water between mosses. Methylocystis-related type II MOB dominated the community. In a following experiment, SAM inactive mosses were bathed overnight in non-sterile and sterile-filtered SAM active site flark water. Only mosses bathed with non-sterile flark water became SAM active, which was also shown by the pmoA copy number increase of over 60 times. Thus, it was evident that MOB present in the water can colonize Sphagnum mosses. This colonization could act as a resilience mechanism for peatland CH4 dynamics by allowing the re-emergence of CH4 oxidation activity in Sphagnum.

  5. A Robust Molecular Catalyst Generated In Situ for Photo- and Electrochemical Water Oxidation.

    Science.gov (United States)

    Younus, Hussein A; Ahmad, Nazir; Chughtai, Adeel H; Vandichel, Matthias; Busch, Michael; Van Hecke, Kristof; Yusubov, Mekhman; Song, Shaoxian; Verpoort, Francis

    2017-03-09

    Water splitting is the key step towards artificial photosystems for solar energy conversion and storage in the form of chemical bonding. The oxidation of water is the bottle-neck of this process that hampers its practical utility; hence, efficient, robust, and easy to make catalytic systems based on cheap and earth-abundant materials are of exceptional importance. Herein, an in situ generated cobalt catalyst, [Co II (TCA) 2 (H 2 O) 2 ] (TCA=1-mesityl-1,2,3-1H-triazole-4-carboxylate), that efficiently conducts photochemical water oxidation under near-neutral conditions is presented. The catalyst showed high stability under photolytic conditions for more than 3 h of photoirradiation. During electrochemical water oxidation, the catalytic system assembled a catalyst film, which proved not to be cobalt oxide/hydroxide as normally expected, but instead, and for the first time, generated a molecular cobalt complex that incorporated the organic ligand bound to cobalt ions. The catalyst film exhibited a low overpotential for electrocatalytic water oxidation (360 mV) and high oxygen evolution peak current densities of 9 and 2.7 mA cm -2 on glassy carbon and indium-doped tin oxide electrodes, respectively, at only 1.49 and 1.39 V (versus a normal hydrogen electrode), respectively, under neutral conditions. This finding, exemplified on the in situ generated cobalt complex, might be applicable to other molecular systems and suggests that the formation of a catalytic film in electrochemical water oxidation experiments is not always an indication of catalyst decomposition and the formation of nanoparticles. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Effects of electrolyzed oxidizing water on reducing Listeria monocytogenes contamination on seafood processing surfaces.

    Science.gov (United States)

    Liu, Chengchu; Duan, Jingyun; Su, Yi-Cheng

    2006-02-15

    The effects of electrolyzed oxidizing (EO) water on reducing Listeria monocytogenes contamination on seafood processing surfaces were studied. Chips (5 x 5 cm(2)) of stainless steel sheet (SS), ceramic tile (CT), and floor tile (FT) with and without crabmeat residue on the surface were inoculated with L. monocytogenes and soaked in tap or EO water for 5 min. Viable cells of L. monocytogenes were detected on all chip surfaces with or without crabmeat residue after being held at room temperature for 1 h. Soaking contaminated chips in tap water resulted in small-degree reductions of the organism (0.40-0.66 log cfu/chip on clean surfaces and 0.78-1.33 log cfu/chip on dirty surfaces). Treatments of EO water significantly (peffectiveness of EO water on inactivating Listeria cells. However, treatments of EO water also resulted in significant reductions of L. monocytogenes on dirty surfaces (2.33 log on SS and CT and 1.52 log on FT) when compared with tap water treatments. The antimicrobial activity of EO water was positively correlated with its chlorine content. High oxidation-reduction potential (ORP) of EO water also contributed significantly to its antimicrobial activity against L. monocytogenes. EO water was more effective than chlorine water on inactivating L. monocytogenes on surfaces and could be used as a chlorine alternative for sanitation purpose. Application of EO water following a thorough cleaning process could greatly reduce L. monocytogenes contamination in seafood processing environments.

  7. Spacecraft Water Regeneration by Catalytic Wet Air Oxidation Project

    Data.gov (United States)

    National Aeronautics and Space Administration — The objective of this project is to develop advanced catalysts for a volatile removal assembly used to purify spacecraft water. The innovation of the proposed...

  8. Advanced Electrochemical Oxidation Cell for Purification of Water Project

    Data.gov (United States)

    National Aeronautics and Space Administration — Vesitech, Inc. has developed a totally new class of water treatment technology utilizing novel carbon based electrodes that have been shown to electrochemically...

  9. Electrochemical and Spectroscopic Study of Mononuclear Ruthenium Water Oxidation Catalysts: A Combined Experimental and Theoretical Investigation

    KAUST Repository

    de Ruiter, J. M.

    2016-09-20

    One of the key challenges in designing light-driven artificial photosynthesis devices is the optimization of the catalytic water oxidation process. For this optimization it is crucial to establish the catalytic mechanism and the intermediates of the catalytic cycle, yet a full description is often difficult to obtain using only experimental data. Here we consider a series of mononuclear ruthenium water oxidation catalysts of the form [Ru(cy)(L)(H2O)](2+) (cy = p-cymene, L = 2,2\\'-bipyridine and its derivatives). The proposed catalytic cycle and intermediates are examined using density functional theory (DFT), radiation chemistry, spectroscopic techniques, and electrochemistry to establish the water oxidation mechanism. The stability of the catalyst is investigated using online electrochemical mass spectrometry (OLEMS). The comparison between the calculated absorption spectra of the proposed intermediates with experimental spectra, as well as free energy calculations with electrochemical data, provides strong evidence for the proposed pathway: a water oxidation catalytic cycle involving four proton-coupled electron transfer (PCET) steps. The thermodynamic bottleneck is identified as the third PCET step, which involves O-O bond formation. The good agreement between the optical and thermodynamic data and DFT predictions further confirms the general applicability of this methodology as a powerful tool in the characterization of water oxidation catalysts and for the interpretation of experimental observables.

  10. Ligand exchange and redox processes in iridium triazolylidene complexes relevant to catalytic water oxidation.

    Science.gov (United States)

    Petronilho, Ana; Llobet, Antoni; Albrecht, Martin

    2014-12-15

    Iridium(III) complexes containing a bidentate spectator ligand have emerged as powerful catalyst precursors for water oxidation. Here we investigate the initial steps of the transformation at the iridium center when using complex [IrCp*(pyr-trz)Cl] 1 (Cp* = pentamethylcyclopentadienyl, pyr-trz = 4-(2-pyridyl)-1,2,3-triazol-5-ylidene), a potent water oxidation catalyst precursor. Ligand exchange with water is facile and is reversed in the presence of chloride ions, while MeCN substitution is effective only from the corresponding aqua complex. A pKa of 8.3 for the aqua complex was determined, which is in agreement with strong electron donation from the triazolylidene ligand that is comparable to aryl anions. Evaluation of the pH-dependent oxidation process in aqueous media reveals two regimes (pH 4-8.5 and above pH 10.5) where proton-coupled electron transfer processes occur. These investigations will help to further optimize water oxidation catalysts and indicate that MeCN as a cosolvent has adverse effects for initiating water coordination in the oxidation process.

  11. The anti-aging and anti-oxidation effects of tea water extract in Caenorhabditis elegans.

    Science.gov (United States)

    Fei, Tianyi; Fei, Jian; Huang, Fang; Xie, Tianpei; Xu, Jifeng; Zhou, Yi; Yang, Ping

    2017-10-15

    Tea includes puer tea, black tea, green tea and many others. By using model organism Caenorhabditis elegans, the anti-aging and anti-oxidation effects of tea water extract were systemically examined in this study. We found that water extract of puer tea, black tea and green tea all increased the lifespan of worms, postponed Aβ-induced progressive paralysis in Alzheimer's disease transgenic worms, and improved the tolerance of worms to the oxidative stress induced by heavy metal Cr6+. Moreover, the anti-oxidation effects of tea water extract at low concentration were different among 4 kinds of brands of green tea. The underlying mechanisms were further explored using genetically manipulated-mutant worms. The anti-oxidative stress effects of green tea water extract depend on the dietary restriction and germline signaling pathways, but not the FOXO and mitochondrial respiratory chain signals. Therefore, tea water extract provides benefits of anti-aging, anti-AD and anti-oxidation. Copyright © 2017. Published by Elsevier Inc.

  12. Tracking Dynamic Northern Surface Water Changes with High-Frequency Planet CubeSat Imagery

    Directory of Open Access Journals (Sweden)

    Sarah W. Cooley

    2017-12-01

    Full Text Available Recent deployments of CubeSat imagers by companies such as Planet may advance hydrological remote sensing by providing an unprecedented combination of high temporal and high spatial resolution imagery at the global scale. With approximately 170 CubeSats orbiting at full operational capacity, the Planet CubeSat constellation currently offers an average revisit time of <1 day for the Arctic and near-daily revisit time globally at 3 m spatial resolution. Such data have numerous potential applications for water resource monitoring, hydrologic modeling and hydrologic research. Here we evaluate Planet CubeSat imaging capabilities and potential scientific utility for surface water studies in the Yukon Flats, a large sub-Arctic wetland in north central Alaska. We find that surface water areas delineated from Planet imagery have a normalized root mean square error (NRMSE of <11% and geolocation accuracy of <10 m as compared with manual delineations from high resolution (0.3–0.5 m WorldView-2/3 panchromatic satellite imagery. For a 625 km2 subarea of the Yukon Flats, our time series analysis reveals that roughly one quarter of 268 lakes analyzed responded to changes in Yukon River discharge over the period 23 June–1 October 2016, one half steadily contracted, and one quarter remained unchanged. The spatial pattern of observed lake changes is heterogeneous. While connections to Yukon River control the hydrologically connected lakes, the behavior of other lakes is complex, likely driven by a combination of intricate flow paths, underlying geology and permafrost. Limitations of Planet CubeSat imagery include a lack of an automated cloud mask, geolocation inaccuracies, and inconsistent radiometric calibration across multiple platforms. Although these challenges must be addressed before Planet CubeSat imagery can achieve its full potential for large-scale hydrologic research, we conclude that CubeSat imagery offers a powerful new tool for the study and

  13. Historical Tracking of Nitrate in Contrasting Vineyard Using Water Isotopes and Nitrate Depth Profiles

    Science.gov (United States)

    Sprenger, M.; Erhardt, M.; Riedel, M.; Weiler, M.

    2015-12-01

    The European Water Framework Directive (EWFD) aims to achieve a good chemical status for the groundwater bodies in Europe by the year 2015. Despite the effort to reduce the nitrate pollution from agriculture within the last two decades, there are still many groundwater aquifers that exceed nitrate concentrations above the EWFD threshold of 50 mg/l. Viticulture is seen as a major contributor of nitrate leaching and sowing of a green cover was shown to have a positive effect on lowering the nitrate loads in the upper 90 cm of the soil. However, the consequences for nitrate leaching into the subsoil were not yet tested. We analyzed the nitrate concentrations and pore water stable isotope composition to a depth of 380 cm in soil profiles under an old vineyard and a young vineyard with either soil tillage or permanent green cover in between the grapevines. The pore water stable isotopes were used to calibrate a soil physical model, which was then used to infer the age of the soil water at different depths. This way, we could relate elevated nitrate concentrations below an old vineyard to tillage processes that took place during the winter two years before the sampling. We further showed that the elevated nitrate concentration in the subsoil of a young vineyard can be related to the soil tillage prior to the planting of the new vineyard. If the soil is kept bare due to tillage, a nitrate concentration of 200 kg NO3--N/ha is found in 290 to 380 cm depth 2.5 years after the installation of the vineyard. The amount of nitrate leaching is considerably reduced due to a seeded green cover between the grapevines that takes up a high share of the mobilized nitrate reducing a potential contamination of the groundwater.

  14. Tracking Bottom Waters in the Southern Adriatic Sea Applying Seismic Oceanography Techniques

    Science.gov (United States)

    2011-10-05

    profile so the weak thermohaline reflections can be visualized 3. The Adriatic context The general circulation of the Adriatic Sea is characterized by...Reflectivity Thermohaline structures Southern Adriatic Sea ABSTRACT We present the first results from the seismic oceanography (SO) cruise ADRIASE1SMIC...where we successfully imaged thermohaline fine structures in the shallow water environment (50-150 m) of the southern Adriatic Sea during March

  15. Tracking atmospheric boundary layer dynamics with water vapor D-excess observations

    KAUST Repository

    Parkes, Stephen

    2015-04-01

    Stable isotope water vapor observations present a history of hydrological processes that have impacted on an air mass. Consequently, there is scope to improve our knowledge of how different processes impact on humidity budgets by determining the isotopic end members of these processes and combining them with in-situ water vapor measurements. These in-situ datasets are still rare and cover a limited geographical expanse, so expanding the available data can improve our ability to define isotopic end members and knowledge about atmospheric humidity dynamics. Using data collected from an intensive field campaign across a semi-arid grassland site in eastern Australia, we combine multiple methods including in-situ stable isotope observations to study humidity dynamics associated with the growth and decay of the atmospheric boundary layer and the stable nocturnal boundary layer. The deuterium-excess (D-excess) in water vapor is traditionally thought to reflect the sea surface temperature and relative humidity at the point of evaporation over the oceans. However, a number of recent studies suggest that land-atmosphere interactions are also important in setting the D-excess of water vapor. These studies have shown a highly robust diurnal cycle for the D-excess over a range of sites that could be exploited to better understand variations in atmospheric humidity associated with boundary layer dynamics. In this study we use surface radon concentrations as a tracer of surface layer dynamics and combine these with the D-excess observations. The radon concentrations showed an overall trend that was inversely proportional to the D-excess, with early morning entrainment of air from the residual layer of the previous day both diluting the radon concentration and increasing the D-excess, followed by accumulation of radon at the surface and a decrease in the D-excess as the stable nocturnal layer developed in the late afternoon and early evening. The stable nocturnal boundary layer

  16. The production of magnetic nanoparticles of Iron Oxide by arc discharge in water

    Science.gov (United States)

    Yousefi, Hamid Reza; Fathollah, Sara; Nikeyn, Maryam; Khatami, Shohreh

    2012-10-01

    Nanoparticles can be utilized for any practical application. In recent years; considerable attention has been paid to iron oxide magnetic. Iron oxide nanoparticles are the class of nanoparticle which can have useful magnetic properties. In this research, magnetic iron oxide nanoparticles were produced by Arc discharge method in water. Structural analysis carried out by X-ray diffraction analysis (XRD), Scanning Electron Microscopy (SEM), and Spectrophotometer. Various magnetic nanoparticles like iron carbide (Fe3c), magnetic iron oxide (magnetite /maghemite) are obtained by arc discharge method in water. In this work have been showed, the influence of the time duration on the number of magnetic nanoparticles and the influence of the gap between the two electrodes on particle structure and size distribution. Furthermore, when iron nanoparticles are used under applied magnetic field, the particles would move in the direction of magnetic field. When the magnetic field is removed, the particles stop moving and still remain stably suspend in the dielectric liquid.

  17. Catalyzed Water Oxidation by Solar Irradiation of Band-Gap-Narrowed Semiconductors (Part 2. Overview).

    Energy Technology Data Exchange (ETDEWEB)

    Fujita,E.; Khalifah, P.; Lymar, S.; Muckerman, J.T.; Rodriguez, J.

    2008-03-18

    The objectives of this report are: (1) Investigate the catalysis of water oxidation by cobalt and manganese hydrous oxides immobilized on titania or silica nanoparticles, and dinuclear metal complexes with quinonoid ligands in order to develop a better understanding of the critical water oxidation chemistry, and rationally search for improved catalysts. (2) Optimize the light-harvesting and charge-separation abilities of stable semiconductors including both a focused effort to improve the best existing materials by investigating their structural and electronic properties using a full suite of characterization tools, and a parallel effort to discover and characterize new materials. (3) Combine these elements to examine the function of oxidation catalysts on Band-Gap-Narrowed Semiconductor (BGNSC) surfaces and elucidate the core scientific challenges to the efficient coupling of the materials functions.

  18. Catalyzed Water Oxidation by Solar Irradiation of Band-Gap-Narrowed Semiconductors (Part 1. Overview).

    Energy Technology Data Exchange (ETDEWEB)

    Fujita,E.; Khalifah, P.; Lymar, S.; Muckerman, J.T.; Rodgriguez, J.

    2008-03-18

    The objectives of this report are: (1) Investigate the catalysis of water oxidation by cobalt and manganese hydrous oxides immobilized on titania or silica nanoparticles, and dinuclear metal complexes with quinonoid ligands in order to develop a better understanding of the critical water oxidation chemistry, and rationally search for improved catalysts. (2) Optimize the light-harvesting and charge-separation abilities of stable semiconductors including both a focused effort to improve the best existing materials by investigating their structural and electronic properties using a full suite of characterization tools, and a parallel effort to discover and characterize new materials. (3) Combine these elements to examine the function of oxidation catalysts on Band-Gap-Narrowed Semiconductor (BGNSC) surfaces and elucidate the core scientific challenges to the efficient coupling of the materials functions.

  19. Treatment of sewage sludge in supercritical water and evaluation of the combined process of supercritical water gasification and oxidation.

    Science.gov (United States)

    Qian, Lili; Wang, Shuzhong; Xu, Donghai; Guo, Yang; Tang, Xingying; Wang, Longfei

    2015-01-01

    Influences of temperature and oxidation coefficient (n) on sewage sludge treatment in supercritical water and its corresponding reaction mechanism were studied. Moreover, the combined process of supercritical water gasification (SCWG) and supercritical water oxidation (SCWO) was also investigated. The results show that ammonia nitrogen, phenols and pyridines are main refractory intermediates. The weight of solid products at 873K and n=4 is only 3.5wt.% of the initial weight, which is lower than that after combustion. Volatile organics in solid phase have almost released at 723K and n=0. Highest yield of combustible gases was obtained at n=0, and H2 yield can reach 11.81mol/kg at 873K. Furthermore, the combination of SCWG at 723K and SCWO at 873K with a total n=1 is feasible for its good effluent quality and low operation costs. Copyright © 2014 Elsevier Ltd. All rights reserved.

  20. Tracking stormwater discharge plumes and water quality of the Tijuana River with multispectral aerial imagery

    Science.gov (United States)

    Svejkovsky, Jan; Nezlin, Nikolay P.; Mustain, Neomi M.; Kum, Jamie B.

    2010-04-01

    Spatial-temporal characteristics and environmental factors regulating the behavior of stormwater runoff from the Tijuana River in southern California were analyzed utilizing very high resolution aerial imagery, and time-coincident environmental and bacterial sampling data. Thirty nine multispectral aerial images with 2.1-m spatial resolution were collected after major rainstorms during 2003-2008. Utilizing differences in color reflectance characteristics, the ocean surface was classified into non-plume waters and three components of the runoff plume reflecting differences in age and suspended sediment concentrations. Tijuana River discharge rate was the primary factor regulating the size of the freshest plume component and its shorelong extensions to the north and south. Wave direction was found to affect the shorelong distribution of the shoreline-connected fresh plume components much more strongly than wind direction. Wave-driven sediment resuspension also significantly contributed to the size of the oldest plume component. Surf zone bacterial samples collected near the time of each image acquisition were used to evaluate the contamination characteristics of each plume component. The bacterial contamination of the freshest plume waters was very high (100% of surf zone samples exceeded California standards), but the oldest plume areas were heterogeneous, including both polluted and clean waters. The aerial imagery archive allowed study of river runoff characteristics on a plume component level, not previously done with coarser satellite images. Our findings suggest that high resolution imaging can quickly identify the spatial extents of the most polluted runoff but cannot be relied upon to always identify the entire polluted area. Our results also indicate that wave-driven transport is important in distributing the most contaminated plume areas along the shoreline.

  1. Oxidation of the antibacterial agent norfloxacin during sodium hypochlorite disinfection of marine culture water.

    Science.gov (United States)

    Zhang, Yuanyuan; Rong, Chuan; Song, Yanqun; Wang, Yinghui; Pei, Jiying; Tang, Xinying; Zhang, Ruijie; Yu, Kefu

    2017-09-01

    Chlorination disinfection and antibiotic addition are two universal processes of marine culture. The generation of disinfection byproducts (DBPs) is unavoidable. Antibiotic residue not only pollutes water but also acts as a precursor to the production of new DBPs. The fate of antibiotic norfloxacin (NOR) in chlorination disinfection was investigated. It was observed that NOR could be oxidized by disinfection agent sodium hypochlorite, but the oxidation rate varied considerably with the type of disinfected water. For fresh water, marine culture water and sea water, the reaction rate constant was 0.066 min(-1), 0.466 min(-1) and 1.241 min(-1), respectively. The difference was primarily attributed to the promotion role of bromide ions in seawater and marine culture water. Moreover, the bromide ions could result in the generation of brominated DBPs (Br-DBPs). The kinetics, products, reaction centers and mechanisms were investigated. The active site of NOR was found to be the N4 atom on piperazinyl in fresh water. During marine culture water and sea water disinfection, the carboxyl on NOR was oxidized and two Br-DBPs were formed. This was attributed to the lowering of the reaction's required activation energy when performed in the presence of bromide ions. The Br-DBPs were also confirmed in real shrimp pond brackish water. Quantitative structure activity relationships and the total organic halogen analysis showed that the DBPs in marine culture water possessed stronger toxicological properties than the DBPs in fresh water. The toxicity increase was attributed to the production of Br-DBPs in the disinfection process of marine culture water. Copyright © 2017 Elsevier Ltd. All rights reserved.

  2. Heterogeneous Catalysis for Water Oxidation by an Iridium Complex Immobilized on Bipyridine-Periodic Mesoporous Organosilica.

    Science.gov (United States)

    Liu, Xiao; Maegawa, Yoshifumi; Goto, Yasutomo; Hara, Kenji; Inagaki, Shinji

    2016-07-04

    Heterogenization of metal-complex catalysts for water oxidation without loss of their catalytic activity is important for the development of devices simulating photosynthesis. In this study, efficient heterogeneous iridium complexes for water oxidation were prepared using bipyridine-bridged periodic mesoporous organosilica (BPy-PMO) as a solid chelating ligand. The BPy-PMO-based iridium catalysts (Ir-BPy-PMO) were prepared by postsynthetic metalation of BPy-PMO and characterized through physicochemical analyses. The Ir-BPy-PMOs showed high catalytic activity for water oxidation. The turnover frequency (TOF) values for Ir-BPy-PMOs were one order of magnitude higher than those of conventional heterogeneous iridium catalysts. The reusability and stability of Ir-BPy-PMO were also examined, and detailed characterization was conducted using powder X-ray diffraction, nitrogen adsorption, (13) C DD MAS NMR spectroscopy, TEM, and XAFS methods. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Supercritical water oxidation technology development paths for prevention of corrosion and deposition

    Energy Technology Data Exchange (ETDEWEB)

    Shapiro, C.; Garcia, K.; Barnes, C.; Beller, J. [EG and G Idaho Inc., Idaho Falls, ID (United States). Idaho National Engineering Lab.

    1994-12-31

    Supercritical Water Oxidation is being developed by the Department of Energy as a promising technology for treatment of mixed waste--that is waste that contains hazardous and radioactive constituents. The aim of this program has been to identify and resolve key technical challenges that have been barriers to commercialization of supercritical water oxidation. Initial testing with benchscale systems indicated that the overriding technical challenge for this technology was prevention of corrosion and deposition inside the reactor. A number of approaches are being pursued to resolve the issue of corrosion and deposition including alternate reactor designs, advanced material development and testing, salt separation processes, and analytical modeling of supercritical water oxidation systems. Ongoing projects in these areas are discussed along with plans for pilot plant testing with promising configurations.

  4. Influence of oxide films on primary water stress corrosion cracking initiation of alloy 600

    Energy Technology Data Exchange (ETDEWEB)

    Panter, J. [Framatome, Centre Technique, BP 181, 71205 Le Creusot cedex (France); Viguier, B. [Centre Inter-Universitaire de Recherche et d' Ingenierie des Materiaux (CIRIMAT), CNRS/INPT/UPS, ENSIACET, 118 Route de Narbonne, 31077 Toulouse cedex 04 (France)]. E-mail: Bernard.Viguier@ensiacet.fr; Cloue, J.-M. [Framatome, Centre Technique, BP 181, 71205 Le Creusot cedex (France); Foucault, M. [Framatome, Centre Technique, BP 181, 71205 Le Creusot cedex (France); Combrade, P. [Framatome, Centre Technique, BP 181, 71205 Le Creusot cedex (France); Andrieu, E. [Centre Inter-Universitaire de Recherche et d' Ingenierie des Materiaux (CIRIMAT), CNRS/INPT/UPS, ENSIACET, 118 Route de Narbonne, 31077 Toulouse cedex 04 (France)

    2006-01-01

    In the present study alloy 600 was tested in simulated pressurised water reactor (PWR) primary water, at 360 deg. C, under an hydrogen partial pressure of 30 kPa. These testing conditions correspond to the maximum sensitivity of alloy 600 to crack initiation. The resulting oxidised structures (corrosion scale and underlying metal) were characterised. A chromium rich oxide layer was revealed, the underlying metal being chromium depleted. In addition, analysis of the chemical composition of the metal close to the oxide scale had allowed to detect oxygen under the oxide scale and particularly in a triple grain boundary. Implication of such a finding on the crack initiation of alloy 600 is discussed. Significant diminution of the crack initiation time was observed for sample oxidised before stress corrosion tests. In view of these results, a mechanism for stress corrosion crack initiation of alloy 600 in PWR primary water was proposed.

  5. Influence of oxide films on primary water stress corrosion cracking initiation of alloy 600

    Science.gov (United States)

    Panter, J.; Viguier, B.; Cloué, J.-M.; Foucault, M.; Combrade, P.; Andrieu, E.

    2006-01-01

    In the present study alloy 600 was tested in simulated pressurised water reactor (PWR) primary water, at 360 °C, under an hydrogen partial pressure of 30 kPa. These testing conditions correspond to the maximum sensitivity of alloy 600 to crack initiation. The resulting oxidised structures (corrosion scale and underlying metal) were characterised. A chromium rich oxide layer was revealed, the underlying metal being chromium depleted. In addition, analysis of the chemical composition of the metal close to the oxide scale had allowed to detect oxygen under the oxide scale and particularly in a triple grain boundary. Implication of such a finding on the crack initiation of alloy 600 is discussed. Significant diminution of the crack initiation time was observed for sample oxidised before stress corrosion tests. In view of these results, a mechanism for stress corrosion crack initiation of alloy 600 in PWR primary water was proposed.

  6. Monitoring Interfacial Lipid Oxidation in Oil-in-Water Emulsions Using Spatially Resolved Optical Techniques.

    Science.gov (United States)

    Banerjee, Chiranjib; Westberg, Michael; Breitenbach, Thomas; Bregnhøj, Mikkel; Ogilby, Peter R

    2017-06-06

    The oxidation of lipids is an important phenomenon with ramifications for disciplines that range from food science to cell biology. The development and characterization of tools and techniques to monitor lipid oxidation are thus relevant. Of particular significance in this regard are tools that facilitate the study of oxidations at interfaces in heterogeneous samples (e.g., oil-in-water emulsions, cell membranes). In this article, we establish a proof-of-principle for methods to initiate and then monitor such oxidations with high spatial resolution. The experiments were performed using oil-in-water emulsions of polyunsaturated fatty acids (PUFAs) prepared from cod liver oil. We produced singlet oxygen at a point near the oil-water interface of a given PUFA droplet in a spatially localized two-photon photosensitized process. We then followed the oxidation reactions initiated by this process with the fluorescence-based imaging technique of structured illumination microscopy (SIM). We conclude that the approach reported herein has attributes well-suited to the study of lipid oxidation in heterogeneous samples.

  7. Optical modeling of nickel-base alloys oxidized in pressurized water reactor

    Energy Technology Data Exchange (ETDEWEB)

    Clair, A. [Laboratoire Interdisciplinaire Carnot de Bourgogne, UMR 6303 CNRS, Universite de Bourgogne, 9 avenue Alain Savary, BP 47870, 21078 Dijon cedex (France); Foucault, M.; Calonne, O. [Areva ANP, Centre Technique Departement Corrosion-Chimie, 30 Bd de l' industrie, BP 181, 71205 Le Creusot (France); Finot, E., E-mail: Eric.Finot@u-bourgogne.fr [Laboratoire Interdisciplinaire Carnot de Bourgogne, UMR 6303 CNRS, Universite de Bourgogne, 9 avenue Alain Savary, BP 47870, 21078 Dijon cedex (France)

    2012-10-01

    The knowledge of the aging process involved in the primary water of pressurized water reactor entails investigating a mixed growth mechanism in the corrosion of nickel-base alloys. A mixed growth induces an anionic inner oxide and a cationic diffusion parallel to a dissolution-precipitation process forms the outer zone. The in situ monitoring of the oxidation kinetics requires the modeling of the oxide layer stratification with the full knowledge of the optical constants related to each component. Here, we report the dielectric constants of the alloys 600 and 690 measured by spectroscopic ellipsometry and fitted to a Drude-Lorentz model. A robust optical stratification model was determined using focused ion beam cross-section of thin foils examined by transmission electron microscopy. Dielectric constants of the inner oxide layer depleted in chromium were assimilated to those of the nickel thin film. The optical constants of both the spinels and extern layer were determined. - Highlights: Black-Right-Pointing-Pointer Spectroscopic ellipsometry of Ni-base alloy oxidation in pressurized water reactor Black-Right-Pointing-Pointer Measurements of the dielectric constants of the alloys Black-Right-Pointing-Pointer Optical simulation of the mixed oxidation process using a three stack model Black-Right-Pointing-Pointer Scattered crystallites cationic outer layer; linear Ni-gradient bottom layer Black-Right-Pointing-Pointer Determination of the refractive index of the spinel and the Cr{sub 2}O{sub 3} layers.

  8. Selective oxidation of organic compounds in waste water by ozone-based oxidation processes

    NARCIS (Netherlands)

    Boncz, M.A.

    2002-01-01

    For many different types of waste water, treatment systems have been implemented in the past decades. Waste water treatment is usually performed by biological processes, either aerobic or anaerobic, complemented with physical / chemical post treatment techniques.

  9. Transparent semiconducting amorphous cadmium-gallium-tin oxide films by magnetron sputtering with water vapor

    Science.gov (United States)

    Yanagi, Hiroshi; Koyamaishi, Yusuke; Sato, Chiyuki; Kimura, Yota

    2017-06-01

    Amorphous oxide semiconductors (including transparent ones) are attractive materials for next-generation optoelectronic applications. One of the difficulties with amorphous oxide semiconductors is the lack of high mobility (>10 cm2 V-1 s-1) at low carrier density (radio-frequency magnetron sputtering with a water-vapor pressure ≥0.25 Pa. In these amorphous films, the threshold carrier density for obtaining high mobility (˜10 cm2 V-1 s-1) is possibly four orders of magnitude lower than that in conventional amorphous oxide semiconductors such as amorphous In-Ga-Zn-O.

  10. An Alternative Reaction Pathway for Iridium Catalyzed Water Oxidation Driven by CAN

    KAUST Repository

    Bucci, Alberto

    2016-06-10

    The generation of solar fuels by means of a photosynthetic apparatus strongly relies on the development of an efficient water oxidation catalyst (WOC). Cerium ammonium nitrate (CAN) is the most commonly used sacrificial oxidant to explore the potentiality of WOCs. It is usually assumed that CAN has the unique role to oxidatively energize WOCs, making them capable to offer a low energy reaction pathway to transform H2O to O2. Herein we show that CAN might have a much more relevant and direct role in WO, mainly related to the capture and liberation of O–O containing molecular moieties.

  11. Water and the oxidation state of subduction zone magmas.

    Science.gov (United States)

    Kelley, Katherine A; Cottrell, Elizabeth

    2009-07-31

    Mantle oxygen fugacity exerts a primary control on mass exchange between Earth's surface and interior at subduction zones, but the major factors controlling mantle oxygen fugacity (such as volatiles and phase assemblages) and how tectonic cycles drive its secular evolution are still debated. We present integrated measurements of redox-sensitive ratios of oxidized iron to total iron (Fe3+/SigmaFe), determined with Fe K-edge micro-x-ray absorption near-edge structure spectroscopy, and pre-eruptive magmatic H2O contents of a global sampling of primitive undegassed basaltic glasses and melt inclusions covering a range of plate tectonic settings. Magmatic Fe3+/SigmaFe ratios increase toward subduction zones (at ridges, 0.13 to 0.17; at back arcs, 0.15 to 0.19; and at arcs, 0.18 to 0.32) and correlate linearly with H2O content and element tracers of slab-derived fluids. These observations indicate a direct link between mass transfer from the subducted plate and oxidation of the mantle wedge.

  12. Possibilities of practical usage of dispersed aluminim oxidation by liquid water

    Science.gov (United States)

    Larichev, M. N.; Laricheva, O. O.; Shaitura, N. S.; Shkolnikov, E. I.

    2012-12-01

    The goal of this work is to show the possibility of practical usage of the environmentally pure oxidation process of preliminarily dispersed aluminum (aluminum powders of the ASD or PAD grade according to TU (Technical Specifications) 48-5-226-87, which are serially produced in industry) with liquid water in order to obtain gaseous hydrogen in volumes sufficient to provide the operation of energizers based on airhydrogen fuel cells (AHFC) for portable and stationary devices (up to 3 kW). It is shown that the synthesis of aluminum oxides-hydroxides with the specified phase and chemical compositions as well as the particle shape and size can be provided simultaneously with producing commercial hydrogen. The practical usage of hydrogen, which is formed in the oxidation reaction of metallic aluminum with liquid water at pressures close to atmospheric (particularly, to service AHFCs), requires reaction intensification to increase the oxidation rate of aluminum. In this work, we considered the aspects of practical implementation of thermal, ultrasonic, and chemical activation as well as their combinations for this purpose. As the chemical activator of oxidation, we used the additives of calcium oxide (<5% of the mass of oxidized aluminum). Application of each activation method affects the phase and chemical compositions as well as the structure of formed aluminum hydroxides, which provides the possibility of their reproducible production. Thus, simultaneously with the production of commercial hydrogen, solid oxidation products satisfying the needs of industry in aluminum oxides and having the specified composition, purity, and particle shape and size can be synthesized. The acquired experimental results and elements of the design of specially developed industrial apparatuses, which were used when performing this work, can be applied when designing the model of the hydrogen generator—the prototype of the hydrogen generator for portable and stationary devices or devices

  13. Lipid oxidation in water-in-olive oil emulsions initiated by a lipophilic radical source.

    Science.gov (United States)

    Mosca, Monica; Ceglie, Andrea; Ambrosone, Luigi

    2010-03-18

    The lipophilic 2,2'-azobis(2,4-dimethylvaleronitrile) (AMVN) was used to study thoroughly the oxidation reaction in a model water-in-olive oil emulsion system. This radical species decomposes thermally generating a constant flux of radicals in the oil phase. The dissociation constant k(d) in olive oil at 40 degrees C for AMVN was calculated as 2.5 x 10(-4) min(-1) and the rate of initiation of the oxidation reaction, R(i) was calculated by using vitamin E as antioxidant. The olive oil oxidation in emulsion was monitored by measuring the hydroperoxide concentration by a sensitive fluorimetric method. The DPPP (diphenyl-1-pyrenylphosphine) was used as a probe because it reacts stoichiometrically with hydroperoxides to yield a fluorescent product, the diphenyl-1-pyrenylphosphine oxide (DPPP-O). Oxidation data together with emulsion droplet size data showed that in the presence of radical initiator and a large interface, the oxidation reaction is accelerated in W/Olive oil emulsion with respect to whole oil. The mediation of the surface area of water droplets is surely involved in this process because the addition of saturated solutions of ascorbic acid (AA) dispersed in the oil brings about the strong reduction of the oxidation rate even in the presence of the highest AMVN quantity.

  14. Crossing the divide between homogeneous and heterogeneous catalysis in water oxidation.

    Science.gov (United States)

    Vannucci, Aaron K; Alibabaei, Leila; Losego, Mark D; Concepcion, Javier J; Kalanyan, Berç; Parsons, Gregory N; Meyer, Thomas J

    2013-12-24

    Enhancing the surface binding stability of chromophores, catalysts, and chromophore-catalyst assemblies attached to metal oxide surfaces is an important element in furthering the development of dye sensitized solar cells, photoelectrosynthesis cells, and interfacial molecular catalysis. Phosphonate-derivatized catalysts and molecular assemblies provide a basis for sustained water oxidation on these surfaces in acidic solution but are unstable toward hydrolysis and loss from surfaces as the pH is increased. Here, we report enhanced surface binding stability of a phosphonate-derivatized water oxidation catalyst over a wide pH range (1-12) by atomic layer deposition of an overlayer of TiO2. Increased stability of surface binding, and the reactivity of the bound catalyst, provides a hybrid approach to heterogeneous catalysis combining the advantages of systematic modifications possible by chemical synthesis with heterogeneous reactivity. For the surface-stabilized catalyst, greatly enhanced rates of water oxidation are observed upon addition of buffer bases -H2PO(-)(4)/HPO(2-)(4), B(OH)3/B(OH)2 O-, HPO(2-)4 /PO(3-)(4) - and with a pathway identified in which O-atom transfer to OH(-) occurs with a rate constant increase of 10(6) compared to water oxidation in acid.

  15. Polyoxometalate electrocatalysts based on earth-abundant metals for efficient water oxidation in acidic media

    Science.gov (United States)

    Blasco-Ahicart, Marta; Soriano-López, Joaquín; Carbó, Jorge J.; Poblet, Josep M.; Galan-Mascaros, J. R.

    2018-01-01

    Water splitting is a promising approach to the efficient and cost-effective production of renewable fuels, but water oxidation remains a bottleneck in its technological development because it largely relies on noble-metal catalysts. Although inexpensive transition-metal oxides are competitive water oxidation catalysts in alkaline media, they cannot compete with noble metals in acidic media, in which hydrogen production is easier and faster. Here, we report a water oxidation catalyst based on earth-abundant metals that performs well in acidic conditions. Specifically, we report the enhanced catalytic activity of insoluble salts of polyoxometalates with caesium or barium counter-cations for oxygen evolution. In particular, the barium salt of a cobalt-phosphotungstate polyanion outperforms the state-of-the-art IrO2 catalyst even at pH < 1, with an overpotential of 189 mV at 1 mA cm-2. In addition, we find that a carbon-paste conducting support with a hydrocarbon binder can improve the stability of metal-oxide catalysts in acidic media by providing a hydrophobic environment.

  16. Using Iron-Manganese Co-Oxide Filter Film to Remove Ammonium from Surface Water

    Directory of Open Access Journals (Sweden)

    Ruifeng Zhang

    2017-07-01

    Full Text Available An iron-manganese co-oxide filter film (MeOx has been proven to be a good catalyst for the chemical catalytic oxidation of ammonium in groundwater. Compared with groundwater, surface water is generally used more widely and has characteristics that make ammonium removal more difficult. In this study, MeOx was used to remove ammonium from surface water. It indicated that the average ammonium removal efficiency of MeOx was greater than 90%, even though the water quality changed dramatically and the water temperature was reduced to about 6–8 °C. Then, through inactivating microorganisms, it showed that the removal capability of MeOx included both biological (accounted for about 41.05% and chemical catalytic oxidation and chemical catalytic oxidation (accounted for about 58.95%. The investigation of the characterizations suggested that MeOx was formed by abiotic ways and the main elements on the surface of MeOx were distributed homogenously. The analysis of the catalytic oxidation process indicated that ammonia nitrogen may interact with MeOx as both ammonia molecules and ammonium ions and the active species of O2 were possibly •O and O2−.

  17. BEHAVIOR OF THE CHANGJIANG DILUTED WATER IN THE EAST CHINA SEA OBSERVED WITH SATELLITE TRACKING DRIFTER

    Directory of Open Access Journals (Sweden)

    Syful Anas

    2012-11-01

    Full Text Available The Changjiang River is the largest river in China with an average discharge of 9x1011 m3 /year . The Changjiang river supplies about 80% of total discharge of fresh water from rivers around the Yellow Sea, East China Sea and Bohai Sea. Its monthly mean transport has a large seasonal variation from 103 m3s-1 in January to 4.8x 104 m3s-1 in July around an annual mean of 3 x104 m3s-1 , and large inter annual variation in the annual mean from 2,2x 103 to 3,5 x 103 m3s-1 during the 19-year period from 1970 to 1988 (Yanagi, 1994 . The East China Sea Current, associated with the Changjiang discharge, flows southward along the Fujian and the Zhejiang Coast of China in winter and Northeastward to the Cheju island in summer, which forms thin low salinity plume called Changjiang Diluted Water (CDW in summer (Breadsley. et al , 1983, 1985; Hu, 1994, Guan ,1994.CDW moves differently in season. It moves southward in winter and eastward in summer according to its salinity distribution. The relation between wind and movement of the low salinity water also has been suggested in many ways.Generally all of drifter moved northeastward at first, then after 10 days each drifter moved to different sites. Each drifter moving though velocities is about 0.1 m/s and 0.2 m/s. Most of drifters were generally moving to northeastward to the right of the wind direction at these events. It indicates that the sudden changes of drifters trajectory are caused by abrupt changes of winds.Temporal variation in salinity gradually increase during the drifters were in the moved eastward . The salinity rapidly increase during the typhoon passage. Before and after the salinity rapidly increase during typhoon passage, it was mostly constant or very gentle.The vertical velocity generated by wind just after deployment drifters for ten days in drifter deployment in 2007 was about 10-5 – 10-6 ms-1. The vertical velocity during typhoon passage on August 2007 was larger than on passed the

  18. Oxidative Stress State Is Associated with Left Ventricular Mechanics Changes, Measured by Speckle Tracking in Essential Hypertensive Patients

    OpenAIRE

    Luis Antonio Moreno-Ruíz; David Ibarra-Quevedo; Erika Rodríguez-Martínez; Maldonado, Perla D.; Benito Sarabia-Ortega; José Gustavo Hernández-Martínez; Beda Espinosa-Caleti; Beatriz Mendoza-Pérez; Selva Rivas-Arancibia

    2015-01-01

    The oxidative stress state is characterized by an increase in oxygen reactive species that overwhelms the antioxidant defense; we do not know if these pathological changes are correlated with alterations in left ventricular mechanics. The aim was correlating the oxidative stress state with the left ventricular global longitudinal strain (GLS) and the left ventricular end diastolic pressure (LVEDP). Twenty-five patients with essential hypertension and 25 controls paired by age and gender were ...

  19. Catalysis of the electrochemical water oxidation to oxygen

    NARCIS (Netherlands)

    Díaz Morales, Oscar Alfonso

    2015-01-01

    This thesis discusses the parameters affecting the catalysis for the electrochemical conversion of water into oxygen. The slow kinetics for the oxygen evolution reaction (OER) is one of the major bottlenecks in the solar energy-to-fuels conversion process, which reduces the efficiency for the

  20. Slab track

    OpenAIRE

    Golob, Tina

    2014-01-01

    The last 160 years has been mostly used conventional track with ballasted bed, sleepers and steel rail. Ensuring the high speed rail traffic, increasing railway track capacities, providing comfortable and safe ride as well as high reliability and availability railway track, has led to development of innovative systems for railway track. The so-called slab track was first built in 1972 and since then, they have developed many different slab track systems around the world. Slab track was also b...

  1. Promotion of water-mediated carbon removal by nanostructured barium oxide/nickel interfaces in solid oxide fuel cells

    Science.gov (United States)

    Yang, Lei; Choi, YongMan; Qin, Wentao; Chen, Haiyan; Blinn, Kevin; Liu, Mingfei; Liu, Ping; Bai, Jianming; Tyson, Trevor A.; Liu, Meilin

    2011-01-01

    The existing Ni-yttria-stabilized zirconia anodes in solid oxide fuel cells (SOFCs) perform poorly in carbon-containing fuels because of coking and deactivation at desired operating temperatures. Here we report a new anode with nanostructured barium oxide/nickel (BaO/Ni) interfaces for low-cost SOFCs, demonstrating high power density and stability in C3H8, CO and gasified carbon fuels at 750°C. Synchrotron-based X-ray analyses and microscopy reveal that nanosized BaO islands grow on the Ni surface, creating numerous nanostructured BaO/Ni interfaces that readily adsorb water and facilitate water-mediated carbon removal reactions. Density functional theory calculations predict that the dissociated OH from H2O on BaO reacts with C on Ni near the BaO/Ni interface to produce CO and H species, which are then electrochemically oxidized at the triple-phase boundaries of the anode. This anode offers potential for ushering in a new generation of SOFCs for efficient, low-emission conversion of readily available fuels to electricity. PMID:21694705

  2. Promotion of water-mediated carbon removal by nanostructured barium oxide/nickel interfaces in solid oxide fuel cells.

    Science.gov (United States)

    Yang, Lei; Choi, YongMan; Qin, Wentao; Chen, Haiyan; Blinn, Kevin; Liu, Mingfei; Liu, Ping; Bai, Jianming; Tyson, Trevor A; Liu, Meilin

    2011-06-21

    The existing Ni-yttria-stabilized zirconia anodes in solid oxide fuel cells (SOFCs) perform poorly in carbon-containing fuels because of coking and deactivation at desired operating temperatures. Here we report a new anode with nanostructured barium oxide/nickel (BaO/Ni) interfaces for low-cost SOFCs, demonstrating high power density and stability in C(3)H(8), CO and gasified carbon fuels at 750°C. Synchrotron-based X-ray analyses and microscopy reveal that nanosized BaO islands grow on the Ni surface, creating numerous nanostructured BaO/Ni interfaces that readily adsorb water and facilitate water-mediated carbon removal reactions. Density functional theory calculations predict that the dissociated OH from H(2)O on BaO reacts with C on Ni near the BaO/Ni interface to produce CO and H species, which are then electrochemically oxidized at the triple-phase boundaries of the anode. This anode offers potential for ushering in a new generation of SOFCs for efficient, low-emission conversion of readily available fuels to electricity.

  3. Manganese compounds as catalysts for water oxidation and as CO releasing molecules

    OpenAIRE

    Berends, Hans-Martin

    2011-01-01

    This PhD thesis deals with several aspects of manganese chemistry and is divided into three parts. The first two concern the synthesis and characterization of manganese-based water oxidation catalysts. The four-electron oxidation of water to dioxygen is a key process of oxygenic photosynthesis in which solar energy is captured and stored in the form of carbohydrates. In nature, this reaction is catalyzed by a µ-oxido-Mn4Ca cluster, the oxygen evolving complex (OEC). Mimicking this reacti...

  4. Water as origin of hysteresis in zinc tin oxide thin-film transistors.

    Science.gov (United States)

    Fakhri, M; Johann, H; Görrn, P; Riedl, T

    2012-09-26

    The hysteresis behavior of transparent zinc tin oxide (ZTO) thin film transistors (TFTs) is identified to be a result of short-term bias stress induced by the measurement. The related density of shallow defect states can be adjusted by the amount of water in the ambient. Time-resolved studies of the TFTs under varied ambient demonstrate that hysteresis can be immediately switched on and off by the adsorption and desorption of water, respectively. These findings are expected to be of general importance also for other oxide-based TFTs.

  5. Thermal oxidation synthesis of crystalline iron-oxide nanowires on low-cost steel substrates for solar water splitting

    Science.gov (United States)

    Dlugosch, T.; Chnani, A.; Muralidhar, P.; Schirmer, A.; Biskupek, J.; Strehle, S.

    2017-08-01

    Iron-oxide and in particular its crystallographic phase hematite (α-Fe2O3) is a promising candidate for non-toxic, earth abundant and low cost photo-anodes in the field of photo-electrochemical water splitting. We report here on the synthesis of α-Fe2O3 nanowires by thermal oxidation of low-cost steel substrates. Nanowires grown in this manner exhibit often a blade-like shape but can also possess a wire-like geometry partly decorated at their tip with an iron-rich ellipsoidal head consisting also of crystalline iron-oxide. We show furthermore that these ellipsoidal heads represent suitable growth sites leading in some cases to an additional growth of so-called antenna nanowires. Besides nanowires also nanoflakes were frequently observed at the surface. We discuss the influence of the oxidation temperature and other synthesis parameters as well as dispute the current growth models. Finally, we show that our α-Fe2O3 nanostructures on steel are also photo-electrochemically active supporting in principle their use as photo-anode material.

  6. Water transport through graphene oxide membranes: the roles of driving forces.

    Science.gov (United States)

    Chong, J Y; Wang, B; Li, K

    2018-02-21

    Graphene oxide (GO) membranes have shown excellent selectivities in nanofiltration and pervaporation. However, the water transport mechanisms in the unique membrane laminar structure are still not well understood, especially in pervaporation which involves selective permeation and evaporation. Herein, water transport in GO membranes was tested under two different modes: pressure-driven permeation and pervaporation. The pure water flux was found to be 1-2 orders of magnitude higher in pervaporation due to the large capillary pressure induced by evaporation. The water flux in pervaporation was suggested to be limited by evaporation at room temperature but surface diffusion at high temperature.

  7. Graphene oxide/ferroferric oxide/polyethylenimine nanocomposites for Congo red adsorption from water.

    Science.gov (United States)

    Wang, Lina; Mao, Changming; Sui, Ning; Liu, Manhong; Yu, William W

    2017-04-01

    Graphene oxide/ferroferric oxide/polyethylenimine (GO/Fe 3 O 4 /PEI) nanocomposites were synthesized by an in situ growth of Fe 3 O 4 nanoparticles on GO sheets, and then modified by PEI. The GO/Fe 3 O 4 /PEI nanocomposites showed extremely high removal efficiency for anionic dye Congo Red (CR) due to the positively charged PEI molecules (methylene blue was also tested but with low adsorption capacity due to its cationic property). The CR removal capacity was 574.7 mg g -1 , higher than most of reported results. The adsorption kinetics could be well described by a pseudo-second-order model. Furthermore, GO/Fe 3 O 4 /PEI nanocomposites could be easily recycled by magnetic separation. The removal efficiency remained above 70% after five cycles.

  8. Application of human and animal viral microbial source tracking tools in fresh and marine waters from five different geographical areas.

    Science.gov (United States)

    Rusiñol, Marta; Fernandez-Cassi, Xavier; Hundesa, Ayalkibet; Vieira, Carmen; Kern, Anita; Eriksson, Irene; Ziros, Panos; Kay, David; Miagostovich, Marize; Vargha, Marta; Allard, Annika; Vantarakis, Apostolos; Wyn-Jones, Peter; Bofill-Mas, Sílvia; Girones, Rosina

    2014-08-01

    Integrated river basin management planning to mitigate the impacts of economic, demographic and climate change is an important issue for the future protection of water resources. Identifying sources of microbial contamination via the emerging science of Microbial Source Tracking (MST) plays a key role in risk assessment and the design of remediation strategies. Following an 18-month surveillance program within the EU-FP7-funded VIROCLIME project, specific MST tools were used to assess human markers such as adenoviruses (HAdV) and JC polyomaviruses (JCPyV) and porcine and bovine markers such as porcine adenoviruses (PAdV) and bovine polyomaviruses (BPyV) via quantification with real-time PCR to analyze surface water collected from five sites within different climatic zones: the Negro River (Brazil), Glafkos River (Greece), Tisza River (Hungary), Llobregat River (Spain) and Umeälven River (Sweden). The utility of the viral MST tools and the prevalence and abundance of specific human and animal viruses in the five river catchments and adjacent seawater, which is impacted by riverine contributions from the upstream catchments, were examined. In areas where no sanitation systems have been implemented, sewage can directly enter surface waters, and river water exhibited high viral loads; HAdV and JCPyV could be detected at mean concentrations of 10(5) and 10(4) Genome Copies/Liter (GC/L), respectively. In general, river water samples upstream of urban discharges presented lower human viral loads than downstream sampling sites, and those differences appeared to increase with urban populations but decrease in response to high river flow, as the elevated river water volume dilutes microbial loads. During dry seasons, river water flow decreases dramatically, and secondary effluents can represent the bulk of the riverine discharge. We also observed that ice cover that formed over the river during the winter in the studied areas in North Europe could preserve viral stability

  9. Electrochemical Water Oxidation by a Catalyst-Modified Metal-Organic Framework Thin Film

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Shaoyang; Pineda-Galvan, Yuliana; Maza, William A.; Epley, Charity C.; Zhu, Jie; Kessinger, Matthew C.; Pushkar, Yulia; Morris, Amanda J. (VP); (Purdue)

    2016-12-15

    Water oxidation, a key component in artificial photosynthesis, requires high overpotentials and exhibits slow reaction kinetics that necessitates the use of stable and efficient heterogeneous water-oxidation catalysts (WOCs). Here, we report the synthesis of UiO-67 metal–organic framework (MOF) thin films doped with [Ru(tpy)(dcbpy)OH2]2+ (tpy=2,2':6',2''-terpyridine, dcbpy=5,5'-dicarboxy-2,2'-bipyridine) on conducting surfaces and their propensity for electrochemical water oxidation. The electrocatalyst oxidized water with a turnover frequency (TOF) of (0.2±0.1) s-1 at 1.71 V versus the normal hydrogen electrode (NHE) in buffered solution (pH~7) and exhibited structural and electrochemical stability. The electroactive sites were distributed throughout the MOF thin film on the basis of scan-ratedependent voltammetry studies. This work demonstrates a promising way to immobilize large concentrations of electroactive WOCs into a highly robust MOF scaffold and paves the way for future photoelectrochemical water-splitting systems.

  10. Water Oxidation Catalysis by Co(II) Impurities in Co(III) 4 O 4 Cubanes

    Energy Technology Data Exchange (ETDEWEB)

    Ullman, Andrew M.; Liu, Yi; Huynh, Michael; Bediako, D. Kwabena; Wang, Hongsen; Anderson, Bryce L.; Powers, David C.; Breen, John J.; Abruña, Héctor D.; Nocera, Daniel G.

    2014-12-17

    The observed water oxidation activity of the compound class Co4O4(OAc)4(Py–X)4 emanates from a Co(II) impurity. This impurity is oxidized to produce the well-known Co-OEC heterogeneous cobaltate catalyst, which is an active water oxidation catalyst. We present results from electron paramagnetic resonance spectroscopy, nuclear magnetic resonance line broadening analysis, and electrochemical titrations to establish the existence of the Co(II) impurity as the major source of water oxidation activity that has been reported for Co4O4 molecular cubanes. Differential electrochemical mass spectrometry is used to characterize the fate of glassy carbon at water oxidizing potentials and demonstrate that such electrode materials should be used with caution for the study of water oxidation catalysis.

  11. Light induced oxidative water splitting in photosynthesis: energetics, kinetics and mechanism.

    Science.gov (United States)

    Renger, Gernot

    2011-01-01

    The essential steps of photosynthetic water splitting take place in Photosystem II (PSII) and comprise three different reaction sequences: (i) light induced formation of the radical pair P680(+)Q(A)(-), (ii) P680(+) driven oxidative water splitting into O(2) and four protons, and (iii) two step plastoquinone reduction to plastoquinol by Q(A)(-). This mini-review briefly summarizes our state of knowledge on energetics, kinetics and mechanism of oxidative water splitting. Essential features of the two types of reactions involved are described: (a) P680(+) reduction by the redox active tyrosine Y(z) and (b) sequence of oxidation steps induced by Y(z)(ox) in the water-oxidizing complex (WOC). The rate of the former reaction is limited by the non-adiabatic electron transfer (NET) step and the multi-phase kinetics shown to originate from a sequence of relaxation processes. In marked contrast, the rate of the stepwise oxidation by Y(z)(ox) of the WOC up to the redox level S(3) is not limited by NET but by trigger reactions which probably comprise proton shifts and/or conformational changes. The overall rate of the final reaction sequence leading to formation and release of O(2) is assumed to be limited by the electron transfer step from the S(3) state of WOC to Y(z)(ox) due to involvement of an endergonic redox equilibrium. Currently discussed controversial ideas on possible pathways are briefly outlined. Several crucial points of the mechanism of oxidative water splitting, like O-O bond formation, role of local proton shift(s), details of hydrogen bonding, are still not clarified and remain a challenging topic of future research. Copyright © 2011 Elsevier B.V. All rights reserved.

  12. Permanent water swelling effect in low temperature thermally reduced graphene oxide

    Science.gov (United States)

    Papamatthaiou, S.; Argyropoulos, D.-P.; Masurkar, A.; Cavallari, M. R.; Farmakis, F.; Kymissis, I.; Georgoulas, N.

    2017-06-01

    We demonstrate permanent water trapping in reduced graphene oxide after high relative humidity exposure. For this purpose, we grew graphene oxide films via spin-coating on glass substrates followed by thermal reduction. The electrical resistance of the planar device was then measured. We observed that resistance is significantly increased after water vapor exposure and remains stable even after 250 days in ambient conditions. Various techniques were applied to desorb the water and decrease (recover) the material's resistance, but it was achieved only with low temperature thermal annealing (180 °C) under forming gas (H2/N2 mixture). The permanent effect of water absorption was also detected by x-ray photoelectron spectroscopy.

  13. Post-treatment of reclaimed waste water based on an electrochemical advanced oxidation process

    Science.gov (United States)

    Verostko, Charles E.; Murphy, Oliver J.; Hitchens, G. D.; Salinas, Carlos E.; Rogers, Tom D.

    1992-01-01

    The purification of reclaimed water is essential to water reclamation technology life-support systems in lunar/Mars habitats. An electrochemical UV reactor is being developed which generates oxidants, operates at low temperatures, and requires no chemical expendables. The reactor is the basis for an advanced oxidation process in which electrochemically generated ozone and hydrogen peroxide are used in combination with ultraviolet light irradiation to produce hydroxyl radicals. Results from this process are presented which demonstrate concept feasibility for removal of organic impurities and disinfection of water for potable and hygiene reuse. Power, size requirements, Faradaic efficiency, and process reaction kinetics are discussed. At the completion of this development effort the reactor system will be installed in JSC's regenerative water recovery test facility for evaluation to compare this technique with other candidate processes.

  14. Application of Metal Oxide Heterostructures in Arsenic Removal from Contaminated Water

    Directory of Open Access Journals (Sweden)

    Lei Chen

    2014-01-01

    Full Text Available It has become one of the major environmental problems for people worldwide to be exposed to high arsenic concentrations through contaminated drinking water, and even the long-term intake of small doses of arsenic has a carcinogenic effect. As an efficient and economic approach for the purification of arsenic-containing water, the adsorbents in adsorption processes have been widely studied. Among a variety of adsorbents reported, the metal oxide heterostructures with high surface area and specific affinity for arsenic adsorption from aqueous systems have demonstrated a promising performance in practical applications. This review paper aims to summarize briefly the metal oxide heterostructures in arsenic removal from contaminated water, so as to provide efficient, economic, and robust solutions for water purification.

  15. Oxidative Stress State Is Associated with Left Ventricular Mechanics Changes, Measured by Speckle Tracking in Essential Hypertensive Patients

    Directory of Open Access Journals (Sweden)

    Luis Antonio Moreno-Ruíz

    2015-01-01

    Full Text Available The oxidative stress state is characterized by an increase in oxygen reactive species that overwhelms the antioxidant defense; we do not know if these pathological changes are correlated with alterations in left ventricular mechanics. The aim was correlating the oxidative stress state with the left ventricular global longitudinal strain (GLS and the left ventricular end diastolic pressure (LVEDP. Twenty-five patients with essential hypertension and 25 controls paired by age and gender were studied. All of the participants were subjected to echocardiography and biochemical determination of oxidative stress markers. The hypertensive patients, compared with control subjects, had significantly (p<0.05 higher levels of oxidized proteins (5.03±1.05 versus 4.06±0.63 nmol/mg, lower levels of extracellular superoxide dismutase (EC-SOD activity (0.045±0.02 versus 0.082±0.02 U/mg, higher LVEDP (16.2±4.5 versus 11.3±1.6 mm Hg, and lower GLS (−12% versus −16%. Both groups had preserved ejection fraction and the results showed a positive correlation of oxidized proteins with GLS (r=0.386, p=0.006 and LVEDP (r=0.389, p=0.005; we also found a negative correlation of EC-SOD activity with GLS (r=-0.404, p=0.004 and LVEDP (r=-0.347, p=0.014.

  16. Tracking the Structural and Electronic Configurations of a Cobalt Proton Reduction Catalyst in Water

    Energy Technology Data Exchange (ETDEWEB)

    Moonshiram, Dooshaye; Gimbert-Suriñach, Carolina [Institute; Guda, Alexander [International; Picon, Antonio; Lehmann, C. Stefan; Zhang, Xiaoyi; Doumy, Gilles; March, Anne Marie; Benet-Buchholz, Jordi [Institute; Soldatov, Alexander [International; Llobet, Antoni [Institute; Departament; Southworth, Stephen H.

    2016-08-09

    Time resolved X-ray absorption spectroscopy (X-TAS) has been used to study the light induced hydrogen evolution reaction catalyzed by a highly stable cobalt complex, [Ru(bpy)3]2+ photosensitizer and an equimolar mixture of sodium ascorbate/ascorbic acid electron donor in pure water. XANES and EXAFS analysis of a binary mixture of the octahedral Co(III) pre-catalyst and [Ru(bpy)3]2+ after illumination, revealed in-situ formation of a square pyramidal Co(II) intermediate, with electron transfer kinetics of 51 ns. On the other hand, X-TAS experiments of the complete photocatalytic system in the presence of the electron donor showed the formation of a square planar Co(I) intermediate species within a few nanoseconds followed by its decay in the microsecond timescales. The Co(I) structural assignment is supported by calculations based on density functional theory (DFT). At longer reaction times, we observe the formation of the initial Co(III) species concomitant to the decay of Co(I), thus closing the catalytic cycle. The experimental X-ray absorption spectra of the molecular species formed along the catalytic cycle are modeled using a combination of molecular orbital DFT calculations (DFT-MO) and Finite Difference Method (FDM). These findings allowed us to unequivocally assign the full mechanistic pathway followed by the catalyst as well as to determine the rate limiting step of the process, which consists in the protonation of the Co(I). This study provides a complete kinetics scheme for the hydrogen evolution reaction by a cobalt catalyst, revealing unique information for the development of better catalysts for the reductive side of hydrogen fuel cells.

  17. Human and Animal Fecal Contamination of Community Water Sources, Stored Drinking Water and Hands in Rural India Measured with Validated Microbial Source Tracking Assays.

    Science.gov (United States)

    Schriewer, Alexander; Odagiri, Mitsunori; Wuertz, Stefan; Misra, Pravas R; Panigrahi, Pinaki; Clasen, Thomas; Jenkins, Marion W

    2015-09-01

    We examined pathways of exposure to fecal contamination of human and animal origin in 24 villages in Odisha, India. In a cross-sectional study during the monsoon season, fecal exposure via community water sources (N = 123) and in the home (N = 137) was assessed using human- and nonhuman-associated Bacteroidales microbial source tracking (MST) markers and fecal coliforms (FCs). Detection rates and marker concentrations were examined to pinpoint pathways of human fecal exposure in the public and domestic domains of disease transmission in study communities. Human fecal markers were detected much more frequently in the domestic domain (45% of households) than in public domain sources (8% of ponds; 4% of groundwater drinking sources). Animal fecal markers were widely detected in both domains (74% of ponds, 96% of households, 10% of groundwater drinking sources), indicating ubiquitous risks of exposure to animal feces and zoonotic pathogens. This study confirms an often suggested contamination link from hands to stored water in the home in developing countries separately for mothers' and children's hands and both human and animal fecal contamination. In contrast to MST markers, FCs provided a poor metric to assess risks of exposure to fecal contamination of human origin in this rural setting. © The American Society of Tropical Medicine and Hygiene.

  18. Determination of absorbed dose to water in a clinical carbon ion beam by means of fluorescent nuclear track detectors, ionization chambers, and water calorimetry

    Energy Technology Data Exchange (ETDEWEB)

    Osinga-Blaettermann, Julia-Maria

    2016-12-20

    Until now, dosimetry of carbon ions with ionization chambers has not reached the same level of accuracy as of high-energy photons. This is mainly caused by the threefold higher uncertainty of the k{sub Q,Q{sub 0}}-factor of ionization chambers, which is derived by calculations due to a lack of experimental data. The current thesis comprises two major aims with respect to the dosimetry of carbon ion beams: first, the investigation of the potential of fluorescent nuclear track detectors for fluence-based dosimetry and second, the experimental determination of the k{sub Q,Q{sub 0}}-factor. The direct comparison of fluence- and ionization-based measurements has shown a significant discrepancy of 4.5 %, which re-opened the discussion on the accuracy of calculated k{sub Q,Q{sub 0}}-factors. Therefore, absorbed dose to water measurements by means of water calorimetry have been performed allowing for the direct calibration of ionization chambers and thus for the experimental determination of k{sub Q,Q{sub 0}}. For the first time it could be shown that the experimental determination of k{sub Q,Q{sub 0}} for carbon ion beams is achievable with a standard measurement uncertainty of 0.8 %. This corresponds to a threefold reduction of the uncertainty compared to calculated values and therefore enables to significantly decrease the overall uncertainty related to ionization-based dosimetry of clinical carbon ion beams.

  19. Prevention of enzymatic browning of Chinese yam (Dioscorea spp.) using electrolyzed oxidizing water.

    Science.gov (United States)

    Jia, Guo-Liang; Shi, Jing-Ying; Song, Zhan-Hua; Li, Fa-De

    2015-04-01

    In this study, the effects of electrolyzed oxidizing water (EOW) on the prevention of enzymatic browning of fresh-cut "Jiu Jinhuang" Chinese yam were investigated. The yams were immersed in the inhibitors for 25 min at 20 °C. Compared with the tap water (TW) treatment, the chromatic attributes were significantly different after 72 h of storage (P browning inhibitor. © 2015 Institute of Food Technologists®

  20. Water Radiolysis: Influence of Oxide Surfaces on H2 Production under Ionizing Radiation

    Directory of Open Access Journals (Sweden)

    Sophie Le Caër

    2011-02-01

    Full Text Available The radiolysis of water due to ionizing radiation results in the production of electrons, H· atoms, ·OH radicals, H3O+ ions and molecules (dihydrogen H2 and hydrogen peroxide H2O2. A brief history of the development of the understanding of water radiolysis is presented, with a focus on the H2 production. This H2 production is strongly modified at oxide surfaces. Different parameters accounting for this behavior are presented.

  1. Stripped sour water treatment by advanced oxidation processes

    OpenAIRE

    Guimarães, José R.; Gasparini, Mirthys C.; Maniero,Milena G.; Mendes, Carlos G. N.

    2012-01-01

    This study assessed the application of photolysis (UV), peroxidation (H2O2), peroxidation combined with ultraviolet light (UV/H2O2), Fenton’s reagent (H2O2/Fe(II)) and photo-Fenton (H2O2/Fe(II)/UV) processes in the treatment of stripped sour water from the Petrobras Replan Oil Refinery in Paulínia City, São Paulo State, Brazil. To evaluate the efficiency of the process, the concentration of dissolved organic carbon (DOC) was monitored throughout the reaction period. Among the evaluated proces...

  2. Kinetics of Chronic Oxidation of NBG-17 Nuclear Graphite by Water Vapor

    Energy Technology Data Exchange (ETDEWEB)

    Contescu, Cristian I [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Burchell, Timothy D [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Mee, Robert [Univ. of Tennessee, Knoxville, TN (United States)

    2015-05-01

    This report presents the results of kinetic measurements during accelerated oxidation tests of NBG-17 nuclear graphite by low concentration of water vapor and hydrogen in ultra-high purity helium. The objective is to determine the parameters in the Langmuir-Hinshelwood (L-H) equation describing the oxidation kinetics of nuclear graphite in the helium coolant of high temperature gas-cooled reactors (HTGR). Although the helium coolant chemistry is strictly controlled during normal operating conditions, trace amounts of moisture (predictably < 0.2 ppm) cannot be avoided. Prolonged exposure of graphite components to water vapor at high temperature will cause very slow (chronic) oxidation over the lifetime of graphite components. This behavior must be understood and predicted for the design and safe operation of gas-cooled nuclear reactors. The results reported here show that, in general, oxidation by water of graphite NBG-17 obeys the L-H mechanism, previously documented for other graphite grades. However, the characteristic kinetic parameters that best describe oxidation rates measured for graphite NBG-17 are different than those reported previously for grades H-451 (General Atomics, 1978) and PCEA (ORNL, 2013). In some specific conditions, certain deviations from the generally accepted L-H model were observed for graphite NBG-17. This graphite is manufactured in Germany by SGL Carbon Group and is a possible candidate for the fuel elements and reflector blocks of HTGR.

  3. Water-Gas Shift and Methane Reactivity on Reducible Perovskite-Type Oxides

    Science.gov (United States)

    2015-01-01

    Comparative (electro)catalytic, structural, and spectroscopic studies in hydrogen electro-oxidation, the (inverse) water-gas shift reaction, and methane conversion on two representative mixed ionic–electronic conducting perovskite-type materials La0.6Sr0.4FeO3−δ (LSF) and SrTi0.7Fe0.3O3−δ (STF) were performed with the aim of eventually correlating (electro)catalytic activity and associated structural changes and to highlight intrinsic reactivity characteristics as a function of the reduction state. Starting from a strongly prereduced (vacancy-rich) initial state, only (inverse) water-gas shift activity has been observed on both materials beyond ca. 450 °C but no catalytic methane reforming or methane decomposition reactivity up to 600 °C. In contrast, when starting from the fully oxidized state, total methane oxidation to CO2 was observed on both materials. The catalytic performance of both perovskite-type oxides is thus strongly dependent on the degree/depth of reduction, on the associated reactivity of the remaining lattice oxygen, and on the reduction-induced oxygen vacancies. The latter are clearly more reactive toward water on LSF, and this higher reactivity is linked to the superior electrocatalytic performance of LSF in hydrogen oxidation. Combined electron microscopy, X-ray diffraction, and Raman measurements in turn also revealed altered surface and bulk structures and reactivities. PMID:26045733

  4. Water oxidation by a cytochrome p450: mechanism and function of the reaction.

    Science.gov (United States)

    Prasad, Brinda; Mah, Derrick J; Lewis, Andrew R; Plettner, Erika

    2013-01-01

    P450(cam) (CYP101A1) is a bacterial monooxygenase that is known to catalyze the oxidation of camphor, the first committed step in camphor degradation, with simultaneous reduction of oxygen (O2). We report that P450(cam) catalysis is controlled by oxygen levels: at high O2 concentration, P450(cam) catalyzes the known oxidation reaction, whereas at low O2 concentration the enzyme catalyzes the reduction of camphor to borneol. We confirmed, using (17)O and (2)H NMR, that the hydrogen atom added to camphor comes from water, which is oxidized to hydrogen peroxide (H2O2). This is the first time a cytochrome P450 has been observed to catalyze oxidation of water to H2O2, a difficult reaction to catalyze due to its high barrier. The reduction of camphor and simultaneous oxidation of water are likely catalyzed by the iron-oxo intermediate of P450(cam) , and we present a plausible mechanism that accounts for the 1:1 borneol:H2O2 stoichiometry we observed. This reaction has an adaptive value to bacteria that express this camphor catabolism pathway, which requires O2, for two reasons: 1) the borneol and H2O2 mixture generated is toxic to other bacteria and 2) borneol down-regulates the expression of P450(cam) and its electron transfer partners. Since the reaction described here only occurs under low O2 conditions, the down-regulation only occurs when O2 is scarce.

  5. Removal of fluoride from water using iron oxide-hydroxide nanoparticles.

    Science.gov (United States)

    Raul, Prasanta Kumar; Devi, Rashmi Rekha; Umlong, Iohborlang M; Banerjee, Saumen; Singh, Lokendra; Purkait, Mihir

    2012-05-01

    A novel and facile method for the synthesis of uniform stoichiometric powder form of non-magnetic iron oxide-hydroxide nanoparticles with spherical morphology and its application for defluoridation of drinking water is reported. X-ray powder diffraction analysis (XRD), BET surface area, FTIR, field emission scanning electron microscopy (FESEM) and Transmission electron microscopy (TEM) images were used to characterize nanoscale iron oxide-hydroxide. Transmission electron microscopy (TEM) image revealed the formation of iron oxide-hydroxide nanoparticles with spherical morphology. The iron oxide-hydroxide nanoparticles showed an excellent ability to remove fluoride (F-) from contaminated water over a wide range of pH. The influences of temperature, stirring speed, pH, adsorbent dose and contact time were studied. The equilibrium data were tested with various isotherm models and finally, a calculation procedure was reported for the calculation of adsorbent requirement. The fluoride adsorbed nanoparticles was regenerated upto 70% using sodium hydroxide or hydrochloric acid solution. The iron oxide-hydroxide nanoparticles can be used as an effective and replicable adsorbent media for defluoridation of water in presence of competing anions like chloride, iodate, iodide and sulphate.

  6. Tracking inorganic foulants irreversibly accumulated on low-pressure membranes for treating surface water.

    Science.gov (United States)

    Yamamura, Hiroshi; Kimura, Katsuki; Higuchi, Kumiko; Watanabe, Yoshimasa; Ding, Qing; Hafuka, Akira

    2015-12-15

    While low-pressure membrane filtration processes (i.e., microfiltration and ultrafiltration) can offer precise filtration than sand filtration, they pose the problem of reduced efficiency due to membrane fouling. Although many studies have examined membrane fouling by organic substances, there is still not enough data available concerning membrane fouling by inorganic substances. The present research investigated changes in the amounts of inorganic components deposited on the surface of membrane filters over time using membrane specimens sampled thirteen times at arbitrary time intervals during pilot testing in order to determine the mechanism by which irreversible fouling by inorganic substances progresses. The experiments showed that the inorganic components that primarily contribute to irreversible fouling vary as filtration continues. It was discovered that, in the initial stage of operation, the main membrane-fouling substance was iron, whereas the primary membrane-fouling substances when operation finished were manganese, calcium, and silica. The amount of iron accumulated on the membrane increased up to the thirtieth day of operation, after which it reached a steady state. After the accumulation of iron became static, subsequent accumulation of manganese was observed. The fact that the removal rates of these inorganic components also increased gradually shows that the size of the exclusion pores of the membrane filter narrows as operation continues. Studying particle size distributions of inorganic components contained in source water revealed that while many iron particles are approximately the same size as membrane pores, the fraction of manganese particles slightly smaller than the pores in diameter was large. From these results, it is surmised that iron particles approximately the same size as the pores block them soon after the start of operation, and as the membrane pores narrow with the development of fouling, they become further blocked by manganese

  7. Influence of Adsorbed Water on the Oxygen Evolution Reaction on Oxides

    DEFF Research Database (Denmark)

    Siahrostami, Samira; Vojvodic, Aleksandra

    2015-01-01

    We study the interface between adsorbed water and stoichiometric, defect-free (110) rutile oxide surfaces of TiO2, RuO2, and IrO2 in order to understand how water influences the stabilities of the intermediates of the oxygen evolution reaction (OER). In our model the water is treated as explicitly...... molecules binding to bridging oxygens. The third chain interacts weakly and predominantly with the H2O molecules of the second layer, resembling bulk water. We find that the stability of the water layer close to the oxide surface is almost the same as the one found on flat metal surfaces, such as the Pt(111...... adsorbed H2O molecules, which are found to form two-dimensional water chains (layers) on all investigated oxide surfaces. The first chain formed by the most strongly bound H2O molecules is adsorbed on the 5-fold coordinated surface metal atoms. The second chain is composed of less strongly bound H2O...

  8. Water activity of aqueous solutions of ethylene oxide-propylene oxide block copolymers and maltodextrins

    Directory of Open Access Journals (Sweden)

    N. D. D. Carareto

    2010-03-01

    Full Text Available The water activity of aqueous solutions of EO-PO block copolymers of six different molar masses and EO/PO ratios and of maltodextrins of three different molar masses was determined at 298.15 K. The results showed that these aqueous solutions present a negative deviation from Raoult's law. The Flory-Huggins and UNIFAC excess Gibbs energy models were employed to model the experimental data. While a good agreement was obtained with the Flory-Huggins equation, discrepancies were observed when predicting the experimental behavior with the UNIFAC model. The water activities of ternary systems formed by a synthetic polymer, maltodextrin and water were also measured and used to test the predictive capability of both models.

  9. Plutonium Oxide Containment and the Potential for Water-Borne Transport as a Consequence of ARIES Oxide Processing Operations

    Energy Technology Data Exchange (ETDEWEB)

    Wayne, David Matthew [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Rowland, Joel C. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2015-02-01

    The question of oxide containment during processing and storage has become a primary concern when considering the continued operability of the Plutonium Facility (PF-4) at Los Alamos National Laboratory (LANL). An Evaluation of the Safety of the Situation (ESS), “Potential for Criticality in a Glovebox Due to a Fire” (TA55-ESS-14-002-R2, since revised to R3) first issued in May, 2014 summarizes these concerns: “The safety issue of fire water potentially entering a glovebox is: the potential for the water to accumulate in the bottom of a glovebox and result in an inadvertent criticality due to the presence of fissionable materials in the glovebox locations and the increased reflection and moderation of neutrons from the fire water accumulation.” As a result, the existing documented safety analysis (DSA) was judged inadequate and, while it explicitly considered the potential for criticality resulting from water intrusion into gloveboxes, criticality safety evaluation documents (CSEDs) for the affected locations did not evaluate the potential for fire water intrusion into a glovebox.

  10. Alpha Radiolysis of Sorbed Water on Uranium Oxides and Uranium Oxyfluorides

    Energy Technology Data Exchange (ETDEWEB)

    Icenhour, A.S.

    2003-09-10

    The radiolysis of sorbed water and other impurities contained in actinide oxides has been the focus of a number of studies related to the establishment of criteria for the safe storage and transport of these materials. Gamma radiolysis studies have previously been performed on uranium oxides and oxyfluorides (UO{sub 3}, U{sub 3}O{sub 8}, and UO{sub 2}F{sub 2}) to evaluate the long-term storage characteristics of {sup 233}U. This report describes a similar study for alpha radiolysis. Uranium oxides and oxyfluorides (with {sup 238}U as the surrogate for {sup 233}U) were subjected to relatively high alpha radiation doses (235 to 634 MGy) by doping with {sup 244}Cm. The typical irradiation time for these samples was about 1.5 years, which would be equivalent to more than 50 years irradiation by a {sup 233}U sample. Both dry and wet (up to 10 wt % water) samples were examined in an effort to identify the gas pressure and composition changes that occurred as a result of radiolysis. This study shows that several competing reactions occur during radiolysis, with the net effect that only very low pressures of hydrogen, nitrogen, and carbon dioxide are generated from the water, nitrate, and carbon impurities, respectively, associated with the oxides. In the absence of nitrate impurities, no pressures greater than 1000 torr are generated. Usually, however, the oxygen in the air atmosphere over the oxides is consumed with the corresponding oxidation of the uranium oxide. In the presence of up to 10 wt % water, the oxides first show a small pressure rise followed by a net decrease due to the oxygen consumption and the attainment of a steady-state pressure where the rate of generation of gaseous components is balanced by their recombination and/or consumption in the oxide phase. These results clearly demonstrate that alpha radiolysis of either wet or dry {sup 233}U oxides will not produce deleterious pressures or gaseous components that could compromise the long-term storage of

  11. Application of nanoparticle tracking analysis for characterising the fate of engineered nanoparticles in sediment-water systems.

    Science.gov (United States)

    Luo, Ping; Roca, Alejandro; Tiede, Karen; Privett, Katie; Jiang, Jiachao; Pinkstone, John; Ma, Guibin; Veinot, Jonathan; Boxall, Alisatair

    2018-02-01

    Novel applications of nanotechnology may lead to the release of engineered nanoparticles (ENPs), which result in concerns over their potential environmental hazardous impact. It is essential for the research workers to be able to quantitatively characterise ENPs in the environment and subsequently to assist the risk assessment of the ENPs. This study hence explored the application of nanoparticle tracking system (NTA) to quantitatively describe the behaviour of the ENPs in natural sediment-water systems. The NTA allows the measurement of both particle number concentration (PNC) and particle size distribution (PSD) of the ENPs. The developed NTA method was applied to a range of gold and magnetite ENPs with a selection of surface properties. The results showed that the positively-charged ENPs interacted more strongly with the sediment than neutral and negatively-charged ENPs. It was also found that the citrate coated Au ENPs had a higher distribution percentage (53%) than 11-mercaptoundecanoic acid coated Au ENPs (20%) and citrate coated magnetite ENPs (21%). The principles of the electrostatic interactions between hard (and soft) acids and bases (HSAB) are used to explain such behaviours; the hard base coating (i.e. citrate ions) will interact more strongly with hard acid (i.e. magnetite) than soft acid (i.e. gold). The results indicate that NTA is a complementary method to existing approaches to characterise the fate and behaviour of ENPs in natural sediment. Copyright © 2017. Published by Elsevier B.V.

  12. Oxidative dissolution of unirradiated Mimas MOX fuel (U/Pu oxides) in carbonated water under oxic and anoxic conditions

    Energy Technology Data Exchange (ETDEWEB)

    Odorowski, Mélina [CEA/DEN/DTCD/SECM/LMPA, BP 17171, 30207 Bagnols-sur-Cèze Cedex (France); MINES ParisTech, PSL Research University, Centre de Géosciences, 35 rue St Honoré, 77305 Fontainebleau (France); Jégou, Christophe, E-mail: christophe.jegou@cea.fr [CEA/DEN/DTCD/SECM/LMPA, BP 17171, 30207 Bagnols-sur-Cèze Cedex (France); De Windt, Laurent [MINES ParisTech, PSL Research University, Centre de Géosciences, 35 rue St Honoré, 77305 Fontainebleau (France); Broudic, Véronique; Peuget, Sylvain; Magnin, Magali; Tribet, Magaly [CEA/DEN/DTCD/SECM/LMPA, BP 17171, 30207 Bagnols-sur-Cèze Cedex (France); Martin, Christelle [Agence nationale pour la gestion des déchets radioactifs (Andra), DRD/CM, 1-7 rue Jean-Monnet, 92298 Châtenay-Malabry Cedex (France)

    2016-01-15

    Few studies exist concerning the alteration of Mimas Mixed-OXide (MOX) fuel, a mixed plutonium and uranium oxide, and data is needed to better understand its behavior under leaching, especially for radioactive waste disposal. In this study, two leaching experiments were conducted on unirradiated MOX fuel with a strong alpha activity (1.3 × 10{sup 9} Bq.g{sub MOX}{sup −1} reproducing the alpha activity of spent MOX fuel with a burnup of 47 GWd·t{sub HM}{sup −1} after 60 years of decay), one under air (oxic conditions) for 5 months and the other under argon (anoxic conditions with [O{sub 2}] < 1 ppm) for one year in carbonated water (10{sup −2} mol L{sup −1}). For each experiment, solution samples were taken over time and Eh and pH were monitored. The uranium in solution was assayed using a kinetic phosphorescence analyzer (KPA), plutonium and americium were analyzed by a radiochemical route, and H{sub 2}O{sub 2} generated by the water radiolysis was quantified by chemiluminescence. Surface characterizations were performed before and after leaching using Scanning Electron Microscopy (SEM), Electron Probe Microanalyzer (EPMA) and Raman spectroscopy. Solubility diagrams were calculated to support data discussion. The uranium releases from MOX pellets under both oxic and anoxic conditions were similar, demonstrating the predominant effect of alpha radiolysis on the oxidative dissolution of the pellets. The uranium released was found to be mostly in solution as carbonate species according to modeling, whereas the Am and Pu released were significantly sorbed or precipitated onto the TiO{sub 2} reactor. An intermediate fraction of Am (12%) was also present as colloids. SEM and EPMA results indicated a preferential dissolution of the UO{sub 2} matrix compared to the Pu-enriched agglomerates, and Raman spectroscopy showed the Pu-enriched agglomerates were slightly oxidized during leaching. Unlike Pu-enriched zones, the UO{sub 2} grains were much more

  13. Evaluation of Empirical Tropospheric Models Using Satellite-Tracking Tropospheric Wet Delays with Water Vapor Radiometer at Tongji, China

    Directory of Open Access Journals (Sweden)

    Miaomiao Wang

    2016-02-01

    Full Text Available An empirical tropospheric delay model, together with a mapping function, is commonly used to correct the tropospheric errors in global navigation satellite system (GNSS processing. As is well-known, the accuracy of tropospheric delay models relies mainly on the correction efficiency for tropospheric wet delays. In this paper, we evaluate the accuracy of three tropospheric delay models, together with five mapping functions in wet delays calculation. The evaluations are conducted by comparing their slant wet delays with those measured by water vapor radiometer based on its satellite-tracking function (collected data with large liquid water path is removed. For all 15 combinations of three tropospheric models and five mapping functions, their accuracies as a function of elevation are statistically analyzed by using nine-day data in two scenarios, with and without meteorological data. The results show that (1 no matter with or without meteorological data, there is no practical difference between mapping functions, i.e., Chao, Ifadis, Vienna Mapping Function 1 (VMF1, Niell Mapping Function (NMF, and MTT Mapping Function (MTT; (2 without meteorological data, the UNB3 is much better than Saastamoinen and Hopfield models, while the Saastamoinen model performed slightly better than the Hopfield model; (3 with meteorological data, the accuracies of all three tropospheric delay models are improved to be comparable, especially for lower elevations. In addition, the kinematic precise point positioning where no parameter is set up for tropospheric delay modification is conducted to further evaluate the performance of tropospheric delay models in positioning accuracy. It is shown that the UNB3 model is best and can achieve about 10 cm accuracy for the N and E coordinate component while 20 cm accuracy for the U coordinate component no matter the meteorological data is available or not. This accuracy can be obtained by the Saastamoinen model only when

  14. Water oxidation catalysis with nonheme iron complexes under acidic and basic conditions: homogeneous or heterogeneous?

    Science.gov (United States)

    Hong, Dachao; Mandal, Sukanta; Yamada, Yusuke; Lee, Yong-Min; Nam, Wonwoo; Llobet, Antoni; Fukuzumi, Shunichi

    2013-08-19

    Thermal water oxidation by cerium(IV) ammonium nitrate (CAN) was catalyzed by nonheme iron complexes, such as Fe(BQEN)(OTf)2 (1) and Fe(BQCN)(OTf)2 (2) (BQEN = N,N'-dimethyl-N,N'-bis(8-quinolyl)ethane-1,2-diamine, BQCN = N,N'-dimethyl-N,N'-bis(8-quinolyl)cyclohexanediamine, OTf = CF3SO3(-)) in a nonbuffered aqueous solution; turnover numbers of 80 ± 10 and 20 ± 5 were obtained in the O2 evolution reaction by 1 and 2, respectively. The ligand dissociation of the iron complexes was observed under acidic conditions, and the dissociated ligands were oxidized by CAN to yield CO2. We also observed that 1 was converted to an iron(IV)-oxo complex during the water oxidation in competition with the ligand oxidation. In addition, oxygen exchange between the iron(IV)-oxo complex and H2(18)O was found to occur at a much faster rate than the oxygen evolution. These results indicate that the iron complexes act as the true homogeneous catalyst for water oxidation by CAN at low pHs. In contrast, light-driven water oxidation using [Ru(bpy)3](2+) (bpy = 2,2'-bipyridine) as a photosensitizer and S2O8(2-) as a sacrificial electron acceptor was catalyzed by iron hydroxide nanoparticles derived from the iron complexes under basic conditions as the result of the ligand dissociation. In a buffer solution (initial pH 9.0) formation of the iron hydroxide nanoparticles with a size of around 100 nm at the end of the reaction was monitored by dynamic light scattering (DLS) in situ and characterized by X-ray photoelectron spectra (XPS) and transmission electron microscope (TEM) measurements. We thus conclude that the water oxidation by CAN was catalyzed by short-lived homogeneous iron complexes under acidic conditions, whereas iron hydroxide nanoparticles derived from iron complexes act as a heterogeneous catalyst in the light-driven water oxidation reaction under basic conditions.

  15. Effect of Support in Heterogeneous Ruthenium Catalysts Used for the Selective Aerobic Oxidation of HMF in Water

    DEFF Research Database (Denmark)

    Gorbanev, Yury; Kegnæs, Søren; Riisager, Anders

    2011-01-01

    Heterogeneous ruthenium-based catalysts were applied in the selective, aerobic oxidation of 5-hydroxymethylfurfural, a versatile biomass-derived chemical, to form 2,5-furandicarboxylic acid. The oxidation reactions were performed in water with dioxygen as the oxidant at different pressures without...

  16. Computationally Probing the Performance of Hybrid, Heterogeneous, and Homogeneous Iridium-Based Catalysts for Water Oxidation

    Energy Technology Data Exchange (ETDEWEB)

    García-Melchor, Max [SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering, Stanford University, Stanford CA (United States); Vilella, Laia [Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology (BIST),Tarragona (Spain); Departament de Quimica, Universitat Autonoma de Barcelona, Barcelona (Spain); López, Núria [Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology (BIST), Tarragona (Spain); Vojvodic, Aleksandra [SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, Menlo Park CA (United States)

    2016-04-29

    An attractive strategy to improve the performance of water oxidation catalysts would be to anchor a homogeneous molecular catalyst on a heterogeneous solid surface to create a hybrid catalyst. The idea of this combined system is to take advantage of the individual properties of each of the two catalyst components. We use Density Functional Theory to determine the stability and activity of a model hybrid water oxidation catalyst consisting of a dimeric Ir complex attached on the IrO2(110) surface through two oxygen atoms. We find that homogeneous catalysts can be bound to its matrix oxide without losing significant activity. Hence, designing hybrid systems that benefit from both the high tunability of activity of homogeneous catalysts and the stability of heterogeneous systems seems feasible.

  17. Zinc adsorption effects on arsenite oxidation kinetics at the birnessite-water interface

    Science.gov (United States)

    Power, L.E.; Arai, Y.; Sparks, D.L.

    2005-01-01

    Arsenite is more toxic and mobile than As(V) in soil and sediment environments, and thus it is advantageous to explore factors that enhance oxidation of As(III) to As(V). Previous studies showed that manganese oxides, such as birnessite (??-MnO2), directly oxidized As(III). However, these studies did not explore the role that cation adsorption has on As(III) oxidation. Accordingly, the effects of adsorbed and nonadsorbed Zn on arsenite (As(III)) oxidation kinetics at the birnessite-water interface were investigated using batch adsorption experiments (0.1 g L-1; pH 4.5 and 6.0; I = 0.01 M NaCl). Divalent Zn adsorption on synthetic ??-MnO 2 in the absence of As(III) increased with increasing pH and caused positive shifts in electrophoretic mobility values at pH 4-6, indirectly suggesting inner-sphere Zn adsorption mechanisms. Arsenite was readily oxidized on birnessite in the absence of Zn. The initial As(III) oxidation rate constant decreased with increasing pH from 4.5 to 6.0 and initial As(III) concentrations from 100 to 300 ??M. Similar pH and initial As(III) concentration effects were observed in systems when Zn was present (i.e., presorbed Zn prior to As(III) addition and simultaneously added Zn-As(III) systems), but As(III) oxidation reactions were suppressed compared to the respective control systems. The suppression was more pronounced when Zn was presorbed on the ??-MnO 2 surfaces as opposed to added simultaneously with As(III). This study provides further understanding of As(III) oxidation reactions on manganese oxide surfaces under environmentally applicable conditions where metals compete for reactive sites.

  18. Destabilization of the hydrogen-bond structure of water by the osmolyte trimethylamine N-oxide

    NARCIS (Netherlands)

    Rezus, Y.L.A.; Bakker, H.J.

    2009-01-01

    We use femtosecond mid-infrared pump−probe spectroscopy to investigate the effects of the osmolyte trimethylamine N-oxide (TMAO) on the structural dynamics of water. As a comparison, we also investigate the effects of other amphiphilic molecules: tetramethylurea (TMU), urea, proline, and

  19. Electrochemical oxidation of tetracycline in water and microbiology investigations of products

    Energy Technology Data Exchange (ETDEWEB)

    Baturova, M.; Vedenjapin, A. [N.D. Zelinsky Inst. of Organic Chemistry, Russian Academy of Sciences, Moscow (Russian Federation); Weichgrebe, D.; Danilova, E.; Rosenwinkel, K.H. [Univ. of Hannover, Inst. of Water Quality and Waste Management, Hannover (Germany); Skundin, A. [A.N. Frumkin Inst. of Electrochemistry, Russian Academy of Sciences, Moscow (Russian Federation)

    2003-07-01

    A possibility to use electrochemical treatment for tetracyclinee (TC) removal from waste water and pig farm sewage was studied. It was found that TC can be oxidized at platinum and carbon anodes with formation of harmless products, carbon anode being more effective than platinum one. (orig.)

  20. Iron oxidation kinetics and phosphate immobilization along the flow-path from groundwater into surface water

    NARCIS (Netherlands)

    van der Grift, B.; Rozemeijer, J. C.|info:eu-repo/dai/nl/304838403; Griffioen, J.; van der Velde, Y.

    2014-01-01

    The retention of phosphorus in surface waters though co-precipitation of phosphate with Fe-oxyhydroxides during exfiltration of anaerobic Fe(II) rich groundwater is not well understood. We developed an experimental field set-up to study Fe(II) oxidation and P immobilization along the flow-path from

  1. How to make an efficient and robust molecular catalyst for water oxidation.

    Science.gov (United States)

    Garrido-Barros, Pablo; Gimbert-Suriñach, Carolina; Matheu, Roc; Sala, Xavier; Llobet, Antoni

    2017-10-16

    Energy has been a central subject for human development from Homo erectus to date. The massive use of fossil fuels during the last 50 years has generated a large CO2 concentration in the atmosphere that has led to the so-called global warming. It is very urgent to come up with C-neutral energy schemes to be able to preserve Planet Earth for future generations to come and still preserve our modern societies' life style. One of the potential solutions is water splitting with sunlight (hν-WS) that is also associated with "artificial photosynthesis", since its working mode consists of light capture followed by water oxidation and proton reduction processes. The hydrogen fuel generated in this way is named as "solar fuel". For this set of reactions, the catalytic oxidation of water to dioxygen is one of the crucial processes that need to be understood and mastered in order to build up potential devices based on hν-WS. This tutorial describes the different important aspects that need to be considered to come up with efficient and oxidatively robust molecular water oxidation catalysts (Mol-WOCs). It is based on our own previous work and completed with essential contributions from other active groups in the field. We mainly aim at describing how the ligands can influence the properties of the Mol-WOCs and showing a few key examples that overall provide a complete view of today's understanding in this field.

  2. Water Oxidation by In Situ Generated [RuII(OH2)(NCNHCO)(pic)2].

    Science.gov (United States)

    Su, Wei; Zhou, Kui; Cai, Fanglin; Chen, Cheng; Mousavi, Bibimaryam; Chaemchuen, Somboon; Verpoort, Francis

    2017-09-05

    A dinuclear ruthenium complex [Ru II (NC NHC O)(pic) 2 ] 2 2+ (2) was firstly prepared and characterized spectroscopically and electrochemically. Instead of the conventional ligand exchange, complex 2 dissociates in situ to afford two single-site Ru aqua complexes, [Ru II (OH 2 )(NC NHC O)(pic) 2 ] + , which mediates water oxidation through proton-coupled electron transfer events. In electrokinetic studies, complex 2 demonstrated a TOF of 150.3 s -1 comparable to those state-of-the-art catalysts at neutral conditions. TONs of 2173 and 217 were attained in chemical and photochemical water oxidation when 2 was used as a catalyst, exhibiting good stability. Notably, a TOF of 1.3 s -1 was achieved at CAN-driven water oxidation, which outperformed most of the reported single-site Ru complexes, indicating that complex 2 is one of most active water oxidation catalysts (WOCs) to date. The unique coordination configuration and outstanding catalytic performance of complex 2 might shed light on the design of novel molecular WOCs. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Biological iron(II) oxidation as pre-treatment to limestone neutralisation of acid water

    CSIR Research Space (South Africa)

    Maree, JP

    1998-01-01

    Full Text Available Iron (II) should be oxidised to iron (III) before the neutralisation of acid water with limestone, otherwise the oxidation will occur downstream of the neutralisation plant with the formation of acid (reactions 1 and 2). This study aimed...

  4. Star block-copolymers: Enzyme-inspired catalysts for oxidation of alcohols in water

    KAUST Repository

    Mugemana, Clement

    2014-01-01

    A number of fluorous amphiphilic star block-copolymers containing a tris(benzyltriazolylmethyl)amine motif have been prepared. These polymers assembled into well-defined nanostructures in water, and their mode of assembly could be controlled by changing the composition of the polymer. The polymers were used for enzyme-inspired catalysis of alcohol oxidation. This journal is © the Partner Organisations 2014.

  5. Integrated iron(II) oxidation and limestone neutralisation of acid mine water

    CSIR Research Space (South Africa)

    Maree, JP

    1999-01-01

    Full Text Available Volumetric iron (II) oxidation rates exceeding 100 g/(l.d) were achieved by dosing powdered limestone to a bio-reactor treating artificial acid mine water. Neutralisation and partial sulphate removal were achieved as well. The rate is highly...

  6. Highly selective nitroxyl radical-mediated oxidation of primary alcohol groups in water-soluble glucans

    NARCIS (Netherlands)

    Nooy, A.E.J. de; Besemer, A.C.; Bekkum, H. van

    1995-01-01

    With catalytic amounts of 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) and hypochlorite/bromide as the regenerating oxidant in water, primary alcohol groups in glucans and derivatives thereof were rapidly and completely oxidised. For pyranosides, selectivity was higher than 95% and no side products

  7. Fe(II) oxidation kinetics and Fe hydroxyphosphate precipitation upon aeration of anaerobic (ground)water

    NARCIS (Netherlands)

    van der Grift, B.|info:eu-repo/dai/nl/373433484; Griffioen, J.|info:eu-repo/dai/nl/091129265; Behrends, T.|info:eu-repo/dai/nl/30484358X; Wassen, M.J.|info:eu-repo/dai/nl/07165710X; Schot, P.P.|info:eu-repo/dai/nl/08071563X; Osté, Leonard

    2015-01-01

    Exfiltration of anaerobic Fe-rich groundwater into surface water plays an important role in controlling the transport of phosphate (P) from agricultural areas to the sea. Previous laboratory and field studies showed that Fe(II) oxidation upon aeration leads to effective immobilization of dissolved P

  8. TiO2-Based Advanced Oxidation Nanotechnologies For Water Purification And Reuse

    Science.gov (United States)

    TiO2 photocatalysis, one of the UV-based advanced oxidation technologies (AOTs) and nanotechnologies (AONs), has attracted great attention for the development of efficient water treatment and purification systems due to the effectiveness of TiO2 to generate ...

  9. Spruce galactoglucomannans inhibit the lipid oxidation in rapeseed oil-in-water emulsions

    Science.gov (United States)

    Oil-in-water emulsions are functional and industrially valuable systems, whose large interfacial area makes them prone to deterioration, due in part to as the oxidation and oligomerization of polyunsaturated fatty acids. Spruce galactoglucomannans (GGM), wood biomacromolecules abundantly available f...

  10. The Oxidative Stress Response in Elite Water Polo Players: Effects of Genetic Background

    Directory of Open Access Journals (Sweden)

    Mercurio Vecchio

    2017-01-01

    Full Text Available Acute exercise is known to induce oxidative stress. Here we assessed the effects of gene polymorphisms SOD2 A16V, CAT −844 G>A, and GPx-1 rs1800668 C>T on oxidative stress markers in 28 elite water polo male players prior to and after a routinely programmed friendly match. The mean plasma concentrations of derivatives of reactive oxygen metabolites (dROMs, as well as lactic dehydrogenase (LDH activity, creatine kinase (CK activity, CK-MB, and myoglobin, were significantly increased after exercise, while blood antioxidant potential (BAP and total free thiols were significantly decreased, compared with those measured before exercise. Advanced oxidation protein products (AOPP were also increased after exercise but not significantly. We observed that water polo players having either AV16 or VV16 SOD genotype exhibited a significant increase of postexercise AOPP, LDH, CK, and myoglobin plasma levels in comparison with wild-type athletes. Water polo players having either CAT −844 GA or GPx1 CT genotype showed a significant increase of postexercise dROMs plasma levels and, respectively, GPx and CAT enzyme activities in comparison with wild-type subjects. These preliminary results suggest that the screening for gene variants of antioxidant enzymes could be useful to assess individual susceptibility to oxidative stress and muscle damage in water polo players.

  11. Oxidation kinetics of model compounds of metabolic waste in supercritical water

    Science.gov (United States)

    Webley, Paul A.; Holgate, Henry R.; Stevenson, David M.; Tester, Jefferson W.

    1990-01-01

    In this NASA-funded study, the oxidation kinetics of methanol and ammonia in supercritical water have been experimentally determined in an isothermal plug flow reactor. Theoretical studies have also been carried out to characterize key reaction pathways. Methanol oxidation rates were found to be proportional to the first power of methanol concentration and independent of oxygen concentration and were highly activated with an activation energy of approximately 98 kcal/mole over the temperature range 480 to 540 C at 246 bar. The oxidation of ammonia was found to be catalytic with an activation energy of 38 kcal/mole over temperatures ranging from 640 to 700 C. An elementary reaction model for methanol oxidation was applied after correction for the effect of high pressure on the rate constants. The conversion of methanol predicted by the model was in good agreement with experimental data.

  12. Auto-inhibition effects in anodic oxidation of phenols for electrochemical waste-water purification

    Directory of Open Access Journals (Sweden)

    B. E. CONWAY

    2001-12-01

    Full Text Available Removal or modification of noxious organic impurities in waste-waters is a major challenge for environmental science. Pollutants such as phenols and their derivatives, as well as PCBs, have attracted special attention. In recent years, the possibilities of effecting direct electrocatalytic oxidations at high-area electrodes such as supported Pt or RuO2 have been investigated. However, in a number of cases, especially with phenolic impurities, application of anodic oxidation fails to lead to continuous Faradaic oxidation currents owing to the electrode surfaces becoming blocked with polymeric oxidation products leading to auto-inhibition (“passivation” of the desired electrode process. Examples of such effects with phenols and related compounds are examined comparatively in the present paper by means of cyclic volatammetry and chronoamperometry.

  13. Homogenization conditions affect the oxidative stability of fish oil enriched milk emulsions: oxidation linked to changes in protein composition at the oil-water interface

    DEFF Research Database (Denmark)

    Sørensen, Ann-Dorit M.; Baron, Caroline P.; Let, Mette B.

    2007-01-01

    Fish oil was incorporated into milk under different homogenization temperatures (50 and 72 °C) and pressures (5, 15, and 22.5 MPa). Subsequently, the oxidative stability of the milk and changes in the protein composition of the milk fat globule membrane (MFGM) were examined. Results showed...... casein seemed to be present at the oil−water interface with increasing pressure. Overall, the results indicated that a combination of more β-lactoglobulin and less casein at the oil−water interface gave the most stable emulsions with respect to lipid oxidation....... that high pressure and high temperature (72 °C and 22.5 MPa) resulted in less lipid oxidation, whereas low pressure and low temperature (50 °C and 5 MPa) resulted in faster lipid oxidation. Analysis of protein oxidation indicated that especially casein was prone to oxidation. The level of free thiol groups...

  14. Features of the propagation of pseudorandom pulse signals from the shelf to deep water in the presence of gyre formation on the acoustic track

    Science.gov (United States)

    Akulichev, V. A.; Burenin, A. V.; Ladychenko, S. Yu.; Lobanov, V. B.; Morgunov, Yu. N.

    2017-08-01

    The paper discusses the results of an experiment conducted in the Sea of Japan in March 2016 on an acoustic track 194 km long in winter hydrological conditions. The most complex case of propagation of pseudorandom pulse signals from the shelf to deep water in the presence of gyre formation on the acoustic track. An analysis of the experimentally obtained pulse characteristics show that at all points, a maximum, in terms of amplitude, first arrival of acoustic energy is recorded. This is evidence that at a given depth horizon, pulses that have passed the shortest distance through a near-surface sound channel at small angles close to zero are received first. The calculation method of mean sound velocity on the track, based on the satellite data of surface temperature monitoring, is proposed. We expect that the results obtained with this method can be successfully used for the purposes of acoustic range finding and navigation.

  15. Water growth on metals and oxides: binding, dissociation and role of hydroxyl groups.

    Science.gov (United States)

    Salmeron, M; Bluhm, H; Tatarkhanov, M; Ketteler, G; Shimizu, T K; Mugarza, A; Deng, Xingyi; Herranz, T; Yamamoto, S; Nilsson, A

    2009-01-01

    We discuss the role of the presence of dangling H-bonds from water or from surface hydroxyl species on the wetting behavior of surfaces. Using scanning tunneling and atomic force microscopies and photoelectron spectroscopy, we have examined a variety of surfaces, including mica, oxides and pure metals. We find that in all cases, the availability of free, dangling H-bonds at the surface is crucial for the subsequent growth of wetting water films. In the case of mica, electrostatic forces and H-bonding to surface O atoms determine the water orientation in the first layer and also in subsequent layers with a strong influence in its wetting characteristics. In the case of oxides like TiO2, Cu2O, SiO2 and Al2O3, surface hydroxyls form readily on defects upon exposure to water vapor and help nucleate the subsequent growth of molecular water films. On pure metals, such as Pt, Pd and Ru, the structure of the first water layer and whether or not it exhibits dangling H-bonds is again crucial. Dangling H-bonds are provided by molecules with their plane oriented vertically, or by OH groups formed by the partial dissociation of water. By tying the two H atoms of the water molecules into strong H-bonds with pre-adsorbed O on Ru can also quench the wettability of the surface.

  16. Differential contributions of archaeal ammonia oxidizer ecotypes to nitrification in coastal surface waters.

    Science.gov (United States)

    Smith, Jason M; Casciotti, Karen L; Chavez, Francisco P; Francis, Christopher A

    2014-08-01

    The occurrence of nitrification in the oceanic water column has implications extending from local effects on the structure and activity of phytoplankton communities to broader impacts on the speciation of nitrogenous nutrients and production of nitrous oxide. The ammonia-oxidizing archaea, responsible for carrying out the majority of nitrification in the sea, are present in the marine water column as two taxonomically distinct groups. Water column group A (WCA) organisms are detected at all depths, whereas Water column group B (WCB) are present primarily below the photic zone. An open question in marine biogeochemistry is whether the taxonomic definition of WCA and WCB organisms and their observed distributions correspond to distinct ecological and biogeochemical niches. We used the natural gradients in physicochemical and biological properties that upwelling establishes in surface waters to study their roles in nitrification, and how their activity--ascertained from quantification of ecotype-specific ammonia monooxygenase (amoA) genes and transcripts--varies in response to environmental fluctuations. Our results indicate a role for both ecotypes in nitrification in Monterey Bay surface waters. However, their respective contributions vary, due to their different sensitivities to surface water conditions. WCA organisms exhibited a remarkably consistent level of activity and their contribution to nitrification appears to be related to community size. WCB activity was less consistent and primarily constrained to colder, high nutrient and low chlorophyll waters. Overall, the results of our characterization yielded a strong, potentially predictive, relationship between archaeal amoA gene abundance and the rate of nitrification.

  17. Benefits of neutral electrolyzed oxidizing water as a drinking water additive for broiler chickens

    National Research Council Canada - National Science Library

    Bügener, E; Kump, A. Wilms-Schulze; Casteel, M; Klein, G

    2014-01-01

    .... At each farm, 3 rearing periods were included in the study. With EO water as the water additive, the total viable cell count and the number of Escherichia coli in drinking water samples were reduced compared with the respective control group...

  18. Hematite modified tungsten trioxide nanoparticle photoanode for solar water oxidation

    Science.gov (United States)

    Mao, Aiming; Kim, Jung Kyu; Shin, Kahee; Wang, Dong Hwan; Yoo, Pil J.; Han, Gui Young; Park, Jong Hyeok

    2012-07-01

    Hematite (α-Fe2O3) film is electrochemically deposited onto the surface of tungsten trioxide (WO3) nanoparticulate film. The synthesis of the WO3 nanostructure is directed by surfactants for control of its morphology. The resulting composite shows visible light harvesting and is tested as photoanodes in heterojunction photoelectrochemical cells for the possibility of direct water splitting under visible illumination. The composite's structural and optical properties are characterized by FESEM, EDS, XRD, XPS, and UV-vis spectrometry; its photocurrent responses are also investigated under simulated solar illumination. Coupling WO3 with hematite results in over 9 times greater photocurrent density than that shown by pure WO3 in sodium sulfate electrolyte. This simple modification can significantly improve the performance of WO3.

  19. Detection of viruses in drinking water by concentration on magnetic iron oxide.

    Science.gov (United States)

    Rao, V C; Waghmare, S V; Lakhe, S B

    1981-09-01

    Discharge of raw domestic wastes containing human enteric viruses into water courses, consumption of untreated water from canals, streams, and shallow wells in villages, and cross-contamination of water in the distribution system because of intermittent water supply in urban areas continue to cause widespread outbreaks of infectious hepatitis in India. To detect a low number of viruses in 50- to 100-liter samples of water, a method was developed with magnetic iron oxide as the virus adsorbent. Poliovirus-seeded dechlorinated tap water, adjusted to pH 3.0 and 0.0005 M AlCl3, was filtered through a 10-g bed of iron oxide sandwiched between two AP20 prefilter pads held in a 142-mm-diameter, stainless-steel holder. Virus was eluted from iron oxide by recirculating three times a 100-ml volume of 3% beef extract, pH 9.0. The eluate was reconcentrated to 5 ml by adjusting to pH 3, adding 1 g of iron oxide, stirring for 30 min, and eluting the readsorbed virus with 5 ml of beef extract, pH 9.0. Virus recovery varied from 60 to 80%. Using the above method, we took a survey of drinking water at three locations in Nagpur during 1976 and found the presence of virus in 7 of 50 samples. The quantity of virus recovered ranged from 1 to 7 plaque-forming units per 30 to 60 liters. Virus was detected in some samples even with residual chlorine. No coliforms were detected in the virus-positive samples.

  20. Characterization of interfacial reactions and oxide films on 316L stainless steel in various simulated PWR primary water environments

    Science.gov (United States)

    Chen, Junjie; Xiao, Qian; Lu, Zhanpeng; Ru, Xiangkun; Peng, Hao; Xiong, Qi; Li, Hongjuan

    2017-06-01

    The effect of water chemistry on the electrochemical and oxidizing behaviors of 316L SS was investigated in hydrogenated, deaerated and oxygenated PWR primary water at 310 °C. Water chemistry significantly influenced the electrochemical impedance spectroscopy parameters. The highest charge-transfer resistance and oxide-film resistance occurred in oxygenated water. The highest electric double-layer capacitance and constant phase element of the oxide film were in hydrogenated water. The oxide films formed in deaerated and hydrogenated environments were similar in composition but different in morphology. An oxide film with spinel outer particles and a compact and Cr-rich inner layer was formed in both hydrogenated and deaerated water. Larger and more loosely distributed outer oxide particles were formed in deaerated water. In oxygenated water, an oxide film with hematite outer particles and a porous and Ni-rich inner layer was formed. The reaction kinetics parameters obtained by electrochemical impedance spectroscopy measurements and oxidation film properties relating to the steady or quasi-steady state conditions in the time-period of measurements could provide fundamental information for understanding stress corrosion cracking processes and controlling parameters.

  1. Understanding flocculation mechanism of graphene oxide for organic dyes from water: Experimental and molecular dynamics simulation

    Directory of Open Access Journals (Sweden)

    Jun Liu

    2015-11-01

    Full Text Available Flocculation treatment processes play an important role in water and wastewater pretreatment. Here we investigate experimentally and theoretically the possibility of using graphene oxide (GO as a flocculant to remove methylene blue (MB from water. Experimental results show that GO can remove almost all MB from aqueous solutions at its optimal dosages and molecular dynamics simulations indicate that MB cations quickly congregate around GO in water. Furthermore, PIXEL energy contribution analysis reveals that most of the strong interactions between GO and MB are of a van der Waals (London dispersion character. These results offer new insights for shedding light on the molecular mechanism of interaction between GO and organic pollutants.

  2. Remarkable effect of Pt nanoparticles on visible light-induced oxygen generation from water catalysed by perovskite oxides.

    Science.gov (United States)

    Gupta, Uttam; Naidu, B S; Rao, C N R

    2015-01-14

    Oxidation of water is a challenging process with a positive free energy change and it is purposeful to find good catalysts to facilitate the process. While the perovskite oxides, LaCoO3 and LaMnO3, are good electron transfer catalysts in artificial photosynthesis to produce oxygen by the oxidation of water, the electron transfer is further favoured by the presence of platinum nanoparticles, causing a substantial increase in oxygen evolution.

  3. Synthesis and characterization of alginate beads encapsulated zinc oxide nanoparticles for bacteria disinfection in water.

    Science.gov (United States)

    Motshekga, Sarah Constance; Sinha Ray, Suprakas; Maity, Arjun

    2017-11-03

    The use of polymer nanocomposites as novel materials for water remediation has emerged as a promising alternative for disinfection of bacteria contaminated water. Sodium alginate, a natural biopolymer has been investigated in this study by encapsulating antimicrobial zinc oxide nanoparticles supported bentonite. The confirmation of the alginate nanocomposites was done by use of TEM, SEM-EDS and XRD. The antimicrobial activity of the alginate nanocomposites was investigated by batch studies using surface water and synthetic bacteria contaminated water containing Staphylococcus aureus. The effect of nanocomposite amount and initial bacteria concentration has been studied. The inactivation results indicated that the nanocomposite effectively inactivated bacteria in both the synthetic and surface water. With an amount of 0.5 g of the nanocomposites, no bacteria was observed in the water after 70 min of contact time with initial bacteria concentration of 200 cfu/ml for synthetic water and within a min, no bacteria was observed in the water for surface water. It is worth noting that 200 cfu/ml is the bacteria concentration range in which environmental water is likely to contain. Therefore, the results of this study have indicated that the alginate nanocomposites can be deemed as a potential antimicrobial agent for water disinfection. Copyright © 2017 Elsevier Inc. All rights reserved.

  4. EVALUATING ARSENIC AND MANGANESE REMOVAL FROM WATER BY CHLORINE OXIDATION FOLLOWED BY CLARIFICATION

    Directory of Open Access Journals (Sweden)

    V. G. R. Pires

    2015-06-01

    Full Text Available AbstractThis paper investigates the simultaneous removal of arsenic [As(V or As(III] and manganese [Mn(II] from natural waters of low and high turbidity by clarification (with polyaluminum chloride and aluminum sulfate as primary coagulants associated or not with chlorine pre-oxidation. The results showed that the clarification process exhibited low Mn(II removal, that varied from 6% to 18% and from 19% to 27% for natural waters of low and high turbidity, respectively. The use of chlorine as pre-oxidant increased Mn(II removal up to 77% and was associated with the formation of birnessite. Regarding As(V removal by clarification, particularly for high turbidity water, a concentration lower than that established by the National Drinking Water Quality Standards (10 μg.L-1 was achieved in almost all tests. Oxidation preceding the clarification led to AsIII removal efficiencies from 80% to 90% for both coagulants and types of water.

  5. Pebax®1657/Graphene oxide composite membranes for improved water vapor separation

    KAUST Repository

    Akhtar, Faheem Hassan

    2016-11-02

    In this study composite mixed matrix membranes containing hydrophilic microphase-separated block copolymer (Pebax® 1657) and graphene oxide nanosheets were prepared using a dip coating method. Water vapor and N2 gas permeation were measured as a function of different parameters: (i) layer thickness, (ii) content of graphene oxide (GO), and (iii) content of reduced GO. Surprisingly, a concentration of only 2 wt% of GO nanosheets well dispersed in the Pebax layer boosted the selectivity 8 times by decreasing the water vapor permeance by only 12% whereas N2 gas permeance decreased by 70%. Using reduced GO instead, the water vapor permeance declined by up to 16% with no influence on the N2 gas permeance. We correlated the permeation properties of the mixed matrix membranes with different models and found, that both the modified Nielsen model and the Cussler model give good correlation with experimental findings.

  6. A Co(II)-Ru(II) dyad relevant to light-driven water oxidation catalysis.

    Science.gov (United States)

    López, Alejandro Montellano; Natali, Mirco; Pizzolato, Erica; Chiorboli, Claudio; Bonchio, Marcella; Sartorel, Andrea; Scandola, Franco

    2014-06-28

    Artificial photosynthesis aims at efficient water splitting into hydrogen and oxygen, by exploiting solar light. As a priority requirement, this process entails the integration of suitable multi-electron catalysts with light absorbing units, where charge separation is generated in order to drive the catalytic routines. The final goal could be the transposition of such an asset into a photoelectrocatalytic cell, where the two half-reactions, proton reduction to hydrogen and water oxidation to oxygen, take place at two appropriately engineered photoelectrodes. We herein report a covalent approach to anchor a Co(II) water oxidation catalyst to a Ru(II) polypyridine photosensitizer unit; photophysical characterisation and the catalytic activity of such a dyad in a light activated cycle are reported, and implications for the development of regenerative systems are discussed.

  7. Effect of supplementation of water-soluble vitamins on oxidative stress and blood pressure in prehypertensives.

    Science.gov (United States)

    Talikoti, Prashanth; Bobby, Zachariah; Hamide, Abdoul

    2015-01-01

    The objective of the study was to evaluate the effect of water-soluble vitamins on oxidative stress and blood pressure in prehypertensives. Sixty prehypertensives were recruited and randomized into 2 groups of 30 each. One group received water-soluble vitamins and the other placebo for 4 months. Further increase in blood pressure was not observed in the vitamin group which increased significantly in the placebo group at the end of 4 months. Malonedialdehyde and protein carbonylation were reduced during the course of treatment with vitamins whereas in the placebo group there was an increase in the level of malondialdehyde. In conclusion, supplementation of water-soluble vitamins in prehypertension reduces oxidative stress and its progression to hypertension.

  8. THE EVOLUTION OF BIOCHEMICAL OXIDATION OF AMMONIA IONS IN SMALL RIVERS WATER

    Directory of Open Access Journals (Sweden)

    Elena Mosanu

    2010-06-01

    Full Text Available Nitrification is the oxidation of ammonia to nitrate, via nitrite and it occupies a central position within the global nitrogen cycle. Nitrifying bacteria are the organisms capable of converting the most reduced form of nitrogen, ammonia, to the most oxidized form, nitrate, but their activity is influenced by pollution level. Starting with the assumption that pollution of small internal water courses in the Republic of Moldova remained severe (phenols, detergents and copper regularly exceed the MACs the work presented in the paper discusses the evolution of ammonia ions nitrification in the water of river Prut tributaries and its correlation with the content of pollutants in water: surface-active substances, Cu, BOD5, COD and other compounds.

  9. Electrochemical oxidation of drug residues in water by the example of tetracycline, gentamicin and Aspirin {sup trademark}

    Energy Technology Data Exchange (ETDEWEB)

    Weichgrebe, D.; Danilova, E.; Rosenwinkel, K.H. [Inst. of Water Quality and Waste Management, Univ. of Hannover, Hannover (Germany); Vedenjapin, A.; Baturova, M. [Inst. of Organic Chemistry, Russian Academy of Science, Moscow (Russian Federation)

    2003-07-01

    The electrochemical oxidation as a method to destroy drug residues like Aspirin {sup trademark}, tetracycline or gentamicin in water was investigated with C-Anode (modified by manganese oxides) and Pt Anode. The mechanism of Aspirin {sup trademark} and tetracycline oxidation and the influence of the biocide effect was observed using GC-MS and three different microbiological tests. In general the biological availability increases with progressive oxidation of the antibiotics. (orig.)

  10. Hierarchical Load Tracking Control of a Grid-connected Solid Oxide Fuel Cell for Maximum Electrical Efficiency Operation

    DEFF Research Database (Denmark)

    Li, Yonghui; Wu, Qiuwei; Zhu, Haiyu

    2015-01-01

    Based on the benchmark solid oxide fuel cell (SOFC) dynamic model for power system studies and the analysis of the SOFC operating conditions, the nonlinear programming (NLP) optimization method was used to determine the maximum electrical efficiency of the grid-connected SOFC subject to the const......Based on the benchmark solid oxide fuel cell (SOFC) dynamic model for power system studies and the analysis of the SOFC operating conditions, the nonlinear programming (NLP) optimization method was used to determine the maximum electrical efficiency of the grid-connected SOFC subject...... to the constraints of fuel utilization factor, stack temperature and output active power. The optimal operating conditions of the grid-connected SOFC were obtained by solving the NLP problem considering the power consumed by the air compressor. With the optimal operating conditions of the SOFC for the maximum...

  11. Arsenic and antimony removal from drinking water by adsorption on granular ferric oxide.

    Science.gov (United States)

    Sazakli, Eleni; Zouvelou, Stavroula V; Kalavrouziotis, Ioannis; Leotsinidis, Michalis

    2015-01-01

    Arsenic and antimony occur in drinking water due to natural weathering or anthropogenic activities. There has been growing concern about their impact on health. The aim of this study was to assess the efficiency of a granular ferric oxide adsorbent medium to remove arsenic and antimony from drinking water via rapid small-scale column tests (RSSCTs). Three different water matrices - deionized, raw water treated with a reverse osmosis domestic device and raw water - were spiked with arsenic and/or antimony to a concentration of 100 μg L⁻¹. Both elements were successfully adsorbed onto the medium. The loadings until the guideline value was exceeded in the effluent were found to be 0.35-1.63 mg g⁻¹ for arsenic and 0.12-2.11 mg g⁻¹ for antimony, depending on the water matrix. Adsorption of one element was not substantially affected by the presence of the other. Aeration did not affect significantly the adsorption capacity. Granular ferric oxide could be employed for the simultaneous removal of arsenic and antimony from drinking water, whereas full-scale systems should be assessed via laboratory tests before their implementation.

  12. Rigidity, conformation, and solvation of native and oxidized tannin macromolecules in water-ethanol solution

    Science.gov (United States)

    Zanchi, Dražen; Konarev, Petr V.; Tribet, Christophe; Baron, Alain; Svergun, Dmitri I.; Guyot, Sylvain

    2009-06-01

    We studied by light scattering and small angle x-rays scattering (SAXS) conformations and solvation of plant tannins (oligomers and polymers) in mixed water-ethanol solutions. Their structures are not simple linear chains but contain about 6% of branching. Ab initio reconstruction reveals that monomers within a branch are closely bound pairwise. The chains are rather rigid, with the Kuhn length b =13±3 nm, corresponding to about 35 linearly bound monomers. Contribution of solvation layer to SAXS intensity varies in a nonmonotonic way with ethanol content ϕA, which is an indication of amphipathic nature of tannin molecules. Best solvent composition ϕAB is a decreasing function of polymerization degree N, in agreement with increasing water solubility of tannins with N. Polymers longer than b present a power-law behavior I ˜Q-d in the SAXS profile at high momentum transfer Q. The monotonic decrease in d with increasing ϕA (from 2.4 in water to 1.9 in ethanol) points that the tannins are more compact in water than in ethanol, presumably due to attractive intramolecular interactions in water. Tannins were then oxidized in controlled conditions similar to real biological or food systems. Oxidation does not produce any intermolecular condensation, but generates additional intramolecular links. Some oxidation products are insoluble in water rich solvent. For that reason, we identify these species as a fraction of natural tannins called "T1" in the notation of Zanchi et al. [Langmuir 23, 9949 (2007)]. Within the fraction left soluble after oxidation, conformations of polymeric tannins, despite their higher rigidity, remain sensitive to solvent composition.

  13. Oxidation of PCEA nuclear graphite by low water concentrations in helium

    Energy Technology Data Exchange (ETDEWEB)

    Contescu, Cristian I [ORNL; Mee, Robert [University of Tennessee (UT); Wang, Peng [ORNL; Romanova, Anna V [University of Tennessee, Knoxville (UTK); Burchell, Timothy D [ORNL

    2014-10-01

    Accelerated oxidation tests were performed to determine kinetic parameters of the chronic oxidation reaction of PCEA graphite in contact with helium coolant containing low moisture concentrations in high temperature gas-cooled reactors. To the authors best knowledge such a study has not been done since the detailed analysis of reaction of H-451 graphite with steam [Velasquez, Hightower, Burnette, 1978]. Since that H-451 graphite is now unavailable, it is urgently needed to characterize chronic oxidation behavior of new graphite grades under qualification for gas-cooled reactors. The Langmuir-Hinshelwood mechanism of carbon oxidation by water results in a non-linear reaction rate expression, with at least six different parameters. They were determined in accelerated oxidation experiments that covered a large range of temperatures (800 to 1100 oC), and partial pressures of water (15 to 850 Pa) and hydrogen (30 to 150 Pa) and used graphite specimens thin enough (4 mm) in order to avoid diffusion effects. Data analysis employed a statistical method based on multiple likelihood estimation of parameters and simultaneous fitting of non-linear equations. The results show significant material-specific differences between graphite grades PCEA and H-451 which were attributed to microstructural dissimilarity of the two materials. It is concluded that kinetic data cannot be transferred from one graphite grade to another.

  14. Oxidation of PCEA nuclear graphite by low water concentrations in helium

    Energy Technology Data Exchange (ETDEWEB)

    Contescu, Cristian I., E-mail: ContescuCI@ornl.gov [Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831-6087 (United States); Mee, Robert W. [Department of Business Analytics and Statistics, University of Tennessee, Knoxville, TN 37996-0525 (United States); Wang, Peng [Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831-6087 (United States); Romanova, Anna V.; Burchell, Timothy D. [Department of Business Analytics and Statistics, University of Tennessee, Knoxville, TN 37996-0525 (United States)

    2014-10-15

    Accelerated oxidation tests were performed to determine kinetic parameters of the chronic oxidation reaction (i.e. slow, continuous, and persistent) of PCEA graphite in contact with helium coolant containing low moisture concentrations in high temperature gas-cooled reactors. To the authors’ knowledge such a study has not been done since the detailed analysis of reaction of H-451 graphite with steam (Velasquez, Hightower, Burnette, 1978). Since that H-451 graphite is now unavailable, it is urgently needed to characterize chronic oxidation behavior of new graphite grades that are being considered for use in gas-cooled reactors. The Langmuir–Hinshelwood mechanism of carbon oxidation by water results in a non-linear reaction rate expression, with at least six different parameters. They were determined in accelerated oxidation experiments that covered a large range of temperatures (800–1100 °C), and partial pressures of water (15–850 Pa) and hydrogen (30–150 Pa) and used graphite specimens thin enough (4 mm) in order to avoid diffusion effects. Data analysis employed a statistical method based on multiple likelihood estimation of parameters and simultaneous fitting of non-linear equations. The results show significant material-specific differences between graphite grades PCEA and H-451 which were attributed to microstructural dissimilarity between the two materials. It is concluded that kinetic data cannot be transferred from one graphite grade to another.

  15. Adsorption of Cadmium Ions from Water on Double-walled Carbon Nanotubes/Iron Oxide Composite

    Directory of Open Access Journals (Sweden)

    Karima Seffah

    2017-12-01

    Full Text Available A new material (DWCNT/iron oxide for heavy metals removal was developed by combining the adsorption features of double-walled carbon nanotubes with the magnetic properties of iron oxides. Batch experiments were applied in order to evaluate adsorption capacity of the DWCNT/iron oxide composite for cadmium ions. The influence of operating parameters such as pH value, amount of adsorbent, initial adsorbate concentration and agitation speed was studied. The adsorption capacity of the DWCNT/iron oxide adsorbent for Cd2+ ions was 20.8 mg g-1, which is at the state of the art. The obtained results revealed that DWCNT/iron oxide composite is a very promising adsorbent for removal of Cd2+ ions from water under natural conditions. The advantage of the magnetic composite is that it can be used as adsorbent for contaminants in water and can be subsequently controlled and removed from the medium by a simple magnetic process.

  16. Effect of Leaves of Caesalpinia decapetala on Oxidative Stability of Oil-in-Water Emulsions

    Directory of Open Access Journals (Sweden)

    María Gabriela Gallego

    2017-03-01

    Full Text Available Caesalpinia decapetala (Roth Alston (Fabaceae (CD is used in folk medicine to prevent colds and treat bronchitis. This plant has antitumor and antioxidant activity. The antioxidant effects of an extract from Caesalpinia decapetala (Fabaceae were assessed by storage of model food oil-in-water emulsions with analysis of primary and secondary oxidation products. The antioxidant capacity of the plant extract was evaluated by the diphenylpicrylhydrazyl (DPPH, Trolox equivalent antioxidant capacity (TEAC, oxygen radical absorbance capacity (ORAC and ferric reducing antioxidant power (FRAP assays and by electron paramagnetic resonance (EPR spectroscopy. Lyophilized extracts of CD were added at concentrations of 0.002%, 0.02% and 0.2% into oil-in-water emulsions, which were stored for 30 days at 33 ± 1 °C, and then, oxidative stability was evaluated. The CD extract had high antioxidant activity (700 ± 70 µmol Trolox/g dry plant for the ORAC assay, mainly due to its phenolic components: gallic acid, quercetin, catechin, 4-hydroxybenzoic acid and p-coumaric acid. At a concentration of 0.2%, the extract significantly reduced the oxidative deterioration of oil-in-water emulsions. The results of the present study show the possibility of utilizing CD as a promising source of natural antioxidants for retarding lipid oxidation in the food and cosmetic industries.

  17. Effect of Leaves of Caesalpinia decapetala on Oxidative Stability of Oil-in-Water Emulsions

    Science.gov (United States)

    Gallego, María Gabriela; Skowyra, Monika; Gordon, Michael H.; Azman, Nurul Aini Mohd; Almajano, María Pilar

    2017-01-01

    Caesalpinia decapetala (Roth) Alston (Fabaceae) (CD) is used in folk medicine to prevent colds and treat bronchitis. This plant has antitumor and antioxidant activity. The antioxidant effects of an extract from Caesalpinia decapetala (Fabaceae) were assessed by storage of model food oil-in-water emulsions with analysis of primary and secondary oxidation products. The antioxidant capacity of the plant extract was evaluated by the diphenylpicrylhydrazyl (DPPH), Trolox equivalent antioxidant capacity (TEAC), oxygen radical absorbance capacity (ORAC) and ferric reducing antioxidant power (FRAP) assays and by electron paramagnetic resonance (EPR) spectroscopy. Lyophilized extracts of CD were added at concentrations of 0.002%, 0.02% and 0.2% into oil-in-water emulsions, which were stored for 30 days at 33 ± 1 °C, and then, oxidative stability was evaluated. The CD extract had high antioxidant activity (700 ± 70 µmol Trolox/g dry plant for the ORAC assay), mainly due to its phenolic components: gallic acid, quercetin, catechin, 4-hydroxybenzoic acid and p-coumaric acid. At a concentration of 0.2%, the extract significantly reduced the oxidative deterioration of oil-in-water emulsions. The results of the present study show the possibility of utilizing CD as a promising source of natural antioxidants for retarding lipid oxidation in the food and cosmetic industries. PMID:28273843

  18. Preparation of water-dispersible graphene by facile surface modification of graphite oxide.

    Science.gov (United States)

    Kuila, Tapas; Khanra, Partha; Bose, Saswata; Kim, Nam Hoon; Ku, Bon-Cheol; Moon, Bongho; Lee, Joong Hee

    2011-07-29

    Water-dispersible graphene was prepared by reacting graphite oxide and 6-amino-4-hydroxy-2-naphthalenesulfonic acid (ANS). X-ray diffraction study showed that the basal reflection (002) peak of graphite oxide was absent in the ANS-functionalized graphene (ANS-G), indicating crystal layer delamination. Ultraviolet-visible spectral data were recorded to assess the solubility of the ANS-G in water. Fourier transform infrared spectral analysis suggested the attachment of ANS molecules to the surface of graphene. Raman and x-ray photoelectron spectroscopy revealed that oxygen functionality in the graphite oxide had been removed during reduction. Atomic force microscopy found that the thickness of ANS-G in water was about 1.8 nm, much higher than that of single layer graphene. Thermal stability measurements also indicated successful removal of oxygen functionality from the graphite oxide and the attachment of thermally unstable ANS to the graphene surfaces. The electrical conductivity of ANS-G, determined by a four-point probe, was 145 S m(-1) at room temperature.

  19. REMOVAL OF ORGANIC DYES FROM CONTAMINATED WATER USING COFE2O4 /REDUCED GRAPHENE OXIDE NANOCOMPOSITE

    Directory of Open Access Journals (Sweden)

    F. Sakhaei

    2016-12-01

    Full Text Available Up to now, lots of materials such as active carbon, iron, manganese, zirconium, and metal oxides have been widely used for removal of dyes from contaminated water. Among these, ferrite nanoparticle is an interesting magnetic material due to its moderate saturation magnetization, excellent chemical stability and mechanical hardness. Graphene, a new class of 2D carbonaceous material with atom thick layer features, has attracted much attention recently due to its high specific surface area. Reduced graphene oxide (rGO has also been of great interest because of its unique properties, which are similar to those of graphene, such as specific surface area, making it an ideal candidate for dye removal. Thus far, few works have been carried out on the preparation of CoFe2O4-rGO composite and its applications in removal of contaminants from water. In this paper, CoFe2O4 reduced graphene oxide nanocomposite was fabricated using hydrothermal process. During the hydrothermal process, the reduction of graphene oxide and growth of CoFe2O4 simultaneously occurred on the carbon basal planes under the conditions generated in the hydrothermal system. The samples were characterized by X-ray diffraction (XRD, scanning electron microscopy (SEM, and Fourier transform infrared spectroscopy contaminant and UV-Vis spectroscopy as the analytical method. The experimental results suggest that this material has great potential for treating Congo red contaminated water.

  20. Effect of Leaves of Caesalpinia decapetala on Oxidative Stability of Oil-in-Water Emulsions.

    Science.gov (United States)

    Gallego, María Gabriela; Skowyra, Monika; Gordon, Michael H; Azman, Nurul Aini Mohd; Almajano, María Pilar

    2017-03-04

    Caesalpinia decapetala (Roth) Alston (Fabaceae) (CD) is used in folk medicine to prevent colds and treat bronchitis. This plant has antitumor and antioxidant activity. The antioxidant effects of an extract from Caesalpinia decapetala (Fabaceae) were assessed by storage of model food oil-in-water emulsions with analysis of primary and secondary oxidation products. The antioxidant capacity of the plant extract was evaluated by the diphenylpicrylhydrazyl (DPPH), Trolox equivalent antioxidant capacity (TEAC), oxygen radical absorbance capacity (ORAC) and ferric reducing antioxidant power (FRAP) assays and by electron paramagnetic resonance (EPR) spectroscopy. Lyophilized extracts of CD were added at concentrations of 0.002%, 0.02% and 0.2% into oil-in-water emulsions, which were stored for 30 days at 33 ± 1 °C, and then, oxidative stability was evaluated. The CD extract had high antioxidant activity (700 ± 70 µmol Trolox/g dry plant for the ORAC assay), mainly due to its phenolic components: gallic acid, quercetin, catechin, 4-hydroxybenzoic acid and p-coumaric acid. At a concentration of 0.2%, the extract significantly reduced the oxidative deterioration of oil-in-water emulsions. The results of the present study show the possibility of utilizing CD as a promising source of natural antioxidants for retarding lipid oxidation in the food and cosmetic industries.

  1. Reaction pattern and mechanism of light induced oxidative water splitting in photosynthesis.

    Science.gov (United States)

    Renger, Gernot; Kühn, Philipp

    2007-06-01

    This mini review is an attempt to briefly summarize our current knowledge on light driven oxidative water splitting in photosynthesis. The reaction leading to molecular oxygen and four protons via photosynthesis comprises thermodynamic and kinetic constraints that require a balanced fine tuning of the reaction coordinates. The mode of coupling between electron (ET) and proton transfer (PT) reactions is shown to be of key mechanistic relevance for the redox turnover of Y(Z) and the reactions within the WOC. The WOC is characterized by peculiar energetics of its oxidation steps in the WOC. In all oxygen evolving photosynthetic organisms the redox state S(1) is thermodynamically most stable and therefore this general feature is assumed to be of physiological relevance. Available information on the Gibbs energy differences between the individual redox states S(i+1) and S(i) and on the activation energies of their oxidative transitions are used to construct a general reaction coordinate of oxidative water splitting in photosystem II (PS II). Finally, an attempt is presented to cast our current state of knowledge into a mechanism of oxidative water splitting with special emphasis on the formation of the essential O-O bond and the active role of the protein environment in tuning the local proton activity that depends on time and redox state S(i). The O-O linkage is assumed to take place within a multistate equilibrium at the redox level of S(3), comprising both redox isomerism and proton tautomerism. It is proposed that one state, S(3)(P), attains an electronic configuration and nuclear geometry that corresponds with a hydrogen bonded peroxide which acts as the entatic state for the generation of complexed molecular oxygen through S(3)(P) oxidation by Y(Z)(ox).

  2. Self-propagating solar light reduction of graphite oxide in water

    Energy Technology Data Exchange (ETDEWEB)

    Todorova, N.; Giannakopoulou, T.; Boukos, N.; Vermisoglou, E. [Institute of Nanoscience and Nanotechnology, NCSR “Demokritos”, 153 41 Attikis (Greece); Lekakou, C. [Division of Mechanical, Medical, and Aerospace Engineering, Faculty of Engineering and Physical Sciences, University of Surrey, Guildford (United Kingdom); Trapalis, C., E-mail: c.trapalis@inn.demokritos.gr [Institute of Nanoscience and Nanotechnology, NCSR “Demokritos”, 153 41 Attikis (Greece)

    2017-01-01

    Highlights: • Graphite oxide was partially reduced by solar light irradiation in water media. • No addition of catalysts nor reductive agent were used for the reduction. • Specific capacitance increased stepwise with increase of irradiation time. • Self-propagating reduction of graphene oxide by solar light is suggested. - Abstract: Graphite Oxide (GtO) is commonly used as an intermediate material for preparation of graphene in the form of reduced graphene oxide (rGO). Being a semiconductor with tunable band gap rGO is often coupled with various photocatalysts to enhance their visible light activity. The behavior of such rGO-based composites could be affected after prolonged exposure to solar light. In the present work, the alteration of the GtO properties under solar light irradiation is investigated. Water dispersions of GtO manufactured by oxidation of natural graphite via Hummers method were irradiated into solar light simulator for different periods of time without addition of catalysts or reductive agent. The FT-IR analysis of the treated dispersions revealed gradual reduction of the GtO with the increase of the irradiation time. The XRD, FT-IR and XPS analyses of the obtained solid materials confirmed the transition of GtO to rGO under solar light irradiation. The reduction of the GtO was also manifested by the CV measurements that revealed stepwise increase of the specific capacitance connected with the restoration of the sp{sup 2} domains. Photothermal self-propagating reduction of graphene oxide in aqueous media under solar light irradiation is suggested as a possible mechanism. The self-photoreduction of GtO utilizing solar light provides a green, sustainable route towards preparation of reduced graphene oxide. However, the instability of the GtO and partially reduced GO under irradiation should be considered when choosing the field of its application.

  3. Photosynthetic oxygen evolution: Changes in magnetism of the water-oxidizing enzyme

    Energy Technology Data Exchange (ETDEWEB)

    Sivaraja, M.; Dismukes, G.C. (Princeton Univ., NJ (USA)); Philo, J.S.; Lary, J. (Univ. of Connecticut, Storrs (USA))

    1989-04-26

    Changes in magnetic susceptibility produced by single-turnover flashes of light have been measured for the first time for four of the oxidation states, so-called S states, produced during oxygen evolution in Photosystem II (PSII) complexes of spinach. The data reveal new insights into the structure and bonding of the manganese cluster responsible for catalysis of water oxidation. In samples that have been dark adapted for 15 min or longer to favor population of the resting S{sub 1} state, a train of six flashes increases the paramagnetism on flashes 1, 3, and 5, while no or small increases are observed on flashes 2, 4, and 6. Advancement to the S{sub 1} state does not restore the dark level of S{sub 1} magnetism. This is due to two effects: formation of net paramagnetism from O{sub 2} release on the S{sub 4} {yields} S{sub 0} reaction (scavengeable by glucose oxidase) and a large increase in magnetism for the S{sub 1}(resting) {yields} S{sub 2} reaction, which is not restored without dark readaptation. Comparison of these data with models proposed for the structure of the manganese site reveals that models in which oxidation of substrate water occurs prior to S{sub 4} or oxidation of magnetically isolated Mn ions cannot account for the susceptibility changes observed. The large increase of 17 {mu}{sub B}{sup 2}/PSII observed for the S{sub 1} (resting) {yields} S{sub 2} oxidation is opposite in sign to the decrease in paramagnetism reported for oxidation of synthetic Mn dimers containing the {mu}{sub 2}-oxo-di-{mu}{sub 2}-carboxylato and di-{mu}{sub 2}-oxo-{mu}{sub 2}-carboxylato bridges undergoing the oxidation Mn{sub 2}(III,III) {yields} Mn{sub 2}(III,IV).

  4. Intramolecular Proton Transfer Boosts Water Oxidation Catalyzed by a Ru Complex

    Energy Technology Data Exchange (ETDEWEB)

    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 [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 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 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.

  5. Induced dipole in vanadium-doped zinc oxide nanosheets and its effects on photoelectrochemical water splitting

    Science.gov (United States)

    Lee, Song Mi; Shin, Sung-Ho; Nah, Junghyo; Lee, Min Hyung

    2017-09-01

    Appropriate control of energy band bending at the interface between semiconductors and electrolytes are closely related to performance of photoelectrochemical (PEC) water splitting. Dipoles formed near the surface of semiconductors induces energy band bending at the interface. Energy band bending control has been demonstrated by employing charged molecules and piezoelectric materials. However, chemical and piezoelectric approaches have demerit of chemical instability and inducement of instantaneous dipole, respectively. To overcome these problems, we adopted the ferroelectric material for PEC water splitting, where spontaneous dipoles in the material can be oriented by applying external electric field. In this work, we hydrothermally synthesized vanadium (V)-doped ferroelectric ZnO nanosheets and employed to systematically investigate the dipole effect on performance of V-doped ZnO PEC for water oxidation. Consequently, positively polarized V-doped ZnO photoanode exhibits 125% enhanced water splitting efficiency compared to negatively polarized ones due to favorable band bending for carrier transport from semiconductor to water.

  6. Development of bioinspired Mn4O4-cubane water oxidation catalysts: lessons from photosynthesis.

    Science.gov (United States)

    Dismukes, G Charles; Brimblecombe, Robin; Felton, Greg A N; Pryadun, Ruslan S; Sheats, John E; Spiccia, Leone; Swiegers, Gerhard F

    2009-12-21

    Hydrogen is the most promising fuel of the future owing to its carbon-free, high-energy content and potential to be efficiently converted into either electrical or thermal energy. The greatest technical barrier to accessing this renewable resource remains the inability to create inexpensive catalysts for the solar-driven oxidation of water. To date, the most efficient system that uses solar energy to oxidize water is the photosystem II water-oxidizing complex (PSII-WOC), which is found within naturally occurring photosynthetic organisms. The catalytic core of this enzyme is a CaMn(4)O(x) cluster, which is present in all known species of oxygenic phototrophs and has been conserved since the emergence of this type of photosynthesis about 2.5 billion years ago. The key features that facilitate the catalytic success of the PSII-WOC offer important lessons for the design of abiological water oxidation catalysts. In this Account, we examine the chemical principles that may govern the PSII-WOC by comparing the water oxidation capabilities of structurally related synthetic manganese-oxo complexes, particularly those with a cubical Mn(4)O(4) core ("cubanes"). We summarize this research, from the self-assembly of the first such clusters, through the elucidation of their mechanism of photoinduced rearrangement to release O(2), to recent advances highlighting their capability to catalyze sustained light-activated electrolysis of water. The [Mn(4)O(4)](6+) cubane core assembles spontaneously in solution from monomeric precursors or from [Mn(2)O(2)](3+) core complexes in the presence of metrically appropriate bidentate chelates, for example, diarylphosphinates (ligands of Ph(2)PO(2)(-) and 4-phenyl-substituted derivatives), which bridge pairs of Mn atoms on each cube face (Mn(4)O(4)L(6)). The [Mn(4)O(4)](6+) core is enlarged relative to the [Mn(2)O(2)](3+) core, resulting in considerably weaker Mn-O bonds. Cubanes are ferocious oxidizing agents, stronger than analogous complexes

  7. Sulfur Poisoning of the Water Gas Shift Reaction on Anode Supported Solid Oxide Fuel Cells

    DEFF Research Database (Denmark)

    Hagen, Anke

    2013-01-01

    resistance increased both in the high and low frequency region, which indicates a strong poisoning of the water gas shift reaction and thus a lack of hydrogen fuel in addition to the poisoning of the electrochemical hydrogen oxidation. All poisoning effects are reversible under the applied operating......Investigation of fuels containing sulfur impurities is important regarding durability of solid oxide fuel cells (SOFC) because they are present in various potential fuels for SOFC applications. The effect of H2S in the ppm range on the performance of state-of-the-art anode supported SOFC at 850...

  8. Formation of bioactive benzofuran via oxidative coupling, using coconut water (Cocos nucifera L. as biocatalyst

    Directory of Open Access Journals (Sweden)

    Luís Cezar Rodrigues

    2017-04-01

    Full Text Available The capacity of simple coconut water, which contains natural peroxidases, to act as a biocatalyst for the oxidative coupling-cyclization of p-(OH-phenylpropanoids, was evaluated in this work. As a result, dimeric forms of isoeugenol (licarin A and methyl p-coumarate (methyl dehydrodicoumarate were obtained. The products of the reactions were characterized by optical rotatory dispersion, and 1H-NMR and 13C-NMR spectroscopy. The oxidative coupling-cyclization mechanism for coniferyl alcohol is proposed.

  9. Biomarkers of oxidative damage in bacteria for the assessment of sanitation efficacy in lettuce wash water.

    Science.gov (United States)

    Cossu, Andrea; Dou, Fang; Young, Glenn M; Nitin, Nitin

    2017-07-01

    In the fresh produce industry, validation of sanitation efficacy is critical to prevent cross-contamination of produce. The current validation approaches are either based on time-consuming plate counting assays or indirect measurements of chemical properties of wash water. In the study, the focus was to identify biomarkers that can provide direct assessment of oxidative damage in bacteria upon exposure to sanitizers in the presence of fresh produce and correlation of these oxidative biomarkers with logarithmic inactivation of bacteria. Two endogenous bacterial biomarkers, protein carbonylation and thiol oxidation, were evaluated for assessing oxidative damage in Escherichia coli O157:H7 and Listeria innocua during sanitation of pre-cut lettuce leaves with NaOCl or H2O2. Results show that NaOCl treatment was more effective than H2O2 for oxidation of both the intracellular thiols and protein carbonylation in the selected strains. Statistical analysis of the measurements illustrates that oxidation of the intracellular thiol induced by NaOCl or H2O2 was correlated with logarithmic reduction of E. coli O157:H7 and L. innocua. In contrast, changes in the protein carbonylation content were not correlated with reduction in bacterial cell viability. In summary, these results provide a novel approach to validate sanitation efficacy for the fresh produce industry.

  10. Oxidation of Oil Sands Process-Affected Water by Potassium Ferrate(VI).

    Science.gov (United States)

    Wang, Chengjin; Klamerth, Nikolaus; Huang, Rongfu; Elnakar, Haitham; Gamal El-Din, Mohamed

    2016-04-19

    This paper investigates the oxidation of oil sands process-affected water (OSPW) by potassium ferrate(VI). Due to the selectivity of ferrate(VI) oxidation, two-ring and three-ring fluorescing aromatics were preferentially removed at doses oxidation achieved 64.0% and 78.4% removal of naphthenic acids (NAs) at the dose of 200 mg/L and 400 mg/L Fe(VI) respectively, and NAs with high carbon number and ring number were removed preferentially. (1)H nuclear magnetic resonance ((1)H NMR) spectra indicated that the oxidation of fluorescing aromatics resulted in the opening of some aromatic rings. Electron paramagnetic resonance (EPR) analysis detected signals of organic radical intermediates, indicating that one-electron transfer is one of the probable mechanisms in the oxidation of NAs. The inhibition effect of OSPW on Vibrio fischeri and the toxicity effect on goldfish primary kidney macrophages (PKMs) were both reduced after ferrate(VI) oxidation. The fluorescing aromatics in OSPW were proposed to be an important contributor to this acute toxicity. Degradation of model compounds with ferrate(VI) was also investigated and the results confirmed our findings in OSPW study.

  11. Ammonia-oxidizing Archaea in the Arctic Ocean and Antarctic coastal waters.

    Science.gov (United States)

    Kalanetra, Karen M; Bano, Nasreen; Hollibaugh, James T

    2009-09-01

    We compared abundance, distributions and phylogenetic composition of Crenarchaeota and ammonia-oxidizing Archaea (AOA) in samples collected from coastal waters west of the Antarctic Peninsula during the summers of 2005 and 2006, with samples from the central Arctic Ocean collected during the summer of 1997. Ammonia-oxidizing Archaea and Crenarchaeota abundances were estimated from quantitative PCR measurements of amoA and 16S rRNA gene abundances. Crenarchaeota and AOA were approximately fivefold more abundant at comparable depths in the Antarctic versus the Arctic Ocean. Crenarchaeota and AOA were essentially absent from the Antarctic Summer Surface Water (SSW) water mass (0-45 m depth). The ratio of Crenarchaeota 16S rRNA to archaeal amoA gene abundance in the Winter Water (WW) water mass (45-105 m depth) of the Southern Ocean was much lower (0.15) than expected and in sharp contrast to the ratio (2.0) in the Circumpolar Deep Water (CDW) water mass (105-3500 m depth) immediately below it. We did not observe comparable segregation of this ratio by depth or water mass in Arctic Ocean samples. A ubiquitous, abundant and polar-specific crenarchaeote was the dominant ribotype in the WW and important in the upper halocline of the Arctic Ocean. Our data suggest that this organism does not contain an ammonia monooxygenase gene. In contrast to other studies where Crenarchaeota populations apparently lacking amoA genes are found in bathypelagic waters, this organism appears to dominate in well-defined, ammonium-rich, near-surface water masses in polar oceans.

  12. Efficient Light-Driven Water Oxidation Catalysis by Dinuclear Ruthenium Complexes.

    Science.gov (United States)

    Berardi, Serena; Francàs, Laia; Neudeck, Sven; Maji, Somnath; Benet-Buchholz, Jordi; Meyer, Franc; Llobet, Antoni

    2015-11-01

    Mastering the light-induced four-electron oxidation of water to molecular oxygen is a key step towards the achievement of overall water splitting to produce alternative solar fuels. In this work, we report two rugged molecular pyrazolate-based diruthenium complexes that efficiently catalyze visible-light-driven water oxidation. These complexes were fully characterized both in the solid state (by X-ray diffraction analysis) and in solution (spectroscopically and electrochemically). Benchmark performances for homogeneous oxygen production have been obtained for both catalysts in the presence of a photosensitizer and a sacrificial electron acceptor at pH 7, and a turnover frequency of up to 11.1 s(-1) and a turnover number of 5300 were obtained after three successive catalytic runs. Under the same experimental conditions with the same setup, the pyrazolate-based diruthenium complexes outperform other well-known water oxidation catalysts owing to both electrochemical and mechanistic aspects. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Dioxygen and water activation processes on multi-Ru-substituted polyoxometalates: comparison with the "blue-dimer" water oxidation catalyst.

    Science.gov (United States)

    Kuznetsov, Aleksey E; Geletii, Yurii V; Hill, Craig L; Morokuma, Keiji; Musaev, Djamaladdin G

    2009-05-20

    Dioxygen and water activation on multi-Ru-substituted polyoxometalates were studied using the B3LYP density functional method. It was shown that the reaction of the Ru(2)-substituted gamma-Keggin polyoxotungstate {gamma-[(H(2)O)Ru(III)-(mu-OH)(2)-Ru(III)(H(2)O)][SiW(10)O(36)]}(4-), I(H(2)O), with O(2) is a 4-electron highly exothermic [DeltaE(gas) = 62.5 (DeltaE(gas) + DeltaG(solv(water)) = 24.6) kcal/mol] process and leads to formation of (H(2)O){gamma-[(O)Ru-(mu-OH)(2)-Ru(O)](H(2)O)[SiW(10)O(36)]}(4-), IV(H(2)O). Both the stepwise (or dissociative) and the concerted (or associative) pathways of this reaction occurring with and without water dissociation, respectively, were examined, and the latter has been found to be kinetically more favorable. It was shown that the first 1e-oxidation is achieved by the H(2)O-to-O(2) substitution, which might occur with a maximum of 23.1 (10.5) kcal/mol barrier and leads to the formation of {gamma-[(OO)Ru-(mu-OH)(2)-Ru(H(2)O)](H(2)O)[SiW(10)O(36)]}(4-), II(H(2)O). The second 1e-oxidation is initiated by the proton transfer from the coordinated water molecule to the superoxide (OO(-)) ligand in II(H(2)O) and is completed upon formation of hydroperoxo-hydroxo intermediate {gamma-[(OOH)Ru-(mu-OH)(2)-Ru(OH)](H(2)O)[SiW(10)O(36)]}(4-), III-1(H(2)O). The final 2e-oxidation occurs upon the proton transfer from the terminal OH-ligand to the Ru-coordinated OOH fragment and is completed at the formation of (H(2)O)...{gamma-[(O)Ru-(mu-OH)(2)-Ru(O)](H(2)O)[SiW(10)O(36)]}(4-), IV(H(2)O), with two Ru=O bonds. Each step in the associative pathway is exothermic and occurs with small energy barriers. During the process, the oxidation state of Ru centers increases from +3 to +4. The resulting IV(H(2)O) with a {Ru(O)-(mu-OH)(2)-Ru(O)} core should be formulated to have the Ru(IV)=O(*) units, rather than the Ru(V)=O groups. The reverse reaction, water oxidation by IV(H(2)O), is found to be highly endothermic and cannot occur; this finding is

  14. Effects of Water Molecule on CO Oxidation by OH: Reaction Pathways, Kinetic Barriers, and Rate Constants.

    Science.gov (United States)

    Zhang, Linyao; Yang, Li; Zhao, Yijun; Zhang, Jiaxu; Feng, Dongdong; Sun, Shaozeng

    2017-07-06

    The water dilute oxy-fuel combustion is a clean combustion technology for near-zero emission power; and the presence of water molecule could have both kinetic and dynamic effects on combustion reactions. The reaction OH + CO → CO 2 + H, one of the most important elementary reactions, has been investigated by extensive electronic structure calculations. And the effects of a single water molecule on CO oxidation have been studied by considering the preformed OH(H 2 O) complex reacts with CO. The results show little change in the reaction pathways, but the additional water molecule actually increases the vibrationally adiabatic energy barriers (V a G ). Further thermal rate constant calculations in the temperature range of 200 to 2000 K demonstrate that the total low-pressure limit rate constant for the water assisted OH(H 2 O) + CO → CO 2 + H 2 O + H reaction is 1-2 orders lower than that of the water unassisted one, which is consistent with the change of V a G . Therefore, the hydrated radical OH(H 2 O) would actually slow down the oxidation of CO. Meanwhile, comparisons show that the M06-2X/aug-cc-pVDZ method gives a much better estimation in energy and thus is recommended to be employed for direct dynamics simulations.

  15. Photocatalytic Oxidation of Oil Contaminated Water Using TiO2/UV

    Science.gov (United States)

    Vargas Solla, Monica; Romero Rojas, Jairo

    2017-04-01

    Currently, oil is one of the most used energy sources all around the world, for example to make motor engines work. That prevailing usage of oil is the reason why water sources are under serious pollution risks with compounds that are hard to remove, such as hydrocarbons. There are a few water treatment processes known as Advanced Oxidation Processes, which search for a way to treat polluted water with toxic refractory compounds, to make its reuse more feasible and to avoid or at least appease the injurious effects of pollution over ecosystems. A heterogeneous photocatalysis water treatment technology, sorted as an Advanced Oxidation Process, which is intended to treat refractory compound polluted water by the use of TiO2 and UV light, is presented in this investigation. The evidence about its efficiency in hydrocarbon removal from used motor oil polluted water, since it is an extremely important pollutant due to its complexity, toxicity and recalcitrant characteristics, is also presented through COD, Oil and Grease and Hydrocarbons analysis.

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

    Science.gov (United States)

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

    2012-09-25

    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 [Ru(II)(tpy)(bpm)(OH(2))](2+) (i.e., [Ru(II)-OH(2)](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 pK(a) calculations for the first two proton-coupled electron transfers (PCETs) from [Ru(II)-OH(2)](2+) to [Ru(IV) = O](2+) and the following electron-transfer process to [Ru(V) = O](3+) suggest that these processes can proceed readily in acidic or weakly basic conditions. The subsequent water splitting process involves two water molecules, [Ru(V) = O](3+) to generate [Ru(III)-OOH](2+), and H(3)O(+) 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 [Ru(III)-OOH](2+) to [Ru(IV)-OO](2+) when the pH is lower than 3.7. Two possible forms of [Ru(IV)-OO](2+), open and closed, can exist and interconvert with a low activation barrier (catalytic cycle. This understanding is helpful in the design of new catalysts for water oxidation.

  17. Chemical oxidation methods in the closure of paper mill water circulations; Hapetustekniikoiden kaeyttoe metsaeteollisuuden vesikiertojen sulkemisessa - EKT 04

    Energy Technology Data Exchange (ETDEWEB)

    Laari, A.; Kallas, J. [Lappeenranta Univ. of Technology (Finland); Korhonen, S. [Kuopio Univ. (Finland); Tuhkanen, T. [Mikkelin Ammattikorkeakoulu, Mikkeli (Finland)

    1998-12-31

    When water circulations are closed some harmful compounds tend to accumulate in the circulation waters. These compounds include lipophilic extractives, like resin and fatty acids, triglycerides and sterols, but also other compounds, like lignins, lignans and sugars. Microbial growth will increase due to elevated organic concentrations. The purpose of this project is to find out the possibilities of the use of ozonation and wet oxidation in the treatment of paper mill water circulations. In chemical oxidation organic matter is destroyed in oxidation reactions. Especially lipophilic extractives are selectively oxidated by ozone. Chemical oxidation reactions are carried out in gas-liquid reactors, where ozone or oxygen are transferred from gas to liquid phase where the oxidation reactions happen. One target of the project is to estimate kinetic parameters for different groups of compounds on the basis of experimental data. Kinetic parameters are then used in modelling of reactors and in estimation of process costs. (orig.)

  18. Laser-induced breakdown spectroscopy of light water reactor simulated used nuclear fuel: Main oxide phase

    Science.gov (United States)

    Campbell, Keri R.; Judge, Elizabeth J.; Barefield, James E.; Colgan, James P.; Kilcrease, David P.; Czerwinski, Ken R.; Clegg, Samuel M.

    2017-07-01

    The analysis of light water reactor simulated used nuclear fuel using laser-induced breakdown spectroscopy (LIBS) is explored using a simplified version of the main oxide phase. The main oxide phase consists of the actinides, lanthanides, and zirconium. The purpose of this study is to develop a rapid, quantitative technique for measuring zirconium in a uranium dioxide matrix without the need to dissolve the material. A second set of materials including cerium oxide is also analyzed to determine precision and limit of detection (LOD) using LIBS in a complex matrix. Two types of samples are used in this study: binary and ternary oxide pellets. The ternary oxide, (U,Zr,Ce)O2 pellets used in this study are a simplified version the main oxide phase of used nuclear fuel. The binary oxides, (U,Ce)O2 and (U,Zr)O2 are also examined to determine spectral emission lines for Ce and Zr, potential spectral interferences with uranium and baseline LOD values for Ce and Zr in a UO2 matrix. In the spectral range of 200 to 800 nm, 33 cerium lines and 25 zirconium lines were identified and shown to have linear correlation values (R2) > 0.97 for both the binary and ternary oxides. The cerium LOD in the (U,Ce)O2 matrix ranged from 0.34 to 1.08 wt% and 0.94 to 1.22 wt% in (U,Ce,Zr)O2 for 33 of Ce emission lines. The zirconium limit of detection in the (U,Zr)O2 matrix ranged from 0.84 to 1.15 wt% and 0.99 to 1.10 wt% in (U,Ce,Zr)O2 for 25 Zr lines. The effect of multiple elements in the plasma and the impact on the LOD is discussed.

  19. Spectroscopic Characterization of the Water Oxidation Intermediates in the Blue Dimer Ru-Based Catalyst for Artificial Photosynthesis

    Science.gov (United States)

    Moonshiram, Dooshaye; Pushkar, Yulia; Jurss, Jonah; Concepcion, Javier; Meyer, Thomas; Zakharova, Taisiya; Alperovich, Igor

    2012-02-01

    Utilization of sunlight requires solar capture, light-to-energy conversion and storage. One effective way to store energy is to convert it into chemical energy by fuel-forming reactions, such as water splitting into hydrogen and oxygen. Ruthenium complexes are among few molecular-defined catalysts capable of water splitting. Mechanistic insights about such catalysts can be acquired by spectroscopic analysis of short-lived intermediates of catalytic water oxidation. Use of techniques such as EPR and X-ray absorption spectroscopy (XAS) are used to determine electronic requirements of catalytic water oxidation. About 30 years ago Meyer and coworkers reported first ruthenium-based catalyst for water oxidation, the ``blue dimer''. We performed EPR studies and characterized structures and electronic configurations of intermediates of water oxidation by the ``blue dimer''. Intermediates were prepared chemically by oxidation of Ru-complexes with defined number of Ce (IV) equivalents and freeze-quenched at controlled times. Changes in oxidation state of Ru atom were detected by XANES at Ru K-edges. K-edges are sensitive to changes in Ru oxidation state for Blue Dimer [3,3]^4+, [3,4]^4+, [3,4]'^4+ and [4,5]^3+ allowing a clear assignment of Ru oxidation state in intermediates. EXAFS demonstrated structural changes.

  20. Research Update: Strategies for efficient photoelectrochemical water splitting using metal oxide photoanodes

    Directory of Open Access Journals (Sweden)

    Seungho Cho

    2014-01-01

    Full Text Available Photoelectrochemical (PEC water splitting to hydrogen is an attractive method for capturing and storing the solar energy in the form of chemical energy. Metal oxides are promising photoanode materials due to their low-cost synthetic routes and higher stability than other semiconductors. In this paper, we provide an overview of recent efforts to improve PEC efficiencies via applying a variety of fabrication strategies to metal oxide photoanodes including (i size and morphology-control, (ii metal oxide heterostructuring, (iii dopant incorporation, (iv attachments of quantum dots as sensitizer, (v attachments of plasmonic metal nanoparticles, and (vi co-catalyst coupling. Each strategy highlights the underlying principles and mechanisms for the performance enhancements.

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

    Science.gov (United States)

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

    2015-08-05

    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.

  2. Direct in Situ Measurement of Charge Transfer Processes During Photoelectrochemical Water Oxidation on Catalyzed Hematite.

    Science.gov (United States)

    Qiu, Jingjing; Hajibabaei, Hamed; Nellist, Michael R; Laskowski, Forrest A L; Hamann, Thomas W; Boettcher, Shannon W

    2017-09-27

    Electrocatalysts improve the efficiency of light-absorbing semiconductor photoanodes driving the oxygen evolution reaction, but the precise function(s) of the electrocatalysts remains unclear. We directly measure, for the first time, the interface carrier transport properties of a prototypical visible-light-absorbing semiconductor, α-Fe2O3, in contact with one of the fastest known water oxidation catalysts, Ni0.8Fe0.2O x , by directly measuring/controlling the current and/or voltage at the Ni0.8Fe0.2O x catalyst layer using a second working electrode. The measurements demonstrate that the majority of photogenerated holes in α-Fe2O3 directly transfer to the catalyst film over a wide range of conditions and that the Ni0.8Fe0.2O x is oxidized by photoholes to an operating potential sufficient to drive water oxidation at rates that match the photocurrent generated by the α-Fe2O3. The Ni0.8Fe0.2O x therefore acts as both a hole-collecting contact and a catalyst for the photoelectrochemical water oxidation process. Separate measurements show that the illuminated junction photovoltage across the α-Fe2O3|Ni0.8Fe0.2O x interface is significantly decreased by the oxidation of Ni(2+) to Ni(3+) and the associated increase in the Ni0.8Fe0.2O x electrical conductivity. In sum, the results illustrate the underlying operative charge-transfer and photovoltage generation mechanisms of catalyzed photoelectrodes, thus guiding their continued improvement.

  3. Molybdenum oxide nanocolloids prepared by an external field-assisted laser ablation in water

    Science.gov (United States)

    Spadaro, Salvatore; Bonsignore, Martina; Fazio, Enza; Cimino, Francesco; Speciale, Antonio; Trombetta, Domenico; Barreca, Francesco; Saija, Antonina; Neri, Fortunato

    2018-01-01

    he synthesis of extremely stable molybdenum oxide nanocolloids by pulsed laser ablation was studied. This green technique ensures the formation of contaminant-free nanostructures and the absence of by-products. A focused picosecond pulsed laser beam was used to ablate a solid molybdenum target immersed in deionized water. Molybdenum oxide nearly spherical nanoparticles with dimensions within few nanometers (20-100 nm) are synthesized when the ablation processes were carried out, in water, at room temperature and 80°C. The application of an external electric field during the ablation process induces a nanostructures reorganization, as indicated by Scanning-Transmission Electron Microscopy images analysis. The ablation products were also characterized by some spectroscopic techniques: conventional UV-vis optical absorption, atomic absorption, dynamic light scattering, micro-Raman and X-ray photoelectron spectroscopies. Finally, NIH/3T3 mouse fibroblasts were used to evaluate cell viability by the sulforhodamine B assay

  4. Molybdenum oxide nanocolloids prepared by an external field-assisted laser ablation in water

    Directory of Open Access Journals (Sweden)

    Spadaro Salvatore

    2018-01-01

    Full Text Available he synthesis of extremely stable molybdenum oxide nanocolloids by pulsed laser ablation was studied. This green technique ensures the formation of contaminant-free nanostructures and the absence of by-products. A focused picosecond pulsed laser beam was used to ablate a solid molybdenum target immersed in deionized water. Molybdenum oxide nearly spherical nanoparticles with dimensions within few nanometers (20-100 nm are synthesized when the ablation processes were carried out, in water, at room temperature and 80°C. The application of an external electric field during the ablation process induces a nanostructures reorganization, as indicated by Scanning-Transmission Electron Microscopy images analysis. The ablation products were also characterized by some spectroscopic techniques: conventional UV-vis optical absorption, atomic absorption, dynamic light scattering, micro-Raman and X-ray photoelectron spectroscopies. Finally, NIH/3T3 mouse fibroblasts were used to evaluate cell viability by the sulforhodamine B assay

  5. Carrier dynamics of a visible-light-responsive Ta3N5 photoanode for water oxidation

    KAUST Repository

    Ziani, Ahmed

    2015-01-01

    The physicochemical properties of a tantalum nitride (Ta3N5) photoanode were investigated in detail to understand the fundamental aspects associated with the photoelectrochemical (PEC) water oxidation. The Ta3N5 thin films were synthesized using DC magnetron sputtering followed by annealing in air and nitridation under ammonia (NH3). A polycrystalline structure with a dense morphology of the monoclinic Ta3N5 films was obtained. A relatively low absorption coefficient (104 to 105 cm-1) in the visible light range was measured for Ta3N5, consistent with the nature of the indirect band-gap. Ultra-fast spectroscopic measurements revealed that the Ta3N5 with different thicknesses films possess low transport properties and fast carrier recombination (<10 ps). These critical kinetic properties of Ta3N5 as a photoanode may necessitate high overpotentials to achieve appreciable photocurrents for water oxidation (onset ∼0.6 V vs. RHE). This journal is

  6. Bioinspired Cobalt-Citrate Metal-Organic Framework as an Efficient Electrocatalyst for Water Oxidation.

    Science.gov (United States)

    Jiang, Jing; Huang, Lan; Liu, Xiaomin; Ai, Lunhong

    2017-03-01

    Efficient and cost-effective oxygen evolution reaction (OER) electrocatalysts are closely associated with many important energy conversion technologies. Herein, we first report an oxygen-evolving cobalt-citrate metal-organic framework (MOF, UTSA-16) for highly efficient electrocatalytic water oxidation. Benefiting from synergistic cooperation of intrinsic open porous structure, in situ formed high valent cobalt species, and existing Co4O4 cubane, the UTSA-16 exhibits excellent activity toward OER catalysis in alkaline medium. The UTSA-16 needs only 408 mV to offer a current density of 10 mA cm-2 for OER catalysis, which is superior to that of most MOF-based electrocatalysts and the standard Co3O4 counterpart. The present finding provides a better understanding of electroactive MOFs for water oxidation.

  7. Reduction in exhaled nitric oxide tracks improved patient inhaler compliance in difficult asthma-a case study.

    Science.gov (United States)

    Hunt, Eoin; Flynn, Deirdre; MacHale, Elaine; Costello, Richard W; Murphy, Desmond M

    2017-12-26

    Exhaled nitric oxide is believed be a useful surrogate for airways inflammation while non-adherence with therapy is known to be associated with worsening of asthma control. We present the case of a 49-year-old female with steroid-dependent asthma and an exacerbation rate of >20/year. She was enrolled in a 3-month-long prospective study using a validated diagnostic inhaler device that provided objective evidence of inhaler compliance. Fractional exhaled nitric oxide (FeNO), peak expiratory flow rates, asthma control questionnaires were measured throughout the study period. Peripheral eosinophil count was obtained prior to the study, during the study, and immediately afterwards. Improvement in compliance at the end of the study led to significant improvements in lung function peak expiratory flow rate (PEFR), and objective scores of asthma. There was an observed improvement in PEFR after 4 weeks, with an associated decrease in FeNO from 92 to 9 ppb that plateaued over the remainder of the study. Her eosinophil count was 0.79 × 10 9 /litre prior to starting in the study, 0.37 × 10 9 /litre after 2 months, and 0.1 × 10 9 /litre at the end of the study. We believe that this is the first case study to objectively prove that improvements in compliance can lead to dramatic reductions in the overall inflammatory airway response and in particular that improvements in patient compliance are mirrored by marked reduction in FeNO levels. These changes occurred in tandem with an observed clinical improvement in our patient.

  8. Magnetic Resonance Cell-Tracking Studies: Spectrophotometry-Based Method for the Quantification of Cellular Iron Content after Loading with Superparamagnetic Iron Oxide Nanoparticles

    Directory of Open Access Journals (Sweden)

    Ingrid Böhm

    2011-07-01

    Full Text Available The purpose of this article is to present a user-friendly tool for quantifying the iron content of superparamagnetic labeled cells before cell tracking by magnetic resonance imaging (MRI. Iron quantification was evaluated by using Prussian blue staining and spectrophotometry. White blood cells were labeled with superparamagnetic iron oxide (SPIO nanoparticles. Labeling was confirmed by light microscopy. Subsequently, the cells were embedded in a phantom and scanned on a 3 T magnetic resonance tomography (MRT whole-body system. Mean peak wavelengths Λpeak was determined at A720nm (range 719–722 nm. Linearity was proven for the measuring range 0.5 to 10 μg Fe/mL (r = .9958; p = 2.2 × 10−12. The limit of detection was 0.01 μg Fe/mL (0.1785 mM, and the limit of quantification was 0.04 μg Fe/mL (0.714 mM. Accuracy was demonstrated by comparison with atomic absorption spectrometry. Precision and robustness were also proven. On T2-weighted images, signal intensity varied according to the iron concentration of SPIO-labeled cells. Absorption spectrophotometry is both a highly sensitive and user-friendly technique that is feasible for quantifying the iron content of magnetically labeled cells. The presented data suggest that spectrophotometry is a promising tool for promoting the implementation of magnetic resonance-based cell tracking in routine clinical applications (from bench to bedside.

  9. Fullerene-reduced graphene oxide composites obtained by ultrashort laser ablation of fullerite in water

    Energy Technology Data Exchange (ETDEWEB)

    De Bonis, A., E-mail: angela.debonis@unibas.it [Dipartimento di Scienze, Università degli Studi della Basilicata, Viale dell’Ateneo Lucano, 10-85100, Potenza (Italy); Curcio, M. [Dipartimento di Scienze, Università degli Studi della Basilicata, Viale dell’Ateneo Lucano, 10-85100, Potenza (Italy); Santagata, A. [CNR-ISM, U.O.S. Tito Scalo, Zona Industriale, 85050, Tito Scalo (PZ) (Italy); Rau, J.V. [CNR-ISM, Via del Fosso del Cavaliere, 100-00133, Rome (Italy); Galasso, A.; Teghil, R. [Dipartimento di Scienze, Università degli Studi della Basilicata, Viale dell’Ateneo Lucano, 10-85100, Potenza (Italy)

    2015-05-01

    Highlights: • Laser ablation of a fullerite target in water performed by an ultra-short laser source has been reported. • The formation of reduced graphene oxide has been described considering the laser ablation in liquid mechanism. • Fullerene-reduced graphene oxide composite, in the form of self assembled microtubes, has been described. - Abstract: The laser ablation in liquid of carbon-based solid targets is of particular interest thanks to the possibility of obtaining different carbon allotropes by varying the experimental parameters employed. The ablation of a fullerite target in water using a frequency-doubled Nd:glass laser source with a pulse duration of 250 fs and a frequency repetition rate of 10 Hz is presented. The obtained products have been characterized by transmission electron and atomic force microscopies and by X-ray photoelectron and micro-Raman spectroscopies. During the femtosecond laser ablation, the collapse of fullerene cages has been considered with the consequent formation of graphene oxide (GO) and its successive hydrogenation. The process of self-assembling in microtube structures of the formed reduced graphene oxide-fullerene composites has then been reported.

  10. Ligand Fluorination to Optimize Preferential Oxidation (PROX) of Carbon Monoxide by Water-Soluble Rhodium Porphyrins

    Science.gov (United States)

    Biffinger, Justin C.; Uppaluri, ShriHarsha; Sun, Haoran

    2011-01-01

    Catalytic, low temperature preferential oxidation (PROX) of carbon monoxide by aqueous [5,10,15,20-tetrakis(4-sulfonatophenyl)-2,3,7,8,12,13,17,18-octafluoroporphyrinato]rhodium(III) tetrasodium salt, (1[Rh(III)]) and [5,10,15,20-tetrakis(3-sulfonato-2,6-difluorophenyl)-2,3,7,8,12,13,17,18-octafluoroporphyrinato]rhodium(III) tetrasodium salt, (2[Rh(III)]) is reported. The PROX reaction occurs at ambient temperature in buffered (4 ≤ pH ≤ 13) aqueous solutions. Fluorination on the porphyrin periphery is shown to increase the CO PROX reaction rate, shift the metal centered redox potentials, and acidify ligated water molecules. Most importantly, β-fluorination increases the acidity of the rhodium hydride complex (pKa = 2.2 ± 0.2 for 2[Rh-D]); the dramatically increased acidity of the Rh(III) hydride complex precludes proton reduction and hydrogen activation near neutral pH, thereby permitting oxidation of CO to be unaffected by the presence of H2. This new fluorinated water-soluble rhodium porphyrin-based homogenous catalyst system permits preferential oxidation of carbon monoxide in hydrogen gas streams at 308 °K using dioxygen or a sacrificial electron acceptor (indigo carmine) as the terminal oxidant. PMID:21949596

  11. Oxidative treatments used to make water potable; Tratamientos oxidativos en la potabilizacion del agua

    Energy Technology Data Exchange (ETDEWEB)

    Gracia, R.; Cortes, S.; Sarasa, J.; Ormad, P.; Ovelleiro, J. L. [Universidad de Zaragoza (Spain)

    1999-08-01

    It is studied with pre-ozonation replacing pre-chlorination during drinking-water treatment for improving the water quality since the discovery of potentially harmful chlorination by products such as trihalomethanes (THM). Raw Ebro river (Spain) water is ozonated in the presence of titanium dioxide (TiO{sub 2}) supported on alumina as a catalyst and later chlorinated. It is shown that using this catalyst during ozonation of the natural water allowed reductions in organic matter and therefore in THM formation. Characterization of the organic compounds resulting from oxidation techniques was made by concentrating the sample through liquid-liquid extraction, along with the gas chromatography/mass spectrometry (GC/MS). THMs were measured by an head space connected to a gas chromatograph equipped with an electron capture detector (GC/ECD). (Author) 12 refs.

  12. Reduced Graphene Oxide Bipolar Membranes for Integrated Solar Water Splitting in Optimal pH.

    Science.gov (United States)

    McDonald, Michael B; Bruce, Jared P; McEleney, Kevin; Freund, Michael S

    2015-08-24

    The integration of light absorbers and catalysts for the water splitting process requires a membrane capable of both ion and electron management and product separation to realize efficient solar fuels systems. Bipolar membranes can maintain a pH gradient for optimal reaction conditions by the dissociation of water. Such membranes that contain graphene in the interfacial layer are fabricated by the chemical reduction of a uniformly deposited graphene oxide layer to convert sp(3) catalyst regions to sp(2) conductive regions. The resulting electrical and water dissociation properties are optimized by adjusting the exposure conditions, and treatments of less than 5 min render an interface that exceeds the conductivity requirements for integrated solar water splitting and increases the overpotential by graphene and Si microwires, and we found that efficient Ohmic junctions are possible. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Theoretical study of water oxidation and reduction mechanisms by aminopyridine first row transition metal catalysts

    OpenAIRE

    Acuña-Parés, Ferran

    2016-01-01

    One of the major current scientific goals is the development of renewable energy sources. An effective alternative to fossil fuels consists in the conversion of the sunlight energy into chemical fuels. The molecular hydrogen from water is considered the most promising energy carrier. In the natural photosynthesis the solar energy is stored into the carbohydrate chemical bonds derived from water and CO2. The key step of this process is the photo-oxidation of H2O molecules into O2, which provi...

  14. Implementing supercritical water oxidation technology in a lunar base environmental control/life support system

    Science.gov (United States)

    Meyer Sedej, M.

    1985-01-01

    A supercritical water oxidation system (SCWOS) offers several advantages for a lunar base environmental control/life support system (ECLSS) compared to an ECLSS based on Space Station technology. In supercritically heated water (630 K, 250 atm) organic materials mix freely with oxygen and undergo complete combustion. Inorganic salts lose solubility and precipitate out. Implementation of SCWOS can make an ECLSS more efficient and reliable by elimination of several subsystems and by reduction in potential losses of life support consumables. More complete closure of the total system reduces resupply requirements from the earth, a crucial cost item in maintaining a lunar base.

  15. Antioxidant effect of water and acetone extracts of Fucus vesiculosuson oxidative stability of skin care emulsions

    DEFF Research Database (Denmark)

    Poyato, Candelaria; Thomsen, Birgitte Raagaard; Hermund, Ditte Baun

    2017-01-01

    A water and an acetone extract of the Icelandic brown algae Fucus vesiculosus were evaluated as potential natural sources of antioxidant compounds in skin care emulsions. To assess their efficacy in inhibiting lipid oxidation caused by photo- or thermoxidation, they were stored in darkness and room...... temperature. High temperature also caused greater increments in the droplet size of the emulsions. The analysis of the tocopherol content, peroxide value and volatile compounds during the storage revealed that, whereas both water and acetone extracts showed (at 2 mg/g of emulsion) protective effect against...

  16. Enzyme-inspired functional surfactant for aerobic oxidation of activated alcohols to aldehydes in water

    KAUST Repository

    Chen, Batian

    2015-02-06

    We describe an enzyme-inspired catalytic system based on a rationally designed multifunctional amphiphile. The resulting micelles feature metal-binding sites and stable free radical moieties as well as fluorous pockets that attract and preconcentrate molecular oxygen. In the presence of copper ions, the micelles effect chemoselective aerobic alcohol oxidation under ambient conditions in water, a transformation that is challenging to achieve nonenzymatically.

  17. A new water oxidation catalyst: lithium manganese pyrophosphate with tunable Mn valency.

    Science.gov (United States)

    Park, Jimin; Kim, Hyunah; Jin, Kyoungsuk; Lee, Byung Ju; Park, Yong-Sun; Kim, Hyungsub; Park, Inchul; Yang, Ki Dong; Jeong, Hui-Yun; Kim, Jongsoon; Hong, Koo Tak; Jang, Ho Won; Kang, Kisuk; Nam, Ki Tae

    2014-03-19

    The development of a water oxidation catalyst has been a demanding challenge for the realization of overall water-splitting systems. Although intensive studies have explored the role of Mn element in water oxidation catalysis, it has been difficult to understand whether the catalytic capability originates mainly from either the Mn arrangement or the Mn valency. In this study, to decouple these two factors and to investigate the role of Mn valency on catalysis, we selected a new pyrophosphate-based Mn compound (Li2MnP2O7), which has not been utilized for water oxidation catalysis to date, as a model system. Due to the monophasic behavior of Li2MnP2O7 with delithiation, the Mn valency of Li(2-x)MnP2O7 (x = 0.3, 0.5, 1) can be controlled with negligible change in the crystal framework (e.g., volume change ~1%). Moreover, inductively coupled plasma mass spectrometry, X-ray photoelectron spectroscopy, ex-situ X-ray absorption near-edge structure, galvanostatic charging-discharging, and cyclic voltammetry analysis indicate that Li(2-x)MnP2O7 (x = 0.3, 0.5, 1) exhibits high catalytic stability without additional delithiation or phase transformation. Notably, we observed that, as the averaged oxidation state of Mn in Li(2-x)MnP2O7 increases from 2 to 3, the catalytic performance is enhanced in the series Li2MnP2O7 catalyst under neutral conditions with controlled Mn valency and atomic arrangement.

  18. [Removal of arsenic (II) by ferrate oxidation-coagulation from drinking water].

    Science.gov (United States)

    Yuan, Bao-ling; Li, Kun-lin; Deng, Lin-li; Zhang, Zhi-dong

    2006-02-01

    Ferrate is multi-function agent in water treatment and shows great oxidizing ability and excellent purifying effect. This experiment evaluated the performance of ferrate for arsenic removal. Experimental results show that the best rate of ferrate and arsenic (III) is 15:1, the efficiency of As removal can be achieved 98%, and the residual concentration of As3 + is removal arsenic. This method is easy, very effective comparing with ferric method and KMnO4-Ferric method.

  19. Oxidation of substituted phenols in supercritical water. Final technical report, September 1992--August 1996

    Energy Technology Data Exchange (ETDEWEB)

    Savage, P.E.

    1996-11-01

    Wastewaters from coal-conversion processes contain phenolic compounds in appreciable concentrations. These compounds need to be removed so that the water can be discharged or reused. Oxidation in supercritical water is one potential means of treating coal-conversion wastewaters, and this project examined the reactions of model pollutants in supercritical water. The decomposition of cresols, hydroxybenzaidehydes, nitrophenols, and benzenediols was studied in dilute aqueous solutions in both the presence and absence of oxygen at 460{degrees}C and 250 atm. Experimental data from the oxidation of these compounds were fit to global, power-law rate expressions. The resulting rate laws showed that the reactivity of the different isomers at 460{degrees}C was in the order of ortho > para > meta for cresols and hydroxybenzaldehydes. Moreover, the CHO-substituted phenol was more reactive than the analogous CH{sub 3}-substituted phenol, and all of these substituted phenols were more reactive than phenol itself. Identifying and quantifying the reaction products of incomplete oxidation allowed us to assemble a general reaction network for the oxidation of cresols in supercritical water. This network comprises parallel primary paths to phenol, to a hydroxybenzaldehyde, and to ring-opening products. The hydroxybenzaldehyde reacts through parallel paths to phenol and to ring-opening products. Phenol also reacts via two parallel paths, but these lead to phenol dimers; and ring-opening products. The dimers are eventually converted to ring-opening products, and the ring-opening products are ultimately converted to CO{sub 2} The relative rates of the different paths in the reaction network are strong functions of the location of the substituent on the phenolic ring.

  20. Chlorination of bromide-containing waters: enhanced bromate formation in the presence of synthetic metal oxides and deposits formed in drinking water distribution systems.

    Science.gov (United States)

    Liu, Chao; von Gunten, Urs; Croué, Jean-Philippe

    2013-09-15

    Bromate formation from the reaction between chlorine and bromide in homogeneous solution is a slow process. The present study investigated metal oxides enhanced bromate formation during chlorination of bromide-containing waters. Selected metal oxides enhanced the decay of hypobromous acid (HOBr), a requisite intermediate during the oxidation of bromide to bromate, via (i) disproportionation to bromate in the presence of nickel oxide (NiO) and cupric oxide (CuO), (ii) oxidation of a metal to a higher valence state in the presence of cuprous oxide (Cu2O) and (iii) oxygen formation by NiO and CuO. Goethite (α-FeOOH) did not enhance either of these pathways. Non-charged species of metal oxides seem to be responsible for the catalytic disproportionation which shows its highest rate in the pH range near the pKa of HOBr. Due to the ability to catalyze HOBr disproportionation, bromate was formed during chlorination of bromide-containing waters in the presence of CuO and NiO, whereas no bromate was detected in the presence of Cu2O and α-FeOOH for analogous conditions. The inhibition ability of coexisting anions on bromate formation at pH 8.6 follows the sequence of phosphate > sulfate > bicarbonate/carbonate. A black deposit in a water pipe harvested from a drinking water distribution system exerted significant residual oxidant decay and bromate formation during chlorination of bromide-containing waters. Energy dispersive spectroscopy (EDS) analyses showed that the black deposit contained copper (14%, atomic percentage) and nickel (1.8%, atomic percentage). Cupric oxide was further confirmed by X-ray diffraction (XRD). These results indicate that bromate formation may be of concern during chlorination of bromide-containing waters in distribution systems containing CuO and/or NiO. Copyright © 2013 Elsevier Ltd. All rights reserved.

  1. Chlorination of bromide-containing waters: Enhanced bromate formation in the presence ofsynthetic metal oxides and deposits formed indrinking water distribution systems

    KAUST Repository

    Liu, Chao

    2013-09-01

    Bromate formation from the reaction between chlorine and bromide in homogeneous solution is a slow process. The present study investigated metal oxides enhanced bromate formation during chlorination of bromide-containing waters. Selected metal oxides enhanced the decay of hypobromous acid (HOBr), a requisite intermediate during the oxidation of bromide to bromate, via (i) disproportionation to bromate in the presence of nickel oxide (NiO) and cupric oxide (CuO), (ii) oxidation of a metal to a higher valence state in the presence of cuprous oxide (Cu2O) and (iii) oxygen formation by NiO and CuO. Goethite (α-FeOOH) did not enhance either of these pathways. Non-charged species of metal oxides seem to be responsible for the catalytic disproportionation which shows its highest rate in the pH range near the pKa of HOBr. Due to the ability to catalyze HOBr disproportionation, bromate was formed during chlorination of bromide-containing waters in the presence of CuO and NiO, whereas no bromate was detected in the presence of Cu2O and α-FeOOH for analogous conditions. The inhibition ability of coexisting anions on bromate formation at pH 8.6 follows the sequence of phosphate>>sulfate>bicarbonate/carbonate. A black deposit in a water pipe harvested from a drinking water distribution system exerted significant residual oxidant decay and bromate formation during chlorination of bromide-containing waters. Energy dispersive spectroscopy (EDS) analyses showed that the black deposit contained copper (14%, atomic percentage) and nickel (1.8%, atomic percentage). Cupric oxide was further confirmed by X-ray diffraction (XRD). These results indicate that bromate formation may be of concern during chlorination of bromide-containing waters in distribution systems containing CuO and/or NiO. © 2013 Elsevier Ltd.

  2. Role of Oxygen Functionalities in Graphene Oxide Architectural Laminate Subnanometer Spacing and Water Transport.

    Science.gov (United States)

    Amadei, Carlo Alberto; Montessori, Andrea; Kadow, Julian P; Succi, Sauro; Vecitis, Chad D

    2017-04-18

    Active research in nanotechnology contemplates the use of nanomaterials for environmental engineering applications. However, a primary challenge is understanding the effects of nanomaterial properties on industrial device performance and translating unique nanoscale properties to the macroscale. One emerging example consists of graphene oxide (GO) membranes for separation processes. Thus, here we investigate how individual GO properties can impact GO membrane characteristics and water permeability. GO chemistry and morphology were controlled with easy-to-implement photoreduction and sonication techniques and were quantitatively correlated, offering a valuable tool for accelerating characterization. Chemical GO modification allows for fine control of GO oxidation state, allowing control of GO architectural laminate (GOAL) spacing and permeability. Water permeability was measured for eight GOALs characterized by different GOAL chemistry and morphology and indicates that GOAL nanochannel height dictates water transport. The experimental outputs were corroborated with mesoscale water transport simulations of relatively large domains (thousands of square nanometers) and indicate a no-slip Darcy-like behavior inside the GOAL nanochannels. The experimental and simulation evidence presented in this study helps create a clearer picture of water transport in GOAL and can be used to rationally design more effective and efficient GO membranes.

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

    Science.gov (United States)

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

    2018-03-01

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

  4. Potential climate change effects on water tables and pyrite oxidation in headwater catchments in Colorado

    Science.gov (United States)

    Webb, Richard M.; Mast, M. Alisa; Manning, Andrew H.; Clow, David W.; Campbell, Donald H.; Medley, C. Nicholas; Patterson, Glenn; Parker, Melanie J.

    2011-01-01

    A water, energy, and biogeochemical model (WEBMOD) was constructed to simulate hydrology and pyrite oxidation for the period October 1992 through September 1997. The hydrologic model simulates processes in Loch Vale, a 6.6-km² granitic watershed that drains the east side of the Continental Divide. Parameters describing pyrite oxidation were derived sulfate concentrations measured in pore water and stream water in Handcart Gulch, a naturally acidic watershed in the Colorado Mineral Belt. Average monthly differences in precipitation and temperature between current and future climates, as predicted by using six global circulation models and three carbondioxide emission scenarios, were input into WEBMOD to identify possible shifts in the quantity and quality of the water flowing from the watershed for the period 2005 through 2100. Initial results suggest that increased air temperatures will result in earlier snowmelt compared to current conditions. Average sulfate concentrations and acidity in streams draining hydrothermally altered terrain may decrease as water tables rise in response to greater overall precipitation and earlier snowmelt, although a net increase of sulfate load was simulated as a result of greater overall discharge. Evapotranspiration is expected to increase but not enough to offset the increase in precipitation.

  5. Iminium salts and their derivatives as models for catalytic water oxidation

    Science.gov (United States)

    Khatmullin, Renat R.

    The solar energy utilization is one of the most promising strategies for catering the ever-increasing energy demand in a renewable manner. For this reason, several approaches are pursued for solar energy storage, one of which involves the photocatalytic splitting of water. Over recent years, much research has been directed towards the design of transition-metal based water oxidation catalysts to obtain oxygen based on transition metal complexes. The major drawback of most of these catalysts is the cost of transition- metal complexes. For these reasons, the main focus of our research is based on the design of a fully organic catalyst suitable for water oxidation. Our group recently discovered that a flavinium ion performs electrode-mediated electrocatalytic water oxidation at large overpotentials. It was found that catalysis occurs only in the presence of the electrodes that produce active oxides on their surfaces. The mechanism of the catalysis by the flavinium ions was proposed to involve the coupling reaction two oxygen-centered radicals, one of which is derived from to the flavin moiety and the other one is formed at the electrode surface. The electrochemical oxidation of the formed peroxide species then proposed to release the oxygen molecule and recover the catalyst. However, it is important to note, that the detailed study of the mechanism is limited due the fact that electrode participates in the catalytic cycle. For these reasons, it is crucial to develop a fully homogeneous system to study the mechanism of the catalysis. One approach towards a fully molecular catalysis involves a system composed of two- iminium ion moieties joined covalently by a suitable linker. The mechanism of a catalysis is proposed to involve four individual steps: (i) pseudobase formation via a reaction of flavinium ions with water; (ii) proton-coupled oxidation of pseudobases to generate alkoxyl radicals; (iii) coupling of alkoxyl radicals to generate the peroxide intermediate; (iv

  6. Effectiveness of electrolyzed oxidizing water treatment in removing pesticide residues and its effect on produce quality.

    Science.gov (United States)

    Qi, Hang; Huang, Qingguo; Hung, Yen-Con

    2018-01-15

    This study evaluated the effects of electrolyzed oxidizing (EO) water treatment on the removal of pesticide residues (diazinon, cyprodinil and phosmet) from spinach, snap beans and grapes, and the effect on produce quality. High available chlorine content (ACC) and long treatment time of EO water resulted in high pesticide removals. Up to 59.2, 66.5 and 37.1% of diazinon; 43.8, 50.0 and 31.5% of cyprodinil; 85.7, 73.0 and 49.4% of phosmet; were removed from spinach, snap beans and grapes, respectively, after 15min EO water treatment at 120mg/l ACC. EO water was also more effective than electrolyzed reduced water, bleach, VegWash and DI water on pesticide removal. In addition, no significant colour or texture deterioration were found on produce samples treated with EO water. It was concluded, EO water can be very effective in pesticide residue removal from fresh produce without affecting the produce quality. Copyright © 2017 Elsevier Ltd. All rights reserved.

  7. Degradation of fluoroquinolone antibiotics by ferrate(VI): Effects of water constituents and oxidized products.

    Science.gov (United States)

    Feng, Mingbao; Wang, Xinghao; Chen, Jing; Qu, Ruijuan; Sui, Yunxia; Cizmas, Leslie; Wang, Zunyao; Sharma, Virender K

    2016-10-15

    The degradation of five fluoroquinolone (FQ) antibiotics (flumequine (FLU), enrofloxacin (ENR), norfloxacin (NOR), ofloxacin (OFL) and marbofloxacin (MAR)) by ferrate(VI) (Fe(VI)O4(2-), Fe(VI)) was examined to demonstrate the potential of this iron-based chemical oxidant to treat antibiotics in water. Experiments were conducted at different molar ratios of Fe(VI) to FQs at pH 7.0. All FQs, except FLU, were degraded within 2 min at [Fe(VI)]:[FQ] ≤ 20.0. Multiple additions of Fe(VI) improved the degradation efficiency, and provided greater degradation than a single addition of Fe(VI). The effects of anions, cations, and humic acid (HA), usually present in source waters and wastewaters, on the removal of FLU were investigated. Anions (Cl(-), SO4(2-), NO3(-), and HCO3(-)) and monovalent cations (Na(+) and K(+)) had no influence on the removal of FLU. However, multivalent cations (Ca(2+), Mg(2+), Cu(2+), and Fe(3+)) in water decreased the efficiency of FLU removal by Fe(VI). An increase in the ionic strength of the solution, and the presence of HA in the water, also decreased the percentage of FLU removed by Fe(VI). Experiments on the removal of selected FQs, present as co-existing antibiotics in pure water, river water, synthetic water and wastewater, were also conducted to demonstrate the practical application of Fe(VI) to remove the antibiotics during water treatment. The seventeen oxidized products (OPs) of FLU were identified using solid phase extraction-liquid chromatography-high-resolution mass spectrometry. The reaction pathways are proposed, and are theoretically confirmed by molecular orbital calculations. Copyright © 2016 Elsevier Ltd. All rights reserved.

  8. Distribution of manganese species in an oxidative dimerization reaction of a bis-terpyridine mononuclear manganese (II) complex and their heterogeneous water oxidation activities.

    Science.gov (United States)

    Takahashi, Kosuke; Sato, Taisei; Yamazaki, Hirosato; Yagi, Masayuki

    2015-11-01

    Heterogeneous water oxidation catalyses were studied as a synthetic model of oxygen evolving complex (OEC) in photosynthesis using mica adsorbing various manganese species. Distribution of manganese species formed in the oxidative dimerization reaction of [Mn(II)(terpy)2](2+) (terpy=2,2':6',2″-terpyridine) (1') with various oxidants in water was revealed. 1' was stoichiometrically oxidized to form di-μ-oxo dinuclear manganese complex, [(OH2)(terpy)Mn(III)(μ-O)2Mn(IV)(terpy)(OH2)](3+) (1) by KMnO4 as an oxidant. When Oxone and Ce(IV) oxidants were used, the further oxidation of 1 to [(OH2)(terpy)Mn(IV)(μ-O)2Mn(IV)(terpy)(OH2)](4+) (2) was observed after the oxidative dimerization reaction of 1'. The mica adsorbates with various composition of 1', 1 and 2 were prepared by adding mica suspension to the various oxidant-treated solutions followed by filtration. The heterogeneous water oxidation catalysis by the mica adsorbates was examined using a Ce(IV) oxidant. The observed catalytic activity of the mica adsorbates corresponded to a content of 1 (1ads) adsorbed on mica for KMnO4- and Oxone-treated systems, indicating that 1' (1'ads) and 2 (2ads) adsorbed on mica do not work for the catalysis. The kinetic analysis suggested that 1ads works for the catalysis through cooperation with adjacent 1ads or 2ads, meaning that 2ads assists the cooperative catalysis by 1ads though 2ads is not able to work for the catalysis alone. For the Ce(IV)-treated system, O2 evolution was hardly observed although the sufficient amount of 1ads was contained in the mica adsorbates. This was explained by the impeded penetration of Ce(IV) ions (as an oxidant for water oxidation) into mica by Ce(3+) cations (generated in oxidative dimerization of 1') co-adsorbed with 1ads. Copyright © 2015 Elsevier B.V. All rights reserved.

  9. Supercritical water oxidation of Quinazoline: Effects of conversion parameters and reaction mechanism.

    Science.gov (United States)

    Gong, Yanmeng; Guo, Yang; Wang, Shuzhong; Song, Wenhan

    2016-09-01

    The supercritical water oxidation reaction of quinazoline and a set of related reaction products were investigated in batch reactors by varying the temperature (T, 400-600 °C), time (t, 0-400 s), water density (ρ, 70.79-166.28  kg m(-3)) and oxidation coefficient (OC, 0-4.0). The TOC removal efficiency (CRE) increased significantly as the OC increased, whereas this effect was very limited at high OC (>2.0). Lack of oxygen resulted in low CRE and TN removal efficiency (NRE), also cause coke-formation, and giving high yield of NH3 and nitrogenous organic intermediates. Prolonging reaction time did not provide an appreciable improvement on CRE but remarkably increased NRE at temperature higher than 500 °C. Pyrimidines and pyridines as the nitrogenous intermediates were largely found in GC-MS spectrum. Polymerization among benzene, phenyl radical and benzyl radical played important roles in the formation of PAHs, such as naphthalene, biphenyl, phenanthrene. These collective results showed how the yield of intermediate products responded to changes in the process variables, which permitted the development of a potential reaction network for supercritical water oxidation of quinazoline. Copyright © 2016 Elsevier Ltd. All rights reserved.

  10. Supercritical Water Oxidation: A Solution for the Elimination of Back-End Organic Reprocessing Wastes

    Energy Technology Data Exchange (ETDEWEB)

    Leybros, A.; Roubaud, A.; Turc, H.A.; Fournel, B. [Supercritical fluids and membranes Laboratory, CEA Valrho, BP 17171, 30207 Bagnols/Ceze Cedex (France)

    2008-07-01

    Supercritical water oxidation (SCWO) is a very efficient technique for total elimination of organic wastes from reprocessing activities on the way of 'zero wastes' facilities. This technology uses the properties of supercritical water (P > 221 bars and T > 647 K) to obtain a good mixing between oxygen (the oxidant) and the organic waste. Thereby, the oxidation reaction is fast and complete. Using the SCWO process, contamination contained in organic materials like spent solvents can be confined in a closed space, like a reactor in a glovebox. A new application is tested for the treatment of solid organic wastes like ion exchange resins (IER). Experiments are made with suspensions of IER in water and isopropyl-alcohol. A nuclear version of the process with the double shell reactor has been constructed and is being tested. The aim of this work is to obtain a treatment capacity of 1 kg/h for the nuclear version with the same global set-up, concept of process and security as well as contamination management as for a 200 g/h pilot. (authors)

  11. Foot of the Wave Analysis for Mechanistic Elucidation and Benchmarking Applications in Molecular Water Oxidation Catalysis.

    Science.gov (United States)

    Matheu, Roc; Neudeck, Sven; Meyer, Franc; Sala, Xavier; Llobet, Antoni

    2016-12-08

    The description of the foot of the wave analysis (FOWA) applied to the electrocatalytic oxidation of water to dioxygen is reported for cases where the rate determining step is first order and second order with regard to catalyst concentration, coinciding mechanistically with the so-called water nucleophilic attack (WNA) and the interaction of two M-O units (I2M, where M represents the metal center of the catalyst), respectively. The newly adapted equations are applied to a range of relevant molecular catalysts, both in homogeneous and heterogeneous phase, and the kinetic parameters are determined, including apparent rate constants and turnover frequencies. In this respect, the application of FOWA at different catalyst concentrations allows elucidation of the reaction mechanism that operates in each case. In addition, catalytic Tafel plots are used for assessing the performance of several molecular water oxidation catalysts (WOCs) as a function of overpotential under analogous conditions, and thus can be used for benchmarking purposes. This analysis was carried out earlier for oxide-based WOCs; however, this is the first report using molecular WOCs. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Efficient Photoelectrochemical Water Oxidation by Metal-Doped Bismuth Vanadate Photoanode with Iron Oxyhydroxide Electrocatalyst

    Directory of Open Access Journals (Sweden)

    Eun Jin Joo

    2016-01-01

    Full Text Available Intensive attention has been currently focused on the discovery of semiconductor and proficient cocatalysts for eventual applications to the photoelectrochemical water splitting system. A W-Mo-doped BiVO4 semiconductor was prepared by the surfactant-assisted thermal decomposition method on a fluorine-doped tin oxide conductive film. The W-Mo-doped BiVO4 films showed a porous morphology with the grain sizes of about 270 nm. Because the hole diffusion length of BiVO4 is about 100 nm, the W-Mo-doped BiVO4 film in this study is an ideal candidate for the photoelectrochemical water oxidation. Iron oxyhydroxide (FeOOH electrocatalyst was chemically deposited on the W-Mo-doped BiVO4 to investigate the effect of the electrocatalyst on the semiconductor. The W-Mo-doped BiVO4/FeOOH composite electrode showed enhanced activity compared to the pristine W-Mo-doped BiVO4 electrode for water oxidation reaction. The chemical deposition is a promising method for the deposition of FeOOH on semiconductor.

  13. Oxidation of chlorfenvinphos in ultrapure and natural waters by ozonation and photochemical processes.

    Science.gov (United States)

    Acero, Juan L; Real, Francisco J; Javier Benitez, F; González, Antonio

    2008-06-01

    The chemical oxidation of the organophosphorus insecticide chlorfenvinphos, a priority pollutant in aquatic environments, has been conducted in ultrapure water, by means of single degradation agents (ozone and UV radiation), and by the Advanced Oxidation Processes constituted by combinations of these oxidants (O(3)/H(2)O(2) and UV/H(2)O(2)). The influence of the operating variables was discussed, and the degradation rates were evaluated by determining the rate constants for the reactions with ozone (k(O)(3)=3.7+/-0.2 L mol(-1)s(-1)) and OH radicals (k(OH)=(3.2+/-0.2)x10(9) L mol(-1)s(-1)), as well as the quantum yield for the photodegradation (around 0.1 mol E(-1), depending on the pH). Additionally, the ozonation of chlorfenvinphos in a natural water system (a surface water from a reservoir) was studied. The influence of the operating conditions on the insecticide removal efficiency was established, and the R(ct) parameter was evaluated. A kinetic model was proposed for the prediction of the elimination rate of chlorfenvinphos in the ozonation process and the results obtained reveal a good agreement between experimental results and predicted values.

  14. Direct Energy Recovery from Primary and Secondary Sludges by Supercritical Water Oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Svanstroem, Magdalena; Modell, Michael; Tester, Jefferson

    2003-07-01

    Supercritical water oxidation (SCWO) oxidizes organic and biological materials virtually completely to benign products without the need for stack gas scrubbing. Heavy metals are recovered as stabilized solid, along with the sand and clay that is present in the feed. The technology has been under development for twenty years. The major obstacle to commercialization has been developing reactors that are not clogged by inorganic solid deposits. That problem has been solved by using tubular reactors with fluid velocities that are high enough to keep solids in suspension. Recently, system designs have been created that reduce the cost of processing sewage sludges below that of incineration. At 10 wt-% dry solids, sludge can be oxidized with virtually complete recovery of the sludge heating value as hot water or high-pressure steam. Liquid carbon dioxide of high purity can be recovered from the gaseous effluent and excess oxygen can be recovered for recycle. The net effect is to reduce the stack to a harmless vent with minimal flow rate of a clean gas. Complete simulations have been developed using physical property models that accurately simulate the thermodynamic properties of sub- and supercritical water in mixtures with O{sub 2}, N{sub 2}, CO{sub 2}. and organics. Capital and operating cost estimates are given for sewage sludge treatment, which are less costly than incineration. The scenario of direct recovery of energy from sludges has inherent benefits compared to other gasification or liquefaction options. (author)

  15. Partial oxidation of n-hexadecane through decomposition of hydrogen peroxide in supercritical water

    KAUST Repository

    Alshammari, Y.M.

    2015-01-01

    © 2014 The Institution of Chemical Engineers. This work reports the experimental analysis of partial oxidation of n-hexadecane under supercritical water conditions. A novel reactor flow system was developed which allows for total decomposition of hydrogen peroxide in a separate reactor followed partial oxidation of n-hexadecane in a gasification reactor instead of having both reactions in one reactor. The kinetics of hydrothermal decomposition of hydrogen peroxide was studied in order to confirm its full conversion into water and oxygen under the desired partial oxidation conditions, and the kinetic data were found in a good agreement with previously reported literature. The gas yield and gasification efficiency were investigated under different operating parameters. Furthermore, the profile of C-C/C=C ratio was studied which showed the favourable conditions for maximising yields of n-alkanes via hydrogenation of their corresponding 1-alkenes. Enhanced hydrogenation of 1-alkenes was observed at higher O/C ratios and higher residence times, shown by the increase in the C-C/C=C ratio to more than unity, while increasing the temperature has shown much less effect on the C-C/C=C ratio at the current experimental conditions. In addition, GC-MS analysis of liquid samples revealed the formation of heavy oxygenated compounds which may suggest a new addition reaction to account for their formation under the current experimental conditions. Results show new promising routes for hydrogen production with in situ hydrogenation of heavy hydrocarbons in a supercritical water reactor.

  16. Probabilistic analysis showing that a combination of bacteroides and methanobrevibacter source tracking markers is effective for identifying waters contaminated by human fecal pollution

    Science.gov (United States)

    Johnston, Christopher; Byappanahalli, Muruleedhara N.; Gibson, Jacqueline MacDonald; Ufnar, Jennifer A.; Whitman, Richard L.; Stewart, Jill R.

    2013-01-01

    Microbial source tracking assays to identify sources of waterborne contamination typically target genetic markers of host-specific microorganisms. However, no bacterial marker has been shown to be 100% host-specific, and cross-reactivity has been noted in studies evaluating known source samples. Using 485 challenge samples from 20 different human and animal fecal sources, this study evaluated microbial source tracking markers including the Bacteroides HF183 16S rRNA, M. smithii nifH, and Enterococcus esp gene targets that have been proposed as potential indicators of human fecal contamination. Bayes' Theorem was used to calculate the conditional probability that these markers or a combination of markers can correctly identify human sources of fecal pollution. All three human-associated markers were detected in 100% of the sewage samples analyzed. Bacteroides HF183 was the most effective marker for determining whether contamination was specifically from a human source, and greater than 98% certainty that contamination was from a human source was shown when both Bacteroides HF183 and M. smithii nifH markers were present. A high degree of certainty was attained even in cases where the prior probability of human fecal contamination was as low as 8.5%. The combination of Bacteroides HF183 and M. smithii nifH source tracking markers can help identify surface waters impacted by human fecal contamination, information useful for prioritizing restoration activities or assessing health risks from exposure to contaminated waters.

  17. Semiconductor Metal Oxide Sensors in Water and Water Based Biological Systems

    Directory of Open Access Journals (Sweden)

    Marina V. Strobkova

    2003-10-01

    Full Text Available The results of implementation of In2O3-based semiconductor sensors for oxygen concentration evaluation in water and the LB-nutrient media (15.5 g/l Luria Broth Base, Miller (Sigma, Lot-1900 and NaCl without bacteria and with E.coli bacteria before and after UV-irradiation are presented.

  18. Influence of water column dynamics on sulfide oxidation and other major biogeochemical processes in the chemocline of Mariager Fjord (Denmark)

    DEFF Research Database (Denmark)

    Zopfi, J.; Ferdelman, TG; Jørgensen, BB

    2001-01-01

    steady-stare conditions, the upward fluxes of reductants and downward fluxes of oxidants in the water column were balanced. However, changes in the hydrographical conditions caused a transient nonsteady-state at the chemocline and had a great impact on process rates and the distribution of chemical...... species. Maxima of S-0 (17.8 mu mol l(-1)), thiosulfate (5.2 mu mol l(-1)) and sulfite (1.1 mu mol l(-1)) occurred at the chemocline, but were hardly detectable in the sulfidic deep water. The distribution of S-0 suggested that the high concentration of S-0 was (a) more likely due to a low turnover than...... oxidation may account for more than 88% of the total sulfide oxidation. Under nonsteady-state conditions, where oxic and sulfidic water masses were recently mixed, resulting in an expanded chemocline, the proportion of chemical sulfide oxidation increased. The sulfide oxidation rate determined by incubation...

  19. Direct technique for monitoring lipid oxidation in water-in-oil emulsions based on micro-calorimetry.

    Science.gov (United States)

    Dridi, Wafa; Toutain, Jean; Sommier, Alain; Essafi, Wafa; Leal-Calderon, Fernando; Cansell, Maud

    2017-09-01

    An experimental device based on the measurement of the heat flux dissipated during chemical reactions, previously validated for monitoring lipid oxidation in plant oils, was extended to follow lipid oxidation in water-in-oil emulsions. Firstly, validation of the approach was performed by correlating conjugated diene concentrations measured by spectrophotometry and the heat flux dissipated by oxidation reactions and measured directly in water-in-oil emulsions, in isothermal conditions at 60°C. Secondly, several emulsions based on plant oils differing in their n-3 fatty acid content were compared. The oxidability parameter derived from the enthalpy curves reflected the α-linolenic acid proportion in the oils. On the whole, the micro-calorimetry technique provides a sensitive method to assess lipid oxidation in water-in-oil emulsions without requiring any phase extraction. Copyright © 2017 Elsevier Ltd. All rights reserved.

  20. Protein-functionalized magnetic iron oxide nanoparticles: time efficient potential-water treatment

    Energy Technology Data Exchange (ETDEWEB)

    Okoli, Chuka [Royal Institute of Technology (KTH), Environmental Microbiology (Sweden); Boutonnet, Magali; Jaeras, Sven [Royal Institute of Technology (KTH), Chemical Technology (Sweden); Rajarao-Kuttuva, Gunaratna, E-mail: gkr@kth.se [Royal Institute of Technology (KTH), Environmental Microbiology (Sweden)

    2012-10-15

    Recent advances in nanoscience suggest that the existing issues involving water quality could be resolved or greatly improved using nanomaterials, especially magnetic iron oxide nanoparticles. Magnetic nanoparticles have been synthesized for the development and use, in association with natural coagulant protein for water treatment. The nanoparticles size, morphology, structure, and magnetic properties were characterized by transmission electron microscope, X-ray diffraction, and superconducting quantum interference device magnetometry. Purified Moringa oleifera protein was attached onto microemulsions-prepared magnetic iron oxide nanoparticles (ME-MION) to form stable protein-functionalized magnetic nanoparticles (PMO+ME-MION). The turbidity removal efficiency in both synthetic and surface water samples were investigated and compared with the commonly used synthetic coagulant (alum) as well as PMO. More than 90 % turbidity could be removed from the surface waters within 12 min by magnetic separation of PMO+ME-MION; whereas gravimetrically, 70 % removal in high and low turbid waters can be achieved within 60 min. In contrast, alum requires 180 min to reduce the turbidity of low turbid water sample. These data support the advantage of separation with external magnetic field (magnetophoresis) over gravitational force. Time kinetics studies show a significant enhancement in ME-MION efficiency after binding with PMO implying the availability of large surface of the ME-MION. The coagulated particles (impurities) can be removed from PMO+ME-MION by washing with mild detergent or cleaning solution. To our knowledge, this is the first report on surface water turbidity removal using protein-functionalized magnetic nanoparticle.

  1. Protein-functionalized magnetic iron oxide nanoparticles: time efficient potential-water treatment

    Science.gov (United States)

    Okoli, Chuka; Boutonnet, Magali; Järås, Sven; Rajarao-Kuttuva, Gunaratna

    2012-10-01

    Recent advances in nanoscience suggest that the existing issues involving water quality could be resolved or greatly improved using nanomaterials, especially magnetic iron oxide nanoparticles. Magnetic nanoparticles have been synthesized for the development and use, in association with natural coagulant protein for water treatment. The nanoparticles size, morphology, structure, and magnetic properties were characterized by transmission electron microscope, X-ray diffraction, and superconducting quantum interference device magnetometry. Purified Moringa oleifera protein was attached onto microemulsions-prepared magnetic iron oxide nanoparticles (ME-MION) to form stable protein-functionalized magnetic nanoparticles (PMO+ME-MION). The turbidity removal efficiency in both synthetic and surface water samples were investigated and compared with the commonly used synthetic coagulant (alum) as well as PMO. More than 90 % turbidity could be removed from the surface waters within 12 min by magnetic separation of PMO+ME-MION; whereas gravimetrically, 70 % removal in high and low turbid waters can be achieved within 60 min. In contrast, alum requires 180 min to reduce the turbidity of low turbid water sample. These data support the advantage of separation with external magnetic field (magnetophoresis) over gravitational force. Time kinetics studies show a significant enhancement in ME-MION efficiency after binding with PMO implying the availability of large surface of the ME-MION. The coagulated particles (impurities) can be removed from PMO+ME-MION by washing with mild detergent or cleaning solution. To our knowledge, this is the first report on surface water turbidity removal using protein-functionalized magnetic nanoparticle.

  2. Online Tracking

    Science.gov (United States)

    ... for other purposes, such as research, measurement, and fraud prevention. Mobile browsers work much like traditional web ... users’ Do Not Track preferences. Can I block online tracking? Consumers can learn about tracker-blocking browser ...

  3. DNA damage and oxidative stress in human liver cell L-02 caused by surface water extracts during drinking water treatment in a waterworks in China.

    Science.gov (United States)

    Xie, Shao-Hua; Liu, Ai-Lin; Chen, Yan-Yan; Zhang, Li; Zhang, Hui-Juan; Jin, Bang-Xiong; Lu, Wen-Hong; Li, Xiao-Yan; Lu, Wen-Qing

    2010-04-01

    Because of the daily and life-long exposure to disinfection by-products formed during drinking water treatment, potential adverse human health risk of drinking water disinfection is of great concern. Toxicological studies have shown that drinking water treatment increases the genotoxicity of surface water. Drinking water treatment is comprised of different potabilization steps, which greatly influence the levels of genotoxic products in the surface water and thus may alter the toxicity and genotoxicity of surface water. The aim of the present study was to understand the influence of specific steps on toxicity and genotoxicity during the treatment of surface water in a water treatment plant using liquid chlorine as the disinfectant in China. An integrated approach of the comet and oxidative stress assays was used in the study, and the results showed that both the prechlorination and postchlorination steps increased DNA damage and oxidative stress caused by water extracts in human derived L-02 cells while the tube settling and filtration steps had the opposite effect. This research also highlighted the usefulness of an integrated approach of the comet and oxidative stress assays in evaluating the genotoxicity of surface water during drinking water treatment. Copyright 2009 Wiley-Liss, Inc.

  4. Dynamics, Stability, and Adsorption States of Water on Oxidized RuO 2 (110)

    Energy Technology Data Exchange (ETDEWEB)

    Nguyen, Manh-Thuong [Physical; Institute; Mu, Rentao [Physical; Institute; Cantu, David C. [Physical; Institute; Lyubinetsky, Igor [Institute; Environmental; Glezakou, Vassiliki-Alexandra [Physical; Institute; Dohnálek, Zdenek [Physical; Institute; Voiland; Rousseau, Roger [Physical; Institute

    2017-08-18

    Identifying and understanding how excess oxygen atoms affect the adsorption of water on metal oxides is crucial for their use in water splitting. Here, by means of high-resolution scanning tunneling microscopy and density-functional calculations, we show that excess oxygen atoms on the stoichiometric RuO2(110) significantly change the clustering, conformation, and deprotonation equilibrium of adsorbed water. We considered two reactive scenarios during which the stoichiometric surface was exposed to: (i) first to oxygen followed by water, and (ii) first to water followed by oxygen. In both cases the [OH-OH] complex on Ru rows is the dominant species, showing a significant difference from water-only adsorption on the stoichiometric surface in which the [OH-H2O] species is found to be prevalent. Surface reactivity at almost full O coverage is also addressed; there we show that site selectivity of the surface for H adsorption and dissociation of H2O is hindered, notwithstanding the increase of the dynamical motion of both species. We found that the work function of RuO2 can serve as a descriptor for the reactivity of this surface to water and its constituents.

  5. Tracking nitrous oxide emission processes at a suburban site with semicontinuous, in situ measurements of isotopic composition

    Science.gov (United States)

    Harris, Eliza; Henne, Stephan; Hüglin, Christoph; Zellweger, Christoph; Tuzson, Béla; Ibraim, Erkan; Emmenegger, Lukas; Mohn, Joachim

    2017-02-01

    The isotopic composition of atmospheric nitrous oxide (N2O) was measured semicontinuously, at ˜35 min frequency in intermittent periods of 1-6 days over one and a half years, using preconcentration coupled to a quantum cascade laser spectrometer at the suburban site of Dübendorf, Switzerland. The achieved measurement repeatability was 0.08‰, 0.11‰, and 0.10‰ for δ18O, site preference, and δ15Nbulk respectively, which is better than or equal to standard flask sampling-based isotope ratio mass spectrometry performance. The observed mean diurnal cycle reflected the buildup of N2O from isotopically light sources on an isotopically heavy tropospheric background. The measurements were used to determine the source isotopic composition, which varied significantly compared to chemical and meteorological parameters monitored at the site. FLEXPART-COSMO transport modeling in combination with modified Emissions Database for Global Atmospheric Research inventory emissions was used to model N2O mole fractions at the site. Additionally, isotopic signatures were estimated for different source categories using literature data and used to simulate N2O isotopic composition over the measurement period. The model was able to capture variability in N2O mole fraction well, but simulations of isotopic composition showed little agreement with observations. In particular, measured source isotopic composition exhibited one magnitude larger variability than simulated, clearly indicating that the range of isotopic source signatures estimated from literature significantly underestimates true variability of source signatures. Source δ18O signature was found to be the most sensitive tracer for urban/industry versus agricultural N2O. δ15Nbulk and site preference may provide more insight into microbial and chemical emission processes than partitioning of anthropogenic source categories.

  6. Release of ANP and fat oxidation in overweight persons during aerobic exercise in water.

    Science.gov (United States)

    Fenzl, M; Schnizer, W; Aebli, N; Schlegel, C; Villiger, B; Disch, A; Gredig, J; Zaugg, T; Krebs, J

    2013-09-01

    Exercise in water compared to land-based exercise (LE) results in a higher release of natriuretic peptides, which are involved in the regulation of exercise-induced adipose tissue lipolysis. The present study was performed to compare the release of atrial natriuretic peptide (ANP) and free fatty acids (FFA) during prolonged aerobic water-based exercise (WE) with the release after an identical LE. 14 untrained overweight subjects performed 2 steady state workload tests on the same ergometer in water and on land. Before and after exercise, venous blood samples were collected for measuring ANP, FFA, epinephrine, norepinephrine, insulin and glucose. The respiratory exchange ratio (RER) was determined for fat oxidation.The exercises resulted in a significant increase in ANP in LE (61%) and in WE (177%), and FFA increased about 3-fold in LE and WE with no significant difference between the groups. Epinephrine increased, while insulin decreased similarly in both groups. The RER values decreased during the exercises, but there was no significant difference between LE and WE. In conclusion, the higher ANP concentrations in WE had no additional effect on lipid mobilization, FFA release and fat oxidation. Moderate-intensity exercises in water offer no benefit regarding adipose tissue lipolysis in comparison to LE. © Georg Thieme Verlag KG Stuttgart · New York.

  7. Preparation and Application of Water-in-Oil Emulsions Stabilized by Modified Graphene Oxide.

    Science.gov (United States)

    Fei, Xiaoma; Xia, Lei; Chen, Mingqing; Wei, Wei; Luo, Jing; Liu, Xiaoya

    2016-08-26

    A series of alkyl chain modified graphene oxides (AmGO) with different alkyl chain length and content was fabricated using a reducing reaction between graphene oxide (GO) and alkyl amine. Then AmGO was used as a graphene-based particle emulsifier to stabilize Pickering emulsion. Compared with the emulsion stabilized by GO, which was oil-in-water type, all the emulsions stabilized by AmGO were water-in-oil type. The effects of alkyl chain length and alkyl chain content on the emulsion properties of AmGO were investigated. The emulsions stabilized by AmGO showed good stability within a wide range of pH (from pH = 1 to pH = 13) and salt concentrations (from 0.1 to 1000 mM). In addition, the application of water-in-oil emulsions stabilized by AmGO was investigated. AmGO/polyaniline nanocomposite (AmGO/PANi) was prepared through an emulsion approach, and its supercapacitor performance was investigated. This research broadens the application of AmGO as a water-in-oil type emulsion stabilizer and in preparing graphene-based functional materials.

  8. Preparation and Application of Water-in-Oil Emulsions Stabilized by Modified Graphene Oxide

    Directory of Open Access Journals (Sweden)

    Xiaoma Fei

    2016-08-01

    Full Text Available A series of alkyl chain modified graphene oxides (AmGO with different alkyl chain length and content was fabricated using a reducing reaction between graphene oxide (GO and alkyl amine. Then AmGO was used as a graphene-based particle emulsifier to stabilize Pickering emulsion. Compared with the emulsion stabilized by GO, which was oil-in-water type, all the emulsions stabilized by AmGO were water-in-oil type. The effects of alkyl chain length and alkyl chain content on the emulsion properties of AmGO were investigated. The emulsions stabilized by AmGO showed good stability within a wide range of pH (from pH = 1 to pH = 13 and salt concentrations (from 0.1 to 1000 mM. In addition, the application of water-in-oil emulsions stabilized by AmGO was investigated. AmGO/polyaniline nanocomposite (AmGO/PANi was prepared through an emulsion approach, and its supercapacitor performance was investigated. This research broadens the application of AmGO as a water-in-oil type emulsion stabilizer and in preparing graphene-based functional materials.

  9. Preparation of Silica/Reduced Graphene Oxide Nanosheet Composites for Removal of Organic Contaminants from Water.

    Science.gov (United States)

    Li, Wen; Liu, Wei; Wang, Haifei; Lu, Wensheng

    2016-06-01

    Graphene-based composites open up new opportunities as effective adsorbents for the removal of organic contaminants from water. In this article, we report a novel and facile process to synthesize well-dispersed silica/reduced graphene oxide (SiO2/RGO) nanosheet composites. The SiO2/RGO nanosheet composites are prepared through a modified sol-gel process with in situ hydrolysis of tetraethoxysilane (TEOS) on graphene oxide (GO) nanosheet, followed by reduction of GO to graphene. In comparison with the RGO nanosheets, the as-prepared SiO2/RGO nanosheet composites have a larger surface area and good aqueous disperse ability. In addition, the application of SiO2/RGO nanosheet composites was demonstrated on removing organic dyes from water. The SiO2/RGO nanosheet composites show rapid and stable adsorption performance on removal of Methylene Blue (MB) and thionine (TH) from water. It is indicated that the resulting SiO2/RGO composites can be utilized as efficient adsorbents for the removal of organic contaminants from water.

  10. Inactivation of dinoflagellate Scripsiella trochoidea in synthetic ballast water by advanced oxidation processes.

    Science.gov (United States)

    Yang, Zhishan; Jiang, Wenju; Zhang, Yi; Lim, T M

    2015-01-01

    Ship-borne ballast water contributes significantly to the transfer of non-indigenous species across aquatic environments. To reduce the risk of bio-invasion, ballast water should be treated before discharge. In this study, the efficiencies of several conventional and advanced oxidation processes were investigated for potential ballast water treatment, using a marine dinoflagellate species, Scripsiella trochoidea, as the indicator organism. A stable and consistent culture was obtained and treated by ultraviolet (UV) light, ozone (O3), hydrogen peroxide (H2O2), and their various combinations. UV apparently inactivated the cells after only 10 s of irradiation, but subsequently photo-reactivation of the cells was observed for all methods involving UV. O3 exhibited 100% inactivation efficiency after 5 min treatment, while H2O2 only achieved maximum 80% inactivation in the same duration. Combined methods, e.g. UV/O3 and UV/H2O2, were found to inhibit photo-reactivation and improve treatment efficiency to some degree, indicating the effectiveness of using combined treatment processes. The total residual oxidant (TRO) levels of the methods were determined, and the results indicated that UV and O3 generated the lowest and highest TRO, respectively. The synergic effect of combined processes on TRO generation was found to be insignificant, and thus UV/O3 was recommended as a potentially suitable treatment process for ballast water.

  11. Solar-Enhanced Advanced Oxidation Processes for Water Treatment: Simultaneous Removal of Pathogens and Chemical Pollutants.

    Science.gov (United States)

    Tsydenova, Oyuna; Batoev, Valeriy; Batoeva, Agniya

    2015-08-14

    The review explores the feasibility of simultaneous removal of pathogens and chemical pollutants by solar-enhanced advanced oxidation processes (AOPs). The AOPs are based on in-situ generation of reactive oxygen species (ROS), most notably hydroxyl radicals •OH, that are capable of destroying both pollutant molecules and pathogen cells. The review presents evidence of simultaneous removal of pathogens and chemical pollutants by photocatalytic processes, namely TiO2 photocatalysis and photo-Fenton. Complex water matrices with high loads of pathogens and chemical pollutants negatively affect the efficiency of disinfection and pollutant removal. This is due to competition between chemical substances and pathogens for generated ROS. Other possible negative effects include light screening, competitive photon absorption, adsorption on the catalyst surface (thereby inhibiting its photocatalytic activity), etc. Besides, some matrix components may serve as nutrients for pathogens, thus hindering the disinfection process. Each type of water/wastewater would require a tailor-made approach and the variables that were shown to influence the processes-catalyst/oxidant concentrations, incident radiation flux, and pH-need to be adjusted in order to achieve the required degree of pollutant and pathogen removal. Overall, the solar-enhanced AOPs hold promise as an environmentally-friendly way to substitute or supplement conventional water/wastewater treatment, particularly in areas without access to centralized drinking water or sewage/wastewater treatment facilities.

  12. Parabens abatement from surface waters by electrochemical advanced oxidation with boron doped diamond anodes.

    Science.gov (United States)

    Domínguez, Joaquín R; Muñoz-Peña, Maria J; González, Teresa; Palo, Patricia; Cuerda-Correa, Eduardo M

    2016-10-01

    The removal efficiency of four commonly-used parabens by electrochemical advanced oxidation with boron-doped diamond anodes in two different aqueous matrices, namely ultrapure water and surface water from the Guadiana River, has been analyzed. Response surface methodology and a factorial, composite, central, orthogonal, and rotatable (FCCOR) statistical design of experiments have been used to optimize the process. The experimental results clearly show that the initial concentration of pollutants is the factor that influences the removal efficiency in a more remarkable manner in both aqueous matrices. As a rule, as the initial concentration of parabens increases, the removal efficiency decreases. The current density also affects the removal efficiency in a statistically significant manner in both aqueous matrices. In the water river aqueous matrix, a noticeable synergistic effect on the removal efficiency has been observed, probably due to the presence of chloride ions that increase the conductivity of the solution and contribute to the generation of strong secondary oxidant species such as chlorine or HClO/ClO -. The use of a statistical design of experiments made it possible to determine the optimal conditions necessary to achieve total removal of the four parabens in ultrapure and river water aqueous matrices.

  13. Solar-Enhanced Advanced Oxidation Processes for Water Treatment: Simultaneous Removal of Pathogens and Chemical Pollutants

    Directory of Open Access Journals (Sweden)

    Oyuna Tsydenova

    2015-08-01

    Full Text Available The review explores the feasibility of simultaneous removal of pathogens and chemical pollutants by solar-enhanced advanced oxidation processes (AOPs. The AOPs are based on in-situ generation of reactive oxygen species (ROS, most notably hydroxyl radicals •OH, that are capable of destroying both pollutant molecules and pathogen cells. The review presents evidence of simultaneous removal of pathogens and chemical pollutants by photocatalytic processes, namely TiO2 photocatalysis and photo-Fenton. Complex water matrices with high loads of pathogens and chemical pollutants negatively affect the efficiency of disinfection and pollutant removal. This is due to competition between chemical substances and pathogens for generated ROS. Other possible negative effects include light screening, competitive photon absorption, adsorption on the catalyst surface (thereby inhibiting its photocatalytic activity, etc. Besides, some matrix components may serve as nutrients for pathogens, thus hindering the disinfection process. Each type of water/wastewater would require a tailor-made approach and the variables that were shown to influence the processes—catalyst/oxidant concentrations, incident radiation flux, and pH—need to be adjusted in order to achieve the required degree of pollutant and pathogen removal. Overall, the solar-enhanced AOPs hold promise as an environmentally-friendly way to substitute or supplement conventional water/wastewater treatment, particularly in areas without access to centralized drinking water or sewage/wastewater treatment facilities.

  14. Theoretical investigation of water oxidation processes on small Mn(x)Ti(2-x)O4 (x = 0-2) complexes.

    Science.gov (United States)

    Lee, Choongkeun; Aikens, Christine M

    2014-09-18

    Understanding the water oxidation process on small metal oxide complexes is fundamental for developing photocatalysts for solar fuel production. Titanium oxide and manganese oxide complexes have high potential as components of a cheap, nontoxic, and stable photocatalyst. In this theoretical work, the water oxidation process on Mn(x)Ti(2-x)O4 (x = 0-2) clusters is investigated at the BP86 level of theory using two water molecules and fully saturated systems. In the oxidation cycle using two water molecules, Mn reduces the reaction energy; however, Mn does not reduce the reaction energy on the fully saturated system. When two water molecules are used, the highest reaction energy in the water oxidation cycle is lower than 3 eV, but the highest reaction energy is higher than 3 eV on fully saturated systems except for the pure titanium oxide complex which has a highest reaction energy of 2.56 eV. Dehydrogenation processes in the water oxidation cycle require higher energy than the O-O formation or water adsorption processes. The overall dehydrogenation energy is usually smaller on complexes including at least one Mn atom and it is smallest on the Mn2O4 complex that has two water molecules. Considering the highest reaction energy in the overall water oxidation cycle, water oxidation at the manganese atom of MnTiO4 hydrated with two water molecules is the most favorable in energy.

  15. EFFECTIVENESS OF ELECTROLYZED OXIDIZING WATER FOR INACTIVATING Listeria monocytogenes IN LETTUCE

    Directory of Open Access Journals (Sweden)

    Casadiego Laíd Paola

    2005-06-01

    Full Text Available The effectiveness of electrolyzed oxidizing (EO water for the inactivation of L. monocytogenes in suspension and when inoculated on lettuce leaves was evaluated. An electrolytic cell for the production of EO water was built and a solution of 5% NaCl was used. The EO water produced had a residual chlorine concentration of 29 parts per million (ppm and pH 2.83. Ten strains of L. monocytogenes isolated from processed chicken (109 CFU/ml were inoculated into 9 ml of EO water or 9 ml of deionized water (control and incubated at 15°C for 5, 10, 15 and 20 min. The surviving population of each strain was determined on Columbia agar. An exposure time of 5 min reduced the populations by approximately 6.6 log CFU/ml. The most resistant strains to sodium hypochlorite (NaOCl were selected and used in a strain mixture (9.56 log CFU/ml, 109UFC/ml approximately for the inoculation of 35 lettuce samples, by the dip inoculation method using distilled water as control. The population mean of L. monocytogenes after treatment with EO water and distilled water was reduced by 3.92 and 2.46 log CFU/ml respectively (p=0.00001. EO water and 6% acetic acid (vinegar were combined to improve the EO water effect on L. monocytogenes inoculated in lettuce; the effectiveness of this combination was examined. The results showed that there was a synergistic effect of both antimicrobial agents (population reduction by 5.49 log CFU/ml approximately on the viability of L. monocytogenes cells.

  16. Longitudinal tracking of human fetal cells labeled with super paramagnetic iron oxide nanoparticles in the brain of mice with motor neuron disease.

    Science.gov (United States)

    Bigini, Paolo; Diana, Valentina; Barbera, Sara; Fumagalli, Elena; Micotti, Edoardo; Sitia, Leopoldo; Paladini, Alessandra; Bisighini, Cinzia; De Grada, Laura; Coloca, Laura; Colombo, Laura; Manca, Pina; Bossolasco, Patrizia; Malvestiti, Francesca; Fiordaliso, Fabio; Forloni, Gianluigi; Morbidelli, Massimo; Salmona, Mario; Giardino, Daniela; Mennini, Tiziana; Moscatelli, Davide; Silani, Vincenzo; Cova, Lidia

    2012-01-01

    Stem Cell (SC) therapy is one of the most promising approaches for the treatment of Amyotrophic Lateral Sclerosis (ALS). Here we employed Super Paramagnetic Iron Oxide nanoparticles (SPIOn) and Hoechst 33258 to track human Amniotic Fluid Cells (hAFCs) after transplantation in the lateral ventricles of wobbler (a murine model of ALS) and healthy mice. By in vitro, in vivo and ex vivo approaches we found that: 1) the main physical parameters of SPIOn were maintained over time; 2) hAFCs efficiently internalized SPIOn into the cytoplasm while Hoechst 33258 labeled nuclei; 3) SPIOn internalization did not alter survival, cell cycle, proliferation, metabolism and phenotype of hAFCs; 4) after transplantation hAFCs rapidly spread to the whole ventricular system, but did not migrate into the brain parenchyma; 5) hAFCs survived for a long time in the ventricles of both wobbler and healthy mice; 6) the transplantation of double-labeled hAFCs did not influence mice survival.

  17. Longitudinal tracking of human fetal cells labeled with super paramagnetic iron oxide nanoparticles in the brain of mice with motor neuron disease.

    Directory of Open Access Journals (Sweden)

    Paolo Bigini

    Full Text Available Stem Cell (SC therapy is one of the most promising approaches for the treatment of Amyotrophic Lateral Sclerosis (ALS. Here we employed Super Paramagnetic Iron Oxide nanoparticles (SPIOn and Hoechst 33258 to track human Amniotic Fluid Cells (hAFCs after transplantation in the lateral ventricles of wobbler (a murine model of ALS and healthy mice. By in vitro, in vivo and ex vivo approaches we found that: 1 the main physical parameters of SPIOn were maintained over time; 2 hAFCs efficiently internalized SPIOn into the cytoplasm while Hoechst 33258 labeled nuclei; 3 SPIOn internalization did not alter survival, cell cycle, proliferation, metabolism and phenotype of hAFCs; 4 after transplantation hAFCs rapidly spread to the whole ventricular system, but did not migrate into the brain parenchyma; 5 hAFCs survived for a long time in the ventricles of both wobbler and healthy mice; 6 the transplantation of double-labeled hAFCs did not influence mice survival.

  18. Ceriodaphnia dubia as a potential bio-indicator for assessing acute aluminum oxide nanoparticle toxicity in fresh water environment

    National Research Council Canada - National Science Library

    Pakrashi, Sunandan; Dalai, Swayamprava; Humayun, Ahmed; Chakravarty, Sujay; Chandrasekaran, Natarajan; Mukherjee, Amitava

    2013-01-01

    .... The current study reveals the potential of Ceriodaphnia dubia (C. dubia) as a bio-indicator for aluminum oxide nanoparticles in a fresh water aquatic ecosystem where it occupies an important ecological niche as a primary consumer...

  19. Amphiphilic hollow porous shell encapsulated Au@Pd bimetal nanoparticles for aerobic oxidation of alcohols in water

    KAUST Repository

    Zou, Houbing

    2015-01-01

    © The Royal Society of Chemistry 2015. This work describes the design, synthesis and analysis of an amphiphilic hollow mesoporous shell encapsulating catalytically active Au@Pd bimetal nanoparticles. The particles exhibited excellent catalytic activity and stability in the aerobic oxidation of primary and secondary alcohols to their corresponding aldehydes or ketones in water when using air as an oxidizing agent under atmospheric pressure.

  20. Synergy of licorice extract and pea protein hydrolysate for oxidative stability of soybean oil-in-water emulsions.

    Science.gov (United States)

    Zhang, Xin; Xiong, Youling L; Chen, Jie; Zhou, Lirong

    2014-08-13

    Previously developed radical-scavenging pea protein hydrolysates (PPHs) prepared with Flavourzyme (Fla-PPH) and Protamex (Pro-PPH) were used as cosurfactants with Tween 20 to produce soybean oil-in-water (O/W) emulsions, and the suppression of lipid oxidation was investigated. Both PPHs significantly retarded oxidation (P activity when coupled with PPHs.

  1. Decoupled catalytic hydrogen evolution from a molecular metal oxide redox mediator in water splitting.

    Science.gov (United States)

    Rausch, Benjamin; Symes, Mark D; Chisholm, Greig; Cronin, Leroy

    2014-09-12

    The electrolysis of water using renewable energy inputs is being actively pursued as a route to sustainable hydrogen production. Here we introduce a recyclable redox mediator (silicotungstic acid) that enables the coupling of low-pressure production of oxygen via water oxidation to a separate, catalytic hydrogen production step outside the electrolyzer that requires no post-electrolysis energy input. This approach sidesteps the production of high-pressure gases inside the electrolytic cell (a major cause of membrane degradation) and essentially eliminates the hazardous issue of product gas crossover at the low current densities that characterize renewables-driven water-splitting devices. We demonstrated that a platinum-catalyzed system can produce pure hydrogen over 30 times faster than state-of-the-art proton exchange membrane electrolyzers at equivalent platinum loading. Copyright © 2014, American Association for the Advancement of Science.

  2. Oxidation of zirconium alloys in 2.5 kPa water vapor for tritium readiness.

    Energy Technology Data Exchange (ETDEWEB)

    Mills, Bernice E.

    2007-11-01

    A more reactive liner material is needed for use as liner and cruciform material in tritium producing burnable absorber rods (TPBAR) in commercial light water nuclear reactors (CLWR). The function of these components is to convert any water that is released from the Li-6 enriched lithium aluminate breeder material to oxide and hydrogen that can be gettered, thus minimizing the permeation of tritium into the reactor coolant. Fourteen zirconium alloys were exposed to 2.5 kPa water vapor in a helium stream at 300 C over a period of up to 35 days. Experimental alloys with aluminum, yttrium, vanadium, titanium, and scandium, some of which also included ternaries with nickel, were included along with a high nitrogen impurity alloy and the commercial alloy Zircaloy-2. They displayed a reactivity range of almost 500, with Zircaloy-2 being the least reactive.

  3. Atomically Monodisperse Nickel Nanoclusters as Highly Active Electrocatalysts for Water Oxidation

    KAUST Repository

    Joya, Khurram

    2016-04-08

    Achieving water splitting at low overpotential with high oxygen evolution efficiency and stability is important for realizing solar to chemical energy conversion devices. Herein we report the synthesis, characterization and electrochemical evaluation of highly active nickel nanoclusters (Ni NCs) for water oxidation at low overpotential. These atomically precise and monodisperse Ni NCs are characterized by using UV-visible absorption spectroscopy, single crystal X-ray diffraction and mass spectrometry. The molecular formulae of these Ni NCs are found to be Ni4(PET)8 and Ni6(PET)12 and are highly active electrocatalysts for oxygen evolution without any pre-conditioning. Ni4(PET)8 are slightly better catalysts than Ni6(PET)12 and initiate the oxygen evolution at an amazingly low overpotential of ~1.51 V (vs RHE; η ≈ 280 mV). The peak oxygen evolution current density (J) of ~150 mA cm–2 at 2.0 V (vs. RHE) with a Tafel slope of 38 mV dec–1 is observed using Ni4(PET)8. These results are comparable to the state-of-the art RuO2 electrocatalyst, which is highly expensive and rare compared to Ni-based materials. Sustained oxygen generation for several hours with an applied current density of 20 mA cm–2 demonstrates the long-term stability and activity of these Ni NCs towards electrocatalytic water oxidation. This unique approach provides a facile method to prepare cost-effective, nanoscale and highly efficient electrocatalysts for water oxidation.

  4. Conduction and Reactivity in Heterogeneous-Molecular Catalysis: New Insights in Water Oxidation Catalysis by Phosphate Cobalt Oxide Films.

    Science.gov (United States)

    Costentin, Cyrille; Porter, Thomas R; Savéant, Jean-Michel

    2016-05-04

    Cyclic voltammetry of phosphate cobalt oxide (CoPi) films catalyzing O2-evolution from water oxidation as a function of scan rate, phosphate concentration and film thickness allowed for new insights into the coupling between charge transport and catalysis. At pH = 7 and low buffer concentrations, the film is insulating below 0.8 (V vs SHE) but becomes conductive above 0.9 (V vs SHE). Between 1.0 to 1.3 (V vs SHE), the mesoporous structure of the film gives rise to a large thickness-dependent capacitance. At higher buffer concentrations, two reversible proton-coupled redox couples appear over the capacitive response with 0.94 and 1.19 (V vs SHE) pH = 7 standard potentials. The latter is, at most, very weakly catalytic and not responsible for the large catalytic current observed at higher potentials. CV-response analysis showed that the amount of redox-active cobalt-species in the film is small, less than 10% of total. The catalytic process involves a further proton-coupled-electron-transfer and is so fast that it is controlled by diffusion of phosphate, the catalyst cofactor. CV-analysis with newly derived relationships led to a combination of the catalyst standard potential with the catalytic rate constant and a lower-limit estimation of these parameters. The large currents resulting from the fast catalytic reaction result in significant potential losses related to charge transport through the film. CoPi films appear to combine molecular catalysis with semiconductor-type charge transport. This mode of heterogeneous molecular catalysis is likely to occur in many other catalytic films.

  5. Disinfection of Spacecraft Potable Water Systems by Photocatalytic Oxidation Using UV-A Light Emitting Diodes

    Science.gov (United States)

    Birmele, Michele N.; O'Neal, Jeremy A.; Roberts, Michael S.

    2011-01-01

    Ultraviolet (UV) light has long been used in terrestrial water treatment systems for photodisinfection and the removal of organic compounds by several processes including photoadsorption, photolysis, and photocatalytic oxidation/reduction. Despite its effectiveness for water treatment, UV has not been explored for spacecraft applications because of concerns about the safety and reliability of mercury-containing UV lamps. However, recent advances in ultraviolet light emitting diodes (UV LEDs) have enabled the utilization of nanomaterials that possess the appropriate optical properties for the manufacture of LEDs capable of producing monochromatic light at germicidal wavelengths. This report describes the testing of a commercial-off-the-shelf, high power Nichia UV-A LED (250mW A365nnJ for the excitation of titanium dioxide as a point-of-use (POD) disinfection device in a potable water system. The combination of an immobilized, high surface area photocatalyst with a UV-A LED is promising for potable water system disinfection since toxic chemicals and resupply requirements are reduced. No additional consumables like chemical biocides, absorption columns, or filters are required to disinfect and/or remove potentially toxic disinfectants from the potable water prior to use. Experiments were conducted in a static test stand consisting of a polypropylene microtiter plate containing 3mm glass balls coated with titanium dioxide. Wells filled with water were exposed to ultraviolet light from an actively-cooled UV-A LED positioned above each well and inoculated with six individual challenge microorganisms recovered from the International Space Station (ISS): Burkholderia cepacia, Cupriavidus metallidurans, Methylobacterium fujisawaense, Pseudomonas aeruginosa, Sphingomonas paucimobilis and Wautersia basilensis. Exposure to the Nichia UV-A LED with photocatalytic oxidation resulted in a complete (>7-log) reduction of each challenge bacteria population in <180 minutes of contact

  6. Promotion of Water-mediated Carbon Removal by Nanostructured Barium Oxide/nickel Interfaces

    Energy Technology Data Exchange (ETDEWEB)

    L Yang; Y Choi; W Qin; H Chen; K Blinn; M Liu; P Liu; J Bai; T Tyson; M Liu

    2011-12-31

    The existing Ni-yttria-stabilized zirconia anodes in solid oxide fuel cells (SOFCs) perform poorly in carbon-containing fuels because of coking and deactivation at desired operating temperatures. Here we report a new anode with nanostructured barium oxide/nickel (BaO/Ni) interfaces for low-cost SOFCs, demonstrating high power density and stability in C{sub 3}H{sub 8}, CO and gasified carbon fuels at 750 C. Synchrotron-based X-ray analyses and microscopy reveal that nanosized BaO islands grow on the Ni surface, creating numerous nanostructured BaO/Ni interfaces that readily adsorb water and facilitate water-mediated carbon removal reactions. Density functional theory calculations predict that the dissociated OH from H2O on BaO reacts with C on Ni near the BaO/Ni interface to produce CO and H species, which are then electrochemically oxidized at the triple-phase boundaries of the anode. This anode offers potential for ushering in a new generation of SOFCs for efficient, low-emission conversion of readily available fuels to electricity.

  7. Removal of Trace Arsenic to Meet Drinking Water Standards Using Iron Oxide Coated Multiwall Carbon Nanotubes.

    Science.gov (United States)

    Ntim, Susana Addo; Mitra, Somenath

    2011-05-12

    This study presents the removal of trace level arsenic to meet drinking water standards using an iron oxide-multi-walled carbon nanotube (Fe-MWCNT) hybrid as a sorbent. The synthesis was facilitated by the high degree of nanotube functionalization using a microwave assisted process, and a controlled assembly of iron oxide was possible where the MWCNT served as an effective support for the oxide. In the final product, 11 % of the carbon atoms were attached to Fe. The Fe-MWCNT was effective in arsenic removal to below the drinking water standard levels of 10 µg L(-1). The absorption capacity of the composite was 1723 µg g(-1) and 189 µg g(-1) for As(III) and As(V) respectively. The adsorption of As(V) on Fe-MWCNT was faster than that of As(III). The pseudo-second order rate equation was found to effectively describe the kinetics of arsenic adsorption. The adsorption isotherms for As(III) and As(V) fitted both the Langmuir and Freundlich models.

  8. Mechanism of Water Oxidation Catalyzed by a Dinuclear Ruthenium Complex Bridged by Anthraquinone

    Directory of Open Access Journals (Sweden)

    Tohru Wada

    2017-02-01

    Full Text Available We synthesized 1,8-bis(2,2′:6′,2″-terpyrid-4′-ylanthraquinone (btpyaq as a new dimerizing ligand and determined its single crystal structure by X-ray analysis. The dinuclear Ruthenium complex [Ru2(µ-Cl(bpy2(btpyaq](BF43 ([3](BF43, bpy = 2,2′-bipyridine was used as a catalyst for water oxidation to oxygen with (NH42[Ce(NO36] as the oxidant (turnover numbers = 248. The initial reaction rate of oxygen evolution was directly proportional to the concentration of the catalyst and independent of the oxidant concentration. The cyclic voltammogram of [3](BF43 in water at pH 1.3 showed an irreversible catalytic current above +1.6 V (vs. SCE, with two quasi-reversible waves and one irreversible wave at E1/2 = +0.62, +0.82 V, and Epa = +1.13 V, respectively. UV-vis and Raman spectra of [3](BF43 with controlled-potential electrolysis at +1.40 V revealed that [Ru(IV=O O=Ru(IV]4+ is stable under electrolysis conditions. [Ru(III, Ru(II] species are recovered after dissociation of an oxygen molecule from the active species in the catalytic cycle. These results clearly indicate that an O–O bond is formed via [Ru(V=O O=Ru(IV]5+.

  9. Microbial oxidation of soluble sulfide in produced water from the Bakkeen Sands

    Energy Technology Data Exchange (ETDEWEB)

    Gevertz, D.; Zimmerman, S. [Agouron Institute, La Jolla, CA (United States); Jenneman, G.E. [Phillips Petroleum Company, Bartlesville, OK (United States)] [and others

    1995-12-31

    The presence of soluble sulfide in produced water results in problems for the petroleum industry due to its toxicity, odor, corrosive nature, and potential for wellbore plugging. Sulfide oxidation by indigenous nitrate-reducing bacteria (NRB) present in brine collected from wells at the Coleville Unit (CVU) in Saskatchewan, Canada, was investigated. Sulfide oxidation took place readily when nitrate and phosphate were added to brine enrichment cultures, resulting in a decrease in sulfide levels of 99-165 ppm to nondetectable levels (< 3.3 ppm). Produced water collected from a number of producing wells was screened to determine the time required for complete sulfide oxidation, in order to select candidate wells for treatment. Three wells were chosen, based on sulfide removal in 48 hours or less. These wells were treated down the backside of the annulus with a solution containing 10 mM KNO{sub 3} and 100 {mu}M NaH{sub 2}PO{sub 4}. Following a 24- to 72-hour shut-in, reductions in pretreatment sulfide levels of greater than 90% were observed for two of the wells, as well as sustained sulfide reductions of 50% for at least two days following startup. NRB populations in the produced brine were observed to increase significantly following treatment, but no significant increases in sulfate-reducing bacteria were observed. These results demonstrate the technical feasibility of stimulating indigenous populations of NRB to remediate and control sulfide in produced brine.

  10. Hydrophobic Fe-zeolites for removal of MTBE from water by combination of adsorption and oxidation.

    Science.gov (United States)

    Gonzalez-Olmos, Rafael; Kopinke, Frank-Dieter; Mackenzie, Katrin; Georgi, Anett

    2013-03-05

    Several zeolites were evaluated as adsorbents for the removal of MTBE from water in a screening process. It was observed that the SiO2/Al2O3 molar ratio is a decisive factor for the adsorption properties, at least in the case of ZSM5 zeolites. ZSM5 zeolites with SiO2/Al2O3 ratios >200 were found to provide the best sorption properties for MTBE. To design a combined sorption/reaction method, regeneration of the loaded zeolites by selected advanced oxidation processes (AOP) was studied: (1) Fenton treatment using H2O2 with dissolved iron salts and (2) heterogeneous Fenton-like oxidation with Fe immobilized on the zeolites. The first was ineffective in regenerating loaded zeolites. However, heterogeneous catalysis using Fe species immobilized on the zeolite by liquid ion exchange was markedly more effective. Although these hydrophobic zeolites have a low ion exchange capacity, resulting in iron loadings of ≤ 0.09 wt %, it was possible to obtain sufficiently active catalysts. Hydrophobic Fe-zeolites can therefore be regarded as promising materials for the removal of MTBE from water, since they allow the combination of efficient adsorption and oxidative degradation of MTBE by H2O2. In contrast to the homogeneous catalysis by dissolved iron ions, these heterogeneous catalysts work at near-neutral pH and can be easily reused. Fe-zeolites as adsorbents/catalysts showed a good stability in both batch and column experiments.

  11. Photoactivation: The light-driven assembly of the water oxidation complex of photosystem II

    Directory of Open Access Journals (Sweden)

    Han eBao

    2016-05-01

    Full Text Available Photosynthetic water oxidation is catalyzed by the Mn4CaO5 cluster of photosystem II. The assembly of the Mn4O5Ca requires light and involves a sequential process called photoactivation. This process harnesses the charge-separation of the photochemical reaction center and the coordination environment provided by the amino acid side chains of the protein to oxidize and organize the incoming manganese ions to form the oxo-bridged metal cluster capable of H2O-oxidation. Although most aspects of this assembly process remain poorly understood, recent advances in the elucidation of the crystal structure of the fully assembled cyanobacterial PSII complex help in the interpretation of the rich history of experiments designed to understand this process. Moreover, recent insights on the structure and stability of the constituent ions of the Mn4CaO5 cluster may guide future experiments. Here we consider the literature and give a possible model of assembly involving single Mn2+ oxidation site and ion relocation.

  12. Manganese-Cobalt Oxido Cubanes Relevant to Manganese-Doped Water Oxidation Catalysts.

    Science.gov (United States)

    Nguyen, Andy I; Suess, Daniel L M; Darago, Lucy E; Oyala, Paul H; Levine, Daniel S; Ziegler, Micah S; Britt, R David; Tilley, T Don

    2017-04-19

    Incorporation of Mn into an established water oxidation catalyst based on a Co(III)4O4 cubane was achieved by a simple and efficient assembly of permanganate, cobalt(II) acetate, and pyridine to form the cubane oxo cluster MnCo3O4(OAc)5py3 (OAc = acetate, py = pyridine) (1-OAc) in good yield. This allows characterization of electronic and chemical properties for a manganese center in a cobalt oxide environment, and provides a molecular model for Mn-doped cobalt oxides. The electronic properties of the cubane are readily tuned by exchange of the OAc- ligand for Cl- (1-Cl), NO3- (1-NO3), and pyridine ([1-py]+). EPR spectroscopy, SQUID magnetometry, and DFT calculations thoroughly characterized the valence assignment of the cubane as [MnIVCoIII3]. These cubanes are redox-active, and calculations reveal that the Co ions behave as the reservoir for electrons, but their redox potentials are tuned by the choice of ligand at Mn. This MnCo3O4 cubane system represents a new class of easily prepared, versatile, and redox-active oxido clusters that should contribute to an understanding of mixed-metal, Mn-containing oxides.

  13. Partial oxidation of municipal sludge with activited carbon catalyst in supercritical water.

    Science.gov (United States)

    Guo, Yang; Wang, Shuzhong; Gong, Yanmeng; Xu, Donghai; Tang, Xingying; Ma, Honghe

    2010-08-15

    The partial oxidation (POX) characteristics of municipal sludge in supercritical water (SCW) were investigated by using batch reactor. Effects of reaction parameters such as oxidant equivalent ratio (OER), reaction time and temperature were investigated. Activated carbon (AC) could effectively improve the mole fraction of H(2) in gas product at low OER. However, high OER (greater than 0.3) not only led to the combustion reaction of CO and H(2), but also caused corrosion of reactor inner wall. Hydrogenation and polymerization of the intermediate products are possible reasons for the relative low COD removal rate in our tests. Metal oxide leached from the reactor inner wall and the main components of the granular sludge were deposited in the AC catalyst. Reaction time had more significant effect on BET surface area of AC than OER had. Long reaction time led to the methanation reaction following hydrolysis and oxidation reaction of AC in SCW in the presence of oxygen. Correspondingly, the possible reaction mechanisms were proposed. Copyright 2010 Elsevier B.V. All rights reserved.

  14. Structural Analysis of Surface-Modified Oxidation-Resistant Zirconium Alloy Cladding for Light Water Reactors

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Youho; No, Hee Cheon; Lee, Jeong Ik [Korea Advanced Institute of Science and Technology, Daejeon (Korea, Republic of)

    2014-05-15

    While the current zirconium-based alloy cladding (Zircaloy, here after) has served well for fission-product barrier and heat transfer medium for the nuclear fuel of light water reactors (LWRs) in steady-states, concerns surrounding its mechanical behavior during accidents have drawn serious attentions. In accidents, strength degradation of the current-zirconium based alloy cladding manifests at temperature around ∼800 .deg. C, which results in fuel ballooning. Above 1000 .deg. C, zircaloy undergoes rapid oxidation with steam. Formation of brittle oxide (ZrO{sub 2}) and underlying oxygen-saturated α-zircaloy as a consequence of steam oxidation leads to loss of cladding ductility. Indeed, the loss of zircaloy ductility upon the steam oxidation has been taken as a measure of fuel failure criteria as stated in 10 CFR 50.46. In addition, zircaloy steam oxidation is an exothermic reaction, which is an energy source that sharply accelerates temperature increase under loss of coolant accidents, decreasing allowable coping time for loss of coolant accidents, decreasing allowable coping time for loss of coolant accidents (LOCA) before significant fuel/core melting starts. Hydrogen generated as a result of zircaloy oxidation could cause an explosion if certain conditions are met. In steady-state operation, zircaloy embrittlement limits the burnup of the fuel rod to assure remaining cladding ductility to cope with accidents. As a way to suppress hydrogen generation and cladding embrittlement by oxidation, ideas of cladding coating with an oxidation-preventive layer have emerged. Indeed, among a numbers of 'accident-tolerant-fuel (ATF)' concepts, the concept of coating the current fuel rod. Some signs of success on the lab-scale oxidation-prevention have been confirmed with a few coating candidates. Yet, relatively less attention has been given to structural integrity of coated zirconium-based alloy cladding. It is important to note that oxidation

  15. Particle tracking

    CERN Document Server

    Safarík, K; Newby, J; Sørensen, P

    2002-01-01

    In this lecture we will present a short historical overview of different tracking detectors. Then we will describe currently used gaseous and silicon detectors and their performance. In the second part we will discuss how to estimate tracking precision, how to design a tracker and how the track finding works. After a short description of the LHC the main attention is drawn to the ALICE experiment since it is dedicated to study new states in hadronic matter at the LHC. The ALICE tracking procedure is discussed in detail. A comparison to the tracking in ATLAS, CMS and LHCb is given. (5 refs).

  16. Facile Routes To Improve Performance of Solution-Processed Amorphous Metal Oxide Thin Film Transistors by Water Vapor Annealing.

    Science.gov (United States)

    Park, Won-Tae; Son, Inyoung; Park, Hyun-Woo; Chung, Kwun-Bum; Xu, Yong; Lee, Taegweon; Noh, Yong-Young

    2015-06-24

    Here, we report on a simple and high-rate oxidization method for producing solution-based compound mixtures of indium zinc oxide (IZO) and indium gallium zinc oxide (IGZO) metal-oxide semiconductors (MOS) for thin-film transistor (TFT) applications. One of the issues for solution-based MOS fabrication is how to sufficiently oxidize the precursor in order to achieve high performance. As the oxidation rate of solution processing is lower than vacuum-based deposition such as sputtering, devices using solution-processed MOS exhibit relatively poorer performance. Therefore, we propose a method to prepare the metal-oxide precursor upon exposure to saturated water vapor in a closed volume for increasing the oxidization efficiency without requiring additional oxidizing agent. We found that the hydroxide rate of the MOS film exposed to water vapor is lower than when unexposed (≤18%). Hence, we successfully fabricated oxide TFTs with high electron mobility (27.9 cm(2)/V·s) and established a rapid process (annealing at 400 °C for 5 min) that is much shorter than the conventional as-deposited long-duration annealing (at 400 °C for 1 h) whose corresponding mobility is even lower (19.2 cm(2)/V·s).

  17. Improving the performance of water desalination through ultra-permeable functionalized nanoporous graphene oxide membrane

    Science.gov (United States)

    Hosseini, Mostafa; Azamat, Jafar; Erfan-Niya, Hamid

    2018-01-01

    Molecular dynamics simulations were performed to investigate the water desalination performance of nanoporous graphene oxide (NPGO) membranes. The simulated systems consist of a NPGO as a membrane with a functionalized pore in its center immersed in an aqueous ionic solution and a graphene sheet as a barrier. The considered NPGO membranes are involved four types of pore with different size and chemistry. The results indicated that the NPGO membrane has effective efficiency in salt rejection as well as high performance in water flux. For all types of pore with the radius size of 2.9-4.5 Å, the NPGO shows salt rejection of >89%. Functional groups on the surface and edge of pores have a great effect on water flux. To precisely understand the effect of functional groups on the surface of nanostructured membranes, nanoporous graphene was simulated under the same condition for comparison. Hydrophilic groups on the surface make the NPGO as an ultra-permeable membrane. As a result, the obtained water flux for NPGO was about 77% greater than graphene. Also, it was found that the water flux of NPGO is 2-5 orders of magnitude greater than other existing reverse osmosis membranes. Therefore, the investigated systems can be recommended as a model for the water desalination.

  18. Comparison of Microbial and Chemical Source Tracking Markers To Identify Fecal Contamination Sources in the Humber River (Toronto, Ontario, Canada) and Associated Storm Water Outfalls.

    Science.gov (United States)

    Staley, Zachery R; Grabuski, Josey; Sverko, Ed; Edge, Thomas A

    2016-11-01

    Storm water runoff is a major source of pollution, and understanding the components of storm water discharge is essential to remediation efforts and proper assessment of risks to human and ecosystem health. In this study, culturable Escherichia coli and ampicillin-resistant E. coli levels were quantified and microbial source tracking (MST) markers (including markers for general Bacteroidales spp., human, ruminant/cow, gull, and dog) were detected in storm water outfalls and sites along the Humber River in Toronto, Ontario, Canada, and enumerated via endpoint PCR and quantitative PCR (qPCR). Additionally, chemical source tracking (CST) markers specific for human wastewater (caffeine, carbamazepine, codeine, cotinine, acetaminophen, and acesulfame) were quantified. Human and gull fecal sources were detected at all sites, although concentrations of the human fecal marker were higher, particularly in outfalls (mean outfall concentrations of 4.22 log10 copies, expressed as copy numbers [CN]/100 milliliters for human and 0.46 log10 CN/100 milliliters for gull). Higher concentrations of caffeine, acetaminophen, acesulfame, E. coli, and the human fecal marker were indicative of greater raw sewage contamination at several sites (maximum concentrations of 34,800 ng/liter, 5,120 ng/liter, 9,720 ng/liter, 5.26 log10 CFU/100 ml, and 7.65 log10 CN/100 ml, respectively). These results indicate pervasive sewage contamination at storm water outfalls and throughout the Humber River, with multiple lines of evidence identifying Black Creek and two storm water outfalls with prominent sewage cross-connection problems requiring remediation. Limited data are available on specific sources of pollution in storm water, though our results indicate the value of using both MST and CST methodologies to more reliably assess sewage contamination in impacted watersheds. Storm water runoff is one of the most prominent non-point sources of biological and chemical contaminants which can potentially

  19. Photocatalytic segmented nanowires and single-step iron oxide nanotube synthesis: Templated electrodeposition as all-round tool

    NARCIS (Netherlands)

    Maas, M.G.; Rodijk, E.J.B.; Maijenburg, A.W.; ten Elshof, Johan E.; Blank, David H.A.; Nielsch, K.; Fontcuberta i Morral, A.; Holt, J.K.; Thomson, C.V.

    2010-01-01

    Templated electrodeposition was used to synthesize silver-zinc oxide nanowires and iron oxide (Fe2O3) nanotubes in polycarbonate track etched (PCTE) membranes. Metal/oxide segmented nanowires were made to produce hydrogen gas from a water/methanol mixture under ultraviolet irradiation. It was

  20. Surface modification of iron oxide nanoparticles and their conjuntion with water soluble polymers for biomedical application

    Energy Technology Data Exchange (ETDEWEB)

    Nguyen Thanh Huong; Lam Thi Kieu Giang; Nguyen Thanh Binh; Le Quoc Minh [Institute of Materials Science, Vietnam Academy of Science and Technology 18 Hoang Quoc Viet Road, Cau Giay District, Hanoi (Viet Nam)], E-mail: nthuong@ims.vast.ac.vn

    2009-09-01

    Superparamagnetic iron oxide nanoparticles (SPION) coated with suitable bio-compatible substances have been used in biomedicine, particularly in magnetic resonance imaging (MRI), tissue engineering, and hyperthermia and drug delivery. In this study, we describe the synthesis of SPION and its surface modification for in-vitro experiments. The particle diameter and structure were estimated by FESEM, TEM, XRD analyses. The saturation magnetization was characterized. SPION with a mean size of 12 nm have been prepared under N{sub 2} atmosphere, with support of natural polymeric starch, by controlling chemical coprecipitation of magnetite phase from aqueous solutions containing suitable salts ratios of Fe{sup 2+} and Fe{sup 3+}. The surface of SPION-nanoparticles was treated with a coordinatable agent for higher dispersion ability in water and remaining the superparamagnetic behavior. The prepared iron oxide nanoparticles were coated with starch, dextran, PEG or MPEG to extend the application potential in the quite different engineering field of nano biomedicine.

  1. Indefinitely stable iron(IV) cage complexes formed in water by air oxidation

    Science.gov (United States)

    Tomyn, Stefania; Shylin, Sergii I.; Bykov, Dmytro; Ksenofontov, Vadim; Gumienna-Kontecka, Elzbieta; Bon, Volodymyr; Fritsky, Igor O.

    2017-01-01

    In nature, iron, the fourth most abundant element of the Earth's crust, occurs in its stable forms either as the native metal or in its compounds in the +2 or +3 (low-valent) oxidation states. High-valent iron (+4, +5, +6) compounds are not formed spontaneously at ambient conditions, and the ones obtained synthetically appear to be unstable in polar organic solvents, especially aqueous solutions, and this is what limits their studies and use. Here we describe unprecedented iron(IV) hexahydrazide clathrochelate complexes that are assembled in alkaline aqueous media from iron(III) salts, oxalodihydrazide and formaldehyde in the course of a metal-templated reaction accompanied by air oxidation. The complexes can exist indefinitely at ambient conditions without any sign of decomposition in water, nonaqueous solutions and in the solid state. We anticipate that our findings may open a way to aqueous solution and polynuclear high-valent iron chemistry that remains underexplored and presents an important challenge.

  2. Water based suspensions of iron oxide obtained by laser target evaporation for biomedical applications

    Energy Technology Data Exchange (ETDEWEB)

    Novoselova, I.P. [Ural Federal University, Department of Magnetism and Magnetic Nanomaterials, Lenin Ave. 51, 620083 Yekaterinburg (Russian Federation); Immanuel Kant Baltic Federal University, Science and Technology Park “Fabrica”, Gaidara St. 6, 236022 Kaliningrad (Russian Federation); Safronov, A.P. [Ural Federal University, Department of Magnetism and Magnetic Nanomaterials, Lenin Ave. 51, 620083 Yekaterinburg (Russian Federation); Institute of Electrophysics UD RAS, Amundsena St. 106, 620016 Yekaterinburg (Russian Federation); Samatov, O.M. [Institute of Electrophysics UD RAS, Amundsena St. 106, 620016 Yekaterinburg (Russian Federation); Beketov, I.V.; Medvedev, A.I. [Ural Federal University, Department of Magnetism and Magnetic Nanomaterials, Lenin Ave. 51, 620083 Yekaterinburg (Russian Federation); Institute of Electrophysics UD RAS, Amundsena St. 106, 620016 Yekaterinburg (Russian Federation); Kurlyandskaya, G.V. [Ural Federal University, Department of Magnetism and Magnetic Nanomaterials, Lenin Ave. 51, 620083 Yekaterinburg (Russian Federation); Universidad del País Vasco, UPV/EHU, Dpto. de Electricidad y Electrónica, P.O. Box 644, Bilbao 48080 (Spain)

    2016-10-01

    In this work spherical magnetic nanoparticles (MNPs) of iron oxide were obtained by laser target evaporation technique (LTE). Water based suspensions were prepared on the basis of obtained MNPs and their properties were also studied including inductive heat capacity. Their structure and properties were studied by a number of techniques including magnetometry and heat capacity measurements. Magnetic induction heating experiment show the specific loss power (SLP) value in the narrow range from 1.30 to 1.45 W/g for all samples under consideration when using alternating magnetic field of 1.7 kA/m and frequency of 210 kHz. These parameters insure that LTE MNPs are interesting materials promising for magnetic fluid hyperthermia. - Highlights: • Spheric oxide nanoparticles obtained by productive laser target evaporation method. • Experiment shows the specific loss power value in the narrow range for all samples. • Obtained results insure these objects as interesting material for hyperthermia.

  3. Physical and Oxidative Stability of Fish Oil-In-Water Emulsions Stabilized with Fish Protein Hydrolysates

    DEFF Research Database (Denmark)

    García Moreno, Pedro Jesús; Guadix, Antonio; Guadix, Emilia M.

    2016-01-01

    The emulsifying and antioxidant properties of fish protein hydrolysates (FPH) for the physical and oxidative stabilization of 5% (by weight) fish oil-in-water emulsions were investigated. Muscle proteins from sardine (Sardina pilchardus) and small-spotted catshark (Scyliorhinus canicula) were...... hydrolyzed to degrees of hydrolysis (DH) of 3-4-5-6% with subtilisin. Sardine hydrolysates with low DH, 3% and 4%, presented the most effective peptides to physically stabilize emulsions with smaller droplet size. This implied more protein adsorbed at the interface to act as physical barrier against...... prooxidants. This fact might also be responsible for the higher oxidative stability of these emulsions, as shown by their lowest peroxide value and concentration of volatiles such as 1-penten-3-one and 1-penten-3-ol. Among the hydrolysates prepared from small-spotted catshark only the hydrolysate with DH 3...

  4. Stabilization of oil-in-water emulsions by enzyme catalyzed oxidative gelation of sugar beet pectin

    DEFF Research Database (Denmark)

    Abang Zaidel, Dayang Norulfairuz; Chronakis, Ioannis S.; Meyer, Anne S.

    2013-01-01

    Enzyme catalyzed oxidative cross-linking of feruloyl groups can promote gelation of sugar beet pectin (SBP). It is uncertain how the enzyme kinetics of this cross-linking reaction are affected in emulsion systems and whether the gelation affects emulsion stability. In this study, SBP (2.5% w....../v) was mixed into an oil-in-water emulsion system (4.4% w/w oil, 0.22% w/w whey protein, pH 4.5). Two separate, identically composed, emulsion systems were prepared by different methods of preparation. The emulsions prepared separately and subsequently mixed with SBP (referred as Mix A) produced significantly...... larger average particle sizes than the emulsions in which the SBP was homogenized into the emulsion system during emulsion preparation (referred as Mix B). Mix B type emulsions were stable. Enzyme catalyzed oxidative gelation of SBP helped stabilize the emulsions in Mix A. The kinetics of the enzyme...

  5. Discovery of Overcoating Metal Oxides on Photoelectrode for Water Splitting by Automated Screening.

    Science.gov (United States)

    Saito, Rie; Miseki, Yugo; Nini, Wang; Sayama, Kazuhiro

    2015-10-12

    We applied an automated semiconductor synthesis and screen system to discover overcoating film materials and optimize coating conditions on the BiVO4/WO3 composite photoelectrode to enhance stability and photocurrent. Thirteen metallic elements for overcoating oxides were examined with various coating amounts. The stability of the BiVO4/WO3 photoelectrode in a highly concentrated carbonate electrolyte aqueous solution was significantly improved by overcoating with Ta2O5 film, which was amorphous and porous when calcined at 550 °C. The photocurrent for the water oxidation reaction was only minimally inhibited by the presence of the Ta2O5 film on the BiVO4/WO3 photoelectrode.

  6. Observation of a water droplet motion by using an oxide nanowire transistor covered by a nanofiber mesh.

    Science.gov (United States)

    Lee, Jonghun; Han, Junebeom; Yeo, Chang Su; Lim, Taekyung; Park, Sangyoon; Ju, Sanghyun

    2016-12-16

    The motion, in particular the flow speed and dropping height, of a water droplet was observed using a tin oxide (SnO2) nanowire transistor with a polyurethane (PU) nanofiber mesh as a selective filter. The changes in the SnO2 nanowire transistor characteristics, particularly the threshold voltage and on-current, were due to the adsorbed water molecules that acted as electron donors on the surface of the oxide nanowire semiconducting channel. The role of the PU nanofiber mesh, allowing the passage of water vapor while blocking liquid water, was to restrict the direct contact between the water droplet and the oxide nanowire semiconducting channel and electrodes, which could cause abnormal transistor characteristics. The selective filtering properties of the PU nanofiber mesh could be controlled by changing the number of PU layers.

  7. Accelerated corrosion and oxide dissolution in 316L stainless steel irradiated in situ in high temperature water

    Science.gov (United States)

    Raiman, Stephen S.; Was, Gary S.

    2017-09-01

    316L stainless steel samples were irradiated with a proton beam while simultaneously exposed to high temperature water with added hydrogen (320 °C, 3 wppm H2, neutral pH) to study the effect of radiation on stainless steel corrosion. Irradiated samples had thinner and more porous inner oxides with a lower chromium content when compared to unirradiated samples. Observations suggest that depletion of chromium from the inner oxide can be attributed to the dissolution of chromium-rich spinel oxides in irradiated water, leading to an accelerated rate of inner oxide dissolution. Sample areas which were not irradiated, but were exposed to the flow of irradiated water were also found to be porous and deficient in chromium, indicating that these phenomena can be attributed primarily to water radiolysis. A new empirical equation for oxide growth and dissolution is used to describe the observed changes in oxide thickness under irradiation. An experiment in which a stainless steel sample was exposed to high temperature water (320 °C, 3 wppm H2, neutral pH) without irradiation, and then exposed for a second time with irradiation was conducted to observe the effect of irradiation on a pre-formed protective film. After the irradiated exposure, the sample exhibited chromium loss in regions which were directly irradiated, but not on regions exposed only to irradiated water, suggesting that a pre-formed protective oxide may be effective in preventing chromium loss due to irradiated water. Additionally, this observation suggests that enhanced kinetics under irradiation may have accelerated dissolution of chromium from the inner oxide.

  8. Importance of trivalency and the e(g)(1) configuration in the photocatalytic oxidation of water by Mn and Co oxides.

    Science.gov (United States)

    Maitra, Urmimala; Naidu, B S; Govindaraj, A; Rao, C N R

    2013-07-16

    Prompted by the early results on the catalytic activity of LiMn2O4 and related oxides in the photochemical oxidation of water, our detailed study of several manganese oxides has shown that trivalency of Mn is an important factor in determining the catalytic activity. Thus, Mn2O3, LaMnO3, and MgMn2O4 are found to be very good catalysts with turnover frequencies of 5 × 10(-4) s(-1), 4.8 × 10(-4) s(-1), and 0.8 × 10(-4) s(-1), respectively. Among the cobalt oxides, Li2Co2O4 and LaCoO3--especially the latter--exhibit excellent catalytic activity, with the turnover frequencies being 9 × 10(-4) s(-1) and 1.4 × 10(-3) s(-1), respectively. The common feature among the catalytic Mn and Co oxides is not only that Mn and Co are in the trivalent state, but Co(3+) in the Co oxides is in the intermediate t2g(5)e(g)(1) state whereas Mn(3+) is in the t2g(3e(g)(1) state. The presence of the e(g)(1) electron in these Mn and Co oxides is considered to play a crucial role in the photocatalytic properties of the oxides.

  9. Water-mediated interactions between trimethylamine-N-oxide and urea.

    Science.gov (United States)

    Hunger, Johannes; Ottosson, Niklas; Mazur, Kamila; Bonn, Mischa; Bakker, Huib J

    2015-01-07

    The amphiphilic osmolyte trimethylamine-N-oxide (TMAO) is commonly found in natural organisms, where it counteracts biochemical stress associated with urea in aqueous environments. Despite the important role of TMAO as osmoprotectant, the mechanism behind TMAO's action has remained elusive. Here, we study the interaction between urea, TMAO, and water in solution using broadband (100 MHz-1.6 THz) dielectric spectroscopy. We find that the previously reported tight hydrogen bonds between 3 water molecules and the hydrophilic amine oxide group of TMAO, remain intact at all investigated concentrations of urea, showing that no significant hydrogen bonding occurs between the two co-solutes. Despite the absence of direct TMAO-urea interactions, the solute reorientation times of urea and TMAO show an anomalous nonlinear increase with concentration, for ternary mixtures containing equal amounts of TMAO and urea. The nonlinear increase of the reorientation correlates with changes in the viscosity, showing that the combination of TMAO and urea cooperatively enhances the hydrogen-bond structure of the ternary solutions. This nonlinear increase is indicative of water mediated interaction between the two solutes and is not observed if urea is combined with other amphiphilic solutes.

  10. Porous NiFe-Oxide Nanocubes as Bifunctional Electrocatalysts for Efficient Water-Splitting.

    Science.gov (United States)

    Kumar, Ashwani; Bhattacharyya, Sayan

    2017-12-06

    Electrocatalytic water-splitting, a combination of oxygen and hydrogen evolution reactions (OER and HER), is highly attractive in clean energy technologies, especially for high-purity hydrogen production, whereas developing stable, earth-abundant, bifunctional catalysts has continued to pose major challenges. Herein, a mesoporous NiFe-oxide nanocube (NiFe-NC) system is developed from a NiFe Prussian blue analog metal-organic framework as an efficient bifunctional catalyst for overall water-splitting. The NiFe-NCs with ∼200 nm side length have a Ni/Fe molar ratio of 3:2 and is a composite of NiO and α/γ-Fe 2 O 3 . The NCs demonstrate overpotentials of 271 and 197 mV for OER and HER, respectively, in 1 M KOH at 10 mA cm -2 , which outperform those of 339 and 347 mV for the spherical NiFe-oxide nanoparticles having a similar composition. The electrolyzer constructed using NiFe-NCs requires an impressive cell voltage of 1.67 V to deliver a current density of 10 mA cm -2 . Along with a mesoporous structure with a broad pore size distribution, the NiFe-NCs demonstrate the qualities of a desired corrosion-resistant water-splitting catalyst with long-term stability. The exposure of active sites at the edges and vertices of the NCs was validated to play a crucial role in their overall catalytic performance.

  11. [Effect of ammonia-oxidizing bacteria (AOB) on chloraminated disinfection attenuation in drinking water distribution system].

    Science.gov (United States)

    Bai, Xiao-Hui; Cai, Yun-Long; Zhou, Bin-Hui; Zhi, Xing-Hua

    2009-06-15

    The growth of microbe and formation of biofilm in water distribution system were important factors affecting the security of water quality. The number of ammonia-oxidizing bacteria (AOB) in biofilm of a chloraminated drinking water distribution system in Shanghai was detected by MPN-Griess method, and the relations among AOB, nitrification and chloraminated disinfection were analyzed. Meanwhile, the effects of AOB on chloraminated disinfection fastness and attenuation by simulation experiment were studied. The result indicated that the number of ammonia-oxidizing bacteria in pipe biofilm was between 1.0 x 10(2)-4.3 x 10(5) MPN/g dry biofilm. Correlation coefficients of AOB with ammonia, nitrite and nitrate were -0.563, 0.603 and -0.563. Correlation coefficients of AOB with total chlorine and mono-chloramine were -0.659 and -0.571. Fastness of AOB to chloramine was higher than heterotrophic bacteria and AOB can deplete more chloramine than HPC.

  12. Characterization of a trinuclear ruthenium species in catalytic water oxidation by Ru(bda)(pic)2 in neutral media.

    Science.gov (United States)

    Zhang, Biaobiao; Li, Fei; Zhang, Rong; Ma, Chengbing; Chen, Lin; Sun, Licheng

    2016-06-30

    A Ru(III)-O-Ru(IV)-O-Ru(III) type trinuclear species was crystallographically characterized in water oxidation by Ru(bda)(pic)2 (H2bda = 2,2'-bipyridine-6,6'-dicarboxylic acid; pic = 4-picoline) under neutral conditions. The formation of a ruthenium trimer due to the reaction of Ru(IV)[double bond, length as m-dash]O with Ru(II)-OH2 was fully confirmed by chemical, electrochemical and photochemical methods. Since the oxidation of the trimer was proposed to lead to catalyst decomposition, the photocatalytic water oxidation activity was rationally improved by the suppression of the formation of the trimer.

  13. X-ray photoelectron spectroscopic studies of the oxidation of aluminium by liquid water monitored in an anaerobic cell.

    Science.gov (United States)

    Rotole, J A; Sherwood, P M

    2001-02-01

    The oxidation of clean polycrystalline aluminium foil was performed in a previously described anaerobic cell and studied by core level and valence band X-ray photoelectron spectroscopy. Oxide free sample surfaces were exposed under inert atmosphere at room temperature to increasingly oxidative environments of water vapor and liquid water beginning with an oxide free metal foil each time. Minor oxidative environments were found to produce a film of boehmite with a thinner outer film of gibbsite. Harsher oxidation in liquid water resulted in an oxide film much thicker than that found on the as received sample which contained an inner composition of gamma alumina with an outer film of gibbsite. As expected, the oxide film observed for ultra high purity polycrystalline aluminiurm foil in the as received state was gibbsite. The valence band of the cleaned metal is discussed in terms of residual surface species. The evaluation and determination of these residual surface species is evaluated following an analysis of two different band structure calculations which use different d orbital exponents. It is found that while the density of states is almost unaltered by changes in the d exponent, the predicted spectrum is substantially changed. The work makes extensive use of valence band X-ray photoelectron spectroscopy.

  14. Simultaneous oxidation and adsorption of As(III) from water by cerium modified chitosan ultrafine nanobiosorbent

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Lingfan [School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237 (China); Research Center of Analysis and Test, East China University of Science and Technology, Shanghai 200237 (China); Zhu, Tianyi [School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237 (China); Liu, Xin, E-mail: liuxin@ecust.edu.cn [School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237 (China); Zhang, Wenqing, E-mail: zhwqing@ecust.edu.cn [School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237 (China)

    2016-05-05

    Highlights: • A novel ultrafine nanobiosorbent of cerium modified chitosan (Ce-CNB) was prepared. • The Ce-CNB possessed properties for simultaneous oxidation and adsorption As(III). • Adsorption of As(III) by Ce-CNB was in high efficiency. • Mechanisms for As(III) adsorption on Ce-CNB were elucidated. - Abstract: Since most existing arsenic removal adsorbents are difficult to effectively remove arsenite (As(III)), an urgent need is to develop an efficient adsorbent for removing As(III) from contaminated water. In this study, a novel ultrafine nanobiosorbent of cerium modified chitosan (Ce-CNB) with simultaneous oxidation and adsorption As(III) performance has been successfully developed. The resulting Ce-CNB with or without As(III) adsorption was characterized by FTIR, XRD, SEM, EDS, TEM, EMI and XPS analysis. Batch of adsorption experiments were performed to investigate the effects of various conditions on the As(III) adsorption. The adsorption behaviors were well described by the Langmuir isotherm and the pseudo-second-order kinetic model, with the maximum adsorption capacities of 57.5 mg g{sup −1}. The adsorption mechanisms for As(III) were (i) formed monodentate and bidentate complexes between hydroxyl groups and arsenite; and (ii) partial As(III) oxidized to As(V) followed by simultaneously adsorbed on the surface of Ce-CNB. This novel nanocomposite can be reused while maintaining a high removal efficiency and can be applied to treat 5.8 L of As(III)-polluted water with the effluent concentration lower than the World Health Organization standard, which suggests its great potential to remove As(III) from contaminated water.

  15. Reduced Graphene Oxide Membranes: Applications in Fog Collection and Water Purification

    KAUST Repository

    Tang, Bo

    2017-05-01

    Reduced graphene oxide (rGO) has attracted considerable interest recently as the low cost and chemical stable derivative of pristine graphene with application in many applications such as energy storage, water purification and electronic devices. This dissertation thoroughly investigated stacked rGO membrane fabrication process by vacuum-driven filtration, discovered asymmetry of the two surfaces of the rGO membrane, explored application perspectives of the asymmetric rGO membrane in fog collection and microstructure patterning, and disclosed membrane compaction issue during water filtration and species rejection. In more details, this dissertation revealed that, with suitable pore size, the filtration membrane substrate would leave its physical imprint on the bottom surface of the rGO membrane in the form of surface microstructures, which result in asymmetric dynamic water wettability properties of the two surfaces of the rGO membrane. The asymmetric wettability of the rGO membrane would lead to contrasting fog harvesting behavior of its two surfaces. The physical imprint mechanism was further extended to engineering pre-designed patterns selectively on the bottom surface of the rGO membrane. This dissertation, for the first time, reported the water flux and rejection kinetics, which was related to the compaction of the rGO membrane under pressure in the process of water filtration.

  16. Extended friction elucidates the breakdown of fast water transport in graphene oxide membranes

    Science.gov (United States)

    Montessori, A.; Amadei, C. A.; Falcucci, G.; Sega, M.; Vecitis, C. D.; Succi, S.

    2016-12-01

    The understanding of water transport in graphene oxide (GO) membranes stands out as a major theoretical problem in graphene research. Notwithstanding the intense efforts devoted to the subject in the recent years, a consolidated picture of water transport in GO membranes is yet to emerge. By performing mesoscale simulations of water transport in ultrathin GO membranes, we show that even small amounts of oxygen functionalities can lead to a dramatic drop of the GO permeability, in line with experimental findings. The coexistence of bulk viscous dissipation and spatially extended molecular friction results in a major decrease of both slip and bulk flow, thereby suppressing the fast water transport regime observed in pristine graphene nanochannels. Inspection of the flow structure reveals an inverted curvature in the near-wall region, which connects smoothly with a parabolic profile in the bulk region. Such inverted curvature is a distinctive signature of the coexistence between single-particle zero-temperature (noiseless) Langevin friction and collective hydrodynamics. The present mesoscopic model with spatially extended friction may offer a computationally efficient tool for future simulations of water transport in nanomaterials.

  17. Water-Induced shape memory effect of nanocellulose papers from sisal cellulose nanofibers with graphene oxide.

    Science.gov (United States)

    Song, Laifu; Li, Yuqi; Xiong, Zhongqiang; Pan, Lulu; Luo, Qiyun; Xu, Xu; Lu, Shaorong

    2018-01-01

    A novel water-induced shape memory nanocomposites were prepared by introducing graphene oxide (GO), which was based on microcrystalline cellulose nanofibers (MSF-g-COOH) extracting from sisal fibers. The results showed that the water-induced shape memory properties of MSF-g-COOH were significantly improved by the strong hydrogen bonding interaction between MSF-g-COOH and GO, It leads to some additional physically cross-linked points in MSF-g-COOH. On the other hand, at 0.5wt% GO loading, tensile strength and Young modulus of the nanocomposite increased from 139 to 184MPa, and from 5.77 to 8.54GPa, respectively, compared to those of pure MSF-g-COOH. Furthermore, a water-induced model was proposed to discuss the water-induced shape memory behaviors of the MSF-g-COOH/GO nanocomposites. This study provides a framework for developing a cellulose based shape memory polymers (CSMPs) and better understanding the shape recovery mechanism in water-induced CSMPs. Copyright © 2017 Elsevier Ltd. All rights reserved.

  18. Decoupling photochemical Fe(II) oxidation from shallow-water BIF deposition

    DEFF Research Database (Denmark)

    Konhauser, Kurt O.; Amskold, Larry; Lalonde, Stefan V.

    2007-01-01

    to the rise of atmospheric oxygen and the development of a protective ozone layer, the Earth's surface was subjected to high levels of ultraviolet radiation. Bulk ocean waters that were anoxic at this time could have supported high concentrations of dissolved Fe(II). Under such conditions, dissolved ferrous...... for biology [Fran??ois, L.M., 1986, Extensive deposition of banded iron formations was possible without photosynthesis. Nature 320, 352-354]. Here, we evaluate the potential importance of photochemical oxidation using a combination of experiments and thermodynamic models. The experiments simulate...

  19. Oxidation of phenyl alanine by pyridinium chlorochromate in acidic DMF–water medium: A kinetic study

    Directory of Open Access Journals (Sweden)

    B.L. Hiran

    2016-11-01

    Full Text Available The kinetics of oxidation of phenyl alanine by pyridinium chlorochromate in DMF–water (70:30% mixture in presence of perchloric acid leads to the formation of corresponding aldehyde. The reaction is of first order each in [PCC], [HClO4] and [AA]. Michaelis–Menten type kinetics was observed with phenyl alanine. The reaction rates were determined at different temperatures [25, 30, 35, 40, 45, 50 °C] and the activation parameters were calculated. The reaction does not induce polymerization of acrylonitrile. With an increase in the amount of DMF in its aqueous mixture, the rate increases. A suitable mechanism for the reaction was postulated.

  20. Final report on the oxidation of energetic materials in supercritical water. Final Air Force report

    Energy Technology Data Exchange (ETDEWEB)

    Buelow, S.J.; Allen, D.; Anderson, G.K. [and others

    1995-04-03

    The objective of this project was to determine the suitability of oxidation in supercritical fluids (SCO), particularly water (SCWO), for disposal of propellants, explosives, and pyrotechnics (PEPs). The SCO studies of PEPs addressed the following issues: The efficiency of destruction of the substrate. The products of destruction contained in the effluents. Whether the process can be conducted safely on a large scale. Whether energy recovery from the process is economically practicable. The information essential for process development and equipment design was also investigated, including issues such as practical throughput of explosives through a SCWO reactor, reactor materials and corrosion, and models for process design and optimization.

  1. Photoassisted Oxidation of Sulfides Catalyzed by Artificial Metalloenzymes Using Water as an Oxygen Source †

    Directory of Open Access Journals (Sweden)

    Christian Herrero

    2016-12-01

    Full Text Available The Mn(TpCPP-Xln10A artificial metalloenzyme, obtained by non-covalent insertion of Mn(III-meso-tetrakis(p-carboxyphenylporphyrin [Mn(TpCPP, 1-Mn] into xylanase 10A from Streptomyces lividans (Xln10A as a host protein, was found able to catalyze the selective photo-induced oxidation of organic substrates in the presence of [RuII(bpy3]2+ as a photosensitizer and [CoIII(NH35Cl]2+ as a sacrificial electron acceptor, using water as oxygen atom source.

  2. Highly Conductive Semitransparent Graphene Circuits Screen-Printed from Water-Based Graphene Oxide Ink

    DEFF Research Database (Denmark)

    Overgaard, Marc H.; Kuhnel, Martin; Hvidsten, Rasmus

    2017-01-01

    The use of graphene materials as conductive inks for flexible and transparent electronics is promising, but challenged by the need for stabilizers, specialized organic solvents, and/or high temperature annealing, severely limiting performance or compatibility with substrates and printing techniques....... Here, the development of a scalable water-based graphene oxide ink is reported that can be screen-printed on flexible plastic substrates and subsequently reduced using a 1: 1 mixture of trifluoroacetic acid and hydroiodic acid, thereby creating an electric circuit. The reduced prints exhibit low sheet...

  3. Corrosion of oxide nuclear fuels in high-temperature water (LWBR Development Program

    Energy Technology Data Exchange (ETDEWEB)

    Markowitz, J M; Clayton, J C

    1970-02-01

    The corrosion behavior of a group of nuclear fuel oxides including urania, thoria, urania-zirconia, urania-calcia-zirconia, and urania-thoria has been studied in 360/sup 0/C, pH 10 flowing water, both degassed and oxygenated (5 and 100 ppM). Weight gains of the specimens, which were of plate or cylindrical pellet shape, were determined periodically during the corrosion exposures, some of which were as long as 500 days; in addition, ceramographic examinations, x-ray diffraction measurements, and chemical analyses were carried out on selected specimens. The results are summarized and discussed. (NSA 24: 25764)

  4. Discrete-Time Dynamical Maximum Power Tracking Control for a Vertical Axis Water Turbine with Retractable Blades

    Directory of Open Access Journals (Sweden)

    Zhaoyong Mao

    2016-01-01

    Full Text Available This paper addresses the power generation control system of a new drag-type Vertical Axis Turbine with several retractable blades. The returning blades can be entirely hidden in the drum, and negative torques can then be considerably reduced as the drum shields the blades. Thus, the power efficiency increases. Regarding the control, a Linear Quadratic Tracking (LQT optimal control algorithm for Maximum Power Point Tracking (MPPT is proposed to ensure that the wave energy conversion system can operate highly effectively under fluctuating conditions and that the tracking process accelerates over time. Two-dimensional Computational Fluid Dynamics (CFD simulations are performed to obtain the maximum power points of the turbine’s output. To plot the tip speed ratio curve, the least squares method is employed. The efficacy of the steady and dynamic performance of the control strategy was verified using Matlab/Simulink software. These validation results show that the proposed system can compensate for power fluctuations and is effective in terms of power regulation.

  5. Water oxidation by electrodeposited cobalt oxides--role of anions and redox-inert cations in structure and function of the amorphous catalyst.

    Science.gov (United States)

    Risch, Marcel; Klingan, Katharina; Ringleb, Franziska; Chernev, Petko; Zaharieva, Ivelina; Fischer, Anna; Dau, Holger

    2012-03-12

    For the production of nonfossil fuels, water oxidation by inexpensive cobalt-based catalysts is of high interest. Films for the electrocatalysis of water oxidation were obtained by oxidative self-assembly (electrodeposition) from aqueous solutions containing, apart from Co, either K, Li or Ca with either a phosphate, acetate or chloride anion. X-ray absorption spectroscopy (XAS) at the Co K-edge revealed clusters of edge-sharing CoO(6) octahedra in all films, but the size or structural disorder of the Co-oxido clusters differed. Whereas potassium binding is largely unspecific, CaCo(3) O(4) cubanes, which resemble the CaMn(3) O(4) cubane of the biological catalyst in oxygenic photosynthesis, may form, as suggested by XAS at the Ca K-edge. Cyclic voltammograms in a potassium phosphate buffer at pH 7 revealed that no specific combination of anions and redox-inactive cations is required for catalytic water oxidation. However, the anion type modulates not only the size (or order) of the Co-oxido clusters, but also electrodeposition rates, redox potentials, the capacity for oxidative charging, and catalytic currents. On these grounds, structure-activity relations are discussed. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. QSAR analysis for nano-sized layered manganese-calcium oxide in water oxidation: An application of chemometric methods in artificial photosynthesis.

    Science.gov (United States)

    Shahbazy, Mohammad; Kompany-Zareh, Mohsen; Najafpour, Mohammad Mahdi

    2015-11-01

    Water oxidation is among the most important reactions in artificial photosynthesis, and nano-sized layered manganese-calcium oxides are efficient catalysts toward this reaction. Herein, a quantitative structure-activity relationship (QSAR) model was constructed to predict the catalytic activities of twenty manganese-calcium oxides toward water oxidation using multiple linear regression (MLR) and genetic algorithm (GA) for multivariate calibration and feature selection, respectively. Although there are eight controlled parameters during synthesizing of the desired catalysts including ripening time, temperature, manganese content, calcium content, potassium content, the ratio of calcium:manganese, the average manganese oxidation state and the surface of catalyst, by using GA only three of them (potassium content, the ratio of calcium:manganese and the average manganese oxidation state) were selected as the most effective parameters on catalytic activities of these compounds. The model's accuracy criteria such as R(2)test and Q(2)test in order to predict catalytic rate for external test set experiments; were equal to 0.941 and 0.906, respectively. Therefore, model reveals acceptable capability to anticipate the catalytic activity. Copyright © 2015 Elsevier B.V. All rights reserved.

  7. Enhanced chlorine dioxide decay in the presence of metal oxides: Relevance to drinking water distribution systems

    KAUST Repository

    Liu, Chao

    2013-07-19

    Chlorine dioxide (ClO2) decay in the presence of typical metal oxides occurring in distribution systems was investigated. Metal oxides generally enhanced ClO2 decay in a second-order process via three pathways: (1) catalytic disproportionation with equimolar formation of chlorite and chlorate, (2) reaction to chlorite and oxygen, and (3) oxidation of a metal in a reduced form (e.g., cuprous oxide) to a higher oxidation state. Cupric oxide (CuO) and nickel oxide (NiO) showed significantly stronger abilities than goethite (α-FeOOH) to catalyze the ClO2 disproportionation (pathway 1), which predominated at higher initial ClO2 concentrations (56-81 μM). At lower initial ClO2 concentrations (13-31 μM), pathway 2 also contributed. The CuO-enhanced ClO2 decay is a base-assisted reaction with a third-order rate constant of 1.5 × 10 6 M-2 s-1 in the presence of 0.1 g L -1 CuO at 21 ± 1 C, which is 4-5 orders of magnitude higher than in the absence of CuO. The presence of natural organic matter (NOM) significantly enhanced the formation of chlorite and decreased the ClO 2 disproportionation in the CuO-ClO2 system, probably because of a higher reactivity of CuO-activated ClO2 with NOM. Furthermore, a kinetic model was developed to simulate CuO-enhanced ClO 2 decay at various pH values. Model simulations that agree well with the experimental data include a pre-equilibrium step with the rapid formation of a complex, namely, CuO-activated Cl2O4. The reaction of this complex with OH- is the rate-limiting and pH-dependent step for the overall reaction, producing chlorite and an intermediate that further forms chlorate and oxygen in parallel. These novel findings suggest that the possible ClO2 loss and the formation of chlorite/chlorate should be carefully considered in drinking water distribution systems containing copper pipes. © 2013 American Chemical Society.

  8. Electrocatalytic Water Oxidation by a Water-Soluble Copper(II) Complex with a Copper-Bound Carbonate Group Acting as a Potential Proton Shuttle.

    Science.gov (United States)

    Chen, Fangfang;