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Sample records for fluctuating redox conditions

  1. Ediacaran Redox Fluctuations

    Science.gov (United States)

    Sahoo, S. K.; Jiang, G.; Planavsky, N. J.; Kendall, B.; Owens, J. D.; Anbar, A. D.; Lyons, T. W.

    2013-12-01

    Evidence for pervasive oxic conditions, and likely even deep ocean oxygenation has been documented at three intervals in the lower (ca. 632 Ma), middle (ca. 580 Ma) and upper (ca. 551 Ma) Ediacaran. The Doushantuo Formation in South China hosts large enrichments of redox-sensitive trace element (e.g., molybdenum, vanadium and uranium) in anoxic shales, which are indicative of a globally oxic ocean-atmosphere system. However, ocean redox conditions between these periods continue to be a topic of debate and remain elusive. We have found evidence for widespread anoxic conditions through much of the Ediacaran in the deep-water Wuhe section in South China. During most of the Ediacaran-early Cambrian in basinal sections is characterized by Fe speciation data and pyrite morphologies that indicate deposition under euxinic conditions with near-crustal enrichments of redox-sensitive element and positive pyrite-sulfur isotope values, which suggest low levels of marine sulfate and widespread euxinia. Our work reinforces an emerging view that the early Earth, including the Ediacaran, underwent numerous rises and falls in surface oxidation state, rather than a unidirectional rise as originally imagined. The Ediacaran ocean thus experienced repetitive expansion and contraction of marine chalcophilic trace-metal levels that may have had fundamental impact on the slow evolution of early animals and ecosystems. Further, this framework forces us to re-examine the relationship between Neoproterozoic oxygenation and metazoan diversification. Varying redox conditions through the Cryogenian and Ediacaran may help explain molecular clock and biomarker evidence for an early appearance and initial diversification of metazoans but with a delay in the appearance of most major metazoan crown groups until close to Ediacaran-Cambrian boundary.

  2. Carbon Mineralization Can Be Sustained or Even Stimulated under Fluctuating Redox Conditions in Tropical and Temperate Soils

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    Huang, W.; Hall, S. J.

    2017-12-01

    Soil carbon (C) mineralization is widely thought to be affected by O2 availability, and anaerobiosis represents a significant global mechanism of C stabilization. However, mineral-associated organic C (e.g. Fe-bound organic C) may be vulnerable to redox fluctuations due to release following Fe reduction, which could counteract protective effects of anaerobiosis. Many soils, including temperate Mollisols and tropical Oxisols, experience fluctuating redox conditions following moisture variations that could impact C cycling and stabilization. Here we incubated two soils with C4 leaf litter at different duration and frequencies of anaerobic periods for 128 days to investigate how redox fluctuations affect soil C mineralization. The treatments included static aerobic (control), and 2-, 4-, 8- and 12- day anaerobic followed by 4-day aerobic. We measured CO2, CH4, and their C isotope ratios. Longer durations of anaerobic conditions promoted greater Fe reduction and more DOC released. Notably, in both soils despite their large differences in composition, the production of CO2 and CH4 was stimulated under aerobic conditions following anaerobic conditions (relative to the control), which compensated for the decrease under anaerobic conditions. After 128 days, cumulative C mineralization in the control was similar between the Mollisol (9.7 mg C g-1) and the Oxisol (10.1 mg C g-1). The value in the Mollisol was significantly higher in the 12-day anaerobic treatment (11.2 mg C g-1) than the aerobic control and the 2-day anaerobic treatment (9.7 mg C g-1). In the Oxisol, cumulative C mineralization was not significantly affected by any of the fluctuating redox treatments relative to the control. Our findings challenge theory by showing that redox fluctuations can counteract the suppressive effects of O2 limitation on decomposition.

  3. Redox Fluctuations Increase the Contribution of Lignin to Soil Respiration

    Science.gov (United States)

    Hall, S. J.; Silver, W. L.; Timokhin, V.; Hammel, K.

    2014-12-01

    Lignin mineralization represents a critical flux in the terrestrial carbon (C) cycle, yet little is known about mechanisms and environmental factors controlling lignin breakdown in mineral soils. Hypoxia has long been thought to suppress lignin decomposition, yet variation in oxygen (O2) availability in surface soils accompanying moisture fluctuations could potentially stimulate this process by generating reactive oxygen species via coupled biotic and abiotic iron (Fe) redox cycling. Here, we tested the impact of redox fluctuations on lignin breakdown in humid tropical forest soils during ten-week laboratory incubations. We used synthetic lignins labeled with 13C in either of two positions (aromatic methoxyl and propyl Cβ) to provide highly sensitive and specific measures of lignin mineralization not previously employed in soils. Four-day redox fluctuations increased the percent contribution of methoxyl C to soil respiration, and cumulative methoxyl C mineralization was equivalent under static aerobic and fluctuating redox conditions despite lower total C mineralization in the latter treatment. Contributions of the highly stable Cβ to mineralization were also equivalent in static aerobic and fluctuating redox treatments during periods of O2 exposure, and nearly doubled in the fluctuating treatment after normalizing to cumulative O2 exposure. Oxygen fluctuations drove substantial net Fe reduction and oxidation, implying that reactive oxygen species generated during abiotic Fe oxidation likely contributed to the elevated contribution of lignin to C mineralization. Iron redox cycling provides a mechanism for lignin breakdown in soils that experience conditions unfavorable for canonical lignin-degrading organisms, and provides a potential mechanism for lignin depletion in soil organic matter during late-stage decomposition. Thus, close couplings between soil moisture, redox fluctuations, and lignin breakdown provide potential a link between climate variability and

  4. Redox fluctuations in the Early Ordovician oceans

    DEFF Research Database (Denmark)

    D'Arcy, Joan Mary; Gilleaudeau, Geoffrey Jon; Peralta, Silvio

    2017-01-01

    Chromium (Cr) stable isotopes are a useful tracer of changes in redox conditions because changes in its oxidation state are accompanied by an isotopic fractionation. Recent co-precipitation experiments have shown that Cr(VI) is incorporated into the calcite lattice, suggesting that carbonates......, accompanied by exceptionally low Cr concentrations (runoff or hydrothermal input into the global...

  5. Characterization of redox conditions in pollution plumes

    DEFF Research Database (Denmark)

    Christensen, Thomas Højlund; Bjerg, Poul Løgstrup; Banwart, Steven A.

    2000-01-01

    Evalution of redox conditions in groundwater pollution plumes is often a prerequisite for understanding the behviour of the pollutants in the plume and for selecting remediation approaches. Measuring of redox conditions in pollution plumes is, however, a fairly recent issue and yet relative few...

  6. Soil phosphorus redistribution among iron-bearing minerals under redox fluctuation

    Science.gov (United States)

    Lin, Y.; Bhattacharyya, A.; Campbell, A.; Nico, P. S.; Pett-Ridge, J.; Silver, W. L.

    2016-12-01

    Phosphorus (P) is a key limiting nutrient in tropical forests that governs primary production, litter decomposition, and soil respiration. A large proportion of P in these highly weathered soils is bound to short-range ordered or poorly crystalline iron (Fe) minerals. It is well-documented that these Fe minerals are redox-sensitive; however, little is known about how Fe-redox interactions affect soil P turnover. We evaluated the impacts of oxic/anoxic fluctuation on soil P fractions and reactive Fe species in a laboratory incubation experiment. Soils from a humid tropical forest were amended with plant biomass and incubated for up to 44 days under four redox regimes: static oxic, static anoxic, high frequency fluctuating (4-day oxic/4-day anoxic), and low frequency fluctuating (8-day oxic/4-day anoxic). We found that the static anoxic treatment induced a 10-fold increase in Fe(II) (extracted by hydrochloric acid) and a 1.5-fold increase in poorly crystalline Fe (extracted by ammonium oxalate), suggesting that anoxic conditions drastically increased Fe(III) reduction and the formation of amorphous Fe minerals. Static anoxic conditions also increased Fe-bound P (extracted by sodium hydroxide) and increased the oxalate-extractable P by up to 110% relative to static oxic conditions. In two fluctuating treatments, Fe(II) and oxalate-extractable Fe and P were all increased by short-term reduction events after 30 minutes, but fell back to their initial levels after 3 hours. These results suggest that reductive dissolution of Fe(III) minerals mobilized a significant amount of P; however, this P could be rapidly re-adsorbed. Furthermore, bioavailable P extracted by sodium bicarbonate solution was largely unaffected by redox regimes and was only increased by static anoxic conditions after 20 days. Overall, our data demonstrate that a significant amount of soil P may be liberated and re-adsorbed by Fe minerals during redox fluctuation. Even though bioavailable P appears to be

  7. Sediment phosphorus speciation and mobility under dynamic redox conditions

    Science.gov (United States)

    Parsons, Chris T.; Rezanezhad, Fereidoun; O'Connell, David W.; Van Cappellen, Philippe

    2017-07-01

    Anthropogenic nutrient enrichment has caused phosphorus (P) accumulation in many freshwater sediments, raising concerns that internal loading from legacy P may delay the recovery of aquatic ecosystems suffering from eutrophication. Benthic recycling of P strongly depends on the redox regime within surficial sediment. In many shallow environments, redox conditions tend to be highly dynamic as a result of, among others, bioturbation by macrofauna, root activity, sediment resuspension and seasonal variations in bottom-water oxygen (O2) concentrations. To gain insight into the mobility and biogeochemistry of P under fluctuating redox conditions, a suspension of sediment from a hypereutrophic freshwater marsh was exposed to alternating 7-day periods of purging with air and nitrogen gas (N2), for a total duration of 74 days, in a bioreactor system. We present comprehensive data time series of bulk aqueous- and solid-phase chemistry, solid-phase phosphorus speciation and hydrolytic enzyme activities demonstrating the mass balanced redistribution of P in sediment during redox cycling. Aqueous phosphate concentrations remained low ( ˜ 2.5 µM) under oxic conditions due to sorption to iron(III) oxyhydroxides. During anoxic periods, once nitrate was depleted, the reductive dissolution of iron(III) oxyhydroxides released P. However, only 4.5 % of the released P accumulated in solution while the rest was redistributed between the MgCl2 and NaHCO3 extractable fractions of the solid phase. Thus, under the short redox fluctuations imposed in the experiments, P remobilization to the aqueous phase remained relatively limited. Orthophosphate predominated at all times during the experiment in both the solid and aqueous phase. Combined P monoesters and diesters accounted for between 9 and 16 % of sediment particulate P. Phosphatase activities up to 2.4 mmol h-1 kg-1 indicated the potential for rapid mineralization of organic P (Po), in particular during periods of aeration when the

  8. Dissolution of UO2 in redox conditions

    International Nuclear Information System (INIS)

    Casas, I.; Pablo de, J.; Rovira, M.

    1998-01-01

    The performance assessment of the final disposal of the spent nuclear fuel in geological formations is strongly dependent on the spent fuel matrix dissolution. Unirradiated uranium (IV) dioxide has shown to be very useful for such purposes. The stability of UO 2 is very dependent on vault redox conditions. At reducing conditions, which are expected in deep groundwaters, the dissolution of the UO 2 -matrix can be explained in terms of solubility, while under oxidizing conditions, the UO 2 is thermodynamically unstable and the dissolution is kinetically controlled. In this report the parameters which affect the uranium solubility under reducing conditions, basically pH and redox potential are discussed. Under oxidizing conditions, UO 2 dissolution rate equations as a function of pH, carbonate concentration and oxidant concentration are reported. Dissolution experiments performed with spent fuel are also reviewed. The experimental equations presented in this work, have been used to model independent dissolution experiments performed with both unirradiated and irradiated UO 2 . (Author)

  9. Effect of redox conditions on bacterial community structure in Baltic Sea sediments with contrasting redox conditions

    NARCIS (Netherlands)

    Steenbergh, A.K.; Bodelier, P.L.E.; Slomp, C.P; Laanbroek, H.J.

    2014-01-01

    Phosphorus release from sediments can exacerbate the effect of eutrophication in coastal marine ecosystems. The flux of phosphorus from marine sediments to the overlying water is highly dependent on the redox conditions at the sediment-water interface. Bacteria are key players in the biological

  10. Characterization of redox conditions in groundwater contaminant plumes

    Science.gov (United States)

    Christensen, Thomas H.; Bjerg, Poul L.; Banwart, Steven A.; Jakobsen, Rasmus; Heron, Gorm; Albrechtsen, Hans-Jørgen

    2000-10-01

    Evaluation of redox conditions in groundwater pollution plumes is often a prerequisite for understanding the behaviour of the pollutants in the plume and for selecting remediation approaches. Measuring of redox conditions in pollution plumes is, however, a fairly recent issue and yet relative few cases have been reported. No standardised or generally accepted approach exists. Slow electrode kinetics and the common lack of internal equilibrium of redox processes in pollution plumes make, with a few exceptions, direct electrochemical measurement and rigorous interpretation of redox potentials dubious, if not erroneous. Several other approaches have been used in addressing redox conditions in pollution plumes: redox-sensitive compounds in groundwater samples, hydrogen concentrations in groundwater, concentrations of volatile fatty acids in groundwater, sediment characteristics and microbial tools, such as MPN counts, PLFA biomarkers and redox bioassays. This paper reviews the principles behind the different approaches, summarizes methods used and evaluates the approaches based on the experience from the reported applications.

  11. Modelling sulfamethoxazole degradation under different redox conditions

    Science.gov (United States)

    Sanchez-Vila, X.; Rodriguez-Escales, P.

    2015-12-01

    Sulfamethoxazole (SMX) is a low adsorptive, polar, sulfonamide antibiotic, widely present in aquatic environments. Degradation of SMX in subsurface porous media is spatially and temporally variable, depending on various environmental factors such as in situ redox potential, availability of nutrients, local soil characteristics, and temperature. It has been reported that SMX is better degraded under anoxic conditions and by co-metabolism processes. In this work, we first develop a conceptual model of degradation of SMX under different redox conditions (denitrification and iron reducing conditions), and second, we construct a mathematical model that allows reproducing different experiments of SMX degradation reported in the literature. The conceptual model focuses on the molecular behavior and contemplates the formation of different metabolites. The model was validated using the experimental data from Barbieri et al. (2012) and Mohatt et al. (2011). It adequately reproduces the reversible degradation of SMX under the presence of nitrite as an intermediate product of denitrification. In those experiments degradation was mediated by the transient formation of a diazonium cation, which was considered responsible of the substitution of the amine radical by a nitro radical, forming the 4-nitro-SMX. The formation of this metabolite is a reversible process, so that once the concentration of nitrite was back to zero due to further advancement of denitrification, the concentration of SMX was fully recovered. The forward reaction, formation of 4-nitro SMX, was modeled considering a kinetic of second order, whereas the backward reaction, dissociation of 4-nitro-SMX back to the original compound, could be modeled with a first order degradation reaction. Regarding the iron conditions, SMX was degraded due to the oxidation of iron (Fe2+), which was previously oxidized from goethite due to the degradation of a pool of labile organic carbon. As the oxidation of iron occurred on the

  12. Measuring intracellular redox conditions using GFP-based sensors

    DEFF Research Database (Denmark)

    Björnberg, Olof; Ostergaard, Henrik; Winther, Jakob R

    2006-01-01

    Recent years have seen the development of methods for analyzing the redox conditions in specific compartments in living cells. These methods are based on genetically encoded sensors comprising variants of Green Fluorescent Protein in which vicinal cysteine residues have been introduced at solvent......-exposed positions. Several mutant forms have been identified in which formation of a disulfide bond between these cysteine residues results in changes of their fluorescence properties. The redox sensors have been characterized biochemically and found to behave differently, both spectroscopically and in terms...... of redox properties. As genetically encoded sensors they can be expressed in living cells and used for analysis of intracellular redox conditions; however, which parameters are measured depends on how the sensors interact with various cellular redox components. Results of both biochemical and cell...

  13. On the initial condition of inflationary fluctuations

    International Nuclear Information System (INIS)

    Jiang, Hongliang; Wang, Yi; Zhou, Siyi

    2016-01-01

    It is usually assumed that the inflationary fluctuations start from the Bunch-Davies (BD) vacuum and the iε prescription is used when interactions are calculated. We show that those assumptions can be verified explicitly by calculating the loop corrections to the inflationary two-point and three-point correlation functions. Those loop corrections can be resummed to exponential factors, which suppress non-BD coefficients and behave as the iε factor for the case of the BD initial condition. A new technique of loop chain diagram resummation is developed for this purpose. For the non-BD initial conditions which is setup at finite time and has not fully decayed, explicit correction to the two-point and three-point correlation functions are calculated. Especially, non-Gaussianity in the folded limit is regularized due to the interactions.

  14. The impact of oscillating redox conditions: Arsenic immobilisation in contaminated calcareous floodplain soils

    International Nuclear Information System (INIS)

    Parsons, Christopher T.; Couture, Raoul-Marie; Omoregie, Enoma O.; Bardelli, Fabrizio; Greneche, Jean-Marc; Roman-Ross, Gabriela; Charlet, Laurent

    2013-01-01

    Arsenic contamination of floodplain soils is extensive and additional fresh arsenic inputs to the pedosphere from human activities are ongoing. We investigate the cumulative effects of repetitive soil redox cycles, which occur naturally during flooding and draining, on a calcareous fluvisol, the native microbial community and arsenic mobility following a simulated contamination event. We show through bioreactor experiments, spectroscopic techniques and modelling that repetitive redox cycling can decrease arsenic mobility during reducing conditions by up to 45%. Phylogenetic and functional analyses of the microbial community indicate that iron cycling is a key driver of observed changes to solution chemistry. We discuss probable mechanisms responsible for the arsenic immobilisation observed in-situ. The proposed mechanisms include, decreased heterotrophic iron reduction due to the depletion of labile particulate organic matter (POM), increases to the proportion of co-precipitated vs. aqueous or sorbed arsenic with α-FeOOH/Fe(OH) 3 and potential precipitation of amorphous ferric arsenate. Highlights: •Oscillating redox conditions and heterotrophic metabolism are implemented in PHREEQC. •Depletion of labile organic matter limits iron reduction and arsenic release. •Amorphous FeAsO 4 ∙2H 2 O precipitation potentially limits arsenic mobility during redox cycling. •Water fluctuating zones may naturally attenuate arsenic liberation during flooding. -- We demonstrate through batch experiments, spectroscopy and modelling that repetitive cycles of oxidation and reduction decrease arsenic mobility in soils during subsequent reducing conditions

  15. THE STUDY OF REDOX CONDITIONS IN THE DNIESTER RIVER

    Directory of Open Access Journals (Sweden)

    Viorica Gladchi

    2008-06-01

    Full Text Available The work presented in the paper discusses the contribution of the Novodnestrovsc water system to the formation of redox conditions in the lower Dniester. The conclusions were drawn on the basis of a long-term protocol of analyses that included the analysis of the oxygen regime, evaluation of the content of hydrogen peroxide, rH2, biological oxygen demand as well as other additional parameters.

  16. Biodegradation of NSO-compounds under different redox-conditions

    DEFF Research Database (Denmark)

    Dyreborg, S.; Arvin, E.; Broholm, K.

    1997-01-01

    Laboratory experiments were carried out to investigate the potential of groundwater microorganisms to degrade selected heterocyclic aromatic compounds containing nitrogen, sulphur, or oxygen (NSO-compounds) under four redox-conditions over a period of 846 days. Eight compounds (pyrrole, 1...... anaerobic conditions, even though the microorganisms present in the anaerobic microcosms were active throughout the incubation period. A high variability in the lag period among the NSO-compounds was observed under aerobic conditions. While quinoline, indole, and carbazole were degraded with a lag period...

  17. Assessment of redox conditions based on fracture mineralogy

    International Nuclear Information System (INIS)

    Tullborg, E.L.

    1999-01-01

    The frequency and distribution of fracture minerals like calcite, Fe-oxides/hydroxides, and sulphides can be used in performance assessment since their presence reflects the redox processes that are active or have been active in the fractures. The advantage in using fracture minerals is that they undoubtedly represent conditions prior to disturbances caused by drilling or tunnel excavations. In addition, they give a continuous record from the surface to great depth. On the other hand the disadvantage is that the fracture mineral distribution is a result of both past and present processes such that the mineral distribution alone can not discriminate between old and recent processes. Nevertheless it is suggested that the fracture mineral distribution provides important information about the redox capacity in the fracture system. (author)

  18. Competing for phosphors under changing redox conditions: biological versus geochemical sinks

    Science.gov (United States)

    Gross, A.; Pett-Ridge, J.; Silver, W. L.

    2016-12-01

    Competing for phosphorus under changing redox conditions: biological versus geochemical sinksAvner Gross1, Jennifer Pett-Ridge2 and Whendee L Silver1 University of California Berkeley, Department of Environmental Science, Policy, & Management, Berkeley, CA, USA. Lawrence Livermore National Laboratory, Physical and Life Science Directorate, Livermore, CA, USA. The cycling of phosphorous (P) in highly weathered, humid tropical forest soils is tightly regulated by P sorption dynamics to the surfaces of Fe(III) (hydr)oxides and root and microbial demands for P. Periods of anoxic soil conditions, which are common in humid environments, induce the reduction of Fe (III) to Fe (II) and may release sorbed P into the soil solution. The microbial demand for P is influenced by the C and nutrient composition of their available substrates. Therefore, we hypothesize that soil redox conditions and substrate quality and availability will control the partitioning of P between microbial biomass and the soil mineral phase. The aim of this study was to examine how fluctuations in soil redox conditions and changes in microbial P demand affect the fate of new P that enters the soil solution. To achieve this aim we conducted a series of soil incubation experiments using a wet tropical soil from Puerto Rico (where redox conditions and P availability naturally oscillate) with a single pulse of phosphate (PO4), altering both the microbial activity and redox conditions. To follow the fate the added P, the added phosphate was labeled with 18O. As the exchange of oxygen between phosphate and water only occurs during biological processes, P-18O labeling can be used as an indicator of microbial use. To quantify sizes of the microbial and mineral P pools we used traditional chemical extractions in the bulk scale. We used NanoSIMS isotopic imaging to map the distribution of P-16O and P-18O and co-localization with Fe minerals at the nano scale. Our results show that the amount of the added P fixed

  19. Dissipation of oxytetracycline in soils under different redox conditions

    International Nuclear Information System (INIS)

    Yang Jigeng; Ying Guangguo; Zhou Lijun; Liu Shan; Zhao Jianliang

    2009-01-01

    This study investigated the dissipation kinetics of oxytetracycline in soils under aerobic and anoxic conditions. Laboratory experiments showed that the dissipation of oxytetracycline in soil followed first-order reaction kinetics and its dissipation rates decreased with increasing concentration. Oxytetracycline dissipated faster in soil under aerobic conditions than under anoxic conditions. The half-lives for oxytetracycline in soil under aerobic conditions ranged between 29 and 56 days for non-sterile treatments and 99-120 days for sterile treatments, while under anoxic conditions the half-lives of oxytetracycline ranged between 43 and 62 days in the non-sterile soil and between 69 and 104 days in the sterile soil. This suggests microbes can degrade oxytetracycline in agricultural soil. Abiotic factors such as strong sorption onto soil components also played a role in the dissipation of oxytetracycline in soil. - Oxytetracycline dissipation in soils is influenced by redox conditions and soil properties.

  20. Dissipation of oxytetracycline in soils under different redox conditions

    Energy Technology Data Exchange (ETDEWEB)

    Jigeng, Yang [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, 511 Kehua Street, Tianhe District, Guangzhou 510640 (China); Department of Chemistry and Chemical Engineering, Hunan University of Arts and Sciences, Changde 415000 (China); Ying Guangguo, E-mail: guangguo.ying@gmail.co [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, 511 Kehua Street, Tianhe District, Guangzhou 510640 (China); Lijun, Zhou; Shan, Liu; Jianliang, Zhao [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, 511 Kehua Street, Tianhe District, Guangzhou 510640 (China)

    2009-10-15

    This study investigated the dissipation kinetics of oxytetracycline in soils under aerobic and anoxic conditions. Laboratory experiments showed that the dissipation of oxytetracycline in soil followed first-order reaction kinetics and its dissipation rates decreased with increasing concentration. Oxytetracycline dissipated faster in soil under aerobic conditions than under anoxic conditions. The half-lives for oxytetracycline in soil under aerobic conditions ranged between 29 and 56 days for non-sterile treatments and 99-120 days for sterile treatments, while under anoxic conditions the half-lives of oxytetracycline ranged between 43 and 62 days in the non-sterile soil and between 69 and 104 days in the sterile soil. This suggests microbes can degrade oxytetracycline in agricultural soil. Abiotic factors such as strong sorption onto soil components also played a role in the dissipation of oxytetracycline in soil. - Oxytetracycline dissipation in soils is influenced by redox conditions and soil properties.

  1. New lab scale approaches for quantification of redox conditions

    Science.gov (United States)

    Fernandez, P. M.; Dathe, A.; Nadeem, S.; Bakken, L. R.; Bloem, E.; French, H. K.; Binley, A. M.

    2013-12-01

    Degradation of organic chemicals in the unsaturated zone is a process highly relevant for developing remediation techniques for protecting groundwater. Degradation causes changes in chemical composition of the water phase and gas releases. These changes can potentially be mapped with electrical resistivity measurements in the bulk soil and gas measurements at the soil surface. The redox potential combined with the local geological conditions determines the composition of available electron acceptors as well as microbial degradation pathways and how the soil system is affected in the long term. After oxygen and nitrate are depleted, manganese and iron should be reduced. However, in experiments conducted in the unsaturated zone at Gardermoen airport, Norway, it was found that for the degradation of the de-icing agent propylene glycol (PG), manganese and iron were preferred over nitrate as electron acceptor. A key hypothesis for the work presented is that for a designated soil, the redox potential affects gas releases and soil solution composition profoundly. As the redox potential decreases, the reactants of the degradation change and therefore the composition of the soil-water system changes. These changes can be quantified dynamically by gas measurements and changes in electrical conductivity of the pore water and electrical resistivity of the bulk soil. Batch experiments were conducted to examine whether nitrate is a preferred electron acceptor over iron and manganese oxides as described in classical redox reaction theory. Gas releases during PG and glutamate degradation were measured in a sandy pristine soil with and without nitrate under anaerobic condition during two weeks of incubation. Chemical reactions were quantified with the modelling tool ORCHESTRA. We are currently investigating whether dynamical measurements of electrical conductivity and bulk resistivity are suited to trace which electron acceptors (nitrate, manganese or iron) are being reduced. First

  2. Organic chemical degradation by remote study of the redox conditions

    Science.gov (United States)

    Fernandez, P. M.; Revil, A.; Binley, A. M.; Bloem, E.; French, H. K.

    2014-12-01

    Monitoring the natural (and enhanced) degradation of organic contaminants is essential for managing groundwater quality in many parts of the world. Contaminated sites often have limited access, hence non-intrusive methods for studying redox processes, which drive the degradation of organic compounds, are required. One example is the degradation of de-icing chemicals (glycols and organic salts) released to the soil near airport runways during winter. This issue has been broadly studied at Oslo airport, Gardermoen, Norway using intrusive and non-intrusive methods. Here, we report on laboratory experiments that aim to study the potential of using a self-potential, DCresistivity, and time-domain induced polarization for geochemical characterization of the degradation of Propylene Glycol (PG). PG is completely miscible in water, does not adsorb to soil particles and does not contribute to the electrical conductivity of the soil water. When the contaminant is in the unsaturated zone near the water table, the oxygen is quickly consumed and the gas exchange with the surface is insufficient to ensure aerobic degradation, which is faster than anaerobic degradation. Since biodegradation of PG is highly oxygen demanding, anaerobic pockets can exist causing iron and manganese reduction. It is hypothesised that nitrate would boost the degradation rate under such conditions. In our experiment, we study PG degradation in a sand tank. We provide the system with an electron highway to bridge zones with different redox potential. This geo-battery system is characterized by self-potential, resistivity and induced polarization anomalies. An example of preliminary results with self-potential at two different times of the experiment can be seen in the illustration. These will be supplemented with more direct information on the redox chemistry: in-situ water sampling, pH, redox potential and electrical conductivity measurements. In parallel, a series of batch experiments have been

  3. Targeting the Redox Balance in Inflammatory Skin Conditions

    Directory of Open Access Journals (Sweden)

    Ditte M. S. Lundvig

    2013-04-01

    Full Text Available Reactive oxygen species (ROS can be both beneficial and deleterious. Under normal physiological conditions, ROS production is tightly regulated, and ROS participate in both pathogen defense and cellular signaling. However, insufficient ROS detoxification or ROS overproduction generates oxidative stress, resulting in cellular damage. Oxidative stress has been linked to various inflammatory diseases. Inflammation is an essential response in the protection against injurious insults and thus important at the onset of wound healing. However, hampered resolution of inflammation can result in a chronic, exaggerated response with additional tissue damage. In the pathogenesis of several inflammatory skin conditions, e.g., sunburn and psoriasis, inflammatory-mediated tissue damage is central. The prolonged release of excess ROS in the skin can aggravate inflammatory injury and promote chronic inflammation. The cellular redox balance is therefore tightly regulated by several (enzymatic antioxidants and pro-oxidants; however, in case of chronic inflammation, the antioxidant system may be depleted, and prolonged oxidative stress occurs. Due to the central role of ROS in inflammatory pathologies, restoring the redox balance forms an innovative therapeutic target in the development of new strategies for treating inflammatory skin conditions. Nevertheless, the clinical use of antioxidant-related therapies is still in its infancy.

  4. Lignin decomposition and microbial community in paddy soils: effects of alternating redox conditions

    Science.gov (United States)

    Cerli, Chiara; Liu, Qin; Hanke, Alexander; Kaiser, Klaus; Kalbitz, Karsten

    2013-04-01

    Paddy soils are characterised by interchanging cycles of anaerobic and aerobic conditions. Such fluctuations cause continuous changes in soil solution chemistry as well as in the composition and physiological responses of the microbial community. Temporary deficiency in oxygen creates conditions favourable to facultative or obligates anaerobic bacteria, while aerobic communities can thrive in the period of water absence. These alterations can strongly affect soil processes, in particular organic matter (OM) accumulation and mineralization. In submerged soils, lignin generally constitutes a major portion of the total OM because of hampered degradation under anoxic conditions. The alternating redox cycles resulting from paddy soil management might promote both degradation and preservation of lignin, affecting the overall composition and reactivity of total and dissolved OM. We sampled soils subjected to cycles of anoxic (rice growing period) and oxic (harvest and growth of other crops) conditions since 700 and 2000 years. We incubated suspended Ap material, sampled from the two paddy plus two corresponding non-paddy control soils under oxic and anoxic condition, for 3 months, interrupted by a short period of three weeks (from day 21 to day 43) with reversed redox conditions. At each sampling time (day 2, 21, 42, 63, 84), we determined lignin-derived phenols (by CuO oxidation) as well as phospholipids fatty acids contents and composition. We aimed to highlight changes in lignin decomposition as related to the potential rapid changes in microbial community composition. Since the studied paddy soils had a long history of wet rice cultivation, the microbial community should be well adapted to interchanging oxic and anoxic cycles, therefore fully expressing its activity at both conditions. In non-paddy soil changes in redox conditions caused modification of quantity and composition of the microbial community. On the contrary, in well-established paddy soils the microbial

  5. Redox conditions and protein oxidation in plant mitochondria

    DEFF Research Database (Denmark)

    Møller, Ian Max; Kasimova, Marina R.; Krab, Klaas

    2005-01-01

    Redox conditions and protein oxidation in plant mitochondria NAD(P)H has a central position in respiratory metabolism. It is produced by a large number of enzymes, e.g. the Krebs cycle dehydrogenases, in the mitochondrial matrix and is oxidised by, amongst others, the respiratory chain. Most...... of this NAD(P)H appears to be bound to proteins, in fact free NAD(P)H – an important parameter in metabolic regulation - has never been observed in mitochondria. We have estimated free and bound NAD(P)H in isolated plant mitochondria under different metabolic conditions. The fluorescence spectra of free...... and bound NADH was determined and used to deconvolute fluorescence spectra of actively respiring mitochondria. Most of the mitochondrial NADH is bound in states 2 and 4. The amount of free NADH is lower but relatively constant even increasing a little in state 3 where it is about equal to bound NADH...

  6. Development of an investigation method for redox condition of rocks by self potential (SP) method

    International Nuclear Information System (INIS)

    Kubota, Kenji; Inohara, Yoshiki; Oyama, Takahiro

    2012-01-01

    One of the major issues in subsurface disposal of low level radioactive wastes is that long term behaviors of sedimentary rocks can be affected by geochemical factors. Redox conditions can affect to corrosion of metal included in artificial barrier or wastes and adsorption characteristics of a nuclide. Therefore, it is necessary to develop a method for evaluating the redox conditions around natural barrier at waste facilities. In general, geochemical properties are acquired by rock samples or water sampling at a borehole. However, there is a possibility not to acquire data we want to evaluate. If geophysical methods are applied, redox conditions can be evaluated widely and briefly. There is a possibility that self potential (SP) and redox conditions have a correlation. So we have conducted self potential method around test caverns where redox front can be observed at the Rokkasho site. The results demonstrated that self potential decreased around redox front. There was a positive correlation between self potential and pH. One of the factors of self potential change is difference of elevation, however, self potential change around redox front was larger than that expected from elevation difference. Zeta potential is one of the important factors for determination of self potential, and it had a correlation with self potential or pH. Therefore, there is a possibility that self potential change occurs by geochemical condition changes around redox front, and redox condition can be detected by self potential method. (author)

  7. Field scale heterogeneity of redox conditions in till-upscaling to a catchment nitrate model

    DEFF Research Database (Denmark)

    Hansen, J.R.; Erntsen, V.; Refsgaard, J.C.

    2008-01-01

    Point scale studies in different settings of glacial geology show a large local variation of redox conditions. There is a need to develop an upscaling methodology for catchment scale models. This paper describes a study of field-scale heterogeneity of redox-interfaces in a till aquitard within an...

  8. Redox Conditions in Selected Principal Aquifers of the United States

    Science.gov (United States)

    McMahon, P.B.; Cowdery, T.K.; Chapelle, F.H.; Jurgens, B.C.

    2009-01-01

    Reduction/oxidation (redox) processes affect the quality of groundwater in all aquifer systems. Redox processes can alternately mobilize or immobilize potentially toxic metals associated with naturally occurring aquifer materials, contribute to the degradation or preservation of anthropogenic contami-nants, and generate undesirable byproducts, such as dissolved manganese (Mn2+), ferrous iron (Fe2+), hydrogen sulfide (H2S), and methane (CH4). Determining the kinds of redox processes that occur in an aquifer system, documenting their spatial distribution, and understanding how they affect concentrations of natural or anthropogenic contaminants are central to assessing and predicting the chemical quality of groundwater. This Fact Sheet extends the analysis of U.S. Geological Survey authors to additional principal aquifer systems by applying a framework developed by the USGS to a larger set of water-quality data from the USGS national water databases. For a detailed explanation, see the 'Introduction' in the Fact Sheet.

  9. Characterization of redox conditions in groundwater contaminant plumes

    DEFF Research Database (Denmark)

    Christensen, Thomas Højlund; Bjerg, Poul Løgstrup; Banwarth, Steven A.

    2000-01-01

    tools, such as MPN counts, PLFA biomarkers and redox bioassays. This paper reviews the principles behind the different approaches, summarizes methods used and evaluates the approaches based on the experience from the reported applications. C 2000 Elsevier Science B.V. All rights reserved....

  10. Effect of redox conditions on pharmaceutical loss during biological wastewater treatment using sequencing batch reactors

    Energy Technology Data Exchange (ETDEWEB)

    Stadler, Lauren B., E-mail: lstadler@umich.edu [Department of Civil and Environmental Engineering, University of Michigan, 1351 Beal Avenue, EWRE, Ann Arbor, MI 48109 (United States); Su, Lijuan, E-mail: lijuansu@buffalo.edu [Department of Chemistry, University at Buffalo, State University of New York, Buffalo, NY 14260 (United States); Moline, Christopher J., E-mail: christopher.moline@hdrinc.com [Department of Civil and Environmental Engineering, University of Michigan, 1351 Beal Avenue, EWRE, Ann Arbor, MI 48109 (United States); Ernstoff, Alexi S., E-mail: alexer@dtu.dk [Department of Civil and Environmental Engineering, University of Michigan, 1351 Beal Avenue, EWRE, Ann Arbor, MI 48109 (United States); Aga, Diana S., E-mail: dianaaga@buffalo.edu [Department of Chemistry, University at Buffalo, State University of New York, Buffalo, NY 14260 (United States); Love, Nancy G., E-mail: nglove@umich.edu [Department of Civil and Environmental Engineering, University of Michigan, 1351 Beal Avenue, EWRE, Ann Arbor, MI 48109 (United States)

    2015-01-23

    Highlights: • Pharmaceutical fate was studied in SBRs operated at different redox conditions. • Stable carbon oxidation and nitrification occurred under microaerobic conditions. • Losses of atenolol and trimethoprim were highest under fully aerobic conditions. • Loss of sulfamethoxazole was highest under microaerobic conditions. • Deconjugation occurred during treatment to form sulfamethoxazole and desvenlafaxine. - Abstract: We lack a clear understanding of how wastewater treatment plant (WWTP) process parameters, such as redox environment, impact pharmaceutical fate. WWTPs increasingly install more advanced aeration control systems to save energy and achieve better nutrient removal performance. The impact of redox condition, and specifically the use of microaerobic (low dissolved oxygen) treatment, is poorly understood. In this study, the fate of a mixture of pharmaceuticals and several of their transformation products present in the primary effluent of a local WWTP was assessed in sequencing batch reactors operated under different redox conditions: fully aerobic, anoxic/aerobic, and microaerobic (DO concentration ≈0.3 mg/L). Among the pharmaceuticals that were tracked during this study (atenolol, trimethoprim, sulfamethoxazole, desvenlafaxine, venlafaxine, and phenytoin), overall loss varied between them and between redox environments. Losses of atenolol and trimethoprim were highest in the aerobic reactor; sulfamethoxazole loss was highest in the microaerobic reactors; and phenytoin was recalcitrant in all reactors. Transformation products of sulfamethoxazole and desvenlafaxine resulted in the reformation of their parent compounds during treatment. The results suggest that transformation products must be accounted for when assessing removal efficiencies and that redox environment influences the degree of pharmaceutical loss.

  11. Effect of redox conditions on pharmaceutical loss during biological wastewater treatment using sequencing batch reactors

    International Nuclear Information System (INIS)

    Stadler, Lauren B.; Su, Lijuan; Moline, Christopher J.; Ernstoff, Alexi S.; Aga, Diana S.; Love, Nancy G.

    2015-01-01

    Highlights: • Pharmaceutical fate was studied in SBRs operated at different redox conditions. • Stable carbon oxidation and nitrification occurred under microaerobic conditions. • Losses of atenolol and trimethoprim were highest under fully aerobic conditions. • Loss of sulfamethoxazole was highest under microaerobic conditions. • Deconjugation occurred during treatment to form sulfamethoxazole and desvenlafaxine. - Abstract: We lack a clear understanding of how wastewater treatment plant (WWTP) process parameters, such as redox environment, impact pharmaceutical fate. WWTPs increasingly install more advanced aeration control systems to save energy and achieve better nutrient removal performance. The impact of redox condition, and specifically the use of microaerobic (low dissolved oxygen) treatment, is poorly understood. In this study, the fate of a mixture of pharmaceuticals and several of their transformation products present in the primary effluent of a local WWTP was assessed in sequencing batch reactors operated under different redox conditions: fully aerobic, anoxic/aerobic, and microaerobic (DO concentration ≈0.3 mg/L). Among the pharmaceuticals that were tracked during this study (atenolol, trimethoprim, sulfamethoxazole, desvenlafaxine, venlafaxine, and phenytoin), overall loss varied between them and between redox environments. Losses of atenolol and trimethoprim were highest in the aerobic reactor; sulfamethoxazole loss was highest in the microaerobic reactors; and phenytoin was recalcitrant in all reactors. Transformation products of sulfamethoxazole and desvenlafaxine resulted in the reformation of their parent compounds during treatment. The results suggest that transformation products must be accounted for when assessing removal efficiencies and that redox environment influences the degree of pharmaceutical loss

  12. Overexpression of the transcription factor Yap1 modifies intracellular redox conditions and enhances recombinant protein secretion

    Directory of Open Access Journals (Sweden)

    Marizela Delic

    2014-10-01

    Full Text Available Oxidative folding of secretory proteins in the endoplasmic reticulum (ER is a redox active process, which also impacts the redox conditions in the cytosol. As the transcription factor Yap1 is involved in the transcriptional response to oxidative stress, we investigate its role upon the production of secretory proteins, using the yeast Pichia pastoris as model, and report a novel important role of Yap1 during oxidative protein folding. Yap1 is needed for the detoxification of reactive oxygen species (ROS caused by increased oxidative protein folding. Constitutive co-overexpression of PpYAP1 leads to increased levels of secreted recombinant protein, while a lowered Yap1 function leads to accumulation of ROS and strong flocculation. Transcriptional analysis revealed that more than 150 genes were affected by overexpression of YAP1, in particular genes coding for antioxidant enzymes or involved in oxidation-reduction processes. By monitoring intracellular redox conditions within the cytosol and the ER using redox-sensitive roGFP1 variants, we could show that overexpression of YAP1 restores cellular redox conditions of protein-secreting P. pastoris by reoxidizing the cytosolic redox state to the levels of the wild type. These alterations are also reflected by increased levels of oxidized intracellular glutathione (GSSG in the YAP1 co-overexpressing strain. Taken together, these data indicate a strong impact of intracellular redox balance on the secretion of (recombinant proteins without affecting protein folding per se. Re-establishing suitable redox conditions by tuning the antioxidant capacity of the cell reduces metabolic load and cell stress caused by high oxidative protein folding load, thereby increasing the secretion capacity.

  13. Effect of redox conditions on pharmaceutical loss during biological wastewater treatment using sequencing batch reactors

    DEFF Research Database (Denmark)

    Stadler, Lauren B.; Su, Lijuan; Moline, Christopher J.

    2015-01-01

    We lack a clear understanding of how wastewater treatment plant (WWTP) process parameters, such as redox environment, impact pharmaceutical fate. WWTPs increasingly install more advanced aeration control systems to save energy and achieve better nutrient removal performance. The impact of redox...... under different redox conditions: fully aerobic, anoxic/aerobic, and microaerobic (DO concentration ≈0.3 mg/L). Among the pharmaceuticals that were tracked during this study (atenolol, trimethoprim, sulfamethoxazole, desvenlafaxine, venlafaxine, and phenytoin), overall loss varied between them...... and between redox environments. Losses of atenolol and trimethoprim were highest in the aerobic reactor; sulfamethoxazole loss was highest in the microaerobic reactors; and phenytoin was recalcitrant in all reactors. Transformation products of sulfamethoxazole and desvenlafaxine resulted in the reformation...

  14. TIC/TOC and Redox Sensitive Trace Element (RSTEs) Signals Indicating Redox Conditions of the Lower Part of the Cabo Formation Near Organya (Organya Basin), Catalunya, Spain

    Science.gov (United States)

    Herdocia, C.; Maurrasse, F. J.

    2017-12-01

    The thick (> 4.5 km) sedimentary succession of the Organya Basin includes the Cabo Formation [1] which is well exposed in the Cabo valley area and is characteristically composed of black to dark gray marlstones and limestones that accumulated during the greenhouse climate and contain variable amount of organic matter [2-4]. Here we present geochemical results to assess redox conditions of 35.6 m of the Cabo Formation near the Barremian / Aptian boundary, along Catalunya Route C-14, immediately north of the town of Organya. TOC values range between 1 wt% and 5.8 wt%, and peak in all black limestones (0.43 m, 4.38 m, 14.85 m, 29.95 m, and 35.6 m). These TOC values average about 2.0 wt %, except at a height of 0.43 m, where the TOC has a strong peak (5.78 wt%). TIC values oscillated between 86.7 wt% and 96.8 wt%, and averaged at 92.7 wt% and show a strong negative correlation with TOC (r = -0.78). Measured carbon isotope on the organic carbon fraction (δ13Corg) showed fluctuations that ranged from -24.41‰ to -22.15‰. The TOC and δ13Corg curves show a positive correlation (r = 0.58), suggesting that carbon sequestration in the basin followed the overall global signature. Redox sensitive trace elements (V, Ni, Cu, and Mo) correlate with TOC values (r > 0.6), suggesting that dysoxic conditions were responsible for the preservation of organic matter. Biolimiting trace elements (Fe, P) also correlate positively with redox trace elements, and both have highest concentrations at 14.85 m, in concurrence with a high TOC value (2.93 wt%) indicating high primary productivity at that level. Major elements (Al, Si, and Ti) also correlates slightly with TOC (Al: r = 0.39; Si: r = 0.36; Ti: r = 0.43). References: [1] García-Senz, J., 2002, PhD Thesis, University of Barcelona, 310 pp. [2] Bernaus, J.M., et al., 2003. Sedimentary Geology 159 (3-4), 177-201. [3] Caus, E., et al., 1990. Cret. Research 11, 313-320. [4] Sanchez-Hernandez, Y., Maurrasse, F.J-M.R. 2014. Chem

  15. Fate of Pharmaceuticals and Personal Care Products (PPCPs) in Saturated Soil Under Various Redox Conditions

    Science.gov (United States)

    Dror, I.; Menahem, A.; Berkowitz, B.

    2014-12-01

    The growing use of PPCPs results in their increasing release to the aquatic environment. Consequently, understanding the fate of PPCPs under environmentally relevant conditions that account for dynamic flow and varying redox states is critical. In this study, the transport of two organometallic PPCPs, Gd-DTPA and Roxarsone (As complex) and their metal salts (Gd(NO3)3, AsNaO2), is investigated. The former is used widely as a contrasting agent for MRI, while the latter is applied extensively as a food additive in the broiler poultry industry. Both of these compounds are excreted from the body, almost unchanged chemically. Gadolinium complexes are not fully eliminated in wastewater treatment and can reach groundwater via irrigation with treated wastewater; Roxarsone can enter groundwater via leaching from manure used as fertilizer. Studies have shown that the transport of PPCPs in groundwater is affected by environmental conditions such as redox states, pH, and soil type. For this study, column experiments using sand or Mediterranean red sandy clay soil were performed under several redox conditions: aerobic, nitrate-reducing, iron-reducing, sulfate-reducing, methanogenic, and very strongly chemical reducing. Batch experiments to determine adsorption isotherms were also performed for the complexes and metal salts. We found that Gd-DTPA transport was affected by the soil type and was not affected by the redox conditions. In contrast, Roxarsone transport was affected mainly by the different redox conditions, showing delayed breakthrough curves as the conditions became more biologically reduced (strong chemical reducing conditions did not affect the transport). We also observed that the metal salts show essentially no transport while the organic complexes display much faster breakthrough. The results suggest that transport of these PPCPs through soil and groundwater is determined by the redox conditions, as well as by soil type and the form of the applied metal (as salt

  16. Very high gravity ethanol fermentation by flocculating yeast under redox potential-controlled conditions

    Directory of Open Access Journals (Sweden)

    Liu Chen-Guang

    2012-08-01

    Full Text Available Abstract Background Very high gravity (VHG fermentation using medium in excess of 250 g/L sugars for more than 15% (v ethanol can save energy consumption, not only for ethanol distillation, but also for distillage treatment; however, stuck fermentation with prolonged fermentation time and more sugars unfermented is the biggest challenge. Controlling redox potential (ORP during VHG fermentation benefits biomass accumulation and improvement of yeast cell viability that is affected by osmotic pressure and ethanol inhibition, enhancing ethanol productivity and yield, the most important techno-economic aspect of fuel ethanol production. Results Batch fermentation was performed under different ORP conditions using the flocculating yeast and media containing glucose of 201 ± 3.1, 252 ± 2.9 and 298 ± 3.8 g/L. Compared with ethanol fermentation by non-flocculating yeast, different ORP profiles were observed with the flocculating yeast due to the morphological change associated with the flocculation of yeast cells. When ORP was controlled at −100 mV, ethanol fermentation with the high gravity (HG media containing glucose of 201 ± 3.1 and 252 ± 2.9 g/L was completed at 32 and 56 h, respectively, producing 93.0 ± 1.3 and 120.0 ± 1.8 g/L ethanol, correspondingly. In contrast, there were 24.0 ± 0.4 and 17.0 ± 0.3 g/L glucose remained unfermented without ORP control. As high as 131.0 ± 1.8 g/L ethanol was produced at 72 h when ORP was controlled at −150 mV for the VHG fermentation with medium containing 298 ± 3.8 g/L glucose, since yeast cell viability was improved more significantly. Conclusions No lag phase was observed during ethanol fermentation with the flocculating yeast, and the implementation of ORP control improved ethanol productivity and yield. When ORP was controlled at −150 mV, more reducing power was available for yeast cells to survive, which in turn improved their viability and VHG

  17. Groundwater redox conditions and conductivity in a contaminant plume from geoelectrical investigations

    Directory of Open Access Journals (Sweden)

    V. Naudet

    2004-01-01

    Full Text Available Accurate mapping of the electrical conductivity and of the redox potential of the groundwater is important in delineating the shape of a contaminant plume. A map of redox potential in an aquifer is indicative of biodegradation of organic matter and of concentrations of redox-active components; a map of electrical conductivity provides information on the mineralisation of the groundwater. Both maps can be used to optimise the position of pumping wells for remediation. The self-potential method (SP and electrical resistivity tomography (ERT have been applied to the contaminant plume associated with the Entressen landfill in south-east France. The self-potential depends on groundwater flow (electrokinetic contribution and redox conditions ('electro-redox' contribution. Using the variation of the piezometric head in the aquifer, the electrokinetic contribution is removed from the SP signals. A good linear correlation (R2=0.85 is obtained between the residual SP data and the redox potential values measured in monitoring wells. This relationship is used to draw a redox potential map of the overall contaminated site. The electrical conductivity of the subsoil is obtained from 3D-ERT analysis. A good linear correlation (R2=0.91 is observed between the electrical conductivity of the aquifer determined from the 3D-ERT image and the conductivity of the groundwater measured in boreholes. This indicates that the formation factor is nearly homogeneous in the shallow aquifer at the scale of the ERT. From this correlation, a map of the pore water conductivity of the aquifer is obtained. Keywords: self-potential, redox potential, electrical resistivity tomography, fluid conductivity, contaminant plume

  18. Laboratory Eh simulations in relation to the Redox conditions in natural granitic groundwaters

    International Nuclear Information System (INIS)

    Wikberg, P.

    1992-01-01

    Redox conditions are one of the prime parameters affecting the sorption of radionuclides released from a nuclear waste repository. The swedish granitic groundwaters are all reducing from a depth of approximately 100 m, the vast majority already from a depth of a few tens of metres. The contents of ferrous iron reaches a maximum at the same depth due to the weathering of iron rich minerals. At greater depths the iron content decreases while sulphide contents increases. The redox buffering capacity (in groundwater) lies mainly in the rock. The contents of iron, sulphide and manganese constitute the buffer in the groundwater. The redox potential (Eh) is controlled by the iron system in the groundwater and the rock. Sulphate is not involved in the groundwater redox processes. Laboratory simulations of the groundwater rock interactions with respect to the redox conditions have been realized, but there is still a difference compared to the natural system. This difference is due to the fact that traces of oxygen diffuses into the laboratory system causing a continuous oxidation. 20 refs., 4 figs., 1 tab

  19. Transport of gadolinium- and arsenic-based pharmaceuticals in saturated soil under various redox conditions.

    Science.gov (United States)

    Menahem, Adi; Dror, Ishai; Berkowitz, Brian

    2016-02-01

    The release of pharmaceuticals and personal care products (PPCPs) to the soil-water environment necessitates understanding of PPCP transport behavior under conditions that account for dynamic flow and varying redox states. This study investigates the transport of two organometallic PPCPs, Gd-DTPA and roxarsone (arsenic compound) and their metal salts (Gd(NO3)3, AsNaO2); Gd-DTPA is used widely as a contrasting agent for MRI, while roxarsone is applied extensively as a food additive in the broiler poultry industry. Here, we present column experiments using sand and Mediterranean red sandy clay soil, performed under several redox conditions. The metal salts were almost completely immobile. In contrast, transport of Gd-DTPA and roxarsone was affected by the soil type. Roxarsone was also affected by the different redox conditions, showing delayed breakthrough curves as the redox potential became more negative due to biological activity (chemically-strong reducing conditions did not affect the transport). Mechanisms that include adsorptive retardation for aerobic and nitrate-reducing conditions, and non-adsorptive retardation for iron-reducing, sulfate-reducing and biologically-strong reducing conditions, are suggested to explain the roxarsone behavior. Gd-DTPA is found to be a stable complex, with potential for high mobility in groundwater systems, whereas roxarsone transport through groundwater systems is affected by redox environments, demonstrating high mobility under aerobic and nitrate-reducing conditions and delayed transport under iron-reducing, sulfate-reducing and biologically-strong reducing conditions. Copyright © 2015 Elsevier Ltd. All rights reserved.

  20. Targeting the redox balance in inflammatory skin conditions

    NARCIS (Netherlands)

    Wagener, F.A.D.T.G.; Carels, C.E.L.; Lundvig, D.M.S.

    2013-01-01

    Reactive oxygen species (ROS) can be both beneficial and deleterious. Under normal physiological conditions, ROS production is tightly regulated, and ROS participate in both pathogen defense and cellular signaling. However, insufficient ROS detoxification or ROS overproduction generates oxidative

  1. Model development to evaluate evolution of redox conditions in the near field

    International Nuclear Information System (INIS)

    Chiba, Tamotsu; Miki, Takahito; Inagaki, Manabu; Sasamoto, Hiroshi; Yui, Mikazu

    1999-02-01

    Deep underground is thought to be a potential place for high level radioactive waste repository. It is believed that the chemical condition of deep groundwater is generally anoxic and reducing. However, during construction and operation phase of repository, oxygen will diffuse some distance into the surrounding rock mass, and diffused oxygen may remain in the surrounding rock mass even after repository closure. In such a case, the transitional redox condition around the drift is not preferable in view point of safety assessment for HLW disposal. Hence, it is very important to evaluate evolution of redox conditions in the near field. This report describes the status of model development to evaluate evolution of redox conditions in the near field. We use the commercial solver to equate the mathematical equations which mean evolution of redox condition in the near field. The target area modeled in this report are near field rock mass and engineered barrier (buffer). In case of near field rock mass, we consider the following two geological media: (1) porous media for sedimentary rock, (2) fractured media for crystalline rock. In case of the engineered barrier, we regard the buffer as porous media. We simulate the behavior of dissolved oxygen and Fe 2+ in groundwater during evolution of redox condition in the near field rock mass and the buffer. In case of the porous media, we consider diffusion of chemical species as dominant transport mechanism. On the other hand, in case of the fractured media, we consider diffusion of chemical species in rock matrix and advection of that (only dissolved oxygen considered in this model) in fracture as transport mechanism. We also use the rate law of iron oxidation reaction and dissolution of Fe-bearing minerals in this model besides. (author)

  2. Generating wind fluctuations for Large Eddy Simulation inflow boundary condition

    International Nuclear Information System (INIS)

    Bekele, S.A.; Hangan, H.

    2004-01-01

    Large Eddy Simulation (LES) studies of flows over bluff bodies immersed in a boundary layer wind environment require instantaneous wind characteristics. The influences of the wind environment on the building pressure distribution are a well-established fact in the experimental study of wind engineering. Measured wind data of full or model scale are available only at a limited number of points. A method of obtaining instantaneous wind data at all mesh points of the inlet boundary for LES computation is necessary. Herein previous and new wind inflow generation techniques are presented. The generated wind data is then applied to a LES computation of a channel flow. The characteristics of the generated wind fluctuations in comparison to the measured data and the properties of the flow field computed from these two wind data are discussed. (author)

  3. Preliminary analysis for evolution of redox conditions in the near field

    International Nuclear Information System (INIS)

    Chiba, Tamotsu; Miki, Takahito; Inagaki, Manabu; Sasamoto, Hiroshi; Yui, Mikazu

    1999-06-01

    It is planned that high level radioactive waste is going to be disposed under deep geological environment. It is believed that the chemical condition of deep groundwater is generally anoxic and reducing. However, during construction and operation phase of repository, oxygen will diffuse some distance into the surrounding rock mass, and diffused oxygen may remain in the surrounding rock mass even after repository closure. In such a case, the transitional redox condition around the drift is not preferable in view point of safety assessment for HLW disposal. Hence, it is very important to evaluate evolution of redox conditions in the near field. This report describes results of preliminary analysis for evolution of redox conditions in the near field rock mass and buffer after repository closure based on the model developed by Chiba et al. (1999). The results of preliminary analysis are summarized as follows: The decrease of oxygen in the near field rock mass and buffer are affected by pH of groundwater and surface area of iron-bearing minerals. The decrease of oxygen in the near field rock mass takes place at time scales lower than 500 years in considering the hypothetical reference groundwater pH range for H12 report. It is implicated that the redox conditions in the near field rock mass will recover to reducing conditions. The decrease of oxygen in the buffer takes place at time scales lower several tens years under neutral to weakly alkaline pH values of porewater in the buffer, even if it is assumed that residual oxygen in the near field rock mass after repository closure will diffuse into the buffer. On the other hand, under weakly acid pH values of porewater in the buffer, it may be presumed that oxygen remain in the buffer at time scale more than 500 years. (author)

  4. 3D imaging of the mitochondrial redox state of rat hearts under normal and fasting conditions

    Directory of Open Access Journals (Sweden)

    He N. Xu

    2014-03-01

    Full Text Available The heart requires continuous ATP availability that is generated in the mitochondria. Although studies using the cell culture and perfused organ models have been carried out to investigate the biochemistry in the mitochondria in response to a change in substrate supply, mitochondrial bioenergetics of heart under normal feed or fasting conditions has not been studied at the tissue level with a sub-millimeter spatial resolution either in vivo or ex vivo. Oxidation of many food-derived metabolites to generate ATP in the mitochondria is realized through the NADH/NAD+ couple acting as a central electron carrier. We employed the Chance redox scanner — the low-temperature fluorescence scanner to image the three-dimensional (3D spatial distribution of the mitochondrial redox states in heart tissues of rats under normal feeding or an overnight starvation for 14.5 h. Multiple consecutive sections of each heart were imaged to map three redox indices, i.e., NADH, oxidized flavoproteins (Fp, including flavin adenine dinucleotide (FAD and the redox ratio NADH/Fp. The imaging results revealed the micro-heterogeneity and the spatial distribution of these redox indices. The quantitative analysis showed that in the fasted hearts the standard deviation of both NADH and Fp, i.e., SD_NADH and SD_Fp, significantly decreased with a p value of 0.032 and 0.045, respectively, indicating that the hearts become relatively more homogeneous after fasting. The fasted hearts contained 28.6% less NADH (p = 0.038. No significant change in Fp was found (p = 0.4. The NADH/Fp ratio decreased with a marginal p value (0.076. The decreased NADH in the fasted hearts is consistent with the cardiac cells' reliance of fatty acids consumption for energy metabolism when glucose becomes scarce. The experimental observation of NADH decrease induced by dietary restriction in the heart at tissue level has not been reported to our best knowledge. The Chance redox scanner demonstrated the

  5. 3D IMAGING OF THE MITOCHONDRIAL REDOX STATE OF RAT HEARTS UNDER NORMAL AND FASTING CONDITIONS.

    Science.gov (United States)

    Xu, He N; Zhou, Rong; Moon, Lily; Feng, Min; Li, Lin Z

    2014-03-01

    The heart requires continuous ATP availability that is generated in the mitochondria. Although studies using the cell culture and perfused organ models have been carried out to investigate the biochemistry in the mitochondria in response to a change in substrate supply, mitochondrial bioenergetics of heart under normal feed or fasting conditions has not been studied at the tissue level with a sub-millimeter spatial resolution either in vivo or ex vivo . Oxidation of many food-derived metabolites to generate ATP in the mitochondria is realized through the NADH/NAD + couple acting as a central electron carrier. We employed the Chance redox scanner - the low-temperature fluorescence scanner to image the three-dimensional (3D) spatial distribution of the mitochondrial redox states in heart tissues of rats under normal feeding or an overnight starvation for 14.5 h. Multiple consecutive sections of each heart were imaged to map three redox indices, i.e., NADH, oxidized flavoproteins (Fp, including flavin adenine dinucleotide (FAD)) and the redox ratio NADH/Fp. The imaging results revealed the micro-heterogeneity and the spatial distribution of these redox indices. The quantitative analysis showed that in the fasted hearts the standard deviation of both NADH and Fp, i.e., SD_NADH and SD_Fp, significantly decreased with a p value of 0.032 and 0.045, respectively, indicating that the hearts become relatively more homogeneous after fasting. The fasted hearts contained 28.6% less NADH ( p = 0.038). No significant change in Fp was found ( p = 0.4). The NADH/Fp ratio decreased with a marginal p value (0.076). The decreased NADH in the fasted hearts is consistent with the cardiac cells' reliance of fatty acids consumption for energy metabolism when glucose becomes scarce. The experimental observation of NADH decrease induced by dietary restriction in the heart at tissue level has not been reported to our best knowledge. The Chance redox scanner demonstrated the feasibility of 3D

  6. Subsurface Conditions Controlling Uranium Incorporation in Iron Oxides: A Redox Stable Sink

    International Nuclear Information System (INIS)

    Fendorf, Scott

    2016-01-01

    Toxic metals and radionuclides throughout the U.S. Department of Energy Complex pose a serious threat to ecosystems and to human health. Of particular concern is the redox-sensitive radionuclide uranium, which is classified as a priority pollutant in soils and groundwaters at most DOE sites owing to its large inventory, its health risks, and its mobility with respect to primary waste sources. The goal of this research was to contribute to the long-term mission of the Subsurface Biogeochemistry Program by determining reactions of uranium with iron (hydr)oxides that lead to long-term stabilization of this pervasive contaminant. The research objectives of this project were thus to (1) identify the (bio)geochemical conditions, including those of the solid-phase, promoting uranium incorporation in Fe (hydr)oxides, (2) determine the magnitude of uranium incorporation under a variety of relevant subsurface conditions in order to quantify the importance of this pathway when in competition with reduction or adsorption; (3) identify the mechanism(s) of U(VI/V) incorporation in Fe (hydr)oxides; and (4) determine the stability of these phases under different biogeochemical (inclusive of redox) conditions. Our research demonstrates that redox transformations are capable of achieving U incorporation into goethite at ambient temperatures, and that this transformation occurs within days at U and Fe(II) concentrations that are common in subsurface geochemical environments with natural ferrihydrites - inclusive of those with natural impurities. Increasing Fe(II) or U concentration, or initial pH, made U(VI) reduction to U(IV) a more competitive sequestration pathway in this system, presumably by increasing the relative rate of U reduction. Uranium concentrations commonly found in contaminated subsurface environments are often on the order of 1-10 μM, and groundwater Fe(II) concentrations can reach exceed 1 mM in reduced zones of the subsurface. The redox-driven U(V) incorporation

  7. Subsurface Conditions Controlling Uranium Incorporation in Iron Oxides: A Redox Stable Sink

    Energy Technology Data Exchange (ETDEWEB)

    Fendorf, Scott [Stanford Univ., CA (United States)

    2016-04-05

    Toxic metals and radionuclides throughout the U.S. Department of Energy Complex pose a serious threat to ecosystems and to human health. Of particular concern is the redox-sensitive radionuclide uranium, which is classified as a priority pollutant in soils and groundwaters at most DOE sites owing to its large inventory, its health risks, and its mobility with respect to primary waste sources. The goal of this research was to contribute to the long-term mission of the Subsurface Biogeochemistry Program by determining reactions of uranium with iron (hydr)oxides that lead to long-term stabilization of this pervasive contaminant. The research objectives of this project were thus to (1) identify the (bio)geochemical conditions, including those of the solid-phase, promoting uranium incorporation in Fe (hydr)oxides, (2) determine the magnitude of uranium incorporation under a variety of relevant subsurface conditions in order to quantify the importance of this pathway when in competition with reduction or adsorption; (3) identify the mechanism(s) of U(VI/V) incorporation in Fe (hydr)oxides; and (4) determine the stability of these phases under different biogeochemical (inclusive of redox) conditions. Our research demonstrates that redox transformations are capable of achieving U incorporation into goethite at ambient temperatures, and that this transformation occurs within days at U and Fe(II) concentrations that are common in subsurface geochemical environments with natural ferrihydrites—inclusive of those with natural impurities. Increasing Fe(II) or U concentration, or initial pH, made U(VI) reduction to U(IV) a more competitive sequestration pathway in this system, presumably by increasing the relative rate of U reduction. Uranium concentrations commonly found in contaminated subsurface environments are often on the order of 1-10 μM, and groundwater Fe(II) concentrations can reach exceed 1 mM in reduced zones of the subsurface. The redox-driven U(V) incorporation

  8. Non-equilibrium concentration fluctuations in binary liquids with realistic boundary conditions.

    Science.gov (United States)

    Ortiz de Zárate, J M; Kirkpatrick, T R; Sengers, J V

    2015-09-01

    Because of the spatially long-ranged nature of spontaneous fluctuations in thermal non-equilibrium systems, they are affected by boundary conditions for the fluctuating hydrodynamic variables. In this paper we consider a liquid mixture between two rigid and impervious plates with a stationary concentration gradient resulting from a temperature gradient through the Soret effect. For liquid mixtures with large Lewis and Schmidt numbers, we are able to obtain explicit analytical expressions for the intensity of the non-equilibrium concentration fluctuations as a function of the frequency ω and the wave number q of the fluctuations. In addition we elucidate the spatial dependence of the intensity of the non-equilibrium fluctuations responsible for a non-equilibrium Casimir effect.

  9. Theoretical and experimental study of redox processes combined with adsorption phenomena under conditions of square-wave voltammetry

    OpenAIRE

    Gulaboski, Rubin

    2001-01-01

    Theoretical models of four electrode reactions coupled with adsorption phenomena under conditions of square-wave voltammetry are developed: simple surface redox reaction, surface catalytic reaction, cathodic stripping reaction of I order, and cathodic stripping reaction of II order.

  10. Effect of the soil's redox conditions on the mobility of Se

    International Nuclear Information System (INIS)

    Darcheville, O.; Fevrier, L.; Martin-Garin, A.

    2005-01-01

    Full text of publication follows: 79 Se is a long-life fission product found in the nuclear wastes. Understanding its behaviour in soils is of major concern because of its bioavailability with almost all living organisms (plants and animals). This study is part of a wider multi-disciplinary program that aims at studying 'the effect of the geochemical transformations and the microbial activities on the fate of Se in soils' [1]. The first part of this program is focused on the interactions between Se and the organic compartment of soils, including both biotic (microorganisms, plants,...) and abiotic (humic, fulvic substances,...) components. Special attention is paid to their consequence on the mobility of Se. The second part of the study, presented here, aims specifically at understanding the effect of the soil's redox status on the mobility of Se and at identifying the nature of the processes involved (microbiological vs chemical). Different types of experiments are performed under laboratory controlled conditions. They consist in mixing a 2 mm-sieved sandy soil from the Rhone borders (France) with radio-labelled selenite ( 75 SeIV). In batch experiments, the soil is incubated in a closed vessel under various atmospheres (O 2 or N 2 ) and amended with specific nutrients in order to create contrasted redox conditions and to stimulate specific microbial communities. These conditions are also used in column experiments to determine their impact on Se mobility. They are completed by varying the degree of water saturation in the column and the structure of the soil. The percolation front of Se is followed in-situ with a mobile gamma detector without disturbing the system. In both experimental designs, mass recoveries of 75 Se are precisely determined in the soil-solution systems thanks to the quantification of Se concentrations in the aqueous, solid and gaseous phases. In addition, the non reversibly sorbed Se fraction is assessed by performing sequential extractions

  11. Lignin decomposition is sustained under fluctuating redox conditions in humid tropical forest soils

    Science.gov (United States)

    Steven J. Hall; Whendee L. Silver; Vitaliy I. Timokhin; Kenneth E. Hammel

    2015-01-01

    Lignin mineralization represents a critical flux in the terrestrial carbon (C) cycle, yet little is known about mechanisms and environmental factors controlling lignin breakdown in mineral soils. Hypoxia is thought to suppress lignin decomposition, yet potential effects of oxygen (O2) variability in surface soils have not been explored. Here, we...

  12. Kinetics of trace metal removal from tidal water by mangrove sediments under different redox conditions

    International Nuclear Information System (INIS)

    Suzuki, K.N.; Machado, E.C.; Machado, W.; Bellido, A.V.B.; Bellido, L.F.; Osso, J.A.; Lopes, R.T.

    2014-01-01

    The extent in which redox conditions can affect the removal kinetics of 58 Co and 65 Zn from tidal water by mangrove sediments was evaluated in microcosm experiments, simulating a tidal flooding period of 6 h. The average half-removal time (t 1/2 ) of 58 Co from overlaying water was slightly higher (7.3 h) under an N 2 -purged water column than under an aerated water column (5.4 h). A lower difference was found for 65 Zn (1.9 h vs. 1.5 h, respectively). Average removals of 58 Co activities from water were 54.6% (N 2 treatment) and 43.5% (aeration treatment), whereas these values were 88.0% and 92.7% for 65 Zn, respectively. Very contrasting sorption kinetics of different radiotracers occurred, while more oxidising conditions favoured only a slightly higher removal. Average 58 Co and 65 Zn inventories within sediments were 30.4% and 18.8% higher in the aeration treatment, respectively. A stronger particle-reactive behaviour was found for 65 Zn that was less redox-sensitive and more efficiently removed by sediments than 58 Co. - Highlights: ► Radiotracer experiments evidenced the role of mangrove sediments in trapping trace metals. ► Very contrasting removal kinetics from tidal water were observed for 65 Zn and 58 Co. ► Nearly 40%–50% of 58 Co activities and nearly 90% of 65 Zn activities in overlying water were removed. ► 65 Zn showed a stronger particle-reactive behaviour than observed for 58 Co. ► 58 Co was more sensitive to redox conditions in tidal water than observed for 65 Zn

  13. Redox conditions effect on flow accelerated corrosion: Influence of hydrazine and oxygen

    Energy Technology Data Exchange (ETDEWEB)

    Bouvier, O. de [EDF, R and D Div., Moret sur Loing (France); Bouchacourt, M. [EDF, Engineering and Service Div., Villeurbanne (France); Fruzzetti, K. [EPRI, Science and Technology Div., Palo Alto, CA (United States)

    2002-07-01

    Flow accelerated corrosion (FAC) of carbon steels has been studied world-wide for more than twenty years and is now fairly well understood. The influence of several parameters like water chemistry (i.e. pH and oxygen content), temperature, hydrodynamic or mass transfer conditions (i.e. flow velocity, geometry, steam quality..) and steel composition on the corrosion kinetics has been demonstrated both theoretically and experimentally. However, the effect of a reducing environment and variable redox conditions have not yet been fully explored. It's well known that a reducing environment is effective in increasing the resistance of steam generator tubing to intergranular attack / stress corrosion cracking (IGA/SCC) and pitting. In that way, secondary water chemistry specifications have been modified from low hydrazine to high hydrazine chemistry in the steam-water circuit. Nevertheless, increasing hydrazine levels up to 200 {mu}g/kg could have a detrimental effect by potentially enhancing the FAC process. Moreover, in order to have a complete understanding of the possible impact of the water chemistry environment it is also important to consider the impact of redox conditions during shutdowns (cold and/or hot shutdowns) and start up periods when aerated water injections are made to maintain a constant water level in the Steam Generators from the auxiliary feedwater circuit. Therefore, a common EDF and EPRI R and D effort has been recently carried out to study the effects of hydrazine and oxygen on FAC. The results are presented as follows. (authors)

  14. Time evolution of dissolved oxygen and redox conditions in a HLW repository

    International Nuclear Information System (INIS)

    Wersin, P.; Spahiu, K.; Bruno, J.

    1994-02-01

    The evolution of oxygen in a HLW repository has been studied using presently available geochemical background information. The important processes affecting oxygen migration in the near-field include diffusion and oxidation of pyrite and dissolved Fe(II). The evaluation of time scales of oxygen decrease is carried out with 1. an analytical approach involving the coupling of diffusion and chemical reaction, 2. a numerical geochemical approach involving the application of a newly developed diffusion-extended version of the STEADYQL code. Both approaches yield consistent rates of oxygen decrease and indicate that oxidation of pyrite impurities in the clay is the dominant process. The results obtained fRom geochemical modelling are interpreted in terms of evolution of redox conditions. Moreover, a sensitivity analysis of the major geochemical and physical parameters is performed. These results indicate that the uncertainties associated with reactive pyrite surface area impose the overall uncertainties of prediction of time scales. Thus, the obtained time of decrease to 1% of initial O 2 concentrations range between 7 and 290 years. The elapsed time at which the transition to anoxic conditions occurs is estimated to be within the same time range. Additional experimental information on redox sensitive impurities in the envisioned buffer and backfill material would further constrain the evaluated time scales. 41 refs

  15. Combining discrepancy analysis with sensorless signal resampling for condition monitoring of rotating machines under fluctuating operations

    CSIR Research Space (South Africa)

    Heyns, T

    2012-12-01

    Full Text Available This paper proposes a novel framework for monitoring the condition of a rotating machine (for example a gearbox or a bearing) that may be subject to load and speed fluctuations. The methodology is especially relevant in situations where no (or only...

  16. Microcosm experiments to control anaerobic redox conditions when studying the fate of organic micropollutants in aquifer material.

    Science.gov (United States)

    Barbieri, Manuela; Carrera, Jesús; Sanchez-Vila, Xavier; Ayora, Carlos; Cama, Jordi; Köck-Schulmeyer, Marianne; López de Alda, Miren; Barceló, Damià; Tobella Brunet, Joana; Hernández García, Marta

    2011-11-01

    The natural processes occurring in subsurface environments have proven to effectively remove a number of organic pollutants from water. The predominant redox conditions revealed to be one of the controlling factors. However, in the case of organic micropollutants the knowledge on this potential redox-dependent behavior is still limited. Motivated by managed aquifer recharge practices microcosm experiments involving aquifer material, settings potentially feasible in field applications, and organic micropollutants at environmental concentrations were carried out. Different anaerobic redox conditions were promoted and sustained in each set of microcosms by adding adequate quantities of electron donors and acceptors. Whereas denitrification and sulfate-reducing conditions are easily achieved and maintained, Fe- and Mn-reduction are strongly constrained by the slower dissolution of the solid phases commonly present in aquifers. The thorough description and numerical modeling of the evolution of the experiments, including major and trace solutes and dissolution/precipitation of solid phases, have been proven necessary to the understanding of the processes and closing the mass balance. As an example of micropollutant results, the ubiquitous beta-blocker atenolol is completely removed in the experiments, the removal occurring faster under more advanced redox conditions. This suggests that aquifers constitute a potentially efficient alternative water treatment for atenolol, especially if adequate redox conditions are promoted during recharge and long enough residence times are ensured. Copyright © 2011 Elsevier B.V. All rights reserved.

  17. Redox Conditions and Related Color Change in Eastern Equatorial Pacific Sediments: IODP Site U1334

    Science.gov (United States)

    Kordesch, W. E.; Gussone, N. C.; Hathorne, E. C.; Kimoto, K.; Delaney, M. L.

    2011-12-01

    This study was prompted by a 65 m thick brown-green color change in deep-sea sediments of IODP Site U1334 (0-38 Ma, 4799 m water depth) that corresponds to its equatorial crossing (caused by the Northward movement of the pacific plate). Green sediment is a visual indicator of reducing conditions in sediment due to enhanced organic matter deposition and burial. Here we use geochemical redox indicators to characterize the effect of equatorial upwelling on bottom water. The modern redox signal is captured in porewater profiles (nitrate, manganese, iron, sulfate) while trace metal Enrichment Factors (EF) in bulk sediment (manganese, uranium, molybdenum, rhenium) normalized to the detrital component (titanium) record redox state at burial. To measure export productivity we also measure biogenic barium. Porewater profiles reveal suboxic diagenesis; profiles follow the expected sequence of nitrate, manganese oxide, and iron oxide reduction with increasing depth. Constant sulfate (~28 μM) implies anoxia has not occurred. Bulk sediment Mn EF are enriched (EF > 1) throughout the record (Mn EF = 15-200) while U and Mo enrichment corresponds to green color and equatorial proximity (U EF = 4-19; Mo EF = 0-7). Constant Mn enrichment implies continuous oxygenation. Uranium and Mo enrichment near the equator represents suboxic conditions also seen in the porewater. Low Re concentrations (below detection) provide additional evidence against anoxia. A comparison of Mn EF from total digestions to samples treated with an additional reductive cleaning step distinguishes between Mn-oxides and Mn-carbonates, indicating oxygenated and reducing conditions respectively. Mn-carbonate occurrence agrees with U and Mo EF; conditions were more reducing near the equator. Bio-Ba shows significant variability over this interval (22-99 mmol g-1). Our geochemical results indicate that bottom waters became suboxic at the equator as a result of equatorial upwelling-influenced increases in organic

  18. Experimental investigation of factors affecting the control of redox conditions within a radwaste repository

    International Nuclear Information System (INIS)

    Guppy, R.M.; Atkinson, A.

    1991-04-01

    The maximum aqueous concentration of multivalent radioelements in a radwaste repository can be estimated from the expected Eh (the oxidising or reducing tendency of the solution) and pH of the aqueous phase in the repository so long as equilibrium between all oxidising and reducing species can be guaranteed. The objective of the work reported here was to ascertain whether any significant departures from redox equilibrium are likely to arise. Technetium (VII) species were exposed under anaerobic conditions to concentrations of ferrous, hydrogen sulphide and thiosulphate species likely to be present in a repository environment to establish which species are capable of reducing aqueous Tc(VII) to a less soluble Tc(IV) solid compound. Potential catalytic solid phases and phases capable of electron exchange were also exposed to Tc(VII) species under anaerobic, aerobic and hydrogen atmospheres. We have not been able to demonstrate conclusively that mutual equilibrium was attained between technetium and iron redox couples, nor that the apparent solubility of technetium was that expected from the resulting Eh and pH of the solution, although some technetium was removed from solution. Hydrogen did not reduce Tc(VII) within the timescale of the experiments and no catalytic effects by haematite or a cementitious backfill grout for reductions involving hydrogen were observable. Magnetite removed some technetium from solution, apparently by surface reaction, under inert (argon) and reducing (hydrogen) atmospheres. Sulphides, and to a lesser extent thiosulphates, will reduce the solubility of technetium to a very low level. (author)

  19. Applying linear discriminant analysis to predict groundwater redox conditions conducive to denitrification

    Science.gov (United States)

    Wilson, S. R.; Close, M. E.; Abraham, P.

    2018-01-01

    Diffuse nitrate losses from agricultural land pollute groundwater resources worldwide, but can be attenuated under reducing subsurface conditions. In New Zealand, the ability to predict where groundwater denitrification occurs is important for understanding the linkage between land use and discharges of nitrate-bearing groundwater to streams. This study assesses the application of linear discriminant analysis (LDA) for predicting groundwater redox status for Southland, a major dairy farming region in New Zealand. Data cases were developed by assigning a redox status to samples derived from a regional groundwater quality database. Pre-existing regional-scale geospatial databases were used as training variables for the discriminant functions. The predictive accuracy of the discriminant functions was slightly improved by optimising the thresholds between sample depth classes. The models predict 23% of the region as being reducing at shallow depths (water table, and low-permeability clastic sediments. The coastal plains are an area of widespread groundwater discharge, and the soil and hydrology characteristics require the land to be artificially drained to render the land suitable for farming. For the improvement of water quality in coastal areas, it is therefore important that land and water management efforts focus on understanding hydrological bypassing that may occur via artificial drainage systems.

  20. Solar wind fluctuations at large scale - A comparison between low and high solar activity conditions

    Science.gov (United States)

    Bavassano, B.; Bruno, R.

    1991-02-01

    The influence of the sun's activity cycle on the solar wind fluctuations at time scales from 1 hour to 3 days in the inner heliosphere (0.3 to 1 AU) is investigated. Hourly averages of plasma and magnetic field data by Helios spacecraft are used. Since fluctuations behave quite differently with changing scale, the analysis is performed separately for two different ranges in time scale. Between 1 and 6 hours Alfvenic fluctuations and pressure-balanced structures are extensively observed. At low solar activity and close to 0.3 AU Alfvenic fluctuations are more frequent than pressure-balanced structures. This predominance, however, weakens for rising solar activity and radial distance, to the point that a role-exchange, in terms of occurrence rate, is found at the maximum of the cycle close to 1 AU. On the other hand, in all cases Alfvenic fluctuations have a larger amplitude than pressure-balanced structures. The Alfvenic contribution to the solar wind energy spectrum comes out to be dominant at all solar activity conditions. These findings support the conclusion that the solar cycle evolution of the large-scale velocity pattern is the factor governing the observed variations.

  1. Solar wind fluctuations at large scale: A comparison between low and high solar activity conditions

    International Nuclear Information System (INIS)

    Bavassano, B.; Bruno, R.

    1991-01-01

    The influence of the Sun's activity cycle on the solar wind fluctuations at time scales from 1 hour to 3 days in the inner heliosphere (0.3 to 1 AU) is investigated. Hourly averages of plasma and magnetic field data by Helios spacecraft are used. Since fluctuations behave quite differently with changing scale, the analysis is performed separately for two different ranges in time scale. Between 1 and 6 hours Alfvenic fluctuations and pressure-balanced structures are extensively observed. At low solar activity and close to 0.3 AU, Alfvenic fluctuations are more frequent than pressure-balanced structures. This predominance, however, weakens for rising solar activity and radial distance, to the point that a role exchange, in terms of occurrence rate, is found at the maximum of the cycle close to 1 AU. On the other hand, in all cases Alfvenic fluctuations have a larger amplitude than pressure-balanced structures. On the whole, the Alfvenic contribution to the solar wind energy spectrum comes out to be dominant at all solar activity conditions. At scales from 0.5 to 3 days the most important feature is the growth, as the solar wind expansion develops, of strong positive correlations between magnetic and thermal pressures. These structures are progressively built up by the interaction between different wind flows. This effect is more pronounced at low than at high activity. Our findings support the conclusion that the solar cycle evolution of the large-scale velocity pattern is the factor governing the observed variations

  2. Crude oil degradation by bacterial consortia under four different redox and temperature conditions.

    Science.gov (United States)

    Xiong, Shunzi; Li, Xia; Chen, Jianfa; Zhao, Liping; Zhang, Hui; Zhang, Xiaojun

    2015-02-01

    There is emerging interest in the anaerobic degradation of crude oil. However, there is limited knowledge about the geochemical effects and microbiological activities for it. A mixture of anaerobic sludge and the production water from an oil well was used as an inoculum to construct four consortia, which were incubated under sulfate-reducing or methanogenic conditions at either mesophilic or thermophilic temperatures. Significant degradation of saturated and aromatic hydrocarbons and the changing quantities of some marker compounds, such as pristane, phytane, hopane and norhopane, and their relative quantities, suggested the activity of microorganisms in the consortia. Notably, the redox conditions and temperature strongly affected the diversity and structure of the enriched microbial communities and the oil degradation. Although some specific biomarker showed larger change under methanogenic condition, the degradation efficiencies for total aromatic and saturated hydrocarbon were higher under sulfate-reducing condition. After the 540-day incubation, bacteria of unknown classifications were dominant in the thermophilic methanogenic consortia, whereas Clostridium dominated the mesophilic methanogenic consortia. With the exception of the dominant phylotypes that were shared with the methanogenic consortia, the sulfate-reducing consortia were predominantly composed of Thermotogae, Deltaproteobacteria, Spirochaeta, and Synergistetes phyla. In conclusion, results in this study demonstrated that the different groups of degraders were responsible for degradation in the four constructed crude oil degrading consortia and consequently led to the existence of different amount of marker compounds under these distinct conditions. There might be distinct metabolic mechanism for degrading crude oil under sulfate-reducing and methanogenic conditions.

  3. Determination of Pressure Fluctuations in Rotor Bundle of Centrifugal Compressor at Critical Conditions of Operation

    Science.gov (United States)

    Levashov, V. A.; Lyubchenko, K. Yu

    2017-08-01

    This article describes the physical processes that occur in the stage flow part of the compressor while it is operating and can create conditions for the occurrence of forced vibrations, which in turn can lead to the destruction of the impellers. Critical conditions of compressor operation are determined. To understand that critical condition of operation is cause of the destruction of the impellers, transient CFD analysis was carried for test stage of compressor. The obtained pressure fluctuation amplitudes allow to evaluate the critical conditions of compressor operation.

  4. Influence of redox condition in iron, silicon and hydrogen contents of leached glass surface

    International Nuclear Information System (INIS)

    Manara, A.; Lanza, F.; Della Mea, G.; Rossi, C.; Salvagno, G.

    1984-01-01

    Surface analysis has been conducted on samples leached in a Sochlet apparatus at 100 0 C in the presence and in the absence of air. The XPS technique was applied to analyze the content of iron and silicon while the nuclear reaction method was utilized to analyze the content of hydrogen. Samples leached in argon atmosphere have shown a smaller content of iron and silicon with respect to the samples leached in air atmosphere. The H concentration has shown the same behavior. The results are discussed in terms of possible formation of iron compounds in the different redox condition and of their different stabilities and in terms of their efficiency in reducing exchange between Na + and H + ions. 11 references, 3 figures, 1 table

  5. Role of biotransformation, sorption and mineralization of (14)C-labelled sulfamethoxazole under different redox conditions.

    Science.gov (United States)

    Alvarino, T; Nastold, P; Suarez, S; Omil, F; Corvini, P F X; Bouju, H

    2016-01-15

    (14)C-sulfamethoxazole biotransformation, sorption and mineralization was studied with heterotrophic and autotrophic biomass under aerobic and anoxic conditions, as well as with anaerobic biomass. The (14)C-radiolabelled residues distribution in the solid, liquid and gas phases was closely monitored along a total incubation time of 190 h. Biotransformation was the main removal mechanism, mineralization and sorption remaining below 5% in all the cases, although the presence of a carbon source exerted a positive effect on the mineralization rate by the aerobic heterotrophic bacteria. In fact, an influence of the type of primary substrate and the redox potential was observed in all cases on the biotransformation and mineralization rates, since an enhancement of the removal rate was observed when an external carbon source was used as a primary substrate under aerobic conditions, while a negligible effect was observed under nitrifying conditions. In the liquid phases collected from all assays, up to three additional peaks corresponding to (14)C-radiolabelled residues were detected. The highest concentration was observed under anaerobic conditions, where two radioactive metabolites were detected representing each around 15% of the total applied radioactivity after 180 h incubation. One of the metabolites detected under anoxic and anaerobic conditions, is probably resulting from ring cleavage of the isoxazole ring. Copyright © 2015 Elsevier B.V. All rights reserved.

  6. Long-term competitive dynamics of two cryptic rotifer species: diapause and fluctuating conditions.

    Directory of Open Access Journals (Sweden)

    Carmen Gabaldón

    Full Text Available Life-history traits may have an important role in promoting species coexistence. However, the complexity of certain life cycles makes it difficult to draw conclusions about the conditions for coexistence or exclusion based on the study of short-term competitive dynamics. Brachionus plicatilis and B. manjavacasare two cryptic rotifer species co-occurring in many lakes on the Iberian Peninsula. They have a complex life cycle in which cyclical parthenogenesis occurs with diapausing stages being the result of sexual reproduction. B. plicatilis and B. manjavacasare identical in morphology and size, their biotic niches are broadly overlapping, and they have similar competitive abilities. However, the species differ in life-history traits involving sexual reproduction and diapause, and respond differently to salinity and temperature. As in the case of certain other species that are extremely similar in morphology, a fluctuating environment are considered to be important for their coexistence. We studied the long-term competitive dynamics of B. plicatilis and B. manjavacas under different salinity regimes (constant and fluctuating. Moreover, we focused on the dynamics of the diapausing egg bank to explore how the outcome of the entire life cycle of these rotifers can work to mediate stable coexistence. We demonstrated that these species do not coexist under constant-salinity environment, as the outcome of competition is affected by the level of salinity-at low salinity, B. plicatilis excluded B. manjavacas, and the opposite outcome occurred at high salinity. Competitive dynamics under fluctuating salinity showed that the dominance of one species over the other also tended to fluctuate. The duration of co-occurrence of these species was favoured by salinity fluctuation and perhaps by the existence of a diapausing egg bank. Stable coexistence was not found in our system, which suggests that other factors or other salinity fluctuation patterns might act as

  7. Long-term competitive dynamics of two cryptic rotifer species: diapause and fluctuating conditions.

    Science.gov (United States)

    Gabaldón, Carmen; Carmona, María José; Montero-Pau, Javier; Serra, Manuel

    2015-01-01

    Life-history traits may have an important role in promoting species coexistence. However, the complexity of certain life cycles makes it difficult to draw conclusions about the conditions for coexistence or exclusion based on the study of short-term competitive dynamics. Brachionus plicatilis and B. manjavacasare two cryptic rotifer species co-occurring in many lakes on the Iberian Peninsula. They have a complex life cycle in which cyclical parthenogenesis occurs with diapausing stages being the result of sexual reproduction. B. plicatilis and B. manjavacasare identical in morphology and size, their biotic niches are broadly overlapping, and they have similar competitive abilities. However, the species differ in life-history traits involving sexual reproduction and diapause, and respond differently to salinity and temperature. As in the case of certain other species that are extremely similar in morphology, a fluctuating environment are considered to be important for their coexistence. We studied the long-term competitive dynamics of B. plicatilis and B. manjavacas under different salinity regimes (constant and fluctuating). Moreover, we focused on the dynamics of the diapausing egg bank to explore how the outcome of the entire life cycle of these rotifers can work to mediate stable coexistence. We demonstrated that these species do not coexist under constant-salinity environment, as the outcome of competition is affected by the level of salinity-at low salinity, B. plicatilis excluded B. manjavacas, and the opposite outcome occurred at high salinity. Competitive dynamics under fluctuating salinity showed that the dominance of one species over the other also tended to fluctuate. The duration of co-occurrence of these species was favoured by salinity fluctuation and perhaps by the existence of a diapausing egg bank. Stable coexistence was not found in our system, which suggests that other factors or other salinity fluctuation patterns might act as stabilizing

  8. Response of Microbial Community Function to Fluctuating Geochemical Conditions within a Legacy Radioactive Waste Trench Environment.

    Science.gov (United States)

    Vázquez-Campos, Xabier; Kinsela, Andrew S; Bligh, Mark W; Harrison, Jennifer J; Payne, Timothy E; Waite, T David

    2017-09-01

    During the 1960s, small quantities of radioactive materials were codisposed with chemical waste at the Little Forest Legacy Site (Sydney, Australia) in 3-meter-deep, unlined trenches. Chemical and microbial analyses, including functional and taxonomic information derived from shotgun metagenomics, were collected across a 6-week period immediately after a prolonged rainfall event to assess the impact of changing water levels upon the microbial ecology and contaminant mobility. Collectively, results demonstrated that oxygen-laden rainwater rapidly altered the redox balance in the trench water, strongly impacting microbial functioning as well as the radiochemistry. Two contaminants of concern, plutonium and americium, were shown to transition from solid-iron-associated species immediately after the initial rainwater pulse to progressively more soluble moieties as reducing conditions were enhanced. Functional metagenomics revealed the potentially important role that the taxonomically diverse microbial community played in this transition. In particular, aerobes dominated in the first day, followed by an increase of facultative anaerobes/denitrifiers at day 4. Toward the mid-end of the sampling period, the functional and taxonomic profiles depicted an anaerobic community distinguished by a higher representation of dissimilatory sulfate reduction and methanogenesis pathways. Our results have important implications to similar near-surface environmental systems in which redox cycling occurs. IMPORTANCE The role of chemical and microbiological factors in mediating the biogeochemistry of groundwaters from trenches used to dispose of radioactive materials during the 1960s is examined in this study. Specifically, chemical and microbial analyses, including functional and taxonomic information derived from shotgun metagenomics, were collected across a 6-week period immediately after a prolonged rainfall event to assess how changing water levels influence microbial ecology and

  9. A novelty detection diagnostic methodology for gearboxes operating under fluctuating operating conditions using probabilistic techniques

    Science.gov (United States)

    Schmidt, S.; Heyns, P. S.; de Villiers, J. P.

    2018-02-01

    In this paper, a fault diagnostic methodology is developed which is able to detect, locate and trend gear faults under fluctuating operating conditions when only vibration data from a single transducer, measured on a healthy gearbox are available. A two-phase feature extraction and modelling process is proposed to infer the operating condition and based on the operating condition, to detect changes in the machine condition. Information from optimised machine and operating condition hidden Markov models are statistically combined to generate a discrepancy signal which is post-processed to infer the condition of the gearbox. The discrepancy signal is processed and combined with statistical methods for automatic fault detection and localisation and to perform fault trending over time. The proposed methodology is validated on experimental data and a tacholess order tracking methodology is used to enhance the cost-effectiveness of the diagnostic methodology.

  10. Dynamic heterogeneity and conditional statistics of non-Gaussian temperature fluctuations in turbulent thermal convection

    Science.gov (United States)

    He, Xiaozhou; Wang, Yin; Tong, Penger

    2018-05-01

    Non-Gaussian fluctuations with an exponential tail in their probability density function (PDF) are often observed in nonequilibrium steady states (NESSs) and one does not understand why they appear so often. Turbulent Rayleigh-Bénard convection (RBC) is an example of such a NESS, in which the measured PDF P (δ T ) of temperature fluctuations δ T in the central region of the flow has a long exponential tail. Here we show that because of the dynamic heterogeneity in RBC, the exponential PDF is generated by a convolution of a set of dynamics modes conditioned on a constant local thermal dissipation rate ɛ . The conditional PDF G (δ T |ɛ ) of δ T under a constant ɛ is found to be of Gaussian form and its variance σT2 for different values of ɛ follows an exponential distribution. The convolution of the two distribution functions gives rise to the exponential PDF P (δ T ) . This work thus provides a physical mechanism of the observed exponential distribution of δ T in RBC and also sheds light on the origin of non-Gaussian fluctuations in other NESSs.

  11. Decreasing diameter fluctuation of polymer optical fiber with optimized drawing conditions

    Science.gov (United States)

    Çetinkaya, Onur; Wojcik, Grzegorz; Mergo, Pawel

    2018-05-01

    The diameter fluctuations of poly(methyl methacrylate) based polymer optical fibers, during drawing processes, have been comprehensively studied. In this study, several drawing parameters were selected for investigation; such as drawing tensions, preform diameters, preform feeding speeds, and argon flows. Varied drawing tensions were used to draw fibers, while other parameters were maintained at constant. At a later stage in the process, micro-structured polymer optical fibers were drawn under optimized drawing conditions. Fiber diameter deviations were reduced to 2.2%, when a 0.2 N drawing tension was employed during the drawing process. Higher drawing tensions led to higher diameter fluctuations. The Young’s modulus of fibers drawn with different tensions was also measured. Our results showed that fiber elasticity increased as drawing tensions decreased. The inhomogeneity of fibers was also determined by comparing the deviation of Young’s modulus.

  12. RANS simulation of cavitation and hull pressure fluctuation for marine propeller operating behind-hull condition

    Science.gov (United States)

    Paik, Kwang-Jun; Park, Hyung-Gil; Seo, Jongsoo

    2013-12-01

    Simulations of cavitation flow and hull pressure fluctuation for a marine propeller operating behind a hull using the unsteady Reynolds-Averaged Navier-Stokes equations (RANS) are presented. A full hull body submerged under the free surface is modeled in the computational domain to simulate directly the wake field of the ship at the propeller plane. Simulations are performed in design and ballast draught conditions to study the effect of cavitation number. And two propellers with slightly different geometry are simulated to validate the detectability of the numerical simulation. All simulations are performed using a commercial CFD software FLUENT. Cavitation patterns of the simulations show good agreement with the experimental results carried out in Samsung CAvitation Tunnel (SCAT). The simulation results for the hull pressure fluctuation induced by a propeller are also compared with the experimental results showing good agreement in the tendency and amplitude, especially, for the first blade frequency.

  13. RANS simulation of cavitation and hull pressure fluctuation for marine propeller operating behind-hull condition

    Directory of Open Access Journals (Sweden)

    Kwang-Jun Paik

    2013-12-01

    Full Text Available Simulations of cavitation flow and hull pressure fluctuation for a marine propeller operating behind a hull using the unsteady Reynolds-Averaged Navier-Stokes equations (RANS are presented. A full hull body submerged under the free surface is modeled in the computational domain to simulate directly the wake field of the ship at the propeller plane. Simulations are performed in design and ballast draught conditions to study the effect of cavitation number. And two propellers with slightly different geometry are simulated to validate the detectability of the numerical simulation. All simulations are performed using a commercial CFD software FLUENT. Cavitation patterns of the simulations show good agreement with the experimental results carried out in Samsung CAvitation Tunnel (SCAT. The simulation results for the hull pressure fluctuation induced by a propeller are also compared with the experimental results showing good agreement in the tendency and amplitude, especially, for the first blade frequency.

  14. The evolution of redox conditions and groundwater geochemistry in recharge-discharge environments on the Canadian Shield

    International Nuclear Information System (INIS)

    Gascoyne, M.

    1996-10-01

    Groundwater composition evolves along flow paths from recharge to discharge in response to interactions with bedrock and fracture-filling minerals, and dissolution of soluble (Cl-rich) salts in the rock matrix. The groundwater redox potential changes from oxidizing to reducing conditions due, initially, to rapid consumption of dissolved oxygen by organics in the upper ∼100 m of bedrock and, subsequently, interaction with Fe (II)-containing minerals. Measured Eh values of groundwaters at depth in the granitic Lac du Bonnet batholith indicate that biotite and chlorite control groundwater redox potential. This is supported by other geochemical characteristics such as absence of CH 4 , H 2 S, H 2 , NO 3 , low concentrations of Fe (II), and abundance of SO 4 . Further evidence of evolution of redox conditions is given by variations in U concentration ranging from up to 1000 μg/L in dilute near-surface waters to <1 μg/L in some deep, saline groundwaters. Groundwaters at about 400 m depth in a recharge area on the Lac du Bonnet batholith contain significantly more U than groundwaters further along the flow path or near surface in discharge areas. Uranium concentration is found to be a useful and sensitive indicator of redox conditions. (author)

  15. Conditional analysis of floating potential fluctuations at the edge of the Texas Experimental Tokamak Upgrade (TEXT-U)

    International Nuclear Information System (INIS)

    Filippas, A.V.; Bengston, R.D.; Li, G.; Meier, M.; Ritz, C.P.; Powers, E.J.

    1995-01-01

    Fluctuations in floating potential in the scrape-off layer and plasma edge were analyzed using a conditional statistical analysis technique. The floating potential fluctuations had a nearly Gaussian probability density function with the largest deviation from a Gaussian at the shear layer. The conditional averaging technique followed the statistical evolution of selected conditions in the floating potential signal. The decay rate of a conditional feature in time or space showed a small systematic variation with the amplitude of condition chosen. Either long-lived coherent structures are not present in statistically significant numbers, or the fluctuations are dominated by a large number of coherent structures with a nearly Gaussian distribution of fluctuation amplitudes, or conditional analysis using the amplitude of the floating potential as a condition is not a sensitive technique for identifying coherent structures

  16. The Cr Redox Record of fO2 Variation in Angrites. Evidence for Redox Conditions of Angrite Petrogenesis and Parent Body

    Science.gov (United States)

    Shearer, Charles K.; Bell, Aaron S.; Burger, Paul V.; Papike, James J.; Jones, John; Le, Loan

    2016-01-01

    Angrites represent some of the earliest stages of planetesimal differentiation. Not surprisingly, there is no simple petrogenetic model for their origin. Petrogenesis has been linked to both magmatic and impact processes. Studies demonstrated that melting of chondritic material (e.g. CM, CV) at redox conditions where pure iron metal is unstable (e.g., IW+1 to IW+2) produced angrite-like melts. Alternatively, angrites were produced at more reducing conditions (redox conditions during crystallization (e.g., Fe metal and a Fe-Ti oxide with potential Fe3+. There have been several estimates of fO2 for angrites. Most notably, experiments examined the variation of DEu/DGd with fO2, between plagioclase and fassaitic pyroxene in equilibrium with an angrite melt composition. They used their observations to estimate the fO2 of crystallization to be approximately IW+0.6 for angrite LEW 86010. This estimate is only a "snapshot" of fO2 conditions during co-crystallization of plagioclase and pyroxene. Preliminary XANES analyses of V redox state in pyroxenes from D'Orbigny reported changes in fO2 from IW-0.7 during early pyroxene crystallization to IW+0.5 during latter episodes of pyroxene crystallization [15]. As this was a preliminary report, it presented limited information concerning the effects of pyroxene orientation and composition on the V valence measurements, and the effect of melt composition on valence and partitioning behavior of V. A closer examination of fO2 as recorded by Cr valence state in olivine will allow us to test models for primordial melting of chondritic material to produce the angrite parent melts. Here, we report the our initial stages of examining the origin and conditions of primordial melting on the angrite parent body and test some of the above models by integrating an experimental study of Cr and V valence partitioning between olivine [OL] and an angrite melt, with micro-scale determinations of Cr and V oxidation state in OL in selected "volcanic

  17. Reconstruction of Redox Conditions and Productivity in Coastal Waters of the Bothnian Sea during the Holocene

    Science.gov (United States)

    Dijkstra, N.; Quintana Krupinski, N. B.; Slomp, C. P.

    2014-12-01

    Hypoxia is a growing problem in coastal waters worldwide, and is a well-known cause of benthic mortality. The semi-enclosed Baltic Sea is currently the world's largest human-induced dead zone. During the early Holocene, it experienced several periods of natural hypoxia following the intrusion of seawater into the previous freshwater lake. Recent studies suggest that at that time, the hypoxia expanded north to include the deep basin of the Bothnian Sea. In this study, we assess whether the coastal zone of the Bothnian Sea was also hypoxic during the early Holocene. We analysed a unique sediment record (0 - 30 mbsf) from the Ångermanälven estuary, which was retrieved during the International Ocean Discovery Programme (IODP) Baltic Sea Paleoenvironment Expedition 347 in 2013. Using geochemical proxies and foraminifera abundances, we reconstruct the changes in redox conditions, salinity and productivity in the estuary. Our preliminary results suggest that bottom waters in this coastal basin became anoxic upon the intrusion of brackish seawater in the early Holocene and that the productivity was elevated. The presence of benthic foraminifera in this estuary during the mid-Holocene suggests more saline conditions in the Bothnian Sea than today. Due to isostatic uplift, the estuary likely gradually became more isolated from the Bothnian Sea, which itself became more isolated from the Baltic Sea. Both factors likely explain the subsequent re-oxygenation of bottom waters and gradual refreshening of the estuary as recorded in the sediments. Interestingly, the upper meters of sediment are enriched in minerals that contain iron, phosphorus and manganese. We postulate that the refreshening of the estuary triggered the formation of these minerals, thereby increasing the phosphorus retention in these sediments and further reducing primary productivity. This enhanced retention linked to refreshening may contribute to the current oligotrophic conditions in the Bothnian Sea.

  18. Examination of Technetium Transport Through Soils Under Contrasting Redox Conditions: Batch and Column Work

    Science.gov (United States)

    Dozier, R.; Montgomery, D.; Wylie, E. M.; Dogan, M.; Moysey, S. M.; Powell, B. A.; Martinez, N. E.

    2015-12-01

    Experiments were performed under various reducing conditions to evaluate the transport behavior of technetium-99 (99Tc) in the presence of sandy clay loam soil from the Savannah River Site (SRS) and goethite, magnetite, and iron sulfide, which were selected for their increasing reducing potential. The experiments were conducted to investigate how redox reaction equilibria and rates affect the overall mobility of 99Tc as it transitions between the mobile Tc(VII) and immobile Tc(IV). Under oxygen-rich conditions, batch sorption isotherms measured for TcO4- across the concentration range 0.5 to 50 μg/L were linear with distribution coefficients (Kd) of 0.78 mL/g or lower, with decreasing sorption for goethite, magnetite, and iron sulfide, respectively. Addition of Na2S resulted in a marked increase in apparent 99Tc sorption to the solid phase, with Kd of 43 mL/g, 35 mL/g, and 29 mL/g, following the same mineral trend as previously. The increased Kd values are possibly due to reduction of Tc(VII) to Tc(IV), resulting in the formation of TcO2(s). SRS soil batch sorption isotherms measured for TcO4- across the same concentration range were also linear, with Kd of 0.7 mL/g for unadjusted pH, 5.1 mL/g for pH of around 6, and 6.7 mL/g for pH of around 4. Kinetic batch sorption tests showed less than 10% 99Tc sorption in an oxidizing environment and greater than 95% sorption in a reducing environment, with both reactions occurring on the order of minutes. In contrast, desorption experiments initiated by transferring the samples from a reducing environment (0.1% H2(g)/99.9% N2(g)) to atmospheric conditions resulted in a slow desorption step on the order of days. Column experiments conducted with the SRS sands indicate a retardation factor of 1.17 for 99Tc under oxygen rich conditions. Additional column experiments are being conducted to evaluate 99Tc transport dependencies on transitions between oxygen rich and poor conditions.

  19. Chemical resilience of clay rich barrier materials to redox-oscillating conditions and implications for contaminant mobility

    International Nuclear Information System (INIS)

    Parsons, Chris; Rossetto, Lionel; Charlet, Laurent; Made, Benoit

    2012-01-01

    Document available in extended abstract form only. The mineralogical composition of argillaceous barrier materials is often considered to be static, and therefore, that interactions with contaminants and nutrients may be well constrained. Typically, solid/aqueous partition coefficients (K d values) are obtained empirically to determine the proportion of contaminant immobilised by the solid phase for individual barrier material/contaminant combinations at defined contaminant loadings and pH. These values may then be used as indicators of potential contaminant mobility around waste storage facilities following the eventual failure of engineered barriers (1). While K d values are a useful tool to modellers estimating contaminant mobility through porous media at thermodynamic equilibrium, over time and under dynamic biogeochemical conditions, matrix mineralogy, and therefore K d values, are liable to change (2). Near surface environments implicated in back-filled or excavated storage solutions, currently proposed for low-level long-lived waste (LL-LLW), will result in more dynamic redox conditions than those predicted in deep, anoxic geological storage conditions (2). Such dynamic conditions are similar to those experienced in pluvial, fluvial or phreatic influenced soils and are likely to be far from thermodynamic equilibrium (3). Cyclic redox conditions of varying periodicity are likely to occur around near surface repositories due to a combination of microbial activity and variations in substrate saturation caused by changes to groundwater level and rates of pluvial infiltration. Upon saturation of near surface substrates reducing conditions occur rapidly due to slow inward diffusion of oxygen from the surface and rapid oxygen consumption by aerobic heterotrophic bacteria gaining energy from the mineralisation of organic matter (4, 5). Subsequent to the exhaustion of residual oxygen, anaerobic metabolism dominates in such environments resulting in the depletion of

  20. Identification of Large-Scale Structure Fluctuations in IC Engines using POD-Based Conditional Averaging

    Directory of Open Access Journals (Sweden)

    Buhl Stefan

    2016-01-01

    Full Text Available Cycle-to-Cycle Variations (CCV in IC engines is a well-known phenomenon and the definition and quantification is well-established for global quantities such as the mean pressure. On the other hand, the definition of CCV for local quantities, e.g. the velocity or the mixture distribution, is less straightforward. This paper proposes a new method to identify and calculate cyclic variations of the flow field in IC engines emphasizing the different contributions from large-scale energetic (coherent structures, identified by a combination of Proper Orthogonal Decomposition (POD and conditional averaging, and small-scale fluctuations. Suitable subsets required for the conditional averaging are derived from combinations of the the POD coefficients of the second and third mode. Within each subset, the velocity is averaged and these averages are compared to the ensemble-averaged velocity field, which is based on all cycles. The resulting difference of the subset-average and the global-average is identified as a cyclic fluctuation of the coherent structures. Then, within each subset, remaining fluctuations are obtained from the difference between the instantaneous fields and the corresponding subset average. The proposed methodology is tested for two data sets obtained from scale resolving engine simulations. For the first test case, the numerical database consists of 208 independent samples of a simplified engine geometry. For the second case, 120 cycles for the well-established Transparent Combustion Chamber (TCC benchmark engine are considered. For both applications, the suitability of the method to identify the two contributions to CCV is discussed and the results are directly linked to the observed flow field structures.

  1. Disentangling the record of diagenesis, local redox conditions, and global seawater chemistry during the latest Ordovician glaciation

    DEFF Research Database (Denmark)

    Ahm, Anne-Sofie Crüger; Bjerrum, Christian J.; Hammarlund, Emma U.

    2017-01-01

    as pyrite in core samples, while outcrop samples have been significantly altered as pyrite has been oxidized and remobilized by modern weathering processes. Fe speciation in the more pristine core samples indicates persistent deep water anoxia, at least locally through the Late Ordovician, in contrast...... to the prevailing interpretation of increased Hirnantian water column oxygenation in shallower environments. Deep water redox conditions were likely decoupled from shallower environments by a basinal shift in organic matter export driven by decreasing rates of organic matter degradation and decreasing shelf areas......The Late Ordovician stratigraphic record integrates glacio-eustatic processes, water-column redox conditions and carbon cycle dynamics. This complex stratigraphic record, however, is dominated by deposits from epeiric seas that are susceptible to local physical and chemical processes decoupled from...

  2. Synergistic effects of seasonal rainfall, parasites and demography on fluctuations in springbok body condition

    Science.gov (United States)

    Turner, Wendy C.; Versfeld, Wilferd D.; Kilian, J. Werner; Getz, Wayne M.

    2011-01-01

    Summary 1. Seasonality of rainfall can exert a strong influence on animal condition and on host-parasite interactions. The body condition of ruminants fluctuates seasonally in response to changes in energy requirements, foraging patterns and resource availability, and seasonal variation in parasite infections may further alter ruminant body condition. 2. This study disentangles effects of rainfall and gastrointestinal parasite infections on springbok (Antidorcas marsupialis) body condition and determines how these factors vary among demographic groups. 3. Using data from four years and three study areas, we investigated i) the influence of rainfall variation, demographic factors and parasite interactions on parasite prevalence or infection intensity, ii) whether parasitism or rainfall is a more important predictor of springbok body condition and iii) how parasitism and condition vary among study areas along a rainfall gradient. 4. We found that increased parasite intensity is associated with reduced body condition only for adult females. For all other demographic groups, body condition was significantly related to prior rainfall and not to parasitism. Rainfall lagged by two months had a positive effect on body condition. 5. Adult females showed evidence of a “periparturient rise” in parasite intensity, and had higher parasite intensity and lower body condition than adult males after parturition and during early lactation. After juveniles were weaned, adult females had lower parasite intensity than adult males. Sex differences in parasitism and condition may be due to differences between adult females and males in the seasonal timing of reproductive effort and its effects on host immunity, as well as documented sex differences in vulnerability to predation. 6. Our results highlight that parasites and the environment can synergistically affect host populations, but that these interactions might be masked by their interwoven relationships, their differential

  3. Evaluation of heart tissue viability under redox-magnetohydrodynamics conditions: toward fine-tuning flow in biological microfluidics applications.

    Science.gov (United States)

    Cheah, Lih Tyng; Fritsch, Ingrid; Haswell, Stephen J; Greenman, John

    2012-07-01

    A microfluidic system containing a chamber for heart tissue biopsies, perfused with Krebs-Henseleit buffer containing glucose and antibiotic (KHGB) using peristaltic pumps and continuously stimulated, was used to evaluate tissue viability under redox-magnetohydrodynamics (redox-MHD) conditions. Redox-MHD possesses unique capabilities to control fluid flow using ionic current from oxidation and reduction processes at electrodes in a magnetic field, making it attractive to fine-tune fluid flow around tissues for "tissue-on-a-chip" applications. The manuscript describes a parallel setup to study two tissue samples simultaneously, and 6-min static incubation with Triton X100. Tissue viability was subsequently determined by assaying perfusate for lactate dehydrogenase (LDH) activity, where LDH serves as an injury marker. Incubation with KHGB containing 5 mM hexaammineruthenium(III) (ruhex) redox species with and without a pair of NdFeB magnets (∼ 0.39 T, placed parallel to the chamber) exhibited no additional tissue insult. MHD fluid flow, viewed by tracking microbeads with microscopy, occurred only when the magnet was present and stimulating electrodes were activated. Pulsating MHD flow with a frequency similar to the stimulating waveform was superimposed over thermal convection (from a hotplate) for Triton-KHGB, but fluid speed was up to twice as fast for ruhex-Triton-KHGB. A large transient ionic current, achieved when switching on the stimulating electrodes, generates MHD perturbations visible over varying peristaltic flow. The well-controlled flow methodology of redox-MHD is applicable to any tissue type, being useful in various drug uptake and toxicity studies, and can be combined equally with on- or off-device analysis modalities. Copyright © 2012 Wiley Periodicals, Inc.

  4. Modulation of redox homeostasis under suboptimal conditions by Arabidopsis nudix hydrolase 7

    Directory of Open Access Journals (Sweden)

    Jambunathan Niranjani

    2010-08-01

    differences observed in growth phenotypes of the Atnudt7-1 knockout mutants can be due to differences in the nutrient composition of potting mix. Our data suggests AtNUDT7 plays an important role in maintaining redox homeostasis, particularly for maintaining NADH:NAD+ balance for normal growth and development. During stress conditions, rapid induction of AtNUDT7 is important for regulating the activation of stress/defense signaling and cell death pathways.

  5. Evidence for local and global redox conditions at an Early Ordovician (Tremadocian) mass extinction

    Science.gov (United States)

    Edwards, Cole T.; Fike, David A.; Saltzman, Matthew R.; Lu, Wanyi; Lu, Zunli

    2018-01-01

    Profound changes in environmental conditions, particularly atmospheric oxygen levels, are thought to be important drivers of several major biotic events (e.g. mass extinctions and diversifications). The early Paleozoic represents a key interval in the oxygenation of the ocean-atmosphere system and evolution of the biosphere. Global proxies (e.g. carbon (δ13C) and sulfur (δ34S) isotopes) are used to diagnose potential changes in oxygenation and infer causes of environmental change and biotic turnover. The Cambrian-Ordovician contains several trilobite extinctions (some are apparently local, but others are globally correlative) that are attributed to anoxia based on coeval positive δ13C and δ34S excursions. These extinction and excursion events have yet to be coupled with more recently developed proxies thought to be more reflective of local redox conditions in the water column (e.g. I/Ca) to confirm whether these extinctions were associated with oxygen crises over a regional or global scale. Here we examine an Early Ordovician (Tremadocian Stage) extinction event previously interpreted to reflect a continuation of recurrent early Paleozoic anoxic events that expanded into nearshore environments. δ13C, δ34S, and I/Ca trends were measured from three sections in the Great Basin region to test whether I/Ca trends support the notion that anoxia was locally present in the water column along the Laurentian margin. Evidence for anoxia is based on coincident, but not always synchronous, positive δ13C and δ34S excursions (mainly from carbonate-associated sulfate and less so from pyrite data), a 30% extinction of standing generic diversity, and near-zero I/Ca values. Although evidence for local water column anoxia from the I/Ca proxy broadly agrees with intervals of global anoxia inferred from δ13C and δ34S trends, a more complex picture is evident where spatially and temporally variable local trends are superimposed on time-averaged global trends. Stratigraphic

  6. Magnetic Field Fluctuations in the High Ionosphere at Polar Latitudes: Impact of the IMF Conditions

    Science.gov (United States)

    De Michelis, P.; Consolini, G.; Tozzi, R.

    2016-12-01

    The characterization of ionospheric turbulence plays an important role for all those communication systems affected by the ionospheric medium. For instance, independently of geomagnetic latitude, ionospheric turbulence represents a considerable issue for all Global Navigation Satellite Systems (GNSS). Swarm constellation measurements of the Earth's magnetic field allow a precise characterization of ionospheric turbulence. This is possible using a range of indices derived from the analysis of the scaling properties of the geomagnetic field. In particular, by the scaling properties of the 1st order structure function, a scale index can be obtained, with a consequent characterization of the degree of persistence of the fluctuations and of their spectral properties. The knowledge of this index provides a global characterization of the nature and level of ionospheric turbulence on a local scale, which can be displayed along a single satellite orbit or through maps over the region of interest. The present work focuses on the analysis of the scaling properties of the 1st order structure function of magnetic field fluctuations measured by Swarm constellation at polar latitudes in the Northern Hemisphere. They are studied according to different interplanetary magnetic field conditions and Earth's seasons to characterize the possible drivers of magnetic field variability. The obtained results are discussed in the framework of Sun-Earth relationship and ionospheric polar convection. This work is supported by the Italian National Program for Antarctic Research (PNRA) Research Project 2013/AC3.08

  7. Physiological response of Crocosphaera watsonii to enhanced and fluctuating carbon dioxide conditions.

    Directory of Open Access Journals (Sweden)

    Mary R Gradoville

    Full Text Available We investigated the effects of elevated pCO2 on cultures of the unicellular N2-fixing cyanobacterium Crocosphaera watsonii WH8501. Using CO2-enriched air, cultures grown in batch mode under high light intensity were exposed to initial conditions approximating current atmospheric CO2 concentrations (∼ 400 ppm as well as CO2 levels corresponding to low- and high-end predictions for the year 2100 (∼ 750 and 1000 ppm. Following acclimation to CO2 levels, the concentrations of particulate carbon (PC, particulate nitrogen (PN, and cells were measured over the diurnal cycle for a six-day period spanning exponential and early stationary growth phases. High rates of photosynthesis and respiration resulted in biologically induced pCO2 fluctuations in all treatments. Despite this observed pCO2 variability, and consistent with previous experiments conducted under stable pCO2 conditions, we observed that elevated mean pCO2 enhanced rates of PC production, PN production, and growth. During exponential growth phase, rates of PC and PN production increased by ∼ 1.2- and ∼ 1.5-fold in the mid- and high-CO2 treatments, respectively, when compared to the low-CO2 treatment. Elevated pCO2 also enhanced PC and PN production rates during early stationary growth phase. In all treatments, PC and PN cellular content displayed a strong diurnal rhythm, with particulate C:N molar ratios reaching a high of 22:1 in the light and a low of 5.5:1 in the dark. The pCO2 enhancement of metabolic rates persisted despite pCO2 variability, suggesting a consistent positive response of Crocosphaera to elevated and fluctuating pCO2 conditions.

  8. Numerical simulation of pressure fluctuation of a pump-turbine with MGV at no-load condition

    International Nuclear Information System (INIS)

    Liu, J T; Wang, L Q; Liu, S H; Sun, Y K; Wu, Y L

    2012-01-01

    In order to analyse the pressure fluctuation caused by misaligned guide vanes (MGV) during starting period at no-load condition, 3-D (three dimensional), unsteady flows in a pump-turbine were numerically studied. Pressure fluctuations of different points at no-load condition are obtained. Fast Fourier Transform(FFT) was used to analyse the frequency spectrum of pressure fluctuations. The amplitude and dominant frequency of pressure fluctuation at vaneless space between the runner and guide vane, as well as the inlet of draft tube, was investigated. The amplitude of pressure fluctuation of the pump-turbine with MGV device is twice that of synchronous vanes. This might be caused by the non-uniform flow in the pump-turbine due to the pre-opened guide vanes. The pump-turbine with synchronous vanes has a low frequency which is 0.33f n , while the low frequency changes into 0.63f n when the MGV device is used. The vortex rope in the draft tube is large than that of synchronize vanes. Resultsof pressure fluctuations with synchronous vanes agree with each other between computational and testing results. The numerical study of pressure fluctuations with MGV can provide a basic understanding for the improvement of the instability of a pump-turbine.

  9. Determination of dissolution rates of spent fuel in carbonate solutions under different redox conditions with a flow-through experiment

    International Nuclear Information System (INIS)

    Roellin, S.; Spahiu, K.; Eklund, U.-B.

    2001-01-01

    Dissolution rates of spent UO 2 fuel have been investigated using flow-through experiments under oxidizing, anoxic and reducing conditions. For oxidizing conditions, approximately congruent dissolution rates were obtained in the pH range 3-9.3 for U, Np, Ba, Tc, Cs, Sr and Rb. For these elements, steady-state conditions were obtained in the flow rate range 0.02-0.3 ml min -1 . The dissolution rates were about 3 mg d -1 m -2 for pH>6. For pH 2 (g) saturated solutions dropped by up to four orders of magnitude as compared to oxidizing conditions. Because of the very low concentrations, only U, Pu, Am, Mo, Tc and Cs could be measured. For anoxic conditions, both the redox potential and dissolution rates increased approaching the same values as under oxidizing conditions

  10. An anaerobic field injection experiment in a landfill leachate plume, Grindsted, Denmark: 2. Deduction of anaerobic (methanogenic, sulfate-, and Fe (III)-reducing) redox conditions

    Science.gov (United States)

    Albrechtsen, Hans-JøRgen; Bjerg, Poul L.; Ludvigsen, Liselotte; Rügge, Kirsten; Christensen, Thomas H.

    1999-04-01

    Redox conditions may be environmental factors which affect the fate of the xenobiotic organic compounds. Therefore the redox conditions were characterized in an anaerobic, leachate-contaminated aquifer 15-60 m downgradient from the Grindsted Landfill, Denmark, where an field injection experiment was carried out. Furthermore, the stability of the redox conditions spatially and over time were investigated, and different approaches to deduce the redox conditions were evaluated. The redox conditions were evaluated in a set of 20 sediment and groundwater samples taken from locations adjacent to the sediment samples. Samples were investigated with respect to groundwater chemistry, including hydrogen and volatile fatty acids (VFAs) and sediment geochemistry, and bioassays were performed. The groundwater chemistry, including redox sensitive species for a large number of samples, varied over time during the experimental period of 924 days owing to variations in the leachate from the landfill. However, no indication of change in the redox environment resulting from the field injection experiment or natural variation was observed in the individual sampling points. The methane, Fe(II), hydrogen, and VFA groundwater chemistry parameters strongly indicated a Fe(III)-reducing environment. This was further supported by the bioassays, although methane production and sulfate-reduction were also observed in a few samples close to the landfill. On the basis of the calculated carbon conversion, Fe(III) was the dominant electron acceptor in the region of the aquifer, which was investigated. Because of the complexity of a landfill leachate plume, several redox processes may occur simultaneously, and an array of methods must be applied for redox characterization in such multicomponent systems.

  11. Prediction and visualization of redox conditions in the groundwater of Central Valley, California

    Science.gov (United States)

    Rosecrans, Celia Z.; Nolan, Bernard T.; Gronberg, JoAnn M.

    2017-03-01

    Regional-scale, three-dimensional continuous probability models, were constructed for aspects of redox conditions in the groundwater system of the Central Valley, California. These models yield grids depicting the probability that groundwater in a particular location will have dissolved oxygen (DO) concentrations less than selected threshold values representing anoxic groundwater conditions, or will have dissolved manganese (Mn) concentrations greater than selected threshold values representing secondary drinking water-quality contaminant levels (SMCL) and health-based screening levels (HBSL). The probability models were constrained by the alluvial boundary of the Central Valley to a depth of approximately 300 m. Probability distribution grids can be extracted from the 3-D models at any desired depth, and are of interest to water-resource managers, water-quality researchers, and groundwater modelers concerned with the occurrence of natural and anthropogenic contaminants related to anoxic conditions. Models were constructed using a Boosted Regression Trees (BRT) machine learning technique that produces many trees as part of an additive model and has the ability to handle many variables, automatically incorporate interactions, and is resistant to collinearity. Machine learning methods for statistical prediction are becoming increasing popular in that they do not require assumptions associated with traditional hypothesis testing. Models were constructed using measured dissolved oxygen and manganese concentrations sampled from 2767 wells within the alluvial boundary of the Central Valley, and over 60 explanatory variables representing regional-scale soil properties, soil chemistry, land use, aquifer textures, and aquifer hydrologic properties. Models were trained on a USGS dataset of 932 wells, and evaluated on an independent hold-out dataset of 1835 wells from the California Division of Drinking Water. We used cross-validation to assess the predictive performance of

  12. Prediction and visualization of redox conditions in the groundwater of Central Valley, California

    Science.gov (United States)

    Rosecrans, Celia Z.; Nolan, Bernard T.; Gronberg, JoAnn M.

    2017-01-01

    Regional-scale, three-dimensional continuous probability models, were constructed for aspects of redox conditions in the groundwater system of the Central Valley, California. These models yield grids depicting the probability that groundwater in a particular location will have dissolved oxygen (DO) concentrations less than selected threshold values representing anoxic groundwater conditions, or will have dissolved manganese (Mn) concentrations greater than selected threshold values representing secondary drinking water-quality contaminant levels (SMCL) and health-based screening levels (HBSL). The probability models were constrained by the alluvial boundary of the Central Valley to a depth of approximately 300 m. Probability distribution grids can be extracted from the 3-D models at any desired depth, and are of interest to water-resource managers, water-quality researchers, and groundwater modelers concerned with the occurrence of natural and anthropogenic contaminants related to anoxic conditions.Models were constructed using a Boosted Regression Trees (BRT) machine learning technique that produces many trees as part of an additive model and has the ability to handle many variables, automatically incorporate interactions, and is resistant to collinearity. Machine learning methods for statistical prediction are becoming increasing popular in that they do not require assumptions associated with traditional hypothesis testing. Models were constructed using measured dissolved oxygen and manganese concentrations sampled from 2767 wells within the alluvial boundary of the Central Valley, and over 60 explanatory variables representing regional-scale soil properties, soil chemistry, land use, aquifer textures, and aquifer hydrologic properties. Models were trained on a USGS dataset of 932 wells, and evaluated on an independent hold-out dataset of 1835 wells from the California Division of Drinking Water. We used cross-validation to assess the predictive performance of

  13. Direct approach for the fluctuation-dissipation theorem under nonequilibrium steady-state conditions

    Science.gov (United States)

    Komori, Kentaro; Enomoto, Yutaro; Takeda, Hiroki; Michimura, Yuta; Somiya, Kentaro; Ando, Masaki; Ballmer, Stefan W.

    2018-05-01

    The test mass suspensions of cryogenic gravitational-wave detectors such as the KAGRA project are tasked with extracting the heat deposited on the optics. These suspensions have a nonuniform temperature, requiring the calculation of thermal noise in nonequilibrium conditions. While it is not possible to describe the whole suspension system with one temperature, the local temperature at every point in the system is still well defined. We therefore generalize the application of the fluctuation-dissipation theorem to mechanical systems, pioneered by Saulson and Levin, to nonequilibrium conditions in which a temperature can only be defined locally. The result is intuitive in the sense that the thermal noise in the observed degree of freedom is given by averaging the temperature field, weighted by the dissipation density associated with that particular degree of freedom. After proving this theorem, we apply the result to examples of increasing complexity: a simple spring, the bending of a pendulum suspension fiber, and a model of the KAGRA cryogenic suspension. We conclude by outlining the application to nonequilibrium thermoelastic noise.

  14. Benthic flux of dissolved organic matter from lake sediment at different redox conditions and the possible effects of biogeochemical processes.

    Science.gov (United States)

    Yang, Liyang; Choi, Jung Hyun; Hur, Jin

    2014-09-15

    The benthic fluxes of dissolved organic carbon (DOC), chromophoric and fluorescent dissolved organic matter (CDOM and FDOM) were studied for the sediment from an artificial lake, based on laboratory benthic chamber experiments. Conservative estimates for the benthic flux of DOC were 71 ± 142 and 51 ± 101 mg m(-2) day(-1) at hypoxic and oxic conditions, respectively. Two humic-like (C1 and C2), one tryptophan-like (C3), and one microbial humic-like (C4) components were identified from the samples using fluorescence excitation emission matrices and parallel factor analysis (EEM-PARAFAC). During the incubation period, C3 was removed while C4 was accumulated in the overlying water with no significant difference in the trends between the redox conditions. The humification index (HIX) increased with time. The combined results for C3, C4 and HIX suggested that microbial transformation may be an important process affecting the flux behaviors of DOM. In contrast, the overall accumulations of CDOM, C1, and C2 in the overlying water occurred only for the hypoxic condition, which was possibly explained by their enhanced photo-degradation and sorption to redox-sensitive minerals under the oxic condition. Our study demonstrated significant benthic flux of DOM in lake sediment and also the possible involvement of biogeochemical transformation in the processes, providing insight into carbon cycling in inland waters. Copyright © 2014 Elsevier Ltd. All rights reserved.

  15. The Redox Code.

    Science.gov (United States)

    Jones, Dean P; Sies, Helmut

    2015-09-20

    The redox code is a set of principles that defines the positioning of the nicotinamide adenine dinucleotide (NAD, NADP) and thiol/disulfide and other redox systems as well as the thiol redox proteome in space and time in biological systems. The code is richly elaborated in an oxygen-dependent life, where activation/deactivation cycles involving O₂ and H₂O₂ contribute to spatiotemporal organization for differentiation, development, and adaptation to the environment. Disruption of this organizational structure during oxidative stress represents a fundamental mechanism in system failure and disease. Methodology in assessing components of the redox code under physiological conditions has progressed, permitting insight into spatiotemporal organization and allowing for identification of redox partners in redox proteomics and redox metabolomics. Complexity of redox networks and redox regulation is being revealed step by step, yet much still needs to be learned. Detailed knowledge of the molecular patterns generated from the principles of the redox code under defined physiological or pathological conditions in cells and organs will contribute to understanding the redox component in health and disease. Ultimately, there will be a scientific basis to a modern redox medicine.

  16. Effect of redox conditions on bacterial and fungal biomass and carbon dioxide production in Louisiana coastal swamp forest sediment

    International Nuclear Information System (INIS)

    Seo, Dong Cheol; DeLaune, Ronald D.

    2010-01-01

    Fungal and bacterial carbon dioxide (CO 2 ) production/emission was determined under a range of redox conditions in sediment from a Louisiana swamp forest used for wastewater treatment. Sediment was incubated in microcosms at 6 Eh levels (-200, -100, 0, + 100, + 250 and + 400 mV) covering the anaerobic range found in wetland soil and sediment. Carbon dioxide production was determined by the substrate-induced respiration (SIR) inhibition method. Cycloheximide (C 15 H 23 NO 4 ) was used as the fungal inhibitor and streptomycin (C 21 H 39 N 7 O 12 ) as the bacterial inhibitor. Under moderately reducing conditions (Eh > + 250 mV), fungi contributed more than bacteria to the CO 2 production. Under highly reducing conditions (Eh ≤ 0 mV), bacteria contributed more than fungi to the total CO 2 production. The fungi/bacteria (F/B) ratios varied between 0.71-1.16 for microbial biomass C, and 0.54-0.94 for microbial biomass N. Under moderately reducing conditions (Eh ≥ + 100 mV), the F/B ratios for microbial biomass C and N were higher than that for highly reducing conditions (Eh ≤ 0 mV). In moderately reducing conditions (Eh ≥ + 100 mV), the C/N microbial biomass ratio for fungi (C/N: 13.54-14.26) was slightly higher than for bacteria (C/N: 9.61-12.07). Under highly reducing redox conditions (Eh ≤ 0 mV), the C/N microbial biomass ratio for fungi (C/N: 10.79-12.41) was higher than for bacteria (C/N: 8.21-9.14). For bacteria and fungi, the C/N microbial biomass ratios under moderately reducing conditions were higher than that in highly reducing conditions. Fungal CO 2 production from swamp forest could be of greater ecological significance under moderately reducing sediment conditions contributing to the greenhouse effect (GHE) and the global warming potential (GWP). However, increases in coastal submergence associated with global sea level rise and resultant decrease in sediment redox potential from increased flooding would likely shift CO 2 production to bacteria

  17. Redox-Magnetohydrodynamic Microfluidics Without Channels and Compatible with Electrochemical Detection Under Immunoassay Conditions

    Science.gov (United States)

    Weston, Melissa C.; Nash, Christena K.; Fritsch, Ingrid

    2010-01-01

    A unique capability of redox-magnetohydrodynamics (redox-MHD) for handling liquids on a small scale was demonstrated. A 1.2-μL solution plug was pumped from an injection site to a detector without the need for a channel to direct the flow. The redox pumping species did not interfere with enzymatic activity in a solution compatible with enzyme-linked immunoassays. Alkaline phosphatase (AP), a common enzyme label, converted p-aminophenyl phosphate (PAPP) to p-aminophenol (PAPR) in the presence of 2.5 mM Ru(NH3)6Cl2 and 2.5 mM Ru(NH3)6 Cl3, in 0.1 M Tris buffer (pH=9). A solution plug containing PAPP (no AP) was pumped through the surrounding solution containing AP (no PAPP), and the enzymatically-generated PAPR was easily detected and distinguishable electrochemically from the pumping species with square wave voltammetry down to 0.1 mM concentrations. The test device consisted of a silicon chip containing individually-addressable microband electrodes, placed on a 0.5-T NdFeB permanent magnet with the field oriented perpendicular to the chip. A 8.0-mm wide × 15.5-mm long × 1.5-mm high volume of solution was contained by a poly(dimethylsiloxane) gasket and capped with a glass slide. A steady-state fluid velocity of ~30 μm/s was generated in a reinforcing flow configuration between oppositely polarized sets of pumping electrodes with ~2.1 μA. PMID:20681513

  18. Mobility of Iron-Cyanide Complexes in a Humic Topsoil under Varying Redox Conditions

    Directory of Open Access Journals (Sweden)

    Thilo Rennert

    2009-01-01

    Full Text Available The potentially toxic Fe-CN complexes ferricyanide, [FeIII(CN6]3−, and ferrocyanide, [FeII(CN6]4−, undergo a variety of redox processes in soil, which affect their mobility. We carried out microcosm experiments with suspensions of a humic topsoil (pH 5.3; Corg 107 g kg-1 to which we added ferricyanide (20 mg l-1. We varied the redox potential (EH from −280 to 580 mV by using O2, N2 and glucose. The decrease of EH led to decreasing concentrations of Fe-CN complexes and partial reductive dissolution of (hydrous Fe and Mn oxides. The dynamics of aqueous Fe-CN concentrations was characterized by decreasing concentrations when the pH rose and the EH dropped. We attribute these dependencies to adsorption on organic surfaces, for which such a pH/EH behavior has been shown previously. Adsorption was reversible, because when the pH and EH changed into the opposite direction, desorption occurred. This study demonstrates the possible impact of soil organic matter on the fate of Fe-CN complexes in soil.

  19. Modelling growth of Penicillium expansum and Aspergillus niger at constant and fluctuating temperature conditions.

    Science.gov (United States)

    Gougouli, Maria; Koutsoumanis, Konstantinos P

    2010-06-15

    The growth of Penicillium expansum and Aspergillus niger, isolated from yogurt production environment, was investigated on malt extract agar with pH=4.2 and a(w)=0.997, simulating yogurt, at isothermal conditions ranging from -1.3 to 35 degrees C and from 5 to 42.3 degrees C, respectively. The growth rate (mu) and (apparent) lag time (lambda) of the mycelium growth were modelled as a function of temperature using a Cardinal Model with Inflection (CMI). The results showed that the CMI can describe successfully the effect of temperature on fungal growth within the entire biokinetic range for both isolates. The estimated values of the CMI for mu were T(min)=-5.74 degrees C, T(max)=30.97 degrees C, T(opt)=22.08 degrees C and mu(opt)=0.221 mm/h for P. expansum and T(min)=10.13 degrees C, T(max)=43.13 degrees C, T(opt)=31.44 degrees C, and mu(opt)=0.840 mm/h for A. niger. The cardinal values for lambda were very close to the respective values for mu indicating similar temperature dependence of the growth rate and the lag time of the mycelium growth. The developed models were further validated under fluctuating temperature conditions using various dynamic temperature scenarios. The time-temperature conditions studied included single temperature shifts before or after the end of the lag time and continuous periodic temperature fluctuations. The prediction of growth at changing temperature was based on the assumption that after a temperature shift the growth rate is adopted instantaneously to the new temperature, while the lag time was predicted using a cumulative lag approach. The results showed that when the temperature shifts occurred before the end of the lag, they did not cause any significant additional lag and the observed total lag was very close to the cumulative lag predicted by the model. In experiments with temperature shifts after the end of the lag time, accurate predictions were obtained when the temperature profile included temperatures which were inside the

  20. Electrodialytic extraction of Cr from water-washed MSWI fly ash by changing pH and redox conditions

    DEFF Research Database (Denmark)

    Chen, Wan; Kirkelund, Gunvor Marie; Jensen, Pernille Erland

    2018-01-01

    Electrodialytic process offers a range of possibilities to waste management by electrodialytic separation (EDS) of heavy metals, depending on how the process is designed. Using three EDS cell setups (two two-compartment and one three-compartment) and their combinations, the extraction of Cr from...... rate of 27.5%, is an improvement on the single-step that extracted maximum 3.1%. The highest extraction was obtained due to the combined extraction of Cr(III) under low pH (accompanied with high redox) conditions and Cr(VI) under high pH (low redox) conditions subsequently. The Cr leaching from...... the treated ashes with acidic pH was lower than from those with alkaline pH; after the three-step treatment, Cr leaching was much lower from the coarse fraction (> 50 µm), as compared to the fine (≤ 50 µm) or the unsieved ash. As for the coarse fraction, two/three-step treatment reduced the leaching of Cr...

  1. The influence of grating shape formation fluctuation on DFB laser diode threshold condition

    Science.gov (United States)

    Bao, Shiwei; Song, Qinghai; Xie, Chunmei

    2018-03-01

    Not only the grating material refractive index itself but also the Bragg grating physical shape formation affects the coupling strength greatly. The Bragg grating shape includes three factors, namely grating depth, duty ratio and grating angle. During the lithography and wet etching process, there always will be some fluctuation between the target and real grating shape formation after fabrication process. This grating shape fluctuation will affect the DFB coupling coefficient κ , and then consequently threshold current and corresponding wavelength. This paper studied the grating shape formation fluctuation influence to improve the DFB fabrication yield. A truncated normal random distribution fluctuation is considered in this paper. The simulation results conclude that it is better to choose relative thicker grating depth with lower refractive index to obtain a better fabrication tolerance, while not quite necessary to spend too much effort on improving lithography and wet etching process to get a precisely grating duty ratio and grating angle.

  2. Phosphorus recycling and burial in Baltic Sea sediments with contrasting redox conditions

    DEFF Research Database (Denmark)

    Mort, Haydon P; Slomp, Caroline P; Gustafson, Bo G

    2010-01-01

    . Most burial of P takes place as organic P. We find no evidence for significant authigenic Ca–P formation or biogenic Ca–P burial. The lack of major inorganic P burial sinks makes the Baltic Sea very sensitive to the feedback loop between increased hypoxia, enhanced regeneration of P and increased......In this study, redox-dependent phosphorus (P) recycling and burial at 6 sites in the Baltic Sea is investigated using a combination of porewater and sediment analyses and sediment age dating (210Pb and 137Cs). We focus on sites in the Kattegat, Danish Straits and Baltic Proper where present...... be accounted for in budgets and models for the Baltic Sea....

  3. Normalized rare earth elements in water, sediments, and wine: identifying sources and environmental redox conditions

    Science.gov (United States)

    Piper, David Z.; Bau, Michael

    2013-01-01

    The concentrations of the rare earth elements (REE) in surface waters and sediments, when normalized on an element-by-element basis to one of several rock standards and plotted versus atomic number, yield curves that reveal their partitioning between different sediment fractions and the sources of those fractions, for example, between terrestrial-derived lithogenous debris and seawater-derived biogenous detritus and hydrogenous metal oxides. The REE of ancient sediments support their partitioning into these same fractions and further contribute to the identification of the redox geochemistry of the sea water in which the sediments accumulated. The normalized curves of the REE that have been examined in several South American wine varietals can be interpreted to reflect the lithology of the bedrock on which the vines may have been grown, suggesting limited fractionation during soil development.

  4. Role of biotransformation, sorption and mineralization of "1"4C-labelled sulfamethoxazole under different redox conditions

    International Nuclear Information System (INIS)

    Alvarino, T.; Nastold, P.; Suarez, S.; Omil, F.; Corvini, P.F.X.; Bouju, H.

    2016-01-01

    "1"4C-sulfamethoxazole biotransformation, sorption and mineralization was studied with heterotrophic and autotrophic biomass under aerobic and anoxic conditions, as well as with anaerobic biomass. The "1"4C-radiolabelled residues distribution in the solid, liquid and gas phases was closely monitored along a total incubation time of 190 h. Biotransformation was the main removal mechanism, mineralization and sorption remaining below 5% in all the cases, although the presence of a carbon source exerted a positive effect on the mineralization rate by the aerobic heterotrophic bacteria. In fact, an influence of the type of primary substrate and the redox potential was observed in all cases on the biotransformation and mineralization rates, since an enhancement of the removal rate was observed when an external carbon source was used as a primary substrate under aerobic conditions, while a negligible effect was observed under nitrifying conditions. In the liquid phases collected from all assays, up to three additional peaks corresponding to "1"4C-radiolabelled residues were detected. The highest concentration was observed under anaerobic conditions, where two radioactive metabolites were detected representing each around 15% of the total applied radioactivity after 180 h incubation. One of the metabolites detected under anoxic and anaerobic conditions, is probably resulting from ring cleavage of the isoxazole ring. - Highlights: • New procedure based on "1"4C to determine sulfamethoxazole (SMX) removal • Complete SMX mass balances in solid, liquid and gas phases • Quantification of SMX biotransformation, mineralization and sorption • Influence of the primary metabolism and redox potential on SMX removal • SMX metabolites have been detected and a possible chemical structure was proposed.

  5. Role of biotransformation, sorption and mineralization of {sup 14}C-labelled sulfamethoxazole under different redox conditions

    Energy Technology Data Exchange (ETDEWEB)

    Alvarino, T., E-mail: teresa.alvarino@usc.es [Department of Chemical Engineering, Institute of Technology, University of Santiago de Compostela, E-15782 Santiago de Compostela (Spain); Nastold, P. [Institute for Ecopreneurship, School of Life Sciences, University of Applied Sciences Northwestern Switzerland, 40 Grundenstrasse, CH 4132 Muttenz (Switzerland); Suarez, S.; Omil, F. [Department of Chemical Engineering, Institute of Technology, University of Santiago de Compostela, E-15782 Santiago de Compostela (Spain); Corvini, P.F.X. [Institute for Ecopreneurship, School of Life Sciences, University of Applied Sciences Northwestern Switzerland, 40 Grundenstrasse, CH 4132 Muttenz (Switzerland); State Key Laboratory for Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210093 (China); Bouju, H. [Institute for Ecopreneurship, School of Life Sciences, University of Applied Sciences Northwestern Switzerland, 40 Grundenstrasse, CH 4132 Muttenz (Switzerland)

    2016-01-15

    {sup 14}C-sulfamethoxazole biotransformation, sorption and mineralization was studied with heterotrophic and autotrophic biomass under aerobic and anoxic conditions, as well as with anaerobic biomass. The {sup 14}C-radiolabelled residues distribution in the solid, liquid and gas phases was closely monitored along a total incubation time of 190 h. Biotransformation was the main removal mechanism, mineralization and sorption remaining below 5% in all the cases, although the presence of a carbon source exerted a positive effect on the mineralization rate by the aerobic heterotrophic bacteria. In fact, an influence of the type of primary substrate and the redox potential was observed in all cases on the biotransformation and mineralization rates, since an enhancement of the removal rate was observed when an external carbon source was used as a primary substrate under aerobic conditions, while a negligible effect was observed under nitrifying conditions. In the liquid phases collected from all assays, up to three additional peaks corresponding to {sup 14}C-radiolabelled residues were detected. The highest concentration was observed under anaerobic conditions, where two radioactive metabolites were detected representing each around 15% of the total applied radioactivity after 180 h incubation. One of the metabolites detected under anoxic and anaerobic conditions, is probably resulting from ring cleavage of the isoxazole ring. - Highlights: • New procedure based on {sup 14}C to determine sulfamethoxazole (SMX) removal • Complete SMX mass balances in solid, liquid and gas phases • Quantification of SMX biotransformation, mineralization and sorption • Influence of the primary metabolism and redox potential on SMX removal • SMX metabolites have been detected and a possible chemical structure was proposed.

  6. Harmonic Injection-Based Power Fluctuation Control of Three-Phase PV Systems under Unbalanced Grid Voltage Conditions

    Directory of Open Access Journals (Sweden)

    Nian-Cheng Zhou

    2015-02-01

    Full Text Available Unbalanced voltage will inevitably cause power and DC voltage fluctuations in a three-phase PV system. The deterioration of power quality will do great harm to the PV panels and the loads, so it is necessary to suppress the power fluctuations. This paper further explores the coefficients control strategy of PV converters under unbalanced voltage conditions, aiming to suppress power fluctuations by controlling the injection of some specific orders of current harmonics into the grid. In order to achieve this, the current reference of the PV inverter has been changed by bringing in two control coefficients, and the expression of each order of the current harmonics has been deduced. Based on the standards of PV systems, the regions from which the coefficients can be selected are determined. Then, by tuning these coefficients in the feasible regions, the output parameters (power fluctuation, current THD and odd harmonics can be controlled precisely. The model of this method is built and simulated in PSCAD/EMTDC, and as a result, it is shown that the power fluctuations can be restricted according to different power quality requirements.

  7. Photosynthetic acclimation of WS and WS-gpt2 in Arabidopsis thaliana under fluctuating natural light condition

    Science.gov (United States)

    Pa'ee, Furzani; Johnson, Giles

    2017-10-01

    Photoacclimation is a process by which photosynthetic capacity is regulated in response to environmental adjustments in terms of light regime. Photoacclimation is essential in determining the photosynthetic capacity to optimize light use and to avoid potentially damaging effects. Previous work in our laboratory has identified a gene, gpt2 (At1g61800) that is essential for plants to acclimate to an increase and decrease of growth irradiance, separately. To investigate the photoacclimation ability towards fluctuating natural light condition in Arabidopsis thaliana, photosynthetic capacity was measured in plants of the accession Wassileskija (WS) and in plants lacking expression of the gene At1g61800 (WS-gpt2). The experiment was carried out over a time span from early Autumn to early Spring season in 2010-2011 and 2011-2012. The seedlings were grown in an unheated greenhouse in Manchester, UK without supplementary lighting. Gas exchange measurements and chlorophyll content estimation were performed on WS and WS-gpt2 and it showed that both sets of plants were able to acclimate to fluctuating natural light condition. Therefore, it is suggested that the mechanisms of acclimation in a separate growth light condition is mechanistically distinct than the mechanism under fluctuating natural light condition.

  8. The elemental geochemistry of Lower Triassic shallow-marine carbonates from central Saudi Arabia: Implications for redox conditions in the immediate aftermath of the latest Permian mass extinction

    Science.gov (United States)

    Eltom, Hassan A.; Abdullatif, Osman M.; Babalola, Lamidi O.

    2018-03-01

    The southern margin of the Tethys Ocean was occupied by a broad, shallow continental shelf during the Permian-Triassic boundary interval, with the area of present-day Saudi Arabia located from 10° to 30° south of the paleo-equator. The strata deposited in modern Saudi Arabia in the aftermath of the latest Permian mass extinction (LPME) are dominated by oolitic microbialite limestone (OML), which are overlain by skeletal oolitic limestones (SOL) capped by dolostones and dolomitic limestones (DDL). This succession reflects changes in depositional setting, which can be potentially tied to redox conditions using redox sensitive trace elements and rare earth elements (REEs). Statistical analyses reveals that trace elements and REEs are associated with detrital material, and possibly with diagenetic minerals as well. Proxies such as the Y/Ho, Pr/Pr*, Smn/Ybn, Lan/Smn and Lan/Ybn ratios indicate that REEs do not record a seawater-like pattern, and cannot be used as redox indicator. The presence of a normal marine fauna implies oxic conditions during deposition of the DDL and SOL units. However, the OML unit, which represents the immediate aftermath of LPME, lacks both a normal marine fauna and reliable geochemical signals, making it difficult to infer redox conditions in the depositional environment. Similar to published data from sections that reflect shallow marine condition in the LPME of the Tethys Ocean, chemical index of alteration values are consistently high throughout the study succession, suggesting globally intense chemical weathering in the aftermath of the LPME. As a result, geochemical redox proxies in shallow marine carbonates of the Tethys Ocean are likely to be contaminated by detrital material that have been generated by chemical weathering, and thus, other methods are required to determine depositional redox conditions.

  9. Microbial C:P stoichiometry is shaped by redox conditions along an elevation gradient in humid tropical rainforests

    Science.gov (United States)

    Lin, Y.; Gross, A.; Silver, W. L.

    2017-12-01

    Elemental stoichiometry of microorganisms is intimately related to ecosystem carbon and nutrient fluxes and is ultimately controlled by the chemical (plant tissue, soil, redox) and physical (temperature, moisture, aeration) environment. Previous meta-analyses have shown that the C:P ratio of soil microbial biomass exhibits significant variations among and within biomes. Little is known about the underlying causes of this variability. We examined soil microbial C:P ratios along an elevation gradient in the Luquillo Experimental Forest in Puerto Rico. We analyzed soils from mixed forest paired with monodominant palm forest every 100 m from 300 m to 1000 m a.s.l.. Mean annual precipitation increased with increasing elevation, resulting in stronger reducing conditions and accumulation of soil Fe(II) at higher elevations. The mean value and variability of soil microbial C:P ratios generally increased with increasing elevation except at 1000 m. At high elevations (600-900 m), the average value of microbial C:P ratio (108±10:1) was significantly higher than the global average ( 55:1). We also found that soil organic P increased with increasing elevation, suggesting that an inhibition of organic P mineralization, not decreased soil P availability, may cause the high microbial C:P ratio. The soil microbial C:P ratio was positively correlated with soil HCl-extractable Fe(II), suggesting that reducing conditions may be responsible for the elevational changes observed. In a follow-up experiment, soils from mixed forests at four elevation levels (300, 500, 700, and 1000 m) were incubated under aerobic and anaerobic conditions for two weeks. We found that anaerobic incubation consistently increased the soil microbial C:P ratio relative to the aerobic incubation. Overall, our results indicate that redox conditions can shift the elemental composition of microbial biomass. The high microbial C:P ratios induced under anoxic conditions may reflect inhibition of microbial P

  10. Effects of redox conditions on the control of arsenic mobility in shallow alluvial aquifers on the Venetian Plain (Italy)

    Energy Technology Data Exchange (ETDEWEB)

    Carraro, A. [Institute of Geosciences and Earth Resources, National Research Council (CNR) of Italy, Padova, Italy c/o Department of Geosciences, University of Padova, 35131 Padova (Italy); Fabbri, P. [Institute of Geosciences and Earth Resources, National Research Council (CNR) of Italy, Padova, Italy c/o Department of Geosciences, University of Padova, 35131 Padova (Italy); Department of Geosciences, University of Padova, 35131 Padova (Italy); Giaretta, A.; Peruzzo, L.; Tateo, F.; Tellini, F. [Institute of Geosciences and Earth Resources, National Research Council (CNR) of Italy, Padova, Italy c/o Department of Geosciences, University of Padova, 35131 Padova (Italy)

    2015-11-01

    The Venetian Plain is known for the occurrence of areas with high concentrations of arsenic in groundwater (greater than 400 μg/L). The study area represents the typical residential, industrial and agricultural features of most Western countries and is devoid of hydrothermal, volcanic or anthropogenic sources of arsenic. The aim of the study is to model the arsenic mobilization and the water–rock interaction by a complete hydrogeochemical investigation (analyses of filtered and unfiltered groundwater sediment mineralogy and geochemistry). The groundwater arsenic contamination and redox conditions are highly variable. Groundwaters with oxidizing and strongly reducing potentials have much lower arsenic concentrations than do mildly reducing waters. The grain size of the aquifer sediments includes gravels, sands and silty-clays. A continuous range of organic material concentrations is observed (from zero to 40%). The amount of sedimentary organic matter is highly correlated with the arsenic content of the sediments (up to 300 mg/kg), whereas no relationships are detectable between arsenic and other chemical parameters. The occurrence of arsenic minerals was observed as a peculiar feature under the scanning electron microscope. Arsenic and sulfur are the sole constituents of small tufts or thin crystals concentrated in small masses. These arsenic minerals were clearly observed in the peat sediments, in agreement with the geochemical modeling that requires very reducing conditions for their precipitation from the groundwater. The modeling suggests that, under oxidizing conditions, arsenic is adsorbed; moreover, a continuous decrease in the redox potential causes increasing desorption of arsenic. If the reducing conditions become more intense, the formation of As-S minerals would explain the lower concentration of arsenic measured in the strongly reducing groundwater. Even if As-sulfides are rare under low-temperature conditions, the anomalous abundance of reductants

  11. Effects of redox conditions on the control of arsenic mobility in shallow alluvial aquifers on the Venetian Plain (Italy)

    International Nuclear Information System (INIS)

    Carraro, A.; Fabbri, P.; Giaretta, A.; Peruzzo, L.; Tateo, F.; Tellini, F.

    2015-01-01

    The Venetian Plain is known for the occurrence of areas with high concentrations of arsenic in groundwater (greater than 400 μg/L). The study area represents the typical residential, industrial and agricultural features of most Western countries and is devoid of hydrothermal, volcanic or anthropogenic sources of arsenic. The aim of the study is to model the arsenic mobilization and the water–rock interaction by a complete hydrogeochemical investigation (analyses of filtered and unfiltered groundwater sediment mineralogy and geochemistry). The groundwater arsenic contamination and redox conditions are highly variable. Groundwaters with oxidizing and strongly reducing potentials have much lower arsenic concentrations than do mildly reducing waters. The grain size of the aquifer sediments includes gravels, sands and silty-clays. A continuous range of organic material concentrations is observed (from zero to 40%). The amount of sedimentary organic matter is highly correlated with the arsenic content of the sediments (up to 300 mg/kg), whereas no relationships are detectable between arsenic and other chemical parameters. The occurrence of arsenic minerals was observed as a peculiar feature under the scanning electron microscope. Arsenic and sulfur are the sole constituents of small tufts or thin crystals concentrated in small masses. These arsenic minerals were clearly observed in the peat sediments, in agreement with the geochemical modeling that requires very reducing conditions for their precipitation from the groundwater. The modeling suggests that, under oxidizing conditions, arsenic is adsorbed; moreover, a continuous decrease in the redox potential causes increasing desorption of arsenic. If the reducing conditions become more intense, the formation of As-S minerals would explain the lower concentration of arsenic measured in the strongly reducing groundwater. Even if As-sulfides are rare under low-temperature conditions, the anomalous abundance of reductants

  12. Hydrologic influence on redox dynamics in estuarine environments

    Science.gov (United States)

    Michael, H. A.; Kim, K. H.; Guimond, J. A.; Heiss, J.; Ullman, W. J.; Seyfferth, A.

    2017-12-01

    Redox conditions in coastal aquifers control reactions that impact nutrient cycling, contaminant release, and carbon budgets, with implications for water resources and ecosystem health. Hydrologic changes can shift redox boundaries and inputs of reactants, especially in dynamic coastal systems subject to fluctuations on tidal, lunar, and longer timescales. We present two examples of redox shifts in estuarine systems in Delaware, USA: a beach aquifer and a saltmarsh. Beach aquifers are biogeochemical hot spots due to mixing between fresh groundwater and infiltrating seawater. At Cape Henlopen, DE, geochemical measurements identified reactions in the intertidal aquifer that include cycling of carbon, nitrogen, iron, and sulfur. Measurements and modeling illustrate that redox potential as well as the locations of redox reactions shift on tidal to seasonal timescales and in response to changing beach and aquifer properties, impacting overall rates of reactions such as denitrification that reduces N loads to coastal waters. In the St. Jones National Estuarine Research Reserve, tidal fluctuations in channels cause periodic groundwater-surface water exchange, water table movement, and intermittent flooding that varies spatially across the saltmarsh. These changes create shifts in redox potential that are greatest near channels and in the top 20 cm of sediments. The magnitude of redox change depends on hydrologic setting (near channels or in marsh interior), hydrologic conditions (tidal stage, seasonal shifts), as well as prevalence of macropores created by crab burrows that change seasonally with crab activity. These shifts correspond to changes in porewater chemistry that have implications for nutrient cycling and carbon export to the ocean. Understanding hydrologic influence on redox geochemistry is critical for predicting how these systems and their ecosystem services may change in the future in response to anthropogenic and climate change.

  13. Biodegradation of RDX within soil-water slurries using a combination of differing redox incubation conditions

    International Nuclear Information System (INIS)

    Waisner, S.; Hansen, L.; Fredrickson, H.; Nestler, C.; Zappi, M.; Banerji, S.; Bajpai, R.

    2002-01-01

    Biodegradation of 14 C-tagged hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) was studied in aerobic, anaerobic, and anaerobic/aerobic slurries to identify the conditions maximizing RDX-mineralization in Cornhusker Army Ammunition Plant (CAAP, NE) groundwater. Supplementation with phosphate and adequate quantities of acetate caused 25% mineralization of RDX in 3 weeks by microorganisms native to CAAP. Under anaerobic conditions, the same supplementation resulted in 20% mineralization in 3 weeks and 30% mineralization in 6 weeks. The highest degree of mineralization (50%) was obtained under aerobic conditions when the contaminated groundwater was augmented with a consortium of three microbes isolated from another RDX contaminated soil (Hastings, NE) in addition to supplemented with phosphate and acetic acid. Use of complex organic sources (potato or corn starch) slowed down the rates of mineralization under anaerobic conditions, but rapid mineralization ensued as soon as the aerobic conditions were created. Final RDX concentrations in aqueous phase were below detection limit under most conditions. Assimilation of RDX by the cells was negligible

  14. Modeling the effects of evolving redox conditions on the corrosion of copper containers

    International Nuclear Information System (INIS)

    Kng, F.; LeNeveu, D.M.; Jobe, D.J.

    1994-01-01

    The corrosive environment around the containers in a Canadian nuclear fuel waste disposal vault will change over time from open-quotes warm and oxidizingclose quotes to open-quotes cool and anoxic.close quotes As the conditions change, so too will the corrosion behaviour of the containers. For copper containers, uniform corrosion and, possibly, pitting will occur during the initial aggressive phase, to be replaced by slow uniform corrosion during the long-term anoxic period. The corrosion behaviour of copper has been studied over a range of conditions representing all phases in the evolution of the vault environment. The results of these studies are summarized and used to illustrate how a model can be developed to predict the corrosion behaviour and container lifetimes over long periods of time. Lifetimes in excess of 10 6 a are predicted for 25-mm-thick copper containers under Canadian disposal conditions

  15. Modeling the lag period and exponential growth of Listeria monocytogenes under conditions of fluctuating temperature and water activity values.

    Science.gov (United States)

    Muñoz-Cuevas, Marina; Fernández, Pablo S; George, Susan; Pin, Carmen

    2010-05-01

    The dynamic model for the growth of a bacterial population described by Baranyi and Roberts (J. Baranyi and T. A. Roberts, Int. J. Food Microbiol. 23:277-294, 1994) was applied to model the lag period and exponential growth of Listeria monocytogenes under conditions of fluctuating temperature and water activity (a(w)) values. To model the duration of the lag phase, the dependence of the parameter h(0), which quantifies the amount of work done during the lag period, on the previous and current environmental conditions was determined experimentally. This parameter depended not only on the magnitude of the change between the previous and current environmental conditions but also on the current growth conditions. In an exponentially growing population, any change in the environment requiring a certain amount of work to adapt to the new conditions initiated a lag period that lasted until that work was finished. Observations for several scenarios in which exponential growth was halted by a sudden change in the temperature and/or a(w) were in good agreement with predictions. When a population already in a lag period was subjected to environmental fluctuations, the system was reset with a new lag phase. The work to be done during the new lag phase was estimated to be the workload due to the environmental change plus the unfinished workload from the uncompleted previous lag phase.

  16. Modeling the Lag Period and Exponential Growth of Listeria monocytogenes under Conditions of Fluctuating Temperature and Water Activity Values▿

    Science.gov (United States)

    Muñoz-Cuevas, Marina; Fernández, Pablo S.; George, Susan; Pin, Carmen

    2010-01-01

    The dynamic model for the growth of a bacterial population described by Baranyi and Roberts (J. Baranyi and T. A. Roberts, Int. J. Food Microbiol. 23:277-294, 1994) was applied to model the lag period and exponential growth of Listeria monocytogenes under conditions of fluctuating temperature and water activity (aw) values. To model the duration of the lag phase, the dependence of the parameter h0, which quantifies the amount of work done during the lag period, on the previous and current environmental conditions was determined experimentally. This parameter depended not only on the magnitude of the change between the previous and current environmental conditions but also on the current growth conditions. In an exponentially growing population, any change in the environment requiring a certain amount of work to adapt to the new conditions initiated a lag period that lasted until that work was finished. Observations for several scenarios in which exponential growth was halted by a sudden change in the temperature and/or aw were in good agreement with predictions. When a population already in a lag period was subjected to environmental fluctuations, the system was reset with a new lag phase. The work to be done during the new lag phase was estimated to be the workload due to the environmental change plus the unfinished workload from the uncompleted previous lag phase. PMID:20208022

  17. Redox conditions and marine microbial community changes during the end-Ordovician mass extinction event

    Science.gov (United States)

    Smolarek, Justyna; Marynowski, Leszek; Trela, Wiesław; Kujawski, Piotr; Simoneit, Bernd R. T.

    2017-02-01

    The end-Ordovician (Hirnantian) crisis is the first globally distinct extinction during the Phanerozoic, but its causes are still not fully known. Here, we present an integrated geochemical and petrographic analysis to understand the sedimentary conditions taking place before, during and after the Late Ordovician ice age. New data from the Zbrza (Holy Cross Mountains) and Gołdap (Baltic Depression) boreholes shows that, like in other worldwide sections, the total organic carbon (TOC) content is elevated in the upper Katian and uppermost Hirnantian to Rhudannian black shales, but depleted (below 1%) during most of the Hirnantian. Euxinic conditions occurred in the photic zone in both TOC-rich intervals. This is based on the maleimide distribution, occurrence of aryl isoprenoids and isorenieratane, as well as a dominance of tiny pyrite framboids. Euxinic conditions were interrupted by the Hirnantian regression caused by glaciation. Sedimentation on the deep shelf changed to aerobic probably due to intense thermohaline circulation. Euxinia in the water column occurred directly during the time associated with the second pulse of the mass extinction with a termination of the end-Ordovician glaciation and sea level rise just at the Ordovician/Silurian (O/S) boundary. In contrast, we suggest based on inorganic proxies that bottom water conditions were generally oxic to dysoxic due to upwelling in the Rheic Ocean. The only episode of seafloor anoxia in the Zbrza basin was found at the O/S boundary, where all inorganic indicators showed elevated values typical for anoxia (U/Th > 1.25; V/Cr > 4.25; V/(V + Ni): 0.54-0.82 and Mo > 10-25 ppm). Significant differences in hopanes to steranes ratio and in C27-C29 sterane distribution between the Katian, Rhudannian and Hirnantian deposits indicate changes in marine microbial communities triggered by sharp climate change and Gondwana glaciation. The increase from biomarkers of cyanobacteria (2α-methylhopanes) after the O

  18. Determination of freeze-out conditions from fluctuations in the Hadron Resonance Gas model

    International Nuclear Information System (INIS)

    Alba, P; Alberico, W; Sarti, V Mantovani; Ratti, C; Bellwied, R; Bluhm, M; Nahrgang, M

    2015-01-01

    Fluctuations of conserved charges measured in Heavy-Ion Collisions (HICs) received increasing attention in recent years, because they are good candidates to explore the phase diagram of QCD matter. During the last year, net-electric charge and net-proton moments of multiplicities measured at RHIC have been published by the STAR collaboration, for a range of collision energies which spans a region of the phase diagram at finite chemical potential. Here we present a new freeze-out curve obtained using the Hadron Resonance Gas (HRG) model approach to fit these experimental data. The HRG model is modified in order to have a realistic description of the HICs: kinematic cuts, resonance feed-down and resonance regeneration are taken into account. Our result is in agreement with preliminary studies by the ALICE collaboration, and is supported by a recent lattice analysis of the same quantities. (paper)

  19. Earthworm responses to Cd and Cu under fluctuating environmental conditions: a comparison with results from laboratory exposures

    International Nuclear Information System (INIS)

    Spurgeon, David J.; Svendsen, Claus; Lister, Lindsay J.; Hankard, Peter K.; Kille, Peter

    2005-01-01

    Laboratory toxicity tests are usually conducted under stable ambient conditions, while exposures in ecosystems occur in a fluctuating climate. To assess how climate influences the toxicity of Cu and Cd for the earthworm Lumbricus rubellus, this study compared effects for life-cycle parameters (survival, reproduction), cellular status (lysosomal membrane stability), gene expression (transcript of the metal binding protein metallothionein-2) and tissue metal concentration measured under outdoor conditions, with the same responses under constant conditions as measured by Spurgeon et al. [Spurgeon, D.J., Svendsen, C., Weeks, J.M., Hankard, P.K., Stubberud, H.E., Kammenga, J.E., 2003. Quantifying copper and cadmium impacts on intrinsic rate of population increase in the terrestrial oligochaete Lumbricus rubellus. Environmental Toxicology and Chemistry 22, 1465-1472]. Both metals were found to significantly influence earthworm reproduction, compromise lysosomal membrane stability and induce MT-2 gene expression in the outdoor system. Comparison with physiological and life-cycle responses in the laboratory indicated similar response patterns and effect concentrations for Cu. For Cd, lysosomal membrane stability and MT-2expression showed comparable responses in both exposures. Juvenile production rate, however, gave different dose response relationships, with the EC- 50 in the outdoor test approximately half that in the laboratory test. A difference in Cd accumulation was also seen. Overall, however, the comparison indicated only a marginal effect of environmental fluctuations typical for northern temperate Europe on earthworm sensitivity to the two metals. - Comparative analysis of life-cycle, physiological and molecular responses to Cu and Cd indicate similar responses under static and fluctuating climate regimes

  20. Redox fronts

    International Nuclear Information System (INIS)

    Chapman, N.; McKinley, I.; Shea, M.; Smellie, J.

    1993-01-01

    This article describes the investigations of redox fronts performed at the Osamu Utsumi mine. Results obtained by modelling groups on the rate of movement of the redox fronts and on the chemical reactions involved are discussed. Some of the most important rockwater interactions which occur at redox fronts can be modelled reasonably well but the complex redox chemistry of elements like sulphur is poorly simulated. The observed enrichment of many trace elements close to the redox fronts could be of significance for high-level waste repositories, but cannot be quantified by existing models. (author) 6 figs., 1 tab

  1. Mercury transformations in resuspended contaminated sediment controlled by redox conditions, chemical speciation and sources of organic matter

    Science.gov (United States)

    Zhu, Wei; Song, Yu; Adediran, Gbotemi A.; Jiang, Tao; Reis, Ana T.; Pereira, Eduarda; Skyllberg, Ulf; Björn, Erik

    2018-01-01

    Mercury (Hg) contaminated sediments can be significant sources of Hg in aquatic ecosystems and, through re-emission processes, to the atmosphere. Transformation and release of Hg may be enhanced by various sediment perturbation processes, and controlling biogeochemical factors largely remain unclear. We investigated how rates of Hg transformations in pulp-fiber enriched sediment contaminated by Hg from chlor-alkali industry were controlled by (i) transient redox-changes in sulfur and iron chemistry, (ii) the chemical speciation and solubility of Hg, and (iii) the sources and characteristics of organic matter (OM). Sediment-bottom water microcosm systems were exposed to four combinations of air and nitrogen gas for a total time of 24 h. The treatments were: 24 h N2, 0.5 h air + 23.5 h N2, 4 h air + 20 h N2 and 24 h of air exposure. As a result of these treatments, microcosms spanned a wide range of redox potential, as reflected by the dissolved sulfide concentration range of ≤0.3-97 μM. Four different chemical species of inorganic divalent Hg (HgII) and methyl mercury (MeHg), enriched in different Hg isotope tracers, were added to the microcosms: 201Hg(NO3)2(aq), 202HgII adsorbed to OM (202HgII-OM(ads)), 198HgII as microcrystalline metacinnabar (β-198HgS(s)) and Me204HgCl(aq). Microcosm systems were composed of bottom water mixed with sediment taken at 0-2, 0-5 and 0-10 cm depth intervals. The composition of OM varied with sediment depth such that compared to deeper sediment, the 0-2 cm depth-interval had a 2-fold higher contribution of labile OM originating from algal and terrestrial inputs, serving as metabolic electron-donors for microorganisms. The potential methylation rate constant (kmeth) of Hg tracers and net formation of ambient MeHg (MeHg/THg molar ratio) increased up to 50% and 400%, respectively at intermediate oxidative conditions, likely because of an observed 2-fold increase in sulfate concentration stimulating the activity of sulfate reducing

  2. Redox Buffer Strength

    Science.gov (United States)

    de Levie, Robert

    1999-04-01

    The proper functioning of enzymes in bodily fluids requires that the pH be maintained within rather narrow limits. The first line of defense against large pH fluctuations in such fluids is the passive control provided by the presence of pH buffers. The ability of pH buffers to stabilize the pH is indicated by the buffer value b introduced in 1922 by van Slyke. It is equally important for many enzymes that the redox potential is kept within a narrow range. In that case, stability of the potential is most readily achieved with a redox buffer. In this communication we define the redox buffer strength by analogy with acid-base buffer strength.

  3. Medium activity long-lived nuclear waste; microbial paradise or hadean environment - Evaluation of biomass and impact on redox conditions

    International Nuclear Information System (INIS)

    Albrecht, A.; Libert, M.

    2010-01-01

    Document available in extended abstract form only. The evaluation of the impact of possible microbial activity in nuclear waste cells has been a subject for more than a quarter of a century. Some of the items of interest in relation to microbial impact on near field biogeochemistry indicated in Table 1 had already been known as pertinent. Recently, it became clear that a distinction needed to be made between high-level, vitrified waste and organic matter containing intermediate-level waste, of which the bituminized waste is used as an example here. For high-level waste the canister walls play an important safety role and the most probable limiting aspects, next to space and water, are the low concentrations in organic matter as a carbon source and phosphorous and nitrogen as essential elements. In this particular case, microbially induced corrosion is of primary concern. In the case of the French intermediate bituminized waste, primary interest is on the impact of microbial activity on redox reactions, with the high pH environment, as a consequence of the concrete engineered barrier, as the most probable limiting condition. The canister wall has no explicit long-term safety role and all components for microbial activity will become readily available. The presence of nitrates, sulphates and Fe(III) as electron acceptors and organic matter, hydrogen gas and zero-valent metals (i.e. Fe) as electron donors allows the system to supply energy for bacterial activity and to move through the entire redox sequence from O 2 (present only shortly after waste-cell closure) to nitrate, Fe(III), sulphate and organic matter reduction. Prevailing uncertainties do not allow specification of timing for the redox-changes. These uncertainties are essentially related to the lack of knowledge regarding microbial catalysis. As no natural or anthropogenic analogues are available, parameters need to be obtained from experiments. Two approaches will be presented that allow estimation of the

  4. Plasma structure change and intermittent fluctuation near magnetic island X-point under detached plasma condition in LHD

    International Nuclear Information System (INIS)

    Ohno, N.; Tsuji, Y.; Tanaka, H.; Masuzaki, S.; Kobayashi, M.; Akiyama, T.; Morisaki, T.; Motojima, G.; Narushima, Y.

    2014-10-01

    Plasma profiles and intermittent fluctuations near the helical divertor X-point and on a divertor plate were investigated using a fast scanning Langmuir probe and a probe array embedded on a divertor plate in detached divertor condition that was sustained by applying a resonant magnetic perturbation (RMP) field in LHD. When the RMP induced magnetic island X-point (n/m = 1/1) is located near the helical divertor X-point, the reduction of particle flux accompanied by the plasma detachment occurred near the helical divertor X-point (n/m = 2/10), which leads to the reduction of the particle flux at the strike point on the divertor plate. We also found that when the divertor plasma turned to be the detached condition, the enhanced plasma fluctuations were confirmed between the helical divertor X-point and ergodic region, which exhibited a dynamic behavior having a large amount of positive-spike components with highly intermittent property. (author)

  5. Thermo-mechanical modelling of salt caverns due to fluctuating loading conditions.

    Science.gov (United States)

    Böttcher, N.

    2015-12-01

    This work summarizes the development and application of a numerical model for the thermo-mechanical behaviour of salt caverns during cyclic gas storage. Artificial salt caverns are used for short term energy storage, such as power-to-gas or compressed air energy storage. Those applications are characterized by highly fluctuating operation pressures due to the unsteady power levels of power plants based on renewable energy. Compression and expansion of the storage gases during loading and unloading stages lead to rapidly changing temperatures in the host rock of the caverns. This affects the material behaviour of the host rock within a zone that extends several meters into the rock mass adjacent to the cavern wall, and induces thermo-mechanical stresses and alters the creep response.The proposed model features the thermodynamic behaviour of the storage medium, conductive heat transport in the host rock, as well as temperature dependent material properties of rock salt using different thermo-viscoplastic material models. The utilized constitutive models are well known and state-of-the-art in various salt mechanics applications. The model has been implemented into the open-source software platform OpenGeoSys. Thermal and mechanical processes are solved using a finite element approach, coupled via a staggered coupling scheme. The simulation results allow the conclusion, that the cavern convergence rate (and thus the efficiency of the cavern) is highly influenced by the loading cycle frequency and the resulting gas temperatures. The model therefore allows to analyse the influence of operation modes on the cavern host rock or on neighbouring facilities.

  6. Redox oscillation impact on natural and engineered biogeochemical systems: chemical resilience and implications for contaminant mobility

    Energy Technology Data Exchange (ETDEWEB)

    Charlet, Laurent [ISTerre, University of Grenoble, B.P. 53X, 38041 Grenoble (France); Institut Universitaire de France, Paris (France); Markelova, Ekaterina [ISTerre, University of Grenoble, B.P. 53X, 38041 Grenoble (France); Department of Earth and Environmental Sciences, University of Waterloo, Waterloo, ON N2L3G1 4 (Canada); Parsons, Chris; Couture, Raoul-Marie [Department of Earth and Environmental Sciences, University of Waterloo, Waterloo, ON N2L3G1 4 (Canada); Made, Benoit [Andra / DRD-TR, Direction Recherche et Developpement, 1-7 rue Jean Monnet, 92298 Chatenay-Malabry cedex (France)

    2013-07-01

    Many geochemical systems fluctuate regularly from oxic to anoxic conditions (flooded soils and nuclear waste surface repositories, for instance). In these conditions many inorganic contaminants including Sb, Se, Cr, As, and U are highly sensitive to changes in redox conditions. These oscillations may result in changes to their speciation, toxicity, and mobility. We demonstrate through the combination of redox-stat batch-reactor experiments that periodic and cumulative changes to matrix mineralogy, contaminant speciation, and mineral surface properties occur following periodic cycles of reduction and oxidation. These changes result in both short-term (intra-cycle) and long-term (inter-cycle) changes to K{sub d} values for a range of redox sensitive contaminants. These results demonstrate that naturally occurring redox oscillations may result in long-term immobilization of contaminants in the solid phase in addition to short-term variations in mobility. (authors)

  7. Conditionally Pathogenic Gut Microbes Promote Larval Growth by Increasing Redox-Dependent Fat Storage in High-Sugar Diet-Fed Drosophila.

    Science.gov (United States)

    Whon, Tae Woong; Shin, Na-Ri; Jung, Mi-Ja; Hyun, Dong-Wook; Kim, Hyun Sik; Kim, Pil Soo; Bae, Jin-Woo

    2017-12-01

    Changes in the composition of the gut microbiota contribute to the development of obesity and subsequent complications that are associated with metabolic syndrome. However, the role of increased numbers of certain bacterial species during the progress of obesity and factor(s) controlling the community structure of gut microbiota remain unclear. Here, we demonstrate the inter-relationship between Drosophila melanogaster and their resident gut microbiota under chronic high-sugar diet (HSD) conditions. Chronic feeding of an HSD to Drosophila resulted in a predominance of resident uracil-secreting bacteria in the gut. Axenic insects mono-associated with uracil-secreting bacteria or supplemented with uracil under HSD conditions promoted larval development. Redox signaling induced by bacterial uracil promoted larval growth by regulating sugar and lipid metabolism via activation of p38a mitogen-activated protein kinase. The present study identified a new redox-dependent mechanism by which uracil-secreting bacteria (previously regarded as opportunistic pathobionts) protect the host from metabolic perturbation under chronic HSD conditions. These results illustrate how Drosophila and gut microbes form a symbiotic relationship under stress conditions, and changes in the gut microbiota play an important role in alleviating deleterious diet-derived effects such as hyperglycemia. Antioxid. Redox Signal. 27, 1361-1380.

  8. Redox behavior of Tc(VII)/Tc(IV) under various reducing conditions in 0.1 M NaCl solutions

    International Nuclear Information System (INIS)

    Kobayashi, T.; Gaona, X.; Altmaier, M.; Scheinost, A.C.; Fellhauer, D.; European Commission Joint Research Centre, Karlsruhe

    2013-01-01

    Redox behaviour of Tc(VII)/Tc(IV) was investigated in 0.1 M NaCl solutions containing different reducing agents in the pH range 2 to 13 at 22 C under inert Ar atmosphere. In several samples, the 1 x 10 -5 mol/dm 3 (M) initially added TcO 4 - was reduced to form a Tc(IV) oxide solid phase with low solubility. The observed Tc redox transformation processes are systematized according to E h -pH conditions in solution, indicating that a borderline for the reduction of Tc(VII) to Tc(IV), TcO 4 - + 3e - + 4H + TcO 2 . xH 2 O(coll, hyd) + (2-x)H 2 O exists, independent of the reducing chemical system. This experimentally derived borderline is about 100 mV lower than the equilibrium line calculated from the reported standard redox potential of TcO 2 . 1.6H 2 O(s). This behaviour can be related to the existence of more soluble solid phase modifications, i.e. nanoparticulate Tc(IV) oxide species TcO 2 . xH 2 O(coll, hyd). The reaction kinetics likewise correlate to the redox potential measured in solution. Slow reduction of Tc(VII) to Tc(IV) was observed when the redox potential in the system was slightly below the above mentioned reduction borderline. Fast reduction was observed in the systems far below the borderline, but also in those systems containing Fe(II) solids, suggesting a specific surface mediated effect in the reduction process. EXAFS analysis on two magnetite samples indicate reduced Tc(IV) species which do not remain adsorbed at the reactive mineral surface and are incorporated in the magnetite structure. (orig.)

  9. Accuracy of circadian entrainment under fluctuating light conditions : Contributions of phase and period responses

    NARCIS (Netherlands)

    Beersma, DGM; Daan, S; Hut, RA

    The accuracy with which a circadian pacemaker can entrain to an environmental 24-h zeitgeber signal depends on (a) characteristics of the entraining signal and (b) response characteristics and intrinsic stability of the pacemaker itself. Position of the sun, weather conditions, shades, and

  10. How does organic matter occurrence set limit onto the use of Ce anomaly as a reliable proxy of redox conditions in shallow groundwaters?

    Science.gov (United States)

    Dia, A.; Gruau, G.; Davranche, M.; Vidy, A.; Henin, O.; Petitjean, P.; Le Coz-Bouhnik, M.

    2003-04-01

    This study is dedicated to the effects of organic matter on the hydrochemistry of Rare Earth Elements (REE) and the ability of using the Ce anomaly as a reliable proxy of redox conditions in surface waters when organic matter occurs. The data include a : i) two-year survey of SREE and Ce anomalies in organic-rich waters recovered from a catchment located in Brittany (western Europe) and (ii) experimental incubation of organic soils from this catchment set under controlled conditions, as well as, (iii) a REE speciation calculation in both the natural organic-rich waters from the wetlands and the experimental solutions. Field and experimental data appear to be extremely coherent, displaying good correlation between the SREE, the Dissolved Organic Carbon (DOC) contents and the redox state. The field data show a strong increase of the SREE and DOC concentrations in soil waters when the environment becomes more reducing. The onset of DOC and SREE contents is seen to be in phase with the increase of dissolved Fe and Mn. The role of Fe-, Mn-oxyhydroxides is confirmed by the experimental data as the maximum of DOC and SREE content is reached when Fe2+ reaches a maximum in the soil solution, suggesting that reductive dissolution of Fe, Mn-oxyhydroxides happens. Despite the strong redox changes and the known redox sensitive behaviour of Ce as compared to other REE, none Ce anomaly variation is observed during either, the experimental procedure, or the field survey through time. Speciation calculations were performed showing that in both such pH range and moderately oxidizing waters in DOC-rich waters, REE should have an organic speciation. Such an organic speciation prevents the formation of Ce(IV) and therefore the development of any Ce anomaly. However, since the studied waters are highly oxidizing (high nitrate contents), the nitrates impose the redox formation of Ce(IV) and a Ce anomaly should appear. Therefore, Ce(IV) is not formed in these waters either because (i) the

  11. Fluctuating water depths affect American alligator (Alligator mississippiensis) body condition in the Everglades, Florida, USA

    Science.gov (United States)

    Brandt, Laura A.; Beauchamp, Jeffrey S.; Jeffery, Brian M.; Cherkiss, Michael S.; Mazzotti, Frank J.

    2016-01-01

    Successful restoration of wetland ecosystems requires knowledge of wetland hydrologic patterns and an understanding of how those patterns affect wetland plant and animal populations.Within the Everglades, Florida, USA restoration, an applied science strategy including conceptual ecological models linking drivers to indicators is being used to organize current scientific understanding to support restoration efforts. A key driver of the ecosystem affecting the distribution and abundance of organisms is the timing, distribution, and volume of water flows that result in water depth patterns across the landscape. American alligators (Alligator mississippiensis) are one of the ecological indicators being used to assess Everglades restoration because they are a keystone species and integrate biological impacts of hydrological operations through all life stages. Alligator body condition (the relative fatness of an animal) is one of the metrics being used and targets have been set to allow us to track progress. We examined trends in alligator body condition using Fulton’s K over a 15 year period (2000–2014) at seven different wetland areas within the Everglades ecosystem, assessed patterns and trends relative to restoration targets, and related those trends to hydrologic variables. We developed a series of 17 a priori hypotheses that we tested with an information theoretic approach to identify which hydrologic factors affect alligator body condition. Alligator body condition was highest throughout the Everglades during the early 2000s and is approximately 5–10% lower now (2014). Values have varied by year, area, and hydrology. Body condition was positively correlated with range in water depth and fall water depth. Our top model was the “Current” model and included variables that describe current year hydrology (spring depth, fall depth, hydroperiod, range, interaction of range and fall depth, interaction of range and hydroperiod). Across all models, interaction

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

    Directory of Open Access Journals (Sweden)

    K.-H. Knorr

    2013-02-01

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

  13. Zirconolite glass-ceramics for plutonium immobilization: The effects of processing redox conditions on charge compensation and durability

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yingjie, E-mail: yzx@ansto.gov.au; Gregg, Daniel J.; Kong, Linggen; Jovanovich, Miodrag; Triani, Gerry

    2017-07-15

    Zirconolite glass-ceramic samples doped with plutonium have been prepared via hot isostatic pressing. The effects of processing redox and plutonium loadings on plutonium valences, the presence of cation vacancies, zirconolite phase compositions, microstructures and durability have been investigated. Either tetravalent or trivalent plutonium ions may be incorporated on the Ca-site of CaZrTi{sub 2}O{sub 7} zirconolite with the Ca-site cation vacancies and the incorporation of Al{sup 3+} ions on the Ti-site for charge compensation. Plutonium and gadolinium (as a neutron absorber) are predominantly partitioned in zirconolite phases leading to the formation of chemically durable glass-ceramics suitable for the immobilization of impure plutonium wastes arising from the nuclear fuel cycle. - Highlights: •Plutonium validations of zirconolite glass-ceramics. •Effects of processing redox and plutonium loading. •Zirconolite phase compositions and plutonium valences. •Cation vacancies and chemical durability.

  14. Sliding-window analysis tracks fluctuations in amygdala functional connectivity associated with physiological arousal and vigilance during fear conditioning.

    Science.gov (United States)

    Baczkowski, Blazej M; Johnstone, Tom; Walter, Henrik; Erk, Susanne; Veer, Ilya M

    2017-06-01

    We evaluated whether sliding-window analysis can reveal functionally relevant brain network dynamics during a well-established fear conditioning paradigm. To this end, we tested if fMRI fluctuations in amygdala functional connectivity (FC) can be related to task-induced changes in physiological arousal and vigilance, as reflected in the skin conductance level (SCL). Thirty-two healthy individuals participated in the study. For the sliding-window analysis we used windows that were shifted by one volume at a time. Amygdala FC was calculated for each of these windows. Simultaneously acquired SCL time series were averaged over time frames that corresponded to the sliding-window FC analysis, which were subsequently regressed against the whole-brain seed-based amygdala sliding-window FC using the GLM. Surrogate time series were generated to test whether connectivity dynamics could have occurred by chance. In addition, results were contrasted against static amygdala FC and sliding-window FC of the primary visual cortex, which was chosen as a control seed, while a physio-physiological interaction (PPI) was performed as cross-validation. During periods of increased SCL, the left amygdala became more strongly coupled with the bilateral insula and anterior cingulate cortex, core areas of the salience network. The sliding-window analysis yielded a connectivity pattern that was unlikely to have occurred by chance, was spatially distinct from static amygdala FC and from sliding-window FC of the primary visual cortex, but was highly comparable to that of the PPI analysis. We conclude that sliding-window analysis can reveal functionally relevant fluctuations in connectivity in the context of an externally cued task. Copyright © 2017 Elsevier Inc. All rights reserved.

  15. Sulphate chemistry under pressurized oxidizing, reducing and fluctuating conditions; Sulfatkemi under trycksatta oxiderande, reducerande och fluktuerande foerhaallanden

    Energy Technology Data Exchange (ETDEWEB)

    Hupa, M.; Yrjas, P.; Backman, P. [Aabo Akademi, Turku (Finland). Combustion Chemistry Research Group

    1997-10-01

    In the literature it has been reported that sulfur capture with limestone (CaCO{sub 3}) under atmospheric fluidized bed combustion conditions reaches a maximum at about 850 deg C. Previously, the maximum has been attributed to the sintering of sorbent particles which decreases the reactive surface area. Lately, also another explanation has been reported. In this case the sulfur capture decrease at higher temperatures was concluded to be due to fluctuating oxidizing/reducing conditions in the atmospheric combustor. In this work the influence of alternating oxidizing/reducing conditions on SO{sub 2} capture at atmospheric and elevated pressure (15 bar) has been studied. In the pressurized case, the CO{sub 2} partial pressure was kept high enough to prevent CaCO{sub 3} from calcining and therefore the CaSO{sub 4} would not form CaO but CaCO{sub 3} under reducing conditions. The experiments were done with a pressurized TGA by periodically changing the gas environment between oxidizing (O{sub 2}. SO{sub 2}, CO{sub 2} and N{sub 2}) and slightly reducing (CO, SO{sub 2}, CO{sub 2} and N{sub 2}) gas mixtures at different temperatures. The results from the experiments showed that under normal pressure and slightly reducing conditions CaO formation from CaSO{sub 4} increased with temperature as expected. However, no significant amounts of CaCO{sub 3} were formed from CaSO{sub 4} at elevated pressure. It was also concluded that since the formation of CaO from CaSO{sub 4} was relatively slow it could not explain the sharp sulfur capture maximum at about 850 deg C. Therefore, it was assumed that the strongly reducing zones, where CaS thermodynamically is the stable compound, play a more important role concerning the sulfur capture in fluidized bed combustors. (orig.)

  16. Health Effects of Short-Term Fluctuations in Macroeconomic Conditions: The Case of Hypertension for Older Americans.

    Science.gov (United States)

    Angrisani, Marco; Lee, Jinkook

    2016-11-01

    We investigate the health effects of short-term macroeconomic fluctuations as described by changes in unemployment rate, house, and stock market price indexes. The 'Great Recession' provides the opportunity to conduct this analysis as it involved contemporaneous shocks to the labor, housing, and stock markets. Using panel data from the Health and Retirement Study over the period 2004-2010, we relate changes in hypertension status to changes in state-level unemployment rate and house prices and to changes in stock market prices. We consider hypertension, a disease related to stress and of high prevalence among older adults, that has received little attention in the literature linking macroeconomic conditions to individual health. Our analysis exploits self-reports of hypertension diagnosis as well as directly measured blood pressure readings. Using both measures, we find that the likelihood of developing hypertension is negatively related to changes in house prices. Also, decreasing house prices lower the probability of stopping hypertension medication treatment for individuals previously diagnosed with the condition. We do not observe significant associations between hypertension and either changes in unemployment rate or stock market prices. We document heterogeneity in the estimated health effects of the recession by gender, education, asset ownership, and work status. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  17. Crystal chemistry of iron in low-temperature chlorites, implications for geo-thermometry and the determination of redox paleo-conditions in uranium deposits

    International Nuclear Information System (INIS)

    Rigault, Cecile

    2010-01-01

    In contexts of uranium deposits, redox conditions constitute the main factor controlling the uranium deposition. Often observed in these deposits, chlorites are the unique clay mineral which can be able to record in their structure the redox conditions through their Fe"3"+/SFe ratio. However, the common presence of several populations of chlorites makes difficult to understand the message carried out by these minerals. Thanks to μ-XANES spectroscopy, we are now able to measure on thin sections the Fe"3"+/SFe ratio in chlorites with an accuracy of 5 %. Measurements show that it can reach 60 % in di-tri-octahedral chlorites and 5 % to more than 40 % for tri-octahedral chlorites. In hydrothermal contexts where chlorites crystallize through a dissolution-recrystallization process, their Fe"3"+/SFe ratio decreases with the increase of the global Fe content. Diagenetic chlorites observed resulting from the polymorphic transformation of berthierine have a different behavior because there is no link between their total iron content and their Fe"3"+/SFe ratio: their chemistry is directly inherited from the one of the precursor mineral because this transformation does not allow a reorganization of cations in the structure. This transformation explains that thermodynamic models cannot work for these phases. For the use of chlorites as makers of redox paleo-conditions in contexts of uranium deposits where diagenetic and hydrothermal chlorites can be present, it is decisive to determine their origin, for example analyzing their polytype: Ib (b=90 degrees) for chlorites crystallized from solid-state transformation and IIb for chlorites crystallized through dissolution-recrystallization process. (author)

  18. Impact of Redox Condition on Fractionation and Bioaccessibility of Arsenic in Arsenic-Contaminated Soils Remediated by Iron Amendments: A Long-Term Experiment

    Directory of Open Access Journals (Sweden)

    Quan Zhang

    2018-01-01

    Full Text Available Iron-bearing amendments, such as iron grit, are proved to be effective amendments for the remediation of arsenic- (As- contaminated soils. In present study, the effect of redox condition on As fractions in As-contaminated soils remediated by iron grit was investigated, and the bioaccessibility of As in soils under anoxic condition was evaluated. Results showed that the labile fractions of As in soils decreased significantly after the addition of iron grit, while the unlabile fractions of As increased rapidly, and the bioaccessibility of As was negligible after 180 d incubation. More labile fractions of As in iron-amended soils were transformed into less mobilizable or unlabile fractions with the contact time. Correspondingly, the bioaccessibility of As in iron-amended soils under the aerobic condition was lower than that under the anoxic condition after 180 d incubation. The redistribution of loosely adsorbed fraction of As in soils occurred under the anoxic condition, which is likely ascribed to the reduction of As(V to As(III and the reductive dissolution of Fe-(hydroxides. The stabilization processes of As in iron-amended soils under the anoxic and aerobic conditions were characterized by two stages. The increase of crystallization of Fe oxides, decomposition of organic matter, molecular diffusion, and the occlusion within Fe-(hydroxides cocontrolled the transformation of As fractions and the stabilization process of As in iron-amended soils under different redox conditions. In terms of As bioaccessibility, the stabilization process of As in iron-amended soils was shortened under the aerobic condition in comparison with the anoxic condition.

  19. Water-level fluctuation in wetlands as a function of landscape condition in the prairie pothole region

    Science.gov (United States)

    Euliss, Ned H.; Mushet, David M.

    1996-01-01

    We evaluated water-level fluctuation (maximum water depth - minimum water depth/catchment size) in 12 temporary, 12 seasonal, and 12 semipermanent wetlands equally distributed among landscapes dominated by tilled agricultural lands and landscapes dominated by grassland. Water levels fluctuated an average of 14.14 cm in wetlands within tilled agricultural landscapes, while water levels in wetlands within grassland landscapes fluctuated an average of only 4.27 cm. Tillage reduces the natural capacity of catch meets to mitigate surface flow into wetland basins during precipitation events, resulting in greater water-level fluctuations in wetlands with tilled catchments. In addition, water levels in temporary and seasonal wetlands fluctuated an average of 13.74 cm and 11.82 cm, respectively, while water levels in semipermanent wetlands fluctuated only 2.77 cm. Semipermanent wetlands receive a larger proportion of their water as input from ground water than do either temporary or seasonal wetlands. This input of water from the ground has a stabilizing effect on water-levels of semipermanent wetlands. Increases in water-level fluctuation due to tillage or due to alteration of ground-water hydrology may ultimately affect the composition of a wetland's flora and fauna. In this paper, we also describe an inexpensive device for determining absolute maximum and minimum water levels in wetlands.

  20. The effect of redox conditions and adaptation time on organic micropollutant removal during river bank filtration: A laboratory-scale column study.

    Science.gov (United States)

    Bertelkamp, C; Verliefde, A R D; Schoutteten, K; Vanhaecke, L; Vanden Bussche, J; Singhal, N; van der Hoek, J P

    2016-02-15

    This study investigated the redox dependent removal and adaptive behaviour of a mixture of 15 organic micropollutants (OMPs) in laboratory-scale soil columns fed with river water. Three separate pilot systems were used consisting of: (1) two columns, (2) ten columns and (3) twenty two columns to create oxic, suboxic (partial nitrate removal) and anoxic (complete nitrate removal). The pilot set-up has some unique features--it can simulate fairly long residence times (e.g., 45 days using the 22 column system) and reduced conditions developed naturally within the system. Dimethoate, diuron, and metoprolol showed redox dependent removal behaviour with higher biodegradation rates in the oxic zone compared to the suboxic/anoxic zone. The redox dependent behaviour of these three OMPs could not be explained based on their physico-chemical properties (hydrophobicity, charge and molecular weight) or functional groups present in the molecular structure. OMPs that showed persistent behaviour in the oxic zone (atrazine, carbamazepine, hydrochlorothiazide and simazine) were also not removed under more reduced conditions. Adaptive behaviour was observed for five OMPs: dimethoate, chloridazon, lincomycin, sulfamethoxazole and phenazone. However, the adaptive behaviour could not be explained by the physico-chemical properties (hydrophobicity, charge and molecular weight) investigated in this study and only rough trends were observed with specific functional groups (e.g. ethers, sulphur, primary and secondary amines). Finally, the adaptive behaviour of OMPs was found to be an important factor that should be incorporated in predictive models for OMP removal during river bank filtration. Copyright © 2015 Elsevier B.V. All rights reserved.

  1. Experimental evidence for non-redox transformations between magnetite and hematite under H 2-rich hydrothermal conditions

    Science.gov (United States)

    Otake, Tsubasa; Wesolowski, David J.; Anovitz, Lawrence M.; Allard, Lawrence F.; Ohmoto, Hiroshi

    2007-05-01

    Transformations of magnetite (Fe IIFe 2IIIO 4) to hematite (Fe 2IIIO 3) (and vice versa) have been thought by many scientists and engineers to require molecular O 2 and/or H 2. Thus, the presence of magnetite and/or hematite in rocks has been linked to a specific oxidation environment. However, the availability of reductants or oxidants in many geologic and industrial environments appears to have been too low to account for the transformations of iron oxides through redox reactions. Here, we report the results of hydrothermal experiments in mildly acidic and H 2-rich aqueous solutions at 150 °C, which demonstrate that transformations of magnetite to hematite, and hematite to magnetite, occur rapidly without involving molecular O 2 or H 2: Fe3O 4(Mt) + 2H (aq)+ ↔ Fe 2O 3(Hm) + Fe (aq)2+ + H 2O. The transformation products are chemically and structurally homogeneous, and typically occur as euhedral single crystals much larger than the precursor minerals. This suggests that, in addition to the expected release of aqueous ferrous species to solution, the transformations involve release of aqueous ferric species from the precursor oxides to the solution, which reprecipitate without being reduced by H 2. These redox-independent transformations may have been responsible for the formation of some iron oxides in natural systems, such as high-grade hematite ores that developed from Banded Iron Formations (BIFs), hematite-rich deposits formed on Mars, corrosion products in power plants and other industrial systems.

  2. The reactivity of Fe(II) associated with goethite formed during short redox cycles toward Cr(VI) reduction under oxic conditions

    Energy Technology Data Exchange (ETDEWEB)

    Tomaszewski, Elizabeth J.; Lee, Seungyeol; Rudolph, Jared; Xu, Huifang; Ginder-Vogel, Matthew (UW)

    2017-08-01

    Chromium (Cr) is a toxic metal that causes a myriad of health problems and enters the environment as a result of anthropogenic activities and/or natural processes. The toxicity and solubility of chromium is linked to its oxidation state; Cr(III) is poorly soluble and relatively nontoxic, while Cr(VI) is soluble and a known carcinogen. Solid Fe(II) in iron-bearing minerals, such as pyrite, magnetite, and green rusts, reduce the oxidation state of chromium, reducing its toxicity and mobility. However, these minerals are not the only potential sources of solid-associated Fe(II) available for Cr(VI) reduction. For example, ferric (Fe(III)) (hydr)oxides, such as goethite or hematite, can have Fe(II) in the solid without phase transformation; however, the reactivity of Fe(II) within Fe(III) (hydr)oxides with contaminants, has not been previously investigated. Here, we cyclically react goethite with dissolved Fe(II) followed by dissolved O2, leading to the formation of reactive Fe(II) associated with goethite. In separate reactors, the reactivity of this Fe(II) is probed under oxic conditions, by exposure to chromate (CrO42 -) after either one, two, three or four redox cycles. Cr is not present during redox cycling; rather, it is introduced to a subset of the solid after each oxidation half-cycle. Analysis of X-ray absorption near edge structure (XANES) spectra reveals that the extent of Cr(VI) reduction to Cr(III) depends not only on solid Fe(II) content but also surface area and mean size of ordered crystalline domains, determined by BET surface area analysis and X-ray diffraction (XRD), respectively. Shell-by-shell fitting of the extended X-ray absorption fine structure (EXAFS) spectra demonstrates chromium forms both single and double corner sharing complexes on the surface of goethite, in addition to sorbed Cr(III) species. Finally, transmission electron microscope (TEM) imaging and X-ray energy-dispersive spectroscopy (EDS) illustrate that Cr preferentially

  3. The Association of Arsenic With Redox Conditions, Depth, and Ground-Water Age in the Glacial Aquifer System of the Northern United States

    Science.gov (United States)

    Thomas, Mary Ann

    2007-01-01

    More than 800 wells in the glacial aquifer system of the Northern United States were sampled for arsenic as part of U.S. Geological Survey National Water-Quality Assessment (NAWQA) studies during 1991-2003. Elevated arsenic concentrations (greater than or equal to 10 micrograms per liter) were detected in 9 percent of samples. Elevated arsenic concentrations were associated with strongly reducing conditions. Of the samples classified as iron reducing or sulfate reducing, arsenic concentrations were elevated in 19 percent. Of the methanogenic samples, arsenic concentrations were elevated in 45 percent. In contrast, concentrations of arsenic were elevated in only 1 percent of oxic samples. Arsenic concentrations were also related to ground-water age. Elevated arsenic concentrations were detected in 34 percent of old waters (recharged before 1953) as compared to 4 percent of young waters (recharged since 1953). For samples classified as both old and methanogenic, elevated arsenic concentrations were detected in 62 percent of samples, as compared to 1 percent for samples classified as young and oxic. Arsenic concentrations were also correlated with well depth and concentrations of several chemical constituents, including (1) constituents linked to redox processes and (2) anions or oxyanions that sorb to iron oxides. Observations from the glacial aquifer system are consistent with the idea that the predominant source of arsenic is iron oxides and the predominant mechanism for releasing arsenic to the ground water is reductive desorption or reductive dissolution. Arsenic is also released from iron oxides under oxic conditions, but on a more limited basis and at lower concentrations. Logistic regression was used to investigate the relative significance of redox, ground-water age, depth, and other water-quality constituents as indicators of elevated arsenic concentrations in the glacial aquifer system. The single variable that explained the greatest amount of variation in

  4. Engineering redox balance through cofactor systems.

    Science.gov (United States)

    Chen, Xiulai; Li, Shubo; Liu, Liming

    2014-06-01

    Redox balance plays an important role in the production of enzymes, pharmaceuticals, and chemicals. To meet the demands of industrial production, it is desirable that microbes maintain a maximal carbon flux towards target metabolites with no fluctuations in redox. This requires functional cofactor systems that support dynamic homeostasis between different redox states or functional stability in a given redox state. Redox balance can be achieved by improving the self-balance of a cofactor system, regulating the substrate balance of a cofactor system, and engineering the synthetic balance of a cofactor system. This review summarizes how cofactor systems can be manipulated to improve redox balance in microbes. Copyright © 2014 Elsevier Ltd. All rights reserved.

  5. Effect of redox conditions on the fate of emergin organic micropollutants during artificial recharge of groundwater: batch experiment

    OpenAIRE

    Barbieri, Manuela

    2011-01-01

    La recarrega artificial de les aigües subterrànies consisteix en infiltrar aigua als aqüífers per mitjà de les instal·lacions dissenyades per a tal fi i representa una eina important en la gestió dels recursos. A més de l’augment dels recursos d'aigües subterrànies, la recàrrega pot suposar una millora natural de la seva qualitat durant el seu pas pel subsòl. Els processos que tenen lloc en el sistema sòl-aqüífer (filtració, adsorció, reaccions de mescla , redox, biodegradació, et...

  6. Geochemistry of Natural Redox Fronts

    International Nuclear Information System (INIS)

    Hofmann, B.A.

    1999-05-01

    Redox fronts are important geochemical boundaries which need to be considered in safety assessment of deep repositories for radioactive waste. In most cases, selected host-rock formations will be reducing due to the presence of ferrous minerals, sulphides, etc. During construction and operation of the repository, air will be introduced into the formation. After repository closure, oxidising conditions may persist locally until all oxygen is consumed. In the case of high-level waste, radiolysis of water may provide an additional source of oxidants. Oxidising conditions within a repository are thus possible and potentially have a strong influence on the mobility of many elements. The rate of movement of redox fronts, the boundary between oxidising and reducing environments, and their influence on migrating radionuclides are thus important factors influencing repository performance. The present report is a review of elemental behaviour at natural redox fronts, based on published information and work of the author. Redox fronts are geochemically and geometrically variable manifestations of a global interface between generally oxidising geochemical milieux in contact with the atmosphere and generally reducing milieux in contact with rocks containing ferrous iron, sulphide and/or organic carbon. A classification of redox fronts based on a subdivision into continental near-surface, marine near-surface, and deep environments is proposed. The global redox interface is often located close to the surface of rocks and sediments and, sometimes, within bodies of water. Temperature conditions are close to ambient. A deeper penetration of the global redox front to depths of several kilometres is found in basins containing oxidised sediments (red beds) and in some hydrothermal circulation systems. Temperatures at such deep redox fronts may reach 200 o C. Both near-surface and deep redox fronts are sites of formation of economic deposits of redox-sensitive elements, particularly of

  7. The Earth's passage of the April 11, 1997 coronal ejecta: geomagnetic field fluctuations at high and low latitude during northward interplanetary magnetic field conditions

    Directory of Open Access Journals (Sweden)

    S. Lepidi

    1999-10-01

    Full Text Available An analysis of the low frequency geomagnetic field fluctuations at an Antarctic (Terra Nova Bay and a low latitude (L'Aquila, Italy station during the Earth's passage of a coronal ejecta on April 11, 1997 shows that major solar wind pressure variations were followed at both stations by a high fluctuation level. During northward interplanetary magnetic field conditions and when Terra Nova Bay is close to the local geomagnetic noon, coherent fluctuations, at the same frequency (3.6 mHz and with polarization characteristics indicating an antisunward propagation, were observed simultaneously at the two stations. An analysis of simultaneous measurements from geosynchronous satellites shows evidence for pulsations at approximately the same frequencies also in the magnetospheric field. The observed waves might then be interpreted as oscillation modes, triggered by an external stimulation, extending to a major portion of the Earth's magnetosphere. Key words. Magnetospheric physics (MHD waves and instabilities; solar wind-magnetosphere interactions

  8. Hourly and daily variation of sediment redox potential in tidal wetland sediments

    Science.gov (United States)

    Catallo, W. James

    1999-01-01

    Variation of electrochemical oxidation-reduction (redox) potential was examined in surface salt march sediments under conditions of flooding and tidal simulation in mesocosms and field sites. Time series were generated of redox potential measured in sediment profiles at 2-10 cm depth using combination Pt-Ag/AgCl (ORP) electrodes. Redox potential data were acquired at rapid rates (1-55 samples/h) over extended periods (3-104 days) along with similar times series of temperature (water, air, soil) and pH. It was found that redox potential vaired as a result of water level changes and was unrelated to diurnal changes in temperature or pH, the latter of which changed by 370 mV redox potential decrease in under 48 hours). Attenuatoin of microbial activity by [gamma] y-radiation and toxic chemicals elimintated this response. In tidal salt marsh mesocosms where the sediment-plant assemblages were exposed to a simulated diurnal tide, redox potenial oscillations of 40-300 mV amplitude were recoded that has the same periodicity as the flood-drain cycle. Periodic redoc potential time series were observed repeatedly in sediments receiving tidal pulsing but not in those sediments exposed to static hydrological conditions. Data collected over 12 days from a coastal marsh site experiencing diurnal tides showed similar fluctuations in redox potential. Data from the experimentents indicated that (a) redox potential can be a dynamic, nonlinear variable in coastal and estuarine wetland sediments over hourly and daily scales, and the designs of biogeochemical experiments should reflect this, (b) redox potential can change rapidly and signigicantly in coastal wetland sediments in response of flooding and draining, (c) microbial community processes are primarily determinants of the time course of redox potential in wetland sediments, and elimination of inhibition of microbial activity (e.g. by pollutants) can significantly alter that behavior, and (d) fast redox potential dynamics appear

  9. Attenuation of bulk organic matter, nutrients (N and P), and pathogen indicators during soil passage: Effect of temperature and redox conditions in simulated soil aquifer treatment (SAT)

    KAUST Repository

    Abel, Chol D T

    2012-07-22

    Soil aquifer treatment (SAT) is a costeffective natural wastewater treatment and reuse technology. It is an environmentally friendly technology that does not require chemical usage and is applicable to both developing and developed countries. However, the presence of organic matter, nutrients, and pathogens poses a major health threat to the population exposed to partially treated wastewater or reclaimed water through SAT. Laboratory-based soil column and batch experiments simulating SAT were conducted to examine the influence of temperature variation and oxidation-reduction (redox) conditions on removal of bulk organic matter, nutrients, and indicator microorganisms using primary effluent. While an average dissolved organic carbon (DOC) removal of 17.7 % was achieved in soil columns at 5 °C, removal at higher temperatures increased by 10 % increments with increase in temperature by 5 °C over the range of 15 to 25 °C. Furthermore, soil column and batch experiments conducted under different redox conditions revealed higher DOC removal in aerobic (oxic) experiments compared to anoxic experiments. Aerobic soil columns exhibited DOC removal 15 % higher than that achieved in the anoxic columns, while aerobic batch showed DOC removal 7.8 % higher than the corresponding anoxic batch experiments. Ammonium-nitrogen removal greater than 99 % was observed at 20 and 25 °C, while 89.7 % was removed at 15 °C, but the removal substantially decreased to 8.8 % at 5 °C. While ammonium-nitrogen was attenuated by 99.9 % in aerobic batch reactors carried out at room temperature, anoxic experiments under similar conditions revealed 12.1 % ammonium-nitrogen reduction, corresponding to increase in nitrate-nitrogen and decrease in sulfate concentration. © Springer Science+Business Media B.V. 2012.

  10. Influence of the redox state on the neptunium sorption under alkaline conditions. Batch sorption studies on titanium dioxide and calcium silicate hydrates

    International Nuclear Information System (INIS)

    Tits, Jan; Laube, Andreas; Wieland, Erich; Gaona, Xavier

    2014-01-01

    Wet chemistry experiments were carried out to investigate the effect of the redox state and aqueous speciation on the uptake of neptunium by titanium dioxide (TiO 2 ) and by calcium silicate hydrates (C-S-H) under alkaline conditions. TiO 2 was chosen as a reference sorbent to determine the surface complexation behaviour of neptunium under alkaline conditions. C-S-H phases are important constituents of cement and concrete. They may contribute significantly to radionuclide retention due to their high recrystallization rates making incorporation the dominating sorption mechanism for many radionuclides (e.g. the actinides) on these materials. The sorption of neptunium on both solids was found to depend strongly on the degree of hydrolysis. On TiO 2 R d values for Np(IV), Np(V) and Np(VI) are identical at pH = 10 and decrease with progressing hydrolysis in case of Np(V) and Np(VI). On C-S-H phases, R d values for the three redox states are also identical at pH = 10. While the R d values for Np(VI) sorption on C-S-H phases decrease with progressing hydrolysis, the R d values for Np(IV) and Np(V) sorption are not affected by the pH. In addition to the effect of hydrolysis, the presence of Ca is found to promote Np(V) and Np(VI) sorption on TiO 2 whereas on C-S-H phases, the present wet chemistry data do not give unambiguous evidence. Thus, the aqueous speciation appears to have a similar influence on the sorption of the actinides on both types of solids despite the different sorption mechanism. The similar R d values for Np(IV,V,VI) sorption at pH = 10 can be explained qualitatively by invoking inter-ligand electrostatic repulsion between OH groups in the coordination sphere of Np(V) and Np(VI). This mechanism was proposed earlier in the literature for the prediction of actinide complexation constants with inorganic ligands. A limiting coordination number for each Np redox state, resulting from the inter-ligand electrostatic repulsion, allows the weaker sorption of the

  11. DC-Voltage Fluctuation Elimination Through a DC-Capacitor Current Control for DFIG Converters Under Unbalanced Grid Voltage Conditions

    DEFF Research Database (Denmark)

    Liu, Changjin; Xu, Dehong; Zhu, Nan

    2013-01-01

    Unbalanced grid voltage causes a large second-order harmonic current in the dc-link capacitors as well as dc-voltage fluctuation, which potentially will degrade the lifespan and reliability of the capacitors in voltage source converters. This paper proposes a novel dc-capacitor current control...... method for a grid-side converter (GSC) to eliminate the negative impact of unbalanced grid voltage on the dc-capacitors. In this method, a dc-capacitor current control loop, where a negative-sequence resonant controller is used to increase the loop gain, is added to the conventional GSC current control...... loop. The rejection capability to the unbalanced grid voltage and the stability of the proposed control system are discussed. The second-order harmonic current in the dc capacitor as well as dc-voltage fluctuation is very well eliminated. Hence, the dc capacitors will be more reliable under unbalanced...

  12. Biogeochemical reactive-transport modelling of the interactions of medium activity long-lived nuclear waste in fractured argillite and the effect on redox conditions

    International Nuclear Information System (INIS)

    Small, J.S.; Steele, H.; Kwong, S.; Albrecht, A.

    2010-01-01

    Document available in extended abstract form only. The role of anaerobic microbial processes in mediating gas generation and redox reactions in organic (cellulose) containing low level activity nuclear wastes (LLW) is well established through monitoring of operational near-surface LLW disposal sites and municipal waste disposal sites. Modelling approaches based on Monod kinetic growth models to represent the complex suite of anaerobic processes have been developed and these models are able to reproduce the evolving biogeochemistry and gas generation of large scale and long term (10 year) experiments on cellulose waste degradation. In the case of geological disposal of medium activity long-lived nuclear waste (MAVL) microbial processes have the potential to exploit metabolic energy sources present in the waste, engineered barriers and host geological formation and as a consequence influence redox potential. Several electron donors and electron acceptors may be present in MAVL. Electron donors include; hydrogen (resulting from radiolysis and anaerobic corrosion of metals), and hydrolysis products of organic waste materials. Sulphate, nitrate and Fe(III) containing minerals and corrosion products are examples of electron acceptors present in intermediate level wastes. Significant amounts of organic matter, sulphate and iron minerals may also be present in host geological formations and have the potential to act as microbial energy sources once the system is perturbed by electron donors/acceptors from the waste. The construction of a geological disposal facility will physically disturb the host formation, potentially causing fracturing of the excavation damage zone (EDZ). The EDZ may thus provide environmental conditions, such as space and free water that together with nutrient and energy sources to promote microbial activity. In this study the Generalised Repository Model (GRM) developed to simulate the coupled microbiological, chemical and transport processes in near

  13. Effects of Varying RedoxConditions on Natural Attenuation of Inorganic Contaminants from the D-Area Coal Pile Runoff Basin (U)

    Energy Technology Data Exchange (ETDEWEB)

    Kaplan, D

    2004-05-30

    The objective of this study was to provide geochemical parameters to characterize the D-Area Coal Pile Runoff Basin (DCPRB) sediment as a potential source term. It is anticipated that the measured values will be used in risk calculations and will provide additional technical support for imposing Monitored Natural Attenuation at D-Area. This study provides a detailed evaluation of the DCPRB sediment and is part of another study that quantified the Monitored Natural Attenuation of inorganic contaminants more broadly at the D-Area Expanded Operable Unit, which includes the DCPRB (Powell et al. 2004). Distribution coefficients (K{sub d} values; a solid to liquid contaminant concentration ratio) and the Potentially Leachable Fraction (the percent of the total contaminant concentration in the sediment that can likely contribute to a contaminant plume) were measured in a DCPRB sediment as a function of redox conditions. Redox conditions at the DCPRB are expected to vary greatly as the system undergoes varying drying and flooding conditions. Conservative values; K{sub d} values that err on the side of being too low and Potentially Leachable Fraction values that err on the side of being too high, are presented. The K{sub d} values are high compared to conservative literature values, and underscores the importance of measuring site-specific values to provide estimates of sediments natural attenuation/sorption capacities. The Potentially Leachable Fraction indicates that as little as 27% of the As, but all of the Cu and Tl will be part of the source term. In the case of the As, the remaining 83% will likely never leach out of the sediment, thereby providing a form of natural attenuation. Importantly, Be, Cr, Cu, Ni, and V concentrations in the sediment were less-than twice background levels, indicating this sediment was not a potential source for these contaminants. K{sub d} values generally increased significantly (As, Cd, Co, Cr, Cu, Ni, Se, and Tl) when the sediment was

  14. Aqueous liquid redox desulfurisation

    Energy Technology Data Exchange (ETDEWEB)

    Reicher, M.; Niemiec, B.; Katona, T.

    1999-12-01

    The LO-CAT II process is an aqueous liquid redox process which uses ferric and ferrous iron catalysts to oxidise hydrogen sulfide (from sour gas) to elemental sulfur: the relevant chemical equations are given. Chelating agents keep the iron in solution. The system is described under the headings of (i) LO-CAT chemistry, (ii) design parameters, (iii) startup challenges, (iv) present situation and (v) anticipated future conditions. Further improvements to the system are anticipated.

  15. Laminated sediments from the central Peruvian continental slope: A 500 year record of upwelling system productivity, terrestrial runoff and redox conditions

    Science.gov (United States)

    Sifeddine, A.; Gutiérrez, D.; Ortlieb, L.; Boucher, H.; Velazco, F.; Field, D.; Vargas, G.; Boussafir, M.; Salvatteci, R.; Ferreira, V.; García, M.; Valdés, J.; Caquineau, S.; Mandeng Yogo, M.; Cetin, F.; Solis, J.; Soler, P.; Baumgartner, T.

    2008-10-01

    Sedimentological studies including X-ray digital analyses, mineralogy, inorganic contents, and organic geochemistry on cores of laminated sediments accumulated in the oxygen minimum zone of the central Peruvian margin reveal variable oceanographic and climate conditions during the last 500 yr. Coherent upcore variations in sedimentological and geochemical markers in box cores taken off Pisco (B0405-6) and Callao (B0405-13) indicate that variability in the climate proxies examined has regional significance. Most noteworthy is a large shift in proxies at ˜1820 AD, as determined by 210Pb and 14C radiometric dating. This shift is characterized by an increase in total organic carbon (TOC) in parallel with an abrupt increase in the enrichment factor for molybdenum Mo indicating a regional intensification of redox conditions, at least at the sediment water interface. In addition there was lower terrestrial input of quartz, feldspar and clays to the margin. Based on these results, we interpret that during several centuries prior to 1820, which corresponds to the little ice age (LIA), the northern Humboldt current region was less productive and experienced higher terrestrial input related to more humid conditions on the continent. These conditions were probably caused by a southward displacement of the inter-tropical convergence zone and the subtropical high pressure cell during the LIA. Since 1870, increases in TOC and terrigenous mineral fluxes suggest an increase of wind-driven upwelling and higher productivity. These conditions continued to intensify during the late 20th century, as shown by instrumental records of wind forcing.

  16. No Abrupt Changes in redox conditions associated with the end-Permian marine ecosystem collapse in the east Greenland basin

    DEFF Research Database (Denmark)

    Nielsen, Jesper K.; Shen, Y; Piasecki, Stefan

    2010-01-01

    compositions of pyrites from the East Greenland Basin. The size distributions of framboidal pyrites in sediments from a continuous section across the Permian–Triassic boundary reveal that sulfidic conditions in water columns were established about 0.7 m above the extinction event in the East Greenland Basin...

  17. Effect of stable and fluctuating temperatures on the life history traits of Anopheles arabiensis and An. quadriannulatus under conditions of inter- and intra-specific competition.

    Science.gov (United States)

    Davies, Craig; Coetzee, Maureen; Lyons, Candice L

    2016-06-14

    Constant and fluctuating temperatures influence important life-history parameters of malaria vectors which has implications for community organization and the malaria disease burden. The effects of environmental temperature on the hatch rate, survivorship and development rate of Anopheles arabiensis and An. quadriannulatus under conditions of inter- and intra-specific competition are studied. The eggs and larvae of laboratory established colonies were reared under controlled conditions at one constant (25 °C) and two fluctuating (20-30 °C and 18-35 °C) temperature treatments at a ratio of 1:0 or 1:1 (An. arabiensis: An. quadriannulatus). Monitoring of hatch rate, development rate and survival was done at three intervals, 6 to 8 h apart depending on developmental stage. Parametric ANOVAs were used where assumptions of equal variances and normality were met, and a Welch ANOVA where equal variance was violated (α = 0.05). Temperature significantly influenced the measured life-history traits and importantly, this was evident when these species co-occurred. A constant temperature resulted in a higher hatch rate in single species, larval treatments (P competitor (P < 0.05). The influence of temperature treatment on the development rate and survival from egg/larvae to adult differed across species treatments. Fluctuating temperatures incorporating the extremes influence the key life-history parameters measured here with An. arabiensis outcompeting An. quadriannulatus under these conditions. The quantification of the response variables measured here improve our knowledge of the link between temperature and species interactions and provide valuable information for modelling of vector population dynamics.

  18. A Membrane‐Free Redox Flow Battery with Two Immiscible Redox Electrolytes

    OpenAIRE

    Navalpotro, Paula; Palma, Jesus; Anderson, Marc; Marcilla, Rebeca

    2017-01-01

    Abstract Flexible and scalable energy storage solutions are necessary for mitigating fluctuations of renewable energy sources. The main advantage of redox flow batteries is their ability to decouple power and energy. However, they present some limitations including poor performance, short‐lifetimes, and expensive ion‐selective membranes as well as high price, toxicity, and scarcity of vanadium compounds. We report a membrane‐free battery that relies on the immiscibility of redox electrolytes ...

  19. Anaerobic degradation of a mixture of MtBE, EtBE, TBA, and benzene under different redox conditions.

    Science.gov (United States)

    van der Waals, Marcelle J; Pijls, Charles; Sinke, Anja J C; Langenhoff, Alette A M; Smidt, Hauke; Gerritse, Jan

    2018-04-01

    The increasing use of biobased fuels and fuel additives can potentially change the typical fuel-related contamination in soil and groundwater. Anaerobic biotransformation of the biofuel additive ethyl tert-butyl ether (EtBE), as well as of methyl tert-butyl ether (MtBE), benzene, and tert-butyl alcohol (TBA, a possible oxygenate metabolite), was studied at an industrially contaminated site and in the laboratory. Analysis of groundwater samples indicated that in the field MtBE was degraded, yielding TBA as major product. In batch microcosms, MtBE was degraded under different conditions: unamended control, with medium without added electron acceptors, or with ferrihydrite or sulfate (with or without medium) as electron acceptor, respectively. Degradation of EtBE was not observed under any of these conditions tested. TBA was partially depleted in parallel with MtBE. Results of microcosm experiments with MtBE substrate analogues, i.e., syringate, vanillate, or ferulate, were in line with the hypothesis that the observed TBA degradation is a cometabolic process. Microcosms with ferulate, syringate, isopropanol, or diethyl ether showed EtBE depletion up to 86.5% of the initial concentration after 83 days. Benzene was degraded in the unamended controls, with medium without added electron acceptors and with ferrihydrite, sulfate, or chlorate as electron acceptor, respectively. In the presence of nitrate, benzene was only degraded after addition of an anaerobic benzene-degrading community. Nitrate and chlorate hindered MtBE, EtBE, and TBA degradation.

  20. Numerical evaluation for a five-sensor probe method to measure the interfacial area concentration under the bubble fluctuation condition

    International Nuclear Information System (INIS)

    Euh, D. J.; Yun, B. J.; Song, C. H.

    2003-01-01

    Interfacial area concentration is an important parameter in the two phase flow models. Currently, two types of probe methods, double-sensor and four-sensor, are widely used to measure the interfacial area concentration. In this study, a configuration of five-sensor probe sensor tips and a measuring method for the interfacial area concentration by using the probe are proposed to improve the performance of the previous probe methods. The five-sensor probe method proposed in this study is essentially based on the four-sensor probe method but improves it by adapting one more sensor. The passing types of the interfaces through the sensors are categorized into four and independent methods are applied to the interfaces belonging to each category. This method has an advantage such that a more systematic approach for missing bubbles can be made when compared with the classical four sensor probe method. To verify the applicability of the five-sensor probe method, numerical tests are performed with consideration of the bubble lateral movement. The effects of bubble size and intensity of the bubble lateral motion on the measurement of the interfacial area concentration are also investigated. The bubble parameters related to the bubble fluctuation and interface geometry are determined by the Monte Carlo approach

  1. AN APPROACH TO PROVENANCE, TECTONIC AND REDOX CONDITIONS OF JURASSIC-CRETACEOUS AKKUYU FORMATION, CENTRAL TAURIDS, TURKEY

    Directory of Open Access Journals (Sweden)

    Ali SARI

    2012-06-01

    Full Text Available - Late Jurassic-Early Cretaceous Akkuyu formation was deposited in a marine carbonate platform in Central Tarurids. The organic material of the unit is composed of Type III kerogen which is woody material transported from the land. Late Jurassic- Early Cretaceous is an important period which great anoxic events in deep sea bottom occurred due to the primary organic productivity in global sea surface. Use of several trace elements values (Ni, V, U, Cr, Co, Th revealed that Late Jurassic-Early Cretaceous Akkuyu formation shows oxic, disoxic and anoxic paleoredox conditions. In this period the primary productivity was considerably high. Examination of specimen derived from Akkuyu formation revealed that there exists a very good positive relationship between the major oxides of Al2O3, SiO2, Fe2O3, TiO2, and K2O. These combinations of major oxides indicate a detrital origin of source rock. Chemical weathering evaluations of Central Taurids in the Jurassic-Cretaceous period indicated moderate and strong weathering of source rock. K2O/Na2O versus SiO2; SiO2/Al2O3 versus K2O/Na2O; Al2O3/ SiO2 versus Fe2O3 + MgO ve TiO2 versus Fe2O3 + MgO diagrams indicated that Akkuyu formation was deposited along active and/or passive continental margin and derived from basalt and basalt+granite mixed rocks.

  2. Assessment of the performance of SMFCs in the bioremediation of PAHs in contaminated marine sediments under different redox conditions and analysis of the associated microbial communities

    KAUST Repository

    Hamdan, Hamdan Z.

    2016-10-09

    The biodegradation of naphthalene, 2-methylnaphthalene and phenanthrene was evaluated in marine sediment microbial fuel cells (SMFCs) under different biodegradation conditions, including sulfate reduction as a major biodegradation pathway, employment of anode as terminal electron acceptor (TEA) under inhibited sulfate reducing bacteria activity, and combined sulfate and anode usage as electron acceptors. A significant removal of naphthalene and 2-methylnaphthalene was observed at early stages of incubation in all treatments and was attributed to their high volatility. In the case of phenanthrene, a significant removal (93.83 ± 1.68%) was measured in the closed circuit SMFCs with the anode acting as the main TEA and under combined anode and sulfate reduction conditions (88.51 ± 1.3%). A much lower removal (40.37 ± 3.24%) was achieved in the open circuit SMFCs operating with sulfate reduction as a major biodegradation pathway. Analysis of the anodic bacterial community using 16S rRNA gene pyrosequencing revealed the enrichment of genera with potential exoelectrogenic capability, namely Geoalkalibacter and Desulfuromonas, on the anode of the closed circuit SMFCs under inhibited SRB activity, while they were not detected on the anode of open circuit SMFCs. These results demonstrate the role of the anode in enhancing PAHs biodegradation in contaminated marine sediments and suggest a higher system efficiency in the absence of competition between microbial redox processes (under SRB inhibition), namely due to the anode enrichment with exoelectrogenic bacteria, which is a more energetically favorable mechanism for PAHs oxidation than sulfate.

  3. Biogeochemical Barriers: Redox Behavior of Metals and Metalloids

    Science.gov (United States)

    Redox conditions and pH are arguably the most important geochemical parameters that control contaminant transport and fate in groundwater systems. Oxidation-reduction (redox) reactions mediate the chemical behavior of both inorganic and organic chemical constituents by affecting...

  4. Life cycle and reproductive patterns of Triatoma rubrovaria (Blanchard, 1843 (Hemiptera: Reduviidae under constant and fluctuating conditions of temperature and humidity

    Directory of Open Access Journals (Sweden)

    Damborsky Miryam P.

    2005-01-01

    Full Text Available The aim of this study was to evaluate the temperature and relative humidity influence in the life cycle, mortality and fecundity patterns of Triatoma rubrovaria. Four cohorts with 60 recently laid eggs each were conformed. The cohorts were divided into two groups. In the controlled conditions group insects were maintained in a dark climatic chamber under constant temperature and humidity, whereas triatomines of the ambiental temperature group were maintained at room temperature. Average incubation time was 15.6 days in the controlled conditions group and 19.1 days in the ambiental temperature. In group controlled conditions the time from egg to adult development lasted 10 months while group ambiental temperature took four months longer. Egg eclosion rate was 99.1% and 98.3% in controlled conditions and ambiental temperature, respectively. Total nymphal mortality in controlled conditions was 52.6% whereas in ambiental temperature was 51.8%. Mean number of eggs/female was 817.6 controlled conditions and 837.1 ambiental temperature. Fluctuating temperature and humidity promoted changes in the life cycle duration and in the reproductive performance of this species, although not in the species mortality.

  5. Soil Metabolome and Metabolic Fate: Microbial Insights into Freshwater Tidal Wetland Redox Biogeochemistry

    Science.gov (United States)

    Roy Chowdhury, T.; Bramer, L.; Hoyt, D. W.; Kim, Y. M.; Metz, T. O.; McCue, L. A.; Jansson, J.; Bailey, V. L.

    2017-12-01

    Earth System Models predict climate extremes that will impact regional and global hydrology. Aquatic-terrestrial transition zones like wetlands will experience the immediate consequence of climate change as shifts in the magnitude and dynamics of hydrologic flow. Such fluctuating hydrology can alter the structure and function of the soil microbial populations that in turn will alter the nature and rate of biogeochemical transformations and significantly impact the carbon balance of the ecosystem. We tested the impacts of shifting hydrology on the soil microbiome and the role of antecedent moisture condition on redox active microbial processes in soils sampled from a tidal freshwater wetland system in the lower Columbia River, WA, USA. Our objectives were to characterize changes in the soil microbial community composition in response to soil moisture legacy effects, and to elucidate relationships between community response, geochemical signatures and metabolite profiles in this soil. The 16S rRNA gene sequencing showed significant decreases in bacterial abundance capable of anaerobic metabolism in response to drying, but quickly recovered to the antecedent moisture condition, as observed by redox processes. Metabolomics and biogeochemical process rates generated evidence for moisture-driven redox conditions as principal controls on the community and metabolic function. Fluctuating redox conditions altered terminal electron acceptor and donor availability and recovery strengths of these pools in soil such that a disproportionate release of carbon dioxide stemmed from alternative anaerobic degradation processes like sulfate and iron reduction in compared to methanogenesis. Our results show that anoxic conditions impact microbial communities in both permanently and temporarily saturated conditions and that rapid change in hydrology can increase substrate availability for both aerobic and anaerobic decomposition processes, including methanogenesis.

  6. Fully Quantum Fluctuation Theorems

    Science.gov (United States)

    Åberg, Johan

    2018-02-01

    Systems that are driven out of thermal equilibrium typically dissipate random quantities of energy on microscopic scales. Crooks fluctuation theorem relates the distribution of these random work costs to the corresponding distribution for the reverse process. By an analysis that explicitly incorporates the energy reservoir that donates the energy and the control system that implements the dynamic, we obtain a quantum generalization of Crooks theorem that not only includes the energy changes in the reservoir but also the full description of its evolution, including coherences. Moreover, this approach opens up the possibility for generalizations of the concept of fluctuation relations. Here, we introduce "conditional" fluctuation relations that are applicable to nonequilibrium systems, as well as approximate fluctuation relations that allow for the analysis of autonomous evolution generated by global time-independent Hamiltonians. We furthermore extend these notions to Markovian master equations, implicitly modeling the influence of the heat bath.

  7. Quantum fluctuations

    International Nuclear Information System (INIS)

    Reynaud, S.; Giacobino, S.; Zinn-Justin, J.

    1997-01-01

    This course is dedicated to present in a pedagogical manner the recent developments in peculiar fields concerned by quantum fluctuations: quantum noise in optics, light propagation through dielectric media, sub-Poissonian light generated by lasers and masers, quantum non-demolition measurements, quantum electrodynamics applied to cavities and electrical circuits involving superconducting tunnel junctions. (A.C.)

  8. Zinc and the modulation of redox homeostasis

    Science.gov (United States)

    Oteiza, Patricia I.

    2012-01-01

    Zinc, a redox inactive metal, has been long viewed as a component of the antioxidant network, and growing evidence points to its involvement in redox-regulated signaling. These actions are exerted through several mechanisms based on the unique chemical and functional properties of zinc. Overall, zinc contributes to maintain the cell redox balance through different mechanisms including: i) the regulation of oxidant production and metal-induced oxidative damage; ii) the dynamic association of zinc with sulfur in protein cysteine clusters, from which the metal can be released by nitric oxide, peroxides, oxidized glutathione and other thiol oxidant species; iii) zinc-mediated induction of the zinc-binding protein metallothionein, which releases the metal under oxidative conditions and act per se scavenging oxidants; iv) the involvement of zinc in the regulation of glutathione metabolism and of the overall protein thiol redox status; and v) a direct or indirect regulation of redox signaling. Findings of oxidative stress, altered redox signaling, and associated cell/tissue disfunction in cell and animal models of zinc deficiency, stress the relevant role of zinc in the preservation of cell redox homeostasis. However, while the participation of zinc in antioxidant protection, redox sensing, and redox-regulated signaling is accepted, the involved molecules, targets and mechanisms are still partially known and the subject of active research. PMID:22960578

  9. Redox regulation of cell proliferation: Bioinformatics and redox proteomics approaches to identify redox-sensitive cell cycle regulators.

    Science.gov (United States)

    Foyer, Christine H; Wilson, Michael H; Wright, Megan H

    2018-03-29

    Plant stem cells are the foundation of plant growth and development. The balance of quiescence and division is highly regulated, while ensuring that proliferating cells are protected from the adverse effects of environment fluctuations that may damage the genome. Redox regulation is important in both the activation of proliferation and arrest of the cell cycle upon perception of environmental stress. Within this context, reactive oxygen species serve as 'pro-life' signals with positive roles in the regulation of the cell cycle and survival. However, very little is known about the metabolic mechanisms and redox-sensitive proteins that influence cell cycle progression. We have identified cysteine residues on known cell cycle regulators in Arabidopsis that are potentially accessible, and could play a role in redox regulation, based on secondary structure and solvent accessibility likelihoods for each protein. We propose that redox regulation may function alongside other known posttranslational modifications to control the functions of core cell cycle regulators such as the retinoblastoma protein. Since our current understanding of how redox regulation is involved in cell cycle control is hindered by a lack of knowledge regarding both which residues are important and how modification of those residues alters protein function, we discuss how critical redox modifications can be mapped at the molecular level. Crown Copyright © 2018. Published by Elsevier Inc. All rights reserved.

  10. Are bioassays useful tools to assess redox processes and biodegradation?

    DEFF Research Database (Denmark)

    Albrechtsen, Hans-Jørgen; Pedersen, Philip Grinder; Ludvigsen, L.

    2002-01-01

    sensitive hydrochemical or geochemical parameters, levels of hydrogen, and redox potential. However, all these approaches have to be evaluated against TEAP-bioassays as the most direct measure. We assessed successfully ongoing microbial-mediated redox processes by TEAP-bioassays in degradation studies...... of aromatic and chlorinated aliphatic compounds in landfill leachate plumes, and of pesticides in aquifers with various redox conditions....

  11. The redox-Mannich reaction.

    Science.gov (United States)

    Chen, Weijie; Seidel, Daniel

    2014-06-06

    A complement to the classic three-component Mannich reaction, the redox-Mannich reaction, utilizes the same starting materials but incorporates an isomerization step that enables the facile preparation of ring-substituted β-amino ketones. Reactions occur under relatively mild conditions and are facilitated by benzoic acid.

  12. Redox regulation of plant development.

    Science.gov (United States)

    Considine, Michael J; Foyer, Christine H

    2014-09-20

    We provide a conceptual framework for the interactions between the cellular redox signaling hub and the phytohormone signaling network that controls plant growth and development to maximize plant productivity under stress-free situations, while limiting growth and altering development on exposure to stress. Enhanced cellular oxidation plays a key role in the regulation of plant growth and stress responses. Oxidative signals or cycles of oxidation and reduction are crucial for the alleviation of dormancy and quiescence, activating the cell cycle and triggering genetic and epigenetic control that underpin growth and differentiation responses to changing environmental conditions. The redox signaling hub interfaces directly with the phytohormone network in the synergistic control of growth and its modulation in response to environmental stress, but a few components have been identified. Accumulating evidence points to a complex interplay of phytohormone and redox controls that operate at multiple levels. For simplicity, we focus here on redox-dependent processes that control root growth and development and bud burst. The multiple roles of reactive oxygen species in the control of plant growth and development have been identified, but increasing emphasis should now be placed on the functions of redox-regulated proteins, along with the central roles of reductants such as NAD(P)H, thioredoxins, glutathione, glutaredoxins, peroxiredoxins, ascorbate, and reduced ferredoxin in the regulation of the genetic and epigenetic factors that modulate the growth and vigor of crop plants, particularly within an agricultural context.

  13. Bioconversion of Coal: Hydrologic indicators of the extent of coal biodegradation under different redox conditions and coal maturity, Velenje Basin case study, Slovenia

    Science.gov (United States)

    Kanduč, Tjaša; Grassa, Fausto; Lazar, Jerneja; Jamnikar, Sergej; Zavšek, Simon; McIntosh, Jennifer

    2014-05-01

    Underground mining of coal and coal combustion for energy has significant environmental impacts. In order to reduce greenhouse gas emissions, other lower -carbon energy sources must be utilized. Coalbed methane (CBM) is an important source of relatively low-carbon energy. Approximately 20% of world's coalbed methane is microbial in origin (Bates et al., 2011). Interest in microbial CBM has increased recently due to the possibility of stimulating methanogenesis. Despite increasing interest, the hydrogeochemical conditions and mechanisms for biodegradation of coal and microbial methane production are poorly understood. This project aims to examine geochemical characteristics of coalbed groundwater and coalbed gases in order to constrain biogeochemical processes to better understand the entire process of coal biodegradation of coal to coalbed gases. A better understanding of geochemical processes in CBM areas may potentially lead to sustainable stimulation of microbial methanogenesis at economical rates. Natural analogue studies of carbon dioxide occurring in the subsurface have the potential to yield insights into mechanisms of carbon dioxide storage over geological time scales (Li et al., 2013). In order to explore redox processes related to methanogenesis and determine ideal conditions under which microbial degradation of coal is likely to occur, this study utilizes groundwater and coalbed gas samples from Velenje Basin. Determination of the concentrations of methane, carbondioxide, nitrogen, oxygen, argon was performed with homemade NIER mass spectrometer. Isotopic composition of carbon dioxide, isotopic composition of methane, isotopic composition of deuterium in methane was determined with Europa-Scientific IRMS with an ANCA-TG preparation module and Thermo Delta XP GC-TC/CF-IRMS coupled to a TRACE GC analyzer. Total alkalinity of groundwater was measured by Gran titration. Major cations were analyzed by ICP-OES and anions by IC method. Isotopic composition of

  14. Redox Behavior of Fe2+/Fe3+ Redox Couple by Absorption Spectroscopy and Measurement

    International Nuclear Information System (INIS)

    Oh, J. Y.; Park, S.; Yun, J. I.

    2010-01-01

    Redox behavior has influences on speciation and other geochemical reactions of radionuclides such as sorption, solubility, and colloid formation, etc. It is one of the factors for evaluation of long-term safety assessment under high-level radioactive waste (HLW) disposal conditions. Accordingly, redox potential (Eh) measurement in aquatic system is important to investigate the redox conditions. Eh is usually measured with redox active electrodes (Pt, Au, glassy carbon, etc.). Nevertheless, Eh measurements by general methods using electrodes provide low accuracy and high uncertainty problem. Therefore, Eh calculated from the concentration of redox active elements with a proper complexing reagent by using UV-Vis absorption spectroscopy is progressed. Iron exists mostly as spent nuclear waste container material and in hydro-geologic minerals. In this system, iron controls the redox condition in near-field area and influences chemical behavior and speciation of radionuclides including redox sensitive actinides such as U, Np, and Pu. In the present work, we present the investigation on redox phenomena of iron in aquatic system by a combination of absorption spectroscopy and redox potential measurements

  15. Plant redox proteomics

    DEFF Research Database (Denmark)

    Navrot, Nicolas; Finnie, Christine; Svensson, Birte

    2011-01-01

    PTMs in regulating enzymatic activities and controlling biological processes in plants. Notably, proteins controlling the cellular redox state, e.g. thioredoxin and glutaredoxin, appear to play dual roles to maintain oxidative stress resistance and regulate signal transduction pathways via redox PTMs......In common with other aerobic organisms, plants are exposed to reactive oxygen species resulting in formation of post-translational modifications related to protein oxidoreduction (redox PTMs) that may inflict oxidative protein damage. Accumulating evidence also underscores the importance of redox....... To get a comprehensive overview of these types of redox-regulated pathways there is therefore an emerging interest to monitor changes in redox PTMs on a proteome scale. Compared to some other PTMs, e.g. protein phosphorylation, redox PTMs have received less attention in plant proteome analysis, possibly...

  16. Stability conditions for exact-exchange Kohn-Sham methods and their relation to correlation energies from the adiabatic-connection fluctuation-dissipation theorem.

    Science.gov (United States)

    Bleiziffer, Patrick; Schmidtel, Daniel; Görling, Andreas

    2014-11-28

    The occurrence of instabilities, in particular singlet-triplet and singlet-singlet instabilities, in the exact-exchange (EXX) Kohn-Sham method is investigated. Hessian matrices of the EXX electronic energy with respect to the expansion coefficients of the EXX effective Kohn-Sham potential in an auxiliary basis set are derived. The eigenvalues of these Hessian matrices determine whether or not instabilities are present. Similar as in the corresponding Hartree-Fock case instabilities in the EXX method are related to symmetry breaking of the Hamiltonian operator for the EXX orbitals. In the EXX methods symmetry breaking can easily be visualized by displaying the local multiplicative exchange potential. Examples (N2, O2, and the polyyne C10H2) for instabilities and symmetry breaking are discussed. The relation of the stability conditions for EXX methods to approaches calculating the Kohn-Sham correlation energy via the adiabatic-connection fluctuation-dissipation (ACFD) theorem is discussed. The existence or nonexistence of singlet-singlet instabilities in an EXX calculation is shown to indicate whether or not the frequency-integration in the evaluation of the correlation energy is singular in the EXX-ACFD method. This method calculates the Kohn-Sham correlation energy through the ACFD theorem theorem employing besides the Coulomb kernel also the full frequency-dependent exchange kernel and yields highly accurate electronic energies. For the case of singular frequency-integrands in the EXX-ACFD method a regularization is suggested. Finally, we present examples of molecular systems for which the self-consistent field procedure of the EXX as well as the Hartree-Fock method can converge to more than one local minimum depending on the initial conditions.

  17. Stability conditions for exact-exchange Kohn-Sham methods and their relation to correlation energies from the adiabatic-connection fluctuation-dissipation theorem

    International Nuclear Information System (INIS)

    Bleiziffer, Patrick; Schmidtel, Daniel; Görling, Andreas

    2014-01-01

    The occurrence of instabilities, in particular singlet-triplet and singlet-singlet instabilities, in the exact-exchange (EXX) Kohn-Sham method is investigated. Hessian matrices of the EXX electronic energy with respect to the expansion coefficients of the EXX effective Kohn-Sham potential in an auxiliary basis set are derived. The eigenvalues of these Hessian matrices determine whether or not instabilities are present. Similar as in the corresponding Hartree-Fock case instabilities in the EXX method are related to symmetry breaking of the Hamiltonian operator for the EXX orbitals. In the EXX methods symmetry breaking can easily be visualized by displaying the local multiplicative exchange potential. Examples (N 2 , O 2 , and the polyyne C 10 H 2 ) for instabilities and symmetry breaking are discussed. The relation of the stability conditions for EXX methods to approaches calculating the Kohn-Sham correlation energy via the adiabatic-connection fluctuation-dissipation (ACFD) theorem is discussed. The existence or nonexistence of singlet-singlet instabilities in an EXX calculation is shown to indicate whether or not the frequency-integration in the evaluation of the correlation energy is singular in the EXX-ACFD method. This method calculates the Kohn-Sham correlation energy through the ACFD theorem theorem employing besides the Coulomb kernel also the full frequency-dependent exchange kernel and yields highly accurate electronic energies. For the case of singular frequency-integrands in the EXX-ACFD method a regularization is suggested. Finally, we present examples of molecular systems for which the self-consistent field procedure of the EXX as well as the Hartree-Fock method can converge to more than one local minimum depending on the initial conditions

  18. Metabolic Control of Redox and Redox Control of Metabolism in Plants

    Science.gov (United States)

    Fernie, Alisdair R.

    2014-01-01

    Abstract Significance: Reduction-oxidation (Redox) status operates as a major integrator of subcellular and extracellular metabolism and is simultaneously itself regulated by metabolic processes. Redox status not only dominates cellular metabolism due to the prominence of NAD(H) and NADP(H) couples in myriad metabolic reactions but also acts as an effective signal that informs the cell of the prevailing environmental conditions. After relay of this information, the cell is able to appropriately respond via a range of mechanisms, including directly affecting cellular functioning and reprogramming nuclear gene expression. Recent Advances: The facile accession of Arabidopsis knockout mutants alongside the adoption of broad-scale post-genomic approaches, which are able to provide transcriptomic-, proteomic-, and metabolomic-level information alongside traditional biochemical and emerging cell biological techniques, has dramatically advanced our understanding of redox status control. This review summarizes redox status control of metabolism and the metabolic control of redox status at both cellular and subcellular levels. Critical Issues: It is becoming apparent that plastid, mitochondria, and peroxisome functions influence a wide range of processes outside of the organelles themselves. While knowledge of the network of metabolic pathways and their intraorganellar redox status regulation has increased in the last years, little is known about the interorganellar redox signals coordinating these networks. A current challenge is, therefore, synthesizing our knowledge and planning experiments that tackle redox status regulation at both inter- and intracellular levels. Future Directions: Emerging tools are enabling ever-increasing spatiotemporal resolution of metabolism and imaging of redox status components. Broader application of these tools will likely greatly enhance our understanding of the interplay of redox status and metabolism as well as elucidating and

  19. The Redox Proteome*

    Science.gov (United States)

    Go, Young-Mi; Jones, Dean P.

    2013-01-01

    The redox proteome consists of reversible and irreversible covalent modifications that link redox metabolism to biologic structure and function. These modifications, especially of Cys, function at the molecular level in protein folding and maturation, catalytic activity, signaling, and macromolecular interactions and at the macroscopic level in control of secretion and cell shape. Interaction of the redox proteome with redox-active chemicals is central to macromolecular structure, regulation, and signaling during the life cycle and has a central role in the tolerance and adaptability to diet and environmental challenges. PMID:23861437

  20. Fluctuation analysis

    International Nuclear Information System (INIS)

    Clarke, J.

    1980-01-01

    This paper briefly reviews sources of noise in Josephson junctions, and the limits they impose on the sensitivity of dc and rf SQUIDS. The results are strictly valid only for a resistively shunted junction (RSJ) with zero capacitance, but should be applicable to point contact junctions and microbridges in so far as these devices can be approximated by the RSJ model. Fluctuations arising from Nyquist noise in the resistive shunt of a single junction are discussed in the limit eI/sub o/R/k/sub B/T << 1 in which a classical treatment is appropriate, and then extend the treatment to the limit eI/sub o/R/k/sub B/T greater than or equal to 1 in which quantum effects become important. The Nyquist limit theory is used to calculate the noise in a dc SQUID, and the results are compared with a number of practical devices. The quantum limit is briefly considered. Results for the predicted sensitivity of rf SQUIDS are presented, and also compared with a number of practical devices. Finally, the importance of l/f noise (f is the frequency) in limiting the low frequency performance of SQUIDS is discussed

  1. Evaluation of I/Ca ratios in benthic foraminifera from the Peruvian oxygen minimum zone as proxy for redox conditions in the ambient water masses

    Science.gov (United States)

    Glock, N.; Liebetrau, V.; Eisenhauer, A.

    2014-12-01

    Tropical oxygen minimum zones (OMZs) are most important areas of oxygen depletion in today´s oceans and nutrient cycling in these regions has a large socio-economic impact because they account for about 17% of the global commercial fish catches(1). Possibly increasing magnitude and area of oxygen depletion in these regions, might endanger rich pelagic fish habitats in the future threatening the global marine food supply. By the use of a quantitative redox proxy in OMZs, reconstruction of the temporal variation in OMZ extension eventually providing information about past and future changes in oxygenation and the anthropogenic role in the recent trend of expanding OMZs(2). Recent work has shown that iodine/calcium (I/Ca) ratios in marine carbonates are a promising proxy for ambient oxygen concentration(3). Our study explores the correlation of I/Ca ratios in four benthic foraminiferal species (three calcitic, one aragonitic) from the Peruvian OMZ to bottom water oxygen concentrations ([O2]BW) and evaluates foraminiferal I/Ca ratios as a possible redox proxy for the ambient water masses. Our results show that all species have a positive trend in the I/Ca ratios as a function of [O2]BW. Only for the aragonitic species Hoeglundina elegans this trend is not significant. The highest significance has been found for Uvigerina striata (I/Ca = 0.032(±0.004).[O2]BW + 0.29(±0.03), R² = 0.61, F = 75, P solutions, (ii) a species dependency of the I/Ca-[O2]BW relationship which is either related to a strong vital effect or toa species dependency on the calcification depth within sediment, and (iii) the inter-test variability of I/Ca between different specimens from the same species and habitat. (1): FAO FishStat: Fisheries and aquaculture software. In: FAO Fisheries and Aquaculture Department[online]. Rome. Updated 28 Nov. 2013. (2): Stramma et al.: Expanding Oxygen-Minimum Zones in the Tropical Oceans, Science, 320, 655-658, 2008. (3): Lu et al.: Iodine to calcium ratios in

  2. Biotite and chlorite weathering at 25 degrees C: the dependence of pH and (bi)carbonate on weathering kinetics, dissolution stoichiometry, and solubility; and the relation to redox conditions in granitic aquifers

    Energy Technology Data Exchange (ETDEWEB)

    Malmstroem, M.; Banwart, S. [Royal Inst. of Technology, Stockholm (Sweden). Dept. of Inorganic Chemistry; Duro, L. [Universidad Politecnica de Cataluna, Barcelona (Spain). Dept. de Ingneria Quimica; Wersin, P.; Bruno, J. [MBT Technologia Ambiental, Cerdanyola (Spain)

    1995-01-01

    We have studied the kinetics and thermodynamics of biotite and chlorite weathering in the pH range 2redox potentials in the range of -200-400 mV at neutral pH and qualitatively agrees with field data reported in the literature. We use observed iron release rate to make conservative estimates of timescales of 1. the depletion of molecular oxygen from deep aquifers (810{sup 2}-10{sup 2} year); and 2. the development of characteristic Fe(III) concentrations (10{sup -5} M in 10{sup -}1 years). The Fe(III)-bearing clay minerals formed during these experiments are similar to the fracture-filling-material observed at the Aespoe Hard Rock Laboratory. Such clays can provide reducing capacity to a repository. They can help maintain anoxic conditions by consuming oxygen that enters the repository during the construction and operation phases thereby helping maintain the redox stability of the repository regarding canister corrosion. The half-life of oxygen trapped in the repository at the time of closure depends on the rate of oxygen uptake by Fe(II) minerals, sulfide minerals and organic carbon. Fe(II)-clay minerals are important to the redox stability of a repository, as well as providing a sorption barrier to radionuclide migration. 107 refs, 52 figs, 35 tabs.

  3. Redox signaling in plants.

    Science.gov (United States)

    Foyer, Christine H; Noctor, Graham

    2013-06-01

    Our aim is to deliver an authoritative and challenging perspective of current concepts in plant redox signaling, focusing particularly on the complex interface between the redox and hormone-signaling pathways that allow precise control of plant growth and defense in response to metabolic triggers and environmental constraints and cues. Plants produce significant amounts of singlet oxygen and other reactive oxygen species (ROS) as a result of photosynthetic electron transport and metabolism. Such pathways contribute to the compartment-specific redox-regulated signaling systems in plant cells that convey information to the nucleus to regulate gene expression. Like the chloroplasts and mitochondria, the apoplast-cell wall compartment makes a significant contribution to the redox signaling network, but unlike these organelles, the apoplast has a low antioxidant-buffering capacity. The respective roles of ROS, low-molecular antioxidants, redox-active proteins, and antioxidant enzymes are considered in relation to the functions of plant hormones such as salicylic acid, jasmonic acid, and auxin, in the composite control of plant growth and defense. Regulation of redox gradients between key compartments in plant cells such as those across the plasma membrane facilitates flexible and multiple faceted opportunities for redox signaling that spans the intracellular and extracellular environments. In conclusion, plants are recognized as masters of the art of redox regulation that use oxidants and antioxidants as flexible integrators of signals from metabolism and the environment.

  4. Chloroplast Redox Poise

    DEFF Research Database (Denmark)

    Steccanella, Verdiana

    the redox status of the plastoquinone pool and chlorophyll biosynthesis. Furthermore, in the plant cell, the equilibrium between redox reactions and ROS signals is also maintained by various balancing mechanisms among which the thioredoxin reductase-thioredoxin system (TR-Trx) stands out as a mediator......The redox state of the chloroplast is maintained by a delicate balance between energy production and consumption and is affected by the need to avoid increased production of reactive oxygen species (ROS). Redox power and ROS generated in the chloroplast are essential for maintaining physiological...... metabolic pathways and for optimizing chloroplast functions. The redox poise of photosynthetic electron transport components like plastoquinone is crucial to initiate signaling cascades and might also be involved in key biosynthetic pathways such as chlorophyll biosynthesis. We, therefore, explored...

  5. Iron Redox Dynamics in Humid Tropical Forest Soils: Carbon Stabilization vs. Degradation?

    Science.gov (United States)

    Hall, S. J.; Silver, W. L.; Hammel, K.

    2015-12-01

    Most terrestrial soils exhibit a patchwork of oxygen (O2) availability that varies over spatial scales of microsites to catenas to landscapes, and over temporal scales of minutes to seasons. Oxygen fluctuations often drive microbial iron (Fe) reduction and abiotic/biotic Fe oxidation at the microsite scale, contributing to anaerobic carbon (C) mineralization and changes in soil physical and chemical characteristics, especially the dissolution and precipitation of short-range ordered Fe phases thought to stabilize C. Thus, O2 fluctuations and Fe redox cycling may have multiple nuanced and opposing impacts on different soil C pools, illustrated by recent findings from Fe-rich Oxisols and Ultisols in the Luquillo Experimental Forest, Puerto Rico. Spatial patterns in surface soil C stocks at the landscape scale correlated strongly (R2 = 0.98) with concentrations of reduced Fe (Fe(II)), reflecting constitutive differences in reducing conditions within and among sites that promote C accumulation in mineral soil horizons. Similarly, turnover times of a decadal-cycling pool of mineral-associated organic matter increased with Fe(II) across a catena, possibly reflecting the role of anaerobic microsites in long-term C stabilization. However, two different indices of short-range order Fe showed highly significant opposing relationships (positive and negative) with spatial variation in soil C concentrations, possibly reflecting a dual role of Fe in driving C stabilization via co-precipitation, and C solubilization and loss following dissimilatory Fe reduction. Consistent with the field data, laboratory incubations demonstrated that redox fluctuations can increase the contribution of biochemically recalcitrant C (lignin) to soil respiration, whereas addition of short-range order Fe dramatically suppressed lignin mineralization but had no impact on bulk soil respiration. Thus, understanding spatial and temporal patterns of Fe redox cycling may provide insight into explaining the

  6. Imaging dynamic redox processes with genetically encoded probes.

    Science.gov (United States)

    Ezeriņa, Daria; Morgan, Bruce; Dick, Tobias P

    2014-08-01

    Redox signalling plays an important role in many aspects of physiology, including that of the cardiovascular system. Perturbed redox regulation has been associated with numerous pathological conditions; nevertheless, the causal relationships between redox changes and pathology often remain unclear. Redox signalling involves the production of specific redox species at specific times in specific locations. However, until recently, the study of these processes has been impeded by a lack of appropriate tools and methodologies that afford the necessary redox species specificity and spatiotemporal resolution. Recently developed genetically encoded fluorescent redox probes now allow dynamic real-time measurements, of defined redox species, with subcellular compartment resolution, in intact living cells. Here we discuss the available genetically encoded redox probes in terms of their sensitivity and specificity and highlight where uncertainties or controversies currently exist. Furthermore, we outline major goals for future probe development and describe how progress in imaging methodologies will improve our ability to employ genetically encoded redox probes in a wide range of situations. This article is part of a special issue entitled "Redox Signalling in the Cardiovascular System." Copyright © 2014 Elsevier Ltd. All rights reserved.

  7. Calibration and fluctuation of the secular frequency peak amplitude versus initial condition distribution of the ion cloud confined into a three-dimensional quadrupole ion trap using a fourier transform operating mode and a steady ion flow injection mode

    International Nuclear Information System (INIS)

    Janulyte, A.; Andre, J.; Carette, M.; Mercury, M.; Reynard, C; Zerega, Y.

    2009-01-01

    A specific Fourier transform operating mode is applied to a 3-dimensional quadrupolar ion trap for mass analysis (Fourier Transform Quadrupolar Ion Trap (FTQIT) Operating Mode or Mass Spectrometer). With this operating mode, an image signal, which is representative of the collective motion of simultaneously confined ions, is made up from a set of recorded time-of-flight histograms. In an ion trap, the secular frequency of ion motion depends on m/Z ratio of the ion. By Fourier transformation of the image signal, one observes the frequency peak of each confined ionic species. When only one ionic species is confined, the peak amplitude is proportional to the maximal amplitude of the image signal. The maximal amplitude of the image signal is expressed according to the operating parameters, the initial conditions of the ions and the number of ions. Simulation tools lead to fluctuation calculation of the maximal amplitude of the image signal. Two origins are explored: (1) the fluctuation of the numbers of ions according to the steady ion flow injection mode (SIFIM) used with this operating mode and (2) the distribution fluctuation of the initial positions and velocities. Initial confinement conditions, obtained with SIFIM injection mode, lead to optimal detection with small fluctuations of the peak amplitude for Fourier transform operating mode applied to an ion trap. (authors)

  8. Biotite and chlorite weathering at 25 degrees C: the dependence of pH and (bi)carbonate on weathering kinetics, dissolution stoichiometry, and solubility; and the relation to redox conditions in granitic aquifers

    International Nuclear Information System (INIS)

    Malmstroem, M.; Banwart, S.

    1995-01-01

    We have studied the kinetics and thermodynamics of biotite and chlorite weathering in the pH range 2 2 -10 2 year); and 2. the development of characteristic Fe(III) concentrations (10 -5 M in 10 - 1 years). The Fe(III)-bearing clay minerals formed during these experiments are similar to the fracture-filling-material observed at the Aespoe Hard Rock Laboratory. Such clays can provide reducing capacity to a repository. They can help maintain anoxic conditions by consuming oxygen that enters the repository during the construction and operation phases thereby helping maintain the redox stability of the repository regarding canister corrosion. The half-life of oxygen trapped in the repository at the time of closure depends on the rate of oxygen uptake by Fe(II) minerals, sulfide minerals and organic carbon. Fe(II)-clay minerals are important to the redox stability of a repository, as well as providing a sorption barrier to radionuclide migration. 107 refs, 52 figs, 35 tabs

  9. Redox characteristics of the eukaryotic cytosol

    DEFF Research Database (Denmark)

    López-Mirabal, H Reynaldo; Winther, Jakob R

    2007-01-01

    The eukaryotic cytoplasm has long been regarded as a cellular compartment in which the reduced state of protein cysteines is largely favored. Under normal conditions, the cytosolic low-molecular weight redox buffer, comprising primarily of glutathione, is highly reducing and reactive oxygen species...... (ROS) and glutathionylated proteins are maintained at very low levels. In the present review, recent progress in the understanding of the cytosolic thiol-disulfide redox metabolism and novel analytical approaches to studying cytosolic redox properties are discussed. We will focus on the yeast model...... organism, Saccharomyces cerevisiae, where the combination of genetic and biochemical approaches has brought us furthest in understanding the mechanisms underlying cellular redox regulation. It has been shown in yeast that, in addition to the enzyme glutathione reductase, other mechanisms may exist...

  10. Water table fluctuations and soil biogeochemistry: An experimental approach using an automated soil column system

    Science.gov (United States)

    Rezanezhad, F.; Couture, R.-M.; Kovac, R.; O'Connell, D.; Van Cappellen, P.

    2014-02-01

    Water table fluctuations significantly affect the biological and geochemical functioning of soils. Here, we introduce an automated soil column system in which the water table regime is imposed using a computer-controlled, multi-channel pump connected to a hydrostatic equilibrium reservoir and a water storage reservoir. The potential of this new system is illustrated by comparing results from two columns filled with 45 cm of the same homogenized riparian soil. In one soil column the water table remained constant at -20 cm below the soil surface, while in the other the water table oscillated between the soil surface and the bottom of the column, at a rate of 4.8 cm d-1. The experiment ran for 75 days at room temperature (25 ± 2 °C). Micro-sensors installed at -10 and -30 cm below the soil surface in the stable water table column recorded constant redox potentials on the order of 600 and -200 mV, respectively. In the fluctuating water table column, redox potentials at the same depths oscillated between oxidizing (∼700 mV) and reducing (∼-100 mV) conditions. Pore waters collected periodically and solid-phase analyses on core material obtained at the end of the experiment highlighted striking geochemical differences between the two columns, especially in the time series and depth distributions of Fe, Mn, K, P and S. Soil CO2 emissions derived from headspace gas analysis exhibited periodic variations in the fluctuating water table column, with peak values during water table drawdown. Transient redox conditions caused by the water table fluctuations enhanced microbial oxidation of soil organic matter, resulting in a pronounced depletion of particulate organic carbon in the midsection of the fluctuating water table column. Denaturing Gradient Gel Electrophoresis (DGGE) revealed the onset of differentiation of the bacterial communities in the upper (oxidizing) and lower (reducing) soil sections, although no systematic differences in microbial community structure

  11. Redox Regulation of Endothelial Cell Fate

    Science.gov (United States)

    Song, Ping; Zou, Ming-Hui

    2014-01-01

    Endothelial cells (ECs) are present throughout blood vessels and have variable roles in both physiological and pathological settings. EC fate is altered and regulated by several key factors in physiological or pathological conditions. Reactive nitrogen species and reactive oxygen species derived from NAD(P)H oxidases, mitochondria, or nitric oxide-producing enzymes are not only cytotoxic but also compose a signaling network in the redox system. The formation, actions, key molecular interactions, and physiological and pathological relevance of redox signals in ECs remain unclear. We review the identities, sources, and biological actions of oxidants and reductants produced during EC function or dysfunction. Further, we discuss how ECs shape key redox sensors and examine the biological functions, transcriptional responses, and post-translational modifications evoked by the redox system in ECs. We summarize recent findings regarding the mechanisms by which redox signals regulate the fate of ECs and address the outcome of altered EC fate in health and disease. Future studies will examine if the redox biology of ECs can be targeted in pathophysiological conditions. PMID:24633153

  12. Nonequilibrium quantum fluctuations of work.

    Science.gov (United States)

    Allahverdyan, A E

    2014-09-01

    The concept of work is basic for statistical thermodynamics. To gain a fuller understanding of work and its (quantum) features, it needs to be represented as an average of a fluctuating quantity. Here I focus on the work done between two moments of time for a thermally isolated quantum system driven by a time-dependent Hamiltonian. I formulate two natural conditions needed for the fluctuating work to be physically meaningful for a system that starts its evolution from a nonequilibrium state. The existing definitions do not satisfy these conditions due to issues that are traced back to noncommutativity. I propose a definition of fluctuating work that is free of previous drawbacks and that applies for a wide class of nonequilibrium initial states. It allows the deduction of a generalized work-fluctuation theorem that applies for an arbitrary (out-of-equilibrium) initial state.

  13. Fluctuations in quantum chaos

    International Nuclear Information System (INIS)

    Casati, G.; Chirikov, B.V.

    1996-01-01

    Various fluctuations in quantum systems with discrete spectrum are discussed, including recent unpublished results. Open questions and unexplained peculiarities of quantum fluctuations are formulated [ru

  14. [A study on the relation between stomatognathic system and the systemic condition, concerning the influence of experimental occlusal interference on upright posture, particularly on gravity fluctuation and the antigravity muscles].

    Science.gov (United States)

    Miyata, T

    1990-06-01

    The purpose of this study is to reveal the relation between stomatognathic system and the systemic condition. In the present study, experimental occlusal interference was given to the first molar on main mastication side of 6 healthy subjects and the influence on the upright posture was evaluated through simultaneous measurements of changes in activity of antigravity muscles via electromyography, other than the measurement of loci of the gravity fluctuation for stabilograph before and after the interference was provided. The following results were obtained, 1. Loci of gravity fluctuation 1) All parameters tended increase 24 hours after the interference was provided. 2) The decreasing trend was noted 24 hours after the interference was removed. 3) At one week after the interference was removed all analysis items tended to restore to the normal range. 2. Activity of antigravity muscles In some of the subjects, the muscular activity showed the same trend as the changes of analysis items of gravity fluctuation. 3. The above results suggest that the evaluation of the loci of the gravity fluctuation may be helpful to assess the therapeutic effect of malocclusion.

  15. Redox Species of Redox Flow Batteries: A Review.

    Science.gov (United States)

    Pan, Feng; Wang, Qing

    2015-11-18

    Due to the capricious nature of renewable energy resources, such as wind and solar, large-scale energy storage devices are increasingly required to make the best use of the renewable power. The redox flow battery is considered suitable for large-scale applications due to its modular design, good scalability and flexible operation. The biggest challenge of the redox flow battery is the low energy density. The redox active species is the most important component in redox flow batteries, and the redox potential and solubility of redox species dictate the system energy density. This review is focused on the recent development of redox species. Different categories of redox species, including simple inorganic ions, metal complexes, metal-free organic compounds, polysulfide/sulfur and lithium storage active materials, are reviewed. The future development of redox species towards higher energy density is also suggested.

  16. Redox Species of Redox Flow Batteries: A Review

    Directory of Open Access Journals (Sweden)

    Feng Pan

    2015-11-01

    Full Text Available Due to the capricious nature of renewable energy resources, such as wind and solar, large-scale energy storage devices are increasingly required to make the best use of the renewable power. The redox flow battery is considered suitable for large-scale applications due to its modular design, good scalability and flexible operation. The biggest challenge of the redox flow battery is the low energy density. The redox active species is the most important component in redox flow batteries, and the redox potential and solubility of redox species dictate the system energy density. This review is focused on the recent development of redox species. Different categories of redox species, including simple inorganic ions, metal complexes, metal-free organic compounds, polysulfide/sulfur and lithium storage active materials, are reviewed. The future development of redox species towards higher energy density is also suggested.

  17. Impacto dos mediadores redox na remoção de cor de corantes azo e antraquinônico por lodo granular anaeróbio sob condições mesofílicas e termofílicas Impact of redox mediators on colour removal of azo and anthraquinone dyes by anaerobic granular sludge under mesophilic and thermophilic conditions

    Directory of Open Access Journals (Sweden)

    André Bezerra dos Santos

    2007-03-01

    Full Text Available Investigou-se o efeito de diferentes mediadores redox (MR na remoção de cor de corantes azo e antraquinônico pelo uso de lodo granular anaeróbio sob condições mesofílicas (30ºC e termofílicas (55ºC. Comprovou-se em experimento em batelada que a adição de concentrações catalíticas de MR pode ter um efeito marcante nas taxas de descoloração do corante azo Reactive Red 2 (RR2, mas o mesmo comportamento não pode ser obtido com o corante antraquinônico Reactive Blue 5 (RB5. Entretanto, com ambos os corantes, o simples aumento da temperatura de incubação para condições termofílicas fez acelerar consideravelmente os processos de descoloração, comparados com condições mesofílicas. Por exemplo, a constante de primeira ordem "k" da redução dos corantes RR2 e RB5, foi aumentada em 6,2 e 11 vezes, respectivamente, à 55ºC quando comparado com 30ºC. Por fim, comprovou-se em experimentos de fluxo contínuo, a boa performance do tratamento termofílico na descoloração redutiva de corantes azo.The effect of different redox mediators (RM on colour removal of azo and anthraquinone dyes was investigated with anaerobic granular sludge under mesophilic (30ºC and thermophilic (55ºC conditions. Batch experiments revealed that an addition of catalytic concentrations of RM provided a remarkable effect on the decolourisation rates of the azo dye Reactive Red 2 (RR2, but the same effect could not be obtained with the anthraquinone dye Reactive Blue 5 (RB5. Nevertheless, for both dyes, the temperature increase to thermophilic conditions was an effective strategy to considerably accelerate the decolourisation process compared to mesophilic conditions. For instance, the first-order rate constant "k" of RR2 and RB5 reduction, was increased in 6.2 and 11-fold, respectively, at 55ºC in comparison with 30ºC. Such an effect of the temperature on the reductive decolourisation of azo dye was also verified in continuous flow experiments.

  18. How the redox state of tobacco 'Bel-W3' is modified in response to ozone and other environmental factors in a sub-tropical area?

    Energy Technology Data Exchange (ETDEWEB)

    Dias, Ana P.L.; Dafre, Marcelle; Rinaldi, Mirian C.S. [Instituto de Botanica, Caixa Postal 3005, 01061-970 Sao Paulo, SP (Brazil); Domingos, Marisa, E-mail: mmingos@superig.com.b [Instituto de Botanica, Caixa Postal 3005, 01061-970 Sao Paulo, SP (Brazil)

    2011-02-15

    This study intended to determine whether the redox state in plants of Nicotiana tabacum 'Bel-W3' fluctuates in response to the environmental factors in a sub-tropical area contaminated by ozone (Sao Paulo, SE - Brazil) and which environmental factors are related to this fluctuation, discussing their biomonitoring efficiency. We comparatively evaluated the indicators of redox state (ascorbic acid, glutathione, superoxide dismutase, ascorbate peroxidase, and glutathione reductase) and leaf injury in 17 field experiments performed in 2008. The redox state was explained by the combined effects of chronic levels of O{sub 3} and meteorological variables 4-6 days prior to the plant sampling. Moderate leaf injury was observed in most cases. The redox state of tobacco decreases few days after their placement in the sub-tropical environment, causing them to become susceptible to oxidative stress imposed by chronic doses of O{sub 3}. Its bioindicator efficiency would not be diminished in such levels of atmospheric contamination. - Research highlights: Nicotiana tabacum 'Bel-W3' is potentially a bioindicator of O{sub 3} in the sub-tropics. However, it is unknown if its redox state would affect its bioindicator performance under sub-tropical environmental conditions. This study revealed that the redox state of tobacco decreases few days after their placement in the sub-tropical environment, causing them to become susceptible to oxidative stress imposed by chronic doses of O{sub 3}. Therefore, its bioindicator efficiency would not be diminished in such levels of atmospheric contamination. However, the bioindicator efficiency N. tabacum 'Bel-W3' for biomonitoring O{sub 3} should be regionally modeled in the sub-tropics, based on both its redox state and on the flux of O{sub 3} through stomata, in response to the varying micro-meteorological conditions that govern both physiological processes. - The bioindicator efficiency of tobacco plants is not

  19. How the redox state of tobacco 'Bel-W3' is modified in response to ozone and other environmental factors in a sub-tropical area?

    International Nuclear Information System (INIS)

    Dias, Ana P.L.; Dafre, Marcelle; Rinaldi, Mirian C.S.; Domingos, Marisa

    2011-01-01

    This study intended to determine whether the redox state in plants of Nicotiana tabacum 'Bel-W3' fluctuates in response to the environmental factors in a sub-tropical area contaminated by ozone (Sao Paulo, SE - Brazil) and which environmental factors are related to this fluctuation, discussing their biomonitoring efficiency. We comparatively evaluated the indicators of redox state (ascorbic acid, glutathione, superoxide dismutase, ascorbate peroxidase, and glutathione reductase) and leaf injury in 17 field experiments performed in 2008. The redox state was explained by the combined effects of chronic levels of O 3 and meteorological variables 4-6 days prior to the plant sampling. Moderate leaf injury was observed in most cases. The redox state of tobacco decreases few days after their placement in the sub-tropical environment, causing them to become susceptible to oxidative stress imposed by chronic doses of O 3 . Its bioindicator efficiency would not be diminished in such levels of atmospheric contamination. - Research highlights: → Nicotiana tabacum 'Bel-W3' is potentially a bioindicator of O 3 in the sub-tropics. → However, it is unknown if its redox state would affect its bioindicator performance under sub-tropical environmental conditions. → This study revealed that the redox state of tobacco decreases few days after their placement in the sub-tropical environment, causing them to become susceptible to oxidative stress imposed by chronic doses of O 3 . → Therefore, its bioindicator efficiency would not be diminished in such levels of atmospheric contamination. → However, the bioindicator efficiency N. tabacum 'Bel-W3' for biomonitoring O 3 should be regionally modeled in the sub-tropics, based on both its redox state and on the flux of O 3 through stomata, in response to the varying micro-meteorological conditions that govern both physiological processes. - The bioindicator efficiency of tobacco plants is not restrained under chronic doses of O 3 in

  20. Assessment of the performance of SMFCs in the bioremediation of PAHs in contaminated marine sediments under different redox conditions and analysis of the associated microbial communities

    KAUST Repository

    Hamdan, Hamdan Z.; Salam, Darine A.; Rao, Hari Ananda; Semerjian, Lucy; Saikaly, Pascal

    2016-01-01

    The biodegradation of naphthalene, 2-methylnaphthalene and phenanthrene was evaluated in marine sediment microbial fuel cells (SMFCs) under different biodegradation conditions, including sulfate reduction as a major biodegradation pathway

  1. Combining sedimentological, trace metal (Mn, Mo) and molecular evidence for reconstructing past water-column redox conditions: The example of meromictic Lake Cadagno (Swiss Alps)

    DEFF Research Database (Denmark)

    Wirth, S. B.; Gilli, A.; Niemann, H.

    2013-01-01

    reducing conditions and subsequent rapid precipitation of Mn-(oxyhydr) oxide minerals during episodic and short-term water-column mixing events mainly due to flood-induced underflows. At 9800 +/- 130 cal yr BP, a rapid transition to fully sulfidic conditions is indicated by the marked enrichment of Mo......-transition period beginning shortly after the lake formation similar to 12.5 kyr ago. The oxic period is characterized by low sedimentary Mn and Mo concentrations, as well as by the absence of any remnants of anoxygenic phototrophic sulfur bacteria. Enhanced accumulation/preservation of Mn (up to 5.6 wt...

  2. Biotransformation of gabapentin in surface water matrices under different redox conditions and the occurrence of one major TP in the aquatic environment.

    Science.gov (United States)

    Henning, Nina; Kunkel, Uwe; Wick, Arne; Ternes, Thomas A

    2018-06-15

    Laboratory-scale incubation experiments in water/sediment systems were conducted to test the transformation behavior of the anticonvulsant gabapentin (GBP) under different environmental conditions (aerobic, anaerobic, with abiotic controls). GBP was transformed by biological processes as it was eliminated quickly under aerobic conditions (dissipation time 50% of initial concentration (DT 50 ): 2-7 days) whereas no decrease was observed under anaerobic conditions. Measurements via high resolution mass spectrometry (LC-Orbitrap-MS) revealed eight biological transformation products (TPs). Three of them were identified with reference standards (GBP-Lactam, TP186, TP213), while for the other five TPs tentative structures were proposed from information by MS 2 /MS 3 experiments. Furthermore, the quantitatively most relevant TP GBP-Lactam was formed via intramolecular amidation (up to 18% of initial GBP concentration). Incubation experiments with GBP-Lactam revealed a higher stability against biotic degradation (DT 50 : 12 days) in contrast to GBP, while it was stable under anaerobic and abiotic conditions. Besides GBP, GBP-Lactam was detected in surface water in the μg L -1 range. Finally, GBP and GBP-Lactam were found in potable water with concentrations up to 0.64 and 0.07 μg L -1 , respectively. According to the elevated environmental persistence of GBP-Lactam compared to GBP and its presumed enhanced toxicity, we recommend to involve GBP-Lactam into monitoring programs. Copyright © 2018 Elsevier Ltd. All rights reserved.

  3. Separate effects of flooding and anaerobiosis on soil greenhouse gas emissions and redox sensitive biogeochemistry

    Science.gov (United States)

    Gavin McNicol; Whendee L. Silver

    2014-01-01

    Soils are large sources of atmospheric greenhouse gases, and both the magnitude and composition of soil gas emissions are strongly controlled by redox conditions. Though the effect of redox dynamics on greenhouse gas emissions has been well studied in flooded soils, less research has focused on redox dynamics without total soil inundation. For the latter, all that is...

  4. Simultaneous anionic and cationic redox

    Science.gov (United States)

    Jung, Sung-Kyun; Kang, Kisuk

    2017-12-01

    It is challenging to unlock anionic redox activity, accompanied by full utilization of available cationic redox process, to boost capacity of battery cathodes. Now, material design by tuning the metal-oxygen interaction is shown to be a promising solution.

  5. Redox Regulation of Mitochondrial Function

    Science.gov (United States)

    Handy, Diane E.

    2012-01-01

    Abstract Redox-dependent processes influence most cellular functions, such as differentiation, proliferation, and apoptosis. Mitochondria are at the center of these processes, as mitochondria both generate reactive oxygen species (ROS) that drive redox-sensitive events and respond to ROS-mediated changes in the cellular redox state. In this review, we examine the regulation of cellular ROS, their modes of production and removal, and the redox-sensitive targets that are modified by their flux. In particular, we focus on the actions of redox-sensitive targets that alter mitochondrial function and the role of these redox modifications on metabolism, mitochondrial biogenesis, receptor-mediated signaling, and apoptotic pathways. We also consider the role of mitochondria in modulating these pathways, and discuss how redox-dependent events may contribute to pathobiology by altering mitochondrial function. Antioxid. Redox Signal. 16, 1323–1367. PMID:22146081

  6. Measurement of Redox Potential in Nanoecotoxicological Investigations

    Directory of Open Access Journals (Sweden)

    Ratna Tantra

    2012-01-01

    Full Text Available Redox potential has been identified by the Organisation for Economic Co-operation and Development (OECD as one of the parameters that should be investigated for the testing of manufactured nanomaterials. There is still some ambiguity concerning this parameter, i.e., as to what and how to measure, particularly when in a nanoecotoxicological context. In this study the redox potentials of six nanomaterials (either zinc oxide (ZnO or cerium oxide (CeO2 dispersions were measured using an oxidation-reduction potential (ORP electrode probe. The particles under testing differed in terms of their particle size and dispersion stability in deionised water and in various ecotox media. The ORP values of the various dispersions and how they fluctuate relative to each other are discussed. Results show that the ORP values are mainly governed by the type of liquid media employed, with little contributions from the nanoparticles. Seawater was shown to have reduced the ORP value, which was attributed to an increase in the concentration of reducing agents such as sulphites or the reduction of dissolved oxygen concentration. The lack of redox potential value contribution from the particles themselves is thought to be due to insufficient interaction of the particles at the Pt electrode of the ORP probe.

  7. Measurement of redox potential in nanoecotoxicological investigations.

    Science.gov (United States)

    Tantra, Ratna; Cackett, Alex; Peck, Roger; Gohil, Dipak; Snowden, Jacqueline

    2012-01-01

    Redox potential has been identified by the Organisation for Economic Co-operation and Development (OECD) as one of the parameters that should be investigated for the testing of manufactured nanomaterials. There is still some ambiguity concerning this parameter, i.e., as to what and how to measure, particularly when in a nanoecotoxicological context. In this study the redox potentials of six nanomaterials (either zinc oxide (ZnO) or cerium oxide (CeO(2))) dispersions were measured using an oxidation-reduction potential (ORP) electrode probe. The particles under testing differed in terms of their particle size and dispersion stability in deionised water and in various ecotox media. The ORP values of the various dispersions and how they fluctuate relative to each other are discussed. Results show that the ORP values are mainly governed by the type of liquid media employed, with little contributions from the nanoparticles. Seawater was shown to have reduced the ORP value, which was attributed to an increase in the concentration of reducing agents such as sulphites or the reduction of dissolved oxygen concentration. The lack of redox potential value contribution from the particles themselves is thought to be due to insufficient interaction of the particles at the Pt electrode of the ORP probe.

  8. Transition from confined to phreatic conditions as the factor controlling salinization and change in redox state, Upper subaquifer of the Judea Group, Israel

    Science.gov (United States)

    Gavrieli, Ittai; Burg, Avi; Guttman, Joseph

    2002-08-01

    An increase in salinity and change from oxic to anoxic conditions are observed in the Upper subaquifer of the Judea Group in the Kefar Uriyya pumping field at the western foothills of the Judea Mountains, Israel. Hydrogeological data indicate that the change, which occurs over a distance of only a few kilometers, coincides with a transition from confined to phreatic conditions in the aquifer. The deterioration in the water quality is explained as a result of seepage of more saline, organic-rich water from above, into the phreatic "roofed" part of the aquifer. The latter is derived from the bituminous chalky rocks of the Mount Scopus Group, which confine the aquifer in its southeastern part. In this confined part, water in perched horizons within the Mount Scopus Group cannot leak down and flow westward while leaching organic matter and accumulating salts. However, upon reaching the transition area from confined to phreatic conditions, seepage to the Judea Upper subaquifer is possible, thereby allowing it to be defined as a leaky aquifer. The incoming organic matter consumes the dissolved oxygen and allows bacterial sulfate reduction. The latter accounts for the H2S in the aquifer, as indicated by sulfur isotopic analyses of coexisting sulfate and sulfide. Thus, from an aquifer management point of view, in order to maintain the high quality of the water in the confined southeastern part of the Kefar Uriyya field, care should be taken not to draw the confined-roofed transition area further east by over pumping.

  9. Redox Flow Batteries, a Review

    Energy Technology Data Exchange (ETDEWEB)

    Knoxville, U. Tennessee; U. Texas Austin; U, McGill; Weber, Adam Z.; Mench, Matthew M.; Meyers, Jeremy P.; Ross, Philip N.; Gostick, Jeffrey T.; Liu, Qinghua

    2011-07-15

    Redox flow batteries are enjoying a renaissance due to their ability to store large amounts of electrical energy relatively cheaply and efficiently. In this review, we examine the components of redox flow batteries with a focus on understanding the underlying physical processes. The various transport and kinetic phenomena are discussed along with the most common redox couples.

  10. Magnetic fluctuations in turbulent flow

    International Nuclear Information System (INIS)

    Ruzmaikin, A.A.

    1990-01-01

    For dynamo excitation of the magnetic fluctuations in infinite fluid only a sufficient large magnetic Reynolds number is needed. In a infinite region an additional condition appears. Due to the diffusion of the magnetic field through the boundaries a size of the region must be large enough compare with a correlation length of the turbulence. Author)

  11. Firm default and aggregate fluctuations

    NARCIS (Netherlands)

    Jacobson, Tor; Linde, Jesper; Roszbach, Kasper

    This paper studies the relationship between macroeconomic fluctuations and corporate defaults while conditioning on industry affiliation and an extensive set of firm-specific factors. By using a panel data set for virtually all incorporated Swedish businesses over 1990-2009, a period which includes

  12. Intense molybdenum accumulation in sediments underneath a nitrogenous water column and implications for the reconstruction of paleo-redox conditions based on molybdenum isotopes

    Science.gov (United States)

    Scholz, Florian; Siebert, Christopher; Dale, Andrew W.; Frank, Martin

    2017-09-01

    The concentration and isotope composition of molybdenum (Mo) in sediments and sedimentary rocks are widely used proxies for anoxic conditions in the water column of paleo-marine systems. While the mechanisms leading to Mo fixation in modern restricted basins with anoxic and sulfidic (euxinic) conditions are reasonably well constrained, few studies have focused on Mo cycling in the context of open-marine anoxia. Here we present Mo data for water column particulate matter, modern surface sediments and a paleo-record covering the last 140,000 years from the Peruvian continental margin. Mo concentrations in late Holocene and Eemian (penultimate interglacial) shelf sediments off Peru range from ∼70 to 100 μg g-1, an extent of Mo enrichment that is thought to be indicative of (and limited to) euxinic systems. To investigate if this putative anomaly could be related to the occasional occurrence of sulfidic conditions in the water column overlying the Peruvian shelf, we compared trace metal (Mo, vanadium, uranium) enrichments in particulate matter from oxic, nitrate-reducing (nitrogenous) and sulfidic water masses. Coincident enrichments of iron (Fe) (oxyhydr)oxides and Mo in the nitrogenous water column as well as co-variation of dissolved Fe and Mo in the sediment pore water suggest that Mo is delivered to the sediment surface by Fe (oxyhydr)oxides. Most of these precipitate in the anoxic-nitrogenous water column due to oxidation of sediment-derived dissolved Fe with nitrate as a terminal electron acceptor. Upon reductive dissolution in the surface sediment, a fraction of the Fe and Mo is re-precipitated through interaction with pore water sulfide. The Fe- and nitrate-dependent mechanism of Mo accumulation proposed here is supported by the sedimentary Mo isotope composition, which is consistent with Mo adsorption onto Fe (oxyhydr)oxides. Trace metal co-variation patterns as well as Mo and nitrogen isotope systematics suggest that the same mechanism of Mo delivery

  13. Fluctuations and Photons

    International Nuclear Information System (INIS)

    Gupta, Sourendu

    2007-01-01

    In this talk I discuss measures of fluctuations, especially those leading to the proof that the quark gluon plasma indeed contains quarks. I discuss the quark mass dependence of the critical end point of QCD. Then I discuss probes of the QCD critical point. Non-gaussian behaviour of event-to-event fluctuations of conserved quantum numbers is one such probe. Another is due to the coupling of fluctuations in baryon number and electrical charge, giving rise to long range random fluctuations of local charge density which relax slowly. These fluctuations can scatter photons, giving rise to critical opalescence

  14. Fluctuations and Photons

    Science.gov (United States)

    Gupta, Sourendu

    2007-02-01

    In this talk I discuss measures of fluctuations, especially those leading to the proof that the quark gluon plasma indeed contains quarks. I discuss the quark mass dependence of the critical end point of QCD. Then I discuss probes of the QCD critical point. Non-gaussian behaviour of event-to-event fluctuations of conserved quantum numbers is one such probe. Another is due to the coupling of fluctuations in baryon number and electrical charge, giving rise to long range random fluctuations of local charge density which relax slowly. These fluctuations can scatter photons, giving rise to critical opalescence.

  15. Fluctuations and Photons

    Energy Technology Data Exchange (ETDEWEB)

    Gupta, Sourendu [Department of Theoretical Physics, Tata Institute of Fundamental Research, Homi Bhabha Road, Mumbai 400005 (India)

    2007-02-15

    In this talk I discuss measures of fluctuations, especially those leading to the proof that the quark gluon plasma indeed contains quarks. I discuss the quark mass dependence of the critical end point of QCD. Then I discuss probes of the QCD critical point. Non-gaussian behaviour of event-to-event fluctuations of conserved quantum numbers is one such probe. Another is due to the coupling of fluctuations in baryon number and electrical charge, giving rise to long range random fluctuations of local charge density which relax slowly. These fluctuations can scatter photons, giving rise to critical opalescence.

  16. Dimensional behavior of Ni-YSZ composites during redox cycling

    DEFF Research Database (Denmark)

    Pihlatie, Mikko; Kaiser, Andreas; Larsen, Peter Halvor

    2009-01-01

    The dimensional behavior of Ni-yttria-stabilized zirconia (YSZ) cermets during redox cycling was tested in dilatometry within the temperature range 600-1000 degrees C. The effect Of humidity oil redox stability was investigated at intermediate and low temperatures. We show that both the sintering...... of nickel depending on temperature of the initial reduction and the operating conditions, and the temperature of reoxidation are very important for the size of the dimensional change. Cumulative redox strain (CRS) is shown to be correlated with temperature. Measured maximum CRS after three redox cycles...... varies within 0.25-3.2% dL/L in dry gas and respective temperature range of 600-1000 degrees C. A high degree of redox reversibility was reached at low temperature. however. reversibility is lost at elevated temperatures. We found that at 850 degrees C, 6% steam and a very high p(H2O)/p(H2) ratio...

  17. Redox-Based Regulation of Bacterial Development and Behavior.

    Science.gov (United States)

    Sporer, Abigail J; Kahl, Lisa J; Price-Whelan, Alexa; Dietrich, Lars E P

    2017-06-20

    Severe changes in the environmental redox potential, and resulting alterations in the oxidation states of intracellular metabolites and enzymes, have historically been considered negative stressors, requiring responses that are strictly defensive. However, recent work in diverse organisms has revealed that more subtle changes in the intracellular redox state can act as signals, eliciting responses with benefits beyond defense and detoxification. Changes in redox state have been shown to influence or trigger chromosome segregation, sporulation, aerotaxis, and social behaviors, including luminescence as well as biofilm establishment and dispersal. Connections between redox state and complex behavior allow bacteria to link developmental choices with metabolic state and coordinate appropriate responses. Promising future directions for this area of study include metabolomic analysis of species- and condition-dependent changes in metabolite oxidation states and elucidation of the mechanisms whereby the redox state influences circadian regulation.

  18. Redox-capacitor to connect electrochemistry to redox-biology.

    Science.gov (United States)

    Kim, Eunkyoung; Leverage, W Taylor; Liu, Yi; White, Ian M; Bentley, William E; Payne, Gregory F

    2014-01-07

    It is well-established that redox-reactions are integral to biology for energy harvesting (oxidative phosphorylation), immune defense (oxidative burst) and drug metabolism (phase I reactions), yet there is emerging evidence that redox may play broader roles in biology (e.g., redox signaling). A critical challenge is the need for tools that can probe biologically-relevant redox interactions simply, rapidly and without the need for a comprehensive suite of analytical methods. We propose that electrochemistry may provide such a tool. In this tutorial review, we describe recent studies with a redox-capacitor film that can serve as a bio-electrode interface that can accept, store and donate electrons from mediators commonly used in electrochemistry and also in biology. Specifically, we (i) describe the fabrication of this redox-capacitor from catechols and the polysaccharide chitosan, (ii) discuss the mechanistic basis for electron exchange, (iii) illustrate the properties of this redox-capacitor and its capabilities for promoting redox-communication between biology and electrodes, and (iv) suggest the potential for enlisting signal processing strategies to "extract" redox information. We believe these initial studies indicate broad possibilities for enlisting electrochemistry and signal processing to acquire "systems level" redox information from biology.

  19. Hydrodynamical fluctuations in smooth shear flows

    International Nuclear Information System (INIS)

    Chagelishvili, G.D.; Khujadze, G.R.; Lominadze, J.G.

    1999-11-01

    Background of hydrodynamical fluctuations in a intrinsically/stochastically forced, laminar, uniform shear flow is studied. The employment of so-called nonmodal mathematical analysis makes it possible to represent the background of fluctuations in a new light and to get more insight into the physics of its formation. The basic physical processes responsible for the formation of vortex and acoustic wave fluctuation backgrounds are analyzed. Interplay of the processes at low and moderate shear rates is described. Three-dimensional vortex fluctuations around a given macroscopic state are numerically calculated. The correlation functions of the fluctuations of physical quantities are analyzed. It is shown that there exists subspace D k in the wave-number space (k-space) that is limited externally by spherical surface with radius k ν ≡ A/ν (where A is the velocity shear parameter, ν - the kinematic viscosity) in the nonequilibrium open system under study. The spatial Fourier harmonics of vortex as well as acoustic wave fluctuations are strongly subjected by flow shear (by the open character of the system) at wave-numbers satisfying the condition k ν . Specifically it is shown that in D k : The fluctuations are non-Markovian; the spatial spectral density of energy of the vortex fluctuations by far exceeds the white-noise; the term of a new type associated to the hydrodynamical fluctuation of velocity appears in the correlation function of pressure; the fluctuation background of the acoustic waves is completely different at low and moderate shear rates (at low shear rates it is reduced in D k in comparison to the uniform (non-shear) flow; at moderate shear rates it it comparable to the background of the vortex fluctuations). The fluctuation background of both the vortex and the acoustic wave modes is anisotropic. The possible significance of the fluctuation background of vortices for the subcritical transition to turbulence and Brownian motion of small macroscopic

  20. Microfluidic redox battery.

    Science.gov (United States)

    Lee, Jin Wook; Goulet, Marc-Antoni; Kjeang, Erik

    2013-07-07

    A miniaturized microfluidic battery is proposed, which is the first membraneless redox battery demonstrated to date. This unique concept capitalizes on dual-pass flow-through porous electrodes combined with stratified, co-laminar flow to generate electrical power on-chip. The fluidic design is symmetric to allow for both charging and discharging operations in forward, reverse, and recirculation modes. The proof-of-concept device fabricated using low-cost materials integrated in a microfluidic chip is shown to produce competitive power levels when operated on a vanadium redox electrolyte. A complete charge/discharge cycle is performed to demonstrate its operation as a rechargeable battery, which is an important step towards providing sustainable power to lab-on-a-chip and microelectronic applications.

  1. Determining redox properties of clay-rich sedimentary deposits in the context of performance assessment of radioactive waste repositories : Conceptual and practical aspects

    NARCIS (Netherlands)

    Behrends, T.; Bruggeman, Christophe

    Redox reactions play a key factor controlling the mobility of redox sensitive radionuclides in clay-rich sediments which might serve as host formations for radioactive waste repositories. Assessing the redox speciation of radionuclides requires information about the redox conditions in the formation

  2. Redox electrode materials for supercapatteries

    OpenAIRE

    Yu, Linpo; Chen, George Z.

    2016-01-01

    Redox electrode materials, including transition metal oxides and electronically conducting polymers, are capable of faradaic charge transfer reactions, and play important roles in most electrochemical energy storage devices, such as supercapacitor, battery and supercapattery. Batteries are often based on redox materials with low power capability and safety concerns in some cases. Supercapacitors, particularly those based on redox inactive materials, e.g. activated carbon, can offer high power...

  3. An Excel Workbook for Identifying Redox Processes in Ground Water

    Science.gov (United States)

    Jurgens, Bryant C.; McMahon, Peter B.; Chapelle, Francis H.; Eberts, Sandra M.

    2009-01-01

    The reduction/oxidation (redox) condition of ground water affects the concentration, transport, and fate of many anthropogenic and natural contaminants. The redox state of a ground-water sample is defined by the dominant type of reduction/oxidation reaction, or redox process, occurring in the sample, as inferred from water-quality data. However, because of the difficulty in defining and applying a systematic redox framework to samples from diverse hydrogeologic settings, many regional water-quality investigations do not attempt to determine the predominant redox process in ground water. Recently, McMahon and Chapelle (2008) devised a redox framework that was applied to a large number of samples from 15 principal aquifer systems in the United States to examine the effect of redox processes on water quality. This framework was expanded by Chapelle and others (in press) to use measured sulfide data to differentiate between iron(III)- and sulfate-reducing conditions. These investigations showed that a systematic approach to characterize redox conditions in ground water could be applied to datasets from diverse hydrogeologic settings using water-quality data routinely collected in regional water-quality investigations. This report describes the Microsoft Excel workbook, RedoxAssignment_McMahon&Chapelle.xls, that assigns the predominant redox process to samples using the framework created by McMahon and Chapelle (2008) and expanded by Chapelle and others (in press). Assignment of redox conditions is based on concentrations of dissolved oxygen (O2), nitrate (NO3-), manganese (Mn2+), iron (Fe2+), sulfate (SO42-), and sulfide (sum of dihydrogen sulfide [aqueous H2S], hydrogen sulfide [HS-], and sulfide [S2-]). The logical arguments for assigning the predominant redox process to each sample are performed by a program written in Microsoft Visual Basic for Applications (VBA). The program is called from buttons on the main worksheet. The number of samples that can be analyzed

  4. Tuning of redox regulatory mechanisms, reactive oxygen species and redox homeostasis under salinity stress

    Directory of Open Access Journals (Sweden)

    Hossain eSazzad

    2016-05-01

    Full Text Available Soil salinity is a crucial environmental constraint which limits biomass production at many sites on a global scale. Saline growth conditions cause osmotic and ionic imbalances, oxidative stress and perturb metabolism, e.g. the photosynthetic electron flow. The plant ability to tolerate salinity is determined by multiple biochemical and physiological mechanisms protecting cell functions, in particular by regulating proper water relations and maintaining ion homeostasis. Redox homeostasis is a fundamental cell property. Its regulation includes control of reactive oxygen species (ROS generation, sensing deviation from and readjustment of the cellular redox state. All these redox related functions have been recognized as decisive factors in salinity acclimation and adaptation. This review focuses on the core response of plants to overcome the challenges of salinity stress through regulation of ROS generation and detoxification systems and to maintain redox homeostasis. Emphasis is given to the role of NADH oxidase (RBOH, alternative oxidase (AOX, the plastid terminal oxidase (PTOX and the malate valve with the malate dehydrogenase isoforms under salt stress. Overwhelming evidence assigns an essential auxiliary function of ROS and redox homeostasis to salinity acclimation of plants.

  5. Arteriovenous oscillations of the redox potential: Is the redox state influencing blood flow?

    Science.gov (United States)

    Poznanski, Jaroslaw; Szczesny, Pawel; Pawlinski, Bartosz; Mazurek, Tomasz; Zielenkiewicz, Piotr; Gajewski, Zdzislaw; Paczek, Leszek

    2017-09-01

    Studies on the regulation of human blood flow revealed several modes of oscillations with frequencies ranging from 0.005 to 1 Hz. Several mechanisms were proposed that might influence these oscillations, such as the activity of vascular endothelium, the neurogenic activity of vessel wall, the intrinsic activity of vascular smooth muscle, respiration, and heartbeat. These studies relied typically on non-invasive techniques, for example, laser Doppler flowmetry. Oscillations of biochemical markers were rarely coupled to blood flow. The redox potential difference between the artery and the vein was measured by platinum electrodes placed in the parallel homonymous femoral artery and the femoral vein of ventilated anesthetized pigs. Continuous measurement at 5 Hz sampling rate using a digital nanovoltmeter revealed fluctuating signals with three basic modes of oscillations: ∼ 1, ∼ 0.1 and ∼ 0.01 Hz. These signals clearly overlap with reported modes of oscillations in blood flow, suggesting coupling of the redox potential and blood flow. The amplitude of the oscillations associated with heart action was significantly smaller than for the other two modes, despite the fact that heart action has the greatest influence on blood flow. This finding suggests that redox potential in blood might be not a derivative but either a mediator or an effector of the blood flow control system.

  6. Analytical redox reactions and redox potentials of tungsten and its concomitants

    Energy Technology Data Exchange (ETDEWEB)

    Wuensch, G.; Mintrop, L.; Tracht, U.

    1985-01-01

    It is demonstrated that tungsten can be more effectively determined by redox titrimetry than by gravimetry. In addition to its inherent greater simplicity the volumetric approach offers to determine several components of the sample from consecutive redox titrations. To provide the necessary information the conditional redox potentials of W, Mo, Fe, V, Ti, Sn, Cu, Cr in HCl, HCl + HF and HCl + H/sub 3/PO/sub 4/ have been determined. Use of HF and/or H/sub 3/PO/sub 4/ allows sample preparations without any precipitation of tungstic acid. The influence of these auxiliary complexing agents on the potentials and kinetics is discussed. The titrations can be performed reductimetrically or more conveniently oxidimetrically using potentiometric or amperometric indication. The use of strongly reducing agents restricts the tolerance interval to +-0.6%, so that the gravimetric determination of tungsten remains superior for high precision analyses.

  7. Analytical redox reactions and redox potentials of tungsten and its concomitants

    International Nuclear Information System (INIS)

    Wuensch, G.; Mintrop, L.; Tracht, U.

    1985-01-01

    It is demonstrated that tungsten can be more effectively determined by redox titrimetry than by gravimetry. In addition to its inherent greater simplicity the volumetric approach offers to determine several components of the sample from consecutive redox titrations. To provide the necessary information the conditional redox potentials of W, Mo, Fe, V, Ti, Sn, Cu, Cr in HCl, HCl + HF and HCl + H 3 PO 4 have been determined. Use of HF and/or H 3 PO 4 allows sample preparations without any precipitation of tungstic acid. The influence of these auxiliary complexing agents on the potentials and kinetics is discussed. The titrations can be performed reductimetrically or more conveniently oxidimetrically using potentiometric or amperometric indication. The use of strongly reducing agents restricts the tolerance interval to +-0.6%, so that the gravimetric determination of tungsten remains superior for high precision analyses. (orig.) [de

  8. Superconductivity and spin fluctuations

    International Nuclear Information System (INIS)

    Scalapino, D.J.

    1999-01-01

    The organizers of the Memorial Session for Herman Rietschel asked that the author review some of the history of the interplay of superconductivity and spin fluctuations. Initially, Berk and Schrieffer showed how paramagnon spin fluctuations could suppress superconductivity in nearly-ferromagnetic materials. Following this, Rietschel and various co-workers wrote a number of papers in which they investigated the role of spin fluctuations in reducing the Tc of various electron-phonon superconductors. Paramagnon spin fluctuations are also believed to provide the p-wave pairing mechanism responsible for the superfluid phases of 3 He. More recently, antiferromagnetic spin fluctuations have been proposed as the mechanism for d-wave pairing in the heavy-fermion superconductors and in some organic materials as well as possibly the high-Tc cuprates. Here the author will review some of this early history and discuss some of the things he has learned more recently from numerical simulations

  9. Interspecific competition among the secondary hole-nesting birds under the conditions of large interannual fluctuations of spring temperatures in Karelia

    Directory of Open Access Journals (Sweden)

    Khokhlova Tatyana

    2014-11-01

    Full Text Available Data on the reproduction of birds in bird boxes (n=167-196 in Karelia in consequent years with drastic changes in spring temperature were analysed: 1975 - extremely early and warm spring, 1976 - late and cold one, 1977 - with medium indices. The changes in fertility, reproductive success and the number of Great tit Parus major L. (77 nests, Pied Flycatcher Ficedula hypoleuca L. (171, Redstart Phoenicurus phoenicurus (L. (10 and Wryneck Jynx torquilla L.-(6 were estimated. It was shown, that under the unstable conditions of the North, competition can make a considerable contribution to the dynamics of the population characteristics of birds and serve as one of the significant elements of the mechanism of their number regulation. Its influence is enhanced due to the convergence of the time of the breeding start of wintering and migratory birds in a year with late spring. The result of that is the rise in the number of nests lost due to anxiety or ruined by competitors, and increasing proportion of recycled clutch smaller in size and late on terms. These contributed to the fall of population productivity, the growth of the necessary reproductive effort in a significant part of individuals as well as the increase in the proportion of late broods, changing plumage at late time. After the year with early spring the number of all secondary hole-nesting birds grew, but after that with late spring, it reduced. The most significant decline in the population (in 3 times was showed by Great tits – species with bicyclical reproduction. Because of the high percent of late second and repeated nests in 1976 the large number of individuals moulted at late time and under the extremely adverse conditions and it resulted in their increased mortality.

  10. Fate of redox-sensitive elements in two different East-African wetland systems

    Science.gov (United States)

    Glasner, Björn; Fiedler, Sabine

    2017-04-01

    We expect that an intensified cropping alters soil pH and Eh, and negatively affects the production potential of wetlands. Therefore, we investigated the redox-conditions in combination with the fate of different redox-sensitive elements in two prototypical wetland systems that show a high potential for food production in East-Africa. While the floodplains (observed near Ifakara, Kilombero District/Tanzania) serve as major crop producing areas in the region, the Inland Valleys (observed in Namulonge, Central District/Uganda) show a high potential for future production. Both systems have been divided into three positions; the fringe near to the slope, the center near to the river and the middle in between these two positions. In order to get a better understanding of the two systems we installed continuously measuring redox-electrodes in three different positions within both systems. Additionally, the fate of mineral elements was measured using ion-exchange resins with an installation period of 3-4 months. At the Tanzanian field sites the Eh-potential shows one major dry period with moderately reducing to well drained conditions in all sampling depths (10, 30, and 50 cm below ground) in all three positions during the measuring period from March 2015 to Dec 2016. Starting with the rains the Eh-potential drops from 700 mV (in 10 and 30 cm depth) to reducing conditions at all three sites - with intermediate brakes in the middle and fringe positions, showing that there has been no rain during these periods. At the Ugandan field sites the Eh-potential shows more fluctuations during the measuring period, especially in the center position in 2015 ( 750 to -200 mV in 30 and 50 cm depth). Having just the Eh-potential from the first 30 cm below ground it is not really possible to differentiate between dry- and rainy-seasons at the sites. The fate of redox-sensitive elements (Fe, Mn, and P) does not always correlate with the overall Eh-conditions (median) of the installation

  11. Ruthenium nanocatalysis on redox reactions.

    Science.gov (United States)

    Veerakumar, Pitchaimani; Ramdass, Arumugam; Rajagopal, Seenivasan

    2013-07-01

    Nanoparticles have generated intense interest over the past 20 years due to their high potential applications in different areas such as catalysis, sensors, nanoscale electronics, fuel and solar cells and optoelectronics. As the large fractions of metal atoms are exposed to the surface, the use of metal nanoparticles as nanocatalysts allows mild reaction conditions and high catalytic efficiency in a large number of chemical transformations. They have emerged as sustainable heterogeneous catalysts and catalyst supports alternative to conventional materials. This review focuses on the synthesis, characterization and catalytic role of ruthenium nanoparticles (RuNPs) on the redox reactions of heteroatom containing organic compounds with the green reagent H2O2, a field that has attracted immense interest among the chemical, materials and industrial communities. We intend to present a broad overview of Ru nanocatalysts for redox reactions with an emphasis on their performance, stability and reusability. The growth in the chemistry of organic sulfoxides and N-oxides during last decade was due to their importance as synthetic intermediates for the production of a wide range of chemically and biologically active molecules. Thus design of efficient methods for the synthesis of sulfoxides and N-oxides becomes important. This review concentrates on the catalysis of RuNPs on the H2O2 oxidation of organic sulfides to sulfoxides and amines to N-oxides. The deoxygenation reactions of sulfoxides to sulfides and reduction of nitro compounds to amines are fundamental reactions in both chemistry and biology. Here, we also highlight the catalysis of metal nanoparticles on the deoxygenation of sulfoxides and sulfones and reduction of nitro compounds with particular emphasis on the mechanistic aspects.

  12. Electrochemical redox processes involving soluble cerium species

    International Nuclear Information System (INIS)

    Arenas, L.F.; Ponce de León, C.; Walsh, F.C.

    2016-01-01

    Highlights: • The relevance of cerium in laboratory and industrial electrochemistry is considered. • The history of fundamental electrochemical studies and applications is considered. • The chemistry, redox thermodynamics and electrode kinetics of cerium are summarised. • The uses of cerium ions in synthesis, energy storage, analysis and environmental treatment are illustrated. • Research needs and development perspectives are discussed. - Abstract: Anodic oxidation of cerous ions and cathodic reduction of ceric ions, in aqueous acidic solutions, play an important role in electrochemical processes at laboratory and industrial scale. Ceric ions, which have been used for oxidation of organic wastes and off-gases in environmental treatment, are a well-established oxidant for indirect organic synthesis and specialised cleaning processes, including oxide film removal from tanks and process pipework in nuclear decontamination. They also provide a classical reagent for chemical analysis in the laboratory. The reversible oxidation of cerous ions is an important reaction in the positive compartment of various redox flow batteries during charge and discharge cycling. A knowledge of the thermodynamics and kinetics of the redox reaction is critical to an understanding of the role of cerium redox species in these applications. Suitable choices of electrode material (metal or ceramic; coated or uncoated), geometry/structure (2-or 3-dimensional) and electrolyte flow conditions (hence an acceptable mass transport rate) are critical to achieving effective electrocatalysis, a high performance and a long lifetime. This review considers the electrochemistry of soluble cerium species and their diverse uses in electrochemical technology, especially for redox flow batteries and mediated electrochemical oxidation.

  13. Evaluation of Redox Conditions and Enhanced Arsenic Mobility from Waste Disposal in a Complex Fractured Crystalline-Rock Aquifer, Raymond, New Hampshire, USA (Note: article rewritten under new title)

    Science.gov (United States)

    (Note: This entry is no longer valid; the paper was rewritten and submitted to a different journal.) This paper highlights some methods that can be used at a local scale to assess whether waste disposal activities are responsible for enhanced arsenic mobility through redox-contro...

  14. Hadronic Correlations and Fluctuations

    Energy Technology Data Exchange (ETDEWEB)

    Koch, Volker

    2008-10-09

    We will provide a review of some of the physics which can be addressed by studying fluctuations and correlations in heavy ion collisions. We will discuss Lattice QCD results on fluctuations and correlations and will put them into context with observables which have been measured in heavy-ion collisions. Special attention will be given to the QCD critical point and the first order co-existence region, and we will discuss how the measurement of fluctuations and correlations can help in an experimental search for non-trivial structures in the QCD phase diagram.

  15. Quantum fluctuations and inflation

    International Nuclear Information System (INIS)

    Bardeen, J.M.; Bublik, G.J.

    1986-05-01

    We study the effect of quantum fluctuations on the roll-down rate of the inflation field in a semiclassical approximation; this is done by treating the inflation field as a classical random field. The quantum fluctuations are simulated by a noise term in the equation of motion. We consider two different inflationary scenarios (new and chaotic inflation) and find that the roll-down rate of the median value of the inflation field is increased by the quantum fluctuations. Non-linear effects may become important in the later stages of the inflationary regime. 8 refs., 2 figs

  16. Quantum fluctuations and inflation

    International Nuclear Information System (INIS)

    Bardeen, J.M.; Bublik, G.J.

    1987-01-01

    The authors study the effect of quantum fluctuations on the roll-down rate of the inflation field in a semiclassical approximation; this is done by treating the inflation field as a classical random field. The quantum fluctuations are simulated by a noise term in the equation of motion. Two different inflationary scenarios (new and chaotic inflation) are considered and it is found that the roll-down rate of the median value of the inflation field is increased by the quantum fluctuations. Non-linear effects may become important in the later stages of the inflationary regime. (author)

  17. Consideration of fluctuation in secondary beam intensity of heavy ion beam probe measurements

    Energy Technology Data Exchange (ETDEWEB)

    Fujisawa, A.; Iguchi, H.; Lee, S.; Hamada, Y.

    1997-01-01

    Heavy ion beam probes have capability to detect local electron density fluctuation in the interior of plasmas through the detected beam intensity fluctuation. However, the intensity fluctuation should suffer a certain degree of distortion from electron density and temperature fluctuations on the beam orbits, and as a result the signal can be quite different from the local density fluctuation. This paper will present a condition that the intensity fluctuation can be regarded as being purely local electron density fluctuation, together with discussion about the contamination of the fluctuation along the beam orbits to the beam intensity fluctuation. (author)

  18. Multiple redox states of multiheme cytochromes may enable bacterial response to changing redox environments

    Science.gov (United States)

    Arbour, T.; Wrighton, K. C.; Mullin, S. W.; Castelle, C.; Luef, B.; Gilbert, B.; Banfield, J. F.

    2013-12-01

    Multiheme c-type cytochromes (MHCs) are key components in electron-transport pathways that enable some microorganisms to transfer electron byproducts of metabolism to a variety of minerals. As a response to changes in mineral redox potential, microbial communities may shift their membership, or individual organisms may adjust protein expression. Alternatively, the ability to respond may be conferred by the innate characteristics of certain electron-transport-chain components. Here, we used potentiostat-controlled microbial fuel cells (MFCs) to measure the timescale of response to imposed changes in redox conditions, thus placing constraints on the importance of these different mechanisms. In the experiments, a solid electrode acts as an electron-accepting mineral whose redox potential can be precisely controlled. We inoculated duplicate MFCs with a sediment/groundwater mixture from an aquifer at Rifle, Colorado, supplied acetate as an electron donor, and obtained stable, mixed-species biofilms dominated by Geobacter and a novel Geobacter-related family. We poised the anode at potentials spanning the range of natural Fe(III)-reduction, then performed cyclic voltammetry (CV) to characterize the overall biofilm redox signature. The apparent biofilm midpoint potential shifted directly with anode set potential when the latter was changed within the range from about -250 to -50 mV vs. SHE. Following a jump in set potential by 200 mV, the CV-midpoint shift by ~100 mV over a timescale of ~30 minutes to a few hours, depending on the direction of the potential change. The extracellular electron transfer molecules, whose overall CV signature is very similar to those of purified MHCs, appear to span a broad redox range (~200 mV), supporting the hypothesis that MHCs confer substantial redox flexibility. This flexibility may be a principle reason for the abundance of MHCs expressed by microorganisms capable of extracellular electron transfer to minerals.

  19. Fluorescence fluctuation spectroscopy (FFS)

    CERN Document Server

    Tetin, Sergey

    2012-01-01

    This new volume of Methods in Enzymology continues the legacy of this premier serial with quality chapters authored by leaders in the field. This volume covers fluorescence fluctuation spectroscopy and includes chapters on such topics as Förster resonance energy transfer (fret) with fluctuation algorithms, protein corona on nanoparticles by FCS, and FFS approaches to the study of receptors in live cells. Continues the legacy of this premier serial with quality chapters authored by leaders in the field Covers fluorescence fluctuation spectroscopy Contains chapters on such topics as Förster resonance energy transfer (fret) with fluctuation algorithms, protein corona on nanoparticles by FCS, and FFS approaches to the study of receptors in live cells.

  20. Current fluctuations of interacting active Brownian particles

    OpenAIRE

    Pre, Trevor Grand; Limmer, David T.

    2018-01-01

    We derive the distribution function for particle currents for a system of interacting active Brownian particles in the long time limit using large deviation theory and a weighted many body expansion. We find the distribution is non-Gaussian, except in the limit of passive particles. The non-Gaussian fluctuations can be understood from the effective potential the particles experience when conditioned on a given current. This potential suppresses fluctuations of the particle's orientation, and ...

  1. Environmental Risk of Metal Mining Contaminated River Bank Sediment at Redox-Transitional Zones

    Directory of Open Access Journals (Sweden)

    Sarah F. L. Lynch

    2014-01-01

    Full Text Available Diffuse metal pollution from mining impacted sediment is widely recognised as a potential source of contamination to river systems and may significantly hinder the achievement of European Union Water Framework Directive objectives. Redox-transitional zones that form along metal contaminated river banks as a result of flood and drought cycles could cause biogeochemical changes that alter the behaviour of polyvalent metals iron and manganese and anions such as sulphur. Trace metals are often partitioned with iron, manganese and sulphur minerals in mining-contaminated sediment, therefore the dissolution and precipitation of these minerals may influence the mobility of potentially toxic trace metals. Research indicates that freshly precipitated metal oxides and sulphides may be more “reactive” (more adsorbent and prone to dissolution when conditions change than older crystalline forms. Fluctuations at the oxic-anoxic interface brought about through changes in the frequency and duration of flood and drought episodes may therefore influence the reactivity of secondary minerals that form in the sediment and the flux of dissolved trace metal release. UK climate change models predict longer dry periods for some regions, interspersed with higher magnitude flood events. If we are to fully comprehend the future environmental risk these climate change events pose to mining impacted river systems it is recommended that research efforts focus on identifying the primary controls on trace metal release at the oxic-anoxic interface for flood and drought cycles of different duration and frequency. This paper critically reviews the literature regarding biogeochemical processes that occur at different temporal scales during oxic, reducing and dry periods and focuses on how iron and sulphur based minerals may alter in form and reactivity and influence the mobility of trace metal contaminants. It is clear that changes in redox potential can alter the composition

  2. Influence of iron redox transformations on plutonium sorption to sediments

    Energy Technology Data Exchange (ETDEWEB)

    Hixon, A.E.; Powell, B.A. [Environmental Engineering and Earth Sciences, Clemson Univ., Clemson, SC (United States); Hu, Y.J.; Nitsche, H. [Dept. of Chemistry, Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab., Berkeley, CA (United States); Kaplan, D.I. [Savannah River National Lab., Aiken, SC (United States); Kukkadapu, R.K.; Qafoku, O. [Pacific Northwest National Lab., Richland, WA (United States)

    2010-07-01

    (IV). Similar to the sorption kinetics, the reduction rate appears to be correlated with sediment Fe(II) concentration. The correlation between Fe(II) concentrations and Pu(V) reduction demonstrates the potential impact of changing iron mineralogy on plutonium subsurface transport through redox transition areas. These findings should influence the conceptual models of long-term stewardship of Pu contaminated sites that have fluctuating redox conditions, such as vadose zones or riparian zones. (orig.)

  3. Redox cofactor engineering in industrial microorganisms: strategies, recent applications and future directions.

    Science.gov (United States)

    Liu, Jiaheng; Li, Huiling; Zhao, Guangrong; Caiyin, Qinggele; Qiao, Jianjun

    2018-05-01

    NAD and NADP, a pivotal class of cofactors, which function as essential electron donors or acceptors in all biological organisms, drive considerable catabolic and anabolic reactions. Furthermore, they play critical roles in maintaining intracellular redox homeostasis. However, many metabolic engineering efforts in industrial microorganisms towards modification or introduction of metabolic pathways, especially those involving consumption, generation or transformation of NAD/NADP, often induce fluctuations in redox state, which dramatically impede cellular metabolism, resulting in decreased growth performance and biosynthetic capacity. Here, we comprehensively review the cofactor engineering strategies for solving the problematic redox imbalance in metabolism modification, as well as their features, suitabilities and recent applications. Some representative examples of in vitro biocatalysis are also described. In addition, we briefly discuss how tools and methods from the field of synthetic biology can be applied for cofactor engineering. Finally, future directions and challenges for development of cofactor redox engineering are presented.

  4. Universal mesoscopic conductance fluctuations

    International Nuclear Information System (INIS)

    Evangelou, S.N.

    1992-01-01

    The theory of conductance fluctuations in disordered metallic systems with size large compared to the mean free path of the electron but small compared to localization length is considered. It is demonstrates that fluctuations have an universal character and are due to repulsion between levels and spectral rigidity. The basic fluctuation measures for the energy spectrum in the mesoscopic regime of disordered systems are consistent with the Gaussian random matrix ensemble predictions. Although our disordered electron random matrix ensemble does not belong to the Gaussian ensemble the two ensembles turn out to be essentially similar. The level repulsion and the spectral rigidity found in nuclear spectra should also be observed in the metallic regime of Anderson localization. 7 refs. (orig.)

  5. Spin fluctuations and the

    Directory of Open Access Journals (Sweden)

    V.M. Loktev

    2008-09-01

    Full Text Available We analyze the spectral properties of a phenomenological model for a weakly doped two-dimensional antiferromagnet, in which the carriers move within one of the two sublattices where they were introduced. Such a constraint results in the free carrier spectra with the maxima at k=(± π/2 , ± π/2 observed in some cuprates. We consider the spectral properties of the model by taking into account fluctuations of the spins in the antiferromagnetic background. We show that such fluctuations lead to a non-pole-like structure of the single-hole Green's function and these fluctuations can be responsible for some anomalous "strange metal" properties of underdoped cuprates in the nonsuperconducting regime.

  6. Proteostasis and REDOX state in the heart

    Science.gov (United States)

    Christians, Elisabeth S.

    2012-01-01

    Force-generating contractile cells of the myocardium must achieve and maintain their primary function as an efficient mechanical pump over the life span of the organism. Because only half of the cardiomyocytes can be replaced during the entire human life span, the maintenance strategy elicited by cardiac cells relies on uninterrupted renewal of their components, including proteins whose specialized functions constitute this complex and sophisticated contractile apparatus. Thus cardiac proteins are continuously synthesized and degraded to ensure proteome homeostasis, also termed “proteostasis.” Once synthesized, proteins undergo additional folding, posttranslational modifications, and trafficking and/or become involved in protein-protein or protein-DNA interactions to exert their functions. This includes key transient interactions of cardiac proteins with molecular chaperones, which assist with quality control at multiple levels to prevent misfolding or to facilitate degradation. Importantly, cardiac proteome maintenance depends on the cellular environment and, in particular, the reduction-oxidation (REDOX) state, which is significantly different among cardiac organelles (e.g., mitochondria and endoplasmic reticulum). Taking into account the high metabolic activity for oxygen consumption and ATP production by mitochondria, it is a challenge for cardiac cells to maintain the REDOX state while preventing either excessive oxidative or reductive stress. A perturbed REDOX environment can affect protein handling and conformation (e.g., disulfide bonds), disrupt key structure-function relationships, and trigger a pathogenic cascade of protein aggregation, decreased cell survival, and increased organ dysfunction. This review covers current knowledge regarding the general domain of REDOX state and protein folding, specifically in cardiomyocytes under normal-healthy conditions and during disease states associated with morbidity and mortality in humans. PMID:22003057

  7. Longitudinal fluctuations and decorrelation of anisotropic flow

    Energy Technology Data Exchange (ETDEWEB)

    Pang, Long-Gang [Frankfurt Institute for Advanced Studies, Ruth-Moufang-Strasse 1, 60438 Frankfurt am Main (Germany); Petersen, Hannah [Frankfurt Institute for Advanced Studies, Ruth-Moufang-Strasse 1, 60438 Frankfurt am Main (Germany); Institute for Theoretical Physics, Goethe University, Max-von-Laue-Strasse 1, 60438 Frankfurt am Main (Germany); GSI Helmholtzzentrum für Schwerionenforschung, Planckstr. 1, 64291 Darmstadt (Germany); Qin, Guang-You [Key Laboratory of Quark & Lepton Physics (MOE) and Institute of Particle Physics, Central China Normal University, Wuhan 430079 (China); Roy, Victor [Institute for Theoretical Physics, Goethe University, Max-von-Laue-Strasse 1, 60438 Frankfurt am Main (Germany); Wang, Xin-Nian [Key Laboratory of Quark & Lepton Physics (MOE) and Institute of Particle Physics, Central China Normal University, Wuhan 430079 (China); Nuclear Science Division MS70R0319, Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (United States)

    2016-12-15

    We investigate the decorrelation of 2nd and 3rd order anisotropic flow for charged particles in two different pseudo rapidity (η) windows by varying the pseudo rapidity gap, in an event-by-event (3+1)D ideal hydrodynamic model, with fluctuating initial conditions from A Multi-Phase Transport (AMPT) model. We visualize the parton distribution at initial state for Pb+Pb collisions at LHC and Au+Au collisions at RHIC, and demonstrate the longitudinal fluctuations originating from the asymmetry between forward and backward going participants, the fluctuations of the string length and the fluctuations due to finite number of partons at different beam energies. The decorrelation of anisotropic flow of final hadrons with large η gaps is found to originate from the spatial decorrelation along the longitudinal direction in the AMPT initial conditions through hydrodynamic evolution. The agreement between our results and recent CMS data in most centralities suggests that the string-like mechanism of initial parton production in AMPT model captures the initial longitudinal fluctuation that is responsible for the measured decorrelation of anisotropic flow in Pb+Pb collisions at LHC. Our predictions for Au+Au collisions at the highest RHIC energy show stronger longitudinal decorrelation than at LHC, indicating larger longitudinal fluctuations at lower beam energies.

  8. The fluctuating gap model

    Energy Technology Data Exchange (ETDEWEB)

    Cao, Xiaobin

    2011-01-15

    The quasi-one-dimensional systems exhibit some unusual phenomenon, such as the Peierls instability, the pseudogap phenomena and the absence of a Fermi-Dirac distribution function line shape in the photoemission spectroscopy. Ever since the discovery of materials with highly anisotropic properties, it has been recognized that fluctuations play an important role above the three-dimensional phase transition. This regime where the precursor fluctuations are presented can be described by the so called fluctuating gap model (FGM) which was derived from the Froehlich Hamiltonian to study the low energy physics of the one-dimensional electron-phonon system. Not only is the FGM of great interest in the context of quasi-one-dimensional materials, liquid metal and spin waves above T{sub c} in ferromagnets, but also in the semiclassical approximation of superconductivity, it is possible to replace the original three-dimensional problem by a directional average over effectively one-dimensional problem which in the weak coupling limit is described by the FGM. In this work, we investigate the FGM in a wide temperature range with different statistics of the order parameter fluctuations. We derive a formally exact solution to this problem and calculate the density of states, the spectral function and the optical conductivity. In our calculation, we show that a Dyson singularity appears in the low energy density of states for Gaussian fluctuations in the commensurate case. In the incommensurate case, there is no such kind of singularity, and the zero frequency density of states varies differently as a function of the correlation lengths for different statistics of the order parameter fluctuations. Using the density of states we calculated with non-Gaussian order parameter fluctuations, we are able to calculate the static spin susceptibility which agrees with the experimental data very well. In the calculation of the spectral functions, we show that as the correlation increases, the

  9. The fluctuating gap model

    International Nuclear Information System (INIS)

    Cao, Xiaobin

    2011-01-01

    The quasi-one-dimensional systems exhibit some unusual phenomenon, such as the Peierls instability, the pseudogap phenomena and the absence of a Fermi-Dirac distribution function line shape in the photoemission spectroscopy. Ever since the discovery of materials with highly anisotropic properties, it has been recognized that fluctuations play an important role above the three-dimensional phase transition. This regime where the precursor fluctuations are presented can be described by the so called fluctuating gap model (FGM) which was derived from the Froehlich Hamiltonian to study the low energy physics of the one-dimensional electron-phonon system. Not only is the FGM of great interest in the context of quasi-one-dimensional materials, liquid metal and spin waves above T c in ferromagnets, but also in the semiclassical approximation of superconductivity, it is possible to replace the original three-dimensional problem by a directional average over effectively one-dimensional problem which in the weak coupling limit is described by the FGM. In this work, we investigate the FGM in a wide temperature range with different statistics of the order parameter fluctuations. We derive a formally exact solution to this problem and calculate the density of states, the spectral function and the optical conductivity. In our calculation, we show that a Dyson singularity appears in the low energy density of states for Gaussian fluctuations in the commensurate case. In the incommensurate case, there is no such kind of singularity, and the zero frequency density of states varies differently as a function of the correlation lengths for different statistics of the order parameter fluctuations. Using the density of states we calculated with non-Gaussian order parameter fluctuations, we are able to calculate the static spin susceptibility which agrees with the experimental data very well. In the calculation of the spectral functions, we show that as the correlation increases, the quasi

  10. Bifunctional redox flow battery

    International Nuclear Information System (INIS)

    Wen, Y.H.; Cheng, J.; Xun, Y.; Ma, P.H.; Yang, Y.S.

    2008-01-01

    A new bifunctional redox flow battery (BRFB) system, V(III)/V(II)-L-cystine(O 2 ), was systematically investigated by using different separators. It is shown that during charge, water transfer is significantly restricted with increasing the concentration of HBr when the Nafion 115 cation exchange membrane is employed. The same result can be obtained when the gas diffusion layer (GDL) hot-pressed separator is used. The organic electro-synthesis is directly correlated with the crossover of vanadium. When employing the anion exchange membrane, the electro-synthesis efficiency is over 96% due to a minimal crossover of vanadium. When the GDL hot-pressed separator is applied, the crossover of vanadium and water transfer are noticeably prevented and the electro-synthesis efficiency of over 99% is obtained. Those impurities such as vanadium ions and bromine can be eliminated through the purification of organic electro-synthesized products. The purified product is identified to be L-cysteic acid by IR spectrum. The BRFB shows a favorable discharge performance at a current density of 20 mA cm -2 . Best discharge performance is achieved by using the GDL hot-pressed separator. The coulombic efficiency of 87% and energy efficiency of about 58% can be obtained. The cause of major energy losses is mainly associated with the cross-contamination of anodic and cathodic active electrolytes

  11. A Membrane‐Free Redox Flow Battery with Two Immiscible Redox Electrolytes

    Science.gov (United States)

    Navalpotro, Paula; Palma, Jesus; Anderson, Marc

    2017-01-01

    Abstract Flexible and scalable energy storage solutions are necessary for mitigating fluctuations of renewable energy sources. The main advantage of redox flow batteries is their ability to decouple power and energy. However, they present some limitations including poor performance, short‐lifetimes, and expensive ion‐selective membranes as well as high price, toxicity, and scarcity of vanadium compounds. We report a membrane‐free battery that relies on the immiscibility of redox electrolytes and where vanadium is replaced by organic molecules. We show that the biphasic system formed by one acidic solution and one ionic liquid, both containing quinoyl species, behaves as a reversible battery without any membrane. This proof‐of‐concept of a membrane‐free battery has an open circuit voltage of 1.4 V with a high theoretical energy density of 22.5 Wh L−1, and is able to deliver 90 % of its theoretical capacity while showing excellent long‐term performance (coulombic efficiency of 100 % and energy efficiency of 70 %). PMID:28658538

  12. A Membrane-Free Redox Flow Battery with Two Immiscible Redox Electrolytes.

    Science.gov (United States)

    Navalpotro, Paula; Palma, Jesus; Anderson, Marc; Marcilla, Rebeca

    2017-10-02

    Flexible and scalable energy storage solutions are necessary for mitigating fluctuations of renewable energy sources. The main advantage of redox flow batteries is their ability to decouple power and energy. However, they present some limitations including poor performance, short-lifetimes, and expensive ion-selective membranes as well as high price, toxicity, and scarcity of vanadium compounds. We report a membrane-free battery that relies on the immiscibility of redox electrolytes and where vanadium is replaced by organic molecules. We show that the biphasic system formed by one acidic solution and one ionic liquid, both containing quinoyl species, behaves as a reversible battery without any membrane. This proof-of-concept of a membrane-free battery has an open circuit voltage of 1.4 V with a high theoretical energy density of 22.5 Wh L -1 , and is able to deliver 90 % of its theoretical capacity while showing excellent long-term performance (coulombic efficiency of 100 % and energy efficiency of 70 %). © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  13. Fluctuating Asymmetry and Intelligence

    Science.gov (United States)

    Bates, Timothy C.

    2007-01-01

    The general factor of mental ability ("g") may reflect general biological fitness. If so, "g"-loaded measures such as Raven's progressive matrices should be related to morphological measures of fitness such as fluctuating asymmetry (FA: left-right asymmetry of a set of typically left-right symmetrical body traits such as finger…

  14. Organic Redox Species in Aqueous Flow Batteries: Redox Potentials, Chemical Stability and Solubility

    OpenAIRE

    Kristina Wedege; Emil Dražević; Denes Konya; Anders Bentien

    2016-01-01

    Organic molecules are currently investigated as redox species for aqueous low-cost redox flow batteries (RFBs). The envisioned features of using organic redox species are low cost and increased flexibility with respect to tailoring redox potential and solubility from molecular engineering of side groups on the organic redox-active species. In this paper 33, mainly quinone-based, compounds are studied experimentially in terms of pH dependent redox potential, solubility and stability, combined ...

  15. Characterisation of the Redox Sensitive NMDA Receptor

    KAUST Repository

    Alzahrani, Ohood

    2016-05-01

    Glucose entry into the brain and its subsequent metabolism to L-lactate, regulated by astrocytes, plays a major role in synaptic plasticity and memory formation. A recent study has shown that L-lactate produced by the brain upon stimulation of glycolysis, and glycogen-derived L-lactate from astrocytes and its transport into neurons, is crucial for memory formation. A recent study revealed the molecular mechanisms that underlie the role of L-lactate in neuronal plasticity and long-term memory formation. L-lactate was shown to induce a cascade of molecular events via modulation of redox-sensitive N-Methyl-D-aspartate (NMDA) receptor activity that was mimicked by nicotinamide adenine dinucleotide hydride (NADH) co-enzyme. This indicated that changes in cellular redox state, following L-lactate transport inside the cells and its subsequent metabolism, production of NADH, and favouring a reduced state are the key effects of L-lactate. Therefore, we are investigating the role of L-lactate in modulating NMDA receptor function via redox modulatory sites. Accordingly, crucial redox-sensitive cysteine residues, Cys320 and Cys87, of the NR2A NMDA receptor subunit are mutated using site-directed mutation, transfected, and expressed in HEK293 cells. This cellular system will then be used to characterise and monitor its activity upon Llactate stimulation, compared to the wild type. This will be achieved by calcium imaging, using fluorescent microscopy. Our data shows that L-lactate potentiated NMDA receptor activity and increased intracellular calcium influx in NR1/NR2A wild type compared to the control condition (WT NR1/NR2A perfused with (1μM) glutamate and (1μM) glycine agonist only), showing faster response initiation and slower decay rate of the calcium signal to the baseline. Additionally, stimulating with L-lactate associated with greater numbers of cells having high fluorescent intensity (peak amplitude) compared to the control. Furthermore, L-lactate rescued the

  16. Synthesis and characterization of redox-active ferric nontronite

    Energy Technology Data Exchange (ETDEWEB)

    Ilgen, A. G.; Kukkadapu, R. K.; Dunphy, D. R.; Artyushkova, K.; Cerrato, J. M.; Kruichak, J. N.; Janish, M. T.; Sun, C. J.; Argo, J. M.; Washington, R. E.

    2017-10-01

    Heterogeneous redox reactions on clay mineral surfaces control mobility and bioavailability of redox-sensitive nutrients and contaminants. Iron (Fe) residing in clay mineral structures can either catalyze or directly participate in redox reactions; however, chemical controls over its reactivity are not fully understood. In our previous work we demonstrated that converting a minor portion of Fe(III) to Fe(II) (partial reduction) in the octahedral sheet of natural Fe-rich clay mineral nontronite (NAu-1) activates its surface, making it redox-active. In this study we produced and characterized synthetic ferric nontronite (SIP), highlighting structural and chemical similarities and differences between this synthetic nontronite and its natural counterpart NAu-1, and probed whether mineral surface is redox-active by reacting it with arsenic As(III) under oxic and anoxic conditions. We demonstrate that synthetic nontronite SIP undergoes the same activation as natural nontronite NAu-1 following the partial reduction treatment. Similar to NAu-1, SIP oxidized As(III) to As(V) under both oxic (catalytic pathway) and anoxic (direct oxidation) conditions. The similar reactivity trends observed for synthetic nontronite and its natural counterpart make SIP an appropriate analog for laboratory studies. The development of chemically pure analogs for ubiquitous soil minerals will allow for systematic research of the fundamental properties of these minerals.

  17. Population fluctuation and vertical distribution of meiofauna in the Red Sea interstitial environment.

    Science.gov (United States)

    El-Serehy, Hamed A; Al-Misned, Fahad A; Al-Rasheid, Khaled A

    2015-07-01

    The composition and distribution of the benthic meiofauna assemblages of the Egyptian coasts along the Red Sea are described in relation to abiotic variables. Sediment samples were collected seasonally from three stations chosen along the Red Sea to observe the meiofaunal community structure, its temporal distribution and vertical fluctuation in relation to environmental conditions of the Red Sea marine ecosystem. The temperature, salinity, pH, dissolved oxygen, and redox potential were measured at the time of collection. The water content of the sediments, total organic matters and chlorophyll a values were determined, and sediment samples were subjected to granulometric analysis. A total of 10 meiofauna taxa were identified, with the meiofauna being primarily represented by nematodes (on annual average from 42% to 84%), harpacticoids, polycheates and ostracodes; and the meiofauna abundances ranging from 41 to 167 ind./10 cm(2). The meiofaunal population density fluctuated seasonally with a peak of 192.52 ind./10 cm(2) during summer at station II. The vertical zonation in the distribution of meiofaunal community was significantly correlated with interstitial water, chlorophyll a and total organic matter values. The present study indicates the existence of the well diversified meiofaunal group which can serve as food for higher trophic levels in the Red Sea interstitial environment.

  18. Fluctuations in quantum devices

    Directory of Open Access Journals (Sweden)

    H.Haken

    2004-01-01

    Full Text Available Logical gates can be formalized by Boolean algebra whose elementary operations can be realized by devices that employ the interactions of macroscopic numbers of elementary excitations such as electrons, holes, photons etc. With increasing miniaturization to the nano scale and below, quantum fluctuations become important and can no longer be ignored. Based on Heisenberg equations of motion for the creation and annihilation operators of elementary excitations, I determine the noise sources of composite quantum systems.

  19. Fluctuations and Instability in Sedimentation

    KAUST Repository

    Guazzelli, É lisabeth; Hinch, John

    2011-01-01

    This review concentrates on the fluctuations of the velocities of sedimenting spheres, and on the structural instability of a suspension of settling fibers. For many years, theoretical estimates and numerical simulations predicted the fluctuations

  20. Quantitative proteomic characterization of redox-dependent post-translational modifications on protein cysteines

    Energy Technology Data Exchange (ETDEWEB)

    Duan, Jicheng; Gaffrey, Matthew J.; Qian, Wei-Jun

    2017-01-01

    Protein cysteine thiols play a crucial role in redox signaling, regulation of enzymatic activity and protein function, and maintaining redox homeostasis in living systems. The unique chemical reactivity of thiol groups makes cysteine susceptible to oxidative modifications by reactive oxygen and nitrogen species to form a broad array of reversible and irreversible protein post-translational modifications (PTMs). The reversible modifications in particular are one of the major components of redox signaling and are involved in regulation of various cellular processes under physiological and pathological conditions. The biological significance of these redox PTMs in health and diseases has been increasingly recognized. Herein, we review the recent advances of quantitative proteomic approaches for investigating redox PTMs in complex biological systems, including the general considerations of sample processing, various chemical or affinity enrichment strategies, and quantitative approaches. We also highlight a number of redox proteomic approaches that enable effective profiling of redox PTMs for addressing specific biological questions. Although some technological limitations remain, redox proteomics is paving the way towards a better understanding of redox signaling and regulation in human health and diseases.

  1. Redox potentials and kinetics of the Ce 3+/Ce 4+ redox reaction and solubility of cerium sulfates in sulfuric acid solutions

    Science.gov (United States)

    Paulenova, A.; Creager, S. E.; Navratil, J. D.; Wei, Y.

    Experimental work was performed with the aim of evaluating the Ce 4+/Ce 3+ redox couple in sulfuric acid electrolyte for use in redox flow battery (RFB) technology. The solubility of cerium sulfates in 0.1-4.0 M sulfuric acid at 20-60 °C was studied. A synergistic effect of both sulfuric acid concentration and temperature on the solubility of cerous sulfate was observed. The solubility of cerous sulfate significantly decreased with rising concentration of sulfuric acid and rising temperature, while the solubility of ceric sulfate goes through a significant maximum at 40 °C. Redox potentials and the kinetics of the cerous/ceric redox reaction were also studied under the same temperature-concentration conditions. The redox potentials were measured using the combined redox electrode (Pt-Ag/AgCl) in equimolar Ce 4+/Ce 3+ solutions (i.e.[Ce 3+]=[Ce 4+]) in sulfuric acid electrolyte. The Ce 3+/Ce 4+ redox potentials significantly decrease (i.e. shift to more negative values) with rising sulfuric acid concentration; a small maximum is observed at 40 °C. Cyclic voltammetric experiments confirmed slow electrochemical kinetics of the Ce 3+/Ce 4+ redox reaction on carbon glassy electrodes (CGEs) in sulfuric acid solutions. The observed dependencies of solubilities, the redox potentials and the kinetics of Ce 3+/Ce 4+ redox reaction on sulfuric acid concentration are thought to be the result of inequivalent complexation of the two redox species by sulfate anions: the ceric ion is much more strongly bound to sulfate than is the cerous ion. The best temperature-concentration conditions for the RFB electrolytes appear to be 40 °C and 1 M sulfuric acid, where the relatively good solubility of both cerium species, the maximum of redox potentials, and the more or less satisfying stability of CGE s were found. Even so, the relatively low solubility of cerium salts in sulfuric acid media and slow redox kinetics of the Ce 3+/Ce 4+ redox reaction at carbon indicate that the Ce 3+/Ce

  2. Redox Couples with Unequal Diffusion Coefficients: Effect on Redox Cycling

    NARCIS (Netherlands)

    Mampallil Augustine, Dileep; Mathwig, Klaus; Kang, Shuo; Lemay, Serge Joseph Guy

    2013-01-01

    Redox cycling between two electrodes separated by a narrow gap allows dramatic amplification of the faradaic current. Unlike conventional electrochemistry at a single electrode, however, the mass-transport-limited current is controlled by the diffusion coefficient of both the reduced and oxidized

  3. Surface Fluctuation Scattering using Grating Heterodyne Spectroscopy

    DEFF Research Database (Denmark)

    Edwards, R. V.; Sirohi, R. S.; Mann, J. A.

    1982-01-01

    Heterodyne photon spectroscopy is used for the study of the viscoelastic properties of the liquid interface by studying light scattered from thermally generated surface fluctuations. A theory of a heterodyne apparatus based on a grating is presented, and the heterodyne condition is given in terms...

  4. Fluctuations in Schottky barrier heights

    International Nuclear Information System (INIS)

    Mahan, G.D.

    1984-01-01

    A double Schottky barrier is often formed at the grain boundary in polycrystalline semiconductors. The barrier height is shown to fluctuate in value due to the random nature of the impurity positions. The magnitude of the fluctuations is 0.1 eV, and the fluctuations cause the barrier height measured by capacitance to differ from the one measured by electrical conductivity

  5. Redox zones of a landfill leachate pollution plume (Vejen, Denmark)

    DEFF Research Database (Denmark)

    Lyngkilde, John; Christensen, Thomas Højlund

    1992-01-01

    Downgradient from an old municipal landfill allowing leachate, rich in dissolved organic carbon, to enter a shallow sandy aerobic aquifer, a sequence of redoxe zones is identified from groundwater chemical analysis. Below the landfill, methanogenic conditions prevail, followed by sulfidogenic...... the fate of reactive pollutants leached from the landfill....

  6. Sedimentary cobalt concentrations track marine redox evolution

    Science.gov (United States)

    Swanner, Elizabeth; Planavsky, Noah; Lalonde, Stefan; Robbins, Jamie; Bekker, Andrey; Rouxel, Olivier; Konhauser, Kurt O.; Mojzsis, Stephen J.

    2013-04-01

    Oxygen production by photosynthesis drove the redox evolution of the atmosphere and ocean. Primary productivity by oxygenic photosynthesizers in the modern surface ocean is limited by trace nutrients such as iron, but previous studies have also observed high Co uptake associated with natural cyanobacterial populations. Constraining the size and variation of the oceanic reservoir of Co through time will help to understand the regulation of primary productivity and hence oxygenation through time. In this study, Co concentrations from iron formations (IF), shales and marine pyrites deposited over nearly 4 billion years of Earth's history are utilized to reconstruct secular changes in the mechanisms of Co removal from the oceanic reservoir. The Co reservoir prior to ~2 Ga was dominated by hydrothermal inputs and Fe(III)oxyhydroxides were likely involved in the removal of Co from the water column. Fe(II) oxidation in the water column resulted in the deposition of IF in the Archean and Paleoproterozoic, and the Co inventory of IF records a large oceanic reservoir of Co during this time. Lower Co concentrations in sediments during the Middle Proterozoic signify a decrease in the oceanic reservoir due to the expansion euxinic environments, corresponding to the results of previous studies. A transition to an oxidized deep ocean in the Phanerozoic is evidenced by correlation between Co and manganese (Mn) concentrations in hydrothermal and exhalative deposits, and in marine pyrites. This relationship between Co and Mn, signifying deposition of Co in association with Mn(IV)oxides, does not occur in the Precambrian. Mn(II) oxidation occurs at higher redox potentials than that required for Fe(II) oxidation, and the extent of Mn redox cycling prior to full ventilation of the oceans at the end of the Neoproterozoic was likely limited to spatially restricted oxic surface waters. In this regard, Co is another valuable redox proxy for tracking the growth and decline in oxygenated

  7. Molecular Controls of the Oxygenation and Redox Reactions of Hemoglobin

    Science.gov (United States)

    Henkens, Robert; Alayash, Abdu I.; Banerjee, Sambuddha; Crumbliss, Alvin L.

    2013-01-01

    Abstract Significance: The broad classes of O2-binding proteins known as hemoglobins (Hbs) carry out oxygenation and redox functions that allow organisms with significantly different physiological demands to exist in a wide range of environments. This is aided by allosteric controls that modulate the protein's redox reactions as well as its O2-binding functions. Recent Advances: The controls of Hb's redox reactions can differ appreciably from the molecular controls for Hb oxygenation and come into play in elegant mechanisms for dealing with nitrosative stress, in the malarial resistance conferred by sickle cell Hb, and in the as-yet unsuccessful designs for safe and effective blood substitutes. Critical Issues: An important basic principle in consideration of Hb's redox reactions is the distinction between kinetic and thermodynamic reaction control. Clarification of these modes of control is critical to gaining an increased understanding of Hb-mediated oxidative processes and oxidative toxicity in vivo. Future Directions: This review addresses emerging concepts and some unresolved questions regarding the interplay between the oxygenation and oxidation reactions of structurally diverse Hbs, both within red blood cells and under acellular conditions. Developing methods that control Hb-mediated oxidative toxicity will be critical to the future development of Hb-based blood substitutes. Antioxid. Redox Signal. 18, 2298–2313. PMID:23198874

  8. Electrode redox reactions with polarizable molecules

    Science.gov (United States)

    Matyushov, Dmitry V.

    2018-04-01

    A theory of redox reactions involving electron transfer between a metal electrode and a polarizable molecule in solution is formulated. Both the existence of molecular polarizability and its ability to change due to electron transfer distinguish this problem from classical theories of interfacial electrochemistry. When the polarizability is different between the oxidized and reduced states, the statistics of thermal fluctuations driving the reactant over the activation barrier becomes non-Gaussian. The problem of electron transfer is formulated as crossing of two non-parabolic free energy surfaces. An analytical solution for these free energy surfaces is provided and the activation barrier of electrode electron transfer is given in terms of two reorganization energies corresponding to the oxidized and reduced states of the molecule in solution. The new non-Gaussian theory is, therefore, based on two theory parameters in contrast to one-parameter Marcus formulation for electrode reactions. The theory, which is consistent with the Nernst equation, predicts asymmetry between the cathodic and anodic branches of the electrode current. They show different slopes at small electrode overpotentials and become curved at larger overpotentials. However, the curvature of the Tafel plot is reduced compared to the Marcus-Hush model and approaches the empirical Butler-Volmer form with different transfer coefficients for the anodic and cathodic currents.

  9. Crossover transition in the fluctuation of Internet

    Science.gov (United States)

    Qian, Jiang-Hai

    2018-06-01

    The inconsistent fluctuation behavior of Internet predicted by preferential attachment(PA) and Gibrat's law requires empirical investigations on the actual system. By using the interval-tunable Gibrat's law statistics, we find the actual fluctuation, characterized by the conditional standard deviation of the degree growth rate, changes with the interval length and displays a crossover transition from PA type to Gibrat's law type, which has not yet been captured by any previous models. We characterize the transition dynamics quantitatively and determine the applicative range of PA and Gibrat's law. The correlation analysis indicates the crossover transition may be attributed to the accumulative correlation between the internal links.

  10. Strain fluctuations and elastic constants

    Energy Technology Data Exchange (ETDEWEB)

    Parrinello, M.; Rahman, A.

    1982-03-01

    It is shown that the elastic strain fluctuations are a direct measure of elastic compliances in a general anisotropic medium; depending on the ensemble in which the fluctuation is measured either the isothermal or the adiabatic compliances are obtained. These fluctuations can now be calculated in a constant enthalpy and pressure, and hence, constant entropy, ensemble due to recent develpments in the molecular dynamics techniques. A calculation for a Ni single crystal under uniform uniaxial 100 tensile or compressive load is presented as an illustration of the relationships derived between various strain fluctuations and the elastic modulii. The Born stability criteria and the behavior of strain fluctuations are shown to be related.

  11. Gambling with Superconducting Fluctuations

    Science.gov (United States)

    Foltyn, Marek; Zgirski, Maciej

    2015-08-01

    Josephson junctions and superconducting nanowires, when biased close to superconducting critical current, can switch to a nonzero voltage state by thermal or quantum fluctuations. The process is understood as an escape of a Brownian particle from a metastable state. Since this effect is fully stochastic, we propose to use it for generating random numbers. We present protocol for obtaining random numbers and test the experimentally harvested data for their fidelity. Our work is prerequisite for using the Josephson junction as a tool for stochastic (probabilistic) determination of physical parameters such as magnetic flux, temperature, and current.

  12. Fluctuations in the hadronization

    International Nuclear Information System (INIS)

    Bozek, P.; Ploszajaczak, M.

    1992-01-01

    The multiscaling in the fluctuations of the multiparticle distributions at small scales is studied. Similarly to the multiscaling effect, recently found in multifractal models, the dependence of the intermittency patterns on the low density cut-off in the cascade is analyzed. The effect changes the scaling behaviour and leads to stronger dependence of the scaled factorial moments on the resolution than the power law. This could be an explanation of the behaviour observed recently in the experimental 3-dimensional data. The multiscaling analysis allows to restore the universality in the processes with different cut-offs and could be used in the analysis of the experimental data. (author) 17 refs., 5 figs

  13. Classical and quantum temperature fluctuations via holography

    Energy Technology Data Exchange (ETDEWEB)

    Balatsky, Alexander V. [KTH Royal Inst. of Technology, Stockholm (Sweden); Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Gudnason, Sven Bjarke [KTH Royal Inst. of Technology, Stockholm (Sweden); Thorlacius, Larus [KTH Royal Inst. of Technology, Stockholm (Sweden); University of Iceland, Reykjavik (Iceland); Zarembo, Konstantin [KTH Royal Inst. of Technology, Stockholm (Sweden); Inst. of Theoretical and Experimental Physics (ITEP), Moscow (Russian Federation); Uppsala Univ. (Sweden); Krikun, Alexander [KTH Royal Inst. of Technology, Stockholm (Sweden); Inst. of Theoretical and Experimental Physics (ITEP), Moscow (Russian Federation); Kedem, Yaron [KTH Royal Inst. of Technology, Stockholm (Sweden)

    2014-05-27

    We study local temperature fluctuations in a 2+1 dimensional CFT on the sphere, dual to a black hole in asymptotically AdS space-time. The fluctuation spectrum is governed by the lowest-lying hydrodynamic sound modes of the system whose frequency and damping rate determine whether temperature fluctuations are thermal or quantum. We calculate numerically the corresponding quasinormal frequencies and match the result with the hydrodynamics of the dual CFT at large temperature. As a by-product of our analysis we determine the appropriate boundary conditions for calculating low-lying quasinormal modes for a four-dimensional Reissner-Nordstrom black hole in global AdS.

  14. Influence of intensity fluctuations on laser damage in optical materials

    International Nuclear Information System (INIS)

    Koldunov, M.F.; Manenkov, A.A.; Pocotilo, I.L.

    1995-01-01

    A study is reported of the influence of temporal fluctuations of laser radiation on the development of thermal explosion of absorbing inclusions and on the statistical properties of the laser induced damage in transparent dielectrics. A fluctuation time scale in which the fluctuations affect the thermal explosion of inclusions is established. An analysis is made of the conditions ensuring control of temporal fluctuations of laser radiation so as to eliminate their influence on the experimental statistical relationships governing laser damage associated with the distribution of absorbing inclusions in the bulk and on the surface of a sample

  15. Fluctuation characteristics in detached recombining plasmas

    International Nuclear Information System (INIS)

    Ohno, Noriyasu; Tanaka, Naoyuki; Takamura, Shuichi; Budaev, Viatcheslav

    2002-01-01

    Fluctuation in detached recombining plasmas has been investigated experimentally in the linear divertor plasma simulator, NAGDIS-II. As increasing neutral gas pressure, floating potential fluctuation of the target plate installed at the end of the NADIS-II device becomes larger and bursty negative spikes are observed in the signal associated with a transition from attached to detached a plasmas. The fluctuation property has been analyzed by using Fast Fourier Transform (FFT), probability distribution function (PDF) and wavelet transform. The PDF of the floating potential fluctuation in the attached plasma condition obeys the Gaussian distribution function, on the other hand, the PDF in detached plasma shows a strong deviation from the Gaussian distribution function, which can be characterized by flatness and skewness. Comparison of the fluctuation properties between the floating potential and the optical emission from the detached plasma has been done based on the wavelet transform to show that a strong correlation between them, which could indicate bursty transport of energetic electrons from upstream to downstream region along the magnetic field. (author)

  16. Hemoglobin redox reactions and red blood cell aging.

    Science.gov (United States)

    Rifkind, Joseph M; Nagababu, Enika

    2013-06-10

    The physiological mechanism(s) for recognition and removal of red blood cells (RBCs) from circulation after 120 days of its lifespan is not fully understood. Many of the processes thought to be associated with the removal of RBCs involve oxidative stress. We have focused on hemoglobin (Hb) redox reactions, which is the major source of RBC oxidative stress. The importance of Hb redox reactions have been shown to originate in large parts from the continuous slow autoxidation of Hb producing superoxide and its dramatic increase under hypoxic conditions. In addition, oxidative stress has been shown to be associated with redox reactions that originate from Hb reactions with nitrite and nitric oxide (NO) and the resultant formation of highly toxic peroxynitrite when NO reacts with superoxide released during Hb autoxidation. The interaction of Hb, particularly under hypoxic conditions with band 3 of the RBC membrane is critical for the generating the RBC membrane changes that trigger the removal of cells from circulation. These changes include exposure of antigenic sites, increased calcium leakage into the RBC, and the resultant leakage of potassium out of the RBC causing cell shrinkage and impaired deformability. The need to understand the oxidative damage to specific membrane proteins that result from redox reactions occurring when Hb is bound to the membrane. Proteomic studies that can pinpoint the specific proteins damaged under different conditions will help elucidate the cellular aging processes that result in cells being removed from circulation.

  17. Thallium isotopes track fluctuations in global manganese oxide burial during the Ediacaran Period

    Science.gov (United States)

    Ostrander, C. M.; Nielsen, S.; Owens, J. D.; Jiang, G.; Planavsky, N.; Sahoo, S. K.; Zhang, F.; Lyons, T. W.; Anbar, A. D.

    2017-12-01

    Complex marine ecosystems appear in the geologic record for the first time during the Ediacaran (635 - 541 Ma), after the Marinoan Glaciation but before the Cambrian Explosion. Much debate surrounds the redox-state of global oceans during this diversification, with some arguing for pervasive anoxic conditions and others for increased oxygenation, including the possibility of episodic oxygen increases. Here, we use thallium (Tl) isotopes preserved in organic-rich shales from a deep-water section at Wuhe, South China, to track large-scale perturbations in Mn oxide burial during the Ediacaran. Changes to the Tl isotope composition of seawater over geologic timescales are driven dominantly by fluctuations in global Mn oxide burial, which require persistent O2 at the sediment-water interface. Importantly, the suite of sedimentary rocks analyzed is thought to have been deposited beneath persistent localized euxinia, which is an environment shown to effectively capture the Tl isotope composition of seawater. Within samples previously suggested to host oceanic oxygenation episodes (OOEs) because of high redox-sensitive element (RSE) enrichments (Sahoo et al. 2016, Geobiology), we find Tl isotope values as light as -5 epsilon units, which are indicative of removal of heavy Tl by Mn oxides elsewhere in the Ediacaran ocean and in-line with the presence of deep-marine O2. Intriguingly, between these events, during periods previously viewed as dominantly anoxic, we find Tl isotope excursions to values that are even lighter than during the OOEs (less than -10 epsilon units). To first order, these results imply that an even larger Mn oxide sink was present between the OOEs, which would require pervasive oceanic oxygenation. This interpretation is in direct conflict with interpretations of low RSE enrichments in these same samples, which invoke reservoir drawdown due to widespread anoxia—as well as many other data that suggest dominantly anoxic deep marine conditions through the

  18. Mesoscale wind fluctuations over Danish waters

    Energy Technology Data Exchange (ETDEWEB)

    Vincent, C.L.

    2010-12-15

    Mesoscale wind fluctuations affect the large scale integration of wind power because they undermine the day-ahead predictability of wind speed and power production, and because they can result in large fluctuations in power generation that must be balanced using reserve power. Large fluctuations in generated power are a particular problem for offshore wind farms because the typically high concentration of turbines within a limited geographical area means that fluctuations can be correlated across large numbers of turbines. Furthermore, organised mesoscale structures that often form over water, such as convective rolls and cellular convection, have length scales of tens of kilometers, and can cause large wind fluctuations on a time scale of around an hour. This thesis is an exploration of the predictability of mesoscale wind fluctuations using observations from the world's first two large offshore wind farms - Horns Rev I in the North Sea, and Nysted in the Baltic Sea. The thesis begins with a climatological analysis of wind fluctuations on time scales of 1-10 hours at the two sites. A novel method for calculating conditional climatologies of spectral information is proposed, based on binning and averaging the time axis of the Hilbert spectrum. Results reveal clear patterns between wind fluctuations and locally observed meteorological conditions. The analysis is expanded by classifying wind fluctuations on time scales of 1-3 hours according to synoptic patterns, satellite pictures and wind classes. Results indicate that cold air outbreaks and open cellular convection are a significant contributor to mesoscale wind variability at Horns Rev. The predictability of mesoscale wind fluctuations is tested by implementing standard statistical models that relate local wind variability to parameters based on a large scale weather analysis. The models show some skill, but only achieve a 15% improvement on a persistence forecast. The possibility of explicitly modelling

  19. NAD(H) and NADP(H) Redox Couples and Cellular Energy Metabolism.

    Science.gov (United States)

    Xiao, Wusheng; Wang, Rui-Sheng; Handy, Diane E; Loscalzo, Joseph

    2018-01-20

    The nicotinamide adenine dinucleotide (NAD + )/reduced NAD + (NADH) and NADP + /reduced NADP + (NADPH) redox couples are essential for maintaining cellular redox homeostasis and for modulating numerous biological events, including cellular metabolism. Deficiency or imbalance of these two redox couples has been associated with many pathological disorders. Recent Advances: Newly identified biosynthetic enzymes and newly developed genetically encoded biosensors enable us to understand better how cells maintain compartmentalized NAD(H) and NADP(H) pools. The concept of redox stress (oxidative and reductive stress) reflected by changes in NAD(H)/NADP(H) has increasingly gained attention. The emerging roles of NAD + -consuming proteins in regulating cellular redox and metabolic homeostasis are active research topics. The biosynthesis and distribution of cellular NAD(H) and NADP(H) are highly compartmentalized. It is critical to understand how cells maintain the steady levels of these redox couple pools to ensure their normal functions and simultaneously avoid inducing redox stress. In addition, it is essential to understand how NAD(H)- and NADP(H)-utilizing enzymes interact with other signaling pathways, such as those regulated by hypoxia-inducible factor, to maintain cellular redox homeostasis and energy metabolism. Additional studies are needed to investigate the inter-relationships among compartmentalized NAD(H)/NADP(H) pools and how these two dinucleotide redox couples collaboratively regulate cellular redox states and cellular metabolism under normal and pathological conditions. Furthermore, recent studies suggest the utility of using pharmacological interventions or nutrient-based bioactive NAD + precursors as therapeutic interventions for metabolic diseases. Thus, a better understanding of the cellular functions of NAD(H) and NADP(H) may facilitate efforts to address a host of pathological disorders effectively. Antioxid. Redox Signal. 28, 251-272.

  20. Benzene dynamics and biodegradation in alluvial aquifers affected by river fluctuations.

    Science.gov (United States)

    Batlle-Aguilar, J; Morasch, B; Hunkeler, D; Brouyère, S

    2014-01-01

    The spatial distribution and temporal dynamics of a benzene plume in an alluvial aquifer strongly affected by river fluctuations was studied. Benzene concentrations, aquifer geochemistry datasets, past river morphology, and benzene degradation rates estimated in situ using stable carbon isotope enrichment were analyzed in concert with aquifer heterogeneity and river fluctuations. Geochemistry data demonstrated that benzene biodegradation was on-going under sulfate reducing conditions. Long-term monitoring of hydraulic heads and characterization of the alluvial aquifer formed the basis of a detailed modeled image of aquifer heterogeneity. Hydraulic conductivity was found to strongly correlate with benzene degradation, indicating that low hydraulic conductivity areas are capable of sustaining benzene anaerobic biodegradation provided the electron acceptor (SO4 (2-) ) does not become rate limiting. Modeling results demonstrated that the groundwater flux direction is reversed on annual basis when the river level rises up to 2 m, thereby forcing the infiltration of oxygenated surface water into the aquifer. The mobilization state of metal trace elements such as Zn, Cd, and As present in the aquifer predominantly depended on the strong potential gradient within the plume. However, infiltration of oxygenated water was found to trigger a change from strongly reducing to oxic conditions near the river, causing mobilization of previously immobile metal species and vice versa. MNA appears to be an appropriate remediation strategy in this type of dynamic environment provided that aquifer characterization and targeted monitoring of redox conditions are adequate and electron acceptors remain available until concentrations of toxic compounds reduce to acceptable levels. © 2013, National Ground Water Association.

  1. Pressure fluctuation characteristics of flow field of mixed flow nuclear primary pump

    International Nuclear Information System (INIS)

    Wang Chunlin; Yang Xiaoyong; Li Changjun; Jia Fei; Zhao Binjuan

    2013-01-01

    In order to research the pressure fluctuation characteristics of flow field of mixed flow nuclear primary pump, this study used the technique of ANSYS-Workbench and CFX fluid solid heat coupling to do numerical simulation analysis for model pump. According to the situation of pressure fluctuation of time domain and frequency domain, the main cause of pressure fluctuation was discussed. For different flow, the pressure fluctuations were compared. This study shows it is feasible that large eddy simulation method is used for the research of pressure fluctuation. The pressure fluctuation amplitudes of four sections are increasing from wheel hub to wheel rim. The pressure fluctuation of inlet and outlet of impeller depends on the rotational frequency of impeller. Along with the fluid flowing away from the impeller, the effect of the impeller on the fluid pressure fluctuation weakens gradually. Comparing the different results of three flow conditions, the pressure fluctuation in design condition flow is superior to the others. (authors)

  2. Fluctuation Relations for Currents

    Science.gov (United States)

    Sinitsyn, Nikolai; Akimov, Alexei; Chernyak, Vladimir; Chertkov, Michael

    2011-03-01

    We consider a non-equilibrium statistical system on a graph or a network. Identical particles are injected, interact with each other, traverse, and leave the graph in a stochastic manner described in terms of Poisson rates, possibly strongly dependent on time and instantaneous occupation numbers at the nodes of the graph. We show that the system demonstrates a profound statistical symmetry, leading to new Fluctuation Relations that originate from the supersymmetry and the principle of the geometric universality of currents rather than from the relations between probabilities of forward and reverse trajectories. NSF/ECCS-0925618, NSF/CHE-0808910 and DOE at LANL under Contract No. DE-AC52-06NA25396.

  3. Analytical expressions for conditional averages: A numerical test

    DEFF Research Database (Denmark)

    Pécseli, H.L.; Trulsen, J.

    1991-01-01

    Conditionally averaged random potential fluctuations are an important quantity for analyzing turbulent electrostatic plasma fluctuations. Experimentally, this averaging can be readily performed by sampling the fluctuations only when a certain condition is fulfilled at a reference position...

  4. Fluctuations in email size

    Science.gov (United States)

    Matsubara, Yoshitsugu; Musashi, Yasuo

    2017-12-01

    The purpose of this study is to explain fluctuations in email size. We have previously investigated the long-term correlations between email send requests and data flow in the system log of the primary staff email server at a university campus, finding that email size frequency follows a power-law distribution with two inflection points, and that the power-law property weakens the correlation of the data flow. However, the mechanism underlying this fluctuation is not completely understood. We collected new log data from both staff and students over six academic years and analyzed the frequency distribution thereof, focusing on the type of content contained in the emails. Furthermore, we obtained permission to collect "Content-Type" log data from the email headers. We therefore collected the staff log data from May 1, 2015 to July 31, 2015, creating two subdistributions. In this paper, we propose a model to explain these subdistributions, which follow log-normal-like distributions. In the log-normal-like model, email senders -consciously or unconsciously- regulate the size of new email sentences according to a normal distribution. The fitting of the model is acceptable for these subdistributions, and the model demonstrates power-law properties for large email sizes. An analysis of the length of new email sentences would be required for further discussion of our model; however, to protect user privacy at the participating organization, we left this analysis for future work. This study provides new knowledge on the properties of email sizes, and our model is expected to contribute to the decision on whether to establish upper size limits in the design of email services.

  5. Vanadium and Chromium Redox Behavior in borosilicate Nuclear Waste Glasses

    International Nuclear Information System (INIS)

    McKeown, D.; Muller, I.; Gan, H.; Feng, Z.; Viragh, C.; Pegg, I.

    2011-01-01

    X-ray absorption spectroscopy (XAS) was used to characterize vanadium (V) and chromium (Cr) environments in low activity nuclear waste (LAW) glasses synthesized under a variety of redox conditions. V 2 O 5 was added to the melt to improve sulfur incorporation from the waste; however, at sufficiently high concentrations, V increased melt foaming, which lowered melt processing rates. Foaming may be reduced by varying the redox conditions of the melt, while small amounts of Cr are added to reduce melter refractory corrosion. Three parent glasses were studied, where CO-CO 2 mixtures were bubbled through the corresponding melt for increasing time intervals so that a series of redox-adjusted-glasses was synthesized from each parent glass. XAS data indicated that V and Cr behaviors are significantly different in these glasses with respect to the cumulative gas bubbling times: V 4+ /V total ranges from 8 to 35%, while Cr 3+ /Cr total can range from 15 to 100% and even to population distributions including Cr 2+ . As Na-content decreased, V, and especially, Cr became more reduced, when comparing equivalent glasses within a series. The Na-poor glass series show possible redox coupling between V and Cr, where V 4+ populations increase after initial bubbling, but as bubbling time increases, V 4+ populations drop to near the level of the parent glass, while Cr becomes more reduced to the point of having increasing Cr 2+ populations.

  6. Fluctuating Thermodynamics for Biological Processes

    Science.gov (United States)

    Ham, Sihyun

    Because biomolecular processes are largely under thermodynamic control, dynamic extension of thermodynamics is necessary to uncover the mechanisms and driving factors of fluctuating processes. The fluctuating thermodynamics technology presented in this talk offers a practical means for the thermodynamic characterization of conformational dynamics in biomolecules. The use of fluctuating thermodynamics has the potential to provide a comprehensive picture of fluctuating phenomena in diverse biological processes. Through the application of fluctuating thermodynamics, we provide a thermodynamic perspective on the misfolding and aggregation of the various proteins associated with human diseases. In this talk, I will present the detailed concepts and applications of the fluctuating thermodynamics technology for elucidating biological processes. This work was supported by Samsung Science and Technology Foundation under Project Number SSTF-BA1401-13.

  7. Redox control of electric melters with complex feed compositions. Part I: analytical methods and models

    International Nuclear Information System (INIS)

    Bickford, D.F.; Diemer, R.B. Jr.

    1985-01-01

    The redox state of glass from electric melters with complex feed compositions is determined by balance between gases above the melt, and transition metals and organic compounds in the feed. Part I discusses experimental and computational methods of relating flowrates and other melter operating conditions to the redox state of glass, and composition of the melter offgas. Computerized thermodynamic computational methods are useful in predicting the sequence and products of redox reactions and in assessing individual process variations. Melter redox state can be predicted by combining monitoring of melter operating conditions, redox measurement of fused melter feed samples, and periodic redox measurement of product. Mossbauer spectroscopy, and other methods which measure Fe(II)/Fe(III) in glass, can be used to measure melter redox state. Part II develops preliminary operating limits for the vitrification of High-Level Radioactive Waste. Limits on reducing potential to preclude the accumulation of combustible gases, accumulation of sulfides and selenides, and degradation of melter components are the most critical. Problems associated with excessively oxidizing conditions, such as glass foaming and potential ruthenium volatility, are controlled when sufficient formic acid is added to adjust melter feed rheology

  8. Work and power fluctuations in a critical heat engine

    Science.gov (United States)

    Holubec, Viktor; Ryabov, Artem

    2017-09-01

    We investigate fluctuations of output work for a class of Stirling heat engines with working fluid composed of interacting units and compare these fluctuations to an average work output. In particular, we focus on engine performance close to a critical point where Carnot's efficiency may be attained at a finite power as reported by M. Campisi and R. Fazio [Nat. Commun. 7, 11895 (2016), 10.1038/ncomms11895]. We show that the variance of work output per cycle scales with the same critical exponent as the heat capacity of the working fluid. As a consequence, the relative work fluctuation diverges unless the output work obeys a rather strict scaling condition, which would be very hard to fulfill in practice. Even under this condition, the fluctuations of work and power do not vanish in the infinite system size limit. Large fluctuations of output work thus constitute inseparable and dominant element in performance of the macroscopic heat engines close to a critical point.

  9. Work and power fluctuations in a critical heat engine.

    Science.gov (United States)

    Holubec, Viktor; Ryabov, Artem

    2017-09-01

    We investigate fluctuations of output work for a class of Stirling heat engines with working fluid composed of interacting units and compare these fluctuations to an average work output. In particular, we focus on engine performance close to a critical point where Carnot's efficiency may be attained at a finite power as reported by M. Campisi and R. Fazio [Nat. Commun. 7, 11895 (2016)2041-172310.1038/ncomms11895]. We show that the variance of work output per cycle scales with the same critical exponent as the heat capacity of the working fluid. As a consequence, the relative work fluctuation diverges unless the output work obeys a rather strict scaling condition, which would be very hard to fulfill in practice. Even under this condition, the fluctuations of work and power do not vanish in the infinite system size limit. Large fluctuations of output work thus constitute inseparable and dominant element in performance of the macroscopic heat engines close to a critical point.

  10. Redox front formation in an uplifting sedimentary rock sequence: An analogue for redox-controlling processes in the geosphere around deep geological repositories for radioactive waste

    International Nuclear Information System (INIS)

    Yoshida, H.; Metcalfe, R.; Yamamoto, K.; Murakami, Y.; Hoshii, D.; Kanekiyo, A.; Naganuma, T.; Hayashi, T.

    2008-01-01

    Subsurface redox fronts control the mobilization and fixation of many trace elements, including potential pollutants such as certain radionuclides. Any safety assessment for a deep geological repository for radioactive wastes needs to take into account adequately the long-term redox processes in the geosphere surrounding the repository. To build confidence in understanding these processes, a redox front in a reduced siliceous sedimentary rock distributed in an uplifting area in Japan has been studied in detail. Geochemical analyses show increased concentrations of Fe and trace elements, including rare earth elements (REEs), at the redox front, even though concentrations of reduced rock matrix constituents show little change. Detailed SEM observations revealed that fossilized microorganisms composed of amorphous granules made exclusively of Fe and Si occur in the rock's pore space. Microbial 16S rDNA analysis suggests that there is presently a zonation of different bacterial groups within the redox band, and bacterial zonation played an important role in the concentration of Fe-oxyhydroxides at the redox front. These water-rock-microbe interactions can be considered analogous to the processes occurring in the redox fronts that would develop around geological repositories for radioactive waste. Once formed, the Fe-oxyhydroxides within such a front would be preserved even after reducing conditions resume following repository closure

  11. Redox front formation in an uplifting sedimentary rock sequence: An analogue for redox-controlling processes in the geosphere around deep geological repositories for radioactive waste

    Energy Technology Data Exchange (ETDEWEB)

    Yoshida, H. [Nagoya University Museum, Material Research Section, Furocho, Nagoya 464-8602 (Japan)], E-mail: dora@num.nagoya-u.ac.jp; Metcalfe, R. [Quintessa Japan, Queen' s Tower A7-707, Minatomirai, Yokohama 220-6007 (Japan); Yamamoto, K. [Nagoya University Museum, Material Research Section, Furocho, Nagoya 464-8602 (Japan); Murakami, Y. [Japan Atomic Energy Agency (JAEA), Tono Geoscience Centre (Japan); Hoshii, D.; Kanekiyo, A.; Naganuma, T. [Hiroshima University, Higashi Hiroshima, Kagamiyama 1-4-4 (Japan); Hayashi, T. [Asahi University, Department of Dental Pharmacology, Hozumi, Gifu (Japan)

    2008-08-15

    Subsurface redox fronts control the mobilization and fixation of many trace elements, including potential pollutants such as certain radionuclides. Any safety assessment for a deep geological repository for radioactive wastes needs to take into account adequately the long-term redox processes in the geosphere surrounding the repository. To build confidence in understanding these processes, a redox front in a reduced siliceous sedimentary rock distributed in an uplifting area in Japan has been studied in detail. Geochemical analyses show increased concentrations of Fe and trace elements, including rare earth elements (REEs), at the redox front, even though concentrations of reduced rock matrix constituents show little change. Detailed SEM observations revealed that fossilized microorganisms composed of amorphous granules made exclusively of Fe and Si occur in the rock's pore space. Microbial 16S rDNA analysis suggests that there is presently a zonation of different bacterial groups within the redox band, and bacterial zonation played an important role in the concentration of Fe-oxyhydroxides at the redox front. These water-rock-microbe interactions can be considered analogous to the processes occurring in the redox fronts that would develop around geological repositories for radioactive waste. Once formed, the Fe-oxyhydroxides within such a front would be preserved even after reducing conditions resume following repository closure.

  12. Cascade redox flow battery systems

    Science.gov (United States)

    Horne, Craig R.; Kinoshita, Kim; Hickey, Darren B.; Sha, Jay E.; Bose, Deepak

    2014-07-22

    A reduction/oxidation ("redox") flow battery system includes a series of electrochemical cells arranged in a cascade, whereby liquid electrolyte reacts in a first electrochemical cell (or group of cells) before being directed into a second cell (or group of cells) where it reacts before being directed to subsequent cells. The cascade includes 2 to n stages, each stage having one or more electrochemical cells. During a charge reaction, electrolyte entering a first stage will have a lower state-of-charge than electrolyte entering the nth stage. In some embodiments, cell components and/or characteristics may be configured based on a state-of-charge of electrolytes expected at each cascade stage. Such engineered cascades provide redox flow battery systems with higher energy efficiency over a broader range of current density than prior art arrangements.

  13. Big Bang or vacuum fluctuation

    International Nuclear Information System (INIS)

    Zel'dovich, Ya.B.

    1980-01-01

    Some general properties of vacuum fluctuations in quantum field theory are described. The connection between the ''energy dominance'' of the energy density of vacuum fluctuations in curved space-time and the presence of singularity is discussed. It is pointed out that a de-Sitter space-time (with the energy density of the vacuum fluctuations in the Einstein equations) that matches the expanding Friedman solution may describe the history of the Universe before the Big Bang. (P.L.)

  14. Redox signaling in acute pancreatitis

    Science.gov (United States)

    Pérez, Salvador; Pereda, Javier; Sabater, Luis; Sastre, Juan

    2015-01-01

    Acute pancreatitis is an inflammatory process of the pancreatic gland that eventually may lead to a severe systemic inflammatory response. A key event in pancreatic damage is the intracellular activation of NF-κB and zymogens, involving also calcium, cathepsins, pH disorders, autophagy, and cell death, particularly necrosis. This review focuses on the new role of redox signaling in acute pancreatitis. Oxidative stress and redox status are involved in the onset of acute pancreatitis and also in the development of the systemic inflammatory response, being glutathione depletion, xanthine oxidase activation, and thiol oxidation in proteins critical features of the disease in the pancreas. On the other hand, the release of extracellular hemoglobin into the circulation from the ascitic fluid in severe necrotizing pancreatitis enhances lipid peroxidation in plasma and the inflammatory infiltrate into the lung and up-regulates the HIF–VEGF pathway, contributing to the systemic inflammatory response. Therefore, redox signaling and oxidative stress contribute to the local and systemic inflammatory response during acute pancreatitis. PMID:25778551

  15. Redox signaling in acute pancreatitis

    Directory of Open Access Journals (Sweden)

    Salvador Pérez

    2015-08-01

    Full Text Available Acute pancreatitis is an inflammatory process of the pancreatic gland that eventually may lead to a severe systemic inflammatory response. A key event in pancreatic damage is the intracellular activation of NF-κB and zymogens, involving also calcium, cathepsins, pH disorders, autophagy, and cell death, particularly necrosis. This review focuses on the new role of redox signaling in acute pancreatitis. Oxidative stress and redox status are involved in the onset of acute pancreatitis and also in the development of the systemic inflammatory response, being glutathione depletion, xanthine oxidase activation, and thiol oxidation in proteins critical features of the disease in the pancreas. On the other hand, the release of extracellular hemoglobin into the circulation from the ascitic fluid in severe necrotizing pancreatitis enhances lipid peroxidation in plasma and the inflammatory infiltrate into the lung and up-regulates the HIF–VEGF pathway, contributing to the systemic inflammatory response. Therefore, redox signaling and oxidative stress contribute to the local and systemic inflammatory response during acute pancreatitis.

  16. Thermodynamic theory of equilibrium fluctuations

    International Nuclear Information System (INIS)

    Mishin, Y.

    2015-01-01

    The postulational basis of classical thermodynamics has been expanded to incorporate equilibrium fluctuations. The main additional elements of the proposed thermodynamic theory are the concept of quasi-equilibrium states, a definition of non-equilibrium entropy, a fundamental equation of state in the entropy representation, and a fluctuation postulate describing the probability distribution of macroscopic parameters of an isolated system. Although these elements introduce a statistical component that does not exist in classical thermodynamics, the logical structure of the theory is different from that of statistical mechanics and represents an expanded version of thermodynamics. Based on this theory, we present a regular procedure for calculations of equilibrium fluctuations of extensive parameters, intensive parameters and densities in systems with any number of fluctuating parameters. The proposed fluctuation formalism is demonstrated by four applications: (1) derivation of the complete set of fluctuation relations for a simple fluid in three different ensembles; (2) fluctuations in finite-reservoir systems interpolating between the canonical and micro-canonical ensembles; (3) derivation of fluctuation relations for excess properties of grain boundaries in binary solid solutions, and (4) derivation of the grain boundary width distribution for pre-melted grain boundaries in alloys. The last two applications offer an efficient fluctuation-based approach to calculations of interface excess properties and extraction of the disjoining potential in pre-melted grain boundaries. Possible future extensions of the theory are outlined.

  17. Real-time quantification of subcellular H2O2 and glutathione redox potential in living cardiovascular tissues.

    Science.gov (United States)

    Panieri, Emiliano; Millia, Carlo; Santoro, Massimo M

    2017-08-01

    Detecting and measuring the dynamic redox events that occur in vivo is a prerequisite for understanding the impact of oxidants and redox events in normal and pathological conditions. These aspects are particularly relevant in cardiovascular tissues wherein alterations of the redox balance are associated with stroke, aging, and pharmacological intervention. An ambiguous aspect of redox biology is how redox events occur in subcellular organelles including mitochondria, and nuclei. Genetically-encoded Rogfp2 fluorescent probes have become powerful tools for real-time detection of redox events. These probes detect hydrogen peroxide (H 2 O 2 ) levels and glutathione redox potential (E GSH ), both with high spatiotemporal resolution. By generating novel transgenic (Tg) zebrafish lines that express compartment-specific Rogfp2-Orp1 and Grx1-Rogfp2 sensors we analyzed cytosolic, mitochondrial, and the nuclear redox state of endothelial cells and cardiomyocytes of living zebrafish embryos. We provide evidence for the usefulness of these Tg lines for pharmacological compounds screening by addressing the blocking of pentose phosphate pathways (PPP) and glutathione synthesis, thus altering subcellular redox state in vivo. Rogfp2-based transgenic zebrafish lines represent valuable tools to characterize the impact of redox changes in living tissues and offer new opportunities for studying metabolic driven antioxidant response in biomedical research. Copyright © 2017 Elsevier Inc. All rights reserved.

  18. Redox reaction studies by nanosecond pulse radiolysis

    International Nuclear Information System (INIS)

    Moorthy, P.N.

    1979-01-01

    Free radicals are formed as intermediates in many chemical and biochemical reactions. An important type of reaction which they can undergo is a one electron or redox process. The direction and rate of such electron transfer reactions is governed by the relative redox potentials of the participating species. Because of the generally short lived nature of free radicals, evaluation of their redox potentials poses a number of problems. Two techniques are described for the experimental determination of the redox potentials of short lived species generated by either a nanosecond electron pulse or laser flash. In the first method, redox titration of the short lived species with stable molecules of known redox potential is carried out, employing the technique of fast kinetic spectrophotometry. Conversely, by the same method it is also possible to evaluate the one electron redox potentials of stable molecules by redox titration with free radicals of known redox potential produced as above. In the second method, electrochemical reduction or oxidation of the short lived species at an appropriate electrode (generally a mercury drop) is carried out at different fixed potentials, and the redox potential evaluated from the current-potential curves (polarograms). Full description of the experimental set up and theoretical considerations for interpretation of the raw data are given. The relative merits of the two methods and their practical applicability are discussed. (auth.)

  19. Dissecting Redox Biology Using Fluorescent Protein Sensors.

    Science.gov (United States)

    Schwarzländer, Markus; Dick, Tobias P; Meyer, Andreas J; Morgan, Bruce

    2016-05-01

    Fluorescent protein sensors have revitalized the field of redox biology by revolutionizing the study of redox processes in living cells and organisms. Within one decade, a set of fundamental new insights has been gained, driven by the rapid technical development of in vivo redox sensing. Redox-sensitive yellow and green fluorescent protein variants (rxYFP and roGFPs) have been the central players. Although widely used as an established standard tool, important questions remain surrounding their meaningful use in vivo. We review the growing range of thiol redox sensor variants and their application in different cells, tissues, and organisms. We highlight five key findings where in vivo sensing has been instrumental in changing our understanding of redox biology, critically assess the interpretation of in vivo redox data, and discuss technical and biological limitations of current redox sensors and sensing approaches. We explore how novel sensor variants may further add to the current momentum toward a novel mechanistic and integrated understanding of redox biology in vivo. Antioxid. Redox Signal. 24, 680-712.

  20. Broad temperature adaptability of vanadium redox flow battery—Part 1: Electrolyte research

    International Nuclear Information System (INIS)

    Xiao, Shuibo; Yu, Lihong; Wu, Lantao; Liu, Le; Qiu, Xinping; Xi, Jingyu

    2016-01-01

    Highlights: • Impact of temperature (-35 °C-50 °C) on properties of VRFB electrolyte is studied. • V 2+ , V 3+ , V 3.5+ , V 4+ (VO 2+ ) and V 5+ (VO 2 + ) electrolytes are tested respectively. • V 2+ , V 3+ and V 3.5+ precipitates at low temperature can redissolve when temperature increases. • V 5+ precipitates at high temperature cannot redissolve when temperature decreases. • Conductivity and viscosity of the electrolytes are greatly affected by temperature. - Abstract: The broad temperature adaptability of vanadium redox flow battery (VRFB) is one of the key issues which affects the large-scale and safety application of VRFB. Typically, five types of vanadium electrolytes, namely V 2+ , V 3+ , V 3.5+ (V 3+ :VO 2+ = 1:1), V 4+ (VO 2+ ) and V 5+ (VO 2 + ), are the most common electrolytes' status existing in VRFB system. In this work, the physicochemical and electrochemical properties of these vanadium electrolytes are studied in detail at a broad temperature range (-35 °C–50 °C). The results show that all types of vanadium electrolytes are stable between -25 °C–30 °C. The temperature fluctuation will largely influence the conductivity and viscosity of the electrolytes. Besides, the electrochemical properties of the positive (VO 2+ ) and negative (V 3+ ) electrolytes are greatly affected by the temperature; and the charge transfer process fluctuates more greatly with the temperature variation than the charge diffusion process does. These results enable us to better and more comprehensively evaluate the performance of the electrolyte changing with the temperature, which will be beneficial for the rational choice of electrolyte for VRFB operation under various conditions.

  1. Magnetic fluctuations associated with density fluctuations in the tokamak edge

    International Nuclear Information System (INIS)

    Kim, Y.J.; Gentle, K.W.; Ritz, C.P.; Rhodes, T.L.; Bengtson, R.D.

    1989-01-01

    Electrostatic density and potential fluctuations occurring with high amplitude near the edge of a tokamak are correlated with components of the fluctuating magnetic field measured outside the limiter radius. It has been established that this turbulence is associated with fluctuations in current as well as density and potential. The correlation extends for substantial toroidal distances, but only if the probes are displaced approximately along field lines, consistent with the short coherence lengths poloidally but long coherence lengths parallel to the field which are characteristic for this turbulence. Furthermore, the correlation can be found only with density fluctuations measured inside the limiter radius; density fluctuations behind the limiter have no detectable magnetic concomitant for the toroidally spaced probes used here. (author). Letter-to-the-editor. 12 refs, 3 figs

  2. Molecular analysis of Ku redox regulation

    Directory of Open Access Journals (Sweden)

    Shatilla Andrea

    2009-08-01

    Full Text Available Abstract Background DNA double-strand breaks (DSBs can occur in response to ionizing radiation (IR, radiomimetic agents and from endogenous DNA-damaging reactive oxygen metabolites. Unrepaired or improperly repaired DSBs are potentially the most lethal form of DNA damage and can result in chromosomal translocations and contribute to the development of cancer. The principal mechanism for the repair of DSBs in humans is non-homologous end-joining (NHEJ. Ku is a key member of the NHEJ pathway and plays an important role in the recognition step when it binds to free DNA termini. Ku then stimulates the assembly and activation of other NHEJ components. DNA binding of Ku is regulated by redox conditions and evidence from our laboratory has demonstrated that Ku undergoes structural changes when oxidized that results in a reduction in DNA binding activity. The C-terminal domain and cysteine 493 of Ku80 were investigated for their contribution to redox regulation of Ku. Results We effectively removed the C-terminal domain of Ku80 generating a truncation mutant and co-expressed this variant with wild type Ku70 in an insect cell system to create a Ku70/80ΔC heterodimer. We also generated two single amino acid variants of Cys493, replacing this amino acid with either an alanine (C493A or a serine (C493S, and over-expressed the variant proteins in SF9 insect cells in complex with wild type Ku70. Neither the truncation nor the amino acid substitutions alters protein expression or stability as determined by SDS-PAGE and Western blot analysis. We show that the C493 mutations do not alter the ability of Ku to bind duplex DNA in vitro under reduced conditions while truncation of the Ku80 C-terminus slightly reduced DNA binding affinity. Diamide oxidation of cysteines was shown to inhibit DNA binding similarly for both the wild-type and all variant proteins. Interestingly, differential DNA binding activity following re-reduction was observed for the Ku70/80

  3. Amplified and in situ detection of redox-active metabolite using a biobased redox capacitor.

    Science.gov (United States)

    Kim, Eunkyoung; Gordonov, Tanya; Bentley, William E; Payne, Gregory F

    2013-02-19

    Redox cycling provides a mechanism to amplify electrochemical signals for analyte detection. Previous studies have shown that diverse mediators/shuttles can engage in redox-cycling reactions with a biobased redox capacitor that is fabricated by grafting redox-active catechols onto a chitosan film. Here, we report that redox cycling with this catechol-chitosan redox capacitor can amplify electrochemical signals for detecting a redox-active bacterial metabolite. Specifically, we studied the redox-active bacterial metabolite pyocyanin that is reported to be a virulence factor and signaling molecule for the opportunistic pathogen P. aeruginosa. We demonstrate that redox cycling can amplify outputs from various electrochemical methods (cyclic voltammetry, chronocoulometry, and differential pulse voltammetry) and can lower the detection limit of pyocyanin to 50 nM. Further, the compatibility of this biobased redox capacitor allows the in situ monitoring of the production of redox-active metabolites (e.g., pyocyanin) during the course of P. aeruginosa cultivation. We anticipate that the amplified output of redox-active virulence factors should permit an earlier detection of life-threatening infections by the opportunistic pathogen P. aeruginosa while the "bio-compatibility" of this measurement approach should facilitate in situ study of the spatiotemporal dynamics of bacterial redox signaling.

  4. Fluid Fuel Fluctuations in the Spherical Tank

    Directory of Open Access Journals (Sweden)

    H. D. Nguyen

    2014-01-01

    Full Text Available Many authors tried to solve a task concerning small fluctuations of the incompressible ideal liquid, which partially fills a stationary tank of any shape. There is a long list of references to this subject. The article presents a task solution on own fluctuations of liquid in spherical capacity, with boundary conditions on a free surface and a surface with a resistance – drain surface. Relevance of problem consists in assessment of influence of intra tank devices (measuring, intaking, damping devices, etc. on the liquid fuel fluctuations. The special attention is paid to finding the own values and frequencies of the equations of disturbed flow fluctuations with dissipation available on the boundary surfaces. In contrast to the previous examples, the lowering speed and the free surface area at undisturbed state are variable.The article also considers a variation formulation of the auxiliary boundary tasks. In solution of variation tasks, the attached Legendre's functions were used as coordinate functions. Further, after substitution of the variation tasks solution in the boundary conditions and the subsequent mathematical operations the characteristic equation was obtained. To obtain solutions of the cubic characteristic equation Cardano formulas were used. The article also considers the task on the own motions of liquid filling a capacity between two concentric spheres and flowing out via the intake in case there is a free surface. Reliability of the obtained numerical results is confirmed by comparison with calculation results of frequencies resulting from solutions of a task on the own fluctuations of liquid in the spherical capacity with the constant depth of liquid. All numerical calculations were performed using the Matlab environment.

  5. Redox reactivity and coordination chemistry of uranium

    International Nuclear Information System (INIS)

    Nocton, G.

    2009-09-01

    The study and the understanding of actinides chemistry have important implications in the nuclear field both for the development of new actinides materials and the retreatment of the nuclear wastes. One of the major issues in that chemistry is that the actinides elements are known to undergo redox reaction and to form assemblies of different size and different topologies. In that context uranium can be a good model of the heavier radioelement because it is much less radioactive. So, this work concerns the synthesis and the study of the spectroscopy and the magnetic properties of several uranium based polymetallic assemblies synthesized by taking advantage of the redox properties and the coordination chemistry of uranium. The hydrolysis reactivity of trivalent uranium has been studied in absence of sterically hindered ligands and led to the synthesis of oxo/hydroxo uranium assemblies with different sizes by changing the starting complex or the reaction conditions. By following the same strategy, the controlled oxidation of trivalent uranium complexes led to an original azido/nitrido uranium complex. The coordination chemistry of the pentavalent uranyl polymer {[UO 2 py 5 ][KI 2 py 3 ]} n has also been studied with different ligand and in different conditions and led to several cation-cation complexes for which the stability is sufficient for studying there dismutation by proton NMR. By changing the ancillary ligands stable monomeric complexes of pentavalent uranyl complexes were also obtained. The magnetic properties of all the complexes, monomers and polymetallic complexes were studied and an antiferromagnetic coupling was observed for the cation-cation pentavalent uranyl dimer [UO 2 (dbm) 2 (K 18 C 6 )] 2 . (author)

  6. Charge Fluctuations in Nanoscale Capacitors

    NARCIS (Netherlands)

    Limmer, D.T.; Merlet, C.; Salanne, M.; Chandler, D.; Madden, P.A.; van Roij, R.H.H.G.; Rotenberg, B.

    2013-01-01

    The fluctuations of the charge on an electrode contain information on the microscopic correlations within the adjacent fluid and their effect on the electronic properties of the interface. We investigate these fluctuations using molecular dynamics simulations in a constant-potential ensemble with

  7. Fluctuating attention in Parkinson's disease

    DEFF Research Database (Denmark)

    Starrfelt, Randi; Aarsland, Dag; Janvin, Carmen

    2001-01-01

    Lewy body dementia (DLB), which share many clinical and pathological features with Parkinson’s disease (PD), is charac- terised by marked fluctuations in cognition and consciousness. Fluctuating cognition has not been formally studied in PD, although some studies indicate that PD patients show...

  8. Redox zonation for different groundwater flow paths during bank filtration: a case study at Liao River, Shenyang, northeastern China

    Science.gov (United States)

    Su, Xiaosi; Lu, Shuai; Yuan, Wenzhen; Woo, Nam Chil; Dai, Zhenxue; Dong, Weihong; Du, Shanghai; Zhang, Xinyue

    2018-03-01

    The spatial and temporal distribution of redox zones in an aquifer is important when designing groundwater supply systems. Redox zonation can have direct or indirect control of the biological and chemical reactions and mobility of pollutants. In this study, redox conditions are characterized by interpreting the hydrogeological conditions and water chemistry in groundwater during bank infiltration at a site in Shenyang, northeast China. The relevant redox processes and zonal differences in a shallow flow path and deeper flow path at the field scale were revealed by monitoring the redox parameters and chemistry of groundwater near the Liao River. The results show obvious horizontal and vertical components of redox zones during bank filtration. Variations in the horizontal extent of the redox zone were controlled by the different permeabilities of the riverbed sediments and aquifer with depth. Horizontally, the redox zone was situated within 17 m of the riverbank for the shallow flow path and within 200 m for the deep flow path. The vertical extent of the redox zone was affected by precipitation and seasonal river floods and extended to 10 m below the surface. During bank filtration, iron and manganese oxides or hydroxides were reductively dissolved, and arsenic that was adsorbed onto the medium surface or coprecipitated is released into the groundwater. This leads to increased arsenic content in groundwater, which poses a serious threat to water supply security.

  9. On statistical fluctuations in the dibaryon spectra

    International Nuclear Information System (INIS)

    Bazhanskij, I.I.; Luk'yanov, V.K.; Reznik, B.L.; Titov, A.I.

    1988-01-01

    The aim of this report is to show, that idea about statistical nature of dibaryon resonances corresponds to the present experimental data. Condition for cross section fluctuation occurrence is linked with value of decay width for isolated dibaryon in nucleon channel. Γ in terms of dibaryon potential quark model and q 6 → NN dibaryon decay for q 6 state with S 6 orbital symmetry and (S=I, I=0) deuteron quantum numbers are calculated as an example. np → ppπ - , dp → ppn and elastic pp-scattering are considered and distributions of cross sections and correlation functions obtained from these reactions are presented to investigate cross section fluctuations in spectra of effective masses of two-nucleon systems. Supposition about fluctuation pattern does not contradict the experiment. Curves, calculated with x l α < or approx. 0.05 partial amplitude parameter and full width of Γ < or approx. 20 MeV dibaryon resonances comply to the present experiment best. Fluctuation peculiarities -peaks in cross sections have approximately the same energy width (Γ ∼ 15-20 MeV) as the observed narrow peak in effective mass spectra of some reactions. 16 refs.; 3 figs

  10. Radii of Redox Components from Absolute Redox Potentials Compared with Covalent and Aqueous Ionic Radii

    Czech Academy of Sciences Publication Activity Database

    Heyrovská, Raji

    2010-01-01

    Roč. 22, č. 9 (2010), s. 903-907 ISSN 1040-0397 Institutional support: RVO:68081707 Keywords : Electrochemistry * Absolute redox potentials * Radii of redox components Subject RIV: BO - Biophysics Impact factor: 2.721, year: 2010

  11. S-Glutathionylation and Redox Protein Signaling in Drug Addiction.

    Science.gov (United States)

    Womersley, Jacqueline S; Uys, Joachim D

    2016-01-01

    Drug addiction is a chronic relapsing disorder that comes at a high cost to individuals and society. Therefore understanding the mechanisms by which drugs exert their effects is of prime importance. Drugs of abuse increase the production of reactive oxygen and nitrogen species resulting in oxidative stress. This change in redox homeostasis increases the conjugation of glutathione to protein cysteine residues; a process called S-glutathionylation. Although traditionally regarded as a protective mechanism against irreversible protein oxidation, accumulated evidence suggests a more nuanced role for S-glutathionylation, namely as a mediator in redox-sensitive protein signaling. The reversible modification of protein thiols leading to alteration in function under different physiologic/pathologic conditions provides a mechanism whereby change in redox status can be translated into a functional response. As such, S-glutathionylation represents an understudied means of post-translational protein modification that may be important in the mechanisms underlying drug addiction. This review will discuss the evidence for S-glutathionylation as a redox-sensing mechanism and how this may be involved in the response to drug-induced oxidative stress. The function of S-glutathionylated proteins involved in neurotransmission, dendritic spine structure, and drug-induced behavioral outputs will be reviewed with specific reference to alcohol, cocaine, and heroin. Copyright © 2016. Published by Elsevier Inc.

  12. Molecular controls of the oxygenation and redox reactions of hemoglobin.

    Science.gov (United States)

    Bonaventura, Celia; Henkens, Robert; Alayash, Abdu I; Banerjee, Sambuddha; Crumbliss, Alvin L

    2013-06-10

    The broad classes of O(2)-binding proteins known as hemoglobins (Hbs) carry out oxygenation and redox functions that allow organisms with significantly different physiological demands to exist in a wide range of environments. This is aided by allosteric controls that modulate the protein's redox reactions as well as its O(2)-binding functions. The controls of Hb's redox reactions can differ appreciably from the molecular controls for Hb oxygenation and come into play in elegant mechanisms for dealing with nitrosative stress, in the malarial resistance conferred by sickle cell Hb, and in the as-yet unsuccessful designs for safe and effective blood substitutes. An important basic principle in consideration of Hb's redox reactions is the distinction between kinetic and thermodynamic reaction control. Clarification of these modes of control is critical to gaining an increased understanding of Hb-mediated oxidative processes and oxidative toxicity in vivo. This review addresses emerging concepts and some unresolved questions regarding the interplay between the oxygenation and oxidation reactions of structurally diverse Hbs, both within red blood cells and under acellular conditions. Developing methods that control Hb-mediated oxidative toxicity will be critical to the future development of Hb-based blood substitutes.

  13. Differential alkylation-based redox proteomics – Lessons learnt

    Science.gov (United States)

    Wojdyla, Katarzyna; Rogowska-Wrzesinska, Adelina

    2015-01-01

    Cysteine is one of the most reactive amino acids. This is due to the electronegativity of sulphur atom in the side chain of thiolate group. It results in cysteine being present in several distinct redox forms inside the cell. Amongst these, reversible oxidations, S-nitrosylation and S-sulfenylation are crucial mediators of intracellular redox signalling, with known associations to health and disease. Study of their functionalities has intensified thanks to the development of various analytical strategies, with particular contribution from differential alkylation-based proteomics methods. Presented here is a critical evaluation of differential alkylation-based strategies for the analysis of S-nitrosylation and S-sulfenylation. The aim is to assess the current status and to provide insights for future directions in the dynamically evolving field of redox proteomics. To achieve that we collected 35 original research articles published since 2010 and analysed them considering the following parameters, (i) resolution of modification site, (ii) quantitative information, including correction of modification levels by protein abundance changes and determination of modification site occupancy, (iii) throughput, including the amount of starting material required for analysis. The results of this meta-analysis are the core of this review, complemented by issues related to biological models and sample preparation in redox proteomics, including conditions for free thiol blocking and labelling of target cysteine oxoforms. PMID:26282677

  14. Differential alkylation-based redox proteomics--Lessons learnt.

    Science.gov (United States)

    Wojdyla, Katarzyna; Rogowska-Wrzesinska, Adelina

    2015-12-01

    Cysteine is one of the most reactive amino acids. This is due to the electronegativity of sulphur atom in the side chain of thiolate group. It results in cysteine being present in several distinct redox forms inside the cell. Amongst these, reversible oxidations, S-nitrosylation and S-sulfenylation are crucial mediators of intracellular redox signalling, with known associations to health and disease. Study of their functionalities has intensified thanks to the development of various analytical strategies, with particular contribution from differential alkylation-based proteomics methods. Presented here is a critical evaluation of differential alkylation-based strategies for the analysis of S-nitrosylation and S-sulfenylation. The aim is to assess the current status and to provide insights for future directions in the dynamically evolving field of redox proteomics. To achieve that we collected 35 original research articles published since 2010 and analysed them considering the following parameters, (i) resolution of modification site, (ii) quantitative information, including correction of modification levels by protein abundance changes and determination of modification site occupancy, (iii) throughput, including the amount of starting material required for analysis. The results of this meta-analysis are the core of this review, complemented by issues related to biological models and sample preparation in redox proteomics, including conditions for free thiol blocking and labelling of target cysteine oxoforms. Copyright © 2015 The Authors. Published by Elsevier B.V. All rights reserved.

  15. The Tumorigenic Roles of the Cellular REDOX Regulatory Systems

    Directory of Open Access Journals (Sweden)

    Stéphanie Anaís Castaldo

    2016-01-01

    Full Text Available The cellular REDOX regulatory systems play a central role in maintaining REDOX homeostasis that is crucial for cell integrity, survival, and proliferation. To date, a substantial amount of data has demonstrated that cancer cells typically undergo increasing oxidative stress as the tumor develops, upregulating these important antioxidant systems in order to survive, proliferate, and metastasize under these extreme oxidative stress conditions. Since a large number of chemotherapeutic agents currently used in the clinic rely on the induction of ROS overload or change of ROS quality to kill the tumor, the cancer cell REDOX adaptation represents a significant obstacle to conventional chemotherapy. In this review we will first examine the different factors that contribute to the enhanced oxidative stress generally observed within the tumor microenvironment. We will then make a comprehensive assessment of the current literature regarding the main antioxidant proteins and systems that have been shown to be positively associated with tumor progression and chemoresistance. Finally we will make an analysis of commonly used chemotherapeutic drugs that induce ROS. The current knowledge of cancer cell REDOX adaptation raises the issue of developing novel and more effective therapies for these tumors that are usually resistant to conventional ROS inducing chemotherapy.

  16. Redox potentials of free radicals. III. Reevaluation of the method

    International Nuclear Information System (INIS)

    Rao, P.S.; Hayon, E.

    1974-01-01

    A reevaluation of the method described in ref 1 and 2 to determine the redox potentials of free radicals (.RH) in water using the techniques of pulse radiolysis and absorption spectrophotometry is presented. This method is based on the dependence of the percentage efficiency for the one-electron oxidation (or reduction) of .RH radicals on the redox potentials E 01 of the electron acceptors, A. The reaction .RH + A → .A - + R + H + (kappa/sub ox/) is not reversible for most radicals under the experimental conditions used, and the derived potentials are, therefore, not thermodynamic values. A reinterpretation of the results is made on the basis of the kinetic competition between the above reaction and .RH + A → .RHA (kappa/sub add/) (radical adducts). Based on kappa/ sub ox/ and kappa/sub add/, it is concluded that the observed experimental ''titration'' curves do represent a measure of the redox property of the free radicals. From the midpoint on the curves, the kinetic potential, E/sub kappa/ 01 : of the free radicals can be derived based on the known two-electron redox potentials of the electron acceptors. These and other questions are discussed. (U.S.)

  17. Nonequilibrium fluctuations in a resistor.

    Science.gov (United States)

    Garnier, N; Ciliberto, S

    2005-06-01

    In small systems where relevant energies are comparable to thermal agitation, fluctuations are of the order of average values. In systems in thermodynamical equilibrium, the variance of these fluctuations can be related to the dissipation constant in the system, exploiting the fluctuation-dissipation theorem. In nonequilibrium steady systems, fluctuations theorems (FT) additionally describe symmetry properties of the probability density functions (PDFs) of the fluctuations of injected and dissipated energies. We experimentally probe a model system: an electrical dipole driven out of equilibrium by a small constant current I, and show that FT are experimentally accessible and valid. Furthermore, we stress that FT can be used to measure the dissipated power P = R I2 in the system by just studying the PDFs' symmetries.

  18. Redox Pioneer: Professor Vadim N. Gladyshev.

    Science.gov (United States)

    Hatfield, Dolph L

    2016-07-01

    Professor Vadim N. Gladyshev is recognized here as a Redox Pioneer, because he has published an article on antioxidant/redox biology that has been cited more than 1000 times and 29 articles that have been cited more than 100 times. Gladyshev is world renowned for his characterization of the human selenoproteome encoded by 25 genes, identification of the majority of known selenoprotein genes in the three domains of life, and discoveries related to thiol oxidoreductases and mechanisms of redox control. Gladyshev's first faculty position was in the Department of Biochemistry, the University of Nebraska. There, he was a Charles Bessey Professor and Director of the Redox Biology Center. He then moved to the Department of Medicine at Brigham and Women's Hospital, Harvard Medical School, where he is Professor of Medicine and Director of the Center for Redox Medicine. His discoveries in redox biology relate to selenoenzymes, such as methionine sulfoxide reductases and thioredoxin reductases, and various thiol oxidoreductases. He is responsible for the genome-wide identification of catalytic redox-active cysteines and for advancing our understanding of the general use of cysteines by proteins. In addition, Gladyshev has characterized hydrogen peroxide metabolism and signaling and regulation of protein function by methionine-R-sulfoxidation. He has also made important contributions in the areas of aging and lifespan control and pioneered applications of comparative genomics in redox biology, selenium biology, and aging. Gladyshev's discoveries have had a profound impact on redox biology and the role of redox control in health and disease. He is a true Redox Pioneer. Antioxid. Redox Signal. 25, 1-9.

  19. Characterization of redox proteins using electrochemical methods

    OpenAIRE

    Verhagen, M.

    1995-01-01

    The use of electrochemical techniques in combination with proteins started approximately a decade ago and has since then developed into a powerfull technique for the study of small redox proteins. In addition to the determination of redox potentials, electrochemistry can be used to obtain information about the kinetics of electron transfer between proteins and about the dynamic behaviour of redox cofactors in proteins. This thesis describes the results of a study, initiated to get a ...

  20. Redox flow batteries having multiple electroactive elements

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Wei; Li, Liyu; Yang, Zhenguo; Nie, Zimin

    2018-05-01

    Introducing multiple redox reactions with a suitable voltage range can improve the energy density of redox flow battery (RFB) systems. One example includes RFB systems utilizing multiple redox pairs in the positive half cell, the negative half cell, or in both. Such RFB systems can have a negative electrolyte, a positive electrolyte, and a membrane between the negative electrolyte and the positive electrolyte, in which at least two electrochemically active elements exist in the negative electrolyte, the positive electrolyte, or both.

  1. Membranes for Redox Flow Battery Applications

    OpenAIRE

    Prifti, Helen; Parasuraman, Aishwarya; Winardi, Suminto; Lim, Tuti Mariana; Skyllas-Kazacos, Maria

    2012-01-01

    The need for large scale energy storage has become a priority to integrate renewable energy sources into the electricity grid. Redox flow batteries are considered the best option to store electricity from medium to large scale applications. However, the current high cost of redox flow batteries impedes the wide spread adoption of this technology. The membrane is a critical component of redox flow batteries as it determines the performance as well as the economic viability of the batteries. Th...

  2. Behavior of uranium during the formation of granitic magma by anatexis (I). Influence of redox conditions and the presence of chloride on the solubility of uranium in the hydrothermal solutions

    International Nuclear Information System (INIS)

    Satoru Nakashima; Toshimichi Iiyama, J.

    1983-01-01

    The behavior of uranium is examined experimentally in the course of partial fusion of natural or synthetic granitic rocks. Uranium is definitely soluble in the associated hydrothermal solutions containing chloride under oxidizing conditions, but it is not soluble in the same fluids under reducing conditions [fr

  3. Regulatory redox state in tree seeds

    Directory of Open Access Journals (Sweden)

    Ewelina Ratajczak

    2017-12-01

    Full Text Available Peroxiredoxins (Prx are important regulators of the redox status of tree seeds during maturation and long-term storage. Thioredoxins (Trx are redox transmitters and thereby regulate Prx activity. Current research is focused on the association of Trx with Prx in tree seeds differing in the tolerance to desiccation. The results will allow for better understanding the regulation of the redox status in orthodox, recalcitrant, and intermediate seeds. The findings will also elucidate the role of the redox status during the loss of viability of sensitive seeds during drying and long-term storage.

  4. Quantum fluctuations from thermal fluctuations in Jacobson formalism

    Energy Technology Data Exchange (ETDEWEB)

    Faizal, Mir [University of British Columbia-Okanagan, Irving K. Barber School of Arts and Sciences, Kelowna, BC (Canada); University of Lethbridge, Department of Physics and Astronomy, Lethbridge, AB (Canada); Ashour, Amani; Alcheikh, Mohammad [Damascus University, Mathematics Department, Faculty of Science, Damascus (Syrian Arab Republic); Alasfar, Lina [Universite Clermont Auvergne, Laboratoire de Physique Corpusculaire de Clermont-Ferrand, Aubiere (France); Alsaleh, Salwa; Mahroussah, Ahmed [King Saud University, Department of Physics and Astronomy, Riyadh (Saudi Arabia)

    2017-09-15

    In the Jacobson formalism general relativity is obtained from thermodynamics. This is done by using the Bekenstein-Hawking entropy-area relation. However, as a black hole gets smaller, its temperature will increase. This will cause the thermal fluctuations to also increase, and these will in turn correct the Bekenstein-Hawking entropy-area relation. Furthermore, with the reduction in the size of the black hole, quantum effects will also start to dominate. Just as the general relativity can be obtained from thermodynamics in the Jacobson formalism, we propose that the quantum fluctuations to the geometry can be obtained from thermal fluctuations. (orig.)

  5. Redox reactions in food fermentations

    DEFF Research Database (Denmark)

    Hansen, Egon Bech

    2018-01-01

    involves oxidative steps in the early part of the pathways whereas a multitude of different reactions are used as compensating reductions. Much of the diversity seen between food fermentations arise from the different routes and the different electron acceptors used by microorganisms to counterbalance...... and this contributes to the diversity in flavor, color, texture, and shelf life. The review concludes that these reactions are still only incompletely understood and that they represent an interesting area for fundamental research and also represent a fertile field for product development through a more conscious use...... of the redox properties of strains used to compose food cultures....

  6. Method for producing redox shuttles

    Science.gov (United States)

    Pupek, Krzysztof Z.; Dzwiniel, Trevor L.; Krumdick, Gregory K.

    2015-03-03

    A single step method for producing a redox shuttle having the formula 2,5-di-tert-butyl-1,4-phenylene tetraethyl bis(phosphate) is provided, the method comprising phosphorylating tert butyl hydroquinone with a phosphate-containing reagent. Also provided is method for producing 2,5-di-tert-butyl-1,4-phenylene tetraethyl bis(phosphate), the method comprising solubilizing tert-butyl hydroquinone and tetrabutylammonium bromide with methyltetrahydrofuran to create a mixture; heating the mixture while adding base to the mixture in an amount to turn the mixture orange; and adding diethyl chlorophosphate to the orange mixture in an amount to phosphorylate the hydroquinone.

  7. Development and testing of a compartmentalized reaction network model for redox zones in contaminated aquifers

    Science.gov (United States)

    Abrams , Robert H.; Loague, Keith; Kent, Douglas B.

    1998-01-01

    The work reported here is the first part of a larger effort focused on efficient numerical simulation of redox zone development in contaminated aquifers. The sequential use of various electron acceptors, which is governed by the energy yield of each reaction, gives rise to redox zones. The large difference in energy yields between the various redox reactions leads to systems of equations that are extremely ill-conditioned. These equations are very difficult to solve, especially in the context of coupled fluid flow, solute transport, and geochemical simulations. We have developed a general, rational method to solve such systems where we focus on the dominant reactions, compartmentalizing them in a manner that is analogous to the redox zones that are often observed in the field. The compartmentalized approach allows us to easily solve a complex geochemical system as a function of time and energy yield, laying the foundation for our ongoing work in which we couple the reaction network, for the development of redox zones, to a model of subsurface fluid flow and solute transport. Our method (1) solves the numerical system without evoking a redox parameter, (2) improves the numerical stability of redox systems by choosing which compartment and thus which reaction network to use based upon the concentration ratios of key constituents, (3) simulates the development of redox zones as a function of time without the use of inhibition factors or switching functions, and (4) can reduce the number of transport equations that need to be solved in space and time. We show through the use of various model performance evaluation statistics that the appropriate compartment choice under different geochemical conditions leads to numerical solutions without significant error. The compartmentalized approach described here facilitates the next phase of this effort where we couple the redox zone reaction network to models of fluid flow and solute transport.

  8. Modeling of fluctuating reaction networks

    International Nuclear Information System (INIS)

    Lipshtat, A.; Biham, O.

    2004-01-01

    Full Text:Various dynamical systems are organized as reaction networks, where the population size of one component affects the populations of all its neighbors. Such networks can be found in interstellar surface chemistry, cell biology, thin film growth and other systems. I cases where the populations of reactive species are large, the network can be modeled by rate equations which provide all reaction rates within mean field approximation. However, in small systems that are partitioned into sub-micron size, these populations strongly fluctuate. Under these conditions rate equations fail and the master equation is needed for modeling these reactions. However, the number of equations in the master equation grows exponentially with the number of reactive species, severely limiting its feasibility for complex networks. Here we present a method which dramatically reduces the number of equations, thus enabling the incorporation of the master equation in complex reaction networks. The method is examplified in the context of reaction network on dust grains. Its applicability for genetic networks will be discussed. 1. Efficient simulations of gas-grain chemistry in interstellar clouds. Azi Lipshtat and Ofer Biham, Phys. Rev. Lett. 93 (2004), 170601. 2. Modeling of negative autoregulated genetic networks in single cells. Azi Lipshtat, Hagai B. Perets, Nathalie Q. Balaban and Ofer Biham, Gene: evolutionary genomics (2004), In press

  9. Current density fluctuations and ambipolarity of transport

    International Nuclear Information System (INIS)

    Shen, W.; Dexter, R.N.; Prager, S.C.

    1991-10-01

    The fluctuation in the plasma current density is measured in the MIST reversed field pinch experiment. Such fluctuations, and the measured radial profile of the k spectrum of magnetic fluctuations, supports the view and that low frequency fluctuations (f r >) demonstrates that radial particle transport from particle motion parallel to a fluctuating magnetic field is ambipolar over the full frequency range

  10. Methods of simulating low redox potential (Eh) for a basalt repository

    International Nuclear Information System (INIS)

    Jantzen, C.M.

    1983-01-01

    Basalt groundwaters have inherently low redox potentials, approximately -0.4V, which can be measured with platinum electrodes, but are difficult to reproduce during leaching experiments. In the presence of deionized water, crushed basalt reaches the measured Eh-pH values of a basalt repository. Other waste package components, such as iron, will interact with groundwater in different ways under oxic or anoxic conditions since the presence of any redox active solid will affect the groundwater Eh. 26 references, 4 figures

  11. Information processing through a bio-based redox capacitor: signatures for redox-cycling.

    Science.gov (United States)

    Liu, Yi; Kim, Eunkyoung; White, Ian M; Bentley, William E; Payne, Gregory F

    2014-08-01

    Redox-cycling compounds can significantly impact biological systems and can be responsible for activities that range from pathogen virulence and contaminant toxicities, to therapeutic drug mechanisms. Current methods to identify redox-cycling activities rely on the generation of reactive oxygen species (ROS), and employ enzymatic or chemical methods to detect ROS. Here, we couple the speed and sensitivity of electrochemistry with the molecular-electronic properties of a bio-based redox-capacitor to generate signatures of redox-cycling. The redox capacitor film is electrochemically-fabricated at the electrode surface and is composed of a polysaccharide hydrogel with grafted catechol moieties. This capacitor film is redox-active but non-conducting and can engage diffusible compounds in either oxidative or reductive redox-cycling. Using standard electrochemical mediators ferrocene dimethanol (Fc) and Ru(NH3)6Cl3 (Ru(3+)) as model redox-cyclers, we observed signal amplifications and rectifications that serve as signatures of redox-cycling. Three bio-relevant compounds were then probed for these signatures: (i) ascorbate, a redox-active compound that does not redox-cycle; (ii) pyocyanin, a virulence factor well-known for its reductive redox-cycling; and (iii) acetaminophen, an analgesic that oxidatively redox-cycles but also undergoes conjugation reactions. These studies demonstrate that the redox-capacitor can enlist the capabilities of electrochemistry to generate rapid and sensitive signatures of biologically-relevant chemical activities (i.e., redox-cycling). Published by Elsevier B.V.

  12. Redox regulation of the Calvin-Benson cycle: something old, something new

    Directory of Open Access Journals (Sweden)

    Laure eMichelet

    2013-11-01

    Full Text Available Reversible redox post-translational modifications such as oxido-reduction of disulfide bonds, S-nitrosylation and S-glutathionylation, play a prominent role in the regulation of cell metabolism and signaling in all organisms. These modifications are mainly controlled by members of the thioredoxin and glutaredoxin families. Early studies in photosynthetic organisms have identified the Calvin-Benson cycle, the photosynthetic pathway responsible for carbon assimilation, as a redox regulated process. Indeed, 4 out of 11 enzymes of the cycle were shown to have a low activity in the dark and to be activated in the light through thioredoxin-dependent reduction of regulatory disulfide bonds. The underlying molecular mechanisms were extensively studied at the biochemical and structural level. Unexpectedly, recent biochemical and proteomic studies have suggested that all enzymes of the cycle and several associated regulatory proteins may undergo redox regulation through multiple redox post-translational modifications including glutathionylation and nitrosylation. The aim of this review is to detail the well-established mechanisms of redox regulation of Calvin-Benson cycle enzymes as well as the most recent reports indicating that this pathway is tightly controlled by multiple interconnected redox post-translational modifications. This redox control is likely allowing fine tuning of the Calvin-Benson cycle required for adaptation to varying environmental conditions, especially during responses to biotic and abiotic stresses.

  13. New insights into redox regulation of stem cell self-renewal and differentiation.

    Science.gov (United States)

    Ren, Fenglian; Wang, Kui; Zhang, Tao; Jiang, Jingwen; Nice, Edouard Collins; Huang, Canhua

    2015-08-01

    Reactive oxygen species (ROS), the natural byproducts of aerobic metabolism, are precisely orchestrated to evoke diverse signaling pathways. To date, studies have focused mainly on the detrimental effects of ROS in stem cells. Recently, accumulating evidence has suggested that ROS also function as second messengers that modulate stem cell self-renewal and differentiation by regulating intricate signaling networks. Although many efforts have been made to clarify the general effects of ROS on signal transduction in stem cells, less is known about the initial and direct executors of ROS signaling, which are known as 'redox sensors'. Modifications of cysteine residues in redox sensors are of significant importance in the modulation of protein function in response to different redox conditions. Intriguingly, most key molecules in ROS signaling and cell cycle regulation (including transcriptional factors and kinases) that are crucial in the regulation of stem cell self-renewal and differentiation have the potential to be redox sensors. We highlight herein the importance of redox regulation of these key regulators in stem cell self-renewal and differentiation. Understanding the mechanisms of redox regulation in stem cell self-renewal and differentiation will open exciting new perspectives for stem cell biology. This article is part of a Special Issue entitled Redox regulation of differentiation and de-differentiation. Copyright © 2015 Elsevier B.V. All rights reserved.

  14. [Effect of the medium redox potential on the growth and metabolism of anaerobic bacteria].

    Science.gov (United States)

    Vasilian, A; Trchunian, A

    2008-01-01

    Based on the available literature data on a decrease in the redox potential of medium to low negative values and a decrease in pH during the growth of sugar-fermenting anaerobic bacteria, it was concluded that these processes cannot be described by the theory of redox potential. A theory was developed according to which the regulation of bacterial metabolism is accomplished through changes in the redox potential. The theory considers the redox potential as a factor determining the growth of anaerobic bacteria, which is regulated by oxidizers and reducers. The assumption is put forward that, under anaerobic conditions, bacteria are sensitive to changes in the redox potential and have a redox taxis. The effect of the redox potential on the transport of protons and other substances through membranes and the activity of membrane-bound enzymes, including the proton F1-F0-ATPase, whose mechanisms of action involve changes in the proton conductance of the membrane, the generation of proton-driving force, and dithiol-disulfide transitions in proteins was studied.

  15. Redox potential dynamics in a grassed swale used for storage and treatment

    Science.gov (United States)

    Vorenhout, Michel; Boogaard, Floris Cornelis

    2016-04-01

    Treatment wetlands are used to remove pollutants from water. Most swales are designed to infiltrate stormwater into the subsurface. A combination of both functions can help to enhance water quality and reduce flooding risks in urban areas. The chemical forms and possible removal of pollutants such as nitrate and heavy metals in wetlands are highly dependent on the redox conditions. The redox conditions are expected to be highly dynamic and dependent on water levels and flow. We studied the correlation between these factors in an urban grassed swale system, and show that more factors play a role in these systems than water levels alone. The study system is located in the World Heritage site "Bryggen" in the city of Bergen, Norway. It consists of a series of SUDS, a socalled treatment train. The system is fed by storm water, which is at first stored in a rain garden then led to grassed swales. Water infiltrates into the subsurface in the swales. The reason for implementation of the system at this site is the protection of the highly organic archaeological layers at the site, which requires reduced conditions. Swales 1 and 2 were equipped with pressure loggers and multi-level redox and temperature probes (-2, -5, -10 and -20cm from surface). Redox and temperature probes were connected to a HYPNOS system. Measurements were taken for more than 1 year at 15 minute interval. A weather station supplemented the dataset with precipitation measurements. The redox potential in the swales show a strong correlation with water level. The regularly flooded swale 2 shows frequent anoxic events (Eh < 200mV) where as swale 1 shows oxic conditions (Eh = 650mV) throughout the same measurement period. Swale 1 has fewer flooding events than Swale 2 and a more coarse soil with less organic matter than swale 2. These redox results are as expected given the local conditions, and show that redox conditions are localised phenomena that depend on local soil conditions. Analysis of the redox

  16. Redox properties of small semiconductor particles

    International Nuclear Information System (INIS)

    Liver, N.; Nitzan, A.

    1992-01-01

    The size dependence of electrical and thermodynamic quantities of intermediate-sized semiconductor particles in an electrolyte solution with a given redox pair are studied. The equilibrium constant for this system is then derived based on the relationship of the electrolytic redox components to the size, charges, and concentration of the semiconductor particles. 25 refs., 9 figs., 1 tab

  17. Characterization of redox proteins using electrochemical methods

    NARCIS (Netherlands)

    Verhagen, M.

    1995-01-01

    The use of electrochemical techniques in combination with proteins started approximately a decade ago and has since then developed into a powerfull technique for the study of small redox proteins. In addition to the determination of redox potentials, electrochemistry can be used to obtain

  18. The Mineralogy, Geochemistry, and Redox State of Multivalent Cations During the Crystallization of Primitive Shergottitic Liquids at Various (f)O2. Insights into the (f)O2 Fugacity of the Martian Mantle and Crustal Influences on Redox Conditions of Martian Magmas.

    Science.gov (United States)

    Shearer, C. K.; Bell, A. S.; Burger, P. V.; Papike, J. J.; Jones, J.; Le, L.; Muttik, N.

    2016-01-01

    The (f)O2 [oxygen fugacity] of crystallization for martian basalts has been estimated in various studies to range from IW-1 to QFM+4 [1-3]. A striking geochemical feature of the shergottites is the large range in initial Sr isotopic ratios and initial epsilon(sup Nd) values. Studies by observed that within the shergottite group the (f)O2 [oxygen fugacity] of crystallization is highly correlated with these chemical and isotopic characteristics with depleted shergottites generally crystallizing at reduced conditions and enriched shergottites crystallizing under more oxidizing conditions. More recent work has shown that (f)O2 [oxygen fugacity] changed during the crystallization of these magmas from one order of magnitude in Y980459 (Y98) to several orders of magnitude in Larkman Nunatak 06319. These real or apparent variations within single shergottitic magmas have been attributed to mixing of a xenocrystic olivine component, volatile loss-water disassociation, auto-oxidation during crystallization of mafic phases, and assimilation of an oxidizing crustal component (e.g. sulfate). In contrast to the shergottites, augite basalts such as NWA 8159 are highly depleted yet appear to be highly oxidized (e.g. QFM+4). As a first step in attempting to unravel petrologic complexities that influence (f)O2 [oxygen fugacity] in martian magmas, this study explores the effect of (f)O2 [oxygen fugacity] on the liquid line of descent (LLD) for a primitive shergottite liquid composition (Y98). The results of this study will provide a fundamental basis for reconstructing the record of (f)O2 [oxygen fugacity] in shergottites and other martian basalts, its effect on both mineral chemistries and valence state partitioning, and a means for examining the role of crystallization (and other more complex processes) on the petrologic linkages between olivine-phyric and pyroxene-plagioclase shergottites.

  19. Localized description of valence fluctuations

    International Nuclear Information System (INIS)

    Alascio, B.; Allub, R.; Aligia, A.

    1979-07-01

    The authors set up a model for intermediate valence equivalent to the ''atomic'' limit of the Anderson Hamiltonian. Detailed analysis of this model shows that most of the essential characteristics of valence fluctuators are already present in this crudely simplified Hamiltonian. The spin-spin and the 4f charge-charge correlation functions are studied and it is shown that it is possible to define a spin fluctuation frequency ωsub(s.f.) and a charge fluctuation frequency ωsub(ch.f.).ωsub(s.f.) and ωsub(ch.f.) can differ considerably for some values of the parameters of the model. The magnetic susceptibility and the specific heat are calculated as functions of temperature and it is shown how the results simulate the behaviour found in valence fluctuators. (author)

  20. The Fluctuation Niche in Plants

    Directory of Open Access Journals (Sweden)

    Jaume Terradas

    2009-01-01

    Full Text Available Classical approaches to niche in coexisting plants have undervalued temporal fluctuations. We propose that fluctuation niche is an important dimension of the total niche and interacts with habitat and life-history niches to provide a better understanding of the multidimensional niche space where ecological interactions occur. To scale a fluctuation niche, it is necessary to relate environmental constrictions or species performance not only to the absolute values of the usual environmental and ecophysiological variables but also to their variances or other measures of variability. We use Mediterranean plant communities as examples, because they present characteristic large seasonal and interannual fluctuations in water and nutrient availabilities, along an episodic-constant gradient, and because the plant responses include a number of syndromes coupled to this gradient.

  1. The Fluctuation Niche in Plants

    International Nuclear Information System (INIS)

    Terradas, J.; Penuelas, J.; Lloret, F.; Penuelas, J.

    2009-01-01

    Classical approaches to niche in coexisting plants have undervalued temporal fluctuations. We propose that fluctuation niche is an important dimension of the total niche and interacts with habitat and life-history niches to provide a better understanding of the multidimensional niche space where ecological interactions occur. To scale a fluctuation niche, it is necessary to relate environmental constrictions or species performance not only to the absolute values of the usual environmental and eco physiological variables but also to their variances or other measures of variability. We use Mediterranean plant communities as examples, because they present characteristic large seasonal and inter annual fluctuations in water and nutrient availabilities, along an episodic-constant gradient, and because the plant responses include a number of syndromes coupled to this gradient.

  2. Insects in fluctuating thermal environments.

    Science.gov (United States)

    Colinet, Hervé; Sinclair, Brent J; Vernon, Philippe; Renault, David

    2015-01-07

    All climate change scenarios predict an increase in both global temperature means and the magnitude of seasonal and diel temperature variation. The nonlinear relationship between temperature and biological processes means that fluctuating temperatures lead to physiological, life history, and ecological consequences for ectothermic insects that diverge from those predicted from constant temperatures. Fluctuating temperatures that remain within permissive temperature ranges generally improve performance. By contrast, those which extend to stressful temperatures may have either positive impacts, allowing repair of damage accrued during exposure to thermal extremes, or negative impacts from cumulative damage during successive exposures. We discuss the mechanisms underlying these differing effects. Fluctuating temperatures could be used to enhance or weaken insects in applied rearing programs, and any prediction of insect performance in the field-including models of climate change or population performance-must account for the effect of fluctuating temperatures.

  3. Quantum fluctuations in insulating ferroelectrics

    International Nuclear Information System (INIS)

    Riseborough, Peter S.

    2010-01-01

    Graphical abstract: It has been proposed that in a ferroelectric insulator, an applied magnetic field may couple the transverse phonon modes and produce left and right circularly polarized phonon modes which are no longer degenerate. We quantize the theory and examine the effects of quantal fluctuations. In particular, we show that the zero point fluctuations result in a large diamagnetic contribution to the magnetic susceptibility. - Abstract: It has been proposed that in a ferroelectric insulator, an applied magnetic field may couple the transverse phonon modes and produce left and right circularly polarized phonon modes which are no longer degenerate. We quantize the theory and examine the effects of quantal fluctuations. In particular, we show that the zero-point fluctuations result in a large diamagnetic contribution to the magnetic susceptibility.

  4. Fluctuations and Instability in Sedimentation

    KAUST Repository

    Guazzelli, Élisabeth

    2011-01-21

    This review concentrates on the fluctuations of the velocities of sedimenting spheres, and on the structural instability of a suspension of settling fibers. For many years, theoretical estimates and numerical simulations predicted the fluctuations of the velocities of spheres to increase with the size of the container, whereas experiments found no such variation. Two ideas have increased our understanding. First, the correlation length of the velocity fluctuations was found experimentally to be 20 interparticle separations. Second, in dilute suspensions, a vertical variation in the concentration due to the spreading of the front with the clear fluid can inhibit the velocity fluctuations. In a very dilute regime, a homogeneous suspension of fibers suffers a spontaneous instability in which fast descending fiber-rich columns are separated by rising fiber-sparse columns. In a semidilute regime, the settling is hindered, more so than for spheres. © 2011 by Annual Reviews. All rights reserved.

  5. Electrostatic fluctuation and fluctuation-induced particle flux during formation of the edge transport barrier in the JFT-2M tokamak

    International Nuclear Information System (INIS)

    Ido, T.; Hamada, Y.; Nagashima, Y.; Nishizawa, A.; Kawasumi, Y.; Miura, Y.; Hoshino, K.; Ogawa, H.; Shinohara, K.; Kamiya, K.; Kusama, Y.

    2005-01-01

    The electrostatic fluctuation with Geodesic-Acoustic-Mode (GAM) frequency is observed in L-mode plasmas. The fluctuation has the poloidal wave number (k θ ) of (-2 ± 24) x 10 -3 (cm -1 ), that corresponds to the poloidal mode number of 1.5 or less, and the radial wave number (k r ) of 0.94 ± 0.05 (cm -1 ), that is corresponds to k r ρ i = 0.26 < 1. The amplitude of the fluctuation changes in the radial direction; it is small near the separatrix and it has maximum at 3 cm inside the separatrix. The relation between the amplitude of potential fluctuation and that of density fluctuation is the same as that of the predicted GAM. The fluctuation is probably GAM. The envelope of ambient density fluctuation and the potential fluctuation have a significant coherence at the GAM frequency. Thus, it is clearly verified that the fluctuation with the GAM frequency correlates with the ambient density fluctuation. The fluctuation with the GAM frequency affects the particle transport through the modulation of the ambient fluctuation. But the effect is not large, and it is not a sufficient condition to form the edge transport barrier and to drive the intermittent particle flux. (author)

  6. Electrostatic fluctuation and fluctuation-induced particle flux during formation of the edge transport barrier in the JFT-2M tokamak

    International Nuclear Information System (INIS)

    Ido, T.; Miura, K.; Hoshino, K.

    2005-01-01

    The electrostatic fluctuation with Geodesic-Acoustic-Mode (GAM) frequency is observed in L-mode plasmas. The fluctuation has the poloidal wave number (k θ ) of (-2 ± 24) x 10 -3 (cm -1 ), that corresponds to the poloidal mode number of 1.5 or less, and the radial wave number (k γ ) of 0.94±0.05 (cm -1 ), that is corresponds to k γ ρ i =0.26 < 1. The amplitude of the fluctuation changes in the radial direction; it is small near the separatrix and it has maximum at 3 cm inside the separatrix. The relation between the amplitude of potential fluctuation and that of density fluctuation is the same as that of the predicted GAM. The fluctuation is probably GAM. The envelope of ambient density fluctuation and the potential fluctuation have a significant coherence at the GAM frequency. Thus, it is clearly verified that the fluctuation with the GAM frequency correlates with the ambient density fluctuation. The fluctuation with the GAM frequency affects the particle transport through the modulation of the ambient fluctuation. But the effect is not large, and it is not a sufficient condition to form the edge transport barrier and to drive the intermittent particle flux. (author)

  7. Collective fluctuations in magnetized plasma: Transition probability approach

    International Nuclear Information System (INIS)

    Sosenko, P.P.

    1997-01-01

    Statistical plasma electrodynamics is elaborated with special emphasis on the transition probability approach and quasi-particles, and on modern applications to magnetized plasmas. Fluctuation spectra in the magnetized plasma are calculated in the range of low frequencies (with respect to the cyclotron one), and the conditions for the transition from incoherent to collective fluctuations are established. The role of finite-Larmor-radius effects and particle polarization drift in such a transition is explained. The ion collective features in fluctuation spectra are studied. 63 refs., 30 figs

  8. Principle of minimal work fluctuations.

    Science.gov (United States)

    Xiao, Gaoyang; Gong, Jiangbin

    2015-08-01

    Understanding and manipulating work fluctuations in microscale and nanoscale systems are of both fundamental and practical interest. For example, in considering the Jarzynski equality 〈e-βW〉=e-βΔF, a change in the fluctuations of e-βW may impact how rapidly the statistical average of e-βW converges towards the theoretical value e-βΔF, where W is the work, β is the inverse temperature, and ΔF is the free energy difference between two equilibrium states. Motivated by our previous study aiming at the suppression of work fluctuations, here we obtain a principle of minimal work fluctuations. In brief, adiabatic processes as treated in quantum and classical adiabatic theorems yield the minimal fluctuations in e-βW. In the quantum domain, if a system initially prepared at thermal equilibrium is subjected to a work protocol but isolated from a bath during the time evolution, then a quantum adiabatic process without energy level crossing (or an assisted adiabatic process reaching the same final states as in a conventional adiabatic process) yields the minimal fluctuations in e-βW, where W is the quantum work defined by two energy measurements at the beginning and at the end of the process. In the classical domain where the classical work protocol is realizable by an adiabatic process, then the classical adiabatic process also yields the minimal fluctuations in e-βW. Numerical experiments based on a Landau-Zener process confirm our theory in the quantum domain, and our theory in the classical domain explains our previous numerical findings regarding the suppression of classical work fluctuations [G. Y. Xiao and J. B. Gong, Phys. Rev. E 90, 052132 (2014)].

  9. Enhanced microbial decolorization of methyl red with oxidized carbon fiber as redox mediator

    Energy Technology Data Exchange (ETDEWEB)

    Emilia Rios-Del Toro, E. [División de Ciencias Ambientales, Instituto Potosino de Investigación Científica y Tecnológica (IPICyT), Camino a la Presa San José 2055, Col. Lomas 4a Sección, San Luis Potosí, SLP 78216 (Mexico); Celis, Lourdes B. [División de Geociencias Aplicadas, Instituto Potosino de Investigación Científica y Tecnológica (IPICyT), Camino a la Presa San José 2055, Col. Lomas 4a Sección, San Luis Potosí, SLP 78216 (Mexico); Cervantes, Francisco J. [División de Ciencias Ambientales, Instituto Potosino de Investigación Científica y Tecnológica (IPICyT), Camino a la Presa San José 2055, Col. Lomas 4a Sección, San Luis Potosí, SLP 78216 (Mexico); Rangel-Mendez, J. Rene, E-mail: rene@ipicyt.edu.mx [División de Ciencias Ambientales, Instituto Potosino de Investigación Científica y Tecnológica (IPICyT), Camino a la Presa San José 2055, Col. Lomas 4a Sección, San Luis Potosí, SLP 78216 (Mexico)

    2013-09-15

    Highlights: • Activated carbon fibers (ACFs) act as redox mediator. • Electron accepting capacity increased with oxidation time of ACF. •ACFs increased 8-fold the reduction of methyl red in biological assays. •Biofilm formed on the ACFs partly blocked their redox mediator capacity. -- Abstract: The anaerobic degradation of azo dyes under anaerobic conditions is possible but at a slow rate. Redox mediators (quinones, activated carbon) are used to improve the reduction rate. The aim of this work was to use activated carbon fiber (ACF) as a redox mediator for the anaerobic reduction of the azo dye methyl red. ACF was chemically modified with 8 M HNO{sub 3} to increase its redox-mediating capacity and used in chemical and anaerobic biological batch assays for the reduction of methyl red. ACF increased its redox-mediating capacity up to 3-fold in chemical assays; in biological assays ACF increased the reduction rate up to 8-fold compared to controls without ACF. However, since the ACF served as support for biomass, a biofilm formed on the fiber significantly reduced its redox-mediating capacity; substrate consumption suggested that the electron transport from ACF to methyl red was the rate-limiting step in the process. These results are the first evidence of the role of ACF as a redox mediator in the reductive decolorization of methyl red, in addition to the effect of biofilm attached to ACF on methyl red reduction. Due to the versatile characteristics of ACF and its redox-mediating capacity, carbon fibers could be used in biological wastewater treatment systems to accelerate the reductive transformation of pollutants commonly found in industrial effluents.

  10. Enhanced microbial decolorization of methyl red with oxidized carbon fiber as redox mediator

    International Nuclear Information System (INIS)

    Emilia Rios-Del Toro, E.; Celis, Lourdes B.; Cervantes, Francisco J.; Rangel-Mendez, J. Rene

    2013-01-01

    Highlights: • Activated carbon fibers (ACFs) act as redox mediator. • Electron accepting capacity increased with oxidation time of ACF. •ACFs increased 8-fold the reduction of methyl red in biological assays. •Biofilm formed on the ACFs partly blocked their redox mediator capacity. -- Abstract: The anaerobic degradation of azo dyes under anaerobic conditions is possible but at a slow rate. Redox mediators (quinones, activated carbon) are used to improve the reduction rate. The aim of this work was to use activated carbon fiber (ACF) as a redox mediator for the anaerobic reduction of the azo dye methyl red. ACF was chemically modified with 8 M HNO 3 to increase its redox-mediating capacity and used in chemical and anaerobic biological batch assays for the reduction of methyl red. ACF increased its redox-mediating capacity up to 3-fold in chemical assays; in biological assays ACF increased the reduction rate up to 8-fold compared to controls without ACF. However, since the ACF served as support for biomass, a biofilm formed on the fiber significantly reduced its redox-mediating capacity; substrate consumption suggested that the electron transport from ACF to methyl red was the rate-limiting step in the process. These results are the first evidence of the role of ACF as a redox mediator in the reductive decolorization of methyl red, in addition to the effect of biofilm attached to ACF on methyl red reduction. Due to the versatile characteristics of ACF and its redox-mediating capacity, carbon fibers could be used in biological wastewater treatment systems to accelerate the reductive transformation of pollutants commonly found in industrial effluents

  11. Engineered Proteins: Redox Properties and Their Applications

    Science.gov (United States)

    Prabhulkar, Shradha; Tian, Hui; Wang, Xiaotang; Zhu, Jun-Jie

    2012-01-01

    Abstract Oxidoreductases and metalloproteins, representing more than one third of all known proteins, serve as significant catalysts for numerous biological processes that involve electron transfers such as photosynthesis, respiration, metabolism, and molecular signaling. The functional properties of the oxidoreductases/metalloproteins are determined by the nature of their redox centers. Protein engineering is a powerful approach that is used to incorporate biological and abiological redox cofactors as well as novel enzymes and redox proteins with predictable structures and desirable functions for important biological and chemical applications. The methods of protein engineering, mainly rational design, directed evolution, protein surface modifications, and domain shuffling, have allowed the creation and study of a number of redox proteins. This review presents a selection of engineered redox proteins achieved through these methods, resulting in a manipulation in redox potentials, an increase in electron-transfer efficiency, and an expansion of native proteins by de novo design. Such engineered/modified redox proteins with desired properties have led to a broad spectrum of practical applications, ranging from biosensors, biofuel cells, to pharmaceuticals and hybrid catalysis. Glucose biosensors are one of the most successful products in enzyme electrochemistry, with reconstituted glucose oxidase achieving effective electrical communication with the sensor electrode; direct electron-transfer-type biofuel cells are developed to avoid thermodynamic loss and mediator leakage; and fusion proteins of P450s and redox partners make the biocatalytic generation of drug metabolites possible. In summary, this review includes the properties and applications of the engineered redox proteins as well as their significance and great potential in the exploration of bioelectrochemical sensing devices. Antioxid. Redox Signal. 17, 1796–1822. PMID:22435347

  12. Analytical expression for the tunnel current through the redox-mediated tunneling contact in the case of the adiabatic electron transfer at one of the working electrodes and any possible type of the electron transfer at the other electrode.

    Science.gov (United States)

    Medvedev, Igor G

    2017-11-21

    We study the tunnel current through a one-level redox molecule immersed into the electrolyte solution for the case when the coupling of the molecule to one of the working electrodes is strong while it is arbitrary to the other electrode. Using the Feynman-Vernon influence functional theory and the perturbation expansion of the effective action of the classical oscillator coupled both to the valence level of the redox molecule and to the thermal bath representing the classical fluctuations of the polarization of the solvent, we obtain, following the canonical way, the Langevin equation for the oscillator. It is found that for the aqueous electrolyte solution, the damping and the stochastic forces which arise due to the tunnel current are much smaller than those due to the thermal bath and therefore can be neglected. We estimate the higher-order corrections to the effective action and show that the Langevin dynamics takes place in this case for arbitrary parameters of the tunneling junction under the condition of the strong coupling of the redox molecule to one of the working electrodes. Then the steady-state coordinate distribution function of the oscillator resulting from the corresponding Fokker-Planck equation is the Boltzmann distribution function which is determined by the adiabatic free energy surface arising from the mean current-induced force. It enables us to obtain the expression for the tunnel current in the case when the coupling of the redox molecule to one of the working electrodes is strong while it is arbitrary to the other electrode.

  13. Quantum work fluctuation theorem: Nonergodic Brownian motion case

    International Nuclear Information System (INIS)

    Bai, Zhan-Wu

    2014-01-01

    The work fluctuations of a quantum Brownian particle driven by an external force in a general nonergodic heat bath are studied under a general initial state. The exact analytical expression of the work probability distribution function is derived. Results show the existence of a quantum asymptotic fluctuation theorem, which is in general not a direct generalization of its classical counterpart. The form of this theorem is dependent on the structure of the heat bath and the specified initial condition.

  14. Theoretical studies on rapid fluctuations in solar flares

    International Nuclear Information System (INIS)

    Vlahos, L.

    1986-01-01

    Rapid fluctuations in the emission of solar bursts may have many different origins, e.g., the acceleration process can have a pulsating structure, the propagation of energetic electrons and ions can be interrupted from plasma instabilities and finally the electromagnetic radiation produced by the interaction of electrostatic and electromagnetic waves may have a pulsating behavior in time. In two separate studies the conditions for rapid fluctuations in solar flare driven emission were analyzed

  15. Theoretical studies on rapid fluctuations in solar flares

    Science.gov (United States)

    Vlahos, Loukas

    1986-01-01

    Rapid fluctuations in the emission of solar bursts may have many different origins e.g., the acceleration process can have a pulsating structure, the propagation of energetic electrons and ions can be interrupted from plasma instabilities and finally the electromagnetic radiation produced by the interaction of electrostatic and electromagnetic waves may have a pulsating behavior in time. In two separate studies the conditions for rapid fluctuations in solar flare driven emission were analyzed.

  16. On the Fluctuations that Order and Frustrate Liquid Water

    OpenAIRE

    Limmer, David

    2013-01-01

    At ambient conditions, water sits close to phase coexistence with its crystal. More so than in many other materials, this fact is manifested in the fluctuations that maintain a large degree of local order in the liquid. These fluctuations and how they result in long-ranged order, or its absence, are emergent features of many interacting molecules. Their study therefore requires using the tools of statistical mechanics for their their systematic understanding. In this dissertation we develop s...

  17. Glutathione in Cellular Redox Homeostasis: Association with the Excitatory Amino Acid Carrier 1 (EAAC1

    Directory of Open Access Journals (Sweden)

    Koji Aoyama

    2015-05-01

    Full Text Available Reactive oxygen species (ROS are by-products of the cellular metabolism of oxygen consumption, produced mainly in the mitochondria. ROS are known to be highly reactive ions or free radicals containing oxygen that impair redox homeostasis and cellular functions, leading to cell death. Under physiological conditions, a variety of antioxidant systems scavenge ROS to maintain the intracellular redox homeostasis and normal cellular functions. This review focuses on the antioxidant system’s roles in maintaining redox homeostasis. Especially, glutathione (GSH is the most important thiol-containing molecule, as it functions as a redox buffer, antioxidant, and enzyme cofactor against oxidative stress. In the brain, dysfunction of GSH synthesis leading to GSH depletion exacerbates oxidative stress, which is linked to a pathogenesis of aging-related neurodegenerative diseases. Excitatory amino acid carrier 1 (EAAC1 plays a pivotal role in neuronal GSH synthesis. The regulatory mechanism of EAAC1 is also discussed.

  18. Literature survey of redox reactions in the near field

    International Nuclear Information System (INIS)

    Miki, Takahito; Chiba, Tamotsu; Inagaki, Manabu; Sasamoto, Hiroshi; Yui, Mikazu

    2000-01-01

    This report presents a summary of literature survey about geochemical reactions which are important to evaluate the redox conditions in the near field rock mass and buffer. The results of literature survey are summarized as follows; Minerals including ferrous iron and organic materials in the rock mass are important reductants. Initial stage after closure of repository, oxygen will be consumed by pyrite, because the reaction rate between pyrite and oxygen is relatively fast. It is possible to estimate the redox capacity for reductants by rock (mineral)-water interaction experiment in a laboratory. And it is expected that the ferrous iron-rich rock and higher porosity rock may have bigger redox capacity. It is impossible to estimate the oxygen consumption rate by reductants such as minerals including ferrous iron. The rate law and rate constant for the oxidation reaction of ferrous iron in the solution are also determined. As a conclusion, it seems that we can evaluate kinetically the evolution of geochemical conditions in the near field rock mass and buffer by excavation of drifts, based on data derived from these existing literatures. (author)

  19. Sawteeth fluctuations detection

    International Nuclear Information System (INIS)

    Vannucci, A.; Nascimento, I.C. do; Caldas, I.L.; Sanada, E.K.; Tuszel, A.G.; Fagundes, A.N.

    1988-01-01

    Sawteeth oscillations were identified during the discharges in the small Tokamak TBR-1 through a pin-hole camera and their main characteristics were studied. Comparing the measured period of the internal disruption (sawteeth) with the ones expected from scaling laws, good agreement is reached. The measured sawteeth crashes agree with the value expected from Kadomtsev's model. However, there some sawteeth oscillations, corresponding to conditions of higher Z eff of the plasma, which showed longer crashes that could not be explained by this model. (author) [pt

  20. Fluctuation analysis of rotational spectra

    International Nuclear Information System (INIS)

    Doessing, T.; Bracco, A.; Broglia, R.A.; Matsuo, M.

    1996-01-01

    The compound state rotational degree of freedom is ''damped'' in the sense that the electric quadrupole decay of a single quantum state with angular momentum I exhibits a spectrum of final states all having spin I-2. In actual experiments, the cascade of γ-rays associated with each of the members of the ensemble of compound nuclei uses each of the ''discrete'' transitions many more times than the ''continuum'' transitions. Relatively large and small fluctuations in the recorded coincidence spectrum ensue, respectively. The analysis of the fluctuations will be shown to be instrumental to gain insight into the phenomenon of rotational damping. For this purpose, two- and higher-fold coincidence spectra emitted from rotating nuclei are analyzed with respect to the count fluctuations. The coincidences from consecutive γ-rays emitted from discrete rotational bands generate ridges in the E γ1 .E γ2 spectrum, and the fluctuation analysis of the ridges is based upon the ansatz of a random selection of transition energies from band to band. This ansatz is supported by a cranked mean-field calculation for the nucleus 168 Yb, as well as by analyzing resolved bands in 168 Yb and its neighbors. The fluctuation analysis of the central valley (E γ1 =E γ2 ) is based upon the ansatz of fluctuations in the intensity of the transitions of Porter-Thomas type superposed on a smooth spectrum of transition energies. This ansatz is again supported by a mixed-band calculation. The mathematical treatment of count fluctuations is formulated in general (orig.)

  1. Organic Redox Species in Aqueous Flow Batteries: Redox Potentials, Chemical Stability and Solubility

    Science.gov (United States)

    Wedege, Kristina; Dražević, Emil; Konya, Denes; Bentien, Anders

    2016-01-01

    Organic molecules are currently investigated as redox species for aqueous low-cost redox flow batteries (RFBs). The envisioned features of using organic redox species are low cost and increased flexibility with respect to tailoring redox potential and solubility from molecular engineering of side groups on the organic redox-active species. In this paper 33, mainly quinone-based, compounds are studied experimentially in terms of pH dependent redox potential, solubility and stability, combined with single cell battery RFB tests on selected redox pairs. Data shows that both the solubility and redox potential are determined by the position of the side groups and only to a small extent by the number of side groups. Additionally, the chemical stability and possible degradation mechanisms leading to capacity loss over time are discussed. The main challenge for the development of all-organic RFBs is to identify a redox pair for the positive side with sufficiently high stability and redox potential that enables battery cell potentials above 1 V. PMID:27966605

  2. Redox behaviors of iron by absorption spectroscopy and redox potential measurement

    International Nuclear Information System (INIS)

    Oh, Jae Yong

    2010-02-01

    This work is performed to study the redox (reduction/oxidation) behaviors of iron in aqueous system by a combination of absorption spectroscopy and redox potential measurements. There are many doubts on redox potential measurements generally showing low accuracies and high uncertainties. In the present study, redox potentials are measured by utilizing various redox electrodes such as Pt, Au, Ag, and glassy carbon (GC) electrodes. Measured redox potentials are compared with calculated redox potentials based on the chemical oxidation speciation of iron and thermodynamic data by absorption spectroscopy, which provides one of the sensitive and selective spectroscopic methods for the chemical speciation of Fe(II/III). From the comparison analyses, redox potential values measured by the Ag redox electrode are fairly consistent with those calculated by the chemical aqueous speciation of iron in the whole system. In summary, the uncertainties of measured redox potentials are closely related with the total Fe concentration and affected by the formation of mixed potentials due to Fe(III) precipitates in the pH range of 6 ∼ 9 beyond the solubility of Fe(III), whilst being independent of the initially prepared concentration ratios between Fe(II) and Fe(III)

  3. Organic Redox Species in Aqueous Flow Batteries: Redox Potentials, Chemical Stability and Solubility

    Science.gov (United States)

    Wedege, Kristina; Dražević, Emil; Konya, Denes; Bentien, Anders

    2016-12-01

    Organic molecules are currently investigated as redox species for aqueous low-cost redox flow batteries (RFBs). The envisioned features of using organic redox species are low cost and increased flexibility with respect to tailoring redox potential and solubility from molecular engineering of side groups on the organic redox-active species. In this paper 33, mainly quinone-based, compounds are studied experimentially in terms of pH dependent redox potential, solubility and stability, combined with single cell battery RFB tests on selected redox pairs. Data shows that both the solubility and redox potential are determined by the position of the side groups and only to a small extent by the number of side groups. Additionally, the chemical stability and possible degradation mechanisms leading to capacity loss over time are discussed. The main challenge for the development of all-organic RFBs is to identify a redox pair for the positive side with sufficiently high stability and redox potential that enables battery cell potentials above 1 V.

  4. Uranium redox transition pathways in acetate-amended sediments

    Science.gov (United States)

    Bargar, John R.; Williams, Kenneth H.; Campbell, Kate M.; Long, Philip E.; Stubbs, Joanne E.; Suvorova, Elenal I.; Lezama-Pacheco, Juan S.; Alessi, Daniel S.; Stylo, Malgorzata; Webb, Samuel M.; Davis, James A.; Giammar, Daniel E.; Blue, Lisa Y.; Bernier-Latmani, Rizlan

    2013-01-01

    Redox transitions of uranium [from U(VI) to U(IV)] in low-temperature sediments govern the mobility of uranium in the environment and the accumulation of uranium in ore bodies, and inform our understanding of Earth’s geochemical history. The molecular-scale mechanistic pathways of these transitions determine the U(IV) products formed, thus influencing uranium isotope fractionation, reoxidation, and transport in sediments. Studies that improve our understanding of these pathways have the potential to substantially advance process understanding across a number of earth sciences disciplines. Detailed mechanistic information regarding uranium redox transitions in field sediments is largely nonexistent, owing to the difficulty of directly observing molecular-scale processes in the subsurface and the compositional/physical complexity of subsurface systems. Here, we present results from an in situ study of uranium redox transitions occurring in aquifer sediments under sulfate-reducing conditions. Based on molecular-scale spectroscopic, pore-scale geochemical, and macroscale aqueous evidence, we propose a biotic–abiotic transition pathway in which biomass-hosted mackinawite (FeS) is an electron source to reduce U(VI) to U(IV), which subsequently reacts with biomass to produce monomeric U(IV) species. A species resembling nanoscale uraninite is also present, implying the operation of at least two redox transition pathways. The presence of multiple pathways in low-temperature sediments unifies apparently contrasting prior observations and helps to explain sustained uranium reduction under disparate biogeochemical conditions. These findings have direct implications for our understanding of uranium bioremediation, ore formation, and global geochemical processes.

  5. Analysis of Meniscus Fluctuation in a Continuous Casting Slab Mold

    Science.gov (United States)

    Zhang, Kaitian; Liu, Jianhua; Cui, Heng; Xiao, Chao

    2018-03-01

    A water model of slab mold was established to analyze the microscopic and macroscopic fluctuation of meniscus. The fast Fourier transform and wavelet entropy were adopted to analyze the wave amplitude, frequency, and components of fluctuation. The flow patterns under the meniscus were measured by using particle image velocimetry measurement and then the mechanisms of meniscus fluctuation were discussed. The results reflected that wavelet entropy had multi-scale and statistical properties, and it was suitable for the study of meniscus fluctuation details both in time and frequency domain. The basic wave, frequency of which exceeding 1 Hz in the condition of no mold oscillation, was demonstrated in this work. In fact, three basic waves were found: long-wave with low frequency, middle-wave with middle frequency, and short-wave with high frequency. In addition, the upper roll flow in mold had significant effect on meniscus fluctuation. When the position of flow impinged was far from the meniscus, long-wave dominated the fluctuation and the stability of meniscus was enhanced. However, when the velocity of flow was increased, the short-wave dominated the meniscus fluctuation and the meniscus stability was decreased.

  6. Redox kinetics and mechanism in silicate melts

    International Nuclear Information System (INIS)

    Cochain, B.

    2009-12-01

    This work contributes to better understand iron redox reactions and mechanisms in silicate melts. It was conducted on compositions in both Na 2 O-B 2 O 3 -SiO 2 -FeO and Na 2 O-Al 2 O 3 -SiO 2 -FeO systems. The influence of boron-sodium and aluminum-sodium substitutions and iron content on properties and structure of glasses and on the iron redox kinetics has been studied by Raman, Moessbauer and XANES spectroscopies at the B and Fe K-edges. In borosilicate glasses, an increase in iron content or in the Fe 3+ /ΣFe redox state implies a structural rearrangement of the BO 4 species in the glass network whereas the BO 3 and BO 4 relative proportions remain nearly constant. In all studied glasses and melts, Fe 3+ is a network former in tetrahedral coordination, unless for aluminosilicates of ratio Al/Na≥1 where Fe 3+ is a network modifier in five-fold coordination. Near Tg, diffusion of network modifying cations controls the iron redox kinetics along with a flux of electron holes. At liquidus temperatures, oxygen diffusion is considered to be the mechanism that governs redox reactions. This study shows the role played by the silicate network polymerization on the redox kinetics. In borosilicate melts, iron redox kinetics depends on the boron speciation between BO 3 and BO 4 that depends itself on the sodium content. Furthermore, an increase in the network-former/network-modifier ratio implies a decrease in oxygen diffusion that results in a slowing down of the redox kinetics. The obtained results allow a description of the iron redox kinetics for more complex compositions as natural lavas or nuclear waste model glasses. (author)

  7. Topics in fluctuating nonlinear hydrodynamics

    International Nuclear Information System (INIS)

    Milner, S.T.

    1986-01-01

    Models of fluctuating nonlinear hydrodynamics have enjoyed much success in explaining the effect of long-wavelength fluctuations in diverse hydrodynamic systems. This thesis explores two such problems; in both, the body of hydrodynamic assumptions powerfully constrains the predictions of a well-posed theory. The effects of layer fluctuations in smectic-A liquid crystals are first examined. The static theory (introduced by Grinstein and Pelcovits) is reviewed. Ward identities, resulting from the arbitrariness of the layering direction, are derived and exploited. The static results motivate an examination of dynamic fluctuation effects. A new sound-damping experiment is proposed that would probe singular dependence of viscosities on applied stress. A theory of Procaccia and Gitterman that reaction rates of chemically reacting binary mixtures are drastically reduced near their thermodynamic critical points is analyzed. Hydrodynamic arguments and Van Hove theory are applied, concluding that the PG idea is drastically slowed, and spatially varying composition fluctuations are at best slowed down over a narrow range of wavenumbers

  8. Electric Field Fluctuations in Water

    Science.gov (United States)

    Thorpe, Dayton; Limmer, David; Chandler, David

    2013-03-01

    Charge transfer in solution, such as autoionization and ion pair dissociation in water, is governed by rare electric field fluctuations of the solvent. Knowing the statistics of such fluctuations can help explain the dynamics of these rare events. Trajectories short enough to be tractable by computer simulation are virtually certain not to sample the large fluctuations that promote rare events. Here, we employ importance sampling techniques with classical molecular dynamics simulations of liquid water to study statistics of electric field fluctuations far from their means. We find that the distributions of electric fields located on individual water molecules are not in general gaussian. Near the mean this non-gaussianity is due to the internal charge distribution of the water molecule. Further from the mean, however, there is a previously unreported Bjerrum-like defect that stabilizes certain large fluctuations out of equilibrium. As expected, differences in electric fields acting between molecules are gaussian to a remarkable degree. By studying these differences, though, we are able to determine what configurations result not only in large electric fields, but also in electric fields with long spatial correlations that may be needed to promote charge separation.

  9. Mechanisms for redox control and their effects upon modelled properties of Aespoe groundwaters

    International Nuclear Information System (INIS)

    Emren, A.T.

    1996-01-01

    In the literature, one finds several models for control of redox properties in groundwater. The proposals for redox controlling substances include iron oxides, chlorites, methane, pyrite and polysulphides. The CRACKER program, which has been successful in modelling of observed Aespoe groundwaters has been used to investigate the influence of several redox control models on the modelled properties of present and possible future Aespoe groundwaters. In the simulations, one or more of the possible redox reactions have been prevented from occurring. The groundwater has then been assumed to react with minerals distributed in the fracture walls. Due to the discreteness of mineral grains, a certain amount of fluctuations in groundwater properties is occurring. The process of sampling water for measurement has been simulated by letting about 900 waters from different locations mix. It has been found that some of the models have difficulties in explaining important groundwater properties, while other models perform quite well. With identical mineral sets, the properties of future groundwaters have been simulated. It is found that some changes in groundwater properties at elevated temperatures may be of importance for assessment of the safety of a future repository for spent nuclear fuel. The difference in behaviour is caused mostly by the fact that the solubility increases with temperature for some minerals, while it decreases for other minerals. (author)

  10. Multi-physics Model for the Aging Prediction of a Vanadium Redox Flow Battery System

    International Nuclear Information System (INIS)

    Merei, Ghada; Adler, Sophie; Magnor, Dirk; Sauer, Dirk Uwe

    2015-01-01

    Highlights: • Present a multi-physics model of vanadium redox-flow battery. • This model is essential for aging prediction. • It is applicable for VRB system of different power and capacity ratings. • Good results comparing with current research in this field. - Abstract: The all-vanadium redox-flow battery is an attractive candidate to compensate the fluctuations of non-dispatchable renewable energy generation. While several models for vanadium redox batteries have been described yet, no model has been published, which is adequate for the aging prediction. Therefore, the present paper presents a multi-physics model which determines all parameters that are essential for an aging prediction. In a following paper, the corresponding aging model of vanadium redox flow battery (VRB) is described. The model combines existing models for the mechanical losses and temperature development with new approaches for the batteries side reactions. The model was implemented in Matlab/Simulink. The modeling results presented in the paper prove to be consistent with the experimental results of other research groups

  11. A molecular theory of chemically modified electrodes with self-assembled redox polyelectrolye thin films: Reversible cyclic voltammetry

    Energy Technology Data Exchange (ETDEWEB)

    Tagliazucchi, Mario; Calvo, Ernesto J. [INQUIMAE, DQIAyQF Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, 1428 Buenos Aires (Argentina); Szleifer, Igal [Department of Biomedical Engineering, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208 (United States)

    2008-10-01

    A molecular theory of chemically modified electrodes is applied to study redox polyelectroyte modified electrodes. The molecular approach explicitly includes the size, shape, charge distribution, and conformations of all of the molecular species in the system as well as the chemical equilibria (redox and acid-base) and intermolecular interactions. An osmium pyridine-bipyridine complex covalently bound to poly(allyl-amine) backbone (PAH-Os) adsorbed onto mercapto-propane sulfonate (MPS) thiolated gold electrode is described. The potential and electrolyte composition dependent redox and nonredox capacitance can be calculated with the molecular theory in very good agreement with voltammetric experiments under reversible conditions without the use of freely adjustable parameter. Unlike existing phenomenological models the theory links the electrochemical behavior with the structure of the polymer layer. The theory predicts a highly inhomogeneous distribution of acid-base and redox states that strongly couples with the spatial arrangement of the molecular species in the nanometric redox film. (author)

  12. Species-Specific Thiol-Disulfide Equilibrium Constant: A Tool To Characterize Redox Transitions of Biological Importance.

    Science.gov (United States)

    Mirzahosseini, Arash; Somlyay, Máté; Noszál, Béla

    2015-08-13

    Microscopic redox equilibrium constants, a new species-specific type of physicochemical parameters, were introduced and determined to quantify thiol-disulfide equilibria of biological significance. The thiol-disulfide redox equilibria of glutathione with cysteamine, cysteine, and homocysteine were approached from both sides, and the equilibrium mixtures were analyzed by quantitative NMR methods to characterize the highly composite, co-dependent acid-base and redox equilibria. The directly obtained, pH-dependent, conditional constants were then decomposed by a new evaluation method, resulting in pH-independent, microscopic redox equilibrium constants for the first time. The 80 different, microscopic redox equilibrium constant values show close correlation with the respective thiolate basicities and provide sound means for the development of potent agents against oxidative stress.

  13. Redox Homeostasis in Plants under Abiotic Stress: Role of electron carriers, energy metabolism mediators and proteinaceous thiols

    Directory of Open Access Journals (Sweden)

    Dhriti Kapoor

    2015-03-01

    Full Text Available Contemporaneous presence of both oxidized and reduced forms of electron carriers is mandatory in efficient flux by plant electron transport cascades. This requirement is considered as redox poising that involves the movement of electron from multiple sites in respiratory and photosynthetic electron transport chains to molecular oxygen. This flux triggers the formation of superoxide, consequently give rise to other reactive oxygen species (ROS under adverse environmental conditions like drought, high or low temperature, heavy metal stress etc. that plants owing during their life span. Plant cells synthesize ascorbate, an additional hydrophilic redox buffer, which protect the plants against oxidative challenge. Large pools of antioxidants also preside over the redox homeostasis. Besides, tocopherol is a liposoluble redox buffer, which efficiently scavenges the ROS like singlet oxygen. In addition, proteinaceous thiol members such as thioredoxin, peroxiredoxin and glutaredoxin, electron carriers and energy metabolism mediators phosphorylated (NADP and non-phosphorylated (NAD+ coenzyme forms interact with ROS, metabolize and maintain redox homeostasis.

  14. Redox sensor proteins for highly sensitive direct imaging of intracellular redox state.

    Science.gov (United States)

    Sugiura, Kazunori; Nagai, Takeharu; Nakano, Masahiro; Ichinose, Hiroshi; Nakabayashi, Takakazu; Ohta, Nobuhiro; Hisabori, Toru

    2015-02-13

    Intracellular redox state is a critical factor for fundamental cellular functions, including regulation of the activities of various metabolic enzymes as well as ROS production and elimination. Genetically-encoded fluorescent redox sensors, such as roGFP (Hanson, G. T., et al. (2004)) and Redoxfluor (Yano, T., et al. (2010)), have been developed to investigate the redox state of living cells. However, these sensors are not useful in cells that contain, for example, other colored pigments. We therefore intended to obtain simpler redox sensor proteins, and have developed oxidation-sensitive fluorescent proteins called Oba-Q (oxidation balance sensed quenching) proteins. Our sensor proteins derived from CFP and Sirius can be used to monitor the intracellular redox state as their fluorescence is drastically quenched upon oxidation. These blue-shifted spectra of the Oba-Q proteins enable us to monitor various redox states in conjunction with other sensor proteins. Copyright © 2015 Elsevier Inc. All rights reserved.

  15. Multiscale fluctuations in nuclear response

    International Nuclear Information System (INIS)

    Lacroix, D.; Chomaz, Ph.

    1999-01-01

    The nuclear collective response is investigated in the framework of a doorway picture in which the spreading width of the collective emotion is described as a coupling to more and more complex configurations. It is shown that this coupling induces fluctuations of the observed strength. In the case of a hierarchy of overlapping decay channels, Ericson fluctuations are observed at different scales. Methods for extracting these scales and the related lifetimes are discussed. Finally, it is shown that the coupling of different states at one level of complexity to some common decay channels at the next level, may produce interference-like patterns in the nuclear response. This quantum effect leads to anew type of fluctuations with a typical width related to the level spacing. (author)

  16. Fluctuation relations for anomalous dynamics

    International Nuclear Information System (INIS)

    Chechkin, A V; Klages, R

    2009-01-01

    We consider work fluctuation relations (FRs) for generic types of dynamics generating anomalous diffusion: Lévy flights, long-correlated Gaussian processes and time-fractional kinetics. By combining Langevin and kinetic approaches we calculate the probability distributions of mechanical and thermodynamical work in two paradigmatic nonequilibrium situations, respectively: a particle subject to a constant force and a particle in a harmonic potential dragged by a constant force. We check the transient FR for two models exhibiting superdiffusion, where a fluctuation-dissipation relation does not exist, and for two other models displaying subdiffusion, where there is a fluctuation-dissipation relation. In the two former cases the conventional transient FR is not recovered, whereas in the latter two it holds either exactly or in the long-time limit. (letter)

  17. Fluctuations in the multiparticle dynamics

    International Nuclear Information System (INIS)

    Bozek, P.; Ploszajczak, M.

    1993-01-01

    The appearance and properties of intermittent fluctuations in physical systems, in particular the formation of rare structures in transport phenomena are discussed. The distribution of fluctuations approaches a limiting log-normal statistical distribution. The log-normal distribution is introduced as a simple parametrization of the energy fluctuations leading to the subthreshold production of particles in nuclear collisions, and it is shown that it fits all available data both for total π 0 production cross section as well as the π 0 kinetic energy spectra for E/A < 90 MeV. It is suggested that the same universal distribution should also describe the subthreshold production of other hadrons like η and K. (author) 36 refs., 11 figs

  18. Multiscale fluctuations in nuclear response

    Energy Technology Data Exchange (ETDEWEB)

    Lacroix, D.; Chomaz, Ph

    1999-01-01

    The nuclear collective response is investigated in the framework of a doorway picture in which the spreading width of the collective emotion is described as a coupling to more and more complex configurations. It is shown that this coupling induces fluctuations of the observed strength. In the case of a hierarchy of overlapping decay channels, Ericson fluctuations are observed at different scales. Methods for extracting these scales and the related lifetimes are discussed. Finally, it is shown that the coupling of different states at one level of complexity to some common decay channels at the next level, may produce interference-like patterns in the nuclear response. This quantum effect leads to anew type of fluctuations with a typical width related to the level spacing. (author) 25 refs.

  19. Determining the Limiting Current Density of Vanadium Redox Flow Batteries

    Directory of Open Access Journals (Sweden)

    Jen-Yu Chen

    2014-09-01

    Full Text Available All-vanadium redox flow batteries (VRFBs are used as energy storage systems for intermittent renewable power sources. The performance of VRFBs depends on materials of key components and operating conditions, such as current density, electrolyte flow rate and electrolyte composition. Mass transfer overpotential is affected by the electrolyte flow rate and electrolyte composition, which is related to the limiting current density. In order to investigate the effect of operating conditions on mass transport overpotential, this study established a relationship between the limiting current density and operating conditions. First, electrolyte solutions with different states of charge were prepared and used for a single cell to obtain discharging polarization curves under various operating conditions. The experimental results were then analyzed and are discussed in this paper. Finally, this paper proposes a limiting current density as a function of operating conditions. The result helps predict the effect of operating condition on the cell performance in a mathematical model.

  20. pH and redox effects of building materials

    International Nuclear Information System (INIS)

    Van der Sloot, H.A.; Van Zomeren, A.; Meeussen, J.C.L.; De Nie, D.S.

    2007-11-01

    The application of relatively fine grained industrial slags as fill material in industrial terrains and parking lots has led to unacceptably elevated pH values and imposed reducing conditions in ground- and surface water. Based on the Dutch Building Materials Decree the materials applied were classified as category 1 materials (free use). There are no limits set to pH and redox in this regulation. In itself a lower or higher pH and a low redox potential are not necessarily critical. Only when the buffer capacity of the surroundings is exceeded, undesirable situations may develop. In this work, the release of alkaline and reducing substances has been studied to assess if regulatory controls are needed and how such controls could be implemented practically. Both pH and redox potential are unsuitable properties for this purpose as it is the buffer capacity of the releasing material and the buffer capacity of the receiving soil and water bodies that determine whether unacceptable conditions develop. As pH and redox are also affected by gas reactions (O2 and CO2), the evaluation becomes relatively complex. Using the chemical speciation-transport model ORCHESTRA, a scenario description has been developed to assess the release of alkaline and reducing species from slag by infiltration under unsaturated conditions. Proper acid neutralization and redox buffering data for the materials were determined. Based on the sophisticated model results, a simplified model description was applied to link observations to impact. Decision schemes for applications above groundwater and in surface water have been developed based on the buffer capacity and particle size distribution of the material to be used, the infiltration rate, the degree of exposure to O2 and CO2 from the atmosphere or from soil air and the dimensions of the application. This has led to a preliminary guidance on implementing rules for acceptance of materials in specific applications. The modeled release predictions

  1. Phase space fluctuations and dynamics of fluctuations of collective variables

    Energy Technology Data Exchange (ETDEWEB)

    Benhassine, B.; Farine, M.; Idier, D.; Remaud, B.; Sebille, F. (Lab. de Physique Nucleaire, IN2P3/CNRS, 44 - Nantes (France) Nantes Univ., 44 (France)); Hernandez, E.S. (Dept. de Fisica, Ciudad Universitaria, Buenos Aires (Argentina))

    1992-08-03

    Within the framework of theoretical approaches based on stochastic transport equation of one-body distribution function, a numerical treatment of the fluctuations of collective observables is studied and checked in comparison with analytical results either at equilibrium or close to it. (orig.).

  2. Phase space fluctuations and dynamics of fluctuations of collective variables

    International Nuclear Information System (INIS)

    Benhassine, B.; Farine, M.; Idier, D.; Remaud, B.; Sebille, F.; Hernandez, E.S.

    1992-01-01

    Within the framework of theoretical approaches based on stochastic transport equation of one-body distribution function, a numerical treatment of the fluctuations of collective observables is studied and checked in comparison with analytical results either at equilibrium or close to it. (orig.)

  3. Entropic Repulsion Between Fluctuating Surfaces

    Science.gov (United States)

    Janke, W.

    The statistical mechanics of fluctuating surfaces plays an important role in a variety of physical systems, ranging from biological membranes to world sheets of strings in theories of fundamental interactions. In many applications it is a good approximation to assume that the surfaces possess no tension. Their statistical properties are then governed by curvature energies only, which allow for gigantic out-of-plane undulations. These fluctuations are the “entropic” origin of long-range repulsive forces in layered surface systems. Theoretical estimates of these forces for simple model surfaces are surveyed and compared with recent Monte Carlo simulations.

  4. Origin of cosmological density fluctuations

    International Nuclear Information System (INIS)

    Carr, B.J.

    1984-11-01

    The density fluctuations required to explain the large-scale cosmological structure may have arisen spontaneously as a result of a phase transition in the early Universe. There are several ways in which such fluctuations may have ben produced, and they could have a variety of spectra, so one should not necessarily expect all features of the large-scale structure to derive from a simple power law spectrum. Some features may even result from astrophysical amplification mechanisms rather than gravitational instability. 128 references

  5. Thioredoxins, Glutaredoxins, and Peroxiredoxins—Molecular Mechanisms and Health Significance: from Cofactors to Antioxidants to Redox Signaling

    Science.gov (United States)

    Hanschmann, Eva-Maria; Godoy, José Rodrigo; Berndt, Carsten; Hudemann, Christoph

    2013-01-01

    Abstract Thioredoxins (Trxs), glutaredoxins (Grxs), and peroxiredoxins (Prxs) have been characterized as electron donors, guards of the intracellular redox state, and “antioxidants”. Today, these redox catalysts are increasingly recognized for their specific role in redox signaling. The number of publications published on the functions of these proteins continues to increase exponentially. The field is experiencing an exciting transformation, from looking at a general redox homeostasis and the pathological oxidative stress model to realizing redox changes as a part of localized, rapid, specific, and reversible redox-regulated signaling events. This review summarizes the almost 50 years of research on these proteins, focusing primarily on data from vertebrates and mammals. The role of Trx fold proteins in redox signaling is discussed by looking at reaction mechanisms, reversible oxidative post-translational modifications of proteins, and characterized interaction partners. On the basis of this analysis, the specific regulatory functions are exemplified for the cellular processes of apoptosis, proliferation, and iron metabolism. The importance of Trxs, Grxs, and Prxs for human health is addressed in the second part of this review, that is, their potential impact and functions in different cell types, tissues, and various pathological conditions. Antioxid. Redox Signal. 19, 1539–1605. PMID:23397885

  6. Mitochondrial redox biology and homeostasis in plants.

    Science.gov (United States)

    Noctor, Graham; De Paepe, Rosine; Foyer, Christine H

    2007-03-01

    Mitochondria are key players in plant cell redox homeostasis and signalling. Earlier concepts that regarded mitochondria as secondary to chloroplasts as the powerhouses of photosynthetic cells, with roles in cell proliferation, death and ageing described largely by analogy to animal paradigms, have been replaced by the new philosophy of integrated cellular energy and redox metabolism involving mitochondria and chloroplasts. Thanks to oxygenic photosynthesis, plant mitochondria often operate in an oxygen- and carbohydrate-rich environment. This rather unique environment necessitates extensive flexibility in electron transport pathways and associated NAD(P)-linked enzymes. In this review, mitochondrial redox metabolism is discussed in relation to the integrated cellular energy and redox function that controls plant cell biology and fate.

  7. Symproportionation versus Disproportionation in Bromine Redox Systems

    International Nuclear Information System (INIS)

    Toporek, Marcin; Michałowska-Kaczmarczyk, Anna M.; Michałowski, Tadeusz

    2015-01-01

    Graphical abstract: Display Omitted -- Highlights: • The disproportionation and symproportionation of bromine in different media is presented. • All the redox systems are elaborated according to the principles of the generalized approach to electrolytic redox systems (GATES/GEB). • All physicochemical knowledge is involved in the algorithm applied for this purpose. • The graphical representation of the systems is the basis of gaining the detailed physicochemical knowledge on the systems in question. -- Abstract: The paper refers to dynamic (titration) redox systems where symproportionation or disproportionation of bromine species occur. The related systems are modeled according to principles assumed in the Generalized Approach to Electrolytic Redox Systems (GATES), with Generalized Electron Balance (GEB) concept involved in the GATES/GEB software. The results obtained from calculations made with use of iterative computer programs prepared according to MATLAB computational software, are presented graphically, as 2D and 3D graphs

  8. Polyarene mediators for mediated redox flow battery

    Science.gov (United States)

    Delnick, Frank M.; Ingersoll, David; Liang, Chengdu

    2018-01-02

    The fundamental charge storage mechanisms in a number of currently studied high energy redox couples are based on intercalation, conversion, or displacement reactions. With exception to certain metal-air chemistries, most often the active redox materials are stored physically in the electrochemical cell stack thereby lowering the practical gravimetric and volumetric energy density as a tradeoff to achieve reasonable power density. In a general embodiment, a mediated redox flow battery includes a series of secondary organic molecules that form highly reduced anionic radicals as reaction mediator pairs for the reduction and oxidation of primary high capacity redox species ex situ from the electrochemical cell stack. Arenes are reduced to stable anionic radicals that in turn reduce a primary anode to the charged state. The primary anode is then discharged using a second lower potential (more positive) arene. Compatible separators and solvents are also disclosed herein.

  9. PHB Biosynthesis Counteracts Redox Stress in Herbaspirillum seropedicae

    Directory of Open Access Journals (Sweden)

    Marcelo B. Batista

    2018-03-01

    Full Text Available The ability of bacteria to produce polyhydroxyalkanoates such as poly(3-hydroxybutyrate (PHB enables provision of a carbon storage molecule that can be mobilized under demanding physiological conditions. However, the precise function of PHB in cellular metabolism has not been clearly defined. In order to determine the impact of PHB production on global physiology, we have characterized the properties of a ΔphaC1 mutant strain of the diazotrophic bacterium Herbaspirillum seropedicae. The absence of PHB in the mutant strain not only perturbs redox balance and increases oxidative stress, but also influences the activity of the redox-sensing Fnr transcription regulators, resulting in significant changes in expression of the cytochrome c-branch of the electron transport chain. The synthesis of PHB is itself dependent on the Fnr1 and Fnr3 proteins resulting in a cyclic dependency that couples synthesis of PHB with redox regulation. Transcriptional profiling of the ΔphaC1 mutant reveals that the loss of PHB synthesis affects the expression of many genes, including approximately 30% of the Fnr regulon.

  10. PHB Biosynthesis Counteracts Redox Stress in Herbaspirillum seropedicae.

    Science.gov (United States)

    Batista, Marcelo B; Teixeira, Cícero S; Sfeir, Michelle Z T; Alves, Luis P S; Valdameri, Glaucio; Pedrosa, Fabio de Oliveira; Sassaki, Guilherme L; Steffens, Maria B R; de Souza, Emanuel M; Dixon, Ray; Müller-Santos, Marcelo

    2018-01-01

    The ability of bacteria to produce polyhydroxyalkanoates such as poly(3-hydroxybutyrate) (PHB) enables provision of a carbon storage molecule that can be mobilized under demanding physiological conditions. However, the precise function of PHB in cellular metabolism has not been clearly defined. In order to determine the impact of PHB production on global physiology, we have characterized the properties of a Δ phaC1 mutant strain of the diazotrophic bacterium Herbaspirillum seropedicae . The absence of PHB in the mutant strain not only perturbs redox balance and increases oxidative stress, but also influences the activity of the redox-sensing Fnr transcription regulators, resulting in significant changes in expression of the cytochrome c -branch of the electron transport chain. The synthesis of PHB is itself dependent on the Fnr1 and Fnr3 proteins resulting in a cyclic dependency that couples synthesis of PHB with redox regulation. Transcriptional profiling of the Δ phaC1 mutant reveals that the loss of PHB synthesis affects the expression of many genes, including approximately 30% of the Fnr regulon.

  11. Redox State of the Neoarchean Earth Environment

    Science.gov (United States)

    Zerkle, Aubrey L.; Claire, Mark W.; Domagal-Goldman, Shawn; Farquhar, James; Poulton, Simon W.

    2011-01-01

    A Titan-like organic haze has been hypothesized for Earth's atmosphere prior to widespread surface oxygenation approx.2.45 billion years ago (Ga). We present a high-resolution record of quadruple sulfur isotopes, carbon isotopes, and Fe speciation from the approx.2.65-2.5 Ga Ghaap Group, South Africa, which suggest a linkage between organic haze and the biogeochemical cycling of carbon, sulfur, oxygen, and iron on the Archean Earth. These sediments provide evidence for oxygen production in microbial mats and localized oxygenation of surface waters. However, this oxygen production occurred under a reduced atmosphere which existed in multiple distinct redox states that correlate to changes in carbon and sulfur isotopes. The data are corroborated by photochemical model results that suggest bi-stable transitions between organic haze and haze-free atmospheric conditions in the Archean. These geochemical correlations also extend to other datasets, indicating that variations in the character of anomalous sulfur fractionation could provide insight into the role of carbon-bearing species in the reducing Archean atmosphere.

  12. Model creation of moving redox reaction boundary in agarose gel electrophoresis by traditional potassium permanganate method.

    Science.gov (United States)

    Xie, Hai-Yang; Liu, Qian; Li, Jia-Hao; Fan, Liu-Yin; Cao, Cheng-Xi

    2013-02-21

    A novel moving redox reaction boundary (MRRB) model was developed for studying electrophoretic behaviors of analytes involving redox reaction on the principle of moving reaction boundary (MRB). Traditional potassium permanganate method was used to create the boundary model in agarose gel electrophoresis because of the rapid reaction rate associated with MnO(4)(-) ions and Fe(2+) ions. MRB velocity equation was proposed to describe the general functional relationship between velocity of moving redox reaction boundary (V(MRRB)) and concentration of reactant, and can be extrapolated to similar MRB techniques. Parameters affecting the redox reaction boundary were investigated in detail. Under the selected conditions, good linear relationship between boundary movement distance and time were obtained. The potential application of MRRB in electromigration redox reaction titration was performed in two different concentration levels. The precision of the V(MRRB) was studied and the relative standard deviations were below 8.1%, illustrating the good repeatability achieved in this experiment. The proposed MRRB model enriches the MRB theory and also provides a feasible realization of manual control of redox reaction process in electrophoretic analysis.

  13. Spatial variability in oceanic redox structure 1.8 billion years ago

    DEFF Research Database (Denmark)

    Poulton, Simon W.; Fralick, Philip W.; Canfield, Donald Eugene

    2010-01-01

    to reconstruct oceanic redox conditions from the 1.88- to 1.83-billion-year-old Animikie group from the Superior region, North America. We find that surface waters were oxygenated, whereas at mid-depths, anoxic and sulphidic (euxinic) conditions extended over 100 km from the palaeoshoreline. The spatial extent...

  14. Membranes for Redox Flow Battery Applications

    Science.gov (United States)

    Prifti, Helen; Parasuraman, Aishwarya; Winardi, Suminto; Lim, Tuti Mariana; Skyllas-Kazacos, Maria

    2012-01-01

    The need for large scale energy storage has become a priority to integrate renewable energy sources into the electricity grid. Redox flow batteries are considered the best option to store electricity from medium to large scale applications. However, the current high cost of redox flow batteries impedes the wide spread adoption of this technology. The membrane is a critical component of redox flow batteries as it determines the performance as well as the economic viability of the batteries. The membrane acts as a separator to prevent cross-mixing of the positive and negative electrolytes, while still allowing the transport of ions to complete the circuit during the passage of current. An ideal membrane should have high ionic conductivity, low water intake and excellent chemical and thermal stability as well as good ionic exchange capacity. Developing a low cost, chemically stable membrane for redox flow cell batteries has been a major focus for many groups around the world in recent years. This paper reviews the research work on membranes for redox flow batteries, in particular for the all-vanadium redox flow battery which has received the most attention. PMID:24958177

  15. Membranes for redox flow battery applications.

    Science.gov (United States)

    Prifti, Helen; Parasuraman, Aishwarya; Winardi, Suminto; Lim, Tuti Mariana; Skyllas-Kazacos, Maria

    2012-06-19

    The need for large scale energy storage has become a priority to integrate renewable energy sources into the electricity grid. Redox flow batteries are considered the best option to store electricity from medium to large scale applications. However, the current high cost of redox flow batteries impedes the wide spread adoption of this technology. The membrane is a critical component of redox flow batteries as it determines the performance as well as the economic viability of the batteries. The membrane acts as a separator to prevent cross-mixing of the positive and negative electrolytes, while still allowing the transport of ions to complete the circuit during the passage of current. An ideal membrane should have high ionic conductivity, low water intake and excellent chemical and thermal stability as well as good ionic exchange capacity. Developing a low cost, chemically stable membrane for redox flow cell batteries has been a major focus for many groups around the world in recent years. This paper reviews the research work on membranes for redox flow batteries, in particular for the all-vanadium redox flow battery which has received the most attention.

  16. Membranes for Redox Flow Battery Applications

    Directory of Open Access Journals (Sweden)

    Maria Skyllas-Kazacos

    2012-06-01

    Full Text Available The need for large scale energy storage has become a priority to integrate renewable energy sources into the electricity grid. Redox flow batteries are considered the best option to store electricity from medium to large scale applications. However, the current high cost of redox flow batteries impedes the wide spread adoption of this technology. The membrane is a critical component of redox flow batteries as it determines the performance as well as the economic viability of the batteries. The membrane acts as a separator to prevent cross-mixing of the positive and negative electrolytes, while still allowing the transport of ions to complete the circuit during the passage of current. An ideal membrane should have high ionic conductivity, low water intake and excellent chemical and thermal stability as well as good ionic exchange capacity. Developing a low cost, chemically stable membrane for redox flow cell batteries has been a major focus for many groups around the world in recent years. This paper reviews the research work on membranes for redox flow batteries, in particular for the all-vanadium redox flow battery which has received the most attention.

  17. Fluctuations in Overlapping Generations Economies

    DEFF Research Database (Denmark)

    Tvede, Mich

    . The approach to existence of endogenous fluctuations is basic in the sense that the prime ingredients are the implicit function theorem and linear algebra. Moreover the approach is applied to show that for an open and dense set of utility functions there exist endowment vectors such that sunspot equilibria...

  18. Fluctuating hydrodynamics for ionic liquids

    Energy Technology Data Exchange (ETDEWEB)

    Lazaridis, Konstantinos [Department of Mathematics and Statistics, Washington State University, Pullman, 99163 (United States); Wickham, Logan [Department of Computer Science, Washington State University, Richland, 99354 (United States); Voulgarakis, Nikolaos, E-mail: n.voulgarakis@wsu.edu [Department of Mathematics and Statistics, Washington State University, Pullman, 99163 (United States)

    2017-04-25

    We present a mean-field fluctuating hydrodynamics (FHD) method for studying the structural and transport properties of ionic liquids in bulk and near electrified surfaces. The free energy of the system consists of two competing terms: (1) a Landau–Lifshitz functional that models the spontaneous separation of the ionic groups, and (2) the standard mean-field electrostatic interaction between the ions in the liquid. The numerical approach used to solve the resulting FHD-Poisson equations is very efficient and models thermal fluctuations with remarkable accuracy. Such density fluctuations are sufficiently strong to excite the experimentally observed spontaneous formation of liquid nano-domains. Statistical analysis of our simulations provides quantitative information about the properties of ionic liquids, such as the mixing quality, stability, and the size of the nano-domains. Our model, thus, can be adequately parameterized by directly comparing our prediction with experimental measurements and all-atom simulations. Conclusively, this work can serve as a practical mathematical tool for testing various theories and designing more efficient mixtures of ionic liquids. - Highlights: • A new fluctuating hydrodynamics method for ionic liquids. • Description of ionic liquid morphology in bulk and near electrified surfaces. • Direct comparison with experimental measurements.

  19. Redox-active labile iron in fortified flours from the Brazilian market Ferro lábil redox-ativo em farinhas fortificadas do mercado brasileiro

    Directory of Open Access Journals (Sweden)

    Breno Pannia Espósito

    2007-08-01

    Full Text Available OBJECTIVE: To quantify the fraction of redox-active labile iron in iron-fortified flours acquired on the Brazilian market. METHODS: Samples of wheat flour, maize flour and breadcrumbs were extracted with buffers that mimic gastric juice, saliva and intestinal juice. Redox-active labile iron levels were assessed through the reaction of autoxidation of ascorbic acid catalyzed by iron in the presence of a fluorescence probe. RESULTS: Redox-active labile iron represents 1% to 9% of the total iron in the flour and breadcrumb samples, with the lowest values found under gastric juice conditions and the highest in the more alkaline media. Redox-active labile iron possibly arises from the decomposition of an iron-phytic acid complex. A positive correlation between redox-active labile iron and total iron was found in saline biomimetic fluids. CONCLUSION: Redox-active labile iron may be a risk factor for people with impaired antioxidant defenses, such as those who are atransferrinemic or iron overloaded (e.g. thalassemic. Total iron can be used to predict redox-active labile iron absorption at each stage of the gastrointestinal tract after ingestion of iron-fortified flours.OBJETIVO: Quantificar a porcentagem de ferro lábil redox ativo em farinhas fortificadas adquiridas no comércio popular. MÉTODOS: Amostras de farinha de trigo, fubá e rosca foram extraídas com tampões miméticos de suco gástrico, saliva e suco intestinal. Os níveis de ferro lábil redox ativo foram determinados por meio da reação de auto-oxidação do ácido ascórbico catalisada pelo ferro, em presença de uma sonda fluorimétrica. RESULTADOS: A fração de ferro lábil redox ativo representa entre 1% e 9% do ferro total nas farinhas estudadas, sendo os menores valores encontrados em condições miméticas do suco gástrico e os maiores nos meios mais alcalinos. Há indícios de que o ferro lábil redox ativo origina-se da decomposição de um complexo entre ferro e ácido f

  20. Transitions in optimal adaptive strategies for populations in fluctuating environments

    Science.gov (United States)

    Mayer, Andreas; Mora, Thierry; Rivoire, Olivier; Walczak, Aleksandra M.

    2017-09-01

    Biological populations are subject to fluctuating environmental conditions. Different adaptive strategies can allow them to cope with these fluctuations: specialization to one particular environmental condition, adoption of a generalist phenotype that compromises between conditions, or population-wise diversification (bet hedging). Which strategy provides the largest selective advantage in the long run depends on the range of accessible phenotypes and the statistics of the environmental fluctuations. Here, we analyze this problem in a simple mathematical model of population growth. First, we review and extend a graphical method to identify the nature of the optimal strategy when the environmental fluctuations are uncorrelated. Temporal correlations in environmental fluctuations open up new strategies that rely on memory but are mathematically challenging to study: We present analytical results to address this challenge. We illustrate our general approach by analyzing optimal adaptive strategies in the presence of trade-offs that constrain the range of accessible phenotypes. Our results extend several previous studies and have applications to a variety of biological phenomena, from antibiotic resistance in bacteria to immune responses in vertebrates.

  1. Redox potential characterization and soil greenhouse gas concentration across a hydrological gradient in a Gulf coast forest

    Science.gov (United States)

    Yu, K.; Faulkner, S.P.; Patrick, W.H.

    2006-01-01

    Soil redox potential (Eh), concentrations of oxygen (O2) and three greenhouse gases (CO2, CH4, and N2O) were measured in the soil profile of a coastal forest at ridge, transition, and swamp across a hydrological gradient. The results delineated a distinct boundary in soil Eh and O2 concentration between the ridge and swamp with essentially no overlap between the two locations. Critical soil Eh to initiate significant CH4 production under this field conditions was about +300 mV, much higher than in the homogenous soils (about -150 mV). The strength of CH4 source to the atmosphere was strong for the swamp, minor for the transition, and negligible or even negative (consumption) for the ridge. Maximum N2O concentration in the soils was found at about Eh +250 mV, and the soil N2O emission was estimated to account for less than 4% for the ridge and transition, and almost negligible for the swamp in the cumulative global warming potential (GWP) of these three gases. The dynamic nature of this study site in response to water table fluctuations across a hydrological gradient makes it an ideal model of impact of future sea level rise to coastal ecosystems. Soil carbon (C) sequestration potential due to increasing soil water content upon sea level rise and subsidence in this coastal forest was likely limited and temporal, and at the expense of increasing soil CH4 production and emission. ?? 2005 Elsevier Ltd. All rights reserved.

  2. Reconstruction of a Broadband Spectrum of Alfvenic Fluctuations

    Science.gov (United States)

    Vinas, Adolfo F.; Fuentes, Pablo S. M.; Araneda, Jaime A.; Maneva, Yana G.

    2014-01-01

    Alfvenic fluctuations in the solar wind exhibit a high degree of velocities and magnetic field correlations consistent with Alfven waves propagating away and toward the Sun. Two remarkable properties of these fluctuations are the tendencies to have either positive or negative magnetic helicity (-1 less than or equal to sigma(sub m) less than or equal to +1) associated with either left- or right- topological handedness of the fluctuations and to have a constant magnetic field magnitude. This paper provides, for the first time, a theoretical framework for reconstructing both the magnetic and velocity field fluctuations with a divergence-free magnetic field, with any specified power spectral index and normalized magnetic- and cross-helicity spectrum field fluctuations for any plasma species. The spectrum is constructed in the Fourier domain by imposing two conditions-a divergence-free magnetic field and the preservation of the sense of magnetic helicity in both spaces-as well as using Parseval's theorem for the conservation of energy between configuration and Fourier spaces. Applications to the one-dimensional spatial Alfvenic propagation are presented. The theoretical construction is in agreement with typical time series and power spectra properties observed in the solar wind. The theoretical ideas presented in this spectral reconstruction provide a foundation for more realistic simulations of plasma waves, solar wind turbulence, and the propagation of energetic particles in such fluctuating fields.

  3. Colloid mobilization and transport during capillary fringe fluctuations.

    Science.gov (United States)

    Aramrak, Surachet; Flury, Markus; Harsh, James B; Zollars, Richard L

    2014-07-01

    Capillary fringe fluctuations due to changing water tables lead to displacement of air-water interfaces in soils and sediments. These moving air-water interfaces can mobilize colloids. We visualized colloids interacting with moving air-water interfaces during capillary fringe fluctuations by confocal microscopy. We simulated capillary fringe fluctuations in a glass-bead-filled column. We studied four specific conditions: (1) colloids suspended in the aqueous phase, (2) colloids attached to the glass beads in an initially wet porous medium, (3) colloids attached to the glass beads in an initially dry porous medium, and (4) colloids suspended in the aqueous phase with the presence of a static air bubble. Confocal images confirmed that the capillary fringe fluctuations affect colloid transport behavior. Hydrophilic negatively charged colloids initially suspended in the aqueous phase were deposited at the solid-water interface after a drainage passage, but then were removed by subsequent capillary fringe fluctuations. The colloids that were initially attached to the wet or dry glass bead surface were detached by moving air-water interfaces in the capillary fringe. Hydrophilic negatively charged colloids did not attach to static air-bubbles, but hydrophobic negatively charged and hydrophilic positively charged colloids did. Our results demonstrate that capillary fringe fluctuations are an effective means for colloid mobilization.

  4. Redox control of arsenic mobilization in Bangladesh groundwater

    International Nuclear Information System (INIS)

    Zheng, Y.; Stute, M.; Geen, A. van; Gavrieli, I.; Dhar, R.; Simpson, H.J.; Schlosser, P.; Ahmed, K.M.

    2004-01-01

    Detailed hydrochemical measurements, δ 34 S SO4 and 3 H analyses were performed on 37 groundwater samples collected during February 1999, January and March 2000 from 6 locations in eastern and southeastern Bangladesh to examine redox processes that lead to As mobilization in groundwater. The study sites were chosen based on available nation-wide As surveys to span the entire spectrum of As concentrations in Bangladesh groundwater, and to represent 3 of 5 major geological units of the Ganges-Brahmaputra Delta: uplifted Pleistocene terrace, fluvial flood plain and delta plain. Arsenic was found to be mobilized under Fe-reducing conditions in shallow aquifers ( 4 -reducing conditions, suggesting that authigenic sulfide precipitation does not constitute a significant sink for As in these groundwaters. The redox state of the water was characterized by a variety of parameters including dissolved O 2 , NO 3 - , Mn 2+ , Fe 2+ concentrations, and SO 4 2- /Cl - ratios. High dissolved [As] (> 50 μg/l; or > 0.7 μM ) were always accompanied by high dissolved [HCO 3 - ] (> 4 mM), and were close to saturation with respect to calcite. Groundwater enriched in As (200-800 μg/l; or 2.7-10.7 μM) and phosphate (30-100 μM) but relatively low in dissolved Fe (5-40 μM) probably resulted from re-oxidation of reducing, As and Fe enriched water. This history was deduced from isotopic signatures of δ 34 S SO4 and 3 H 2 O ( 3 H) to delineate the nature of redox changes for some of the reducing groundwaters. In contrast, As is not mobilized in presumed Pleistocene aquifers, both shallow (30-60 m) and deep (150-270 m), because conditions were not reducing enough due to lack of sufficient O 2 demand

  5. Redox interplay between mitochondria and peroxisomes

    Directory of Open Access Journals (Sweden)

    Celien eLismont

    2015-05-01

    Full Text Available Reduction-oxidation or ‘redox’ reactions are an integral part of a broad range of cellular processes such as gene expression, energy metabolism, protein import and folding, and autophagy. As many of these processes are intimately linked with cell fate decisions, transient or chronic changes in cellular redox equilibrium are likely to contribute to the initiation and progression of a plethora of human diseases. Since a long time, it is known that mitochondria are major players in redox regulation and signaling. More recently, it has become clear that also peroxisomes have the capacity to impact redox-linked physiological processes. To serve this function, peroxisomes cooperate with other organelles, including mitochondria. This review provides a comprehensive picture of what is currently known about the redox interplay between mitochondria and peroxisomes in mammals. We first outline the pro- and antioxidant systems of both organelles and how they may function as redox signaling nodes. Next, we critically review and discuss emerging evidence that peroxisomes and mitochondria share an intricate redox-sensitive relationship and cooperate in cell fate decisions. Key issues include possible physiological roles, messengers, and mechanisms. We also provide examples of how data mining of publicly-available datasets from ‘omics’ technologies can be a powerful means to gain additional insights into potential redox signaling pathways between peroxisomes and mitochondria. Finally, we highlight the need for more studies that seek to clarify the mechanisms of how mitochondria may act as dynamic receivers, integrators, and transmitters of peroxisome-derived mediators of oxidative stress. The outcome of such studies may open up exciting new avenues for the community of researchers working on cellular responses to organelle-derived oxidative stress, a research field in which the role of peroxisomes is currently highly underestimated and an issue of

  6. Hydrogen as indicator for redox conditions and dechlorination

    NARCIS (Netherlands)

    Meer, J. ter; Gerritse, J.; Mauro, C. di; Harkes, M.P.; Rijnaarts, H.H.M.

    2000-01-01

    The use of intrinsic degradation processes (natural attenuation) is becoming the basis for the restoration of many contaminated sites. Within this context, measuring concentrations of hydrogen in groundwater is important in two ways. Firstly, the hydrogen concentration can be used to characterize

  7. Predicting redox conditions in groundwater at a regional scale

    Science.gov (United States)

    Tesoriero, Anthony J.; Terziotti, Silvia; Abrams, Daniel B.

    2015-01-01

    Defining the oxic-suboxic interface is often critical for determining pathways for nitrate transport in groundwater and to streams at the local scale. Defining this interface on a regional scale is complicated by the spatial variability of reaction rates. The probability of oxic groundwater in the Chesapeake Bay watershed was predicted by relating dissolved O2 concentrations in groundwater samples to indicators of residence time and/or electron donor availability using logistic regression. Variables that describe surficial geology, position in the flow system, and soil drainage were important predictors of oxic water. The probability of encountering oxic groundwater at a 30 m depth and the depth to the bottom of the oxic layer were predicted for the Chesapeake Bay watershed. The influence of depth to the bottom of the oxic layer on stream nitrate concentrations and time lags (i.e., time period between land application of nitrogen and its effect on streams) are illustrated using model simulations for hypothetical basins. Regional maps of the probability of oxic groundwater should prove useful as indicators of groundwater susceptibility and stream susceptibility to contaminant sources derived from groundwater.

  8. Probing Fe (III)/Fe (II) redox potential in a clayey material

    International Nuclear Information System (INIS)

    Tournassat, Christophe; Chainet, Fabien; Betelu, Stephanie; Hadi, Jebril; Gaucher, Eric C.; Ignatiadis, Ioannis; Greneche, Jean-Marc; Charlet, Laurent

    2010-01-01

    Document available in extended abstract form only. Redox is one of the main factors affecting the migration of redox-sensitive radionuclides. As a consequence reducing conditions are considered of strategic importance for the confinement properties of a clayey formation towards nuclear waste. A representative redox potential of clay formation such as Callovian- Oxfordian (COx) can be derived from thermodynamic calculations considering equilibrium between observed redox phases such as pyrite and siderite. However, there is little information on the reactivity of the different reservoirs of redox constituents in this type of complex material. The present study aims at investigating the reactivity of the Fe(III)/Fe(II) redox couple in the structure of clay minerals using different investigation methods: electrochemistry and O 2 reduction kinetic experiments. Clay modified electrodes were specifically designed to probe Fe(III)/Fe(II) redox potential in the structure of clay minerals. The clay fraction of a Callovian-Oxfordian argillite sample originating from the same level than ANDRA underground research laboratory was used after pre-treatment to remove organic matter and accessory minerals such as pyrite that could influence redox potential measurements. These electrodes were used to verify the validity of the model of Favre et al. (2006) that links the redox potential (E clay ) to the the Fe(II)/Fe tot ratio in the structure (m rel ), the pH and the sodium concentration in solution: equation 1. The good agreement between direct potential measurements and model prediction provides a strong evidence of the relevance of this model in our experimental conditions although the clay composition and its too low Fe content do not a priori fulfil the conditions set by Drits and Manceau (2000) for the calculation of K 0 parameter. Following the verification of the model, we tried to apply it to the specific case of a Callovian-Oxfordian sample that had been very well preserved

  9. Structure, stabilité et fluctuations

    CERN Document Server

    Glansdorff, P

    1971-01-01

    Théorie générale : lois de conservation et bilans ; le second principe de la thermodynamique et le bilan entropique ; thermodynamique linéaire des phénomènes irréversibles ; théorie de la stabilité de l'équilibre thermodynamique par la méthode Gibbs-Duhem ; théorie générale de la stabilité de l'équilibre thermodynamique ; conditions de stabilité thermodynamique et hydrodynamique des syst¿mes hors d'équilibre ; forme explicite des conditions de stablité des processus hors d'équilibre ; stabilité et fluctuations ; le critère général d'évolution.

  10. Monitoring thioredoxin redox with a genetically encoded red fluorescent biosensor.

    Science.gov (United States)

    Fan, Yichong; Makar, Merna; Wang, Michael X; Ai, Hui-Wang

    2017-09-01

    Thioredoxin (Trx) is one of the two major thiol antioxidants, playing essential roles in redox homeostasis and signaling. Despite its importance, there is a lack of methods for monitoring Trx redox dynamics in live cells, hindering a better understanding of physiological and pathological roles of the Trx redox system. In this work, we developed the first genetically encoded fluorescent biosensor for Trx redox by engineering a redox relay between the active-site cysteines of human Trx1 and rxRFP1, a redox-sensitive red fluorescent protein. We used the resultant biosensor-TrxRFP1-to selectively monitor perturbations of Trx redox in various mammalian cell lines. We subcellularly localized TrxRFP1 to image compartmentalized Trx redox changes. We further combined TrxRFP1 with a green fluorescent Grx1-roGFP2 biosensor to simultaneously monitor Trx and glutathione redox dynamics in live cells in response to chemical and physiologically relevant stimuli.

  11. Possible use of ferrocyanide as a redox additive for prevention of electrolyte decomposition in overcharged nickel batteries

    Energy Technology Data Exchange (ETDEWEB)

    Xiaoming Zhu [Wuhan University (China). Dept. of Chemistry; College of Xianning (China). Dept. of Chemistry; Hanxi Yang; Xingping Ai [Wuhan University (China). Dept. of Chemistry

    2003-11-30

    The redox reaction of ferrocyanide was investigated for possible use as a redox additive for the prevention of the electrolyte decomposition of aqueous secondary Ni-NH batteries in the overcharged condition. It was found that with the presence of ferrocyanide, the charging voltage can be leveled off just above the complete oxidation of the positive nickel electrode. As a result, the oxygen evolution was greatly suppressed and the internal pressure of the batteries was kept at low level even at prolonged overcharging. In addition, no detrimental effects of the redox additive were observed on the normal charge-discharge performance of Ni-MH batteries. (author)

  12. Sonic and microwaves assisted redox reactions of the hydrolysates of protein for the preparation of rechargeable battery

    International Nuclear Information System (INIS)

    Hussain, Z.; Khatak, K.; Sardar, A.

    2016-01-01

    Long recharging time is one of the serious limitations of batteries. One of the best solutions for quick redox reactions via the use of microwave and sound-assisted reversible redox reaction is presented in this work. A wireless charged prototype battery based on the redox reactions of hydrolyzed waste protein was designed. The effect of experimental conditions like time of charging, nature of media and strength of the acid on the voltage of this prototype battery was investigated. The experimental data was explained on the basis of the previous work on protein peptides and amino acids by various workers. (author)

  13. Beyond the Fe-P-redox connection: preferential regeneration of phosphorus from organic matter as a key control on Baltic Sea nutrient cycles

    NARCIS (Netherlands)

    Jilbert, T.; Slomp, C.P.; Gustafsson, B.G.; Boer, W.

    2011-01-01

    Patterns of regeneration and burial of phosphorus (P) in the Baltic Sea are strongly dependent on redox conditions. Redox varies spatially along water depth gradients and temporally in response to the seasonal cycle and multidecadal hydrographic variability. Alongside the welldocumented link

  14. Beyond the Fe-P-redox connection: preferential regeneration of phosphorus from organic matter as a key control on Baltic Sea nutriënt cycles

    NARCIS (Netherlands)

    Jilbert, T.; Slomp, C.P.; Gustafsson, B.G.; Boer, W.

    2011-01-01

    Patterns of regeneration and burial of phosphorus (P) in the Baltic Sea are strongly dependent on redox conditions. Redox varies spatially along water depth gradients and temporally in response to the seasonal cycle and multidecadal hydrographic variability. Alongside the well-documented link

  15. Fluctuation of Dof1/Dof2 expression ratio under the influence of varying nitrogen and light conditions: involvement in differential regulation of nitrogen metabolism in two genotypes of finger millet (Eleusine coracana L.).

    Science.gov (United States)

    Gupta, Supriya; Gupta, Sanjay Mohan; Gupta, Alok Kumar; Gaur, Vikram Singh; Kumar, Anil

    2014-08-10

    In order to gain insights into the mechanism of high nitrogen use efficiency (NUE) of finger millet (FM) the role of Dof2 transcription factor (TF), which is a repressor of genes involved in C/N metabolism was investigated. The partial cDNA fragment of EcDof2 (912-bp; GenBank acc. no. KF261117) was isolated and characterized from finger millet (FM) that showed 63% and 58% homology with Dof2 of Zea mays at nucleotide and protein level, respectively. Its expression studies were carried out along with the activator EcDof1 in two genotypes (GE3885, high protein genotype (HPG); GE1437, low protein genotype (LPG)) of FM differing in grain protein contents (13.8% and 6.2%) showed that EcDof2 is expressed in both shoot and root tissues with significantly (p≤0.05) higher expression in the roots. The diurnal expression of both EcDof1 and EcDof2 in shoots was differential having different time of peak expression indicating a differential response to diurnal condition. Under continuous dark conditions, expression of EcDof1 and EcDof2 oscillated in both the genotypes whereas on illumination, the fold expression of EcDof1 was higher as compared to EcDof2. Under increasing nitrate concentration, EcDof2 expression increases in roots and shoots of LPG while it remains unchanged in HPG. However, the EcDof1 expression was found to increase in both genotypes. Further, time kinetics studies under single nitrate concentration revealed that EcDof2 was repressed in the roots of both genotypes whereas EcDof1 oscillated with time. The EcDof1/EcDof2 ratio measured showed differential response under different light and nitrogen conditions. It was higher in the roots of HPG indicating higher activation of genes involved in N uptake and assimilation resulting in high grain protein accumulation. The results indicate that both light and nitrogen concentration influence Dof1 and Dof2 expression and suggests a complex pattern of regulation of genes influenced by these plant specific TFs. In

  16. Fluctuation current in superconducting loops

    International Nuclear Information System (INIS)

    Berger, Jorge

    2012-01-01

    A superconducting loop that encloses noninteger flux holds a permanent current. On the average, this current is also present above T c , and has been measured in recent years. We are able to evaluate the permanent current within the TDGL or the Kramer-Watts-Tobin models for loops of general configuration, i.e., we don't require uniform cross section, material or temperature. We can also consider situations in which the width is not negligible in comparison to the radius. Our results agree with experiments. The situations with which we deal at present include fluctuation superconductivity in two-band superconductors, equilibrium thermal fluctuations of supercurrent along a weak link, and ratchet effects.

  17. Fluctuations and confinement in ATF

    International Nuclear Information System (INIS)

    Isler, R.C.; Harris, J.H.; Murakami, M.

    1993-01-01

    In the period immediately prior to the suspension of ATF operation in November, 1991, a great deal of emphasis was palced on investigations of the fundamental mechanisms controlling confinement in this device. At that time, measurements of the density fluctuations throughout the plasma volume indicated the existence of theoretically predicted dissipative trapped electron and resistive interchange instabilities. These identifications were supported by results of dynamic configuration scans of the magnetic fields during which the extent of the magnetic well, shear, and fraction of confined trapped particles were changed continuously. Interpretation of the data from these experiments has been an ongoing exercise. Most recently, analysis of discharges employing strong gas puffing to change density gradients and fluctuation levels have strengthened the view that dissipative trapped electron modes may be present but do not play a significant direct role in energy transport. The present paper summarizes the current understanding concerning the identification of instabilities and their relationship to confinement in ATF

  18. Charge Fluctuations in Nanoscale Capacitors

    Science.gov (United States)

    Limmer, David T.; Merlet, Céline; Salanne, Mathieu; Chandler, David; Madden, Paul A.; van Roij, René; Rotenberg, Benjamin

    2013-09-01

    The fluctuations of the charge on an electrode contain information on the microscopic correlations within the adjacent fluid and their effect on the electronic properties of the interface. We investigate these fluctuations using molecular dynamics simulations in a constant-potential ensemble with histogram reweighting techniques. This approach offers, in particular, an efficient, accurate, and physically insightful route to the differential capacitance that is broadly applicable. We demonstrate these methods with three different capacitors: pure water between platinum electrodes and a pure as well as a solvent-based organic electrolyte each between graphite electrodes. The total charge distributions with the pure solvent and solvent-based electrolytes are remarkably Gaussian, while in the pure ionic liquid the total charge distribution displays distinct non-Gaussian features, suggesting significant potential-driven changes in the organization of the interfacial fluid.

  19. Charge fluctuations in nanoscale capacitors.

    Science.gov (United States)

    Limmer, David T; Merlet, Céline; Salanne, Mathieu; Chandler, David; Madden, Paul A; van Roij, René; Rotenberg, Benjamin

    2013-09-06

    The fluctuations of the charge on an electrode contain information on the microscopic correlations within the adjacent fluid and their effect on the electronic properties of the interface. We investigate these fluctuations using molecular dynamics simulations in a constant-potential ensemble with histogram reweighting techniques. This approach offers, in particular, an efficient, accurate, and physically insightful route to the differential capacitance that is broadly applicable. We demonstrate these methods with three different capacitors: pure water between platinum electrodes and a pure as well as a solvent-based organic electrolyte each between graphite electrodes. The total charge distributions with the pure solvent and solvent-based electrolytes are remarkably Gaussian, while in the pure ionic liquid the total charge distribution displays distinct non-Gaussian features, suggesting significant potential-driven changes in the organization of the interfacial fluid.

  20. Fluctuation theorems and atypical trajectories

    International Nuclear Information System (INIS)

    Sahoo, M; Lahiri, S; Jayannavar, A M

    2011-01-01

    In this work, we have studied simple models that can be solved analytically to illustrate various fluctuation theorems. These fluctuation theorems provide symmetries individually to the distributions of physical quantities such as the classical work (W c ), thermodynamic work (W), total entropy (Δs tot ) and dissipated heat (Q), when the system is driven arbitrarily out of equilibrium. All these quantities can be defined for individual trajectories. We have studied the number of trajectories which exhibit behaviour unexpected at the macroscopic level. As the time of observation increases, the fraction of such atypical trajectories decreases, as expected at the macroscale. The distributions for the thermodynamic work and entropy production in nonlinear models may exhibit a peak (most probable value) in the atypical regime without violating the expected average behaviour. However, dissipated heat and classical work exhibit a peak in the regime of typical behaviour only.

  1. Photon counting and fluctuation of molecular movement

    International Nuclear Information System (INIS)

    Inohara, Koichi

    1978-01-01

    The direct measurement of the fluctuation of molecular motions, which provides with useful information on the molecular movement, was conducted by introducing photon counting method. The utilization of photon counting makes it possible to treat the molecular system consisting of a small number of molecules like a radioisotope in the detection of a small number of atoms, which are significant in biological systems. This method is based on counting the number of photons of the definite polarization emitted in a definite time interval from the fluorescent molecules excited by pulsed light, which are bound to the marked large molecules found in a definite spatial region. Using the probability of finding a number of molecules oriented in a definite direction in the definite spatial region, the probability of counting a number of photons in a definite time interval can be calculated. Thus the measurable count rate of photons can be related with the fluctuation of molecular movement. The measurement was carried out under the condition, in which the probability of the simultaneous arrival of more than two photons at a detector is less than 1/100. As the experimental results, the resolving power of photon-counting apparatus, the frequency distribution of the number of photons of some definite polarization counted for 1 nanosecond are shown. In the solution, the variance of the number of molecules of 500 on the average is 1200, which was estimated from the experimental data by assuming normal distribution. This departure from the Poisson distribution means that a certain correlation does exist in molecular movement. In solid solution, no significant deviation was observed. The correlation existing in molecular movement can be expressed in terms of the fluctuation of the number of molecules. (Nakai, Y.)

  2. Analysis of redox additive-based overcharge protection for rechargeable lithium batteries

    Science.gov (United States)

    Narayanan, S. R.; Surampudi, S.; Attia, A. I.; Bankston, C. P.

    1991-01-01

    The overcharge condition in secondary lithium batteries employing redox additives for overcharge protection, has been theoretically analyzed in terms of a finite linear diffusion model. The analysis leads to expressions relating the steady-state overcharge current density and cell voltage to the concentration, diffusion coefficient, standard reduction potential of the redox couple, and interelectrode distance. The model permits the estimation of the maximum permissible overcharge rate for any chosen set of system conditions. Digital simulation of the overcharge experiment leads to numerical representation of the potential transients, and estimate of the influence of diffusion coefficient and interelectrode distance on the transient attainment of the steady state during overcharge. The model has been experimentally verified using 1,1-prime-dimethyl ferrocene as a redox additive. The analysis of the experimental results in terms of the theory allows the calculation of the diffusion coefficient and the formal potential of the redox couple. The model and the theoretical results may be exploited in the design and optimization of overcharge protection by the redox additive approach.

  3. Iterative absolute electroanalytical approach to characterization of bulk redox conducting systems.

    Science.gov (United States)

    Lewera, Adam; Miecznikowski, Krzysztof; Chojak, Malgorzata; Makowski, Oktawian; Golimowski, Jerzy; Kulesza, Pawel J

    2004-05-15

    A novel electroanalytical approach is proposed here, and it is demonstrated with the direct and simultaneous determination of two unknowns: the concentration of redox sites and the apparent diffusion coefficient for charge propagation in a single crystal of dodecatungstophosphoric acid. This Keggin-type polyoxometalate serves as a model bulk redox conducting inorganic material for solid-state voltammetry. The system has been investigated using an ultramicrodisk working electrode in the absence of external liquid supporting electrolyte. The analytical method requires numerical solution of the combination of two equations in which the first one describes current (or charge) in a well-defined (either spherical or linear) diffusional regime and the second general equation describes chronoamperometric (or normal pulse voltammetric current) under mixed (linear-spherical) conditions. The iterative approach is based on successive approximations through calculation and minimizing the least-squares error function. The method is fairly universal, and in principle, it can be extended to the investigation of other bulk systems including sol-gel processed materials, redox melts, and solutions on condition that they are electroactive and well behaved, they contain redox centers at sufficiently high level, and a number of electrons for the redox reaction considered is known.

  4. Random numbers from vacuum fluctuations

    International Nuclear Information System (INIS)

    Shi, Yicheng; Kurtsiefer, Christian; Chng, Brenda

    2016-01-01

    We implement a quantum random number generator based on a balanced homodyne measurement of vacuum fluctuations of the electromagnetic field. The digitized signal is directly processed with a fast randomness extraction scheme based on a linear feedback shift register. The random bit stream is continuously read in a computer at a rate of about 480 Mbit/s and passes an extended test suite for random numbers.

  5. Random numbers from vacuum fluctuations

    Energy Technology Data Exchange (ETDEWEB)

    Shi, Yicheng; Kurtsiefer, Christian, E-mail: christian.kurtsiefer@gmail.com [Department of Physics, National University of Singapore, 2 Science Drive 3, Singapore 117542 (Singapore); Center for Quantum Technologies, National University of Singapore, 3 Science Drive 2, Singapore 117543 (Singapore); Chng, Brenda [Center for Quantum Technologies, National University of Singapore, 3 Science Drive 2, Singapore 117543 (Singapore)

    2016-07-25

    We implement a quantum random number generator based on a balanced homodyne measurement of vacuum fluctuations of the electromagnetic field. The digitized signal is directly processed with a fast randomness extraction scheme based on a linear feedback shift register. The random bit stream is continuously read in a computer at a rate of about 480 Mbit/s and passes an extended test suite for random numbers.

  6. Compartmentation of redox metabolism in malaria parasites.

    Directory of Open Access Journals (Sweden)

    Sebastian Kehr

    Full Text Available Malaria, caused by the apicomplexan parasite Plasmodium, still represents a major threat to human health and welfare and leads to about one million human deaths annually. Plasmodium is a rapidly multiplying unicellular organism undergoing a complex developmental cycle in man and mosquito - a life style that requires rapid adaptation to various environments. In order to deal with high fluxes of reactive oxygen species and maintain redox regulatory processes and pathogenicity, Plasmodium depends upon an adequate redox balance. By systematically studying the subcellular localization of the major antioxidant and redox regulatory proteins, we obtained the first complete map of redox compartmentation in Plasmodium falciparum. We demonstrate the targeting of two plasmodial peroxiredoxins and a putative glyoxalase system to the apicoplast, a non-photosynthetic plastid. We furthermore obtained a complete picture of the compartmentation of thioredoxin- and glutaredoxin-like proteins. Notably, for the two major antioxidant redox-enzymes--glutathione reductase and thioredoxin reductase--Plasmodium makes use of alternative-translation-initiation (ATI to achieve differential targeting. Dual localization of proteins effected by ATI is likely to occur also in other Apicomplexa and might open new avenues for therapeutic intervention.

  7. Characterization of Redox properties of humic materials

    International Nuclear Information System (INIS)

    Choppin, G.R.

    1995-01-01

    An important aspect of humic materials is the presence of stable free radicals as shown by the width of 1 H-NMR lines of humic acid in solution as well as ESR spectra of solid samples. Presumably, these are due to quinohdrone functional groups in the humic structure. These free radicals are assumed to be a source of the redox effects of humics in metal cations. Phenolic groups have also been proposed as a source of reduction potential in these substances. The reduction potential of humic material is 0.5-0.7 V (vs. the normal hydrogen electrode). In addition to this inherent redox property, humics undergo photolysis by sunlight in surface waters which results in the production of hydrogen peroxide. The latter can also result in redox reactions with metal cations. Such direct and indirect redox capability can have significant effects on the migration of reducible cations. Studies of the reduction of hexavalent actinide cations by humic acid showed the reactions Np O 2 2+ -> Np O 2 + (E 1/2 0 = 1.47 V) and Pu O 2 2+ -> Pu +4 (E 1/2 0 = 1.04 V) while U O 2 2+ was not reduced. The reduction of plutonium in sea water by humics is discussed. Evidence of the effects of redox by humic material on metal cations in natural waters and sediments are also reviewed. (authors). 16 refs., 2 figs., 1 tab

  8. De Novo Construction of Redox Active Proteins.

    Science.gov (United States)

    Moser, C C; Sheehan, M M; Ennist, N M; Kodali, G; Bialas, C; Englander, M T; Discher, B M; Dutton, P L

    2016-01-01

    Relatively simple principles can be used to plan and construct de novo proteins that bind redox cofactors and participate in a range of electron-transfer reactions analogous to those seen in natural oxidoreductase proteins. These designed redox proteins are called maquettes. Hydrophobic/hydrophilic binary patterning of heptad repeats of amino acids linked together in a single-chain self-assemble into 4-alpha-helix bundles. These bundles form a robust and adaptable frame for uncovering the default properties of protein embedded cofactors independent of the complexities introduced by generations of natural selection and allow us to better understand what factors can be exploited by man or nature to manipulate the physical chemical properties of these cofactors. Anchoring of redox cofactors such as hemes, light active tetrapyrroles, FeS clusters, and flavins by His and Cys residues allow cofactors to be placed at positions in which electron-tunneling rates between cofactors within or between proteins can be predicted in advance. The modularity of heptad repeat designs facilitates the construction of electron-transfer chains and novel combinations of redox cofactors and new redox cofactor assisted functions. Developing de novo designs that can support cofactor incorporation upon expression in a cell is needed to support a synthetic biology advance that integrates with natural bioenergetic pathways. © 2016 Elsevier Inc. All rights reserved.

  9. Redox-flow battery of actinide complexes

    International Nuclear Information System (INIS)

    Yamamura, Tomoo; Shiokawa, Yoshinobu

    2006-01-01

    Np battery and U battery were developed. We suggested that Np redox-flow battery should be (-)|Np 3+ ,Np 4+ ||NpO 2 + ,NpO 2 2+ |(+), and U battery (-)|[U III T 2 ] - ,[U IV T 2 ] 0 ||[U V O 2 T] - ,[U VI O 2 T] 0 |(+). The electromotive force at 50 % charge of Np and U battery is 1.10 V and 1.04 V, respectively. The energy efficiency of 70 mA/cm 2 of Np and U battery shows 99 % and 98 %, respectively. V redox-flow battery, electrode reactions of An battery, Np battery, U battery and future of U battery are described. The concept of V redox-flow battery, comparison of energy efficiency of Np, U and V battery, oxidation state and ionic species of 3d transition metals and main An, Purbe diagram of Np and U aqueous solution, shift of redox potential of β-diketones by pKa, and specifications of three redox-flow batteries are reported. (S.Y.)

  10. Modeling seasonal redox dynamics and the corresponding fate of the pharmaceutical residue phenazone during artificial recharge of groundwater.

    Science.gov (United States)

    Greskowiak, Janek; Prommer, Henning; Massmann, Gudrun; Nützmann, Gunnar

    2006-11-01

    Reactive multicomponent transport modeling was used to investigate and quantify the factors that affect redox zonation and the fate of the pharmaceutical residue phenazone during artificial recharge of groundwater at an infiltration site in Berlin, Germany. The calibrated model and the corresponding sensitivity analysis demonstrated thattemporal and spatial redox zonation at the study site was driven by seasonally changing, temperature-dependent organic matter degradation rates. Breakthrough of phenazone at monitoring wells occurred primarily during the warmer summer months, when anaerobic conditions developed. Assuming a redox-sensitive phenazone degradation behavior the model results provided an excellent agreement between simulated and measured phenazone concentrations. Therefore, the fate of phenazone was shown to be indirectly controlled by the infiltration water temperature through its effect on the aquifer's redox conditions. Other factors such as variable residence times appeared to be of less importance.

  11. Uranium fixation by mineralization at the redox front

    International Nuclear Information System (INIS)

    Isobe, Hiroshi

    1998-01-01

    The behavior of actinide elements including uranium in geomedia is controlled by redox conditions. Under the oxidized conditions, uranium forms uranyl ion (UO 2 2+ ) and its complexes, and dissolves in ground water. Under the reduced conditions, U(IV) has much lower solubility than uranyl ion. In the Koongarra uranium deposit, Australia, lead-bearing uraninite, uranyl lead oxide and uranyl silicate minerals occur in the unweathered, primary ore zone, and uranyl phosphate minerals occur in the weathered, secondary ore zone. Between unweathered and weathered zones, the transition zone exists as a redox front. In the transition zone, graphite and sulfide minerals react as reducing agents for species dissolved in ground water. By SEM, spherical grains of uraninite were observed in veins with graphite. Pyrite had coffinite rim with crystals of uraninite. Calculation based on the ground water chemistry and hydrology at Koongarra shows that the uranium in the transition zone may be fixed from the ground water. In the Koongarra transition zone, recent mineralization of uranium by reduction takes place. Mineralization is much stronger fixation mechanism than adsorption on clay minerals. Pyrite in the buffer materials of possible radioactive waste repositories can fix radionuclides in oxidized ground water by mineralization with reducing reactions. (author)

  12. Investigation of the cavitation fluctuation characteristics in a Venturi injector

    International Nuclear Information System (INIS)

    Xu, Yuncheng; Chen, Yan; Wang, Zijun; Zhou, Lingjiu; Yan, Haijun

    2015-01-01

    The suction flow rate in a Venturi injector increases to a maximum and appears to be unstable when critical cavitation occurs. This study analyzes changes in the cavitation length in high-speed videos of a Venturi injector with critical cavitation to find periodic fluctuations in the cavitation cloud. Pressure fluctuation measurements show a dominant low frequency fluctuation that is almost as large as the oscillation frequency seen visually for the same conditions. The variation of the cavitation numbers and the measured transient outlet pressure show that critical cavitation occurs in the Venturi injector when the peak-to-peak pressure difference is greater than a critical value. Moreover, when the cavitation numbers become very small in the cavitation areas, the peak-to-peak pressures begin to decrease. The relationship between the suction performance and the outlet pressure fluctuations has a significant inflection point which can be used to determine proper working conditions. These experimental statistics provide a pressure range based on the inlet and outlet pressures for which the improvement of suction performance will not substantially change the outlet pressure fluctuations. Both the high-speed photography and the pressure measurement show the periodic oscillations of the cavitation cloud in a Venturi injector and can be used to detect the occurrence of critical cavitation. (paper)

  13. Investigation of the cavitation fluctuation characteristics in a Venturi injector

    Energy Technology Data Exchange (ETDEWEB)

    Xu, Yuncheng; Chen, Yan; Wang, Zijun; Zhou, Lingjiu; Yan, Haijun, E-mail: yanhj@cau.edu.cn [College of Water Resources and Civil Engineering, China Agricultural University, Beijing 100083 (China)

    2015-04-15

    The suction flow rate in a Venturi injector increases to a maximum and appears to be unstable when critical cavitation occurs. This study analyzes changes in the cavitation length in high-speed videos of a Venturi injector with critical cavitation to find periodic fluctuations in the cavitation cloud. Pressure fluctuation measurements show a dominant low frequency fluctuation that is almost as large as the oscillation frequency seen visually for the same conditions. The variation of the cavitation numbers and the measured transient outlet pressure show that critical cavitation occurs in the Venturi injector when the peak-to-peak pressure difference is greater than a critical value. Moreover, when the cavitation numbers become very small in the cavitation areas, the peak-to-peak pressures begin to decrease. The relationship between the suction performance and the outlet pressure fluctuations has a significant inflection point which can be used to determine proper working conditions. These experimental statistics provide a pressure range based on the inlet and outlet pressures for which the improvement of suction performance will not substantially change the outlet pressure fluctuations. Both the high-speed photography and the pressure measurement show the periodic oscillations of the cavitation cloud in a Venturi injector and can be used to detect the occurrence of critical cavitation. (paper)

  14. Water level fluctuations in a tropical reservoir: the impact of sediment drying, aquatic macrophyte dieback, and oxygen availability on phosphorus mobilization.

    Science.gov (United States)

    Keitel, Jonas; Zak, Dominik; Hupfer, Michael

    2016-04-01

    Reservoirs in semi-arid areas are subject to water level fluctuations (WLF) that alter biogeochemical processes in the sediment. We hypothesized that wet-dry cycles may cause internal eutrophication in such systems when they affect densely vegetated shallow areas. To assess the impact of WLF on phosphorus (P) mobilization and benthic P cycling of iron-rich sediments, we tested the effects of (i) sediment drying and rewetting, (ii) the impact of organic matter availability in the form of dried Brazilian Waterweed (Egeria densa), and (iii) alternating redox conditions in the surface water. In principle, drying led to increased P release after rewetting both in plant-free and in plant-amended sediments. Highest P mobilization was recorded in plant amendments under oxygen-free conditions. After re-establishment of aerobic conditions, P concentrations in surface water decreased substantially owing to P retention by sediments. In desiccated and re-inundated sediments, P retention decreased by up to 30% compared to constantly inundated sediments. We showed that WLF may trigger biochemical interactions conducive to anaerobic P release. Thereby, E. densa showed high P release and even P uptake that was redox-controlled and superimposed sedimentary P cycling. Macrophytes play an important role in the uptake of P from the water but may be also a significant source of P in wet-dry cycles. We estimated a potential for the abrupt release of soluble reactive phosphorus (SRP) by E. densa of 0.09-0.13 g SRP per m(2) after each wet-dry cycle. Released SRP may exceed critical P limits for eutrophication, provoking usage restrictions. Our results have implications for management of reservoirs in semi-arid regions affected by WLF.

  15. Quantum Fluctuations for Gravitational Impulsive Waves

    OpenAIRE

    Enginer, Y.; Hortacsu, M.; Ozdemir, N.

    1998-01-01

    Quantum fluctuations for a massless scalar field in the background metric of spherical impulsive gravitational waves through Minkowski and de Sitter spaces are investigated. It is shown that there exist finite fluctuations for de Sitter space.

  16. Net charge fluctuations and local charge compensation

    International Nuclear Information System (INIS)

    Fu Jinghua

    2006-01-01

    We propose net charge fluctuation as a measure of local charge correlation length. It is demonstrated that, in terms of a schematic multiperipheral model, net charge fluctuation satisfies the same Quigg-Thomas relation as satisfied by charge transfer fluctuation. Net charge fluctuations measured in finite rapidity windows depend on both the local charge correlation length and the size of the observation window. When the observation window is larger than the local charge correlation length, the net charge fluctuation only depends on the local charge correlation length, while forward-backward charge fluctuations always have strong dependence on the observation window size. Net charge fluctuations and forward-backward charge fluctuations measured in the present heavy ion experiments show characteristic features similar to those from multiperipheral models. But the data cannot all be understood within this simple model

  17. REDOX IMAGING OF THE p53-DEPENDENT MITOCHONDRIAL REDOX STATE IN COLON CANCER EX VIVO

    Science.gov (United States)

    XU, HE N.; FENG, MIN; MOON, LILY; DOLLOFF, NATHAN; EL-DEIRY, WAFIK; LI, LIN Z.

    2015-01-01

    The mitochondrial redox state and its heterogeneity of colon cancer at tissue level have not been previously reported. Nor has how p53 regulates mitochondrial respiration been measured at (deep) tissue level, presumably due to the unavailability of the technology that has sufficient spatial resolution and tissue penetration depth. Our prior work demonstrated that the mitochondrial redox state and its intratumor heterogeneity is associated with cancer aggressiveness in human melanoma and breast cancer in mouse models, with the more metastatic tumors exhibiting localized regions of more oxidized redox state. Using the Chance redox scanner with an in-plane spatial resolution of 200 μm, we imaged the mitochondrial redox state of the wild-type p53 colon tumors (HCT116 p53 wt) and the p53-deleted colon tumors (HCT116 p53−/−) by collecting the fluorescence signals of nicotinamide adenine dinucleotide (NADH) and oxidized flavoproteins [Fp, including flavin adenine dinucleotide (FAD)] from the mouse xenografts snap-frozen at low temperature. Our results show that: (1) both tumor lines have significant degree of intratumor heterogeneity of the redox state, typically exhibiting a distinct bi-modal distribution that either correlates with the spatial core–rim pattern or the “hot/cold” oxidation-reduction patches; (2) the p53−/− group is significantly more heterogeneous in the mitochondrial redox state and has a more oxidized tumor core compared to the p53 wt group when the tumor sizes of the two groups are matched; (3) the tumor size dependence of the redox indices (such as Fp and Fp redox ratio) is significant in the p53−/− group with the larger ones being more oxidized and more heterogeneous in their redox state, particularly more oxidized in the tumor central regions; (4) the H&E staining images of tumor sections grossly correlate with the redox images. The present work is the first to reveal at the submillimeter scale the intratumor heterogeneity pattern

  18. Short-Range Electron Transfer in Reduced Flavodoxin: Ultrafast Nonequilibrium Dynamics Coupled with Protein Fluctuations.

    Science.gov (United States)

    Kundu, Mainak; He, Ting-Fang; Lu, Yangyi; Wang, Lijuan; Zhong, Dongping

    2018-05-03

    Short-range electron transfer (ET) in proteins is an ultrafast process on the similar timescales as local protein-solvent fluctuations thus the two dynamics are coupled. Here, we use semiquinone flavodoxin and systematically characterized the photoinduced redox cycle with eleven mutations of different aromatic electron donors (tryptophan and tyrosine) and local residues to change redox properties. We observed the forward and backward ET dynamics in a few picoseconds, strongly following a stretched behavior resulting from a coupling between local environment relaxations and these ET processes. We further observed the hot vibrational-state formation through charge recombination and the subsequent cooling dynamics also in a few picoseconds. Combined with the ET studies in oxidized flavodoxin, these results coherently reveal the evolution of the ET dynamics from single to stretched exponential behaviors and thus elucidate critical timescales for the coupling. The observed hot vibration-state formation is robust and should be considered in all photoinduced back ET processes in flavoproteins.

  19. Redox behaviour of uranium with iron compounds

    International Nuclear Information System (INIS)

    Ithurbide, A.

    2009-10-01

    An option investigated for the management of long-term nuclear waste is a repository in deep geological formations. It is generally admitted that the release of radionuclides from the spent fuel in the geosphere could occur several thousand years after the beginning of the storage. Therefore, to assess the safety of the long-term disposal, it is important to consider the phenomena that can reduce the migration, and in particular the migration of uranium. The aim of this work is to study if siderite, an iron compound present both in the near - and far -field, can limit this migration as well as the role played by the redox process. Siderite thin layers have been obtained by electrochemistry. The layers are adherent and homogeneous. Their thickness is about 1 μm and they are composed of spherical grains. Analytical characterizations performed show that siderite is free of any impurity and does not exhibit any trace of oxidation. The interactions between siderite and uranium (VI) have been carried out in solutions considered as representative of environmental waters, in terms of pH and carbonate concentration. The retention of uranium on the thin layer is important since, after 24 hours of interaction, it corresponds to retention capacities of several hundreds of uranium micro-moles per gram of siderite. XPS analysis show that, in any studied condition, part of uranium present on the thin layer is reduced into an over stoichiometric uranium dioxide. The process of interaction differs depending on the considered environment, specially on the stability of siderite. (author)

  20. Measurement of magnetic fluctuation induced energy transport

    International Nuclear Information System (INIS)

    Fiksel, G.; Prager, S.C.; Shen, W.; Stoneking, M.

    1993-11-01

    The local electron energy flux produced by magnetic fluctuations has been measured directly in the MST reversed field pinch (over the radial range r/a > 0.75). The flux, produced by electrons traveling parallel to a fluctuating magnetic field, is obtained from correlation between the fluctuations in the parallel heat flux and the radial magnetic field. The fluctuation induced flux is large (100 kW/cm 2 ) in the ''core'' (r/a 2 ) in the edge

  1. Zero-point oscillations, zero-point fluctuations, and fluctuations of zero-point oscillations

    International Nuclear Information System (INIS)

    Khalili, Farit Ya

    2003-01-01

    Several physical effects and methodological issues relating to the ground state of an oscillator are considered. Even in the simplest case of an ideal lossless harmonic oscillator, its ground state exhibits properties that are unusual from the classical point of view. In particular, the mean value of the product of two non-negative observables, kinetic and potential energies, is negative in the ground state. It is shown that semiclassical and rigorous quantum approaches yield substantially different results for the ground state energy fluctuations of an oscillator with finite losses. The dependence of zero-point fluctuations on the boundary conditions is considered. Using this dependence, it is possible to transmit information without emitting electromagnetic quanta. Fluctuations of electromagnetic pressure of zero-point oscillations are analyzed, and the corresponding mechanical friction is considered. This friction can be viewed as the most fundamental mechanism limiting the quality factor of mechanical oscillators. Observation of these effects exceeds the possibilities of contemporary experimental physics but almost undoubtedly will be possible in the near future. (methodological notes)

  2. Electrostatic fluctuation in Low-{beta} plasmas

    Energy Technology Data Exchange (ETDEWEB)

    Krane, B

    1997-11-01

    The thesis gives an overview, which by no means is complete, to two dimensional plasma flows. The plasma is taken to be strongly magnetized such that magnetic fields generated by internal currents are small compared to the background magnetic field. This requires that the magnetic pressure exerted by the ambient magnetic field is large compared to the pressure due to thermal fluctuations, i.e. low-{beta} plasma. The author also assume low frequency electrostatic fluctuations with {omega}<<{omega}{sub c}i where {omega}{sub c}i is the ion gyro frequency. A brief introduction to nonlinear phenomena in two dimensional plasma flows has been presented. Particular attention was given to simple models describing flute and drift modes. Although the derivations of the model equations are based on different assumptions regarding the plasma conditions, the resulting equations exhibit similar behavior in some respects. For instance, both the simple guiding center model and the Hasegawa-Mima model have stable dipolar structures. The inverse cascade was also found in both models. However, it is evident that there are significant differences, first of all the Hasegawa-Mima model assumes a background density gradient which makes it an inhomogeneous model. Secondly, in this model the electrons respond instantaneously to variations in the ion density by moving along the magnetic field, thereby introducing Debye shielding.

  3. Does urban poverty increase body fluctuating asymmetry?

    Science.gov (United States)

    Ozener, Bariş

    2011-12-01

    Perturbations during development leave enduring signs on the adult body. Fluctuating asymmetry (FA) is a good bio-indicator of stress during ontogeny. The aim of this study is to determine the effect of urban poverty on the fluctuating asymmetry of young Turkish males. Young males from a lower socioeconomic group (N = 140, Mean age = 18.17 +/- 0.61) were selected from slum areas of Ankara, the capital of Turkey, where urban poverty is intense. An upper socioeconomic group, on the other hand, consisted of students from two private colleges and included children from some of the richest families in Turkey (N = 120, Mean age = 18.08 +/- 0.54). Eight anthropometric traits of all subjects were measured. Considering the seven measurements demonstrate ideal FA, the individuals living in poor areas of the city displayed higher FA. The discrepancy between the two groups was even greater for a measure of composite FA. In conclusion, poor living conditions in Ankara, where urban poverty is intense, adversely impact the developmental stability of young Turkish males.

  4. Fluctuating selection on basal metabolic rate.

    Science.gov (United States)

    Nilsson, Johan F; Nilsson, Jan-Åke

    2016-02-01

    BMR (Basal metabolic rate) is an important trait in animal life history as it represents a significant part of animal energy budgets. BMR has also been shown to be positively related to sustainable work rate and maximal thermoregulatory capacity. To this date, most of the studies have focused on the causes of interspecific and intraspecific variation in BMR, and fairly little is known about the fitness consequences of different metabolic strategies. In this study, we show that winter BMR affects local survival in a population of wild blue tits (Cyanistes caeruleus), but that the selection direction differs between years. We argue that this fluctuating selection is probably a consequence of varying winter climate with a positive relation between survival and BMR during cold and harsh conditions, but a negative relation during mild winters. This fluctuating selection can not only explain the pronounced variation in BMR in wild populations, but will also give us new insights into how energy turnover rates can shape the life-history strategies of animals. Furthermore, the study shows that the process of global warming may cause directional selection for a general reduction in BMR, affecting the general life-history strategy on the population level.

  5. Electrostatic fluctuation in Low-β plasmas

    International Nuclear Information System (INIS)

    Krane, B

    1997-11-01

    The thesis gives an overview, which by no means is complete, to two dimensional plasma flows. The plasma is taken to be strongly magnetized such that magnetic fields generated by internal currents are small compared to the background magnetic field. This requires that the magnetic pressure exerted by the ambient magnetic field is large compared to the pressure due to thermal fluctuations, i.e. low-β plasma. The author also assume low frequency electrostatic fluctuations with ω c i where ω c i is the ion gyro frequency. A brief introduction to nonlinear phenomena in two dimensional plasma flows has been presented. Particular attention was given to simple models describing flute and drift modes. Although the derivations of the model equations are based on different assumptions regarding the plasma conditions, the resulting equations exhibit similar behavior in some respects. For instance, both the simple guiding center model and the Hasegawa-Mima model have stable dipolar structures. The inverse cascade was also found in both models. However, it is evident that there are significant differences, first of all the Hasegawa-Mima model assumes a background density gradient which makes it an inhomogeneous model. Secondly, in this model the electrons respond instantaneously to variations in the ion density by moving along the magnetic field, thereby introducing Debye shielding

  6. Quantum inflaton, primordial perturbations, and CMB fluctuations

    International Nuclear Information System (INIS)

    Cao, F.J.; Vega, H.J. de; Sanchez, N.G.

    2004-01-01

    We compute the primordial scalar, vector and tensor metric perturbations arising from quantum field inflation. Quantum field inflation takes into account the nonperturbative quantum dynamics of the inflaton consistently coupled to the dynamics of the (classical) cosmological metric. For chaotic inflation, the quantum treatment avoids the unnatural requirements of an initial state with all the energy in the zero mode. For new inflation it allows a consistent treatment of the explosive particle production due to spinodal instabilities. Quantum field inflation (under conditions that are the quantum analog of slow-roll) leads, upon evolution, to the formation of a condensate starting a regime of effective classical inflation. We compute the primordial perturbations taking the dominant quantum effects into account. The results for the scalar, vector and tensor primordial perturbations are expressed in terms of the classical inflation results. For a N-component field in a O(N) symmetric model, adiabatic fluctuations dominate while isocurvature or entropy fluctuations are negligible. The results agree with the current Wilkinson Microwave Anisotropy Probe observations and predict corrections to the power spectrum in classical inflation. Such corrections are estimated to be of the order of (m 2 /NH 2 ), where m is the inflaton mass and H the Hubble constant at the moment of horizon crossing. An upper estimate turns to be about 4% for the cosmologically relevant scales. This quantum field treatment of inflation provides the foundations to the classical inflation and permits to compute quantum corrections to it

  7. Carbon Redox-Polymer-Gel Hybrid Supercapacitors

    Science.gov (United States)

    Vlad, A.; Singh, N.; Melinte, S.; Gohy, J.-F.; Ajayan, P.M.

    2016-01-01

    Energy storage devices that provide high specific power without compromising on specific energy are highly desirable for many electric-powered applications. Here, we demonstrate that polymer organic radical gel materials support fast bulk-redox charge storage, commensurate to surface double layer ion exchange at carbon electrodes. When integrated with a carbon-based electrical double layer capacitor, nearly ideal electrode properties such as high electrical and ionic conductivity, fast bulk redox and surface charge storage as well as excellent cycling stability are attained. Such hybrid carbon redox-polymer-gel electrodes support unprecedented discharge rate of 1,000C with 50% of the nominal capacity delivered in less than 2 seconds. Devices made with such electrodes hold the potential for battery-scale energy storage while attaining supercapacitor-like power performances. PMID:26917470

  8. Effect of long-term fertilization on humic redox mediators in multiple microbial redox reactions.

    Science.gov (United States)

    Guo, Peng; Zhang, Chunfang; Wang, Yi; Yu, Xinwei; Zhang, Zhichao; Zhang, Dongdong

    2018-03-01

    This study investigated the effects of different long-term fertilizations on humic substances (HSs), humic acids (HAs) and humins, functioning as redox mediators for various microbial redox biotransformations, including 2,2',4,4',5,5'- hexachlorobiphenyl (PCB 153 ) dechlorination, dissimilatory iron reduction, and nitrate reduction, and their electron-mediating natures. The redox activity of HSs for various microbial redox metabolisms was substantially enhanced by long-term application of organic fertilizer (pig manure). As a redox mediator, only humin extracted from soils with organic fertilizer amendment (OF-HM) maintained microbial PCB 153 dechlorination activity (1.03 μM PCB 153 removal), and corresponding HA (OF-HA) most effectively enhanced iron reduction and nitrate reduction by Shewanella putrefaciens. Electrochemical analysis confirmed the enhancement of their electron transfer capacity and redox properties. Fourier transform infrared analysis showed that C=C and C=O bonds, and carboxylic or phenolic groups in HSs might be the redox functional groups affected by fertilization. This research enhances our understanding of the influence of anthropogenic fertility on the biogeochemical cycling of elements and in situ remediation ability in agroecosystems through microorganisms' metabolisms. Copyright © 2017 Elsevier Ltd. All rights reserved.

  9. Theoretical aspects of several successive two-step redox mechanisms in protein-film cyclic staircase voltammetry

    International Nuclear Information System (INIS)

    Gulaboski, Rubin; Kokoškarova, Pavlinka; Mitrev, Saša

    2012-01-01

    Highlights: ► Theoretical models for 2e− successive mechanisms are considered. ► The models are compatible for various metal-containing redox proteins. ► Diagnostic criteria are provided to recognize the particular redox mechanism. - Abstract: Protein-film voltammetry (PFV) is a versatile tool designed to provide insight into the enzymes physiological functions by studying the redox properties of various oxido-reductases with suitable voltammetric technique. The determination of the thermodynamic and kinetic parameters relevant to protein's physiological properties is achieved via methodologies established from theoretical considerations of various mechanisms in PFV. So far, the majority of the mathematical models in PFV have been developed for redox proteins undergoing a single-step electron transfer reactions. However, there are many oxido-reductases containing quinone moieties or polyvalent ions of transition metals like Mo, Mn, W, Fe or Co as redox centers, whose redox chemistry can be described only via mathematical models considering successive two-step electron transformation. In this work we consider theoretically the protein-film redox mechanisms of the EE (Electrochemical–Electrochemical), ECE (Electrochemical–Chemical–Electrochemical), and EECat (Electrochemical–Electrochemical–Catalytic) systems under conditions of cyclic staircase voltammetry. We also propose methodologies to determine the kinetics of electron transfer steps by all considered mechanisms. The experimentalists working with PFV can get large benefits from the simulated voltammograms given in this work.

  10. Reverse Engineering Applied to Red Human Hair Pheomelanin Reveals Redox-Buffering as a Pro-Oxidant Mechanism

    Science.gov (United States)

    Kim, Eunkyoung; Panzella, Lucia; Micillo, Raffaella; Bentley, William E.; Napolitano, Alessandra; Payne, Gregory F.

    2015-01-01

    Pheomelanin has been implicated in the increased susceptibility to UV-induced melanoma for people with light skin and red hair. Recent studies identified a UV-independent pathway to melanoma carcinogenesis and implicated pheomelanin’s pro-oxidant properties that act through the generation of reactive oxygen species and/or the depletion of cellular antioxidants. Here, we applied an electrochemically-based reverse engineering methodology to compare the redox properties of human hair pheomelanin with model synthetic pigments and natural eumelanin. This methodology exposes the insoluble melanin samples to complex potential (voltage) inputs and measures output response characteristics to assess redox activities. The results demonstrate that both eumelanin and pheomelanin are redox-active, they can rapidly (sec-min) and repeatedly redox-cycle between oxidized and reduced states, and pheomelanin possesses a more oxidative redox potential. This study suggests that pheomelanin’s redox-based pro-oxidant activity may contribute to sustaining a chronic oxidative stress condition through a redox-buffering mechanism. PMID:26669666

  11. Heterogeneous-catalytic redox reactions in nitrate - formate systems

    International Nuclear Information System (INIS)

    Ananiev, A.V.; Shilov, V.P.; Tananaev, I.G.; Brossard, Ph.; Broudic, J.Ch.

    2000-01-01

    It was found that an intensive destruction of various organic and mineral substances - usual components of aqueous waste solutions (oxalic acid, complexones, urea, hydrazine, ammonium nitrate, etc.) takes place under the conditions of catalytic denitration. Kinetics and mechanisms of urea and ammonium nitrate decomposition in the system HNO 3 - HCOOH - Pt/SiO 2 are comprehensively investigated. The behaviour of uranium, neptunium and plutonium under the conditions of catalytic denitration is studied. It is shown, that under the certain conditions the formic acid is an effective reducer of the uranium (VI), neptunium (VI, V) and plutonium (VI, IV) ions. Kinetics of heterogeneous-catalytic red-ox reactions of uranium (VI), neptunium (VI, V) and plutonium (VI, IV) with formic acid are investigated. The mechanisms of the appropriate reactions are evaluated. (authors)

  12. Simulation of Temperature Fluctuations in Stirling Engine Regenerator Matrices

    DEFF Research Database (Denmark)

    Andersen, Stig Kildegaard; Carlsen, Henrik; Thomsen, Per Grove

    2003-01-01

    The objective of this study has been to create a model for studying the effects of fluctuations in regenerator matrix temperatures on Stirling engine performance. A one-dimensional model with axial discretisation of engine components has been formulated using the balance equations for mass, energy...... and accurately calculated. Simulation results have been compared to experimental data for a 9 kW Stirling engine and reasonable agreement has been found over a wide range of operating conditions using Helium or Nitrogen as working gas. Simulation results indicate that fluctuations in the regenerator matrix...... temperatures have significant impact on the regenerator loss, the engine power output, and the cycle efficiency....

  13. Concentration Fluctuations in Smoke Plumes Released Near the Ground

    DEFF Research Database (Denmark)

    Ejsing Jørgensen, Hans; Mikkelsen, Torben; Pécseli, H.L.

    2010-01-01

    results are tested against these hypotheses. We find strong evidence for a simple scaling of the standard deviation, skewness and kurtosis with the average concentrations at the downwind distances observed in our experiments. Near-ground concentration fluctuations in fixed as well as moving frames...... of references are investigated. The scaling is supported by data from several experimental sites and different atmospheric stability conditions. One conclusion of the study is that relatively accurate estimates for the standard deviation, skewness and kurtosis can be obtained for the concentration fluctuations...

  14. Study of thermal - hydraulic sensors signal fluctuations in PWR

    International Nuclear Information System (INIS)

    Hennion, F.

    1987-10-01

    This thesis deals with signal fluctuations of thermal-hydraulic sensors in the main coolant primary of a pressurized water reactor. The aim of this work is to give a first response about the potentiality of use of these noise signals for the functionning monitoring. Two aspects have been studied: - the modelisation of temperature fluctuations of core thermocouples, by a Monte-Carlo method, gives the main characteristics of these signals and their domain of application. - the determination of eigenfrequency in the primary by an acoustic representation could permit the monitoring of local and global thermo-hydraulic conditions [fr

  15. Electronically Induced Redox Barriers for Treatment of Groundwater

    National Research Council Canada - National Science Library

    Sale, Tom; Gilbert, David

    2006-01-01

    ...) and Colorado State University (CSU). The focus is an innovative electrolytic approach for managing redox-sensitive contaminants in groundwater, referred to as electrically induced redox barrier (e-barriers...

  16. Effects of iron concentration and redox states on failure of boron-free ...

    Indian Academy of Sciences (India)

    Effects of iron concentration and redox states on failure of boron-free E-glass fibres under applied stress in different conditions ... Materials, Donghua University, Shanghai 201620, China; Material Research Center, Missouri University of Science and Technology, Rolla 65409, USA; Fiber Glass Science and Technology, ...

  17. Analysis of dynamic multiplicity fluctuations at PHOBOS

    Science.gov (United States)

    Chai, Zhengwei; PHOBOS Collaboration; Back, B. B.; Baker, M. D.; Ballintijn, M.; Barton, D. S.; Betts, R. R.; Bickley, A. A.; Bindel, R.; Budzanowski, A.; Busza, W.; Carroll, A.; Chai, Z.; Decowski, M. P.; García, E.; George, N.; Gulbrandsen, K.; Gushue, S.; Halliwell, C.; Hamblen, J.; Heintzelman, G. A.; Henderson, C.; Hofman, D. J.; Hollis, R. S.; Holynski, R.; Holzman, B.; Iordanova, A.; Johnson, E.; Kane, J. L.; Katzy, J.; Khan, N.; Kucewicz, W.; Kulinich, P.; Kuo, C. M.; Lin, W. T.; Manly, S.; McLeod, D.; Mignerey, A. C.; Nouicer, R.; Olszewski, A.; Pak, R.; Park, I. C.; Pernegger, H.; Reed, C.; Remsberg, L. P.; Reuter, M.; Roland, C.; Roland, G.; Rosenberg, L.; Sagerer, J.; Sarin, P.; Sawicki, P.; Skulski, W.; Steinberg, P.; Stephans, G. S. F.; Sukhanov, A.; Tang, J. L.; Trzupek, A.; Vale, C.; van Nieuwenhuizen, G. J.; Verdier, R.; Wolfs, F. L. H.; Wosiek, B.; Wozniak, K.; Wuosmaa, A. H.; Wyslouch, B.

    2005-01-01

    This paper presents the analysis of the dynamic fluctuations in the inclusive charged particle multiplicity measured by PHOBOS for Au+Au collisions at surdsNN = 200GeV within the pseudo-rapidity range of -3 < η < 3. First the definition of the fluctuations observables used in this analysis is presented, together with the discussion of their physics meaning. Then the procedure for the extraction of dynamic fluctuations is described. Some preliminary results are included to illustrate the correlation features of the fluctuation observable. New dynamic fluctuations results will be available in a later publication.

  18. In Situ Redox Manipulation Field Injection Test Report - Hanford 100-H Area

    International Nuclear Information System (INIS)

    Fruchter, J.S.; Amonette, J.E.; Cole, C.R.

    1996-11-01

    This report presents results of an In Situ Redox Manipulation (ISRM) Field Injection Withdrawal Test performed at the 100-H Area of the US. Department of Energy's (DOE's) Hanford Site in Washington State in Fiscal Year 1996 by researchers at Pacific Northwest National Laboratory (PNNL). The test is part of the overall ISRM project, the purpose of which is to determine the potential for remediating contaminated groundwater with a technology based on in situ manipulation of subsurface reduction-oxidation (redox) conditions. The ISRM technology would be used to treat subsurface contaminants in groundwater zones at DOE sites

  19. Iron oxide redox chemistry and nuclear fuel disposal

    International Nuclear Information System (INIS)

    Jobe, D.J.; Lemire, R.J.; Taylor, P.

    1997-04-01

    Solubility and stability data for iron (III) oxides and aqueous Fe(II) and Fe(III) species are reviewed, and selected values are used to calculate potential-pH diagrams for the iron system at temperatures of 25 and 100 deg C, chloride activities {C1 - } = 10 -2 and 1 mol/kg, total carbonate activity {C T } = 10 -3 mol/kg, and iron(III) oxide/oxyhydroxide solubility products (25 deg C values) K sp = {Fe 3+ }{OH - } 3 = 10 -38.5 , 10 -40 and 10 -42 . The temperatures and anion concentrations bracket the range of conditions expected in a Canadian nuclear fuel waste disposal vault. The three solubility products represent a conservative upper limit, a most probable value, and a minimum credible value, respectively, for the iron oxides likely to be important in controlling redox conditions in a disposal vault for CANDU nuclear reactor fuel. Only in the first of these three cases do the calculated redox potentials significantly exceed values under which oxidative dissolution of the fuel may occur. (author)

  20. Synthesis of redox polymer nanobeads and nanocomposites for glucose biosensors.

    Science.gov (United States)

    Wang, Jen-Yuan; Chen, Lin-Chi; Ho, Kuo-Chuan

    2013-08-28

    Redox polymer nanobeads of branched polyethylenimine binding with ferrocene (BPEI-Fc) were synthesized using a simple chemical process. The functionality and morphology of the redox polymer nanobeads were investigated by Fourier transform infrared spectroscopy (FTIR) and transmission electron microscopy (TEM). This hydrophilic redox nanomaterial could be mixed with glucose oxidase (GOx) for drop-coating on a screen-printed carbon electrode (SPCE) for glucose sensing application. Electrochemical properties of the BPEI-Fc/GOx/SPCE prepared under different conditions were studied by cyclic voltammetry (CV). On the basis of these CV results, the synthetic condition of the BPEI-Fc/GOx/SPCE could be optimized. By incorporating conductive poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), the performance of a redox polymer nanobead–based enzyme electrode could be further improved. The influence of PEDOT:PSS on the nanocomposite enzyme electrode was discussed from the aspects of the apparent electron diffusion coefficient (D(app)) and the charge transfer resistance (R(ct)). The glucose-sensing sensitivity of the BPEI-Fc/PEDOT:PSS/GOx/SPCE is calculated to be 66 μA mM(–1) cm(–2), which is 2.5 times higher than that without PEDOT:PSS. The apparent Michaelis constant (K(M)(app)) of the BPEI-Fc/PEDOT:PSS/GOx/SPCE estimated by the Lineweaver–Burk plot is 2.4 mM, which is much lower than that of BPEI-Fc/GOx/SPCE (11.2 mM). This implies that the BPEI-Fc/PEDOT:PSS/GOx/SPCE can catalytically oxidize glucose in a more efficient way. The interference test was carried out by injection of glucose and three common interferences: ascorbic acid (AA), dopamine (DA), and uric acid (UA) at physiological levels. The interferences of DA (4.2%) and AA (7.8%) are acceptable and the current response to UA (1.6%) is negligible, compared to the current response to glucose.

  1. Noise and fluctuations an introduction

    CERN Document Server

    MacDonald, D K C

    2006-01-01

    An understanding of fluctuations and their role is both useful and fundamental to the study of physics. This concise study of random processes offers graduate students and research physicists a survey that encompasses both the relationship of Brownian Movement with statistical mechanics and the problem of irreversible processes. It outlines the basics of the physics involved, without the strictures of mathematical rigor.The three-part treatment starts with a general survey of Brownian Movement, including electrical Brownian Movement and ""shot-noise,"" Part two explores correlation, frequency

  2. Electrostatic fluctuations in soap films

    International Nuclear Information System (INIS)

    Dean, D.S.; Horgan, R.R.

    2002-01-01

    A field theory to describe electrostatic interactions in soap films, described by electric multilayers with a generalized thermodynamic surface-charging mechanism, is studied. In the limit where the electrostatic interactions are weak, this theory is exactly soluble. The theory incorporates in a consistent way, the surface-charging mechanism and the fluctuations in the electrostatic field that correspond to the zero-frequency component of the van der Waals force. It is shown that these terms lead to a Casimir-like attraction that can be sufficiently large to explain the transition between the common black film to a Newton black film

  3. Chaotic fluctuations in mathematical economics

    Energy Technology Data Exchange (ETDEWEB)

    Yoshida, Hiroyuki, E-mail: yoshida.hiroyuki@nihon-u.ac.jp [College of Economics, Nihon University, Chiyoda-ku, Tokyo 101-8360 (Japan)

    2011-03-01

    In this paper we examine a Cournot duopoly model, which expresses the strategic interaction between two firms. We formulate the dynamic adjustment process and investigate the dynamic properties of the stationary point. By introducing a memory mechanism characterized by distributed lag functions, we presuppose that each firm makes production decisions in a cautious manner. This implies that we have to deal with the system of integro-differential equations. By means of numerical simulations we show the occurrence of chaotic fluctuations in the case of fixed delays.

  4. Intracellular Redox Compartmentation and ROS-Related Communication in Regulation and Signaling.

    Science.gov (United States)

    Noctor, Graham; Foyer, Christine H

    2016-07-01

    Recent years have witnessed enormous progress in understanding redox signaling related to reactive oxygen species (ROS) in plants. The consensus view is that such signaling is intrinsic to many developmental processes and responses to the environment. ROS-related redox signaling is tightly wedded to compartmentation. Because membranes function as barriers, highly redox-active powerhouses such as chloroplasts, peroxisomes, and mitochondria may elicit specific signaling responses. However, transporter functions allow membranes also to act as bridges between compartments, and so regulated capacity to transmit redox changes across membranes influences the outcome of triggers produced at different locations. As well as ROS and other oxidizing species, antioxidants are key players that determine the extent of ROS accumulation at different sites and that may themselves act as signal transmitters. Like ROS, antioxidants can be transported across membranes. In addition, the intracellular distribution of antioxidative enzymes may be modulated to regulate or facilitate redox signaling appropriate to the conditions. Finally, there is substantial plasticity in organellar shape, with extensions such as stromules, peroxules, and matrixules playing potentially crucial roles in organelle-organelle communication. We provide an overview of the advances in subcellular compartmentation, identifying the gaps in our knowledge and discussing future developments in the area. © 2016 American Society of Plant Biologists. All Rights Reserved.

  5. Interaction between heavy metals and thiol-linked redox reactions in germination.

    Science.gov (United States)

    Smiri, M; Chaoui, A; Ferjani, E E

    2010-09-15

    Thioredoxin (TRX) proteins perform important biological functions in cells by changing the redox state of proteins via dithiol disulfide exchange. Several systems are able to control the activity, stability, and correct folding of enzymes through dithiol/disulfide isomerization reactions including the enzyme protein disulfide-isomerase, the glutathione-dependent glutaredoxin system, and the thioredoxin systems. Plants have devised sophisticated mechanisms to cope with biotic and abiotic stresses imposed by their environment. Among these mechanisms, those collectively referred to as redox reactions induced by endogenous systems. This is of agronomical importance since a better knowledge of the involved mechanisms can offer novel means for crop protection. In the plant life cycle, the seed and seedling stages are key developmental stages conditioning the final yield of crops. Both are very sensitive to heavy metal stress. Plant redox reactions are principally studied on adult plant organs and there is only very scarce informations about the onset of redox regulation at the level of seed germination. In the here presented study, we discussed the importance of redox proteins in plant cell metabolism and defence. Special focus is given to TRX, which are involved in detoxification of ROS and also to their targets.

  6. Powering Lithium-Sulfur Battery Performance by Propelling Polysulfide Redox at Sulfiphilic Hosts.

    Science.gov (United States)

    Yuan, Zhe; Peng, Hong-Jie; Hou, Ting-Zheng; Huang, Jia-Qi; Chen, Cheng-Meng; Wang, Dai-Wei; Cheng, Xin-Bing; Wei, Fei; Zhang, Qiang

    2016-01-13

    Lithium-sulfur (Li-S) battery system is endowed with tremendous energy density, resulting from the complex sulfur electrochemistry involving multielectron redox reactions and phase transformations. Originated from the slow redox kinetics of polysulfide intermediates, the flood of polysulfides in the batteries during cycling induced low sulfur utilization, severe polarization, low energy efficiency, deteriorated polysulfide shuttle, and short cycling life. Herein, sulfiphilic cobalt disulfide (CoS2) was incorporated into carbon/sulfur cathodes, introducing strong interaction between lithium polysulfides and CoS2 under working conditions. The interfaces between CoS2 and electrolyte served as strong adsorption and activation sites for polar polysulfides and therefore accelerated redox reactions of polysulfides. The high polysulfide reactivity not only guaranteed effective polarization mitigation and promoted energy efficiency by 10% but also promised high discharge capacity and stable cycling performance during 2000 cycles. A slow capacity decay rate of 0.034%/cycle at 2.0 C and a high initial capacity of 1368 mAh g(-1) at 0.5 C were achieved. Since the propelling redox reaction is not limited to Li-S system, we foresee the reported strategy herein can be applied in other high-power devices through the systems with controllable redox reactions.

  7. MICROSCALE METABOLIC, REDOX AND ABIOTIC REACTIONS IN HANFORD 300 AREA SUBSURFACE SEDIMENTS

    Energy Technology Data Exchange (ETDEWEB)

    Beyenal, Haluk [WSU; McLEan, Jeff [JCVI; Majors, Paul [PNNL; Fredrickson, Jim [PNNL

    2013-11-14

    The Hanford 300 Area is a unique site due to periodic hydrologic influence of river water resulting in changes in groundwater elevation and flow direction. This area is also highly subject to uranium remobilization, the source of which is currently believed to be the region at the base of the vadose zone that is subject to period saturation due to the changes in the water levels in the Columbia River. We found that microbial processes and redox and abiotic reactions which operate at the microscale were critical to understanding factors controlling the macroscopic fate and transport of contaminants in the subsurface. The combined laboratory and field research showed how microscale conditions control uranium mobility and how biotic, abiotic and redox reactions relate to each other. Our findings extended the current knowledge to examine U(VI) reduction and immobilization using natural 300 Area communities as well as selected model organisms on redox-sensitive and redox-insensitive minerals. Using innovative techniques developed specifically to probe biogeochemical processes at the microscale, our research expanded our current understanding of the roles played by mineral surfaces, bacterial competition, and local biotic, abiotic and redox reaction rates on the reduction and immobilization of uranium.

  8. Dynamical charge fluctuation at FAIR energy

    International Nuclear Information System (INIS)

    Ghosh, Somnath; Mukhopadhyay, Amitabha

    2015-01-01

    The Compressed Baryonic Matter (CBM) experiment to be held at the Facility for antiproton and ion research (FAIR) is being designed to investigate the baryonic matter under extreme thermodynamic conditions. The hot and dense matter produced in this experiment will be rich in baryon number. It would be worthwhile to examine how the signatures proposed for identifying and characterizing a baryon free QGP like state behave in a baryon rich environment. Event-by-event fluctuation of net electrical charge and/or baryon number is one such indicator of the formation of the QGP, used and tested in RHIC and LHC heavy-ion experiments. One starts by defining the net charge Q = (N + - N - ) and the total charge N ch = (N + + N - ) where the quantities N + and N - are respectively, the multiplicities of positively and negatively charged particles

  9. A Protocol for Electrochemical Evaluations and State of Charge Diagnostics of a Symmetric Organic Redox Flow Battery

    Energy Technology Data Exchange (ETDEWEB)

    Duan, Wentao; Vemuri, Rama S.; Hu, Dehong; Yang, Zheng; Wei, Xiaoliang

    2017-01-01

    Redox flow batteries have been considered as one of the most promising stationary energy storage solutions for improving the reliability of the power grid and deployment of renewable energy technologies. Among the many flow battery chemistries, nonaqueous flow batteries have the potential to achieve high energy density because of the broad voltage windows of nonaqueous electrolytes. However, significant technical hurdles exist currently limiting nonaqueous flow batteries to demonstrate their full potential, such as low redox concentrations, low operating currents, under-explored battery status monitoring, etc. In an attempt to address these limitations, we report a nonaqueous flow battery based on a highly soluble, redox-active organic nitronyl nitroxide radical compound, 2-phenyl-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide (PTIO). This redox materials exhibits an ambipolar electrochemical property with two reversible redox pairs that are moderately separated by a voltage gap of ~1.7 V. Therefore, PTIO can serve as both anolyte and catholyte redox materials to form a symmetric flow battery chemistry, which affords the advantages such as high effective redox concentrations and low irreversible redox material crossover. The PTIO flow battery shows decent electrochemical cyclability under cyclic voltammetry and flow cell conditions; an improved redox concentration of 0.5 M PTIO and operational current density of 20 mA cm-2 were achieved in flow cell tests. Moreover, we show that Fourier transform infrared (FTIR) spectroscopy could measure the PTIO concentrations during the PTIO flow battery cycling and offer reasonably accurate detection of the battery state of charge (SOC) as cross-validated by electron spin resonance measurements. This study suggests FTIR can be used as a reliable online SOC sensor to monitor flow battery status and ensure battery operations stringently in a safe SOC range.

  10. An Objective Fluctuation Score for Parkinson's Disease

    Science.gov (United States)

    Horne, Malcolm K.; McGregor, Sarah; Bergquist, Filip

    2015-01-01

    Introduction Establishing the presence and severity of fluctuations is important in managing Parkinson’s Disease yet there is no reliable, objective means of doing this. In this study we have evaluated a Fluctuation Score derived from variations in dyskinesia and bradykinesia scores produced by an accelerometry based system. Methods The Fluctuation Score was produced by summing the interquartile range of bradykinesia scores and dyskinesia scores produced every 2 minutes between 0900-1800 for at least 6 days by the accelerometry based system and expressing it as an algorithm. Results This Score could distinguish between fluctuating and non-fluctuating patients with high sensitivity and selectivity and was significant lower following activation of deep brain stimulators. The scores following deep brain stimulation lay in a band just above the score separating fluctuators from non-fluctuators, suggesting a range representing adequate motor control. When compared with control subjects the score of newly diagnosed patients show a loss of fluctuation with onset of PD. The score was calculated in subjects whose duration of disease was known and this showed that newly diagnosed patients soon develop higher scores which either fall under or within the range representing adequate motor control or instead go on to develop more severe fluctuations. Conclusion The Fluctuation Score described here promises to be a useful tool for identifying patients whose fluctuations are progressing and may require therapeutic changes. It also shows promise as a useful research tool. Further studies are required to more accurately identify therapeutic targets and ranges. PMID:25928634

  11. Kinetic and Thermodynamic Aspects of Cellular Thiol-Disulfide Redox Regulation

    DEFF Research Database (Denmark)

    Jensen, Kristine Steen; Hansen, Rosa Erritzøe; Winther, Jakob R

    2009-01-01

    . In the cytosol regulatory disulfide bonds are typically formed in spite of the prevailing reducing conditions and may thereby function as redox switches. Such disulfide bonds are protected from enzymatic reduction by kinetic barriers and are thus allowed to exist long enough to elicit the signal. Factors......Regulation of intracellular thiol-disulfide redox status is an essential part of cellular homeostasis. This involves the regulation of both oxidative and reductive pathways, production of oxidant scavengers and, importantly, the ability of cells to respond to changes in the redox environment...... that affect the rate of thiol-disulfide exchange and stability of disulfide bonds are discussed within the framework of the underlying chemical foundations. This includes the effect of thiol acidity (pKa), the local electrostatic environment, molecular strain and entropy. Even though a thiol-disulfide...

  12. A redox-assisted molecular assembly of molybdenum oxide amine composite nanobelts

    International Nuclear Information System (INIS)

    Luo Haiyan; Wei Mingdeng; Wei Kemei

    2011-01-01

    Research highlights: → Nanobelts of molybdenum oxide amine were first synthesized via a redox-assisted molecular assembly route. → These nanobelts are highly crystalline with a several tens of micrometers in length and 20-30 nm in thickness. - Abstract: In this paper, the nanobelts of molybdenum oxide amine composite were successfully synthesized via a redox-assisted molecular assembly route under the hydrothermal conditions. The synthesized nanobelts were characterized by XRD, SEM, TEM, TG and FT-IR measurements. The thickness of nanobelts is found to be ca. 20-30 nm and their lengths are up to several tens of micrometers. Based on a series of the experimental results, a possible model, redox-intercalation-exfoliation, was suggested for the formation of nanobelts of molybdenum oxide amine composite.

  13. Chaotic Dynamical Ferromagnetic Phase Induced by Nonequilibrium Quantum Fluctuations

    Science.gov (United States)

    Lerose, Alessio; Marino, Jamir; Žunkovič, Bojan; Gambassi, Andrea; Silva, Alessandro

    2018-03-01

    We investigate the robustness of a dynamical phase transition against quantum fluctuations by studying the impact of a ferromagnetic nearest-neighbor spin interaction in one spatial dimension on the nonequilibrium dynamical phase diagram of the fully connected quantum Ising model. In particular, we focus on the transient dynamics after a quantum quench and study the prethermal state via a combination of analytic time-dependent spin wave theory and numerical methods based on matrix product states. We find that, upon increasing the strength of the quantum fluctuations, the dynamical critical point fans out into a chaotic dynamical phase within which the asymptotic ordering is characterized by strong sensitivity to the parameters and initial conditions. We argue that such a phenomenon is general, as it arises from the impact of quantum fluctuations on the mean-field out of equilibrium dynamics of any system which exhibits a broken discrete symmetry.

  14. Conserved number fluctuations in a hadron resonance gas model

    International Nuclear Information System (INIS)

    Garg, P.; Mishra, D.K.; Netrakanti, P.K.; Mohanty, B.; Mohanty, A.K.; Singh, B.K.; Xu, N.

    2013-01-01

    Net-baryon, net-charge and net-strangeness number fluctuations in high energy heavy-ion collisions are discussed within the framework of a hadron resonance gas (HRG) model. Ratios of the conserved number susceptibilities calculated in HRG are being compared to the corresponding experimental measurements to extract information about the freeze-out condition and the phase structure of systems with strong interactions. We emphasize the importance of considering the actual experimental acceptances in terms of kinematics (pseudorapidity (η) and transverse momentum (p T )), the detected charge state, effect of collective motion of particles in the system and the resonance decay contributions before comparisons are made to the theoretical calculations. In this work, based on HRG model, we report that the net-baryon number fluctuations are least affected by experimental acceptances compared to the net-charge and net-strangeness number fluctuations

  15. Prediction of power fluctuation classes for photovoltaic installations and potential benefits of dynamic reserve allocation

    NARCIS (Netherlands)

    Nijhuis, M.; Rawn, B.G.; Gibescu, M.

    2014-01-01

    During partly cloudy conditions, the power delivered by a photovoltaic array can easily fluctuate by three quarters of its rated power in 10 s. Fluctuations from photovoltaics of this size and on this time scale may necessitate adding an additional component to power system secondary and primary

  16. Thermal crackling: study of the mechanical effects of quick temperature fluctuations on metallic surfaces

    International Nuclear Information System (INIS)

    Pradel, P.

    1984-05-01

    After a brief overview of the thermohydraulical conditions of liquid sodium leading to important temperature fluctuations near the metallic surfaces, the author examines the transfer modes of these fluctuations in the structure thickness and the long term mechanical effects. Dimensioning models based on thermal and metallurgical properties are under study for structures subject to such sodium loads [fr

  17. Le reazioni redox: un pasticcio concettuale?

    Directory of Open Access Journals (Sweden)

    Elena Ghibaudi

    2015-10-01

    Full Text Available Le reazioni di ossidoriduzione costituiscono un argomento centrale di qualsiasi corso di base di chimica, sia a livello scolastico che universitario. Il loro apprendimento comporta il superamento di svariati ostacoli concettuali, la cui difficoltà può risultare amplificata da prassi didattiche inadeguate. Gli errori più ricorrenti nel presentare l’argomento sono di due tipi: i fare implicitamente riferimento a modelli esplicativi distinti (es. il numero di ossidazione e il trasferimento elettronico, senza esplicitarli e senza evidenziarne la differente natura e il campo di validità; ii confondere il livello della spiegazione formale con quello della realtà fisica. I fenomeni redox sono normalmente interpretati sulla base di tre distinti modelli empirici, che fanno riferimento al trasferimento di atomi di ossigeno, di atomi di idrogeno, di elettroni; e di un quarto modello, formale, fondato sul cambiamento del numero di ossidazione. La confusione tra questi modelli può generare considerevoli problemi di apprendimento. Il presente lavoro riporta un’analisi critica delle implicazioni concettuali della didattica dei processi redox. L’analisi è articolata in tre sezioni: i disamina della evoluzione storica del concetto di ossidoriduzione; ii analisi dei modelli redox e del loro campo di validità; iii discussione di alcuni aspetti epistemologici inerenti i processi redox che sono rilevanti per la didattica della chimica.

  18. Mitochondrial Energy and Redox Signaling in Plants

    Science.gov (United States)

    Schwarzländer, Markus

    2013-01-01

    Abstract Significance: For a plant to grow and develop, energy and appropriate building blocks are a fundamental requirement. Mitochondrial respiration is a vital source for both. The delicate redox processes that make up respiration are affected by the plant's changing environment. Therefore, mitochondrial regulation is critically important to maintain cellular homeostasis. This involves sensing signals from changes in mitochondrial physiology, transducing this information, and mounting tailored responses, by either adjusting mitochondrial and cellular functions directly or reprogramming gene expression. Recent Advances: Retrograde (RTG) signaling, by which mitochondrial signals control nuclear gene expression, has been a field of very active research in recent years. Nevertheless, no mitochondrial RTG-signaling pathway is yet understood in plants. This review summarizes recent advances toward elucidating redox processes and other bioenergetic factors as a part of RTG signaling of plant mitochondria. Critical Issues: Novel insights into mitochondrial physiology and redox-regulation provide a framework of upstream signaling. On the other end, downstream responses to modified mitochondrial function have become available, including transcriptomic data and mitochondrial phenotypes, revealing processes in the plant that are under mitochondrial control. Future Directions: Drawing parallels to chloroplast signaling and mitochondrial signaling in animal systems allows to bridge gaps in the current understanding and to deduce promising directions for future research. It is proposed that targeted usage of new technical approaches, such as quantitative in vivo imaging, will provide novel leverage to the dissection of plant mitochondrial signaling. Antioxid. Redox Signal. 18, 2122–2144. PMID:23234467

  19. Methods for using redox liposome biosensors

    Science.gov (United States)

    Cheng, Quan; Stevens, Raymond C.

    2002-01-01

    The present invention provides methods and compositions for detecting the presence of biologically-important analytes by using redox liposome biosensors. In particular, the present invention provides liposome/sol-gel electrodes suitable for the detection of a wide variety of organic molecules, including but not limited to bacterial toxins.

  20. Redox processes in radiation biology and cancer

    International Nuclear Information System (INIS)

    Greenstock, C.L.

    1981-01-01

    Free-radical intermediates, particularly the activated oxygen species OH, O - 2 , and 1 O 2 , are implicated in many types of radiation damage to biological systems. In addition, these same species may be formed, either directly or indirectly through biochemical redox reactions, in both essential and aberrant metabolic processes. Cell survival and adaptation to an environment containing ionizing radiation and other physical and chemical carcinogens ultimately depend upon the cell's ability to maintain optimal function in response to free-radical damage at the chemical level. Many of these feedback control mechanisms are redox controlled. Radiation chemical techniques using selective radical scavengers, such as product analysis and pulse radiolysis, enable us to generate, observe, and characterize individually the nature and reactivity of potentially damaging free radicals. From an analysis of the chemical kinetics of free-radical involvement in biological damage, redox mechanisms are proposed to describe the early processes of radiation damage, redox mechanisms are proposed to describe the early processes of radiation damage, its protection and sensitization, and the role of free radicals in radiation and chemical carcinogenesis

  1. Redox regulation in cancer stem cells

    Science.gov (United States)

    Reactive oxygen species (ROS) and ROS-dependent (redox regulation) signaling pathways and transcriptional activities are thought to be critical in stem cell self-renewal and differentiation during growth and organogenesis. Aberrant ROS burst and dysregulation of those ROS-dependent cellular processe...

  2. Investigating improvements on redox flow batteries

    CSIR Research Space (South Africa)

    Swartbooi, AM

    2006-09-01

    Full Text Available storage devices coupled to most of their applications. Lead-acid batteries have long been used as the most economical option to store electricity in many small scale applications, but lately more interest have been shown in redox flow batteries. The low...

  3. Redox cycling of potential antitumor aziridinylquinones

    NARCIS (Netherlands)

    Lusthof, Klaas J.; de Mol, Nicolaas J.; Richter, Wilma; Janssen, Lambert H.M.; Butler, John; Hoey, Brigid M.; Verboom, Willem; Reinhoudt, David

    1992-01-01

    The formation of reactive oxygen intermediates (ROI) during redox cycling of newly synthetized potential antitumor 2,5-bis (1-aziridinyl)-1,4-benzoquinone (BABQ) derivatives has been studied by assaying the production of ROI (superoxide, hydroxyl radical, and hydrogen peroxide) by xanthine oxidase

  4. Redox Control of Skeletal Muscle Regeneration.

    Science.gov (United States)

    Le Moal, Emmeran; Pialoux, Vincent; Juban, Gaëtan; Groussard, Carole; Zouhal, Hassane; Chazaud, Bénédicte; Mounier, Rémi

    2017-08-10

    Skeletal muscle shows high plasticity in response to external demand. Moreover, adult skeletal muscle is capable of complete regeneration after injury, due to the properties of muscle stem cells (MuSCs), the satellite cells, which follow a tightly regulated myogenic program to generate both new myofibers and new MuSCs for further needs. Although reactive oxygen species (ROS) and reactive nitrogen species (RNS) have long been associated with skeletal muscle physiology, their implication in the cell and molecular processes at work during muscle regeneration is more recent. This review focuses on redox regulation during skeletal muscle regeneration. An overview of the basics of ROS/RNS and antioxidant chemistry and biology occurring in skeletal muscle is first provided. Then, the comprehensive knowledge on redox regulation of MuSCs and their surrounding cell partners (macrophages, endothelial cells) during skeletal muscle regeneration is presented in normal muscle and in specific physiological (exercise-induced muscle damage, aging) and pathological (muscular dystrophies) contexts. Recent advances in the comprehension of these processes has led to the development of therapeutic assays using antioxidant supplementation, which result in inconsistent efficiency, underlying the need for new tools that are aimed at precisely deciphering and targeting ROS networks. This review should provide an overall insight of the redox regulation of skeletal muscle regeneration while highlighting the limits of the use of nonspecific antioxidants to improve muscle function. Antioxid. Redox Signal. 27, 276-310.

  5. Redox Modulations, Antioxidants, and Neuropsychiatric Disorders

    Directory of Open Access Journals (Sweden)

    Erik A. Fraunberger

    2016-01-01

    Full Text Available Although antioxidants, redox modulations, and neuropsychiatric disorders have been widely studied for many years, the field would benefit from an integrative and corroborative review. Our primary objective is to delineate the biological significance of compounds that modulate our redox status (i.e., reactive species and antioxidants as well as outline their current role in brain health and the impact of redox modulations on the severity of illnesses. Therefore, this review will not enter into the debate regarding the perceived medical legitimacy of antioxidants but rather seek to clarify their abilities and limitations. With this in mind, antioxidants may be interpreted as natural products with significant pharmacological actions in the body. A renewed understanding of these often overlooked compounds will allow us to critically appraise the current literature and provide an informed, novel perspective on an important healthcare issue. In this review, we will introduce the complex topics of redox modulations and their role in the development of select neuropsychiatric disorders.

  6. Currency speculation and dollar fluctuations

    Directory of Open Access Journals (Sweden)

    Stephan Schulmeister

    1988-12-01

    Full Text Available In this study the reasons behind the wide fluctuations of the dollar exchange rate following the breakdown of the Bretton Woods system, for the most part unexplained by the prevailing exchange rate theories, are explored. To do so, the author investigates the exchange rate between the two most traded currencies, the dollar and the deutschemark, from 1973 to 1988. In the first part, the pattern of the daily exchange rate movements is examined to show that a sequence of upward and downward trends interrupted by non-directional movements is typical of exchange rate dynamics in the short run. Moreover, this pattern is systemically exploited through currency speculation, particularly through the use of “technical analysis”. In the second part, the author focuses on the medium-term, arguing that fluctuations can be explained as the result of interacting disequilibria in the goods and asset markets. Although currency speculation has been systemically profitable for most currencies, it should be considered to be destabilizing since the sequence of price runs caused large and persistent deviations of exchange rates from their equilibrium values (purchasing power parity.

  7. Entropic fluctuations in DNA sequences

    Science.gov (United States)

    Thanos, Dimitrios; Li, Wentian; Provata, Astero

    2018-03-01

    The Local Shannon Entropy (LSE) in blocks is used as a complexity measure to study the information fluctuations along DNA sequences. The LSE of a DNA block maps the local base arrangement information to a single numerical value. It is shown that despite this reduction of information, LSE allows to extract meaningful information related to the detection of repetitive sequences in whole chromosomes and is useful in finding evolutio