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Sample records for changing redox conditions

  1. Modeling CO2 sediment-water flux variations connected with changes of redox conditions

    NASA Astrophysics Data System (ADS)

    Yakushev, Evgeniy; Protsenko, Elizaveta

    2013-04-01

    Changes of bottom redox conditions from oxic to hypoxic, suboxic and anoxic affect rates of sediment-water fluxes of chemical parameters, i.e. oxygen, nutrient (including carbon), redox metals. Chemosynthetic organic matter production in suboxic and anoxic conditions additionally affects transformation of carbon. This work aimed in estimation of a potential influence of changes of the bottom redox conditions on the sediment -water fluxes of carbon. We use a 1-dimensional C-N-P-Si-O-S-Mn-Fe vertical transport-reaction model describing both the sediments and bottom boundary layers coupled with biogeochemical block simulating changeable redox conditions, and the carbonate system processes block. A biogeochemical block is based on ROLM (RedOx Layer Model), that was constructed to simulate basic features of the water column biogeochemical structure changes in oxic, anoxic and changeable conditions (Yakushev et al., 2007). Organic matter formation and decay, reduction and oxidation of species of nitrogen, sulfur, manganese, iron, and the transformation of phosphorus species are parameterized in the model. The model includes blocks for phytoplankton, zooplankton, aerobic autotrophic and heterotrophic bacteria and anaerobic autotrophic and heterotrophic bacteria. In this study we additionally parameterized transformation of Si and C and forms of alkalinity. We simulate changes in the bottom boundary layer pH in different redox conditions under the same leakage scenario.

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

    NASA Astrophysics Data System (ADS)

    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

  3. Effects of changing redox conditions on the dynamics of dissolved organic matter and CO2 in paddy soils

    NASA Astrophysics Data System (ADS)

    Hanke, Alexander; Cao, Zhi Hong; Liu, Qin; Muhr, Jan; Kalbitz, Karsten

    2010-05-01

    The current knowledge about dissolved organic matter (DOM) dynamics in soils and its dependence on different C pools based mainly on observations and experiments in aerobic environments. We have only a limited understanding about the effects of changing redox conditions on production and composition of DOM although this fraction of soil organic matter is important for greenhouse gas emission and carbon storage in soils. In many ecosystems temporal and spatial changes of oxic and anoxic conditions are evident and might even increase in future. It is assumed that changing redox conditions are the key drivers of DOM dynamics in such ecosystems. More detailed we tested the following hypotheses: Anoxic conditions result in relative DOM accumulation due to less mineralization of already produced DOM Close relationship between DOM production and CO2 emission 14C signature of CO2 enables the identification of different C pools degraded at oxic and anoxic conditions We chose paddy soils as a model ecosystem because these soils are anoxic during the rice growing period and oxic during harvest and growth of other crops. Furthermore, paddy soils have oxic and anoxic horizons. Soils of a unique chronosequence of paddy soil evolution (50 to 2000 years, China) were studied in direct comparison to non-paddy soils of the same age. In these soils, exposed to different redox conditions over defined periods of times, the dynamics of DOM, CO2, 14C of the CO2 and other redox sensitive elements were followed in laboratory experiments. In the latter redox conditions were changed every 3 weeks from oxic to anoxic and vice versa. Besides analysis of the composition of the soil solution and the gas phase we determined differences in C pools being respired at oxic and anoxic conditions by 14C AMS of the CO2. The measured redox potentials of -50 mV to 250mV at anoxic conditions and 350 mV to 550 mV at oxic conditions were in the expected range and proofed the appropriate setting of the chosen

  4. Rapid changes in the redox conditions of the western Tethys Ocean during the early Aptian oceanic anoxic event

    NASA Astrophysics Data System (ADS)

    Westermann, Stéphane; Stein, Melody; Matera, Virginie; Fiet, Nicolas; Fleitmann, Dominik; Adatte, Thierry; Föllmi, Karl B.

    2013-11-01

    The early Aptian (125 to 121 Ma) records an episode of severe environmental change including a major perturbation of the carbon cycle, an oceanic anoxic event (OAE 1a, 122.5 Ma), a platform drowning episode and a biocalcification crisis. We propose to trace changes in the oxygenation state of the ocean during the early Aptian anoxic event using the redox-sensitive trace-element (RSTE) distribution, phosphorus accumulation rates (PARs) and organic-matter characterization in three different basins of the western Tethys. The following sections have been investigated: Gorgo a Cerbara (central Italy) in the Umbria Marche basin, Glaise (SE France) in the Vocontian basin and Cassis/La Bédoule (SE France) located in the Provencal basin. In the Gorgo a Cerbara section, RSTE distributions show a low background level along the main part of the section, contrasted by different maxima in concentrations within the Selli level. In the Glaise section, the Goguel level displays a weak increase in RSTE contents coeval with moderate TOC values. At Cassis/La Bédoule, no significant RSTE enrichments have been observed in sediments equivalent to the Selli level. These differences in the records of the geochemical proxies of the Selli level or its equivalent indicate the deposition under different redox conditions, probably related to the paleogeography. Our data indicate the development of anoxic-euxinic conditions in the deeper part of the Tethys during OAE 1a, whereas in the shallower environments, conditions were less reducing. Moreover, at Gorgo a Cerbara, the Selli level is characterized by rapid changes in the intensity of reducing conditions in the water column. Ocean eutrophication seems to be a major factor in the development and the persistence of anoxia as suggested by the PAR evolution. Higher PAR values at the onset of OAE 1a suggest an increase in nutrient input, whereas the return to lower values through the first part of the OAE 1a interval may be related to the

  5. Redox conditions for mantle plumes

    NASA Astrophysics Data System (ADS)

    Heister, L. E.; Lesher, C. E.

    2005-12-01

    The vanadium to scandium ratio (V/Sc) for basalts from mid-ocean ridge (MOR) and arc environments has been proposed as a proxy for fO2 conditions during partial melting (e.g. [1] and [2]). Contrary to barometric measurements of the fO2 of primitive lavas, the V/Sc ratio of the upper mantle at mid-ocean ridges and arcs is similar, leading previous authors to propose that the upper mantle has uniform redox potential and is well-buffered. We have attempted to broaden the applicability of the V/Sc parameter to plume-influenced localities (both oceanic and continental), where mantle heterogeneities associated with recycled sediments, mafic crust, and metasomatized mantle, whether of shallow or deep origin, exist. We find that primitive basalts from the North Atlantic Igneous Province (NAIP), Hawaii (both the Loa and Kea trends), Deccan, Columbia River, and Siberian Traps show a range of V/Sc ratios that are generally higher (average ~9) than those for MOR (average ~ 6.7) or arc (average ~7) lavas. Based on forward polybaric decompression modeling, we attribute these differences to polybaric melting and melt segregation within the garnet stability field rather than the presence of a more oxidized mantle in plume-influenced settings. Like MORB, the V/Sc ratios for plume-influenced basalts can be accounted for by an oxidation state approximately one log unit below the Ni-NiO buffer (NNO-1). Our analysis suggests that source heterogeneities have little, if any, resolvable influence on mantle redox conditions, although they have significant influence on the trace element and isotopic composition of mantle-derived melts. We suggest that variations in the redox of erupted lavas is largely a function of shallow lithospheric processes rather than intrinsic to the mantle source, regardless of tectonic setting. [1] Li and Lee (2004) EPSL, [2] Lee et al. (2005) J. of Petrology

  6. Minor Elements in Nakhlite Pyroxenes: Does Cr Record Changes in REDOX Conditions during Crystallization?

    NASA Technical Reports Server (NTRS)

    McKay, G.; Schwandt, C.; Le, L.; Mikouchi, T.

    2007-01-01

    Nakhlites are olivine-bearing clinopyroxene cumulates. Based on petrographic characteristics, they may be divided into groups that cooled at different rates and may have been formed at different depths in a single flow. The order of cooling rate from slowest to fastest is NWA998conditions under which these samples crystallized. Thus it is important to understand the major and minor element zoning in the cumulus pyroxenes. While major elements are nearly homogeneous, minor elements exhibit distinctive zoning patterns that vary from one nakhlite to another. This abstract reports unusual Cr zoning patterns in pyroxenes from MIL03346 (MIL) and contrast these with pyroxenes from Y593 and Nakhla.

  7. Method for characterization of the redox condition of cementitious materials

    SciTech Connect

    Almond, Philip M.; Langton, Christine A.; Stefanko, David B.

    2015-12-22

    Disclosed are methods for determining the redox condition of cementitious materials. The methods are leaching methods that utilize an in situ redox indicator that is present in the cementitious materials as formed. The in situ redox indicator leaches from cementitious material and, when the leaching process is carried out under anaerobic conditions can be utilized to determine the redox condition of the material. The in situ redox indicator can exhibit distinct characteristics in the leachate depending upon the redox condition of the indicator.

  8. Changes in depth-transect redox conditions spanning the end-Permian mass extinction and their impact on the marine extinction: Evidence from biomarkers and sulfur isotopes

    NASA Astrophysics Data System (ADS)

    Kaiho, Kunio; Oba, Masahiro; Fukuda, Yoshihiko; Ito, Kosuke; Ariyoshi, Shun; Gorjan, Paul; Riu, Yuqing; Takahashi, Satoshi; Chen, Zhong-Qiang; Tong, Jinnan; Yamakita, Satoshi

    2012-08-01

    Changes in redox conditions during the Changhsingian to Griesbachian spanning the end-Permian mass extinction were recently reported based on analyses of organic molecules. We provide more precise organic-molecular data, that detail redox conditions spanning the end-Permian mass extinction at different palaeowater depths in the neritic Palaeotethys (estimated water depths: 10, 40, 100, and 200 m; Bulla, Huangzhishan, Meishan, and Chaohu sections, respectively) during this period. Here we propose that a change from occasional euxinia to anoxia in the shallow Palaeotethys occurred at the time of the mass extinction intercalated with oxic pulses. The second extinction at 0.7 myr after the main extinction was also caused by anoxia. New and published sulfur-isotope ratios (34S/32S) measured in carbonate-associated sulfate from the neritic Palaeotethys and in sulfide from pelagic central Panthalassa sediments show high values during the Changhsingian, consistent with the development of euxinia. The mass extinction coincided with a global fall in δ34S values, as well as a shift in δ13C values, indicating a global oxidation of H2S. This organic and isotopic geochemistry implies that accumulation of hydrogen sulfide in intermediate and deep waters followed by oxidation of hydrogen sulfide led to dissolved oxygen consumption, surface-water anoxia, and acidification, resulting in the end-Permian mass extinction in the seas.

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

    NASA Astrophysics Data System (ADS)

    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.

  10. Modelling sulfamethoxazole degradation under different redox conditions

    NASA Astrophysics Data System (ADS)

    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

  11. Redox Conditions Among the Terrestrial Planets

    NASA Technical Reports Server (NTRS)

    Jones, J. H.

    2004-01-01

    Early solar system conditions should have been extremely reducing. The redox state of the early solar nebula was determined by the H2O/H2 of the gas, which is calculated (based on solar composition) to have been about IW-5. At high temperature under such conditions, ferrous iron would exist only as a trace element in silicates and the most common type of chondritic material should have been enstatite chondrites. The observation that E-chondrites form only a subset of the chondrite suite and that the terrestrial planets (Earth, Moon, Mars, Venus, 4 Vesta) contain ferrous and ferric iron as major and minor elements, respectively, implies that either most chondritic materials formed under conditions that were not solar or that early-formed metals oxidized at low temperature, producing FeO. For example, equilibrated ordinary chondrites (by definition, common chondritic materials), by their phase assemblage of olivine, orthopyroxene and metal, must fall not far from the QFI (Quartz-Fayalite-Iron) oxygen buffer. The QFI buffer is about IW-0.5 and, as we shall see, this fo2 is close to that inferred for many materials in the inner solar system.

  12. New lab scale approaches for quantification of redox conditions

    NASA Astrophysics Data System (ADS)

    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

  13. Conformational changes in redox pairs of protein structures

    PubMed Central

    Fan, Samuel W; George, Richard A; Haworth, Naomi L; Feng, Lina L; Liu, Jason Y; Wouters, Merridee A

    2009-01-01

    Disulfides are conventionally viewed as structurally stabilizing elements in proteins but emerging evidence suggests two disulfide subproteomes exist. One group mediates the well known role of structural stabilization. A second redox-active group are best known for their catalytic functions but are increasingly being recognized for their roles in regulation of protein function. Redox-active disulfides are, by their very nature, more susceptible to reduction than structural disulfides; and conversely, the Cys pairs that form them are more susceptible to oxidation. In this study, we searched for potentially redox-active Cys Pairs by scanning the Protein Data Bank for structures of proteins in alternate redox states. The PDB contains over 1134 unique redox pairs of proteins, many of which exhibit conformational differences between alternate redox states. Several classes of structural changes were observed, proteins that exhibit: disulfide oxidation following expulsion of metals such as zinc; major reorganisation of the polypeptide backbone in association with disulfide redox-activity; order/disorder transitions; and changes in quaternary structure. Based on evidence gathered supporting disulfide redox activity, we propose disulfides present in alternate redox states are likely to have physiologically relevant redox activity. PMID:19598234

  14. INFLUENCE OF PH AND REDOX CONDITIONS ON COPPER LEACHING

    EPA Science Inventory

    Leaching behavior of metals from a mineral processing waste at varying pH and redox conditions was studies. Effect of combinations of pH and Eh on leaching of copper is described. Leaching of copper was found to be dependent on both pH and Eh. Higher concentrations of Cu were ...

  15. Microbial Functional Gene Diversity with a Shift of Subsurface Redox Conditions during In Situ Uranium Reduction

    PubMed Central

    Liang, Yuting; Van Nostrand, Joy D.; N′Guessan, Lucie A.; Peacock, Aaron D.; Deng, Ye; Long, Philip E.; Resch, C. Tom; Wu, Liyou; He, Zhili; Li, Guanghe; Hazen, Terry C.; Lovley, Derek R.

    2012-01-01

    To better understand the microbial functional diversity changes with subsurface redox conditions during in situ uranium bioremediation, key functional genes were studied with GeoChip, a comprehensive functional gene microarray, in field experiments at a uranium mill tailings remedial action (UMTRA) site (Rifle, CO). The results indicated that functional microbial communities altered with a shift in the dominant metabolic process, as documented by hierarchical cluster and ordination analyses of all detected functional genes. The abundance of dsrAB genes (dissimilatory sulfite reductase genes) and methane generation-related mcr genes (methyl coenzyme M reductase coding genes) increased when redox conditions shifted from Fe-reducing to sulfate-reducing conditions. The cytochrome genes detected were primarily from Geobacter sp. and decreased with lower subsurface redox conditions. Statistical analysis of environmental parameters and functional genes indicated that acetate, U(VI), and redox potential (Eh) were the most significant geochemical variables linked to microbial functional gene structures, and changes in microbial functional diversity were strongly related to the dominant terminal electron-accepting process following acetate addition. The study indicates that the microbial functional genes clearly reflect the in situ redox conditions and the dominant microbial processes, which in turn influence uranium bioreduction. Microbial functional genes thus could be very useful for tracking microbial community structure and dynamics during bioremediation. PMID:22327592

  16. Evaluation of redox condition by selenium speciation coprecipitated with barite

    NASA Astrophysics Data System (ADS)

    Tokunaga, K.; Takahashi, Y.; Yokoyama, Y.; Omori, E.; Kawagucci, S.

    2012-12-01

    Redox potential (Eh) is an important factor controlling chemical processes in hydrosphere on the earth, because redox reactions are related to the behaviors of many major and minor species in natural waters. The Eh may be estimated by the information of the oxidation states of redox couples (e.g., Fe(II)/Fe(III) ratio) since the Eh value tends to be controlled by the major elements. In this study, we suggest to use selenium (Se) in barite (BaSO4) as a redox indicator for hydrothermal system where barite is precipitated. Barite is stable under a high P-T condition, and this mineral contains various trace elements that may reflect the physicochemical condition of the seawater and hydrothermal water where they were formed. Selenium can occur in the environment in several oxidation states (-2, 0, +4 and +6), but Se in natural waters is mostly found in inorganic forms as oxyanions of selenite [Se(IV)] or selenate [Se(VI)]. The valence ratio of Se depends on the redox condition. Selenium is often found in minerals by substituting a site of sulfur (S) since they are homologous element. Both Se(IV) and Se(VI) may be incorporated into barite because barite is stable under a wide range of the Eh-pH condition which includes Se(IV)-Se(VI) boundary in the Eh-pH diagram. Therefore, the oxidation state of Se in barite can provide more precise information on the redox condition of the depositional environment. The purpose of this study is to establish a method to estimate the redox condition where barite is precipitated. Coprecipitation experiments of Se with barite were conducted to clarify the relationships between Se(VI)/Se(VI) ratio in artificial seawater (ASW) and that in barite at pH 8.0 and pH 4.0. These experiments were employed to evaluate the relationship between aqueous Se(VI) fraction (RwVI) and that incorporated into barite (RbVI). The initial pH of ASW was adjusted to 4.0 and 8.0 before the barite precipitation. These two pH conditions were adopted considering

  17. Redox-dependent functional switching of plant proteins accompanying with their structural changes

    PubMed Central

    Chi, Yong Hun; Paeng, Seol Ki; Kim, Min Ji; Hwang, Gwang Yong; Melencion, Sarah Mae B.; Oh, Hun Taek; Lee, Sang Yeol

    2013-01-01

    Reactive oxygen species (ROS) can be generated during the course of normal aerobic metabolism or when an organism is exposed to a variety of stress conditions. It can cause a widespread damage to intracellular macromolecules and play a causal role in many degenerative diseases. Like other aerobic organisms plants are also equipped with a wide range of antioxidant redox proteins, such as superoxide dismutase, catalase, glutaredoxin, thioredoxin (Trx), Trx reductase, protein disulfide reductase, and other kinds of peroxidases that are usually significant in preventing harmful effects of ROS. To defend plant cells in response to stimuli, a part of redox proteins have shown to play multiple functions through the post-translational modification with a redox-dependent manner. For the alternative switching of their cellular functions, the redox proteins change their protein structures from low molecular weight to high molecular weight (HMW) protein complexes depending on the external stress. The HMW proteins are reported to act as molecular chaperone, which enable the plants to enhance their stress tolerance. In addition, some transcription factors and co-activators have function responding to environmental stresses by redox-dependent structural changes. This review describes the molecular mechanism and physiological significance of the redox proteins, transcription factors and co-activators to protect the plants from environmental stresses through the redox-dependent structural and functional switching of the plant redox proteins. PMID:23898340

  18. Changes in productivity and redox conditions during the Last Glacial Maximum as recorded in high-resolution geochemical records from Alfonso Basin, Gulf of California

    NASA Astrophysics Data System (ADS)

    Choumiline, K.; Lyons, T. W.; Carriquiry, J. D.; Perez-Cruz, L. L.; Beaufort, L.

    2015-12-01

    The Last Glacial Maximum represents the most recent major sea level low stand in Earth history. Such changes in eustatic sea level impacted the oxygenation of marine basins, yet the characteristics and mechanisms of those impacts remain poorly known. Specific basin conditions are needed to develop, record, and preserve those paleoredox changes through time most effectively, including rapid sedimentation rates and silled basin morphologies. The anoxic Alfonso Basin, partially separated from the Gulf of California by a bathymetric sill, is such a place. The basin is located in a dry semiarid region dominated by dust inputs and only occasional tropical cyclone-induced fluvial contributions. We present the first multi-proxy reconstruction of southern Gulf of California paleoredox that covers an uninterrupted timespan from the Late Pleistocene to the present, with an emphasis on the Last Glacial Maximum. In this research we contrast geochemical data from a 47-meter-long sediment core (collected with the giant CALYPSO corer aboard the R/V Marion Dufresne) with the solid phase and pore water chemical data from a shorter but very detailed box core (collected on the R/V El Puma), both from Alfonso Basin. Our results show that during the Late Pleistocene and throughout the Holocene several paleoredox shifts occurred, often accompanied by differences in lamination (laminated/massive alternations) and trace element (Mo, V, U) compositions; detailed Fe chemistry (FeHR/FeTand Fe/Al ratios); as well as carbon and sulfur concentrations and isotope ratios. For example, FeHR/FeT ratios indicate values of roughly 0.15 during the Last Glacial Maximum (lower than theoretic threshold of 0.2 between oxic and anoxic), suggesting more oxic conditions, in comparison to 0.25 and higher in the Holocene. Most of the variability seen in these proxies is related to global sea level change, while some variability is instead related to local variations in paleoproductivity, often connected to

  19. Microbial communities acclimate to recurring changes in soil redox potential status

    SciTech Connect

    DeAngelis, Kristen M.; Silver, Whendee; Thompson, Andrew; Firestone, Mary K.

    2010-12-03

    Rapidly fluctuating environmental conditions can significantly stress organisms, particularly when fluctuations cross thresholds of normal physiological tolerance. Redox potential fluctuations are common in humid tropical soils, and microbial community acclimation or avoidance strategies for survival will in turn shape microbial community diversity and biogeochemistry. To assess the extent to which indigenous bacterial and archaeal communities are adapted to changing in redox potential, soils were incubated under static anoxic, static oxic or fluctuating redox potential conditions, and the standing (DNA-based) and active (RNA-based) communities and biogeochemistry were determined. Fluctuating redox potential conditions permitted simultaneous CO{sub 2} respiration, methanogenesis, N{sub 2}O production and iron reduction. Exposure to static anaerobic conditions significantly changed community composition, while 4-day redox potential fluctuations did not. Using RNA: DNA ratios as a measure of activity, 285 taxa were more active under fluctuating than static conditions, compared with three taxa that were more active under static compared with fluctuating conditions. These data suggest an indigenous microbialcommunity adapted to fluctuating redox potential.

  20. Redox conditions in sediments and during sedimentation in the Ontong Java Plateau, west equatorial Pacific

    NASA Astrophysics Data System (ADS)

    Lu, Bo; Li, Tiegang; Yu, Xinke; Chang, Fengming; Nan, Qingyun

    2011-11-01

    Redox-sensitive elements in sediments, such as manganese (Mn), vanadium (V), molybdenum (Mo), and uranium (U), are promising indicators of past redox conditions during sedimentation and early diagenesis. However, in the Ontong Java Plateau, west equatorial Pacific, there are sparse datasets of redox-sensitive elements in sediment cores. Here, we present a 250 ka record of redox sensitive elements from a 460 cm gravity core at site WP7 (3°56'S, 156°E, water depth 1 800 m), which was recovered from the southwest Ontong Java Plateau during the 1993 cruise of R/V Science I of the Institute of Oceanology, Chinese Academy of Sciences (IOCAS). Relative to the Post-Archean Australian Shale (PAAS), authigenic Mn, cobalt (Co), nickel (Ni), Mo, V, U, and cadmium (Cd) were found at constantly low levels except when peaks occurred at several depth intervals. Manganese, Co, Ni, and Mo concentrations were elevated at 25-35 cm due to Mn redox cycling. The core was divided into three distinct sections, the top 0-25 cm being oxic, a suboxic section at 25-35 cm and from 35-460 cm which was anoxic. Differential authigenic enrichments of Co, Ni, Mo, V, U, and Cd at the same depth intervals were observed indicating that the enrichments happened during sedimentation or diagenesis and suffered no post settlement redox changes. Therefore, no significant changes in redox conditions during sedimentation must have happened. The water at depth on the Ontong Java Plateau during past 250 ka must have been well oxygenated, possibly resulted from the more or less continuous presence of oxygen-rich deep water like the modern Antarctic Intermediate Water (AAIW) and Antarctic Circumpolar Water (ACW); while it's slightly less oxygenated in glacial intervals, possibly due to ventilation weakening and/or the surface productivity increase.

  1. Pyrite framboid diameter distribution in the Lower Oligocene black shales of the Vrancea Nappe as an indicator of changes in redox conditions, Eastern Outer Carpathians, Romania

    NASA Astrophysics Data System (ADS)

    Wendorff, Małgorzata; Marynowski, Leszek; Rospondek, Mariusz

    2016-04-01

    Studies of recent and ancient sediments revealed that the diameter distribution of pyrite framboids may be reliably used to characterise oxygen-restricted environments and distinguish ancient euxinic conditions (water column hydrogen sulphide bearing thus oxygen-free) from anoxic, non-sulfidic or dysoxic (oxygen-poor) conditions. Such diagnoses are of great importance when reconstructing palaeoenvironments in ancient basins and the processes of source rocks formation. During Oligocene to early Miocene time an extensive accumulation of organic matter (OM)-rich sediments occurred in the entire Paratethys including the Carpathian Foredeep, which was closed forming fold-thrust belt of the Outer Carpathians. These OM-rich black shales are represented by so-called Menilite shales, widely considered as hydrocarbon source rocks, which constitute as well a detailed archive for palaeoenvironmental changes. The purpose of this preliminary study is to characterise the depositional environment of the Lower Oligocene black shales basing on the pyrite framboid diameter distribution. Five samples of finely laminated black shales were selected from the Nechit section outcropping in the Bistrica half-window of the Vrancea Nappe in the Eastern Outer Carpathians, E Romania. At least 100 framboid diameters were measured on polished blocks using scanning electron microscope in a back-scattered electron mode. Framboids from four samples starting from the lowermost part of the section exhibit a narrow range of diameters from 1.0 to 11.5 μm; mean value ranges from 3.65 to 4.85 μm. Small-sized framboids (< 6 μm) account for 70% up to 91% of all framboids, while large framboids (>10 μm) are absent or rare (max. 2%). Within the sample from the uppermost part of the section framboids reveal more variable sizes, 2 - 25 μm, with mean value of 6.63 μm. Small framboids are still numerous (54%), however the amount of framboids >10 μm increases to 15%. The domination of small framboids with

  2. Is vanadate reduced by thiols under biological conditions? Changing the redox potential of V(V)/V(IV) by complexation in aqueous solution.

    PubMed

    Crans, Debbie C; Zhang, Boyan; Gaidamauskas, Ernestas; Keramidas, Anastasios D; Willsky, Gail R; Roberts, Chris R

    2010-05-01

    Although dogma states that vanadate is readily reduced by glutathione, cysteine, and other thiols, there are several examples documenting that vanadium(V)-sulfur complexes can form and be observed. This conundrum has impacted life scientists for more than two decades. Investigation of this problem requires an understanding of both the complexes that form from vanadium(IV) and (V) and a representative thiol in aqueous solution. The reactions of vanadate and hydrated vanadyl cation with 2-mercaptoethanol have been investigated using multinuclear NMR, electron paramagnetic resonance (EPR), and UV-vis spectroscopy. Vanadate forms a stable complex of 2:2 stoichiometry with 2-mercaptoethanol at neutral and alkaline pH. In contrast, vanadate can oxidize 2-mercaptoethanol; this process is favored at low pH and high solute concentrations. The complex that forms between aqueous vanadium(IV) and 2-mercaptoethanol has a 1:2 stoichiometry and can be observed at high pH and high 2-mercaptoethanol concentration. The solution structures have been deduced based on coordination induced chemical shifts and speciation diagrams prepared. This work demonstrates that both vanadium(IV) and (V)-thiol complexes form and that redox chemistry also takes place. Whether reduction of vanadate takes place is governed by a combination of parameters: pH, solute- and vanadate-concentrations and the presence of other complexing ligands. On the basis of these results it is now possible to understand the distribution of vanadium in oxidation states (IV) and (V) in the presence of glutathione, cysteine, and other thiols and begin to evaluate the forms of the vanadium compounds that exert a particular biological effect including the insulin-enhancing agents, antiamoebic agents, and interactions with vanadium binding proteins. PMID:20359175

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

    NASA Astrophysics Data System (ADS)

    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

  4. Targeting the Redox Balance in Inflammatory Skin Conditions

    PubMed Central

    Wagener, Frank A. D. T. G.; Carels, Carine E.; Lundvig, Ditte 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 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. PMID:23624605

  5. The relationship between magnetic mineralogy and redox conditions in Baldeggersee

    NASA Astrophysics Data System (ADS)

    Hirt, Ann; Gilli, Adrian

    2014-05-01

    Many factors contribute and later influence the iron mineralogy in lake sediments, such as catchment geology, climate, and redox conditions in the water and sediment column. Reidar Lovlie was one of the earliest paleomagnetists to examine these factors. Local redox conditions especially play an important role when magnetotactic bacteria are the main source of ferromagnetic grains in the lacustrine sediments. Baldeggersee, a mid-sized lake, which formed in the Molasse Basin of Switzerland during the last glacial retreat, has been shown to undergo extreme anoxia in the past century due to eutrophication. A reliable indicator for anoxic conditions is the preservation of seasonal varves. Previous studies using core transects confirmed that the anoxia intensified during the first half of the 20th century affecting shallower lake areas until oxygen was pumped into the lake as part of a lake restoration program that started in 1982. Two short sediment cores were taken at two different water depths in fall, 2010 to investigate how magnetic mineralogy is affected by the anoxic conditions, which have a different timing at the two coring sites. Both the magnetic properties of sediments and their remanent magnetization were determined. Core BA10-04 was taken from the deepest part of the lake, with a water depth of 61 m. The 85 cm core records the anoxia from its onset around 1910 until the restoration measures in 1982. The second core, BA10-01 is 58 cm long and was taken from intermediate water depth of 35m. At this depth it is postulated that anoxic conditions did not affect the shallower water depth until ca. 1935. A total of 75 samples were taken from BA10-04 and 50 samples from BA10-01. Rock magnetic experiments show that magnetite is the only ferromagnetic phase in both cores. Before 1900 analysis of first-order reversal curves indicate that magnetite is biogenic in origin. After 1900 there is a rapid decrease in the concentration of magnetite, and it occurs as clusters

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

    NASA Astrophysics Data System (ADS)

    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

  7. Adaptive changes in renal mitochondrial redox status in diabetic nephropathy

    SciTech Connect

    Putt, David A.; Zhong, Qing; Lash, Lawrence H.

    2012-01-15

    Nephropathy is a serious and common complication of diabetes. In the streptozotocin (STZ)-treated rat model of diabetes, nephropathy does not typically develop until 30 to 45 days post-injection, although hyperglycemia occurs within 24 h. We tested the hypothesis that chronic hyperglycemia results in a modest degree of oxidative stress that is accompanied by compensatory changes in certain antioxidants and mitochondrial redox status. We propose that as kidneys progress to a state of diabetic nephropathy, further adaptations occur in mitochondrial redox status. Basic parameters of renal function in vivo and several parameters of mitochondrial function and glutathione (GSH) and redox status in isolated renal cortical mitochondria from STZ-treated and age-matched control rats were examined at 30 days and 90 days post-injection. While there was no effect of diabetes on blood urea nitrogen, measurement of other, more sensitive parameters, such as urinary albumin and protein, and histopathology showed significant and progressive worsening in diabetic rats. Thus, renal function is compromised even prior to the onset of frank nephropathy. Changes in mitochondrial respiration and enzyme activities indicated existence of a hypermetabolic state. Higher mitochondrial GSH content and rates of GSH transport into mitochondria in kidneys from diabetic rats were only partially due to changes in expression of mitochondrial GSH carriers and were mostly due to higher substrate supply. Although there are few clear indicators of oxidative stress, there are several redox changes that occur early and change further as nephropathy progresses, highlighting the complexity of the disease. Highlights: ►Adaptive changes in renal mitochondrial and redox status in diabetic rats. ►Modest renal dysfunction even prior to onset of nephropathy. ►Elevated concentrations of mitochondrial GSH in diabetic kidneys. ►Change in GSH due partly to increased protein expression of transporter.

  8. Mineralogical record of the redox conditions on early Mars

    NASA Astrophysics Data System (ADS)

    Dehouck, Erwin; Gaudin, Anne; Chevrier, Vincent; Mangold, Nicolas

    2016-06-01

    Sulfates and Fe-oxides identified on the martian surface by orbital and in situ missions indicate that oxidizing conditions have existed on early Mars, at least locally and/or episodically. In the context of rock alteration and weathering, redox conditions are especially critical for the behavior of iron, which is soluble in its divalent state but insoluble in its trivalent state. Here, we combine results from a series of laboratory experiments conducted under Mars-like conditions to address the influence of highly-oxidizing compounds such as hydrogen peroxide (H2O2) on the alteration pathways of primary materials. We show that, if early Mars had a dense CO2 atmosphere allowing for relatively "warm and wet" conditions and surface weathering, highly-oxidizing conditions would have strongly inhibited the formation of Fe/Mg-smectite clays from alteration of igneous ferromagnesian minerals, and possibly enhanced the formation of carbonates. But a decade of mineral mapping of the martian surface show abundant, widespread Fe/Mg-clays and rare carbonates, which we interpret here as a mineralogical record of poorly-oxidizing (or even reducing) conditions during most of the Noachian era. Oxidizing conditions would have occurred later in martian history as a consequence of a higher rate of H2 escape or of a lower rate of volcanic outgassing, or both.

  9. Bacterial Adaptation of Respiration from Oxic to Microoxic and Anoxic Conditions: Redox Control

    PubMed Central

    Bueno, Emilio; Mesa, Socorro; Bedmar, Eulogio J.; Richardson, David J.

    2012-01-01

    Abstract Under a shortage of oxygen, bacterial growth can be faced mainly by two ATP-generating mechanisms: (i) by synthesis of specific high-affinity terminal oxidases that allow bacteria to use traces of oxygen or (ii) by utilizing other substrates as final electron acceptors such as nitrate, which can be reduced to dinitrogen gas through denitrification or to ammonium. This bacterial respiratory shift from oxic to microoxic and anoxic conditions requires a regulatory strategy which ensures that cells can sense and respond to changes in oxygen tension and to the availability of other electron acceptors. Bacteria can sense oxygen by direct interaction of this molecule with a membrane protein receptor (e.g., FixL) or by interaction with a cytoplasmic transcriptional factor (e.g., Fnr). A third type of oxygen perception is based on sensing changes in redox state of molecules within the cell. Redox-responsive regulatory systems (e.g., ArcBA, RegBA/PrrBA, RoxSR, RegSR, ActSR, ResDE, and Rex) integrate the response to multiple signals (e.g., ubiquinone, menaquinone, redox active cysteine, electron transport to terminal oxidases, and NAD/NADH) and activate or repress target genes to coordinate the adaptation of bacterial respiration from oxic to anoxic conditions. Here, we provide a compilation of the current knowledge about proteins and regulatory networks involved in the redox control of the respiratory adaptation of different bacterial species to microxic and anoxic environments. Antioxid. Redox Signal. 16, 819–852. PMID:22098259

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

    NASA Astrophysics Data System (ADS)

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

    1997-03-01

    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-methylpyrrole, quinoline, indole, carbazole, dibenzothiophene, benzofuran, and dibenzofuran) were degraded under aerobic conditions, whereas thiophene and benzothiophene were degraded only when other compounds were degraded concomitantly. Quinoline and indole were the only two NSO-compounds degraded under 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 of 3-25 days, the lag periods for pyrrole, dibenzothiophene, benzofuran, and dibenzofuran were significantly longer (29-278 days). Under anaerobic conditions, lag periods of 100-300 days were observed. Differences in the degradation rate among the compounds were also observed. Indole, quinoline, carbazole, and benzofuran were quickly degraded in the aerobic microcosms, whereas a slow degradation of dibenzothiophene and dibenzofuran was observed. Pyrrole and 1-methylpyrrole were slowly degraded and 1-methylpyrrole was not completely removed within the 846 days. The anaerobic degradation rate was significantly slower than the aerobic degradation rate. The degradation rate under sulphate-reducing conditions was higher than under denitrifying and methanogenic conditions, though after re-addition of a compound a quick removal was observed. The persistence of many NSO-compounds under anaerobic conditions together with the long lag periods and the low degradation rates under aerobic conditions suggest that NSO-compounds might persist in groundwater at creosote-contaminated sites.

  11. Mantle Redox Conditions in the North Atlantic Igneous Province

    NASA Astrophysics Data System (ADS)

    Heister, L. E.; Gras, M. A.; Lesher, C. E.

    2004-12-01

    The North Atlantic igneous province (NAIP) has long been viewed as a region of anomalous mantle upwelling related to plume activity, continental rifting, and a heterogeneous mantle source. Prior to continental rifting in the Tertiary, the northern portion of the region was the site of closure of the Iapetus ocean basin. This tectonic event may have contributed to heterogeneities within the upper mantle and altered its oxidation state relative to the ambient mantle. Vanadium has been shown to be a useful indicator of redox conditions due to its multiple valence states (e.g. [1-2]). In mantle minerals, vanadium becomes increasingly incompatible under more oxidizing conditions [3]. Because both scandium and vanadium are moderately incompatible during melting, the Sc/V ratio of primitive basalts can be used to investigate the oxidation state of the mantle [1-3]. We have examined the Sc/V ratios of primitive lavas from the mid-Atlantic ridge (MAR), Iceland, and the East Greenland margin to determine if there are spatial or temporal variations in the oxidation state of the NAIP mantle. The Sc/V ratios for MAR basalts are 0.13-0.20 (GEOROC chemical database); while Icelandic basalts range from 0.10-0.25 with an average of 0.16 (1 σ =0.05). The entire range of Sc/V ratios of the Paleogene East Greenland basalts is 0.07-0.17 with an average of 0.10 (1 σ = 0.05). The Sc/V ratios of Icelandic basalts are similar to MAR basalts, but the East Greenland lavas are distinctly lower than both the MAR and Iceland. The Sc/V ratio also can vary as a function of mean pressure of melting (i.e. spinel versus garnet lherzolite). To test the relative importance of melting systematics, source composition, and oxygen fugacity on the Sc/V systematics for NAIP basalts, we incorporated the oxygen-fugacity-dependent V mineral-melt partitioning data of [3] into the polybaric decompression melting model REEBOX [4]. The best-fit model parameters for the majority of the Iceland and MAR basalts

  12. Examining the effect of altered redox conditions on deep soil organic matter stability

    NASA Astrophysics Data System (ADS)

    Gabriel, C.; Kellman, L. M.; Ziegler, S. E.

    2013-12-01

    Since subsoil horizons contribute significantly to terrestrial carbon (C) budgets, understanding the influence of disturbances such as forest harvesting on subsoil C stability is critical. Clearcut harvesting leads to changes in the soil physico-chemical environment, including altering redox conditions arising from changes in soil hydrology that increase soil saturation, soil temperature, and pH. These physico-chemical changes have the potential to alter the adsorption of soil organic matter (SOM) to minerals, particularly at depth where SOM is primarily associated with mineral phases. The objective of this study was to determine the effect of differing redox states (aerobic vs. anaerobic) and temperature upon SOM stability of forested soils representative of the Acadian Forest Region of Eastern North America. Composite soil samples through depth (0-10, 10-20, 20-35, and 35-50 cm) from a mature red spruce forest (110 years) were incubated under optimum (aerobic) or saturated (anaerobic) conditions for 1 or 4 months at two temperatures (5 and 15 C). Following incubation, soil leachate was analyzed for dissolved organic carbon (DOC), and UV-vis absorbance in order to determine soil C losses and its optical character. Specific UV-vis absorbance SUVA (254 nm) and spectral slope ratios were calculated in order to assess the composition of chromophoric dissolved organic matter (CDOM). Preliminary results from the 1 month incubation indicate that under anaerobic conditions, all depths released DOC with a higher SUVA than under aerobic conditions, with the largest change observed in the 0-10 cm depth increment. Soil incubated at 5 C produced leachate with significantly less DOC and with a lower absorbance compared to 15 C under both redox conditions. These results suggest that both temperature and redox state are important in determining the aromaticity of DOC released from soils. Spectral slope ratios revealed that a greater proportion of CDOM of lower molecular weight

  13. Effects of redox conditions on the adsorption of dissolved organic matter to soil minerals and differently aged paddy soils

    NASA Astrophysics Data System (ADS)

    Sauerwein, Meike; Hanke, Alexander; Kaiser, Klaus; Kalbitz, Karsten

    2010-05-01

    Effects of redox conditions on the adsorption of dissolved organic matter to soil minerals and differently aged paddy soils Meike Sauerwein1, Alexander Hanke2, Klaus Kaiser3, Karsten Kalbitz2 1) Dept. of Soil Ecology, Bayreuth Centre of Ecology and Environmental Research (BayCEER), University of Bayreuth, 95440 Bayreuth, Germany, meike.sauerwein@gmail.com 2) Institute of ecosystem dynamics and biodiversity, University of Amsterdam, 1018 WV, Netherlands, a.hanke@uva.nl, k.kalbitz@uva.nl 3) Soil Sciences, Martin Luther University Halle, 06099 Halle, Germany, klaus.kaiser@landw.uni-halle.de Current knowledge on dissolved organic matter (DOM) in soils is based mainly on observations and experiments in aerobic environments. Adsorption to soil minerals is an important mechanism of DOM retention and stabilization against microbial decay under oxic conditions. Under anoxic conditions where hydrous iron oxides, the potential main adsorbents of DOM, possibly dissolve, the importance of adsorption seems questionable. Therefore, we studied the adsorption of DOM to selected soil minerals and to mineral soils under oxic and anoxic conditions. In detail, we tested the following hypotheses: 1. Minerals and soils adsorb less DOM under anoxic conditions than under oxic ones. 2. The reduced adsorption under anoxic conditions is result of the smaller adsorption to hydrous Fe oxides whereas adsorption to clay minerals and Al hydroxides is not sensitive to changes in redox conditions 3. DOM adsorption will increase with the number of redox cycles, thus time of soil formation, due to increasing contents of poorly crystalline Fe oxides. This will, however, cause a stronger sensitivity to redox changes as poor crystalline Fe oxides are more reactive. 4. Aromatic compounds, being preferentially adsorbed under oxic conditions, will be less strongly adsorbed under anoxic conditions. We chose paddy soils as models because their periodically and regular exposure to changing redox cycles, with

  14. The influence of variable hydraulic conditions on hyporheic water flux and redox regime in streambed sediments

    NASA Astrophysics Data System (ADS)

    Schmidt, C.; Trauth, N.; Vieweg, M.; Fleckenstein, J. H.

    2011-12-01

    Magnitudes and directions of water flux in the streambed are controlled by hydraulic gradients between the aquifer and the stream and by bedforms which induce hyporheic exchange flows. Varying hydrologic conditions such as short term flood events or seasonal variations in groundwater flow typically change the flow regime in the streambed. Consequently, the supply of oxygen into the streambed varies depending on the magnitude of upwelling or downwelling water fluxes. Field data and numerical experiments illustrate the relevance of variable hydraulic conditions for the water flux and redox conditions in the streambed for both morphologically rich natural streams and poorly structured, constructed streambeds. In a field study at a small stream with poor morphologic structure, we observed the variability of hydraulic gradients and redox conditions over the course of five months. During the observation period the hydrologic conditions changed from losing to gaining. Redox conditions were highly variable and appeared to depend on the direction of water flux in the shallow streambed at 0.1m depth. In a stream structured with pool-riffle-sequences bedform induced hyporheic exchange dominates water fluxes in the streambed. However, magnitude and direction of water flow depend on the hydraulic conditions. We used variations of electrical conductivity (EC) as a natural tracer. The travel times in the riffle were estimated by non-linearly matching the EC signals in the time domain. The amount of temporal distortion required to obtain the optimal matching is related to the travel time of the signal. This analysis revealed that the travel-times within the studied riffle varied with varying stream flow. In order to generalize this finding we conducted numerical experiments. With a two-phase (air and water) computational fluid dynamics representation of surface water flow it was possible to simulate variable stream flows and the resulting variability of pressure distributions on

  15. The impact of oscillating redox conditions: arsenic immobilisation in contaminated calcareous floodplain soils.

    PubMed

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

    2013-07-01

    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. PMID:23587855

  16. Early diagenesis of carbohydrates and lignin in mangrove sediments subject to variable redox conditions (French Guiana)

    NASA Astrophysics Data System (ADS)

    Marchand, C.; Disnar, J. R.; Lallier-Vergès, E.; Lottier, N.

    2005-01-01

    A comparative study of lignin and neutral carbohydrate compositions, combined with C, N and δ 13C analyses, was carried out on sedimentary cores, and on various vascular plant species collected in mangrove swamps of French Guiana. The main purpose of this study was to assess the diagenesis of carbohydrates and lignin in brackish to hypersaline fine-grained mangrove sediments characterized by great changes in redox conditions. Distribution of carbohydrates in sediments reflects both the lability of these compounds and their efficient recycling. They are subject to selective degradation, cellulosic glucose and xylose appearing to be the two most labile neutral sugars. In contrast a relative increase in arabinose, rhamnose, fucose and hemicellulosic glucose between plants and sediments, suggests that they may be more refractory and/or that they also derive from microbial synthesis. The total carbon from lignin-derived phenols is higher in sediments than in mangrove plants as a consequence of their rather refractory character. Nevertheless, evidence of lignin decomposition was found to be independent of local environmental conditions. The various redox processes that occur in mangrove sediments depend on plant species, stages in forest development and season. Different redox conditions induce different mechanisms for the decomposition of lignin and thus induce changes in phenol distributions. At depth, in most mangroves, an increase in (Ad/Al) v ratios and in deoxy sugars (fucose and rhamnose) content was significantly correlated with increased proportions of oxidized allochthonous organic debris deriving from the Amazonian detrital discharge, thus suggesting a specific source effect rather than a diagenesis induced change. Therefore, this study illustrates that both lignin and cellulose, derived from vascular plant debris, can be degraded in waterlogged mangrove sediments, and that their distribution depends on environmental conditions.

  17. Nitroxides as redox probes of melanins: dark-induced and photoinduced changes in redox equilibria

    SciTech Connect

    Sarna, T.; Korytowski, W.; Sealy, R.C.

    1985-05-15

    The interaction of nitroxide free radicals and their reduced products (hydroxylamines) with synthetic and natural melanins has been studied. Electron spin resonance spectroscopy was used to measure changes in radical concentration in the dark and during irradiation with visible or uv light. Some reduction of nitroxide occurs in the dark, and is reversible: the nitroxide can be completely regenerated by the one-electron oxidant ferricyanide. The kinetics of the process depend strongly on radical charge and pH. For positively charged nitroxides the rate is much faster than for either neutral or anionic radicals. At pH 10 the rate is about 20 times faster than at pH 5. Oxidation of hydroxylamine also can occur so that a redox equilibrium is established. The equilibrium constant has been estimated for the reaction between a nitroxide and melanin from autoxidation of 3,4-dihydroxyphenylalanine. Results are also dependent upon the type of melanin used and chemical modification (oxidation or reduction) of the melanin. Redox equilibria are altered during irradiation with either visible or uv light. Rapid oxidation of hydroxylamine to nitroxide is apparent, together with a slower reduction of nitroxide. Action spectra for these processes are related to those for melanin radical production and oxygen consumption in nitroxide-free melanin systems. Reduction of nitroxide is inhibited by oxygen, suggesting a competition between nitroxide and oxygen for photoinduced reducing equivalents.

  18. Modeling basic features of biogeochemical structure of water column, bottom boundary layer and benthic boundary layer in changeable redox conditions

    NASA Astrophysics Data System (ADS)

    Yakushev, Evgeniy

    2013-04-01

    Climate Change affects oxygen depletion and leads to spreading of the bottom areas with hypoxic and anoxic conditions in the coastal areas of the seas and inland waters. This work aimed in estimation of a role of changes of redox conditions in the biogeochemical structure there. We use a 1-dimensional C-N-P-Si-O-S-Mn-Fe vertical transport-reaction model describing the water column, bottom boundary layer and benthic boundary layer with biogeochemical block simulating redox conditions changeability. A biogeochemical block is based on ROLM (RedOx Layer Model), that was constructed to simulate basic features of the water column biogeochemical structure changes in oxic, anoxic and changeable conditions (Yakushev et al., 2007). Organic matter formation and decay, reduction and oxidation of species of nitrogen, sulfur, manganese, iron, and the transformation of phosphorus species are parameterized in the model. ROLM includes a simplified ecological model with phytoplankton, zooplankton, aerobic autotrophic and heterotrophic bacteria, anaerobic autotrophic and heterotrophic bacteria. We simulate changes in the parameters distributions and fluxes connected with the vertical displacement of redox interface from the sediments to the water.

  19. Impact of redox conditions on arsenic mobilization from tailings in a wetland with neutral drainage.

    PubMed

    Beauchemin, Suzanne; Kwong, Y T John

    2006-10-15

    More than 80 years of silver mining in the Cobalt area (Ontario, Canada) has led to widespread contamination of water with arsenic. The objective of this study was to determine the impact of changes in redox conditions on the stability of As in samples collected from a tailings wetland in the historic mining camp. Dissolved metal concentrations were monitored while tailings samples (approximately 1300 mg of As kg(-1), pH 7.4) were subjected to 30 days of reduction. Reoxidation of the samples was accomplished by air drying. The As oxidation states in the original, reduced, and reoxidized samples were determined using X-ray absorption spectroscopy (XAS). Arsenic speciation was affected by changes in redox conditions, resulting in rapid mobilization of As during reduction. Glucose input had a significant impact on the dissolution and speciation of As, suggesting that the As transformation was microbially mediated. When carbon was not limiting, the combination of reducing conditions and lower pH favored the formation of As(-I) species. PMID:17120556

  20. Neptunium redox behavior and solubility in J-13 conditions

    SciTech Connect

    Efurd, D.W.; Runde, W.; Tait, C.D.

    1997-08-01

    In order to confirm that the redox reaction Np(V) to Np(IV) may occur, studies are being conducted including exposure of Np(V) to solutions of known E{sub h} vs pH, temperature. Analytic results from ongoing solubility experiments from undersaturation, using Np solids formed in previous oversaturation experiments, are reported.

  1. Changes in microbial communities along redox gradients in polygonized Arctic wet tundra soils.

    PubMed

    Lipson, David A; Raab, Theodore K; Parker, Melanie; Kelley, Scott T; Brislawn, Colin J; Jansson, Janet

    2015-08-01

    This study investigated how microbial community structure and diversity varied with depth and topography in ice wedge polygons of wet tundra of the Arctic Coastal Plain in northern Alaska and what soil variables explain these patterns. We observed strong changes in community structure and diversity with depth, and more subtle changes between areas of high and low topography, with the largest differences apparent near the soil surface. These patterns are most strongly correlated with redox gradients (measured using the ratio of reduced Fe to total Fe in acid extracts as a proxy): conditions grew more reducing with depth and were most oxidized in shallow regions of polygon rims. Organic matter and pH also changed with depth and topography but were less effective predictors of the microbial community structure and relative abundance of specific taxa. Of all other measured variables, lactic acid concentration was the best, in combination with redox, for describing the microbial community. We conclude that redox conditions are the dominant force in shaping microbial communities in this landscape. Oxygen and other electron acceptors allowed for the greatest diversity of microbes: at depth the community was reduced to a simpler core of anaerobes, dominated by fermenters (Bacteroidetes and Firmicutes). PMID:26034016

  2. Changes in microbial communities along redox gradients in polygonized Arctic wet tundra soils

    SciTech Connect

    Lipson, David A.; Raab, Theodore K.; Parker, Melanie; Kelley, Scott T.; Brislawn, Colin J.; Jansson, Janet K.

    2015-08-01

    Summary This study investigated how microbial community structure and diversity varied with depth and topography in ice wedge polygons of wet tundra of the Arctic Coastal Plain in northern Alaska and what soil variables explain these patterns. We observed strong changes in community structure and diversity with depth, and more subtle changes between areas of high and low topography, with the largest differences apparent near the soil surface. These patterns are most strongly correlated with redox gradients (measured using the ratio of reduced Fe to total Fe in acid extracts as a proxy): conditions grew more reducing with depth and were most oxidized in shallow regions of polygon rims. Organic matter and pH also changed with depth and topography but were less effective predictors of the microbial community structure and relative abundance of specific taxa. Of all other measured variables, lactic acid concentration was the best, in combination with redox, for describing the microbial community. We conclude that redox conditions are the dominant force in shaping microbial communities in this landscape. Oxygen and other electron acceptors allowed for the greatest diversity of microbes: at depth the community was reduced to a simpler core of anaerobes,

  3. Changes in microbial communities along redox gradients in polygonized Arctic wet tundra soils

    SciTech Connect

    Lipson, David A.; Raab, Theodore K.; Parker, Melanie; Kelley, Scott T.; Brislawn, Colin J.; Jansson, Janet K.

    2015-07-21

    This study investigated how microbial community structure and diversity varied with depth and topography in ice wedge polygons of wet tundra of the Arctic Coastal Plain in northern Alaska, and what soil variables explain these patterns. We observed strong changes in community structure and diversity with depth, and more subtle changes between areas of high and low topography, with the largest differences apparent near the soil surface. These patterns are most strongly correlated with redox gradients (measured using the ratio of reduced Fe to total Fe in acid extracts as a proxy): conditions grew more reducing with depth and were most oxidized in shallow regions of polygon rims. Organic matter and pH also changed with depth and topography, but were less effective predictors of the microbial community structure and relative abundance of specific taxa. Of all other measured variables, lactic acid concentration was the best, in combination with redox, for describing the microbial community. We conclude that redox conditions are the dominant force in shaping microbial communities in this landscape. Oxygen and other electron acceptors allowed for the greatest diversity of microbes: at depth the community was reduced to a simpler core of anaerobes, dominated by fermenters (Bacteroidetes and Firmicutes).

  4. Combination of aquifer thermal energy storage and enhanced bioremediation: resilience of reductive dechlorination to redox changes.

    PubMed

    Ni, Zhuobiao; van Gaans, Pauline; Smit, Martijn; Rijnaarts, Huub; Grotenhuis, Tim

    2016-04-01

    To meet the demand for sustainable energy, aquifer thermal energy storage (ATES) is widely used in the subsurface in urban areas. However, contamination of groundwater, especially with chlorinated volatile organic compounds (CVOCs), is often being encountered. This is commonly seen as an impediment to ATES implementation, although more recently, combining ATES and enhanced bioremediation of CVOCs has been proposed. Issues to be addressed are the high water flow velocities and potential periodic redox fluctuation that accompany ATES. A column study was performed, at a high water flow velocity of 2 m/h, simulating possible changes in subsurface redox conditions due to ATES operation by serial additions of lactate and nitrate. The impacts of redox changes on reductive dechlorination as well as the microbial response of Dehalococcoides (DHC) were evaluated. The results showed that, upon lactate addition, reductive dechlorination proceeded well and complete dechlorination from cis-DCE to ethene was achieved. Upon subsequent nitrate addition, reductive dechlorination immediately ceased. Disruption of microorganisms' retention was also immediate and possibly detached DHC which preferred attaching to the soil matrix under biostimulation conditions. Initially, recovery of dechlorination was possible but required bioaugmentation and nutrient amendment in addition to lactate dosing. Repeated interruption of dechlorination and DHC activity by nitrate dosing appeared to be less easily reversible requiring more efforts for regenerating dechlorination. Overall, our results indicate that the microbial resilience of DHC in biosimulated ATES conditions is sensitive to redox fluctuations. Hence, combining ATES with bioremediation requires dedicated operation and monitoring on the aquifer geochemical conditions. PMID:26711280

  5. Redox conditions and the efficiency of chlorinated ethene biodegradation: Field studies

    USGS Publications Warehouse

    Chapelle, F.H.; Bradley, P.M.

    2000-01-01

    The effect of redox conditions on the efficiency of chlorinated ethene biodegradation was investigated at two field sites. One site (NAS Cecil Field, FL) is characterized by predominantly Fe(III)-reducing conditions in the contaminant source area, grading to predominantly sulfate- reducing conditions downgradient. This sequence of redox conditions led to relatively inefficient biodegradation of chlorinated ethenes, with high concentrations of trichloroethene extending more than 400 meters downgradient of the source area. In contrast, a second site (NBS Kings Bay, GA) characterized by predominantly sulfate-reducing conditions in the source area followed by Fe(III)-reducing conditions downgradient. In this system perchloroethene (PCE) and TCE were rapidly biodegraded and extended less than 100 meters downgradient. Rates of ground- water transport are similar at the two sites (???0.2 m/d) indicating that the succession of redox processes, rather than other hydrologic factors, is the principal control on biodegradation. In particular, redox conditions that favor the initial reduction of highly chlorinated ethenes (methanogenic or sulfate-reducing conditions) followed by more oxidizing conditions (Fe(III)- reducing or oxic conditions) favors efficient biodegradation. Thus, documenting the succession of redox processes is an important step in understanding the efficiency of chlorinated ethene biodegradation in ground-water systems.

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

    PubMed

    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. PMID:25216580

  7. Effects of experimental reheating of natural basaltic ash at different temperatures and redox conditions

    NASA Astrophysics Data System (ADS)

    D'Oriano, C.; Pompilio, M.; Bertagnini, A.; Cioni, R.; Pichavant, M.

    2013-05-01

    A set of experiments have been performed on volcanic materials from Etna, Stromboli and Vesuvius in order to evaluate how the exposure to thermal and redox conditions close to that of active craters affects the texture and composition of juvenile pyroclasts. Selected samples were placed within a quartz tube, in presence of air or under vacuum, and kept at T between 700 and 1,130 °C, for variable time (40 min to 12 h). Results show that reheating reactivates the melt, which, through processes of chemical and thermal diffusion, reaches new equilibrium conditions. In all the experiments performed at T = 700-750 °C, a large number of crystal nuclei and spherulites grows in the groundmass, suggesting conditions of high undercooling. This process creates textural heterogeneities at the scale of few microns but only limited changes of groundmass composition, which remains clustered around that of the natural glasses. Reheating at T = 1,000-1,050 °C promotes massive groundmass crystallization, with a different mineral assemblage as a function of the redox conditions. Morphological modifications of clasts, from softening to sintering as temperature increases, occur under these conditions, accompanied by progressive smoothing of external surfaces, and a reduction in size and abundance of vesicles, until the complete obliteration of the pre-existing vesicularity. The transition from sintering to welding, characteristic of high temperature, is influenced by redox conditions. Experiments at T = 1,100-1,130 °C and under vacuum produce groundmass textures and glass compositions similar to that of the respective starting material. Collapse and welding of the clasts cause significant densification of the whole charge. At the same temperature, but in presence of air, experimental products at least result sintered and show holocrystalline groundmass. In all experiments, sublimates grow on the external surfaces of the clasts or form a lining on the bubble walls. Their shape and

  8. EVALUATION OF IMMOBILIZED REDOX INDICATORS AS REVERSIBLE, IN SITU REDOX SENSORS FOR DETERMINING FE(III)-REDUCING CONDITIONS IN ENVIRONMENTAL SAMPLES. (R828772)

    EPA Science Inventory

    An in situ methodology based on immobilized redox indicators has been developed to determine when Fe(III)-reducing conditions exist in environmental systems. The redox indicators thionine (Thi, formal potential at pH 7 (E70') equals 66 mV), tol...

  9. Quantitative analysis of solid oxide fuel cell anode microstructure change during redox cycles

    NASA Astrophysics Data System (ADS)

    Shimura, Takaaki; Jiao, Zhenjun; Hara, Shotaro; Shikazono, Naoki

    2014-12-01

    In the present study, correlation between solid oxide fuel cell anode microstructure and electrochemical performance during redox cycles was investigated. Electrolyte-support cell with nickel/yttria stabilized zirconia composite anode was prepared and tested under discharge process with redox cycles. Redox treatment was basically conducted every 20 h during discharge process. Polarization resistance decreased just after redox treatment and increased during discharge process. Enhancement of cell performance after every redox cycles and faster degradation in the following discharge process were observed. Polarization resistance gradually increased as redox cycles were repeated. Focused ion beam-scanning electron microscopy (FIB-SEM) observation was conducted for reconstructing the three dimensional microstructures of the tested samples. From the three dimensional microstructure reconstruction, it is found that the shape of nickel particle got thinner and complicated after redox cycles. Triple phase boundary (TPB) length increased after redox treatment and decreased after discharge process. This TPB change was highly associated with Ni connectivity and Ni specific surface area. These microstructure changes are consistent with the change of cell performance enhancement after redox treatment and degradation after discharge process. However, TPB length density kept on increasing as redox cycles are repeated, which is inconsistent with the gradual degradation of anode performance.

  10. Chromium Release from a COPR-Contaminated Soil at Varying Water Content and Redox Conditions.

    PubMed

    Matern, Katrin; Mansfeldt, Tim

    2016-07-01

    Many soils in the region of Kanpur, North India, are heavily affected by the leather industry and its upstream supplier sector, as indicated by elevated chromium (Cr) contents. Under reducing conditions-for instance, at water saturation after monsoon rain or flood irrigation-the dynamic and species distribution of Cr may be affected due to changes in redox potential (E). In this study, the influence of E on the speciation and release of Cr from a contaminated agricultural soil was investigated. A soil sample that was affected by hyperalkaline leachate from chromite ore processing residue, was taken and packed in soil columns, and subjected to a saturation-drainage-saturation cycle. After initial water saturation, the E dropped slowly to minimum values of around ‒100 mV (calculated to pH 7), while E was controlled by CrO/CrO(s), or CrO/(Fe,Cr)OOH redox couples. Soil drainage resulted in a quick return to oxidizing conditions; i.e., E > 300 mV. The Cr species distribution and release showed a clear trend with E. At the beginning of the experiment, under oxidizing and weakly reducing conditions (E range from >100 to 300 mV), Cr(VI) was released in particular. However, under moderately reducing conditions (E range from 100 to -100 mV), Cr was gradually immobilized and irreversible sequestered via reductive precipitation. The results presented in this study provide an improved understanding of the mobility of Cr(VI) in contaminated soils at varying water contents, which is essential for the evaluation of environmental risks in this region. PMID:27380074

  11. The characterization of ferromanganese crust and its redox change, Western Pacific Magellan seamounts

    NASA Astrophysics Data System (ADS)

    Yang, K.; Kim, J. W.; Park, H.; Baik, H.; Park, K.; Kim, J.

    2015-12-01

    Biotic/abiotic redox reaction is a ubiquitous process in mineral formation and growth, and changes in elemental redox states, particularly Fe/Mn may reflect the redox conditions in the sediment/ocean when the mineral forms. Samples were dredged from the seamounts in the western Pacific, OSM11 in order to investigate the formation, growth and its implications to geological history. The crust consist of five well-defined layers (here after called "layer 1" (rim) through "layer 5" (core)). Quartz, feldspar, and hematite are detected only in the layer 1 in addition to the poorly crystallined Fe-rich vernadite, which is likely to be associated with slower growth rate compared to the layers 2-5. CFA were identified in layers 4 and 5 under XRD measurement. Visible size of white colored well crystallined CFA were only observed in layer 4; whereas nano-sized CFA in layer 5 were identified by TEM. Clay minerals such as smectite were observed by TEM with SAED pattern and EDX in layers 1 and 3. The oxidation states of Fe and Mn in Fe-rich vernadite in entire layers were determined by EELS analysis. All the layers of Mn oxide minerals was consisted with dominantly Mn4+, which is consistent with appearance of vernadite in Fe-Mn crust. Fe-rich vernadite in layers 1 and 4 were consisted with 26-52 % of Fe3+/Fetot, dominant reduced form of Fe compared to layers 2, 3, and 5. The observed alternative patterns of Fe oxidation state in five distinct layers of Fe-Mn crust is likely to be associated with the various redox conditions in seawater, changes in growth rate of crust resulting in the various oxygen exposure time, and uplift-subsidence of sea mounts. A non-cultivation-based molecular approach with T-RFLP indicated the presence of functional gene (CumA) association with Mn oxidizing bacteria in Fe-Mn crust layers. The presence of Mn oxidizing gene may suggest that the biotic Mn oxides precipitation may persist locally in the Fe-Mn crust; whereas functional gene of Fe

  12. Specific microbial populations thrive under fluctuating redox conditions in tropical soils

    NASA Astrophysics Data System (ADS)

    Deangelis, K. M.; Silver, W. L.; Thompson, A.; Firestone, M. K.

    2008-12-01

    The highly weathered soils of upland humid tropical forests are characterized by rapidly fluctuating redox conditions, dominated by Fe-oxide mineralogy, and have relatively low sulfate availability. To assess how fluctuating redox conditions and accompanying biogeochemistry impact microbial community structure and function, we collected soil cores from the Luquillo LTER forest in Puerto Rico and incubated them for 32 days under one of three redox regimes: static oxic, static anoxic, and 4-day fluctuating redox. Over this time course we measured CO2, CH4, and N2O production, amorphous iron and Fe(II), and microbial community structure by high density microarray (PhyloChip) analysis. Static oxic, anoxic, and fluctuating redox soils all had statistically indistinguishable respiration rates over the course of the experiment. Fluctuating redox conditions permitted simultaneous methanogenesis, N2O production, and iron reduction, all accompanied by steady CO2 production. We analyzed the standing and active microbial community using the 16S ribosomal DNA and RNA biomarkers, identifying 2489 taxa in these soils. Ordination analysis showed significant separation between the active (RNA-based) and standing (DNA-based) communities, with much more variation in the active community compared to the standing community. Fluctuating redox conditions maintained a microbial community structure similar to that of the pre-incubation samples, while static anaerobic conditions had the most profound effect on the communities. Finally, there was considerable overlap between the taxa that were the most highly correlated with production of CH4 and Fe(II). Association of groups of taxa with specific biogeochemical processes begins to identify organisms potentially responsible for field biogeochemical processing.

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

    NASA Astrophysics Data System (ADS)

    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

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

    NASA Astrophysics Data System (ADS)

    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.

  15. EFFECTS OF TEMPERATURE AND REDOX CONDITIONS ON DEGRADATION OF CHLORINATED PHENOLS IN FRESHWATER SEDIMENTS

    EPA Science Inventory

    The effect of temperature and redox conditions on the anaerobic degradation of 2,4-dichlorophenol (2,4-DCP) was investigated in anaerobic sediment slurries, prepared from local freshwater pond sediments. Under methanogenic conditions, 2,4-DCP dechlorination occurred in the temper...

  16. Real-time monitoring of redox changes in the mammalian endoplasmic reticulum

    PubMed Central

    van Lith, Marcel; Tiwari, Shweta; Pediani, John; Milligan, Graeme; Bulleid, Neil J.

    2011-01-01

    Redox-sensitive GFPs with engineered disulphide bonds have been used previously to monitor redox status in the cytosol and mitochondria of living cells. The usefulness of these redox probes depends on the reduction potential of the disulphide, with low values suiting the cytosol and mitochondrion, and higher values suiting the more oxidising environment of the endoplasmic reticulum (ER). Here, we targeted a modified redox-sensitive GFP (roGFP1-iL), with a relatively high reduction potential, to the ER of mammalian cells. We showed that the disulphide is partially oxidised, allowing roGFP1-iL to monitor changes in ER redox status. When cells were treated with puromycin, the redox balance became more reducing, suggesting that the release of nascent chains from ribosomes alters the ER redox balance. In addition, downregulating Ero1α prevented normal rapid recovery from dithiothreitol (DTT), whereas downregulating peroxiredoxin IV had no such effect. This result illustrates the contribution of the Ero1α oxidative pathway to ER redox balance. This first report of the use of roGFP to study the ER of mammalian cells demonstrates that roGFP1-iL can be used to monitor real-time changes to the redox status in individual living cells. PMID:21693587

  17. Establishment of redox conditions during planetary collisions as an origin of chondrites

    NASA Technical Reports Server (NTRS)

    Tsuchiyama, A.; Kitamura, M.

    1994-01-01

    Collisions between a 'cometlike' body (mixtures of chondritic materials and ice) and a slightly differentiated body were proposed for shock origin of ordinary chondrites. In this model, chondrules were formed with shock melting, and matrices were formed both by fracturing of materials and by recondensation of evaporated materials. This model can explain different redox conditions of chondrite formations by ice evaporation. Although this model was originally proposed for ordinary chondrites, we assume here that the model can be extended to chondrite formation in general. In this paper, redox conditions during chondrite formation by collisions will be discussed in the light of phase diagrams for solid-vapor equilibria.

  18. Arsenic distribution and speciation near rice roots influenced by iron plaques and redox conditions of the soil matrix.

    PubMed

    Yamaguchi, Noriko; Ohkura, Toshiaki; Takahashi, Yoshio; Maejima, Yuji; Arao, Tomohito

    2014-01-01

    Elevated arsenic (As) concentrations in rice and the soil solution result from changes in soil redox conditions, influenced by the water management practices during rice cultivation. Microscale changes in redox conditions from rhizosphere to soil matrix affect the As speciation and Fe plaque deposition. In order to focus on the rhizosphere environment, we observed microscale distribution and speciation of As around the rhizosphere of paddy rice with X-ray fluorescence mapping and X-ray absorption spectroscopy. When the soil matrix was anaerobic during rice growth, Fe-plaque did not cover the entire root, and As(III) was the dominant arsenic species in the soil matrix and rhizosphere. Draining before harvest led the conditions to shift to aerobic. Oxidation of As(III) to As(V) occurred faster in the Fe-plaque than the soil matrix. Arsenic was scavenged by iron mottles originating from Fe-plaque around the roots. The ratio of As(V) to As(III) decreased toward the outer-rim of the subsurface Fe mottles where the soil matrix was not completely aerated. These results provide direct evidence that speciation of As near rice roots depends on spatial and temporal redox variations in the soil matrix. PMID:24384039

  19. Electrode effects on temporal changes in electrolyte pH and redox potential for water treatment.

    PubMed

    Ciblak, Ali; Mao, Xuhui; Padilla, Ingrid; Vesper, Dorothy; Alshawabkeh, Iyad; Alshawabkeh, Akram N

    2012-01-01

    The performance of electrochemical remediation methods could be optimized by controlling the physicochemical conditions of the electrochemical redox system. The effects of anode type (reactive or inert), current density and electrolyte composition on the temporal changes in pH and redox potential of the electrolyte were evaluated in divided and mixed electrolytes. Two types of electrodes were used: iron as a reactive electrode and mixed metal oxide coated titanium (MMO) as an inert electrode. Electric currents of 15, 30, 45 and 60 mA (37.5 mA L(-1), 75 mA L(-1), 112.5 mA L(-1) and 150 mA L(-1)) were applied. Solutions of NaCl, Na(2)SO(4) and NaHCO(3) were selected to mimic different wastewater or groundwater compositions. Iron anodes resulted in highly reducing electrolyte conditions compared to inert anodes. Electrolyte pH was dependent on electrode type, electrolyte composition and current density. The pH of mixed-electrolyte was stable when MMO electrodes were used. When iron electrodes were used, the pH of electrolyte with relatively low current density (37.5 mA L(-1)) did not show significant changes but the pH increased sharply for relatively high current density (150 mA L(-1)). Sulfate solution showed more basic and relatively more reducing electrolyte conditions compared to bicarbonate and chloride solution. The study shows that a highly reducing environment could be achieved using iron anodes in divided or mixed electrolytes and the pH and redox potential could be optimized using appropriate current and polarity reversal. PMID:22416866

  20. Electrode effects on temporal changes in electrolyte pH and redox potential for water treatment

    PubMed Central

    Ciblak, Ali; Mao, Xuhui; Padilla, Ingrid; Vesper, Dorothy; Alshawabkeh, Iyad; Alshawabkeh, Akram N.

    2012-01-01

    The performance of electrochemical remediation methods could be optimized by controlling the physicochemical conditions of the electrochemical redox system. The effects of anode type (reactive or inert), current density and electrolyte composition on the temporal changes in pH and redox potential of the electrolyte were evaluated in divided and mixed electrolytes. Two types of electrodes were used: iron as a reactive electrode and mixed metal oxide coated titanium (MMO) as an inert electrode. Electric currents of 15, 30, 45 and 60 mA (37.5 mA L−1, 75 mA L−1, 112.5 mA L−1 and 150 mA L−1) were applied. Solutions of NaCl, Na2SO4 and NaHCO3 were selected to mimic different wastewater or groundwater composition. Iron anodes resulted in highly reducing electrolyte conditions compared to inert anodes. Electrolyte pH was dependent on electrode type, electrolyte composition and current density. The pH of mixed-electrolyte was stable when MMO electrodes were used. When iron electrodes were used, the pH of electrolyte with relatively low current density (37.5 mA L−1) did not show significant changes but the pH increased sharply for relatively high current density (150 mA L−1). Sulfate solution showed more basic and relatively more reducing electrolyte condition compared to bicarbonate and chloride solution. The study shows that a highly reducing environment could be achieved using iron anodes in divided or mixed electrolytes and the pH and redox potential could be optimized by using appropriate current and polarity reversal. PMID:22416866

  1. Mobilization and Release of colloidal Carbon from a Soil Column Under Redox Oscillation Condition

    NASA Astrophysics Data System (ADS)

    Afsar, M. Z.; Jin, Y.

    2015-12-01

    Dissolved organic matter (DOM), the most mobile form of carbon (C), strongly influences the cycling, distribution and behavior of C in soil. In wetlands, the reductive dissolution of iron and manganese oxy-hydroxides releases large quantities of DOM into the soil solution. The objective of this study is to quantify the changes in aqueous organic carbon concentration in different sized fractions induced by reduction of iron and increase in pH. Twenty four cm long soil columns were prepared. Columns were run under oxic (as control) and anoxic conditions. Two platinum redox probes were inserted at 10 and 17 cm depths from the soil surface to monitor the redox status of the column. Anoxic and oxic conditions were maintained by flushing with either nitrogen or oxygen gas through the soil. No additional organic sources were added. After 35 days of anoxic environment, column leachate samples were separated by differential centrifugation into five colloidal sized fractions (<450 nm, <220 nm, <100 nm, <50 nm and <2.3 nm). Immediately after the 1st reduction half cycle, the leachate samples were collected inside the glove box and the soil columns were flushed with oxygen to prepare for 2nd reduction half cycle. After 1st reduction half cycle, the pH, ionic strength and aqueous (Fe2+) concentration of the column extracts were increased whereas the Eh value was decreased. The range of pH, Eh, ionic strength and concentration of Fe2+ was 6.38 to 6.91, -219 to -275 mV, 13.74 to 18.84 mM and 1.8 to 3.41 mg L-1, respectively. Following the anoxic incubation, the total desorbed C was increased up to 139 mg L-1. The distribution of C across the five particle size fractions was 3.68-11.73% (> 450 nm), 0.59-5.12% (450-220 nm), 0.45-4.91% (220-100 nm), 0.18-2.91% (100-50 nm), 15.48-35.23% (50 nm - 2.3 nm) and 49.15-63.94% (<2.3 nm). The preliminary results confirmed the release of more nanoparticulate (50-2.3 nm) and truly dissolved (<2.3 nm) organic matter from the anoxic soil column

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

    NASA Technical Reports Server (NTRS)

    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 (conditions of angrite crystallization are limited, and only preliminary attempts been made to understand the changes in fO2 that occurred during petrogenesis. Many of the angrites have phase assemblages which provide conflicting signals about 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

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

    PubMed

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

    2015-01-23

    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 ≈0.3mg/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. PMID:25200120

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

    PubMed

    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. PMID:26408978

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

    NASA Astrophysics Data System (ADS)

    Naudet, V.; Revil, A.; Rizzo, E.; Bottero, J.-Y.; Bégassat, P.

    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.

  6. Degradation of the Herbicide Metolachlor in Drummer Soil Under Different Redox Conditions

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Understanding the role of microorganisms and effect of soil environmental conditions on herbicide fate is critical for stewardship of herbicide use in cropping systems. As compared to the modernized perceptions of soil redox status, diminutive progress has been made in characterizing the impact of a...

  7. Redox potential and survival of virulent Treponema pallidum under microaerophilic conditions.

    PubMed

    Steiner, B; McLean, I; Graves, S

    1981-10-01

    A strongly reduced culture medium, capable of maintaining the virulence of Treponema pallidum (Nichols) for several days, was exposed to an atmosphere of 3% oxygen in nitrogen for 2-3 days before inoculation with T pallidum. By using various volumes of medium in uniform tubes a range of redox potentials (Ecal) from -94 mV to -325 mV was produced depending on the surface area-to-volume ratios of the medium. The anaerobic medium had an Ecal value of -387 mV. The medium was inoculated with T pallidum and incubated in an atmosphere of 3% oxygen. The survival of treponemes at different redox potentials was monitored by observing the retention of motility and by measuring the latent period of infection after inoculation of the cultures into the shaved backs of rabbits. Under these conditions T pallidum survived longest at low (electronegative) redox potential. An inverse linear relationship was observed between the redox potential of the culture medium and the survival of T pallidum, as measured by the time required for a 90% reduction of virulent organisms. No optimum redox potential was detected, the most electronegative medium (-325 mV, Ecal) giving the best survival. PMID:7028206

  8. Influence of the redox condition dynamics on the removal efficiency of a laboratory-scale constructed wetland.

    PubMed

    Wiessner, A; Kappelmeyer, U; Kuschk, P; Kästner, M

    2005-01-01

    A laboratory reactor planted with Juncus effusus treating an artificial wastewater was used to investigate the short-term and long-term variations and interactions in the redox conditions as well as the removal efficiency of C and the N turnover. The permanent circulation of the process water enabled the micro-gradient processes to be evaluated for an operating period of 20 months. Steady-state conditions were achieved throughout the operating period with high mean removal efficiencies of 92.7% total organic carbon, 82.0% ammonia and 97.6% nitrate. Daily variations in the redox state of the rhizosphere of a few hundred mV were observed, ranging from about -200 to oxidized conditions of about +200 mV and driven by daylight. Variations in pH associated with changes in light and redox were linked to the dynamics of the fates of organic and inorganic carbon species. The ammonia removal processes were found to be firmly established, including for moderately reduced redox conditions with high efficiencies for E(h)>-50 mV. The enrichment of ammonia (up to 13 mg l(-1)) closely linked to the light, particularly during summertime, indicates the existence of hitherto unconsidered additional N turnover pathways in the rhizoplane involving N(2) produced by microbes or released by plants. C turnover was strongly related to the seasonal variation in illumination with minimum efficiencies during the dark season. In addition, it was characterized by oscillation with periods of approximately 1 month. The relationships found are dominant for biofilms on the rhizoplane and decisive for the removal efficiency of especially simple constructed and natural wetlands. The results highlight the importance of helophytes and their physiological specifics for removal processes. PMID:15607183

  9. Nontronite (NAu-1) Structure Associated with Microbial Fe(III) Reduction in Various Redox Conditions

    NASA Astrophysics Data System (ADS)

    Koo, T.; Kim, S.; Kim, J.

    2011-12-01

    Shewanella oneidensis MR-1 respires the structural Fe(III) of smectite and promotes illite formation in O2-free environment (Kostka et al., 1996, Kim et al., 2004). Since S. oneidensis is a facultative iron reducing bacterium, it is crucial to understand the structural changes induced by bio-reduction of structural Fe(III) in various redox conditions. Furthermore, the changes in cation exchange capacity (CEC) of bio-reduced nontronite upon the modification of mineral structure has not been extensively studied in terms of Fe-cycling. In this present study, we reported the evolution of nontronite structure at various time points in various redox conditions and corresponding CEC upon reduction and re-oxidation. S. oneidensis MR-1 was incubated in M1 medium with Na-lactate as the electron donor and Fe in nontronite (NAu-1) as the sole electron acceptor at pH 7 in anaerobic chamber for 3 hrs, 12 hrs, 1 day, 2 days, 4 days, 7 days, 14 days, and 21 days. O2 gas bubbling was then applied to the sample at each time point for 24 hours for re-oxidation. The triplet samples at each time point for both reduction and re-oxidation experiments were prepared. The extent of Fe(III) reduction measured by 1,10-phenanthroline method (Stucki and Anderson, 1981) indicated that the structural Fe(III) was reduced up to 8.8% of total Fe(III) within 21 days. XRD data with various treatments such as air dried, glycolated and lithium-saturated showed that K-nontronite may be formed because no discrete 10-Å illite peak was observed in Li-saturated sample upon glycolation. The CEC increased from 747 meg/kg to 1145 meg/kg during Fe(III) reduction and decreased to 954 meg/kg upon re-oxidation, supporting the possible formation of K-nontronite. The direct observation by electron microscopy verified the structural changes in nontonite in various redox conditions. The long-term experiment for 6 months, is in progress in anaerobic chamber, and results will be discussed. Kim, J. W., Dong, H., Seabaugh

  10. Molybdenum isotope fractionation in soils: Influence of redox conditions, organic matter, and atmospheric inputs

    NASA Astrophysics Data System (ADS)

    Siebert, C.; Pett-Ridge, J. C.; Opfergelt, S.; Guicharnaud, R. A.; Halliday, A. N.; Burton, K. W.

    2015-08-01

    soils are controlled by redox conditions, organic matter, and atmospheric inputs. In this way Mo isotopes have the potential to react to and record climate driven changes in the weathering environment. The presence of both isotopically light and heavy Mo (relative to parent material) across all sites and within individual soil profiles suggests that it is normal for multiple fractionation mechanisms to operate under the open-system conditions of soils.

  11. Rapidly reversible redox transformation in nanophase manganese oxides at room temperature triggered by changes in hydration

    PubMed Central

    Birkner, Nancy; Navrotsky, Alexandra

    2014-01-01

    Chemisorption of water onto anhydrous nanophase manganese oxide surfaces promotes rapidly reversible redox phase changes as confirmed by calorimetry, X-ray diffraction, and titration for manganese average oxidation state. Surface reduction of bixbyite (Mn2O3) to hausmannite (Mn3O4) occurs in nanoparticles under conditions where no such reactions are seen or expected on grounds of bulk thermodynamics in coarse-grained materials. Additionally, transformation does not occur on nanosurfaces passivated by at least 2% coverage of what is likely an amorphous manganese oxide layer. The transformation is due to thermodynamic control arising from differences in surface energies of the two phases (Mn2O3 and Mn3O4) under wet and dry conditions. Such reversible and rapid transformation near room temperature may affect the behavior of manganese oxides in technological applications and in geologic and environmental settings. PMID:24733903

  12. Does phosphate enhance the natural attenuation of crude oil in groundwater under defined redox conditions?

    PubMed

    Ponsin, Violaine; Mouloubou, Olsen Raïnness; Prudent, Pascale; Höhener, Patrick

    2014-11-15

    After a crude oil spill caused by a broken pipeline in 2009 to a gravel aquifer in southern France, degradation processes under various redox conditions progressively established, but at rates that predict a long life-time of the source under natural attenuation after partial source removal. In this study, we aimed at identifying the rate-limiting factors for each redox condition, with special emphasis on phosphate as limiting nutrient. The study was conducted in laboratory microcosms assembled with material collected on site: sediments, water from monitoring wells, oil and microbial sludge. Redox conditions were promoted by adding electron acceptors (either oxygen, nitrate, limonite (FeO(OH)), cryptomelane (K(Mn(4+),Mn(2+))8O16), or sulfate). For each condition, the role of phosphate was studied by repeated additions for up to 290days. The results showed a very strong stimulation of aerobic and denitrifying rates of oil degradation by phosphate, provided that oxygen and nitrate were repeatedly supplied. Phosphate caused also a marked stimulation of methanogenic degradation, and a relatively small stimulation of metal reduction. These anaerobic processes started only after marked lag phases, and phosphate shortened the lag phase for methanogenic degradation. Degradation of aromatic and aliphatic hydrocarbons with less than 8 carbons, including benzene, was confirmed even under unstimulated conditions. It is concluded that degradation rates at the site are limited by both, availability of electron acceptors and availability of phosphate needed for promoting microbial growth. PMID:24795042

  13. Does phosphate enhance the natural attenuation of crude oil in groundwater under defined redox conditions?

    NASA Astrophysics Data System (ADS)

    Ponsin, Violaine; Mouloubou, Olsen Raïnness; Prudent, Pascale; Höhener, Patrick

    2014-11-01

    After a crude oil spill caused by a broken pipeline in 2009 to a gravel aquifer in southern France, degradation processes under various redox conditions progressively established, but at rates that predict a long life-time of the source under natural attenuation after partial source removal. In this study, we aimed at identifying the rate-limiting factors for each redox condition, with special emphasis on phosphate as limiting nutrient. The study was conducted in laboratory microcosms assembled with material collected on site: sediments, water from monitoring wells, oil and microbial sludge. Redox conditions were promoted by adding electron acceptors (either oxygen, nitrate, limonite (FeO(OH)), cryptomelane (K(Mn4 +,Mn2 +)8O16), or sulfate). For each condition, the role of phosphate was studied by repeated additions for up to 290 days. The results showed a very strong stimulation of aerobic and denitrifying rates of oil degradation by phosphate, provided that oxygen and nitrate were repeatedly supplied. Phosphate caused also a marked stimulation of methanogenic degradation, and a relatively small stimulation of metal reduction. These anaerobic processes started only after marked lag phases, and phosphate shortened the lag phase for methanogenic degradation. Degradation of aromatic and aliphatic hydrocarbons with less than 8 carbons, including benzene, was confirmed even under unstimulated conditions. It is concluded that degradation rates at the site are limited by both, availability of electron acceptors and availability of phosphate needed for promoting microbial growth.

  14. Deepwater redox changes in the southern Okinawa Trough since the last glacial maximum

    NASA Astrophysics Data System (ADS)

    Dou, Yanguang; Yang, Shouye; Li, Chao; Shi, Xuefa; Liu, Jihua; Bi, Lei

    2015-06-01

    In this study, rare earth element (REE) was treated as a paleo-redox proxy to investigate the changes of depositional environment in the southern Okinawa Trough since the last glacial maximum. The acid-leachable fraction (leachate) of the sediments recovered from the ODP Site 1202B is dominated by biogenic and authigenic components while detrital contamination is minor. The significant enrichment of middle REE suggests a large contribution from authigenic Mn oxyhydroxides and cerium (Ce) anomaly can indicate deepwater redox change. The REE parameters including Ce anomaly in the leachate exhibit remarkable and abrupt changes in the early Holocene (∼9.5 ka) and during LGM (∼20 ka). An increase of Ce anomaly at 28-22 ka implies the suboxic deepwater condition probably caused by increased primary productivity. Weak positive Ce anomalies during the last glacial maximum and deglaciation suggest an oxic depositional environment responding to the enhanced deepwater ventilation with the advection of the North Pacific Intermediate Water and/or South China Sea Intermediate Water into the trough. A decrease of Ce anomaly in the early Holocene might be caused by the intrusion and strengthening of the Kuroshio Current in the trough that enhanced the water stratification and induced a gradual development of suboxic depositional condition. Furthermore, an abrupt change of chemical composition at ca. 4 ka probably indicates a decrease of dissolved oxygen in deepwater and a weakening of ventilation in the Okinawa Trough. This study suggests that REE proxy can provide new insights into the linkage among surface current, deepwater circulation and sediment record in the continental margin where terrigenous input dominates.

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

    NASA Astrophysics Data System (ADS)

    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.

  16. Global iridium anomaly, mass extinction, and redox change at the Devonian-Carboniferous boundary

    SciTech Connect

    Wang, K. Univ. of Calgary, Alberta ); Attrep, M. Jr.; Orth, C.J. )

    1993-12-01

    Iridium abundance anomalies have been found on a global scale in the Devonian-Carboniferous (D-C) boundary interval, which records one of the largest Phanerozoic mass-extinction events, an event that devastated many groups of living organisms, such as plants, ammonoids, trilobites, conodonts, fish, foraminiferans, brachiopods, and ostracodes. At or very close to the D-C boundary, there exists a geographically widespread black-shale interval, and Ir abundances reach anomalous maxima of 0.148 ppb (Montagne Noire, France), 0.138 ppb (Alberta, Canada) 0.140 ppb (Carnic Alps, Austria), 0.156 ppb (Guangxi, China), 0.258 ppb (Guizhou, China), and 0.250 ppb (Oklahoma). The discovery of global D-C Ir anomalies argues for an impact-extinction model. However, nonchondritic ratios of Ir to other important elements and a lack of physical evidence (shocked quartz, microtektites) do not support such a scenario. The fact that all Ir abundance maxima are at sharp redox boundaries in these sections leads us to conclude that the Ir anomalies likely resulted from a sudden change in paleo-redox conditions during deposition and/or early diagenesis. 36 refs., 2 figs., 1 tab.

  17. Glutamate-induced metabolic changes influence the cytoplasmic redox state of hippocampal neurons.

    PubMed

    Porras, Omar H; Stutzin, Andrés

    2011-07-22

    Brain cell metabolism is intimately associated with intracellular oxidation-reduction (redox) balance. Glutamatergic transmission is accompanied with changes in substrate preference in neurons. Therefore, we studied cytoplasmatic redox changes in hippocampal neurons in culture exposed to glutamate. Neurons were transfected with HyPer, a genetically encoded redox biosensor for hydrogen peroxide which allows real-time imaging of the redox state. The rate of fluorescence decay, corresponding to the reduction of the biosensor was found to be augmented by low doses of glutamate (10 μM) as well as by pharmacological stimulation of NMDA glutamate receptors. Acute chelation of extracellular Ca(2+) abolished the glutamate-induced effect observed on HyPer fluorescence. Additional experiments indicated that mitochondrial function and hence energetic substrate availability commands the redox state of neurons and is required for the glutamate effect observed on the biosensor signal. Furthermore, our results implicated astrocytic metabolism in the changes of neuronal redox state observed with glutamate. PMID:21708127

  18. Microbial impacts on the geochemistry evolution in a nuclear waste repository -Laboratory experiment of microbially mediated redox changes-

    NASA Astrophysics Data System (ADS)

    Nagaoka, T.

    2010-12-01

    It is important to investigate geochemical evolution around nuclear waste repositories, because geochemical conditions could affect radionuclide migration. Therefore, a laboratory jar experiment was conducted with subsurface sediments, in order to assess the response of the geochemical and microbial communities toward redox processes. The redox process was induced by exposure to air and discontinuation to sediment suspension, which simulated the process occurring during operation of nuclear waste repositories, i.e., tunnel excavation, transport of waste containers, and final backfilling. During the experiments, redox potential, dissolved oxygen, and pH in the suspension were measured, and the concentrations of dissolved ions concentration (e.g., NO3-, SO42- and organic acid), HCl-extractable iron, and also head space gasses (e.g., CO2, CH4) in the jar were analyzed. Moreover, microbial DNA was extracted from the suspension, and PCR-DGGE analysis was performed to analyze the response of microbial communities toward the geochemical changes. As a results, after discontinuation of air exposure with lactate amendment, redox potentials decreased from ca. +300 mV to -430 m V (vs. Ag/AgCl), and the sequential terminal electron-accepting process (TEAPs) was observed with the reactions of aerobic respiration, nitrate reduction, iron reduction, sulfate reduction, and methanogenesis. The related species of the microbes along with TEAPs, e.g., Pseudomonas sp. for nitrate reduction and Desulfovibrio sp. for sulfate reduction, was also detected. These results indicated that the microbial activities would affect the geochemical changes in nuclear repositories.

  19. TRP Channels as Sensors and Signal Integrators of Redox Status Changes

    PubMed Central

    Takahashi, Nobuaki; Mori, Yasuo

    2011-01-01

    Proteins are capable of sensing the redox status of cells. Cysteine residues, which react with oxidants, reductants, and electrophiles, have been increasingly recognized as the mediators of this redox sensitivity. Cation channels encoded by the transient receptor potential (trp) gene superfamily are characterized by a wide variety of activation triggers that act from outside and inside the cell. Recent studies have revealed that a class of TRP channels is sensitive to changes in redox status and is notably susceptible to modifications of cysteine residues, such as oxidation, electrophilic reaction, and S-nitrosylation of sulfhydryls. In this review, we focus on TRP channels, which directly sense redox status, and discuss the biological significance of cysteine modifications and the consequences of this chemical reaction for physiological responses. PMID:22016736

  20. Intermittent fasting results in tissue-specific changes in bioenergetics and redox state.

    PubMed

    Chausse, Bruno; Vieira-Lara, Marcel A; Sanchez, Angélica B; Medeiros, Marisa H G; Kowaltowski, Alicia J

    2015-01-01

    Intermittent fasting (IF) is a dietary intervention often used as an alternative to caloric restriction (CR) and characterized by 24 hour cycles alternating ad libitum feeding and fasting. Although the consequences of CR are well studied, the effects of IF on redox status are not. Here, we address the effects of IF on redox state markers in different tissues in order to uncover how changes in feeding frequency alter redox balance in rats. IF rats displayed lower body mass due to decreased energy conversion efficiency. Livers in IF rats presented increased mitochondrial respiratory capacity and enhanced levels of protein carbonyls. Surprisingly, IF animals also presented an increase in oxidative damage in the brain that was not related to changes in mitochondrial bioenergetics. Conversely, IF promoted a substantial protection against oxidative damage in the heart. No difference in mitochondrial bioenergetics or redox homeostasis was observed in skeletal muscles of IF animals. Overall, IF affects redox balance in a tissue-specific manner, leading to redox imbalance in the liver and brain and protection against oxidative damage in the heart. PMID:25749501

  1. The stability of some selected amino acids under attempted redox constrained hydrothermal conditions.

    PubMed

    Andersson, E; Holm, N G

    2000-02-01

    In order to evaluate the stability of aspartic acid, serine, leucine, and alanine under redox buffered hydrothermal conditions, a series of experiments have been performed. The pyrite-pyrrhotite-magnetite (PPM) mineral assemblage was used in the experimental systems in order to constrain the oxygen fugacity. Likewise, the K-feldspar-muscovite-quartz (KMQ) assemblage was added to control the hydrogen ion activity during the experiments. The purpose was to compare the relative stabilities in buffered and unbuffered experiments. The experiments were conducted at 200 degrees C and 50 bar in Teflon coated autoclaves. Glycine, which was not present initially, started to appear at an early stage in the experimental systems and is believed to be the result of decomposition of serine. Similarly, the increase in relative abundance of alanine is likely to be the result of decomposition of serine. Decomposition rates of leucine, alanine and aspartic acid were found to be lower in experiments containing the redox buffer assemblage pyrite-pyrrhotite-magnetite than in non-redox buffered experiments. The decomposition rate of serine was higher in buffered experiments, which indicates that a transformation pathway via dehydration of serine to dehydroalanine followed by reduction to alanine is promoted by reducing conditions. PMID:10836261

  2. Requirement of ArcA for redox regulation in Escherichia coli under microaerobic but not anaerobic or aerobic conditions.

    PubMed

    Alexeeva, Svetlana; Hellingwerf, Klaas J; Teixeira de Mattos, M Joost

    2003-01-01

    In Escherichia coli, the two-component regulatory ArcAB system functions as a major control system for the regulation of expression of genes encoding enzymes involved in both aerobic and anaerobic catabolic pathways. Previously, we have described the physiological response of wild-type E. coli to changes in oxygen availability through the complete range from anaerobiosis to full aerobiosis (S. Alexeeva, B. de Kort, G. Sawers, K. J. Hellingwerf, and M. J. Teixeira de Mattos, J. Bacteriol. 182:4934-4940, 2000, and S. Alexeeva, K. J. Hellingwerf, and M. J. Teixeira de Mattos, J. Bacteriol. 184:1402-1406, 2002). Here, we address the question of the contribution of the ArcAB-dependent transcriptional regulation to this response. Wild-type E. coli and a mutant lacking the ArcA regulator were grown in glucose-limited chemostat cultures at controlled levels of oxygen availability ranging from full aerobiosis to complete anaerobiosis. A flux analysis of the distribution of catabolic fluxes over parallel pathways was carried out, and the intracellular redox state (as reflected by the NADH/NAD ratio) was monitored for all steady states. Deletion of ArcA neither significantly altered the in vivo activity of the pyruvate dehydrogenase complex and pyruvate formate lyase nor significantly affected catabolism under fully aerobic and fully anaerobic conditions. In contrast, profound effects of the absence of ArcA were seen under conditions of oxygen-restricted growth: increased respiration, an altered electron flux distribution over the cytochrome o- and d-terminal oxidases, and a significant change in the intracellular redox state were observed. Thus, the ArcA regulator was found to exert major control on flux distribution, and it is concluded that the ArcAB system should be considered a microaerobic redox regulator. PMID:12486057

  3. Robustness of fossil fish teeth for seawater neodymium isotope reconstructions under variable redox conditions in an ancient shallow marine setting

    NASA Astrophysics Data System (ADS)

    Huck, Claire E.; van de Flierdt, Tina; Jiménez-Espejo, Francisco J.; Bohaty, Steven M.; Röhl, Ursula; Hammond, Samantha J.

    2016-03-01

    Fossil fish teeth from pelagic open ocean settings are considered a robust archive for preserving the neodymium (Nd) isotopic composition of ancient seawater. However, using fossil fish teeth as an archive to reconstruct seawater Nd isotopic compositions in different sedimentary redox environments and in terrigenous-dominated, shallow marine settings is less proven. To address these uncertainties, fish tooth and sediment samples from a middle Eocene section deposited proximal to the East Antarctic margin at Integrated Ocean Drilling Program Site U1356 were analyzed for major and trace element geochemistry, and Nd isotopes. Major and trace element analyses of the sediments reveal changing redox conditions throughout deposition in a shallow marine environment. However, variations in the Nd isotopic composition and rare earth element (REE) patterns of the associated fish teeth do not correspond to redox changes in the sediments. REE patterns in fish teeth at Site U1356 carry a typical mid-REE-enriched signature. However, a consistently positive Ce anomaly marks a deviation from a pure authigenic origin of REEs to the fish tooth. Neodymium isotopic compositions of cleaned and uncleaned fish teeth fall between modern seawater and local sediments and hence could be authigenic in nature, but could also be influenced by sedimentary fluxes. We conclude that the fossil fish tooth Nd isotope proxy is not sensitive to moderate changes in pore water oxygenation. However, combined studies on sediments, pore waters, fish teeth, and seawater are needed to fully understand processes driving the reconstructed signature from shallow marine sections in proximity to continental sources.

  4. Tracking changes in ocean redox during the PETM using stable chromium isotopes

    NASA Astrophysics Data System (ADS)

    Dixon, S. K.; Parkinson, I. J.; Sexton, P.; Fehr, M.; James, R. H.; Peacock, C.

    2012-12-01

    Climate models predict a decline in oceanic dissolved oxygen under global warming conditions and observations suggest the expansion of tropical oxygen minimum zones is already underway1, with concern over the trend for future seawater oxygen levels. Therefore, previous deoxygenation events in the geological record may provide insight into the dynamics of changing oxygen levels in the Earth's oceans. One such event, is the Palaeocene-Eocene Thermal Maximum (PETM) at ~55Ma which represents a period of rapid global warming. Multiple lines of evidence suggest that at least on a local scale, near bottom anoxia occurred during the event2,3 and further understanding of changing redox conditions during this period may provide insight into future sea level oxygenation. To track seawater oxygenation during the PETM, we are utilising stable Cr isotope composition of marine carbonates, a new palaeo-redox proxy, which has shown potential when applied to modern and ancient carbonates 4,5. We present δ53Cr, trace element and REE data of foraminiferal ooze deposits over the PETM interval. Samples were taken from the North East Atlantic DSDP site 401, which preserves an exceptional and complete carbonate sequence over the interval, at a time when ocean acidification lead to massive sea floor carbonate dissolution6. Foraminifera were taken from the 63 - 150μm size fraction and planktic count data indicate that the relative proportions of dominant species do not change significantly over the event7. Systematic changes occur in REEs, Cr concentration and δ53Cr coincident with the onset of the negative δ13C excursion. The Cr concentrations of the carbonates decrease into the event, which suggests the sea level Cr concentration has fallen. We interpret this to reflect falling oxygen concentration in the seawater, leading to a decrease in aqueous Cr (VI) via precipitation of Cr out of the water column in the form of insoluble Cr (III) hydroxide. Additionally, we will demonstrate how

  5. The effect of redox conditions and bioirrigation on nitrogen isotope fractionation in marine sediments

    NASA Astrophysics Data System (ADS)

    Rooze, J.; Meile, C.

    2016-07-01

    Nitrogen isotopic signatures of sources and sinks of fixed nitrogen (N) can be used to constrain marine nitrogen budgets. However, the reported fractionation during benthic N2 production varies substantially. To assess the range and mechanisms responsible for such observations, we conducted a model study to evaluate the extent to which nitrification, denitrification, and anaerobic ammonium oxidation contribute to the isotopic composition of in situ N2 production. Different hydrodynamic regimes were taken into account, ranging from bioirrigation to diffusion-dominated transport. The benthic redox conditions were found to control the N isotope effect, which under reducing conditions is driven by fractionation during nitrification and anaerobic ammonium oxidation and under oxidizing conditions by fractionation during denitrification. Environmental parameters, such as the mineralization rate, the bioirrigation intensity, and chemical composition of the overlying water affect the benthic redox zonation and therefore also the benthic N isotope effect. The N isotope effect of benthic N2 production was computed for a wide range of bioirrigation intensities and mineralization rates, and found to be approximately -3‰ for commonly encountered conditions. This value is similar to previous estimates of the global N isotope effect of benthic N2 production, and further constrains the relative importance of water column vs. benthic N2 production.

  6. Changes in redox properties of humic acids upon sorption to alumina

    NASA Astrophysics Data System (ADS)

    Subdiaga, Edisson; Orsetti, Silvia; Jindal, Sharmishta; Haderlein, Stefan B.

    2016-04-01

    1. Introduction A prominent role of Natural Organic Matter (NOM) in biogeochemical processes is its ability to act as an electron shuttle, accelerating rates between a bulk electron donor and an acceptor. The underlying processes are reversible redox reactions of quinone moieties.1 This shuttling effect has been studied in two major areas: transformation of redox active pollutants and microbial respiration.2-3 Previous studies primarily compared effects in the presence or absence of NOM without addressing the redox properties of NOM nor its speciation. The interaction between humic acids (HA) and minerals might change properties and reactivity of organic matter. Specifically, we investigate whether changes in the redox properties of a HA occur upon sorption to redox inactive minerals. Since fractionation and conformational rearrangements of NOM moieties upon sorption are likely to happen, the redox properties of the NOM fractions upon sorption might differ as well. 2. Materials and methods Elliot Soil Humic Acid (ESHA), Pahokee Peat Humic Acid (PPHA) and Suwannee River Humic Acid (SRHA) were used as received from IHSS. Aluminum oxide (Al2O3) was suspended in 0.1M KCl. Sorption was studied at pH 7.0 in duplicate batch experiments for several HA/Al2O3 ratios. For the suspension (mineral + sorbed HA, plus dissolved HA), the filtrate (0.45μm) and the HA stock solution, the electron donating and accepting capacities (EDC and EAC) were determined following established procedures.4 3. Results All studied HA-Al2O3 systems showed similar behavior with regard to changes in redox properties. There was a significant increase in the EDC of the whole suspension compared to the stock solutions and the non-sorbed HA in the filtrate (up to 300% for PPHA). This effect was more pronounced with increasing amounts of sorbed HA in the suspension. Although ESHA had the highest sorption capacity on Al2O3 (~ 6 times higher than PPHA & SRHA), it showed the smallest changes in redox

  7. Fungal and bacterial mediated denitrification in wetlands: influence of sediment redox condition.

    PubMed

    Seo, Dong Cheol; DeLaune, R D

    2010-04-01

    Fungal and bacterial denitrification rates were 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) ranging from strongly reducing to moderately oxidizing conditions. Denitrification was determined using the substrate-induced respiration (SIR) inhibition and acetylene inhibition methods. Cycloheximide (C15H23NO4) was used as the fungal inhibitor and streptomycin (C21H39N7O12) as the bacterial inhibitor. At Eh values of +250 mV and +400 mV, denitrification rates by fungi and bacteria were 34.3-35.1% and 1.46-1.59% of total denitrification, respectively, indicating that fungi were responsible for most of the denitrification under aerobic or weakly reducing conditions. On the other hand, at Eh -200 mV, denitrification rates of fungi and bacteria were 17.6% and 64.9% of total denitrification, respectively, indicating that bacteria were responsible for most of the denitrification under strongly reducing conditions. Results show fungal denitrification was dominant under moderately reducing to weakly oxidizing conditions (Eh>+250 mV), whereas bacterial denitrification was dominant under strongly reducing condition (Eh<-100 mV). At Eh values between -100 to +100 mV, denitrification by fungi and bacteria were 37.9-43.2% and 53.0-51.1% of total denitrification, respectively, indicating that both bacteria and fungi contributed significantly to denitrification under these redox conditions. Because N2O is an important gaseous denitrification product in sediment, fungal denitrification could be of greater ecological significance under aerobic or moderately reducing conditions contributing to greenhouse gas emission and global warming potential (GWP). PMID:20122708

  8. Release of arsenic from a Haplic Gleysol under controlled redox conditions

    NASA Astrophysics Data System (ADS)

    Mansfeldt, T.; Overesch, M.

    2009-04-01

    The redox potential (EH) governs the solubility of trace elements in soils, mainly by the reductive dissolution of iron (hydr)oxides, which are important adsorbents. Similarly the species distribution of some trace elments in soils strongly depends on EH. Species distribution in turn affects the solubility and toxicity of trace elements. Hence, the EH is a master variable for the behaviour of trace elements in soil. Arsenic is such a redox-sensitive trace element. In the lowlands of southern Münsterland, North Rhine-Westphalia (Germany), various Gleysols under grassland recently have been found to be naturally enriched with arsenic. Field measurements at such a site revealed high variations in soil EH during the course of the time with a range of 900 mV. We initiated a laboratory study to determine the effects of different redox regimes (oxidizing, moderately reducing and reducing soil conditions) both on the solubility and speciation of As. The batch study was performed using the AhBg, Bg1 and Bg2 horizons from a Haplic Gleysol. Total arsenic contents increased with increasing soil depth from 121, 613 to 1.004 mg/kg As. Fixed redox potentials in stirred soil suspensions were achieved by flushing closed glass microcosms with either N2 or air during 40 days. Redox potential and pH of the suspension were continuously recorded. In intervals of 48 hours, subsamples of 40 ml were taken from a sampling port by a tube connected to a vacuum filtration device (0.45 µm). The filtrates were analyzed for DOC, TIC, nitrate, sulfate, phosphate, and total Mn, Fe and total As. Also, Fe2+ and As(III) were determined. First results indicate that lowering EH from 450 to -100 mV (pH 7) results in a significant increase of pH and concentrations of DOC, TIC, total Fe, Fe2+, Mn, and total As in solution. Significant concentrations of As(III) could be observed at EH values below 100 mV.

  9. Impact of hydroquinone used as a redox effector model on potential denitrification, microbial activity and redox condition of a cultivable soil.

    PubMed

    Perotti, Elda B R

    2015-01-01

    In this microcosm study, we analyzed the effect produced by hydroquinone on the expression of soil biological denitrification, in relation to the redox state of the soil, both in terms of intensity factor (Eh') and capacity factor (amount of oxidized or reduced compounds). The supplementation of an Argiudoll soil with hydroquinone decreased the soil apparent reduction potential (Eh') and soil dehydrogenase activity (formazan production from tetrazolium chloride reduction; redox capacity factor), the relationship between both factors being highly significative, r=0.99 (p<0.001). The bacterial population (measured by colony forming units) increased, and the production of N2O was greater (p<0.001) at 200 and 400μg/g dry soil doses. Furthermore, there was an inverse relationship between soil dehydrogenase activity and the number of bacteria (r=-0.82; p<0.05), increased denitrification activity and changes in the CO2/N2O ratio value. These results suggest that hydroquinone at supplemented doses modified the soil redox state and the functional structure of the microbial population. Acetate supplementation on soil with hydroquinone, to ensure the availability of an energy source for microbial development, confirmed the tendency of the results obtained with the supplementation of hydroquinone alone. The differences observed at increased doses of hydroquinone might be explained by differences on the hydroquinone redox species between treatments. PMID:26364186

  10. Influence of pH and Redox Conditions on Copper Leaching

    SciTech Connect

    Kavanaugh, Rathi; Al-Abed, Souhail R.; Purandare, Jaydeep; Allen, Derrick

    2004-03-31

    The Toxicity Characteristic Leaching Procedure (TCLP) is a regulatory leach test in the RCRA programs. It was developed to determine the leaching potential of landfilled waste in order to assess the hazards associated with the leachates. The test was developed to study concentration of hazardous materials in leachates, under a mismanagement scenario, when they are co-disposed with municipal waste. The test uses leaching of waste at either of two acidic pH values i.e., 2.8 and 4.93. While low pH leachant can extract many metals, some metals soluble at higher pH values are either underestimated or totally unaccounted for. The method also has limitations for application to different waste matrices. The procedure does not take into account the effect of redox conditions on leaching. Leaching studies are, therefore, being conducted to determine the effect of combinations of Eh and pH on the leaching potential of mineral and organic wastes. The goal of this study is to propose alternate methods applicable for a variety of waste matrices. The presentation will discuss the effects of combinations of pH and redox conditions on the leaching behavior of copper from a mineral processing waste.

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

    NASA Astrophysics Data System (ADS)

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

    2014-02-01

    The extent in which redox conditions can affect the removal kinetics of 58Co and 65Zn from tidal water by mangrove sediments was evaluated in microcosm experiments, simulating a tidal flooding period of 6 h. The average half-removal time (t1/2) of 58Co from overlaying water was slightly higher (7.3 h) under an N2-purged water column than under an aerated water column (5.4 h). A lower difference was found for 65Zn (1.9 h vs. 1.5 h, respectively). Average removals of 58Co activities from water were 54.6% (N2 treatment) and 43.5% (aeration treatment), whereas these values were 88.0% and 92.7% for 65Zn, respectively. Very contrasting sorption kinetics of different radiotracers occurred, while more oxidising conditions favoured only a slightly higher removal. Average 58Co and 65Zn inventories within sediments were 30.4% and 18.8% higher in the aeration treatment, respectively. A stronger particle-reactive behaviour was found for 65Zn that was less redox-sensitive and more efficiently removed by sediments than 58Co.

  12. Effect of Oxygen and Redox Potential on Glucose Fermentation in Thermotoga maritima under Controlled Physicochemical Conditions

    PubMed Central

    Lakhal, Raja; Auria, Richard; Davidson, Sylvain; Ollivier, Bernard; Dolla, Alain; Hamdi, Moktar; Combet-Blanc, Yannick

    2010-01-01

    Batch cultures of Thermotoga maritima were performed in a bioreactor equipped with instruments adapted for experiments performed at 80°C to mimic the fluctuating oxidative conditions in the hot ecosystems it inhabits. When grown anaerobically on glucose, T. maritima was shown to significantly decrease the redox potential (Eh) of the culture medium down to about −480 mV, as long as glucose was available. Addition of oxygen into T. maritima cultures during the stationary growth phase led to a drastic reduction in glucose consumption rate. However, although oxygen was toxic, our experiment unambiguously proved that T. maritima was able to consume it during a 12-hour exposure period. Furthermore, a shift in glucose metabolism towards lactate production was observed under oxidative conditions. PMID:21461371

  13. A New Dimensionless Number for Redox Conditions within the Hyporheic Zone: Morphological and Biogeochemical Controls

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

    We introduce a new Damköhler number, Da, to quantify the biogeochemical status of the hyporheic zone and to upscale local hyporheic processes to reach scale. Da is defined as the ratio between the median hyporheic residence time, τup,50, which is a representative time scale of the hyporheic flow, and a representative time scale of biogeochemical reactions, which we define as the time τlim needed to consume dissolved oxygen to a prescribed threshold concentration below which reducing reactions are activated: Da = τup,50/τlim. This approach accounts for streambed topography and surface hydraulics via the hyporheic residence time and biogeochemical reaction via the time limit τlim. Da can readily evaluate the redox status of the hyporheic zone. Values of Da larger than 1 indicate prevailing anaerobic conditions, whereas values smaller than 1 prevailing aerobic conditions. This new Damköhler number can quantify the efficiency of hyporheic zone in transforming dissolved inorganic nitrogen species such as ammonium and nitrate, whose transformation depends on the redox condition of the hyporheic zone. We define a particular value of Da, Das, that indicates when the hyporheic zone is a source or a sink of nitrate. This index depends only on the relative abundance of ammonium and nitrate. The approach can be applied to any hyporheic zone of which the median hyporheic residence time is known. Application to streams with pool-riffle morphology shows that Da increases passing from small to large streams implying that the fraction of the hyporheic zone in anaerobic conditions increases with stream size.

  14. Instability of bottom-water redox conditions during accumulation of Quaternary sediment in the Japan Sea

    USGS Publications Warehouse

    Piper, D.Z.; Isaacs, C.M.

    1996-01-01

    The concentrations of Cd, Cr, Cu, Mo, Ni, Sb, U, V, and Zn were measured in early Quaternary sediment (1.32 to 1.08 Ma) from the Oki Ridge in the Japan Sea. The elements were partitioned between a detrital fraction, composed of terrigenous and volcaniclastic aluminosilicate debris, and a marine fraction, composed of biogenic and hydrogenous debris derived from seawater. The most important factors controlling minor-element accumulation rates in the marine fraction were (1) primary productivity in the photic zone, which largely controlled the flux of particulate organic-matter-bound minor elements settling through the water column and onto the seafloor, and (2) bottom-water redox, which determined the suite of elements that accumulated directly from seawater. This marine fraction of minor elements on Oki Ridge recorded six periods of high minor-element abundance. Assuming a constant bulk sediment accumulation rate, each period lasted roughly 5,000 to 10,000 years with a 41,000-year cycle. Accumulation rates of individual elements such as Cd, Mo, and U suggest sulfate-reducing conditions were established in the bottom water during the 10,000-year periods; accumulation rates of Cr and V during the intervening periods are indicative of less reducing, denitrifying conditions. Interelement ratios, for example, Cu:Mo, V:Cr, and Sb:Mo, further reflect bottom-water instability, such that bottom-water redox actually varied from sulfate reducing to denitrifying during the periods of highest minor-element accumulation rates; it varied from denitrifying to oxidizing during the intervening periods. Sediment lithology supports these interpretations of the minor-element distributions; the sediment is finely laminated for several of the periods represented by Cd, Mo, and U maxima and weakly laminated to bioturbated for the intervening periods. The geochemistry of this sediment demonstrates the unambiguous signal of Mo, principally, but of several other minor elements as well in

  15. Modeling the Time-dependent Changes in Electrical Conductivity of Basaltic Melts With Redox State

    NASA Astrophysics Data System (ADS)

    Pommier, A.; Gaillard, F.; Pichavant, M.

    2008-12-01

    The electrical conductivity σ is an efficient probe of mass transfer processes within silicate melts and magmas. Little attention has been given to the influence of redox state (fO2) on the melts conductivity. We present an experimental setup allowing electrical conductivity measurements for basaltic melts under variable fO2. We demonstrate a significant dependence of σ with fO2, allowing to characterize in situ the mechanisms and kinetics of redox changes in the melt. Experiments were conducted on basalts from Pu'u 'O'o, Hawaii, and Mt.Vesuvius, Italy. Measurements were performed cylindrical glass samples (OD: 6mm, ID: 1mm, L: 8mm) using an impedance spectrometer. Experiments were conducted in a 1atm vertical furnace, from 1200°C to 1400°C. Variable gas atmosphere (air, CO2 or CO-CO2 gas mixtures) were used, imposing ΔNNO from -1 to +7. Electrical conductivities were determined for the two melts at constant fO2, different T (constant fO2) and constant T, different fO2 (variable fO2) obtained by changing the gas composition. Isothermal reduction and oxidation cycles were performed. Glasses quenched from different T and fO2 conditions were analyzed by electron microprobe, the FeO concentration was determined by wet chemistry. In constant fO2 experiments, a small but detectable effect of fO2 on σ is evidenced. At 1300°C, the difference in the Kilauea sample conductivity between reduced (ΔNNO=-1) and oxidized (ΔNNO=+7) fO2 is <1(ohm.m)-1, the sample being more conductive when reduced. The temperature dependence of σ was fitted using Arrhenian equations, the activation energy Ea being 100kJ/mol. Sodium was identified as the main charge carrier in the melts. The fO2-effect on σ can thus be attributed to the influence of the Fe2+/Fe3+ ratio on sodium mobility. The fO2-dependence of σ was included in the model of Pommier et al.(2008), allowing the conductivity of natural melts to be calculated as a function of T, P, H2O, and fO2. Variable fO2 experiments

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

    PubMed

    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. PMID:22115096

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

    NASA Astrophysics Data System (ADS)

    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.

  18. Redox-linked conformational changes of a multiheme cytochrome from Geobacter sulfurreducens

    SciTech Connect

    Morgado, Leonor; Bruix, Marta; Londer, Yuri Y.; Pokkuluri, P. Raj; Schiffer, Marianne; Salgueiro, Carlos A. . E-mail: csalgueiro@dq.fct.unl.pt

    2007-08-17

    Multiheme c-type cytochromes from members of the Desulfovibrionacea and Geobactereacea families play crucial roles in the bioenergetics of these microorganisms. Thermodynamic studies using NMR and visible spectroscopic techniques on tetraheme cytochromes c {sub 3} isolated from Desulfovibrio spp. and more recently on a triheme cytochrome from Geobacter sulfurreducens showed that the properties of each redox centre are modulated by the neighbouring redox centres enabling these proteins to perform energy transduction and thus contributing to cellular energy conservation. Electron/proton transfer coupling relies on redox-linked conformational changes that were addressed for some multiheme cytochromes from the comparison of protein structure of fully reduced and fully oxidised forms. In this work, we identify for the first time in a multiheme cytochrome the simultaneous presence of two different conformations in solution. This was achieved by probing the different oxidation stages of a triheme cytochrome isolated from G. sulfurreducens using 2D-NMR techniques. The results presented here will be the foundations to evaluate the modulation of the redox centres properties by conformational changes that occur during the reoxidation of a multiheme protein.

  19. RoGFP1 is a quantitative biosensor in maize cells for cellular redox changes caused by environmental and endogenous stimuli.

    PubMed

    Liu, Xiaoning; Wu, Jiamei; Liu, Hao; Zong, Na; Zhao, Jun

    2014-09-26

    Reduction-oxidation-sensitive green fluorescent proteins (roGFPs) have been demonstrated to be valuable tools in sensing cellular redox changes in mammalian cells and model plants, yet have not been applied in crops such as maize. Here we report the characteristics of roGFP1 in transiently transformed maize mesophyll protoplasts in response to environmental stimuli and knocked-down expression of ROS-scavenging genes. We demonstrated that roGFP1 in maize cells ratiometrically responds to cellular redox changes caused by H2O2 and DTT, as it does in mammalian cells and model plants. Moreover, we found that roGFP1 is sensitive enough to cellular redox changes caused by genetic perturbation of single ROS genes, as exemplified by knocked-down expression of individual ZmAPXs, in maize protoplasts under controlled culture conditions and under stress conditions imposed by H2O2 addition. These data provide evidence that roGFP1 functions in maize cells as a biosensor for cellular redox changes triggered by genetic lesion of single ROS genes even under stress conditions, and suggest a potential application of roGFP1 in large-scale screening for maize mutants of ROS signaling involved in development and stress resistance. PMID:25173931

  20. Benthic Redox Conditions and Oceanographic Variability in the Upper Central Peruvian Margin since the Nineteenth Century Depicted from Benthic Foraminifera

    NASA Astrophysics Data System (ADS)

    Cardich, J.; Sifeddine, A.; Salvatecci, R.; Briceño, F. J., Sr.; Almeida, C.; Romero, D.; Gutierrez, D.

    2014-12-01

    Benthic foraminifera compose the dominant biota in the central Peruvian margin, which is impinged by an intense Oxygen Minimum Zone (OMZ). Here subsurface and benthic biogeochemical conditions are characterized by oxygen deficiency in the bottom waters, strong fluxes of settling organic matter and reducing conditions in the surface sediments. These processes interact among each other and are amplified or relaxed according to the variability of oceanic conditions at different spatial and temporal scales. Recent studies on living foraminiferal assemblages determined the association of species to a geochemical condition (in terms of redox and organic matter (OM)). Species such as Bolivina costata, Nonionella auris and Virgulinella fragilis were characteristic of sulphidic/labile OM-rich sediments, whereas Bolivina pacifica headed the assemblage representative of postoxia (no oxygen, non sulphidic)/preserved OM. The present study aims to reconstruct the decadal to multidecadal variation of benthic paleo-redox conditions for the last two centuries, based on laminated sedimentary records of benthic foraminiferal assemblages and redox-sensitive metals (Mo, Re, etc.) in the upper margin off Callao (12°S). Three major multidecadal periods were determined for the record: i) the mid to late nineteenth century, characterized by the occurrence of massive diatom-rich sedimentation events, development of bottom anoxia, and higher abundance of Bolivina costata and Nonionella auris; ii) the late nineteenth century to mid-twentieth century, featuring interdecadal variations of redox conditions; and iii) the late twentieth century until the early 2000's, in which redox-sensitive metal records exhibit a trend towards less reducing conditions, accompanied by higher relative abundances of postoxia foraminiferal species (e.g. Bolivina pacifica or Bolivina plicata). Remarkably, the first multidecadal period is associated with a higher ENSO activity, whereas the latest one is parallel to

  1. Ageing-induced changes in the redox status of peripheral motor nerves imply an effect on redox signalling rather than oxidative damage

    PubMed Central

    McDonagh, Brian; Scullion, Siobhan M.; Vasilaki, Aphrodite; Pollock, Natalie; McArdle, Anne; Jackson, Malcolm J.

    2016-01-01

    Ageing is associated with loss of skeletal muscle fibres, atrophy of the remaining fibres and weakness. These changes in muscle are accompanied by disruption of motor neurons and neuromuscular junctions although the direct relationship between the nerve and muscle degeneration is not understood. Oxidative changes have been implicated in the mechanisms leading to age-related loss of muscle mass and in degeneration of the central nervous system, but little is known about age-related changes in oxidation in specific peripheral nerves that supply muscles that are affected by ageing. We have therefore examined the sciatic nerve of old mice at an age when loss of tibialis anterior muscle mass and function is apparent. Sciatic nerve from old mice did not show a gross increase in oxidative damage, but electron paramagnetic resonance (EPR) studies indicated an increase in the activity of superoxide and/or peroxynitrite in the nerves of old mice at rest that was further exacerbated by electrical stimulation of the nerve to activate muscle contractions. Proteomic analyses indicated that specific redox-sensitive proteins are increased in content in the nerves of old mice that may reflect an adaptation to regulate the increased superoxide/peroxynitrite and maintain redox homoeostasis. Analysis of redox active cysteines showed some increase in reversible oxidation in specific proteins in nerves of old mice, but this was not universally seen across all redox-active cysteines. Detailed analysis of the redox-active cysteine in one protein in the nerve of old mice that is key to redox signalling (Peroxiredoxin 6, Cys 47) showed a minor increase in reversible oxidation that would be compatible with a change in its redox signalling function. In conclusion, the data presented indicate that sciatic nerve from old mice does not show a gross increase in oxidative damage similar to that seen in the TA and other muscles that it innervates. Our results indicate an adaptation to increased

  2. Ageing-induced changes in the redox status of peripheral motor nerves imply an effect on redox signalling rather than oxidative damage.

    PubMed

    McDonagh, Brian; Scullion, Siobhan M; Vasilaki, Aphrodite; Pollock, Natalie; McArdle, Anne; Jackson, Malcolm J

    2016-05-01

    Ageing is associated with loss of skeletal muscle fibres, atrophy of the remaining fibres and weakness. These changes in muscle are accompanied by disruption of motor neurons and neuromuscular junctions although the direct relationship between the nerve and muscle degeneration is not understood. Oxidative changes have been implicated in the mechanisms leading to age-related loss of muscle mass and in degeneration of the central nervous system, but little is known about age-related changes in oxidation in specific peripheral nerves that supply muscles that are affected by ageing. We have therefore examined the sciatic nerve of old mice at an age when loss of tibialis anterior muscle mass and function is apparent. Sciatic nerve from old mice did not show a gross increase in oxidative damage, but electron paramagnetic resonance (EPR) studies indicated an increase in the activity of superoxide and/or peroxynitrite in the nerves of old mice at rest that was further exacerbated by electrical stimulation of the nerve to activate muscle contractions. Proteomic analyses indicated that specific redox-sensitive proteins are increased in content in the nerves of old mice that may reflect an adaptation to regulate the increased superoxide/peroxynitrite and maintain redox homoeostasis. Analysis of redox active cysteines showed some increase in reversible oxidation in specific proteins in nerves of old mice, but this was not universally seen across all redox-active cysteines. Detailed analysis of the redox-active cysteine in one protein in the nerve of old mice that is key to redox signalling (Peroxiredoxin 6, Cys 47) showed a minor increase in reversible oxidation that would be compatible with a change in its redox signalling function. In conclusion, the data presented indicate that sciatic nerve from old mice does not show a gross increase in oxidative damage similar to that seen in the TA and other muscles that it innervates. Our results indicate an adaptation to increased

  3. Macroform and microform-induced change in redox-sensitive chemistries of river channel surface sediments

    NASA Astrophysics Data System (ADS)

    Byrne, P.; Zhang, H.; Heathwaite, A. L.; Binley, A.; Ullah, S.; Kaeser, D.; Heppell, C. M.; Lansdown, K.; Trimmer, M.

    2012-04-01

    In-stream geomorphological features such as riffle-pool sequences (macroforms) can produce steep hydraulic gradients which induce flow in and out of the riverbed - hyporheic exchange flow (HEF). The acceleration of flow over channel obstacles such as large cobbles and boulders (microforms) can create variation in surface-subsurface pressure gradients and generation of HEF. HEF in shallow surface sediments affect the transformation of redox-sensitive chemical forms and, therefore, the attenuation or release of nutrients in river systems. Here, we examine the relationship between stream geomorphological environment (microform and macroform) and concentration profiles of redox-sensitive species (nitrate, sulphate, iron, manganese) in shallow (15cm) subsurface sediments. In-situ passive samplers (diffusive equilibrium in thin films - DET) are used to obtain biogeochemical data from armoured environments at fine scale (cm) depth resolution where there is strong upwelling. The probes were deployed in a 50m reach of the River Eden, Cumbria, UK, during baseflow conditions. The experimental setup allowed for the assessment of differences in redox-sensitive chemistries between a riffle and pool environment and between smooth and rough bed surfaces in the pool. The passive sensing basis of the DET methodology provided a means for investigating how HEF systems generated at two different geomorphological scales influence the concentration and spatial patterns of redox-sensitive species. DET's capability of measuring at high spatial resolution allowed the extent of hyporheic mixing to be targeted, even though it is often limited to the top few centimetres of sediment.

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

    PubMed

    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. PMID:26546766

  5. Chromium Redox Equilibria in Fluids and Minerals under Hydrothermal and Subduction-zone Conditions

    NASA Astrophysics Data System (ADS)

    Hao, J.; Sverjensky, D. A.; Hazen, R. M.

    2015-12-01

    Chromium mobility and isotopic variations have been reported from a variety of high-temperature environments from hydrothermal to diamond-forming at elevated temperatures and pressures [1, 2, 3]. In addition, experiments under upper mantle conditions reported Cr-rich fluids in equilibrium with chromium oxide (Cr3+2O3) [4]. These studies suggest the need for theoretical models of the aqueous speciation of chromium in fluids and the stabilities of Cr minerals under deep crustal and upper mantle conditions. We estimated the thermodynamic properties of aqueous Cr2+, Cr3+, HCrO4-, CrO42-, and Cr2O72- using published data [5, 6] and the Deep Earth Water Model [7] to predict the different oxidation states of aqueous Cr to 1,000 °C and 5.0 GPa. We show that Cr(II) becomes the major redox state of Cr in hydrothermal fluids at 100 to 400 °C, with log fO2,g at magnetite/hematite over a wide range of pH values. In subduction zones, with log fO2,g at QFM to QFM - 2, a range of Cr redox states (II, III, and VI) may exist at 600 °C and 5 GPa depending on the pH. However, at higher temperatures (1000 °C), aqueous Cr(III) disappears and Cr(II) is favored relative to Cr(VI), again depending on the pH. Our predicted stability of Cr(II) in aqueous fluids at high temperatures suggests new mechanisms for redox/pH dependent Cr isotopic fractionation. We also estimated the thermodynamic properties of Cr(II)- and Cr(III)-garnets with the Sverjensky-Molling equation [8] to investigate the stability of Cr-garnet-fluid equilibria at elevated pressures and temperatures. References: [1] Schoenberg et al., 2008, Chem Geol 249, 294-306; [2] Farkaš et al., 2013, GCA 123, 74-92; [3] Stachel & Harris, 2008, Ore Geol. Rev, 34, 5-32; [4] Klein-BenDavid et al., 2011, Lithos 125, 122-130; [5] Ball & Nordstrom, 1998, J Chem Eng Data 43, 895-918; [6] Johnson & Nelson, 2012, Inorg Chem 51, 6116-6128; [7] Sverjensky et al. 2014, GCA 129, 125-145; [8] Sverjensky & Molling, 1992, Nature 356, 231-234.

  6. A system for conducting igneous petrology experiments under controlled redox conditions in reduced gravity

    NASA Technical Reports Server (NTRS)

    Williams, R. J.

    1986-01-01

    The Space Shuttle and the planned Space Station will permit experimentation under conditions of reduced gravitational acceleration offering experimental petrologists the opportunity to study crystal growth, element distribution, and phase chemistry. In particular the confounding effects of macro and micro scale buoyancy-induced convection and crystal settling or floatation can be greatly reduced over those observed in experiments in the terrestrial laboratory. Also, for experiments in which detailed replication of the environment is important, the access to reduced gravity will permit a more complete simulation of processes that may have occurred on asteroids or in free space. A technique that was developed to control, measure, and manipulate oxygen fugacites with small quantities of gas which are recirculated over the sample is described. This system should be adaptable to reduced gravity space experiments requiring redox control. Experiments done conventionally and those done using this technique yield identical results done in a 1-g field.

  7. A system for conducting igneous petrology experiments under controlled redox conditions in reduced gravity

    NASA Technical Reports Server (NTRS)

    Williams, Richard J.

    1987-01-01

    The Space Shuttle and the planned Space Station will permit experimentation under conditions of reduced gravitational acceleration offering experimental petrologists the opportunity to study crystal growth, element distribution, and phase chemistry. In particular the confounding effects of macro and micro scale buoyancy-induced convection and crystal settling or flotation can be greatly reduced over those observed in experiments in the terrestrial laboratory. Also, for experiments in which detailed replication of the environment is important, the access to reduced gravity will permit a more complete simulation of processes that may have occurred on asteroids or in free space. A technique that was developed to control, measure, and manipulate oxygen fugacities with small quantities of gas which are recirculated over the sample. This system could be adaptable to reduced gravity space experiments requiring redox control.

  8. Modeling microbial degradation of propylene glycol: electron acceptors and their related redox conditions

    NASA Astrophysics Data System (ADS)

    Dathe, Annette; Fernandez, Perrine M.; Bloem, Esther; Meeussen, Johannes C. L.; French, Helen K.

    2014-05-01

    De-icing chemicals are applied in large amounts at airports during winter conditions to keep the runways and aircrafts ice-free. The commonly used propylene glycol (PG) is easily degradable by local microbial communities, but anoxic zones develop and soluble Fe+2 and Mn+2 ions can reach the groundwater. To enhance microbial induced remediation and reduce the release of iron and manganese, it was proposed to add NO3- together with PG. However, experiments conducted in the unsaturated zone at Gardermoen airport, Norway, revealed that manganese and iron were preferred over NO3- as electron acceptor [1]. The objectives of this study are to quantify mechanisms which control the order of reduction processes in an unsaturated sandy soil, and to test whether measured redox potentials can help to determine underlying biogeochemical reactions. We are modelling the microbial degradation of PG using Monod kinetics described for the chemical equilibrium tool ORCHESTRA [2], following an approach of [1]. The model is calibrated against gas measurements of CO2, NO2 and N2 released from batch experiments performed under controlled conditions. Fe+2 and Mn+2 were measured for the start and end of the experiment, as well as bulk resistivity, pH and electrical conductivity. With the calibrated model we are working towards a tool to quantify microbial induced redox reactions under different soil water saturations to account for seasonal water fluxes especially during snowmelt. [1] Schotanus, D., Meeussen, J.C.L., Lissner, H., van der Ploeg, M.J., Wehrer, M., Totsche, K.U., van der Zee, S.E.A.T.M., 2013. Transport and degradation of propylene glycol in the vadose zone: model development and sensitivity analysis. Environ Sci Pollut Res Int. [2] Meeussen, J.C.L., 2003. ORCHESTRA: An Object-Oriented Framework for Implementing Chemical Equilibrium Models. Environ. Sci. Technol. 37, 1175-1182.

  9. Reconstructing the redox conditions of Paleoproterozoic oceans: Insights from the Zaonega Formation

    NASA Astrophysics Data System (ADS)

    Patel, Neel; Zerkle, Aubrey; Izon, Gareth; Romashkin, Alexander; Rychanchik, Dmtriy; Upraus, Kärt; Kirsimäe, Kalle; Wing, Boswell; Lepland, Aivo

    2015-04-01

    The Paleoproterozoic is marked by profound changes in global tectonics, climate and biogeochemical cycling of redox sensitive elements. Determining the redox state of marine environments at this point in Earth's history is fundamental in understanding the connections between the geosphere and biosphere, including possible microbially-assisted phosphogenesis. One hypothesis suggests that oxidative weathering following Earth's first significant rise in atmospheric oxygen, resulted in an increased supply of sulfate and phosphate to the oceans, culminating in the first significant phosphorite deposits some 300-400 Ma later (Lepland et al., 2013). Thus Paleoproterozoic ocean structure has been envisaged as stratified, through mildly oxygenated shallow water and anoxic deep water, with temporally and spatially variable phases of euxinia possibly linked to transient changes in the size of the seawater sulfate reservoir (Scott et al., 2014). New cores obtained from the upper part of the 2 Ga Zaonega Formation in the Onega Basin of Karelia, NW Russia, have recovered a variety of organic-rich mudstones and carbonate rocks, containing several discrete mm-cm scale P-rich beds that may represent seep or hydrothermally-influenced depositional settings (Lepland et al., 2013). Here we present new Fe-speciation data and pyrite derived S-isotope data spanning one of these new cores in order to: i) evaluate the redox state of the water column, determining the extent of water column euxinia, and ii) assess the potential influence of S-cycling on phosphogenesis. Preliminary Fe extractions show that total Fe is broadly dictated by lithology, but generally lower in samples where the P-rich intervals occur, possibly supporting extensive sulfate reduction and the formation of a euxinic water column. Further S-isotope analyses on associated pyrites will determine the extent to which additional biogeochemical S-cycling (e.g., sulfide oxidation) could also have contributed to the P

  10. Stability of uranium incorporated into Fe(hydr)oxides under fluctuating redox conditions

    SciTech Connect

    Stewart, B.D.; Nico, P.S.; Fendorf, S.

    2009-04-01

    Reaction pathways resulting in uranium bearing solids that are stable (i.e., having limited solubility) under both aerobic and anaerobic conditions will limit dissolved concentrations and migration of this toxin. Here we examine the sorption mechanism and propensity for release of uranium reacted with Fe (hydr)oxides under cyclic oxidizing and reducing conditions. Upon reaction of ferrihydrite with Fe(II) under conditions where aqueous Ca-UO{sub 2}-CO{sub 3} species predominate (3 mM Ca and 3.8 mM CO{sub 3}-total), dissolved uranium concentrations decrease from 0.16 mM to below detection limit (BDL) after 5 to 15 d, depending on the Fe(II) concentration. In systems undergoing 3 successive redox cycles (15 d of reduction followed by 5 d of oxidation) and a pulsed decrease to 0.15 mM CO{sub 3}-total, dissolved uranium concentrations varied depending on the Fe(II) concentration during the initial and subsequent reduction phases - U concentrations resulting during the oxic 'rebound' varied inversely with the Fe(II) concentration during the reduction cycle. Uranium removed from solution remains in the oxidized form and is found both adsorbed on and incorporated into the structure of newly formed goethite and magnetite. Our 15 results reveal that the fate of uranium is dependent on anaerobic/aerobic conditions, aqueous uranium speciation, and the fate of iron.

  11. Sedimentary Trace Metal-Organic Interactions as Proxies for Oceanic Redox Conditions

    NASA Astrophysics Data System (ADS)

    Cruse, A. M.; Lyons, T. W.; Hannigan, R.

    2007-12-01

    Knowledge of trace-metal partitioning in oceanic sediments (e.g., Fe, Mo, U, Zn) are requisite to the construction of accurate models of geochemical cycling in modern and ancient waters. Factors such as oxygen penetration depth and bottom-water redox; sedimentation rate; and supply of reactants, such as dissolved sulfide, are known to affect metal sequestration in and remobilization from coastal sediments. In addition to these factors, the flux of organic carbon (OC) and the composition of this carbon are also a key in the sequestration of these metals. Currently, however, there is an absence of quantitative information on the mass balance of metals fixed in coastal sediments through direct interactions with OC, how OC remineralization affects this mass balance, and the specific nature of the metal-OC relationship. To address these issues, we have undertaken a field-based study to test the hypothesis that porewater redox conditions are recorded in the concentrations of trace metals bound in the sedimentary OC pool. We have collected sediments from several modern anoxic/euxinic basins: the central Black Sea, the Orca Basin, the Cariaco Basin, and Effingham Inlet (Vancouver Island). These environments vary in terms of dissolved sulfide concentrations and sedimentary iron sulfide geochemistry. Additionally, the sediments are characterized by a range in OC concentrations, and proximity to terrestrial sources. Extractable organic carbon was characterized with gas chromatography, and OC-bound metals are quantified using high-performance liquid chromatography- inductively coupled mass spectrometry. The preliminary results suggest that variations in the ratios of aromatic to saturate hydrocarbons may control the speciation of metals in the organic carbon pool. Bottomwater redox may be one factor controlling this relationship, although it is currently unclear if this is due to variations in metal speciation or the direct involvement of S in the OC-metal reaction mechanism

  12. Amendment of biochar reduces the release of toxic elements under dynamic redox conditions in a contaminated floodplain soil.

    PubMed

    Rinklebe, Jörg; Shaheen, Sabry M; Frohne, Tina

    2016-01-01

    Biochar (BC) can be used to remediate soils contaminated with potential toxic elements (PTEs). However, the efficiency of BC to immobilize PTEs in highly contaminated floodplain soils under dynamic redox conditions has not been studied up to date. Thus, we have (i) quantified the impact of pre-definite redox conditions on the release dynamics of dissolved aluminum (Al), arsenic (As), cadmium (Cd), copper (Cu), nickel (Ni), and zinc (Zn) in a highly contaminated soil (CS) (non-treated) and in the same soil treated with 10 g kg(-1) biochar based material (CS+BC), and (ii) assessed the efficacy of the material to reduce the concentrations of PTEs in soil solution under dynamic redox conditions using an automated biogeochemical microcosm apparatus. The impact of redox potential (EH), pH, dissolved organic carbon (DOC), dissolved inorganic carbon (DIC), iron (Fe), manganese (Mn), and sulfate (SO4(2-)) on dynamics of PTEs was also determined. The EH was lowered to +68 mV and afterwards increased stepwise to +535 mV. Significant negative correlation between EH and pH in CS and CS+BC was detected. The systematic increase of EH along with decrease of pH favors the mobilization of PTEs in CS and CS+BC. The material addition seems to have little effect on redox processes because pattern of EH/pH and release dynamics of PTEs was basically similar in CS and CS+BC. However, concentrations of dissolved PTEs were considerably lower in CS+BC than in CS which demonstrates that BC is able to decrease concentrations of dissolved PTEs even under dynamic redox conditions. PMID:25900116

  13. Redox conditions and the efficiency of chlorinated ethene biodegradation: Laboratory studies

    USGS Publications Warehouse

    Bradley, P.M.; Chapelle, F.H.

    2000-01-01

    The potential for biodegradation of highly reduced groundwater contaminants is greatest under aerobic conditions and least under CO2-reducing (methanogenic) conditions. Laboratory studies conducted using [1,2-14C] vinyl chloride (VC) indicate the same pattern applies to the anaerobic oxidation of relatively reduced chloroethylenes. Recent studies, showing that CH4 can be a significant product of microbial degradation of VC under methanogenic conditions, clarified mechanisms underlying anaerobic VC mineralization and emphasized the redox dependence of this process. A microcosm study conducted with stream bed sediments demonstrated rapid degradation of [1,2-14C] VC and simultaneous production of 14CO2 and 14CH4. The results of acetate mineralization studies indicated that these sediments contained active acetotrophic methanogens. VC degradation involved an initial transformation to acetate via oxidative acetogenesis followed by acetotrophic methanogenesis to yield CO2 and CH4 as final products. Based on these recent results, a conceptual model for anaerobic microbial degradation of VC to non-chlorinated products can be proposed.

  14. Arsenic Speciation in Bituminous Coal Fly Ash and Transformations in Response to Redox Conditions.

    PubMed

    Deonarine, Amrika; Kolker, Allan; Foster, Andrea L; Doughten, Michael W; Holland, James T; Bailoo, Jeremy D

    2016-06-01

    The risk of the mobilization of coal ash into the environment has highlighted the need for the assessment of the environmental behavior of coal ash, particularly with respect to toxic trace elements such as arsenic (As). Here, we examined As speciation in coal fly ash samples and transformations in response to aquatic redox conditions. X-ray absorption spectroscopy indicated that 92-97% of total As occurred as As(V), with the remainder present as As(III). Major As-bearing hosts in unamended ashes were glass, iron (oxyhydr)oxides, and calcium arsenate. Oxic leaching resulted in immediate As mobilization to the aqueous phase, reprecipitation of As-iron ferrihydrite, and As adsorption to mineral surfaces. Under anoxic conditions, the (reductive) dissolution of As-bearing phases such as iron ferrihydrite resulted in increased dissolved As compared to oxic conditions and reprecipitation of iron arsenate. Overall, As in coal ash is not environmentally stable and can participate in local biogeochemical cycles. PMID:27186791

  15. Effects of temperature and redox conditions on degradation of chlorinated phenols in freshwater sediments

    SciTech Connect

    Rogers, J.E.; Kohring, G.W.; Wiegel, J.

    1988-11-01

    The effect of temperature and redox conditions on the anaerobic degradation of 2,4-dichlorophenol (2,4-DCP) was investigated in anaerobic sediment slurries, prepared from local freshwater pond sediments. Under methanogenic conditions, 2,4-DCP dechlorination occurred in the temperature range between 5 and 50 C. Although dechlorination was not observed above 50 C, anaerobic bacterial activity was indicated by methane formation up to 60 C. In sediment samples from two sites and at all temperatures from 5 to 50 C, 2,4-DCP was transformed to 4-chlorophenol (4-CP). The 4-CP intermediate was subsequently degraded after an extended lag period. Adaptation periods for 2,4-DCP transformation decreased between 5 and 25 C, were essentially constant between 25 and 35 C, and increased between 35 and 40 C. Degradation rates increased exponentially between 15 and 30 C, had a second peak at 35 C, and decreased to about 5% of the peak activity by 40 C. In one sediment sample, an increase in degradation rates was observed following the minimum at 40 C, suggesting that at least two different organisms were involved in the 2,4-DCP dechlorination. Storage of the original sediment slurries for 2 months at 12 C resulted in increased adaptation times but did not affect the degradation rates.

  16. Selective detection of the structural changes upon photoreactions of several redox cofactors in photosystem II by means of light-induced ATR-FTIR difference spectroscopy

    NASA Astrophysics Data System (ADS)

    Okubo, Tatsunori; Noguchi, Takumi

    2007-04-01

    Attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy was applied for the first time to detect the structural changes upon photoreactions of redox cofactors in photosystem II (PSII). The PSII-enriched membranes from spinach were adsorbed on the surface of a silicon prism, and FTIR measurements of various redox cofactors were performed for the same sample but under different conditions by exchanging buffers in a flow cell. Light-induced FTIR difference spectra upon redox reactions of the oxygen-evolving Mn cluster, the primary quinone electron acceptor Q A, the redox-active tyrosine Y D, the primary electron acceptor pheophytin, and the primary electron donor chlorophyll P680 were successively recorded in buffers including different redox reagents and inhibitors. All of these cofactors remained active in the PSII membranes on the silicon surface, and the resultant spectra were basically identical to those previously recorded by the conventional transmission method. These ATR-FTIR measurements enable accurate comparison between reactions of different active sites in a single PSII sample. The present results demonstrated that the ATR-FTIR spectroscopy is a useful technique for investigation of the reaction mechanism of PSII.

  17. Spatio-temporal changes in glutathione and thioredoxin redox couples during ionizing radiation-induced oxidative stress regulate tumor radio-resistance.

    PubMed

    Patwardhan, R S; Sharma, D; Checker, R; Thoh, M; Sandur, S K

    2015-10-01

    Ionizing radiation (IR)-induced oxidative stress in tumor cells is effectively managed by constitutive and inducible antioxidant defense systems. This study was initiated to understand the relative contribution of different redox regulatory systems in determining the tumor radio-resistance. In this study, human T-cell lymphoma (Jurkat) cells were exposed to IR (4 Gy) and monitored for the spatio-temporal changes in cellular redox regulatory parameters. We monitored the changes in the levels of reactive oxygen species (ROS) (total, mitochondrial, primary, and secondary), thiols (total, surface, and intracellular), GSH/GSSG ratio, antioxidant enzyme activity viz. thioredoxin (Trx), Trx reductase (TrxR), glutathione peroxidase, and glutathione reductase with respect to time. We have also measured protein glutathionylation. We observed that tumor cells mount a biphasic response after IR exposure which can be divided into early (0-6 h) and late (16-48 h) responses in terms of changes in cellular redox parameters. During early response, constitutively active GSH and Trx systems respond to restore cellular redox balance to pre-exposure levels and help in activation of redox-sensitive transcription factor Nrf-2. During late response, increase in the levels of antioxidants GSH and Trx rescue cells against IR-mediated damage. We observed that disruption of either glutathione or thioredoxin metabolism led to partial impairment of ability of cells to survive against IR-induced damage. But simultaneous disruption of both the pathways significantly increased radio sensitivity of Jurkat cells. This highlighted the importance of these two antioxidant pathways in regulating redox homeostasis under conditions of IR-induced oxidative stress. PMID:26021764

  18. Characterizing Redox Conditions in Oxygen-deficient Waters Off Peru During the 2013 US GEOTRACES Zonal Transect

    NASA Astrophysics Data System (ADS)

    Cutter, G. A.; Nielsdottir, M.

    2014-12-01

    The oxygen-deficient zone that extends from coastal Peru well into the tropical Pacific Ocean has been described as "suboxic," but recent measurements of sulfate reduction suggest it may have some anoxic characteristics (e.g., free sulfide). The redox poise of suboxia strongly affects the solubility/stability of a wide variety of trace elements and therefore their vertical and horizontal transport. The problem is that suboxic is not chemically well defined, but certainly represents a very wide range of redox conditions (pE of ca. 10 to -2). During the 2013 US GEOTRACES Pacific cruise (International GEOTRACES section GP16) we determined a suite of redox couples to help define the redox poise in the water column: oxygen(/water), iodate/iodide, nitrate/nitrite, selenate/elemental Se, arsenate/arsenite, and sulfate/hydrogen sulfide. Using the RV Thomas Thompson we occupied a total of 11 stations along 12° S from coastal Peru to 94° W to sample the oxygen deficient waters using a conventional CTD/rosette and the trace metal-clean US GEOTRACES CTD/carousel. Determinations of all the redox tracers were made on board ship except for selenium. On the Peru shelf, oxygen concentrations were less than 10 μM from 30m to the bottom, while farther offshore the depth of this oxygen minimum was 700 m thick starting at ca. 80 m depth; the layer thickness steadily decreased moving west. In spite of the low oxygen conditions, nitrate and iodate were still detectable, while their corresponding reduced species had maxima in the low O2 waters. Dissolved hydrogen sulfide was below the detection limit of 70 pM, and no evidence of As(V) reduction was found; selenium speciation has yet to be determined. The lack of detectable dissolved hydrogen sulfide shows the redox conditions are certainly not anoxic, and incomplete iodate and nitrate reduction suggest the redox environment is more oxidizing than previously reported. The apparent temporal and spatial variability of the redox poise will

  19. Physical Training Status Determines Oxidative Stress and Redox Changes in Response to an Acute Aerobic Exercise.

    PubMed

    Seifi-Skishahr, Farnaz; Damirchi, Arsalan; Farjaminezhad, Manoochehr; Babaei, Parvin

    2016-01-01

    Objective. To assess the influence of different physical training status on exercise-induced oxidative stress and changes in cellular redox state. Methods. Thirty male subjects participated in this study and were assigned as well-trained (WT), moderately trained (MT), and untrained (UT) groups. The levels of cortisol, creatine kinase, plasma reduced glutathione to oxidized glutathione (GSH/GSSG), cysteine/cystine (Cys/CySS), and GSH/GSSG ratio in red blood cells (RBCs) were measured immediately and 10 and 30 min after exercise. Results. Following the exercise, plasma GSH/GSSG (p = 0.001) and Cys/CySS (p = 0.005) were significantly reduced in all groups. Reduction in plasma GSH/GSSG ratio in all groups induced a transient shift in redox balance towards a more oxidizing environment without difference between groups (p = 0.860), while RBCs GSH/GSSG showed significant reduction (p = 0.003) and elevation (p = 0.007) in UT and MT groups, respectively. The highest level of RBCs GSH/GSSG ratio was recorded in MT group, and the lowest one was recorded in the WT group. Conclusion. Long term regular exercise training with moderate intensity shifts redox balance towards more reducing environment, versus intensive exercise training leads to more oxidizing environment and consequently development of related diseases. PMID:27064342

  20. Physical Training Status Determines Oxidative Stress and Redox Changes in Response to an Acute Aerobic Exercise

    PubMed Central

    Damirchi, Arsalan; Farjaminezhad, Manoochehr

    2016-01-01

    Objective. To assess the influence of different physical training status on exercise-induced oxidative stress and changes in cellular redox state. Methods. Thirty male subjects participated in this study and were assigned as well-trained (WT), moderately trained (MT), and untrained (UT) groups. The levels of cortisol, creatine kinase, plasma reduced glutathione to oxidized glutathione (GSH/GSSG), cysteine/cystine (Cys/CySS), and GSH/GSSG ratio in red blood cells (RBCs) were measured immediately and 10 and 30 min after exercise. Results. Following the exercise, plasma GSH/GSSG (p = 0.001) and Cys/CySS (p = 0.005) were significantly reduced in all groups. Reduction in plasma GSH/GSSG ratio in all groups induced a transient shift in redox balance towards a more oxidizing environment without difference between groups (p = 0.860), while RBCs GSH/GSSG showed significant reduction (p = 0.003) and elevation (p = 0.007) in UT and MT groups, respectively. The highest level of RBCs GSH/GSSG ratio was recorded in MT group, and the lowest one was recorded in the WT group. Conclusion. Long term regular exercise training with moderate intensity shifts redox balance towards more reducing environment, versus intensive exercise training leads to more oxidizing environment and consequently development of related diseases. PMID:27064342

  1. [Effect of sulfur on the species of Fe and As under redox condition in paddy soil].

    PubMed

    Tang, Bing-Pei; Yang, Shi-Jie; Wang, Dai-Zhang; Rao, Wei; Zhang, Ya-Nan; Wang, Dan; Zhu, Yun-Ji

    2014-10-01

    Redox conditions of the polluted paddy soil with exogenous As were simulated by redox reaction apparatus after flowing N2 and O2 applied with different forms of inorganic sulfur(CK-S0, elemental sulfur-S1 and sulfate-S2). Results showed that redox potential (Eh) was about -100 - -200 mV and the pH 7.0-8.0 and the pe + pH 4-7 in soil solution when flowed N2, and Eh about 200 mV and the pH 6.5-7.5 and pe + pH 9-12 when continuously flowed O2. Concentrations of the dissolved Fe in soil solution were in 1.2-1.6 mg x L(-1) either flowed N2 or O2, and the order of Fe concentrations was AsS0 treatment > AsS1 treatment > AsS2 treatment. Amounts of soil Fe oxide by HCl extraction from different treatments were 5 g · kg(-1) lower than the original soil [(21.4 ± 0.3) g · kg(-1)] when flowed N2, and it was in favor of the transformation of crystal Fe into amorphous iron and Fe2+. Activity of Fe oxides from different treatments increased comparing to that of the original soil (46. 8%), and the order of activity of Fe oxides was AsS2 treatment (49.4%) < AsS1 treatment (60%). Fe2+ in solution and FeS were oxidized into Fe3+, and hydrolysis of Fe3+ was produced into Fe(OH)3 precipitation when flowed O2. It increased the contents of acid-soluble and crystal Fe oxide, and the order of activity of Fe oxides was AsS1 (41.2%) treatment > AsS2 (36.1%) treatment. Concentrations of As in soil solution were in the order of AsS0 [(1.13 ± 0.04) mg · L(-1)] > AsS1 [(0.89 ± 0.01) mg L(- 1)] > AsS2 [ (0.77 ± 0.04 )mg · L(-1)] when flowed N2 and was AsS1 [(0.77 ± 0.01) mg · L(-1)] > AsS0 [(0.20 ± 0.09 ) mg · L(-1)] > AsS2 [(0.09 ± 0.01) mg · L(-1)] when flowed O2. The proportions of arsenic fractions followed the order of the residual phases (34.9%-41.4%) ≈ specifically-sorbed (37.4%-39.5%) > well-crystallized hydrous oxides of Fe/Mn (23.3%-25.6%) > non-specifically sorbed (2.4%-3.3%) > amorphous hydrous oxides of Fe/Mn (0.5%-0.8%) when flowed N2, and was the residual phases (30

  2. Decomposition of jellyfish carrion in situ: Short-term impacts on infauna, benthic nutrient fluxes and sediment redox conditions.

    PubMed

    Chelsky, Ariella; Pitt, Kylie A; Ferguson, Angus J P; Bennett, William W; Teasdale, Peter R; Welsh, David T

    2016-10-01

    Jellyfish often form blooms that persist for weeks to months before they collapse en masse, resulting in the sudden release of large amounts of organic matter to the environment. This study investigated the biogeochemical and ecological effects of the decomposition of jellyfish in a shallow coastal lagoon in New South Wales, Australia. Catostylus mosaicus carrion was added to the surface of shallow sub-tidal sediments and biogeochemical parameters and macrofaunal abundance immediately below the jellyfish carrion were measured over three days. Sediment plots without jellyfish served as controls. Sediment oxygen demand and carbon and nitrogen efflux increased by up to 60-fold in the jellyfish plots, compared to control plots, and dissolved organic nutrient fluxes were more sustained than in previous studies due to the use of fresh rather than frozen biomass. The decomposing jellyfish progressively altered sediment redox conditions, indicated by an increase in porewater iron (II) and sulfide concentrations measured by high-resolution in situ diffusive samplers. Abundance of some macrofaunal taxa in the jellyfish plots decreased relative to controls, however, the abundance of a carnivorous gastropod, which was presumably feeding on the carrion, increased in the jellyfish plots. While jellyfish carrion may be a food source for some macrofauna, low oxygen conditions coupled with the accumulation of toxic dissolved sulfides in the near-surface sediments may explain the overall change in the macroinfaunal community. PMID:27285534

  3. Characterizing redox conditions and monitoring attenuation of selected pharmaceuticals during artificial recharge through a reactive layer.

    PubMed

    Valhondo, Cristina; Carrera, Jesús; Ayora, Carlos; Tubau, Isabel; Martinez-Landa, Lurdes; Nödler, Karsten; Licha, Tobias

    2015-04-15

    A permeable reactive layer was installed at the floor of an infiltration basin. The reactive layer comprised 1) vegetable compost to provide a sorption surface for neutral organic compounds and to release easily degradable organic matter, thus generating a sequence of redox states, and 2) minor amounts of clay and iron oxide to increase sorption of cationic and anionic species, respectively. Field application of this design was successful in generating denitrification, and manganese-, and iron-reducing conditions beneath the basin. This, together with the increase in types of sorption sites, may explain the improved removal of three of the four selected pharmaceuticals compared with their behavior prior to installation of the layer. After installation of the reactive layer, atenolol concentrations were below the detection limits in the vadose zone. Moreover, concentrations of gemfibrozil and cetirizine were reduced to 20% and 40% of their initial concentrations, respectively, after 200 h of residence time. In contrast, prior to installation of the reactive layer, the concentrations of these three pharmaceuticals in both the vadose zone and the aquifer were more than 60% of the initial concentration. Carbamazepine exhibited recalcitrant behavior both prior to and after the reactive barrier installation. PMID:25625636

  4. Redox conditions and trace metal cycling in coastal sediments from the maritime Antarctic

    NASA Astrophysics Data System (ADS)

    Monien, Patrick; Lettmann, Karsten Alexander; Monien, Donata; Asendorf, Sanja; Wölfl, Anne-Cathrin; Lim, Chai Heng; Thal, Janis; Schnetger, Bernhard; Brumsack, Hans-Jürgen

    2014-09-01

    Redox-sensitive trace metals (Mn, Fe, U, Mo, Re), nutrients and terminal metabolic products (NO3-, NH4+, PO43-, total alkalinity) were investigated for the first time in pore waters of Antarctic coastal sediments. The results of this study reveal a high spatial variability in redox conditions in surface sediments from Potter Cove, King George Island, western Antarctic Peninsula. Particularly in the shallower areas of the bay the significant correlation between sulphate depletion and total alkalinity, the inorganic product of terminal metabolism, indicates sulphate reduction to be the major pathway of organic matter mineralisation. In contrast, dissimilatory metal oxide reduction seems to be prevailing in the newly ice-free areas and the deeper troughs, where concentrations of dissolved iron of up to 700 μM were found. We suggest a combination of several factors to be responsible for the domination of metal oxide reduction over sulphate reduction in these areas. These include the increased accumulation of fine-grained material with high amounts of reducible metal oxides, a reduced availability of metabolisable organic matter and an enhanced physical and biological disturbance by bottom water currents, ice scouring and burrowing organisms. Based on modelled iron fluxes we calculate the contribution of the Antarctic shelf to the pool of potentially bioavailable iron (Feb) to be 6.9 × 103 to 790 × 103 t yr-1. Consequently, these shelf sediments would provide an Feb flux of 0.35-39.5 mg m-2 yr-1 (median: 3.8 mg m-2 yr-1) to the Southern Ocean. This contribution is in the same order of magnitude as the flux provided by icebergs and significantly higher than the input by aeolian dust. For this reason suboxic shelf sediments form a key source of iron for the high nutrient-low chlorophyll (HNLC) areas of the Southern Ocean. This source may become even more important in the future due to rising temperatures at the WAP accompanied by enhanced glacier retreat and the

  5. Redox-dependent structure change and hyperfine nuclear magnetic resonance shifts in cytochrome c

    SciTech Connect

    Feng, Yiquing; Roder, H.; Englander, S.W. )

    1990-04-10

    Proton nuclear magnetic resonance assignments for reduced and oxidized equine cytochrome c show that many individual protons exhibit different chemical shifts in the two protein forms, reflecting diamagnetic shift effects due to structure change, and in addition contact and pseudocontact shifts that occur only in the paramagnetic oxidized form. To evaluate the chemical shift differences for structure change, the authors removed the pseudocontact shift contribution by a calculation based on knowledge of the electron spin g tensor. The g-tensor calculation, when repeated using only 12 available C{sub {alpha}}H proton resonances for cytochrom c from tuna, proved to be remarkably stable. The derived g tensor was then used together with spatial coordinates for the oxidized form to calculate the pseudocontact shift contribution to proton resonances at 400 identifiable sites throughout the protein, so that the redox-dependent chemical shift discrepancy, could be evaluated. Large residual changes in chemical shift define the Fermi contact shifts, where are found as expected to be limited to the immediate covalent structure of the heme and its ligands and to be asymmetrically distributed over the heme. The chemical shift discrepancies observed appear in the main to reflect structure-dependent diamagnetic shifts rather than hyperfine effects due to displacements in the pseudocontact shift field. Although 51 protons in 29 different residues exhibit significant chemical shift changes, the general impressions one of small structural adjustments to redox-dependent strain rather than sizeable structural displacements or rearrangements.

  6. Predicting Redox Conditions in Groundwater Using Statistical Techniques: Implications for Nitrate Transport in Groundwater and Streams

    NASA Astrophysics Data System (ADS)

    Tesoriero, A. J.; Terziotti, S.

    2014-12-01

    Nitrate trends in streams often do not match expectations based on recent nitrogen source loadings to the land surface. Groundwater discharge with long travel times has been suggested as the likely cause for these observations. The fate of nitrate in groundwater depends to a large extent on the occurrence of denitrification along flow paths. Because denitrification in groundwater is inhibited when dissolved oxygen (DO) concentrations are high, defining the oxic-suboxic interface has been critical in determining pathways for nitrate transport in groundwater and to streams at the local scale. Predicting redox conditions on a regional scale is complicated by the spatial variability of reaction rates. In this study, logistic regression and boosted classification tree analysis were used to predict the probability of oxic water in groundwater in the Chesapeake Bay watershed. The probability of oxic water (DO > 2 mg/L) was predicted by relating DO concentrations in over 3,000 groundwater samples to indicators of residence time and/or electron donor availability. Variables that describe position in the flow system (e.g., depth to top of the open interval), soil drainage and surficial geology were the most important predictors of oxic water. Logistic regression and boosted classification tree analysis correctly predicted the presence or absence of oxic conditions in over 75 % of the samples in both training and validation data sets. Predictions of the percentages of oxic wells in deciles of risk were very accurate (r2>0.9) in both the training and validation data sets. Depth to the bottom of the oxic layer was predicted and is being used to estimate the effect that groundwater denitrification has on stream nitrate concentrations and the time lag between the application of nitrogen at the land surface and its effect on streams.

  7. [Hygiene communication - conditions for change.

    PubMed

    Kjærbeck, Susanne; Petersen, Helle

    2014-06-01

    The article focuses on strengths and weaknesses of the local hygiene communication in a hospital ward. Efficient change communication consists of central and local communication activities. The hygiene coordinator is an important local "change agent", but in practice the role is difficult. The communicative interaction between the central infection control organization and a specific ward as well as between the department management and the hygiene coordinator should be strengthened in order to create change in staff behaviour. PMID:25352079

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

    PubMed

    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. PMID:22271160

  9. Redox Redone.

    ERIC Educational Resources Information Center

    Petty, John T.

    1996-01-01

    Presents an extension of the change in oxidation number method that is used for balancing skeletal redox reactions in aqueous solutions. Retains most of the simplicity of the change in oxidation number method but provides the additional step-by-step process necessary for the beginner to balance an equation. (JRH)

  10. Redox-sensitive YFP sensors for monitoring dynamic compartment-specific glutathione redox state.

    PubMed

    Banach-Latapy, Agata; He, Tiantian; Dardalhon, Michèle; Vernis, Laurence; Chanet, Roland; Huang, Meng-Er

    2013-12-01

    Intracellular redox homeostasis is crucial for many cellular functions but accurate measurements of cellular compartment-specific redox states remain technically challenging. Genetically encoded biosensors including the glutathione-specific redox-sensitive yellow fluorescent protein (rxYFP) may provide an alternative way to overcome the limitations of conventional glutathione/glutathione disulfide (GSH/GSSG) redox measurements. This study describes the use of rxYFP sensors for investigating compartment-specific steady redox state and their dynamics in response to stress in human cells. RxYFP expressed in the cytosol, nucleus, or mitochondrial matrix of HeLa cells was responsive to the intracellular redox state changes induced by reducing as well as oxidizing agents. Compartment-targeted rxYFP sensors were able to detect different steady-state redox conditions among the cytosol, nucleus, and mitochondrial matrix. These sensors expressed in human epidermal keratinocytes HEK001 responded to stress induced by ultraviolet A radiation in a dose-dependent manner. Furthermore, rxYFP sensors were able to sense dynamic and compartment-specific redox changes caused by 100 μM hydrogen peroxide (H2O2). Mitochondrial matrix-targeted rxYFP displayed a greater dynamics of oxidation in response to a H2O2 challenge than the cytosol- and nucleus-targeted sensors, largely due to a more alkaline local pH environment. These observations support the view that mitochondrial glutathione redox state is maintained and regulated independently from that of the cytosol and nucleus. Taken together, our data show the robustness of the rxYFP sensors to measure compartmental redox changes in human cells. Complementary to existing redox sensors and conventional redox measurements, compartment-targeted rxYFP sensors provide a novel tool for examining mammalian cell redox homeostasis, permitting high-resolution readout of steady glutathione state and dynamics of redox changes. PMID:23891676

  11. Investigating the impacts of deep ocean euxinia on continental shelf environments during the Great Ordovician Biodiversification Event: did changes in global oceanic redox have any effect?

    NASA Astrophysics Data System (ADS)

    Marenco, P. J.; Marenco, K. N.; Phillips, D. E.; Garcia, E.; Toure, N.; Fullem, A.

    2013-12-01

    The Great Ordovician Biodiversification Event was one of the most important radiations in the history of animal life. In particular, the GOBE was characterized by pronounced increases in diversity within the Paleozoic and Modern Evolutionary Faunas (e.g., Droser and Finnegan, 2003). Rather than being attributable to a singular cause, a number of tectonic, ecologic, and climate-related factors are thought to have contributed to this biodiversification event (e.g., Servais et al., 2009). For example, continental shelf area during the GOBE was more extensive than at any other time during the Phanerozoic, and the availability of these warm, shallow-water, well-oxygenated environments likely influenced the radiation (e.g., Servais et al., 2009). Despite this evidence for favorable conditions, recent geochemical studies suggest that the early Paleozoic, including the Ordovician, was a time of episodic deep ocean euxinia (e.g., Gill et al., 2011, Thompson and Kah, 2012). It remains unclear how the hypothesized deep ocean euxinia may have affected the GOBE. For example, it is possible that episodic incursions of euxinic deep water onto the continental shelves may have acted to slow down the GOBE or even dampen its magnitude. On the other hand, such incursions may have accelerated the radiation by adding additional selection pressures to communities that were already adapting to new predation and substrate conditions. Alternatively, the GOBE may have proceeded without any incursions of euxinic deep water onto the continental shelves. One way to address this issue is to investigate short-term, localized redox changes in shallow marine settings. Here we present results from our ongoing investigation of redox changes in shallow-water environments from the Lower and Middle Ordovician of Utah. Specifically, we use abundances of total organic carbon (TOC) and total sulfur (TS) as localized redox proxies. We use the isotopic composition of carbonate associated sulfate (δ34SCAS

  12. Redox Imbalance and Morphological Changes in Skin Fibroblasts in Typical Rett Syndrome

    PubMed Central

    Amabile, Sonia; Belmonte, Giuseppe; Valacchi, Giuseppe; Galano, Jean-Marie; Ciccoli, Lucia; Renieri, Alessandra; Hayek, Joussef

    2014-01-01

    Evidence of oxidative stress has been reported in the blood of patients with Rett syndrome (RTT), a neurodevelopmental disorder mainly caused by mutations in the gene encoding the Methyl-CpG-binding protein 2. Little is known regarding the redox status in RTT cellular systems and its relationship with the morphological phenotype. In RTT patients (n = 16) we investigated four different oxidative stress markers, F2-Isoprostanes (F2-IsoPs), F4-Neuroprostanes (F4-NeuroPs), nonprotein bound iron (NPBI), and (4-HNE PAs), and glutathione in one of the most accessible cells, that is, skin fibroblasts, and searched for possible changes in cellular/intracellular structure and qualitative modifications of synthesized collagen. Significantly increased F4-NeuroPs (12-folds), F2-IsoPs (7.5-folds) NPBI (2.3-folds), 4-HNE PAs (1.48-folds), and GSSG (1.44-folds) were detected, with significantly decreased GSH (−43.6%) and GSH/GSSG ratio (−3.05 folds). A marked dilation of the rough endoplasmic reticulum cisternae, associated with several cytoplasmic multilamellar bodies, was detectable in RTT fibroblasts. Colocalization of collagen I and collagen III, as well as the percentage of type I collagen as derived by semiquantitative immunofluorescence staining analyses, appears to be significantly reduced in RTT cells. Our findings indicate the presence of a redox imbalance and previously unrecognized morphological skin fibroblast abnormalities in RTT patients. PMID:24987493

  13. Sedimentary Redox Conditions, Biogenic Production, and Oxygenation of Southeast Pacific Intermediate Waters Over the Past 30 ky.

    NASA Astrophysics Data System (ADS)

    Muratli, J.; Mix, A.; Chase, Z.; McManus, J.

    2007-12-01

    We present data from SE Pacific sediments in an effort to characterize the paleo-redox conditions of shallow (~400-1000 m) subsurface sediments, and the water masses that overlie them, over the past 30 ky. The sediments were recovered during ODP Leg 202, and come from three sites: 1233, 1234, and 1235; together these three sites constitute a vertical transect of Antarctic Intermediate Water (AAIW). Site 1233, at 41°S, sits in the core of AAIW at 838 m depth. Site 1234, at 36°S, is located between AAIW and the Pacific Central Water (PCW) mass. Site 1235 (489 m) is located close to Site 1234, but is between AAIW and the overlying low- dissolved-oxygen Gunther Undercurrent (GUC) water mass. Recent sediments for sites 1234 and 1235 contain a rich signature of biogenic opal production and enrichments of iron and the authigenic metals U, Mo, and Re. At site 1234 there is a minimum in biogenic Si at approximately 20 ky followed by a slight increase and a second minimum between 12 and 5 ky. At both sites 1233 and 1234 the trace metals exhibit more structure during the period of roughly 15 to 30 ky as compared to the most recent 15 ky. The trace metal data at site 1234 shows a sharp reducing signature at ~17 ky (higher Mo, lower U:Mo ratios), bracketed by periods of more oxygenated conditions (lower Mo, higher U:Mo) back to ~22 ky, and forward to ~12 ky. This combination of low biological production and more oxygenated bottom water may suggest a period of increased AAIW ventilation as far north as site 1234. Although it is difficult at this point to unequivocally separate the impact of ventilation from production using our current data base, it does appear that some of the observed changes in sedimentary character may be ventilation-driven rather than driven by local production.

  14. Redox condition in molten salts and solute behavior: A first-principles molecular dynamics study

    NASA Astrophysics Data System (ADS)

    Nam, Hyo On; Morgan, Dane

    2015-10-01

    Molten salts technology is of significant interest for nuclear, solar, and other energy systems. In this work, first-principles molecular dynamics (FPMD) was used to model the solute behavior in eutectic LiCl-KCl and FLiBe (Li2BeF4) melts at 773 K and 973 K, respectively. The thermo-kinetic properties for solute systems such as the redox potential, solute diffusion coefficients and structural information surrounding the solute were predicted from FPMD modeling and the calculated properties are generally in agreement with the experiments. In particular, we formulate an approach to model redox energetics vs. chlorine (or fluorine) potential from first-principles approaches. This study develops approaches for, and demonstrates the capabilities of, FPMD to model solute properties in molten salts.

  15. The Redox Code

    PubMed Central

    Jones, Dean P.

    2015-01-01

    Abstract Significance: 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. Recent Advances: 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. Critical Issues: Complexity of redox networks and redox regulation is being revealed step by step, yet much still needs to be learned. Future Directions: 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. Antioxid. Redox Signal. 23, 734–746. PMID:25891126

  16. The Influence of the Biological Pump on Marine Redox Conditions During Earth History

    NASA Astrophysics Data System (ADS)

    Meyer, K. M.; Ridgwell, A.; Payne, J.

    2015-12-01

    Evidence for bottom-water anoxia on the continental shelves waned over the course of the Phanerozoic, which may be influenced by secular changes in the biological pump that led to weaker positive feedbacks within the oceans. The biological pump describes the transfer of carbon from the atmosphere to the deep ocean, which creates vertical gradients in nutrients and oxygen, both important influences in the structure of marine ecosystems. We used the cGENIE Earth system model to quantitatively test the hypothesis that reductions in the efficiency of the nutrient recycling loop of the biological pump during the past 550 Ma reduced the extent of anoxia on the shelves and acted as an important control on marine animal ecosystems. When the modeled remineralization depth is shallow relative to the modern ocean, anoxia tends to be more widespread at continental shelf depths. As the modeled remineralization depth increases toward modern conditions, anoxia is less prevalent and occurs at depths below the continental shelves. Reduced marine productivity in the closed system configuration of cGENIE cannot produce the frequent bottom-water anoxia conditions envisioned for the Paleozoic. We hypothesize that evidence for greater animal abundance and metabolic demand during the Phanerozoic was driven by progressive oxygenation of shelf environments related to changes in the biological pump rather than greater food availability. In general, these model simulations suggest changes in the depth distribution of organic carbon remineralization may have controlled observed shifts in ocean chemistry, biogeochemical cycling, and ecosystem structure during the Phanerozoic.

  17. Arsenic redox changes by microbially and chemically formed semiquinone radicals and hydroquinones in a humic substance model quinone.

    PubMed

    Jiang, Jie; Bauer, Iris; Paul, Andrea; Kappler, Andreas

    2009-05-15

    Arsenic is a redox-active metalloid whose toxicity and mobility strongly depends on its oxidation state, with arsenite (As(III)) being more toxic and mobile than arsenate (As(V)). Humic substances (HS) are also redox-active and can potentially react with arsenic and change its redox state. In this study we show that semiquinone radicals produced during microbial or chemical reduction of a HS model quinone (AQDS, 9,10-anthraquinone-2,6-disulfonic acid) are strong oxidants. They oxidize arsenite to arsenate, thus decreasing As toxicity and mobility. This reaction depends strongly on pH with more arsenite (up to 67.3%) being oxidized at pH 11 compared to pH 7 (12.6% oxidation) and pH 3 (0.5% oxidation). In addition to As(III) oxidation by semiquinone radicals, hydroquinones that were also produced during quinone reduction reduced As(V) to As(III) at neutral and acidic pH values (less than 12%) but not at alkaline pH. In order to understand redox reactions between arsenite/arsenate and reduced/oxidized HS, we quantified the radical content in reduced quinone solutions and constructed Eh-pH diagrams that explain the observed redox reactions. The results from this study can be used to better predict the fate of arsenic in the environment and potentially explain the occurrence of oxidized As(V) in anoxic environments. PMID:19544866

  18. Plant Defense Response to Fungal Pathogens (II. G-Protein-Mediated Changes in Host Plasma Membrane Redox Reactions).

    PubMed Central

    Vera-Estrella, R.; Higgins, V. J.; Blumwald, E.

    1994-01-01

    Elicitor preparations containing the avr5 gene products from races 4 and 2.3 of Cladosporium fulvum, and tomato (Lycopersicon esculentum L.) cells containing the resistance gene Cf5 were used to investigate the involvement of redox processes in the production of active oxygen species associated with the plant response to the fungal elicitors. Here we demonstrate that certain race-specific elicitors of C. fulvum induced an increase in ferricyanide reduction in enriched plasma membrane fractions of tomato cells. The addition of elicitors to plasma membranes also induced increases in NADH oxidase and NADH-dependent cytochrome c reductase activities, whereas ascorbate peroxidase activity was decreased. These results suggest that changes in the host plasma membrane redox processes, transferring electrons from reducing agents to oxygen, could be involved in the increased production of active oxygen species by the race-specific elicitors. Our results also show that the dephosphorylation of enzymes involved in redox reactions is responsible for the race-specific induced redox activity. The effects of guanidine nucleotide analogs and mastoparan on the activation of plasma membrane redox reactions support the role of GTP-binding proteins in the transduction of signals leading to the activation of the defense response mechanisms of tomato against fungal pathogens. PMID:12232307

  19. Heterogeneous redox conditions, arsenic mobility, and groundwater flow in a fractured-rock aquifer near a waste repository site in New Hampshire, USA

    USGS Publications Warehouse

    Harte, Philip T.; Ayotte, Joseph D.; Hoffman, Andrew; Revesz, Kinga M.; Belaval, Marcel; Lamb, Steven; Böhlke, J.K.

    2012-01-01

    Anthropogenic sources of carbon from landfill or waste leachate can promote reductive dissolution of in situ arsenic (As) and enhance the mobility of As in groundwater. Groundwater from residential-supply wells in a fractured crystalline-rock aquifer adjacent to a Superfund site in Raymond, New Hampshire, USA, showed evidence of locally enhanced As mobilization in relatively reducing (mixed oxic-anoxic to anoxic) conditions as determined by redox classification and other lines of evidence. Redox classification was determined from geochemical indicators based on threshold concentrations of dissolved oxygen (DO), nitrate (NO3-), iron (Fe2+), manganese (Mn2+), and sulfate (SO42-). Redox conditions were evaluated also based on methane (CH4), excess nitrogen gas (N2) from denitrification, the oxidation state of dissolved As speciation (As(III) and As(V)), and several stable isotope ratios. Samples from the residential-supply wells primarily exhibit mixed redox conditions, as most have long open boreholes (typically 50–100 m) that receive water from multiple discrete fractures with contrasting groundwater chemistry and redox conditions. The methods employed in this study can be used at other sites to gauge redox conditions and the potential for As mobilization in complex fractured crystalline-rock aquifers where multiple lines of evidence are likely needed to understand As occurrence, mobility, and transport.

  20. Heterogeneous redox conditions, arsenic mobility, and groundwater flow in a fractured-rock aquifer near a waste repository site in New Hampshire, USA

    NASA Astrophysics Data System (ADS)

    Harte, Philip T.; Ayotte, Joseph D.; Hoffman, Andrew; Révész, Kinga M.; Belaval, Marcel; Lamb, Steven; Böhlke, J. K.

    2012-09-01

    Anthropogenic sources of carbon from landfill or waste leachate can promote reductive dissolution of in situ arsenic (As) and enhance the mobility of As in groundwater. Groundwater from residential-supply wells in a fractured crystalline-rock aquifer adjacent to a Superfund site in Raymond, New Hampshire, USA, showed evidence of locally enhanced As mobilization in relatively reducing (mixed oxic-anoxic to anoxic) conditions as determined by redox classification and other lines of evidence. Redox classification was determined from geochemical indicators based on threshold concentrations of dissolved oxygen (DO), nitrate (NO{3/-}), iron (Fe2+), manganese (Mn2+), and sulfate (SO{4/2-}). Redox conditions were evaluated also based on methane (CH4), excess nitrogen gas (N2) from denitrification, the oxidation state of dissolved As speciation (As(III) and As(V)), and several stable isotope ratios. Samples from the residential-supply wells primarily exhibit mixed redox conditions, as most have long open boreholes (typically 50-100 m) that receive water from multiple discrete fractures with contrasting groundwater chemistry and redox conditions. The methods employed in this study can be used at other sites to gauge redox conditions and the potential for As mobilization in complex fractured crystalline-rock aquifers where multiple lines of evidence are likely needed to understand As occurrence, mobility, and transport.

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

    PubMed Central

    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

  2. Redox-magnetohydrodynamic microfluidics without channels and compatible with electrochemical detection under immunoassay conditions.

    PubMed

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

    2010-09-01

    A unique capability of redox-magnetohydrodynamics (redox-MHD) for handling liquids on a small scale was demonstrated. A 1.2 muL 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 (PAP(R)) in the presence of 2.5 mM Ru(NH(3))(6)Cl(2) and 2.5 mM Ru(NH(3))(6) Cl(3), 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 PAP(R) 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 x 15.5 mm long x 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 approximately 30 mum/s was generated in a reinforcing flow configuration between oppositely polarized sets of pumping electrodes with approximately 2.1 muA. PMID:20681513

  3. Organelle redox autonomy during environmental stress.

    PubMed

    Bratt, Avishay; Rosenwasser, Shilo; Meyer, Andreas; Fluhr, Robert

    2016-09-01

    Oxidative stress is generated in plants because of inequalities in the rate of reactive oxygen species (ROS) generation and scavenging. The subcellular redox state under various stress conditions was assessed using the redox reporter roGFP2 targeted to chloroplastic, mitochondrial, peroxisomal and cytosolic compartments. In parallel, the vitality of the plant was measured by ion leakage. Our results revealed that during certain physiological stress conditions the changes in roGFP2 oxidation are comparable to application of high concentrations of exogenous H2 O2 . Under each stress, particular organelles were affected. Conditions of extended dark stress, or application of elicitor, impacted chiefly on the status of peroxisomal redox state. In contrast, conditions of drought or high light altered the status of mitochondrial or chloroplast redox state, respectively. Amalgamation of the results from diverse environmental stresses shows cases of organelle autonomy as well as multi-organelle oxidative change. Importantly, organelle-specific oxidation under several stresses proceeded cell death as measured by ion leakage, suggesting early roGFP oxidation as predictive of cell death. The measurement of redox state in multiple compartments enables one to look at redox state connectivity between organelles in relation to oxidative stress as well as assign a redox fingerprint to various types of stress conditions. PMID:27037976

  4. Changes in sedimentary redox associated with mussel (Mytilus edulis L.) farms on the west-coast of Scotland.

    PubMed

    Wilding, Thomas A

    2012-01-01

    Aquaculture is growing rapidly in response to an increasing demand for protein and the over-exploitation of wild fisheries. Mussel (family Mytilidae) production has doubled over the last decade and currently stands at 1.5 million tones production per annum. Mussels produce organic biodeposits which are dispersed around the production site and, potentially, impact the receiving environment in a number of inter-linked ways. The reported benthic impacts that occur, primarily through the accumulation of these biodeposits and associated organic enrichment, vary widely between studies. The objectives of this research were to determine the nature of the relationship between sediment redox (a proxy for oxygenation) and farm-proximity and covariables whilst accounting for, and quantifying, differences in redox between sites. Sediment cores (N = 159) were taken remotely around a random sample of mussel farms, redox was measured at 10 mm sediment depth and linked to farm-distance and sediment organic/shell content and particle size, using an additive, mixed, weighted regression model. Redox varied considerably between sites and there was a highly significant reduction (50 mV) in redox adjacent to the mussel lines. Redox increased non-linearly with distance, rising rapidly at >7 m from the farm edge. The modest reduction in sediment oxygenation in close proximity to mussel farms reported here suggests that farms located over sediments characterised by pre-existing oxygen stress are likely to exacerbate benthic species impoverishment associated with reducing sedimentary conditions whilst those located over highly oxygenated sediments are likely to increase benthic productivity. PMID:23028817

  5. Modeling biogeochemical processes in subterranean estuaries: Effect of flow dynamics and redox conditions on submarine groundwater discharge of nutrients

    NASA Astrophysics Data System (ADS)

    Spiteri, Claudette; Slomp, Caroline P.; Tuncay, Kagan; Meile, Christof

    2008-02-01

    A two-dimensional density-dependent reactive transport model, which couples groundwater flow and biogeochemical reactions, is used to investigate the fate of nutrients (NO3-, NH4+, and PO4) in idealized subterranean estuaries representing four end-members of oxic/anoxic aquifer and seawater redox conditions. Results from the simplified model representations show that the prevalent flow characteristics and redox conditions in the freshwater-seawater mixing zone determine the extent of nutrient removal and the input of nitrogen and phosphorus to coastal waters. At low to moderate groundwater velocities, simultaneous nitrification and denitrification can lead to a reversal in the depth of freshwater NO3- and NH4+-PO4 plumes, compared to their original positions at the landward source. Model results suggest that autotrophic denitrification pathways with Fe2+ or FeS2 may provide an important, often overlooked link between nitrogen and phosphorus biogeochemistry through the precipitation of iron oxides and subsequent binding of phosphorus. Simulations also highlight that deviations of nutrient data from conservative mixing curves do not necessarily indicate nutrient removal.

  6. The effects of water radiolysis on local redox conditions in the Oklo, Gabon, natural fission reactors 10 and 16

    NASA Astrophysics Data System (ADS)

    Savary, Véronique; Pagel, Maurice

    1997-11-01

    In an underground nuclear waste repository, the chemical behavior of some stored fission products and actinides depends on the redox conditions during their long-term evolution. In this respect, radiolysis is an important phenomenon which can significantly modify the local redox conditions. The Oklo natural fission zones are good examples where the effect of radiolysis can be deduced from a mineralogical and geochemical study. Zones 10 and 16 were studied because they are located at depth of 270 m in an area devoid of any recent water circulation and not subject to the effect of the lateritic alteration occurring elsewhere in this area. In zone 10, there is a marked evolution of the UPbFeS mineralogy from the center to the periphery of the reactor zone. In the center, uraninite shows silicification and coffinitisation with the formation of galena and native lead; the PbO content of uraninite can be as much as 20 wt%. In the periphery of the reactor zone, some radiogenic lead is present as minium (Pb 30 4) and in Pb-bearing calcite. In the surrounding sandstones, hematite is widespread. In zone 16, the mineral paragenesis is generally comparable with that of zone 10 but with some differences. Galena is the only Pb-bearing mineral associated with uraninite crystals. The PbO content of uraninite is always <7 wt%. In the periphery of the alteration zone, barite partly replaces quartz. In the reactor zone, hematite is sometimes replaced by pyrite. In an area where the fission zone 10 is in contact with sandstones devoid of organic matter, H 2OH 2O 2 and H 20H 2 ± CH 4 inclusions were observed in healed microcracks in the detrital quartz grains. Based on microthermometric measurements, the salinity of the aqueous solution ranges from 0.2 to 18 wt% eq. NaCl. Raman analysis of the gas phase indicates that the hydrogen to oxygen ratio differs from an inclusion to the other. The presence of H 2- and O 2-bearing fluid inclusions confirms the existence of water

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

    USGS Publications Warehouse

    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.

  8. NOVELTY DETECTION UNDER CHANGING ENVIRONMENTAL CONDITIONS

    SciTech Connect

    H. SOHN; K. WORDER; C. R. FARRAR

    2001-04-01

    The primary objective of novelty detection is to examine a system's dynamic response to determine if the system significantly deviates from an initial baseline condition. In reality, the system is often subject to changing environmental and operation conditions that affect its dynamic characteristics. Such variations include changes in loading, boundary conditions, temperature, and moisture. Most damage diagnosis techniques, however, generally neglect the effects of these changing ambient conditions. Here, a novelty detection technique is developed explicitly taking into account these natural variations of the system in order to minimize false positive indications of true system changes. Auto-associative neural networks are employed to discriminate system changes of interest such as structural deterioration and damage from the natural variations of the system.

  9. Relationship between Prevailing Redox Conditions, Water Type, Topographic Location and Methane Concentrations in Susquehanna County, NE Pennsylvania

    NASA Astrophysics Data System (ADS)

    Molofsky, L. J.; McHugh, T. E.; Connor, J. A.; Richardson, S. D.

    2014-12-01

    Historical occurrence of methane in residential water wells in parts of the Appalachian basin (Pennsylvania, New York, West Virginia) has long been recognized as a natural phenomenon. The recent increase in shale gas extraction activities in these areas has highlighted the need to distinguish between baseline methane concentrations and those that may results from gas extraction activities. For the first time, this study shows that natural dissolved methane in Northeastern Pennsylvania exhibits a relationship with prevailing redox conditions of groundwater, though this relationship is not entirely as predicted. Specifically, methane concentrations in 806 pre-drill samples from residential water wells in Susquehanna County, NE Pennsylvania, were found to be highest in samples with low SO4 concentrations but low Fe(II) concentrations. This is opposite from what would be expected if high methane concentrations were associated with a reduction of insoluble Fe(III)-minerals resulting in the release of soluble Fe(II) (and therefore, an increase in measurable dissolved iron). The water type (i.e., Na-rich vs. Ca-rich), and topographic location (i.e., valley vs. upland) was also evaluated for each of the prevailing redox states to identify associations and potential driving factors. Based on this information, this talk identifies a combination of easily identifiable natural environmental "risk" factors (i.e., advanced redox state, Na-rich water type, and valley setting) that are highly predictive of naturally elevated methane concentrations in water wells. These findings highlight simple and meaningful relationships that may be used to infer whether methane in residential water sources is natural or associated with stray gas migration.

  10. Determination of Cr isotopic composition in low-level carbonates by MC-ICP-MS: a sensitive proxy for redox changes?

    NASA Astrophysics Data System (ADS)

    Bonnand, Pierre; Parkinson, Ian; James, Rachael; Karjalainen, Anne-Mari; Fehr, Manuela; Fairchild, Ian

    2010-05-01

    Geochemical data suggest that atmospheric oxygen increased during two major steps: the Great oxidation event (~2.4 Ga) and the Neoproterozoic (~1Ga-545Ma). The O2 concentration in the atmosphere is strongly linked to the redox condition of the oceans. Therefore the study of redox sensitive elements in marine sediments can be used to evaluate the evolution of O2 concentrations in the atmosphere. Chromium is a redox sensitive element which significantly fractionates its isotopes during the reduction of Cr(VI) to Cr(III) (Ellis et al., 2002). Thus, Cr isotopes can be used to assess redox changes in the past oceans. Chromium isotopic compositions in sedimentary rocks (BIFs) have been used to determine the evolution of the O2 concentration in the atmosphere during the Proterozoic (Frei et al., 2009). We have developed a chemical procedure for the purification of Cr in carbonates by using a single cation column to separate the Cr from the matrix, Fe, Ti and V. Cr isotopic compositions are determined used a 50Cr-54Cr double spike method and analysed on a ThermoFisher Neptune MC-ICP-MS using HR and MR in order to be able to discriminate Ar interferences. Standards and samples are analysed as 50ppb Cr solutions and yield an external reproducibility 50 and 70ppm. This new method allowed us to analyse samples with a Cr concentrations as low as 1ppm. We have analysed a suite of Neoproterozoic carbonates from Australia, but also modern ooids and oolithic limestones through the Phanerozoic. The Cr isotopic data for carbonates record a range of δ53Cr between -0.1 and +1.7. This range indicates that some of these carbonates clearly reflect oxidising conditions in the ocean. By comparison, the Neoproterozoic samples have Cr isotopic compositions close to the continental crust value (-0.1 to 0.1), indicating the Neoproterozoic samples reflect deposition under more reducing conditions These data suggests that the redox condition during the deposition of shallow-water carbonates

  11. Monitoring Intracellular Redox Changes in Ozone-exposed airway epithelial cells

    EPA Science Inventory

    Background: The toxicity of many compounds involves oxidative injury to cells. Direct assessment of mechanistic events involved in xenobiotic-induced oxidative stress is not easily achievable. Development of genetically-encoded probes designed for monitoring intracellular redox s...

  12. Tirapazamine has no Effect on Hepatotoxicity of Cisplatin and 5-fluorouracil but Interacts with Doxorubicin Leading to Side Changes in Redox Equilibrium.

    PubMed

    Mandziuk, Slawomir; Matysiak, Wlodzimierz; Korga, Agnieszka; Burdan, Franciszek; Pasnik, Iwona; Hejna, Marcin; Korobowicz-Markiewicz, Agnieszka; Grzycka-Kowalczyk, Luiza; Kowalczyk, Michal; Poleszak, Ewa; Jodlowska-Jedrych, Barbara; Dudka, Jaroslaw

    2016-09-01

    Tirapazamine is a hypoxia-activated prodrug which was shown to exhibit up to 300 times greater cytotoxicity under anoxic in comparison with aerobic conditions. Thus, the combined anticancer therapy of tirapazamine with a routinely used anticancer drug seems to be a promising solution. Because tirapazamine undergoes redox cycle transformation in this study, the effect of tirapazamine on redox hepatic equilibrium, lipid status and liver morphology was evaluated in rats exposed to cisplatin, doxorubicin and 5-fluorouracil. Rats were intraperitoneally injected with tirapazamine and a particular cytostatic. The animals were killed, and blood and liver were collected. Hepatic glucose, total cholesterol, triglycerides, NADH, NADPH glutathione and the activity of glucose-6-phosphate dehydrogenase were determined. Liver morphology and the immune expression of HMG-CoA-reductase were also assessed. Glucose, total cholesterol, triglycerides, bilirubin concentrations and the activity of aspartate and alanine aminotransferases were determined in the plasma. Tirapazamine displayed insignificant interactions with cisplatin and 5-fluorouracil referring to hepatic morphology and biochemical parameters. However, tirapazamine interacts with doxorubicin, thus leading to side changes in redox equilibrium and lipid peroxidation, but those effects are not severe enough to exclude that drug combination from further studies. Thus, tirapazamine seems to be a promising agent in successive studies on anticancer activity in similar schedules. PMID:26990033

  13. Changes in the redox state of sediments following the 2010 BP blowout

    NASA Astrophysics Data System (ADS)

    Hastings, D. W.; Brooks, G.; Hollander, D. J.; Larson, R. A.; Morford, J. L.; Romero, I.; Hammaker, S.; Hogan, A.; Roeder, T. K.

    2012-12-01

    We have collected multi-core sediment cores from over 40 sites along the NE Gulf of Mexico continental slope following the 2010 Deepwater Horizon oil spill. We present the geochemical results from four select sites collected on August 2010, December 2010, February 2011, September 2011, and August 2012. Cores were extruded at 2 mm intervals, and sediments were analyzed for TOC, 13C, carbonate, short-lived radioisotopes (Pb-210, Cs-137, Be-7, Th-234) and grain size. Cores reveal a well-defined, internally stratified dark brown layer in the top 1-6 cm, with finer grain size than underlying sediments. Samples were digested at high temperature and pressure in concentrated nitric acid to dissolve both the oil and authigenic fractions, but not the detrital component. Samples were subsequently analyzed by ICP-MS. Although the Macondo crude oil is slightly enriched in Ni, V, and Co, with concentrations of 2.8, 0.9, and 0.08ppm, respectively, no significant enrichment of these metals is observed in Gulf of Mexico sediments. Sediment mass accumulation rates following the event range from 0.6 - 20 g/cm2/yr, which are one to two orders of magnitude higher than pre-spill rates. Organic and inorganic carbon deposition rates from the 2010 and February 2011 cores are also elevated one to two orders of magnitude. 13C signatures of this recent deposited material are slightly depleted relative to pre-oil event material. Large sedimentation rates, depleted 13C values and lack of bioturbation on the surface of the deep sediments studied supports the hypothesis of a large sea-snow-like blizzard event during the oil-spill in 2010. Bacterially mediated oxidation of organic matter is reflected in a well-established sequence of oxidation-reduction reactions. We exploit redox sensitive trace elements including Mn, Fe, Re, U, Mo, and V to infer changes in the redox state of sediments following this large pulse of organic matter to the seafloor.

  14. Understanding Biogeochemical Transformations Of Trace Elements In Multi Metal-Rich Geomaterials Under Stimulated Redox Conditions

    EPA Science Inventory

    Natural and anthropogenic influences on hydrological conditions can induce periodic or long-term reduced conditions in geologic materials. Such conditions can cause significant impacts on biogeochemical processes of trace elements in subsurface or near surface environments. The...

  15. Flavin Redox Switching of Protein Functions

    PubMed Central

    Zhu, Weidong; Moxley, Michael A.

    2011-01-01

    Abstract Flavin cofactors impart remarkable catalytic diversity to enzymes, enabling them to participate in a broad array of biological processes. The properties of flavins also provide proteins with a versatile redox sensor that can be utilized for converting physiological signals such as cellular metabolism, light, and redox status into a unique functional output. The control of protein functions by the flavin redox state is important for transcriptional regulation, cell signaling pathways, and environmental adaptation. A significant number of proteins that have flavin redox switches are found in the Per-Arnt-Sim (PAS) domain family and include flavoproteins that act as photosensors and respond to changes in cellular redox conditions. Biochemical and structural studies of PAS domain flavoproteins have revealed key insights into how flavin redox changes are propagated to the surface of the protein and translated into a new functional output such as the binding of a target protein in a signaling pathway. Mechanistic details of proteins unrelated to the PAS domain are also emerging and provide novel examples of how the flavin redox state governs protein–membrane interactions in response to appropriate stimuli. Analysis of different flavin switch proteins reveals shared mechanistic themes for the regulation of protein structure and function by flavins. Antioxid. Redox Signal. 14, 1079–1091. PMID:21028987

  16. Evidence for Changes in Redox State During Crystallization of Allende Type B1 Inclusions

    NASA Astrophysics Data System (ADS)

    Simon, S. B.; Davis, A. M.; Grossman, L.

    1992-07-01

    /Eu, sharp increases in trivalent REE content. Because the only elements that consistently show spikes, Ti and V, are also the only elements in fassaite with multiple oxidation states at the range of Tfo(sub)2 conditions under which refractory inclusions crystallized (Beckett, 1986), we now believe that the spikes reflect redox reactions that increased the Ti^3+ and V^3+ contents of the residual liquids. Gradual decreases in Ti^3+/Ti^tot from core to rim in fassaite in TS33 and TS34 and before the spikes in TS23 indicate that the residual liquids did not re-equilibrate with the reducing, solar nebular gas throughout most of the interval of fassaite crystallization. Late reequilibration, perhaps by entry of the solar gas via cracks in the cooling CAI, would increase the Ti^3+/Ti^tot of the liquid. The Ti^3+-poor rims of fassaite crystals would then be out of equilibrium with the liquid. Resorption of the rims may have occurred, followed by deposition of relatively Ti^3+-rich fassaite. This is consistent with the observations of sharp, irregular low-Ti/high-Ti boundaries. Of the V species presumed to be present in the CAIs, V^3+ should be favored in fassaite over V^2+, based on its ionic radius. Increasing the V^3+ content of the liquid is a problem, however, because this requires oxidation of V^2+ when Ti is being reduced. Perhaps, prior to reequilibration, the internal fO(sub)2 of the inclusions became high enough to stabilize V^4+, which was reduced to V%3+. REFERENCES: Beckett J.R. (1986) Ph.D. Thesis, University of Chicago, 373 pp. Simon S.B. and Grossman L. (1991) Meteoritics 26, 395.

  17. Proxies for Redox Conditions during early Aptian Ocean Anoxic Event 1a

    NASA Astrophysics Data System (ADS)

    Brassell, S. C.

    2012-04-01

    addition, the elevated Mo concentrations (7 - 540 ppm) in these sediments are typical of euxinic conditions, and yet marcasite, a likely product of pyrite oxidation, is prevalent throughout the section. Comparison of these proxies reveals a correspondence between the lycopane index and Mo concentrations, with higher values for both parameters during warmer intervals. These results suggest that specific indicators for levels of oxygenation may perhaps be controlled by environmental variables including changes in ocean temperatures that exert an influence on surface ocean conditions that govern seasonal productivity and affect stratification in the water column, and yet are independent from the controls on anoxia within the sediment after deposition.

  18. Regulation of gap junction channels and hemichannels by phosphorylation and redox changes: a revision.

    PubMed

    Pogoda, Kristin; Kameritsch, Petra; Retamal, Mauricio A; Vega, José L

    2016-01-01

    Post-translational modifications of connexins play an important role in the regulation of gap junction and hemichannel permeability. The prerequisite for the formation of functional gap junction channels is the assembly of connexin proteins into hemichannels and their insertion into the membrane. Hemichannels can affect cellular processes by enabling the passage of signaling molecules between the intracellular and extracellular space. For the intercellular communication hemichannels from one cell have to dock to its counterparts on the opposing membrane of an adjacent cell to allow the transmission of signals via gap junctions from one cell to the other. The controlled opening of hemichannels and gating properties of complete gap junctions can be regulated via post-translational modifications of connexins. Not only channel gating, but also connexin trafficking and assembly into hemichannels can be affected by post-translational changes. Recent investigations have shown that connexins can be modified by phosphorylation/dephosphorylation, redox-related changes including effects of nitric oxide (NO), hydrogen sulfide (H2S) or carbon monoxide (CO), acetylation, methylation or ubiquitination. Most of the connexin isoforms are known to be phosphorylated, e.g. Cx43, one of the most studied connexin at all, has 21 reported phosphorylation sites. In this review, we provide an overview about the current knowledge and relevant research of responsible kinases, connexin phosphorylation sites and reported effects on gap junction and hemichannel regulation. Regarding the effects of oxidants we discuss the role of NO in different cell types and tissues and recent studies about modifications of connexins by CO and H2S. PMID:27229925

  19. Virgin coconut oil maintains redox status and improves glycemic conditions in high fructose fed rats.

    PubMed

    Narayanankutty, Arunaksharan; Mukesh, Reshma K; Ayoob, Shabna K; Ramavarma, Smitha K; Suseela, Indu M; Manalil, Jeksy J; Kuzhivelil, Balu T; Raghavamenon, Achuthan C

    2016-01-01

    Virgin Coconut Oil (VCO), extracted from fresh coconut kernel possess similar fatty acid composition to that of Copra Oil (CO), a product of dried kernel. Although CO forms the predominant dietary constituent in south India, VCO is being promoted for healthy life due to its constituent antioxidant molecules. High fructose containing CO is an established model for insulin resistance and steatohepatitis in rodents. In this study, replacement of CO with VCO in high fructose diet markedly improved the glucose metabolism and dyslipidemia. The animals fed VCO diet had only 17 % increase in blood glucose level compared to CO fed animals (46 %). Increased level of GSH and antioxidant enzyme activities in VCO fed rats indicate improved hepatic redox status. Reduced lipid peroxidation and carbonyl adducts in VCO fed rats well corroborate with the histopathological findings that hepatic damage and steatosis were comparatively reduced than the CO fed animals. These results suggest that VCO could be an efficient nutraceutical in preventing the development of diet induced insulin resistance and associated complications possibly through its antioxidant efficacy. PMID:26788013

  20. Investigating redox processes under diffusive and advective flow conditions using a coupled omics and synchrotron approach

    NASA Astrophysics Data System (ADS)

    Kemner, K. M.; Boyanov, M.; Flynn, T. M.; O'Loughlin, E. J.; Antonopoulos, D. A.; Kelly, S.; Skinner, K.; Mishra, B.; Brooks, S. C.; Watson, D. B.; Wu, W. M.

    2015-12-01

    FeIII- and SO42--reducing microorganisms and the mineral phases they produce have profound implications for many processes in aquatic and terrestrial systems. In addition, many of these microbially-catalysed geochemical transformations are highly dependent upon introduction of reactants via advective and diffusive hydrological transport. We have characterized microbial communities from a set of static microcosms to test the effect of ethanol diffusion and sulfate concentration on UVI-contaminated sediment. The spatial distribution, valence states, and speciation of both U and Fe were monitored in situ throughout the experiment by synchrotron x-ray absorption spectroscopy, in parallel with solution measurements of pH and the concentrations of sulfate, ethanol, and organic acids. After reaction initiation, a ~1-cm thick layer of sediment near the sediment-water (S-W) interface became visibly dark. Fe XANES spectra of the layer were consistent with the formation of FeS. Over the 4 year duration of the experiment, U LIII-edge XANES indicated reduction of U, first in the dark layer and then throughout the sediment. Next, the microcosms were disassembled and samples were taken from the overlying water and different sediment regions. We extracted DNA and characterized the microbial community by sequencing 16S rRNA gene amplicons with the Illumina MiSeq platform and found that the community evolved from its originally homogeneous composition, becoming significantly spatially heterogeneous. We have also developed an x-ray accessible column to probe elemental transformations as they occur along the flow path in a porous medium with the purpose of refining reactive transport models (RTMs) that describe coupled physical and biogeochemical processes in environmental systems. The elemental distribution dynamics and the RTMs of the redox driven processes within them will be presented.

  1. Redox Imbalance in Lung Cancer of Patients with Underlying Chronic Respiratory Conditions

    PubMed Central

    Mateu-Jiménez, Mercè; Sánchez-Font, Albert; Rodríguez-Fuster, Alberto; Aguiló, Rafael; Pijuan, Lara; Fermoselle, Clara; Gea, Joaquim; Curull, Víctor; Barreiro, Esther

    2016-01-01

    Chronic respiratory diseases such as obstructive pulmonary disease (COPD) and oxidative stress may underlie lung cancer (LC). We hypothesized that the profile of oxidative and antioxidant events may differ in lung tumors and blood compartments of patients with non-small cell LC (NSCLC) with and without COPD. Redox markers (immunoblotting, ELISA, chemiluminescence, 2D electrophoresis and proteomics) were analyzed in blood samples of 17 control subjects and 80 LC patients (59 LC-COPD and 21 LC) and lung specimens (tumor and nontumor) from those undergoing thoracotomy (35 patients: 23 LC-COPD and 12 LC). As smoking history was more prevalent in LC-COPD patients, these were further analyzed post hoc as heavy and moderate smokers (cutoff, 60 pack-years). Malondialdehyde (MDA)–protein adducts and SOD1 levels were higher in tumor and nontumor samples of LC-COPD than in LC. In tumors compared with nontumors, SOD2 protein content was greater, whereas catalase levels were decreased in both LC and LC-COPD patients. Blood superoxide anion levels, protein carbonylation and nitration were greater in LC and LC-COPD patients than in the controls, and in the latter patients compared with the former. Systemic superoxide anion, protein carbonyls and nitrotyrosine above specific cutoff values best identified underlying COPD among all patients. Smoking did not influence the study results. A differential expression profile of oxidative stress markers exists in blood and, to a lesser extent, in the tumors of LC-COPD patients. These findings suggest that systemic oxidative stress and lung antioxidants (potential biomarkers) may predispose patients with chronic respiratory diseases to a higher risk for LC. PMID:26772773

  2. Trace elements geochemistry of kerogen in Upper Cretaceous sediments, Chad (Bornu) Basin, northeastern Nigeria: Origin and paleo-redox conditions

    NASA Astrophysics Data System (ADS)

    Adegoke, Adebanji Kayode; Abdullah, Wan Hasiah; Hakimi, Mohammed Hail; Sarki Yandoka, Babangida M.; Mustapha, Khairul Azlan; Aturamu, Adeyinka Oluyemi

    2014-12-01

    Trace element contents in isolated kerogen from Upper Cretaceous sediments within Gongila and Fika formations in the Chad (Bornu) Basin, northeastern Nigeria were determined using Inductively-coupled plasma mass spectrometer (ICP-MS), in order to infer the origin of the organic matter and the paleo-redox conditions during their sedimentation. The concentrations of the elements in the kerogen samples varied from 1.01 to 24,740 ppm. The distribution of elements shows that Fe is the most abundant element in Chad (Bornu) Basin kerogen, followed by Ce. Among the biophile elements, V is the most abundant, followed by Ni and Co in that order. Statistical evaluation of the elemental composition data shows that As, Ce, Pb, V, Cr, Fe, Co, Ni and U exhibit good positive correlations with each other. Molybdenum, on the other hand displays no obvious correlation with most of the trace elements determined including TOC, but has good positive correlation with TS and negative correlation with Tmax, Ce and Th, which suggests that the concentration of Mo decreases with increasing maturity and vice versa. Some trace element concentrations and their ratios suggest mixed marine and terrigenous source input for the organic matter (kerogen) in Chad (Bornu) Basin. More so, the concentrations of redox-sensitive elements, such as V, Ni, Cu, Cr Mo and Mn, in the kerogen samples suggest dysoxic bottom water conditions within the Gongila and Fika sediments. Cross-plots of V and Ni and V/(V + Ni) ratio also indicate that the organic matter of these samples was deposited in slightly reducing environments.

  3. Redox Regulation of Cytosolic Translation in Plants.

    PubMed

    Moore, Marten; Gossmann, Nikolaj; Dietz, Karl-Josef

    2016-05-01

    Control of protein homeostasis is crucial for environmental acclimation of plants. In this context, translational control is receiving increasing attention, particularly since post-translational modifications of the translational apparatus allow very fast and highly effective control of protein synthesis. Reduction and oxidation (redox) reactions decisively control translation by modifying initiation, elongation, and termination of translation. This opinion article compiles information on the redox sensitivity of cytosolic translation factors and the significance of redox regulation as a key modulator of translation for efficient acclimation to changing environmental conditions. PMID:26706442

  4. Changes in glutathione-dependent redox status and mitochondrial energetic strategies are part of the adaptive response during the filamentation process in Candida albicans.

    PubMed

    Hala, Guedouari; Rachel, Gergondey; Arthur, Bourdais; Océane, Vanparis; Anne-Laure, Bulteau; Jean-Michel, Camadro; Françoise, Auchère

    2014-10-01

    Candia albicans is an opportunist pathogen responsible for a large spectrum of infections, from superficial mycosis to systemic diseases called candidiasis. Its ability to grow in various morphological forms, such as unicellular budding yeast, filamentous pseudohyphae and hyphae, contributes to its survival in the diverse microenvironments it encounters in the host. During infection in vivo, C. albicans is faced with high levels of ROS generated by phagocytes, and the thiol-dependent redox status of the cells reflects their levels of oxidative stress. We investigated the role of glutathione during the transition between the yeast and hyphal forms of the pathogen, in relation to possible changes in mitochondrial bioenergetic pathways. Using various growth media and selective mutations affecting the filamentation process, we showed that C. albicans filamentation was always associated with a depletion of intracellular glutathione levels. Moreover, the induction of hypha formation resulted in general changes in thiol metabolism, including the oxidation of cell surface -SH groups and glutathione excretion. Metabolic adaptation involved TCA cycle activation, acceleration of mitochondrial respiration and a redistribution of electron transfer pathways, with an increase in the contribution of the alternative oxidase and rotenone-insensitive dehydrogenase. Changes in redox status and apparent oxidative stress may be necessary to the shift to adaptive metabolic pathways, ensuring normal mitochondrial function and ATP levels. The consumption of intracellular glutathione levels during the filamentation process may thus be the price paid by C. albicans for survival in the conditions encountered in the host. PMID:26461308

  5. Monitoring Changes in the Redox State of Myoglobin in Cardiomyocytes by Raman Spectroscopy Enables the Protective Effect of NO Donors to Be Evaluated.

    PubMed

    Almohammedi, Abdullah; Kapetanaki, Sofia M; Hudson, Andrew J; Storey, Nina M

    2015-10-20

    Raman microspectroscopy has been used to monitor changes in the redox and ligand-coordination states of the heme complex in myoglobin during the preconditioning of ex vivo cardiomyocytes with pharmacological drugs that release nitric oxide (NO). These chemical agents are known to confer protection on heart tissue against ischemia-reperfusion injury. Subsequent changes in the redox and ligand-coordination states during experimental simulations of ischemia and reperfusion have also been monitored. We found that these measurements, in real time, could be used to evaluate the preconditioning treatment of cardiomyocytes and to predict the likelihood of cell survival following a potentially lethal period of ischemia. Evaluation of the preconditioning treatment was done at the single-cell level. The binding of NO to myoglobin, giving a 6-coordinate ferrous-heme complex, was inferred from the measured Raman bands of a cardiomyocyte by comparison to pure solution of the protein in the presence of NO. A key change in the Raman spectrum was observed after perfusion of the NO-donor was completed, where, if the preconditioning treatment was successful, the bands corresponding to the nitrosyl complex were replaced by bands corresponding to metmyoglobin, Mb(III). An observation of Mb(III) bands in the Raman spectrum was made for all of the cardiomyocytes that recovered contractile function, whereas the absence of Mb(III) bands always indicated that the cardiomyocyte would be unable to recover contractile function following the simulated conditions of ischemia and reperfusion in these experiments. PMID:26407187

  6. Redox-dependent Structural Changes in Archaeal and Bacterial Rieske-type [2Fe-2S] Clusters

    SciTech Connect

    Cosper, N. J.

    2002-01-01

    Proteins containing Rieske-type [2Fe-2S] clusters play important roles in many biological electron transfer reactions. Typically, [2Fe-2S] clusters are not directly involved in the catalytic transformation of substrate, but rather supply electrons to the active site. We report herein X-ray absorption spectroscopic (XAS) data that directly demonstrate an average increase in the iron-histidine bond length of at least 0.1 {angstrom} upon reduction of two distantly related Rieske-type clusters in archaeal Rieske ferredoxin from Sulfolobus solfataricus strain P-1 and bacterial anthranilate dioxygenases from Acinetobacter sp. strain ADP1. This localized redox-dependent structural change may fine tune the protein-protein interaction (in the case of ARF) or the interdomain interaction (in AntDO) to facilitate rapid electron transfer between a lower potential Rieske-type cluster and its redox partners, thereby regulating overall oxygenase reactions in the cells.

  7. Changes in the redox state in the retina and brain during the onset of diabetes in rats.

    PubMed

    Salceda, R; Vilchis, C; Coffe, V; Hernández-Muñoz, R

    1998-06-01

    Diabetic retinopathy is thought to result from chronic changes in the metabolic pathways of the retina. Hyperglycemia leads to increased intracellular glucose concentrations, alterations in glucose degradation and an increase in lactate/pyruvate ratio. We measured lactate content in retina and other ocular and non-ocular tissues from normal and diabetic rats in the early stages of streptozotocin-induced diabetes. The intracellular redox state was calculated from the cytoplasmic [lactate]/[pyruvate] ratio. Elevated lactate concentration were found in retina and cerebral cortex from diabetic rats. These concentrations led to a significant and progressive decrease in the NAD+/NADH ratio, suggesting that altered glucose metabolism is an initial step of retinopathy. It is thus possible that tissues such as cerebral cortex have mechanisms that prevent the damaging effect of lactate produced by hyperglycemia and/or alterations of the intracellular redox state. PMID:9580389

  8. From climate change to molecular response: redox proteomics of ozone-induced responses in soybean

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Ozone (O3) causes significant agricultural losses with soybean being highly sensitive to this oxidant. Here we assess the effect of elevated seasonal O3 exposure on the total and redox proteomes of soybean. To understand the molecular responses to O3 exposure, soybean grown at the Soybean Free Air C...

  9. Biodegradation of fat, oil and grease (FOG) deposits under various redox conditions relevant to sewer environment.

    PubMed

    He, Xia; Zhang, Qian; Cooney, Michael J; Yan, Tao

    2015-07-01

    Fat, oil and, grease (FOG) deposits are one primary cause of sanitary sewer overflows (SSOs). While numerous studies have examined the formation of FOG deposits in sewer pipes, little is known about their biodegradation under sewer environments. In this study, FOG deposit biodegradation potential was determined by studying the biodegradation of calcium palmitate in laboratory under aerobic, nitrate-reducing, sulfate-reducing, and methanogenic conditions. Over 110 days of observation, calcium palmitate was biodegraded to CO2 under aerobic and nitrate-reducing conditions. An approximate 13 times higher CO2 production rate was observed under aerobic condition than under nitrate-reducing condition. Under sulfate-reducing condition, calcium palmitate was recalcitrant to biodegradation as evidenced by small reduction in sulfate. No evidence was found to support calcium palmitate degradation under methanogenic condition in the simulated sewer environment. Dominant microbial populations in the aerobic and nitrate-reducing microcosms were identified by Illumina seqeuncing, which may contain the capability to degrade calcium palmitate under both aerobic and nitrate-reducing conditions. Further study on these populations and their functional genes could shed more light on this microbial process and eventually help develop engineering solutions for SSOs control in the future. PMID:25715780

  10. Resveratrol and N-acetylcysteine influence redox balance in equine articular chondrocytes under acidic and very low oxygen conditions

    PubMed Central

    Collins, John A.; Moots, Robert J.; Clegg, Peter D.; Milner, Peter I.

    2015-01-01

    Mature articular cartilage is an avascular tissue characterized by a low oxygen environment. In joint disease, acidosis and further reductions in oxygen levels occur, compromising cartilage integrity.This study investigated how acidosis and very low oxygen levels affect components of the cellular redox system in equine articular chondrocytesand whether the antioxidants resveratrol and N-acetylcysteine could modulate this system. We used articular chondrocytes isolated from nondiseased equine joints and cultured them in a 3-D alginate bead system for 48 h in <1, 2, 5, and 21% O2 at pH 7.2 or 6.2 in the absence or presence of the proinflammatory cytokine, interleukin-1β (10 ng/ml).In addition, chondrocytes were cultured with resveratrol (10 µM) or N-acetylcysteine (NAC) (2 mM).Cell viability, glycosaminoglycan (GAG) release, mitochondrial membrane potential (ΔΨm), reactive oxygen species (ROS), GSH:GSSG ratio, and SOD1 and SOD2 protein expression were measured. Very low levels of oxygen (<1%), acidosis (pH 6.2), and exposure to IL-1β led to reductions in cell viability, increased GAG release, alterations in ΔΨm and ROS levels, and reduced GSH:GSSG ratio. In addition, SOD1 and SOD2 protein expressions were reduced. Both resveratrol and NAC partially restored ΔΨm and ROS levels and prevented GAG release and cell loss and normalized SOD1 and SOD2 protein expression. In particular NAC was highly effective at restoring the GSH:GSSG ratio.These results show that the antioxidants resveratrol and N-acetylcysteine can counteract the redox imbalance in articular chondrocytes induced by low oxygen and acidic conditions. PMID:25998424

  11. Redox chemistry of the molecular interactions between tea catechins and human serum proteins under simulated hyperglycemic conditions.

    PubMed

    Özyurt, Hazal; Luna, Carolina; Estévez, Mario

    2016-03-01

    Carbonylation is an irreversible modification in oxidized proteins that has been directly related to a number of health disorders including Type 2 diabetes. Dietary antioxidants have been proposed to counteract the oxidative stress occurring under hyperglycemic conditions. An understanding of the nature and consequences of the molecular interactions between phytochemicals and human plasma proteins is of utmost scientific interest. Three tea catechins namely epicatechin (EC), epigallocatechin (EGC) and epigallocatechin-3-gallate (EGCG) were tested for (i) their affinity to bind to human serum albumin (HSA) and human hemoglobin (HH) and (ii) their ability to inhibit tryptophan (Trp) depletion and for the formation of specific protein carbonyls and pentosidine in the aforementioned proteins. Both proteins (20 mg mL(-1)) were allowed to react with postprandial plasmatic concentrations of the catechins (EC: 0.7 μM, EGC: 1.8 μM, and EGCG: 0.7 μM) under simulated hyperglycemic conditions (12 mM glucose/0.2 mM Fe(3+)/37 °C/10 days). The three catechins were able to inhibit Trp oxidation and protein carbonylation in both plasma proteins. Some anti-glycation properties were linked to their binding affinities. The molecular interactions reported in the present study may explain the alleged beneficial effects of tea catechins against the redox impairment linked to hyperglycemic conditions. PMID:26839039

  12. Conditioned Reinforcement Value and Resistance to Change

    ERIC Educational Resources Information Center

    Shahan, Timothy A.; Podlesnik, Christopher A.

    2008-01-01

    Three experiments examined the effects of conditioned reinforcement value and primary reinforcement rate on resistance to change using a multiple schedule of observing-response procedures with pigeons. In the absence of observing responses in both components, unsignaled periods of variable-interval (VI) schedule food reinforcement alternated with…

  13. GLOBAL CHANGE EFFECTS ON CORAL REEF CONDITION

    EPA Science Inventory

    Fisher, W., W. Davis, J. Campbell, L. Courtney, P. Harris, B. Hemmer, M. Parsons, B. Quarles and D. Santavy. In press. Global Change Effects on Coral Reef Condition (Abstract). To be presented at the EPA Science Forum: Healthy Communities and Ecosystems, 1-3 June 2004, Washington...

  14. Mitochondria and Redox Signaling in Steatohepatitis

    PubMed Central

    Morris, E. Matthew; Rector, R. Scott; Thyfault, John P.

    2011-01-01

    Abstract Alcoholic and nonalcoholic fatty liver diseases are potentially pathological conditions that can progress to steatohepatitis, fibrosis, and cirrhosis. These conditions affect millions of people throughout the world in part through poor lifestyle choices of excess alcohol consumption, overnutrition, and lack of regular physical activity. Abnormal mitochondrial and cellular redox homeostasis has been documented in steatohepatitis and results in alterations of multiple redox-sensitive signaling cascades. Ultimately, these changes in signaling lead to altered enzyme function and transcriptional activities of proteins critical to mitochondrial and cellular function. In this article, we review the current hypotheses linking mitochondrial redox state to the overall pathophysiology of alcoholic and nonalcoholic steatohepatitis and briefly discuss the current therapeutic options under investigation. Antioxid. Redox Signal. 15, 485–504. PMID:21128703

  15. Conditioned Reinforcement Value and Resistance to Change

    PubMed Central

    Shahan, Timothy A; Podlesnik, Christopher A

    2008-01-01

    Three experiments examined the effects of conditioned reinforcement value and primary reinforcement rate on resistance to change using a multiple schedule of observing-response procedures with pigeons. In the absence of observing responses in both components, unsignaled periods of variable-interval (VI) schedule food reinforcement alternated with extinction. Observing responses in both components intermittently produced 15 s of a stimulus associated with the VI schedule (i.e., S+). In the first experiment, a lower-valued conditioned reinforcer and a higher rate of primary reinforcement were arranged in one component by adding response-independent food deliveries uncorrelated with S+. In the second experiment, one component arranged a lower valued conditioned reinforcer but a higher rate of primary reinforcement by increasing the probability of VI schedule periods relative to extinction periods. In the third experiment, the two observing-response components provided similar rates of primary reinforcement but arranged different valued conditioned reinforcers. Across the three experiments, observing-response rates were typically higher in the component associated with the higher valued conditioned reinforcer. Resistance to change was not affected by conditioned reinforcement value, but was an orderly function of the rate of primary reinforcement obtained in the two components. One interpretation of these results is that S+ value does not affect response strength and that S+ deliveries increase response rates through a mechanism other than reinforcement. Alternatively, because resistance to change depends on the discriminative stimulus–reinforcer relation, the failure of S+ value to impact resistance to change could have resulted from a lack of transfer of S+ value to the broader discriminative context. PMID:18540215

  16. How Escherichia coli Is Equipped to Oxidize Hydrogen under Different Redox Conditions*

    PubMed Central

    Lukey, Michael J.; Parkin, Alison; Roessler, Maxie M.; Murphy, Bonnie J.; Harmer, Jeffrey; Palmer, Tracy; Sargent, Frank; Armstrong, Fraser A.

    2010-01-01

    The enterobacterium Escherichia coli synthesizes two H2 uptake enzymes, Hyd-1 and Hyd-2. We show using precise electrochemical kinetic measurements that the properties of Hyd-1 and Hyd-2 contrast strikingly, and may be individually optimized to function under distinct environmental conditions. Hyd-2 is well suited for fast and efficient catalysis in more reducing environments, to the extent that in vitro it behaves as a bidirectional hydrogenase. In contrast, Hyd-1 is active for H2 oxidation under more oxidizing conditions and cannot function in reverse. Importantly, Hyd-1 is O2 tolerant and can oxidize H2 in the presence of air, whereas Hyd-2 is ineffective for H2 oxidation under aerobic conditions. The results have direct relevance for physiological roles of Hyd-1 and Hyd-2, which are expressed in different phases of growth. The properties that we report suggest distinct technological applications of these contrasting enzymes. PMID:19917611

  17. Conformational Change Near the Redox Center of Dihydrolipoamide Dehydrogenase Induced by NAD(+) to Regulate the Enzyme Activity.

    PubMed

    Fukamichi, Tomoe; Nishimoto, Etsuko

    2015-05-01

    Dihydrolipoamide dehydrogenase (LipDH) transfers two electrons from dihydrolipoamide (DHL) to NAD(+) mediated by FAD. Since this reaction is the final step of a series of catalytic reaction of pyruvate dehydrogenase multi-enzyme complex (PDC), LipDH is a key enzyme to maintain the fluent metabolic flow. We reported here the conformational change near the redox center of LipDH induced by NAD(+) promoting the access of the DHL to FAD. The increase in the affinity of DHL to redox center was evidenced by the decrease in K M responding to the increase in the concentration of NAD(+) in Lineweaver-Burk plots. The fluorescence intensity of FAD transiently reduced by the addition of DHL was not recovered but rather reduced by the binding of NAD(+) with LipDH. The fluorescence decay lifetimes of FAD and Trp were prolonged in the presence of NAD(+) to show that FAD would be free from the electron transfer from the neighboring Tyrs and the resonance energy transfer efficiency between Trp and FAD lowered. These results consistently reveal that the conformation near the FAD and the surroundings would be so rearranged by NAD(+) to allow the easier access of DHL to the redox center of LipDH. PMID:25757537

  18. Redox-sensitive structural change in the A-domain of HMGB1 and its implication for the binding to cisplatin modified DNA

    SciTech Connect

    Wang, Jing; Tochio, Naoya; Takeuchi, Aya; Uewaki, Jun-ichi; Research Center for the Mathematics on Chromatin Live Dynamics , Graduate School of Science, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima 739-8526 ; Kobayashi, Naohiro; Tate, Shin-ichi; Research Center for the Mathematics on Chromatin Live Dynamics , Graduate School of Science, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima 739-8526

    2013-11-29

    Highlights: •The structure of the oxidized A-domain of human HMGB1 was solved. •Phe38 ring was flipped in the oxidized structure from that in the reduced form. •The flipped ring disables the intercalation into the cisplatinated lesions. •The functionally relevant redox-dependent structural change was described. -- Abstract: HMGB1 (high-mobility group B1) is a ubiquitously expressed bifunctional protein that acts as a nuclear protein in cells and also as an inflammatory mediator in the extracellular space. HMGB1 changes its functions according to the redox states in both intra- and extra-cellular environments. Two cysteines, Cys23 and Cys45, in the A-domain of HMGB1 form a disulfide bond under oxidative conditions. The A-domain with the disulfide bond shows reduced affinity to cisplatin modified DNA. We have solved the oxidized A-domain structure by NMR. In the structure, Phe38 has a flipped ring orientation from that found in the reduced form; the phenyl ring in the reduced form intercalates into the platinated lesion in DNA. The phenyl ring orientation in the oxidized form is stabilized through intramolecular hydrophobic contacts. The reorientation of the Phe38 ring by the disulfide bond in the A-domain may explain the reduced HMGB1 binding affinity towards cisplatinated DNA.

  19. Effect of redox conditions on MTBE biodegradation in surface water Sediments

    USGS Publications Warehouse

    Bradley, P.M.; Chapelle, F.H.; Landmeyer, J.E.

    2001-01-01

    Microbial degradation of methyl tert-butyl ether (MTBE) was observed in surface water-sediment microcosms under anaerobic conditions. The efficiency and products of anaerobic MTBE biodegradation were dependent on the predominant terminal electron-accepting conditions. In the presence of substantial methanogenic activity, MTBE biodegradation was nominal and involved reduction of MTBE to the toxic product, tert-butyl alcohol (TBA). In the absence of significant methanogenic activity, accumulation of [14C]TBA generally decreased, and mineralization of [U-14C]MTBE to 14CO2 generally increased as the oxidative potential of the predominant terminal electron acceptor increased in the order of SO4, Fe(III), Mn(IV) < NO3 < O2. Microbial mineralization of MTBE to CO2 under Mn(IV)or SO4-reducing conditions has not been reported previously. The results of this study indicate that microorganisms inhabiting the sediments of streams and lakes can degrade MTBE effectively under a range of anaerobic terminal electron-accepting conditions. Thus, anaerobic bed sediment microbial processes may provide a significant environmental sink for MTBE in surface water systems throughout the United States.

  20. Redox change during magma ascent; Observation from three volcanoes and implication for gas monitoring

    NASA Astrophysics Data System (ADS)

    Moussallam, Yves; Oppenheimer, Clive; Schipper, Ian C.; Hartley, Magaret; Scaillet, Bruno; Gaillard, Fabrice; Peters, Nial; Kyle, Phil

    2015-04-01

    The oxidation state of volcanic gases dictates their speciation and hence their reactivity in the atmosphere. It has become increasingly recognized that the oxidation state of a magma can be strongly affected by degassing. The oxidation state of gases will equally be impacted and the composition of gases emitted by volcanoes will therefore be function of the magma degassing history. This presentation will show results from three volcanoes where the oxidation state of the magma has been tracked during degassing. At Erebus and Laki we used Fe X-ray absorption near-edge structure spectroscopy (XANES) on extensive suites of melt inclusions and glasses, while at Surtsey we used S-Kα peak shifts measurements by electron microprobe (EPMA) on melt inclusions, embayment and glasses. At all three locations we found that a strong reduction of both Fe and S is associated with magma ascent. At Erebus this reduction is greatest, corresponding to a fall in magmatic fO2 of more than two log units. We propose that sulfur degassing can explain the observed evolution of the redox state with ascent and show that forward modeling using initial melt composition can successfully predict the composition of the gas phase measured at the surface. We suggest that the redox state of volcanic gases (expressed in term of redox couples: H2O/H2, SO2/H2S and CO2/CO) can be used to monitor the depth of gas-melt segregation at active volcanoes.

  1. The effects of water radiolysis on local redox conditions in the Oklo, Gabon, natural fission reactors 10 and 16

    SciTech Connect

    Savary, V.; Pagel, M.

    1997-11-01

    In an underground nuclear waste repository, the chemical behavior of some stored fission products and actinides depends on the redox conditions during their long-term evolution. In this respect, radiolysis is an important phenomenon which can significantly modify the local redox conditions. The Oklo natural fission zones are good examples where the effect of radiolysis can be deduced from a mineralogical and geochemical study. Zones 10 and 16 were studied because they are located at depth of 270 m in an area devoid of any recent water circulation and not subject to the effect of the lateritic alteration occurring elsewhere in this area. In zone 10, there is a marked evolution of the U-Pb-Fe-S mineralogy from the center to the periphery of the reactor zone. In the center, uraninite shows silicification and coffinitisation with the formation of galena and native lead; the PbO content of uraninite can be as much as 20 wt%. In the periphery of the reactor zone, some radiogenic lead is present as minimum (Pb{sub 3}O{sub 4}) and in Pb-bearing calcite. In the surrounding sandstones, hematite is widespread. In zone 16, the mineral paragenesis is generally comparable with that of zone 10 but with some differences. Galena is the only Pb-bearing mineral associated with uraninite crystals. The PbO content of uraninite is always <7 wt%. In the periphery of the alteration zone, barite partly replaces quartz. In the reactor zone, hematite is sometimes replaced by pyrite. In an area where the fission zone 10 is in contact with sandstones devoid of organic matter, H{sub 2}O-H{sub 2} {+-} CH{sub 4} inclusions were observed in healed microcracks in the detrital quartz grains. Based on microthermometric measurements, the salinity of the aqueous solution ranges from 0.2 to 18 wt% eq. NaCl. Raman analysis of the gas phase indicates that the hydrogen to oxygen ratio differs from an inclusion to the other. 41 refs., 15 figs., 3 tabs.

  2. Influence of redox conditions on the intensity of Mars crustal magnetic anomalies

    NASA Astrophysics Data System (ADS)

    Brachfeld, Stefanie; Shah, Deepa; First, Emily; Hammer, Julia; Bowles, Julie

    2015-10-01

    We evaluate the relationship between the intensity of remanent magnetization and fO2 in natural and synthetic Mars meteorites. The olivine-phyric shergottite meteorite Yamato 980459 (Y-980459) and a sulfur-free synthetic analog (Y-98*) of identical major element composition were analyzed to explore the rock magnetic and remanence properties of a basalt crystallized from a primitive melt, and to explore the role of magmatic and alteration environment fO2 on Mars crustal anomalies. The reducing conditions under which Y-980459 is estimated to have formed (QFM-2.5; Shearer et al. 2006) were replicated during the synthesis of Y-98*. Y-980459 contains pyrrhotite and chromite. Chromite is the only magnetic phase in Y-98*. The remanence-carrying capacity of Y-980459 is comparable to other shergottites that formed in the fO2 range of QFM-3 to QFM-1. The remanence-carrying capacity of these low fO2 basalts is 1-2 orders of magnitude too weak to account for the intense crustal anomalies observed in Mars's southern cratered highlands. Moderately oxidizing conditions of >QFM-1, which are more commonly observed in nakhlites and Noachian breccias, are key to generating either a primary igneous assemblage or secondary alteration assemblage capable of acquiring an intense remanent magnetization, regardless of the basalt character or thermal history. This suggests that if igneous rocks are responsible for the intensely magnetized crust, these oxidizing conditions must have existed in the magmatic plumbing systems of early Mars or must have existed in the crust during secondary processes that led to acquisition of a chemical remanent magnetization.

  3. Effect of H2 and redox condition on biotic and abiotic MTBE transformation

    USGS Publications Warehouse

    Bradley, P.M.; Chapelle, F.H.; Landmeyer, J.E.

    2006-01-01

    Laboratory studies conducted with surface water sediment from a methyl tert-butyl ether (MTBE)-contaminated site in South Carolina demonstrated that, under methanogenic conditions, [U-14C] MTBE was transformed to 14C tert-butyl alcohol (TBA) with no measurable production of 14CO2. Production of TBA was not attributed to the activity of methanogenic microorganisms, however, because comparable transformation of [U-14C] MTBE to 14C-TBA also was observed in heat-sterilized controls with dissolved H2 concentrations > 5 nM. The results suggest that the transformation of MTBE to TBA may be an abiotic process that is driven by biologically produced H2 under in situ conditions. In contrast, mineralization of [U-14C] MTBE to 14CO2 was completely inhibited by heat sterilization and only observed in treatments characterized by dissolved H2 concentrations < 2 nM. These results suggest that the pathway of MTBE transformation is influenced by in situ H2 concentrations and that in situ H2 concentrations may be an useful indicator of MTBE transformation pathways in ground water systems.

  4. Effect of ozone pre-conditioning on redox activity in a rat model of septic shock.

    PubMed

    Guanche, Dailen; Hernandez, Frank; Zamora, Zullyt; Alonso, Yaima

    2010-10-01

    The confirmed advantageous effects of oxygen/ozone therapy in several clinical conditions stimulated experimental studies on effects of the therapy in induced septic shock. This study researches the influence of Ozone Oxidative Pre-conditioning (OOP) in unbalance between pro-oxidant and antioxidant activity generated in liver and lung during a process of sepsis. The study was conducted on male rats. Sepsis was induced by intraperitoneal injection of fecal material and pre-treatment with ozone/oxygen mixture was administered before fecal material injection. Activities of catalase, glutathione peroxide, and superoxide dismutase were measured, as well as conjugated dienes (CD) and thiobarbituric acid reactive substances (TBARS) were estimated. The results demonstrated that OOP not cause oxidative damage. It reduced levels of pro-oxidant biomarkers in lung and liver, with decreased total pro-oxidant activity and elevated total antioxidant activity from a system for diagnosis of oxidative stress in both tissues. These results suggest that OOP protected liver and lung for oxidative stress in septic shock. PMID:20626256

  5. Redox-induced changes in flavin structure and roles of flavin N(5) and the ribityl 2'-OH group in regulating PutA--membrane binding.

    PubMed

    Zhang, Weimin; Zhang, Min; Zhu, Weidong; Zhou, Yuzhen; Wanduragala, Srimevan; Rewinkel, Dustin; Tanner, John J; Becker, Donald F

    2007-01-16

    PutA is a novel flavoprotein in Escherichia coli that switches from a transcriptional repressor to a membrane-bound proline catabolic enzyme. Previous crystallographic studies of the PutA proline dehydrogenase (PRODH) domain under oxidizing conditions revealed that FAD N(5) and the ribityl 2'-OH group form hydrogen bonds with Arg431 and Arg556, respectively. Here we identify molecular interactions in the PutA PRODH active site that underlie redox-dependent functional switching of PutA. We report that reduction of the PRODH domain induces major structural changes in the FAD cofactor, including a 22 degrees bend of the isoalloxazine ring along the N(5)-N(10) axis, crankshaft rotation of the upper part of the ribityl chain, and formation of a new hydrogen bond network involving the ribityl 2'-OH group, FAD N(1), and Gly435. The roles of the FAD 2'-OH group and the FAD N(5)-Arg431 hydrogen bond pair in regulating redox-dependent PutA-membrane associations were tested using FAD analogues and site-directed mutagenesis. Kinetic membrane binding measurements and cell-based reporter gene assays of modified PutA proteins show that disrupting the FAD N(5)-Arg431 interaction impairs the reductive activation of PutA-membrane binding. We also show that the FAD 2'-OH group acts as a redox-sensitive toggle switch that controls PutA-membrane binding. These results illustrate a new versatility of the ribityl chain in flavoprotein mechanisms. PMID:17209558

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

    NASA Astrophysics Data System (ADS)

    Slomp, Caroline P.; Mort, Haydon P.; Reed, Dan C.; Jilbert, Tom; Gustafsson, Bo G.

    2010-05-01

    The Baltic Sea is a classical example of a coastal system that is subject to an increased intensity and spatial extent of hypoxia due to human activities. The expansion of hypoxia since the 1960s is the result of increased inputs of nutrients from land (both from fertilizer and wastewater) and is negatively affecting living conditions for benthic organisms. In addition, the biogeochemical cycling of carbon and nutrients has been significantly altered. Water column studies have shown that the availability of dissolved inorganic phosphorus (DIP) is positively correlated with hypoxia due to release of phosphorus from sediment Fe-oxides and from organic matter upon the transition from oxic to hypoxic conditions. Thus, a large internal source of phosphorus exists in the sediment that largely controls short-term variability in water column DIP concentrations. In this presentation, we focus on results of recent field and modeling work for various parts of the Baltic Sea that confirm the role of Fe-bound P from seasonally hypoxic sediments at intermediate water depths as a major source of DIP. We also show that extended hypoxia and anoxia leads to depletion of sediment Fe-bound P and, ultimately, lower rates of sediment-water exchange of P. Authigenic Ca-P minerals appear to be only a relatively minor burial sink for P. The lack of major inorganic P burial makes the Baltic Sea sensitive to the feedback loop between increased hypoxia, enhanced regeneration of P and increased primary productivity. Historical records of bottom water oxygen at two sites (Bornholm, Northern Gotland) show a decline over the past century which is accompanied by a rise in values of typical sediment proxies for anoxia (total sulfur, molybdenum and organic C/P ratios). While sediment reactive P concentrations in anoxic basins are equal to or higher than at oxic sites, burial rates of P at hypoxic and anoxic sites are up to 20 times lower because of lower sedimentation rates. Nevertheless, burial of

  7. Salt Stress Affects the Redox Status of Arabidopsis Root Meristems

    PubMed Central

    Jiang, Keni; Moe-Lange, Jacob; Hennet, Lauriane; Feldman, Lewis J.

    2016-01-01

    We report the redox status (profiles) for specific populations of cells that comprise the Arabidopsis root tip. For recently germinated, 3–5-day-old seedlings we show that the region of the root tip with the most reduced redox status includes the root cap initials, the quiescent center and the most distal portion of the proximal meristem, and coincides with (overlays) the region of the auxin maximum. As one moves basally, further into the proximal meristem, and depending on the growth conditions, the redox status becomes more oxidized, with a 5–10 mV difference in redox potential between the two borders delimiting the proximal meristem. At the point on the root axis at which cells of the proximal meristem cease division and enter the transition zone, the redox potential levels off, and remains more or less unchanged throughout the transition zone. As cells leave the transition zone and enter the zone of elongation the redox potentials become more oxidized. Treating roots with salt (50, 100, and 150 mM NaCl) results in marked changes in root meristem structure and development, and is preceded by changes in the redox profile, which flattens, and initially becomes more oxidized, with pronounced changes in the redox potentials of the root cap, the root cap initials and the quiescent center. Roots exposed to relatively mild levels of salt (<100 mM) are able to re-establish a normal, pre-salt treatment redox profile 3–6 days after exposure to salt. Coincident with the salt-associated changes in redox profiles are changes in the distribution of auxin transporters (AUX1, PIN1/2), which become more diffuse in their localization. We conclude that salt stress affects root meristem maintenance, in part, through changes in redox and auxin transport. PMID:26904053

  8. Permeable Reactive Barriers Designed To Mitigate Eutrophication Alter Bacterial Community Composition and Aquifer Redox Conditions.

    PubMed

    Hiller, Kenly A; Foreman, Kenneth H; Weisman, David; Bowen, Jennifer L

    2015-10-01

    Permeable reactive barriers (PRBs) consist of a labile carbon source that is positioned to intercept nitrate-laden groundwater to prevent eutrophication. Decomposition of carbon in the PRB drives groundwater anoxic, fostering microbial denitrification. Such PRBs are an ideal habitat to examine microbial community structure under high-nitrate, carbon-replete conditions in coastal aquifers. We examined a PRB installed at the Waquoit Bay National Estuarine Research Reserve in Falmouth, MA. Groundwater within and below the PRB was depleted in oxygen compared to groundwater at sites upgradient and at adjacent reference sites. Nitrate concentrations declined from a high of 25 μM upgradient and adjacent to the barrier to <0.1 μM within the PRB. We analyzed the total and active bacterial communities filtered from groundwater flowing through the PRB using amplicons of 16S rRNA and of the 16S rRNA genes. Analysis of the 16S rRNA genes collected from the PRB showed that the total bacterial community had high relative abundances of bacteria thought to have alternative metabolisms, such as fermentation, including candidate phyla OD1, OP3, TM7, and GN02. In contrast, the active bacteria had lower abundances of many of these bacteria, suggesting that the bacterial taxa that differentiate the PRB groundwater community were not actively growing. Among the environmental variables analyzed, dissolved oxygen concentration explained the largest proportion of total community structure. There was, however, no significant correlation between measured environmental parameters and the active microbial community, suggesting that controls on the active portion may differ from the community as a whole. PMID:26231655

  9. Permeable Reactive Barriers Designed To Mitigate Eutrophication Alter Bacterial Community Composition and Aquifer Redox Conditions

    PubMed Central

    Hiller, Kenly A.; Foreman, Kenneth H.; Weisman, David

    2015-01-01

    Permeable reactive barriers (PRBs) consist of a labile carbon source that is positioned to intercept nitrate-laden groundwater to prevent eutrophication. Decomposition of carbon in the PRB drives groundwater anoxic, fostering microbial denitrification. Such PRBs are an ideal habitat to examine microbial community structure under high-nitrate, carbon-replete conditions in coastal aquifers. We examined a PRB installed at the Waquoit Bay National Estuarine Research Reserve in Falmouth, MA. Groundwater within and below the PRB was depleted in oxygen compared to groundwater at sites upgradient and at adjacent reference sites. Nitrate concentrations declined from a high of 25 μM upgradient and adjacent to the barrier to <0.1 μM within the PRB. We analyzed the total and active bacterial communities filtered from groundwater flowing through the PRB using amplicons of 16S rRNA and of the 16S rRNA genes. Analysis of the 16S rRNA genes collected from the PRB showed that the total bacterial community had high relative abundances of bacteria thought to have alternative metabolisms, such as fermentation, including candidate phyla OD1, OP3, TM7, and GN02. In contrast, the active bacteria had lower abundances of many of these bacteria, suggesting that the bacterial taxa that differentiate the PRB groundwater community were not actively growing. Among the environmental variables analyzed, dissolved oxygen concentration explained the largest proportion of total community structure. There was, however, no significant correlation between measured environmental parameters and the active microbial community, suggesting that controls on the active portion may differ from the community as a whole. PMID:26231655

  10. Single-cell sequencing of Thiomargarita reveals genomic flexibility for adaptation to dynamic redox conditions

    DOE PAGESBeta

    Winkel, Matthias; Salman-Carvalho, Verena; Woyke, Tanja; Richter, Michael; Schulz-Vogt, Heide N.; Flood, Beverly E.; Bailey, Jake V.; Mußmann, Marc

    2016-06-21

    Large, colorless sulfur-oxidizing bacteria (LSB) of the family Beggiatoaceae form thick mats at sulfidic sediment surfaces, where they efficiently detoxify sulfide before it enters the water column. The genus Thiomargarita harbors the largest known free-living bacteria with cell sizes of up to 750 μm in diameter. In addition to their ability to oxidize reduced sulfur compounds, some Thiornargarita spp. are known to store large amounts of nitrate, phosphate and elemental sulfur internally. To date little is known about their energy yielding metabolic pathways, and how these pathways compare to other Beggiatoaceae. Here, we present a draft single-cell genome of amore » chain-forming "Candidatus Thiomargarita nelsonii Thio36", and conduct a comparative analysis to five draft and one full genome of other members of the Beggiatoaceae. "Ca. T. nelsonii Thio36" is able to respire nitrate to both ammonium and dinitrogen, which allows them to flexibly respond to environmental changes. Genes for sulfur oxidation and inorganic carbon fixation confirmed that "Ca. T. nelsonii Thio36" can function as a chemolithoautotroph. Carbon can be fixed via the Calvin-Benson-Bassham cycle, which is common among the Beggiatoaceae. In addition we found key genes of the reductive tricarboxylic acid cycle that point toward an alternative CO2 fixation pathway. Surprisingly, "Ca. T. nelsonii Thio36" also encodes key genes of the C2-cycle that convert 2-phosphoglycolate to 3-phosphoglycerate during photorespiration in higher plants and cyanobacteria. Moreover, we identified a novel trait of a flavin-based energy bifurcation pathway coupled to a Na+-translocating membrane complex (Rnf). The coupling of these pathways may be key to surviving long periods of anoxia. As other Beggiatoaceae "Ca. T. nelsonii Thio36" encodes many genes similar to those of (filamentous) cyanobacteria. In conclusion, the genome of "Ca. T. nelsonii Thio36" provides additional insight into the ecology of giant sulfur

  11. Single-cell Sequencing of Thiomargarita Reveals Genomic Flexibility for Adaptation to Dynamic Redox Conditions

    PubMed Central

    Winkel, Matthias; Salman-Carvalho, Verena; Woyke, Tanja; Richter, Michael; Schulz-Vogt, Heide N.; Flood, Beverly E.; Bailey, Jake V.; Mußmann, Marc

    2016-01-01

    Large, colorless sulfur-oxidizing bacteria (LSB) of the family Beggiatoaceae form thick mats at sulfidic sediment surfaces, where they efficiently detoxify sulfide before it enters the water column. The genus Thiomargarita harbors the largest known free-living bacteria with cell sizes of up to 750 μm in diameter. In addition to their ability to oxidize reduced sulfur compounds, some Thiomargarita spp. are known to store large amounts of nitrate, phosphate and elemental sulfur internally. To date little is known about their energy yielding metabolic pathways, and how these pathways compare to other Beggiatoaceae. Here, we present a draft single-cell genome of a chain-forming “Candidatus Thiomargarita nelsonii Thio36”, and conduct a comparative analysis to five draft and one full genome of other members of the Beggiatoaceae. “Ca. T. nelsonii Thio36” is able to respire nitrate to both ammonium and dinitrogen, which allows them to flexibly respond to environmental changes. Genes for sulfur oxidation and inorganic carbon fixation confirmed that “Ca. T. nelsonii Thio36” can function as a chemolithoautotroph. Carbon can be fixed via the Calvin–Benson–Bassham cycle, which is common among the Beggiatoaceae. In addition we found key genes of the reductive tricarboxylic acid cycle that point toward an alternative CO2 fixation pathway. Surprisingly, “Ca. T. nelsonii Thio36” also encodes key genes of the C2-cycle that convert 2-phosphoglycolate to 3-phosphoglycerate during photorespiration in higher plants and cyanobacteria. Moreover, we identified a novel trait of a flavin-based energy bifurcation pathway coupled to a Na+-translocating membrane complex (Rnf). The coupling of these pathways may be key to surviving long periods of anoxia. As other Beggiatoaceae “Ca. T. nelsonii Thio36” encodes many genes similar to those of (filamentous) cyanobacteria. In summary, the genome of “Ca. T. nelsonii Thio36” provides additional insight into the ecology of

  12. Single-cell Sequencing of Thiomargarita Reveals Genomic Flexibility for Adaptation to Dynamic Redox Conditions.

    PubMed

    Winkel, Matthias; Salman-Carvalho, Verena; Woyke, Tanja; Richter, Michael; Schulz-Vogt, Heide N; Flood, Beverly E; Bailey, Jake V; Mußmann, Marc

    2016-01-01

    Large, colorless sulfur-oxidizing bacteria (LSB) of the family Beggiatoaceae form thick mats at sulfidic sediment surfaces, where they efficiently detoxify sulfide before it enters the water column. The genus Thiomargarita harbors the largest known free-living bacteria with cell sizes of up to 750 μm in diameter. In addition to their ability to oxidize reduced sulfur compounds, some Thiomargarita spp. are known to store large amounts of nitrate, phosphate and elemental sulfur internally. To date little is known about their energy yielding metabolic pathways, and how these pathways compare to other Beggiatoaceae. Here, we present a draft single-cell genome of a chain-forming "Candidatus Thiomargarita nelsonii Thio36", and conduct a comparative analysis to five draft and one full genome of other members of the Beggiatoaceae. "Ca. T. nelsonii Thio36" is able to respire nitrate to both ammonium and dinitrogen, which allows them to flexibly respond to environmental changes. Genes for sulfur oxidation and inorganic carbon fixation confirmed that "Ca. T. nelsonii Thio36" can function as a chemolithoautotroph. Carbon can be fixed via the Calvin-Benson-Bassham cycle, which is common among the Beggiatoaceae. In addition we found key genes of the reductive tricarboxylic acid cycle that point toward an alternative CO2 fixation pathway. Surprisingly, "Ca. T. nelsonii Thio36" also encodes key genes of the C2-cycle that convert 2-phosphoglycolate to 3-phosphoglycerate during photorespiration in higher plants and cyanobacteria. Moreover, we identified a novel trait of a flavin-based energy bifurcation pathway coupled to a Na(+)-translocating membrane complex (Rnf). The coupling of these pathways may be key to surviving long periods of anoxia. As other Beggiatoaceae "Ca. T. nelsonii Thio36" encodes many genes similar to those of (filamentous) cyanobacteria. In summary, the genome of "Ca. T. nelsonii Thio36" provides additional insight into the ecology of giant sulfur

  13. Redox states of underground brine system along the southern coast of the Laizhou Bay

    NASA Astrophysics Data System (ADS)

    Jiang, Xueyan; Yu, Zhigang; Ning, Jinsong; Chen, Hongtao; Mi, Tiezhu

    2008-05-01

    Underground brine samples were collected along the southern coast of the Laizhou Bay, Shangdong, China in two field investigations in 2003. The brines are confined in the Quaternary sediment and underwent a series of geochemical changes. The redox states of these brines were assessed qualitatively based on the measurements of Eh and redox-sensitive species such as DO, NO NO{3/-}, Mn2+, Fe2+, SO{4/2-} in the brines. The redox condition of the underground brine is anoxic, and the redox reactions that controlled the redox potential of brines should be Fe(III) reduction and sulfate reduction.

  14. Morphology Changing at Incipient Crystallization Condition

    NASA Astrophysics Data System (ADS)

    Toshima, Takeshi; Hamai, Ryo; Fujita, Saya; Takemura, Yuka; Takamatsu, Saori; Tafu, Masamoto

    2015-04-01

    Brushite (Dicalcium phosphate dihydrate, (DCPD), CaHPO4·2H2O) is one of key components in calcium phosphate system due to wide attractive material not only as bioceramics but also environmental materials. Morphology of DCPD crystals is important factor when one uses its functionality with chemical reaction; because its surface crystal face, shape and size rule the chemical reactivity, responsiveness. Moreover, physical properties are also changed the morphology; such as cohesion, dispersiveness, permeability and so on. If one uses DCPD crystals as environmental renovation materials to catch the fluoride ions, their shape require 020 crystal surfaces; which usually restricts their shape as plate-like structure. After the chemical reaction, the shape of sludge is not good for handling due to their agglutinate property. Therefore searching an effective parameter and developing the method to control the morphology of DCPD crystals is required. In past, we reported that initial concentration and pH value of starting solution, prepared by dissolving calcium nitrate, Ca(NO3)2 and ammonium dihydrogen phosphate, NH4H2PO4, changes the morphology of DCPD crystals and phase diagram of morphology of DCPD crystal depend on those parameter. The DCPD crystallization shows unique behaviour; products obtained higher initial concentration form single crystal-like structure and under lower condition, they form agglomerate crystal-like structure. These results contradict usual crystallization. Here we report that the effect of mixing process of two solutions. The morphology of DCPD crystals is changed from plate structure to petal structure by the arrangement. Our result suggests that morphology of DCPD crystals strongly depends at incipient crystallization condition and growth form is controllable by setting initial crystallization condition.

  15. Manipulation of microbial extracellular electron transfer by changing molecular structure of phenazine-type redox mediators.

    PubMed

    Chen, Jie-Jie; Chen, Wei; He, Hui; Li, Dao-Bo; Li, Wen-Wei; Xiong, Lu; Yu, Han-Qing

    2013-01-15

    Phenazines, as a type of electron shuttle, are involved in various biological processes to facilitate microbial energy metabolism and electron transfer. They constitute a large group of nitrogen-containing heterocyclic compounds, which can be produced by a diverse range of bacteria or by artificial synthesis. They vary significantly in their properties, depending mainly on the nature and position of substitutent group. Thus, it is of great interest to find out the most favorable substituent type and molecular structure of phenazines for electron transfer routes. Here, the impacts of the substituent group on the reduction potentials of phenazine-type redox mediators in aqueous solution were investigated by quantum chemical calculations, and the calculation results were further validated with experimental data. The results show that the reaction free energy was substantially affected by the location of substituent groups on the phenazine molecule and the protonated water clusters. For the main proton addition process, the phenazines substituted with electron-donating groups and those with electron-withdrawing groups interacted with different protonated water clusters, attributed to the proximity effect of water molecules on proton transfer. Thus, high energy conversion efficiency could be achieved by controlling electron flow route with appropriate substituted phenazines to reduce the biological energy acquisition. This study provides useful information for designing efficient redox mediators to promote electron transfer between microbes and terminal acceptors, which are essential to bioenergy recovery from wastes and environmental bioremediation. PMID:23244024

  16. Redox Regulation of Plant Development

    PubMed Central

    Considine, Michael J.

    2014-01-01

    Abstract Significance: 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. Recent Advances: 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. Critical Issues: 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. Future Directions: 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. Antioxid. Redox Signal. 21, 1305–1326. PMID:24180689

  17. Redox-Dependent Conformational Changes in Cytochrome c Oxidase Suggest a Gating Mechanism for Proton Uptake

    SciTech Connect

    Qin, Ling; Liu, Jian; Mills, Denise A.; Proshlyakov, Denis A.; Hiser, Carrie; Ferguson-Miller, Shelagh

    2009-08-05

    A role for conformational change in the coupling mechanism of cytochrome c oxidase is the subject of controversy. Relatively small conformational changes have been reported in comparisons of reduced and oxidized crystal structures of bovine oxidase but none in bacterial oxidases. Comparing the X-ray crystal structures of the reduced (at 2.15 {angstrom} resolution) and oxidized forms of cytochrome c oxidase from Rhodobacter sphaeroides, we observe a displacement of heme a3 involving both the porphyrin ring and the hydroxyl farnesyl tail, accompanied by protein movements in nearby regions, including the mid part of helix VIII of subunit I which harbors key residues of the K proton uptake path, K362 and T359. The conformational changes in the reduced form are reversible upon reoxidation. They result in an opening of the top of the K pathway and more ordered waters being resolved in that region, suggesting an access path for protons into the active site. In all high-resolution structures of oxidized R. sphaeroides cytochrome c oxidase, a water molecule is observed in the hydrophobic region above the top of the D path, strategically positioned to facilitate the connection of residue E286 of subunit I to the active site or to the proton pumping exit path. In the reduced and reduced plus cyanide structures, this water molecule disappears, implying disruption of proton conduction from the D path under conditions when the K path is open, thus providing a mechanism for alternating access to the active site.

  18. The effect of the periodic boundary conditions of a ZnO-coated nanospring on its surface redox-induced electrical response

    NASA Astrophysics Data System (ADS)

    Bakharev, Pavel V.; McIlroy, David N.

    2014-11-01

    A redox chemical sensor (chemiresistor) was constructed with a single ZnO coated silica nanospring. The chemiresistor response to toluene vapor as a function of the sensor temperature (TNS) and vapor temperature (TV) was measured and analyzed. The maximum sensitivity of the single ZnO coated nanospring device occurred at the sensor temperature (TNS) of 310 °C and at the vapor temperature (TV) of 250 °C. The characteristics of the electrical response of a single ZnO coated nanospring device were compared to those of a ZnO thin film. The single ZnO nanospring sensor was less responsive to small changes in toluene concentration relative to the ZnO thin film, but has a lower ultimate detection level. A computational model to simulate an electrical response of the single nanospring sensor and the thin film indicated that the differences between their response characteristics is due to the geometry of the nanospring and corresponding periodic boundary conditions imposed by the nanospring geometry, which is absent in a thin film.

  19. Redox Regulation of Mitochondrial Function

    PubMed Central

    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

  20. Temperature micro-mapping and redox conditions of a chlorite zoning pattern in green-schist facies fault zone

    NASA Astrophysics Data System (ADS)

    Trincal, Vincent; Lanari, Pierre; Lacroix, Brice; Buatier, Martine D.; Charpentier, Delphine; Labaume, Pierre; Muñoz, Manuel

    2014-05-01

    Faults are major discontinuities driving fluid flows and playing a major role in precipitation of ore deposits. Mineral paragenesis and crystal chemistry depend on Temperature (T) condition, fluid composition but also on the redox environment of precipitation. The studied samples come from the Pic de Port Vieux thrust sheet, a minor thrust sheet associated to Gavarnie thrust fault zone (Central Pyrenees). The Pic de Port Vieux Thrust sheet comprises a 1-20 meter thick layer of Triassic red beds and mylonitized Cretaceous limestone. The thrust sheet is affected by faults and cleavage; the other important deformation product is a set of veins filled by quartz and chlorite. Microstructural and mineralogical investigations were performed based on the previous work of Grant (1992). The crystallization of chlorite is syn-tectonic and strongly controlled by the fluid circulation during the Gavarnie thrust sheet emplacement. Chlorite precipitated in extension veins, crack-seal shear veins or in open cavities. The chlorite filling the open cavities occurs as pseudo-uniaxial plates arranged in rosette-shaped aggregates. These aggregates appear to have developed as a result of radial growth of the chlorite platelets. According to point and microprobe X-ray images, these chlorites display oscillatory chemical zoning patterns with alternating iron rich and magnesium rich bands. The chlorite composition ranges from Fe rich pole (Si2.62Al1.38O10(Al1.47Fe1.87Mg2.61)6(OH)8) to Mg rich pole (Si2.68Al1.31O10(Al1.45Fe1.41Mg3.06)6(OH)8). In metamorphic rocks, zoning pattern or rimmed minerals results for varying P or T conditions and can be used to unravel the P-T history of the sample. In the present study, temperature maps are derived from standardized microprobe X-ray images using the program XMapTools (Lanari et al 2014). The (Fe3+/Fetot) value in chlorite was directly measured using μXANES spot analyses collected at the Fe-K edge. The results indicate a homogeneous temperature of

  1. Redox Changes Induced by General Anesthesia in Critically Ill Patients with Multiple Traumas

    PubMed Central

    Papurica, Marius; Rogobete, Alexandru Florin; Sandesc, Dorel; Dumache, Raluca; Nartita, Radu; Sarandan, Mirela; Cradigati, Alina Carmen; Luca, Loredana; Vernic, Corina; Bedreag, Ovidiu Horea

    2015-01-01

    The critically ill polytrauma patient is a constant challenge for the trauma team due to the complexity of the complications presented. Intense inflammatory response and infections, as well as multiple organ dysfunctions, significantly increase the rate of morbidity and mortality in these patients. Moreover, due to the physiological and biochemical imbalances present in this type of patients, the bioproduction of free radicals is significantly accelerated, thus installing the oxidative stress. In the therapeutic management of such patients, multiple surgical interventions are required and therefore they are being subjected to repeated general anesthesia. In this paper, we want to present the pathophysiological implications of oxidative stress in critically ill patients with multiple traumas and the implications of general anesthesia on the redox mechanisms of the cell. We also want to summarize the antioxidant treatments able to reduce the intensity of oxidative stress by modulating the biochemical activity of some cellular mechanisms. PMID:26693352

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

    NASA Astrophysics Data System (ADS)

    Wirth, Stefanie B.; Gilli, Adrian; Niemann, Helge; Dahl, Tais W.; Ravasi, Damiana; Sax, Nadja; Hamann, Yvonne; Peduzzi, Raffaele; Peduzzi, Sandro; Tonolla, Mauro; Lehmann, Moritz F.; Anselmetti, Flavio S.

    2013-11-01

    Here, we present sedimentological, trace metal, and molecular evidence for tracking bottom water redox-state conditions during the past 12,500 years in nowadays sulfidic and meromictic Lake Cadagno (Switzerland). A 10.5 m long sediment core from the lake covering the Holocene period was investigated for concentration variations of the trace metals Mn and Mo (XRF core scanning and ICP-MS measurements), and for the presence of anoxygenic phototrophic sulfur bacteria (carotenoid pigment analysis and 16S rDNA real time PCR). Our trace metal analysis documents an oxic-intermediate-sulfidic redox-transition period beginning shortly after the lake formation ˜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%) in the sediments indicates an intermediate, Mn-enriched oxygenation state with fluctuating redox conditions during a ˜2300-year long transition interval between ˜12.1 and 9.8 kyr BP. We propose that the high Mn concentrations are the result of enhanced Mn2+ leaching from the sediments during 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 in the sediments (up to 490 ppm), accompanied by an abrupt drop in Mn concentrations and the increase of molecular biomarkers that indicate the presence of anoxygenic photosynthetic bacteria in the water column. Persistently high Mo concentrations >80 ppm provide evidence that sulfidic conditions prevailed thereafter until modern times, without any lasting hypolimnetic ventilation and reoxygenation. Hence, Lake Cadagno with its persistently stable chemocline offers a framework to study in great

  3. Clostridium thermocellum DSM 1313 transcriptional responses to redox perturbation

    DOE PAGESBeta

    Sander, Kyle B.; Wilson, Charlotte M.; M. Rodriquez, Jr.; Klingeman, Dawn Marie; Davison, Brian H.; Brown, Steven D.; Rydzak, T.

    2015-12-12

    Clostridium thermocellum is a promising consolidated bioprocessing candidate organism capable of directly converting lignocellulosic biomass to ethanol. Current ethanol yields, productivities, and growth inhibitions are industrial deployment impediments for commodity fuel production by this bacterium. Redox imbalance under certain conditions and in engineered strains may contribute to incomplete substrate utilization and may direct fermentation products to undesirable overflow metabolites. As a result, towards a better understanding of redox metabolism in C. thermocellum, we established continuous growth conditions and analyzed global gene expression during addition of two stress chemicals (methyl viologen and hydrogen peroxide) which changed the fermentation redox potential.

  4. Dependence of particle concentration effect on pH and redox for arsenic removal by FeS-coated sand under anoxic conditions.

    PubMed

    Han, Young-Soo; Demond, Avery H; Gallegos, Tanya J; Hayes, Kim F

    2015-09-01

    FeS has been recognized as a good scavenger for arsenic under anoxic conditions. To create a suitable adsorbent for flow-through reactors such as permeable reactive barriers, it has been suggested that this material may be coated onto sand. However, previous work on FeS-coated sand has focused on batch reactors, while flow-through reactors usually have higher solid-solution ratios. To ascertain whether differences in the solid-solution ratio (SSR) are important in this system, batch sorption experiments were conducted as a function of pH using As(III) and FeS-coated sands at various solid-solution ratios. The results showed little variation in the distribution coefficient with SSR at pH 7 and 9. However, at pH 5, the results showed lower values of the distribution coefficient at lower SSRs, the reverse of typically reported SSR effects. Measured pe values showed a dependence on SSR, which, when coupled with chemical modeling of the Fe-As-S-H2O system, suggested a change in the removal mechanism with SSR, from adsorption to a reduced Fe(II) oxyhydroxide phase (represented by Fe2(OH)5) to precipitation as As2S3 or AsS. On the other hand, at pH 7 and 9, arsenite adsorption is the most probable removal mechanism regardless of the pe. Thus, this study identified variations in pH and redox conditions, and the removal mechanisms that these parameters govern, as the reason for the apparent SSR effect. PMID:25553897

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

    PubMed

    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. PMID:26657377

  6. Redox condition of the late Neoproterozoic pelagic deep ocean: 57Fe Mössbauer analyses of pelagic mudstones in the Ediacaran accretionary complex, Wales, UK

    NASA Astrophysics Data System (ADS)

    Sato, Tomohiko; Sawaki, Yusuke; Asanuma, Hisashi; Fujisaki, Wataru; Okada, Yoshihiro; Maruyama, Shigenori; Isozaki, Yukio; Shozugawa, Katsumi; Matsuo, Motoyuki; Windley, Brian F.

    2015-11-01

    We report geological and geochemical analysis of Neoproterozoic pelagic deep-sea mudstones in an accretionary complex in Lleyn, Wales, UK. Ocean plate stratigraphy at Porth Felen, NW Lleyn, consists of mid-ocean ridge basalt (> 4 m), bedded dolostone (2 m), black mudstone (5 m), hemipelagic siliceous mudstone (1 m,) and turbiditic sandstone (15 m), in ascending order. The absence of terrigenous clastics confirms that the black and siliceous mudstone was deposited in a pelagic deep-sea. Based on the youngest U-Pb age (564 Ma) of detrital zircons separated from overlying sandstone, the deep-sea black mudstone was deposited in the late Ediacaran. The 5 m-thick black mudstone contains the following distinctive lithologies: (i) black mudstone with thin pyritic layers (0.8 m), (ii) alternation of black mudstone and gray/dark gray siliceous mudstone (2.4 m), (iii) thinly-laminated dark gray shale (1 m), and (iv) black mudstone with thin pyritic layers (1 m). 57Fe Mössbauer spectroscopy confirms that these black mudstones contain pyrite without hematite. In contrast, red bedded claystones (no younger than 542 Ma) in the neighboring Braich section contain hematite as their main iron mineral. These deep-sea mudstones in the Lleyn Peninsula record a change of redox condition on the pelagic deep-sea floor during the Ediacaran. The black mudstone at Porth Felen shows that deep-sea anoxia existed in the late Ediacaran. The eventual change from a reducing to an oxidizing deep-sea environment likely occurred in the late Ediacaran (ca. 564-542 Ma).

  7. Increasing tetrahydrobiopterin in cardiomyocytes adversely affects cardiac redox state and mitochondrial function independently of changes in NO production.

    PubMed

    Sethumadhavan, Savitha; Whitsett, Jennifer; Bennett, Brian; Ionova, Irina A; Pieper, Galen M; Vasquez-Vivar, Jeannette

    2016-04-01

    Tetrahydrobiopterin (BH4) represents a potential strategy for the treatment of cardiac remodeling, fibrosis and/or diastolic dysfunction. The effects of oral treatment with BH4 (Sapropterin™ or Kuvan™) are however dose-limiting with high dose negating functional improvements. Cardiomyocyte-specific overexpression of GTP cyclohydrolase I (mGCH) increases BH4 several-fold in the heart. Using this model, we aimed to establish the cardiomyocyte-specific responses to high levels of BH4. Quantification of BH4 and BH2 in mGCH transgenic hearts showed age-based variations in BH4:BH2 ratios. Hearts of mice (<6 months) have lower BH4:BH2 ratios than hearts of older mice while both GTPCH activity and tissue ascorbate levels were higher in hearts of young than older mice. No evident changes in nitric oxide (NO) production assessed by nitrite and endogenous iron-nitrosyl complexes were detected in any of the age groups. Increased BH4 production in cardiomyocytes resulted in a significant loss of mitochondrial function. Diminished oxygen consumption and reserve capacity was verified in mitochondria isolated from hearts of 12-month old compared to 3-month old mice, even though at 12 months an improved BH4:BH2 ratio is established. Accumulation of 4-hydroxynonenal (4-HNE) and decreased glutathione levels were found in the mGCH hearts and isolated mitochondria. Taken together, our results indicate that the ratio of BH4:BH2 does not predict changes in neither NO levels nor cellular redox state in the heart. The BH4 oxidation essentially limits the capacity of cardiomyocytes to reduce oxidant stress. Cardiomyocyte with chronically high levels of BH4 show a significant decline in redox state and mitochondrial function. PMID:26826575

  8. Calcium Dynamics of Ex Vivo Long-Term Cultured CD8+ T Cells Are Regulated by Changes in Redox Metabolism

    PubMed Central

    Gran, Margaret A.; Potnis, Anish; Hill, Abby; Lu, Hang

    2016-01-01

    T cells reach a state of replicative senescence characterized by a decreased ability to proliferate and respond to foreign antigens. Calcium release associated with TCR engagement is widely used as a surrogate measure of T cell response. Using an ex vivo culture model that partially replicates features of organismal aging, we observe that while the amplitude of Ca2+ signaling does not change with time in culture, older T cells exhibit faster Ca2+ rise and a faster decay. Gene expression analysis of Ca2+ channels and pumps expressed in T cells by RT-qPCR identified overexpression of the plasma membrane CRAC channel subunit ORAI1 and PMCA in older T cells. To test whether overexpression of the plasma membrane Ca2+ channel is sufficient to explain the kinetic information, we adapted a previously published computational model by Maurya and Subramaniam to include additional details on the store-operated calcium entry (SOCE) process to recapitulate Ca2+ dynamics after T cell receptor stimulation. Simulations demonstrated that upregulation of ORAI1 and PMCA channels is not sufficient to explain the observed alterations in Ca2+ signaling. Instead, modeling analysis identified kinetic parameters associated with the IP3R and STIM1 channels as potential causes for alterations in Ca2+ dynamics associated with the long term ex vivo culturing protocol. Due to these proteins having known cysteine residues susceptible to oxidation, we subsequently investigated and observed transcriptional remodeling of metabolic enzymes, a shift to more oxidized redox couples, and post-translational thiol oxidation of STIM1. The model-directed findings from this study highlight changes in the cellular redox environment that may ultimately lead to altered T cell calcium dynamics during immunosenescence or organismal aging. PMID:27526200

  9. Endoplasmic reticulum stress triggers ROS signalling, changes the redox state, and regulates the antioxidant defence of Arabidopsis thaliana

    PubMed Central

    Turkan, Ismail

    2014-01-01

    Inefficient chaperone activity in endoplasmic reticulum (ER) causes accumulation of unfolded proteins and is called ER stress, which triggers the unfolded protein response. For proper oxidative protein folding, reactive oxygen species (ROS) such as H2O2 are produced in the ER. Although the role of ROS during abiotic stresses such as salinity is well documented, the role of ER-related ROS production and its signalling is not yet known. Moreover, how H2O2 production, redox regulation, and antioxidant defence are affected in salt-treated plants when ER protein-folding machinery is impaired needs to be elucidated. For this aim, changes in NADPH-oxidase-dependent ROS signalling and H2O2 content at sequential time intervals and after 48h of ER stress, induced by tunicamycin (Tm), salinity, and their combination were determined in Arabidopsis thaliana. The main root growth was inhibited by ER stress, while low levels of Tm caused an increase in lateral root density. Salt stress and Tm induced the expression of ER-stress-related genes (bZIP17, bZIP28, bZIP60, TIN1, BiP1, BiP3) and ERO1. Tm induced expression of RBOHD and RBOHF, which led to an early increase in H2O2 and triggered ROS signalling. This study is the first report that ER stress induces the antioxidant system and the Asada–Halliwell pathway of A. thaliana in a similar way to salinity. ER stress caused oxidative damage, as evident by increased H2O2 accumulation, lipid peroxidation, and protein oxidation. As a result, this study shows that ER stress triggers ROS signalling, changes the redox state, and regulates the antioxidant defence of A. thaliana. PMID:24558072

  10. 48 CFR 52.243-5 - Changes and Changed Conditions.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... notify the Contracting Officer, in writing, of subsurface or latent physical conditions differing materially from those indicated in this contract or unknown unusual physical conditions at the site...

  11. 48 CFR 52.243-5 - Changes and Changed Conditions.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... notify the Contracting Officer, in writing, of subsurface or latent physical conditions differing materially from those indicated in this contract or unknown unusual physical conditions at the site...

  12. 48 CFR 52.243-5 - Changes and Changed Conditions.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... notify the Contracting Officer, in writing, of subsurface or latent physical conditions differing materially from those indicated in this contract or unknown unusual physical conditions at the site...

  13. 48 CFR 52.243-5 - Changes and Changed Conditions.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... notify the Contracting Officer, in writing, of subsurface or latent physical conditions differing materially from those indicated in this contract or unknown unusual physical conditions at the site...

  14. 48 CFR 52.243-5 - Changes and Changed Conditions.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... notify the Contracting Officer, in writing, of subsurface or latent physical conditions differing materially from those indicated in this contract or unknown unusual physical conditions at the site...

  15. Dissolution of UO{sub 2} (s) in MgCl{sub 2}-brines under different redox conditions

    SciTech Connect

    Casas, I.; Gimenez, J.; De Pablo, J.; Torrero, M.E.

    1993-12-31

    The dissolution of unirradiated UO{sub 2} (s), with a particle size of 1 mm, has been studied in MgCl{sub 2} brines at 298 K under both reducing and oxidizing conditions. Results obtained under reducing conditions (h{sub 2} atmosphere in the presence of a palladium catalyst) show an initial increase of the total uranium concentration in solution and a subsequent decrease until equilibrium (or steady state) values are reached. Results obtained under oxidizing conditions (nominal oxygen partial pressures of 0.05, 0.21 and 1 atm) show two different trends. A relatively fast initial dissolution rate and, after approximately two or three weeks, a slower dissolution rate. X-ray Photoelectron Spectroscopy (XPS) has shown that the UO{sub 2} surface composition changes during the experiment.

  16. Studying Iron Mineralogy to Understand Redox Conditions in the Mesoproterozoic Belt Basin, USA Using Complementary Microscopic, Spectroscopic, and Magnetic Techniques

    NASA Astrophysics Data System (ADS)

    Slotznick, S. P.; Webb, S.; Kirschvink, J. L.; Fischer, W. W.

    2015-12-01

    Observations of iron chemistry and mineralogy over time provide a valuable tool for studying paleoenvironments, but questions still remain as to the redox character of Proterozoic basins after the rise of oxygen. To evaluate the mechanisms of iron mineralization in Proterozoic samples, we developed an approach that pairs the microscale textural techniques of light microscopy, magnetic scanning microscopy, and (synchrotron-based) microprobe x-ray spectroscopy with sensitive bulk rock magnetic experiments. Samples were collected from stratigraphic sections across the ~1.4 Ga lower Belt Group, Belt Supergroup, MT and ID, USA with a focus on excellently preserved sedimentary rocks, but also including those altered by a variety of diagenetic, metamorphic, and metasomatic events. Results show that even in the best-preserved parts of the Belt Basin, late diagenetic and/or metasomatic fluids affected (in some cases very mildly) the primary iron phases as evidenced by prevalent post-depositional alterations such as rare base metal sulfides. In more heavily altered rocks, the appearance of pyrrhotite and other minerals signaled transformations in iron mineralogy through metamorphism and metasomatism. Despite these secondary phases crystallizing in an open fluid-rich system, primary records of redox chemistry were preserved in the recrystallized early diagenetic framboidal pyrite and (sub)micron-sized detrital magnetite grains. Detrital magnetite is not the most abundant iron-bearing phase in any of the samples (typically <0.01 wt%), but is widely observed in both proximal and deeper basin facies, illustrating an important detrital flux of iron to the basin and a highly reactive iron source for early diagenetic pyrite. Based on our analyses, we interpret the shallow waters of the Belt Basin to be oxic with sulfidic pore fluids and deeper waters in parts of the basin as likely euxinic, consistent with the results of some bulk geochemical proxies. This redox reconstruction also

  17. The NHS reforms. Conditions for successful change.

    PubMed

    Forster, D P; Hadley, R

    1989-10-01

    The NHS Review has proposed the most radical organisational change in health care since the inception of the service itself in 1948. Yet, the problems entailed in gaining acceptance for reforms of such magnitude are scarcely touched on in the white paper. The scale and strength of opposition which the proposals have subsequently met within the NHS have shown clearly that the issue of the management of change is likely to be central in the acceptance or otherwise of the proposals and subsequently their success or failure. Donald Forster and Roger Hadley outline the framework within which the issues posed by change can be analysed and assessed. In keeping with the government's preference for a management perspective, they emphasise insights from the literature on the management of change rather than the detail of the white paper. PMID:10296172

  18. Microbial Fingerprints of Community Structure Correlate with Changes in Ecosystem Function Induced by Perturbing the Redox Environment

    NASA Astrophysics Data System (ADS)

    Mills, A. L.; Ford, R. M.; Vallino, J. J.; Herman, J. S.; Hornberger, G. M.

    2001-12-01

    Restoration of high-quality groundwater has been an elusive engineering goal. Consequently, natural microbially-mediated reactions are increasingly relied upon to degrade organic contaminants, including hydrocarbons and many synthetic compounds. Of concern is how the introduction of an organic chemical contaminant affects the indigenous microbial communities, the geochemistry of the aquifer, and the function of the ecosystem. The presence of functional redundancy in microbial communities suggests that recovery of the community after a disturbance such as a contamination event could easily result in a community that is similar in function to that which existed prior to the contamination, but which is compositionally quite different. To investigate the relationship between community structure and function we observed the response of a diverse microbial community obtained from raw sewage to a dynamic redox environment using an aerobic/anaerobic/aerobic cycle. To evaluate changes in community function CO2, pH, ammonium and nitrate levels were monitored. A phylogenetically-based DNA technique (tRFLP) was used to assess changes in microbial community structure. Principal component analysis of the tRFLP data revealed significant changes in the composition of the microbial community that correlated well with changes in community function. Results from our experiments will be discussed in the context of a metabolic model based the biogeochemistry of the system. The governing philosophy of this thermodynamically constrained metabolic model is that living systems synthesize and allocate cellular machinery in such a way as to "optimally" utilize available resources in the environment. The robustness of this optimization-based approach provides a powerful tool for studying relationships between microbial diversity and ecosystem function.

  19. Biochemical and structural characterization of Pseudomonas aeruginosa Bfd and FPR: ferredoxin NADP+ reductase and not ferredoxin is the redox partner of heme oxygenase under iron-starvation conditions.

    PubMed

    Wang, An; Zeng, Yuhong; Han, Huijong; Weeratunga, Saroja; Morgan, Bailey N; Moënne-Loccoz, Pierre; Schönbrunn, Ernst; Rivera, Mario

    2007-10-30

    Among the 118 genes upregulated by Pseudomonas aeruginosa in response to iron starvation [Ochsner, U. A., Wilderman, P. J., Vasil, A. I., and Vasil, M. L. (2002) Mol. Microbiol. 45, 1277-1287], we focused on the products of the two genes encoding electron transfer proteins, as a means of identifying the redox partners of the heme oxygenase (pa-HO) expressed under low-iron stress conditions. Biochemical and spectroscopic investigations demonstrated that the bfd gene encodes a 73-amino acid protein (pa-Bfd) that incorporates a [2Fe-2S]2+/+ center, whereas the fpr gene encodes a 258-residue NADPH-dependent ferredoxin reductase (pa-FPR) that utilizes FAD as a cofactor. In vitro reconstitution of pa-HO catalytic activity with the newly characterized proteins led to the surprising observation that pa-FPR efficiently supports the catalytic cycle of pa-HO, without the need of a ferredoxin. In comparison, electron transfer from pa-Bfd to pa-HO is sluggish, which strongly argues against the possibility that the seven electrons needed by pa-HO to degrade biliverdin are transferred from NADPH to pa-HO in a ferredoxin (Bfd)-dependent manner. Given that pa-HO functions to release iron from exogenous heme acquired under iron-starvation conditions, the use of a flavoenzyme rather than an iron-sulfur center-containing protein to support heme degradation is an efficient use of resources in the cell. The crystal structure of pa-FPR (1.6 A resolution) showed that its fold is comparable that of the superfamily of ferredoxin reductases and most similar to the structure of Azotobacter vinelandii FPR and Escherichia coli flavodoxin reductase. The latter two enzymes interact with distinct redox partners, a ferredoxin and a flavodoxin, respectively. Hence, findings reported herein extend the range of redox partners recognized by the fold of pa-FPR to include a heme oxygenase (pa-HO). PMID:17915950

  20. Electrochemical response of a biofilm community to changes in electron-acceptor redox potential elucidated using microbial fuel cells

    NASA Astrophysics Data System (ADS)

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

    2012-12-01

    Currently, we have limited insight into how mineral properties affect dissimilatory metal-reducing bacteria (DMRB) or the microbial communities that contain them. Advances in our understanding of DMRB metabolism have been achieved using microbial fuel cells (MFCs), which exploit the ability of these organisms to transfer electrons extracellularly. By replacing the mineral electron acceptor with a conductive electrode under potentiostat control, the activity of microorganisms capable of interfacial electron transfer can be quantified by the current flowing through the electrode and related to the thermodynamics of respiration. We seek to understand how communities and their individual members respond to changes in mineralogy, and expect mineral redox potential to be a primary control. The ability to precisely control the redox potential of the electron-accepting anodic electrode is our primary motivation for using MFCs. We inoculated duplicate MFCs containing 10 mM acetate in phosphate buffered media with a slurry of subsurface sediment and groundwater obtained from the Integrated Field-Scale Research Challenge Site at Rifle, CO. Electroactive biofilms were established on graphite anodes poised at a favorable potential (0.0 V vs. SHE) before poising at -0.2 V—a potential representative of natural iron reduction. The current was stable across both anodes over more than 100 days of operation, and the percentage of the electrons in acetate recovered as current ("Coulombic efficiency") was typically 70 to >90%. Current density reached 0.4 A/m2 at -0.2 V, to a max of over 1.0 A/m2 at or above ~0.0 V (based on geometric electrode surface area). Media exchanges and biofilm cyclic voltammetry (CV) experiments indicate that electrode-attached microbial communities were responsible for primary electron transfer. Cryo-electron and confocal fluorescence microscopies of the biofilm reveal numerous morphologies of viable microorganisms that are currently being characterized

  1. Studying the relationship between redox and cell growth using quantitative phase imaging (Conference Presentation)

    NASA Astrophysics Data System (ADS)

    Sridharan, Shamira; Leslie, Matthew T.; Bapst, Natalya; Smith, John; Gaskins, H. Rex; Popescu, Gabriel

    2016-03-01

    Quantitative phase imaging has been used in the past to study the dry mass of cells and study cell growth under various treatment conditions. However, the relationship between cellular redox and growth rates has not yet been studied in this context. This study employed the recombinant Glrx-roGFP2 redox biosensor targeted to the mitochondrial matrix or cytosolic compartments of A549 lung epithelial carcinoma cells. The Glrx-roGFP2s biosensor consists of a modified GFP protein containing internal cysteine residues sensitive to the local redox environment. The formation/dissolution of sulfide bridges contorts the internal chromophore, dictating corresponding changes in florescence emission that provide direct measures of the local redox potential. Combining 2-channel florescent imaging of the redox sensor with quantitative phase imaging allowed observation of redox homeostasis alongside measurements of cellular mass during full cycles of cellular division. The results indicate that mitochondrial redox showed a stronger inverse correlation with cell growth than cytoplasmic redox states; although redox changes are restricted to a 5% range. We are now studying the relationship between mitochondrial redox and cell growth in an isogenic series of breast cell lines built upon the MCF-10A genetic background that vary both in malignancy and metastatic potential.

  2. Hydrogeological Conditions Changes of Tomsk, Russia

    NASA Astrophysics Data System (ADS)

    Pokrovsky, V. D.; Dutova, E. M.; Kuzevanov, K. I.; Pokrovsky, D. S.; Nalivaiko, N. G.

    2015-11-01

    The hydro-geological conditions of Tomsk are determined by both natural factors and the impact of the urban infrastructure. Important impact on subsurface water flows involves the complex hydraulic relationship of several geological layers and the ancient and modern relief. Increasing groundwater abstraction has generally led to lowered piezometric heads in the deeper aquifer horizons, while in the uppermost horizons, rises in the water table and formation of new perched water tables are experienced due to leaking pipes and impedance of groundwater flow by deep foundations. In this paper special attention is paid to the Quaternary aquifer complex. Barrage effects of pile foundations and the intensive development of perched water distributed on flat surfaces of the watersheds and high terraces, complicated conditions for the construction and operation of facilities, leading in some cases to emergency situations.

  3. Redox-coupled structural changes in nitrite reductase revealed by serial femtosecond and microfocus crystallography.

    PubMed

    Fukuda, Yohta; Tse, Ka Man; Suzuki, Mamoru; Diederichs, Kay; Hirata, Kunio; Nakane, Takanori; Sugahara, Michihiro; Nango, Eriko; Tono, Kensuke; Joti, Yasumasa; Kameshima, Takashi; Song, Changyong; Hatsui, Takaki; Yabashi, Makina; Nureki, Osamu; Matsumura, Hiroyoshi; Inoue, Tsuyoshi; Iwata, So; Mizohata, Eiichi

    2016-05-01

    Serial femtosecond crystallography (SFX) has enabled the damage-free structural determination of metalloenzymes and filled the gaps of our knowledge between crystallographic and spectroscopic data. Crystallographers, however, scarcely know whether the rising technique provides truly new structural insights into mechanisms of metalloenzymes partly because of limited resolutions. Copper nitrite reductase (CuNiR), which converts nitrite to nitric oxide in denitrification, has been extensively studied by synchrotron radiation crystallography (SRX). Although catalytic Cu (Type 2 copper (T2Cu)) of CuNiR had been suspected to tolerate X-ray photoreduction, we here showed that T2Cu in the form free of nitrite is reduced and changes its coordination structure in SRX. Moreover, we determined the completely oxidized CuNiR structure at 1.43 Å resolution with SFX. Comparison between the high-resolution SFX and SRX data revealed the subtle structural change of a catalytic His residue by X-ray photoreduction. This finding, which SRX has failed to uncover, provides new insight into the reaction mechanism of CuNiR. PMID:26769972

  4. Redox-coupled structural changes in nitrite reductase revealed by serial femtosecond and microfocus crystallography

    PubMed Central

    Fukuda, Yohta; Suzuki, Mamoru; Matsumura, Hiroyoshi; Inoue, Tsuyoshi; Iwata, So; Mizohata, Eiichi

    2016-01-01

    Serial femtosecond crystallography (SFX) has enabled the damage-free structural determination of metalloenzymes and filled the gaps of our knowledge between crystallographic and spectroscopic data. Crystallographers, however, scarcely know whether the rising technique provides truly new structural insights into mechanisms of metalloenzymes partly because of limited resolutions. Copper nitrite reductase (CuNiR), which converts nitrite to nitric oxide in denitrification, has been extensively studied by synchrotron radiation crystallography (SRX). Although catalytic Cu (Type 2 copper (T2Cu)) of CuNiR had been suspected to tolerate X-ray photoreduction, we here showed that T2Cu in the form free of nitrite is reduced and changes its coordination structure in SRX. Moreover, we determined the completely oxidized CuNiR structure at 1.43 Å resolution with SFX. Comparison between the high-resolution SFX and SRX data revealed the subtle structural change of a catalytic His residue by X-ray photoreduction. This finding, which SRX has failed to uncover, provides new insight into the reaction mechanism of CuNiR. PMID:26769972

  5. Terrain on Europa under Changing Lighting Conditions

    NASA Technical Reports Server (NTRS)

    1997-01-01

    These images obtained by the Solid State Imaging (CCD) system aboard NASA's Galileo spacecraft show the same region of Europa under different lighting conditions. The upper image was obtained on June 28th, 1996 during Galileo's first orbit around Jupiter under 'high-sun' conditions -- the equivalent of taking a picture from a high altitude at noon (with the sun directly overhead). Note that albedo (light/dark) features are emphasized. Compare this to the lower image containing a higher-resolution inset. This (inset) image was taken on November 6th, 1996 during the spacecraft's third orbit under 'low-sun' illumination -- the equivalent of taking a picture from a high altitude at sunrise or sunset. Note that in this image the albedo features are not readily apparent. Instead, the topography of the terrain is emphasized. Planetary geologists use information from images acquired under a variety of lighting conditions to identify different types of structures and interpret how they formed. Note that the bright linear features in the upper image are seen to be ridges in the lower image. The circular feature on the right side of both images, Cilix, is approximately 25 kilometers (15 miles) across.

    The area seen in the upper image is 312 kilometers (187 miles) by 570 kilometers (342 miles) across; the area covered by the inset is 36 kilometers (22 miles) by 315 kilometers (190 miles) across. Both of these images are centered near 2 South latitude, 185 West longitude. North is to the top of the frames.

    The Jet Propulsion Laboratory, Pasadena, CA manages the mission for NASA's Office of Space Science, Washington, DC.

    This image and other images and data received from Galileo are posted on the World Wide Web, on the Galileo mission home page at URL http://galileo.jpl.nasa.gov. Background information and educational context for the images can be found at URL http://www.jpl.nasa.gov/galileo/sepo

  6. Ultrastructural changes in osteocytes in microgravity conditions

    NASA Astrophysics Data System (ADS)

    Rodionova, N. V.; Oganov, V. S.; Zolotova, N. V.

    We examined the histology and morphometry of biosamples (biopsies) of the iliac crest of monkeys, flown 14 days aboard the "Bion-11", using electron microscopy. We found, that some young osteocytes take part in the activization of collagen protein biosynthesis in the adaptive remodeling process of the bone tissue to microgravity conditions. Osteocyte lacunae filled with collagen fibrils; this correlates with fibrotic osteoblast reorganization in such zones. The osteolytic activity in mature osteocytes is intensified. As a result of osteocyte destruction, the quantity of empty osteocytic lacunae in the bone tissue increases.

  7. Sensing of redox status by TRP channels.

    PubMed

    Ogawa, Nozomi; Kurokawa, Tatsuki; Mori, Yasuo

    2016-08-01

    Cellular redox status is maintained by the balance between series of antioxidant systems and production of reactive oxygen/nitrogenous species. Cells utilize this redox balance to mediate diverse physiological functions. Transient receptor potential (TRP) channels are non-selective cation channels that act as biosensors for environmental and noxious stimuli, such as capsaicin and allicin, as well as changes in temperature and conditions inside the cell. TRP channels also have an emerging role as essential players in detecting cellular redox status to regulate cellular signals mediating physiological phenomena. Reactive species activate TRP channels either directly through oxidative amino acid modifications or indirectly through second messengers. For instance, TRPA1, TRPV1 and TRPC5 channels are directly activated by oxidizing agents through cysteine modification; whereas, TRPM2 channel is indirectly activated by production of ADP-ribose. One intriguing property of several TRP channels is susceptibility to both oxidizing and reducing stimuli, suggesting TRP channels could potentially act as a bidirectional sensor for detecting deviations in redox status. In this review, we discuss the unique chemical physiologies of redox sensitive TRP channels and their physiological significance in Ca(2+) signaling. PMID:26969190

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

    USGS Publications Warehouse

    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

  9. Superoxide Dismutase 1 Loss Disturbs Intracellular Redox Signaling, Resulting in Global Age-Related Pathological Changes

    PubMed Central

    2014-01-01

    Aging is characterized by increased oxidative stress, chronic inflammation, and organ dysfunction, which occur in a progressive and irreversible manner. Superoxide dismutase (SOD) serves as a major antioxidant and neutralizes superoxide radicals throughout the body. In vivo studies have demonstrated that copper/zinc superoxide dismutase-deficient (Sod1−/−) mice show various aging-like pathologies, accompanied by augmentation of oxidative damage in organs. We found that antioxidant treatment significantly attenuated the age-related tissue changes and oxidative damage-associated p53 upregulation in Sod1−/− mice. This review will focus on various age-related pathologies caused by the loss of Sod1 and will discuss the molecular mechanisms underlying the pathogenesis in Sod1−/− mice. PMID:25276767

  10. Experimental Evidence for Non-Redox Transformation Between Magnetite and Hermatite Under H2-Rich Hydrothermal Conditions

    SciTech Connect

    Otake, Tsubasa; Ohmoto, Hiroshi; Wesolowski, David J; Anovitz, Lawrence {Larry} M; Allard Jr, Lawrence Frederick

    2007-01-01

    Transformations of magnetite (Fe{sup II}Fe{sub 2}{sup III}O{sub 4}) to hematite (Fe{sub 2}{sup III}O{sub 3}) (and vice versa) have been thought by many scientists and engineers to require molecular O{sub 2} and/or H{sub 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{sub 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{sub 2} or H{sub 2}: Fe{sub 3}O{sub 4}(Mt) + 2H{sub (aq)}{sup +} {leftrightarrow} Fe{sub 2}O{sub 3}(Hm) + Fe{sub (aq)}{sup 2+} + H{sub 2}O 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{sub 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.

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

    SciTech Connect

    Otake, Tsubasa; Wesolowski, David J; Anovitz, Lawrence {Larry} M

    2007-05-01

    Transformations of magnetite (Fe{sup II}Fe{sub 2}{sup III}O{sub 4}) to hematite (Fe{sub 2}{sup III}O{sub 3}) (and vice versa) have been thought by many scientists and engineers to require molecular O{sub 2} and/or H{sub 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{sub 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{sub 2} or H{sub 2}: Fe{sub 3}O{sub 4}(Mt) + 2H{sub (aq)}{sup +} {leftrightarrow} Fe{sub 2}O{sub 3}(Hm) + Fe{sub (aq)}{sup 2+} + H{sub 2}O. 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{sub 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.

  12. Changing CS Features Alters Evaluative Responses in Evaluative Conditioning

    ERIC Educational Resources Information Center

    Unkelbach, Christian; Stahl, Christoph; Forderer, Sabine

    2012-01-01

    Evaluative conditioning (EC) refers to changes in people's evaluative responses toward initially neutral stimuli (CSs) by mere spatial and temporal contiguity with other positive or negative stimuli (USs). We investigate whether changing CS features from conditioning to evaluation also changes people's evaluative response toward these CSs. We used…

  13. Ultra-oxidized redox conditions in subduction mélanges? Decoupling between oxygen fugacity and oxygen availability in a metasomatic environment

    NASA Astrophysics Data System (ADS)

    Tumiati, Simone; Poli, Stefano; Godard, Gaston; Martin, Silvana; Malaspina, Nadia

    2014-05-01

    The manganese ore of Praborna (Italian Western Alps) is embedded within a metasedimentary sequence belonging to a subduction mélange equilibrated at high-pressure conditions (~2 GPa) during the Alpine orogenesis and record environmental conditions typical for a subducting slab setting. The pervasive veining of the ore and the growth of "pegmatoid" HP minerals suggest an open system with large fluid/rock ratio and a strong interaction with slab-derived fluids. This natural case provides an excellent natural laboratory for the study of the oxygen mobility in subducting oceanic slab mélanges at high-P, fluid-present conditions. The Mn-rich rocks in contact with the underlying sulphide- and magnetite-bearing metabasites, in textural and chemical equilibrium with the veins, contain braunite (Mn2+Mn3+6SiO12) + quartz + pyroxmangite (Mn2+SiO3), and minor hematite, omphacite, the epidote piemontite and spessartine-rich garnet. Similarly to Fe-bearing systems, Mn oxides and silicates can be regarded as natural redox-sensors, capable to monitor a process of fluid infiltration that could fix externally the intensive variable fO2 (or μO2). Sulphides are absent in these Mn-rich rocks, sulphates (barite, celestine) occurring instead together with As- and Sb oxides and silicates. On the basis of the observed assemblages, new thermodynamic calculations show that these mélange rocks are characterized by unrealistic ultra-oxidized states (ΔFMQ up to +12) if the chemical potential of oxygen (or the oxygen fugacity) is accounted for. However, if the molar quantity of oxygen in excess with reference to with reference to a system where all iron and manganese are considered to be ferrous, the ore appears only moderately oxidized, and comparable to typical subduction-slab mafic eclogites. Therefore, oxygen can be hardly considered a perfectly mobile component, even in the most favourable conditions. In the Earth's interior redox reactions take place mainly among solid oxides and

  14. Postural responses to changing task conditions.

    PubMed

    Hansen, P D; Woollacott, M H; Debu, B

    1988-01-01

    The experimental goal was to investigate discrepancies in the literature concerning postural adaptation and to determine if the prior presentation of horizontal perturbations affected the amplitude of responses to rotational perturbations. Surface EMG recordings from lower leg muscles (gastrocnemius (GAS) and tibialis anterior (TA)) were recorded in twelve subjects, and the amplitudes of the responses were statistically analyzed. We did not find differences between the responses to rotational perturbations which preceded or followed horizontal perturbations. This finding did not support the hypothesis that differences in the order of presentation of the different types of perturbations accounted for the discrepancies in the literature. Furthermore, our design did not show the progressive elimination of the GAS response within three to five sequential trials. Instead, we found a slow but significant response amplitude reduction over ten trials without yielding a permanent disappearance of the response. When analyzing the GAS responses to the rotational perturbations only, we found two components that contributed to the response reduction: 1) an initial reduction between trials one and subsequent trials, which could be due to habituation of a startle-like response; and 2) a second reduction which was more gradual. Our results also showed an immediate change in the response amplitude on the first trial, when the type of perturbation was changed. This is inconsistent with the view that ankle musculature stretch and joint movement are the primary inputs driving the postural responses. Since small ankle dorsiflexing rotations produced by the platform translations caused large GAS responses while large ankle dorsiflexing rotations produced by direct platform rotations caused small GAS responses, this suggests that multiple sensory inputs contribute to the responses. We propose that an initial compensation to a new perturbation type occurs within the first trial by the

  15. Chromium isotopes in carbonates — A tracer for climate change and for reconstructing the redox state of ancient seawater

    NASA Astrophysics Data System (ADS)

    Frei, R.; Gaucher, C.; Døssing, L. N.; Sial, A. N.

    2011-12-01

    powerful tool for reconstructing the redox state of ancient seawater since positive values indicate that, at least locally, Neoproterozoic shallow ocean waters were sufficiently oxidized to fractionate chromium and/or that oxygen levels of the atmosphere were sufficient to transform Cr(III) into the more mobile hexavalent Cr(VI) formed during weathering processes on land. The fact that 87Sr/ 86Sr values, despite δ 13C fluctuations, remain low (indicative of a strong hydrothermal input into the basin at his time) implies that CO 2 limitation was the cause of negative δ 13C and δ 53Cr excursions in otherwise nutrient rich late Neoproterozoic basins, and that glaciation is only one more consequence of a tectonically driven, biologically mediated system. In such a scenario, glaciation acts as an amplifier of δ 53Cr signals. These signals in marine carbonates are a sensitive tracer for redox processes in the ocean and/or on land and have the potential to contribute significantly, in combination with the other commonly used isotopic tracers, to the reconstruction of climatic changes, particularly those that are associated with major glaciation periods in Earth's history.

  16. Chromium Isotopes in Carbonates - a Tracer for Climate Change and for Reconstructing the Redox state of Ancient Seawater

    NASA Astrophysics Data System (ADS)

    Frei, R.; Gaucher, C.; Dossing, L. N.; Sial, A. N.

    2011-12-01

    the redox state of ancient seawater since positive values indicate that, at least locally, Neoproterozoic shallow ocean waters were sufficiently oxidized to fractionate chromium and/or that oxygen levels of the atmosphere were sufficient to transform Cr(III) into the more mobile hexavalent Cr(VI) formed during weathering processes on land. The fact that 87Sr/86Sr values, despite δ13C fluctuations, remain low (indicative of a strong hydrothermal input into the basin at his time) implies that CO2 limitation was the cause of negative δ13C and δ53Cr excursions in otherwise nutrient rich late Vendian basins, and that glaciation is only one more consequence of a tectonically driven, biologically mediated system. In such a scenario, glaciation acts as an amplifier of δ53Cr signals. These signals in marine carbonates are a sensitive tracer for redox processes in the ocean and/or on land and have the potential to contribute significantly to the reconstruction of climatic changes, particularly those that are associated with major glaciation periods in Earth's history.

  17. 49 CFR 1542.107 - Changed conditions affecting security.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... § 1542.103; or (3) Layout or physical structure of any area under the control of the airport operator... notification of the change condition(s). TSA will notify the airport operator of the disposition of...

  18. 49 CFR 1542.107 - Changed conditions affecting security.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... § 1542.103; or (3) Layout or physical structure of any area under the control of the airport operator... notification of the change condition(s). TSA will notify the airport operator of the disposition of...

  19. 49 CFR 1542.107 - Changed conditions affecting security.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... § 1542.103; or (3) Layout or physical structure of any area under the control of the airport operator... notification of the change condition(s). TSA will notify the airport operator of the disposition of...

  20. 49 CFR 1542.107 - Changed conditions affecting security.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... § 1542.103; or (3) Layout or physical structure of any area under the control of the airport operator... notification of the change condition(s). TSA will notify the airport operator of the disposition of...

  1. 49 CFR 1542.107 - Changed conditions affecting security.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... § 1542.103; or (3) Layout or physical structure of any area under the control of the airport operator... notification of the change condition(s). TSA will notify the airport operator of the disposition of...

  2. Ordovician Jeleniów Claystone Formation of the Holy Cross Mountains, Poland - Reconstruction of Redox Conditions Using Pyrite Framboid Study

    NASA Astrophysics Data System (ADS)

    Smolarek, Justyna; Marynowski, Leszek; Trela, Wiesław

    2014-09-01

    The aim of this research is to reconstruct palaeoredox conditions during sedimentation of the Jeleniów Claystone Formation deposits, using framboid pyrite diameter measurements. Analysis of pyrite framboids diameter distribution is an effective method in the palaeoenvironmental interpretation which allow for a more detailed insight into the redox conditions, and thus the distinction between euxinic, dysoxic and anoxic conditions. Most of the samples is characterized by framboid indicators typical for anoxic/euxinic conditions in the water column, with average (mean) values ranging from 5.29 to 6.02 urn and quite low standard deviation (SD) values ranging from 1.49 to 3.0. The remaining samples have shown slightly higher values of framboid diameter typical for upper dysoxic conditions, with average values (6.37 to 7.20 um) and low standard deviation (SD) values (1.88 to 2.88). From the depth of 75.5 m till the shallowest part of the Jeleniów Claystone Formation, two samples have been examined and no framboids has been detected. Because secondary weathering should be excluded, the lack of framboids possibly indicates oxic conditions in the water column. Oxic conditions continue within the Wólka Formation based on the lack of framboids in the ZB 51.6 sample.

  3. Ordovician Jeleniów Claystone Formation of the Holy Cross Mountains, Poland - Reconstruction of redox conditions using pyrite framboid study

    NASA Astrophysics Data System (ADS)

    Smolarek, Justyna; Marynowski, Leszek; Trela, Wiesław

    2014-09-01

    The aim of this research is to reconstruct palaeoredox conditions during sedimentation of the Jeleniów Claystone Formation deposits, using framboid pyrite diameter measurements. Analysis of pyrite framboids diameter distribution is an effective method in the palaeoenvironmental interpretation which allow for a more detailed insight into the redox conditions, and thus the distinction between euxinic, dysoxic and anoxic conditions. Most of the samples is characterized by framboid indicators typical for anoxic/euxinic conditions in the water column, with average (mean) values ranging from 5.29 to 6.02 μm and quite low standard deviation (SD) values ranging from 1.49 to 3.0. The remaining samples have shown slightly higher values of framboid diameter typical for upper dysoxic conditions, with average values (6.37 to 7.20 μm) and low standard deviation (SD) values (1.88 to 2.88). From the depth of 75.5 m till the shallowest part of the Jeleniów Claystone Formation, two samples have been examined and no framboids has been detected. Because secondary weathering should be excluded, the lack of framboids possibly indicates oxic conditions in the water column. Oxic conditions continue within the Wólka Formation based on the lack of framboids in the ZB 51.6 sample

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

    NASA Astrophysics Data System (ADS)

    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 < 0.0001). Although I/Ca ratios in benthic foraminifera appear to be a robust redox proxy there are some methodical issues which have to be considered. These "pitfalls" include: (i) the volatility of iodine in acidic 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

  5. Quantitative measures for redox signaling.

    PubMed

    Pillay, Ché S; Eagling, Beatrice D; Driscoll, Scott R E; Rohwer, Johann M

    2016-07-01

    Redox signaling is now recognized as an important regulatory mechanism for a number of cellular processes including the antioxidant response, phosphokinase signal transduction and redox metabolism. While there has been considerable progress in identifying the cellular machinery involved in redox signaling, quantitative measures of redox signals have been lacking, limiting efforts aimed at understanding and comparing redox signaling under normoxic and pathogenic conditions. Here we have outlined some of the accepted principles for redox signaling, including the description of hydrogen peroxide as a signaling molecule and the role of kinetics in conferring specificity to these signaling events. Based on these principles, we then develop a working definition for redox signaling and review a number of quantitative methods that have been employed to describe signaling in other systems. Using computational modeling and published data, we show how time- and concentration- dependent analyses, in particular, could be used to quantitatively describe redox signaling and therefore provide important insights into the functional organization of redox networks. Finally, we consider some of the key challenges with implementing these methods. PMID:27151506

  6. Morphine Induces Redox-Based Changes in Global DNA Methylation and Retrotransposon Transcription by Inhibition of Excitatory Amino Acid Transporter Type 3–Mediated Cysteine Uptake

    PubMed Central

    Trivedi, Malav; Shah, Jayni; Hodgson, Nathaniel; Byun, Hyang-Min

    2014-01-01

    Canonically, opioids influence cells by binding to a G protein–coupled opioid receptor, initiating intracellular signaling cascades, such as protein kinase, phosphatidylinositol 3-kinase, and extracellular receptor kinase pathways. This results in several downstream effects, including decreased levels of the reduced form of glutathione (GSH) and elevated oxidative stress, as well as epigenetic changes, especially in retrotransposons and heterochromatin, although the mechanism and consequences of these actions are unclear. We characterized the acute and long-term influence of morphine on redox and methylation status (including DNA methylation levels) in cultured neuronal SH-SY5Y cells. Acting via μ-opioid receptors, morphine inhibits excitatory amino acid transporter type 3–mediated cysteine uptake via multiple signaling pathways, involving different G proteins and protein kinases in a temporal manner. Decreased cysteine uptake was associated with decreases in both the redox and methylation status of neuronal cells, as defined by the ratios of GSH to oxidized forms of glutathione and S-adenosylmethionine to S-adenosylhomocysteine levels, respectively. Further, morphine induced global DNA methylation changes, including CpG sites in long interspersed nuclear elements (LINE-1) retrotransposons, resulting in increased LINE-1 mRNA. Together, these findings illuminate the mechanism by which morphine, and potentially other opioids, can influence neuronal-cell redox and methylation status including DNA methylation. Since epigenetic changes are implicated in drug addiction and tolerance phenomenon, this study could potentially extrapolate to elucidate a novel mechanism of action for other drugs of abuse. PMID:24569088

  7. The distribution of rare earth elements in groundwaters: assessing the role of source-rock composition, redox changes and colloidal particles

    NASA Astrophysics Data System (ADS)

    Dia, Aline; Gruau, Gérard; Olivié-Lauquet, Gwenaelle; Riou, Christine; Molénat, Jérome; Curmi, Pierre

    2000-12-01

    are seen to vary in phase with both redox changes and DOC, Fe, U and Th content variations. Three REE-rich water samples (one DOC-rich and two DOC-poor) were also filtered through membranes of decreasing pore size (100,000 D, 30,000 D, 5,000 D). The results show that between about 40% to 65% of the REE present in the shallow, DOC-poor groundwater samples are controlled by the colloidal fraction, which is likely to consist in these inorganic waters of a mixture of mineral phases. In the wetland groundwaters, the fraction of REE controlled by microparticles is higher than 65%, which confirms the predominant role of organic colloids as major REE carriers in wetland waters. Using the above data set in conjunction with analyses of soil samples, we show that the deep Ce anomalies found in the upper non organic part of the aquifer are probably not source-rock inherited features: most likely, these anomalies arise from the oxidative precipitation of Ce. The very low REE content displayed by waters flooding the deep fresh schists is interpreted as due to the combined effects of (i) pH variation, (ii) secondary sulfate mineral precipitation and (iii) the trapping of colloids-borne REE by the aquifer-rock pores. Data from wetland groundwaters show that the REE, Fe, U and Th budgets of these waters are mainly controlled by seasonal changes in redox conditions and organic matter content. However, unlike organic-poor waters, it appears difficult to relate the Ce behaviour in these organic-rich waters solely to redox conditions. It is likely that the complexation of Ce by organic colloids in the organic-rich waters may mask redox changes by inhibiting the development of negative Ce anomalies.

  8. General Chemoselective and Redox-Responsive Ligation and Release Strategy

    PubMed Central

    2015-01-01

    We report a switchable redox click and cleave reaction strategy for conjugating and releasing a range of molecules on demand. This chemoselective redox-responsive ligation (CRRL) and release strategy is based on a redox switchable oxime linkage that is controlled by mild chemical or electrochemical redox signals and can be performed at physiological conditions without the use of a catalyst. Both conjugation and release reactions are kinetically well behaved and quantitative. The CRRL strategy is synthetically modular and easily monitored and characterized by routine analytical techniques. We demonstrate how the CRRL strategy can be used for the dynamic generation of cyclic peptides and the ligation of two different peptides that are stable but can be selectively cleaved upon changes in the redox environment. We also demonstrate a new redox based delivery of cargoes to live cells strategy via the CRRL methodology by synthesizing a FRET redox-responsive probe that is selectively activated within a cellular environment. We believe the ease of the CRRL strategy should find wide use in a range of applications in biology, tissue engineering, nanoscience, synthetic chemistry, and material science and will expand the suite of current conjugation and release strategies. PMID:24559434

  9. General chemoselective and redox-responsive ligation and release strategy.

    PubMed

    Park, Sungjin; Westcott, Nathan P; Luo, Wei; Dutta, Debjit; Yousaf, Muhammad N

    2014-03-19

    We report a switchable redox click and cleave reaction strategy for conjugating and releasing a range of molecules on demand. This chemoselective redox-responsive ligation (CRRL) and release strategy is based on a redox switchable oxime linkage that is controlled by mild chemical or electrochemical redox signals and can be performed at physiological conditions without the use of a catalyst. Both conjugation and release reactions are kinetically well behaved and quantitative. The CRRL strategy is synthetically modular and easily monitored and characterized by routine analytical techniques. We demonstrate how the CRRL strategy can be used for the dynamic generation of cyclic peptides and the ligation of two different peptides that are stable but can be selectively cleaved upon changes in the redox environment. We also demonstrate a new redox based delivery of cargoes to live cells strategy via the CRRL methodology by synthesizing a FRET redox-responsive probe that is selectively activated within a cellular environment. We believe the ease of the CRRL strategy should find wide use in a range of applications in biology, tissue engineering, nanoscience, synthetic chemistry, and material science and will expand the suite of current conjugation and release strategies. PMID:24559434

  10. Mixing interfaces, fluxes, residence times and redox conditions of the hyporheic zones induced by dune-like bedforms and ambient groundwater flow

    NASA Astrophysics Data System (ADS)

    Marzadri, Alessandra; Tonina, Daniele; Bellin, Alberto; Valli, Alberto

    2016-02-01

    Recent studies highlighted the importance of the interface between streams and their surrounding sediment, known as the hyporheic zone, where stream waters flow through the alluvium. These pore water fluxes stem from the interaction among streambed morphology, stream hydraulics and surrounding groundwater flow. We analytically model the hyporheic hydraulics induced by a spatially uniform ambient groundwater flow made of a horizontal, underflow, and a vertical, basal, component, which mimics gaining and losing stream conditions. The proposed analytical solution allows to investigate the control of simple hydromorphological quantities on the extent, residence time and redox conditions of the hyporheic zone, and the thickness of the mixing interface between hyporheic and groundwater cells. Our analysis shows that the location of the mixing zone shallows or deepens in the sediment as a function of bedform geometry, surface hydraulic and groundwater flow. The point of stagnation, where hyporheic flow velocities vanish and where the separation surface passes through, is shallower than or coincides with the deepest point of the hyporheic zone only due to underflow. An increase of the ambient flow causes a reduction of the hyporheic zone volume similarly in both losing and gaining conditions. The hyporheic residence time is lognormally distributed under neutral, losing and gaining conditions, with the residence time moments depending on the same set of parameters describing dune morphology and stream flow.

  11. Thiol-based redox switches.

    PubMed

    Groitl, Bastian; Jakob, Ursula

    2014-08-01

    Regulation of protein function through thiol-based redox switches plays an important role in the response and adaptation to local and global changes in the cellular levels of reactive oxygen species (ROS). Redox regulation is used by first responder proteins, such as ROS-specific transcriptional regulators, chaperones or metabolic enzymes to protect cells against mounting levels of oxidants, repair the damage and restore redox homeostasis. Redox regulation of phosphatases and kinases is used to control the activity of select eukaryotic signaling pathways, making reactive oxygen species important second messengers that regulate growth, development and differentiation. In this review we will compare different types of reversible protein thiol modifications, elaborate on their structural and functional consequences and discuss their role in oxidative stress response and ROS adaptation. This article is part of a Special Issue entitled: Thiol-Based Redox Processes. PMID:24657586

  12. Redox controls UPR to control redox.

    PubMed

    Eletto, Davide; Chevet, Eric; Argon, Yair; Appenzeller-Herzog, Christian

    2014-09-01

    In many physiological contexts, intracellular reduction-oxidation (redox) conditions and the unfolded protein response (UPR) are important for the control of cell life and death decisions. UPR is triggered by the disruption of endoplasmic reticulum (ER) homeostasis, also known as ER stress. Depending on the duration and severity of the disruption, this leads to cell adaptation or demise. In this Commentary, we review reductive and oxidative activation mechanisms of the UPR, which include direct interactions of dedicated protein disulfide isomerases with ER stress sensors, protein S-nitrosylation and ER Ca(2+) efflux that is promoted by reactive oxygen species. Furthermore, we discuss how cellular oxidant and antioxidant capacities are extensively remodeled downstream of UPR signals. Aside from activation of NADPH oxidases, mitogen-activated protein kinases and transcriptional antioxidant responses, such remodeling prominently relies on ER-mitochondrial crosstalk. Specific redox cues therefore operate both as triggers and effectors of ER stress, thus enabling amplification loops. We propose that redox-based amplification loops critically contribute to the switch from adaptive to fatal UPR. PMID:25107370

  13. Sensitive Measures of Condition Change in EEG Data

    SciTech Connect

    Hively, L.M.; Gailey, P.C.; Protopopescu, V.

    1999-03-10

    We present a new, robust, model-independent technique for measuring condition change in nonlinear data. We define indicators of condition change by comparing distribution functions (DF) defined on the attractor for time windowed data sets via L{sub 1}-distance and {chi}{sup 2} statistics. The new measures are applied to EEG data with the objective of detecting the transition between non-seizure and epileptic brain activity in an accurate and timely manner. We find a clear superiority of the new metrics in comparison to traditional nonlinear measures as discriminators of condition change.

  14. Clostridium thermocellum DSM 1313 transcriptional responses to redox perturbation

    SciTech Connect

    Sander, Kyle B.; Wilson, Charlotte M.; M. Rodriquez, Jr.; Klingeman, Dawn Marie; Davison, Brian H.; Brown, Steven D.; Rydzak, T.

    2015-12-12

    Clostridium thermocellum is a promising consolidated bioprocessing candidate organism capable of directly converting lignocellulosic biomass to ethanol. Current ethanol yields, productivities, and growth inhibitions are industrial deployment impediments for commodity fuel production by this bacterium. Redox imbalance under certain conditions and in engineered strains may contribute to incomplete substrate utilization and may direct fermentation products to undesirable overflow metabolites. As a result, towards a better understanding of redox metabolism in C. thermocellum, we established continuous growth conditions and analyzed global gene expression during addition of two stress chemicals (methyl viologen and hydrogen peroxide) which changed the fermentation redox potential.

  15. [The role of redox-dependent signal systems in the regulation of apoptosis under oxidative stress condition].

    PubMed

    Riazantseva, N V; Novitskiĭ, V V; Chasovskikh, N Iu; Kaĭgorodova, E V; Starikova, E G; Starikov, Iu V; Radzivil, T T; Krat, N V

    2009-01-01

    Programmed death of peripheral blood mononuclear cells from donors with acute inflammatory diseases (an acute appendicitis, a community-acquired pneumonia) was investigated under condition of oxidative stress in vitro and under effect of selective inhibitors of MAP-kinases JNK and p38. Levels of active and inactive forms of MAP-kinases, and factors of transcription were determined by immunoblotting (western blot analysis). The increase in the activity of apoptosis under condition of oxidative stress in vivo and during the acute inflammatory diseases is associated with the increase in the level of reactive oxygen species (ROS) in the cells. The action of inhibitors of MAP-kinases JNK (SP600125) and p38 (ML3403) in vitro under condition of oxidative stress prevents increase in the quantity of annexin-positive mononuclear leucocytes that testifies to involving JNK and p38 MAP-kinases in apoptosis deregulation oxidative mechanisms. The appearance of NF-kappaB in the mononuclear leucocytes under condition of oxidative stress during the acute inflammatory diseases and at the experiment was shown; p53 was registered only under condition of oxidative stress in vitro. The effect of p53 and NF-kappaB results in the increase in the quantity of apoptosis annexin-positive mononuclear leucocytes that testify to inoperativeness of antiapoptotic regulation NF-kappaB. PMID:19505051

  16. Redox regulation in the thylakoid lumen.

    PubMed

    Kang, Zhen-Hui; Wang, Gui-Xue

    2016-03-15

    Higher plants need to balance the efficiency of light energy absorption and dissipative photo-protection when exposed to fluctuations in light quantity and quality. This aim is partially realized through redox regulation within the chloroplast, which occurs in all chloroplast compartments except the envelope intermembrane space. In contrast to the chloroplast stroma, less attention has been paid to the thylakoid lumen, an inner, continuous space enclosed by the thylakoid membrane in which redox regulation is also essential for photosystem biogenesis and function. This sub-organelle compartment contains at least 80 lumenal proteins, more than 30 of which are known to contain disulfide bonds. Thioredoxins (Trx) in the chloroplast stroma are photo-reduced in the light, transferring reducing power to the proteins in the thylakoid membrane and ultimately the lumen through a trans-thylakoid membrane-reduced, equivalent pathway. The discovery of lumenal thiol oxidoreductase highlights the importance of the redox regulation network in the lumen for controlling disulfide bond formation, which is responsible for protein activity and folding and even plays a role in photo-protection. In addition, many lumenal members involved in photosystem assembly and non-photochemical quenching are likely required for reduction and/or oxidation to maintain their proper efficiency upon changes in light intensity. In light of recent findings, this review summarizes the multiple redox processes that occur in the thylakoid lumen in great detail, highlighting the essential auxiliary roles of lumenal proteins under fluctuating light conditions. PMID:26812087

  17. Ediacaran Redox Fluctuations

    NASA Astrophysics Data System (ADS)

    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.

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

    USGS Publications Warehouse

    Catallo, W. James, (Edited By)

    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

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

    SciTech Connect

    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

  20. 1H- and 13C-NMR investigation of redox-state-dependent and temperature-dependent conformation changes in horse cytochrome c.

    PubMed

    Turner, D L; Williams, R J

    1993-02-01

    The redox-state dependent changes in chemical shift, which have been measured for almost 100 CHn groups in the 13C-NMR spectra of horse cytochrome c [Santos, H., and Turner, D. L. (1992) Eur. J. Biochem. 206, 721-728], have been used to investigate the nature of the redox-related change in conformation. Apart from the haem and its axial ligands, the shifts are found to be dominated by the electron-nuclear dipolar coupling in the oxidised form, as was the case in 1H-NMR studies. These pseudocontact shifts are well described by using an empirically determined magnetic susceptibility tensor in conjunction with atomic coordinates for the horse cytochrome c. The groups which fit least well are located in the vicinity of Trp59. Comparison between 1H and 13C shifts and their temperature dependence shows that the differences from expectation based on a single structure for both oxidation states are caused largely by changes in the diamagnetic contribution to the chemical shifts. Since these are different for 1H and 13C resonances they indicate, independently from crystal structure data, some redox-related movement of the protein under the haem. The significance of these results for understanding electron transfer pathways is discussed. Finally, the temperature dependence of the pseudocontact shifts in the range 30-50 degrees C is shown to be anomalous. Approximately half of the anomalous effect may be attributed to Zeeman mixing of the electronic wavefunctions with a spin-orbit coupling constant lambda = 241 cm-1, while the other half is attributed to thermal expansion of the protein. PMID:8382154

  1. Redox-Dependent Modulation of Anthocyanin Biosynthesis by the TCP Transcription Factor TCP15 during Exposure to High Light Intensity Conditions in Arabidopsis1[OPEN

    PubMed Central

    Viola, Ivana L.; Gonzalez, Daniel H.

    2016-01-01

    TCP proteins integrate a family of transcription factors involved in the regulation of developmental processes and hormone responses. It has been shown that most members of class I, one of the two classes in which the TCP family is divided, contain a conserved Cys that leads to inhibition of DNA binding when oxidized. In this work, we describe that the class-I TCP protein TCP15 inhibits anthocyanin accumulation during exposure of plants to high light intensity by modulating the expression of transcription factors involved in the induction of anthocyanin biosynthesis genes, as suggested by the study of plants that express TCP15 from the 35SCaMV promoter and mutants in TCP15 and the related gene TCP14. In addition, the effect of TCP15 on anthocyanin accumulation is lost after prolonged incubation under high light intensity conditions. We provide evidence that this is due to inactivation of TCP15 by oxidation of Cys-20 of the TCP domain. Thus, redox modulation of TCP15 activity in vivo by high light intensity may serve to adjust anthocyanin accumulation to the duration of exposure to high irradiation conditions. PMID:26574599

  2. Redox-Dependent Modulation of Anthocyanin Biosynthesis by the TCP Transcription Factor TCP15 during Exposure to High Light Intensity Conditions in Arabidopsis.

    PubMed

    Viola, Ivana L; Camoirano, Alejandra; Gonzalez, Daniel H

    2016-01-01

    TCP proteins integrate a family of transcription factors involved in the regulation of developmental processes and hormone responses. It has been shown that most members of class I, one of the two classes in which the TCP family is divided, contain a conserved Cys that leads to inhibition of DNA binding when oxidized. In this work, we describe that the class-I TCP protein TCP15 inhibits anthocyanin accumulation during exposure of plants to high light intensity by modulating the expression of transcription factors involved in the induction of anthocyanin biosynthesis genes, as suggested by the study of plants that express TCP15 from the 35SCaMV promoter and mutants in TCP15 and the related gene TCP14. In addition, the effect of TCP15 on anthocyanin accumulation is lost after prolonged incubation under high light intensity conditions. We provide evidence that this is due to inactivation of TCP15 by oxidation of Cys-20 of the TCP domain. Thus, redox modulation of TCP15 activity in vivo by high light intensity may serve to adjust anthocyanin accumulation to the duration of exposure to high irradiation conditions. PMID:26574599

  3. Fasting, but Not Aging, Dramatically Alters the Redox Status of Cysteine Residues on Proteins in Drosophila melanogaster.

    PubMed

    Menger, Katja E; James, Andrew M; Cochemé, Helena M; Harbour, Michael E; Chouchani, Edward T; Ding, Shujing; Fearnley, Ian M; Partridge, Linda; Murphy, Michael P

    2015-06-30

    Altering the redox state of cysteine residues on protein surfaces is an important response to environmental challenges. Although aging and fasting alter many redox processes, the role of cysteine residues is uncertain. To address this, we used a redox proteomic technique, oxidative isotope-coded affinity tags (OxICAT), to assess cysteine-residue redox changes in Drosophila melanogaster during aging and fasting. This approach enabled us to simultaneously identify and quantify the redox state of several hundred cysteine residues in vivo. Cysteine residues within young flies had a bimodal distribution with peaks at ∼10% and ∼85% reversibly oxidized. Surprisingly, these cysteine residues did not become more oxidized with age. In contrast, 24 hr of fasting dramatically oxidized cysteine residues that were reduced under fed conditions while also reducing cysteine residues that were initially oxidized. We conclude that fasting, but not aging, dramatically alters cysteine-residue redox status in D. melanogaster. PMID:26095360

  4. Episodic Enhanced Carbon Sequestration and Redox Conditions in a Late Barremian-Early Aptian Restricted Marine Basin: El Pui Section, Organyà Basin

    NASA Astrophysics Data System (ADS)

    Sanchez-hernandez, Y.; Maurrasse, F. J.

    2013-05-01

    A major episode of intensified carbon sequestration (TOC) and enhanced redox conditions in the lower Cretaceous is associated with the well-known Oceanic Anoxic Event 1a (OAE1a) worldwide. Increased TOC values (up to 3.0wt%) concurrent with positive excursions in δ13C (up to 2.5‰) have been documented in different areas in the Late Barremian as well as in the middle Aptian prior to, and after OAE-1a, respectively. Such indicators imply that environmental conditions conducive to increased carbon sequestration (although less intense) developed in isolated basins not synchronous with major global forcing mechanisms recorded in the major events. In this study, geochemical analyses: organic (TOC; δ13C; biomarker analysis), and inorganic: (trace and major element concentrations, and clay mineralogy) reveal the occurrence of intermittent reducing conditions in a restricted marine basin from the latest Barremian to the lower Aptian that led to enhanced C sequestration. We also document later occurrence of OAE-1a in the basin sedimentary succession, and the impact of regional physiographic conditions in the local expression of the global event. Temporal behavior in the concentration of major elements (Al, Si and Ti) reveals variations in sedimentation patterns and nutrient availability controlled by fluctuation in terrigenous fluxes from continental runoffs. Such fluctuations controlled primary producers (both Prokaryotes: cyanobacteria; and Eukaryotes: nanno-phytoplankton) that constitute the calcareous and organic matter (OM) components of the matrix where their relative abundance co-varies with the intensity of terrigenous fluxes. The presence of benthic fauna also responded to episodic alterations in the oxygen levels with lower abundance or absence at dysoxic to anoxic intervals. Oxygen depleted levels are associated with enhanced primary productivity as indicated by positive excursions in the δ13C-org and trace element indices.

  5. Proteomic changes in rice leaves grown under open field high temperature stress conditions.

    PubMed

    Das, Smruti; Krishnan, P; Mishra, Vagish; Kumar, Ritesh; Ramakrishnan, B; Singh, N K

    2015-11-01

    The interactive effect of temperature with other climatic and soil factors has profound influences on the growth and development of rice. The responses of rice to high temperatures under field conditions are more important than those under the controlled conditions. To understand the genes associated with high temperature stress response in general and tolerance in particular, the expression of all those genes associated with adaptation and tolerance in rice requires proteomic analysis. High temperature stress-tolerant cv. N22 was subjected to 28/18 °C (control) and 42/32 °C (high temperature stress) at flowering stage. The plants were grown in the field under the free air temperature increment condition. The proteomic changes in rice leaves due to high temperature stress were discussed. The proteomes of leaves had about 3000 protein spots, reproducibly detected on 2-dimensional electrophoretic gels with 573 proteins differentially expressed between the control and the high temperature treatments. Putative physiological functions suggested five categories such as growth (15.4%), heat shock proteins (7.7%), regulatory proteins (26.9%), redox homeostasis proteins (11.5%) and energy and metabolism (38.5%) related proteins. The results of the present study suggest that cv. N22, an agronomically recognized temperature tolerant rice cultivar copes with high temperature stress in a complex manner. Several functional proteins play important roles in its responses. The predicted climate change events necessitate more studies using this cultivar under different simulated ecological conditions to identify proteomic changes and the associated genes to be used as biomarkers and to gain a better understanding on the biochemical pathways involved in tolerance. PMID:26323334

  6. Redox regulated peroxisome homeostasis

    PubMed Central

    Wang, Xiaofeng; Li, Shuo; Liu, Yu; Ma, Changle

    2014-01-01

    Peroxisomes are ubiquitous organelles present in nearly all eukaryotic cells. Conserved functions of peroxisomes encompass beta-oxidation of fatty acids and scavenging of reactive oxygen species generated from diverse peroxisomal metabolic pathways. Peroxisome content, number, and size can change quickly in response to environmental and/or developmental cues. To achieve efficient peroxisome homeostasis, peroxisome biogenesis and degradation must be orchestrated. We review the current knowledge on redox regulated peroxisome biogenesis and degradation with an emphasis on yeasts and plants. PMID:25545794

  7. Redox regulated peroxisome homeostasis.

    PubMed

    Wang, Xiaofeng; Li, Shuo; Liu, Yu; Ma, Changle

    2015-01-01

    Peroxisomes are ubiquitous organelles present in nearly all eukaryotic cells. Conserved functions of peroxisomes encompass beta-oxidation of fatty acids and scavenging of reactive oxygen species generated from diverse peroxisomal metabolic pathways. Peroxisome content, number, and size can change quickly in response to environmental and/or developmental cues. To achieve efficient peroxisome homeostasis, peroxisome biogenesis and degradation must be orchestrated. We review the current knowledge on redox regulated peroxisome biogenesis and degradation with an emphasis on yeasts and plants. PMID:25545794

  8. High resolution redox potential measurements: techniques, interpretation and value

    NASA Astrophysics Data System (ADS)

    Vorenhout, Michel; van der Geest, Harm G.

    2013-04-01

    The ongoing improvement of techniques for the in situ measurement of redox potentials has led to a large number of studies on redox variability in various environments. These studies originate from a wide array of scientific disciplines, amongst which ecology (sediment biogeochemistry), environmental chemistry (degradation studies) and archaeology (in situ preservation). To gain insight in the potential applications, this paper presents three examples of studies in which a newly developed measurement technique was used in soils and where spatial and temporal variation plays an important role. The first one is a microcosm study on the effects of biota on the dynamics of redox conditions in the toplayer of aquatic sediments, showing that the presence of microbiota has a direct influence on biogeochemical parameters. The second is the study of the redox potential in the world heritage site of Bryggen (Bergen, NO) that is under threat of oxidation. The oxidation, caused by a lowered groundwater table, causes soil degradation and unstable conditions for the monumental buildings of the Medieval site. The third study shows variability in a sandy flood plain in Bangladesh, where redox processes dictate the environmental behaviour of Arsenic. This toxic metal is present in many wells used for drinking water, but shows very local variation in dissolution dynamics. In these three studies, continuous measurements of (changes in) redox conditions revealed a strong variability in these systems and consequences for the interpretation of single point measurements or low frequency sampling campaigns are discussed. In these and many other cases, the continuous measurement of the redox potential in soil media will aid in the understanding of the system under study.

  9. Redox kinetics and colloid formation during water-chlorite interactions

    NASA Astrophysics Data System (ADS)

    Kim, E. G.; Ahn, H.; Ryu, J. H.; Jo, H. Y.

    2014-12-01

    For the isolation of high-level radioactive wastes from biosphere, the deep geological repository should be maintained reducing conditions. Surface groundwater can flow along fractures into the deep geological repository, which may cause oxic conditions. In the oxic conditions, uranium can be oxidized from U(Ⅳ) to U(Ⅵ) and U(Ⅵ) can easily migrate in groundwater due to its high mobility. Chlorite with Fe(Ⅱ), which is a phyllosilicate minerals generally occurred in fractures, can help maintenance of the reducing condition because chlorite can consume oxidizing agents by redox reactions. In this study, redox kinetics of chlorite were investigated by conducting redox batch kinetic tests at various conditions (i.e., concentration of oxidizing agent, pH, and presence of NaCl). Colloidal particle formation during redox reactions of chlorite was also investigated. Two types of chlorite samples: low iron content (CCa-2) and high iron content (Chlorite from Daejeon, South Korea) were used. Redox batch kinetic tests were conducted for 60 days. The solutions, reactants, and colloidal particles collected from the redox batch kinetic tests every 10 days were characterized. Results show that the concentration of oxidizing agent decreased more in the chlorite sample having higher Fe(Ⅱ) content than that having lower Fe(Ⅱ) content. After 10 days, both the chlorite samples tend to be reached steady-state conditions and then no changes in the concentration of oxidizing agent were observed. SEM analysis shows that surface and edge of the chlorite samples tend to be crispy and smoothy with increasing reaction time. SEM-EDS analysis on colloidal particles shows that colloidal particles consisted of Fe and O, which were identified as ferrihydrite.

  10. Neutral sphingomyelinase-2 is a redox sensitive enzyme: role of catalytic cysteine residues in regulation of enzymatic activity through changes in oligomeric state

    PubMed Central

    Dotson, P. Patrick; Karakashian, Alexander A.; Nikolova-Karakashian, Mariana N.

    2015-01-01

    Neutral sphingomyelinase-2 (nSMase-2) is the major sphingomyelinase activated in response to pro-inflammatory cytokines and during oxidative stress. It is a membrane-bound 655 amino acid protein containing 22 cysteine residues. In this study, we expressed recombinant mouse nSMase-2 protein in Escherichia coli, and investigated whether nSMase-2 is a redox sensitive enzyme. Our results demonstrate that nSMase-2 exists as both monomers and multimers that are associated with high and low enzymatic activity respectively. Mutational analysis of nSMase-2 identified within its C-terminal catalytic domain several oxidant-sensitive cysteine residues that were shown to be involved in enzyme oligomerization. Changing Cys617 to Ser for example is a gain-of-function mutation associated with a decreased propensity for oligomerization. Alternatively, nSMase-2 expression in a bacterial strain that lacks endogenous thioredoxin, Rosetta-gami2, results in increased oligomer formation and lower enzyme activity. Phenotypic rescue was accomplished by treating nSMase-2 lysates with recombinant human thioredoxin. This indicates that nSMase-2 may be a novel substrate for thioredoxin. FRET analysis confirmed the presence of nSMase-2 multimers in mammalian HEK cells and their localization to the plasma membrane. In conclusion, our results identify nSMase-2 as a redox-sensitive enzyme, whose basal activity is influenced by thioredoxin-mediated changes in its oligomeric state. PMID:25287744

  11. Neutral sphingomyelinase-2 is a redox sensitive enzyme: role of catalytic cysteine residues in regulation of enzymatic activity through changes in oligomeric state.

    PubMed

    Dotson, P Patrick; Karakashian, Alexander A; Nikolova-Karakashian, Mariana N

    2015-02-01

    Neutral sphingomyelinase-2 (nSMase-2) is the major sphingomyelinase activated in response to pro-inflammatory cytokines and during oxidative stress. It is a membrane-bound 655 amino acid protein containing 22 cysteine residues. In this study, we expressed recombinant mouse nSMase-2 protein in Escherichia coli, and investigated whether nSMase-2 is a redox sensitive enzyme. Our results demonstrate that nSMase-2 exists as both monomers and multimers that are associated with high and low enzymatic activity respectively. Mutational analysis of nSMase-2 identified within its C-terminal catalytic domain several oxidant-sensitive cysteine residues that were shown to be involved in enzyme oligomerization. Changing Cys(617) to Ser for example is a gain-of-function mutation associated with a decreased propensity for oligomerization. Alternatively, nSMase-2 expression in a bacterial strain that lacks endogenous thioredoxin, Rosetta-gami2, results in increased oligomer formation and lower enzyme activity. Phenotypic rescue was accomplished by treating nSMase-2 lysates with recombinant human thioredoxin. This indicates that nSMase-2 may be a novel substrate for thioredoxin. FRET analysis confirmed the presence of nSMase-2 multimers in mammalian HEK cells and their localization to the plasma membrane. In conclusion, our results identify nSMase-2 as a redox-sensitive enzyme, whose basal activity is influenced by thioredoxin-mediated changes in its oligomeric state. PMID:25287744

  12. Microbial Response to Experimentally Controlled Redox Transitions at the Sediment Water Interface

    PubMed Central

    Frindte, Katharina; Allgaier, Martin; Grossart, Hans-Peter; Eckert, Werner

    2015-01-01

    The sediment–water interface of freshwater lakes is characterized by sharp chemical gradients, shaped by the interplay between physical, chemical and microbial processes. As dissolved oxygen is depleted in the uppermost sediment, the availability of alternative electron acceptors, e.g. nitrate and sulfate, becomes the limiting factor. We performed a time series experiment in a mesocosm to simulate the transition from aerobic to anaerobic conditions at the sediment–water interface. Our goal was to identify changes in the microbial activity due to redox transitions induced by successive depletion of available electron acceptors. Monitoring critical hydrochemical parameters in the overlying water in conjunction with a new sampling strategy for sediment bacteria enabled us to correlate redox changes in the water to shifts in the active microbial community and the expression of functional genes representing specific redox-dependent microbial processes. Our results show that during several transitions from oxic-heterotrophic condition to sulfate-reducing condition, nitrate-availability and the on-set of sulfate reduction strongly affected the corresponding functional gene expression. There was evidence of anaerobic methane oxidation with NOx. DGGE analysis revealed redox-related changes in microbial activity and expression of functional genes involved in sulfate and nitrite reduction, whereas methanogenesis and methanotrophy showed only minor changes during redox transitions. The combination of high-frequency chemical measurements and molecular methods provide new insights into the temporal dynamics of the interplay between microbial activity and specific redox transitions at the sediment–water interface. PMID:26599000

  13. Microbial Response to Experimentally Controlled Redox Transitions at the Sediment Water Interface.

    PubMed

    Frindte, Katharina; Allgaier, Martin; Grossart, Hans-Peter; Eckert, Werner

    2015-01-01

    The sediment-water interface of freshwater lakes is characterized by sharp chemical gradients, shaped by the interplay between physical, chemical and microbial processes. As dissolved oxygen is depleted in the uppermost sediment, the availability of alternative electron acceptors, e.g. nitrate and sulfate, becomes the limiting factor. We performed a time series experiment in a mesocosm to simulate the transition from aerobic to anaerobic conditions at the sediment-water interface. Our goal was to identify changes in the microbial activity due to redox transitions induced by successive depletion of available electron acceptors. Monitoring critical hydrochemical parameters in the overlying water in conjunction with a new sampling strategy for sediment bacteria enabled us to correlate redox changes in the water to shifts in the active microbial community and the expression of functional genes representing specific redox-dependent microbial processes. Our results show that during several transitions from oxic-heterotrophic condition to sulfate-reducing condition, nitrate-availability and the on-set of sulfate reduction strongly affected the corresponding functional gene expression. There was evidence of anaerobic methane oxidation with NOx. DGGE analysis revealed redox-related changes in microbial activity and expression of functional genes involved in sulfate and nitrite reduction, whereas methanogenesis and methanotrophy showed only minor changes during redox transitions. The combination of high-frequency chemical measurements and molecular methods provide new insights into the temporal dynamics of the interplay between microbial activity and specific redox transitions at the sediment-water interface. PMID:26599000

  14. Responding changes systematically within sessions during conditioning procedures.

    PubMed Central

    McSweeney, F K; Roll, J M

    1993-01-01

    When the procedure is held constant within an experimental session, responding often changes systematically within that session. Many of these within-session changes in responding cannot be dismissed as learning curves or by-products of satiation. They have been observed in studies of positive reinforcement, avoidance, punishment, extinction, discrimination, delayed matching to sample, concept formation, maze and alley running, and laboratory analogues of foraging, as well as in the unconditioned substrates of conditioned behavior. When aversive stimuli are used, responding usually increases early in the session. When positive reinforcers are used, responding changes in a variety of ways, including increasing, decreasing, and bitonic functions. Both strong and minimal reinforcement procedures produce within-session decreases in positively reinforced behavior. Within-session changes in responding have substantial theoretical and methodological implications for research in conditioning. PMID:8283153

  15. Ceramic production during changing environmental/climatic conditions

    NASA Astrophysics Data System (ADS)

    Oestreich, Daniela B.; Glasmacher, Ulrich A.

    2015-04-01

    Ceramics, with regard to their status as largely everlasting everyday object as well as on the basis of their chronological sensitivity, reflect despite their simplicity the technological level of a culture and therefore also, directly or indirectly, the adaptability of a culture with respect to environmental and/or climatic changes. For that reason the question arises, if it is possible to identify changes in production techniques and raw material sources for ceramic production, as a response to environmental change, e.g. climate change. This paper will present results of a research about Paracas Culture (800 - 200 BC), southern Peru. Through several investigations (e.g. Schittek et al., 2014; Eitel and Mächtle, 2009) it is well known that during Paracas period changes in climate and environmental conditions take place. As a consequence, settlement patterns shifted several times through the various stages of Paracas time. Ceramics from three different sites (Jauranga, Cutamalla, Collanco) and temporal phases of the Paracas period are detailed archaeometric, geochemical and mineralogical characterized, e.g. Raman spectroscopy, XRD, and ICP-MS analyses. The aim of this research is to resolve potential differences in the chemical composition of the Paracas ceramics in space and time and to compare the data with the data sets of pre-Columbian environmental conditions. Thus influences of changing environmental conditions on human societies and their cultural conditions will be discussed. References Eitel, B. and Mächtle, B. 2009. Man and Environment in the eastern Atacama Desert (Southern Peru): Holocene climate changes and their impact on pre-Columbian cultures. In: Reindel, M. & Wagner, G. A. (eds.) New Technologies for Archaeology. Berlin Heidelberg: Springer-Verlag. Schittek, K., Mächtle, B., Schäbitz, F., Forbriger, M., Wennrich, V., Reindel, M., and Eitel, B.. Holocene environmental changes in the highlands of the southern Peruvian Andes (14° S) and their

  16. Development of a stable ERroGFP variant suitable for monitoring redox dynamics in the ER

    PubMed Central

    Hoseki, Jun; Oishi, Asami; Fujimura, Takaaki; Sakai, Yasuyoshi

    2016-01-01

    The endoplasmic reticulum (ER) is an essential organelle for cellular metabolic homeostasis including folding and maturation of secretory and membrane proteins. Disruption of ER proteostasis has been implicated in the pathogenesis of various diseases such as diabetes and neurodegenerative diseases. The ER redox state, which is an oxidative environment suitable for disulfide-bond formation, is essential for ER protein quality control. Hence, detection of the ER redox state, especially in living cells, is essential to understand the mechanism by which the redox state of the ER is maintained. However, methods to detect the redox state of the ER have not been well-established because of inefficient folding and stability of roGFP variants with oxidative redox potential like roGFP-iL. Here we have improved the folding efficiency of ER-targeted roGFP-iL (ERroGFP-iL) in cells by introducing superfolder GFP (sfGFP) mutations. Four specific amino acid substitutions (S30R, Y39N, T105N and I171V) greatly improved folding efficiency in Escherichia coli and in the ER of HeLa cells, as well as the thermostability of the purified proteins. Introduction of these mutations also enhanced the dynamic range for redox change both in vitro and in the ER of living cells. ER-targeted roGFP-S4 (ERroGFP-S4) possessing these four mutations could detect physiological redox changes within the ER. ERroGFP-S4 is therefore a novel probe suitable for monitoring redox change in the ER. ERroGFP-S4 can be applied to detect aberrant ER redox states associated with various pathological conditions and to identify the mechanisms used to maintain the redox state of the ER. PMID:26934978

  17. Future Risks of Pest Species under Changing Climatic Conditions.

    PubMed

    Biber-Freudenberger, Lisa; Ziemacki, Jasmin; Tonnang, Henri E Z; Borgemeister, Christian

    2016-01-01

    Most agricultural pests are poikilothermic species expected to respond to climate change. Currently, they are a tremendous burden because of the high losses they inflict on crops and livestock. Smallholder farmers in developing countries of Africa are likely to suffer more under these changes than farmers in the developed world because more severe climatic changes are projected in these areas. African countries further have a lower ability to cope with impacts of climate change through the lack of suitable adapted management strategies and financial constraints. In this study we are predicting current and future habitat suitability under changing climatic conditions for Tuta absoluta, Ceratitis cosyra, and Bactrocera invadens, three important insect pests that are common across some parts of Africa and responsible for immense agricultural losses. We use presence records from different sources and bioclimatic variables to predict their habitat suitability using the maximum entropy modelling approach. We find that habitat suitability for B. invadens, C. cosyra and T. absoluta is partially increasing across the continent, especially in those areas already overlapping with or close to most suitable sites under current climate conditions. Assuming a habitat suitability at three different threshold levels we assessed where each species is likely to be present under future climatic conditions and if this is likely to have an impact on productive agricultural areas. Our results can be used by African policy makers, extensionists and farmers for agricultural adaptation measures to cope with the impacts of climate change. PMID:27054718

  18. Future Risks of Pest Species under Changing Climatic Conditions

    PubMed Central

    Biber-Freudenberger, Lisa; Ziemacki, Jasmin; Tonnang, Henri E. Z.; Borgemeister, Christian

    2016-01-01

    Most agricultural pests are poikilothermic species expected to respond to climate change. Currently, they are a tremendous burden because of the high losses they inflict on crops and livestock. Smallholder farmers in developing countries of Africa are likely to suffer more under these changes than farmers in the developed world because more severe climatic changes are projected in these areas. African countries further have a lower ability to cope with impacts of climate change through the lack of suitable adapted management strategies and financial constraints. In this study we are predicting current and future habitat suitability under changing climatic conditions for Tuta absoluta, Ceratitis cosyra, and Bactrocera invadens, three important insect pests that are common across some parts of Africa and responsible for immense agricultural losses. We use presence records from different sources and bioclimatic variables to predict their habitat suitability using the maximum entropy modelling approach. We find that habitat suitability for B. invadens, C. cosyra and T. absoluta is partially increasing across the continent, especially in those areas already overlapping with or close to most suitable sites under current climate conditions. Assuming a habitat suitability at three different threshold levels we assessed where each species is likely to be present under future climatic conditions and if this is likely to have an impact on productive agricultural areas. Our results can be used by African policy makers, extensionists and farmers for agricultural adaptation measures to cope with the impacts of climate change. PMID:27054718

  19. Redox potential: An indicator of site productivity in forest management

    NASA Astrophysics Data System (ADS)

    Sajedi, Toktam; Prescott, Cindy; Lavkulich, Les

    2010-05-01

    less than +300 mv in the forest floor; whereas only 15 percent of the HA plots had such low values. Composition of the forest understory species was related to soil moisture/aeration. Soil aeration was the most important soil variable influencing plant species composition, explaining 25% of the plant community variability. Eh was always greater than +300 mv in the mineral soil of old growth HA forests but below +300 mv in HA clearcuts, suggesting paludification; however it was below or at this threshold in both CH forests and clearcuts. The reduction in measured redox without a noticeable change in the watertable in HA sites suggests that harvesting HA forests shifts the ecosystem towards more anaerobic conditions more similar to CH sites. In a complimentary study, the significance of redox was assessed in a cedar swamp cutover by exploring the relationships between soil redox potential and tree growth, and mineralization of C and soil C store along a gradient of moisture caused by drainage. Drainage improved aeration in the rooting zone, expressed as redox, and above- and below ground C storage; however C mineralization measured as CO2 evolution was not affected. Tree growth was positively correlated with redox potential. Our results indicate that drainage could be a useful silvicultural practice for improving the productivity of these ecosystems and that it may be possible to improve tree growth without stimulating loss of soil C. This requires that drainage improve aeration in the rooting zone while maintaining redox levels of less than +300 mV in the bulk soil, indicating that redox measurements should be incorporated into silviculture interventions to improve productivity of these forests.

  20. Changes in complex spike activity during classical conditioning.

    PubMed

    Rasmussen, Anders; Jirenhed, Dan-Anders; Wetmore, Daniel Z; Hesslow, Germund

    2014-01-01

    The cerebellar cortex is necessary for adaptively timed conditioned responses (CRs) in eyeblink conditioning. During conditioning, Purkinje cells acquire pause responses or "Purkinje cell CRs" to the conditioned stimuli (CS), resulting in disinhibition of the cerebellar nuclei (CN), allowing them to activate motor nuclei that control eyeblinks. This disinhibition also causes inhibition of the inferior olive (IO), via the nucleo-olivary pathway (N-O). Activation of the IO, which relays the unconditional stimulus (US) to the cortex, elicits characteristic complex spikes in Purkinje cells. Although Purkinje cell activity, as well as stimulation of the CN, is known to influence IO activity, much remains to be learned about the way that learned changes in simple spike firing affects the IO. In the present study, we analyzed changes in simple and complex spike firing, in extracellular Purkinje cell records, from the C3 zone, in decerebrate ferrets undergoing training in a conditioning paradigm. In agreement with the N-O feedback hypothesis, acquisition resulted in a gradual decrease in complex spike activity during the conditioned stimulus, with a delay that is consistent with the long N-O latency. Also supporting the feedback hypothesis, training with a short interstimulus interval (ISI), which does not lead to acquisition of a Purkinje cell CR, did not cause a suppression of complex spike activity. In contrast, observations that extinction did not lead to a recovery in complex spike activity and the irregular patterns of simple and complex spike activity after the conditioned stimulus are less conclusive. PMID:25140129

  1. Morphodynamic controls on redox conditions and on nitrogen dynamics within the hyporheic zone: Application to gravel bed rivers with alternate-bar morphology

    NASA Astrophysics Data System (ADS)

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

    2012-09-01

    Hyporheic flows, which stem from the interaction between stream flow and bedform, transport solute-laden surface waters into the streambed sediments, where reactive solutes undergo biogeochemical transformations. Despite the importance of hyporheic exchange on riverine ecosystem and biogeochemical cycles, research is limited on the effects of hyporheic fluxes on the fate of reactive solutes within the hyporheic zone. Consequently, we investigate the controls of hyporheic flowpaths, which we link to stream morphology and streamflow, on prevailing hyporheic redox conditions and on biogeochemical transformations occurring within streambeds. We focus on the dissolved inorganic reactive forms of nitrogen, ammonium and nitrate, because nitrogen is one of the most common reactive solutes and an essential nutrient found in stream waters. Our objectives are to explore the influence of stream morphology, hyporheic water temperature and relative abundance of ammonium and nitrate, on transformation of ammonium, removal of nitrates and production of nitrous oxide, a potent greenhouse gas. We address our objectives with analytical solutions of the Multispecies Reactive Advection-Dispersion Equation coupled with linearized Monod's kinetics and analytical solutions of the hyporheic flow for alternate-bar morphology. We introduce a new Damköhler number,Da, defined as the ratio between the median hyporheic residence time and the time scale of oxygen consumption, which we prove to be a good indicator of where aerobic or anaerobic conditions prevail. In addition, Dais a key index to quantify hyporheic nitrification and denitrification efficiencies and defines a new theoretical framework for scaling results at both the morphological-unit and stream-reach scales.

  2. Changes in the Redox Potential of Primary and Secondary Electron-Accepting Quinones in Photosystem II Confer Increased Resistance to Photoinhibition in Low-Temperature-Acclimated Arabidopsis1

    PubMed Central

    Sane, Prafullachandra Vishnu; Ivanov, Alexander G.; Hurry, Vaughan; Huner, Norman P.A.; Öquist, Gunnar

    2003-01-01

    Exposure of control (non-hardened) Arabidopsis leaves for 2 h at high irradiance at 5°C resulted in a 55% decrease in photosystem II (PSII) photochemical efficiency as indicated by Fv/Fm. In contrast, cold-acclimated leaves exposed to the same conditions showed only a 22% decrease in Fv/Fm. Thermoluminescence was used to assess the possible role(s) of PSII recombination events in this differential resistance to photoinhibition. Thermoluminescence measurements of PSII revealed that S2QA- recombination was shifted to higher temperatures, whereas the characteristic temperature of the S2QB- recombination was shifted to lower temperatures in cold-acclimated plants. These shifts in recombination temperatures indicate higher activation energy for the S2QA- redox pair and lower activation energy for the S2QB- redox pair. This results in an increase in the free-energy gap between P680+QA- and P680+Pheo- and a narrowing of the free energy gap between primary and secondary electron-accepting quinones in PSII electron acceptors. We propose that these effects result in an increased population of reduced primary electron-accepting quinone in PSII, facilitating non-radiative P680+QA- radical pair recombination. Enhanced reaction center quenching was confirmed using in vivo chlorophyll fluorescence-quenching analysis. The enhanced dissipation of excess light energy within the reaction center of PSII, in part, accounts for the observed increase in resistance to high-light stress in cold-acclimated Arabidopsis plants. PMID:12913169

  3. Two distinct redox cascades cooperatively regulate chloroplast functions and sustain plant viability.

    PubMed

    Yoshida, Keisuke; Hisabori, Toru

    2016-07-01

    The thiol-based redox regulation system is believed to adjust chloroplast functions in response to changes in light environments. A redox cascade via the ferredoxin-thioredoxin reductase (FTR)/thioredoxin (Trx) pathway has been traditionally considered to serve as a transmitter of light signals to target enzymes. However, emerging data indicate that chloroplasts have a complex redox network composed of diverse redox-mediator proteins and target enzymes. Despite extensive research addressing this system, two fundamental questions are still unresolved: How are redox pathways orchestrated within chloroplasts, and why are chloroplasts endowed with a complicated redox network? In this report, we show that NADPH-Trx reductase C (NTRC) is a key redox-mediator protein responsible for regulatory functions distinct from those of the classically known FTR/Trx system. Target screening and subsequent biochemical assays indicated that NTRC and the Trx family differentially recognize their target proteins. In addition, we found that NTRC is an electron donor to Trx-z, which is a key regulator of gene expression in chloroplasts. We further demonstrate that cooperative control of chloroplast functions via the FTR/Trx and NTRC pathways is essential for plant viability. Arabidopsis double mutants impaired in FTR and NTRC expression displayed lethal phenotypes under autotrophic growth conditions. This severe growth phenotype was related to a drastic loss of photosynthetic performance. These combined results provide an expanded map of the chloroplast redox network and its biological functions. PMID:27335455

  4. Mantle redox evolution and the oxidation state of the Archean atmosphere

    NASA Technical Reports Server (NTRS)

    Kasting, J. F.; Eggler, D. H.; Raeburn, S. P.

    1993-01-01

    Current models predict that the early atmosphere consisted mostly of CO2, N2, and H2O, along with traces of H2 and CO. Such models are based on the assumption that the redox state of the upper mantle has not changed, so that volcanic gas composition has remained approximately constant with time. We argue here that this assumption is probably incorrect: the upper mantle was originally more reduced than today, although not as reduced as the metal arrest level, and has become progressively more oxidized as a consequence of the release of reduced volcanic gases and the subduction of hydrated, oxidized seafloor. Data on the redox state of sulfide and chromite inclusions in diamonds imply that the process of mantle oxidation was slow, so that reduced conditions could have prevailed for as much as half of the earth's history. To be sure, other oxybarometers of ancient rocks give different results, so the question of when the mantle redox state has changed remains unresolved. Mantle redox evolution is intimately linked to the oxidation state of the primitive atmosphere: A reduced Archean atmosphere would have had a high hydrogen escape rate and should correspond to a changing mantle redox state; an oxidized Archean atmosphere should be associated with a constant mantle redox state. The converses of these statements are also true. Finally, our theory of mantle redox evolution may explain why the Archean atmosphere remained oxygen-deficient until approximately 2.0 billion years ago (Ga) despite a probable early origin for photosynthesis.

  5. Redox response model for partly substituted cuprates

    SciTech Connect

    Oesterreicher, H. . Dept. of Chemistry)

    1994-05-01

    Inhomogeneous substitutions (e.g. clustering and preferential site occupations) in compounds such as YBa[sub 2](Cu[sub 1[minus]x]M[sub x])[sub 3]O[sub y] with M = Fe, Co, Ni, etc. are an unavoidable response to the changing redox environments in these O intercalation compounds. The authors collect here experimental evidence for various types of inhomogeneous distributions predicted on a thermodynamic model which considers the preferential desorption'' of O from various local environments. The parameter organizing the redox environment is [Delta]H* (incremental enthalpy of oxygen desorption per mol O[sub 2]). Theory suggests a sequence of discernible states represented by the acronym CLUSTER. With decreasing [Delta]H*, indications for several of these states are obtained from Moessbauer and other experiments. These states are characteristically shifted in [Delta]H* for different M. Also, further substitutions according to (YX)(BaZ)[sub 2](CuM)[sub 3]O[sub y] with X = Ca, Z = Sr, La can change the relevant [Delta]H* for these states, allowing prediction of their preparation conditions. Aspects of the complex electronic phase diagram as a function of redox preparation are discussed.

  6. Redox Conditions on Small Bodies

    NASA Technical Reports Server (NTRS)

    Jones, J. H.

    2004-01-01

    The Eucrite Parent Body (4 Vesta). The eucrites are basalts that contain approx. 18 wt% FeO and contain trace metal. The eucrites are very depleted in siderophile elements, so it appears that the source regions of these basalts once equilibrated with Fe-Ni metal. Therefore, it is of interest to ask what fo2 is required to precipitate metal from a liquid of eucrite composition. Or in other words, what f02 did eucrites form under? This fo2 has been determined experimentally by and was found to be IW-1. Therefore, eucrites formed at about IW-1. In addition, it is interesting to note that assuming X(sub feo) = alpha(sub FeO) allows calculation of eucrite fo2 (assuming equilibrium with Fe metal). This calculation yields the same result as the experiments to within approx. 0.25 log units, reinforcing this result.

  7. Biogeochemical Barriers: Redox Behavior of Metals and Metalloids

    EPA Science Inventory

    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...

  8. Site-dependant redox ratio in healthy oral cavity

    NASA Astrophysics Data System (ADS)

    Shanmugam, Sivabalan; Koteeswaran, Dornadula; Aruna, Prakasarao; Ganesan, Singaravelu

    2011-03-01

    The metabolic coenzymes NADH and FAD are autofluorescent and can be monitored non-destructively and without exogenous labels, using optical techniques. These endogenous fluorophores which are present in the cells and tissues gives rise to different fluorescence emission/excitation spectra between the normal and different diseased conditions. In the resent years, finding the optical redox ratio i.e., the ratio of the fluorescence intensity of FAD and NADH, gives the relative change in the oxidation-reduction state of the cells. Unlike other organs oral cavity has lined with variety of mucosal types. We investigated in vivo Optical redox ratio for four different anatomical locations viz., cheek mucosa, vermilion border of the lip, Hard palate, dorsal side of the tongue of healthy oral cavity. We measured this ratio for 20 healthy subjects and the redox ratio was significantly different between the different anatomical locations. The statistical significance was also investigated.

  9. Global flood risks under changing climate and socioeconomic conditions

    NASA Astrophysics Data System (ADS)

    Sperna Weiland, Frederiek; Ward, Philip; Bouwman, Arno; Ligtvoet, Willem; van Beek, Rens; Winsemius, Hessel

    2013-04-01

    Worldwide major flood events result in both economic losses and large numbers of casualties. Recent global scale studies indicate that in many regions of the world discharge extremes are likely to increase under changing climate conditions. However, few studies have so far examined how these changes in climate conditions may affect flood risk (defined here as the probability of a flood multiplied by the consequences). In the current study we investigate the impacts of changing climate and socioeconomic conditions on flood extents and depths, and also assess the potential impacts on flood risk. The study is conducted on a global scale, thereby indicating in which regions of the world flood risk is likely to change most. To assess global food risk under changing conditions, we combined socio-economic data from the Integrated Model to Assess the Global Environment (IMAGE) framework of the Netherlands Environmental Assessment Agency (PBL) with high resolution maps of inundation depth (1 km). To this end, projections from a number of GCMs were bias-corrected and used to force the global hydrological model PCR-GLOBWB which simulates (amongst other variables) global maps with daily flood volumes on a 0.5 degree resolution. These time series were used to derive flood volume maps for multiple return periods, which were downscaled to inundation depth maps at 1 km resolution using a 1 km resolution DEM. Finally, these high resolution flood maps were combined with spatial datasets on future GDP and population density from the IMAGE model. Results are presented on both the global scale and at the country level. We believe that the obtained flood extend and flood risk maps can assist development agencies in planning climate adaptation investments that aim to reduce flood risks.

  10. Geochemistry of Lower Cretaceous limestones of the Alisitos Formation, Baja California, México: Implications for REE source and paleo-redox conditions

    NASA Astrophysics Data System (ADS)

    Madhavaraju, J.; Löser, Hannes; Lee, Yong Il; Santacruz, R. Lozano; Pi-Puig, T.

    2016-03-01

    Measurement of the major and trace elements were carried out on the Lower Cretaceous limestones interbedded in the volcano-sedimentary Alisitos Formation, northwestern México to understand the source of rare earth elements (REEs) and paleo-redox conditions. The five limestone beds (from the base up, Unit 5 to Unit 9) of the Alisitos Formation show large variations in SiO2 content (0.9-27.9%). A low concentration of CaO is observed in Unit 6 and Unit 8, and high content of CaO is observed in Unit 5, Unit 7 and Unit 9. The limestones are depleted in many trace elements with respect to Post-Archaean Australian Shale (PAAS), whereas Sr shows slight enrichment when compared to PAAS. The concentrations of ΣREE are higher in Unit 6 and Unit 8 (37.4 ± 7.5; 46.6 ± 19.4; respectively) than Unit5, Unit7, and Unit 9 (9.1 ± 3.2; 11.3 ± 9.4; 4.2 ± 2.5; respectively). The limestones of the Alisitos Formation show a non-seawater-like REE + Y pattern with positive Eu anomalies relative to PAAS (0.95-2.47). Variations in ΣREE, Al2O3, Zr, Sc, REE + Y patterns, and Y/Ho ratios are influenced mainly by the amount of terrigenous materials. The variations in the Eu/Eu*, La/Sc and La/Co suggest that the terrigenous materials included in the lower four limestone beds (from Unit 5, Unit 6, Unit 7 and Unit 8) were likely contributed by intermediate to felsic rocks whereas terrigenous materials from Unit 9 were derived from mafic to intermediate source rocks. The slightly negative to slightly positive Ce anomalies in the studied limestones resulted from variations in the bottom water oxygenation. This was also corroborated by V/Cr and Ni/Co ratios suggesting that the depositional environments experienced large fluctuations in oxygenation conditions ranging from oxic to anoxic conditions during the deposition of limestones of the Alisitos Formation.

  11. Pushing the Limits of Delta Bonding in Metal-Chromium Complexes with Redox Changes and Metal Swapping.

    PubMed

    Eisenhart, Reed J; Rudd, P Alex; Planas, Nora; Boyce, David W; Carlson, Rebecca K; Tolman, William B; Bill, Eckhard; Gagliardi, Laura; Lu, Connie C

    2015-08-01

    Into the metalloligand Cr[N(o-(NCH2P((i)Pr)2)C6H4)3] (1, CrL) was inserted a second chromium atom to generate the dichromium complex Cr2L (2), which is a homobimetallic analogue of the known MCrL complexes, where M is manganese (3) or iron (4). The cationic and anionic counterparts, [MCrL](+) and [MCrL](-), respectively, were targeted, and each MCr pair was isolated in at least one other redox state. The solid-state structures of the [MCrL](+,0,-) redox members are essentially the same, with ultrashort metal-metal bonds between 1.96 and 1.74 Å. The formal shortness ratios (r) of these interactions are between 0.84 and 0.74 and are interpreted as triple to quintuple metal-metal bonds with the aid of theory. The trio of (d-d)(10) species [Cr2L](-) (2(red)), MnCrL (3), and [FeCrL](+) (4(ox)) are S = 0 diamagnets. On the basis of M-Cr bond distances and theoretical calculations, the strength of the metal-metal bond across the (d-d)(10) series increases in the order Fe < Mn < Cr. The methylene protons in the ligand are shifted downfield in the (1)H NMR spectra, and the diamagnetic anisotropy of the metal-metal bond was calculated as -3500 × 10(-36), -3900 × 10(-36), and -5800 × 10(-36) m(3) molecule(-1) for 2(red), 3, and 4(ox) respectively. The magnitude of diamagnetic anisotropy is, thus, affected more by bond polarity than by bond order. A comparative vis-NIR study of quintuply bonded 2(red) and 3 revealed a large red shift in the δ(4) → δ(3)δ* transition energy upon swapping from the (Cr2)(2+) to the (MnCr)(3+) core. Complex 2(red) was further investigated by resonance Raman spectroscopy, and a band at 434 cm(-1) was assigned as the Cr-Cr bond vibration. Finally, 4(ox) exhibited a Mössbauer doublet with an isomer shift of 0.18 mm/s that suggests a primarily Fe-based oxidation to Fe(I). PMID:26168331

  12. Forecasting conditional climate-change using a hybrid approach

    USGS Publications Warehouse

    Esfahani, Akbar Akbari; Friedel, Michael J.

    2014-01-01

    A novel approach is proposed to forecast the likelihood of climate-change across spatial landscape gradients. This hybrid approach involves reconstructing past precipitation and temperature using the self-organizing map technique; determining quantile trends in the climate-change variables by quantile regression modeling; and computing conditional forecasts of climate-change variables based on self-similarity in quantile trends using the fractionally differenced auto-regressive integrated moving average technique. The proposed modeling approach is applied to states (Arizona, California, Colorado, Nevada, New Mexico, and Utah) in the southwestern U.S., where conditional forecasts of climate-change variables are evaluated against recent (2012) observations, evaluated at a future time period (2030), and evaluated as future trends (2009–2059). These results have broad economic, political, and social implications because they quantify uncertainty in climate-change forecasts affecting various sectors of society. Another benefit of the proposed hybrid approach is that it can be extended to any spatiotemporal scale providing self-similarity exists.

  13. Free energy distribution and hydrothermal mineral precipitation in Hadean submarine alkaline vent systems: Importance of iron redox reactions under anoxic conditions

    NASA Astrophysics Data System (ADS)

    Shibuya, Takazo; Russell, Michael J.; Takai, Ken

    2016-02-01

    Thermodynamic calculations of mixing between hypothetical seawater and hydrothermal fluid in the Hadean deep ocean were carried out to predict saturation states of mineral precipitates and redox reactions that could occur in Hadean submarine alkaline hydrothermal systems associated with the serpentinization of ultramafic rocks. In the calculations, the seawater was assumed to be weakly acidic (pH = 5.5) and to include carbon dioxide, ferrous iron and silica, with or without nitrate, while the Hadean hydrothermal fluid was assumed to be highly alkaline (pH = 11) and to contain abundant molecular hydrogen, methane and bisulfide, based on the Archean geologic record, the modern low-temperature alkaline hydrothermal vent fluid (Lost City field), and experimental and theoretical considerations. The modeling indicates that potential mineral precipitates in the mixing zone (hydrothermal chimney structures) could consist mainly of iron sulfides but also of ferrous serpentine and brucite, siderite, and ferric iron-bearing minerals such as goethite, hematite and/or magnetite as minor phases. The precipitation of ferric iron-bearing minerals suggests that chemical iron oxidation would be made possible by pH shift even under anoxic condition. In the mixing zone, comprising an inorganic barrier precipitated at the interface of the two contrasting solutions, various redox reactions release free energy with the potential to drive endergonic reactions, assuming the involvement of coupling inorganic protoenzymes. Hydrogenotrophic methanogenesis and acetogenesis - long considered the most ancient forms of biological energy metabolisms - are able to achieve higher maximum energy yield (>0.5 kJ/kg hydrothermal fluid) than those in the modern serpentinization-associated seafloor hydrothermal systems (e.g., Kairei field). Furthermore, the recently proposed methanotrophic acetogenesis pathway was also thermodynamically investigated. It is known that methanotrophic acetogenesis would

  14. Hydrological Responses to Land-Use Change Scenarios under Constant and Changed Climatic Conditions.

    PubMed

    Zhang, Ling; Nan, Zhuotong; Yu, Wenjun; Ge, Yingchun

    2016-02-01

    This study quantified the hydrological responses to land-use change scenarios in the upper and middle Heihe River basin (HRB), northwest China, under constant and changed climatic conditions by combining a land-use/cover change model (dynamic conversion of land use and its effects, Dyna-CLUE) and a hydrological model (soil and water assessment tool, SWAT). Five land-use change scenarios, i.e., historical trend (HT), ecological protection (EP), strict ecological protection (SEP), economic development (ED), and rapid economic development (RED) scenarios, were established. Under constant climatic condition, hydrological variations are only induced by land-use changes in different scenarios. The changes in mean streamflow at the outlets of the upper and the middle HRB are not pronounced, although the different scenarios produce different outcomes. However, more pronounced changes are observed on a subbasin level. The frequency of extreme flood is projected to decrease under the SEP scenario, while under the other scenarios, no changes can be found. Two emission scenarios (A1B and B1) of three general circulation models (HadCM3, CGCM3, and CCSM3) were employed to generate future possible climatic conditions. Under changed climatic condition, hydrological variations are induced by the combination of land-use and climatic changes. The results indicate that the impacts of land-use changes become secondary when the changed climatic conditions have been considered. The frequencies of extreme flood and drought are projected to decrease and increase, respectively, under all climate scenarios. Although some agreements can be reached, pronounced difference of hydrological responses can be observed for different climate scenarios of different GCMs. PMID:26429363

  15. Hydrological Responses to Land-Use Change Scenarios under Constant and Changed Climatic Conditions

    NASA Astrophysics Data System (ADS)

    Zhang, Ling; Nan, Zhuotong; Yu, Wenjun; Ge, Yingchun

    2016-02-01

    This study quantified the hydrological responses to land-use change scenarios in the upper and middle Heihe River basin (HRB), northwest China, under constant and changed climatic conditions by combining a land-use/cover change model (dynamic conversion of land use and its effects, Dyna-CLUE) and a hydrological model (soil and water assessment tool, SWAT). Five land-use change scenarios, i.e., historical trend (HT), ecological protection (EP), strict ecological protection (SEP), economic development (ED), and rapid economic development (RED) scenarios, were established. Under constant climatic condition, hydrological variations are only induced by land-use changes in different scenarios. The changes in mean streamflow at the outlets of the upper and the middle HRB are not pronounced, although the different scenarios produce different outcomes. However, more pronounced changes are observed on a subbasin level. The frequency of extreme flood is projected to decrease under the SEP scenario, while under the other scenarios, no changes can be found. Two emission scenarios (A1B and B1) of three general circulation models (HadCM3, CGCM3, and CCSM3) were employed to generate future possible climatic conditions. Under changed climatic condition, hydrological variations are induced by the combination of land-use and climatic changes. The results indicate that the impacts of land-use changes become secondary when the changed climatic conditions have been considered. The frequencies of extreme flood and drought are projected to decrease and increase, respectively, under all climate scenarios. Although some agreements can be reached, pronounced difference of hydrological responses can be observed for different climate scenarios of different GCMs.

  16. Redox biology of tuberculosis pathogenesis.

    PubMed

    Trivedi, Abhishek; Singh, Nisha; Bhat, Shabir Ahmed; Gupta, Pawan; Kumar, Ashwani

    2012-01-01

    Mycobacterium tuberculosis (Mtb) is one of the most successful human pathogens. Mtb is persistently exposed to numerous oxidoreductive stresses during its pathogenic cycle of infection and transmission. The distinctive ability of Mtb, not only to survive the redox stress manifested by the host but also to use it for synchronizing the metabolic pathways and expression of virulence factors, is central to its success as a pathogen. This review describes the paradigmatic redox and hypoxia sensors employed by Mtb to continuously monitor variations in the intracellular redox state and the surrounding microenvironment. Two component proteins, namely, DosS and DosT, are employed by Mtb to sense changes in oxygen, nitric oxide, and carbon monoxide levels, while WhiB3 and anti-sigma factor RsrA are used to monitor changes in intracellular redox state. Using these and other unidentified redox sensors, Mtb orchestrates its metabolic pathways to survive in nutrient-deficient, acidic, oxidative, nitrosative, and hypoxic environments inside granulomas or infectious lesions. A number of these metabolic pathways are unique to mycobacteria and thus represent potential drug targets. In addition, Mtb employs versatile machinery of the mycothiol and thioredoxin systems to ensure a reductive intracellular environment for optimal functioning of its proteins even upon exposure to oxidative stress. Mtb also utilizes a battery of protective enzymes, such as superoxide dismutase (SOD), catalase (KatG), alkyl hydroperoxidase (AhpC), and peroxiredoxins, to neutralize the redox stress generated by the host immune system. This chapter reviews the current understanding of mechanisms employed by Mtb to sense and neutralize redox stress and their importance in TB pathogenesis and drug development. PMID:22633061

  17. The CFE Treaty and changed conditions in Europe

    SciTech Connect

    Allentuck, J.

    1994-08-01

    The Treaty on Conventional Forces in Europe (CFE) was signed in November 1990 by sixteen nations, members of the North Atlantic Treaty Organization (NATO), and six nations, members of the Warsaw Treaty Organization (WTO). It was resigned to prevent a major surprise attack in Europe by the conventional forces of one Treaty Organization against those of the other and was the first major arms control treaty to address conventional weapons. This paper focuses on how CFE adapted to changes in the military-political situation in Europe which occurred after 1990 and failed to adapt to others. Suggestions are offered on how it might be changed to make it more relevant under these changed conditions.

  18. [Patient role in changing conditions: yesterday--today--tomorrow].

    PubMed

    Zahner, J

    2001-06-01

    Changing conditions within the German healthcare system and new trends of information management will decisively change the patient's role. Increase in morbidity caused by the ageing population aggravates the economic pressure within the social healthcare system. Due to the ongoing medical progress, this will inevitably lead to the restriction of medical services trough budgeting. Whereas the patient's role in the past was rather passive, his position will change in future. This is not only caused by an increase in patient education and social status, but also by the availability of information provided by the worldwide web. The number of educated patients who are gathering information via the worldwide web and discussing their diseases with fellow patients via e-mail will rapidly grow. The traditional doctor-patient relationship will be less exclusive in future and will be embedded in the network of reimbursement facilities, patients' groups and information management. PMID:11411321

  19. EVALUATION OF CHEMICAL AMENDMENTS FOR PH AND REDOX STABILIZTION IN AQUEOUS SUSPENSIONS OF THREE CALIFORNIA SOILS

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Many chemically and biologically important trace element, heavy metal, and organic contaminant reactions in soils are constrained by pH and redox conditions and changes in these conditions can significantly affect reaction rates. Although closed-system, batch methods have been used for many years to...

  20. Changes in the redox potential of primary and secondary electron-accepting quinones in photosystem II confer increased resistance to photoinhibition in low-temperature-acclimated Arabidopsis.

    PubMed

    Sane, Prafullachandra Vishnu; Ivanov, Alexander G; Hurry, Vaughan; Huner, Norman P A; Oquist, Gunnar

    2003-08-01

    Exposure of control (non-hardened) Arabidopsis leaves for 2 h at high irradiance at 5 degrees C resulted in a 55% decrease in photosystem II (PSII) photochemical efficiency as indicated by F(v)/F(m). In contrast, cold-acclimated leaves exposed to the same conditions showed only a 22% decrease in F(v)/F(m). Thermoluminescence was used to assess the possible role(s) of PSII recombination events in this differential resistance to photoinhibition. Thermoluminescence measurements of PSII revealed that S(2)Q(A)(-) recombination was shifted to higher temperatures, whereas the characteristic temperature of the S(2)Q(B)(-) recombination was shifted to lower temperatures in cold-acclimated plants. These shifts in recombination temperatures indicate higher activation energy for the S(2)Q(A)(-) redox pair and lower activation energy for the S(2)Q(B)(-) redox pair. This results in an increase in the free-energy gap between P680(+)Q(A)(-) and P680(+)Pheo(-) and a narrowing of the free energy gap between primary and secondary electron-accepting quinones in PSII electron acceptors. We propose that these effects result in an increased population of reduced primary electron-accepting quinone in PSII, facilitating non-radiative P680(+)Q(A)(-) radical pair recombination. Enhanced reaction center quenching was confirmed using in vivo chlorophyll fluorescence-quenching analysis. The enhanced dissipation of excess light energy within the reaction center of PSII, in part, accounts for the observed increase in resistance to high-light stress in cold-acclimated Arabidopsis plants. PMID:12913169

  1. Improving the transferability of hydrological model parameters under changing conditions

    NASA Astrophysics Data System (ADS)

    Huang, Yingchun; Bárdossy, András

    2014-05-01

    Hydrological models are widely utilized to describe catchment behaviors with observed hydro-meteorological data. Hydrological process may be considered as non-stationary under the changing climate and land use conditions. An applicable hydrological model should be able to capture the essential features of the target catchment and therefore be transferable to different conditions. At present, many model applications based on the stationary assumptions are not sufficient for predicting further changes or time variability. The aim of this study is to explore new model calibration methods in order to improve the transferability of model parameters. To cope with the instability of model parameters calibrated on catchments in non-stationary conditions, we investigate the idea of simultaneously calibration on streamflow records for the period with dissimilar climate characteristics. In additional, a weather based weighting function is implemented to adjust the calibration period to future trends. For regions with limited data and ungauged basins, the common calibration was applied by using information from similar catchments. Result shows the model performance and transfer quantity could be well improved via common calibration. This model calibration approach will be used to enhance regional water management and flood forecasting capabilities.

  2. Changes in alpine plant growth under future climate conditions

    NASA Astrophysics Data System (ADS)

    Rammig, A.; Jonas, T.; Zimmermann, N. E.; Rixen, C.

    2010-06-01

    Alpine shrub- and grasslands are shaped by extreme climatic conditions such as a long-lasting snow cover and a short vegetation period. Such ecosystems are expected to be highly sensitive to global environmental change. Prolonged growing seasons and shifts in temperature and precipitation are likely to affect plant phenology and growth. In a unique experiment, climatology and plant growth was monitored for almost a decade at 17 snow meteorological stations in different alpine regions along the Swiss Alps. Regression analyses revealed highly significant correlations between mean air temperature in May/June and snow melt out, onset of plant growth, and plant height. These correlations were used to project plant growth phenology for future climate conditions based on the gridded output of a set of regional climate models runs. Melt out and onset of growth were projected to occur on average 17 days earlier by the end of the century than in the control period from 1971-2000 under the future climate conditions of the low resolution climate model ensemble. Plant height and biomass production were expected to increase by 77% and 45%, respectively. The earlier melt out and onset of growth will probably cause a considerable shift towards higher growing plants and thus increased biomass. Our results represent the first quantitative and spatially explicit estimates of climate change impacts on future growing season length and the respective productivity of alpine plant communities in the Swiss Alps.

  3. Changes in alpine plant growth under future climate conditions

    NASA Astrophysics Data System (ADS)

    Rammig, A.; Jonas, T.; Zimmermann, N. E.; Rixen, C.

    2009-11-01

    Alpine shrub- and grasslands are shaped by extreme climatic conditions such as a long-lasting snow cover and a short vegetation period. Such ecosystems are expected to be highly sensitive to global environmental change. Prolonged growing seasons and shifts in temperature and precipitation are likely to affect plant phenology and growth. In a unique experiment, climatology and plant growth was monitored for almost a decade at 17 snow meteorological stations in different alpine regions along the Swiss Alps. Regression analyses revealed highly significant correlations between mean air temperature in May/June and snow melt-out, onset of plant growth, and plant height. These correlations were used to project plant growth phenology for future climate conditions based on the gridded output of a set of regional climate models runs. Melt-out and onset of growth were projected to occur on average 17 days earlier by the end of the century than in the control period from 1971-2000 under the future climate conditions of the low resolution climate model ensemble. Plant height and biomass production were expected to increase by 77% and 45%, respectively. The earlier melt-out and onset of growth will probably cause a considerable shift towards higher growing plants and thus increased biomass. Our results represent the first quantitative and spatially explicit estimates of climate change impacts on future growing season length and the respective productivity of alpine plant communities in the Swiss Alps.

  4. Redox properties of dissolved organic matter along redox gradients in two peatland-dominated forested catchments

    NASA Astrophysics Data System (ADS)

    Schmitt, Markus; Sander, Michael; Blodau, Christian; Peiffer, Stefan; Knorr, Klaus-Holger

    2015-04-01

    Dissolved organic matter (DOM) contributes significantly to the carbon cycle and influence the mobility of metals and contaminants. Water logged, riparian wetlands have been identified as an important source of DOM in catchments. As DOM export from wetlands often involves transitions in redox conditions, for a more mechanistic understanding of sources, mobilization processes and fate of DOM under different redox conditions additional analytical approaches are needed. In this study we combined established methods for DOM characterization, such as fluorescence spectroscopy and δ13CDOC, with mediated electrochemical reduction and oxidation of DOM for the determination the electron accepting and donating capacity (EAC/EDC). With this approach, we intended to test if the redox state of DOM can be used to identify and characterize its sources in catchments. To this end, we collected samples in two catchments - one dominated by fens and forest, the other by an ombrotrophic bog - from different hydrological compartments and from different source materials. EAC strongly decreased from oxic groundwater (6.4 ± 2.1 mmole- gC -1) to anoxic peat pore water (0.6 ± 0.5 mmole- gC -1). Contrarily, for EDC, there was no clear pattern to separate water compartments with different redox states. EDC seemed thus to depend mainly on the DOM source materials. Results of fluorescence spectroscopy and δ13CDOCconfirmed that changes in EDC were presumably due to changes in DOC quality rather than redox state. Moreover, comparing peat pore water and DOM in an adjacent erosion rill, EDC increased from 0.7 mmole- gC -1 in the anoxic pore water to 1.7 ± 0.2 mmole- gC -1 along the flow path in the oxic stream. This further suggested a different mobility of different DOM fractions, with higher EDC in more mobile DOM. This study indicates that combining electrochemical and spectroscopic methods for characterization of DOM quality and redox state can improve our understanding of source and fate

  5. Using Modis Imagery to Track Changes in Forest Condition

    NASA Astrophysics Data System (ADS)

    Chastain, R. A.

    2011-12-01

    The objective of the Real-Time Forest Disturbance (RTFD) project is to provide timely information regarding changes in forest conditions to assist the digital aerial sketch-mapping community in flight mission planning. To this end, a digital change detection methodology has been developed and implemented over the conterminous 48 U.S. states (CONUS) in 2008, 2009, and 2010 to track forest disturbances in near real-time (updated every 8 days). The RTFD approach uses MODIS satellite imagery, which provides daily observations to track developing disturbances that may also be ephemeral in nature. Also, the spectral grain of MODIS data permits the calculation of spectral indices, which the RTFD approach uses to characterize changes in forest condition. Baseline image data used in the RTFD method are produced using MODIS data composited from five years prior to the current growing season. In 2011, an additional 3-year baseline has been used in the change detection process. The RTFD approach has detected and tracked numerous defoliation events in the eastern deciduous biome, decline and mortality associated with beetle activity in the western coniferous biome, and forest damage associated with severe weather events. A quantitative retrospective assessment of 2010 RTFD results was performed to identify potential modifications to the analytical logic of the RTFD approach in order to improve detection efficiency. This assessment was performed within six study areas wherein forest disturbances occurred during 2010. Various methodological alterations were assessed within these study areas; principally, the use of different vegetation indices and alterations in baseline definition. Two-date Landsat change detection results acted as reference data to which RTFD results were compared. Differences in levels of agreement between various RTFD results and Landsat results were evaluated for significance using McNemar's test. The findings of this retrospective assessment indicate that a

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

    NASA Astrophysics Data System (ADS)

    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

  7. Zinc and the modulation of redox homeostasis

    PubMed Central

    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

  8. Screening of redox couples and electrode materials

    NASA Technical Reports Server (NTRS)

    Giner, J.; Swette, L.; Cahill, K.

    1976-01-01

    Electrochemical parameters of selected redox couples that might be potentially promising for application in bulk energy storage systems were investigated. This was carried out in two phases: a broad investigation of the basic characteristics and behavior of various redox couples, followed by a more limited investigation of their electrochemical performance in a redox flow reactor configuration. In the first phase of the program, eight redox couples were evaluated under a variety of conditions in terms of their exchange current densities as measured by the rotating disk electrode procedure. The second phase of the program involved the testing of four couples in a redox reactor under flow conditions with a varity of electrode materials and structures.

  9. Flux change in viscous laminar flow under oscillating boundary condition

    NASA Astrophysics Data System (ADS)

    Ueda, R.; Mikada, H.; Goto, T.; Takekawa, J.

    2012-12-01

    The behavior of interstitial fluid is one of major interest in earth sciences in terms of the exploitation of water resources, the initiation of earthquakes, enhanced oil recovery (EOR), etc. Seismic waves are often known to increase the flux of interstitial fluid but the relationship between the flux and propagating seismic waves have not been well investigated in the past, although seismic stimulation has been applied in the oil industry for enhanced oil recovery (EOR). Many observations indicated that seismic waves could stimulate the oil production due to lowering of apparent viscosity coefficient, to the coalescence and/or the dispersion of droplets of a phase in multiphase fluids. However, the detailed mechanism of seismic stimulation has not been fully understood, either. In this study, We attempt to understand the mechanism of the flux change in viscous laminar flow under oscillating boundary condition for the simulation of interstitial flow. Here, we analyze a monophase flow in a pore throat. We first assume a Hagen-Poiseuille flow of incompressible fluid through a pore-throat in a porous medium. We adopt the Lattice Boltzmann method (LBM) in which the motion of fluid is simulated through the variation of velocity distribution function representing the distribution of discrete particle velocities. We use an improved incompressible LBKG model (d2q9i) proposed in Zou et. al. (1995) to accurately accommodate the boundary conditions of pressure and velocity in the Hagen-Poiseuille flow. We also use an half-way bounce back boundary condition as the velocity boundary condition. Also, we assume a uniform pressure (density) difference between inlet and outlet flow, and the density difference could initiate the flow in our simulation. The oscillating boundary condition is given by the body force acting on fluid particles. In this simulation, we found that the flux change is negligible under small amplitude of oscillation in both horizontal and vertical directions

  10. NASA Redox Project status summary

    NASA Technical Reports Server (NTRS)

    Hagedorn, N. H.

    1983-01-01

    This report is a summary of the results of the Redox Project effort during Cy 1982. It was presented at the Fifth U.S. Department of Energy Battery and Electrochemical Contractors Conference, Arlington, Va., Dec. 7-9, 1982. The major development during 1982 was the shift from Redox system operation at 25 C with unmixed reactants to operation at 65 C with mixed reactants. This change has made possible a two- or three-fold increase in operating current density, to about 65 mA/sq cm, and an increase in reactant utilization from 40% to about 90%. Both of these improvements will lead to significant system cost reductions. Contract studies have indicated that Redox reactant costs also will be moderate. A new catalyst for the chromuim electrode offers all the advantages of the conventional gold-lead catalyst while being easier to apply and more forgiving in use.

  11. Redox regulation of vascular remodeling.

    PubMed

    Karimi Galougahi, Keyvan; Ashley, Euan A; Ali, Ziad A

    2016-01-01

    Vascular remodeling is a dynamic process of structural and functional changes in response to biochemical and biomechanical signals in a complex in vivo milieu. While inherently adaptive, dysregulation leads to maladaptive remodeling. Reactive oxygen species participate in homeostatic cell signaling in tightly regulated- and compartmentalized cellular circuits. It is well established that perturbations in oxidation-reduction (redox) homeostasis can lead to a state of oxidative-, and more recently, reductive stress. We provide an overview of the redox signaling in the vasculature and review the role of oxidative- and reductive stress in maladaptive vascular remodeling. Particular emphasis has been placed on essential processes that determine phenotype modulation, migration and fate of the main cell types in the vessel wall. Recent advances in systems biology and the translational opportunities they may provide to specifically target the redox pathways driving pathological vascular remodeling are discussed. PMID:26483132

  12. Propaganda, News, or Education: Reporting Changing Arctic Sea Ice Conditions

    NASA Astrophysics Data System (ADS)

    Leitzell, K.; Meier, W.

    2010-12-01

    The National Snow and Ice Data Center provides information on Arctic sea ice conditions via the Arctic Sea Ice News & Analysis (ASINA) website. As a result of this effort to explain climatic data to the general public, we have attracted a huge amount of attention from our readers. Sometimes, people write to thank us for the information and the explanation. But people also write to accuse us of bias, slant, or outright lies in our posts. The topic of climate change is a minefield full of political animosity, and even the most carefully written verbiage can appear incomplete or biased to some audiences. Our strategy has been to report the data and stick to the areas in which our scientists are experts. The ASINA team carefully edits our posts to make sure that all statements are based on the science and not on opinion. Often this means using some technical language that may be difficult for a layperson to understand. However, we provide concise definitions for technical terms where appropriate. The hope is that by communicating the data clearly, without an agenda, we can let the science speak for itself. Is this an effective strategy to communicate clearly about the changing climate? Or does it downplay the seriousness of climate change? By writing at a more advanced level and avoiding oversimplification, we require our readers to work harder. But we may also maintain the attention of skeptics, convincing them to read further and become more knowledgeable about the topic.

  13. Structural change in molten basalt at deep mantle conditions.

    PubMed

    Sanloup, Chrystèle; Drewitt, James W E; Konôpková, Zuzana; Dalladay-Simpson, Philip; Morton, Donna M; Rai, Nachiketa; van Westrenen, Wim; Morgenroth, Wolfgang

    2013-11-01

    Silicate liquids play a key part at all stages of deep Earth evolution, ranging from core and crust formation billions of years ago to present-day volcanic activity. Quantitative models of these processes require knowledge of the structural changes and compression mechanisms that take place in liquid silicates at the high pressures and temperatures in the Earth's interior. However, obtaining such knowledge has long been impeded by the challenging nature of the experiments. In recent years, structural and density information for silica glass was obtained at record pressures of up to 100 GPa (ref. 1), a major step towards obtaining data on the molten state. Here we report the structure of molten basalt up to 60 GPa by means of in situ X-ray diffraction. The coordination of silicon increases from four under ambient conditions to six at 35 GPa, similar to what has been reported in silica glass. The compressibility of the melt after the completion of the coordination change is lower than at lower pressure, implying that only a high-order equation of state can accurately describe the density evolution of silicate melts over the pressure range of the whole mantle. The transition pressure coincides with a marked change in the pressure-evolution of nickel partitioning between molten iron and molten silicates, indicating that melt compressibility controls siderophile-element partitioning. PMID:24201283

  14. A direct way of redox sensing.

    PubMed

    Benoit, Roger; Auer, Manfred

    2011-01-01

    The function and activity of many proteins can be regulated by changes in the intracellular redox potential. This regulation can involve posttranslational modifications mediated by redox-sensitive pathways. A more direct way to sense redox changes is through reversible covalent modification of cysteine residues of proteins by reactive oxygen species (ROS), e.g. H2O2, and reactive nitrogen species (RNS), e.g. NO. Known cysteine modifications include disulfide bonds, S-nitrosylation, S-glutathionylation, as well as sulphenic acid or sulphinic acid formation. Cysteine-based redox switches are difficult to predict because currently the knowledge of precise consensus sequences is limited. One recurrent feature of known redox switches is the close proximity of polar amino acids to the reactive cysteine, resulting in stabilization of the reactive thiolate anion form. There is growing evidence that intracellular thiol-based redox sensing and signaling mechanisms may also be involved in the regulation of RNA-binding proteins. Here, we discuss the concept of cysteine-based redox sensing and signaling, the potential importance of redox switches in RNA-binding proteins and open questions in the field. PMID:21220941

  15. New insights into redox control of starch degradation.

    PubMed

    Santelia, Diana; Trost, Paolo; Sparla, Francesca

    2015-06-01

    Starch is one of the major sinks of fixed carbon in photosynthetic tissues of higher plants. Carbon fixation and the synthesis of primary starch occur during the day in the chloroplast stroma, whereas starch degradation typically occurs during the following night to fuel the whole plant with energy and carbon in the absence of photosynthesis. Redox-based regulatory systems play a central role in the modulation of several chloroplastic pathways. Reversible oxidations of cysteine residues are post-translational modifications that orchestrate the precise functioning of chloroplast pathways together with changes in pH, Mg(2+) and concentrations of metabolic intermediates. Leaf starch metabolism has been intensively studied. The enzymes involved in starch synthesis and degradation have been identified and characterized. However, the redox control of the enzymes responsible for starch degradation at night remains elusive, and their response to redox transitions conflicts with the timing of the physiological events. Most of the enzymes of starch degradation are activated by reducing conditions, characteristic of daytime. Thus, redox control may have only a minor role during starch degradation at night, but could become relevant for daily stomatal opening in guard cells or in the re-allocation of fixed carbon in mesophyll cells in response to stress conditions. PMID:25899330

  16. Nitrate bioreduction in redox-variable low permeability sediments

    SciTech Connect

    Yan, Sen; Liu, Yuanyuan; Liu, Chongxuan; Shi, Liang; Shang, Jianying; Shan, Huimei; Zachara, John M.; Fredrickson, Jim K.; Kennedy, David W.; Resch, Charles T.; Thompson, Christopher J.; Fansler, Sarah J.

    2015-09-09

    Denitrification is a microbial process that reduces nitrate and nitrite to nitrous oxide (N2O) or dinitrogen (N2) with a strong implication to global nitrogen cycling and climate change. This paper reports the effect of sediment redox conditions on the rate and end product of denitrification. The sediments were collected from a redox transition zone consisting of oxic and reduced layers at US Department of Energy’s Hanford Site where N2O was locally accumulated in groundwater. The results revealed that denitrification rate and end product varied significantly with initial sediment redox state. The denitrification rate was relatively faster, limited by organic carbon content and bioavailability in the oxic sediment. In contrast, the rate was much slower in the reduced sediment, limited by biomass and microbial function. A significant amount of N2O was accumulated in the reduced sediment; while in the oxic sediment, N2O was further reduced to N2. RT-PCR analysis revealed that nosZ, the gene that codes for N2O reductase, was below detection in the reduced sediment. The results implied that redox transition zones can be important sinks or sources of N2O depending on local biogeochemical and microbial conditions, and are important systems for understanding and modeling denitrification in subsurface environments.

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

    PubMed Central

    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. PMID:26809999

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

    PubMed

    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. PMID:26809999

  19. WATERSHED BOUNDARY CONDITIONS FOR GLOBAL CHANGE IMPACT ANALYSIS

    EPA Science Inventory

    The US Global Change Research Program (USGCRP) studies (among other issues) the impact of global change on water quality. This field study evaluates the impact of global changes (land-use change and climate change) on source water quality. Changes in source water quality change...

  20. Thioredoxins, Glutaredoxins, and Peroxiredoxins—Molecular Mechanisms and Health Significance: from Cofactors to Antioxidants to Redox Signaling

    PubMed Central

    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

  1. Comparing Observed Hurricane Conditions Against Potential Future Climate Change Influences

    NASA Astrophysics Data System (ADS)

    Graham, W. D.

    2012-12-01

    Climate Adaptation Science Investigators: (CASI) is to advance and apply NASA's scientific expertise and products to develop climate adaptation strategies that support NASA's overall mission by minimizing risks to each center's operations, physical assets, and personnel. Using Hurricane Katrina observations as a baseline, we use ADCIRC to model surge extent with simple modifications of the storm track. We examine two time now (T0) scenarios of present-day climatological factors: 1) translating the 2005 path 7 km west; and 2) rotating the approach angle from due-north to WNW. Second, we examine two future time scenarios (TX) by infusing climate change conditions, such as sea level rise and increased storm intensity, into a T0 baseline to assess future impacts. The primary goal of this work entails planning and protecting NASA assets and infrastructure. The adjacent communities, state and local emergency managers, gain benefit from this NASA work as data and analysis includes the surrounding geography.

  2. Millennial-scale Changes of Surface and Bottom Water Conditions in the Northwest Pacific during the Last Deglacial Period

    NASA Astrophysics Data System (ADS)

    Khim, B. K.; Kim, S.; Ikehara, K.; Itaki, T.; Shibahara, A.; Yamamoto, M.

    2015-12-01

    The last deglacial changes of the water column conditions in the Northwest Pacific were reconstructed using geochemical and isotope proxies (biogenic opal, CaCO3, total organic carbon (TOC), redox sensitive elements, bulk nitrogen isotopes (δ15N), and silicon isotopes (δ30Sidiatom) of diatom frustules) along with the published data (alkenone temperatures and benthic foraminiferal faunas) at core GH02-1030 recovered from the slope off Tokachi. Age model for core GH02-1030 was determined using both planktonic and benthic foraminiferal AMC 14C dates (Ikehara et al., 2006). Alkenone sea surface temperature (SST) shows that biogenic opal productivity was related to the degree of spring-summer mixed layer depth (MLD). Biogenic opal and TOC contents change almost in parallel. δ30Sidiatom values are high (~+1‰) during the Holocene and low (~-0.4‰) during the last glacial maximum. During the Bølling-Allerød (BA) and the Pre-Boreal (PB), silicic acid utilization represented by δ30Sidiatom increased when the biogenic opal productivity and export TOC productivity are high under shoaling of spring-summer MLD. The BA and the PB intervals contain laminated sediment layers, which are characterized by increases of CaCO3 contents, bulk δ15N values, and redox element concentrations (Mo/Al, Cd/Al, and U/Al). All these indicate low dissolved oxygen content of the bottom water during the BA and PB periods, which is supported by the good preservation of dysoxic benthic foraminifera. In addition, compared to the Holocene biogenic opal productivity and related silicic acid utilization, the high δ15N values during the BA and the PB seemed to be attributed more to denitrification through the water column rather than complete utilization of nitrate. Another distinct feature based on benthic foraminiferal assemblage, CaCO3 contents and redox element concentrations is that the dissolved oxygen content in bottom water was lower during the BA than the PB. Because biogenic opal

  3. Arctic hillslope hydrologic response to changing water storage conditions

    NASA Astrophysics Data System (ADS)

    Rushlow, C. R.; Godsey, S.

    2013-12-01

    Solute transport from terrestrial to aquatic environments depends on dynamics of water storage and flux. In the arctic, these dynamics are related to changes in permafrost and hydrological conditions that vary with climate across multiple scales. In order to predict the continued trajectory of arctic landscape and ecosystem evolution, observed changes to the hydrologic regime and riverine nutrient fluxes require properly scaled, mechanistic explanations. We address this issue at the hillslope scale by quantifying hydrologic response to changing storage as part of a collaborative effort to understand the coupled hydrology and biogeochemistry of arctic hillslopes. Hillslopes underlain by continuous permafrost experience gradual, summer-season increases in potential water storage through active layer thaw, as well as stochastic changes in available water storage as soil moisture conditions change due to storm events, evapotranspiration, and subsurface flow. Preferential flowpaths called water tracks are ubiquitous features draining arctic hillslopes and are the focus of our study. We predict that water track hydrologic response to precipitation is a function of snowmelt or storm characteristics and available storage. We hypothesize that ¬the ratio of runoff to precipitation will decrease as available storage increases, whether due to the seasonal increase in active layer thaw, or an extended dry period. Intensive snow and thaw depth surveys on a water track on the hillslopes of the Upper Kuparuk River watershed in northern Alaska during May to June 2013 reveal that snow persisted one week longer in a water track than the adjacent hillslope, and thus active layer thaw initiated earlier on the adjacent hillslope. Despite this earlier thaw timing, thaw depth in the water track exceeded that on the non-track hillslope within five days of being uncovered. Thaw, and thus subsurface storage, in water tracks remained greater than the rest of the hillslope for at least the

  4. Conditioned hearing sensitivity change in the harbor porpoise (Phocoena phocoena).

    PubMed

    Nachtigall, Paul E; Supin, Alexander Ya; Pacini, Aude F; Kastelein, Ronald A

    2016-08-01

    Hearing sensitivity, during trials in which a warning sound preceding a loud sound, was investigated in two harbor porpoises (Phocoena phocoena). Sensitivity was measured using pip-train test stimuli and auditory evoked potential recording. When a hearing test/warning stimulus, with a frequency of either 45 or 32 kHz, preceded a loud 32 kHz tone with a sound pressure level of 152 dB re 1 μPa root mean square, lasting 2 s yielding an sound exposure level (SEL) of 155 dB re 1 μPa(2)s, pooled hearing thresholds measured just before the loud sound increased relative to baseline thresholds. During two experimental sessions the threshold increased up to 17 dB for the test frequency of 45 kHz and up to 11 dB for the test frequency of 32 kHz. An extinction test revealed very rapid threshold recovery within the first two experimental sessions. The SEL producing the hearing dampening effect was low compared to previous other odontocete hearing change efforts with each individual trial equal to 155 dB re 1 μPa(2) but the cumulative SEL for each subsession may have been as high as 168 dB re 1 μPa(2). Interpretations of conditioned hearing sensation change and possible change due to temporary threshold shifts are considered for the harbor porpoise and discussed in the light of potential mechanisms and echolocation. PMID:27586728

  5. Redox activity of naphthalene secondary organic aerosol

    NASA Astrophysics Data System (ADS)

    McWhinney, R. D.; Zhou, S.; Abbatt, J. P. D.

    2013-04-01

    Chamber secondary organic aerosol (SOA) from low-NOx photooxidation of naphthalene by hydroxyl radical was examined with respect to its redox cycling behaviour using the dithiothreitol (DTT) assay. Naphthalene SOA was highly redox active, consuming DTT at an average rate of 118 ± 14 pmol per minute per μg of SOA material. Measured particle-phase masses of the major previously identified redox active products, 1,2- and 1,4-naphthoquinone, accounted for only 21 ± 3% of the observed redox cycling activity. The redox-active 5-hydroxy-1,4-naphthoquinone was identified as a new minor product of naphthalene oxidation, and including this species in redox activity predictions increased the predicted DTT reactivity to 30 ± 5% of observations. Similar attempts to predict redox behaviour of oxidised two-stroke engine exhaust particles by measuring 1,2-naphthoquinone, 1,4-naphthoquinone and 9,10-phenanthrenequinone predicted DTT decay rates only 4.9 ± 2.5% of those observed. Together, these results suggest that there are substantial unidentified redox-active SOA constituents beyond the small quinones that may be important toxic components of these particles. A gas-to-SOA particle partitioning coefficient was calculated to be (7.0 ± 2.5) × 10-4 m3 μg-1 for 1,4-naphthoquinone at 25 °C. This value suggests that under typical warm conditions, 1,4-naphthoquinone is unlikely to contribute strongly to redox behaviour of ambient particles, although further work is needed to determine the potential impact under conditions such as low temperatures where partitioning to the particle is more favourable. As well, higher order oxidation products that likely account for a substantial fraction of the redox cycling capability of the naphthalene SOA are likely to partition much more strongly to the particle phase.

  6. Dynamic Structural Changes of SiO₂ Supported Pt-Ni Bimetallic Catalysts over Redox Treatments Revealed by NMR and EPR

    SciTech Connect

    Xu, Suochang; Walter, Eric D.; Zhao, Zhenchao; Hu, Mary Y.; Han, Xiuwen; Hu, Jian Z.; Bao, Xinhe

    2015-08-18

    SiO2 supported Pt-Ni bimetallic catalysts with different nickel loadings were prepared and their structural changes after redox treatments were studied by XRD, NMR, and EPR. It is found that the paramagnetic Ni species are mainly located on the surface of silica lattice. The relaxation of detected 29Si nuclei in our samples is mainly governed by a spin-diffusion mechanism. The paramagnetic effects are reflected in the spin-lattice relaxation of Q4 species, with the oxidized samples presenting faster relaxation rates than the corresponding reduced ones. Meanwhile the Q3 species, which are in close contact with the paramagnetic nickel ions, are “spectrally invisible”. In reducing atmosphere Ni gradually diffuses into Pt NPs to form PtNi alloys. While under oxidization treatment, the alloyed Ni atoms migrate outward from the core of Pt NPs and are oxidized. The main EPR spectrum results from reduced nickel species, and the reduced samples show stronger EPR signal than the corresponding oxidized ones. However, in the reduced samples, the superparamagnetic or ferromagnetic metallic Ni particles were inside the PtNi NPs, making their influence on the 29Si relaxation in the SiO2 support weaker than the oxidized samples.

  7. Redox active motifs in selenoproteins.

    PubMed

    Li, Fei; Lutz, Patricia B; Pepelyayeva, Yuliya; Arnér, Elias S J; Bayse, Craig A; Rozovsky, Sharon

    2014-05-13

    Selenoproteins use the rare amino acid selenocysteine (Sec) to act as the first line of defense against oxidants, which are linked to aging, cancer, and neurodegenerative diseases. Many selenoproteins are oxidoreductases in which the reactive Sec is connected to a neighboring Cys and able to form a ring. These Sec-containing redox motifs govern much of the reactivity of selenoproteins. To study their fundamental properties, we have used (77)Se NMR spectroscopy in concert with theoretical calculations to determine the conformational preferences and mobility of representative motifs. This use of (77)Se as a probe enables the direct recording of the properties of Sec as its environment is systematically changed. We find that all motifs have several ring conformations in their oxidized state. These ring structures are most likely stabilized by weak, nonbonding interactions between the selenium and the amide carbon. To examine how the presence of selenium and ring geometric strain governs the motifs' reactivity, we measured the redox potentials of Sec-containing motifs and their corresponding Cys-only variants. The comparisons reveal that for C-terminal motifs the redox potentials increased between 20-25 mV when the selenenylsulfide bond was changed to a disulfide bond. Changes of similar magnitude arose when we varied ring size or the motifs' flanking residues. This suggests that the presence of Sec is not tied to unusually low redox potentials. The unique roles of selenoproteins in human health and their chemical reactivities may therefore not necessarily be explained by lower redox potentials, as has often been claimed. PMID:24769567

  8. Redox active motifs in selenoproteins

    PubMed Central

    Li, Fei; Lutz, Patricia B.; Pepelyayeva, Yuliya; Arnér, Elias S. J.; Bayse, Craig A.; Rozovsky, Sharon

    2014-01-01

    Selenoproteins use the rare amino acid selenocysteine (Sec) to act as the first line of defense against oxidants, which are linked to aging, cancer, and neurodegenerative diseases. Many selenoproteins are oxidoreductases in which the reactive Sec is connected to a neighboring Cys and able to form a ring. These Sec-containing redox motifs govern much of the reactivity of selenoproteins. To study their fundamental properties, we have used 77Se NMR spectroscopy in concert with theoretical calculations to determine the conformational preferences and mobility of representative motifs. This use of 77Se as a probe enables the direct recording of the properties of Sec as its environment is systematically changed. We find that all motifs have several ring conformations in their oxidized state. These ring structures are most likely stabilized by weak, nonbonding interactions between the selenium and the amide carbon. To examine how the presence of selenium and ring geometric strain governs the motifs’ reactivity, we measured the redox potentials of Sec-containing motifs and their corresponding Cys-only variants. The comparisons reveal that for C-terminal motifs the redox potentials increased between 20–25 mV when the selenenylsulfide bond was changed to a disulfide bond. Changes of similar magnitude arose when we varied ring size or the motifs’ flanking residues. This suggests that the presence of Sec is not tied to unusually low redox potentials. The unique roles of selenoproteins in human health and their chemical reactivities may therefore not necessarily be explained by lower redox potentials, as has often been claimed. PMID:24769567

  9. Relating hyporheic fluxes, residence times, and redox-sensitive biogeochemical processes upstream of beaver dams

    USGS Publications Warehouse

    Briggs, Martin A.; Lautz, Laura; Hare, Danielle K.

    2013-01-01

    ¨hler number seemed to overestimate the actual transition as indicated by multiple secondary electron acceptors, illustrating the gradient nature of anaerobic transition. Temporal flux variability in low-flux morphologies generated a much greater range in hyporheic redox conditions compared to high-flux zones, and chemical responses to changing flux rates were consistent with those predicted from the empirical relationship between redox condition and residence time. The Raz tracer revealed that hyporheic flow paths have strong net aerobic respiration, particularly at higher residence time, but this reactive exchange did not affect the net stream signal at the reach scale.

  10. Temporal expression of hypoxia-regulated genes is associated with early changes in redox status in irradiated lung

    PubMed Central

    Jackson, Isabel L.; Zhang, Xiuwu; Hadley, Caroline; Rabbani, Zahid N.; Zhang, Yu; Marks, Sam; Vujaskovic, Zeljko

    2013-01-01

    The development of normal lung tissue toxicity after radiation exposure results from multiple changes in cell signaling and communication initiated at the time of the ionizing event. The onset of gross pulmonary injury is preceded by tissue hypoxia and chronic oxidative stress. We have previously shown development of debilitating lung injury can be mitigated or prevented by administration of AEOL10150, a potent catalytic antioxidant, 24 hours after radiation. This suggests that hypoxia-mediated signaling pathways may play a role in late radiation injury, but the exact mechanism remains unclear. The purpose of this study was to evaluate changes in the temporal expression of hypoxia-associated genes in irradiated mouse lung and determine whether AEOL10150 alters expression of these genes. A focused oligo array was used to establish a hypoxia-associated gene expression signature for lung tissue from sham-irradiated or irradiated mice treated with or without AEOL10150. Results were further verified by RT-PCR. 44 genes associated with metabolism, cell growth, apoptosis, inflammation, oxidative stress and extracellular matrix synthesis were upregulated after radiation. Elevated expression of 31 of these genes was attenuated in animals treated with AEOL10150, suggesting that expression of a number of hypoxia-associated genes are regulated by early development of oxidative stress after radiation. Genes identified herein could provide insight into the role of hypoxic signaling in radiation lung injury, suggesting novel therapeutic targets, as well as clues to the mechanism by which AEOL10150 confers pulmonary radioprotection. PMID:22588005

  11. Effect of pH on Structural Changes in Perch Hemoglobin that Can Alter Redox Stability and Heme Affinity

    SciTech Connect

    Richards, Mark P.; Aranda, IV, Roman; He, Cai; Phillips, Jr., George N.

    2010-01-07

    pH can be manipulated to alter the oxidative stability of fish-based foods during storage. X-ray diffraction was used to investigate the ability of reduced pH to cause structural changes in fish hemoglobins that lead to enhanced oxidative degradation. Decreasing pH from 8.0 to 6.3 and 5.7 created a large channel for solvent entry into the heme crevice of perch hemoglobin beta chains. The proton-induced opening of this channel occurred between site CD3 and the heme-6-propionate. Solvent entry into the heme crevice can enhance metHb formation and hemin loss, processes that accelerate lipid oxidation. Reduced pH also decreased the distance between Ile at E11 in one of the alpha chains and the ligand above the heme iron atom. This sterically displaces O{sub 2} and protonated O{sub 2} which increases metHb formation. These studies demonstrate that pH reduction causes structural changes in perch hemoglobin which increase oxidative degradation of the heme pigment.

  12. Changes in hydrological regime under changed climate and forest conditions in mountainous basins in Slovakia

    NASA Astrophysics Data System (ADS)

    Hlavcova, Kamila; Roncak, Peter; Maliarikova, Marcela; Latkova, Tamara; Korbelova, Lenka

    2016-04-01

    The impacts of land use and climate change on hydrological regime have been an important field of research in recent decades, especially with respect to runoff formation. Land use directly impacts basic hydrological processes, such as evapotranspiration, infiltration and runoff. The study focuses on estimating impact of land use and climate changes on runoff generation in selected mountainous basins in Slovakia. Changes in land use were represented by changes in forest distribution and composition induced by changed climate. Two climate scenarios of the daily air temperatures, specific air humidity and precipitation (KNMI A1B and MPI A1B) regionally downscaled for the territory of Slovakia until the time horizon of 2075 were applied. For simulations of runoff and other components of hydrological balance under changed conditions a distributed rainfall-runoff model was used. The simulations were done with an emphasis on the parameterization of the land cover properties (spatially distributed model parameters) and calibration of global parameters of the hydrological model in changed conditions. The outcomes of the runoff simulations indicate that changes in the long-term mean monthly discharges are expected. During the winter and early spring periods, an increase in the long-term mean monthly runoff could be assumed. The period of an increase in runoff could occur from November/December to February/April. This increase could be caused by an increase in air temperature and a shift in the snow melting period from the spring months to the winter period. The period of a decrease in runoff could occur from March/April to September/November. The increase in winter runoff and the decrease in summer runoff are expected to be more extreme for the later time horizons.

  13. Light-induced conformational changes in photosynthetic reaction centers: redox-regulated proton pathway near the dimer.

    PubMed

    Deshmukh, Sasmit S; Williams, JoAnn C; Allen, James P; Kálmán, László

    2011-04-26

    The influence of the hydrogen bonds on the light-induced structural changes were studied in the wild type and 11 mutants with different hydrogen bonding patterns of the primary electron donor of reaction centers from Rhodobacter sphaeroides. Previously, using the same set of mutants at pH 8, a marked light-induced change of the local dielectric constant in the vicinity of the dimer was reported in wild type and in mutants retaining Leu L131 that correlated with the recovery kinetics of the charge-separated state [ Deshmukh et al. (2011) Biochemistry, 50, 340-348]. In this work after prolonged illumination the recovery of the oxidized dimer was found to be multiphasic in all mutants. The fraction of the slowest phase, assigned to a recovery from a conformationally altered state, was strongly pH dependent and found to be extremely long at room temperature, at pH 6, with rate constants of ∼10(-3) s(-1). In wild type and in mutants with Leu at L131 the very long recovery kinetics was coupled to a large proton release at pH 6 and a decrease of up to 79 mV of the oxidation potential of the dimer. In contrast, in the mutants carrying the Leu to His mutation at the L131 position, only a negligible fraction of the dimer exhibited lowered potential, the large proton release was not observed, the oxidized dimer recovered 1 or 2 orders of magnitude faster depending on the pH, and the very long-lived state was not or barely detectable. These results are modeled as arising from the loss of a proton pathway from the bacteriochlorophyll dimer to the solvent when His is present at the L131 position. PMID:21410139

  14. COMPOSITION CHANGES IN REFRIGERANT BLENDS FOR AUTOMOTIVE AIR CONDITIONING

    EPA Science Inventory

    Three refrigerant blends used to replace CFC-12 in automotive air conditioners were evaluated for composition changes due to typical servicing and leakage. When recommended service procedures were followed, changes in blend compositions were relatively small. Small changes in b...

  15. Hydropower Energy in Lebanon: Adaptation for Changing Climatic Conditions

    NASA Astrophysics Data System (ADS)

    Shaban, A.

    2012-12-01

    The mountainous terrain of Lebanon makes it a climatic barrier that receives clod air masses from the west and condensate them as rain and snow. Hence the average precipitation rate is about 950mm, creating tremendous water sources, but large portion of this water runs to the sea before utilizing it properly. The natural patterns of surface run-off on the mountainous terrain provide a chance to generate hydropower energy. Thus, Lebanon has 17 hydropower stations on 8 rivers. The productivity of these stations averages about 722 GWh, which provide an integral portion of the Lebanese electrical energy. The population growth and the failure of the existing electrical plants to supply adequate energy have been increased in the last few decades. Thus, there is proposition to construct 13 new hydropower plants. However, challenges for generating hydropower energy has been exacerbated; especially in the view of changing climatic conditions, including fluctuations in precipitation regime, which results an obvious decrease in the volume of run-off. This threatens constructed dams for energy generation. Hence, adapting new instrumentations became a necessity mechanism to be applied before proposing new hydropower station in Lebanon. This study will introduce the applicable adaptation tools to be followed in this respect.

  16. Icing conditions over Northern Eurasia in changing climate

    NASA Astrophysics Data System (ADS)

    Bulygina, Olga N.; Arzhanova, Natalia M.; Groisman, Pavel Ya

    2015-02-01

    Icing conditions, particularly in combination with wind, affect greatly the operation of overhead communication and transmission lines causing serious failures, which result in tremendous economic damage. Icing formation is dangerous to agriculture, forestry, high seas fishery, for land and off coast man-made infrastructure. Quantitative icing characteristics such as weight, thickness, and duration are very important for the economy and human wellbeing when their maximum values exceed certain thresholds. Russian meteorological stations perform both visual and instrumental monitoring of icing deposits. Visual monitoring is ocular estimation of the type and intensity of icing and the date of ice appearance and disappearance. Instrumental monitoring is performed by ice accretion indicator that in addition to the type, intensity and duration of ice deposits reports also their weight and size. We used observations at 958 Russian stations for the period 1977-2013 to analyze changes in the ice formation frequency at individual meteorological stations and on the territory of quasi-homogeneous climatic regions in Russia. It was found that hoar frosts are observed in most parts of Russia, but icing only occurs in European Russia and the Far East. On the Arctic coast of Russia, this phenomenon can even be observed in summer months. Statistically significant decreasing trends in occurrence of icing and hoar frost events are found over most of Russia. An increasing trend in icing weights (IWs) was found in the Atlantic Arctic region in autumn. Statistically significant large negative trends in IWs were found in the Pacific Arctic in winter and spring.

  17. The Tumorigenic Roles of the Cellular REDOX Regulatory Systems

    PubMed Central

    Castaldo, Stéphanie Anaís; Freitas, Joana Raquel; Conchinha, Nadine Vasconcelos; Madureira, Patrícia Alexandra

    2016-01-01

    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. PMID:26682014

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

    PubMed

    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. PMID:26282677

  19. The Tumorigenic Roles of the Cellular REDOX Regulatory Systems.

    PubMed

    Castaldo, Stéphanie Anaís; Freitas, Joana Raquel; Conchinha, Nadine Vasconcelos; Madureira, Patrícia Alexandra

    2016-01-01

    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. PMID:26682014

  20. Differential alkylation-based redox proteomics – Lessons learnt

    PubMed Central

    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

  1. Redox-controlled molecular permeability of composite-wall microcapsules

    NASA Astrophysics Data System (ADS)

    Ma, Yujie; Dong, Wen-Fei; Hempenius, Mark A.; Möhwald, Helmuth; Julius Vancso, G.

    2006-09-01

    Many smart materials in bioengineering, nanotechnology and medicine allow the storage and release of encapsulated drugs on demand at a specific location by an external stimulus. Owing to their versatility in material selection, polyelectrolyte multilayers are very promising systems in the development of microencapsulation technologies with permeation control governed by variations in the environmental conditions. Here, organometallic polyelectrolyte multilayer capsules, composed of polyanions and polycations of poly(ferrocenylsilane) (PFS), are introduced. Their preparation involved layer-by-layer self-assembly onto colloidal templates followed by core removal. PFS polyelectrolytes feature redox-active ferrocene units in the main chain. Incorporation of PFS into the capsule walls allowed us to explore the effects of a new stimulus, that is, changing the redox state, on capsule wall permeability. The permeability of these capsules could be sensitively tuned via chemical oxidation, resulting in a fast capsule expansion accompanied by a drastic permeability increase in response to a very small trigger. The substantial swelling could be suppressed by the application of an additional coating bearing common redox-inert species of poly(styrene sulfonate) (PSS-) and poly(allylamine hydrochloride) (PAH+) on the outer wall of the capsules. Hence, we obtained a unique capsule system with redox-controlled permeability and swellability with a high application potential in materials as well as in bioscience.

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

    PubMed Central

    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

  3. Redox proteomics of fat globules unveils broad protein lactosylation and compositional changes in milk samples subjected to various technological procedures.

    PubMed

    Arena, Simona; Renzone, Giovanni; Novi, Gianfranco; Scaloni, Andrea

    2011-10-19

    The Maillard reaction between lactose and proteins occurs during thermal treatment of milk and lactosylated β-lactoglobulin, α-lactalbumin and caseins have widely been used to monitor the quality of dairy products. We recently demonstrated that a number of other whey milk proteins essential for nutrient delivery, defense against bacteria/virus and cellular proliferation become lactosylated during milk processing. The extent of their modification is associated with the harshness of product manufacturing. Since fat globule proteins are also highly important for the health-beneficial properties of milk, an evaluation of their lactosylation is crucial for a complete understanding of aliment nutritional characteristics. This is more important when milk is the unique dietary source, as in the infant diet. To this purpose, a sequential proteomic procedure involving an optimized milk fat globule (MFG) preparation/electrophoretic resolution, shot-gun analysis of gel portions for protein identification, selective trapping of lactosylated peptides by phenylboronate chromatography and their analysis by nanoLC-ESI-electron transfer dissociation (ETD) tandem MS was used for systematic characterization of fat globule proteins in milk samples subjected to various manufacturing procedures. Significant MFG protein compositional changes were observed between samples, highlighting the progressive adsorption of caseins and whey proteins on the fat globule surface as result of the technological process used. A significant lactosylation of MFG proteins was observed in ultra-high temperature sterilized and powdered for infant nutrition milk preparations, which well paralleled with the harshness of thermal treatment. Globally, this study allowed the identification of novel 157 non-redundant modification sites and 35 MFG proteins never reported so far as being lactosylated, in addition to the 153 ones ascertained here as present on other 21 MFG-adsorbed proteins whose nature was already

  4. Redox Potential of Peroxidases

    NASA Astrophysics Data System (ADS)

    Ayala, Marcela

    Redox potential of peroxidases greatly influences the range of oxidizable substrates: in principle, peroxidases may only catalyze the oxidation of substrates with lower redox potential. There is substantial information on the factors that modulate the redox potential of heme proteins. Both theoretical and experimental evidence highlight the most significant contributions arising from the interaction of heme iron with the axial ligands, as well as the electrostatic interactions surrounding the heme group. However, for different proteins, the factors contribute to different extents. Understanding the electrochemistry of heme peroxidases is fundamental in order to design enhanced biocatalysts. In this chapter, current knowledge of the forces influencing redox potential of heme peroxidases is reviewed.

  5. Cerium stable isotope ratios in ferromanganese deposits and their potential as a paleo-redox proxy

    NASA Astrophysics Data System (ADS)

    Nakada, Ryoichi; Takahashi, Yoshio; Tanimizu, Masaharu

    2016-05-01

    The cerium (Ce) anomaly observed in rare earth element (REE) patterns has been used to estimate the redox state of paleo-marine environments. Cerium is unique because it forms tetravalent cations under oxic conditions, in contrast to the other REEs that occur in a trivalent state. This characteristic leads to anomalously high or low Ce concentrations relative to neighboring REEs. However, the use of Ce anomaly as a paleo-redox proxy is not well calibrated. This study shows that coupling of the Ce anomaly and Ce stable isotope ratio (δ142Ce) is more quantitative redox proxy to distinguish suboxic and oxic redox conditions. Our results revealed a progressive enrichment in heavy Ce isotopes in consecutive formations of iron (Fe) and manganese (Mn) precipitate from hot spring water without any associated change in REE patterns. The δ142Ce values of Mn precipitates were approximately 0.35‰ heavier than those of the Fe precipitates, which was consistent with experiment-based predictions. The δ142Ce values of marine ferromanganese deposits with three different formation processes were hydrogenetic (+0.25‰) > diagenetic (+0.10‰) ⩾ hydrothermal (+0.05‰), which also reflects redox conditions of their formation environment. These observations suggest that the Ce stable isotope ratios yield more quantitative information regarding redox state than REE patterns alone. We thus suggest that this novel proxy can be successfully utilized to reconstruct marine redox states, particularly from slightly oxic to highly oxic conditions such as the Great Oxidation Event (GOE).

  6. Implications of phosphorus redox geochemistry

    NASA Astrophysics Data System (ADS)

    Pasek, Matthew

    2015-04-01

    Phosphorus is the limiting nutrient in many environments. Until recently, redox changes to phosphorus speciation have been confined to the realm of chemical laboratories as phosphorus was considered to be synonymous with phosphate in the natural environment. The few known phosphorus species with a reduced redox state, such as phosphine gas, were considered novelties. Recent work has revealed a surprising role for low redox state organophosphorus compounds -- the phosphonates -- in biogeochemistry. Additionally, phosphite and hypophosphite (the lower oxyanions of phosphorus) have been identified from natural sources, and microbial genomics suggests these compounds may be ubiquitous in nature. Recent work from our laboratory suggests that reduced phosphorus compounds such as phosphite and hypophosphite may be ubiquitous (Pasek et al. 2014). If so, then these species maybe important in the global phosphorus biogeochemical cycle, and could influence global phosphorus sustainability. Additionally, these compounds could have been relevant on the early earth environment, priming the earth with reactive phosphorus for prebiotic chemistry. Reference: Pasek, M. A., Sampson, J. M., & Atlas, Z. (2014). Redox chemistry in the phosphorus biogeochemical cycle. Proceedings of the National Academy of Sciences, 111(43), 15468-15473.

  7. Icing Conditions Over Northern Eurasia in Changing Climate

    NASA Astrophysics Data System (ADS)

    Bulygina, O.; Arzhanova, N.; Groisman, P. Y.

    2013-12-01

    Climate of the Russian Federation for the national territory. This Reference Book addresses the current state of these weather phenomena. However, the ongoing and projected humidity changes in the high latitudes will strongly affect the circum-polar area (land and ocean) and impact the frequency and intensity of these potentially dangerous weather phenomena across the entire extratropical land area. Therefore the goal of the present study is to quantify icing conditions over the northern Eurasia. Our analysis includes data of 958 Russian stations from 1977 to 2012. Regional analysis of gololed characteristics was carried out using quasi-homogeneous climatic regions. Maps (climatology, trends) are presented mostly for visualization purposes. The area-averaging technique using station values converted to anomalies with respect to a common reference period (in this study, from 1977 to 2012). Anomalies were arithmetically averaged first within 1N x 2E grid cells and thereafter by a weighted average value derived over the quasi-homogeneous climatic regions. This approach provides a more uniform spatial field for averaging.

  8. Morphogenetic changes occurring in the regenerating newt tail under changed gravity conditions

    NASA Astrophysics Data System (ADS)

    Radugina, Elena A.; Grigoryan, Eleonora N.; Dvorochkin, Natasha; Almeida, Eduardo

    2012-07-01

    It is widely accepted that gravity greatly affects animal physiology, development, and alters gene expression. Recently it became apparent that it can also affect tissue morphogenesis. In our work, we developed special laboratory conditions that allow us to produce the gravity-dependent alterations in tail regenerates of the newt Pleurodeles waltl. We examined the dynamic morphogenetic changes during 50-day tail regeneration using computer morphometric analysis. Changes that we observed under these conditions were comparable with those found earlier in our spaceflight experiments. The newts kept in aquarium deep water (low g) after 1/3 tail amputation developed normal lanceolate regenerates. In contrast, the animals that stayed on the moist mat (1g) developed tail regenerates curved ventrally, with tips almost touching the mat. The similar results were obtained with a 12-day centrifugation at 2g. The study of the regenerate morphology in low g, 1g, and 2g animal groups allowed us to determine the stage at which the morphological changes in regenerates become apparent, and to detect the main morphological events associated with the development of tail curve, such as bending of ependymal tube and reorientation of the forming cartilage. We describe cellular processes foregoing observed tissue morphogenetic changes, such as cell migration, condensation in cell population, and unequal proliferation in different areas of epidermis and blastema. Cell proliferation in epidermis and blastema of tails regenerated under the conditions of different gravitational load was evaluated by BrdU assay. In 1g newts, cell proliferation increased within the dorso-apical region of the regenerates compared with that in low g group. These results provide us with a valuable insight into the regenerative tissue homostasis that involves cell division, cell death, and migration in the newt regenerating tail. In addition, these findings could provide us with better understanding of the

  9. Composition changes in refrigerant blends for automotive air conditioning

    SciTech Connect

    Jetter, J.J.; Delafield, F.R.; Ng, A.S.; Ratanaphruks, K.; Tufts, M.W.

    1999-07-01

    Three refrigerant blends used to replace the chlorofluorocarbon R-12 in automotive air conditioners were evaluated for composition changes due to typical servicing and leakage. When recommended service procedures were followed, changes in blend compositions were relatively small. Small changes in blend compositions caused no significant changes in refrigeration capacities. However, when recommended procedures were not followed, changes in compositions were relatively large. The amount of change in composition and the resulting effect on performance varied among the three refrigerant blends that were tested. Of the three blends, a quaternary blend containing hydrochlorofluorocarbon R-22 had the greatest changes in composition, while a binary blend containing hydrofluorocarbon R-134a had the smallest changes in composition.

  10. Climate Change and Crop Exposure to Adverse Weather: Changes to Frost Risk and Grapevine Flowering Conditions

    PubMed Central

    Mosedale, Jonathan R.; Wilson, Robert J.; Maclean, Ilya M. D.

    2015-01-01

    The cultivation of grapevines in the UK and many other cool climate regions is expected to benefit from the higher growing season temperatures predicted under future climate scenarios. Yet the effects of climate change on the risk of adverse weather conditions or events at key stages of crop development are not always captured by aggregated measures of seasonal or yearly climates, or by downscaling techniques that assume climate variability will remain unchanged under future scenarios. Using fine resolution projections of future climate scenarios for south-west England and grapevine phenology models we explore how risks to cool-climate vineyard harvests vary under future climate conditions. Results indicate that the risk of adverse conditions during flowering declines under all future climate scenarios. In contrast, the risk of late spring frosts increases under many future climate projections due to advancement in the timing of budbreak. Estimates of frost risk, however, were highly sensitive to the choice of phenology model, and future frost exposure declined when budbreak was calculated using models that included a winter chill requirement for dormancy break. The lack of robust phenological models is a major source of uncertainty concerning the impacts of future climate change on the development of cool-climate viticulture in historically marginal climatic regions. PMID:26496127

  11. A Numerical Study of Tidal Impacts on Denitrification and Redox Zonation in Coastal Sediments

    NASA Astrophysics Data System (ADS)

    Knights, D. H.; Sawyer, A. H.

    2014-12-01

    In coastal settings, tidally induced surface water-groundwater exchange (tidal pumping) controls nitrate fluxes between sediments and the water column and denitrification rates in shallow sediments. A one-dimensional, coupled fluid flow and solute transport model was used to capture the influence of tidal pumping on redox zonation and nitrate removal in sediments within coastal settings such as tidal rivers, deltas, and marshes. Upwelling groundwater was assumed to be rich in nitrate but low in dissolved oxygen (DO) and dissolved organic carbon (DOC). Tidal pumping enhances exchange of DO-rich surface water across the sediment-water interface and creates a deep, oscillating zone of aerobic respiration. Relative to non-tidal conditions, denitrification rates are diminished. As redox conditions shift with spring-neap tides, redox gradients should also shift and drive a change in denitrification rates within aquatic sediments.

  12. Assessing the Practical Equivalence of Conversions when Measurement Conditions Change

    ERIC Educational Resources Information Center

    Liu, Jinghua; Dorans, Neil J.

    2012-01-01

    At times, the same set of test questions is administered under different measurement conditions that might affect the psychometric properties of the test scores enough to warrant different score conversions for the different conditions. We propose a procedure for assessing the practical equivalence of conversions developed for the same set of test…

  13. 23 CFR 635.109 - Standardized changed condition clauses.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... State developed clause or clauses, however, must be in conformance with 23 U.S.C., 23 CFR and other... latent physical conditions are encountered at the site differing materially from those indicated in the contract or if unknown physical conditions of an unusual nature, differing materially from those...

  14. 23 CFR 635.109 - Standardized changed condition clauses.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... State developed clause or clauses, however, must be in conformance with 23 U.S.C., 23 CFR and other... latent physical conditions are encountered at the site differing materially from those indicated in the contract or if unknown physical conditions of an unusual nature, differing materially from those...

  15. 23 CFR 635.109 - Standardized changed condition clauses.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... State developed clause or clauses, however, must be in conformance with 23 U.S.C., 23 CFR and other... latent physical conditions are encountered at the site differing materially from those indicated in the contract or if unknown physical conditions of an unusual nature, differing materially from those...

  16. 23 CFR 635.109 - Standardized changed condition clauses.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... State developed clause or clauses, however, must be in conformance with 23 U.S.C., 23 CFR and other... latent physical conditions are encountered at the site differing materially from those indicated in the contract or if unknown physical conditions of an unusual nature, differing materially from those...

  17. 23 CFR 635.109 - Standardized changed condition clauses.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... State developed clause or clauses, however, must be in conformance with 23 U.S.C., 23 CFR and other... latent physical conditions are encountered at the site differing materially from those indicated in the contract or if unknown physical conditions of an unusual nature, differing materially from those...

  18. Comparison of methods probing the intracellular redox milieu in Plasmodium falciparum.

    PubMed

    Mohring, Franziska; Jortzik, Esther; Becker, Katja

    2016-01-01

    Glutathione plays a crucial role in the redox regulation of the malaria parasite Plasmodium falciparum and is linked to drug resistance mechanisms, especially in resistance against the antimalarial drug chloroquine (CQ). The determination of the glutathione-dependent redox potential was recently established in living parasites using a cytosolically expressed biosensor comprising redox-sensitive green fluorescent protein coupled to human glutaredoxin 1 (hGrx1-roGFP2). In order to further elucidate redox changes induced by antimalarial drugs and to consolidate the application spectrum of the ratiometric biosensor we systematically compared it to other methods probing thiol and redox metabolism. Among these methods were cell disruptive and non-disruptive approaches including spectrophotometric assays with Ellman's reagent and naphthalene dicarboxyaldehyde as well as molecular probes such as ThiolTracker™ Violet and the dichlorofluorescein-based probe CM-H2DCFDA. To directly compare the methods, blood stages of the CQ-sensitive P. falciparum 3D7 strain were challenged with the oxidative agent diamide and the antimalarial drugs artemisinin and CQ for 1h, 4h, and 24h. For all conditions, dose-dependent changes in the different redox parameters could be monitored which are compared and discussed. We furthermore detected slight differences in thiol status of parasites transiently transfected with hGrx1-roGFP2 in comparison with control 3D7 cells. In conclusion, ThiolTracker™ Violet and, even more so, the hGrx1-roGFP2 probe reacted reliably and sensitively to drug induced changes in intracellular redox metabolism. These results were substantiated by classical cell disruptive methods. PMID:26593282

  19. Characterising Redox-Related Isotope Effects

    NASA Astrophysics Data System (ADS)

    Black, J. R.; John, S.; Young, E. D.; Kavner, A.

    2008-12-01

    Redox processes have played a pivotal role in shaping Earth's interior and surface and making life possible. A record of this evolution is found within stable isotope signatures arising from chemical redox changes occurring in our continents, oceans and atmosphere over time. Experimental and theoretical studies of redox- related transition metal isotope fractionation provide a physical basis to understand how isotopes are fractionated under natural conditions, relating geochemical signatures to earth processes from which they arise. Here we present experimental evidence that charge transfer processes drive the fractionation of stable isotopes of Fe and Zn, and the magnitude of fractionation can be tuned as a function of redox potential and other physical variables. To quantitatively evaluate isotopic signatures of redox processes, we have conducted electrochemical experiments measuring the fractionation of Fe and Zn isotopes during their electrodeposition from aqueous solution: M2+ + 2e- = M(s). The electrochemical cell consisted of anodic and cathodic half- cells separated by a salt bridge, and connected to a potentiostat which applied an adjustable constant voltage (vs. Ag/AgCl). Metallic Fe and Zn plated on glassy carbon electrodes was recovered in acid for analysis of the stable isotope composition on a Thermo-Finnigan Neptune MC-ICP-MS. Results are reported as a large delta difference between the isotopic composition (56Fe/54Fe and 66Zn/64Zn) of plated metal relative to the stock solution. The results show some clear trends; fractionation is a function of applied voltage (overpotential: η = E- E0 Volts), ranging from Δ56Fe ~ -4 to -0.9 ‰, and Δ66Zn ~ - 5.5 to -4 ‰ at η = -0.5 to -1.25 V and -0.1 to -0.5 V, respectively. Temperature affects fractionation in a counter-intuitive manner, with fractionation increasing with increasing temperature (at η = -1.0 V: Δ56Fe ~ -1.25 ‰ at 0°C and -1.62 ‰ at 35°C). The results can be explained in terms of two

  20. Ontogenetic Change in the Auditory Conditioned Stimulus Pathway for Eyeblink Conditioning

    ERIC Educational Resources Information Center

    Freeman, John H.; Campolattaro, Matthew M.

    2008-01-01

    Two experiments examined the neural mechanisms underlying the ontogenetic emergence of auditory eyeblink conditioning. Previous studies found that the medial auditory thalamus is necessary for eyeblink conditioning with an auditory conditioned stimulus (CS) in adult rats. In experiment 1, stimulation of the medial auditory thalamus was used as a…

  1. Assessing the Vulnerability of Water Supply to Changing Streamflow Conditions

    NASA Astrophysics Data System (ADS)

    Nazemi, Alireza (Ali); Wheater, Howard S.

    2014-08-01

    Natural streamflows are major water supplies globally and are sensitive to climate change. This has serious implications for water resource management: While changes in climate perturb water availability, human activities are developed around certain streamflow characteristics, such as flow seasonality and volume. Therefore, any shifts in streamflow regime can greatly affect human livelihoods.

  2. A Changing Federalism: The Condition of the States.

    ERIC Educational Resources Information Center

    Adams, E. Kathleen

    A majority of the 50 states are currently experiencing budget problems as a result of recent changes in the fiscal roles of federal, state, and local governments. Four major factors are responsible for the recent deterioration of state budgets: (1) reductions in federal aid to states and localities, (2) changes in the federal corporate and…

  3. Redox Fluctuation Structures Microbial Communities in a Wet Tropical Soil

    PubMed Central

    Pett-Ridge, J.; Firestone, M. K.

    2005-01-01

    Frequent high-amplitude redox fluctuation may be a strong selective force on the phylogenetic and physiological composition of soil bacterial communities and may promote metabolic plasticity or redox tolerance mechanisms. To determine effects of fluctuating oxygen regimens, we incubated tropical soils under four treatments: aerobic, anaerobic, 12-h oxic/anoxic fluctuation, and 4-day oxic/anoxic fluctuation. Changes in soil bacterial community structure and diversity were monitored with terminal restriction fragment length polymorphism (T-RFLP) fingerprints. These profiles were correlated with gross N cycling rates, and a Web-based phylogenetic assignment tool was used to infer putative community composition from multiple fragment patterns. T-RFLP ordinations indicated that bacterial communities from 4-day oxic/anoxic incubations were most similar to field communities, whereas those incubated under consistently aerobic or anaerobic regimens developed distinctly different molecular profiles. Terminal fragments found in field soils persisted either in 4-day fluctuation/aerobic conditions or in anaerobic/12-h treatments but rarely in both. Only 3 of 179 total fragments were ubiquitous in all soils. Soil bacterial communities inferred from in silico phylogenetic assignment appeared to be dominated by Actinobacteria (especially Micrococcus and Streptomycetes), “Bacilli,” “Clostridia,” and Burkholderia and lost significant diversity under consistently or frequently anoxic incubations. Community patterns correlated well with redox-sensitive processes such as nitrification, dissimilatory nitrate reduction to ammonium (DNRA), and denitrification but did not predict patterns of more general functions such as N mineralization and consumption. The results suggest that this soil's indigenous bacteria are highly adapted to fluctuating redox regimens and generally possess physiological tolerance mechanisms which allow them to withstand unfavorable redox periods. PMID

  4. Redox conditions in the Late Cretaceous Chalk Sea: the possible use of cerium anomalies as palaeoredox indicators in the Cenomanian and Turonian Chalk of England

    NASA Astrophysics Data System (ADS)

    Jeans, Christopher V.; Wray, David S.; Williams, C. Terry

    2015-09-01

    The cerium anomalies preserved in the Chalk have been investigated as possible palaeoredox indicators of the Late Cretaceous Sea and its sediment. This has been based upon over a hundred new rare earth element analyses of selected samples and grain size fractions from the Chalk. Particular attention has been given to the methodology of differentiating between the cerium anomalies preserved in the bioclastic calcite and those in carbonate-fluorapatite preserved in the acetic acid insoluble residues of chalks. Variations in the cerium anomaly of different particle size fractions of uncemented chalks suggest that fractionation of rare earth elements between the Chalk's seawater and the various organisms that contributed skeletal material to the bioclastic calcite of the Chalk may have occurred. Post-depositional processes of calcite cementation and late diagenetic sulphidisation have had no apparent effect on the cerium anomaly of the acetic acid insoluble residues. The cerium anomalies associated with the acetic acid insoluble residues from (1) an alternating sequence of chalks and marls from Ballard Cliff (Dorset, UK) typical of Milankovitch cyclicity show a marked diagenetic pattern, whereas those from (2) non-volcanic and volcanic marls display a pattern that is best explained by the variations in the availability of phosphorus and the timing of argillisation of volcanic glass during diagenesis. The general conclusion is drawn that the cerium anomalies preserved in the Chalk can provide an insight into the changing palaeoredox conditions in the Late Cretaceous Sea as well as in the pore fluids of its sediments.

  5. Changing hydrological conditions in the Po basin under global warming.

    PubMed

    Coppola, Erika; Verdecchia, Marco; Giorgi, Filippo; Colaiuda, Valentina; Tomassetti, Barbara; Lombardi, Annalina

    2014-09-15

    The Po River is a crucial resource for the Italian economy, since 40% of the gross domestic product comes from this area. It is thus crucial to quantify the impact of climate change on this water resource in order to plan for future water use. In this paper a mini ensemble of 8 hydrological simulations is completed from 1960 to 2050 under the A1B emission scenario, by using the output of two regional climate models as input (REMO and RegCM) at two different resolutions (25 km-10 km and 25 km-3 km). The river discharge at the outlet point of the basin shows a change in the spring peak of the annual cycle, with a one month shift from May to April. This shift is entirely due to the change in snowmelt timing which drives most of the discharge during this period. Two other important changes are an increase of discharge in the wintertime and a decrease in the fall from September to November. The uncertainty associated with the winter change is larger compared to that in the fall. The spring shift and the fall decrease of discharge imply an extension of the hydrological dry season and thus an increase in water stress over the basin. The spatial distributions of the discharge changes are in agreement with what is observed at the outlet point and the uncertainty associated with these changes is proportional to the amplitude of the signal. The analysis of the changes in the anomaly distribution of discharge shows that both the increases and decreases in seasonal discharge are tied to the changes in the tails of the distribution, i.e. to the increase or decrease of extreme events. PMID:24656403

  6. Mycobacterium tuberculosis WhiB3 Responds to Vacuolar pH-induced Changes in Mycothiol Redox Potential to Modulate Phagosomal Maturation and Virulence*

    PubMed Central

    Mehta, Mansi; Rajmani, Raju S.; Singh, Amit

    2016-01-01

    The ability of Mycobacterium tuberculosis to resist intraphagosomal stresses, such as oxygen radicals and low pH, is critical for its persistence. Here, we show that a cytoplasmic redox sensor, WhiB3, and the major M. tuberculosis thiol, mycothiol (MSH), are required to resist acidic stress during infection. WhiB3 regulates the expression of genes involved in lipid anabolism, secretion, and redox metabolism, in response to acidic pH. Furthermore, inactivation of the MSH pathway subverted the expression of whiB3 along with other pH-specific genes in M. tuberculosis. Using a genetic biosensor of mycothiol redox potential (EMSH), we demonstrated that a modest decrease in phagosomal pH is sufficient to generate redox heterogeneity in EMSH of the M. tuberculosis population in a WhiB3-dependent manner. Data indicate that M. tuberculosis needs low pH as a signal to alter cytoplasmic EMSH, which activates WhiB3-mediated gene expression and acid resistance. Importantly, WhiB3 regulates intraphagosomal pH by down-regulating the expression of innate immune genes and blocking phagosomal maturation. We show that this block in phagosomal maturation is in part due to WhiB3-dependent production of polyketide lipids. Consistent with these observations, MtbΔwhiB3 displayed intramacrophage survival defect, which can be rescued bypharmacological inhibition of phagosomal acidification. Last, MtbΔwhiB3 displayed marked attenuation in the lungs of guinea pigs. Altogether, our study revealed an intimate link between vacuolar acidification, redox physiology, and virulence in M. tuberculosis and discovered WhiB3 as crucial mediator of phagosomal maturation arrest and acid resistance in M. tuberculosis. PMID:26637353

  7. Mycobacterium tuberculosis WhiB3 Responds to Vacuolar pH-induced Changes in Mycothiol Redox Potential to Modulate Phagosomal Maturation and Virulence.

    PubMed

    Mehta, Mansi; Rajmani, Raju S; Singh, Amit

    2016-02-01

    The ability of Mycobacterium tuberculosis to resist intraphagosomal stresses, such as oxygen radicals and low pH, is critical for its persistence. Here, we show that a cytoplasmic redox sensor, WhiB3, and the major M. tuberculosis thiol, mycothiol (MSH), are required to resist acidic stress during infection. WhiB3 regulates the expression of genes involved in lipid anabolism, secretion, and redox metabolism, in response to acidic pH. Furthermore, inactivation of the MSH pathway subverted the expression of whiB3 along with other pH-specific genes in M. tuberculosis. Using a genetic biosensor of mycothiol redox potential (EMSH), we demonstrated that a modest decrease in phagosomal pH is sufficient to generate redox heterogeneity in EMSH of the M. tuberculosis population in a WhiB3-dependent manner. Data indicate that M. tuberculosis needs low pH as a signal to alter cytoplasmic EMSH, which activates WhiB3-mediated gene expression and acid resistance. Importantly, WhiB3 regulates intraphagosomal pH by down-regulating the expression of innate immune genes and blocking phagosomal maturation. We show that this block in phagosomal maturation is in part due to WhiB3-dependent production of polyketide lipids. Consistent with these observations, MtbΔwhiB3 displayed intramacrophage survival defect, which can be rescued bypharmacological inhibition of phagosomal acidification. Last, MtbΔwhiB3 displayed marked attenuation in the lungs of guinea pigs. Altogether, our study revealed an intimate link between vacuolar acidification, redox physiology, and virulence in M. tuberculosis and discovered WhiB3 as crucial mediator of phagosomal maturation arrest and acid resistance in M. tuberculosis. PMID:26637353

  8. Changes of the corrosion potential of iron in stagnation and flow conditions and their relationship with metal release.

    PubMed

    Fabbricino, Massimiliano; Korshin, Gregory V

    2014-10-01

    This study examined the behavior of corrosion potential (Ecorr) of iron exposed to drinking water during episodes of stagnation and flow. These measurements showed that during stagnation episodes, Ecorr values decrease prominently and consistently. This decrease is initially rapid but it becomes slower as the stagnation time increases. During flow episodes, the Ecorr values increase and reach a quasi-steady state. Experiments with varying concentrations of dissolved oxygen showed that the decrease of Ecorr values characteristic for stagnation is likely to be associated with the consumption of dissolved oxygen by the exposed metal. The corrosion potential of iron and its changes during stagnation were sensitive to the concentrations of sulfate and chloride ions. Measurements of iron release showed that both the absolute values of Ecorr measured prior to or after stagnation episodes were well correlated with the logarithms of concentrations of total iron. The slope of this dependence showed that the observed correlations between Ecorr values and Fe concentrations corresponded to the coupling between the oxidant consumption and changes of Fe redox status. These results demonstrate that in situ Ecorr measurements can be a sensitive method with which to ascertain effects of hydrodynamic conditions and short-term variations of water chemistry on metal release and corrosion in drinking water. This approach is valuable practically because Ecorr measurements are precise, can be carried out in situ with any desired time resolution, do not affect the state of exposed surface in any extent and can be carried out with readily available equipment. PMID:24950460

  9. Redox Regulation of Endothelial Cell Fate

    PubMed Central

    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

  10. Detailed Vertical and Lateral Delineation of Redox Zones in Contaminant Plumes Using Redox-Sensitive Tapes (RST)

    NASA Astrophysics Data System (ADS)

    Blum, P.; Oeste, F. D.; Melzer, R.; Martus, P.

    2006-12-01

    Innovative redox-sensitive tapes (RST) have been developed for a detailed vertical and lateral delineation of redox zones in contaminated aquifers. The RST have the potential to become an integral part of a data acquisition strategy for monitored natural attenuation (MNA). The tape material, consists of a 2 cm wide synthetic textile coated with reactive manganese dioxide minerals. The RST are submerged into existing monitoring wells for approximately one month. This time period is sufficient to allow for a reaction of the mineral coating with groundwater. The RST are aimed at investigating four different redox-zones in contaminated aquifers: Mn(II)-oxidizing, Mn(IV)-reducing, Fe(III)-reducing and sulfate-reducing. Two RST case studies are presented. The RST investigations on a coal tar contaminated site allowed for a precise lateral and vertical delineation of the contaminant plume using the existing monitoring well network. The RST investigations on a BTEX contaminated site yielded a good correlation of RST data with hydrochemical data at the wells sampled. In the majority of plume wells located 50 m downstream of the source area and beyond, Mn(IV)-reducing environment appeared to be prevailing. Comparing the RST data with hydrochemical data indicated evidence for the transport of transformation products with groundwater flow. The repeated application of the RST facilitated an assessment of the plume dynamics. No significant seasonal variation with respect to the redox zone distribution was observed within the contaminant plume. However, the assessment of the changes in redox conditions over a time period of 2.5 years showed that the iron-reducing zone is shrinking and the sulfate-reducing zone disappeared completely indicating that the contaminant plume might decrease in the near future. Thus, the application of the RST facilitated an assessment of the plume dynamics on a centimeter-scale without the necessity of pumping and treating contaminated groundwater.

  11. Glutathione and redox signaling in substance abuse

    PubMed Central

    Uys, Joachim D.; Mulholland, Patrick J.; Townsend, Danyelle M.

    2015-01-01

    Throughout the last couple decades, the cause and consequences of substance abuse has expanded to identify the underlying neurobiological signaling mechanisms associated with addictive behavior. Chronic use of drugs, such as cocaine, methamphetamine and alcohol leads to the formation of oxidative or nitrosative stress (ROS/RNS) and changes in glutathione and redox homeostasis. Of importance, redox-sensitive post-translational modifications on cysteine residues, such as S-glutathionylation and S-nitrosylation could impact on the structure and function of addiction related signaling proteins. In this commentary, we evaluate the role of glutathione and redox signaling in cocaine-, methamphetamine- and alcohol addiction and conclude by discussing the possibility of targeting redox pathways for the therapeutic intervention of these substance abuse disorders. PMID:25027386

  12. Glutathione and redox signaling in substance abuse.

    PubMed

    Uys, Joachim D; Mulholland, Patrick J; Townsend, Danyelle M

    2014-07-01

    Throughout the last couple decades, the cause and consequences of substance abuse has expanded to identify the underlying neurobiological signaling mechanisms associated with addictive behavior. Chronic use of drugs, such as cocaine, methamphetamine and alcohol leads to the formation of oxidative or nitrosative stress (ROS/RNS) and changes in glutathione and redox homeostasis. Of importance, redox-sensitive post-translational modifications on cysteine residues, such as S-glutathionylation and S-nitrosylation could impact on the structure and function of addiction related signaling proteins. In this commentary, we evaluate the role of glutathione and redox signaling in cocaine-, methamphetamine- and alcohol addiction and conclude by discussing the possibility of targeting redox pathways for the therapeutic intervention of these substance abuse disorders. PMID:25027386

  13. Marine water quality under climate change conditions/scenarios

    NASA Astrophysics Data System (ADS)

    Rizzi, Jonathan; Torresan, Silvia; Critto, Andrea; Zabeo, Alex; Brigolin, Daniele; Carniel, Sandro; Pastres, Roberto; Marcomini, Antonio

    2016-04-01

    The increase of sea temperature and the changes in marine currents are generating impacts on coastal waters such as changes in water biogeochemical and physical parameters (e.g. primary production, pH, salinity) leading to progressive degradation of the marine environment. With the main aim of analysing the potential impacts of climate change on coastal water quality, a Regional Risk Assessment (RRA) methodology was developed and applied to coastal marine waters of the North Adriatic (i.e. coastal water bodies of the Veneto and Friuli Venezia Giulia regions, Italy). RRA integrates the outputs of regional models providing information on macronutrients (i.e. dissolved inorganic nitrogen e reactive phosphorus), dissolved oxygen, pH, salinity and temperature, etc., under future climate change scenarios with site-specific environmental and socio-economic indicators (e.g. biotic index, presence and extension of seagrasses, presence of aquaculture). The presented approach uses Geographic Information Systems to manage, analyse, and visualize data and employs Multi-Criteria Decision Analysis for the integration of stakeholders preferences and experts judgments into the evaluation process. RRA outputs are hazard, exposure, vulnerability, risk and damage maps useful for the identification and prioritization of hot-spot areas and vulnerable targets in the considered region. Therefore, the main aim of this contribution is to apply the RRA methodology to integrate, visualize, and rank according to spatial distribution, physical and chemical data concerning the coastal waters of the North Adriatic Sea in order to predict possible changes of the actual water quality.

  14. Modelling Visual Change Detection and Identification under Free Viewing Conditions.

    PubMed

    McAnally, Ken; Martin, Russell

    2016-01-01

    We examined whether the abilities of observers to perform an analogue of a real-world monitoring task involving detection and identification of changes to items in a visual display could be explained better by models based on signal detection theory (SDT) or high threshold theory (HTT). Our study differed from most previous studies in that observers were allowed to inspect the initial display for 3s, simulating the long inspection times typical of natural viewing, and their eye movements were not constrained. For the majority of observers, combined change detection and identification performance was best modelled by a SDT-based process that assumed that memory resources were distributed across all eight items in our displays. Some observers required a parameter to allow for sometimes making random guesses at the identities of changes they had missed. However, the performance of a small proportion of observers was best explained by a HTT-based model that allowed for lapses of attention. PMID:26882348

  15. Systemic conditions in children associated with pigmentary changes.

    PubMed

    Treadwell, Patricia A

    2015-01-01

    Systemic conditions may have pigmentary associations. Prompt recognition of these associations allows the practitioner to initiate the appropriate workup and therapy when indicated. This contribution highlights some of the clinical features of neurofibromatosis 1, LEOPARD syndrome, acanthosis nigricans, hypomelanosis of Ito, incontinentia pigmenti, CHILD syndrome, and piebaldism to assist the dermatologist in making the proper diagnosis. PMID:25889139

  16. State Financing of Higher Education under Changing Conditions.

    ERIC Educational Resources Information Center

    Lyddon, Jan W.

    The literature on funding formulas for higher education is reviewed, and the historical roots of state higher education funding relationships is traced, including three 20th century budget reform movements that were the antecedents of formulas. Attention is directed to conditions that will affect funding of higher education and formula responses…

  17. Changes in osteoblastic activity due to simulated weightless conditions

    NASA Technical Reports Server (NTRS)

    Doty, S. B.; Morey-Holton, E. R.

    1982-01-01

    Using histochemistry and electron microscopy, the reduced bone formation which occurs in the hypokinetic, orthostatically treated adult rat has been studied. The two major changes noted occurred in the osteoblast population, indicated by a reduced alkaline phosphatase activity and reduced numbers of gap junctions between cells. These results were most noticeable in the periosteum and endosteum of the long bones. Changes in osteoblasts lining the surface of trabecular bone were not as evident. These results indicate that the cells lining the surfaces of weight bearing bones are most affected by hypokinesia and this reduction in cellular activity may be a mechanically induced effect.

  18. MICROSCALE METABOLIC, REDOX AND ABIOTIC REACTIONS IN HANFORD 300 AREA SUBSURFACE SEDIMENTS

    SciTech Connect

    Beyenal, Haluk; McLEan, Jeff; Majors, Paul; Fredrickson, Jim

    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.

  19. Pettaquamscutt Cove Salt Marsh: Environmental Conditions and Historical Ecological Change

    EPA Science Inventory

    Using historic air photos and U.S. Coast Survey maps, historic vegetation changes were identified. Using surveys of vegetation and elevation, we measure elevation of Narrow River salt marshes, and compare it with other salt marshes in Rhode Island and neighboring states. Water ...

  20. Living Conditions, Ecology and Social Changes in the Indian Context.

    ERIC Educational Resources Information Center

    Rao, D. Subba

    1984-01-01

    Major problems faced in India's development are discussed, including rapid industrialization and urbanization and needs for ecological protection as well as food and industry, literacy, and rapid social change in a multilingual and multireligious society. The roles of higher education and international cooperation are also examined. (MSE)

  1. Effect of culture conditions on morphological changes of Helicobacter pylori.

    PubMed

    Tominaga, K; Hamasaki, N; Watanabe, T; Uchida, T; Fujiwara, Y; Takaishi, O; Higuchi, K; Arakawa, T; Ishii, E; Kobayashi, K; Yano, I; Kuroki, T

    1999-01-01

    The morphological conversion of Helicobacter pylori from the spiral form to the coccoid form may be the expression of a transitory adaptation to an unsuitable environment. The mechanism(s) of this conversion are not clear. In this study, we examined whether the morphological conversion of H. pylori is affected by various culture conditions, such as oxygen concentration, pH, temperature, or the presence of beta-cyclodextrin. H. pylori (NTCC11916) was cultured on Brucella agar, followed by culture in Brucella broth containing 1% agar under several conditions. Morphological conversion of individual H. pylori on the agar plate was investigated with time after incubation under phase contrast microscopy. When H. pylori was inoculated in Brucella broth containing beta-cyclodextrin, the spiral form of the organism was observed even after 6 days of incubation under standard culture conditions: 37 degrees C, pH 7, and microaerobic atmosphere (5% O2/10% CO2/85% N2) (control). The morphological conversion of H. pylori was completed on day 3 in an aerobic atmosphere (20% O2 supply) and on day 2 in an undermicroaerobic atmosphere (<0.1% O2). Its complete morphological conversion was observed at pH 8 on day 5 and at pH 4 on day 6. All of the H. pylori (100%) incubated at 20 degrees or 42 degrees C had converted from the bacillary to the coccoid form on day 4. Conditioned medium without beta-cyclodextrin caused complete conversion on day 5. These results suggest that oxygen concentration, pH, temperature, and beta-cyclodextrin may be related to the H. pylori morphological conversion from the bacillary to the coccoid form. PMID:10616762

  2. Overuse tendon conditions: time to change a confusing terminology.

    PubMed

    Maffulli, N; Khan, K M; Puddu, G

    1998-01-01

    In overuse clinical conditions in and around tendons, frank inflammation is infrequent, and is associated mostly with tendon ruptures. Tendinosis implies tendon degeneration without clinical or histological signs of intratendinous inflammation, and is not necessarily symptomatic. Patients undergoing an operation for Achilles tendinopathy show similar areas of degeneration. When the term tendinitis is used in a clinical context, it does not refer to a specific histopathological entity. However, tendinitis is commonly used for conditions that are truly tendinoses, and this leads athletes and coaches to underestimate the proven chronicity of the condition. Paratenonitis is characterized by acute edema and hypermia of the paratenon, with infiltration of inflammatory cells, possibly with production of a fibrinous exudate that fills the tendon sheath, causing the typical crepitus that can be felt on clinical examination. The term partial tear of a tendon should describe a macroscopically evident subcutaneous partial tear of a tendon, an uncommon acute lesion. Most articles describing the surgical treatment of 'partial tears' of a given tendon in reality deal with degenerative tendinopathies. The combination of pain, swelling, and impaired performance should be labeled tendinopathy. According to the tissues affected, the terms tendinopathy, paratendinopathy, or pantendinopathy should be used. PMID:9848596

  3. Compromised redox homeostasis, altered nitroso–redox balance, and therapeutic possibilities in atrial fibrillation

    PubMed Central

    Simon, Jillian N.; Ziberna, Klemen; Casadei, Barbara

    2016-01-01

    Although the initiation, development, and maintenance of atrial fibrillation (AF) have been linked to alterations in myocyte redox state, the field lacks a complete understanding of the impact these changes may have on cellular signalling, atrial electrophysiology, and disease progression. Recent studies demonstrate spatiotemporal changes in reactive oxygen species production shortly after the induction of AF in animal models with an uncoupling of nitric oxide synthase activity ensuing in the presence of long-standing persistent AF, ultimately leading to a major shift in nitroso–redox balance. However, it remains unclear which radical or non-radical species are primarily involved in the underlying mechanisms of AF or which proteins are targeted for redox modification. In most instances, only free radical oxygen species have been assessed; yet evidence from the redox signalling field suggests that non-radical species are more likely to regulate cellular processes. A wider appreciation for the distinction of these species and how both species may be involved in the development and maintenance of AF could impact treatment strategies. In this review, we summarize how redox second-messenger systems are regulated and discuss the recent evidence for alterations in redox regulation in the atrial myocardium in the presence of AF, while identifying some critical missing links. We also examine studies looking at antioxidants for the prevention and treatment of AF and propose alternative redox targets that may serve as superior therapeutic options for the treatment of AF. PMID:26786158

  4. Redox Indicator Mice Stably Expressing Genetically Encoded Neuronal roGFP: Versatile Tools to Decipher Subcellular Redox Dynamics in Neuropathophysiology

    PubMed Central

    Wagener, Kerstin C.; Kolbrink, Benedikt; Dietrich, Katharina; Kizina, Kathrin M.; Terwitte, Lukas S.; Kempkes, Belinda; Bao, Guobin

    2016-01-01

    Abstract Aims: Reactive oxygen species (ROS) and downstream redox alterations not only mediate physiological signaling but also neuropathology. For long, ROS/redox imaging was hampered by a lack of reliable probes. Genetically encoded redox sensors overcame this gap and revolutionized (sub)cellular redox imaging. Yet, the successful delivery of sensor-coding DNA, which demands transfection/transduction of cultured preparations or stereotaxic microinjections of each subject, remains challenging. By generating transgenic mice, we aimed to overcome limiting cultured preparations, circumvent surgical interventions, and to extend effectively redox imaging to complex and adult preparations. Results: Our redox indicator mice widely express Thy1-driven roGFP1 (reduction–oxidation-sensitive green fluorescent protein 1) in neuronal cytosol or mitochondria. Negative phenotypic effects of roGFP1 were excluded and its proper targeting and functionality confirmed. Redox mapping by ratiometric wide-field imaging reveals most oxidizing conditions in CA3 neurons. Furthermore, mitochondria are more oxidized than cytosol. Cytosolic and mitochondrial roGFP1s reliably report cell endogenous redox dynamics upon metabolic challenge or stimulation. Fluorescence lifetime imaging yields stable, but marginal, response ranges. We therefore developed automated excitation ratiometric 2-photon imaging. It offers superior sensitivity, spatial resolution, and response dynamics. Innovation and Conclusion: Redox indicator mice enable quantitative analyses of subcellular redox dynamics in a multitude of preparations and at all postnatal stages. This will uncover cell- and compartment-specific cerebral redox signals and their defined alterations during development, maturation, and aging. Cross-breeding with other disease models will reveal molecular details on compartmental redox homeostasis in neuropathology. Combined with ratiometric 2-photon imaging, this will foster our mechanistic understanding

  5. Dynamic Redox Regulation of IL-4 Signaling

    PubMed Central

    Dwivedi, Gaurav; Gran, Margaret A.; Bagchi, Pritha; Kemp, Melissa L.

    2015-01-01

    Quantifying the magnitude and dynamics of protein oxidation during cell signaling is technically challenging. Computational modeling provides tractable, quantitative methods to test hypotheses of redox mechanisms that may be simultaneously operative during signal transduction. The interleukin-4 (IL-4) pathway, which has previously been reported to induce reactive oxygen species and oxidation of PTP1B, may be controlled by several other putative mechanisms of redox regulation; widespread proteomic thiol oxidation observed via 2D redox differential gel electrophoresis upon IL-4 treatment suggests more than one redox-sensitive protein implicated in this pathway. Through computational modeling and a model selection strategy that relied on characteristic STAT6 phosphorylation dynamics of IL-4 signaling, we identified reversible protein tyrosine phosphatase (PTP) oxidation as the primary redox regulatory mechanism in the pathway. A systems-level model of IL-4 signaling was developed that integrates synchronous pan-PTP oxidation with ROS-independent mechanisms. The model quantitatively predicts the dynamics of IL-4 signaling over a broad range of new redox conditions, offers novel hypotheses about regulation of JAK/STAT signaling, and provides a framework for interrogating putative mechanisms involving receptor-initiated oxidation. PMID:26562652

  6. Dynamic Redox Regulation of IL-4 Signaling.

    PubMed

    Dwivedi, Gaurav; Gran, Margaret A; Bagchi, Pritha; Kemp, Melissa L

    2015-11-01

    Quantifying the magnitude and dynamics of protein oxidation during cell signaling is technically challenging. Computational modeling provides tractable, quantitative methods to test hypotheses of redox mechanisms that may be simultaneously operative during signal transduction. The interleukin-4 (IL-4) pathway, which has previously been reported to induce reactive oxygen species and oxidation of PTP1B, may be controlled by several other putative mechanisms of redox regulation; widespread proteomic thiol oxidation observed via 2D redox differential gel electrophoresis upon IL-4 treatment suggests more than one redox-sensitive protein implicated in this pathway. Through computational modeling and a model selection strategy that relied on characteristic STAT6 phosphorylation dynamics of IL-4 signaling, we identified reversible protein tyrosine phosphatase (PTP) oxidation as the primary redox regulatory mechanism in the pathway. A systems-level model of IL-4 signaling was developed that integrates synchronous pan-PTP oxidation with ROS-independent mechanisms. The model quantitatively predicts the dynamics of IL-4 signaling over a broad range of new redox conditions, offers novel hypotheses about regulation of JAK/STAT signaling, and provides a framework for interrogating putative mechanisms involving receptor-initiated oxidation. PMID:26562652

  7. Regional feedbacks under changing climate and land-use conditions

    NASA Astrophysics Data System (ADS)

    Batlle Bayer, L.; van den Hurk, B. J. J. M.; Strengers, B. J.; van Minnen, J. G.

    2012-04-01

    Ecosystem responses to a changing climate and human-induced climate forcings (e.g. deforestation) might amplify (positive feedback) or dampen (negative feedback) the initial climate response. Feedbacks may include the biogeochemical (e.g. carbon cycle) and biogeophysical feedbacks (e.g. albedo and hydrological cycle). Here, we first review the most important feedbacks and put them into the context of a conceptual framework, including the major processes and interactions between terrestrial ecosystems and climate. We explore potential regional feedbacks in four hot spots with pronounced potential changes in land-use/management and local climate: sub-Saharan Africa (SSA), Europe, the Amazon Basin and South and Southeast Asia. For each region, the relevant human-induced climate forcings and feedbacks were identified based on published literature. When evapotranspiration is limited by a soil water deficit, heat waves in Europe are amplified (positive soil moisture-temperature feedback). Drought events in the Amazon lead to further rainfall reduction when water recycling processes are affected (positive soil moisture-precipitation feedback). In SSA, the adoption of irrigation in the commonly rainfed systems can modulate the negative soil moisture-temperature feedback. In contrast, future water shortage in South and Southeast Asia can turn the negative soil moisture-temperature feedback into a positive one. Further research including advanced modeling strategies is needed to isolate the dominant processes affecting the strength and sign of the feedbacks. In addition, the socio-economic dimension needs to be considered in the ecosystems-climate system to include the essential role of human decisions on land-use and land-cover change (LULCC). In this context, enhanced integration between Earth System (ES) and Integrated Assessment (IA) modeling communities is strongly recommended.

  8. Redox proteomics of tomato in response to Pseudomonas syringae infection

    PubMed Central

    Balmant, Kelly Mayrink; Parker, Jennifer; Yoo, Mi-Jeong; Zhu, Ning; Dufresne, Craig; Chen, Sixue

    2015-01-01

    Unlike mammals with adaptive immunity, plants rely on their innate immunity based on pattern-triggered immunity (PTI) and effector-triggered immunity (ETI) for pathogen defense. Reactive oxygen species, known to play crucial roles in PTI and ETI, can perturb cellular redox homeostasis and lead to changes of redox-sensitive proteins through modification of cysteine sulfhydryl groups. Although redox regulation of protein functions has emerged as an important mechanism in several biological processes, little is known about redox proteins and how they function in PTI and ETI. In this study, cysTMT proteomics technology was used to identify similarities and differences of protein redox modifications in tomato resistant (PtoR) and susceptible (prf3) genotypes in response to Pseudomonas syringae pv tomato (Pst) infection. In addition, the results of the redox changes were compared and corrected with the protein level changes. A total of 90 potential redox-regulated proteins were identified with functions in carbohydrate and energy metabolism, biosynthesis of cysteine, sucrose and brassinosteroid, cell wall biogenesis, polysaccharide/starch biosynthesis, cuticle development, lipid metabolism, proteolysis, tricarboxylic acid cycle, protein targeting to vacuole, and oxidation–reduction. This inventory of previously unknown protein redox switches in tomato pathogen defense lays a foundation for future research toward understanding the biological significance of protein redox modifications in plant defense responses. PMID:26504582

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

    PubMed

    Pan, Feng; Wang, Qing

    2015-01-01

    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. PMID:26593894

  10. Effects of Changing Atmospheric Conditions on Wind Turbine Performance (Poster)

    SciTech Connect

    Clifton, A.

    2012-12-01

    Multi-megawatt, utility-scale wind turbines operate in turbulent and dynamic winds that impact turbine performance in ways that are gradually becoming better understood. This poster presents a study made using a turbulent flow field simulator (TurbSim) and a Turbine aeroelastic simulator (FAST) of the response of a generic 1.5 MW wind turbine to changing inflow. The turbine power output is found to be most sensitive to wind speed and turbulence intensity, but the relationship depends on the wind speed with respect to the turbine's rated wind speed. Shear is found to be poorly correlated to power. A machine learning method called 'regression trees' is used to create a simple model of turbine performance that could be used as part of the wind resource assessment process. This study has used simple flow fields and should be extended to more complex flows, and validated with field observations.

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

    NASA Astrophysics Data System (ADS)

    McNicol, Gavin; Silver, Whendee L.

    2014-04-01

    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 required are soil conditions where the rate of oxygen (O2) consumption exceeds the rate of atmospheric replenishment. We investigated the effects of soil anaerobiosis, generated with and without flooding, on greenhouse gas emissions and redox-sensitive biogeochemistry. We collected a Histosol from a regularly flooded peatland pasture and an Ultisol from a humid tropical forest where soil experiences frequent low redox events. We used a factorial design of flooding and anaerobic dinitrogen (N2) headspace treatments applied to replicate soil microcosms. An N2 headspace suppressed carbon dioxide (CO2) emissions by 50% in both soils. Flooding, however, led to greater anaerobic CO2 emissions from the Ultisol. Methane emissions under N2 were also significantly greater with flooding in the Ultisol. Flooding led to very low N2O emissions after an initial pulse in the Histosol, while higher emission rates were maintained in control and N2 treatments. We conclude that soil greenhouse gas emissions are sensitive to the redox effects of O2 depletion as a driver of anaerobiosis and that flooding can have additional effects independent of O2 depletion. We emphasize that changes to the soil diffusive environment under flooding impacts transport of all gases, not only O2, and changes in dissolved solute availability under flooding may lead to increased mineralization of C.

  12. Biological Redox Cycling Of Iron In Nontronite And Its Potential Application In Nitrate Removal

    SciTech Connect

    Zhao, Linduo; Dong, Hailiang; Kukkadapu, Ravi K.; Zeng, Qiang; Edelmann, Richard E.; Pentrak, Martin; Agrawal, Abinash

    2015-05-05

    Redox cycling of structural Fe in phyllosilicates provides a potential method to remediate nitrate contamination in natural environment. Past research has only studied chemical redox cycles or a single biologically mediated redox cycle of Fe in phyllosilicates. The objective of this research was to study three microbially driven redox cycles of Fe in one phyllosilicate, nontronite (NAu-2). During the reduction phase structural Fe(III) in NAu-2 served as electron acceptor, lactate as electron donor, AQDS as electron shuttle, and dissimilatory Fe(III)-reducing bacteria Shewanella putrefaciens CN32 as mediator in bicarbonate-buffered and PIPES-buffered media. During the oxidation phase, biogenic Fe(II) served an electron donor, nitrate as electron acceptor, and nitrate-dependent Fe(II)-oxidizing bacteria Pseudogulbenkiania sp. strain 2002 as mediator in the same media. For all three cycles, structural Fe in NAu-2 was able to reversibly undergo 3 redox cycles without significant reductive or oxidative dissolution. X-ray diffraction and scanning and transmission electron microscopy revealed that NAu-2 was the dominant residual mineral throughout the 3 redox cycles with some dissolution textures but no significant secondary mineralization. Mössbauer spectroscopy revealed that Fe(II) in bio-reduced samples likely occurred in two distinct environments, at edges and the interior of the NAu-2 structure. Nitrate was completely reduced to nitrogen gas under both buffer conditions and this extent and rate did not change with Fe redox cycles. Mössbauer spectroscopy further revealed that nitrate reduction was coupled to predominant/preferred oxidation of edge Fe(II). These results suggest that structural Fe in phyllosilicates may represent a renewable source to continuously remove nitrate in natural environments.

  13. Collaborative Research for Water Resource Management under Climate Change Conditions

    NASA Astrophysics Data System (ADS)

    Brundiers, K.; Garfin, G. M.; Gober, P.; Basile, G.; Bark, R. H.

    2010-12-01

    We present an ongoing project to co-produce science and policy called Collaborative Planning for Climate Change: An Integrated Approach to Water-Planning, Climate Downscaling, and Robust Decision-Making. The project responds to motivations related to dealing with sustainability challenges in research and practice: (a) state and municipal water managers seek research that addresses their planning needs; (b) the scientific literature and funding agencies call for more meaningful engagement between science and policy communities, in ways that address user needs, while advancing basic research; and (c) empirical research contributes to methods for the design and implementation of collaborative projects. To understand how climate change might impact water resources and management in the Southwest US, our project convenes local, state, and federal water management practitioners with climate-, hydrology-, policy-, and decision scientists. Three areas of research inform this collaboration: (a) the role of paleo-hydrology in water resources scenario construction; (b) the types of uncertainties that impact decision-making beyond climate and modeling uncertainty; and (c) basin-scale statistical and dynamical downscaling of climate models to generate hydrologic projections for regional water resources planning. The project engages all participants in the research process, from research design to workshops that build capacity for understanding data generation and sources of uncertainty to the discussion of water management decision contexts. A team of “science-practice translators” facilitates the collaboration between academic and professional communities. In this presentation we contextualize the challenges and opportunities of use-inspired science-policy research collaborations by contrasting the initial project design with the process of implementation. We draw from two sources to derive lessons learned: literature on collaborative research, and evaluations provided by

  14. Ultrastructural morphologic changes in mycobacterial biofilm in different extreme condition.

    PubMed

    Kumar, Virendra; Sachan, Tarun Kumar; Sharma, Pragya; Rawat, Krishna Dutta

    2015-02-01

    The aim of this study was to investigate the morphologic and ultrastructural features of biofilms of slow and fast-growing mycobacteria in different stress conditions, presence and absence of oleic acid albumin dextrose catalase (OADC) enrichment and at different temperatures: 30, 37 and 42 °C. Four hundred mycobacterial isolates were taken. The biomass of each biofilm was quantified using a modified microtiter plate assay method. Isolates were divided into those that formed fully established biofilms, moderately attached biofilms and weakly adherent biofilms by comparison with a known biofilm-forming strain. The large quantity of biofilm was produced by Mycobacterium smegmatis at temperature 37 and 42 °C as compared to 30 °C. Mycobacterium fortuitum and M. avium developed large amount of biofilm at 30 °C as compared to 37 and 42 °C. Mycobacterium tuberculosis developed strong biofilm at 37 °C and no biofilm at 30 and 42 °C in Sauton's media. The selected non-tuberculous mycobacteria and H37Rv developed strong biofilm in the presence of OADC enrichment in Sauton's medium. Microscopic examination of biofilms by scanning electron microscopy revealed that poorly adherent biofilm formers failed to colonize the entire surface of the microtiter well. While moderately adherent biofilm formers grew in uniform monolayers but failed to develop a mature three-dimensional structure. SEM analysis of an isolate representative of the group formed fully established biofilms with a textured, multi-layered, three-dimensional structure. PMID:25192360

  15. Monitoring cutting tool operation and condition with a magnetoelastic rate of change of torque sensor

    SciTech Connect

    Garshelis, Ivan J.; Kari, Ryan J.; Tollens, Stijn P. L.; Cuseo, James M.

    2008-04-01

    Application of a magnetoelastic rate of change of torque sensor to monitor the condition of milling cutters and operating parameters is described. Cutting tools naturally degrade with use by wear, chipping, or fracture, and the efficiency and quality of the product are highly dependent on the tool condition. The theoretical analysis is compared to experimental data in detecting changes in torque during each cutting event, and the rate of change of torque signal is investigated for a variety of cutting tool conditions.

  16. Intracellular Redox Compartmentation and ROS-Related Communication in Regulation and Signaling1[OPEN

    PubMed Central

    2016-01-01

    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. PMID:27208308

  17. 43 CFR 417.4 - Changed conditions, emergency, or hardship modifications.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... RECLAMATION, DEPARTMENT OF THE INTERIOR PROCEDURAL METHODS FOR IMPLEMENTING COLORADO RIVER WATER CONSERVATION MEASURES WITH LOWER BASIN CONTRACTORS AND OTHERS § 417.4 Changed conditions, emergency, or...

  18. 43 CFR 417.4 - Changed conditions, emergency, or hardship modifications.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... RECLAMATION, DEPARTMENT OF THE INTERIOR PROCEDURAL METHODS FOR IMPLEMENTING COLORADO RIVER WATER CONSERVATION MEASURES WITH LOWER BASIN CONTRACTORS AND OTHERS § 417.4 Changed conditions, emergency, or...

  19. 43 CFR 417.4 - Changed conditions, emergency, or hardship modifications.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... RECLAMATION, DEPARTMENT OF THE INTERIOR PROCEDURAL METHODS FOR IMPLEMENTING COLORADO RIVER WATER CONSERVATION MEASURES WITH LOWER BASIN CONTRACTORS AND OTHERS § 417.4 Changed conditions, emergency, or...

  20. 43 CFR 417.4 - Changed conditions, emergency, or hardship modifications.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... RECLAMATION, DEPARTMENT OF THE INTERIOR PROCEDURAL METHODS FOR IMPLEMENTING COLORADO RIVER WATER CONSERVATION MEASURES WITH LOWER BASIN CONTRACTORS AND OTHERS § 417.4 Changed conditions, emergency, or...

  1. On the resolvent of multidimensional operators with frequently changing boundary conditions in the case of the homogenized Dirichlet condition

    SciTech Connect

    Sharapov, T F

    2014-10-31

    We consider an elliptic operator in a multidimensional domain with frequently changing boundary conditions in the case when the homogenized operator contains the Dirichlet boundary condition. We prove the uniform resolvent convergence of the perturbed operator to the homogenized operator and obtain estimates for the rate of convergence. A complete asymptotic expansion is constructed for the resolvent when it acts on sufficiently smooth functions. Bibliography: 41 titles.

  2. Rhodium(III) Catalyzed Carboamination of Alkenes Triggered by C-H Activation of N-Phenoxyacetamides under Redox-Neutral Conditions.

    PubMed

    Hu, Zhiyong; Tong, Xiaofeng; Liu, Guixia

    2016-04-01

    N-Alkoxyacrylamides are coupled with N-phenoxyacetamides by Rh(III) catalysis through C-H functionalization and amido group transfer under external oxidant-free conditions, which affords acyclic alkene carboamination products in an atom-economical way. Mechanistic insight into this transformation indicates the amide group in N-alkoxyacrylamide plays a critical role in this C-C/C-N bond formation reaction. This methodology provides a highly efficient way to construct o-tyrosine derivatives under mild conditions. PMID:27002932

  3. Chloroplastic thioredoxin-f and thioredoxin-m1/4 play important roles in brassinosteroids-induced changes in CO2 assimilation and cellular redox homeostasis in tomato

    PubMed Central

    Cheng, Fei; Zhou, Yan-Hong; Xia, Xiao-Jian; Shi, Kai; Zhou, Jie; Yu, Jing-Quan

    2014-01-01

    Chloroplast thioredoxins (TRXs) and glutathione function as redox messengers in the regulation of photosynthesis. In this work, the roles of chloroplast TRXs in brassinosteroids (BRs)-induced changes in cellular redox homeostasis and CO2 assimilation were studied in the leaves of tomato plants. BRs-deficient d ^im plants showed decreased transcripts of TRX-f, TRX-m2, TRX-m1/4, and TRX-x, while exogenous BRs significantly induced CO2 assimilation and the expression of TRX-f, TRX-m2, TRX-m1/4, and TRX-x. Virus-induced gene silencing (VIGS) of the chloroplast TRX-f, TRX-m2, TRX-m1/4, and TRX-y genes individually increased membrane lipid peroxidation and accumulation of 2-Cys peroxiredoxin dimers, and decreased the activities of the ascorbate–glutathione cycle enzymes and the ratio of reduced glutathione to oxidized glutathione (GSH/GSSG) in the leaves. Furthermore, partial silencing of TRX-f, TRX-m2, TRX-m1/4, and TRX-y resulted in decreased expression of genes involved in the Benson–Calvin cycle and decreased activity of the associated enzymes. Importantly, the BRs-induced increase in CO2 assimilation and the increased expression and activities of antioxidant- and photosynthesis-related genes and enzymes were compromised in the partially TRX-f- and TRX-m1/4-silenced plants. All of these results suggest that TRX-f and TRX-m1/4 are involved in the BRs-induced changes in CO2 assimilation and cellular redox homeostasis in tomato. PMID:24847092

  4. Thiol-Based Redox Switches and Gene Regulation

    PubMed Central

    2011-01-01

    Abstract Cysteine is notable among the universal, proteinogenic amino acids for its facile redox chemistry. Cysteine thiolates are readily modified by reactive oxygen species (ROS), reactive electrophilic species (RES), and reactive nitrogen species (RNS). Although thiol switches are commonly triggered by disulfide bond formation, they can also be controlled by S-thiolation, S-alkylation, or modification by RNS. Thiol-based switches are common in both prokaryotic and eukaryotic organisms and activate functions that detoxify reactive species and restore thiol homeostasis while repressing functions that would be deleterious if expressed under oxidizing conditions. Here, we provide an overview of the best-understood examples of thiol-based redox switches that affect gene expression. Intra- or intermolecular disulfide bond formation serves as a direct regulatory switch for several bacterial transcription factors (OxyR, OhrR/2-Cys, Spx, YodB, CrtJ, and CprK) and indirectly regulates others (the RsrA anti-σ factor and RegB sensory histidine kinase). In eukaryotes, thiol-based switches control the yeast Yap1p transcription factor, the Nrf2/Keap1 electrophile and oxidative stress response, and the Chlamydomonas NAB1 translational repressor. Collectively, these regulators reveal a remarkable range of chemical modifications exploited by Cys residues to effect changes in gene expression. Antioxid. Redox Signal. 14, 1049—1063. PMID:20626317

  5. Synthesis and atomic level in situ redox characterization in ceria and ceria zirconia

    NASA Astrophysics Data System (ADS)

    Wang, Ruigang

    2007-12-01

    Nanocrystalline ceria-based oxides are widely used in automotive three-way catalytic converters to reduce the emissions of carbon monoxide, nitrogen oxides, and unburned hydrocarbons. The primary function of ceria-based oxides in the catalytic process is to adjust the local oxygen partial pressure and maintain an air-to-fuel ratio near the stoichiometric value (˜14.5) required for the optimal catalyst performance for carbon monoxide, hydrocarbon oxidation, and nitrogen oxides reduction. In this dissertation, a study of the relationship between the nanoscale structure, chemistry, and the redox behavior on high surface area ceria and ceria zirconia is presented. Precipitation and spray freezing methods were used to synthesize nanocrystalline ceria and ceria zirconia solid solution powders respectively. The effect of thermal treatments in oxidizing and reducing atmospheres on the reducibility of the materials has been systematically investigated. X-ray diffraction and thermogravimetric analysis were used to characterize the average structure and reducibility. In situ environmental transmission electron microscope was exploited to visualize the dynamic changes during redox processes at the atomic level. This resulted in the identification of the nanoscale structure and chemistry for the most active nanoparticles in these oxides. The correlation between ex situ macroscopic redox properties and in situ redox behavior of individual nanoparticles is demonstrated. The addition of zirconia to ceria clearly enhances the reducibility and thermal stability of ceria. A fundamental difference between ceria and ceria zirconia during in situ redox processes is related to oxygen vacancy ordering. Ceria showed oxygen vacancy ordering during reduction, whereas ceria zirconia did not. It is suggested that the absence of oxygen vacancy ordering might be a fundamental factor for improved redox properties of ceria zirconia compared with pure ceria. The 50% ceria-50% zirconia solid

  6. Formation of CaS-MgS in Enstatite Chondrites and Achondrites as a Function of Redox Conditions and Temperature: Constraints on Their Evolution in a Planetesimal and in a Proto-planet

    NASA Technical Reports Server (NTRS)

    Malavergne, Valerie; Berthet, S.; Righter, K.

    2007-01-01

    The cubic monosulfide series with the general formula (Mg,Mn,Ca,Fe)S are common phases in the enstatite chondrite (EH) and aubrite meteorite groups. In the Earth s mantle, sulfide minerals are associated with peridotites and eclogites. Study of these sulfide mineral systems is of interest for the mineralogy and petrology of planetary mantles. For example, MgS could occur in the primitive Earth and because it remains a low density phase compared to metal, would stay a separate phase during the core formation process, and thus not segregate to the core. (Mg,Ca,Mn,Fe)S sulphides might thus be important phases even in planetary differentiation processes. The importance of such minerals, and their formation, composition and textural relationships for understanding the genesis of enstatite chondrites and aubrites, has long been recognized. The main objective of this experimental study is to understand the formation and evolution of (Mg,Ca,Mn,Fe)S sulphides, particularly the oldhamite CaS and ningerite MgS, with pressure, temperature but also with redox conditions because EH and aubrites are meteorites that formed under reduced conditions. Piston-cylinder (PC) and multi-anvil (MA) experiments at high pressure (HP) and high temperature (HT) have been performed in order to simulate the evolution of these phases in a small planetary body from a planetesimal (with PC experiments) up to a proto-planet (with MA experiments).

  7. Fasting, but Not Aging, Dramatically Alters the Redox Status of Cysteine Residues on Proteins in Drosophila melanogaster

    PubMed Central

    Menger, Katja E.; James, Andrew M.; Cochemé, Helena M.; Harbour, Michael E.; Chouchani, Edward T.; Ding, Shujing; Fearnley, Ian M.; Partridge, Linda; Murphy, Michael P.

    2015-01-01

    Summary Altering the redox state of cysteine residues on protein surfaces is an important response to environmental challenges. Although aging and fasting alter many redox processes, the role of cysteine residues is uncertain. To address this, we used a redox proteomic technique, oxidative isotope-coded affinity tags (OxICAT), to assess cysteine-residue redox changes in Drosophila melanogaster during aging and fasting. This approach enabled us to simultaneously identify and quantify the redox state of several hundred cysteine residues in vivo. Cysteine residues within young flies had a bimodal distribution with peaks at ∼10% and ∼85% reversibly oxidized. Surprisingly, these cysteine residues did not become more oxidized with age. In contrast, 24 hr of fasting dramatically oxidized cysteine residues that were reduced under fed conditions while also reducing cysteine residues that were initially oxidized. We conclude that fasting, but not aging, dramatically alters cysteine-residue redox status in D. melanogaster. PMID:26095360

  8. Redox control of teratogenesis.

    PubMed

    Hansen, Jason M; Harris, Craig

    2013-01-01

    A number of human teratogens elicit their deleterious effects through mechanisms involving the generation of reactive oxygen species (ROS) and oxidative stress. However, classic definitions of oxidative stress do not fully coincide with basic fundamental principles of teratology. Newer definitions of oxidative stress focus on the targeted redox modification of cysteine/thiol functional groups found in the regulatory domains of critical signaling pathway proteins, suggesting that the targeted disruption of signaling through specific redox couples may account for the specificity of teratogen-induced malformations which previously could not be rationalized. Here, we review examples of teratogens that induce ROS and oxidative injury, describe oxidative stress-related teratogenic mechanisms, and provide rationale for developmental periods of sensitivity and species susceptibility. Understanding how chemicals disrupt redox status, induce oxidative stress leading to dysmorphogenesis becomes important to identify potential teratogens and develop therapeutic interventions for attenuation of harmful chemical effects in utero following exposure. PMID:23089153

  9. Tracer test with As(V) under variable redox conditions controlling arsenic transport in the presence of elevated ferrous iron concentrations.

    PubMed

    Höhn, R; Isenbeck-Schröter, M; Kent, D B; Davis, J A; Jakobsen, R; Jann, S; Niedan, V; Scholz, C; Stadler, S; Tretner, A

    2006-11-20

    To study transport and reactions of arsenic under field conditions, a small-scale tracer test was performed in an anoxic, iron-reducing zone of a sandy aquifer at the USGS research site on Cape Cod, Massachusetts, USA. For four weeks, a stream of groundwater with added As(V) (6.7 muM) and bromide (1.6 mM), was injected in order to observe the reduction of As(V) to As(III). Breakthrough of bromide (Br(-)), As(V), and As(III) as well as additional parameters characterizing the geochemical conditions was observed at various locations downstream of the injection well over a period of 104 days. After a short lag period, nitrate and dissolved oxygen from the injectate oxidized ferrous iron and As(V) became bound to the freshly formed hydrous iron oxides. Approximately one week after terminating the injection, anoxic conditions had been reestablished and increases in As(III) concentrations were observed within 1 m of the injection. During the observation period, As(III) and As(V) were transported to a distance of 4.5 m downgradient indicating significant retardation by sorption processes for both species. Sediment assays as well as elevated concentrations of hydrogen reflected the presence of As(V) reducing microorganisms. Thus, microbial As(V) reduction was thought to be one major process driving the release of As(III) during the tracer test in the Cape Cod aquifer. PMID:16945450

  10. The measurement of reversible redox dependent post-translational modifications and their regulation of mitochondrial and skeletal muscle function

    SciTech Connect

    Kramer, Philip A.; Duan, Jicheng; Qian, Weijun; Marcinek, David J.

    2015-11-25

    Mitochondrial oxidative stress is a common feature of skeletal myopathies across multiple conditions; however, the mechanism by which it contributes to skeletal muscle dysfunction remains controversial. Oxidative damage to proteins, lipids, and DNA has received the most attention, yet an important role for reversible redox post-translational modifications (PTMs) in pathophysiology is emerging. The possibility that these PTMs can exert dynamic control of muscle function implicates them as a mechanism contributing to skeletal muscle dysfunction in chronic disease. Herein, we discuss the significance of thiol-based redox dependent modifications to mitochondrial, myofibrillar and excitation-contraction (EC) coupling proteins with an emphasis on how these changes could alter skeletal muscle performance under chronically stressed conditions. A major barrier to a better mechanistic understanding of the role of reversible redox PTMs in muscle function is the technical challenges associated with accurately measuring the changes of site-specific redox PTMs. Here we will critically review current approaches with an emphasis on sample preparation artifacts, quantitation, and specificity. Despite these challenges, the ability to accurately quantify reversible redox PTMs is critical to understanding the mechanisms by which mitochondrial oxidative stress contributes to skeletal muscle dysfunction in chronic diseases.

  11. The Measurement of Reversible Redox Dependent Post-translational Modifications and Their Regulation of Mitochondrial and Skeletal Muscle Function

    PubMed Central

    Kramer, Philip A.; Duan, Jicheng; Qian, Wei-Jun; Marcinek, David J.

    2015-01-01

    Mitochondrial oxidative stress is a common feature of skeletal myopathies across multiple conditions; however, the mechanism by which it contributes to skeletal muscle dysfunction remains controversial. Oxidative damage to proteins, lipids, and DNA has received the most attention, yet an important role for reversible redox post-translational modifications (PTMs) in pathophysiology is emerging. The possibility that these PTMs can exert dynamic control of muscle function implicates them as a mechanism contributing to skeletal muscle dysfunction in chronic disease. Herein, we discuss the significance of thiol-based redox dependent modifications to mitochondrial, myofibrillar, and excitation-contraction (EC) coupling proteins with an emphasis on how these changes could alter skeletal muscle performance under chronically stressed conditions. A major barrier to a better mechanistic understanding of the role of reversible redox PTMs in muscle function is the technical challenges associated with accurately measuring the changes of site-specific redox PTMs. Here we will critically review current approaches with an emphasis on sample preparation artifacts, quantitation, and specificity. Despite these challenges, the ability to accurately quantify reversible redox PTMs is critical to understanding the mechanisms by which mitochondrial oxidative stress contributes to skeletal muscle dysfunction in chronic diseases. PMID:26635632

  12. Redox-based epigenetic status in drug addiction: a potential contributor to gene priming and a mechanistic rationale for metabolic intervention

    PubMed Central

    Trivedi, Malav S.; Deth, Richard

    2015-01-01

    Alcohol and other drugs of abuse, including psychostimulants and opioids, can induce epigenetic changes: a contributing factor for drug addiction, tolerance, and associated withdrawal symptoms. DNA methylation is a major epigenetic mechanism and it is one of more than 200 methylation reactions supported by methyl donor S-adenosylmethionine (SAM). Levels of SAM are controlled by cellular redox status via the folate and vitamin B12-dependent enzyme methionine synthase (MS). For example, under oxidative conditions MS is inhibited, diverting its substrate homocysteine (HCY) to the trans sulfuration pathway. Alcohol, dopamine, and morphine, can alter intracellular levels of glutathione (GSH)-based cellular redox status, subsequently affecting SAM levels and DNA methylation status. Here, existing evidence is presented in a coherent manner to propose a novel hypothesis implicating the involvement of redox-based epigenetic changes in drug addiction. Further, we discuss how a “gene priming” phenomenon can contribute to the maintenance of redox and methylation status homeostasis under various stimuli including drugs of abuse. Additionally, a new mechanistic rationale for the use of metabolic interventions/redox-replenishers as symptomatic treatment of alcohol and other drug addiction and associated withdrawal symptoms is also provided. Hence, the current review article strengthens the hypothesis that neuronal metabolism has a critical bidirectional coupling with epigenetic changes in drug addiction exemplified by the link between redox-based metabolic changes and resultant epigenetic consequences under the effect of drugs of abuse. PMID:25657617

  13. Redox-based epigenetic status in drug addiction: a potential contributor to gene priming and a mechanistic rationale for metabolic intervention.

    PubMed

    Trivedi, Malav S; Deth, Richard

    2014-01-01

    Alcohol and other drugs of abuse, including psychostimulants and opioids, can induce epigenetic changes: a contributing factor for drug addiction, tolerance, and associated withdrawal symptoms. DNA methylation is a major epigenetic mechanism and it is one of more than 200 methylation reactions supported by methyl donor S-adenosylmethionine (SAM). Levels of SAM are controlled by cellular redox status via the folate and vitamin B12-dependent enzyme methionine synthase (MS). For example, under oxidative conditions MS is inhibited, diverting its substrate homocysteine (HCY) to the trans sulfuration pathway. Alcohol, dopamine, and morphine, can alter intracellular levels of glutathione (GSH)-based cellular redox status, subsequently affecting SAM levels and DNA methylation status. Here, existing evidence is presented in a coherent manner to propose a novel hypothesis implicating the involvement of redox-based epigenetic changes in drug addiction. Further, we discuss how a "gene priming" phenomenon can contribute to the maintenance of redox and methylation status homeostasis under various stimuli including drugs of abuse. Additionally, a new mechanistic rationale for the use of metabolic interventions/redox-replenishers as symptomatic treatment of alcohol and other drug addiction and associated withdrawal symptoms is also provided. Hence, the current review article strengthens the hypothesis that neuronal metabolism has a critical bidirectional coupling with epigenetic changes in drug addiction exemplified by the link between redox-based metabolic changes and resultant epigenetic consequences under the effect of drugs of abuse. PMID:25657617

  14. Redox-active quinones induces genome-wide DNA methylation changes by an iron-mediated and Tet-dependent mechanism

    PubMed Central

    Zhao, Bailin; Yang, Ying; Wang, Xiaoli; Chong, Zechen; Yin, Ruichuan; Song, Shu-Hui; Zhao, Chao; Li, Cuiping; Huang, Hua; Sun, Bao-Fa; Wu, Danni; Jin, Kang-Xuan; Song, Maoyong; Zhu, Ben-Zhan; Jiang, Guibin; Rendtlew Danielsen, Jannie M.; Xu, Guo-Liang; Yang, Yun-Gui; Wang, Hailin

    2014-01-01

    DNA methylation has been proven to be a critical epigenetic mark important for various cellular processes. Here, we report that redox-active quinones, a ubiquitous class of chemicals found in natural products, cancer therapeutics and environment, stimulate the conversion of 5mC to 5hmC in vivo, and increase 5hmC in 5751 genes in cells. 5hmC increase is associated with significantly altered gene expression of 3414 genes. Interestingly, in quinone-treated cells, labile iron-sensitive protein ferritin light chain showed a significant increase at both mRNA and protein levels indicating a role of iron regulation in stimulating Tet-mediated 5mC oxidation. Consistently, the deprivation of cellular labile iron using specific chelator blocked the 5hmC increase, and a delivery of labile iron increased the 5hmC level. Moreover, both Tet1/Tet2 knockout and dimethyloxalylglycine-induced Tet inhibition diminished the 5hmC increase. These results suggest an iron-regulated Tet-dependent DNA demethylation mechanism mediated by redox-active biomolecules. PMID:24214992

  15. Seasonality of temperatures and redox zonations during bank filtration - A modeling approach

    NASA Astrophysics Data System (ADS)

    Henzler, Aline F.; Greskowiak, Janek; Massmann, Gudrun

    2016-04-01

    Bank filtration (BF) is a common technique for supplying drinking water, using the ability of the infiltration zone and aquifer passage to attenuate or degrade undesired substances that infiltrate from surface waters to groundwater abstraction wells. Temporal and spatial changes of temperatures and redox conditions are often the controlling factors for the fate and behavior of micropollutants during subsurface passage and consequently for the extracted raw water quality. A 2-dimensional cross-sectional heat transport and multi-species reactive transport model was set up to simulate the seasonally varying temperatures and redox conditions on the infiltration path at a bank filtration site in Berlin, Germany. The calibrated model was able to capture the observed variations in O2 and NO3- when considering temperature dependence of the redox reaction kinetics. The observed Mn2+- and Fe2+-concentrations were not well replicated by the model, presumably due to mineral reactions that were not accounted for in the simulations. SO42- was found to behave conservative, i.e., the observed concentration could be well simulated without any reactions. The simulations reveal the transience of BF systems with regard to temperatures and redox conditions, which has important implications for the BF quality and should therefore be accounted for.

  16. Electronegativity and redox reactions.

    PubMed

    Miranda-Quintana, Ramón Alain; Martínez González, Marco; Ayers, Paul W

    2016-08-10

    Using the maximum hardness principle, we show that the oxidation potential of a molecule increases as its electronegativity increases and also increases as its electronegativity in its oxidized state increases. This insight can be used to construct a linear free energy relation for the oxidation potential, which we train on a set of 31 organic redox couples and test on a set of 10 different redox reactions. Better results are obtained when the electronegativity of the oxidized/reduced reagents are adjusted to account for the reagents' interaction with their chemical environment. PMID:27451962

  17. Marine redox conditions in the middle Proterozoic ocean and isotopic constraints on authigenic carbonate formation: Insights from the Chuanlinggou Formation, Yanshan Basin, North China

    NASA Astrophysics Data System (ADS)

    Li, Chao; Planavsky, Noah J.; Love, Gordon D.; Reinhard, Christopher T.; Hardisty, Dalton; Feng, Lianjun; Bates, Steven M.; Huang, Jing; Zhang, Qirui; Chu, Xuelei; Lyons, Timothy W.

    2015-02-01

    To improve our understanding of ocean chemistry and biogeochemical cycling following the termination of large-scale Paleoproterozoic iron formation (IF) deposition (∼1.85 billion years ago [Ga]), we conducted a Fe-S-C-Mo geochemical study of the ∼1.65 Ga Chuanlinggou Formation, Yanshan Basin, North China. Despite the cessation of IF deposition, our results suggest the presence of anoxic but non-euxinic (ferruginous) conditions persisted below the surface mixed layer for the deepest portion of the continental rifting basin and that this pattern is apparently independent of the local organic carbon content. However, our paired S-isotope data of carbonate-associated sulfate and pyrite suggest presence of sulfate in pore fluids, which is not consistent with insufficient sulfate for bacterial sulfate reduction in the water column. Despite evidence for deposition under anoxic conditions, sedimentary molybdenum (Mo) concentrations are mostly not enriched relative to average continental crust. This relationship is consistent with the notion that sulfide-dominated conditions in the water column and/or the sediments are required for Mo enrichment and validates past assertions that Mo enrichment patterns in ancient shales track both the local presence and global distribution of euxinia specifically. In addition, we identified extensive diagenetic carbonate precipitation in the upper Chuanlinggou Formation with only moderately negative δ13C values (-3.4 ± 1.4‰). We propose, with support from a numerical model, that these diagenetic carbon isotope values were most likely derived from precipitation of carbonates dominantly in the methanic zone within the sediments. Diagenetic carbonate precipitation in the methanic zone is likely to have been more extensive in the Proterozoic than the Phanerozoic due to porewater oxidant limitation.

  18. Real-Time Imaging of the Intracellular Glutathione Redox Potential in the Malaria Parasite Plasmodium falciparum

    PubMed Central

    Kasozi, Denis; Mohring, Franziska; Rahlfs, Stefan; Meyer, Andreas J.; Becker, Katja

    2013-01-01

    In the malaria parasite Plasmodium falciparum, the cellular redox potential influences signaling events, antioxidant defense, and mechanisms of drug action and resistance. Until now, the real-time determination of the redox potential in malaria parasites has been limited because conventional approaches disrupt sub-cellular integrity. Using a glutathione biosensor comprising human glutaredoxin-1 linked to a redox-sensitive green fluorescent protein (hGrx1-roGFP2), we systematically characterized basal values and drug-induced changes in the cytosolic glutathione-dependent redox potential (EGSH) of drug-sensitive (3D7) and resistant (Dd2) P. falciparum parasites. Via confocal microscopy, we demonstrated that hGrx1-roGFP2 rapidly detects EGSH changes induced by oxidative and nitrosative stress. The cytosolic basal EGSH of 3D7 and Dd2 were estimated to be −314.2±3.1 mV and −313.9±3.4 mV, respectively, which is indicative of a highly reducing compartment. We furthermore monitored short-, medium-, and long-term changes in EGSH after incubation with various redox-active compounds and antimalarial drugs. Interestingly, the redox cyclers methylene blue and pyocyanin rapidly changed the fluorescence ratio of hGrx1-roGFP2 in the cytosol of P. falciparum, which can, however, partially be explained by a direct interaction with the probe. In contrast, quinoline and artemisinin-based antimalarial drugs showed strong effects on the parasites' EGSH after longer incubation times (24 h). As tested for various conditions, these effects were accompanied by a drop in total glutathione concentrations determined in parallel with alternative methods. Notably, the effects were generally more pronounced in the chloroquine-sensitive 3D7 strain than in the resistant Dd2 strain. Based on these results hGrx1-roGFP2 can be recommended as a reliable and specific biosensor for real-time spatiotemporal monitoring of the intracellular EGSH in P. falciparum. Applying this technique in further

  19. Redox interplay between mitochondria and peroxisomes

    PubMed Central

    Lismont, Celien; Nordgren, Marcus; Van Veldhoven, Paul P.; Fransen, Marc

    2015-01-01

    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 discussion. PMID:26075204

  20. Stability and Change in Children's Home Environments: The Effects of Parental Occupational Experiences and Family Conditions.

    ERIC Educational Resources Information Center

    Menaghan, Elizabeth G.; Parcel, Toby L.

    This study examined the effects of mothers' and fathers' occupational conditions on children's home environments, and of change in occupational and family conditions on change in home environments. The study used the 1986 and 1988 supplements to the National Longitudinal Surveys of Youth. Subjects were 781 married mothers with children aged 3…

  1. 30 CFR 203.77 - May I voluntarily give up relief if conditions change?

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 30 Mineral Resources 2 2010-07-01 2010-07-01 false May I voluntarily give up relief if conditions change? 203.77 Section 203.77 Mineral Resources MINERALS MANAGEMENT SERVICE, DEPARTMENT OF THE INTERIOR... voluntarily give up relief if conditions change? Yes, you may voluntarily give up relief by sending a...

  2. Axial Ligation and Redox Changes at the Cobalt Ion in Cobalamin Bound to Corrinoid Iron-Sulfur Protein (CoFeSP) or in Solution Characterized by XAS and DFT

    PubMed Central

    Schrapers, Peer; Mebs, Stefan; Goetzl, Sebastian; Hennig, Sandra E.; Dau, Holger; Dobbek, Holger; Haumann, Michael

    2016-01-01

    A cobalamin (Cbl) cofactor in corrinoid iron-sulfur protein (CoFeSP) is the primary methyl group donor and acceptor in biological carbon oxide conversion along the reductive acetyl-CoA pathway. Changes of the axial coordination of the cobalt ion within the corrin macrocycle upon redox transitions in aqua-, methyl-, and cyano-Cbl bound to CoFeSP or in solution were studied using X-ray absorption spectroscopy (XAS) at the Co K-edge in combination with density functional theory (DFT) calculations, supported by metal content and cobalt redox level quantification with further spectroscopic methods. Calculation of the highly variable pre-edge X-ray absorption features due to core-to-valence (ctv) electronic transitions, XANES shape analysis, and cobalt-ligand bond lengths determination from EXAFS has yielded models for the molecular and electronic structures of the cobalt sites. This suggested the absence of a ligand at cobalt in CoFeSP in α-position where the dimethylbenzimidazole (dmb) base of the cofactor is bound in Cbl in solution. As main species, (dmb)CoIII(OH2), (dmb)CoII(OH2), and (dmb)CoIII(CH3) sites for solution Cbl and CoIII(OH2), CoII(OH2), and CoIII(CH3) sites in CoFeSP-Cbl were identified. Our data support binding of a serine residue from the reductive-activator protein (RACo) of CoFeSP to the cobalt ion in the CoFeSP-RACo protein complex that stabilizes Co(II). The absence of an α-ligand at cobalt not only tunes the redox potential of the cobalamin cofactor into the physiological range, but is also important for CoFeSP reactivation. PMID:27384529

  3. Assessment of mycotoxin risk on corn in the Philippines under current and future climate change conditions.

    PubMed

    Salvacion, Arnold R; Pangga, Ireneo B; Cumagun, Christian Joseph R

    2015-01-01

    This study attempts to assess the risk of mycotoxins (aflatoxins and fumonisins) contamination on corn in the Philippines under current and projected climate change conditions using fuzzy logic methodology based on the published range of temperature and rainfall conditions that favor mycotoxin development. Based on the analysis, projected climatic change will reduce the risk of aflatoxin contamination in the country due to increased rainfall. In the case of fumonisin contamination, most parts of the country are at a very high risk both under current conditions and the projected climate change conditions. PMID:26351797

  4. K-8th Grade Korean Students' Conceptions of 'Changes of State' and 'Conditions for Changes of State'. Research Report

    ERIC Educational Resources Information Center

    Paik, Seoung-Hey; Kim, Hyo-Nam; Cho, Boo-Kyoung; Park, Jae-Won

    2004-01-01

    This study investigates the various conceptions held by K-8th Korean grade students regarding the 'changes of state' and the 'conditions for changes of state'. The study used a sample of five kindergarteners, five secondgrade students, five fourth-grade students, five sixth-grade students, and five eighth-grade students. The 25 students attend…

  5. Effect of coupled dissolution and redox reactions on Cr(VI)aq attenuation during transport in the sediments under hyperalkaline conditions.

    PubMed

    Qafoku, Nikolla P; Ainsworth, Calvin C; Szecsody, James E; Qafoku, Odeta S; Heald, Steve M

    2003-08-15

    Aluminum-rich, hyperalkaline (pH > 13.5) and saline high-level nuclear waste (HLW) fluids at elevated temperatures (>50 degrees C), that possibly contained as much as 0.41 mol L(-1) Cr(VI), accidentally leaked to the sediments at the Hanford Site, WA. These extreme conditions promote base-induced dissolution of soil minerals which may affect Cr(VI)aq mobility. Our objective was to investigate Cr(VI)aq transport in sediments leached with HLW simulants at 50 degrees C, under CO2 and O2 free conditions. Results demonstrated that Cr(VI)aq fate was closely related to dissolution, and Cr(VI)aq mass loss was negligible in the first pore volumes but increased significantly thereafter. Similar to dissolution, Cr(VI)aq attenuation increased with increasing fluid residence time and NaOH concentration but decreased with Al concentrations in the leaching solutions. Aqueous Cr(VI) removal rate half-lives varied from 1.2 to 230 h with the fastest at the highest base concentration, lowest Al concentration, greatest reaction time, and lowest Cr(VI) concentration in the leaching solution. The rate of Cr(VI) removal (normalized to 1 kg of solution) varied from 0.83 x 10(-9) (+/-0.44 x 10(-9)) to 9.16 x 10(-9) (+/-1.10 x 10(-9)) mol s(-1). The predominant mechanism responsible for removing Cr(VI) from the aqueous phase appears to be homogeneous Cr(VI) reduction to Cr(III) by Fe(II) released during mineral dissolution. Cr(VI)aq removal was time-limited probably because it was controlled by the rate of Fe(II) release into the soil solution upon mineral dissolution, which was also a time-limited process, and other processes that may act to lower Fe(II)aq activity. PMID:12953877

  6. Lycopene Inhibits NF-kB-Mediated IL-8 Expression and Changes Redox and PPARγ Signalling in Cigarette Smoke–Stimulated Macrophages

    PubMed Central

    Simone, Rossella E.; Russo, Marco; Catalano, Assunta; Monego, Giovanni; Froehlich, Kati; Boehm, Volker; Palozza, Paola

    2011-01-01

    Increasing evidence suggests that lycopene, the major carotenoid present in tomato, may be preventive against smoke-induced cell damage. However, the mechanisms of such a prevention are still unclear. The aim of this study was to investigate the role of lycopene on the production of the pro-inflammatory cytokine IL-8 induced by cigarette smoke and the possible mechanisms implicated. Therefore, human THP-1 macrophages were exposed to cigarette smoke extract (CSE), alone and following a 6-h pre-treatment with lycopene (0.5–2 µM). CSE enhanced IL-8 production in a time- and a dose-dependent manner. Lycopene pre-treatment resulted in a significant inhibition of CSE-induced IL-8 expression at both mRNA and protein levels. NF-kB controlled the transcription of IL-8 induced by CSE, since PDTC prevented such a production. Lycopene suppressed CSE-induced NF-kB DNA binding, NF-kB/p65 nuclear translocation and phosphorylation of IKKα and IkBα. Such an inhibition was accompanied by a decrease in CSE-induced ROS production and NOX-4 expression. Lycopene further inhibited CSE-induced phosphorylation of the redox-sensitive ERK1/2, JNK and p38 MAPKs. Moreover, the carotenoid increased PPARγ levels which, in turn, enhanced PTEN expression and decreased pAKT levels in CSE-exposed cells. Such effects were abolished by the PPARγ inhibitor GW9662. Taken together, our data indicate that lycopene prevented CSE-induced IL-8 production through a mechanism involving an inactivation of NF-kB. NF-kB inactivation was accompanied by an inhibition of redox signalling and an activation of PPARγ signalling. The ability of lycopene in inhibiting IL-8 production, NF-kB/p65 nuclear translocation, and redox signalling and in increasing PPARγ expression was also found in isolated rat alveolar macrophages exposed to CSE. These findings provide novel data on new molecular mechanisms by which lycopene regulates cigarette smoke-driven inflammation in human macrophages. PMID:21625550

  7. Lycopene inhibits NF-kB-mediated IL-8 expression and changes redox and PPARγ signalling in cigarette smoke-stimulated macrophages.

    PubMed

    Simone, Rossella E; Russo, Marco; Catalano, Assunta; Monego, Giovanni; Froehlich, Kati; Boehm, Volker; Palozza, Paola

    2011-01-01

    Increasing evidence suggests that lycopene, the major carotenoid present in tomato, may be preventive against smoke-induced cell damage. However, the mechanisms of such a prevention are still unclear. The aim of this study was to investigate the role of lycopene on the production of the pro-inflammatory cytokine IL-8 induced by cigarette smoke and the possible mechanisms implicated. Therefore, human THP-1 macrophages were exposed to cigarette smoke extract (CSE), alone and following a 6-h pre-treatment with lycopene (0.5-2 µM). CSE enhanced IL-8 production in a time- and a dose-dependent manner. Lycopene pre-treatment resulted in a significant inhibition of CSE-induced IL-8 expression at both mRNA and protein levels. NF-kB controlled the transcription of IL-8 induced by CSE, since PDTC prevented such a production. Lycopene suppressed CSE-induced NF-kB DNA binding, NF-kB/p65 nuclear translocation and phosphorylation of IKKα and IkBα. Such an inhibition was accompanied by a decrease in CSE-induced ROS production and NOX-4 expression. Lycopene further inhibited CSE-induced phosphorylation of the redox-sensitive ERK1/2, JNK and p38 MAPKs. Moreover, the carotenoid increased PPARγ levels which, in turn, enhanced PTEN expression and decreased pAKT levels in CSE-exposed cells. Such effects were abolished by the PPARγ inhibitor GW9662. Taken together, our data indicate that lycopene prevented CSE-induced IL-8 production through a mechanism involving an inactivation of NF-kB. NF-kB inactivation was accompanied by an inhibition of redox signalling and an activation of PPARγ signalling. The ability of lycopene in inhibiting IL-8 production, NF-kB/p65 nuclear translocation, and redox signalling and in increasing PPARγ expression was also found in isolated rat alveolar macrophages exposed to CSE. These findings provide novel data on new molecular mechanisms by which lycopene regulates cigarette smoke-driven inflammation in human macrophages. PMID:21625550

  8. The Need for Change in Industrial Arts Based on Societal and Industrial Conditions.

    ERIC Educational Resources Information Center

    Barry, Owen J.

    The author has presented a historical review of societal/industrial conditions affecting the development of manual education to determine if a need for change in industrial arts exists at the present time. Societal conditions, industrial conditions, and the resulting educational response are examined in: Russia (mid-19th century), Sweden (19th…

  9. Eye-Blink Conditioning Is Associated with Changes in Synaptic Ultrastructure in the Rabbit Interpositus Nuclei

    ERIC Educational Resources Information Center

    Weeks, Andrew C. W.; Connor, Steve; Hinchcliff, Richard; LeBoutillier, Janelle C.; Thompson, Richard F.; Petit, Ted L.

    2007-01-01

    Eye-blink conditioning involves the pairing of a conditioned stimulus (usually a tone) to an unconditioned stimulus (air puff), and it is well established that an intact cerebellum and interpositus nucleus, in particular, are required for this form of classical conditioning. Changes in synaptic number or structure have long been proposed as a…

  10. K-8th grade Korean students' conceptions of 'changes of state' and 'conditions for changes of state'

    NASA Astrophysics Data System (ADS)

    Paik, Seoung-Hey; Kim, Hyo-Nam; Cho, Boo-Kyoung; Park, Jae-Won

    2004-02-01

    This study investigates the various conceptions held by K-8th Korean grade students regarding the 'changes of state' and the 'conditions for changes of state'. The study used a sample of five kindergarteners, five secondgrade students, five fourth-grade students, five sixth-grade students, and five eighth-grade students. The 25 students attend schools in a rural district of South Korea. Some activities that involved a change in the state of water, including condensation, solidification, and melting, were chosen from K-8th grade science textbooks and attempted by the students. Subsequently, we conducted interviews with the students. While most kindergarteners and second-grade students were able to perceive the phenomena involving changes of state, they were unable to express conceptions related to the changes of state and the conditions under which the state the changes. The upper-grade students, on the other hand, had some conception of the invisible gas state. Most of these students held conceptions about the boiling water's change of state from liquid to gas, but few of them held conceptions about the changes of state involving condensation. Most students understood heat and temperature as conditions of the changes of state, but only applied the heat concept to situations involving rising temperatures. In situations involving cooling, students applied the temperature concept. The younger students understood the concept of heat without understanding the concept of temperature.

  11. Redox regulation of protein damage in plasma.

    PubMed

    Griffiths, Helen R; Dias, Irundika H K; Willetts, Rachel S; Devitt, Andrew

    2014-01-01

    The presence and concentrations of modified proteins circulating in plasma depend on rates of protein synthesis, modification and clearance. In early studies, the proteins most frequently analysed for damage were those which were more abundant in plasma (e.g. albumin and immunoglobulins) which exist at up to 10 orders of magnitude higher concentrations than other plasma proteins e.g. cytokines. However, advances in analytical techniques using mass spectrometry and immuno-affinity purification methods, have facilitated analysis of less abundant, modified proteins and the nature of modifications at specific sites is now being characterised. The damaging reactive species that cause protein modifications in plasma principally arise from reactive oxygen species (ROS) produced by NADPH oxidases (NOX), nitric oxide synthases (NOS) and oxygenase activities; reactive nitrogen species (RNS) from myeloperoxidase (MPO) and NOS activities; and hypochlorous acid from MPO. Secondary damage to proteins may be caused by oxidized lipids and glucose autooxidation. In this review, we focus on redox regulatory control of those enzymes and processes which control protein maturation during synthesis, produce reactive species, repair and remove damaged plasma proteins. We have highlighted the potential for alterations in the extracellular redox compartment to regulate intracellular redox state and, conversely, for intracellular oxidative stress to alter the cellular secretome and composition of extracellular vesicles. Through secreted, redox-active regulatory molecules, changes in redox state may be transmitted to distant sites. PMID:24624332

  12. NASA Redox Storage System Development Project

    NASA Technical Reports Server (NTRS)

    Hagedorn, N. H.

    1984-01-01

    The Redox Storage System Technology Project was jointly supported by the U.S. Department of Energy and NASA. The objectives of the project were to develop the Redox flow battery concept and to probe its technical and economic viability. The iron and chromium redox couples were selected as the reactants. Membranes and electrodes were developed for the original mode of operating at 25 C with the reactants separated by an ion-exchange membrane. Analytical capabilities and system-level operating concepts were developed and verified in a 1-kW, 13-kWh preprototype system. A subsequent change was made in operating mode, going to 65 C and using mixed reactants. New membranes and a new electrode catalyst were developed, resulting in single cell operation as high as 80 mA/sq cm with energy efficiencies greater than 80 percent. Studies indicate a likely system cost of about $75/kWh. Standard Oil of Ohio (Sohio) has undertaken further development of the Redox system. An exclusive patent license was obtained from NASA by Sohio. Transfer of Redox technology to Sohio is supported by the NASA Technology Utilization Office.

  13. Redox Flow Batteries, a Review

    SciTech Connect

    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.

  14. Ce K edge XAS of ceria-based redox materials under realistic conditions for the two-step solar thermochemical dissociation of water and/or CO2.

    PubMed

    Rothensteiner, Matthäus; Sala, Simone; Bonk, Alexander; Vogt, Ulrich; Emerich, Hermann; van Bokhoven, Jeroen A

    2015-10-28

    X-ray absorption spectroscopy was used to characterise ceria-based materials under realistic conditions present in a reactor for solar thermochemical two-step water and carbon dioxide splitting. A setup suitable for in situ measurements in transmission mode at the cerium K edge from room temperature up to 1773 K is presented. Time-resolved X-ray absorption near-edge structure (XANES) data, collected for a 10 mol% hafnium-doped ceria sample (Ce0.9Hf0.1O2-δ) during reduction at 1773 K in a flow of inert gas and during re-oxidation by CO2 at 1073 K, enables the quantitative determination of the non-stoichiometry δ of the fluorite-type structure. XANES analysis suggests the formation of the hexagonal Ce2O3 phase upon reduction in 2% hydrogen/helium at 1773 K. We discuss the experimental limitations and possibilities of high-temperature in situ XAS at edges of lower energy as well as the importance of the technique for understanding and improving the properties of ceria-based oxygen storage materials for thermochemical solar energy conversion. PMID:26412705

  15. Cellular Redox Imbalance and Changes of Protein S-glutathionylation Patterns Are Associated with Senescence Induced by Oncogenic H-Ras

    PubMed Central

    Urbanelli, Lorena; Magini, Alessandro; Magherini, Francesca; Pugnaloni, Armanda; Piva, Francesco; Modesti, Alessandra; Emiliani, Carla; Principato, Giovanni

    2012-01-01

    H-Ras oncogene requires deregulation of additional oncogenes or inactivation of tumor suppressor proteins to increase cell proliferation rate and transform cells. In fact, the expression of the constitutively activated H-RasV12 induces cell growth arrest and premature senescence, which act like barriers in pre-neoplastic lesions. In our experimental model, human fibroblasts transfected with H-RasV12 show a dramatic modification of morphology. H-RasV12 expressing cells also show premature senescence followed by cell death, induced by autophagy and apoptosis. In this context, we provide evidence that in H-RasV12 expressing cells, the premature senescence is associated with cellular redox imbalance as well as with altered post-translation protein modification. In particular, redox imbalance is due to a strong reduction of total antioxidant capacity, and significant decrease of glutathione level. As the reversible addition of glutathione to cysteinyl residues of proteins is an important post-translational regulative modification, we investigated S-glutathionylation in cells expressing active H-Ras. In this contest we observed different S-glutathionylation patterns in control and H-RasV12 expressing cells. Particularly, the GAPDH enzyme showed S-glutathionylation increase and significant enzyme activity depletion in H-Ras V12 cells. In conclusion, we proposed that antioxidant defense reduction, glutathione depletion and subsequent modification of S-glutathionylation of target proteins contribute to arrest cell growth, leading to death of fibroblasts expressing constitutively active H-Ras oncogene, thus acting as oncogenic barriers that obstacle the progression of cell transformation. PMID:23284910

  16. Redox proteomics for the assessment of redox-related posttranslational regulation in plants.

    PubMed

    Mock, Hans-Peter; Dietz, Karl-Josef

    2016-08-01

    The methodological developments of in vivo and in vitro protein labeling and subsequent detection enable sensitive and specific detection of redox modifications. Such methods are presently applied to diverse cells and tissues, subproteomes and developmental as well as environmental conditions. The chloroplast proteome is particularly suitable for such kind of studies, because redox regulation of chloroplast proteins is well established, many plastid proteins are abundant, redox network components have been inventoried in great depth, and functional consequences explored. Thus the repertoire of redox-related posttranslational modifications on the one hand side and their abundance on the other pose a challenge for the near future to understand their contribution to physiological regulation. The various posttranslational redox modifications are introduced, followed by a description of the available proteomics methods. The significance of the redox-related posttranslational modification is exemplarily worked out using established examples from photosynthesis. This article is part of a Special Issue entitled: Plant Proteomics - a bridge between fundamental processes and crop production, edited by Dr. Hans-Peter Mock. PMID:26784836

  17. Mobility of metals over the redox boundary in Peru Basin sediments

    NASA Astrophysics Data System (ADS)

    Stummeyer, Jens; Marchig, Vesna

    Downcore variations and phase distribution of metals in the Quaternary sediments from six areas of the Peru Basin were investigated. The sediments are characterised by a 5-20 cm thick, oxic layer at the water/sediment interface formed under the influence of dissolved oxygen in the bottom water. In deeper sediment sections, suboxic conditions are found due to the degradation of organic matter. Variations in the downcore abundance of metals (e.g., Fe, Mn, Co, Ni, Cu, Zn, V, Mo, Cr) were determined by bulk chemical methods. A significant accumulation of manganese is observed at the depth of the manganese redox boundary, caused by diagenetic remobilisation under suboxic conditions and reprecipitation under oxic conditions. To investigate their phase distributions, partitioning of elements in selected samples over the sediment column was carried out in sequential leaching experiments. A comparison between the surface layer and deeper sediment layers shows a distinct change in the element distribution between operationally defined host phases (carbonates, oxy-hydroxides, detrital components). Above the redox boundary at the sediment surface, transition metals are enriched in the reducible Mn-oxide fraction. When the horizontal position of the Mn-redox boundary moves upward, influenced by naturally occurring enhancement of surface-water productivity, these elements are mobilised and available to the manganese nodule accretion process if the redox boundary reaches the level of growth of the nodules. In contrast to the naturally induced mobilisation of metals, a technical impact (e.g., mining of manganese nodules) would be a rapid event occurring under completely different redox conditions. Metals would be released into the bottom water, an oxic environment, where scavenging of dissolved metals and resedimentation takes place in relatively short periods of time. Presumably, a long-distance transport of contaminants will not happen.

  18. Controlling Scattering Instabilities and Adapting to Unknown and Changing Plasma Conditions Using STUD Pulses

    NASA Astrophysics Data System (ADS)

    Afeyan, Bedros; Hüller, Stefan

    2012-10-01

    We will show the results of changing STUD pulse configurations in order to maintain strict control of parametric instabilities in high energy density plasmas (HEDP). Nonlinear optical processes (NLOP) in HEDP respond to changing plasma conditions which are unknown and not easily knowable by standard experimental procedures. Adapting to changing and unknown plasma conditions is one feature of STUD pulses which is absent in other beam conditioning techniques. We demonstrate this by simulating long enough that plasma conditions change, instability gains are altered and new STUD pulse configurations become necessary. Two such configurations are spliced together or run independently and compared. All available methods of changing STUD pulse characteristics are explored, such as duty cycle (20% vs 50%) and modulation period (cutting hot spots in half and into quarters) as well as phase scrambling and number of spikes before the spatial distribution of hot spots is randomized (1, 2, 3 and infinity).

  19. Changes in winter conditions impact forest management in north temperate forests.

    PubMed

    Rittenhouse, Chadwick D; Rissman, Adena R

    2015-02-01

    Climate change may impact forest management activities with important implications for forest ecosystems. However, most climate change research on forests has focused on climate-driven shifts in species ranges, forest carbon, and hydrology. To examine how climate change may alter timber harvesting and forest operations in north temperate forests, we asked: 1) How have winter conditions changed over the past 60 years? 2) Have changes in winter weather altered timber harvest patterns on public forestlands? 3) What are the implications of changes in winter weather conditions for timber harvest operations in the context of the economic, ecological, and social goals of forest management? Using meteorological information from Climate Data Online and Autoregressive Integrated Moving Average (ARIMA) models we document substantial changes in winter conditions in Wisconsin, including a two- to three-week shortening of frozen ground conditions from 1948 to 2012. Increases in minimum and mean soil temperatures were spatially heterogeneous. Analysis of timber harvest records identified a shift toward greater harvest of jack pine and red pine and less harvest of aspen, black spruce, hemlock, red maple, and white spruce in years with less frozen ground or snow duration. Interviews suggested that frozen ground is a mediating condition that enables low-impact timber harvesting. Climate change may alter frozen ground conditions with complex implications for forest management. PMID:25463581

  20. The redox budget of subduction zones

    NASA Astrophysics Data System (ADS)

    Evans, K. A.

    2012-06-01

    , that is, there is addition of Fe, C and S that are oxidised relative to the Fe, C and S in the mantle. The fate of this redox budget can be constrained by consideration of element mobility under mantle conditions. If slab fluids are assumed to be dominantly aqueous and relatively low salinity then fluxes of Fe3 +, C4 +, and S6 + are limited to less than 109, 2.3 × 1012 mol year- 1 and 2 × 1012 mol year- 1 respectively by the low solubility of these elements in slab-derived fluids. Nevertheless, such fluxes can produce the increased fO2 inferred for sub-arc mantle from arc lavas after around 10 Ma subduction. The rest of the redox budget added by the subduction process is likely to be carried to the deep mantle by the slab, and mix slowly with the whole mantle reservoir, depending on the timescale of reincorporation of subducted lithosphere into the mantle. Simple mixing calculations indicate that these fluxes will only cause a measurable difference to mantle redox on a 1 Ga timescale, which is longer than the 550 Ma during which redox budget fluxes are likely to have been at present day levels. However, measurable effects, with potential consequences for the Earth's evolution may be expected in the future.

  1. Redox processes as revealed by voltammetry in the surface sediments of the Gotland Basin, Baltic Sea

    NASA Astrophysics Data System (ADS)

    Yücel, Mustafa; Dale, Andy; Sommer, Stefan; Pfannkuche, Olaf

    2014-05-01

    Sulfur cycling in marine sediments undergoes dramatic changes with changing redox conditions of the overlying waters. The upper sediments of the anoxic Gotland Basin, central Baltic Sea represent a dynamic redox environment with extensive mats of sulfide oxidizing bacteria covering the seafloor beneath the chemocline. In order to investigate sulfur redox cycling at the sediment-water interface, sediment cores were sampled over a transect covering 65 - 174 m water depth in August-September 2013. High resolution (0.25 mm minimum) vertical microprofiles of electroactive redox species including dissolved sulfide and iron were obtained with solid state Au-Hg voltammetric microelectrodes. This approach enabled a fine-scale comparison of porewater profiles across the basin. The steepest sulfide gradients (i.e. the highest sulfide consumption) occurred within the upper 10 mm in sediments covered by surficial mats (2.10 to 3.08 mmol m-2 day-1). In sediments under permanently anoxic waters (>140m), voltammetric signals for Fe(II) and aqueous FeS were detected below a subsurface maximum in dissolved sulfide, indicating a Fe flux originating from older, deeper sedimentary layers. Our results point to a unique sulfur cycling in the Gotland basin seafloor where sulfide accumulation is moderated by sulfide oxidation at the sediment surface and by FeS precipitation in deeper sediment layers. These processes may play an important role in minimizing benthic sulfide fluxes to bottom waters around the major basins of the Baltic Sea.

  2. The Importance of Redox Reactions in Fluid Transport Systems in the Earth's Deep Mantle: Evidence from Nano-Inclusions

    NASA Astrophysics Data System (ADS)

    Jacob, D. E.; Wirth, R.; Dobrzhinetskaya, L.

    2014-12-01

    Focused Ion beam assisted TEM studies of inclusions in diamond have opened up a new perspective on the Earth's deep mantle processes. They enabled direct observation of fluids and have shown a large chemical and redox heterogeneity at the submicron scale, which is not observed in micron-sized inclusions. While crustal metamorphic diamonds are generally formed under oxidizing conditions, polycrystalline diamonds from the Earth's mantle and carbonado have inclusion suites reflecting variable, and sometimes extreme, redox conditions. Diamond fluid compositions, however, fall in the same compositional field for worldwide diamond fluids, regardless of their geodynamic environment. They conform with the fluid end-members established by studies on fibrous diamonds, suggesting a universally important role of a limited number of basic ingredients, namely carbonates, silicates, halides and water. Strong redox gradients reflected by the micro-inclusions indicate diamond precipitation via small-scale, ephemeral redox processes driven by the contrasting oxidation states of fluids and their depositional environment. The susceptibility of the melting point of mantle rocks to the presence of even small amounts of volatiles promotes melting simultaneous to diamond precipitation, which is further enhanced by the changing of fluid composition towards higher water activity. This creates a chemically heterogeneous environment, in which diamonds and their inclusions are precipitated via redox-freezing processes.

  3. Determining the Desorption Kinetics of U(VI) from Contaminated Sediments Under Complex and Changing Solution Conditions

    NASA Astrophysics Data System (ADS)

    Hay, M. B.; Curtis, G. P.; Johnson, K. J.; Greskowiak, J.; Davis, J. A.

    2009-12-01

    Uranium(VI) transport in contaminated sediments is strongly controlled by the thermodynamics and kinetics of adsorption on mineral surfaces. Many studies on natural sediments and synthetic mineral phases have demonstrated the dependence of U(VI) sorption equilibrium on aqueous chemical conditions, with alkalinity, pH, ionic strength, and Ca concentration of particular importance in many natural systems. Desorption of U(VI) from contaminated sediments from DOE sites in Hanford, WA, Rifle, CO, and Naturita, CO also exhibits a significant kinetic limitation, with timescales of several weeks to months required to reach desorption equilibrium in some cases. This kinetic limitation is believed to be due to diffusion in intragranular pore space, which includes small fractures within grains and pores within clay aggregates and grain coatings. Development of appropriate reactive transport models that can be applied to predict the fate and transport of U(VI) in contaminated aquifers relies on accurately quantifying sorption equilibrium and kinetics at the grain scale, which vary from site to site based on sediment characteristics. This analysis typically involves laboratory batch- and column-scale adsorption/desorption experiments performed under a variety of chemical conditions to fully constrain surface complexation and kinetic models, requiring a constant set of chemical conditions over the duration of the experiment. In practice, however, this can be difficult in experiments aiming to quantify long-term kinetics (weeks to months time scale), due to slow ion exchange, mineral dissolution/precipitation, and redox processes. Long-term changes in solution conditions affect U(VI) sorption equilibrium, making it necessary to determine model parameters for U(VI) surface complexation, diffusion kinetics, and chemical weathering/ion exchange processes simultaneously from a given data set. We will present kinetic surface complexation model results obtained for size

  4. Proton gradient regulation 5-mediated cyclic electron flow under ATP- or redox-limited conditions: a study of ΔATpase pgr5 and ΔrbcL pgr5 mutants in the green alga Chlamydomonas reinhardtii.

    PubMed

    Johnson, Xenie; Steinbeck, Janina; Dent, Rachel M; Takahashi, Hiroko; Richaud, Pierre; Ozawa, Shin-Ichiro; Houille-Vernes, Laura; Petroutsos, Dimitris; Rappaport, Fabrice; Grossman, Arthur R; Niyogi, Krishna K; Hippler, Michael; Alric, Jean

    2014-05-01

    The Chlamydomonas reinhardtii proton gradient regulation5 (Crpgr5) mutant shows phenotypic and functional traits similar to mutants in the Arabidopsis (Arabidopsis thaliana) ortholog, Atpgr5, providing strong evidence for conservation of PGR5-mediated cyclic electron flow (CEF). Comparing the Crpgr5 mutant with the wild type, we discriminate two pathways for CEF and determine their maximum electron flow rates. The PGR5/proton gradient regulation-like1 (PGRL1) ferredoxin (Fd) pathway, involved in recycling excess reductant to increase ATP synthesis, may be controlled by extreme photosystem I acceptor side limitation or ATP depletion. Here, we show that PGR5/PGRL1-Fd CEF functions in accordance with an ATP/redox control model. In the absence of Rubisco and PGR5, a sustained electron flow is maintained with molecular oxygen instead of carbon dioxide serving as the terminal electron acceptor. When photosynthetic control is decreased, compensatory alternative pathways can take the full load of linear electron flow. In the case of the ATP synthase pgr5 double mutant, a decrease in photosensitivity is observed compared with the single ATPase-less mutant that we assign to a decreased proton motive force. Altogether, our results suggest that PGR5/PGRL1-Fd CEF is most required under conditions when Fd becomes overreduced and photosystem I is subjected to photoinhibition. CEF is not a valve; it only recycles electrons, but in doing so, it generates a proton motive force that controls the rate of photosynthesis. The conditions where the PGR5 pathway is most required may vary in photosynthetic organisms like C. reinhardtii from anoxia to high light to limitations imposed at the level of carbon dioxide fixation. PMID:24623849

  5. The geochemistry of redox sensitive trace metals in sediments

    SciTech Connect

    Morford, J.L.; Emerson, S.

    1999-06-01

    The authors analyzed the redox sensitive elements V, Mo, U, Re and Cd in surface sediments from the Northwest African margin, the US Northwest margin and the Arabian Sea to determine their response under a range of redox conditions. Where oxygen penetrates 1 cm or less into the sediments, Mo and V diffuse to the overlying water as Mn is reduced and remobilized. Authigenic enrichments of U, Re and Cd are evident under these redox conditions. With the onset of sulfate reduction, all of the metals accumulate authigenically with Re being by far the most enriched. General trends in authigenic metal accumulation are described by calculating authigenic fluxes for the 3 main redox regimes: oxic, reducing where oxygen penetrates {le} 1 cm, and anoxic conditions. Using a simple diagenesis model and global estimates of organic carbon rain rate and bottom water oxygen concentrations, the authors calculate the area of sediments below 1,000 m water depth in which oxygen penetration is {le} 1 cm to be 4% of the ocean floor. They conclude that sediments where oxygen penetrates {le} 1 cm release Mn, V and Mo to seawater at rates of 140%--260%, 60%--150% and 5%--10% of their respective riverine fluxes, using the authigenic metal concentrations and accumulation rates from this work and other literature. These sediments are sinks for Re, Cd and U, with burial fluxes of 70%--140%, 30%--80% and 20%--40%, respectively, of their dissolved riverine inputs. They modeled the sensitivity of the response of seawater Re, Cd and V concentrations to changes in the area of reducing sediments where oxygen penetrates {le} 1 cm. The analysis suggests a negligible change in seawater Re concentration, whereas seawater concentrations of Cd and V could have decreased and increased, respectively, by 5%--10% over 20 kyr if the area of reducing sediments increased by a factor of 2 and by 10%--20% if the area increased by a factor of 3. The concentration variations for a factor of 2 increase in the area of

  6. Changing epistemologies under conditions of social change in two Arab communities in Israel.

    PubMed

    Weinstock, Michael

    2015-02-01

    The study of epistemic thinking focuses on how people understand and coordinate objective and subjective aspects of knowing and make sense of multiple and discrepant knowledge claims. Typically described in terms of normative development, cross-cultural studies show differences in epistemic development and characteristics of epistemic thinking. This study focuses on within-culture variations of epistemic thinking, with the assumption that social change will produce changes in development. Arab society in Israel has undergone notable change over the last half century. In this cross-sectional research design, cross-generational comparison and rural-urban comparison were used as proxies for longitudinal social change. Three generations of Muslim Arab women in a village in Israel (20 adolescents, 20 mothers and 20 grandmothers) and 20 Muslim Arab adolescents from a large, mixed city in the same region responded to six dilemmas invoking epistemic thinking. Village adolescents were more subjectivist than their mothers and grandmothers. Sociodemographic characteristics representing greater exposure to diverse people and ideas accounted for generational differences. Both urban and rural adolescents tended towards subjectivist perspectives, and they did not differ. Parents' education levels emerged as the sociodemographic variables most consistently related to epistemic thinking. Epistemic thinking mediated the relationship between generation and gender role/cross-sex relation values. PMID:25521529

  7. Redox theory of aging

    PubMed Central

    Jones, Dean P.

    2015-01-01

    Metazoan genomes encode exposure memory systems to enhance survival and reproductive potential by providing mechanisms for an individual to adjust during lifespan to environmental resources and challenges. These systems are inherently redox networks, arising during evolution of complex systems with O2 as a major determinant of bioenergetics, metabolic and structural organization, defense, and reproduction. The network structure decreases flexibility from conception onward due to differentiation and cumulative responses to environment (exposome). The redox theory of aging is that aging is a decline in plasticity of genome–exposome interaction that occurs as a consequence of execution of differentiation and exposure memory systems. This includes compromised mitochondrial and bioenergetic flexibility, impaired food utilization and metabolic homeostasis, decreased barrier and defense capabilities and loss of reproductive fidelity and fecundity. This theory accounts for hallmarks of aging, including failure to maintain oxidative or xenobiotic defenses, mitochondrial integrity, proteostasis, barrier structures, DNA repair, telomeres, immune function, metabolic regulation and regenerative capacity. PMID:25863726

  8. Redox effects on the microbial degradation of refractory organic matter in marine sediments

    NASA Astrophysics Data System (ADS)

    Reimers, Clare E.; Alleau, Yvan; Bauer, James E.; Delaney, Jennifer; Girguis, Peter R.; Schrader, Paul S.; Stecher, Hilmar A.

    2013-11-01

    Microbially mediated reduction-oxidation (redox) reactions are often invoked as being the mechanisms by which redox state influences the degradation of sedimentary organic matter (OM) in the marine environment. To evaluate the effects of elevated, oscillating and reduced redox potentials on the fate of primarily aged, mineral-adsorbed OM contained in continental shelf sediments, we used microbial fuel cells to control redox state within and around marine sediments, without amending the sediments with reducing or oxidizing substances. We subsequently followed electron fluxes in the redox elevated and redox oscillating treatments, and related sediment chemical, isotopic and bacterial community changes to redox conditions over a 748-day experimental period. The electron fluxes of the elevated and oscillating redox cells were consistent with models of organic carbon (OC) oxidation with time-dependent first-order rate constants declining from 0.023 to 0.005 y-1, in agreement with rate constants derived from typical OC profiles and down core ages of offshore sediments, or from sulfate reduction rate measurements in similar sediments. Moreover, although cumulative electron fluxes were higher in the continuously elevated redox treatment, incremental rates of electron harvesting in the two treatments converged over the 2 year experiment. These similar rates were reflected in chemical indicators of OM metabolism such as dissolved OC and ammonia, and particulate OC concentrations, which were not significantly different among all treatments and controls over the experimental time-scale. In contrast, products of carbonate and opal dissolution and metal mobilization showed greater enrichments in sediments with elevated and oscillating redox states. Microbial community composition in anode biofilms and surrounding sediments was assessed via high-throughput 16S rRNA gene sequencing, and these analyses revealed that the elevated and oscillatory redox treatments led to the

  9. Co-variation of nitrogen isotopes and redox states through glacial-interglacial cycles in the Black Sea

    NASA Astrophysics Data System (ADS)

    Quan, Tracy M.; Wright, James D.; Falkowski, Paul G.

    2013-07-01

    In all aquatic environments, nitrogen cycling within the water column is strongly influenced by oxygen. We hypothesize that the nitrogen isotopic composition (δ15N) of organic matter deposited in the sediments is a proxy for the redox state of the water column at the time of deposition. We tested the hypothesis by measuring the bulk sedimentary δ15N values in a drill core from the Black Sea, a basin that alternates between oxic, less saline conditions and anoxic, marine conditions on glacial-interglacial time scales. We reconstructed these changes in Black Sea redox conditions using sedimentary δ15N, total organic carbon (TOC), total nitrogen (TN), redox-sensitive metals, and micropaleontological data from a deep-sea core (DSDP Site 380). The sedimentary data reveal that during the transitions between oxic and anoxic conditions, δ15N values increased relative to the preceding and succeeding quasi-steady-state oxic and anoxic periods. The results indicate that the reciprocal transitional states from anoxic to oxic conditions were accompanied by intense denitrification; during the quasi-stable oxic and anoxic states (characterized by glacial fresh water and interglacial marine conditions) nitrification and complete nitrate utilization, respectively, dominate the nitrogen cycle. While other factors may influence the δ15N record, our results support the hypothesis that the variations in nitrogen isotopic composition of organic matter are strongly influenced by changes in redox state in the Black Sea subphotic zone on glacial-interglacial time scales, and can be explained by a relatively simple model describing the effects of oxygen on the microbial processes that drive the nitrogen cycle in marine ecosystems. Our model suggests that the nitrogen isotopic composition of marine sediments, on geological time scales, can be used to reconstruct the redox state of the overlying water column.

  10. Contrasting Redox Stories from Trace Metal and Iron Proxy Records of the Late Cretaceous Western Interior Seaway

    NASA Astrophysics Data System (ADS)

    Tessin, A. C.; Sheldon, N. D.; Hendy, I. L.; Chappaz, A.

    2015-12-01

    The sedimentary record of the Cretaceous Western Interior Seaway (North America) is characterized by periods of enhanced organic carbon burial known as Oceanic Anoxic Events (OAEs). Compared to more typical OAEs, the last Cretaceous OAE, the Coniacian-Santonian OAE 3 (~86 Ma), is enigmatic and its driving mechanism less understood. While OAE 3 was geographically limited to restricted basins and shallow seaways, it also had a longer duration (~3 myrs) of organic carbon burial than earlier OAEs., Constraining paleoredox conditions during organic carbon burial events, such as OAEs, is important for understanding the relationship between ocean anoxia and carbon burial. Iron proxies (FeHR/FeT, Fepy/FeHR, and FeT/Al) provide an important tool in the reconstruction of paleoredox conditions through geologic time. Here we present sequential Fe and pyrite Fe measurements from the Niobrara Formation recovered in the USGS #1 Portland core from Cañon City Basin, Colorado. The new results indicate that Fe redox proxies from the Portland core are not always in agreement with other redox proxies. Pyrite Fe measurements indicate a single stepwise change in seaway oxygen limitation, whereas other paleoredox proxies (Mo, Re, U, bioturbation indices) indicate fluctuating redox conditions and a variable degree of euxinia throughout the record. Interpretation of pyrite Fe values may be complicated by the development of a highly reactive Fe limitation. Another commonly used redox proxy, FeT/Al, indicates oxic conditions when other redox proxies suggest anoxia and vice versa. Interpretation FeT/Al may be complicated by a number of factors, including sequestration of Fe in diagenetic carbonate phases, variable supply of external Fe, atypical basin geometry, and the development of shallow marine euxinia. Taken together, these observations clearly support the importance of using a multi proxy approach to accurately reconstruct oceanic redox history.

  11. Monitoring of WUT grand hall roof in conditions of high temperature changes

    NASA Astrophysics Data System (ADS)

    Wozniak, M.

    2009-04-01

    The geodetic control measurements of changes in object's geometry should satisfy high accuracy and reliability. New tacheometers equipped with Automatic Target Recognition automatically moves the telescope to the center of the prism and supports control points measurements. The accuracy of using ATR system and stability of instrument in precise measurements were controlled in laboratory and field conditions. This paper will present the results of monitoring measurements using Leica TDA 5005 during investigations of roof geometry in conditions of high temperature changes.

  12. Experimentally observed iron redox kinetics in silicic liquids: Implications for Fe/sup 3 +//Fe/sup 2 +/ variations in rhyolite lava

    SciTech Connect

    Naney, M.T.; Swanson, S.E.

    1989-01-01

    Iron redox kinetics in silicate liquids were investigated by melting 100 mg pellets of compacted rhyolite, pantellerite, pantelleritic trachyte, and andesite rock powders at 1243 and 1343/degree/C in a moderately reducing furnace atmosphere (log fO/sub 2/ = /minus/7.83) for periods of 1 to 4320 minutes. The redox state of glasses produced by quenching these liquids was determined by colorimetric analysis of the ferrous iron and total iron content. Redox equilibrium, indicated by the attainment of a constant FeO/FeO/sub tot/ ratio, was observed for all temperature-composition conditions studied, except for 1243/degree/C experiments with USGS rhyolite standard RGM-1. This is consistent with the low diffusivity of reacting components in high viscosity rhyolite liquids. In the 1243/degree/C experiments with RGM-1, no change in the FeO/FeO/sub tot/ ratio was observed after 4320 minutes. This implies that redox equilibrium is not maintained in natural rhyolite lavas which erupt as significantly lower temperatures (720--850/degree/C). We conclude that sluggish redox kinetics precludes major changes in the oxidation state of a rhyolite magma during the eruption process. If this is true, then the quenched magma, represented by glassy rhyolites, preserves the pre-eruption redox signature of the magma. 2 refs.

  13. Corrosion fatigue behavior and life prediction method under changing temperature condition

    SciTech Connect

    Kanasaki, Hiroshi; Hirano, Akihiko; Iida, Kunihiro; Asada, Yasuhide

    1997-12-01

    Axially strain controlled low cycle fatigue tests of a carbon steel in oxygenated high temperature water were carried out under changing temperature conditions. Two patterns of triangular wave were selected for temperature cycling. One was in-phase pattern synchronizing with strain cycling and the other was an out-of-phase pattern in which temperature was changed in anti-phase to the strain cycling. The fatigue life under changing temperature condition was in the range of the fatigue life under various constant temperature within the range of the changing temperature. The fatigue life of in-phase pattern was equivalent to that of out-of-phase pattern. The corrosion fatigue life prediction method was proposed for changing temperature condition, and was based on the assumption that the fatigue damage increased in linear proportion to increment of strain during cycling. The fatigue life predicted by this method was in good agreement with the test results.

  14. Should flood regimes change in a warming climate? The role of antecedent moisture conditions

    NASA Astrophysics Data System (ADS)

    Woldemeskel, Fitsum; Sharma, Ashish

    2016-07-01

    Assessing changes to flooding is important for designing new and redesigning existing infrastructure to withstand future climates. While there is speculation that floods are likely to intensify in the future, this question is often difficult to assess due to inadequate records on streamflow extremes. An alternate way of determining possible extreme flooding is through assessment of the two key factors that lead to the intensification of floods: the intensification of causative rainfall and changes in the wetness conditions prior to rainfall. This study assesses global changes in the antecedent wetness prior to extreme rainfall. Our results indicate a significant increase in the antecedent moisture in Australia and Africa over the last century; however, there was also a decrease in Eurasia and insignificant change in North America. Given the nature of changes found in this study, any future flood assessment for global warming conditions should take into account antecedent moisture conditions.

  15. A lack of response of the financial behaviors of biodiversity conservation nonprofits to changing economic conditions.

    PubMed

    Larson, Eric R; Boyer, Alison G; Armsworth, Paul R

    2014-12-01

    The effectiveness of conservation organizations is determined in part by how they adapt to changing conditions. Over the previous decade, economic conditions in the United States (US) showed marked variation including a period of rapid growth followed by a major recession. We examine how biodiversity conservation nonprofits in the US responded to these changes through their financial behaviors, focusing on a sample of 90 biodiversity conservation nonprofits and the largest individual organization (The Nature Conservancy; TNC). For the 90 sampled organizations, an analysis of financial ratios derived from tax return data revealed little response to economic conditions. Similarly, more detailed examination of conservation expenditures and land acquisition practices of TNC revealed only one significant relationship with economic conditions: TNC accepted a greater proportion of conservation easements as donated in more difficult economic conditions. Our results suggest that the financial behaviors of US biodiversity conservation nonprofits are unresponsive to economic conditions. PMID:25512840

  16. A lack of response of the financial behaviors of biodiversity conservation nonprofits to changing economic conditions

    PubMed Central

    Larson, Eric R; Boyer, Alison G; Armsworth, Paul R

    2014-01-01

    The effectiveness of conservation organizations is determined in part by how they adapt to changing conditions. Over the previous decade, economic conditions in the United States (US) showed marked variation including a period of rapid growth followed by a major recession. We examine how biodiversity conservation nonprofits in the US responded to these changes through their financial behaviors, focusing on a sample of 90 biodiversity conservation nonprofits and the largest individual organization (The Nature Conservancy; TNC). For the 90 sampled organizations, an analysis of financial ratios derived from tax return data revealed little response to economic conditions. Similarly, more detailed examination of conservation expenditures and land acquisition practices of TNC revealed only one significant relationship with economic conditions: TNC accepted a greater proportion of conservation easements as donated in more difficult economic conditions. Our results suggest that the financial behaviors of US biodiversity conservation nonprofits are unresponsive to economic conditions. PMID:25512840

  17. Rate of Conditioned Reinforcement Affects Observing Rate but Not Resistance to Change

    ERIC Educational Resources Information Center

    Shahan, Timothy A.; Podlesnik, Christopher A.

    2005-01-01

    The effects of rate of conditioned reinforcement on the resistance to change of operant behavior have not been examined. In addition, the effects of rate of conditioned reinforcement on the rate of observing have not been adequately examined. In two experiments, a multiple schedule of observing-response procedures was used to examine the effects…

  18. 30 CFR 203.77 - May I voluntarily give up relief if conditions change?

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 30 Mineral Resources 2 2011-07-01 2011-07-01 false May I voluntarily give up relief if conditions... Expansion Projects § 203.77 May I voluntarily give up relief if conditions change? Yes, you may voluntarily give up relief by sending a letter to that effect to the MMS Regional office for your region....

  19. 30 CFR 203.77 - May I voluntarily give up relief if conditions change?

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 30 Mineral Resources 2 2013-07-01 2013-07-01 false May I voluntarily give up relief if conditions... Sulfur General § 203.77 May I voluntarily give up relief if conditions change? Yes, you may voluntarily give up relief by sending a letter to that effect to the BSEE Regional office for your region....

  20. 30 CFR 203.77 - May I voluntarily give up relief if conditions change?

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 30 Mineral Resources 2 2012-07-01 2012-07-01 false May I voluntarily give up relief if conditions... Sulfur General § 203.77 May I voluntarily give up relief if conditions change? Yes, you may voluntarily give up relief by sending a letter to that effect to the BSEE Regional office for your region....