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Sample records for changing redox conditions

  1. Seasonal changes in magnetic parameters of sediments with changing redox conditions in Hiroshima Bay, Japan

    NASA Astrophysics Data System (ADS)

    Kawamura, Noriko; Amano, Yuka; Ishikawa, Naoto

    2016-07-01

    To describe and interpret the relationship between spatial and seasonal changes in the sedimentary environment of nearshore sediments and their magnetic properties, magnetic and geochemical analyses were performed on sediment samples from three stations in Hiroshima Bay, Japan. Vertical stratification of the water column in the bay changes throughout the year, and magnetic hysteresis parameters and mineralogy in the bay sediments vary in response to changes in redox conditions of bottom waters. Magnetite and hematite are present year-round at all stations. The presence of maghemitized magnetite is inferred at a station located at the entrance to the bay. Greigite is recognized at all stations in September 2011 but is not found at the entrance to the bay when water column stratification is disturbed from October 2011. The presence of maghemite and goethite is inferred at two stations in the inner bay when the sedimentary environment is oxic. The remanent coercivity/coercivity ratio (Hcr/Hc) also varies, both spatially and temporally, which reflects changes in magnetic mineralogy. Increased of Hcr/Hc values are likely to be caused by goethite and/or maghemite formation when water column stratification is disturbed and the seafloor is oxic. Concentration-dependent magnetic parameters do not respond to seasonal changes in the redox conditions of bottom waters. Reaction times and/or changes in chemical and physical conditions may be insufficient to affect these parameters in the sediments of Hiroshima Bay.

  2. Changes in sediment redox conditions following the BP DWH blowout event

    NASA Astrophysics Data System (ADS)

    Hastings, D. W.; Schwing, P. T.; Brooks, G. R.; Larson, R. A.; Morford, J. L.; Roeder, T.; Quinn, K. A.; Bartlett, T.; Romero, I. C.; Hollander, D. J.

    2016-07-01

    Following the blowout of the Macondo well, a pulse in sedimentation resulted in changes in sedimentary redox conditions. This is demonstrated by downcore and temporal changes in the concentration of redox sensitive metals: Mn, Re, and Cd. Sediment cores collected in the NE Gulf of Mexico (GoM) reveal increased sedimentation after the Deepwater Horizon (DWH) blowout. The formation of mucous-rich marine snow in surface waters and subsequent rapid deposition to underlying sediments is the likely cause. Respiration of this material resulted in decreased pore-water oxygen concentration and a shoaled redoxcline, resulting in two distinct Mn peaks in sediments following the event, one typically in the top 10 mm, with the other at 20-30 mm. Most cores near the wellhead reveal this non-steady state behavior for up to two years after the event. Associated with the Mn minimum between the two Mn peaks, a modest (15-30%) enrichment of Re consistent with reducing sediments typically exists. A three-year time series of three stations following the event reveal that sediment Re increased 3-4 times compared to the pre-impact baseline value for two years, indicating sediments are increasingly more reducing for two years. In the third year, Re concentration decreased, suggesting a return towards pre-impact conditions. In select sites where the density of benthic foraminifera was determined, an assemblage-wide decrease occurred coincident with reducing conditions as determined by redox sensitive metals, demonstrating the important consequences of changing redox conditions on benthic ecosystems. Determination of redox sensitive metals will continue to constrain the temporal evolution of reducing conditions, which will serve to document the long-term effects of the spill, and the possible return to pre-event conditions.

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

    NASA Astrophysics Data System (ADS)

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

    2016-12-01

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

  4. Changes in the Precambrian ocean U cycle linked to the evolution of surficial redox conditions

    NASA Astrophysics Data System (ADS)

    Partin, C. A.; Bekker, A.; Scott, C.; Gill, B. C.; Lyons, T. W.

    2009-12-01

    The rise of atmospheric oxygen between 2.47 and 2.32 Ga undoubtedly had a significant impact on global biogeochemical cycles and particularly, the intensity of oxidative continental weathering. While the timing of atmospheric oxygenation is well-constrained, the redox -state of the deep ocean throughout the Proterozoic is less known. The distribution of redox-sensitive elements, such as uranium and molybdenum, in ancient sedimentary rocks provides insight into the response of the deep ocean to this dramatic geochemical change. Here we present a compilation of U concentrations in marine black shales, from the Archean to the present to track the coupled redox evolution of the atmosphere and oceans, and to decipher changes in the uranium cycle itself. Since riverine delivery represents the only significant source of uranium to the oceans, and scavenging by organic matter-rich sediments beneath suboxic to anoxic waters represents the only significant sink, uranium concentrations in black shales hold a record of the evolution of the uranium cycle through time. Temporal changes in the concentrations of U in black shales can be attributed to two first-order controls: variable delivery of riverine U to the ocean, a reflection of levels of oxygen in the atmosphere, and the extent of ocean anoxic conditions. The compiled data show a series of changes in the uranium cycle through time. Phanerozoic uranium enrichments are associated with ocean-wide anoxic events coupled with a fully developed oxidative continental weathering cycle. Enrichments are muted in Proterozoic sediments, reflecting either a weaker riverine delivery of uranium to the oceans, and/or a strong sink associated with widespread anoxia. Authigenic uranium enrichments significantly above crustal levels, which reflect strong oxidative continental weathering, do not appear until several hundred million years after the Great Oxidation Event. We propose that the U cycle in the Archean oceans was dominated by the

  5. The nitrogen cycle under changing redox conditions during late Neoproterozoic: the Ediacaran nitrate revolution?

    NASA Astrophysics Data System (ADS)

    Prokopenko, M.; Corsetti, F. A.; Gaines, R. R.; Loyd, S. J.; Cordova, A.; Berelson, W.

    2016-12-01

    The oxidation state of fixed (non-gaseous) nitrogen, a major limiting nutrient for the marine primary production, is dictated by the ambient environmental redox conditions: in the absence of O2, fixed inorganic N is stable in the form of ammonium, while in the presence of dissolved O2 nitrate is the main form. Therefore, the prevalence of nitrate vs. ammonium most likely reflects the availability of dissolved O2. We have developed a method of determining nitrate content in carbonates, Carbonate Associated Nitrate (CAN), as a proxy for the oceanic nitrate content. To investigate changes in the global O2 and marine nitrogen cycles through time, concentrations of CAN have been evaluated in both limestones and dolostones from multiple localities around the world, spanning the ages from 3 Ga through modern. The highest CAN values were found as several distinct peaks in the late Neoproterozoic carbonates from two locations: Caborca in Sonora, Mexico, within a stratigraphic sequence deposited through the Ediacaran, and within the Rainstorm Member of the Johnnie Formation in the Death Valley, California, likely deposited at the onset of the Shuram d13C excursion. The sharp increases in nitrate recorded in these rocks may be linked to a rapid, possibly multi-stage increase in the atmospheric O2 during this time. Transformation of the fixed N from the reduced to the oxidized forms (from ammonium to nitrate) may have caused a major restructuring of the global N cycle, possibly contributing to the diversification of the eukaryotic phytoplankton communities, forced to adapt to using nitrate instead of ammonium as the major nitrogen source.

  6. 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

  7. A 22,000 year record of changing redox conditions from the Peruvian Oxygen Minimum Zone (OMZ): benthic foraminifera approach

    NASA Astrophysics Data System (ADS)

    Erdem, Z.; Schönfeld, J.; Glock, N.

    2015-12-01

    Benthic foraminifera have been used as proxies for the prevailing conditions at the sediment-water interface. Their distribution patterns are thought to facilitate reconstruction of past environmental conditions. Variations of bottom water oxygenation can be traced by the downcore distribution of benthic foraminifera and some of their morphological characters. Being one of the strongest and most pronounced OMZs in today's world oceans, the Peruvian OMZ is a key area to study such variations in relation with changing climate. Spatial changes or an extension of the OMZ through time and space are investigated using sediment cores from the lower OMZ boundary. We focus on time intervals Late Holocene, Early Holocene, Bølling Allerød, Heinrich-Stadial 1 and Last Glacial Maximum (LGM) to investigate changes in bottom-water oxygen and redox conditions. The recent distributions of benthic foraminiferal assemblages provide background data for an interpretation of the past conditions. Living benthic foraminiferal faunas from the Peruvian margin are structured with the prevailing bottom-water oxygen concentrations today (Mallon et al., 2012). Downcore distribution of benthic foraminiferal assemblages showed fluctuations in the abundance of the indicator species depicting variations and a decreasing trend in bottom water oxygen conditions since the LGM. In addition, changes in bottom-water oxygen and nitrate concentrations are reconstructed for the same time intervals by the pore density in tests of Planulina limbata and Bolivina spissa (Glock et al., 2011), respectively. The pore densities also indicate a trend of higher oxygen and nitrate concentrations in the LGM compared to the Holocene. Combination of both proxies provide information on past bottom-water conditions and changes of oxygen concentrations for the Peruvian margin. Glock et al., 2011: Environmental influences on the pore density of Bolivina spissa (Cushman), Journal of Foraminiferal Research, v. 41, no. 1, p

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

    NASA Astrophysics Data System (ADS)

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

    2017-02-01

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

  9. 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

  10. 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

  11. 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.

  12. 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.

  13. 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.

  14. Behavioral responses of Escherichia coli to changes in redox potential.

    PubMed

    Bespalov, V A; Zhulin, I B; Taylor, B L

    1996-09-17

    Escherichia coli bacteria sensed the redox state in their surroundings and they swam to a niche that had a preferred reduction potential. In a spatial redox gradient of benzoquinone/benzoquinol, E. coli cells migrated to form a sharply defined band. Bacteria swimming out of either face of the band tumbled and returned to the preferred conditions at the site of the band. This behavioral response was named redox taxis. Redox molecules, such as substituted quinones, that elicited redox taxis, interact with the bacterial electron transport system, thereby altering electron transport and the proton motive force. The magnitude of the behavioral response was dependent on the reduction potential of the chemoeffector. The Tsr, Tar, Trg, Tap, and CheR proteins, which have a role in chemotaxis, were not essential for redox taxis. A cheB mutant had inverted responses in redox taxis, as previously demonstrated in aerotaxis. A model is proposed in which a redox effector molecule perturbs the electron transport system, and an unknown sensor in the membrane detects changes in the proton motive force or the redox status of the electron transport system, and transduces this information into a signal that regulates phosphorylation of the CheA protein. A similar mechanism has been proposed for aerotaxis. Redox taxis may play an important role in the distribution of bacterial species in natural environments.

  15. The influence of sulfur and iron on dissolved arsenic concentrations in the shallow subsurface under changing redox conditions

    PubMed Central

    O'Day, Peggy A.; Vlassopoulos, Dimitri; Root, Robert; Rivera, Nelson

    2004-01-01

    The chemical speciation of arsenic in sediments and porewaters of aquifers is the critical factor that determines whether dissolved arsenic accumulates to potentially toxic levels. Sequestration of arsenic in solid phases, which may occur by adsorption or precipitation processes, controls dissolved concentrations. We present synchrotron x-ray absorption spectra of arsenic in shallow aquifer sediments that indicate the local structure of realgar (AsS) as the primary arsenic-bearing phase in sulfate-reducing conditions at concentrations of 1–3 mmol·kg–1, which has not previously been verified in sediments at low temperature. Spectroscopic evidence shows that arsenic does not substitute for iron or sulfur in iron sulfide minerals at the molecular scale. A general geochemical model derived from our field and spectroscopic observations show that the ratio of reactive iron to sulfur in the system controls the distribution of solid phases capable of removing arsenic from solution when conditions change from oxidized to reduced, the rate of which is influenced by microbial processes. Because of the difference in solubility of iron versus arsenic sulfides, precipitation of iron sulfide may remove sulfide from solution but not arsenic if precipitation rates are fast. The lack of incorporation of arsenic into iron sulfides may result in the accumulation of dissolved As(III) if adsorption is weak or inhibited. Aquifers particularly at risk for such geochemical conditions are those in which oxidized and reduced waters mix, and where the amount of sulfate available for microbial reduction is limited. PMID:15356340

  16. [Local changes in the rabbit brain cortex redox potential accompanying the formation of a conditioned defensive reflex].

    PubMed

    Shvets-Ténéta-Guriĭ, T B; Troshin, G I; Dubinin, A G

    2006-03-01

    The brain E is determined by ratio in rate of processes occuring in two energy compartments--in glycolysis (the more ancient one in evolution) in which glucose is splitted whithout oxygen utilization, and in oxidative metabolism which is younger in evolution than glycolysis and more effective than glycolysis. In the present investigation, the brain cortex E changes were recorded with implanted platinum electrodes. CDR was established by combination of light and electric shock applied to the left ear. It has been found that the combinations started to be accompanied by the E shift after the first 5-20 combinations. The E shifts were widely generalized over the cortex, and both increasing and decreasing E were well expressed within 50-200 combinations. As the number of combination increased, the increases in E were gradually replaced by the decreases in E. This dynamic in the balance of the major sources of the brain energy supply during the formation of CDR demonstrates, in our opinion, that subcellular structures or complexes of cells which appeared at the same stages of evolution as the compartment of oxidative metabolism make a significant contribution to the CDR acquisition when memory traces are created, while brain function during realization of well consolidated CDR are supported mainly by glycolysis.

  17. 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

  18. 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.

  19. 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.

  20. 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

  1. 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.

  2. Mobility and phytoavailability of As and Pb in a contaminated soil using pine sawdust biochar under systematic change of redox conditions.

    PubMed

    Beiyuan, Jingzi; Awad, Yasser M; Beckers, Felix; Tsang, Daniel C W; Ok, Yong Sik; Rinklebe, Jörg

    2017-03-08

    Biochar has been adopted to control the mobility and phytoavailability of trace elements (TEs) in soils. To date, no attempt has been made to determine the mobility and phytoavailability of arsenic (As) and lead (Pb) in a contaminated soil with biochars as amendments under predefined redox potentials (EH). Thus, in this study, a soil contaminated with As and Pb (2047 and 1677 mg kg(-1), respectively) was pre-incubated for 105 days with three amendments (pine sawdust biomass (BM) and two biochars produced from the same feedstock at 300 °C (BC300) and 550 °C (BC550)). The aged samples were then exposed to dynamic EH conditions to evaluate the mobility and phytoavailability of As and Pb after immobilization. The BM amendment significantly decreased and the BC300 slightly reduced the mobility and phytoavailability of As and Pb, which may be related to the oxygen-containing functional groups on the surface of BM and BC300. In contrast, BC550 increased the mobility of As at -300 to -100 mV and 100 mV, enhanced the phytoavailability of As under oxidizing condition (>100 mV), but reduced the phytoavailability of Pb, which might be caused by the properties of amendments and redox chemistry of the TEs. The effectiveness of BM and biochars for the stabilization of As and Pb varied under dynamic EH conditions, which indicates that detailed investigations should be conducted before the applications of biochar as soil amendment under variable environmental conditions, especially for contaminated paddy soils.

  3. The roles of conditional disorder in redox proteins

    PubMed Central

    Reichmann, Dana; Jakob, Ursula

    2013-01-01

    Cells are constantly exposed to various oxidants, either generated endogenously due to metabolic activity or exogenously. One way that cells respond to oxidants is through the action of redox-regulated proteins. These proteins also play important roles in oxidant signaling and protein biogenesis events. The key sensors built into redox-regulated proteins are cysteines, which undergo reversible thiol oxidation in response to changes in the oxidation status of the cellular environment. In this review, we discuss three examples of redox-regulated proteins found in bacteria, mitochondria, and chloroplasts. These proteins use oxidation of their redox-sensitive cysteines to reversibly convert large structural domains into more disordered regions or vice versa. These massive structural rearrangements are directly implicated in the functions of these proteins. PMID:23477949

  4. The roles of conditional disorder in redox proteins.

    PubMed

    Reichmann, Dana; Jakob, Ursula

    2013-06-01

    Cells are constantly exposed to various oxidants, either generated endogenously due to metabolic activity or exogenously. One way that cells respond to oxidants is through the action of redox-regulated proteins. These proteins also play important roles in oxidant signaling and protein biogenesis events. The key sensors built into redox-regulated proteins are cysteines, which undergo reversible thiol oxidation in response to changes in the oxidation status of the cellular environment. In this review, we discuss three examples of redox-regulated proteins found in bacteria, mitochondria, and chloroplasts. These proteins use oxidation of their redox-sensitive cysteines to reversibly convert large structural domains into more disordered regions or vice versa. These massive structural rearrangements are directly implicated in the functions of these proteins. Copyright © 2013 Elsevier Ltd. All rights reserved.

  5. Copper dynamics under alternating redox conditions is influenced by soil properties and contamination source.

    PubMed

    Balint, Ramona; Said-Pullicino, Daniel; Ajmone-Marsan, Franco

    2015-02-01

    Understanding the effect of soil redox conditions on contaminant dynamics is of significant importance for evaluating their lability, mobility and potential transfer to other environmental compartments. Under changing redox conditions, soil properties and constituents such as Fe and Mn (hydr)oxides and organic matter (OM) may influence the behavior of associated metallic elements (MEs). In this work, the redox-driven release and redistribution of Cu between different soil pools was studied in three soils having different contamination sources. This was achieved by subjecting soil columns to a series of alternating reducing and oxidizing cycles under non-limiting C conditions, and assessing their influence on soil pore water, leachate and solid phase composition. Results showed that, in all soils, alternating redox conditions led to an increase in the distribution of Cu in the more labile fractions, consequently enhancing its susceptibility to loss. This was generally linked to the redox-driven cycling of Fe, Mn and dissolved organic matter (DOM). In fact, results suggested that the reductive dissolution of Fe and Mn (hydr)oxides and subsequent reprecipitation as poorly-ordered phases under oxic conditions contributed to the release and mobilization of Cu and/or Cu-containing organometallic complexes. However, the behavior of Cu, as well as the mechanisms controlling Cu release and loss with redox cycling, was influenced by both soil properties (e.g. pH, contents of easily reducible Fe and Mn (hydr)oxides) and source of Cu contamination.

  6. Copper dynamics under alternating redox conditions is influenced by soil properties and contamination source

    NASA Astrophysics Data System (ADS)

    Balint, Ramona; Said-Pullicino, Daniel; Ajmone-Marsan, Franco

    2015-02-01

    Understanding the effect of soil redox conditions on contaminant dynamics is of significant importance for evaluating their lability, mobility and potential transfer to other environmental compartments. Under changing redox conditions, soil properties and constituents such as Fe and Mn (hydr)oxides and organic matter (OM) may influence the behavior of associated metallic elements (MEs). In this work, the redox-driven release and redistribution of Cu between different soil pools was studied in three soils having different contamination sources. This was achieved by subjecting soil columns to a series of alternating reducing and oxidizing cycles under non-limiting C conditions, and assessing their influence on soil pore water, leachate and solid phase composition. Results showed that, in all soils, alternating redox conditions led to an increase in the distribution of Cu in the more labile fractions, consequently enhancing its susceptibility to loss. This was generally linked to the redox-driven cycling of Fe, Mn and dissolved organic matter (DOM). In fact, results suggested that the reductive dissolution of Fe and Mn (hydr)oxides and subsequent reprecipitation as poorly-ordered phases under oxic conditions contributed to the release and mobilization of Cu and/or Cu-containing organometallic complexes. However, the behavior of Cu, as well as the mechanisms controlling Cu release and loss with redox cycling, was influenced by both soil properties (e.g. pH, contents of easily reducible Fe and Mn (hydr)oxides) and source of Cu contamination.

  7. 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

  8. 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 ...

  9. Distinct Redox Regulation in Sub-Cellular Compartments in Response to Various Stress Conditions in Saccharomyces cerevisiae

    PubMed Central

    Ayer, Anita; Sanwald, Julia; Pillay, Bethany A.; Meyer, Andreas J.; Perrone, Gabriel G.; Dawes, Ian W.

    2013-01-01

    Responses to many growth and stress conditions are assumed to act via changes to the cellular redox status. However, direct measurement of pH-adjusted redox state during growth and stress has never been carried out. Organellar redox state (EGSH) was measured using the fluorescent probes roGFP2 and pHluorin in Saccharomyces cerevisiae. In particular, we investigated changes in organellar redox state in response to various growth and stress conditions to better understand the relationship between redox-, oxidative- and environmental stress response systems. EGSH values of the cytosol, mitochondrial matrix and peroxisome were determined in exponential and stationary phase in various media. These values (−340 to −350 mV) were more reducing than previously reported. Interestingly, sub-cellular redox state remained unchanged when cells were challenged with stresses previously reported to affect redox homeostasis. Only hydrogen peroxide and heat stress significantly altered organellar redox state. Hydrogen peroxide stress altered the redox state of the glutathione disulfide/glutathione couple (GSSG, 2H+/2GSH) and pH. Recovery from moderate hydrogen peroxide stress was most rapid in the cytosol, followed by the mitochondrial matrix, with the peroxisome the least able to recover. Conversely, the bulk of the redox shift observed during heat stress resulted from alterations in pH and not the GSSG, 2H+/2GSH couple. This study presents the first direct measurement of pH-adjusted redox state in sub-cellular compartments during growth and stress conditions. Redox state is distinctly regulated in organelles and data presented challenge the notion that perturbation of redox state is central in the response to many stress conditions. PMID:23762325

  10. Distinct redox regulation in sub-cellular compartments in response to various stress conditions in Saccharomyces cerevisiae.

    PubMed

    Ayer, Anita; Sanwald, Julia; Pillay, Bethany A; Meyer, Andreas J; Perrone, Gabriel G; Dawes, Ian W

    2013-01-01

    Responses to many growth and stress conditions are assumed to act via changes to the cellular redox status. However, direct measurement of pH-adjusted redox state during growth and stress has never been carried out. Organellar redox state (E GSH) was measured using the fluorescent probes roGFP2 and pHluorin in Saccharomyces cerevisiae. In particular, we investigated changes in organellar redox state in response to various growth and stress conditions to better understand the relationship between redox-, oxidative- and environmental stress response systems. E GSH values of the cytosol, mitochondrial matrix and peroxisome were determined in exponential and stationary phase in various media. These values (-340 to -350 mV) were more reducing than previously reported. Interestingly, sub-cellular redox state remained unchanged when cells were challenged with stresses previously reported to affect redox homeostasis. Only hydrogen peroxide and heat stress significantly altered organellar redox state. Hydrogen peroxide stress altered the redox state of the glutathione disulfide/glutathione couple (GSSG, 2H(+)/2GSH) and pH. Recovery from moderate hydrogen peroxide stress was most rapid in the cytosol, followed by the mitochondrial matrix, with the peroxisome the least able to recover. Conversely, the bulk of the redox shift observed during heat stress resulted from alterations in pH and not the GSSG, 2H(+)/2GSH couple. This study presents the first direct measurement of pH-adjusted redox state in sub-cellular compartments during growth and stress conditions. Redox state is distinctly regulated in organelles and data presented challenge the notion that perturbation of redox state is central in the response to many stress conditions.

  11. 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

  12. Microbial functional gene diversity with a shift of subsurface redox conditions during In Situ uranium reduction.

    PubMed

    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; Zhou, Jizhong

    2012-04-01

    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 (E(h)) 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.

  13. Assessing the regulation of leaf redox status under water stress conditions in Arabidopsis thaliana

    PubMed Central

    Brossa, Ricard; Pintó-Marijuan, Marta; Jiang, Keni; Alegre, Leonor; Feldman, Lewis J.

    2013-01-01

    Using Arabidopsis plants Col-0 and vtc2 transformed with a redox sensitive green fluorescent protein, (c-roGFP) and (m-roGFP), we investigated the effects of a progressive water stress and re-watering on the redox status of the cytosol and the mitochondria. Our results establish that water stress affects redox status differently in these two compartments, depending on phenotype and leaf age, furthermore we conclude that ascorbate plays a pivotal role in mediating redox status homeostasis and that Col-0 Arabidopsis subjected to water stress increase the synthesis of ascorbate suggesting that ascorbate may play a role in buffering changes in redox status in the mitochondria and the cytosol, with the presumed buffering capacity of ascorbate being more noticeable in young compared with mature leaves. Re-watering of water-stressed plants was paralleled by a return of both the redox status and ascorbate to the levels of well-watered plants. In contrast to the effects of water stress on ascorbate levels, there were no significant changes in the levels of glutathione, thereby suggesting that the regeneration and increase in ascorbate in water-stressed plants may occur by other processes in addition to the regeneration of ascorbate via the glutathione. Under water stress in vtc2 lines it was observed stronger differences in redox status in relation to leaf age, than due to water stress conditions compared with Col-0 plants. In the vtc2 an increase in DHA was observed in water-stressed plants. Furthermore, this work confirms the accuracy and sensitivity of the roGFP1 biosensor as a reporter for variations in water stress-associated changes in redox potentials. PMID:23656871

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

    NASA Astrophysics Data System (ADS)

    Gavrieli, Ittai; Burg, Avi; Guttman, Joseph

    2002-08-01

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

  15. 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.

  16. 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

  17. Bicarbonate Induced Redox Proteome Changes in Arabidopsis Suspension Cells.

    PubMed

    Yin, Zepeng; Balmant, Kelly; Geng, Sisi; Zhu, Ning; Zhang, Tong; Dufresne, Craig; Dai, Shaojun; Chen, Sixue

    2017-01-01

    Climate change as a result of increasing atmospheric CO2 affects plant growth and productivity. CO2 is not only a carbon donor for photosynthesis but also an environmental signal that can perturb cellular redox homeostasis and lead to modifications of redox-sensitive proteins. Although redox regulation of protein functions has emerged as an important mechanism in several biological processes, protein redox modifications and how they function in plant CO2 response remain unclear. Here a new iodoTMTRAQ proteomics technology was employed to analyze changes in protein redox modifications in Arabidopsis thaliana suspension cells in response to bicarbonate (mimic of elevated CO2) in a time-course study. A total of 47 potential redox-regulated proteins were identified with functions in carbohydrate and energy metabolism, transport, ROS scavenging, cell structure modulation and protein turnover. This inventory of previously unknown redox responsive proteins in Arabidopsis bicarbonate responses lays a foundation for future research toward understanding the molecular mechanisms underlying plant CO2 responses.

  18. Bicarbonate Induced Redox Proteome Changes in Arabidopsis Suspension Cells

    PubMed Central

    Yin, Zepeng; Balmant, Kelly; Geng, Sisi; Zhu, Ning; Zhang, Tong; Dufresne, Craig; Dai, Shaojun; Chen, Sixue

    2017-01-01

    Climate change as a result of increasing atmospheric CO2 affects plant growth and productivity. CO2 is not only a carbon donor for photosynthesis but also an environmental signal that can perturb cellular redox homeostasis and lead to modifications of redox-sensitive proteins. Although redox regulation of protein functions has emerged as an important mechanism in several biological processes, protein redox modifications and how they function in plant CO2 response remain unclear. Here a new iodoTMTRAQ proteomics technology was employed to analyze changes in protein redox modifications in Arabidopsis thaliana suspension cells in response to bicarbonate (mimic of elevated CO2) in a time-course study. A total of 47 potential redox-regulated proteins were identified with functions in carbohydrate and energy metabolism, transport, ROS scavenging, cell structure modulation and protein turnover. This inventory of previously unknown redox responsive proteins in Arabidopsis bicarbonate responses lays a foundation for future research toward understanding the molecular mechanisms underlying plant CO2 responses. PMID:28184230

  19. Sediment phosphorus speciation and mobility under dynamic redox conditions

    NASA Astrophysics Data System (ADS)

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

    2017-07-01

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

  20. 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

  1. 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

  2. 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

  3. EQCM Measurements: Redox-Induced Changes in Solvent and Ion Content in Anchored Redox Monolayers of Organosulfur Compounds and Their Electrocatalysis on Gold Electrodes

    DTIC Science & Technology

    1990-08-01

    EQCM Mwasurements: Redox-Induced Changes in Solvent and M0 Content in Anchored Redox Monolayers of Organosulfur CD Compounds and their Electrocatalysis ...REDOX-INDUCED CHANGES IN SOLVENT AND ION CONTENT IN ANCHORED REDOX MONOLAYERS OF ORGANOSULFUR COMPOUNDS AND THEIR ELECTROCATALYSIS ON GOLD...Measurements: Redox-Induced Changes in Solvent and Ion Content in Anchored Redox Monolayers of Organosulfur Compounds and their Electrocatalysis on

  4. Bacterial adaptation of respiration from oxic to microoxic and anoxic conditions: redox control.

    PubMed

    Bueno, Emilio; Mesa, Socorro; Bedmar, Eulogio J; Richardson, David J; Delgado, Maria J

    2012-04-15

    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.

  5. 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

  6. 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.

  7. Cadmium induced mitochondrial redox changes in germinating pea seed.

    PubMed

    Smiri, Moêz; Chaoui, Abdelilah; Rouhier, Nicolas; Kamel, Chibani; Gelhaye, Eric; Jacquot, Jean-Pierre; El Ferjani, Ezzedine

    2010-12-01

    Mitochondria play an essential role in producing the energy required for seedling growth following imbibition. Heavy metals, such as cadmium impair mitochondrial functioning in part by altering redox regulation. The activities of two protein redox systems present in mitochondria, thioredoxin (Trx) and glutaredoxin (Grx), were analysed in the cotyledons and embryo of pea (Pisum sativum L.) germinating seeds exposed to toxic Cd concentration. Compared to controls, Cd-treated germinating seeds showed a decrease in total soluble protein content, but an increase in -SH content. Under Cd stress conditions, Grx and glutathione reductase (GR) activities as well as glutathione (GSH) concentrations decreased both in cotyledons and the embryo. Similar results were obtained with the Trx system: Trx and NADPH-dependent thioredoxin reductase (NTR) activities were not stimulated, whereas total NAD(P) contents diminished in the embryo. However, Cd enhanced the levels of all components of the Trx system in the cotyledons. On the other hand, Cd caused a significant increase in oxidative stress parameters such as the redox ratio of coenzymes (oxidized to reduced forms) and NAD(P)H oxidase activities. These results indicate that Cd induces differential redox responses on different seed tissues. We suggest that neither Grx system nor Trx one may improve the redox status of mitochondrial thiols in the embryo of germinating pea seeds exposed to Cd toxicity, but in the cotyledons the contribution of Trx/NTR/NADPH can be established in despite the vulnerability of the coenzyme pools due to enzymatic oxidation.

  8. 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.

  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. The influence of reactive oxygen species on local redox conditions in oxygenated natural waters

    NASA Astrophysics Data System (ADS)

    Rose, Andrew

    2016-11-01

    Redox conditions in natural waters are a fundamental control on biogeochemical processes and ultimately many ecosystem functions. While the dioxygen/water redox couple controls redox thermodynamics in oxygenated aquatic environments on geological timescales, it is kinetically inert in the extracellular environment on the much shorter timescales on which many biogeochemical processes occur. Instead, electron transfer processes on these timescales are primarily mediated by a relatively small group of trace metals and stable radicals, including the reactive oxygen species superoxide. Such processes are of critical biogeochemical importance because many of these chemical species are scarce nutrients, but may also be toxic at high concentrations. Furthermore, their bioavailability and potentially toxicity is typically strongly influenced by their redox state. In this paper, I examine to what extent redox conditions in oxygenated natural waters are expected to be reflected in the redox states of labile redox-active compounds that readily exchange electrons with the dioxygen/superoxide redox couple, and potentially with each other. Additionally, I present the hypothesis that that the relative importance of the dioxygen/superoxide and superoxide/hydrogen peroxide redox couples exerts a governing control on local redox conditions in oxygenated natural waters on biogeochemically important timescales. Given the recent discovery of widespread extracellular superoxide production by a diverse range of organisms, this suggests the existence of a fundamental mechanism for organisms to tightly regulate local redox conditions in their extracellular environment in oxygenated natural waters.

  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. The impact of variable temperatures on the redox conditions and the behaviour of pharmaceutical residues during artificial recharge

    NASA Astrophysics Data System (ADS)

    Massmann, G.; Greskowiak, J.; Dünnbier, U.; Zuehlke, S.; Knappe, A.; Pekdeger, A.

    2006-08-01

    SummaryThe redox conditions below an artificial recharge pond in Berlin were largely dependent on seasonal temperature changes of 0-24 °C in the infiltrate. Aerobic conditions prevailed in winter, when temperatures were low, while anaerobic conditions were reached below the pond when temperatures exceeded 14 °C. In contrast to temperature changes, cyclic changes between saturated or unsaturated conditions below the pond had only a minor effect on the redox conditions. However, the intrusion of gaseous oxygen during unsaturated conditions caused a temporary reinforced increase in oxidation of particulate organic matter. The effect of variable redox conditions on the behaviour of a number of pharmaceutically active compounds, namely carbamazepine, phenazone and several phenazone-type PhACs, was investigated. Phenazone is redox sensitive and was generally fully degraded before reaching the first groundwater well, as long as oxygen was present. When conditions turned anaerobic, phenazone was not fully eliminated. 1-Acetyl-1-methyl-2-dimethyl-oxymoyl-2-phenylhydrazide (AMDOPH) and carbamazepine are very persistent drug residues. However, results suggest that AMDOPH may be slightly degradable under aerobic conditions too, but further studies will be needed to verify this statement.

  13. 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.

  14. 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.

  15. 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.

  16. Optical redox ratio identifies metastatic potential-dependent changes in breast cancer cell metabolism

    PubMed Central

    Alhallak, Kinan; Rebello, Lisa G.; Muldoon, Timothy J.; Quinn, Kyle P.; Rajaram, Narasimhan

    2016-01-01

    The development of prognostic indicators of breast cancer metastatic risk could reduce the number of patients receiving chemotherapy for tumors with low metastatic potential. Recent evidence points to a critical role for cell metabolism in driving breast cancer metastasis. Endogenous fluorescence intensity of nicotinamide adenine dinucleotide (NADH) and flavin adenine dinucleotide (FAD) can provide a label-free method for assessing cell metabolism. We report the optical redox ratio of FAD/(FAD + NADH) of four isogenic triple-negative breast cancer cell lines with varying metastatic potential. Under normoxic conditions, the redox ratio increases with increasing metastatic potential (168FARN>4T07>4T1), indicating a shift to more oxidative metabolism in cells capable of metastasis. Reoxygenation following acute hypoxia increased the redox ratio by 43 ± 9% and 33 ± 4% in the 4T1 and 4T07 cells, respectively; in contrast, the redox ratio decreased 14 ± 7% in the non-metastatic 67NR cell line. These results demonstrate that the optical redox ratio is sensitive to the metabolic adaptability of breast cancer cells with high metastatic potential and could potentially be used to measure dynamic functional changes that are indicative of invasive or metastatic potential. PMID:27895979

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

    USGS Publications Warehouse

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

    2009-01-01

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

  18. 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.

  19. Sediment DSi and DIP fluxes under simulated redox conditions

    NASA Astrophysics Data System (ADS)

    Nteziryayo, Love-Raoul; Danielsson, Åsa

    2017-04-01

    The Baltic Sea is one of the most eutrophic water bodies in the world. This eutrophication of the Baltic Sea has resulted in the expansion of areas of hypoxic bottom waters. Hypoxia is known to cause the release of dissolved inorganic phosphorus (DIP) from sediment. It is largely assumed that dissolved silica (DSi) reacts in an analogous way in hypoxic conditions. From sediment incubation experiments, we found that P reacts faster to oxygen changes than Si. Here we show that DSi and DIP behave differently to changing oxygen concentrations in the bottom waters, and that the adsorption and de-sorption on Fe oxihydroxides may control the release of P more efficiently than of Si. The results showed that DSi fluxes were higher under oxic conditions (2.21±0.28 mmol Si m-2d-1) than under hypoxic conditions (1.36±0.29 mmol Si m-2d-1). The opposite was observed for P fluxes (0.06 ±0.01 and 0.10±0.09 mmol P m-2d-1) under oxic respective hypoxic conditions). Our results indicate that the increase of hypoxic conditions in coastal areas may directly cause the decrease of Si fluxes from sediment and thereby contribute to the diminishing Si concentrations observed in the Baltic Sea waters.

  20. Redox conditions in deep groundwater: recent accomplishments and future directions

    NASA Astrophysics Data System (ADS)

    Ioka, Seiichiro; Iwatsuki, Teruki; Sakai, Toshiaki; Ishijima, Yoji

    Redox potential (Eh) is one of the most important physico-chemical properties of groundwater. Groundwater Eh have been studied in terms of safety of high-level radioactive waste disposals, water resource management and so on. As the results, it is getting clear that redox potential of deep groundwater in sedimentary and crystalline rocks have a remarkable variability. For example, some reported Eh values of deep groundwater decrease with increasing depth, i.e. with residence time. However, there are few reports showing data measured in situ. Only some Eh values of deep groundwater measured from research borehole drilled at crystalline rocks in Japan and Sweden have been reported. Between 200 and 1000m depth, the Eh values of the deep groundwater range from about 0 to -400mV. This essay first briefly summarizes methodology for Eh measurement and reports Eh values of deep groundwater. Then, it discusses the remaining issues of Eh measurement that are to develop of measurement technology applicable for various geological environments and to understand the redox evolution process through the groundwater flow system.

  1. Limitations of ichnofossil approach for evaluating paleo-bottom-water redox conditions

    SciTech Connect

    Savrda, C.E.; Bottjer, D.

    1987-05-01

    Information on trace fossil diversity, burrow size, and depth of burrow penetration has been incorporated into an ichnofossil tiering model designed for the evaluation of paleo-bottom-water redox conditions. Previous applications to a variety of Phanerozoic strata indicate that this trace fossil approach is more effective than previously emphasized criteria for reconstructing relative degree of oxygenation as well as rates and magnitudes of temporal change in oxygenation. However, the trace fossil model is not without limitations. Presently, they recognize four factors that could limit the accuracy of ichnology-based redox reconstructions: (1) information loss - increases in penetration depth (associated with reoxygenation) that occur at rates in excess of sedimentation rate will destroy a portion of the previous record of oxygenation whereas extended residence times of deep-tier organisms may mask the record through excessive overprinting; (2) inadequate structure visibility - required information on trace fossil assemblage composition and cross cutting relationships is unobtainable for strata where original or diagenetically enhanced contrast between burrows and surrounding sediments is lacking; (3) complexity introduced by rapid deposition - periodic turbidite deposition can mask the desired oxygen signal through substrate modification, temporary modification of faunal composition and behavior, and/or temporary water chemistry changes; and (4) changes in substrate consistency - temporal variation in substrate stiffness (e.g., development of firmgrounds) may result in intrastratal variation in trace fossil tiering structure. The success of future applications of the ichnologic approach depends upon thorough consideration of these factors.

  2. 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.

  3. 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).

  4. 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).

  5. 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,

  6. 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.

  7. 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...

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

    PubMed Central

    Delic, Marizela; Graf, Alexandra B.; Koellensperger, Gunda; Haberhauer-Troyer, Christina; Hann, Stephan; Mattanovich, Diethard; Gasser, Brigitte

    2014-01-01

    Oxidative folding of secretory proteins in the endoplasmic reticulum (ER) is a redox active process, which also impacts the redox conditions in the cytosol. As the transcription factor Yap1 is involved in the transcriptional response to oxidative stress, we investigate its role upon the production of secretory proteins, using the yeast Pichia pastoris as model, and report a novel important role of Yap1 during oxidative protein folding. Yap1 is needed for the detoxification of reactive oxygen species (ROS) caused by increased oxidative protein folding. Constitutive co-overexpression of PpYAP1 leads to increased levels of secreted recombinant protein, while a lowered Yap1 function leads to accumulation of ROS and strong flocculation. Transcriptional analysis revealed that more than 150 genes were affected by overexpression of YAP1, in particular genes coding for antioxidant enzymes or involved in oxidation-reduction processes. By monitoring intracellular redox conditions within the cytosol and the ER using redox-sensitive roGFP1 variants, we could show that overexpression of YAP1 restores cellular redox conditions of protein-secreting P. pastoris by reoxidizing the cytosolic redox state to the levels of the wild type. These alterations are also reflected by increased levels of oxidized intracellular glutathione (GSSG) in the YAP1 co-overexpressing strain. Taken together, these data indicate a strong impact of intracellular redox balance on the secretion of (recombinant) proteins without affecting protein folding per se. Re-establishing suitable redox conditions by tuning the antioxidant capacity of the cell reduces metabolic load and cell stress caused by high oxidative protein folding load, thereby increasing the secretion capacity. PMID:28357216

  10. 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.

  11. Effect of redox conditions on bacterial community structure in Baltic Sea sediments with contrasting phosphorus fluxes.

    PubMed

    Steenbergh, Anne K; Bodelier, Paul L E; Slomp, Caroline P; Laanbroek, Hendrikus J

    2014-01-01

    Phosphorus release from sediments can exacerbate the effect of eutrophication in coastal marine ecosystems. The flux of phosphorus from marine sediments to the overlying water is highly dependent on the redox conditions at the sediment-water interface. Bacteria are key players in the biological processes that release or retain phosphorus in marine sediments. To gain more insight in the role of bacteria in phosphorus release from sediments, we assessed the effect of redox conditions on the structure of bacterial communities. To do so, we incubated surface sediments from four sampling sites in the Baltic Sea under oxic and anoxic conditions and analyzed the fingerprints of the bacterial community structures in these incubations and the original sediments. This paper describes the effects of redox conditions, sampling station, and sample type (DNA, RNA, or whole-cell sample) on bacterial community structure in sediments. Redox conditions explained only 5% of the variance in community structure, and bacterial communities from contrasting redox conditions showed considerable overlap. We conclude that benthic bacterial communities cannot be classified as being typical for oxic or anoxic conditions based on community structure fingerprints. Our results suggest that the overall structure of the benthic bacterial community has only a limited impact on benthic phosphate fluxes in the Baltic Sea.

  12. Changes in the Mineral Assemblage of Paddy Soils upon Redox Cycles

    NASA Astrophysics Data System (ADS)

    Vogelsang, Vanessa; Fiedler, Sabine; Jahn, Reinhold

    2010-05-01

    Rice is one of the major cereal crops of global agriculture. World wide more than 10% of the arable land is used for rice production, mainly under temporarily waterlogged conditions. This leads to distinct redox cycles, governing the biogeochemistry of paddy soils. Yet, long-term effects of alternating redox conditions on the soil mineral matrix and properties are still not fully understood. The objective of the project is to elucidate the processes of mineral transformation as related to changing redox conditions and to time of rice cultivation. Long-term effects of rice cultivation on the mineral assemblage were studied along a chronosequence of paddy soils (100, 700 and 2000a paddy soils) developed in comparable parent material in the province of Zhejiang, China. Top soils were analysed for the mineral assemblage and physicochemical properties using x-ray diffraction and chemical analyses, respectively. All studied clay fractions showed a similar clay mineral assemblage (illite, chlorite, kaolinite, vermiculite, smectite). Differences among the paddy sites though could not be related to the time of cultivation. The CECpot of the clay fraction slightly increased from 100 to 2000 a paddy usage, which was partly attributed to a concurrent increase of Corg. With age the Feo/Fed-ratio in both the Alp and Ardp-horizon increased, with a maximum in the Ardp of the 2000 a paddy field. We conclude, that due to an increasing number of redox-cycles, long-term cultivation enhances the formation of microcrystalline Fe-hydroxides in the A-horizons of paddy soils. Chronological changes in the clay mineral assemblage could not be observed in this study.

  13. 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

  14. Redox state changes in human skeletal muscle after isometric contraction.

    PubMed Central

    Henriksson, J; Katz, A; Sahlin, K

    1986-01-01

    Subjects maintained an isometric contraction of the quadriceps femoris muscle at two-thirds maximal voluntary contraction (m.v.c.) force for 5 s (5.0 +/- 0.3 s; mean +/- S.E. of mean; n = 6) or until fatigue (52 +/- 4 s; n = 13). Muscle biopsies were obtained at rest, immediately after the contractions and also at 1 and 4 min of recovery after contraction to fatigue. In all subjects 5 s isometric contraction resulted in an increase of muscle NADH (0.084 +/- 0.012 at rest to 0.203 +/- 0.041 mmol/kg dry wt.) and a decrease of phosphocreatine (PC; change in concentration = -17.3 +/- 3.8 mmol/kg dry wt.). Glucose-6-phosphate concentration was more than doubled whereas lactate increased in only four of the six subjects. The two subjects who did not show any increase in lactate also had the lowest increase in NADH. At fatigue NADH increased to 0.226 +/- 0.032 mmol/kg dry wt. which was not significantly different from the value after 5 s contraction. Muscle PC was nearly depleted and lactate increased 12-fold above resting levels. The major part (65%) of the NADH increase at fatigue had reverted after 1 min recovery but only a slight further decrease occurred between 1 and 4 min of recovery. In relative terms the time course of the changes in muscle NADH during the first minute of recovery was similar to that of PC resynthesis, suggesting a common regulator such as O2 availability. In contrast to the delayed return of NADH concentration, PC resynthesis continued during the later part of the recovery period and PC concentration was almost fully restored after 4 min of recovery. It is concluded that muscle NADH is already maximally increased in the first seconds of muscle contraction at two-thirds m.v.c. Indirect evidence indicates that this increase reflects a reduction of the mitochondrial NAD-NADH redox couple. The rapid establishment of a reduced mitochondrial redox state at the start of muscle contraction will probably lead to a reduction of the redox state in the

  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. Copyright © 2013 Elsevier Ltd. All rights reserved.

  16. 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.

  17. 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.

  18. 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

  19. 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

  20. 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

  1. 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.

  2. The Influence of Cooling History on the Redox Conditions of Subduction Zone Magmas

    NASA Astrophysics Data System (ADS)

    Parks, B. H.; Kelley, K. A.; Cottrell, E.; Posner, E. S.

    2009-12-01

    The availability of oxygen in the Earth’s interior controls mineral assemblages, magmatic crystallization and degassing, and trace element partitioning. Alternative views of redox conditions in the mantle argue either that it varies regionally in response to plate tectonic activity or that it is homogeneous throughout the upper mantle. Bulk analyses of global lava suites suggest that arc basalts are more oxidized than mid-ocean ridge basalts. This may be attributed to either more oxidized arc mantle sources or near-surface magmatic processes such as crystallization and degassing. Glass inclusions in olivine may record changes in the liquid magma as crystals and gases are progressively removed, offering a means of discriminating between these models. We assess the effects of crystallization and degassing on the redox conditions of basaltic arc magmas through the analysis of co-variations in major elements, volatiles (H2 O, CO2, S), and Fe oxidation state (i.e., Fe3+/ΣFe), in a new suite of olivine-hosted glass inclusions from one eruption of Agrigan volcano in the Mariana arc. We use Fe K-edge micro X-ray Absorption Near-Edge Structure spectroscopy to determine Fe3+/ΣFe ratios of glass inclusions at the same spatial scale as major and volatile element analyses of the same glasses. Fe3+/ΣFe ratios of the Agrigan melts (0.19-0.28) are more oxidized than mid-ocean ridge basalts (0.13-0.17). Major element compositions of the melt inclusions are consistent with fractional crystallization of olivine +/- plagioclase, although Fe3+/ΣFe decreases with decreasing MgO, which is not predicted by crystallization of these two phases. Loss of vapor phases during degassing (e.g., CO2, S, H2O) could also drive changes in the redox state of magmas. The Fe3+/ΣFe ratio does not vary systematically with CO2, indicating that redox conditions are unaffected by early stage degassing of CO2. Fe3+/ΣFe does decrease with decreasing S, revealing that a net reduction of Fe occurs as S

  3. The effect of different chemical treatments, pyrolysis conditions and feedstocks on the redox properties of biochar.

    NASA Astrophysics Data System (ADS)

    Chacón, Francisco Javier; Cayuela, María Luz; Roig, Asunción; Ángel Sánchez-Monedero, Miguel

    2017-04-01

    Pyrogenic carbonaceous materials can have a role in several biogeochemical redox reactions as electron transfer catalysts. Low N2O emissions in biochar amended soils can be related to its ability to act as an "electron shuttle", facilitating the transport of electrons to soil denitrifying microorganisms. Modifying biochar redox properties could be an interesting approach to regulate this effect. In this work we propose several methods for the development of biochars from slow pyrolysis with altered electrochemical properties. To improve its electron exchange capacity we aimed to: 1) Increase the number of redox active functional groups in biochar. Several pyrolysis conditions and chemical treatments (KOH, H3PO4 and H2O2) were tested. 2) Raise the fraction of redox active mineral in biochar. The presence of Fe and Mn-based minerals in biochar could also catalyze redox reactions in soil associated with the nitrogen cycle. Different additives (FeCl3, KMnO4 and clay) were combined with the feedstock before the pyrolysis process. Results of their ability to modify biochar redox properties, measured by mediated electrochemical analysis, are presented. Additionally, we characterized biochars produced from different feedstocks to assess how their lignin, holocellulose and ash composition affects these properties. Analytical issues arising from the difficulty of measuring the electron exchange capacity of biochar will also be discussed.

  4. Expression of Bradyrhizobium japonicum cbb(3) terminal oxidase under denitrifying conditions is subjected to redox control.

    PubMed

    Bueno, Emilio; Richardson, David J; Bedmar, Eulogio J; Delgado, María J

    2009-09-01

    Bradyrhizobium japonicum utilizes cytochrome cbb(3) oxidase encoded by the fixNOQP operon to support microaerobic respiration under free-living and symbiotic conditions. It has been previously shown that, under denitrifying conditions, inactivation of the cycA gene encoding cytochrome c(550), the electron donor to the Cu-containing nitrite reductase, reduces cbb(3) expression. In order to establish the role of c(550) in electron transport to the cbb(3) oxidase, in this work, we have analyzed cbb(3) expression and activity in the cycA mutant grown under microaerobic or denitrifying conditions. Under denitrifying conditions, mutation of cycA had a negative effect on cytochrome c oxidase activity, heme c (FixP and FixO) and heme b cytochromes as well as expression of a fixP'-'lacZ fusion. Similarly, cbb(3) oxidase was expressed very weakly in a napC mutant lacking the c-type cytochrome, which transfers electrons to the NapAB structural subunit of the periplasmic nitrate reductase. These results suggest that a change in the electron flow through the denitrification pathway may affect the cellular redox state, leading to alterations in cbb(3) expression. In fact, levels of fixP'-'lacZ expression were largely dependent on the oxidized or reduced nature of the carbon source in the medium. Maximal expression observed in cells grown under denitrifying conditions with an oxidized carbon source required the regulatory protein RegR.

  5. Mercury species transformation near the water-sediment interface at changeable redox conditions: biogeochemistry and ecological consequences

    NASA Astrophysics Data System (ADS)

    Pakhomova, Svetlana; Yakushev, Evgeny; Newton, Alice

    2017-04-01

    Coastal lagoons with restricted mixing with the open sea are subjected to oxygen depletion events and seasonal oscillation of anoxic conditions. Oxygen depletion in the bottom water/upper sediment layer and appearance of hydrogen sulphide can alter the form of presence of other elements and change its benthic fluxes. In particular, in such conditions Hg species can be transformed to toxic methylmercury followed by its release to the water column. The goal of this study is to evaluate the effect of periodical arise of anoxia in the bottom water on transformation and transport of Hg species in the benthic layer in coastal zones by example of the Berre Lagoon. In this study we use the 1-dimensional C-N-P-Si-O-S-Mn-Fe vertical bottom redox model (BROM) describing transport in the sediments, bottom boundary layers (BBL) and the water column coupled with biogeochemical block simulating changeable redox conditions (Yakushev et al., 2017). Modelled results of seasonal variability of distribution of dissolved oxygen, hydrogen sulphide, species of nutrients, iron, manganese and mercury both in water column and in the sediment upper layer are in good agreement with the data of observation for studied region subjected to seasonal anoxia. Simulation of Hg cycle showed the possibility of MeHg presence in the water column under contrasting oxygenation conditions. Ecological state of the Lagoon under different redox conditions has been assessed.

  6. 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

  7. 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

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

  9. 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

  10. 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.

  11. 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

  12. Impacts of microbial redox conditions on the phase distribution of pyrene in soil-water systems.

    PubMed

    Kim, Han S; Roper, J Chadwick; Pfaender, Frederic K

    2008-03-01

    Variations in the soil/sediment organic matter (SOM)-hydrophobic organic contaminant (HOC) bindings upon microbially mediated redox conditions were examined. While the extractability of pyrene associated with soil declined after its biodegradation began during aerobic incubation, its variations were almost constant (+/-3.0-4.4%) during anoxic/anaerobic incubations. The dissolved organic matter released from the soil incubated under highly reduced conditions became more humified and aromatic, had a higher average molecular weight, and was more polydispersed compared to that obtained from oxic incubation, similar to the SOM alterations in the early stage of diagenesis (humification). The concentrations of pyrene in the aqueous phase increased significantly during the soil incubations under highly reduced conditions due to its favorable interaction with the altered DOM. Our results suggest that the microbially mediated redox conditions have significant impacts on SOM and should be considered for the transport, fate, bioavailability, and exposure risk of HOCs in the geo-environments.

  13. Effects of microbially mediated redox conditions on PAH-soil interactions.

    PubMed

    Kim, Han S; Pfaender, Frederic K

    2005-12-01

    The impacts of microbially mediated redox conditions on the bioavailability of persistent polycyclic aromatic hydrocarbons (PAHs) in soils and sediments have received little study, despite the fact that most water-saturated soils and sediments spend a significant portion of the time under reduced conditions. To address this need an uncontaminated surface soil was incubated under various redox conditions (aerobic, nitrate-reducing, sulfate-reducing, and methanogenic). Depending on redox conditions, different quantities of fulvic and humic acids were liberated as dissolved organic matter (DOM) from the soil during incubation. The DOM released under highly reduced conditions was more nonpolar, aromatic, and polydisperse, of higher molecular weight, and had a higher sorption capacity for pyrene compared to that obtained from relatively oxic incubations. The soil-phase organic matter incubated under reduced conditions also became relatively more aromatic, containing nonpolar organic molecules of lower oxygen contents and exhibiting higher capacity and more nonlinear and hysteric sorption/desorption behavior for pyrene. These observations support the hypothesis that reduced environments established by indigenous soil microbes alter soil organic matter in a matter similar to diagenetic processes. Such humification-like alteration occurred principally in relatively more labile fractions of soil organic matter. These findings are important for assessing the ultimate fate and exposure risk of hydrophobic organic contaminants in soils and sediments where living microorganisms play a significant role in formation and evolution of soil/sediment organic matter.

  14. 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.

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

  16. 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.

  17. 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

  18. 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.

  19. 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.

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

    SciTech Connect

    Fendorf, Scott

    2016-04-05

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

  1. Redox Changes During the Cell Cycle in the Embryonic Root Meristem of Arabidopsis thaliana.

    PubMed

    de Simone, Ambra; Hubbard, Rachel; Viñegra de la Torre, Natanael; Velappan, Yazhini; Wilson, Michael; Considine, Michael J; Soppe, Wim J J; Foyer, Christine H

    2017-05-30

    The aim of this study was to characterize redox changes in the nuclei and cytosol occurring during the mitotic cell cycle in the embryonic roots of germinating Arabidopsis seedlings, and to determine how redox cycling was modified in mutants with a decreased capacity for ascorbate synthesis. Using an in vivo reduction-oxidation (redox) reporter (roGFP2), we show that transient oxidation of the cytosol and the nuclei occurred at G1 in the synchronized dividing cells of the Arabidopsis root apical meristem, with reduction at G2 and mitosis. This redox cycle was absent from low ascorbate mutants in which nuclei were significantly more oxidized than controls. The cell cycle-dependent increase in nuclear size was impaired in the ascorbate-deficient mutants, which had fewer cells per unit area in the root proliferation zone. The transcript profile of the dry seeds and size of the imbibed seeds was strongly influenced by low ascorbate but germination, dormancy release and seed aging characteristics were unaffected. These data demonstrate the presence of a redox cycle within the plant cell cycle and that the redox state of the nuclei is an important factor in cell cycle progression. Controlled oxidation is a key feature of the early stages of the plant cell cycle. However, sustained mild oxidation restricts nuclear functions and impairs progression through the cell cycle leading to fewer cells in the root apical meristem. Antioxid. Redox Signal. 00, 000-000.

  2. Changes in mitochondrial homeostasis and redox status in astronauts following long stays in space.

    PubMed

    Indo, Hiroko P; Majima, Hideyuki J; Terada, Masahiro; Suenaga, Shigeaki; Tomita, Kazuo; Yamada, Shin; Higashibata, Akira; Ishioka, Noriaki; Kanekura, Takuro; Nonaka, Ikuya; Hawkins, Clare L; Davies, Michael J; Clair, Daret K St; Mukai, Chiaki

    2016-12-16

    The effects of long-term exposure to extreme space conditions on astronauts were investigated by analyzing hair samples from ten astronauts who had spent six months on the International Space Station (ISS). Two samples were collected before, during and after their stays in the ISS; hereafter, referred to as Preflight, Inflight and Postflight, respectively. The ratios of mitochondrial (mt) to nuclear (n) DNA and mtRNA to nRNA were analyzed via quantitative PCR. The combined data of Preflight, Inflight and Postflight show a significant reduction in the mtDNA/nDNA in Inflight, and significant reductions in the mtRNA/nRNA ratios in both the Inflight and Postflight samples. The mtRNA/mtDNA ratios were relatively constant, except in the Postflight samples. Using the same samples, the expression of redox and signal transduction related genes, MnSOD, CuZnSOD, Nrf2, Keap1, GPx4 and Catalase was also examined. The results of the combined data from Preflight, Inflight and Postflight show a significant decrease in the expression of all of the redox-related genes in the samples collected Postflight, with the exception of Catalase, which show no change. This decreased expression may contribute to increased oxidative stress Inflight resulting in the mitochondrial damage that is apparent Postflight.

  3. Changes in mitochondrial homeostasis and redox status in astronauts following long stays in space

    PubMed Central

    Indo, Hiroko P.; Majima, Hideyuki J.; Terada, Masahiro; Suenaga, Shigeaki; Tomita, Kazuo; Yamada, Shin; Higashibata, Akira; Ishioka, Noriaki; Kanekura, Takuro; Nonaka, Ikuya; Hawkins, Clare L.; Davies, Michael J.; Clair, Daret K. St; Mukai, Chiaki

    2016-01-01

    The effects of long-term exposure to extreme space conditions on astronauts were investigated by analyzing hair samples from ten astronauts who had spent six months on the International Space Station (ISS). Two samples were collected before, during and after their stays in the ISS; hereafter, referred to as Preflight, Inflight and Postflight, respectively. The ratios of mitochondrial (mt) to nuclear (n) DNA and mtRNA to nRNA were analyzed via quantitative PCR. The combined data of Preflight, Inflight and Postflight show a significant reduction in the mtDNA/nDNA in Inflight, and significant reductions in the mtRNA/nRNA ratios in both the Inflight and Postflight samples. The mtRNA/mtDNA ratios were relatively constant, except in the Postflight samples. Using the same samples, the expression of redox and signal transduction related genes, MnSOD, CuZnSOD, Nrf2, Keap1, GPx4 and Catalase was also examined. The results of the combined data from Preflight, Inflight and Postflight show a significant decrease in the expression of all of the redox-related genes in the samples collected Postflight, with the exception of Catalase, which show no change. This decreased expression may contribute to increased oxidative stress Inflight resulting in the mitochondrial damage that is apparent Postflight. PMID:27982062

  4. 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.

  5. Retinal proteins associated with redox regulation and protein folding play central roles in response to high glucose conditions.

    PubMed

    Wang, Ssu-Han; Lee, Wen-Chi; Chou, Hsiu-Chuan

    2015-03-01

    Diabetic retinopathy typically causes poor vision and blindness. A previous study revealed that a high blood glucose concentration induces glycoxidation and weakens the retinal capillaries. Nevertheless, the molecular mechanisms underlying the effects of high blood glucose induced diabetic retinopathy remain to be elucidated. In the present study, we cultured the retinal pigmented epithelial cell line ARPE-19 in mannitol-balanced 5.5, 25, and 100 mM glucose media and investigated protein level alterations. Proteomic analysis revealed significant changes in 137 protein features, of which 124 demonstrated changes in a glucose concentration dependent manner. Several proteins functionally associated with redox regulation, protein folding, or the cytoskeleton are affected by increased glucose concentrations. Additional analyses also revealed that cellular oxidative stress, including endoplasmic reticulum stress, was significantly increased after treatment with high glucose concentrations. However, the mitochondrial membrane potential and cell survival remained unchanged during treatment with high glucose concentrations. To summarize, in this study, we used a comprehensive retinal pigmented epithelial cell based proteomic approach for identifying changes in protein expression associated retinal markers induced by high glucose concentrations. Our results revealed that a high glucose condition can induce cellular oxidative stress and modulate the levels of proteins with functions in redox regulation, protein folding, and cytoskeleton regulation; however, cell viability and mitochondrial integrity are not significantly disturbed under these high glucose conditions.

  6. Detecting changes in the thiol redox state of proteins following a decrease in oxygen concentration using a dual labeling technique.

    PubMed

    Lui, James K C; Lipscombe, Richard; Arthur, Peter G

    2010-01-01

    Cells are routinely exposed to hyperoxic conditions when cultured in the presence of 95% air and 5% carbon dioxide. Hyperoxic conditions can increase the generation of reactive oxygen species and cause oxidative stress. Oxidative stress has been proposed to cause cells in culture to behave differently from cells in vivo. One route by which oxidative stress could affect cellular function is through alterations in protein function caused by the oxidation of thiol groups (-SH) of redox-sensitive cysteine residues. To test whether changes in oxygen concentration were sufficient to cause changes in the thiol redox state of proteins, we developed a sensitive method involving the labeling of reduced and oxidized cysteine residues with fluorescent tags. Using this dual labeling method, we found 62 of 411 protein spots that were significantly more reduced following a 30 min decrease in oxygen concentration. We conclude that the elevated oxygen concentration characteristic of typical cell culture conditions has the potential to affect cellular behavior through changes in the thiol redox state of proteins.

  7. 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.

  8. Intermittent Fasting Results in Tissue-Specific Changes in Bioenergetics and Redox State

    PubMed Central

    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

  9. The Conditions of Institutional Change.

    ERIC Educational Resources Information Center

    Caskey, Owen L.

    The author proposes a method of examining and organizing the principles relating to the conditions of institutional change. Those conditions of change involve principles which relate to three elements--people, places, and things. Within these categories, principles may be enumerated which operate to facilitate or restrain change or innovation…

  10. 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.

  11. Redox-triggered changes in the self-assembly of a ferrocene-peptide conjugate.

    PubMed

    Adhikari, Bimalendu; Kraatz, Heinz-Bernhard

    2014-05-30

    Ultrasonication of a ferrocene conjugate of a short amyloid peptide (Aβ18-20) in toluene causes formation of an organogel, which undergoes dramatic structural changes upon oxidation from a nanofibrillar network to spherical micelles. This morphological change is redox-controlled and reversible.

  12. 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.

  13. Timescales and Mechanisms of Rapid Redox Change in the Mid-Cretaceous Ocean

    NASA Astrophysics Data System (ADS)

    Wagner, T.; Beckmann, B.; Floegel, S.; Hofmann, P.; Schouten, S.; Sinninghe Damsté, J.; Wallmann, K.

    2006-12-01

    Understanding the timing, mechanisms and feedbacks capable of driving parts of the ocean from oxic to either anoxic or sulfidic (euxinic) conditions is critical to identify possible scenarios for the future ocean on a warmer Earth. The mid Cretaceous is well-known as a time of extreme greenhouse conditions, and linked to this were a series of major black shale deposition events associated with global perturbations of the carbon cycle (ocean anoxic events; OAEs). The internal structure of these black shale units potentially document a remarkable record of the driving factors and response of the Earth System to rapid climate change, and have therefore become a focal point for extreme climate research. Recent orbital and shorter time-scale stratigraphic records have demonstrated that the Cretaceous ocean was characterized by repeated rapid changes between oxic and anoxic depositional conditions, which were particularly extreme during black shale deposition and were linked to orbital-driven natural processes. Understanding these short-term redox cycles is essential to improve our understanding of how future predictions of rapid swings in climate may effect ocean chemistry and hence ecosystem stability and climate feedback mechanisms. We present millennial and shorter scale geochemical, isotopic, and molecular records from the low-latitude Atlantic that constrain the effects of orbital-driven fluctuations in continental climate on ocean productivity, chemistry and surface water temperature, and deep ocean carbon burial along the continental margin of the evolving Equatorial Atlantic Gateway and NW-Africa. These marine records cover different critical periods of Mid-Cretaceous extreme warmth (OAE's) and provide evidence on regional to global mechanisms determining tropical African climate, hydrological cycling and continental run-off, and at what time scales the shallow and deep ocean responded to these fluctuations in the atmosphere-land system. The data suggest that

  14. 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.

  15. Global gene expression analysis of Saccharomyces cerevisiae grown under redox potential-controlled very-high-gravity conditions.

    PubMed

    Liu, Chen-Guang; Lin, Yen-Han; Bai, Feng-Wu

    2013-11-01

    Redox potential (ORP) plays a pivotal role in yeast viability and ethanol production during very-high-gravity (VHG) ethanol fermentation. In order to identify the correlation between redox potential profiles and gene expression patterns, global gene expression of Saccharomyces cerevisiae was investigated. Results indicated that significant changes in gene expression occurred at the periods of 0 - 6 h and 30 - 36 h, respectively. Changes noted in the period of 0 - 6 h were mainly related to carbohydrate metabolism. In contrast, gene expression variation at 30 - 36 h could be attributed primarily to stress response. Although CDC19 was down-regulated, expression of PYK2, PDC6 and ADH2 correlated inversely with ORP. Meanwhile, expression of GPD1 decreased due to the depletion of dissolved oxygen in the fermentation broth, but expression of GPD2 correlated with ORP. Transcription of genes encoding heat shock proteins was characterized by uphill, downhill, valley and plateau expression profiles, accordingly to specific function in stress response. These results highlight the role of ORP in modulating yeast physiology and metabolism under VHG conditions.

  16. 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

  17. Mosses influence phosphorus cycling in rich fens by driving redox conditions in shallow soils.

    PubMed

    Crowley, Katherine F; Bedford, Barbara L

    2011-09-01

    Mosses play an integral role in the hydrologic regimes of ecosystems where they cover the soil surface, and thus affect biogeochemical cycling of elements influenced by soil oxidation-reduction (redox) reactions, including the plant growth-limiting nutrients, nitrogen and phosphorus (P). In rich fens where P often limits plant growth, we hypothesized that feedbacks between mosses and redox conditions would determine P availability to shallow-rooted forb species that constitute much of these wetlands' unusually high plant species diversity. In a moss removal experiment in three fens, forb tissue P and microbial P were greater while anion exchange membrane (AEM) resin P was lower where mosses occurred than where they were removed, suggesting both higher availability and greater demand for P in moss-covered soils. Coupled physicochemical and biological mechanisms drove moss effects on P cycling, ultimately through effects on soil oxygenation or reduction: higher redox potential underlying mosses corresponded to greater microbial activity, phosphatase enzyme activity, and colonization by arbuscular mycorrhizal fungi (AMF), all of which can promote greater P availability to plants. These more oxidized soils stimulated: (1) greater microbial activity and root vigor; (2) correspondingly greater P demand via microbial uptake, forb uptake, and iron (Fe)-P reactions; and (3) greater P supply through soil and root phosphatase activity and AMF colonization. This work demonstrates that mosses improve vascular plant P acquisition by alleviating stresses caused by reducing conditions that would otherwise prevail in shallow underlying soils, thus providing a mechanism by which mosses facilitate plant species diversity in rich fens.

  18. 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. Copyright © 2015 Asociación Argentina de Microbiología. Publicado por Elsevier España, S.L.U. All rights reserved.

  19. Understanding redox conditions in the mid-Cretaceous Baffin Bay - a combined model-data approach

    NASA Astrophysics Data System (ADS)

    Lenniger, M.; Bjerrum, C. J.; Pedersen, G. K.; Azhar, M. Al

    2012-04-01

    Cretaceous events of widespread oceanic anoxia are characterized by perturbations in the global carbon cycle and accompanied increased carbon burial in marine sediments. Their occurrence is thought to have been linked to an interaction of greenhouse conditions, palaeogeography and increased nutrient discharge, which led to enhanced surface productivity and improved conditions for carbon preservation. One of the most widespread oceanic anoxic events is the Cenomanian-Turonian boundary event (OAE2). Evidence for anoxic or even euxinic conditions during OAE2 is mainly observed in the Western Interior Seaway and at low- and mid-palaeolatitudes in the proto-Atlantic. However, our understanding of the distribution and characteristics of OAE2 in high palaeolatitudes is still incomplete. In order to investigate the palaeoceanographic conditions in high palaeolatitudes in the mid-Cretaceous, we studied the Umiivik-I stratigraphic core from West Greenland using an integrated approach combining sedimentology and geochemistry with three dimensional regional ocean modeling. Sedimentary rocks from the Umiivik-I core show relative high TOC contents with values up to about 5 %. The organic carbon-to-pyrite sulphur ratio (C/S-ratio) indicates that the organic matter (OM) is predominantly of normal marine origin. Increased C/S-ratios are caused by intermittent input of terrestrial OM and indicate fluctuations in runoff. Redox sensitive trace metal concentrations (e.g. Mo, U and V) were measured in bulk rock samples in order to reconstruct the redox conditions during the deposition. The concentrations of the trace metals (TM) are relatively low and in the same range as reported for average shale reference material. The low TM concentrations in the Umiivik-I core are indicative of deposition under oxygenated bottom water conditions in contrast to usually observed high TM concentrations in anoxic depositional environments during the mid-Cretaceous. These findings are exceptional due to

  20. Low strength wastewater treatment under low temperature conditions by a novel sulfur redox action process.

    PubMed

    Yamaguchi, T; Bungo, Y; Takahashi, M; Sumino, H; Nagano, A; Araki, N; Imai, T; Yamazaki, S; Harada, H

    2006-01-01

    The objective of this research is to make a novel wastewater treatment process activated by a sulfur-redox cycle action of microbes in low temperature conditions. This action is carried out by sulfate-reducing bacteria (SRB) and sulfur-oxidizing bacteria (SOB). The process was comprised of a UASB reactor as pre-treatment and an aerobic downflow hanging sponge (DHS) reactor as post-treatment. As the results of reactor operation, the whole process achieved that over 90% of CODcr removal efficiency, less than 30 mgCODcr/L (less than 15 mgBOD/L) of final effluent, at 12 h of HRT and at 8 degrees C of UASB reactor temperature. Acetobacterium sp. was detected as the predominant species by PCR-DGGE method targeting 16SrDNA with band excision and sequence analysis. In the UASB reactor, various species of sulfate-reducing bacterium, Desulfobulbus sp., Desulfovibrio sp., and Desulfomicrobium sp., were found by cloning analysis. In the DHS reactor, Tetracoccus sp. presented as dominant. The proposed sulfur-redox action process was considered as an applicable process for low strength wastewater treatment in low temperature conditions.

  1. 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.

  2. Evaluation of redox indicators for determining sulfate-reducing and dechlorinating conditions.

    PubMed

    Jones, Brian D; Ingle, James D

    2005-11-01

    An in situ methodology based on covalently bonded redox indicators has been developed for determining when sulfate-reducing conditions exist in environmental samples. Three immobilized redox indicators [thionine (Thi, formal potential at pH 7 (E(0')7) equals 52 mV), cresyl violet (CV, E(0')7 = -81 mV), and phenosafranine (PSaf, E(0')7 = -267 mV)] were tested for their response to sulfide in synthetic solutions and under sulfate-reducing conditions in wastewater slurries. The byproduct of the sulfate-reducing process, sulfide, was found to couple well to CV in the concentration range of 1-100 microM total sulfide ([S(-II)]) and the pH range of 6-8. Thi, the indicator with the highest formal potential, reacts rapidly with sulfide at levels well below 1 microM while PSaf, the indicator with the lowest formal potential, does not couple to sulfide at levels in excess of 100 microM [S(-II)]. The degree of reduction of the indicators (i.e., the fraction of cresyl violet oxidized) in contact with a given level of sulfide can be modeled qualitatively with an equilibrium expression for [S(-II)]-indicator based on the Nernst equation assuming that rhombic sulfur is the product of sulfide oxidation. In a groundwater sample with dechlorinating microbes, reduction of Thi and partial reduction of CV correlated with dechlorination of TCE to cis-DCE.

  3. Heterogenous oceanic redox conditions through the Ediacaran-Cambrian boundary limited the metazoan zonation.

    PubMed

    Zhang, Junpeng; Fan, Tailiang; Zhang, Yuandong; Lash, Gary G; Li, Yifan; Wu, Yue

    2017-08-17

    Recent studies have enhanced our understanding of the linkage of oxygenation and metazoan evolution in Early Cambrian time. However, little of this work has addressed the apparent lag of animal diversification and atmospheric oxygenation during this critical period of Earth history. This study utilizes the geochemical proxy and N isotope record of the Ediacaran-Cambrian boundary preserved in intra-shelf basin, slope, and slope basin deposits of the Yangtze Sea to assess the ocean redox state during the Early Cambrian metazoan radiation. Though ferruginous conditions appear to have prevailed through the water column during this time, episodes of local bottom-water anoxia extending into the photic-zone impacted the slope belt of the basin. Heterogenous oceanic redox conditions are expressed by trace element concentrations and Fe speciation, and spatial variation of N isotopes. We propose that the coupling of ocean chemistry and Early Cambrian animal diversification was not a simple cause-and-effect relationship, but rather a complex interaction. Specifically, it is likely that animal diversification expanded not only temporally but also spatially from the shallow shelf to deep-water environments in tandem with progressive oxygenation of the extensive continental margin.

  4. Resistance training and redox homeostasis: Correlation with age-associated genomic changes.

    PubMed

    Dimauro, Ivan; Scalabrin, Mattia; Fantini, Cristina; Grazioli, Elisa; Beltran Valls, Maria Reyes; Mercatelli, Neri; Parisi, Attilio; Sabatini, Stefania; Di Luigi, Luigi; Caporossi, Daniela

    2016-12-01

    Regular physical activity is effective as prevention and treatment for different chronic conditions related to the ageing processes. In fact, a sedentary lifestyle has been linked to a worsening of cellular ageing biomarkers such as telomere length (TL) and/or specific epigenetic changes (e.g. DNA methylation), with increase of the propensity to aging-related diseases and premature death. Extending our previous findings, we aimed to test the hypothesis that 12 weeks of low frequency, moderate intensity, explosive-type resistance training (EMRT) may attenuate age-associated genomic changes. To this aim, TL, global DNA methylation, TRF2, Ku80, SIRT1, SIRT2 and global protein acetylation, as well as other proteins involved in apoptotic pathway (Bcl-2, Bax and Caspase-3), antioxidant response (TrxR1 and MnSOD) and oxidative damage (myeloperoxidase) were evaluated before and after EMRT in whole blood or peripheral mononuclear cells (PBMCs) of elderly subjects. Our findings confirm the potential of EMRT to induce an adaptive change in the antioxidant protein systems at systemic level and suggest a putative role of resistance training in the reduction of global DNA methylation. Moreover, we observed that EMRT counteracts the telomeres' shortening in a manner that proved to be directly correlated with the amelioration of redox homeostasis and efficacy of training regime, evaluated as improvement of both muscle's power/strength and functional parameters. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

  5. Redox homeostasis and reactive oxygen species scavengers shift during ontogenetic phase changes in apple.

    PubMed

    Du, Zhen; Jia, Xiao Lin; Wang, Yi; Wu, Ting; Han, Zhen Hai; Zhang, Xin Zhong

    2015-07-01

    The change from juvenile to adult phase is a universal phenomenon in perennial plants such as apple. To validate the changes in hydrogen peroxide (H2O2) levels and scavenging during ontogenesis in apple seedlings, the H2O2 contents, its scavenging capacity, and the expression of related genes, as well as miR156 levels, were measured in leaf samples from different nodes in seedlings of 'Zisai Pearl' (Malus asiatica)×'Red Fuji' (M. domestica). Then in vitro shoots were treated with redox modulating chemicals to verify the response of miR156 to redox alteration. The expression of miR156 decreased gradually during ontogenesis, indicating a progressive loss of juvenility. During the phase changes, H2O2 and ascorbate contents, the ratio of ascorbate to dehydroascorbate, the ascorbate peroxidase, catalase and glutathione reductase activities, and the expressions of some MdGR and MdAPX gene family members increased remarkably. However, the glutathione content and glutathione to glutathione disulfide ratio declined. In chemicals treated in vitro shoots, the changes in miR156 levels were coordinated with GSH contents and GSH/GSSG ratio but not H2O2 contents. Conclusively, the relative reductive thiol redox status is critical for the maintenance of juvenility and the reductive ascorbate redox environment was elevated and sustained during the reproductive phase. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

  6. Cu/ZnO nanocatalysts in response to environmental conditions: surface morphology, electronic structure, redox state and CO2 activation.

    PubMed

    Martínez-Suárez, Luis; Frenzel, Johannes; Marx, Dominik

    2014-12-21

    Methanol synthesis is one of the landmarks of heterogeneous catalysis due to the great industrial significance of methanol as a clean liquid fuel and as a raw material for industry. Understanding in atomistic detail the properties of the underlying metal/oxide catalyst materials as a function of temperature and composition of the reactive gas phase is of utmost importance in order to eventually improve the production process. By performing extensive density functional theory based slab calculations in combination with a thermodynamic formalism we establish an atomistic understanding of gas phase-induced changes of surface morphology, redox properties and reactivity of ZnO supported Cu nanocatalysts. Extending our recent insights [Phys. Rev. Lett., 2013, 110, 086108], we explore surface stabilization mechanisms and site-dependent redox states of both catalyst components as well as the pronounced electronic charge transfer processes across the metal-support interface. Moreover, ab initio molecular dynamics simulations unveil the vital role played by dynamical shape fluctuations of the deposited Cu8 cluster. The pronounced structural flexibility of the metal nanoparticle is found to enhance CO2 activation over Cu8 at the elevated temperature conditions of the industrial methanol synthesis process, in addition to activation of CO2via electronic charge transfer from the ZnO support.

  7. 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

  8. 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.

  9. Organization of biogeochemical nitrogen pathways with switch-like adjustment in fluctuating soil redox conditions

    PubMed Central

    Lamba, Sanjay; Bera, Soumen; Rashid, Mubasher; Medvinsky, Alexander B.; Acquisti, Claudia; Li, Bai-Lian

    2017-01-01

    Nitrogen is cycled throughout ecosystems by a suite of biogeochemical processes. The high complexity of the nitrogen cycle resides in an intricate interplay between reversible biochemical pathways alternatively and specifically activated in response to diverse environmental cues. Despite aggressive research, how the fundamental nitrogen biochemical processes are assembled and maintained in fluctuating soil redox conditions remains elusive. Here, we address this question using a kinetic modelling approach coupled with dynamical systems theory and microbial genomics. We show that alternative biochemical pathways play a key role in keeping nitrogen conversion and conservation properties invariant in fluctuating environments. Our results indicate that the biochemical network holds inherent adaptive capacity to stabilize ammonium and nitrate availability, and that the bistability in the formation of ammonium is linked to the transient upregulation of the amo-hao mediated nitrification pathway. The bistability is maintained by a pair of complementary subsystems acting as either source or sink type systems in response to soil redox fluctuations. It is further shown how elevated anthropogenic pressure has the potential to break down the stability of the system, altering substantially ammonium and nitrate availability in the soil, with dramatic effects on biodiversity. PMID:28280580

  10. Redox interactions between Saccharomyces cerevisiae and Saccharomyces uvarum in mixed culture under enological conditions.

    PubMed

    Cheraiti, Naoufel; Guezenec, Stéphane; Salmon, Jean-Michel

    2005-01-01

    Wine yeast starters that contain a mixture of different industrial yeasts with various properties may soon be introduced to the market. The mechanisms underlying the interactions between the different strains in the starter during alcoholic fermentation have never been investigated. We identified and investigated some of these interactions in a mixed culture containing two yeast strains grown under enological conditions. The inoculum contained the same amount (each) of a strain of Saccharomyces cerevisiae and a natural hybrid strain of S. cerevisiae and Saccharomyces uvarum. We identified interactions that affected biomass, by-product formation, and fermentation kinetics, and compared the redox ratios of monocultures of each strain with that of the mixed culture. The redox status of the mixed culture differed from that of the two monocultures, showing that the interactions between the yeast strains involved the diffusion of metabolite(s) within the mixed culture. Since acetaldehyde is a potential effector of fermentation, we investigated the kinetics of acetaldehyde production by the different cultures. The S. cerevisiae-S. uvarum hybrid strain produced large amounts of acetaldehyde for which the S. cerevisiae strain acted as a receiving strain in the mixed culture. Since yeast response to acetaldehyde involves the same mechanisms that participate in the response to other forms of stress, the acetaldehyde exchange between the two strains could play an important role in inhibiting some yeast strains and allowing the growth of others. Such interactions could be of particular importance in understanding the ecology of the colonization of complex fermentation media by S. cerevisiae.

  11. In Situ Raman Study of Redox State Changes of Mitochondrial Cytochromes in a Perfused Rat Heart

    PubMed Central

    Brazhe, Nadezda A.; Treiman, Marek; Faricelli, Barbara; Vestergaard, Jakob H.; Sosnovtseva, Olga

    2013-01-01

    We developed a Raman spectroscopy-based approach for simultaneous study of redox changes in c-and b-type cytochromes and for a semiquantitative estimation of the amount of oxygenated myoglobin in a perfused rat heart. Excitation at 532 nm was used to obtain Raman scattering of the myocardial surface of the isolated heart at normal and hypoxic conditions. Raman spectra of the heart under normal pO2 demonstrate unique peaks attributable to reduced c-and b-type cytochromes and oxymyoglobin (oMb). The cytochrome peaks decreased in intensity upon FCCP treatment, as predicted from uncoupling mitochondrial respiration. Conversely, transient hypoxia causes the reversible increase in the intensity of peaks assigned to cytochromes c and c1, reflecting electron stacking proximal to cytochrome oxidase due to the lack of terminal electron acceptor O2. Intensities of peaks assigned to oxy- and deoxyhemoglobin were used for the semiquantitative estimation of oMb deoxygenation that was found to be of approximately 50 under hypoxia conditions. PMID:24009655

  12. In situ Raman study of redox state changes of mitochondrial cytochromes in a perfused rat heart.

    PubMed

    Brazhe, Nadezda A; Treiman, Marek; Faricelli, Barbara; Vestergaard, Jakob H; Sosnovtseva, Olga

    2013-01-01

    We developed a Raman spectroscopy-based approach for simultaneous study of redox changes in c-and b-type cytochromes and for a semiquantitative estimation of the amount of oxygenated myoglobin in a perfused rat heart. Excitation at 532 nm was used to obtain Raman scattering of the myocardial surface of the isolated heart at normal and hypoxic conditions. Raman spectra of the heart under normal pO2 demonstrate unique peaks attributable to reduced c-and b-type cytochromes and oxymyoglobin (oMb). The cytochrome peaks decreased in intensity upon FCCP treatment, as predicted from uncoupling mitochondrial respiration. Conversely, transient hypoxia causes the reversible increase in the intensity of peaks assigned to cytochromes c and c1, reflecting electron stacking proximal to cytochrome oxidase due to the lack of terminal electron acceptor O2. Intensities of peaks assigned to oxy- and deoxyhemoglobin were used for the semiquantitative estimation of oMb deoxygenation that was found to be of approximately 50[Formula: see text] under hypoxia conditions.

  13. Soil Redox Conditions Are a Strong Determinant of Microbial Community Composition and the Fate of Carbon Following Permafrost Thaw.

    NASA Astrophysics Data System (ADS)

    Bottos, E. M.; Bramer, L.; Kim, Y. M.; Fansler, S.; Nicora, C.; Zink, E.; Chu, R. K.; Tfaily, M. M.; Metz, T. O.; Jansson, J.; Stegen, J.

    2016-12-01

    Permafrost-affected soils contain enormous stocks of carbon, which are becoming increasingly available to microbial transformation as permafrost regions warm; however, how this warming will influence the permafrost microbiome and the transformation of soil carbon remains unclear. We hypothesize that the redox conditions that arise following permafrost thaw will dictate the structure and function of the microbial community, and strongly influence the nature of carbon transformations. To examine this, permafrost-affected soils from Caribou Poker Creek Research Watershed, Alaska were incubated at 4 °C under aerobic and anaerobic conditions for periods of 9 and 94 days. Over the incubation period, rates of CO2 and CH4 production were measured by gas chromatography, shifts in microbial community structure were characterized by 16S rRNA gene sequencing, and changes in metabolite and organic matter composition were analyzed by GC-MS and ESI-FTICR MS, respectively. CO2 production rates were significantly higher in aerobic treatments in 9-day and 94-day incubations, by 3-times and 12-times, respectively. Rates of CH4 production were not significantly different between treatments in 9-day incubations, but were 1.6-times higher in anaerobic treatments in 94-day incubations. The community composition remained largely unchanged in the incubated samples, with the exception of the 94-day aerobic incubations, which shifted strongly to become dominated by a single OTU, Rhodoferax ferrireducens. Metabolite profiles also shifted most strongly in the 94-day aerobic incubations, with the abundance of phosphorylated carbon compounds overrepresented in these samples. This work suggests that the redox conditions that arise following permafrost thaw will be a strong determinant of community composition and will govern the ultimate fate of carbon stocks in permafrost-affected soils. Our results are currently being integrated with numerical models aimed at predicting the coupled microbiome

  14. 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.

  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. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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

  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. 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

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

    PubMed

    Stewart, Brandy D; Nico, Peter S; Fendorf, Scott

    2009-07-01

    Reaction pathways resulting in uranium-bearing solids that are stable (i.e., having limited solubility) under 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-UO2-CO3 species predominate (3 mM Ca and 3.8 mM total CO3), dissolved uranium concentrations decrease from 0.16 mM to below detection limit (BDL) after 5-15 d, depending on the Fe(II) concentration. In systems undergoing 3 successive redox cycles (14 d of reduction, followed by 5 d of oxidation) and a pulsed decrease to 0.15 mM total CO3, 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 adsorbed onto and incorporated into the structure of newly formed goethite and magnetite. Our results reveal that the fate of uranium is dependent on anaerobic/ aerobic conditions, aqueous uranium speciation, and the fate of iron.

  5. 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.

  6. Redox conformation changes in refined tuna cytochrome c.

    PubMed Central

    Takano, T; Dickerson, R E

    1980-01-01

    Tuna ferrocytochrome c and ferricytochrome c have been refined independently at high resolution (1.5 A and 1.8 A) to crystallographic residual errors of 17.3% and 20.8%, respectively. Small but significant conformational differences are seen surrounding a buried water molecule that is hydrogen bonded to Asn-52, Tyr-67, and Thr-78. In the oxidized state, this water molecule is 1.0 A closer to the heme and the heme has moved 0.15 A out of its heme crevice; both changes lead to a more polar microenvironment for the heme. Chemical modification studies, patterns of evolutionary conservatism, structural differences in bacterial cytochromes, and x-ray studies all agree that the "active site" for cytochrome c is bounded by lysines 8, 13,27, 72, 79, 86, and 87 (thus containing the evolutionary conservative 72-87 loop) and has the buried water molecule just below its surface and the opening of the heme crevice slightly to one side. PMID:6256733

  7. 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. Copyright © 2015 Elsevier Ltd. All rights reserved.

  8. 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.

  9. 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

    2016-06-07

    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.

  10. Manganese oxide-coated redox bars as an indicator for reducing soil conditions

    NASA Astrophysics Data System (ADS)

    Dorau, Kristof; Mansfeldt, Tim

    2014-05-01

    Field identification of reducing soil conditions is of concern not only for soil pedogenesis but also for nutrient and pollutant dynamics in soils. We manufactured manganese (Mn) oxide-coated polyvinyl chloride (PVC) bars and proved their suitability for identification of reducing soil conditions in both the laboratory and field. Birnessite (δ-MnO2) was synthesized according to a recently published method and was coated onto white PVC bars. We used microcosm devices with adjusted redox potentials (EH) to distinguish the onset and intensity of depletion patterns along the Mn oxide-coating and soil column experiments combined with field application to validate the enhanced removal of Mn against Fe oxide-coated bars under anaerobe soil conditions. Field application was performed at a site with shallow and strongly fluctuating water tables where water table depth and soil temperature were monitored. Three microcosm experiments adjusted to oxidizing (EH ~500 mV, pH 7), weakly reducing (EH ~175 mV, pH 7) and moderately reducing conditions (EH ~25 mV, pH 7) showed depending on the EH no, slight, or intense removal of the Mn oxide-coating, respectively. Moreover, the removal of Mn oxide (225 mm2 d-1) in soil column experiments exceeded the removal of Fe oxide (118 mm2 d-1). The enhanced removal of the Mn oxide-coating was also found under anaerobe conditions in field application. Consequently, identifying of reducing conditions in soils by Mn oxide-coated bars is possible. We recommend using this methodology for short-term monitoring, e.g. on weekly basis, since tri- and tetravalent Mn is the preferred electron acceptor compared with trivalent Fe.

  11. Linked Redox Precipitation of Sulfur and Selenium under Anaerobic Conditions by Sulfate-Reducing Bacterial Biofilms

    PubMed Central

    Hockin, Simon L.; Gadd, Geoffrey M.

    2003-01-01

    A biofilm-forming strain of sulfate-reducing bacteria (SRB), isolated from a naturally occurring mixed biofilm and identified by 16S rDNA analysis as a strain of Desulfomicrobium norvegicum, rapidly removed 200 μM selenite from solution during growth on lactate and sulfate. Elemental selenium and elemental sulfur were precipitated outside SRB cells. Precipitation occurred by an abiotic reaction with bacterially generated sulfide. This appears to be a generalized ability among SRB, arising from dissimilatory sulfide biogenesis, and can take place under low redox conditions and in the dark. The reaction represents a new means for the deposition of elemental sulfur by SRB under such conditions. A combination of transmission electron microscopy, environmental scanning electron microscopy, and cryostage field emission scanning electron microscopy were used to reveal the hydrated nature of SRB biofilms and to investigate the location of deposited sulfur-selenium in relation to biofilm elements. When pregrown SRB biofilms were exposed to a selenite-containing medium, nanometer-sized selenium-sulfur granules were precipitated within the biofilm matrix. Selenite was therefore shown to pass through the biofilm matrix before reacting with bacterially generated sulfide. This constitutes an efficient method for the removal of toxic concentrations of selenite from solution. Implications for environmental cycling and the fate of sulfur and selenium are discussed, and a general model for the potential action of SRB in selenium transformations is presented. PMID:14660350

  12. Linked redox precipitation of sulfur and selenium under anaerobic conditions by sulfate-reducing bacterial biofilms.

    PubMed

    Hockin, Simon L; Gadd, Geoffrey M

    2003-12-01

    A biofilm-forming strain of sulfate-reducing bacteria (SRB), isolated from a naturally occurring mixed biofilm and identified by 16S rDNA analysis as a strain of Desulfomicrobium norvegicum, rapidly removed 200 micro M selenite from solution during growth on lactate and sulfate. Elemental selenium and elemental sulfur were precipitated outside SRB cells. Precipitation occurred by an abiotic reaction with bacterially generated sulfide. This appears to be a generalized ability among SRB, arising from dissimilatory sulfide biogenesis, and can take place under low redox conditions and in the dark. The reaction represents a new means for the deposition of elemental sulfur by SRB under such conditions. A combination of transmission electron microscopy, environmental scanning electron microscopy, and cryostage field emission scanning electron microscopy were used to reveal the hydrated nature of SRB biofilms and to investigate the location of deposited sulfur-selenium in relation to biofilm elements. When pregrown SRB biofilms were exposed to a selenite-containing medium, nanometer-sized selenium-sulfur granules were precipitated within the biofilm matrix. Selenite was therefore shown to pass through the biofilm matrix before reacting with bacterially generated sulfide. This constitutes an efficient method for the removal of toxic concentrations of selenite from solution. Implications for environmental cycling and the fate of sulfur and selenium are discussed, and a general model for the potential action of SRB in selenium transformations is presented.

  13. Tailoring partially reduced graphene oxide as redox mediator for enhanced biotransformation of iopromide under methanogenic and sulfate-reducing conditions.

    PubMed

    Toral-Sánchez, Eduardo; Rangel-Mendez, J Rene; Ascacio Valdés, Juan A; Aguilar, Cristóbal N; Cervantes, Francisco J

    2016-10-22

    This work reports the first successful application of graphene oxide (GO) and partially reduced GO (rGO) as redox mediator (RM) to increase the biotransformation of the recalcitrant iodinated contrast medium, iopromide (IOP). Results showed that GO-based materials promoted up to 5.5 and 2.8-fold faster biotransformation of IOP by anaerobic sludge under methanogenic and sulfate-reducing conditions, respectively. Correlation between the extent of reduction of GO and its redox-mediating capacity was demonstrated, which was reflected in faster removal and greater extent of biotransformation of IOP. Further analysis indicated that the biotransformation pathway of IOP involved multiple reactions including deiodination, decarboxylation, demethylation, dehydration and N-dealkylation. GO-based materials could be strategically tailored and integrated in biological treatment systems to effectively enhance the redox conversion of recalcitrant pollutants commonly found in wastewater treatment systems and industrial effluents.

  14. Oxidative damage and redox change in pea seeds treated with cadmium.

    PubMed

    Smiri, Moêz; Chaoui, Abdelilah; Rouhier, Nicolas; Gelhaye, Eric; Jacquot, Jean-Pierre; El Ferjani, Ezzedine

    2010-01-01

    Pea seeds (Pisum sativum L.) were germinated by soaking in distilled water or 5mM CdCl2 for 5 days. The relationships among Cd treatment, germination rate, embryonic axis growth, NAD(P)H levels and NAD(P)H oxidase activities in mitochondrial and peroxisomal fractions of cotyledons and embryonic axis were investigated. Heavy metal stress provoked a diminution in germination percent and embryonic axis growth, as compared to the control. A drastic disorder in reducing power was imposed after exposure to cadmium. Heavy metal caused a significant increase in the redox ratio of coenzymes. NADPH oxidase is considered to be oxidative stress-related enzymes. The NAD(P)H oxidase activities were strongly stimulated after Cd exposure. The changes in redox and oxidative properties are discussed in relation to the delay in seed germination and embryonic axis growth.

  15. 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

  16. [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

  17. 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.

  18. Redox conditions in the atmosphere and shallow-marine environments during the first Huronian deglaciation: Insights from Os isotopes and redox-sensitive elements

    NASA Astrophysics Data System (ADS)

    Goto, Kosuke T.; Sekine, Yasuhito; Suzuki, Katsuhiko; Tajika, Eiichi; Senda, Ryoko; Nozaki, Tatsuo; Tada, Ryuji; Goto, Kazuhisa; Yamamoto, Shinji; Maruoka, Teruyuki; Ohkouchi, Naohiko; Ogawa, Nanako O.

    2013-08-01

    The Paleoproterozoic (2.5-2.0 Ga) is one of the most important periods in Earth's history, and was characterized by a rise in atmospheric oxygen levels and repeated (at least three) severe glaciations (the Huronian glaciations). In this study, we investigate redox conditions in the atmosphere and in shallow-marine environments immediately after the first Huronian glaciation based on the isotopic composition of Os, and the abundance of redox-sensitive elements (Os, Re, and Mo) in sedimentary rocks from the Huronian Supergroup, Canada. We found no significant authigenic enrichment of Os in the sedimentary rocks deposited during the first Huronian deglaciation. The initial isotopic composition of Os in the sediments was close to that of chondrite at the time of deposition (Os187/188Os=∼0.11). These results suggest that atmospheric O2 levels were insufficient to mobilize radiogenic Os through continental weathering (pO2<10-5-10-3 present atmospheric level (PAL)). In contrast, we found enrichment of Re in the sedimentary rocks, which suggests the occurrence of oxidative weathering of Re under mildly oxidizing conditions (>10-8-10-5 PAL). Despite the Re enrichment, low abundances of Mo imply possible non-sulfidic conditions in shallow-marine environments at the time of deposition. Together with the results of organic carbon and sulfur analyses, we suggest that atmospheric O2 remained at relatively low levels of around 10-8-10-5 PAL after the first Huronian deglaciation, which contrasts with proposed dramatic increases in O2 after the second and third Huronian deglaciations. These results imply that the second and third Huronian glaciations may have been global events, associated with climatic jumps from severe glaciations to super-greenhouse conditions and the subsequent blooming of photosynthetic cyanobacteria in the glacial aftermath.

  19. Effects of redox mediators on azo dye decolorization by Shewanella algae under saline conditions.

    PubMed

    Meng, Xianming; Liu, Guangfei; Zhou, Jiti; Fu, Q Shiang

    2014-01-01

    Azo dye decolorization by Shewanella algae (SAL) in the presence of high concentrations of NaCl and different quinones or humic acids was investigated to reveal the effects of redox mediator under saline conditions. Growth of SAL and the other two marine Shewanella strains coupled to anthraquinone-2,6-disulfonate (AQDS) reduction was observed in a wide range of NaCl concentrations (0-7%). AQDS showed the best enhancing effects, whereas some other quinones demonstrated poorer stimulating or even inhibiting effects on acid red 27 (AR27) decolorization. Different humic acids could also enhance the decolorization. The correlation between specific AQDS-mediated reduction rate and initial AR27 concentration could be described with Michaelis-Menten kinetics (Km=0.2 mM and Vmax=9.3 μmol mg cell(-1) h(-1)). AQDS reduction by SAL was determined to be the rate-limiting step of mediated reduction. Mediated decolorization products of AR27 were determined to be less phytotoxic aromatic amines.

  20. Sorption of Sr(II) and Eu(III) onto pyrite under different redox potential conditions.

    PubMed

    Naveau, Aude; Monteil-Rivera, Fanny; Dumonceau, Jacques; Catalette, Hubert; Simoni, Eric

    2006-01-01

    Understanding sorption processes is fundamental for the prediction of radionuclide migration in the surroundings of a deep geological disposal of high-level nuclear wastes. Pyrite (FeS2) is a mineral phase often present as inclusions in temperate soils. Moreover, it constitutes an indirect corrosion product of steel, a containment material that is candidate to confine radionuclides in deep geological disposals. The present study was thus initiated to determine the capacity of pyrite to immobilize Sr(II) and Eu(III). An air oxidized pyrite and a freshly acid-washed (non-oxidized) pyrite were used in background electrolytes of varying reducing-oxidizing ability (NaCl, NH3OHCl, and NaClO4) to study the sorption of both cationic species. The sorptive capacity of pyrite appeared directly correlated to the oxidation of the surface. Non-oxidized pyrite had nearly no affinity for the studied cations whereas Sr(II) and Eu(III) species were significantly retained by oxidized pyrite surface. Using the surface complexation theory, sorption mechanisms were modeled with the Fiteql v3.2 and the Jchess 2.0 codes. Sorption of both Sr and Eu was well fitted, assuming hydroxylated species as the major surface species. This study demonstrates that not only the components of a barrier but also the redox conditions and specifications should be well characterized to predict transport of contaminants in the surrounding of a nuclear wastes disposal.

  1. Photosynthetic parameters and redox homeostasis of Artemisia santonica L. under conditions of Elton region.

    PubMed

    Rozentsvet, Olga; Kosobryukhov, Anatoly; Zakhozhiy, Ilya; Tabalenkova, Galina; Nesterov, Viktor; Bogdanova, Elena

    2017-09-01

    Structural and functional parameters and redox homeostasis in leaves of Artemisia santonica L. under environment conditions of Elton lake (the southeast region of the European part of Russia) were measured. The highest photosynthetic apparatus (PA) activity in A. santonica leaves on CO2 gas exchange as well as the highest content of green pigments was observed in the morning. Maximum share of violaxanthin cycle key pigments - zeaxanthin (Zx) and antheraxanthin (Ax) was observed in the afternoon and decreased in the evening. Lipids/chlorophyll (Chl) ratio increased in the evening due to the decrease in Chl concentration, and content of linolenic acid (С18:3n3) was decreased in the middle of the day. The content of TBA-reacting products increased 1.4-fold in the middle of the day, and decreased approximately 2-fold in the evening. The decrease of the activity was observed in diurnal dynamics of superoxide dismutase (SOD) and polyphenol oxidase (PPO). Increased accumulation of phenols and flavonoids, as well as free amino acids (FAA) in A. santonica leaves was observed in the middle of the day. Thus, the ability of A. santonica plants to resist the soil salinization, high levels of solar illumination and temperature consists of a number of protectively-adaptive reactions of metabolic and photosynthetic control. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

  2. Quantification and characterization of colloids and organic carbon released under oscillating redox conditions

    NASA Astrophysics Data System (ADS)

    Jin, Yan; Afsar, Mohammad; Yan, Jing

    2017-04-01

    Wetlands account for 8-10% of the world's land surface but their soils contain 20-30% of globe terrestrial carbon. The carbon is intimately mixed with minerals in the soils. Thus, mineral-associated-organic carbon (MOC), which often exists as colloids, can directly affect global carbon cycling at multiple scales. When wetland soils become reduced, large quantities of MOC are released due to dissolution of metal oxides, and mobilized and discharged into adjacent streams during rainfall events. Despite the clear relevance of wetlands to global carbon reservoirs and cycling, MOC, as an important component of wetland carbon pool, is poorly understood. Further, understanding of the key factors controlling the fluxes and compositional characteristics of MOC thus the underlying reaction mechanisms that are responsible for the sequestration and stabilization of OC is also lacking. Here we present results from both field sampling and laboratory experiments on the amount, size distribution, and composition of MOC as influenced by oscillating redox conditions. Using both conventional and advanced analytical techniques, including x-ray photoelectron spectroscopy (XPS) and isotope ratio mass spectroscopy (IRMS), we identify 4 MOC size fractions: 450-1000 nm, 100-450 nm, 2.3-100 nm and < 2.3 nm. Normalized atomic% of different elements obtained from XPS analysis reveal clear variations in mineral and OC compositions in the different size fractions. In particular, the "nano sized" MOC (i.e., 2.3-100 nm fraction) has the highest Mg/Al ratio and OC/mineral ratio, the lowest percentages of Al and Si, is mostly depleted in C-C/C-H functional groups but enriched with C=0 and C-O/C-N groups in contract to other size groups. IRMS analysis shows depletion of the heavier isotope 13C from the 2.3-100 nm fraction indicating the presence of more lignin derivatives in this size fraction. The observed size-dependent heterogeneity on C attachment and release to/from MOC can lead to more

  3. 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

  4. 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.

  5. Geological records of redox change related to methane seepage in the Ulleung Basin, East Sea

    NASA Astrophysics Data System (ADS)

    Chun, J.; Ryu, B.; Bahk, J.; Choi, J.; Riedel, M.

    2012-12-01

    The sediment mounds related to columnar seismic blanking zone have been reported in the basin plain, reflecting the presence of near-surface gas hydrate and authigenic carbonates in the Ulleung Basin, East Sea. The mounds commonly consist of hemipelagic sediments and buried authigenic carbonates. Recently, exposed carbonate mound (~5 m wide and 2 -3 m high) was found in the site UBGH2-11 at water depth of ~2092 m. Six push cores (70-cm-long) were collected around the area of the exposed carbonate mound using ROV manipulators. The total nitrogen (TN), total carbon (TC), total organic carbon (TOC), and their carbon dioxide (δ13C) and nitrogen (δ15N) isotope values of core sediments were measured to identify the spatial distribution of organic matter related to methane seepages. The trace and rare earth elements of core sediments were analyzed to determine the redox conditions in seafloor sedimentary environments around the area of cold vents. Higher TOC contents (4-8%) were observed in three cores in the area around the exposed carbonate mound, whereas TOC contents ranged from 2-3% in other three cores, about 50 m away from the exposed carbonate mound. Highly negative δ13C values (-40 to -28 ‰) of organic matters show only one core located at the side of exposed carbonate mound. Higher Mn/Ti ratios suggest that the topmost parts of the core sediments outside the exposed carbonate mound were influenced by the effects of oxygenated bottom water. At other locations, there is no evidence of oxygenated bottom water. It suggests that the surface sediments formed under oxygen-depleted condition. Variation of Mo/Al and Co/Al ratios explains by fluctuation of redox conditions around the exposed carbonate mound in the site UBGH2-11. These results indicate that redox conditions of seafloor environments were locally influenced by methane seepages of cold vents associated with columnar seismic blanking zone in the Ulleung Basin.

  6. 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

  7. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

  9. Assessing the regulation of leaf redox status under water stress conditions in Arabidopsis thaliana: Col-0 ecotype (wild-type and vtc-2), expressing mitochondrial and cytosolic roGFP1.

    PubMed

    Brossa, Ricard; Pintó-Marijuan, Marta; Jiang, Keni; Alegre, Leonor; Feldman, Lewis J

    2013-07-01

    Using Arabidopsis plants Col-0 and vtc2 transformed with a redox sensitive green fluorescent protein, (c-roGFP) and (m-roGFP), we investigated the effects of a progressive water stress and re-watering on the redox status of the cytosol and the mitochondria. Our results establish that water stress affects redox status differently in these two compartments, depending on phenotype and leaf age, furthermore we conclude that ascorbate plays a pivotal role in mediating redox status homeostasis and that Col-0 Arabidopsis subjected to water stress increase the synthesis of ascorbate suggesting that ascorbate may play a role in buffering changes in redox status in the mitochondria and the cytosol, with the presumed buffering capacity of ascorbate being more noticeable in young compared with mature leaves. Re-watering of water-stressed plants was paralleled by a return of both the redox status and ascorbate to the levels of well-watered plants. In contrast to the effects of water stress on ascorbate levels, there were no significant changes in the levels of glutathione, thereby suggesting that the regeneration and increase in ascorbate in water-stressed plants may occur by other processes in addition to the regeneration of ascorbate via the glutathione. Under water stress in vtc2 lines it was observed stronger differences in redox status in relation to leaf age, than due to water stress conditions compared with Col-0 plants. In the vtc2 an increase in DHA was observed in water-stressed plants. Furthermore, this work confirms the accuracy and sensitivity of the roGFP1 biosensor as a reporter for variations in water stress-associated changes in redox potentials.

  10. Redox-linked conformation change and electron transfer between monoheme c-type cytochromes and oxides

    NASA Astrophysics Data System (ADS)

    Khare, Nidhi; Lovelace, David M.; Eggleston, Carrick M.; Swenson, Michael; Magnuson, Timothy S.

    2006-09-01

    Electron transfer between redox active proteins and mineral oxides is important in a variety of natural as well as technological processes, including electron transfer from dissimilatory metal-reducing bacteria to minerals. One of the pathways that could trigger electron transfer between proteins and minerals is redox-linked conformation change. We present electrochemical evidence that mitochondrial cytochrome c (Mcc) undergoes significant conformation change upon interaction with hematite and indium-tin oxide (ITO) surfaces. The apparent adsorption-induced conformation change causes the protein to become more reducing, which makes it able to transfer electrons to the hematite conduction band. Although Mcc is not a protein thought to be involved in interaction with mineral surfaces, it shares (or can be conformed so as to share) some characteristics with multiheme outer-membrane cytochromes thought to be involved in the transfer of electrons from dissimilatory iron-reducing bacteria to ferric minerals during respiration. We present evidence that a 10.1 kDa monohoeme cytochrome isolated and purified from Acidiphilium cryptum, with properties similar to those of Mcc, also undergoes conformation change as a result of interaction with hematite surfaces.

  11. Redox-linked conformation change and electron transfer between monoheme c-type cytochromes and oxides

    SciTech Connect

    Khare, Nidhi; Lovelace, David M.; Eggleston, Carrick M.; Swenson, Michael; Magnuson, Timothy S.

    2006-06-15

    Electron transfer between redox active proteins and mineral oxides is important in a variety of natural as well as technological processes, including electron transfer from dissimilatory metal-reducing bacteria to minerals. One of the pathways that could trigger electron transfer between proteins and minerals is redox-linked conformation change. We present electrochemical evidence that mitochondrial cytochrome c (Mcc) undergoes significant conformation change upon interaction with hematite and indium-tin oxide (ITO) surfaces. The apparent adsorption-induced conformation change causes the protein to become more reducing, which makes it able to transfer electrons to the hematite conduction band. Although Mcc is not a protein thought to be involved in interaction with mineral surfaces, it shares (or can be conformed so as to share) some characteristics with multiheme outer-membrane cytochromes thought to be involved in the transfer of electrons from dissimilatory iron-reducing bacteria to ferric minerals during respiration. We present evidence that a 10.1 kDa monohoeme cytochrome isolated and purified from Acidiphilium cryptum, with properties similar to those of Mcc, also undergoes conformation change as a result of interaction with hematite surfaces.

  12. 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)

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

    PubMed Central

    2010-01-01

    growth phenotypes of the Atnudt7-1 knockout mutants can be due to differences in the nutrient composition of potting mix. Our data suggests AtNUDT7 plays an important role in maintaining redox homeostasis, particularly for maintaining NADH:NAD+ balance for normal growth and development. During stress conditions, rapid induction of AtNUDT7 is important for regulating the activation of stress/defense signaling and cell death pathways. PMID:20704736

  14. Arsenic speciation in aquifer sediment under varying groundwater regime and redox conditions at Jianghan Plain of Central China.

    PubMed

    Duan, Yanhua; Gan, Yiqun; Wang, Yanxin; Liu, Chongxuan; Yu, Kai; Deng, Yamin; Zhao, Ke; Dong, Chuangju

    2017-12-31

    At Jianghan Plain of central Yangtze basins where the health of >73, 000 people has been affected by long term intake of high arsenic groundwater, over 100 sediment samples from four boreholes at the field monitoring sites were collected and analyzed to delineate the distribution and speciation of As in the shallow aquifer sediment. Results showed that sediment As concentration is generally dependent on the lithological conditions, with the higher As concentration present in fine particle sediment, especially in the silty sand layers underlying clay or silty clay layers. High As concentration in the sediment mainly occurred in three different depth ranges: <5m, 15-35m, and >35m. Both the groundwater regime and redox conditions played important roles in controlling sediment As speciation. Arsenate (86%) was the dominated As species in the near surface sediment. As the redox turned to be reducing, arsenite (64%) became the dominant species in the underlying clay and silty clay layers. But in the silty sand aquifer near the boundary of unconfined aquifer and confined aquifer, arsenate (85%) became the dominant species again as results of redox potential elevation. In the deep medium to coarse sand aquifers (>35m deep), As-sulfides (49%-63%) were the main species of As. The speciation and reactivity of sediment As strongly controlled the spatial distribution of groundwater As concentration, while seasonal variation in groundwater As concentration and speciation affected the content and speciation of sediment As. Copyright © 2017 Elsevier B.V. All rights reserved.

  15. Standard redox potentials, pKas, and hydricities of inorganic complexes under electrochemical conditions and implications for CO2 reduction.

    PubMed

    Saravanan, K; Keith, J A

    2016-10-21

    We use computational chemistry to systematically study the thermodynamic stabilities of protonated and reduced intermediate states for Ru(2,2'-bipyridine)3, Ru(1,10-phenanthroline)3, and Ru(phen)2(pyrido[3',4':5,6] pyrazino[2,3-f][1,10]phenanthroline) in aqueous solutions. Following our previous studies of aromatic N-heterocycle molecules, we report pKas, standard redox potentials, and hydricities as well as computationally derived Pourbaix diagrams that show which states would be thermodynamically stable at different conditions of pH and applied potential. Locations of added electrons within ligands and complexes after reductions are also shown with electron density difference plots. As with other aromatic N-heterocycle molecules implicated in CO2 reduction, we find that several of the boundary lines from the Pourbaix diagrams are in close proximity to the thermodynamic redox potentials for CO2 electroreductions, making them thermodynamically appropriate for energetically efficient hydrogen shuttling.

  16. The effects of oil well drill cuttings on soil and rice plant development (Oryza sativa) under two redox conditions.

    PubMed

    Magalhães, Marcio Osvaldo Lima; do Amaral Sobrinho, Nelson Moura Brasil; Zonta, Everaldo; Simões, Bruna Farias; de Mattos, Amanda Guimarães; Tolón-Becerra, Alfredo; Lastra-Bravo, Xavier Bolívar

    2014-03-01

    Few studies have focused on the release of toxic elements from oil well drill cuttings and their effect on soil. The present study evaluated these effects using rice growth as the endpoint. Drill cuttings were collected from a Brazilian well and added in doses of 300, 3,000 and 6,000 mg kg(-1) soil, which was maintained at oxidized or reduced conditions. When the redox potential reached approximately -250 mV, barium concentrations were determined by geochemical fractionation. Overall, doses of 300 and 3,000 mg kg(-1) promoted plant development, while a dose of 6,000 mg kg(-1) inhibited it due to the associated increase in electrical conductivity and exchangeable sodium concentration. In addition, the lower redox potential promoted solubilization of barite from the drill cuttings, which increased barium absorption by plants and translocation to grain, posing a risk to human health.

  17. 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

  18. Coupled Changes in Marine Redox and the Global Carbon Cycle During the Toarcian Oceanic Anoxic Event

    NASA Astrophysics Data System (ADS)

    Pearce, C. R.; Cohen, A. S.; Coe, A. L.; Burton, K. W.

    2006-12-01

    The Toarcian Oceanic Anoxic Event (Early Jurassic, ~183 Ma ago) was a period of greatly enhanced organic carbon deposition worldwide that also saw a crisis in marine phytoplankton and the extinction of marine macrofossils. Recent geochemical studies have revealed a stepped δ13Corg excursion of ~-7‰1, marked excursions in the seawater ^{187}Os/^{188}Os and 87Sr/86Sr ratios2, and evidence for a sudden temperature increase of ~10°C3 at this time. However, as with other OAEs, the inter-relationship between this period of major environmental change and the expansion of marine anoxia has not yet been fully resolved. δ^{98/95}Mo, [Mo] and Re/Mo data from a suite of organic rich sediments deposited in Yorkshire, UK, provide the first high-resolution geochemical evidence showing multiple palaeoredox changes during the Toarcian OAE. The onset of marine anoxia is marked by a ~2‰ increase in δ^{98/95}Mo in the semicelatum subzone that coincides with the start of the δ13Corg negative excursion. Re/Mo ratios imply that marine conditions were euxinic during the OAE (i.e. [H2S] was > 100μm during the late semicelatum and exaratum subzones), although the presence of four cyclical δ^{98/95}Mo excursions suggest that the availability of 'Mo-reactive' H2S varied during this period. The actual δ^{98/95}Mo composition of seawater recorded during the four excursions reached unusually low δ^{98/95}Mo values of ~0.8‰ showing that the areal extent of oxic deposition worldwide was reduced significantly during the Toarcian OAE. Each of the four cyclical δ^{98/95}Mo excursions is associated with an abrupt ~-2‰ to ~-3‰ decrease in δ13Corg, although the two geochemical changes do not exactly overlap; the decrease in δ^{98/95}Mo is more gradual and starts before the abrupt shift in δ13Corg. This association is best explained by there being 4 periods within the OAE involving fluctuating levels of oceanic stagnation and seawater redox that each culminated in the sudden

  19. Redox-coupled structural changes of the catalytic a' domain of protein disulfide isomerase.

    PubMed

    Inagaki, Koya; Satoh, Tadashi; Yagi-Utsumi, Maho; Le Gulluche, Anne-Charlotte; Anzai, Takahiro; Uekusa, Yoshinori; Kamiya, Yukiko; Kato, Koichi

    2015-09-14

    Protein disulfide isomerase functions as a folding catalyst in the endoplasmic reticulum. Its b' and a' domains provide substrate-binding sites and undergo a redox-dependent domain rearrangement coupled to an open-closed structural change. Here we determined the first solution structure of the a' domain in its oxidized form and thereby demonstrate that oxidation of the a' domain induces significant conformational changes not only in the vicinity of the active site but also in the distal b'-interfacial segment. Based on these findings, we propose that this conformational transition triggers the domain segregation coupled with the exposure of the hydrophobic surface. Copyright © 2015 Federation of European Biochemical Societies. Published by Elsevier B.V. All rights reserved.

  20. Chemoreceptor discharges and cytochrome redox changes of the rat carotid body: Role of heme ligands

    PubMed Central

    Lahiri, Sukhamay; Ehleben, Wilhelm; Acker, Helmut

    1999-01-01

    In superfused in vitro rat carotid body, we recorded chemoreceptor discharges and the redox state of cytochromes simultaneously to identify the primary oxygen-sensing protein controlling transmitter release and electrical activity of the carotid sinus nerve. These parameters were tested under the influence of heme ligands such as oxygen, cyanide, 4-(2-aminoethyl)-benzenesulfonyl fluoride, and CO. During stimulation, there was an initial increase in discharge frequency followed by a decline or suppression of activity. Photometric changes lagged and were maintained as nerve activity decreased. Reducing mitochondrial cytochromes by cyanide or prolonged severe hypoxia, suppressed the chemoreceptor discharge. 4-(2-Aminoethyl)-benzenesulfonyl fluoride, a specific inhibitor of the phagocytic cytochrome b558, also silenced the chemoreceptors after an initial excitation. CO increased the chemoreceptor discharge under normoxia, an effect inhibited by light, when the cytochromes were not reduced. When the discharges were depressed by severe hypoxia, exposure to light excited the chemoreceptors and the cytochromes were reduced. The rapidity of the chemosensory responses to light and lack of effect on dopamine release from type I cells led us to hypothesize that carotid body type I cells and the apposed nerve endings use different mechanisms for oxygen sensing: the nerve endings generate action potentials in association with membrane heme proteins whereas cytosolic heme proteins signal the redox state, releasing modulators or transmitters from type I cells. PMID:10430959

  1. Changes in athlete's redox state induced by habitual and unaccustomed exercise.

    PubMed

    Djordjevic, Dusica Z; Cubrilo, Dejan G; Puzovic, Vladimir S; Vuletic, Milena S; Zivkovic, Vladimir I; Barudzic, Nevena S; Radovanovic, Dragan S; Djuric, Dragan M; Jakovljevic, Vladimir Lj

    2012-01-01

    The purpose of this study was to assess the influence of sport-specific and nonspecific bouts of exercise on athletes' redox state. Blood samples were collected from 14 handball players immediately before and after graded exercise test on the cycle ergometer and handball training. Levels of superoxide anion radical (O(2) (-)), hydrogen peroxide (H(2)O(2)), nitrites (NO(2) (-)) as markers of nitric oxide, index of lipid peroxidation (TBARs), glutathione (GSH), superoxide dismutase (SOD), and catalase (CAT) activity were determined. Exercise intensity was assessed by a system for heart rate (HR) monitoring. Average athletes' HR was not significantly different between protocols, but protocols differed in total time and time and percentage of time that athletes spent in every HR zone. The laboratory exercise test induced a significant increase of H(2)O(2) and TBARs as well as the decrease of the SOD and CAT activity, while after specific handball training, levels of NO(2) (-) were increased and SOD activity decreased. It seems that unaccustomed short intensive physical activity may induce oxidative stress in trained athletes, while sport-specific activity of longer duration and proper warm-up period may not. Further research should show whether the change of protocol testing and the implementation of various supplementations and manual methods can affect the redox equilibrium.

  2. 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

  3. Changes in glutathione redox cycle during diapause determination and termination in the bivoltine silkworm, Bombyx mori.

    PubMed

    Zhao, Lin-Chuan; Hou, Yi-Sheng; Sima, Yang-Hu

    2014-02-01

    To explore whether glutathione regulates diapause determination and termination in the bivoltine silkworm Bombyx mori, we monitored the changes in glutathione redox cycle in the ovary of both diapause- and nondiapause-egg producers, as well as those in diapause eggs incubated at different temperatures. The activity of thioredoxin reductase (TrxR) was detected in ovaries but not in eggs, while neither ovaries nor eggs showed activity of glutathione peroxidase. A lower reduced glutathione/oxidized glutathione (GSH/GSSG) ratio was observed in the ovary of diapause-egg producers, due to weaker reduction of oxidized glutathione (GSSG) to the reduced glutathione (GSH) catalyzed by glutathione reductase (GR) and TrxR. This indicates an oxidative shift in the glutathione redox cycle during diapause determination. Compared with the 25°C-treated diapause eggs, the 5°C-treated diapause eggs showed lower GSH/GSSG ratio, a result of stronger oxidation of GSH catalyzed by thioredoxin peroxidase and weaker reduction of GSSG catalyzed by GR. Our study demonstrated the important regulatory role of glutathione in diapause determination and termination of the bivoltine silkworm.

  4. Redox imbalance and morphological changes in skin fibroblasts in typical Rett syndrome.

    PubMed

    Signorini, Cinzia; Leoncini, Silvia; De Felice, Claudio; Pecorelli, Alessandra; Meloni, Ilaria; Ariani, Francesca; Mari, Francesca; Amabile, Sonia; Paccagnini, Eugenio; Gentile, Mariangela; Belmonte, Giuseppe; Zollo, Gloria; Valacchi, Giuseppe; Durand, Thierry; 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.

  5. Diquat-induced cellular pyridine nucleotide redox changes and alteration of metabolic enzyme activities in colonic carcinoma cells.

    PubMed

    Circu, Magdalena L; Maloney, Ronald E; Aw, Tak Yee

    2017-02-25

    Previously we have shown that the redox cycler menadione (MQ) induced cellular pyridine nucleotide redox imbalance that was linked to a decrease in aerobic glycolysis and perturbation of the mitochondrial respiratory activity due to the redox cycling of the compound; these processes were potentiated by low glucose. In this study, we investigated how colonic epithelial cells maintained pyridine nucleotide (NAD(+)/NADH and NADP(+)/NADPH) redox homeostasis upon acute metabolic variation and exposure to the redox cycling diquat (DQ). Our results show that DQ challenge disrupted cellular NADH/NAD(+) redox status and enhanced cellular NADPH generation. Notably, DQ-induced NADH decrease was associated with enhanced lactate production, a process that was potentiated by glucose availability, but not by the mitochondrial substrates, succinate or malate/glutamate. In addition, DQ increased glucose 6-phoshate dehydrogenase (G6PDH) activity consistent with glucose diversion towards pentose phosphate pathway. As a consequence, steady-state NADPH levels were maintained during MQ challenge at normal glucose. In contrast and despite increased G6PDH and malic enzyme (ME) activities, DQ induced cellular NADPH-to-NADP(+) shift at low glucose, a situation that was reversed by mitochondrial substrates. Collectively, these results are consistent with increased aerobic glycolysis by DQ and specific metabolic changes leading to enhanced NADPH generation upon oxidative challenge.

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

    NASA Astrophysics Data System (ADS)

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

    2017-03-01

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

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

    USGS Publications Warehouse

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

    2017-01-01

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

  8. Efficient chemisorption of organophosphorous redox probes on indium tin oxide surfaces under mild conditions.

    PubMed

    Forget, Amélie; Limoges, Benoît; Balland, Véronique

    2015-02-17

    We report a mild and straightforward one-step chemical surface functionalization of indium tin oxide (ITO) electrodes by redox-active molecules bearing an organophosphoryl anchoring group (i.e., alkyl phosphate or alkyl phosphonate group). The method takes advantage of simple passive adsorption in an aqueous solution at room temperature. We show that organophosphorus compounds can adsorb much more strongly and stably on an ITO surface than analogous redox-active molecules bearing a carboxylate or a boronate moiety. We provide evidence, through quantitative electrochemical characterization (i.e., by cyclic voltammetry) of the adsorbed organophosphoryl redox-active molecules, of the occurrence of three different adsorbate fractions on ITO, exhibiting different stabilities on the surface. Among these three fractions, one is observed to be strongly chemisorbed, exhibiting high stability and resistance to desorption/hydrolysis in a free-redox probe aqueous buffer. We attribute this remarkable stability to the formation of chemical bonds between the organophosphorus anchoring group and the metal oxide surface, likely occurring through a heterocondensation reaction in water. From XPS analysis, we also demonstrate that the surface coverage of the chemisorbed molecules is highly affected by the degree of surface hydroxylation, a parameter that can be tuned by simply preconditioning the freshly cleaned ITO surfaces in water. The lower the relative surface hydroxide density on ITO, the higher was the surface coverage of the chemisorbed species. This behavior is in line with a chemisorption mechanism involving coordination of a deprotonated phosphoryl oxygen atom to the non-hydroxylated acidic metal sites of ITO.

  9. Solubility and speciation of S in hydrous magmas: Effects of composition and redox conditions at 1050°C and 200 MPa

    NASA Astrophysics Data System (ADS)

    Botcharnikov, R. E.; Wilke, M.; Jugo, P. J.; Holtz, F.

    2009-12-01

    Knowledge on the behaviour of sulphur in natural magmas provides important constraints on geochemical and geophysical processes occurring in magmatic and hydrothermal systems. The partitioning of S between silicate melts and coexisting fluids is mainly controlled by the transformations of S species into sulphide or sulphate form due to changes in the redox conditions of the system. The saturation of a silicate melt in respect of sulphide- or/and sulphate-bearing phase is responsible for the maximum concentrations of dissolved sulphur. Hence, the composition of the silicate melt and activities of melt components, especially Fe and Ca, are critical parameters controlling S partitioning. Here, we present experimental data on the solubility of S in rhyolitic to basaltic magmas equilibrated with aqueous S-bearing fluids of constant bulk composition (5 wt.% H2O and 1 wt.% S in the system) at 1050°C, 200 MPa and redox conditions corresponding to that of logfO2~QFM-2 to QFM+3 (where QFM is quartz-fayalite-magnetite oxygen buffer). For studied melt compositions, the solubility of S systematically increases with increasing fO2 and depolymerisation of the silicate melt. At logfO2 < ~QFM, S solubility is controlled by the stability of FeS phase while at logfO2 > ~QFM+2, CaSO4 is a stable phase. Both S-bearing phases may coexist at intermediate fO2 values. The largest difference in solubilities of sulphide and sulphate S is observed for basaltic melts, where the concentration of sulphide S is 0.07 wt.%, being approximately ten times lower than the concentration of sulphate S of about 0.6 wt.%. Other melt compositions show lower concentration differences between dissolved S species, having, however, similar positive dependence on fO2. Thus, the partition coefficients of S between fluid and silicate melt vary as a function of melt composition and redox conditions. The largest partition coefficients (>1000) are determined for reduced silicic melts. For all investigated melt

  10. Graphene oxide as electron shuttle for increased redox conversion of contaminants under methanogenic and sulfate-reducing conditions.

    PubMed

    Colunga, Alejandra; Rangel-Mendez, J Rene; Celis, Lourdes B; Cervantes, Francisco J

    2015-01-01

    Graphene oxide (GO) is reported for the first time as electron shuttle to increase the redox conversion of the azo compound, reactive red 2 (RR2, 0.5mM), and the nitroaromatic, 3-chloronitrobenzene (3CNB, 0.5mM). GO (5mgL(-1)) increased 10-fold and 7.6-fold the reduction rate of RR2 and 3CNB, respectively, in abiotic incubations with sulfide (2.6mM) as electron donor. GO also increased by 2-fold and 3.6-fold, the microbial reduction rate of RR2 by anaerobic sludge under methanogenic and sulfate-reducing conditions, respectively. Deep characterization of GO showed that it has a proper size distribution (predominantly between 450 and 700nm) and redox potential (+50.8mV) to promote the reduction of RR2 and 3CNB. Further analysis revealed that biogenic sulfide plays a major role on the GO-mediated reduction of RR2. GO is proposed as an electron shuttle to accelerate the redox conversion of recalcitrant pollutants, such as nitro-benzenes and azo dyes. Copyright © 2014 Elsevier Ltd. All rights reserved.

  11. The redox conditions of anhydrous and hydrous xenoliths of suprasubduction and intraplate lithospheric mantle

    NASA Astrophysics Data System (ADS)

    Bonadiman, C.; Coltorti, M.

    2012-12-01

    The oxidation state of the upper mantle, its relationship with C-H-O fluids speciation and tectonic settings has been debated for decades and the various modelling have considered the prevalent role of the hydrous minerals over nominally anhydrous minerals (and the opposite) as well as the dissolution of silicate minerals (as providers of Fe3+ to the system) as directly related to water activity and oxygen fugacity. Each of these modelling has different implications for mantle rheology, seismic structure, and the evolution of the lithosphere (i.e.: Karato and Jung, 1998, Hirshmann, 2006). Upper mantle is the only part of the Earth's mantle where the oxygen fugacity can be directly measured, its values/variation being dependent on various processes such as partial melting and metasomatism often operating in time and space without solution of continuity. Recent general reviews of oxygen thermobarometry measurements (Forst & McCammon, 2008; Foley, 2011) indicate that the oxygen fugacity at the top of the upper mantle falls within ±2 log units of the fayalite-magnetite-quartz (FMQ) oxygen buffer. There is also a general consensus in considering H2O as the strongest oxidizing agent in mantle metasomatic fluids, its activity leading to the formation of amphibole and raising the mantle redox state. This contribution presents fO2 and water activity results from three spinel-bearing mantle xenolith localities and distinct geodynamic settings: Ichinomegata (Japan) amphibole-bearing peridotites entrained in calc-alkaline basalts and Cerro Fraile (South Patagonia, Argentina), mostly anhydrous lherzolites and pirossenites brought up to the surface by alkaline basalts representing fragments of sub-arc mantle and Baker Rocks, Victoria Land (Antarctica), amphibole-bearing lherzolites representing portion of intraplate subcontinental lithospheric mantle. The three mantle sectors records fO2 values in the range of -1.9 to +0.8 log units of the FQM buffer. and low to very low aH2O

  12. Exercise-induced changes in redox status of elite karate athletes.

    PubMed

    Pesic, Snezana; Jakovljevic, Vladimir; Djordjevic, Dusica; Cubrilo, Dejan; Zivkovic, Vladimir; Jorga, Vladimir; Mujovic, Vujadin; Djuric, Dragan; Stojimirovic, Biljana

    2012-02-29

    Regular training has been claimed to increase the activity of antioxidant enzymes and, consequently, augments the resistance to oxidative stress; however, large volumes of training performed by elite sportsmen could lead to a chronic oxidative stress state. The aim of our study was to assess the oxidative status of elite athletes at the beginning of the preparatory and the beginning of the competition training phases, so that the influence of three months of programmed physical activity on redox status could be determined. The chronic effects of exercise on the redox state of the athletes were compared to the effects of a single bout of karate training. Thirty elite karate athletes, 16-30 years old, were subjected to maximal graded exercise test to estimate their aerobic capacity; blood sampling was also performed to measure levels of superoxide anion radical (O₂⁻), hydrogen peroxide (H₂O₂), superoxide dismutase activity (SOD) and catalase activity (CAT). The only significant change after the three-month training process was found in the significantly decreased CAT activity (X ± SE: 7.95 ± 0.13 U/g Hb × 10³ in the preparatory period, 6.65 ± 0.28 U/g Hb × 10³ in the competition stage; P < 0.01). After a single karate training session, there was statistically significant decrease of O₂⁻(X ± SE: 32.7 ± 4.9 nmol/ml in the preparatory period, 24.5 ± 2.5 nmol/ml in the competition stage; P < 0.05) and increase of H₂O₂(X ± SE: 11.8 ± 1.0 nmol/ml in the preparatory period, 14.2 ± 0.9 nmol/ml in the competition stage; P < 0.01), as well as significant CAT increase (X ± SE: 6.6 ± 0.6 U/g Hb × 10³ in the preparatory period, 8.5 ± 0.5 U/g Hb × 10³ in the competition stage; P < 0.05). Although the three-month training process induced, at the first sight, negative changes in the redox state, expressed through the decrease in CAT activity, adequate response of the antioxidant system of our athletes to acute exercise was preserved.

  13. Climate Change, CO2, and Defense: The Metabolic, Redox, and Signaling Perspectives.

    PubMed

    Noctor, Graham; Mhamdi, Amna

    2017-10-01

    Ongoing human-induced changes in the composition of the atmosphere continue to stimulate interest in the effects of high CO2 on plants, but its potential impact on inducible plant defense pathways remains poorly defined. Recently, several studies have reported that growth at elevated CO2 is sufficient to induce defenses such as the salicylic acid pathway, thereby increasing plant resistance to pathogens. These reports contrast with evidence that defense pathways can be promoted by photorespiration, which is inhibited at high CO2. Here, we review signaling, metabolic, and redox processes modulated by CO2 levels and discuss issues to be resolved in elucidating the relationships between primary metabolism, inducible defense, and biotic stress resistance. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

    PubMed

    Seo, Dong Cheol; DeLaune, Ronald D

    2010-08-01

    Fungal and bacterial carbon dioxide (CO2) production/emission was determined under a range of redox conditions in sediment from a Louisiana swamp forest used for wastewater treatment. Sediment was incubated in microcosms at 6 Eh levels (-200, -100, 0, +100, +250 and +400 mV) covering the anaerobic range found in wetland soil and sediment. Carbon dioxide production was determined by the substrate-induced respiration (SIR) inhibition method. Cycloheximide (C15H23NO4) was used as the fungal inhibitor and streptomycin (C21H39N7O12) as the bacterial inhibitor. Under moderately reducing conditions (Eh > +250 mV), fungi contributed more than bacteria to the CO2 production. Under highly reducing conditions (Eh < or = 0 mV), bacteria contributed more than fungi to the total CO2 production. The fungi/bacteria (F/B) ratios varied between 0.71-1.16 for microbial biomass C, and 0.54-0.94 for microbial biomass N. Under moderately reducing conditions (Eh > or = +100 mV), the F/B ratios for microbial biomass C and N were higher than that for highly reducing conditions (Eh < or = 0 mV). In moderately reducing conditions (Eh > or = +100 mV), the C/N microbial biomass ratio for fungi (C/N: 13.54-14.26) was slightly higher than for bacteria (C/N: 9.61-12.07). Under highly reducing redox conditions (Eh < or = 0 mV), the C/N microbial biomass ratio for fungi (C/N: 10.79-12.41) was higher than for bacteria (C/N: 8.21-9.14). For bacteria and fungi, the C/N microbial biomass ratios under moderately reducing conditions were higher than that in highly reducing conditions. Fungal CO2 production from swamp forest could be of greater ecological significance under moderately reducing sediment conditions contributing to the greenhouse effect (GHE) and the global warming potential (GWP). However, increases in coastal submergence associated with global sea level rise and resultant decrease in sediment redox potential from increased flooding would likely shift CO2 production to bacteria rather than

  15. Redox-dependent structural changes in an engineered heme-copper center in myoglobin: insights into chloride binding to CuB in heme copper oxidases.

    PubMed

    Zhao, Xuan; Nilges, Mark J; Lu, Yi

    2005-05-03

    The effects of chloride on the redox properties of an engineered binuclear heme-copper center in myoglobin (Cu(B)Mb) were studied by UV-vis spectroelectrochemistry and EPR spectroscopy. A low-spin heme Fe(III)-Cu(I) intermediate was observed during the redox titration of Cu(B)Mb only in the presence of both Cu(II) and chloride. Upon the first electron transfer to the Cu(B) center, one of the His ligands of Cu(B) center dissociates and coordinates to the heme iron, forming a six-coordinate low-spin ferric heme center and a reduced Cu(B) center. The second electron transfer reduces the ferric heme and causes the release of the coordinated His ligand. Thus, the fully reduced state of the heme-copper center contains a five-coordinate ferrous heme and a reduced Cu(B) center, ready for O(2) binding and reduction to water to occur. In the absence of a chloride ion, formation of the low-spin heme species was not observed. These redox reactions are completely reversible. These results indicate that binding of chloride to the Cu(B) center can induce redox-dependent structural changes, and the bound chloride and hydroxide in the heme-copper center may play different roles in the redox-linked enzymatic reactions of heme-copper oxidases, probably because of their different binding affinity to the copper center and the relatively high concentration of chloride under physiological conditions.

  16. 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.

  17. 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.

  18. Neptunium sorption and redox speciation at the illite surface under highly saline conditions

    NASA Astrophysics Data System (ADS)

    Banik, Nidhu Lal; Marsac, Rémi; Lützenkirchen, Johannes; Marquardt, Christian Michael; Dardenne, Kathy; Rothe, Joerg; Bender, Kerstin; Geckeis, Horst

    2017-10-01

    Neptunium (Np) uptake on illite is investigated in 1 and 3.2 molal (m) NaCl solutions under inert (Ar) atmosphere for 4 < pHm < 10 (pHm = -log mH+) and 5 × 10-8 < [Np(V)]tot < 3 × 10-4 M. In agreement with a previous study in 0.1 m NaCl solutions (Marsac et al., 2015a), Np(V) is the prevailing oxidation state in the aqueous solution, but Np uptake by illite is affected by surface induced reduction. The extent of Np(V) reduction to Np(IV) follows the measured redox potential (or the pe = -log ae-), which is influenced by the introduced Np(V) amount, because of the low redox capacity of the illite. The presence of Np(IV) on the solid phase is verified by X-ray Absorption Near Edge Spectroscopy (XANES). We can conclude that Np uptake by illite is not significantly affected by the variation of mNaCl from 0.1 to 3.2 m and thus is in agreement with reports on tetravalent actinide and Np(V) sorption to clays at high ionic strength. The combination of (i) the two site protolysis non-electrostatic surface complexation and cation exchange model, (ii) the specific ion interaction theory to calculate activity coefficients for dissolved species and (iii) by accounting for redox equilibria and the stability of surface Np species, the overall Np uptake by illite can be simulated as a function of pHm, pe and mNaCl using a single set of parameters. The present experimental and modeling results are particularly important in the context of deep geological nuclear waste disposal since many sedimentary rocks or clay formations that are deemed suitable for this purpose exhibit highly saline porewaters.

  19. 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.

  20. 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

  1. 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.

  2. An evaluation of benthic foraminiferal U/Ca and U/Mn proxies for deep ocean carbonate chemistry and redox conditions

    NASA Astrophysics Data System (ADS)

    Chen, Pujiao; Yu, Jimin; Jin, Zhangdong

    2017-02-01

    The deep ocean is thought to have played a crucial role in modulating atmospheric CO2 changes, and thus reconstructions of deep ocean conditions can place important constraints on the past global carbon cycle. Some previous studies suggested that foraminiferal U/Ca could be used to infer seawater carbonate chemistry changes, but others showed complications from diagenesis and temperature. A recent downcore study suggested that foraminiferal U/Mn may be used for sedimentary redox-conditions, but no core-top work has been done to investigate factors affecting U/Mn. We investigate controlling factors on U/Ca and U/Mn in two benthic foraminiferal species from 120 global core-tops and three Atlantic sediment cores. Our core-top data reveal no significant correlation between core-top benthic U/Ca and carbonate system parameters. The lack of an influence of deep-water [CO32-] on U/Ca is further supported by our downcore results. Together, our data highlight complications to use benthic U/Ca for deep-water carbonate chemistry reconstructions. Although no correlation is found between core-top U/Mn and hydrographic data, high-resolution U/Mn and U/Ca in core TNO57-21 show similar patterns to authigenic U (aU) and vary in tandem with atmospheric CO2 on millennial timescales. Changes in U/Mn, U/Ca and aU in TNO57-21 may reflect postdepositional diagenesis linked to sedimentary oxygen, which is controlled by subantarctic surface productivity and ventilation of deep South Atlantic in the past. We suggest that benthic U/Mn and U/Ca may be used as auxiliary indicators for past sedimentary redox-conditions and along with other proxies could reflect deep-water oxygenation.

  3. 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.

  4. Oxygen and temperature-dependent structural and redox changes in a novel cytochrome c(4) from the purple sulfur photosynthetic bacterium Thiocapsa roseopersicina.

    PubMed

    Branca, Rui M M; Bodó, Gabriella; Várkonyi, Zsuzsanna; Debreczeny, Mónika; Osz, Judit; Bagyinka, Csaba

    2007-11-15

    A novel cytochrome c(4), the first of this type in purple phototrophic bacteria has been discovered in Thiocapsa roseopersicina. The fact that cytochrome c(4) has been found in an anaerobic organism puts in question the up hereto suggested role of cytochromes c(4) in the aerobic respiratory metabolism. The structure of cytochrome c(4) was studied under both aerobic and anaerobic conditions, using differential scanning calorimetry and a combination of redox potentiostatic measurements with CD and UV-Vis absorption techniques. Cytochrome c(4) maintained its functional capability at high temperature (60 degrees C) if it was kept under anaerobic conditions. With increasing temperature under aerobic conditions, however, there are dramatic conformational changes in the protein and coordination changes on the iron side. Presumably oxygen binds to the iron at the position left vacant by the methionine and facilitates conformational changes with low reversibility.

  5. 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.

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

    PubMed

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

    2015-11-01

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

  7. Redox-dependent conformational changes in eukaryotic cytochromes revealed by paramagnetic NMR spectroscopy.

    PubMed

    Volkov, Alexander N; Vanwetswinkel, Sophie; Van de Water, Karen; van Nuland, Nico A J

    2012-03-01

    Cytochrome c (Cc) is a soluble electron carrier protein, transferring reducing equivalents between Cc reductase and Cc oxidase in eukaryotes. In this work, we assessed the structural differences between reduced and oxidized Cc in solution by paramagnetic NMR spectroscopy. First, we have obtained nearly-complete backbone NMR resonance assignments for iso-1-yeast Cc and horse Cc in both oxidation states. These were further used to derive pseudocontact shifts (PCSs) arising from the paramagnetic haem group. Then, an extensive dataset comprising over 450 measured PCSs and high-resolution X-ray and solution NMR structures of both proteins were used to define the anisotropic magnetic susceptibility tensor, Δχ. For most nuclei, the PCSs back-calculated from the Δχ tensor are in excellent agreement with the experimental PCS values. However, several contiguous stretches-clustered around G41, N52, and A81-exhibit large deviations both in yeast and horse Cc. This behaviour is indicative of redox-dependent structural changes, the extent of which is likely conserved in the protein family. We propose that the observed discrepancies arise from the changes in protein dynamics and discuss possible functional implications.

  8. Changes in Select Redox Proteins of the Retinal Pigment Epithelium in Age-related Macular Degeneration

    PubMed Central

    DECANINI, ALEJANDRA; NORDGAARD, CURTIS L.; FENG, XIAO; FERRINGTON, DEBORAH A.; OLSEN, TIMOTHY W.

    2008-01-01

    PURPOSE To examine changes of select reduction-oxidation (redox) sensitive proteins from human donor retinal pigment epithelium (RPE) at four stages of age-related macular degeneration (AMD). DESIGN Experimental study. METHODS Human donor eyes were obtained from the Minnesota Lions Eye Bank and graded using the Minnesota Grading System (MGS) into four stages that correspond to stages defined by the age-related eye disease study (AREDS). Protein content in RPE homogenates was measured using Western immunoblotting with protein-specific antibodies. RESULTS The content of several antioxidant enzymes and specific proteins that facilitate refolding or degradation of oxidatively damaged proteins increased significantly in MGS stage 3. These proteins are involved in the primary (copper-zinc superoxide dismutase [CuZnSOD], manganese superoxide dismutase [MnSOD], and catalase) and secondary (heat shock protein [HSP] 27, HSP 90, and proteasome) defense against oxidative damage. Additionally, the insulin pro-survival receptor exhibited disease-related upregulation. CONCLUSIONS The pattern of protein changes identified in human donor tissue graded using the MGS support the role of oxidative mechanisms in the pathogenesis and progression of AMD. The MGS uses nearly identical clinical definitions and grading criteria of AMD that are used in the AREDS, so our results apply to clinical and epidemiologic studies using similar definitions. Results from our protein analysis of human donor tissue helps to explain altered oxidative stress regulation and cell-survival pathways that occur in progressive stages of AMD. PMID:17280640

  9. Redox- and pH-linked conformational changes in triheme cytochrome PpcA from Geobacter sulfurreducens.

    PubMed

    Morgado, Leonor; Bruix, Marta; Pokkuluri, P Raj; Salgueiro, Carlos A; Turner, David L

    2017-01-15

    The periplasmic triheme cytochrome PpcA from Geobacter sulfurreducens is highly abundant; it is the likely reservoir of electrons to the outer surface to assist the reduction of extracellular terminal acceptors; these include insoluble metal oxides in natural habitats and electrode surfaces from which electricity can be harvested. A detailed thermodynamic characterization of PpcA showed that it has an important redox-Bohr effect that might implicate the protein in e(-)/H(+) coupling mechanisms to sustain cellular growth. This functional mechanism requires control of both the redox state and the protonation state. In the present study, isotope-labeled PpcA was produced and the three-dimensional structure of PpcA in the oxidized form was determined by NMR. This is the first solution structure of a G. sulfurreducens cytochrome in the oxidized state. The comparison of oxidized and reduced structures revealed that the heme I axial ligand geometry changed and there were other significant changes in the segments near heme I. The pH-linked conformational rearrangements observed in the vicinity of the redox-Bohr center, both in the oxidized and reduced structures, constitute the structural basis for the differences observed in the pKa values of the redox-Bohr center, providing insights into the e(-)/H(+) coupling molecular mechanisms driven by PpcA in G. sulfurreducens. © 2017 The Author(s); published by Portland Press Limited on behalf of the Biochemical Society.

  10. 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...

  11. 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...

  12. 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

  13. Surface and redox properties of cobalt-ceria binary oxides: On the effect of Co content and pretreatment conditions

    NASA Astrophysics Data System (ADS)

    Konsolakis, Michalis; Sgourakis, Michalis; Carabineiro, Sónia A. C.

    2015-06-01

    Ceria-based transition metal catalysts have recently received considerable attention both in heterogeneous catalysis and electro-catalysis fields, due to their unique physicochemical characteristics. Their catalytic performance is greatly affected by the surface local chemistry and oxygen vacancies. The present study aims at investigating the impact of Co/Ce ratio and pretreatment conditions on the surface and redox properties of cobalt-ceria binary oxides. Co-ceria mixed oxides with different Co content (0, 20, 30, 60, 100 wt.%) were prepared by impregnation method and characterized by means of N2 adsorption at -196 °C, X-ray diffraction (XRD), H2 temperature-programmed reduction (H2-TPR) and X-ray photoelectron spectroscopy (XPS). The results shown the improved reducibility of Co/CeO2 mixed oxides compared to single oxides, due to a synergistic interaction between cobalt and cerium. Oxidation pretreatment results in a preferential localization of cerium species on the outer surface. In contrast, a uniform distribution of cobalt and cerium species over the entire catalyst surface is obtained by the reduction process, which facilitates the formation of oxygen vacancies though Co3+/Co2+ and Ce3+/Ce4+ redox cycles. Fundamental insights toward tuning the surface chemistry of cobalt-ceria binary oxides are provided, paving the way for real-life industrial applications.

  14. Redox transformations of iron in the presence of exudate from the cyanobacterium Microcystis aeruginosa under conditions typical of natural waters.

    PubMed

    Wang, Kai; Garg, Shikha; Waite, T David

    2017-02-24

    Interaction of the exudate secreted by a toxic strain of the cyanobacterium Microcystis aeruginosa with Fe(II) and Fe(III) was investigated here under both acidic (pH 4) and alkaline (pH 8) conditions. At the concentrations of iron and exudate used, iron was present as dissolved iron (< 0.025 µm) at pH 4 but principally as small (< 0.45 µm) iron oxyhydroxide particles at pH 8 with only ~3-27% present in the dissolved form as a result of iron binding by the organic exudate. The formation of strong Fe(III)-exudate and relatively weak Fe(II)-exudate complexes alters the reduction potential of the Fe(III)/Fe(II) redox couple facilitating more rapid oxidation of Fe(II) at pH 4 and 8 than was the case in the absence of exudate. Our results further show that the organic exudate contains Fe(III) reducing moieties resulting in production of measureable concentrations of Fe(II). However, these reducing moieties are short-lived (with a half-life of 1.9 hours) and easily oxidized in air-saturated environments. A kinetic model was developed that adequately describes the redox transformation of Fe in the presence of exudate both at pH 4 and pH 8.

  15. 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...

  16. 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...

  17. 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.

  18. 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.

  19. Arsenic uptake by rice is influenced by microbe-mediated arsenic redox changes in the rhizosphere.

    PubMed

    Jia, Yan; Huang, Hai; Chen, Zheng; Zhu, Yong-Guan

    2014-01-21

    Arsenic (As) uptake by rice is largely determined by As speciation, which is strongly influenced by microbial activities. However, little is known about interactions between root and rhizosphere microbes, particularly on arsenic oxidation and reduction. In this study, two rice cultivars with different radial oxygen loss (ROL) ability were used to investigate the impact of microbially mediated As redox changes in the rhizosphere on As uptake. Results showed that the cultivar with higher ROL (Yangdao) had lower As uptake than that with lower ROL (Nongken). The enhancement of the rhizospheric effect on the abundance of the arsenite (As(III)) oxidase gene (aroA-like) was greater than on the arsenate (As(V)) reductase gene (arsC), and As(V) respiratory reductase gene (arrA), resulting in As oxidation and sequestration in the rhizosphere, particularly for cultivar Yangdao. The community of As(III)-oxidizing bacteria in the rhizosphere was dominated by α-Proteobacteria and β-Proteobacteria and was influenced by rhizospheric effects, rice straw application, growth stage, and cultivar. Application of rice straw into the soil increased As release and accumulation into rice plants. These results highlighted that uptake of As by rice is influenced by microbial processes, especially As oxidation in the rhizosphere, and these processes are influenced by root ROL and organic matter application.

  20. 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.

  1. Redox Conditions and Microbial Particle Association: A Multi-Year Study in the Cariaco Basin

    NASA Astrophysics Data System (ADS)

    Suter, E.; Pachiadaki, M.; Edgcomb, V. P.; Scranton, M. I.; Taylor, G. T.

    2016-02-01

    Using multiple approaches we have revealed fine-scale complexity in the aggregate association of microbial genes, transcripts, and phylogenetic groups across the redox gradient of the permanently anoxic Cariaco Basin. Spanning 3 years, we examined more than 100 samples from depths between 100 and 1300m. A consistent average of 10% of all microbes were associated with small aggregates (<2.0µm) or organic particles. However, certain biogeochemically relevant processes mediated by microbes (sulfate reduction, sulfur oxidation, denitrification, anammox) had depth-dependent aggregate associations. While certain targeted processes were most common in the upper part of the anoxic portion of the water column, they also occurred in oxic and hypoxic layers. Anaerobic processes that were observed in oxic environments were preferentially associated with aggregates. Thin layers of intruding oxic water into anoxic water also led to the preferential association of these processes with aggregates. RT-qPCR revealed that genes for these anaerobic processes were actively transcribed within the particulate size fraction in both oxic and hypoxic environments. These results widen the conceivable ecological niche of microbial anaerobic processes in the ocean, particularly those associated with nitrogen and sulfur cycling.

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

    NASA Astrophysics Data System (ADS)

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

    2001-09-01

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

  3. Disruption of redox homeostasis and carcinogen metabolizing enzymes changes by administration of vitamin E to rats.

    PubMed

    Vivarelli, Fabio; Canistro, Donatella; Franchi, Paola; Sapone, Andrea; Vornoli, Andrea; Della Croce, Clara; Longo, Vincenzo; Lucarini, Marco; Paolini, Moreno

    2016-01-15

    A large meta-analysis of randomized clinical trials has seriously questioned chemoprevention based on vitamins including vitamin E (VE), and an increased risk for cancer among long-term users was actually seen. However, the mechanism underlying these findings still remain unknown. To clarify the mechanism, in an in vivo model we studied the putative disruption of redox homeostasis and the perturbation of carcinogen metabolizing enzymes determined by VE. Male Sprague-Dawley rats were treated ip with either 100 or 200mg/kg b.w. daily for 7 or 14 consecutive days. Controls received vehicle only. Cytochrome P450 (CYP) content, CYP-reductase, CYP-linked monooxygenases, as well as phase-II and the antioxidant enzymes catalase and quinone reductase were investigated in both liver and kidney. Free radical species in tissue subcellular preparations were measured by electronic paramagnetic resonance (EPR) spectroscopy coupled to a radical probe technique. No substantial changes of hepatic xenobiotic metabolism enzymes were determined by VE. Conversely, a powerful booster effect of various renal phase-I carcinogen bioactivating enzymes at both dosages and observational times was recorded. While no relevant changes of post-oxidative phase-II reactions were found in the liver, a significant inactivating effect was caused by VE in renal tissues. Antioxidant enzymes were found mainly downregulated by the treatment. In the kidney, a marked free radical over-generation linked to CYP induction was observed. This study proved that VE acts as a co-carcinogen and pro-oxidant agent. Such epigenetic mechanisms may contribute to explain the harmful outcomes observed in humans. Copyright © 2015 Elsevier Inc. All rights reserved.

  4. 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.

  5. 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.

  6. Novelty detection under changing environmental conditions

    NASA Astrophysics Data System (ADS)

    Sohn, Hoon; Worden, Keith; Farrar, Charles R.

    2001-07-01

    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.

  7. 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.

  8. Microbial Preference for Soil Organic Carbon Changes Along Redox Gradients as a Function of the Energetic Cost of Respiration

    NASA Astrophysics Data System (ADS)

    Naughton, H.; Keiluweit, M.; Fendorf, S. E.; Farrant, D. N.

    2016-12-01

    within specific redox metabolic zones of soils and sediments to drive carbon utilization. An improved understanding on organic carbon utliization is critical to predict SOC dynamics under changing hydrology (e.g. saltwater intrusion, permafrost melting), temperature, and other factors impacting microbial respiration energetics.

  9. Redox changes in the brains of reproductive female rats during aging.

    PubMed

    Heemann, Fernanda Maciel; da Silva, Ana Carolina Almeida; Salomon, Tiago Boeira; Putti, Jordana Salete; Engers, Vanessa Krüger; Hackenhaar, Fernanda Schäfer; Benfato, Mara Silveira

    2017-01-01

    Reproduction is a critical and demanding phase of an animal's life. In mammals, females usually invest much more in parental care than males, and lactation is the most energetically demanding period of a female's life. Here, we tested whether oxidative stress is a consequence of reproduction in the brains of female Wistar rats. We evaluated the activities of glutathione peroxidase, glutathione S-transferase, and superoxide dismutase; H2O2 consumption; protein carbonylation; NO2 & NO3 levels; and total glutathione, as well as sex hormone levels in brain tissue of animals at 3, 6, 12, and 24months of age. Animals were grouped according to reproductive experience: breeders or non-breeders. Most of the studied parameters showed a difference between non-breeders and breeders at 12 and 24months. At 24months of age, breeders showed higher superoxide dismutase activity, H2O2 consumption, glutathione peroxidase activity, and carbonyl levels than non-breeders. In 12-month-old non-breeders, we observed a higher level of H2O2 consumption and higher superoxide dismutase and glutathione peroxidase activities than breeders. By evaluating the correlation network, we found that there were a larger number of influential nodes and positive links in breeder animals than in non-breeders, indicating a greater number of redox changes in breeder animals. Here, we also demonstrated that the aging process caused higher oxidative damage and higher antioxidant defenses in the brains of breeder female rats at 24months, suggesting that the reproduction process is costly, at least for the female brain. This study shows that there is a strong potential for a link between the cost of reproduction and oxidative stress.

  10. Anion dependent redox changes in iron bis-terdentate nitroxide {NNO} chelates.

    PubMed

    Gass, Ian A; Gartshore, Christopher J; Lupton, David W; Moubaraki, Boujemaa; Nafady, Ayman; Bond, Alan M; Boas, John F; Cashion, John D; Milsmann, Carsten; Wieghardt, Karl; Murray, Keith S

    2011-04-04

    The reaction of [Fe(II)(BF(4))(2)]·6H(2)O with the nitroxide radical, 4,4-dimethyl-2,2-di(2-pyridyl) oxazolidine-N-oxide (L(•)), produces the mononuclear transition metal complex [Fe(II)(L(•))(2)](BF(4))(2) (1) which has been investigated using temperature dependent susceptibility, Mössbauer spectroscopy, electrochemistry, density functional theory (DFT) calculations, and X-ray structure analysis. Single crystal X-ray diffraction analysis and Mössbauer measurements reveal an octahedral low spin Fe(2+) environment where the pyridyl donors from L(•) coordinate equatorially while the oxygen containing the radical from L(•) coordinates axially forming a linear O(•)··Fe(II)··O(•) arrangement. Magnetic susceptibility measurements show a strong radical-radical intramolecular antiferromagnetic interaction mediated by the diamagnetic Fe(2+) center. This is supported by DFT calculations which show a mutual spatial overlap of 0.24 and a spin density population analysis which highlights the antiparallel spin alignment between the two ligands. Similarly the monocationic complex [Fe(III)(L(-))(2)](BPh(4))·0.5H(2)O (2) has been fully characterized with Fe-ligand and N-O bond length changes in the X-ray structure analysis, magnetic measurements revealing a Curie-like S = 1/2 ground state, electron paramagnetic resonance (EPR) spectra, DFT calculations, and electrochemistry measurements all consistent with assignment of Fe in the (III) state and both ligands in the L(-) form. 2 is formed by a rare, reductively induced oxidation of the Fe center, and all physical data are self-consistent. The electrochemical studies were undertaken for both 1 and 2, thus allowing common Fe-ligand redox intermediates to be identified and the results interpreted in terms of square reaction schemes.

  11. 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.

  12. 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

  13. Changing living conditions, life style and health.

    PubMed

    Curtis, Tine; Kvernmo, Siv; Bjerregaard, Peter

    2005-12-01

    Human health is the result of the interaction of genetic, nutritional, socio-cultural, economic, physical infrastructure and ecosystem factors. All of the individual, social, cultural and socioeconomic factors are influenced by the environment they are embedded in and by changes in this environment. The aim of the paper is to illustrate the influence of environmental change on living conditions and life style and some of the mechanisms through which such changes affect physical and mental health. The interrelationship between environmental and societal change is illustrated by an example from a small community in Greenland, where changing environmental conditions have influenced fishing and employment opportunities to the extent that the size of the population has changed dramatically. The link between social change and health is shown with reference to studies on education, housing and occupation as well as life style changes. The paper further illustrates the relationship between the rapid socio-cultural and economic change and the health of the population. Psychosocial stress is reflected in problems such as alcohol abuse, violence and suicide, and these factors have been shown in studies on migration and transitions in health to be connected to changes in lifestyle and living conditions.

  14. Exploring correlation between redox potential and other edaphic factors in field and laboratory conditions in relation to methane efflux.

    PubMed

    Singh, S N

    2001-10-01

    Methane is primarily a biogenic gas, which is implicated in global warming. Although its production in the anoxic conditions is regulated by several edaphic factors, aquatic macrophytes also influence methane emission by providing aerenchyma to act as chimney for CH4 transport from the sediment to troposphere, by releasing root exudates to the sediment to serve as substrate for methanogenic bacteria and by transporting atmospheric O2 to rhizosphere, which stimulates CH4 consumption. Among the edaphic factors, redox potential (Eh) is the most important, which largely determines the action of methanogenic bacteria. Hence, a study was undertaken first to find out the correlation between CH4 emission and edaphic factors in the field conditions and then to understand the relationship between Eh and other edaphic factors. The field studies revealed that natural wetlands were the major source of CH4 emission, and the vegetation plays an important role in CH4 emission from the water bodies. However, it was very difficult to establish a strong relationship between the CH4 emission and the edaphic factors in the field conditions due to other limiting factors and their constant fluctuations. In this connection, the laboratory experiments exhibited that soil temperature, pH, moisture regime and incubation period were negatively correlated with Eh, which determines the initiation of methanogenic process. However, organic carbon and the water regime over the soil surface did not show any impact on Eh in this study.

  15. 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.

  16. The effects of the biogeochemical properties of clay minerals on the Pb sorption and desorption in various redox condition

    NASA Astrophysics Data System (ADS)

    Koo, T. H.; Kim, J. Y.; Kim, J. W.

    2016-12-01

    The fate and transportation of hazardous trace metal in soil environment can be controlled by various factors including temperature, geological location, properties of bed rock or sediment, human behavior, and biogeochemical reactions. The sorption and desorption process is one of the major process for control the transportation of trace metal in soil-water system. Nonetheless, few studies were focused on the biological controlling parameters, particularly redox reaction of structural metal of clay minerals. Thus, the objective of the present study is to investigate the correlation between the sorption and desorption reaction of Pb and biogeochemical properties of clay minerals. The effects of redox state of structural Fe and layer charge of the minerals on the migration/speciation of Pb at the various geochemical environment will be elucidated. The Fe-rich smectite, nontronite (NAu-1), and bulk soil samples which were collected from abandoned mine areas were reduced by microbial respiration by Shewanella Oneidensis MR-1 and/or Na-dithionite to various oxidation state of structural Fe. Then the Pb-stock solution made with common lead and nitric acid were spiked into the mineral/soil slurry with various Pb concentration to test the sorption and desorption reaction upto 7 days. The reaction was stopped at each time point by freezing the pellet and supernatant separately after centrifugation. Then the concentration and stable isotope ratio of Pb in the supernatant were measured using Inductively Coupled Plasma Mass Spectrometer (ICP-MS) and Multicollector (MC)-ICP-MS. The structural as well as chemical modification on nontronite and bulk soil sample were measured using x-ray diffraction (XRD), scanning electron microscopy (SEM) and wet chemistry analysis. The changes in Pb species in supernatant by sorption and desorption and its consequences on the clay structural/biogeochemical properties will be discussed.

  17. 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.

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

    USDA-ARS?s Scientific Manuscript database

    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...

  19. 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

  20. Reversible and contrasting changes of the cloud point temperature of pillar[5]arenes with one quinone unit and tri(ethylene oxide) chains induced by redox chemistry and host-guest complexation.

    PubMed

    Ogoshi, Tomoki; Akutsu, Tomohiro; Tamura, Yuko; Yamagishi, Tada-Aki

    2015-04-28

    A new water-soluble redox-active pillar[5]arene was synthesized by incorporation of one benzoquinone unit. The pillar[5]arene showed redox-responsive reversible lower critical solution temperature changes in aqueous solution.

  1. Thiol switches in redox regulation of chloroplasts: balancing redox state, metabolism and oxidative stress.

    PubMed

    Dietz, Karl-Josef; Hell, Rüdiger

    2015-05-01

    In photosynthesizing chloroplasts, rapidly changing energy input, intermediate generation of strong reductants as well as oxidants and multiple participating physicochemical processes and pathways, call for efficient regulation. Coupling redox information to protein function via thiol modifications offers a powerful mechanism to activate, down-regulate and coordinate interdependent processes. Efficient thiol switching of target proteins involves the thiol-disulfide redox regulatory network, which is highly elaborated in chloroplasts. This review addresses the features of this network. Its conditional function depends on specificity of reduction and oxidation reactions and pathways, thiol redox buffering, but also formation of heterogeneous milieus by microdomains, metabolite gradients and macromolecular assemblies. One major player is glutathione. Its synthesis and function is under feedback redox control. The number of thiol-controlled processes and involved thiol switched proteins is steadily increasing, e.g., in tetrapyrrole biosynthesis, plastid transcription and plastid translation. Thus chloroplasts utilize an intricate and versatile redox regulatory network for intraorganellar and retrograde communication.

  2. 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.

  3. Cylindrospermopsin degradation in sediments--the role of temperature, redox conditions, and dissolved organic carbon.

    PubMed

    Klitzke, Sondra; Fastner, Jutta

    2012-04-01

    One possible consequence of increasing water temperatures due to global warming in middle Europe is the proliferation of cylindrospermopsin-producing species from warmer regions. This may lead to more frequent and increased cylindrospermopsin (CYN) concentrations in surface waters. Hence, efficient elimination of CYN is important where contaminated surface waters are used as a resource for drinking water production via sediment passage. Sediments are often characterized by a lack of oxygen and low temperature (i.e. approx. 10 °C). The presence of dissolved organic carbon (DOC) is not only known to enhance but also to retard contaminant degradation by influencing the extent of lag phases. So far CYN degradation has only been investigated under oxic conditions and at room temperature. Therefore, the aim of our experiments was to understand CYN degradation, focusing on the effects of i) anoxic conditions, ii) low temperature (i.e. 10 °C) in comparison to room temperature (23±4 °C) and iii) DOC on lag phases. We used two natural sandy sediments (virgin and preconditioned) and surface water to conduct closed-loop column experiments. Anoxic conditions either inhibited CYN degradation completely or retarded CYN breakdown in comparison to oxic conditions (T(1/2) (oxic)=2.4 days, T(1/2) (anoxic)=23.6 days). A decrease in temperature from 20 °C to 10 °C slowed down degradation rates by a factor of 10. The presence of DOC shortened lag phases in virgin sediments at room temperature but induced a lag phase in preconditioned sediments at 10 °C, indicating potential substrate competition. These results show that information on physico-chemical conditions in sediments is crucial to assess the risk of CYN breakthrough. Copyright © 2011 Elsevier Ltd. All rights reserved.

  4. Differential neurogenic effects of casein-derived opioid peptides on neuronal stem cells: implications for redox-based epigenetic changes.

    PubMed

    Trivedi, Malav; Zhang, Yiting; Lopez-Toledano, Miguel; Clarke, Andrew; Deth, Richard

    2016-11-01

    Food-derived peptides, such as β-casomorphin BCM7, have potential to cross the gastrointestinal tract and blood-brain barrier and are associated with neurological disorders and neurodevelopmental disorders. We previously established a novel mechanism through which BCM7 affects the antioxidant levels in neuronal cells leading to inflammatory consequences. In the current study, we elucidated the effects of casein-derived peptides on neuronal development by using the neurogenesis of neural stem cells (NSCs) as an experimental model. First, the transient changes in intracellular thiol metabolites during NSC differentiation (neurogenesis) were investigated. Next, the neurogenic effects of food-derived opioid peptides were measured, along with changes in intracellular thiol metabolites, redox status and global DNA methylation levels. We observed that the neurogenesis of NSCs was promoted by human BCM7 to a greater extent, followed by A2-derived BCM9 in contrast to bovine BCM7, which induced increased astrocyte formation. The effect was most apparent when human BCM7 was administered for 1day starting on 3days postplating, consistent with immunocytochemistry. Furthermore, neurogenic changes regulated by bovine BCM7 and morphine were associated with an increase in the glutathione/glutathione disulfide ratio and a decrease in the S-adenosylmethionine/S-adenosylhomocysteine ratio, indicative of changes in the redox and the methylation states. Finally, bovine BCM7 and morphine decreased DNA methylation in differentiating NSCs. In conclusion, these results suggest that food-derived opioid peptides and morphine regulated neurogenesis and differentiation of NSCs through changes in the redox state and epigenetic regulation.

  5. 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.

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

    PubMed

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

    2017-06-20

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

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

    NASA Astrophysics Data System (ADS)

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

    2017-02-01

    The Late Ordovician stratigraphic record integrates glacio-eustatic processes, water-column redox conditions and carbon cycle dynamics. This complex stratigraphic record, however, is dominated by deposits from epeiric seas that are susceptible to local physical and chemical processes decoupled from the open ocean. This study contributes a unique deep water basinal perspective to the Late Ordovician (Hirnantian) glacial record and the perturbations in seawater chemistry that may have contributed to the Hirnantian mass extinction event. We analyze recently drilled cores and outcrop samples from the upper Vinini Formation in central Nevada and report combined trace- and major element geochemistry, Fe speciation (FePy /FeHR and FeHR /FeT), and stable isotope chemostratigraphy (δ13COrg and δ34SPy). Measurements of paired samples from outcrop and core reveal that reactive Fe is preserved mainly as pyrite in core samples, while outcrop samples have been significantly altered as pyrite has been oxidized and remobilized by modern weathering processes. Fe speciation in the more pristine core samples indicates persistent deep water anoxia, at least locally through the Late Ordovician, in contrast to the prevailing interpretation of increased Hirnantian water column oxygenation in shallower environments. Deep water redox conditions were likely decoupled from shallower environments by a basinal shift in organic matter export driven by decreasing rates of organic matter degradation and decreasing shelf areas. The variable magnitude in the record of the Hirnantian carbon isotope excursion may be explained by this increased storage of isotopically light carbon in the deep ocean which, in combination with increased glacio-eustatic restriction, would strengthen lateral- and vertical gradients in seawater chemistry. We adopt multivariate statistical methods to deconstruct the spatial and temporal re-organization of seawater chemistry during the Hirnantian glaciation and attempt to

  8. 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.

  9. Sugar beet factory lime affects the mobilization of Cd, Co, Cr, Cu, Mo, Ni, Pb, and Zn under dynamic redox conditions in a contaminated floodplain soil.

    PubMed

    Shaheen, Sabry M; Rinklebe, Jörg

    2017-01-15

    The impact of sugar beet factory lime (SBFL) on the release dynamics and mobilization of toxic metals (TMs) under dynamic redox conditions in floodplain soils has not been studied up to date. Therefore, the aim of this study was to verify the scientific hypothesis that SBFL is able to immobilize Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, and Zn under different redox potentials (EH) in a contaminated floodplain soil. For this purpose, the non-treated contaminated soil (CS) and the same soil treated with SBFL (CS+SBFL) were flooded in the laboratory using a highly sophisticated automated biogeochemical microcosm apparatus. The experiment was conducted stepwise from reducing (-13 mV) to oxidizing (+519 mV) soil conditions. Soil pH decreased under oxic conditions in CS (from 6.9 to 4.0) and in CS+SBFL (from 7.5 to 4.4). The mobilization of Cu, Cr, Pb, and Fe were lower in CS+SBFL than in CS under both reducing/neutral and oxic/acidic conditions. Those results demonstrate that SBFL is able to decrease concentrations of these elements under a wide range of redox and pH conditions. The mobilization of Cd, Co, Mn, Mo, Ni, and Zn were higher in CS+SBFL than in CS under reducing/neutral conditions; however, these concentrations showed an opposite behavior under oxic/acidic conditions and were lower in CS+SBFL than in CS. We conclude that SBFL immobilized Cu, Cr, Pb, and Fe under dynamic redox conditions and immobilized Cd, Co, Mn, Mo, Ni, and Zn under oxic acidic conditions; however, the latter elements were mobilized under reducing neutral conditions in the studied soil. Therefore, the addition of SBFL to acid floodplain soils contaminated with TMs might be an important alternative for ameliorating these soils with view to a sustainable management of these soils.

  10. 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.

  11. 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; Kobayashi, Naohiro; Tate, Shin-ichi

    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.

  12. 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.

  13. Biofilm-induced bioclogging produces sharp interfaces in hyporheic flow, redox conditions, and microbial community structure

    NASA Astrophysics Data System (ADS)

    Caruso, Alice; Boano, Fulvio; Ridolfi, Luca; Chopp, David L.; Packman, Aaron

    2017-05-01

    Riverbed sediments host important biogeochemical processes that play a key role in nutrient dynamics. Sedimentary nutrient transformations are mediated by bacteria in the form of attached biofilms. The influence of microbial metabolic activity on the hydrochemical conditions within the hyporheic zone is poorly understood. We present a hydrobiogeochemical model to assess how the growth of heterotrophic and autotrophic biomass affects the transport and transformation of dissolved nitrogen compounds in bed form-induced hyporheic zones. Coupling between hyporheic exchange, nitrogen metabolism, and biomass growth leads to an equilibrium between permeability reduction and microbial metabolism that yields shallow hyporheic flows in a region with low permeability and high rates of microbial metabolism near the stream-sediment interface. The results show that the bioclogging caused by microbial growth can constrain rates and patterns of hyporheic fluxes and microbial transformation rate in many streams.

  14. The redox environment triggers conformational changes and aggregation of hIAPP in Type II Diabetes

    PubMed Central

    Rodriguez Camargo, Diana C.; Tripsianes, Konstantinos; Buday, Katalin; Franko, Andras; Göbl, Christoph; Hartlmüller, Christoph; Sarkar, Riddhiman; Aichler, Michaela; Mettenleiter, Gabriele; Schulz, Michael; Böddrich, Annett; Erck, Christian; Martens, Henrik; Walch, Axel Karl; Madl, Tobias; Wanker, Erich E.; Conrad, Marcus; de Angelis, Martin Hrabě; Reif, Bernd

    2017-01-01

    Type II diabetes (T2D) is characterized by diminished insulin production and resistance of cells to insulin. Among others, endoplasmic reticulum (ER) stress is a principal factor contributing to T2D and induces a shift towards a more reducing cellular environment. At the same time, peripheral insulin resistance triggers the over-production of regulatory hormones such as insulin and human islet amyloid polypeptide (hIAPP). We show that the differential aggregation of reduced and oxidized hIAPP assists to maintain the redox equilibrium by restoring redox equivalents. Aggregation thus induces redox balancing which can assist initially to counteract ER stress. Failure of the protein degradation machinery might finally result in β-cell disruption and cell death. We further present a structural characterization of hIAPP in solution, demonstrating that the N-terminus of the oxidized peptide has a high propensity to form an α-helical structure which is lacking in the reduced state of hIAPP. In healthy cells, this residual structure prevents the conversion into amyloidogenic aggregates. PMID:28287098

  15. One electron changes everything: a multispecies copper redox shuttle for dye-sensitized solar cells.

    SciTech Connect

    Hoffeditz, William L.; Katz, Michael J.; Deria, Pravas; Cutsail, George E.; Pellin, Michael J.; Farha, Omar K.; Hupp, Joseph T.

    2016-02-25

    Dye-sensitized solar cells (DSCs) are an established alternative photovoltaic technology that offers numerous potential advantages in solar energy applications. However, this technology has been limited by the availability of molecular redox couples that are both noncorrosive/nontoxic and do not diminish the performance of the device. In an effort to overcome these shortcomings, a copper-containing redox shuttle derived from 1,8-bis(2'-pyridyl)-3,6-dithiaoctane (PDTO) ligand and the common DSC additive 4-tert-butylpyridine (TBP) was investigated. Electrochemical measurements, single-crystal X-ray diffraction, and absorption and electron paramagnetic resonance spectroscopies reveal that, upon removal of one metal-centered electron, PDTO-enshrouded copper ions completely shed the tetradentate PDTO ligand and replace it with four or more TBP ligands. Thus, the Cu(I) and Cu(II) forms of the electron shuttle have completely different coordination spheres and are characterized by widely differing Cu(II/I) formal potentials and reactivities for forward versus reverse electron transfer. Notably, the coordination-sphere replacement process is fully reversed upon converting Cu(II) back to Cu(I). In cells featuring an adsorbed organic dye and a nano- and mesoparticulate, TiO2-based, photoelectrode, the dual species redox shuttle system engenders performance superior to that obtained with shuttles based on the (II/I) forms of either of the coordination complexes in isolation.

  16. 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

  17. 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…

  18. 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...

  19. 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...

  20. 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…

  1. Stable Chromium Isotopes as tracer of changes in weathering processes and redox state of the ocean during Neoproterozoic glaciation

    NASA Astrophysics Data System (ADS)

    Dossing, L. N.; Gaucher, C.; Boggiani, P. C.; Frei, R.

    2010-12-01

    The chemistry of surface environments on Earth has essentially evolved from early anoxic conditions to a present day oxic state. How in detail this transition occurred is still a matter of debate but the last 200 million years (My) of the Neoproterozoic Era [(1000 to 542 million years ago (Ma)] show an emerging picture of large scale fluctuations in the redox state of the oceans [1-2]. The reasons for these fluctuations are to be sought in Earth’s atmospheric oxygenation which led to the rapid radiation of oxygen-utilizing macroscopic metazoans, but details regarding the nature of these fluctuations remain unclear. The Late Neoproterozoic is known for a number of widespread glaciations causing the return of ferruginous oceans which were absent for more than a billion years of Earth history. This study elaborates on the idea that Chromium (Cr) stable isotopes in Fe-rich chemical sediments deposited during glacial events are suitable for tracing oxygenation of surface environments through Earth's history [3]. The focus of this study is to apply the Cr isotope system to one of the Marinoan (650-630 Ma) glacio-marine sequences (Jacadigo Group, Brazil) in order to get a detailed spatial and relative temporal resolution of changes in weathering processes and redox states of the respective ocean basin during the depositional period of the sediments. The Jacadigo Group is a glacio-marine succession which is composed of the Urucum Fm. (sandstones) at the base, the Santa Cruz Fm. (BIFs) and the Puga Fm. (Fe-rich glacial diamictites) at the top. Cr stable isotope measurements on various BIF horizons of the Santa Cruz Fm. yielded positive δ53/52Cr values range from +0.4 to+ 0.9‰, while the overlying Fe-rich glaciogenic diamictites of the Puga Fm. show δ53/52Cr values range from to +0.1 to+ 0.4‰. These positively fractionated values correspond to positive δ53/52Cr values measured in other Late Neoproterozoic BIFs and speak for the occurrence of potential oxygenation

  2. The redox switch/redox coupling hypothesis.

    PubMed

    Cerdán, Sebastián; Rodrigues, Tiago B; Sierra, Alejandra; Benito, Marina; Fonseca, Luis L; Fonseca, Carla P; García-Martín, María L

    2006-01-01

    We provide an integrative interpretation of neuroglial metabolic coupling including the presence of subcellular compartmentation of pyruvate and monocarboxylate recycling through the plasma membrane of both neurons and glial cells. The subcellular compartmentation of pyruvate allows neurons and astrocytes to select between glucose and lactate as alternative substrates, depending on their relative extracellular concentration and the operation of a redox switch. This mechanism is based on the inhibition of glycolysis at the level of glyceraldehyde 3-phosphate dehydrogenase by NAD(+) limitation, under sufficiently reduced cytosolic NAD(+)/NADH redox conditions. Lactate and pyruvate recycling through the plasma membrane allows the return to the extracellular medium of cytosolic monocarboxylates enabling their transcellular, reversible, exchange between neurons and astrocytes. Together, intracellular pyruvate compartmentation and monocarboxylate recycling result in an effective transcellular coupling between the cytosolic NAD(+)/NADH redox states of both neurons and glial cells. Following glutamatergic neurotransmission, increased glutamate uptake by the astrocytes is proposed to augment glycolysis and tricarboxylic acid cycle activity, balancing to a reduced cytosolic NAD(+)/NADH in the glia. Reducing equivalents are transferred then to the neuron resulting in a reduced neuronal NAD(+)/NADH redox state. This may eventually switch off neuronal glycolysis, favoring the oxidation of extracellular lactate in the lactate dehydrogenase (LDH) equilibrium and in the neuronal tricarboxylic acid cycles. Finally, pyruvate derived from neuronal lactate oxidation, may return to the extracellular space and to the astrocyte, restoring the basal redox state and beginning a new loop of the lactate/pyruvate transcellular coupling cycle. Transcellular redox coupling operates through the plasma membrane transporters of monocarboxylates, similarly to the intracellular redox shuttles

  3. Controls on the redox potential of rainwater.

    PubMed

    Willey, Joan D; Mullaugh, Katherine M; Kieber, Robert J; Avery, G Brooks; Mead, Ralph N

    2012-12-18

    Hydrogen peroxide acting as a reductant affects the redox potential of rainwater collected at the Bermuda Atlantic Time Series Station, the South Island of New Zealand, the contiguous USA, and the primary study site in Wilmington, NC. Analytical measurements of both halves of redox couples for dissolved iron, mercury, and the nitrate-nitrite-ammonium system can predict the rainwater redox potential measured directly by a platinum electrode. Measurements of these redox couples along with the pH in rain yields pe⁻ between 8 and 11; the half reaction for hydrogen peroxide acting as a reductant using typical rainwater conditions of 15 μM H₂O₂ at pH 4.7 gives pe⁻ = 9.12, where pe⁻ = negative log of the activity of hydrated electrons. Of the six rainwater redox systems investigated, only manganese speciation appeared to be controlled by molecular oxygen (pe⁻ = 15.90). Copper redox speciation was consistent with superoxide acting as a reductant (pe⁻ = 2.7). The concentration of H₂O₂ in precipitation has more than doubled over the preceding decade due to a decrease in SO₂ emissions, which suggests the redox chemistry of rainwater is dynamic and changing, potentially altering the speciation of many organic compounds and trace metals in atmospheric waters.

  4. 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

  5. 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.

  6. 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

  7. Conditioned reinforcement value and resistance to change.

    PubMed

    Shahan, Timothy A; Podlesnik, Christopher A

    2008-05-01

    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.

  8. 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

  9. 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

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

    DOE PAGES

    Winkel, Matthias; Salman-Carvalho, Verena; Woyke, Tanja; ...

    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. Improvement of the Redox Balance Increases l-Valine Production by Corynebacterium glutamicum under Oxygen Deprivation Conditions

    PubMed Central

    Hasegawa, Satoshi; Uematsu, Kimio; Natsuma, Yumi; Suda, Masako; Hiraga, Kazumi; Jojima, Toru; Inui, Masayuki

    2012-01-01

    Production of l-valine under oxygen deprivation conditions by Corynebacterium glutamicum lacking the lactate dehydrogenase gene ldhA and overexpressing the l-valine biosynthesis genes ilvBNCDE was repressed. This was attributed to imbalanced cofactor production and consumption in the overall l-valine synthesis pathway: two moles of NADH was generated and two moles of NADPH was consumed per mole of l-valine produced from one mole of glucose. In order to solve this cofactor imbalance, the coenzyme requirement for l-valine synthesis was converted from NADPH to NADH via modification of acetohydroxy acid isomeroreductase encoded by ilvC and introduction of Lysinibacillus sphaericus leucine dehydrogenase in place of endogenous transaminase B, encoded by ilvE. The intracellular NADH/NAD+ ratio significantly decreased, and glucose consumption and l-valine production drastically improved. Moreover, l-valine yield increased and succinate formation decreased concomitantly with the decreased intracellular redox state. These observations suggest that the intracellular NADH/NAD+ ratio, i.e., reoxidation of NADH, is the primary rate-limiting factor for l-valine production under oxygen deprivation conditions. The l-valine productivity and yield were even better and by-products derived from pyruvate further decreased as a result of a feedback resistance-inducing mutation in the acetohydroxy acid synthase encoded by ilvBN. The resultant strain produced 1,470 mM l-valine after 24 h with a yield of 0.63 mol mol of glucose−1, and the l-valine productivity reached 1,940 mM after 48 h. PMID:22138982

  12. 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

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

    PubMed

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

    2015-12-15

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

  14. 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

  15. 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

  16. Assessment of MTBE biodegradation pathways by two-dimensional isotope analysis in mixed bacterial consortia under different redox conditions.

    PubMed

    Youngster, Laura K G; Rosell, Mònica; Richnow, Hans H; Häggblom, Max M

    2010-09-01

    The fuel oxygenate, methyl tert-butyl ether (MTBE), although now widely banned or substituted, remains a persistent groundwater contaminant. Multidimensional compound-specific isotope analysis (CSIA) of carbon and hydrogen is being developed for determining the extent of MTBE loss due to biodegradation and can also potentially distinguish between different biodegradation pathways. Carbon and hydrogen isotopic fractionation factors were determined for MTBE degradation in aerobic and anaerobic laboratory cultures. The carbon isotopic enrichment factor (epsilonC) for aerobic MTBE degradation by a bacterial consortium containing the aerobic MTBE-degrading bacterium, Variovorax paradoxus, was -1.1 +/- 0.2 per thousand and the hydrogen isotope enrichment factor (epsilonH) was -15 +/- 2 per thousand. This corresponds to an approximated lambda value (Lambda = epsilonH/epsilonC) of 14. Carbon isotope enrichment factors for anaerobic MTBE-degrading enrichment cultures were -7.0 +/- 0.2 per thousand and did not vary based on the original inoculum source, redox condition of the enrichment, or supplementation with syringic acid as a co-substrate. The hydrogen enrichment factors of cultures without syringic acid were insignificant, however a strong hydrogen enrichment factor of -41 +/- 3 per thousand was observed for cultures which were fed syringic acid during MTBE degradation. The Lambda = 6 obtained for NYsyr cultures might be diagnostic for the stimulation of anaerobic MTBE degradation by methoxylated compounds by an as yet unknown pathway and mechanism. The stable-isotope enrichment factors determined in this study will enhance the use of CSIA for monitoring anaerobic and aerobic MTBE biodegradation in situ.

  17. Optimisation of the operational conditions of trichloroethylene degradation using Trametes versicolor under quinone redox cycling conditions using central composite design methodology.

    PubMed

    Vilaplana, Marcel; García, Ana Belén; Caminal, Gloria; Guillén, Francisco; Sarrà, Montserrat

    2012-04-01

    Extracellular radicals produced by Trametes versicolor under quinone redox cycling conditions can degrade a large variety of pollutant compounds, including trichloroethylene (TCE). This study investigated the effect of the agitation speed and the gas-liquid phase volume ratio on TCE degradation using central composite design (CCD) methodology for a future scale-up to a reactor system. The agitation speed ranged from 90 to 200 rpm, and the volume ratio ranged from 0.5 to 4.4. The results demonstrated the important and positive effect of the agitation speed and an interaction between the two factors on TCE degradation. Although the volume ratio did not have a significant effect if the agitation speed value was between 160 and 200 rpm, at lower speed values, the specific pollutant degradation was clearly more extensive at low volume ratios than at high volume ratios. The fitted response surface was validated by performing an experiment using the parameter combination in the model that maximised TCE degradation. The results of the experiments carried out using different biomass concentrations demonstrated that the biomass concentration had a positive effect on pollutant degradation if the amount of biomass present was lower than 1.6 g dry weight l(-1). The results show that the maximum TCE degradation was obtained at the highest speed (200 rpm), gas-liquid phase volume ratio (4.4), and a biomass concentration of 1.6 g dry weight l(-1).

  18. 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

  19. 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

  20. Inorganic nanoparticles kill Toxoplasma gondii via changes in redox status and mitochondrial membrane potential

    PubMed Central

    Adeyemi, Oluyomi Stephen; Murata, Yuho; Sugi, Tatsuki; Kato, Kentaro

    2017-01-01

    This study evaluated the anti-Toxoplasma gondii potential of gold, silver, and platinum nanoparticles (NPs). Inorganic NPs (0.01–1,000 µg/mL) were screened for antiparasitic activity. The NPs caused >90% inhibition of T. gondii growth with EC50 values of ≤7, ≤1, and ≤100 µg/mL for gold, silver, and platinum NPs, respectively. The NPs showed no host cell cytotoxicity at the effective anti-T. gondii concentrations; the estimated selectivity index revealed a ≥20-fold activity toward the parasite versus the host cell. The anti-T. gondii activity of the NPs, which may be linked to redox signaling, affected the parasite mitochondrial membrane potential and parasite invasion, replication, recovery, and infectivity potential. Our results demonstrated the antiparasitic potential of NPs. The findings support the further exploration of NPs as a possible source of alternative and effective anti-T. gondii agents. PMID:28280332

  1. Inorganic nanoparticles kill Toxoplasma gondii via changes in redox status and mitochondrial membrane potential.

    PubMed

    Adeyemi, Oluyomi Stephen; Murata, Yuho; Sugi, Tatsuki; Kato, Kentaro

    2017-01-01

    This study evaluated the anti-Toxoplasma gondii potential of gold, silver, and platinum nanoparticles (NPs). Inorganic NPs (0.01-1,000 µg/mL) were screened for antiparasitic activity. The NPs caused >90% inhibition of T. gondii growth with EC50 values of ≤7, ≤1, and ≤100 µg/mL for gold, silver, and platinum NPs, respectively. The NPs showed no host cell cytotoxicity at the effective anti-T. gondii concentrations; the estimated selectivity index revealed a ≥20-fold activity toward the parasite versus the host cell. The anti-T. gondii activity of the NPs, which may be linked to redox signaling, affected the parasite mitochondrial membrane potential and parasite invasion, replication, recovery, and infectivity potential. Our results demonstrated the antiparasitic potential of NPs. The findings support the further exploration of NPs as a possible source of alternative and effective anti-T. gondii agents.

  2. Clostridium thermocellum DSM 1313 transcriptional responses to redox perturbation

    DOE PAGES

    Sander, Kyle B.; Wilson, Charlotte M.; M. Rodriquez, Jr.; ...

    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.

  3. 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.

  4. Rare Earth Elements of Methane-Derived Authigenic Carbonates and Its Constraints on Redox Condition in the Gulf of Cadiz

    NASA Astrophysics Data System (ADS)

    Wang, S.; Magalhaes, V. H.; Fuentefria De Menezes Pinheiro, L. F.; Yan, W.

    2014-12-01

    The mineral composition, stable carbon and oxygen isotopes, and the rare earth elements (REE) concentrations in methane-derived authigenic carbonates collected from the Gulf of Cadiz were used to trace fluid sources and provide information on the associated biogeochemical processes during their formation. These samples are composed by a detrital fraction (mainly composed by quartz and clays) cemented by authigenic carbonates: aragonite and Mg-calcite, pure Mg-calcite, or dolomite and Mg-calcite. The δ13C values of the samples vary between -45.78‰ and -9.72‰ VPDB and δ18O values range from 3.67‰ to 6.92‰ VPDB. The δ13C composition is indicative of the methane-derived (probably from thermogenic gas or a mixed of thermogenic and biogenic gas) source of these carbonates. The total REE content (ΣREE) of these seep carbonates range from 13 to 31 ppm and average ΣREE values of 21 ppm, with most of samples lower than the typical marine carbonate value of ~28 ppm. This result suggests that the REE composition of the methane-derived authigenic carbonates is controlled primarily by the migrated methane-rich fluids from which they have precipitated. The results that the REE enrichment of the samples containing dolomite and Mg-calcite minerals is higher than samples with aragonite also suggest that the authigenic mineral composition and the formation setting are important factors on the REE concentration. The shale-normalized REE patterns of the seep carbonates show no abnormality or slight positive Ce anomalies, suggesting that the formation of these seep carbonates occurs in anoxic condition. The correlation results of Ce/Ce* and LaN/SmN, Ce/Ce* and DyN/SmN, Ce/Ce* and ΣREE have also suggested that the REE characteristics of most seep carbonate samples preserve the original redox conditions of their formation and that late diagenesis has little effect on the REE. Therefore, it is feasible to assume that these methane-derived authigenic carbonates represent

  5. Fifty hertz extremely low-frequency electromagnetic field causes changes in redox and differentiative status in neuroblastoma cells.

    PubMed

    Falone, Stefano; Grossi, Maria R; Cinque, Benedetta; D'Angelo, Barbara; Tettamanti, Enzo; Cimini, Annamaria; Di Ilio, Carmine; Amicarelli, Fernanda

    2007-01-01

    The current study was designed to establish whether extremely low-frequency electromagnetic fields might affect neuronal homeostasis through redox-sensitive mechanisms. To this end, intracellular reactive oxygen species production, antioxidant and glutathione-based detoxifying capability and genomic integrity after extremely low-frequency electromagnetic fields exposure were investigated. Moreover, we also studied potential extremely low-frequency electromagnetic fields-dependent changes in the proliferative and differentiative cellular status. Results seem to support redox-mediated extremely low-frequency electromagnetic fields effects on biological models as, although no major oxidative damage was detected, after exposure we observed a positive modulation of antioxidant enzymatic expression, as well as a significant increase in reduced glutathione level, indicating a shift of cellular environment towards a more reduced state. In addition, extremely low-frequency electromagnetic fields treatment induced a more differentiated phenotype as well as an increased expression in peroxisome proliferators-activated receptor isotype beta, a class of transcription factors related to neuronal differentiation and cellular stress response. As second point, to deepen how extremely low-frequency electromagnetic fields treatment could affect neuroblastoma cell antioxidant capacity, we examined the extremely low-frequency electromagnetic fields-dependent modifications of cell susceptibility to pro-oxidants. Results clearly showed that 50 Hz extremely low-frequency electromagnetic fields exposure reduces cell tolerance towards oxidative attacks.

  6. 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.

  7. The positive synergism of CPT and MK-801 in behavioral tests and in reduction of environmental stress and redox signaling changes in mice cerebral cortex.

    PubMed

    Herbet, Mariola; Szopa, Aleksandra; Wośko, Sylwia; Serefko, Anna; Izdebska, Magdalena; Gawrońska-Grzywacz, Monika; Piątkowska-Chmiel, Iwona; Janas, Martyna; Gieroba, Renata; Korga, Agnieszka; Poleszak, Ewa; Dudka, Jarosław

    2016-10-10

    Depressive disorders are associated with oxidative stress. Therefore, it is interesting if antidepressants can affect redox equilibrium and signaling. The first step of our study was to determine the influence of the adenosine system on the antidepressant-like activity of non-competitive antagonist of the NMDA receptor complex - dizocilpine (MK-801). To this aim, two behavioral tests commonly used to assess the antidepressant capability of drugs - the forced swim test (FST) and tail suspension test (TST), were performed. Locomotor activity was estimated to verify and exclude false positive/negative results in the FST and TST. To examine whether antidepressants affect redox equilibrium, we have investigated lipid peroxidation products, GSH, GSSG, NADPH and NADP+ in the cerebral cortex of mice following administration of CPT and MK-801 under environmental stress conditions. The experiments were carried out using male Albino Swiss mice (25-30 g). The drugs were administered ip., alone and simultaneously, 60 min before tests. The behavioural tests results showed that CPT (3 mg/kg) potentiated the antidepressant-like activity of MK-801 (0.05 mg/kg) and the observed effects were not due to the increase in mice locomotor activity. Positive synergism of CPT and MK-801 in reduction of environmental stress conditions was revealed. In this group an increase in GSH and GSSG without changes in GSH/GSSG ratio and reduction of LPO was found. The level of lipid peroxidation products was also decreased in group receiving CPT and MK-801 separately. Examined antidepressant agents may increase antioxidant defences however further studies are needed with different range of time.

  8. 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).

  9. Post-irradiation hypoxic incubation of X-irradiated MOLT-4 cells reduces apoptotic cell death by changing the intracellular redox state and modulating SAPK/JNK pathways.

    PubMed

    Hamasu, T; Inanami, O; Tsujitani, M; Yokoyama, K; Takahashi, E; Kashiwakura, I; Kuwabara, M

    2005-05-01

    To elucidate radiobiological effects of hypoxia on X-ray-induced apoptosis, MOLT-4 cells were treated under four set of conditions: (1) both X irradiation and incubation under normoxia, (2) X irradiation under hypoxia and subsequent incubation under normoxia, (3) X irradiation under normoxia and subsequent incubation under hypoxia, and (4) both X irradiation and incubation under hypoxia, and the induction of apoptosis was examined by fluorescence microscopy. About 28-33% apoptosis was observed in cells treated under conditions 1 and 2, but this value was significantly reduced to around 18-20% in cells treated under conditions 3 and 4, suggesting that post-irradiation hypoxic incubation rather than hypoxic irradiation mainly caused the reduction of apoptosis. The activation and expression of apoptosis signal-related molecules SAPK/JNK, Fas and caspase-3 were also suppressed by hypoxic incubation. Effects of hypoxic incubation were canceled when cells were treated under conditions 3 and 4 with an oxygen-mimicking hypoxic cell radiosensitizer, whereas the addition of N-acetyl-L-cysteine again reduced the induction of apoptosis. From these results it was concluded that hypoxia reduced the induction of apoptosis by changing the intracellular redox state, followed by the regulation of apoptotic signals in X-irradiated MOLT-4 cells.

  10. Role of redox metabolism for adaptation of aquatic animals to drastic changes in oxygen availability.

    PubMed

    Welker, Alexis F; Moreira, Daniel C; Campos, Élida G; Hermes-Lima, Marcelo

    2013-08-01

    Large changes in oxygen availability in aquatic environments, ranging from anoxia through to hyperoxia, can lead to corresponding wide variation in the production of reactive oxygen species (ROS) by animals with aquatic respiration. Therefore, animals living in marine, estuarine and freshwater environments have developed efficient antioxidant defenses to minimize oxidative stress and to regulate the cellular actions of ROS. Changes in oxygen levels may lead to bursts of ROS generation that can be particularly harmful. This situation is commonly experienced by aquatic animals during abrupt transitions from periods of hypoxia/anoxia back to oxygenated conditions (e.g. intertidal cycles). The strategies developed differ significantly among aquatic species and are (i) improvement of their endogenous antioxidant system under hyperoxia (that leads to increased ROS formation) or other similar ROS-related stresses, (ii) increase in antioxidant levels when displaying higher metabolic rates, (iii) presence of constitutively high levels of antioxidants, that attenuates oxidative stress derived from fluctuations in oxygen availability, or (iv) increase in the activity of antioxidant enzymes (and/or the levels of their mRNAs) during hypometabolic states associated with anoxia/hypoxia. This enhancement of the antioxidant system - coined over a decade ago as "preparation for oxidative stress" - controls the possible harmful effects of increased ROS formation during hypoxia/reoxygenation. The present article proposes a novel explanation for the biochemical and molecular mechanisms involved in this phenomenon that could be triggered by hypoxia-induced ROS formation. We also discuss the connections among oxygen sensing, oxidative damage and regulation of the endogenous antioxidant defense apparatus in animals adapted to many natural or man-made challenges of the aquatic environment. Copyright © 2013 Elsevier Inc. All rights reserved.

  11. 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

  12. In Vivo Imaging of Tumor Physiological, Metabolic, and Redox Changes in Response to the Anti-Angiogenic Agent Sunitinib: Longitudinal Assessment to Identify Transient Vascular Renormalization

    PubMed Central

    Matsumoto, Shingo; Saito, Keita; Takakusagi, Yoichi; Matsuo, Masayuki; Munasinghe, Jeeva P.; Morris, Herman D.; Lizak, Martin J.; Merkle, Hellmut; Yasukawa, Keiji; Devasahayam, Nallathamby; Suburamanian, Sankaran; Mitchell, James B.

    2014-01-01

    Abstract Aims: The tumor microenvironment is characterized by a highly reducing redox status, a low pH, and hypoxia. Anti-angiogenic therapies for solid tumors frequently function in two steps: the transient normalization of structurally and functionally aberrant tumor blood vessels with increased blood perfusion, followed by the pruning of tumor blood vessels and the resultant cessation of nutrients and oxygen delivery required for tumor growth. Conventional anatomic or vascular imaging is impractical or insufficient to distinguish between the two steps of tumor response to anti-angiogenic therapies. Here, we investigated whether the noninvasive imaging of the tumor redox state and energy metabolism could be used to characterize anti-angiogenic drug-induced transient vascular normalization. Results: Daily treatment of squamous cell carcinoma (SCCVII) tumor-bearing mice with the multi-tyrosine kinase inhibitor sunitinib resulted in a rapid decrease in tumor microvessel density and the suppression of tumor growth. Tumor pO2 imaging by electron paramagnetic resonance imaging showed a transient increase in tumor oxygenation after 2–4 days of sunitinib treatment, implying improved tumor perfusion. During this window of vascular normalization, magnetic resonance imaging of the redox status using an exogenously administered nitroxide probe and hyperpolarized 13C MRI of the metabolic flux of pyruvate/lactate couple revealed an oxidative shift in tumor redox status. Innovation: Redox-sensitive metabolic couples can serve as noninvasive surrogate markers to identify the vascular normalization window in tumors with imaging techniques. Conclusion: A multimodal imaging approach to characterize physiological, metabolic, and redox changes in tumors is useful to distinguish between the different stages of anti-angiogenic treatment. Antioxid. Redox Signal. 21, 1145–1155. PMID:24597714

  13. Redox changes across the Triassic-Jurassic boundary: From anoxic to euxinic black shale deposition

    NASA Astrophysics Data System (ADS)

    Richoz, Sylvain; van de Schootbrugge, Bas; Püttmann, Wilhelm; Heunisch, Carmen; Quan, Tracy M.; Lindström, Sofie; Fiebig, Jens; Pross, Joerg

    2010-05-01

    The Triassic-Jurassic boundary (T-J; 201.6 Ma) marks one of the so called Big Five mass-extinction events that may have led to the extinction of more than 80% of all marine invertebrates. The extinction of marine and terrestrial biota is increasingly linked to the outgassing of large volumes of CO2 and SO2 during the emplacement of the Central Atlantic Magmatic Province. Here, we present multi-disciplinary data, including organic geochemical proxies, isotope (C, N), and palynological data, from cores in Luxemburg (Rosswinkel), and northern (Mariental) and southern Germany (Mingolsheim) that provide evidence for changes in type of black shale deposition that reflect major environmental perturbations across the T-J boundary. Prior to the T-J extinction, the Uppermost Rhaetian in Germany contains black shales that are rich in dinoflagellate cysts, and show high amplitude nitrogen isotope excursions. No biomarker evidence for photic zone euxinia was found in the Rhaetian. Because cyst-building dinoflagellates require oxygenated bottom waters, Rhaetian organic-rich sediments were deposited through high-productivity in well mixed shallow marine basins. Following the major overturn of terrestrial vegetation (fern spike) and the marine extinction level, black shales in the lowermost Hettangian reveal extremely low dinoflagellate cyst abundance, but high abundance of prasinophyte green algae and acritarchs. These black shales also show elevated quantities of the biomarker isorenieratane. Isorenieratane derives from the brown strains of photosynthetic green sulphur bacteria (Chlorobiaceae) that require both light and free hydrogen sulfide in the water column. The presence of abundant aryl isoprenoids (isorenieratane and its diagenetic products) in Luxemburg and N Germany suggests that marginal marine basins in NW Europe became salinity stratified and developed intense Photic Zone Euxinia (PZE) after the mass extinction event. This change in low oxygen conditions is

  14. Mouse redox histology using genetically encoded probes.

    PubMed

    Fujikawa, Yuuta; Roma, Leticia P; Sobotta, Mirko C; Rose, Adam J; Diaz, Mauricio Berriel; Locatelli, Giuseppe; Breckwoldt, Michael O; Misgeld, Thomas; Kerschensteiner, Martin; Herzig, Stephan; Müller-Decker, Karin; Dick, Tobias P

    2016-03-15

    Mapping the in vivo distribution of endogenous oxidants in animal tissues is of substantial biomedical interest. Numerous health-related factors, including diet, physical activity, infection, aging, toxins, or pharmacological intervention, may cause redox changes. Tools are needed to pinpoint redox state changes to particular organs, tissues, cell types, and subcellular organelles. We describe a procedure that preserves the in vivo redox state of genetically encoded redox biosensors within histological tissue sections, thus providing "redox maps" for any tissue and comparison of interest. We demonstrate the utility of the technique by visualizing endogenous redox differences and changes in the context of tumor growth, inflammation, embryonic development, and nutrient starvation.

  15. Use of dimedone-based chemical probes for sulfenic acid detection evaluation of conditions affecting probe incorporation into redox-sensitive proteins.

    PubMed

    Klomsiri, Chananat; Nelson, Kimberly J; Bechtold, Erika; Soito, Laura; Johnson, Lynnette C; Lowther, W Todd; Ryu, Seong-Eon; King, S Bruce; Furdui, Cristina M; Poole, Leslie B

    2010-01-01

    Sulfenic acids, formed as transient intermediates during the reaction of cysteine residues with peroxides, play significant roles in enzyme catalysis and regulation, and are also involved in the redox regulation of transcription factors and other signaling proteins. Therefore, interest in the identification of protein sulfenic acids has grown substantially in the past few years. Dimedone, which specifically traps sulfenic acids, has provided the basis for the synthesis of a novel group of compounds that derivatize 1,3-cyclohexadione, a dimedone analogue, with reporter tags such as biotin for affinity capture and fluorescent labels for visual detection. These reagents allow identification of the cysteine sites and proteins that are sensitive to oxidation and permit identification of the cellular conditions under which such oxidations occur. We have shown that these compounds are reactive and specific toward sulfenic acids and that the labeled proteins can be detected at high sensitivity using gel analysis or mass spectrometry. Here, we further characterize these reagents, showing that the DCP-Bio1 incorporation rates into three sulfenic acid containing proteins, papaya papain, Escherichia coli fRMsr, and the Salmonella typhimurium peroxiredoxin AhpC, are significantly different and, in the case of fRMsr, are unaffected by changes in buffer pH from 5.5 and 8.0. We also provide protocols to label protein sulfenic acids in cellular proteins, either by in situ labeling of intact cells or by labeling at the time of lysis. We show that the addition of alkylating reagents and catalase to the lysis buffer is critical in preventing the formation of sulfenic acid subsequent to cell lysis. Data presented herein also indicate that the need to standardize, as much as possible, the protein and reagent concentrations during labeling. Finally, we introduce several new test or control proteins that can be used to evaluate labeling procedures and efficiencies.

  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. In vitro susceptibility of thioredoxins and glutathione to redox modification and aging-related changes in skeletal muscle

    PubMed Central

    Dimauro, Ivan; Pearson, Timothy; Caporossi, Daniela; Jackson, Malcolm J.

    2012-01-01

    Thioredoxins (Trx's) regulate redox signaling and are localized to various cellular compartments. Specific redox-regulated pathways for adaptation of skeletal muscle to contractions are attenuated during aging, but little is known about the roles of Trx's in regulating these pathways. This study investigated the susceptibility of Trx1 and Trx2 in skeletal muscle to oxidation and reduction in vitro and the effects of aging and contractions on Trx1, Trx2, and thioredoxin reductase (TrxR) 1 and 2 contents and nuclear and cytosolic Trx1 and mitochondrial Trx2 redox potentials in vivo. The proportions of cytosolic and nuclear Trx1 and mitochondrial Trx2 in the oxidized or reduced forms were analyzed using redox Western blotting. In myotubes, the mean redox potentials were nuclear Trx1, −251 mV; cytosolic Trx1, −242 mV; mitochondrial Trx2, −346 mV, data supporting the occurrence of differing redox potentials between cell compartments. Exogenous treatment of myoblasts and myotubes with hydrogen peroxide or dithiothreitol modified glutathione redox status and nuclear and cytosolic Trx1, but mitochondrial Trx2 was unchanged. Tibialis anterior muscles from young and old mice were exposed to isometric muscle contractions in vivo. Aging increased muscle contents of Trx1, Trx2, and TrxR2, but neither aging nor endogenous ROS generated during contractions modified Trx redox potentials, although oxidation of glutathione and other thiols occurred. We conclude that glutathione redox couples in skeletal muscle are more susceptible to oxidation than Trx and that Trx proteins are upregulated during aging, but do not appear to modulate redox-regulated adaptations to contractions that fail during aging. PMID:23022873

  18. On the potential of redox potential measurements for the characterization of greenhouse gas emissions - preliminary results

    NASA Astrophysics Data System (ADS)

    Wang, Jihuan; Bogena, Heye; Brüggemann, Nicolas

    2017-04-01

    Soil greenhouse gas (GHG) emissions contribute to global warming. In order to support mitigation measures against global warming it is important to understand the controlling processes of GHG emissions. Previous studies focused mainly on the paddy rice fields or wetlands showed a strong relationship between soil redox potential and GHG emission (e.g. N2O). Recent sensor developments open the possibility for the long-term monitoring of field scale soil redox potential changes. Here, we performed laboratory lysimeter experiments to investigate how changes in the redox potential, induced by changes in the water level, affect GHG emissions from agricultural soil. Under our experimental conditions, we found that N2O emissions followed closely the changes in redox potential. The dynamics of redox potential were induced by changing the water-table depth in a laboratory lysimeter. During saturated conditions we found a clear negative correlation between redox potentials and N2O emission rates N2O. After switching from saturated to unsaturated conditions, N2O emission quickly decreased. In contrast, the emissions of CO2 increased with increasing soil redox potentials. The level of N2O emission also depended on the fertilization level of the soil. We propose that redox potential measurements are a viable method for better understanding of the controlling factors of GHG emission and the development agricultural management practices to reduce such emissions.

  19. Short-term cigarette smoke exposure induces reversible changes in energy metabolism and cellular redox status independent of inflammatory responses in mouse lungs.

    PubMed

    Agarwal, Amit R; Zhao, Liqin; Sancheti, Harsh; Sundar, Isaac K; Rahman, Irfan; Cadenas, Enrique

    2012-11-15

    Cigarette smoking leads to alteration in cellular redox status, a hallmark in the pathogenesis of chronic obstructive pulmonary disease. This study examines the role of cigarette smoke (CS) exposure in the impairment of energy metabolism and, consequently, mitochondrial dysfunction. Male A/J mice were exposed to CS generated by a smoking machine for 4 or 8 wk. A recovery group was exposed to CS for 8 wk and allowed to recover for 2 wk. Acute CS exposure altered lung glucose metabolism, entailing a decrease in the rate of glycolysis and an increase in the pentose phosphate pathway, as evidenced by altered expression and activity of GAPDH and glucose-6-phosphate dehydrogenase, respectively. Impairment of GAPDH was found to be due to glutathionylation of its catalytic site cysteines. Metabolic changes were associated with changes in cellular and mitochondrial redox status, assessed in terms of pyridine nucleotides and glutathione. CS exposure elicited an upregulation of the expression of complexes II, III, IV, and V and of the activity of complexes II, IV, and V. Microarray analysis of gene expression in mouse lungs after exposure to CS for 8 wk revealed upregulation of a group of genes involved in metabolism, electron transfer chain, oxidative phosphorylation, mitochondrial transport and dynamics, and redox regulation. These changes occurred independently of inflammatory responses. These findings have implications for the early onset of alterations in energy and redox metabolism upon acute lung exposure to CS.

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

    NASA Astrophysics Data System (ADS)

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

    2007-05-01

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

  1. Redox chemistry changes in the Panthalassic Ocean linked to the end-Permian mass extinction and delayed Early Triassic biotic recovery.

    PubMed

    Zhang, Guijie; Zhang, Xiaolin; Hu, Dongping; Li, Dandan; Algeo, Thomas J; Farquhar, James; Henderson, Charles M; Qin, Liping; Shen, Megan; Shen, Danielle; Schoepfer, Shane D; Chen, Kefan; Shen, Yanan

    2017-02-21

    The end-Permian mass extinction represents the most severe biotic crisis for the last 540 million years, and the marine ecosystem recovery from this extinction was protracted, spanning the entirety of the Early Triassic and possibly longer. Numerous studies from the low-latitude Paleotethys and high-latitude Boreal oceans have examined the possible link between ocean chemistry changes and the end-Permian mass extinction. However, redox chemistry changes in the Panthalassic Ocean, comprising ∼85-90% of the global ocean area, remain under debate. Here, we report multiple S-isotopic data of pyrite from Upper Permian-Lower Triassic deep-sea sediments of the Panthalassic Ocean, now present in outcrops of western Canada and Japan. We find a sulfur isotope signal of negative Δ(33)S with either positive δ(34)S or negative δ(34)S that implies mixing of sulfide sulfur with different δ(34)S before, during, and after the end-Permian mass extinction. The precise coincidence of the negative Δ(33)S anomaly with the extinction horizon in western Canada suggests that shoaling of H2S-rich waters may have driven the end-Permian mass extinction. Our data also imply episodic euxinia and oscillations between sulfidic and oxic conditions during the earliest Triassic, providing evidence of a causal link between incursion of sulfidic waters and the delayed recovery of the marine ecosystem.

  2. Redox chemistry changes in the Panthalassic Ocean linked to the end-Permian mass extinction and delayed Early Triassic biotic recovery

    PubMed Central

    Zhang, Guijie; Zhang, Xiaolin; Hu, Dongping; Li, Dandan; Algeo, Thomas J.; Farquhar, James; Henderson, Charles M.; Qin, Liping; Shen, Megan; Shen, Danielle; Schoepfer, Shane D.; Chen, Kefan; Shen, Yanan

    2017-01-01

    The end-Permian mass extinction represents the most severe biotic crisis for the last 540 million years, and the marine ecosystem recovery from this extinction was protracted, spanning the entirety of the Early Triassic and possibly longer. Numerous studies from the low-latitude Paleotethys and high-latitude Boreal oceans have examined the possible link between ocean chemistry changes and the end-Permian mass extinction. However, redox chemistry changes in the Panthalassic Ocean, comprising ∼85–90% of the global ocean area, remain under debate. Here, we report multiple S-isotopic data of pyrite from Upper Permian–Lower Triassic deep-sea sediments of the Panthalassic Ocean, now present in outcrops of western Canada and Japan. We find a sulfur isotope signal of negative Δ33S with either positive δ34S or negative δ34S that implies mixing of sulfide sulfur with different δ34S before, during, and after the end-Permian mass extinction. The precise coincidence of the negative Δ33S anomaly with the extinction horizon in western Canada suggests that shoaling of H2S-rich waters may have driven the end-Permian mass extinction. Our data also imply episodic euxinia and oscillations between sulfidic and oxic conditions during the earliest Triassic, providing evidence of a causal link between incursion of sulfidic waters and the delayed recovery of the marine ecosystem. PMID:28167796

  3. Redox chemistry changes in the Panthalassic Ocean linked to the end-Permian mass extinction and delayed Early Triassic biotic recovery

    NASA Astrophysics Data System (ADS)

    Zhang, Guijie; Zhang, Xiaolin; Hu, Dongping; Li, Dandan; Algeo, Thomas J.; Farquhar, James; Henderson, Charles M.; Qin, Liping; Shen, Megan; Shen, Danielle; Schoepfer, Shane D.; Chen, Kefan; Shen, Yanan

    2017-02-01

    The end-Permian mass extinction represents the most severe biotic crisis for the last 540 million years, and the marine ecosystem recovery from this extinction was protracted, spanning the entirety of the Early Triassic and possibly longer. Numerous studies from the low-latitude Paleotethys and high-latitude Boreal oceans have examined the possible link between ocean chemistry changes and the end-Permian mass extinction. However, redox chemistry changes in the Panthalassic Ocean, comprising ˜85-90% of the global ocean area, remain under debate. Here, we report multiple S-isotopic data of pyrite from Upper Permian-Lower Triassic deep-sea sediments of the Panthalassic Ocean, now present in outcrops of western Canada and Japan. We find a sulfur isotope signal of negative Δ33S with either positive δ34S or negative δ34S that implies mixing of sulfide sulfur with different δ34S before, during, and after the end-Permian mass extinction. The precise coincidence of the negative Δ33S anomaly with the extinction horizon in western Canada suggests that shoaling of H2S-rich waters may have driven the end-Permian mass extinction. Our data also imply episodic euxinia and oscillations between sulfidic and oxic conditions during the earliest Triassic, providing evidence of a causal link between incursion of sulfidic waters and the delayed recovery of the marine ecosystem.

  4. DNA and redox state induced conformational changes in the DNA-binding domain of the Myb oncoprotein.

    PubMed Central

    Myrset, A H; Bostad, A; Jamin, N; Lirsac, P N; Toma, F; Gabrielsen, O S

    1993-01-01

    The DNA-binding domain of the oncoprotein Myb comprises three imperfect repeats, R1, R2 and R3. Only R2 and R3 are required for sequence-specific DNA-binding. Both are assumed to contain helix-turn-helix (HTH)-related motifs, but multidimensional heteronuclear NMR spectroscopy revealed a disordered structure in R2 where the second HTH helix was predicted [Jamin et al. (1993) Eur. J. Biochem., 216, 147-154]. We propose that the disordered region folds into a 'recognition' helix and generates a full HTH-related motif upon binding to DNA. This would move Cys43 into the hydrophobic core of R2. We observed that Cys43 was accessible to N-ethylmaleimide alkylation in the free protein, but inaccessible in the DNA complex. Mutant proteins with charged (C43D) or polar (C43S) side chains in position 43 bound DNA with reduced affinity, while hydrophobic replacements (C43A, C43V and C43I) gave unaltered or improved DNA-binding. Specific DNA-binding enhanced protease resistance dramatically. Fluorescence emission spectra and quenching experiments supported a DNA-induced conformational change. Moreover, reversible oxidation of Cys43 had an effect similar to the inactivating C43D mutation. The highly oxidizable Cys43 could function as a molecular sensor for a redox regulatory mechanism turning specific DNA-binding on or off by controlling the DNA-induced conformational change in R2. Images PMID:8223472

  5. In vivo imaging of tumor physiological, metabolic, and redox changes in response to the anti-angiogenic agent sunitinib: longitudinal assessment to identify transient vascular renormalization.

    PubMed

    Matsumoto, Shingo; Saito, Keita; Takakusagi, Yoichi; Matsuo, Masayuki; Munasinghe, Jeeva P; Morris, Herman D; Lizak, Martin J; Merkle, Hellmut; Yasukawa, Keiji; Devasahayam, Nallathamby; Suburamanian, Sankaran; Mitchell, James B; Krishna, Murali C

    2014-09-10

    The tumor microenvironment is characterized by a highly reducing redox status, a low pH, and hypoxia. Anti-angiogenic therapies for solid tumors frequently function in two steps: the transient normalization of structurally and functionally aberrant tumor blood vessels with increased blood perfusion, followed by the pruning of tumor blood vessels and the resultant cessation of nutrients and oxygen delivery required for tumor growth. Conventional anatomic or vascular imaging is impractical or insufficient to distinguish between the two steps of tumor response to anti-angiogenic therapies. Here, we investigated whether the noninvasive imaging of the tumor redox state and energy metabolism could be used to characterize anti-angiogenic drug-induced transient vascular normalization. Daily treatment of squamous cell carcinoma (SCCVII) tumor-bearing mice with the multi-tyrosine kinase inhibitor sunitinib resulted in a rapid decrease in tumor microvessel density and the suppression of tumor growth. Tumor pO2 imaging by electron paramagnetic resonance imaging showed a transient increase in tumor oxygenation after 2-4 days of sunitinib treatment, implying improved tumor perfusion. During this window of vascular normalization, magnetic resonance imaging of the redox status using an exogenously administered nitroxide probe and hyperpolarized (13)C MRI of the metabolic flux of pyruvate/lactate couple revealed an oxidative shift in tumor redox status. Redox-sensitive metabolic couples can serve as noninvasive surrogate markers to identify the vascular normalization window in tumors with imaging techniques. A multimodal imaging approach to characterize physiological, metabolic, and redox changes in tumors is useful to distinguish between the different stages of anti-angiogenic treatment.

  6. Soluble oligomers of amyloid-β cause changes in redox state, DNA methylation, and gene transcription by inhibiting EAAT3 mediated cysteine uptake.

    PubMed

    Hodgson, Nathaniel; Trivedi, Malav; Muratore, Christina; Li, Shaomin; Deth, Richard

    2013-01-01

    Oxidative stress, hyperhomocysteinemia, altered DNA methylation, and insulin resistance in the brain are associated with Alzheimer's disease (AD), but the role of amyloid-β (Aβ) in these events remains unclear. Intracellular cysteine is rate-limiting for synthesis of the antioxidant glutathione (GSH), and factors regulating cysteine uptake exert a powerful influence over cellular redox status, especially in mature neurons where cysteine synthesis via transsulfuration of homocysteine (HCY) is restricted. We investigated the effect of soluble Aβ oligomers (oAβ) on basal and insulin-like growth factor-1 (IGF-1)-induced cysteine uptake mediated by the excitatory amino acid transporter 3 (EAAT3) in cultured human neuronal cells. We also examined the effect of oAβ on intracellular thiol metabolite levels, DNA methylation, and the transcription status of redox and methylation-associated genes. oAβ inhibited EAAT3-mediated cysteine uptake, causing a decrease in intracellular cysteine and GSH levels. The ratio of the methyl donor S-adenosylmethionine to the methylation inhibitor S-adenosylhomocysteine was decreased, in association with an increase in HCY and a global decrease in DNA methylation, indicative of decreased activity of the redox-sensitive enzyme methionine synthase. These metabolic effects of oAβ coincided with changes in the expression of redox and methylation pathway genes. The ability of oAβ to modulate gene expression via their redox and methylation-dependent epigenetic effects may contribute to the pathology of AD and recognition of this mechanism may lead to novel treatment approaches. We describe a role of IGF-1 signaling in regulating redox and methylation homeostasis, and propose this to be a pathogenic target of oAβ.

  7. 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.

  8. The redox switch that regulates molecular chaperones.

    PubMed

    Conway, Myra E; Lee, Christopher

    2015-08-01

    Modification of reactive cysteine residues plays an integral role in redox-regulated reactions. Oxidation of thiolate anions to sulphenic acid can result in disulphide bond formation, or overoxidation to sulphonic acid, representing reversible and irreversible endpoints of cysteine oxidation, respectively. The antioxidant systems of the cell, including the thioredoxin and glutaredoxin systems, aim to prevent these higher and irreversible oxidation states. This is important as these redox transitions have numerous roles in regulating the structure/function relationship of proteins. Proteins with redox-active switches as described for peroxiredoxin (Prx) and protein disulphide isomerase (PDI) can undergo dynamic structural rearrangement resulting in a gain of function. For Prx, transition from cysteine sulphenic acid to sulphinic acid is described as an adaptive response during increased cellular stress causing Prx to form higher molecular weight aggregates, switching its role from antioxidant to molecular chaperone. Evidence in support of PDI as a redox-regulated chaperone is also gaining impetus, where oxidation of the redox-active CXXC regions causes a structural change, exposing its hydrophobic region, facilitating polypeptide folding. In this review, we will focus on these two chaperones that are directly regulated through thiol-disulphide exchange and detail how these redox-induced switches allow for dual activity. Moreover, we will introduce a new role for a metabolic protein, the branched-chain aminotransferase, and discuss how it shares common mechanistic features with these well-documented chaperones. Together, the physiological importance of the redox regulation of these proteins under pathological conditions such as Alzheimer's disease, Parkinson's disease, and amyotrophic lateral sclerosis will be discussed to illustrate the impact and importance of correct folding and chaperone-mediated activity.

  9. Augmenting atrazine and hexachlorobenzene degradation under different soil redox conditions in a bioelectrochemistry system and an analysis of the relevant microorganisms.

    PubMed

    Wang, Hui; Cao, Xian; Li, Lei; Fang, Zhou; Li, Xianning

    2017-09-20

    Soil microbial fuel cells (MFCs) are a sustainable technology that degrades organic pollutants while generating electricity. However, there have been no detailed studies of the mechanisms of pollutant degradation in soil MFCs. In this study, the effects of external resistance and electrode effectiveness on atrazine and hexachlorobenzene (HCB) degradation were evaluated, the performance of soil MFCs in the degradation of these pollutants under different soil redox conditions was assessed, and the associated microorganisms in the anode were investigated. With an external resistance of 20Ω, the degradation efficiencies of atrazine and HCB were 95% and 78%, respectively. The degradation efficiency, degradation rate increased with decreasing external resistance, while the half-life decreased. There were different degradation trends for different pollutants under different soil redox conditions. The fastest degradation rate of atrazine was in the upper MFC section (aerobic), whereas that of HCB was in the lower MFC section (anaerobic). The results showed that electrode effectiveness played a significant role in pollution degradation. In addition, the microbial community analysis demonstrated that Proteobacteria, especially Deltaproteobacteria involved in current generation was extremely abundant (27.49%) on soil MFC anodes, although the percentage abundances of atrazine degrading Rhodocyclaceae (8.77%), Desulfitobacterium (0.64%), and HCB degrading Desulfuromonas (0.73%), were considerably lower. The results of the study suggested that soil MFCs can enhance the degradation of atrazine and HCB, and bioelectrochemical reduction was the main mechanism for the pollutants degradation. Copyright © 2017 Elsevier Inc. All rights reserved.

  10. 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.

  11. [Morphogenetic changes during newt tail regeneration under changed gravity conditions].

    PubMed

    Radugina, E A; Grigorian, É N

    2012-01-01

    Gravity-dependent shape alterations in newt tail regenerates are described, which were previously noticed in experiments onboard satellites Foton M2, M3 and in corresponding laboratory controls. Laboratory conditions were developed that allow reproducing this phenomenon persistently in the adult newts Pleurodeles waltl (Michahelles, 1830). The newts kept in an aquarium (in partial weightlessness) after 1/3 tail amputation developed normal lanceolate regenerates, while those that stayed on a moist mat (exposed to greater gravity than in aquarium) developed curved tail regenerates. Dynamics of the shape alterations were described using computer morphometric analysis. The curve was shown to develop at stage III of regeneration and to be caused by bending of the developing axial structures: the ependymal tube and the cartilage rode. Cellular processes were described that accompany the tail shape changes, such as cell migration and formation of dense aggregates. Unequal proliferation throughout the wound epidermis and blastema was revealed using BrdU assay. Proliferation increased within dorsal and apical regions of the regenerates in the newts kept on the mat cell compared with the aquarian animals.

  12. Is regulation of proteolysis associated with redox-state changes in rat skeletal muscle?

    PubMed Central

    Tischler, M E

    1980-01-01

    In isolated rat diaphragms, only those substrates that increased the tissue NADH/NAD+ ratio lowered the rate of proteolysis. However, direct inhibition of proteinase activity by leupeptin promoted oxidation of the NAD couple of the muscles. These results suggest that changes in muscle reduction-oxidation state may be important in the regulation of proteolysis. PMID:7236250

  13. 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

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

    NASA Astrophysics Data System (ADS)

    Zhang, Yingjie; Gregg, Daniel J.; Kong, Linggen; Jovanovich, Miodrag; Triani, Gerry

    2017-07-01

    Zirconolite glass-ceramic samples doped with plutonium have been prepared via hot isostatic pressing. The effects of processing redox and plutonium loadings on plutonium valences, the presence of cation vacancies, zirconolite phase compositions, microstructures and durability have been investigated. Either tetravalent or trivalent plutonium ions may be incorporated on the Ca-site of CaZrTi2O7 zirconolite with the Ca-site cation vacancies and the incorporation of Al3+ ions on the Ti-site for charge compensation. Plutonium and gadolinium (as a neutron absorber) are predominantly partitioned in zirconolite phases leading to the formation of chemically durable glass-ceramics suitable for the immobilization of impure plutonium wastes arising from the nuclear fuel cycle.

  15. 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

  16. 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.

  17. 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.

  18. Response of the human myocardium to ischemic injury and preconditioning: The role of cardiac and comorbid conditions, medical treatment, and basal redox status

    PubMed Central

    Casós, Kelly; Ferrer-Curriu, Gemma; Soler-Ferrer, Paula; Pérez, María L; Permanyer, Eduard; Blasco-Lucas, Arnau; Gracia-Baena, Juan Manuel; Castro, Miguel A; Sureda, Carlos; Barquinero, Jordi

    2017-01-01

    Background The diseased human myocardium is highly susceptible to ischemia/reoxygenation (I/R)-induced injury but its response to protective interventions such as ischemic preconditioning (IPreC) is unclear. Cardiac and other pre-existing clinical conditions as well as previous or ongoing medical treatment may influence the myocardial response to I/R injury and protection. This study investigated the effect of both on myocardial susceptibility to I/R-induced injury and the protective effects of IPreC. Methods and results Atrial myocardium from cardiac surgery patients (n = 300) was assigned to one of three groups: aerobic control, I/R alone, and IPreC. Lactate dehydrogenase leakage, as a marker of cell injury, and cell viability were measured. The basal redox status was determined in samples from 90 patients. The response to I/R varied widely. Myocardium from patients with aortic valve disease was the most susceptible to injury whereas myocardium from dyslipidemia patients was the least susceptible. Tissue from females was better protected than tissue from males. Myocardium from patients with mitral valve disease was the least responsive to IPreC. The basal redox status was altered in the myocardium from patients with mitral and aortic valve disease. Conclusions The response of the myocardium to I/R and IPreC is highly variable and influenced by the underlying cardiac pathology, dyslipidemia, sex, and the basal redox status. These results should be taken into account in the design of future clinical studies on the prevention of I/R injury and protection. PMID:28380047

  19. Response of the human myocardium to ischemic injury and preconditioning: The role of cardiac and comorbid conditions, medical treatment, and basal redox status.

    PubMed

    Casós, Kelly; Ferrer-Curriu, Gemma; Soler-Ferrer, Paula; Pérez, María L; Permanyer, Eduard; Blasco-Lucas, Arnau; Gracia-Baena, Juan Manuel; Castro, Miguel A; Sureda, Carlos; Barquinero, Jordi; Galiñanes, Manuel

    2017-01-01

    The diseased human myocardium is highly susceptible to ischemia/reoxygenation (I/R)-induced injury but its response to protective interventions such as ischemic preconditioning (IPreC) is unclear. Cardiac and other pre-existing clinical conditions as well as previous or ongoing medical treatment may influence the myocardial response to I/R injury and protection. This study investigated the effect of both on myocardial susceptibility to I/R-induced injury and the protective effects of IPreC. Atrial myocardium from cardiac surgery patients (n = 300) was assigned to one of three groups: aerobic control, I/R alone, and IPreC. Lactate dehydrogenase leakage, as a marker of cell injury, and cell viability were measured. The basal redox status was determined in samples from 90 patients. The response to I/R varied widely. Myocardium from patients with aortic valve disease was the most susceptible to injury whereas myocardium from dyslipidemia patients was the least susceptible. Tissue from females was better protected than tissue from males. Myocardium from patients with mitral valve disease was the least responsive to IPreC. The basal redox status was altered in the myocardium from patients with mitral and aortic valve disease. The response of the myocardium to I/R and IPreC is highly variable and influenced by the underlying cardiac pathology, dyslipidemia, sex, and the basal redox status. These results should be taken into account in the design of future clinical studies on the prevention of I/R injury and protection.

  20. Detection of reactive oxygen species-sensitive thiol proteins by redox difference gel electrophoresis: implications for mitochondrial redox signaling.

    PubMed

    Hurd, Thomas R; Prime, Tracy A; Harbour, Michael E; Lilley, Kathryn S; Murphy, Michael P

    2007-07-27

    Reactive oxygen species (ROS) produced by the mitochondrial respiratory chain can be a redox signal, but whether they affect mitochondrial function is unclear. Here we show that low levels of ROS from the respiratory chain under physiological conditions reversibly modify the thiol redox state of mitochondrial proteins involved in fatty acid and carbohydrate metabolism. As these thiol modifications were specific and occurred without bulk thiol changes, we first had to develop a sensitive technique to identify the small number of proteins modified by endogenous ROS. In this technique, redox difference gel electrophoresis, control, and redox-challenged samples are labeled with different thiol-reactive fluorescent tags and then separated on the same two-dimensional gel, enabling the sensitive detection of thiol redox modifications by changes in the relative fluorescence of the two tags within a single protein spot, followed by protein identification by mass spectrometry. Thiol redox modification affected enzyme activity, suggesting that the reversible modification of enzyme activity by ROS from the respiratory chain may be an important and unexplored mode of mitochondrial redox signaling.

  1. Changes in redox states of respiratory pigments recorded from the eyes of live blowflies exposed to light stimuli and hypoxia.

    PubMed

    Meglič, Andrej; Zupančič, Gregor

    2011-03-01

    Time courses of mitochondrial responses to illumination-induced physiological loads and to hypoxia, were recorded optically from eyes of blowflies Calliphora vicina chalky. We isolated changes in redox states of haems a(3), a, c, and b. Two types of responses to light stimulation were observed. Haems b and a(3) responded with transient oxidation and haems a and c with reduction. The same two groups emerged in response to anoxic exposure. The onset of reduction of haems a and c had virtually no latency, while haems a(3) and b exhibited a transient oxidation followed by reduction only after 10-20 s. The dependence of the steady-state reduction level on [Formula: see text] produced the same groups. Haems a and c were significantly reduced at [Formula: see text] levels around 10 kPa while with haems b and a(3) load-induced oxidation was only replaced by reduction below 2 kPa. We propose haems respond to physiological loads in accordance with their steady-state reduction, which in turn depends largely on barriers for electron transport imposed by the mitochondrial membrane potential. We also propose it may be possible to assess the values of tissue [Formula: see text] and O(2) consumption by monitoring haems that are highly oxidized at rest such as haem a.

  2. Dental Usage Under Changing Economic Conditions

    PubMed Central

    Manski, Richard J.; Moeller, John F.; Chen, Haiyan; Schimmel, Jody; St Clair, Patricia A.; Pepper, John V.

    2012-01-01

    Objective The purpose of this article is to examine the relationship between changes in household finances (wealth and income) and changes in dental utilization at the onset of the recent recession in a population of older Americans. Methods Data from the Health and Retirement Study (HRS) were analyzed for U.S. individuals aged 51 years and older during the 2006 and 2008 waves of the HRS. We estimated logistic models of (1) starting and (2) stopping dental use between 2006 and 2008 survey periods as a function of changes in household wealth and income, controlling for other potentially confounding covariates. Results We found that only when household wealth falls by 50 percent or more were older adults less likely to seek dental care. Changes in household income and other changes in household wealth were not associated with changes in dental utilization among this population. Conclusions Older Americans’ dental care utilization appeared to be fairly resilient to changes in household finances; only when wealth fell by 50 percent or more did individuals decrease dental use. This finding might extend to other health care services that are preventive, routine, and relatively inexpensive. PMID:22994647

  3. Dental usage under changing economic conditions.

    PubMed

    Manski, Richard J; Moeller, John F; Chen, Haiyan; Schimmel, Jody; St Clair, Patricia A; Pepper, John V

    2014-01-01

    The purpose of this article is to examine the relationship between changes in household finances (wealth and income) and changes in dental utilization at the onset of the recent recession in a population of older Americans. Data from the Health and Retirement Study (HRS) were analyzed for U.S. individuals aged 51 years and older during the 2006 and 2008 waves of the HRS. We estimated logistic models of (a) starting and (b) stopping dental use between 2006 and 2008 survey periods as a function of changes in household wealth and income, controlling for other potentially confounding covariates. We found that only when household wealth falls by 50 percent or more were older adults less likely to seek dental care. Changes in household income and other changes in household wealth were not associated with changes in dental utilization among this population. Older Americans' dental care utilization appeared to be fairly resilient to changes in household finances; only when wealth fell by 50 percent or more did individuals decrease dental use. This finding might extend to other health-care services that are preventive, routine, and relatively inexpensive. © 2012 American Association of Public Health Dentistry.

  4. Accelerated Oxygen Atom Transfer and C-H Bond Oxygenation by Remote Redox Changes in Fe3 Mn-Iodosobenzene Adducts.

    PubMed

    de Ruiter, Graham; Carsch, Kurtis M; Gul, Sheraz; Chatterjee, Ruchira; Thompson, Niklas B; Takase, Michael K; Yano, Junko; Agapie, Theodor

    2017-03-24

    We report the synthesis, characterization, and reactivity of [LFe3 (PhPz)3 OMn((s) PhIO)][OTf]x (3: x=2; 4: x=3), where 4 is one of very few examples of iodosobenzene-metal adducts characterized by X-ray crystallography. Access to these rare heterometallic clusters enabled differentiation of the metal centers involved in oxygen atom transfer (Mn) or redox modulation (Fe). Specifically, (57) Fe Mössbauer and X-ray absorption spectroscopy provided unique insights into how changes in oxidation state (Fe(III)2 Fe(II) Mn(II) vs. Fe(III)3 Mn(II) ) influence oxygen atom transfer in tetranuclear Fe3 Mn clusters. In particular, a one-electron redox change at a distal metal site leads to a change in oxygen atom transfer reactivity by ca. two orders of magnitude.

  5. Accelerated Oxygen Atom Transfer and C-H Bond Oxygenation by Remote Redox Changes in Fe3Mn-Iodosobenzene Adducts

    DOE PAGES

    de Ruiter, Graham; Carsch, Kurtis M.; Gul, Sheraz; ...

    2017-03-24

    In this paper, we report the synthesis, characterization, and reactivity of [LFe3(PhPz)3OMn(sPhIO)][OTf]x (3: x=2; 4: x=3), where 4 is one of very few examples of iodosobenzene–metal adducts characterized by X-ray crystallography. Access to these rare heterometallic clusters enabled differentiation of the metal centers involved in oxygen atom transfer (Mn) or redox modulation (Fe). Specifically, 57Fe Mössbauer and X-ray absorption spectroscopy provided unique insights into how changes in oxidation state (FeIII2FeIIMnII vs. FeIII3MnII) influence oxygen atom transfer in tetranuclear Fe3Mn clusters. Finally, in particular, a one-electron redox change at a distal metal site leads to a change in oxygen atom transfermore » reactivity by ca. two orders of magnitude.« less

  6. Sequential changes in redox status and nitric oxide synthases expression in the liver after bile duct ligation.

    PubMed

    Vázquez-Gil, M José; Mesonero, M José; Flores, Olga; Criado, Manuela; Hidalgo, Froilán; Arévalo, Miguel A; Sánchez-Rodríguez, Angel; Tuñón, M Jesús; López-Novoa, José M; Esteller, A

    2004-06-25

    Bile duct ligation (BDL) in rats induces portal fibrosis. This process has been linked to changes in the oxidative state of the hepatic cells and in the production of nitric oxide. Our objective was to find possible temporal connections between hepatic redox state, NO synthesis and liver injury. In this work we have characterized hepatic lesions 17 and 31 days after BDL and determined changes in hepatic function, oxidative state, and NO production. We have also analyzed the expression and localization of inducible NO synthase (NOS2) and constitutive NO synthase (NOS3). After 17 and 31 days from ligature, lipid peroxidation is increased and both plasma concentration and biliary excretion of nitrite+nitrate are rised. 17 days after BDL both NOS2 and NOS3 are expressed intensely and in the same regions. 31 days after BDL, the expression of NOS2 remains elevated and is localized mostly in preserved hepatocytes in portal areas and in neighborhoods of centrolobulillar vein. NOS3 is localized in vascular regions of portal spaces and centrolobulillar veins and in preserved sinusoids and although its expression is greater than in control animals (34%), it is clearly lower (50%) than 17 days after BDL. The time after BDL is crucial in the study of NO production, intrahepatic localization of NOS isoforms expression, and cell type involved, since all these parameters change with time. BDL-induced, peroxidation and fibrosis are not ligated by a cause-effect relationship, but rather they both seem to be the consequence of common inductors. Copyright 2004 Elsevier Inc.

  7. Long-term sulphur starvation of Arabidopsis thaliana modifies mitochondrial ultrastructure and activity and changes tissue energy and redox status.

    PubMed

    Ostaszewska, Monika; Juszczuk, Izabela M; Kołodziejek, Izabella; Rychter, Anna M

    2014-04-15

    Sulphur, as a constituent of amino acids (cysteine and methionine), iron-sulphur clusters, proteins, membrane sulpholipids, glutathione, glucosinolates, coenzymes, and auxin precursors, is essential for plant growth and development. Absence or low sulphur concentration in the soil results in severe growth retardation. Arabidopsis thaliana plants grown hydroponically for nine weeks on Knop nutrient medium without sulphur showed morphological symptoms of sulphur deficiency. The purpose of our study was to investigate changes that mitochondria undergo and the role of the highly branched respiratory chain in survival during sulphur deficiency stress. Ultrastructure analysis of leaf mesophyll cells of sulphur-deficient Arabidopsis showed heterogeneity of mitochondria; some of them were not altered, but the majority had swollen morphology. Dilated mitochondria displayed a lower matrix density and fewer cristae compared to control mitochondria. Disintegration of the inner and outer membranes of some mitochondria from the leaves of sulphur-deficient plants was observed. On the contrary, chloroplast ultrastructure was not affected. Sulphur deficiency changed the respiratory activity of tissues and isolated mitochondria; Complex I and IV capacities and phosphorylation rates were lower, but external NAD(P)H dehydrogenase activity increased. Higher external NAD(P)H dehydrogenase activity corresponded to increased cell redox level with doubled NADH/NAD ratio in the leaf and root tissues. Sulphur deficiency modified energy status in the tissues of Arabidopsis plants. The total concentration of adenylates (expressed as ATP+ADP), measured in the light, was lower in the leaves and roots of sulphur-deficient plants than in the controls, which was mainly due to the severely decreased ATP levels. We show that the changes in mitochondrial ultrastructure are compensated by the modifications in respiratory chain activity. Although mitochondria of Arabidopsis tissues are affected by

  8. 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

  9. 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

  10. 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. © The Authors 2016. Published by Oxford University Press on behalf of the Japanese Biochemical Society.

  11. 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. Copyright © 2016 Elsevier Inc. All rights reserved.

  12. 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

  13. Reactive nitrogen species contribute to the rapid onset of redox changes induced by acute immobilization stress in rats.

    PubMed

    Chen, Hsiao-Jou Cortina; Spiers, Jereme G; Sernia, Conrad; Anderson, Stephen T; Lavidis, Nickolas A

    2014-12-01

    Acute stress leads to the rapid secretion of glucocorticoids, which accelerates cellular metabolism, resulting in increased reactive oxygen and nitrogen species generation. Although the nitrergic system has been implicated in numerous stress-related diseases, the time course and extent of nitrosative changes during acute stress have not been characterized. Outbred male Wistar rats were randomly allocated into control (n = 9) or 120 min acute immobilization stress (n = 9) groups. Serial blood samples were collected at 0 (baseline), 60, 90, and 120 min. Plasma corticosterone concentrations increased by approximately 350% at 60, 90, and 120 (p < 0.001) min of stress. The production of nitric oxide, measured as the benzotriazole form of 4-amino-5-methylamino-2',7'-difluorofluorescein, increased during stress exposure by approximately 5%, 10%, and 15% at 60 (p < 0.05), 90 (p < 0.01) and 120 (p < 0.001) min, respectively, compared to controls. Nitric oxide metabolism, measured as the stable metabolites nitrite and nitrate, showed a 40-60% increase at 60, 90, and 120 (p < 0.001) min of stress. The oxidative status of 2',7'-dichlorofluorescein in plasma was significantly elevated at 60 (p < 0.01), 90, and 120 (p < 0.001) min. A delayed decrease of approximately 25% in the glutathione redox ratio at 120 min (p < 0.001) also indicates stress-induced cellular oxidative stress. The peroxidation of plasma lipids increased by approximately 10% at 90 (p < 0.05) and 15% at 120 (p < 0.001) min, indicative of oxidative damage. It was concluded that a single episode of stress causes early and marked changes of both oxidative and nitrosative status sufficient to induce oxidative damage in peripheral tissues.

  14. 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.

  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.; 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.

  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.; 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.

  17. 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

  18. Redox therapy in neonatal sepsis: reasons, targets, strategy, and agents.

    PubMed

    Bajčetić, Milica; Spasić, Snežana; Spasojević, Ivan

    2014-09-01

    Neonatal sepsis is one of the most fulminating conditions in neonatal intensive care units. Antipathogen and supportive care are administered routinely, but do not deliver satisfactory results. In addition, the efforts to treat neonatal sepsis with anti-inflammatory agents have generally shown to be futile. The accumulating data imply that intracellular redox changes intertwined into neonatal sepsis redox cycle represent the main cause of dysfunction of mitochondria and cells in neonatal sepsis. Our aim here is to support the new philosophy in neonatal sepsis treatment, which involves the integration of mechanisms that are responsible for cellular dysfunction and organ failure, the recognition of the most important targets, and the selection of safe agents that can stop the neonatal sepsis redox cycle by hitting the hot spots. Redox-active agents that could be beneficial for neonatal sepsis treatment according to these criteria include lactoferrin, interleukin 10, zinc and selenium supplements, ibuprofen, edaravone, and pentoxifylline.

  19. Modulation of Chlamydomonas reinhardtii flagellar motility by redox poise

    PubMed Central

    Wakabayashi, Ken-ichi; King, Stephen M.

    2006-01-01

    Redox-based regulatory systems are essential for many cellular activities. Chlamydomonas reinhardtii exhibits alterations in motile behavior in response to different light conditions (photokinesis). We hypothesized that photokinesis is signaled by variations in cytoplasmic redox poise resulting from changes in chloroplast activity. We found that this effect requires photosystem I, which generates reduced NADPH. We also observed that photokinetic changes in beat frequency and duration of the photophobic response could be obtained by altering oxidative/reductive stress. Analysis of reactivated cell models revealed that this redox poise effect is mediated through the outer dynein arms (ODAs). Although the global redox state of the thioredoxin-related ODA light chains LC3 and LC5 and the redox-sensitive Ca2+-binding subunit of the docking complex DC3 did not change upon light/dark transitions, we did observe significant alterations in their interactions with other flagellar components via mixed disulfides. These data indicate that redox poise directly affects ODAs and suggest that it may act in the control of flagellar motility. PMID:16754958

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

    PubMed

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

    2013-08-06

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

  1. 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…

  2. 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…

  3. 49 CFR 1542.107 - Changed conditions affecting security.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 49 Transportation 9 2010-10-01 2010-10-01 false Changed conditions affecting security. 1542.107... Security Program § 1542.107 Changed conditions affecting security. (a) After approval of the security program, each airport operator must notify TSA when changes have occurred to the— (1) Measures, training...

  4. Changes in Spatiotemporal Precipitation Patterns in Changing Climate Conditions

    SciTech Connect

    Chang, Won; Stein, Michael; Wang, Jiali; Kotamarthi, Veerabhadra R.; Moyer, Elisabeth J.

    2016-12-01

    Climate models robustly imply that some significant change in precipitation patterns will occur. Models consistently project that the intensity of individual precipitation events increases by approximately 6-7%/K, following the increase in atmospheric water content, but that total precipitation increases by a lesser amount (2-3%/K in the global average). Some other aspect of precipitation events must then change to compensate for this difference. We develop here a new methodology for identifying individual rainstorms and studying their physical characteristics - including starting location, intensity, spatial extent, duration, and trajectory - that allows identifying that compensating mechanism. We apply this technique to precipitation over the contiguous U.S. from both radar-based data products and high-resolution model runs simulating 100 years of business-as-usual warming. In model studies, we find that the dominant compensating mechanism is a reduction of storm size. In summer, rainstorms become more intense but smaller; in winter, rainstorm shrinkage still dominates, but storms also become less numerous and shorter duration. These results imply that flood impacts from climate change will be less severe than would be expected from changes in precipitation intensity alone. We show also that projected changes are smaller than model-observation biases, implying that the best means of incorporating them into impact assessments is via "data-driven simulations" that apply model-projected changes to observational data. We therefore develop a simulation algorithm that statistically describes model changes in precipitation characteristics and adjusts data accordingly, and show that, especially for summertime precipitation, it outperforms simulation approaches that do not include spatial information.

  5. Changes in Spatiotemporal Precipitation Patterns in Changing Climate Conditions

    NASA Astrophysics Data System (ADS)

    Chang, Won; Stein, Michael L.; Wang, Jiali; Kotamarthi, V. Rao; Moyer, Elisabeth J.

    2016-12-01

    Climate models robustly imply that some significant change in precipitation patterns will occur. Models consistently project that the intensity of individual precipitation events increases by approximately 6-7%/K, following the increase in atmospheric water content, but that total precipitation increases by a lesser amount (1-2 %/K in the global average in transient runs). Some other aspect of precipitation events must then change to compensate for this difference. We develop here a new methodology for identifying individual rainstorms and studying their physical characteristics - including starting location, intensity, spatial extent, duration, and trajectory - that allows identifying that compensating mechanism. We apply this technique to precipitation over the contiguous U.S. from both radar-based data products and high-resolution model runs simulating 80 years of business-as-usual warming. In model studies, we find that the dominant compensating mechanism is a reduction of storm size. In summer, rainstorms become more intense but smaller, in winter, rainstorm shrinkage still dominates, but storms also become less numerous and shorter duration. These results imply that flood impacts from climate change will be less severe than would be expected from changes in precipitation intensity alone. We show also that projected changes are smaller than model-observation biases, implying that the best means of incorporating them into impact assessments is via "data-driven simulations" that apply model-projected changes to observational data. We therefore develop a simulation algorithm that statistically describes model changes in precipitation characteristics and adjusts data accordingly, and show that, especially for summertime precipitation, it outperforms simulation approaches that do not include spatial information.

  6. Changes in the redox state and endogenous fluorescence of in vivo human skin due to intrinsic and photo-aging, measured by multiphoton tomography with fluorescence lifetime imaging.

    PubMed

    Sanchez, Washington Y; Obispo, Clara; Ryan, Elizabeth; Grice, Jeffrey E; Roberts, Michael S

    2013-06-01

    Ultraviolet radiation from solar exposure is a key extrinsic factor responsible for premature skin aging (i.e., photo-aging). Recent advances using in vivo multiphoton tomography (MPT) demonstrate the efficacy of this approach to assess intrinsic and extrinsic skin aging as an alternative to existing invasive techniques. In this study, we measured changes in epidermal autofluorescence, dermal collagen second harmonic generation (SHG), and the redox state of solar-exposed and solar-protected human skin by MPT with fluorescence lifetime imaging (MPT-FLIM). Twenty-four volunteers across four age categories (20 to 29, 30 to 39, 40 to 49, and 50 to 59 years old; six volunteers each) were recruited for MPT-FLIM imaging of the dorsal (solar-exposed; photo-damaged) and volar (solar-protected) forearm. We demonstrate a higher intensity of dermal collagen SHG within the volar forearm compared to dorsal solar-exposed skin. Redox imaging of each epidermal skin stratum by FLIM demonstrates an increase in fluorescence lifetime in the solar-exposed dorsal forearm that is more apparent in aged skin. The results of this study suggest the redox state of the viable epidermis is a key marker in assessing intrinsic and photo-damage skin aging, in combination with changes in autofluorescence and SHG.

  7. Changes in the redox state and endogenous fluorescence of in vivo human skin due to intrinsic and photo-aging, measured by multiphoton tomography with fluorescence lifetime imaging

    NASA Astrophysics Data System (ADS)

    Sanchez, Washington Y.; Obispo, Clara; Ryan, Elizabeth; Grice, Jeffrey E.; Roberts, Michael S.

    2013-06-01

    Ultraviolet radiation from solar exposure is a key extrinsic factor responsible for premature skin aging (i.e., photo-aging). Recent advances using in vivo multiphoton tomography (MPT) demonstrate the efficacy of this approach to assess intrinsic and extrinsic skin aging as an alternative to existing invasive techniques. In this study, we measured changes in epidermal autofluorescence, dermal collagen second harmonic generation (SHG), and the redox state of solar-exposed and solar-protected human skin by MPT with fluorescence lifetime imaging (MPT-FLIM). Twenty-four volunteers across four age categories (20 to 29, 30 to 39, 40 to 49, and 50 to 59 years old; six volunteers each) were recruited for MPT-FLIM imaging of the dorsal (solar-exposed; photo-damaged) and volar (solar-protected) forearm. We demonstrate a higher intensity of dermal collagen SHG within the volar forearm compared to dorsal solar-exposed skin. Redox imaging of each epidermal skin stratum by FLIM demonstrates an increase in fluorescence lifetime in the solar-exposed dorsal forearm that is more apparent in aged skin. The results of this study suggest the redox state of the viable epidermis is a key marker in assessing intrinsic and photo-damage skin aging, in combination with changes in autofluorescence and SHG.

  8. 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.

  9. α-Tocopherol administration blocks adaptive changes in cell NADH/NAD+ redox state and mitochondrial function leading to inhibition of gastric mucosa cell proliferation in rats.

    PubMed

    Olguín-Martínez, Marisela; Hernández-Espinosa, Diego R; Hernández-Muñoz, Rolando

    2013-12-01

    In experimentally induced chronic gastritis, a compensatory mucosal cell proliferation occurs with enhanced glucose oxidative metabolism linked to lipoperoxidative events. Therefore, this study was aimed at assessing the participation of cell NAD/NADH redox state and mitochondrial functions during gastric mucosa proliferation and the effects of in vivo α-tocopherol (vitamin E) administration. Glucose oxidation and oxygen consumption were tested in gastric mucosa samples obtained from rats with gastritis and from those also treated with α-tocopherol. Gastric mucosal mitochondria were isolated and structural and functional parameters were determined. Succinate oxidation, ADP phosphorylation, mitochondrial enzyme activities, and membrane lipid composition were measured. In addition, parameters indicative of cellular NAD/NADH redox state, proliferation, apoptosis, and nitric oxide (NO) metabolism were also determined. After ethanol withdrawal, the damaged gastric mucosa increased glucose and oxygen consumption, events associated with a more reduced cytoplasmic NAD/NADH ratio. Enhanced mitochondrial oxidative phosphorylation and increased mitochondrial enzyme activities occurred early, accompanied by recovery of lost mitochondrial protein and lipid composition in the gastric mucosa, events associated with increased NO production. When mitochondrial function and structural events were normalized, apoptosis was initiated as assessed by the mitochondrial Bax/Bcl2 ratio. Treatment with α-tocopherol inhibited cell proliferation and blocked enhanced glucose utilization, mitochondrial substrate oxidation, and changes in redox state, delaying the onset of these adaptive metabolic changes, whereas it inhibited cell proliferation. In conclusion, α-tocopherol could abolish damage-induced "stress" signaling by desynchronizing mitochondrial adaptive responses, including mitochondria biogenesis, and consequently NAD/NADH redox, which seems to regulate gastric mucosal cell

  10. The impact of increased oxygen conditions on metal-contaminated sediments part I: effects on redox status, sediment geochemistry and metal bioavailability.

    PubMed

    De Jonge, M; Teuchies, J; Meire, P; Blust, R; Bervoets, L

    2012-05-01

    In order to evaluate the effect of improved oxygen concentrations in overlying surface water on the redox status, sediment geochemistry and metal bioavailability in metal-polluted sediments a 54 days lab experiment with two different experimental treatments was conducted (90% and 40% O(2)). Changes in redox potential (Eh) in the sediment were monitored over time. At 6 different time points (after 0, 2, 5, 12, 32 and 54 days) and at 4 sediment depths (0-1, 1-4, 4-8 and 8-15 cm), acid volatile sulfides (AVS), simultaneously extracted metals (SEM) and total organic carbon (TOC) were measured and metal release to overlying surface water was determined. Labile metal species in both water and sediment were measured using Diffusive Gradients in Thin films (DGT). Our results showed that elevated oxygen levels in overlying surface water led to an Eh increase in the sediment of the 90% O(2) treatment from 0 to ± 200 mV while AVS concentrations in the upper sediment layer decreased by 70%. Following AVS oxidation metal availability in the pore water was highly elevated after 54 days. However, Cu remained strongly bound to the sediment during the whole experiment. Only a limited metal release to the overlying surface water was noticed, which was due to the fact that SEM(tot) concentrations in the sediment did not yet exceeded AVS levels ([SEM(tot) - AVS]/f(OC) = 0) after 54 days. Additionally, adsorption on Fe and Mn hydroxides and particulate organic carbon also slowed down any potential metal release. Our results indicated that increasing oxygen concentrations due to general water quality improvements can enhance the mobility of trace metals which may result in the leaching of sediment-bound metals to overlying surface water, even in undisturbed watercourses. Copyright © 2012 Elsevier Ltd. All rights reserved.

  11. Redox alters yellow dragonflies into red.

    PubMed

    Futahashi, Ryo; Kurita, Ryoji; Mano, Hiroaki; Fukatsu, Takema

    2012-07-31

    Body color change associated with sexual maturation--so-called nuptial coloration--is commonly found in diverse vertebrates and invertebrates, and plays important roles for their reproductive success. In some dragonflies, whereas females and young males are yellowish in color, aged males turn vivid red upon sexual maturation. The male-specific coloration plays pivotal roles in, for example, mating and territoriality, but molecular basis of the sex-related transition in body coloration of the dragonflies has been poorly understood. Here we demonstrate that yellow/red color changes in the dragonflies are regulated by redox states of epidermal ommochrome pigments. Ratios of reduced-form pigments to oxidized-form pigments were significantly higher in red mature males than yellow females and immature males. The ommochrome pigments extracted from the dragonflies changed color according to redox conditions in vitro: from red to yellow in the presence of oxidant and from yellow to red in the presence of reductant. By injecting the reductant solution into live insects, the yellow-to-red color change was experimentally reproduced in vivo in immature males and mature females. Discontinuous yellow/red mosaicism was observed in body coloration of gynandromorphic dragonflies, suggesting a cell-autonomous regulation over the redox states of the ommochrome pigments. Our finding extends the mechanical repertoire of pigment-based body color change in animals, and highlights an impressively simple molecular mechanism that regulates an ecologically important color trait.

  12. Redox alters yellow dragonflies into red

    PubMed Central

    Futahashi, Ryo; Kurita, Ryoji; Mano, Hiroaki; Fukatsu, Takema

    2012-01-01

    Body color change associated with sexual maturation—so-called nuptial coloration—is commonly found in diverse vertebrates and invertebrates, and plays important roles for their reproductive success. In some dragonflies, whereas females and young males are yellowish in color, aged males turn vivid red upon sexual maturation. The male-specific coloration plays pivotal roles in, for example, mating and territoriality, but molecular basis of the sex-related transition in body coloration of the dragonflies has been poorly understood. Here we demonstrate that yellow/red color changes in the dragonflies are regulated by redox states of epidermal ommochrome pigments. Ratios of reduced-form pigments to oxidized-form pigments were significantly higher in red mature males than yellow females and immature males. The ommochrome pigments extracted from the dragonflies changed color according to redox conditions in vitro: from red to yellow in the presence of oxidant and from yellow to red in the presence of reductant. By injecting the reductant solution into live insects, the yellow-to-red color change was experimentally reproduced in vivo in immature males and mature females. Discontinuous yellow/red mosaicism was observed in body coloration of gynandromorphic dragonflies, suggesting a cell-autonomous regulation over the redox states of the ommochrome pigments. Our finding extends the mechanical repertoire of pigment-based body color change in animals, and highlights an impressively simple molecular mechanism that regulates an ecologically important color trait. PMID:22778425

  13. 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.

  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. Changes in the redox potential of the rabbit cerebral cortex accompanying episodes of ECoG arousal during slow-wave sleep.

    PubMed

    Shvets-Ténéta-Gurii, T B; Troshin, G I; Dubinin, A G

    2008-01-01

    The redox potential (E) is a useful measure of the intensity and quality of shifts in energy metabolism. Brain E depends on the ratio of the rates of processes occurred in two compartments of energy metabolism - the glycolysis compartment, in which glucose is split without oxygen, and the oxidative metabolism compartment. The present report describes recording of local changes in E using platinum electrodes implanted into several points in the cortex. In these conditions, decreases in E correspond to local increases in the rates of glycolytic processes in the tissue surrounding the electrode and are related to mitochondrial processes, while increases in E correspond to local acceleration of processes in oxidative metabolism in the tissues around the electrode. Our previous studies in rats showed that during episodes of slow-wave sleep (SWS), metabolically active points of the rat cerebral cortex show significant decreases in E, and it was suggested that these are associated with increases in the rate of glycolysis. At the same time, E showed characteristic oscillations lasting 20-40 sec with amplitudes of tens of millivolts. The experiments reported here demonstrated that slow oscillations in E developing during SWS are created by regular episodes of ECoG arousal occurring during SWS, accompanied by startling of the animal, decreases in E, and inhibition of respiration. We suggest that a homeostasis system operates during SWS to maintain the animal's level of consciousness at a particular level and that this, like any system with feedback, operates in an oscillatory fashion. The role of glycolysis in supplying energy to the cerebral cortex to support the elevated level of consciousness increases.

  16. Rare Earth Elements of the Permian-Triassic Conodonts from Shelf Basin to Shallow Platform: Implications for Oceanic Redox Conditions immediately After the End-Permian Mass Extinction

    NASA Astrophysics Data System (ADS)

    Li, Y.; Zhao, L.; Chen, Z.; Chen, J.; Chen, Y.

    2013-12-01

    Rare-earth elements (REEs) can provide information regarding the influence of weathering fluxes and hydrothermal inputs on seawater chemistry as well as processes that fractionate REEs between solid and aqueous phases. Of these, cerium (Ce) distributions may provide information about variations in dissolved oxygen in seawater, and thus assess the redox conditions. The short residence times of REEs in seawater (~300-1,000 yr) can result in unique REE signatures in local watermasses. REE patterns preserved in biogenic apatite such as conodonts are ideal proxies for revealing original seawater chemistry. Here, we measured the REE content of in-situ, single albid crowns using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) in combination with an ArF (λ=193 nm) excimer laser (Lambda Physiks GeoLas 2005) and quadrupole ICP-MS (Agilent 7500a). LA-ICP-MS is ideally suited for analyzing conodonts due to its ability to measure compositional variation within single conodont elements. It has the capability to determine, with high spatial resolution, continuous compositional depth profiles through the concentric layered structure of component histologies. To evaluate paleoceanographic conditions immediately after the Permian-Triassic (P-Tr) mass extinction in various depositional settings, we sampled a nearly contemporaneous strata unit, the P-Tr boundary bed, just above the extinction horizon from six sections in South China. They represent various depositional settings from shelf basin (Chaohu and Daxiakou sections), lower part of ramp (Meishan section), normal shallow platform (Yangou section), and platform microbialite (Chongyang and Xiushui sections). The sampled unit is constrained by conodonts Hindeodus changxingensis, H. parvus, and H. staeschei Zones in Meishan. REE results obtained from conodont albid crowns show that the seawater in lower ramp and shelf basin settings contains much higher REE concentrations than that in shallow platform. Ce

  17. 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

  18. Evolutionary development of redox regulation in chloroplasts.

    PubMed

    Balsera, Monica; Uberegui, Estefania; Schürmann, Peter; Buchanan, Bob B

    2014-09-20

    The post-translational modification of thiol groups stands out as a key strategy that cells employ for metabolic regulation and adaptation to changing environmental conditions. Nowhere is this more evident than in chloroplasts-the O2-evolving photosynthetic organelles of plant cells that are fitted with multiple redox systems, including the thioredoxin (Trx) family of oxidoreductases functional in the reversible modification of regulatory thiols of proteins in all types of cells. The best understood member of this family in chloroplasts is the ferredoxin-linked thioredoxin system (FTS) by which proteins are modified via light-dependent disulfide/dithiol (S-S/2SH) transitions. Discovered in the reductive activation of enzymes of the Calvin-Benson cycle in illuminated chloroplast preparations, recent studies have extended the role of the FTS far beyond its original boundaries to include a spectrum of cellular processes. Together with the NADP-linked thioredoxin reductase C-type (NTRC) and glutathione/glutaredoxin systems, the FTS also plays a central role in the response of chloroplasts to different types of stress. The comparisons of redox regulatory networks functional in chloroplasts of land plants with those of cyanobacteria-prokaryotes considered to be the ancestors of chloroplasts-and different types of algae summarized in this review have provided new insight into the evolutionary development of redox regulation, starting with the simplest O2-evolving organisms. The evolutionary appearance, mode of action, and specificity of the redox regulatory systems functional in chloroplasts, as well as the types of redox modification operating under diverse environmental conditions stand out as areas for future study.

  19. Solution structure of horse heart ferricytochrome c and detection of redox-related structural changes by high-resolution 1H NMR.

    PubMed

    Qi, P X; Beckman, R A; Wand, A J

    1996-09-24

    A model for the solution structure of horse heart ferricytochrome c has been determined by nuclear magnetic resonance spectroscopy combined with hybrid distance geometry-simulated annealing calculations. Forty-four highly refined structures were obtained using a total of 1671 distance constraints based on the observed magnitude of nuclear Overhauser effects and 58 torsion angle restrains based on the magnitude of determined J-coupling constants. The model incorporates six long-lived water molecules detected by pseudo-two-dimensional NOESY-TOCSY spectra. The all-residue root mean square deviation about the average structure is 0.33 +/- 0.04 A for the backbone N, C alpha, and C' atoms and 0.83 +/- 0.05 A for all heavy atoms. The overall topology of the model for solution structure is very similar to that seen in previously reported models for crystal structures of homologous c-type cytochromes though there are a number of significant differences in detailed aspects of the structure. Two of the three main helices display localized irregularities in helical hydrogen bonding resulting in bifurcation of main chain hydrogen bond acceptor carbonyls. The N- and C-terminal helices are tightly packed and display several interhelical interactions not seen in reported crystal models. To provide an independent measure of the accuracy of the model for the oxidized protein, the expected pseudocontact shifts induced by the spin 1/2 iron were compared to the observed redox-dependent chemical shift changes. These comparisons confirm the general accuracy of the model for the oxidized protein and its observed differences with the structure of the reduced protein. The structures of the reduced and oxidized states of the protein provide a template to explain a range of physical and biological data spanning the redox properties, folding, molecular recognition, and stability of the cytochrome c molecule. For example, a redox-dependent reorganization of surface residues at the heme edge can

  20. Optical redox ratio using endogenous fluorescence to assess the metabolic changes associated with treatment response of bioconjugated gold nanoparticles in streptozotocin-induced diabetic rats

    NASA Astrophysics Data System (ADS)

    Adavallan, K.; Gurushankar, K.; Nazeer, Shaiju S.; Gohulkumar, M.; Jayasree, Ramapurath S.; Krishnakumar, N.

    2017-06-01

    Fluorescence spectroscopic techniques have the potential to assess the metabolic changes during disease development and evaluation of treatment response in a non-invasive and label-free manner. The present study aims to evaluate the effect of mulberry-mediated gold nanoparticles (MAuNPs) in comparison with mulberry leaf extract alone (MLE) for monitoring endogenous fluorophores and to quantify the metabolic changes associated with mitochondrial redox states during streptozotocin-induced diabetic liver tissues using fluorescence spectroscopy. Two mitochondrial metabolic coenzymes, reduced nicotinamide dinucleotide (NADH) and oxidized flavin adenine dinucleotide (FAD) are autofluorescent and are important optical biomarkers to estimate the redox state of a cell. Significant differences in the autofluorescence spectral signatures between the control and the experimental diabetic animals have been noticed under the excitation wavelength at 320 nm with emission ranging from 350-550 nm. A direct correlation between the progression of diabetes and the levels of collagen and optical redox ratio was observed. The results revealed that a significant increase in the emission of collagen in diabetic liver tissues as compared with the control liver tissues. Moreover, there was a significant decrease in the optical redox ratio (FAD/(FAD  +  NADH)) observed in diabetic control liver tissues, which indicates an increased oxidative stress compared to the liver tissues of control rats. Further, the extent of increased oxidative stress was confirmed by the reduced levels of reduced glutathione (GSH) in diabetic liver tissues. On a comparative basis, treatment with MAuNPs was found to be more effective than MLE for reducing the progression of diabetes and improving the optical redox ratio to a near normal range in streptozotocin-induced diabetic liver tissues. Furthermore, principal component analysis followed by linear discriminant analysis (PC-LDA) has been used to

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

    USGS Publications Warehouse

    Catallo, W. James

    1999-01-01

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

  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.

  3. Redox control of plant growth and development.

    PubMed

    Kocsy, Gábor; Tari, Irma; Vanková, Radomíra; Zechmann, Bernd; Gulyás, Zsolt; Poór, Péter; Galiba, Gábor

    2013-10-01

    Redox changes determined by genetic and environmental factors display well-organized interactions in the control of plant growth and development. Diurnal and seasonal changes in the environmental conditions are important for the normal course of these physiological processes and, similarly to their mild irregular alterations, for stress adaptation. However, fast or large-scale environmental changes may lead to damage or death of sensitive plants. The spatial and temporal redox changes influence growth and development due to the reprogramming of metabolism. In this process reactive oxygen and nitrogen species and antioxidants are involved as components of signalling networks. The control of growth, development and flowering by reactive oxygen and nitrogen species and antioxidants in interaction with hormones at organ, tissue, cellular and subcellular level will be discussed in the present review. Unsolved problems of the field, among others the need for identification of new components and interactions in the redox regulatory network at various organization levels using systems biology approaches will be also indicated.

  4. Iron and sulfur isotope constraints on redox conditions associated with the 3.2 Ga barite deposits of the Mapepe Formation (Barberton Greenstone Belt, South Africa)

    NASA Astrophysics Data System (ADS)

    Busigny, Vincent; Marin-Carbonne, Johanna; Muller, Elodie; Cartigny, Pierre; Rollion-Bard, Claire; Assayag, Nelly; Philippot, Pascal

    2017-08-01

    The occurrence of Early Archean barite deposits is intriguing since this type of sediment requires high availability of dissolved sulfate (SO42-), the oxidized form of sulfur, although most authors argued that the Archean eon was dominated by reducing conditions, with low oceanic sulfate concentration (<10 μM) relative to present day levels of 28,000 μM. In order to better assess the redox state of the paleo-atmosphere and -oceans, we examined Fe and S isotope compositions in a sedimentary sequence from the 3.2 Ga-old Mendon and Mapepe formations (Kaapvaal craton, South Africa), recovered from the drill-core BBDP2 of the Barberton Barite Drilling Project. Major elements were also analyzed to constrain the respective imprints of detrital vs metasomatic processes, in particular using Al, Ti and K interrelations. Bulk rock Fe isotope compositions are linked to mineralogy, with δ56Fe values varying between -2.04‰ in Fe sulfide-dominated barite beds, to +2.14‰ in Fe oxide-bearing cherts. δ34S values of sulfides vary between -10.84 and +3.56‰, with Δ33S in a range comprised between -0.35 and +2.55‰, thus supporting an O2-depleted atmosphere (<10-5 PAL). Iron isotope variations together with major element correlations show that, although the sediments experienced a pervasive stage of hydrothermal alteration, the rocks preserved a primary/authigenic signature predating subsequent hydrothermal stage. Highly positive δ56Fe values recorded in primary Fe-oxides from ferruginous cherts support partial Fe oxidation in a reducing oceanic environment (O2 < 10-4 μM), but are incompatible with a model of complete oxidation at the redox boundary of a stratified water column. Iron oxide precipitation under low O2 levels was likely mediated by anoxygenic photosynthesis, and/or abiotic photo-oxidation processes. Our results are consistent with global anoxic conditions in the 3.2 Ga-old sediments, implying that the barite deposits were most likely sourced by atmospheric

  5. Redox crisis underlies conditional light-dark lethality in cyanobacterial mutants that lack the circadian regulator, RpaA.

    PubMed

    Diamond, Spencer; Rubin, Benjamin E; Shultzaberger, Ryan K; Chen, You; Barber, Chase D; Golden, Susan S

    2017-01-24

    Cyanobacteria evolved a robust circadian clock, which has a profound influence on fitness and metabolism under daily light-dark (LD) cycles. In the model cyanobacterium Synechococcus elongatus PCC 7942, a functional clock is not required for diurnal growth, but mutants defective for the response regulator that mediates transcriptional rhythms in the wild-type, regulator of phycobilisome association A (RpaA), cannot be cultured under LD conditions. We found that rpaA-null mutants are inviable after several hours in the dark and compared the metabolomes of wild-type and rpaA-null strains to identify the source of lethality. Here, we show that the wild-type metabolome is very stable throughout the night, and this stability is lost in the absence of RpaA. Additionally, an rpaA mutant accumulates excessive reactive oxygen species (ROS) during the day and is unable to clear it during the night. The rpaA-null metabolome indicates that these cells are reductant-starved in the dark, likely because enzymes of the primary nighttime NADPH-producing pathway are direct targets of RpaA. Because NADPH is required for processes that detoxify ROS, conditional LD lethality likely results from inability of the mutant to activate reductant-requiring pathways that detoxify ROS when photosynthesis is not active. We identified second-site mutations and growth conditions that suppress LD lethality in the mutant background that support these conclusions. These results provide a mechanistic explanation as to why rpaA-null mutants die in the dark, further connect the clock to metabolism under diurnal growth, and indicate that RpaA likely has important unidentified functions during the day.

  6. 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.

  7. 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

  8. Trial development of unit response changes during conditioning in cats.

    PubMed

    Packham, S C; O'Brien, J H

    1976-10-01

    Single-cell and evoked potential (EP) activity in the postcruciate cortex of acutely prepared cats was recorded during a classical conditioning procedure. The temporal pattern of response (PSH) of the neuron was separated into three components, and the trial development of learning changes for these components was examined individually. Changes over trials in the similarity of the EP waveform and the unit PSH were also examined. The unit response components showed changes in response at different trial periods; these changes could not be accounted for by changes at lower brain levels that projected to the cortex. This suggests that local learning changes were taking places in the cortex. The EP-PSH similarity decreased for neurons showing the largest changes in response during conditioning. Since the EP reflects the response of the whole population of neurons and a majority did not show learning changes, this could account for the observed decrease.

  9. 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.

  10. A Novel Redox State Heme a Marker in Cytochrome c Oxidase Revealed by Raman Spectroscopy

    NASA Astrophysics Data System (ADS)

    Piccoli, C.; Perna, G.; Scrima, R.; Cela, O.; Rinaldi, R.; Boffoli, D.; Capozzi, V.; Capitanio, N.

    2005-01-01

    This study was aimed to characterize by Raman spectroscopy (excitation line 633 nm) different redox states of the mitochondrial cytochrome c oxidase. The results obtained from a systematic analysis carried out on the mitochondrial enzyme prepared under redox conditions, differently affecting the valence state of the metal prosthetic groups, and a comparison with homologous bacterial heme-copper oxidases, cytochrome c and pyridine hemo-chrome extract revealed a novel redox state marker specifically linked to the redox transition of heme a, peaking at 1645 cm-1, and tentatively assigned to the C=C and/or C=N streching mode of the imidazole ring of a proxymal histidine ligand. The possible involvment of this redox-linked conformational change in the catalytic activity of cytochrome oxidase is discussed.

  11. 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.

  12. Degradation of Redox-Sensitive Proteins including Peroxiredoxins and DJ-1 is Promoted by Oxidation-induced Conformational Changes and Ubiquitination

    PubMed Central

    Song, In-Kang; Lee, Jae-Jin; Cho, Jin-Hwan; Jeong, Jihye; Shin, Dong-Hae; Lee, Kong-Joo

    2016-01-01

    Reactive oxygen species (ROS) are key molecules regulating various cellular processes. However, what the cellular targets of ROS are and how their functions are regulated is unclear. This study explored the cellular proteomic changes in response to oxidative stress using H2O2 in dose- and recovery time-dependent ways. We found discernible changes in 76 proteins appearing as 103 spots on 2D-PAGE. Of these, Prxs, DJ-1, UCH-L3 and Rla0 are readily oxidized in response to mild H2O2 stress, and then degraded and active proteins are newly synthesized during recovery. In studies designed to understand the degradation process, multiple cellular modifications of redox-sensitive proteins were identified by peptide sequencing with nanoUPLC-ESI-q-TOF tandem mass spectrometry and the oxidative structural changes of Prx2 explored employing hydrogen/deuterium exchange-mass spectrometry (HDX-MS). We found that hydrogen/deuterium exchange rate increased in C-terminal region of oxidized Prx2, suggesting the exposure of this region to solvent under oxidation. We also found that Lys191 residue in this exposed C-terminal region of oxidized Prx2 is polyubiquitinated and the ubiquitinated Prx2 is readily degraded in proteasome and autophagy. These findings suggest that oxidation-induced ubiquitination and degradation can be a quality control mechanism of oxidized redox-sensitive proteins including Prxs and DJ-1. PMID:27703196

  13. Degradation of Redox-Sensitive Proteins including Peroxiredoxins and DJ-1 is Promoted by Oxidation-induced Conformational Changes and Ubiquitination

    NASA Astrophysics Data System (ADS)

    Song, In-Kang; Lee, Jae-Jin; Cho, Jin-Hwan; Jeong, Jihye; Shin, Dong-Hae; Lee, Kong-Joo

    2016-10-01

    Reactive oxygen species (ROS) are key molecules regulating various cellular processes. However, what the cellular targets of ROS are and how their functions are regulated is unclear. This study explored the cellular proteomic changes in response to oxidative stress using H2O2 in dose- and recovery time-dependent ways. We found discernible changes in 76 proteins appearing as 103 spots on 2D-PAGE. Of these, Prxs, DJ-1, UCH-L3 and Rla0 are readily oxidized in response to mild H2O2 stress, and then degraded and active proteins are newly synthesized during recovery. In studies designed to understand the degradation process, multiple cellular modifications of redox-sensitive proteins were identified by peptide sequencing with nanoUPLC-ESI-q-TOF tandem mass spectrometry and the oxidative structural changes of Prx2 explored employing hydrogen/deuterium exchange-mass spectrometry (HDX-MS). We found that hydrogen/deuterium exchange rate increased in C-terminal region of oxidized Prx2, suggesting the exposure of this region to solvent under oxidation. We also found that Lys191 residue in this exposed C-terminal region of oxidized Prx2 is polyubiquitinated and the ubiquitinated Prx2 is readily degraded in proteasome and autophagy. These findings suggest that oxidation-induced ubiquitination and degradation can be a quality control mechanism of oxidized redox-sensitive proteins including Prxs and DJ-1.

  14. 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.

  15. Thymoquinone: An edible redox-active quinone for the pharmacotherapy of neurodegenerative conditions and glial brain tumors. A short review.

    PubMed

    Elmaci, Ilhan; Altinoz, Meric A

    2016-10-01

    There exist few efficient agents in the neurological and neurosurgical armamentarium for treatment of neurotrauma, refractory seizures and high grade glial tumors. Pathophysiological conditions of diverse neural injuries have converging common pathways including oxidative stress and apoptosis. Targeted therapies have been throughly investigated, but limited success has been achieved until now. Phytochemical drugs may provide easily achievable and cheap adjunctive sources. Thymoquinone is an edible quinone obtained from Nigella sativa seed oil and exerts powerful antiinflammatory, antioxidant and antitumor activities in experimental models. Recently emerging studies conducted with animal models suggest that thymoquinone - bearing a very simple molecular structure - significantly crosses the blood brain barrier and exerts neuromodulatory activities. Indeed, in animal studies, the following actions of thymoquinone were demonstrated: 1-Protection against ischemic brain damage. 2-Reduction of epileptic seizures and associated cerebral oxidative injury. 3-Reduction of morphine tolerance and associated oxidative brain damage. 4-Anxiolytic effects and reduction of immobility stress-associated cerebral oxidative injury. 5-Reduction of diabetes-induced cerebral oxidative stress, 6-Reduction of cerebral oxidative injuries induced by noxious exposures including toluene, lead and ionizing radiation. Substantial in vitro data suggest that thymoquinone may be beneficial in treatment of glial tumors. However, there is no clinical study investigating its antitumor effects. In fact, thymoquinone suppresses growth and invasion, and induces apoptosis of glial tumor cells via degrading tubulins and inhibiting 20S proteasome, telomerase, autophagy, FAK and metalloproteinases. A simple and easily available agent may be a promising adjunctive treatment option in neurological and neurosurgical practice.

  16. Analysis issues due to mapped conditions changing over time

    Treesearch

    Paul. Van Deusen

    2015-01-01

    Plot mapping is one of the innovations that were implemented when FIA moved to the annual forest inventory system. Mapped plots can improve the precision of estimates if the mapped conditions are carefully chosen and used judiciously. However, after plots are remeasured multiple times, it can be difficult to properly track changes in conditions and incorporate this...

  17. ChemCam Observations of Manganese in Rock Targets (Sols 778-1384): An Indicator of Redox and Habitability Conditions

    NASA Astrophysics Data System (ADS)

    Lanza, N.; Lamm, S. N.; Frydenvang, J.; Wiens, R. C.; Kirk, M. F.

    2016-12-01

    Recent results from the Curiosity Mars rover have identified enrichments of manganese in rock targets throughout Gale crater. Some of these are inferred to be Mn-oxide minerals. High concentrations of Mn on Earth are typically found as secondary mineral deposits, requiring abundant liquid water and highly oxidizing conditions to form. The earliest terrestrial manganese deposits are associated with the rise of free oxygen in the atmosphere 2.5 Gya. Thus the discovery of Mn-oxides on Mars raises the possibility that the martian atmosphere once contained more oxygen. Here we assess Mn abundance in all rocks analyzed by ChemCam along the rover's traverse over sols 778-1384. During this time 477 rocks were analyzed with a total of 3296 sampling locations. Of these, 125 ( 4%) on 61 rocks (12%) were found to contain abundances of Mn 2-sigma over the mean, corresponding to 1.3 wt% MnO. This is similar to results for rock targets from the first 777 sols of the traverse. Relationships between Mn and major and minor elements were also assessed for all rock targets. Higher Mn is associated with lower Si and higher Fe, Na, Al, and Li. Elevated Mn was found in a range of rock types, including conglomerates, fine-grained sandstones, and veins. LIBS data were examined for potential shot-to-shot trends to determine whether Mn is associated with surface features such as coatings or layers; no strong trends were identified. Remote Micro-Imager (RMI) images of rock targets were analyzed for texture, grain size, and albedo. No specific rock features were correlated with Mn abundance. Of sampling locations with Mn abundances above 2-sigma, over 50% were in the Stimson formation, the youngest geologic unit identified in Gale to date. Our results suggest that Mn in this region may have be concentrated prior to incorporation into sediments, and the observed compositional and spatial variations may be the result of differing source regions. Work is ongoing to better understand the nature of

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

    SciTech Connect

    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 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 conclusion, the

  19. 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

  20. Dislocation of Type I Membrane Proteins from the ER to the Cytosol Is Sensitive to Changes in Redox Potential

    PubMed Central

    Tortorella, Domenico; Story, Craig M.; Huppa, Johannes B.; Wiertz, Emmanuel J.H.J.; Jones, Thomas R.; Ploegh, Hidde L.

    1998-01-01

    The human cytomegalovirus (HCMV) gene products US2 and US11 dislocate major histocompatibility class I heavy chains from the ER and target them for proteasomal degradation in the cytosol. The dislocation reaction is inhibited by agents that affect intracellular redox potential and/or free thiol status, such as diamide and N-ethylmaleimide. Subcellular fractionation experiments indicate that this inhibition occurs at the stage of discharge from the ER into the cytosol. The T cell receptor α (TCR α) chain is also degraded by a similar set of reactions, yet in a manner independent of virally encoded gene products. Diamide and N-ethylmaleimide likewise inhibit the dislocation of the full-length TCR α chain from the ER, as well as a truncated, mutant version of TCR α chain that lacks cysteine residues. Cytosolic destruction of glycosylated, ER-resident type I membrane proteins, therefore, requires maintenance of a proper redox potential for the initial step of removal of the substrate from the ER environment. PMID:9679137

  1. Thiol-Based Redox Switches

    PubMed Central

    Groitl, Bastian; Jakob, Ursula

    2014-01-01

    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. PMID:24657586

  2. 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

  3. 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.

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

    PubMed

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

    2017-07-28

    The nicotinamide adenine dinucleotide (NAD(+))/reduced NAD(+) (NADH) and NADP(+)/reduced NADP(+) (NADPH) redox couples are essential for maintaining cellular redox homeostasis and for modulating numerous biological events, including cellular metabolism. Deficiency or imbalance of these two redox couples has been associated with many pathological disorders. Recent Advances: Newly identified biosynthetic enzymes and newly developed genetically encoded biosensors enable us to understand better how cells maintain compartmentalized NAD(H) and NADP(H) pools. The concept of redox stress (oxidative and reductive stress) reflected by changes in NAD(H)/NADP(H) has increasingly gained attention. The emerging roles of NAD(+)-consuming proteins in regulating cellular redox and metabolic homeostasis are active research topics. The biosynthesis and distribution of cellular NAD(H) and NADP(H) are highly compartmentalized. It is critical to understand how cells maintain the steady levels of these redox couple pools to ensure their normal functions and simultaneously avoid inducing redox stress. In addition, it is essential to understand how NAD(H)- and NADP(H)-utilizing enzymes interact with other signaling pathways, such as those regulated by hypoxia-inducible factor, to maintain cellular redox homeostasis and energy metabolism. Additional studies are needed to investigate the inter-relationships among compartmentalized NAD(H)/NADP(H) pools and how these two dinucleotide redox couples collaboratively regulate cellular redox states and cellular metabolism under normal and pathological conditions. Furthermore, recent studies suggest the utility of using pharmacological interventions or nutrient-based bioactive NAD(+) precursors as therapeutic interventions for metabolic diseases. Thus, a better understanding of the cellular functions of NAD(H) and NADP(H) may facilitate efforts to address a host of pathological disorders effectively. Antioxid. Redox Signal. 00, 000-000.

  5. Ascorbate oxidase-dependent changes in the redox state of the apoplast modulate gene transcript accumulation leading to modified hormone signaling and orchestration of defense processes in tobacco.

    PubMed

    Pignocchi, Cristina; Kiddle, Guy; Hernández, Iker; Foster, Simon J; Asensi, Amparo; Taybi, Tahar; Barnes, Jeremy; Foyer, Christine H

    2006-06-01

    The role of the redox state of the apoplast in hormone responses, signaling cascades, and gene expression was studied in transgenic tobacco (Nicotiana tabacum) plants with modified cell wall-localized ascorbate oxidase (AO). High AO activity specifically decreased the ascorbic acid (AA) content of the apoplast and altered plant growth responses triggered by hormones. Auxin stimulated shoot growth only when the apoplastic AA pool was reduced in wild-type or AO antisense lines. Oxidation of apoplastic AA in AO sense lines was associated with loss of the auxin response, higher mitogen-activated protein kinase activities, and susceptibility to a virulent strain of the pathogen Pseudomonas syringae. The total leaf glutathione pool, the ratio of reduced glutathione to glutathione disulfide, and glutathione reductase activities were similar in the leaves of all lines. However, AO sense leaves exhibited significantly lower dehydroascorbate reductase and ascorbate peroxidase activities than wild-type and antisense leaves. The abundance of mRNAs encoding antioxidant enzymes was similar in all lines. However, the day/night rhythms in the abundance of transcripts encoding the three catalase isoforms were changed in response to the AA content of the apoplast. Other transcripts influenced by AO included photorespiratory genes and a plasma membrane Ca(2+) channel-associated gene. We conclude that the redox state of the apoplast modulates plant growth and defense responses by regulating signal transduction cascades and gene expression patterns. Hence, AO activity, which modulates the redox state of the apoplastic AA pool, strongly influences the responses of plant cells to external and internal stimuli.

  6. Enhanced hypothalamic glucose sensing in obesity: alteration of redox signaling.

    PubMed

    Colombani, Anne-Laure; Carneiro, Lionel; Benani, Alexandre; Galinier, Anne; Jaillard, Tristan; Duparc, Thibaut; Offer, Géraldine; Lorsignol, Anne; Magnan, Christophe; Casteilla, Louis; Pénicaud, Luc; Leloup, Corinne

    2009-10-01

    Recent data demonstrated that glucose sensing in different tissues is initiated by an intracellular redox signaling pathway in physiological conditions. However, the relevance of such a mechanism in metabolic disease is not known. The aim of the present study was to determine whether brain glucose hypersensitivity present in obese Zücker rats is related to an alteration in redox signaling. Brain glucose sensing alteration was investigated in vivo through the evaluation of electrical activity in arcuate nucleus, changes in reactive oxygen species levels, and hypothalamic glucose-induced insulin secretion. In basal conditions, modifications of redox state and mitochondrial functions were assessed through oxidized glutathione, glutathione peroxidase, manganese superoxide dismutase, aconitase activities, and mitochondrial respiration. Hypothalamic hypersensitivity to glucose was characterized by enhanced electrical activity of the arcuate nucleus and increased insulin secretion at a low glucose concentration, which does not produce such an effect in normal rats. It was associated with 1) increased reactive oxygen species levels in response to this low glucose load, 2) constitutive oxidized environment coupled with lower antioxidant enzyme activity at both the cellular and mitochondrial level, and 3) overexpression of several mitochondrial subunits of the respiratory chain coupled with a global dysfunction in mitochondrial activity. Moreover, pharmacological restoration of the glutathione hypothalamic redox state by reduced glutathione infusion in the third ventricle fully reversed the cerebral hypersensitivity to glucose. The data demonstrated that obese Zücker rats' impaired hypothalamic regulation in terms of glucose sensing is linked to an abnormal redox signaling, which originates from mitochondria dysfunction.

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

    PubMed Central

    Yoshida, Keisuke; Hisabori, Toru

    2016-01-01

    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

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

    PubMed

    Yoshida, Keisuke; Hisabori, Toru

    2016-07-05

    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.

  9. 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.

  10. Changes in phosphorylation of adenosine phosphate and redox state of nicotinamide-adenine dinucleotide (phosphate) in Geobacter sulfurreducens in response to electron acceptor and anode potential variation.

    PubMed

    Rose, Nicholas D; Regan, John M

    2015-12-01

    Geobacter sulfurreducens is one of the dominant bacterial species found in biofilms growing on anodes in bioelectrochemical systems. The intracellular concentrations of reduced and oxidized forms of nicotinamide-adenine dinucleotide (NADH and NAD(+), respectively) and nicotinamide-adenine dinucleotide phosphate (NADPH and NADP(+), respectively) as well as adenosine triphosphate (ATP), adenosine diphosphate (ADP), and adenosine monophosphate (AMP) were measured in G. sulfurreducens using fumarate, Fe(III)-citrate, or anodes poised at different potentials (110, 10, -90, and -190 mV (vs. SHE)) as the electron acceptor. The ratios of CNADH/CNAD+ (0.088±0.022) and CNADPH/CNADP+ (0.268±0.098) were similar under all anode potentials tested and with Fe(III)-citrate (reduced extracellularly). Both ratios significantly increased with fumarate as the electron acceptor (0.331±0.094 for NAD and 1.96±0.37 for NADP). The adenylate energy charge (the fraction of phosphorylation in intracellular adenosine phosphates) was maintained near 0.47 under almost all conditions. Anode-growing biofilms demonstrated a significantly higher molar ratio of ATP/ADP relative to suspended cultures grown on fumarate or Fe(III)-citrate. These results provide evidence that the cellular location of reduction and not the redox potential of the electron acceptor controls the intracellular redox potential in G. sulfurreducens and that biofilm growth alters adenylate phosphorylation.

  11. NMDA Mediated Contextual Conditioning Changes miRNA Expression

    PubMed Central

    Kye, Min Jeong; Zhou, Miou; Steen, Judith A.; Sahin, Mustafa; Kosik, Kenneth S.; Silva, Alcino J.

    2011-01-01

    We measured the expression of 187 miRNAs using quantitative real time PCR in the hippocampal CA1 region of contextually conditioned mice and cultured embryonic rat hippocampal neurons after neuronal stimulation with either NMDA or bicuculline. Many of the changes in miRNA expression after these three types of stimulation were similar. Surprisingly, the expression level of half of the 187 measured miRNAs was changed in response to contextual conditioning in an NMDA receptor-dependent manner. Genes that control miRNA biogenesis and components of the RISC also exhibited activity induced expression changes and are likely to contribute to the widespread changes in the miRNA profile. The widespread changes in miRNA expression are consistent with the finding that genes up-regulated by contextual conditioning have longer 3′ UTRs and more predicted binding sites for miRNAs. Among the miRNAs that changed their expression after contextual conditioning, several inhibit inhibitors of the mTOR pathway. These findings point to a role for miRNAs in learning and memory that includes mTOR-dependent modulation of protein synthesis. PMID:21931811

  12. 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...

  13. 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...

  14. Proteasome inhibitor-adapted myeloma cells are largely independent from proteasome activity and show complex proteomic changes, in particular in redox and energy metabolism

    PubMed Central

    Soriano, G P; Besse, L; Li, N; Kraus, M; Besse, A; Meeuwenoord, N; Bader, J; Everts, B; den Dulk, H; Overkleeft, H S; Florea, B I; Driessen, C

    2016-01-01

    Adaptive resistance of myeloma to proteasome inhibition represents a clinical challenge, whose biology is poorly understood. Proteasome mutations were implicated as underlying mechanism, while an alternative hypothesis based on low activation status of the unfolded protein response was recently suggested (IRE1/XBP1-low model). We generated bortezomib- and carfilzomib-adapted, highly resistant multiple myeloma cell clones (AMO-BTZ, AMO-CFZ), which we analyzed in a combined quantitative and functional proteomic approach. We demonstrate that proteasome inhibitor-adapted myeloma cells tolerate subtotal proteasome inhibition, irrespective of a proteasome mutation, and uniformly show an 'IRE1/XBP1-low' signature. Adaptation of myeloma cells to proteasome inhibitors involved quantitative changes in >600 protein species with similar patterns in AMO-BTZ and AMO-CFZ cells: proteins involved in metabolic regulation, redox homeostasis, and protein folding and destruction were upregulated, while apoptosis and transcription/translation were downregulated. The quantitatively most upregulated protein in AMO-CFZ cells was the multidrug resistance protein (MDR1) protein ABCB1, and carfilzomib resistance could be overcome by MDR1 inhibition. We propose a model where proteasome inhibitor-adapted myeloma cells tolerate subtotal proteasome inhibition owing to metabolic adaptations that favor the generation of reducing equivalents, such as NADPH, which is supported by oxidative glycolysis. Proteasome inhibitor resistance may thus be targeted by manipulating the energy and redox metabolism. PMID:27118406

  15. Proteasome inhibitor-adapted myeloma cells are largely independent from proteasome activity and show complex proteomic changes, in particular in redox and energy metabolism.

    PubMed

    Soriano, G P; Besse, L; Li, N; Kraus, M; Besse, A; Meeuwenoord, N; Bader, J; Everts, B; den Dulk, H; Overkleeft, H S; Florea, B I; Driessen, C

    2016-11-01

    Adaptive resistance of myeloma to proteasome inhibition represents a clinical challenge, whose biology is poorly understood. Proteasome mutations were implicated as underlying mechanism, while an alternative hypothesis based on low activation status of the unfolded protein response was recently suggested (IRE1/XBP1-low model). We generated bortezomib- and carfilzomib-adapted, highly resistant multiple myeloma cell clones (AMO-BTZ, AMO-CFZ), which we analyzed in a combined quantitative and functional proteomic approach. We demonstrate that proteasome inhibitor-adapted myeloma cells tolerate subtotal proteasome inhibition, irrespective of a proteasome mutation, and uniformly show an 'IRE1/XBP1-low' signature. Adaptation of myeloma cells to proteasome inhibitors involved quantitative changes in >600 protein species with similar patterns in AMO-BTZ and AMO-CFZ cells: proteins involved in metabolic regulation, redox homeostasis, and protein folding and destruction were upregulated, while apoptosis and transcription/translation were downregulated. The quantitatively most upregulated protein in AMO-CFZ cells was the multidrug resistance protein (MDR1) protein ABCB1, and carfilzomib resistance could be overcome by MDR1 inhibition. We propose a model where proteasome inhibitor-adapted myeloma cells tolerate subtotal proteasome inhibition owing to metabolic adaptations that favor the generation of reducing equivalents, such as NADPH, which is supported by oxidative glycolysis. Proteasome inhibitor resistance may thus be targeted by manipulating the energy and redox metabolism.

  16. 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.

  17. 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.

  18. 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

  19. 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

  20. Development of redox-sensitive red fluorescent proteins for imaging redox dynamics in cellular compartments.

    PubMed

    Fan, Yichong; Ai, Hui-wang

    2016-04-01

    We recently reported a redox-sensitive red fluorescent protein, rxRFP1, which is one of the first genetically encoded red-fluorescent probes for general redox states in living cells. As individual cellular compartments have different basal redox potentials, we hereby describe a group of rxRFP1 mutants, showing different midpoint redox potentials for detection of redox dynamics in various subcellular domains, such as mitochondria, the cell nucleus, and endoplasmic reticulum (ER). When these redox probes were expressed and subcellularly localized in human embryonic kidney (HEK) 293 T cells, they responded to membrane-permeable oxidants and reductants. In addition, a mitochondrially localized rxRFP1 mutant, Mito-rxRFP1.1, was used to detect mitochondrial oxidative stress induced by doxorubicin-a widely used cancer chemotherapy drug. Our work has expanded the fluorescent protein toolkit with new research tools for studying compartmentalized redox dynamics and oxidative stress under various pathophysiological conditions.

  1. Effects of morin-5'-sulfonic acid sodium salt (NaMSA) on cyclophosphamide-induced changes in oxido-redox state in rat liver and kidney.

    PubMed

    Merwid-Ląd, A; Trocha, M; Chlebda, E; Sozański, T; Magdalan, J; Ksiądzyna, D; Kopacz, M; Kuźniar, A; Nowak, D; Pieśniewska, M; Fereniec-Gołębiewska, L; Kwiatkowska, J; Szeląg, A

    2012-08-01

    Cyclophosphamide (CPX) is an anticancer drug with immunosuppressive properties. Its adverse effects are partly connected to the induction of oxidative stress. Some studies indicate that water-soluble derivative of morin-morin-5'-sulfonic acid sodium salt (NaMSA) exhibits strong antioxidant activity. The aim of present study was to evaluate the effect of NaMSA on CPX-induced changes in oxido-redox state in rat. Experiment was carried out on Wistar rats divided in three experimental groups (N = 12) receiving: 0.9% saline, CPX (15 mg/kg) or CPX (15 mg/kg) + NaMSA (100 mg/kg), respectively, and were given intragastrically for 10 days. Malondialdehyde (MDA) and glutathione (GSH) concentrations and superoxide dismutase (SOD) activity were determined in liver and kidneys. Catalase (CAT) activity was assessed only in liver. Treatment with CPX resulted in significant decrease in MDA level in both tissues, which was completely reversed by NaMSA treatment only in liver. In comparison to the control group significant decrease in SOD activity were observed in both tissues of CPX receiving group. In kidneys this parameter was fully restored by NaMSA administration. CPX evoked significant decrease in GSH concentration in kidneys, which was completely reversed by NaMSA treatment. No significant changes were seen in GSH levels and CAT activity between all groups in liver. Results of our study suggest that CPX may exert significant impact on oxido-redox state in both organs. NaMSA fully reversed the CPX-induced changes, especially MDA level in liver, SOD activity and GSH concentration in kidneys and it may be done by enhancement of activity/concentration of endogenous antioxidants.

  2. 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

  3. 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

    2015-08-03

    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).

  4. Proteotoxic stress and ageing triggers the loss of redox homeostasis across cellular compartments

    PubMed Central

    Kirstein, Janine; Morito, Daisuke; Kakihana, Taichi; Sugihara, Munechika; Minnen, Anita; Hipp, Mark S; Nussbaum-Krammer, Carmen; Kasturi, Prasad; Hartl, F Ulrich; Nagata, Kazuhiro; Morimoto, Richard I

    2015-01-01

    The cellular proteostasis network integrates the protein folding and clearance machineries in multiple sub-cellular compartments of the eukaryotic cell. The endoplasmic reticulum (ER) is the site of synthesis and folding of membrane and secretory proteins. A distinctive feature of the ER is its tightly controlled redox homeostasis necessary for the formation of inter- and intra-molecular disulphide bonds. Employing genetically encoded in vivo sensors reporting on the redox state in an organelle-specific manner, we show in the nematode Caenorhabditis elegans that the redox state of the ER is subject to profound changes during worm lifetime. In young animals, the ER is oxidizing and this shifts towards reducing conditions during ageing, whereas in the cytosol the redox state becomes more oxidizing with age. Likewise, the redox state in the cytosol and the ER change in an opposing manner in response to proteotoxic challenges in C. elegans and in HeLa cells revealing conservation of redox homeostasis. Moreover, we show that organelle redox homeostasis is regulated across tissues within C. elegans providing a new measure for organismal fitness. PMID:26228940

  5. Reproductive responses of an apex predator to changing climatic conditions

    Treesearch

    Susan Rebecca. Salafsky

    2015-01-01

    Apex predators are ideal subjects for evaluating the effects of changing climatic conditions on the productivity of forested landscapes, because the quality of their breeding habitat depends primarily on the availability of resources at lower trophic levels. Identifying the environmental factors that influence the reproductive output of apex predators can, therefore,...

  6. 49 CFR 1542.107 - Changed conditions affecting security.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 49 Transportation 9 2013-10-01 2013-10-01 false Changed conditions affecting security. 1542.107 Section 1542.107 Transportation Other Regulations Relating to Transportation (Continued) TRANSPORTATION SECURITY ADMINISTRATION, DEPARTMENT OF HOMELAND SECURITY CIVIL AVIATION SECURITY AIRPORT SECURITY...

  7. 49 CFR 1542.107 - Changed conditions affecting security.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 49 Transportation 9 2011-10-01 2011-10-01 false Changed conditions affecting security. 1542.107 Section 1542.107 Transportation Other Regulations Relating to Transportation (Continued) TRANSPORTATION SECURITY ADMINISTRATION, DEPARTMENT OF HOMELAND SECURITY CIVIL AVIATION SECURITY AIRPORT SECURITY...

  8. 49 CFR 1542.107 - Changed conditions affecting security.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 49 Transportation 9 2012-10-01 2012-10-01 false Changed conditions affecting security. 1542.107 Section 1542.107 Transportation Other Regulations Relating to Transportation (Continued) TRANSPORTATION SECURITY ADMINISTRATION, DEPARTMENT OF HOMELAND SECURITY CIVIL AVIATION SECURITY AIRPORT SECURITY...

  9. 49 CFR 1542.107 - Changed conditions affecting security.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 49 Transportation 9 2014-10-01 2014-10-01 false Changed conditions affecting security. 1542.107 Section 1542.107 Transportation Other Regulations Relating to Transportation (Continued) TRANSPORTATION SECURITY ADMINISTRATION, DEPARTMENT OF HOMELAND SECURITY CIVIL AVIATION SECURITY AIRPORT SECURITY...

  10. 23 CFR 635.109 - Standardized changed condition clauses.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... anticipated, customary, or inherent to the construction industry) and the contractor believes that additional... OPERATIONS CONSTRUCTION AND MAINTENANCE Contract Procedures § 635.109 Standardized changed condition clauses... clauses shall be made part of, and incorporated in, each highway construction project approved under 23 U...

  11. 23 CFR 635.109 - Standardized changed condition clauses.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... anticipated, customary, or inherent to the construction industry) and the contractor believes that additional... OPERATIONS CONSTRUCTION AND MAINTENANCE Contract Procedures § 635.109 Standardized changed condition clauses... clauses shall be made part of, and incorporated in, each highway construction project approved under 23 U...

  12. 23 CFR 635.109 - Standardized changed condition clauses.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... anticipated, customary, or inherent to the construction industry) and the contractor believes that additional... OPERATIONS CONSTRUCTION AND MAINTENANCE Contract Procedures § 635.109 Standardized changed condition clauses... clauses shall be made part of, and incorporated in, each highway construction project approved under 23 U...

  13. 23 CFR 635.109 - Standardized changed condition clauses.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... anticipated, customary, or inherent to the construction industry) and the contractor believes that additional... OPERATIONS CONSTRUCTION AND MAINTENANCE Contract Procedures § 635.109 Standardized changed condition clauses... clauses shall be made part of, and incorporated in, each highway construction project approved under 23 U...

  14. 23 CFR 635.109 - Standardized changed condition clauses.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... anticipated, customary, or inherent to the construction industry) and the contractor believes that additional... OPERATIONS CONSTRUCTION AND MAINTENANCE Contract Procedures § 635.109 Standardized changed condition clauses... clauses shall be made part of, and incorporated in, each highway construction project approved under 23 U...

  15. 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. Copyright © 2012 Elsevier Ltd. All rights reserved.

  16. Breeding crops for improved mineral nutrition under climate change conditions.

    PubMed

    Pilbeam, David J

    2015-06-01

    Improvements in understanding how climate change may influence chemical and physical processes in soils, how this may affect nutrient availability, and how plants may respond to changed availability of nutrients will influence crop breeding programmes. The effects of increased atmospheric CO2 and warmer temperatures, both individually and combined, on soil microbial activity, including mycorrhizas and N-fixing organisms, are evaluated, together with their implications for nutrient availability. Potential changes to plant growth, and the combined effects of soil and plant changes on nutrient uptake, are discussed. The organization of research on the efficient use of macro- and micronutrients by crops under climate change conditions is outlined, including analysis of QTLs for nutrient efficiency. Suggestions for how the information gained can be used in plant breeding programmes are given.

  17. Organophosphate pesticides-induced changes in the redox status of rat tissues and protective effects of antioxidant vitamins.

    PubMed

    Mishra, Vibhuti; Srivastava, Nalini

    2015-04-01

    Organophosphates (OPs) pesticides are among the most toxic synthetic chemicals purposefully added in the environment. The common use of OP insecticides in public health and agriculture results in an environmental pollution and a number of acute and chronic poisoning events. Present study was aimed to evaluate the potential of monocrotophos and quinalphos to effect the redox status and glutathione (GSH) homeostasis in rat tissues and find out whether antioxidant vitamins have some protection on the pesticide-induced alterations. The results showed that these pesticides alone or in combination, caused decrease in the levels of GSH and the corresponding increase in the levels of GSSG, decreasing the GSH/GSSG ratio. The results also showed that NADPH/NADP(+) and NADH/NAD(+) ratios were decreased in the liver and brain of rats on exposure with mococrotophos, quinalphos, and their mixture. These pesticides, alone or in combination, caused alterations in the activities of GSH reductase and glucose-6-phosphate dehydrogenase in the rat tissues. However, the expression of the GSH recycling enzymes did not show significant alterations as compared to control. From the results, it can be concluded that these pesticides generate oxidative stress but their effects were not synergistic when given together and prior feeding of antioxidant vitamins tend to reduce the toxicities of these pesticides. Copyright © 2013 Wiley Periodicals, Inc.

  18. Monitoring thioredoxin redox with a genetically encoded red fluorescent biosensor.

    PubMed

    Fan, Yichong; Makar, Merna; Wang, Michael X; Ai, Hui-Wang

    2017-09-01

    Thioredoxin (Trx) is one of the two major thiol antioxidants, playing essential roles in redox homeostasis and signaling. Despite its importance, there is a lack of methods for monitoring Trx redox dynamics in live cells, hindering a better understanding of physiological and pathological roles of the Trx redox system. In this work, we developed the first genetically encoded fluorescent biosensor for Trx redox by engineering a redox relay between the active-site cysteines of human Trx1 and rxRFP1, a redox-sensitive red fluorescent protein. We used the resultant biosensor-TrxRFP1-to selectively monitor perturbations of Trx redox in various mammalian cell lines. We subcellularly localized TrxRFP1 to image compartmentalized Trx redox changes. We further combined TrxRFP1 with a green fluorescent Grx1-roGFP2 biosensor to simultaneously monitor Trx and glutathione redox dynamics in live cells in response to chemical and physiologically relevant stimuli.

  19. 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.

  20. 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

  1. [Redox Molecular Imaging Using ReMI].

    PubMed

    Hyodo, Fuminori; Ito, Shinji; Utsumi, Hideo

    2015-01-01

    Tissue redox status is one of the most important parameters to maintain homeostasis in the living body. Numerous redox reactions are involved in metabolic processes, such as energy production in the mitochondrial electron transfer system. A variety of intracellular molecules such as reactive oxygen species, glutathione, thioredoxins, NADPH, flavins, and ascorbic acid may contribute to the overall redox status in tissues. Breakdown of redox balance may lead to oxidative stress and can induce many pathological conditions such as cancer, neurological disorders, and aging. Therefore imaging of tissue redox status and monitoring antioxidant levels in living organisms can be useful in the diagnosis of disease states and assessment of treatment response. In vivo redox molecular imaging technology such as electron spin resonance imaging (ESRI), magnetic resonance imaging (MRI), and dynamic nuclear polarization (DNP)-MRI (redox molecular imaging; ReMI) is emerging as a viable redox status imaging modality. This review focuses on the application of magnetic resonance technologies using MRI or DNP-MRI and redox-sensitive contrast agents.

  2. Practice change in chronic conditions care: an appraisal of theories.

    PubMed

    Harris, Melanie; Lawn, Sharon J; Morello, Andrea; Battersby, Malcolm W; Ratcliffe, Julie; McEvoy, R Doug; Tieman, Jennifer J

    2017-02-28

    Management of chronic conditions can be complex and burdensome for patients and complex and costly for health systems. Outcomes could be improved and costs reduced if proven clinical interventions were better implemented, but the complexity of chronic care services appears to make clinical change particularly challenging. Explicit use of theories may improve the success of clinical change in this area of care provision. Whilst theories to support implementation of practice change are apparent in the broad healthcare arena, the most applicable theories for the complexities of practice change in chronic care have not yet been identified. We developed criteria to review the usefulness of change implementation theories for informing chronic care management and applied them to an existing list of theories used more widely in healthcare. Criteria related to the following characteristics of chronic care: breadth of the field; multi-disciplinarity; micro, meso and macro program levels; need for field-specific research on implementation requirements; and need for measurement. Six theories met the criteria to the greatest extent: the Consolidate Framework for Implementation Research; Normalization Process Theory and its extension General Theory of Implementation; two versions of the Promoting Action on Research Implementation in Health Services framework and Sticky Knowledge. None fully met all criteria. Involvement of several care provision organizations and groups, involvement of patients and carers, and policy level change are not well covered by most theories. However, adaptation may be possible to include multiple groups including patients and carers, and separate theories may be needed on policy change. Ways of qualitatively assessing theory constructs are available but quantitative measures are currently partial and under development for all theories. Theoretical bases are available to structure clinical change research in chronic condition care. Theories will however

  3. Distinct pathways of redox changes from settling to burial in contrasting marine environments of the Gulf of California: Alfonso, La Paz and Pescadero basins

    NASA Astrophysics Data System (ADS)

    Choumiline, K.; Lyons, T. W.; Perez-Cruz, L. L.

    2016-02-01

    The oxygenation fluctuations of marine basins are controlled by complex interplay between circulation, climate, productivity and sea level variability, also enhanced by anthropogenic influence. These variations can cause OMZ expansions and increase coastal hypoxia, thus leading to unforeseen consequences of ecosystem alteration, marine life mortality and release of potentially-toxic trace elements previously sequestered within marine sediments. Despite many findings by the scientific community, accurate past reconstructions and future change predictions are far from perfect. This is mainly due to gaps in the understanding of redox processes occurring during settling and burial especially in coastal, yet iron-limited areas of the oceans. Hereby, we tackle this problem by following the transformation pathways of various paleoproductivity and paleoredox indicators (Mo, Ni, V, U, detailed Fe speciation, C and S concentrations and isotope ratios) from their sources to settling and burial. We emphasize sediment trap, core and pore water geochemistry of contrasting oxic, suboxic and anoxic marine settings of the southern Gulf of California: semi-closed Alfonso Basin, OMZ-influenced La Paz Basin and upper-OMZ Pescadero Basin with cyclic dust and fluvial inputs. Our data show evident physicochemical and microbiological transformations during settling with several event-related U enrichments in the marine snow aggregates, probably related to redox microniche processes. The sediment core solid fraction geochemistry, on the other hand, reveals a diagenetic downcore decrease of most highly reactive Fe phases (including the labile ascorbate-extracted Fe), correlating with trace element trends and dissolved Fe in pore waters. The comparison among basins exhibits an expected FeHR/FeT ratio trend for oxic (less than 0.1) and suboxic/anoxic (0.2 and higher) sediments. Although, Mn, S, Mo, U trends varied from core to core suggesting chemical zone and metabolic pathway differences

  4. 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

  5. Changes in complex spike activity during classical conditioning

    PubMed Central

    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

  6. 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.

  7. 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.

  8. Bayesian theories of conditioning in a changing world.

    PubMed

    Courville, Aaron C; Daw, Nathaniel D; Touretzky, David S

    2006-07-01

    The recent flowering of Bayesian approaches invites the re-examination of classic issues in behavior, even in areas as venerable as Pavlovian conditioning. A statistical account can offer a new, principled interpretation of behavior, and previous experiments and theories can inform many unexplored aspects of the Bayesian enterprise. Here we consider one such issue: the finding that surprising events provoke animals to learn faster. We suggest that, in a statistical account of conditioning, surprise signals change and therefore uncertainty and the need for new learning. We discuss inference in a world that changes and show how experimental results involving surprise can be interpreted from this perspective, and also how, thus understood, these phenomena help constrain statistical theories of animal and human learning.

  9. Redox Strategies for Crop Improvement.

    PubMed

    Kerchev, Pavel; De Smet, Barbara; Waszczak, Cezary; Messens, Joris; Van Breusegem, Frank

    2015-11-10

    Recently, the agro-biotech industry has been driven by overcoming the limitations imposed by fluctuating environmental stress conditions on crop productivity. A common theme among (a)biotic stresses is the perturbation of the redox homeostasis. As a strategy to engineer stress-tolerant crops, many approaches have been centered on restricting the negative impact of reactive oxygen species (ROS) accumulation. In this study, we discuss the scientific background of the existing redox-based strategies to improve crop performance and quality. In this respect, a special focus goes to summarizing the current patent landscape because this aspect is very often ignored, despite constituting the forefront of applied research. The current increased understanding of ROS acting as signaling molecules has opened new avenues to exploit redox biology for crop improvemen