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Sample records for aerobic methane oxidation

  1. Light-Dependent Aerobic Methane Oxidation Reduces Methane Emissions from Seasonally Stratified Lakes

    PubMed Central

    Oswald, Kirsten; Milucka, Jana; Brand, Andreas; Littmann, Sten; Wehrli, Bernhard; Kuypers, Marcel M. M.; Schubert, Carsten J.

    2015-01-01

    Lakes are a natural source of methane to the atmosphere and contribute significantly to total emissions compared to the oceans. Controls on methane emissions from lake surfaces, particularly biotic processes within anoxic hypolimnia, are only partially understood. Here we investigated biological methane oxidation in the water column of the seasonally stratified Lake Rotsee. A zone of methane oxidation extending from the oxic/anoxic interface into anoxic waters was identified by chemical profiling of oxygen, methane and δ13C of methane. Incubation experiments with 13C-methane yielded highest oxidation rates within the oxycline, and comparable rates were measured in anoxic waters. Despite predominantly anoxic conditions within the zone of methane oxidation, known groups of anaerobic methanotrophic archaea were conspicuously absent. Instead, aerobic gammaproteobacterial methanotrophs were identified as the active methane oxidizers. In addition, continuous oxidation and maximum rates always occurred under light conditions. These findings, along with the detection of chlorophyll a, suggest that aerobic methane oxidation is tightly coupled to light-dependent photosynthetic oxygen production both at the oxycline and in the anoxic bottom layer. It is likely that this interaction between oxygenic phototrophs and aerobic methanotrophs represents a widespread mechanism by which methane is oxidized in lake water, thus diminishing its release into the atmosphere. PMID:26193458

  2. Aerobic Methane Oxidation in Alaskan Lakes Along a Latitudinal Transect

    NASA Astrophysics Data System (ADS)

    Martinez-Cruz, K. C.; Sepulveda-Jauregui, A.; Walter Anthony, K. M.; Anthony, P.; Thalasso, F.

    2013-12-01

    Karla Martinez-Cruz* **, Armando Sepulveda-Jauregui*, Katey M. Walter Anthony*, Peter Anthony*, and Frederic Thalasso**. * Water and Environmental Research Center, Institute of Northern Engineering, University of Alaska Fairbanks, Fairbanks, Alaska. ** Biotechnology and Bioengineering Department, Cinvestav, Mexico city, D. F., Mexico. Methane (CH4) is the third most important greenhouse gas in the atmosphere, after carbon dioxide and water vapor. Boreal lakes play an important role in the current global warming by contributing as much as 6% of global atmospheric CH4 sources annually. On the other hand, aerobic methane oxidation (methanotrophy) in lake water is a fundamental process in global methane cycling that reduces the amount of CH4 emissions to the atmosphere. Several environmental factors affect aerobic methane oxidation in the water column both directly and indirectly, including concentration of CH4 and O2, temperature and carbon budgets of lakes. We analyzed the potential of aerobic methane oxidation (PMO) rates in incubations of water collected from 30 Alaskan lakes along a north-south transect during winter and summer 2011. Our findings showed an effect of CH4 and O2 concentrations, temperature and yedoma thawing permafrost on PMO activity in the lake water. The highest PMO rates were observed in summer by lakes situated on thawing yedoma permafrost, most of them located in the interior of Alaska. We also estimated that 60-80% of all CH4 produced in Alaskan lakes could be taken up by methanotrophs in the lake water column, showing the significant influence of aerobic methane oxidation of boreal lakes to the global CH4 budget.

  3. Toxic effects of butyl elastomers on aerobic methane oxidation

    NASA Astrophysics Data System (ADS)

    Niemann, Helge; Steinle, Lea I.; Blees, Jan H.; Krause, Stefan; Bussmann, Ingeborg; Lehmann, Moritz F.; Treude, Tina

    2013-04-01

    Large quantities of the potent greenhouse gas methane are liberated into the water column of marine and lacustrine environments where it may be consumed by aerobic methane oxidising bacteria before reaching the atmosphere.The reliable quantification of aerobic methane oxidation (MOx) rates is consequently of paramount importance for estimating methane budgets and to understand the controls on water column methane cycling. A widely used set of methods for measuring MOx rates is based on the incubation of water samples during which the consumption of methane is monitored, for instance with radio-tracer assays. Typically, incubation vessels are sealed with butyl rubber stoppers because these elastomers are essentially impermeable for gases at the relevant time scales. We tested the effect of different stopper materials (unmodified- and halogenated butyl rubber) on MOx activity in environmental samples and in cultures of methane oxidising bacteria. MOx rates in samples sealed with unmodified butyl rubber were > 75% lower compared to parallel incubations with halogenated butyl rubber seals, suggesting inhibiting/toxic effects associated with the use of unmodified butyl elastomers. To further explore the cause of these effects, we analysed aqueous extracts of the different stoppers. Halogenated butyl rubber stoppers appeared to bleed off comparably little amounts of organics. In stark contrast, extracts of unmodified butyl rubber were contaminated with various organic compounds including potential bactericides such as benzyltoluenes, phenylalkanes and benzuothiazoles. We also found tetramethylthiourea, a scavenger of active oxygen species, which may inhibit the MOx pathway.

  4. Environmental control on aerobic methane oxidation in coastal waters

    NASA Astrophysics Data System (ADS)

    Steinle, Lea; Maltby, Johanna; Engbersen, Nadine; Zopfi, Jakob; Bange, Hermann; Elvert, Marcus; Hinrichs, Kai-Uwe; Kock, Annette; Lehmann, Moritz; Treude, Tina; Niemann, Helge

    2016-04-01

    Large quantities of methane are produced in anoxic sediments of continental margins and may be liberated to the overlying water column, where some of it is consumed by aerobic methane oxidizing bacteria (MOB). Aerobic methane oxidation (MOx) in the water column is consequently the final sink for methane before its release to the atmosphere, where it acts as a potent greenhouse gas. In the context of the ocean's contribution to atmospheric methane, coastal seas are particularly important accounting >75% of global methane emission from marine systems. Coastal oceans are highly dynamic, in particular with regard to the variability of methane and oxygen concentrations as well as temperature and salinity, all of which are potential key environmental factors controlling MOx. To determine important environmental controls on the activity of MOBs in coastal seas, we conducted a two-year time-series study with measurements of physicochemical water column parameters, MOx activity and the composition of the MOB community in a coastal inlet in the Baltic Sea (Boknis Eck Time Series Station, Eckernförde Bay - E-Bay). In addition, we investigated the influence of temperature and oxygen on MOx during controlled laboratory experiments. In E-Bay, hypoxia developed in bottom waters towards the end of the stratification period. Constant methane liberation from sediments resulted in bottom water methane accumulations and supersaturation (with respect to the atmospheric equilibrium) in surface waters. Here, we will discuss the factors impacting MOx the most, which were (i) perturbations of the water column (ii) temperature and (iii) oxygen concentration. (i) Perturbations of the water column caused by storm events or seasonal mixing led to a decrease in MOx, probably caused by replacement of stagnant water with a high standing stock of MOB by 'new' waters with a lower abundance of methanotrophs. b) An increase in temperature generally led to higher MOx rates. c) Even though methane was

  5. Environmental Controls on Aerobic Methane Oxidation in Coastal Waters

    NASA Astrophysics Data System (ADS)

    Steinle, L.; Maltby, J.; Engbersen, N.; Zopfi, J.; Bange, H. W.; Elvert, M.; Hinrichs, K. U.; Kock, A.; Lehmann, M. F.; Treude, T.; Niemann, H.

    2015-12-01

    Large quantities of the greenhouse gas CH4 are produced in anoxic sediments of continental margins and may be liberated to the overlying water column, and later into the atmosphere. Indeed, coastal seas account for more than 75% of global oceanic CH4 emissions. Yet, aerobic CH4 oxidizing bacteria (MOB) consume an important part of CH4 in the water column, thus mitigating CH4 release to the atmosphere. Coastal oceans are highly dynamic systems, in particular with regard to the variability of temperature, salinity and oxygen concentrations, all of which are potential key environmental factors controlling MOx. To determine the most important controlling factors, we conducted a two-year time-series study with measurements of CH4, MOx, the composition of the MOB community, and physicochemical water column parameters in a coastal inlet in the Baltic Sea (Eckernförde(E-) Bay, Boknis Eck Time Series Station). In addition, we investigated the influence of temperature and oxygen on MOx during controlled laboratory experiments. In E-Bay, seasonal stratification leads to hypoxia in bottom waters towards the end of the stratification period. Methane is produced year-round in the sediments, resulting in accumulation of methane in bottom waters, and supersaturation (with respect to the atmospheric equilibrium) in surface waters. Here, we will discuss the factors impacting MOx the most, which were a) perturbations of the water column caused by storm events, currents or seasonal mixing, b) temperature and c) oxygen concentration. a) Perturbations of the water column led to a sharp decrease in MOx within hours, probably caused by replacement of 'old' water with a high standing stock of MOB by 'new' waters with a lower abundance of MOB. b) An increase in temperature generally led to higher MOx rates. c) Even though CH4 was abundant at all depths, MOx was highest in bottom waters (1-5 nM/d), which usually contain the lowest O2 concentrations. Lab-based experiments with adjusted O2

  6. Geographic and seasonal variation of dissolved methane and aerobic methane oxidation in Alaskan lakes

    NASA Astrophysics Data System (ADS)

    Martinez-Cruz, K.; Sepulveda-Jauregui, A.; Anthony, K. Walter; Thalasso, F.

    2015-03-01

    Methanotrophic bacteria play an important role oxidizing a significant fraction of methane (CH4) produced in lakes. Aerobic CH4 oxidation depends on lake CH4 and oxygen (O2) concentrations, temperature, and organic carbon input to lakes, including from thawing permafrost in thermokarst (thaw)-affected lakes. Given the large variability in these environmental factors, CH4 oxidation is expected to be subject to large seasonal and geographic variations, which have been scarcely reported in the literature. In the present study, we measured CH4 oxidation rates in 30 Alaskan lakes along a north-south latitudinal transect during winter and summer with a new field laser spectroscopy method. Additionally, we measured dissolved CH4 and O2 concentrations. We found that in the winter, aerobic CH4 oxidation was mainly controlled by the dissolved O2 concentration, while in the summer it was controlled primarily by the CH4 concentration, which was in deficit compared to dissolved O2. The permafrost environment of the lakes was identified as another key factor. Thermokarst (thaw) lakes formed in yedoma-type permafrost had significantly higher CH4 oxidation rates compared to other thermokarst and non-thermokarst lakes formed in non-yedoma permafrost environments. These results confirm that landscape processes play an important role in lake CH4 cycling.

  7. High resolution and comprehensive techniques to analyze aerobic methane oxidation in mesocosm experiments

    NASA Astrophysics Data System (ADS)

    Chan, E. W.; Kessler, J. D.; Redmond, M. C.; Shiller, A. M.; Arrington, E. C.; Valentine, D. L.; Colombo, F.

    2015-12-01

    Many studies of microbially mediated aerobic methane oxidation in oceanic environments have examined the many different factors that control the rates of oxidation. However, there is debate on how quickly methane is oxidized once a microbial population is established and what factor(s) are limiting in these types of environments. These factors include the availability of CH4, O2, trace metals, nutrients, and the density of cell population. Limits to these factors can also control the temporal aspects of a methane oxidation event. In order to look at this process in its entirety and with higher temporal resolution, a mesocosm incubation system was developed with a Dissolved Gas Analyzer System (DGAS) coupled with a set of analytical tools to monitor aerobic methane oxidation in real time. With the addition of newer laser spectroscopy techniques (cavity ringdown spectroscopy), stable isotope fractionation caused by microbial processes can also be examined on a real time and automated basis. Cell counting, trace metal, nutrient, and DNA community analyses have also been carried out in conjunction with these mesocosm samples to provide a clear understanding of the biology in methane oxidation dynamics. This poster will detail the techniques involved to provide insights into the chemical and isotopic kinetics controlling aerobic methane oxidation. Proof of concept applications will be presented from seep sites in the Hudson Canyon and the Sleeping Dragon seep field, Mississippi Canyon 118 (MC 118). This system was used to conduct mesocosm experiments to examine methane consumption, O2 consumption, nutrient consumption, and biomass production.

  8. Geographic and seasonal variation of dissolved methane and aerobic methane oxidation in Alaskan lakes

    NASA Astrophysics Data System (ADS)

    Martinez-Cruz, K.; Sepulveda-Jauregui, A.; Anthony, K. Walter; Thalasso, F.

    2015-08-01

    Methanotrophic bacteria play an important role oxidizing a significant fraction of methane (CH4) produced in lakes. Aerobic CH4 oxidation depends mainly on lake CH4 and oxygen (O2) concentrations, in such a manner that higher MO rates are usually found at the oxic/anoxic interface, where both molecules are present. MO also depends on temperature, and via methanogenesis, on organic carbon input to lakes, including from thawing permafrost in thermokarst (thaw)-affected lakes. Given the large variability in these environmental factors, CH4 oxidation is expected to be subject to large seasonal and geographic variations, which have been scarcely reported in the literature. In the present study, we measured CH4 oxidation rates in 30 Alaskan lakes along a north-south latitudinal transect during winter and summer with a new field laser spectroscopy method. Additionally, we measured dissolved CH4 and O2 concentrations. We found that in the winter, aerobic CH4 oxidation was mainly controlled by the dissolved O2 concentration, while in the summer it was controlled primarily by the CH4 concentration, which was scarce compared to dissolved O2. The permafrost environment of the lakes was identified as another key factor. Thermokarst (thaw) lakes formed in yedoma-type permafrost had significantly higher CH4 oxidation rates compared to other thermokarst and non-thermokarst lakes formed in non-yedoma permafrost environments. As thermokarst lakes formed in yedoma-type permafrost have been identified to receive large quantities of terrestrial organic carbon from thaw and subsidence of the surrounding landscape into the lake, confirming the strong coupling between terrestrial and aquatic habitats and its influence on CH4 cycling.

  9. Aerobic and anaerobic methane oxidation in terrestrial mud volcanoes in the Northern Apennines

    NASA Astrophysics Data System (ADS)

    Wrede, C.; Brady, S.; Rockstroh, S.; Dreier, A.; Kokoschka, S.; Heinzelmann, S. M.; Heller, C.; Reitner, J.; Taviani, M.; Daniel, R.; Hoppert, M.

    2012-07-01

    Methane oxidizing prokaryotes are ubiquitous in oxic and anoxic habitats wherever C1-compounds are present. Thus, methane saturated mud volcano fluids should be a preferred habitat of methane consuming prokaryotes, using the readily available electron donors. In order to understand the relevance of methane as a carbon and energy source in mud volcano communities, we investigate the diversity of prokaryotic organisms involved in oxidation of methane in fluid samples from the Salse di Nirano mud volcano field situated in the Northern Apennines. Cell counts were at approximately 0.7 × 106 microbial cells/ml. A fraction of the microbial biomass was identified as ANME (anaerobic methanotroph) archaea by fluorescence in situ hybridization (FISH) analysis. They are associated in densely colonized flakes, of some tens of μm in diameter, embedded in a hyaline matrix. Diversity analysis based on the 16S rDNA genes, retrieved from amplified and cloned environmental DNA, revealed a high proportion of archaea, involved in anaerobic oxidation of methane (AOM). Aerobic methane-oxidizing proteobacteria could be highly enriched from mud volcano fluids, indicating the presence of aerobic methanotrophic bacteria, which may contribute to methane oxidation, whenever oxygen is readily available. The results imply that biofilms, dominated by ANME archaea, colonize parts of the mud volcano venting system.

  10. A genomic view of methane oxidation by aerobic bacteria and anaerobic archaea

    PubMed Central

    Chistoserdova, Ludmila; Vorholt, Julia A; Lidstrom, Mary E

    2005-01-01

    Recent sequencing of the genome and proteomic analysis of a model aerobic methanotrophic bacterium, Methylococcus capsulatus (Bath) has revealed a highly versatile metabolic potential. In parallel, environmental genomics has provided glimpses into anaerobic methane oxidation by certain archaea, further supporting the hypothesis of reverse methanogenesis. PMID:15693955

  11. Evaluation of methyl fluoride and dimethyl ether as inhibitors of aerobic methane oxidation

    USGS Publications Warehouse

    Oremland, R.S.; Culbertson, C.W.

    1992-01-01

    Methyl fluoride (MF) and dimethyl ether (DME) were effective inhibitors of aerobic methanotrophy in a variety of soils. MF and DME blocked consumption of CH4 as well as the oxidation of 14CH4 to 14CO2, but neither MF nor DME affected the oxidation of [14C]methanol or [14C]formate to 14CO2. Cooxidation of ethane and propane by methane-oxidizing soils was also inhibited by MF. Nitrification (ammonia oxidation) in soils was inhibited by both MF and DME. Production of N2O via nitrification was inhibited by MF; however, MF did not affect N2O production associated with denitrification. Methanogenesis was partially inhibited by MF but not by DME. Methane oxidation was ~100-fold more sensitive to MF than was methanogenesis, indicating that an optimum concentration could be employed to selectively block methanotrophy. MF inhibited methane oxidation by cell suspensions of Methylococcus capsulatus; however, DME was a much less effective inhibitor.

  12. Fractionation of the methane isotopologues 13CH4, 12CH3D, and 13CH3D during aerobic oxidation of methane by Methylococcus capsulatus (Bath)

    NASA Astrophysics Data System (ADS)

    Wang, David T.; Welander, Paula V.; Ono, Shuhei

    2016-11-01

    Aerobic oxidation of methane plays a major role in reducing the amount of methane emitted to the atmosphere from freshwater and marine settings. We cultured an aerobic methanotroph, Methylococcus capsulatus (Bath) at 30 and 37 °C, and determined the relative abundance of 12CH4, 13CH4, 12CH3D, and 13CH3D (a doubly-substituted, or "clumped" isotopologue of methane) to characterize the clumped isotopologue effect associated with aerobic methane oxidation. In batch culture, the residual methane became enriched in 13C and D relative to starting methane, with D/H fractionation a factor of 9.14 (Dε/13ε) larger than that of 13C/12C. As oxidation progressed, the Δ13CH3D value (a measure of the excess in abundance of 13CH3D relative to a random distribution of isotopes among isotopologues) of residual methane decreased. The isotopologue fractionation factor for 13CH3D/12CH4 was found to closely approximate the product of the measured fractionation factors for 13CH4/12CH4 and 12CH3D/12CH4 (i.e., 13C/12C and D/H). The results give insight into enzymatic reversibility in the aerobic methane oxidation pathway. Based on the experimental data, a mathematical model was developed to predict isotopologue signatures expected for methane in the environment that has been partially-oxidized by aerobic methanotrophy. Measurement of methane clumped isotopologue abundances can be used to distinguish between aerobic methane oxidation and alternative methane-cycling processes.

  13. Aerobic methane oxidation in a coastal environment with seasonal hypoxia - a time series study

    NASA Astrophysics Data System (ADS)

    Steinle, Lea; Bethke, Christina; Schweers, Johanna; Bange, Hermann; Kock, Annette; Lehmann, Moritz F.; Treude, Tina; Niemann, Helge

    2014-05-01

    In the coastal ocean, methane is generally produced in anoxic sediments from where it can migrate through the water column to the atmosphere. A significant amount of methane is consumed along this passage by a series of microbial filter systems. Over the last 15 years, researchers focused on the first filter in marine sediments, the anaerobic oxidation of methane (AOM). Comparably little is known about the second filter, the aerobic methane oxidation (MOx), which is mediated by bacteria and takes place in the oxic water column. MOx is particularly important in shallow coastal environments that account for more than 75 % of the global oceanic methane emissions. Key environmental factors possibly controlling MOx in these systems are subjected to strong temporal variations since coastal regions are highly dynamic systems. We will present results from a time-series study on methane cycling in the water column of a coastal inlet in the southwestern Baltic Sea (Eckernförde Bay, Boknis Eck Time Series Station, 54°31.823 N, 10°02.764 E, 28m water depth; www.bokniseck.de). Results from monthly samplings for the last 8 years revealed year-round methane seepage from the seafloor and methane supersaturation (with respect to the atmospheric equilibrium) of surface waters. Seasonal stratification during the summer months leads to intermittent oxygen depletion (hypoxic to anoxic) in bottom waters in late summer to early fall. The frequency of these low-oxygen events increased over the last 20 years. In addition to oxygen fluctuations, bottom water salinity can vary strongly (17-24 psu) due to regular inflows of salty North Sea water through the Kattegat. Over the course of one and a half years, we investigated MOx rates, the methanotrophic community, methane concentrations and physicochemical parameters of the water column on a quarterly basis. Albeit methane concentrations were high throughout the water column (20-120 nM), methane turnover showed a clear spatial pattern. That

  14. Investigating the chemical and isotopic kinetics of aerobic methane oxidation in the Northern US Atlantic Margin, Hudson Canyon

    NASA Astrophysics Data System (ADS)

    Chan, E. W.; Kessler, J. D.; Shiller, A. M.; Redmond, M. C.; Arrington, E. C.; Valentine, D. L.

    2015-12-01

    Recent discoveries of methane seepage along the US Atlantic margin have led to speculation on the fate of the released methane. Here we examine the kinetics of aerobic methane oxidation to gain a fundamental understanding of this methane sink. In order to look at this process in its entirety, a unique mesocosm incubation system was developed with a Dissolved Gas Analyzer System (DGAS) to monitor in real time the chemical and isotopic changes involved with aerobic methane oxidation. This system measures changes in methane, carbon dioxide, and oxygen concentrations as well as the stable carbon isotopes of methane and carbon dioxide with time. In addition samples are strategically removed to characterize trace metals, nutrients, cell counts, and microbial community genetics. This presentation will detail the results obtained from samples collected inside the Hudson Canyon at the edge of the methane clathrate stability zone and outside the Hudson Canyon, not influenced by the methane seepage. These results show that in both environments along the Atlantic margin, methane was consumed aggressively but the timing of consumption varied based on location. In addition, these results are leading to insights into the chemical requirements needed for aerobic methane oxidation and the resulting isotopic fractionation.

  15. The effect of widespread early aerobic marine ecosystems on methane cycling and the Great Oxidation

    NASA Astrophysics Data System (ADS)

    Daines, Stuart J.; Lenton, Timothy M.

    2016-01-01

    The balance of evidence suggests that oxygenic photosynthesis had evolved by 3.0-2.7 Ga, several hundred million years prior to the Great Oxidation ≈2.4 Ga. Previous work has shown that if oxygenic photosynthesis spread globally prior to the Great Oxidation, this could have supported widespread aerobic ecosystems in the surface ocean, without oxidising the atmosphere. Here we use a suite of models to explore the implications for carbon cycling and the Great Oxidation. We find that recycling of oxygen and carbon within early aerobic marine ecosystems would have restricted the balanced fluxes of methane and oxygen escaping from the ocean, lowering the atmospheric concentration of methane in the Great Oxidation transition and its aftermath. This in turn would have minimised any bi-stability of atmospheric oxygen, by weakening a stabilising feedback on oxygen from hydrogen escape to space. The result would have been a more reversible and probably episodic rise of oxygen at the Great Oxidation transition, consistent with existing geochemical evidence. The resulting drop in methane levels to ≈10 ppm is consistent with climate cooling at the time but adds to the puzzle of what kept the rest of the Proterozoic warm. A key test of the scenario of abundant methanotrophy in oxygen oases before the Great Oxidation is its predicted effects on the organic carbon isotope (δ13Corg) record. Our open ocean general circulation model predicts δC13org ≈ - 30 to -45‰ consistent with most data from 2.65 to 2.45 Ga. However, values of δC13org ≈ - 50 ‰ require an extreme scenario such as concentrated methanotroph production where shelf-slope upwelling of methane-rich water met oxic shelf water.

  16. Aerobic cometabolic degradation of trichloroethene by methane and ammonia oxidizing microorganisms naturally associated with Carex comosa roots.

    PubMed

    Powell, C L; Nogaro, G; Agrawal, A

    2011-06-01

    The degradation potential of trichloroethene by the aerobic methane- and ammonia-oxidizing microorganisms naturally associated with wetland plant (Carex comosa) roots was examined in this study. In bench-scale microcosm experiments with washed (soil free) Carex comosa roots, the activity of root-associated methane- and ammonia-oxidizing microorganisms, which were naturally present on the root surface and/or embedded within the roots, was investigated. Significant methane and ammonia oxidation were observed reproducibly in batch reactors with washed roots incubated in growth media, where methane oxidation developed faster (2 weeks) compared to ammonia oxidation (4 weeks) in live microcosms. After enrichment, the methane oxidizers demonstrated their ability to degrade 150 μg l(-1) TCE effectively at 1.9 mg l(-1) of aqueous CH(4). In contrast, ammonia oxidizers showed a rapid and complete inhibition of ammonia oxidation with 150 μg l(-1) TCE at 20 mg l(-1) of NH(4)(+)-N, which may be attributed to greater sensitivity of ammonia oxidizers to TCE or its degradation product. No such inhibitory effect of TCE degradation was detected on methane oxidation at the above experimental conditions. The results presented here suggest that microorganisms associated with wetland plant roots can assist in the natural attenuation of TCE in contaminated aquatic environments.

  17. Dissimilatory perchlorate reduction linked to aerobic methane oxidation via chlorite dismutase

    NASA Astrophysics Data System (ADS)

    Oremland, R. S.; Baesman, S. M.; Miller, L. G.

    2013-12-01

    The presence of methane (CH4) in the atmosphere of Mars is controversial yet the evidence has aroused scientific interest, as CH4 could be a harbinger of extant or extinct microbial life. There are various oxidized compounds present on the surface of Mars that could serve as electron acceptors for the anaerobic oxidation of CH4, including perchlorate (ClO4-). We examined the role of perchlorate, chlorate (ClO3-) and chlorite (ClO2-) as oxidants linked to CH4 oxidation. Dissimilatory perchlorate reduction begins with reduction of ClO4- to ClO2- and ends with dismutation of chlorite to yield chloride (Cl-) and molecular oxygen (O2). We explored the potential for aerobic CH4 oxidizing bacteria to couple with oxygen derived from chlorite dismutation during dissimilatory perchlorate reduction. Methane (0.2 kPa) was completely removed within several days from the N2-flushed headspace above cell suspensions of methanotrophs (Methylobacter albus strain BG8) and perchlorate reducing bacteria (Dechloromonas agitata strain CKB) in the presence of 5 mM ClO2-. Similar rates of CH4 consumption were observed for these mixed cultures whether they were co-mingled or segregated under a common headspace, indicating that direct contact of cells was not required for methane consumption to occur. We also observed complete removal of 0.2 kPa CH4 in bottles containing dried soil (enriched in methanotrophs by CH4 additions over several weeks) and D. agitata CKB and in the presence of 10 mM ClO2-. This soil (seasonally exposed sediment) collected from the shoreline of a freshwater lake (Searsville Lake, CA) demonstrated endogenous CH4 uptake as well as perchlorate, chlorate and chlorite reduction/dismutation. However, these experiments required physical separation of soil from the aqueous bacterial culture to allow for the partitioning of O2 liberated from chlorite dismutation into the shared headspace. Although dissimilatory reduction of ClO4- and ClO3- could be inferred from the

  18. Diversity and abundance of aerobic and anaerobic methane oxidizers at the Haakon Mosby Mud Volcano, Barents Sea.

    PubMed

    Lösekann, Tina; Knittel, Katrin; Nadalig, Thierry; Fuchs, Bernhard; Niemann, Helge; Boetius, Antje; Amann, Rudolf

    2007-05-01

    Submarine mud volcanoes are formed by expulsions of mud, fluids, and gases from deeply buried subsurface sources. They are highly reduced benthic habitats and often associated with intensive methane seepage. In this study, the microbial diversity and community structure in methane-rich sediments of the Haakon Mosby Mud Volcano (HMMV) were investigated by comparative sequence analysis of 16S rRNA genes and fluorescence in situ hybridization. In the active volcano center, which has a diameter of about 500 m, the main methane-consuming process was bacterial aerobic oxidation. In this zone, aerobic methanotrophs belonging to three bacterial clades closely affiliated with Methylobacter and Methylophaga species accounted for 56%+/-8% of total cells. In sediments below Beggiatoa mats encircling the center of the HMMV, methanotrophic archaea of the ANME-3 clade dominated the zone of anaerobic methane oxidation. ANME-3 archaea form cell aggregates mostly associated with sulfate-reducing bacteria of the Desulfobulbus (DBB) branch. These ANME-3/DBB aggregates were highly abundant and accounted for up to 94%+/-2% of total microbial biomass at 2 to 3 cm below the surface. ANME-3/DBB aggregates could be further enriched by flow cytometry to identify their phylogenetic relationships. At the outer rim of the mud volcano, the seafloor was colonized by tubeworms (Siboglinidae, formerly known as Pogonophora). Here, both aerobic and anaerobic methane oxidizers were found, however, in lower abundances. The level of microbial diversity at this site was higher than that at the central and Beggiatoa species-covered part of the HMMV. Analysis of methyl-coenzyme M-reductase alpha subunit (mcrA) genes showed a strong dominance of a novel lineage, mcrA group f, which could be assigned to ANME-3 archaea. Our results further support the hypothesis of Niemann et al. (54), that high methane availability and different fluid flow regimens at the HMMV provide distinct niches for aerobic and

  19. Diversity and Abundance of Aerobic and Anaerobic Methane Oxidizers at the Haakon Mosby Mud Volcano, Barents Sea▿

    PubMed Central

    Lösekann, Tina; Knittel, Katrin; Nadalig, Thierry; Fuchs, Bernhard; Niemann, Helge; Boetius, Antje; Amann, Rudolf

    2007-01-01

    Submarine mud volcanoes are formed by expulsions of mud, fluids, and gases from deeply buried subsurface sources. They are highly reduced benthic habitats and often associated with intensive methane seepage. In this study, the microbial diversity and community structure in methane-rich sediments of the Haakon Mosby Mud Volcano (HMMV) were investigated by comparative sequence analysis of 16S rRNA genes and fluorescence in situ hybridization. In the active volcano center, which has a diameter of about 500 m, the main methane-consuming process was bacterial aerobic oxidation. In this zone, aerobic methanotrophs belonging to three bacterial clades closely affiliated with Methylobacter and Methylophaga species accounted for 56% ± 8% of total cells. In sediments below Beggiatoa mats encircling the center of the HMMV, methanotrophic archaea of the ANME-3 clade dominated the zone of anaerobic methane oxidation. ANME-3 archaea form cell aggregates mostly associated with sulfate-reducing bacteria of the Desulfobulbus (DBB) branch. These ANME-3/DBB aggregates were highly abundant and accounted for up to 94% ± 2% of total microbial biomass at 2 to 3 cm below the surface. ANME-3/DBB aggregates could be further enriched by flow cytometry to identify their phylogenetic relationships. At the outer rim of the mud volcano, the seafloor was colonized by tubeworms (Siboglinidae, formerly known as Pogonophora). Here, both aerobic and anaerobic methane oxidizers were found, however, in lower abundances. The level of microbial diversity at this site was higher than that at the central and Beggiatoa species-covered part of the HMMV. Analysis of methyl-coenzyme M-reductase alpha subunit (mcrA) genes showed a strong dominance of a novel lineage, mcrA group f, which could be assigned to ANME-3 archaea. Our results further support the hypothesis of Niemann et al. (54), that high methane availability and different fluid flow regimens at the HMMV provide distinct niches for aerobic and

  20. Effect of process design and operating parameters on aerobic methane oxidation in municipal WWTPs.

    PubMed

    Daelman, Matthijs R J; Van Eynde, Tamara; van Loosdrecht, Mark C M; Volcke, Eveline I P

    2014-12-01

    Methane is a potent greenhouse gas and its emission from municipal wastewater treatment plants (WWTPs) should be prevented. One way to do this is to promote the biological conversion of dissolved methane over stripping in aeration tanks. In this study, the well-established Activated Sludge Model n°1 (ASM1) and Benchmark Simulation Model n°1 (BSM1) were extended to study the influence of process design and operating parameters on biological methane oxidation. The aeration function used in BSM 1 was upgraded to more accurately describe gas-liquid transfer of oxygen and methane in aeration tanks equipped with subsurface aeration. Dissolved methane could be effectively removed in an aeration tank at an aeration rate that is in agreement with optimal effluent quality. Subsurface bubble aeration proved to be better than surface aeration, while a CSTR configuration was superior to plug flow conditions in avoiding methane emissions. The conversion of methane in the activated sludge tank benefits from higher methane concentrations in the WWTP's influent. Finally, if an activated sludge tank is aerated with methane containing off-gas, a limited amount of methane is absorbed and converted in the mixed liquor. This knowledge helps to stimulate the methane oxidizing capacity of activated sludge in order to abate methane emissions from wastewater treatment to the atmosphere. PMID:25225767

  1. Effect of process design and operating parameters on aerobic methane oxidation in municipal WWTPs.

    PubMed

    Daelman, Matthijs R J; Van Eynde, Tamara; van Loosdrecht, Mark C M; Volcke, Eveline I P

    2014-12-01

    Methane is a potent greenhouse gas and its emission from municipal wastewater treatment plants (WWTPs) should be prevented. One way to do this is to promote the biological conversion of dissolved methane over stripping in aeration tanks. In this study, the well-established Activated Sludge Model n°1 (ASM1) and Benchmark Simulation Model n°1 (BSM1) were extended to study the influence of process design and operating parameters on biological methane oxidation. The aeration function used in BSM 1 was upgraded to more accurately describe gas-liquid transfer of oxygen and methane in aeration tanks equipped with subsurface aeration. Dissolved methane could be effectively removed in an aeration tank at an aeration rate that is in agreement with optimal effluent quality. Subsurface bubble aeration proved to be better than surface aeration, while a CSTR configuration was superior to plug flow conditions in avoiding methane emissions. The conversion of methane in the activated sludge tank benefits from higher methane concentrations in the WWTP's influent. Finally, if an activated sludge tank is aerated with methane containing off-gas, a limited amount of methane is absorbed and converted in the mixed liquor. This knowledge helps to stimulate the methane oxidizing capacity of activated sludge in order to abate methane emissions from wastewater treatment to the atmosphere.

  2. Molecular characterization of a microbial consortium involved in methane oxidation coupled to denitrification under micro-aerobic conditions

    PubMed Central

    Liu, Jingjing; Sun, Faqian; Wang, Liang; Ju, Xi; Wu, Weixiang; Chen, Yingxu

    2014-01-01

    Methane can be used as an alternative carbon source in biological denitrification because it is nontoxic, widely available and relatively inexpensive. A microbial consortium involved in methane oxidation coupled to denitrification (MOD) was enriched with nitrite and nitrate as electron acceptors under micro-aerobic conditions. The 16S rRNA gene combined with pmoA phylogeny of methanotrophs and nirK phylogeny of denitrifiers were analysed to reveal the dominant microbial populations and functional microorganisms. Real-time quantitative polymerase chain reaction results showed high numbers of methanotrophs and denitrifiers in the enriched consortium. The 16S rRNA gene clone library revealed that Methylococcaceae and Methylophilaceae were the dominant populations in the MOD ecosystem. Phylogenetic analyses of pmoA gene clone libraries indicated that all methanotrophs belonged to Methylococcaceae, a type I methanotroph employing the ribulose monophosphate pathway for methane oxidation. Methylotrophic denitrifiers of the Methylophilaceae that can utilize organic intermediates (i.e. formaldehyde, citrate and acetate) released from the methanotrophs played a vital role in aerobic denitrification. This study is the first report to confirm micro-aerobic denitrification and to make phylogenetic and functional assignments for some members of the microbial assemblages involved in MOD. PMID:24245852

  3. Molecular characterization of a microbial consortium involved in methane oxidation coupled to denitrification under micro-aerobic conditions.

    PubMed

    Liu, Jingjing; Sun, Faqian; Wang, Liang; Ju, Xi; Wu, Weixiang; Chen, Yingxu

    2014-01-01

    Methane can be used as an alternative carbon source in biological denitrification because it is nontoxic, widely available and relatively inexpensive. A microbial consortium involved in methane oxidation coupled to denitrification (MOD) was enriched with nitrite and nitrate as electron acceptors under micro-aerobic conditions. The 16S rRNA gene combined with pmoA phylogeny of methanotrophs and nirK phylogeny of denitrifiers were analysed to reveal the dominant microbial populations and functional microorganisms. Real-time quantitative polymerase chain reaction results showed high numbers of methanotrophs and denitrifiers in the enriched consortium. The 16S rRNA gene clone library revealed that Methylococcaceae and Methylophilaceae were the dominant populations in the MOD ecosystem. Phylogenetic analyses of pmoA gene clone libraries indicated that all methanotrophs belonged to Methylococcaceae, a type I methanotroph employing the ribulose monophosphate pathway for methane oxidation. Methylotrophic denitrifiers of the Methylophilaceae that can utilize organic intermediates (i.e. formaldehyde, citrate and acetate) released from the methanotrophs played a vital role in aerobic denitrification. This study is the first report to confirm micro-aerobic denitrification and to make phylogenetic and functional assignments for some members of the microbial assemblages involved in MOD.

  4. Methane oxidation activity and diversity of aerobic methanotrophs in pH-neutral and semi-neutral thermal springs of the Kunashir Island, Russian Far East.

    PubMed

    Kizilova, A K; Sukhacheva, M V; Pimenov, N V; Yurkov, A M; Kravchenko, I K

    2014-03-01

    Aerobic methane oxidation has been mostly studied in environments with moderate to low temperatures. However, the process also occurs in terrestrial thermal springs, where little research on the subject has been done to date. The potential activity of methane oxidation and diversity of aerobic methanotrophic bacteria were studied in sediments of thermal springs with various chemical and physical properties, sampled across the Kunashir Island, the Kuriles archipelago. Activity was measured by means of the radioisotope tracer technique utilizing (14)C-labeled methane. Biodiversity assessments were based on the particulate methane monooxygenase (pmoA) gene, which is found in all known thermophilic and thermotolerant methanotrophs. We demonstrated the possibility of methane oxidation in springs with temperature exceeding 74 °C, and the most intensive methane uptake was shown in springs with temperatures about 46 °C. PmoA was detected in 19 out of 30 springs investigated and the number of pmoA gene copies varied between 10(4) and 10(6) copies per ml of sediment. Phylogenetic analysis of PmoA sequences revealed the presence of methanotrophs from both the Alpha- and Gammaproteobacteria. Our results suggest that methanotrophs inhabiting thermal springs with temperature exceeding 50 °C may represent novel thermophilic and thermotolerant species of the genera Methylocystis and Methylothermus, as well as previously undescribed Gammaproteobacteria. PMID:24343375

  5. Methane oxidation in a crude oil contaminated aquifer: Delineation of aerobic reactions at the plume fringes

    NASA Astrophysics Data System (ADS)

    Amos, Richard T.; Bekins, Barbara A.; Delin, Geoffrey N.; Cozzarelli, Isabelle M.; Blowes, David W.; Kirshtein, Julie D.

    2011-07-01

    High resolution direct-push profiling over short vertical distances was used to investigate CH 4 attenuation in a petroleum contaminated aquifer near Bemidji, Minnesota. The contaminant plume was delineated using dissolved gases, redox sensitive components, major ions, carbon isotope ratios in CH 4 and CO 2, and the presence of methanotrophic bacteria. Sharp redox gradients were observed near the water table. Shifts in δ 13C CH4 from an average of - 57.6‰ (± 1.7‰) in the methanogenic zone to - 39.6‰ (± 8.7‰) at 105 m downgradient, strongly suggest CH 4 attenuation through microbially mediated degradation. In the downgradient zone the aerobic/anaerobic transition is up to 0.5 m below the water table suggesting that transport of O 2 across the water table is leading to aerobic degradation of CH 4 at this interface. Dissolved N 2 concentrations that exceeded those expected for water in equilibrium with the atmosphere indicated bubble entrapment followed by preferential stripping of O 2 through aerobic degradation of CH 4 or other hydrocarbons. Multivariate and cluster analysis were used to distinguish between areas of significant bubble entrapment and areas where other processes such as the infiltration of O 2 rich recharge water were important O 2 transport mechanisms.

  6. Methane oxidation in a crude oil contaminated aquifer: Delineation of aerobic reactions at the plume fringes

    USGS Publications Warehouse

    Amos, R.T.; Bekins, B.A.; Delin, G.N.; Cozzarelli, I.M.; Blowes, D.W.; Kirshtein, J.D.

    2011-01-01

    High resolution direct-push profiling over short vertical distances was used to investigate CH4 attenuation in a petroleum contaminated aquifer near Bemidji, Minnesota. The contaminant plume was delineated using dissolved gases, redox sensitive components, major ions, carbon isotope ratios in CH4 and CO2, and the presence of methanotrophic bacteria. Sharp redox gradients were observed near the water table. Shifts in ??13CCH4 from an average of - 57.6??? (?? 1.7???) in the methanogenic zone to - 39.6??? (?? 8.7???) at 105 m downgradient, strongly suggest CH4 attenuation through microbially mediated degradation. In the downgradient zone the aerobic/anaerobic transition is up to 0.5 m below the water table suggesting that transport of O2 across the water table is leading to aerobic degradation of CH4 at this interface. Dissolved N2 concentrations that exceeded those expected for water in equilibrium with the atmosphere indicated bubble entrapment followed by preferential stripping of O2 through aerobic degradation of CH4 or other hydrocarbons. Multivariate and cluster analysis were used to distinguish between areas of significant bubble entrapment and areas where other processes such as the infiltration of O 2 rich recharge water were important O2 transport mechanisms. ?? 2011 Elsevier B.V. All rights reserved.

  7. Variability in aerobic methane oxidation over the past 1.2 Myrs recorded in microbial biomarker signatures from Congo fan sediments

    NASA Astrophysics Data System (ADS)

    Talbot, Helen M.; Handley, Luke; Spencer-Jones, Charlotte L.; Dinga, Bienvenu Jean; Schefuß, Enno; Mann, Paul J.; Poulsen, John R.; Spencer, Robert G. M.; Wabakanghanzi, Jose N.; Wagner, Thomas

    2014-05-01

    Methane (CH4) is a strong greenhouse gas known to have perturbed global climate in the past, especially when released in large quantities over short time periods from continental or marine sources. It is therefore crucial to understand and, if possible, quantify the individual and combined response of these variable methane sources to natural climate variability. However, past changes in the stability of greenhouse gas reservoirs remain uncertain and poorly constrained by geological evidence. Here, we present a record from the Congo fan of a highly specific bacteriohopanepolyol (BHP) biomarker for aerobic methane oxidation (AMO), 35-aminobacteriohopane-30,31,32,33,34-pentol (aminopentol), that identifies discrete periods of increased AMO as far back as 1.2 Ma. Fluctuations in the concentration of aminopentol, and other 35-aminoBHPs, follow a pattern that correlates with late Quaternary glacial-interglacial climate cycles, with highest concentrations during warm periods. We discuss possible sources of aminopentol, and the methane consumed by the precursor methanotrophs, within the context of the Congo River setting, including supply of methane oxidation markers from terrestrial watersheds and/or marine sources (gas hydrate and/or deep subsurface gas reservoir). Compound-specific carbon isotope values of -30‰ to -40‰ for BHPs in ODP 1075 and strong similarities between the BHP signature of the core and surface sediments from the Congo estuary and floodplain wetlands from the interior of the Congo River Basin, support a methanotrophic and likely terrigenous origin of the 35-aminoBHPs found in the fan sediments. This new evidence supports a causal connection between marine sediment BHP records of tropical deep sea fans and wetland settings in the feeding river catchments, and thus tropical continental hydrology. Further research is needed to better constrain the different sources and pathways of methane emission. However, this study identifies the large potential

  8. The regulation of methane oxidation in soil

    NASA Technical Reports Server (NTRS)

    Mancinelli, R. L.

    1995-01-01

    The atmospheric concentration of methane, a greenhouse gas, has more than doubled during the past 200 years. Consequently, identifying the factors influencing the flux of methane into the atmosphere is becoming increasingly important. Methanotrophs, microaerophilic organisms widespread in aerobic soils and sediments, oxidize methane to derive energy and carbon for biomass. In so doing, they play an important role in mitigating the flux of methane into the atmosphere. Several physico-chemical factors influence rates of methane oxidation in soil, including soil diffusivity; water potential; and levels of oxygen, methane, ammonium, nitrate, nitrite, and copper. Most of these factors exert their influence through interactions with methane monooxygenase (MMO), the enzyme that catalyzes the reaction converting methane to methanol, the first step in methane oxidation. Although biological factors such as competition and predation undoubtedly play a role in regulating the methanotroph population in soils, and thereby limit the amount of methane consumed by methanotrophs, the significance of these factors is unknown. Obtaining a better understanding of the ecology of methanotrophs will help elucidate the mechanisms that regulate soil methane oxidation.

  9. Carbon isotope fractionation during microbial methane oxidation

    NASA Astrophysics Data System (ADS)

    Barker, James F.; Fritz, Peter

    1981-09-01

    Methane, a common trace constituent of groundwaters, occasionally makes up more than 20% of the total carbon in groundwaters1,2. In aerobic environments CH4-rich waters can enable microbial food chain supporting a mixed culture of bacteria with methane oxidation as the primary energy source to develop3. Such processes may influence the isotopic composition of the residual methane and because 13C/12C analyses have been used to characterize the genesis of methanes found in different environments, an understanding of the magnitude of such effects is necessary. In addition, carbon dioxide produced by the methane-utilizing bacteria can be added to the inorganic carbon pool of affected groundwaters. We found carbon dioxide experimentally produced by methane-utilizing bacteria to be enriched in 12C by 5.0-29.6‰, relative to the residual methane. Where methane-bearing groundwaters discharged into aerobic environments microbial methane oxidation occurred, with the residual methane becoming progressively enriched in 13C. Various models have been proposed to explain the 13C/12C and 14C content of the dissolved inorganic carbon (DIC) of groundwaters in terms of additions or losses during flow in the subsurface4,5. The knowledge of both stable carbon isotope ratios in various pools and the magnitude of carbon isotope fractionation during various processes allows geochemists to use the 13C/12C ratio of the DIC along with water chemistry to estimate corrected 14C groundwater ages4,5. We show here that a knowledge of the carbon isotope fractionation between CH4 and CO2 during microbial methane-utilization could modify such models for application to groundwaters affected by microbial methane oxidation.

  10. Enzymatic Oxidation of Methane

    SciTech Connect

    Sirajuddin, S; Rosenzweig, AC

    2015-04-14

    Methane monooxygenases (MMOs) are enzymes that catalyze the oxidation of methane to methanol in methanotrophic bacteria. As potential targets for new gas-to-liquid methane bioconversion processes, MMOs have attracted intense attention in recent years. There are two distinct types of MMO, a soluble, cytoplasmic MMO (sMMO) and a membrane-bound, particulate MMO (pMMO). Both oxidize methane at metal centers within a complex, multisubunit scaffold, but the structures, active sites, and chemical mechanisms are completely different. This Current Topic review article focuses on the overall architectures, active site structures, substrate reactivities, proteinprotein interactions, and chemical mechanisms of both MMOs, with an emphasis on fundamental aspects. In addition, recent advances, including new details of interactions between the sMMO components, characterization of sMMO intermediates, and progress toward understanding the pMMO metal centers are highlighted. The work summarized here provides a guide for those interested in exploiting MMOs for biotechnological applications.

  11. Non-linear dynamics of stable carbon and hydrogen isotope signatures based on a biological kinetic model of aerobic enzymatic methane oxidation.

    PubMed

    Vavilin, Vasily A; Rytov, Sergey V; Shim, Natalia; Vogt, Carsten

    2016-06-01

    The non-linear dynamics of stable carbon and hydrogen isotope signatures during methane oxidation by the methanotrophic bacteria Methylosinus sporium strain 5 (NCIMB 11126) and Methylocaldum gracile strain 14 L (NCIMB 11912) under copper-rich (8.9 µM Cu(2+)), copper-limited (0.3 µM Cu(2+)) or copper-regular (1.1 µM Cu(2+)) conditions has been described mathematically. The model was calibrated by experimental data of methane quantities and carbon and hydrogen isotope signatures of methane measured previously in laboratory microcosms reported by Feisthauer et al. [ 1 ] M. gracile initially oxidizes methane by a particulate methane monooxygenase and assimilates formaldehyde via the ribulose monophosphate pathway, whereas M. sporium expresses a soluble methane monooxygenase under copper-limited conditions and uses the serine pathway for carbon assimilation. The model shows that during methane solubilization dominant carbon and hydrogen isotope fractionation occurs. An increase of biomass due to growth of methanotrophs causes an increase of particulate or soluble monooxygenase that, in turn, decreases soluble methane concentration intensifying methane solubilization. The specific maximum rate of methane oxidation υm was proved to be equal to 4.0 and 1.3 mM mM(-1) h(-1) for M. sporium under copper-rich and copper-limited conditions, respectively, and 0.5 mM mM(-1) h(-1) for M. gracile. The model shows that methane oxidation cannot be described by traditional first-order kinetics. The kinetic isotope fractionation ceases when methane concentrations decrease close to the threshold value. Applicability of the non-linear model was confirmed by dynamics of carbon isotope signature for carbon dioxide that was depleted and later enriched in (13)C. Contrasting to the common Rayleigh linear graph, the dynamic curves allow identifying inappropriate isotope data due to inaccurate substrate concentration analyses. The non-linear model pretty adequately described experimental

  12. Methane oxidation coupled to oxygenic photosynthesis in anoxic waters

    PubMed Central

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

    2015-01-01

    Freshwater lakes represent large methane sources that, in contrast to the Ocean, significantly contribute to non-anthropogenic methane emissions to the atmosphere. Particularly mixed lakes are major methane emitters, while permanently and seasonally stratified lakes with anoxic bottom waters are often characterized by strongly reduced methane emissions. The causes for this reduced methane flux from anoxic lake waters are not fully understood. Here we identified the microorganisms and processes responsible for the near complete consumption of methane in the anoxic waters of a permanently stratified lake, Lago di Cadagno. Interestingly, known anaerobic methanotrophs could not be detected in these waters. Instead, we found abundant gamma-proteobacterial aerobic methane-oxidizing bacteria active in the anoxic waters. In vitro incubations revealed that, among all the tested potential electron acceptors, only the addition of oxygen enhanced the rates of methane oxidation. An equally pronounced stimulation was also observed when the anoxic water samples were incubated in the light. Our combined results from molecular, biogeochemical and single-cell analyses indicate that methane removal at the anoxic chemocline of Lago di Cadagno is due to true aerobic oxidation of methane fuelled by in situ oxygen production by photosynthetic algae. A similar mechanism could be active in seasonally stratified lakes and marine basins such as the Black Sea, where light penetrates to the anoxic chemocline. Given the widespread occurrence of seasonally stratified anoxic lakes, aerobic methane oxidation coupled to oxygenic photosynthesis might have an important but so far neglected role in methane emissions from lakes. PMID:25679533

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

    PubMed

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

    2015-09-01

    Freshwater lakes represent large methane sources that, in contrast to the Ocean, significantly contribute to non-anthropogenic methane emissions to the atmosphere. Particularly mixed lakes are major methane emitters, while permanently and seasonally stratified lakes with anoxic bottom waters are often characterized by strongly reduced methane emissions. The causes for this reduced methane flux from anoxic lake waters are not fully understood. Here we identified the microorganisms and processes responsible for the near complete consumption of methane in the anoxic waters of a permanently stratified lake, Lago di Cadagno. Interestingly, known anaerobic methanotrophs could not be detected in these waters. Instead, we found abundant gamma-proteobacterial aerobic methane-oxidizing bacteria active in the anoxic waters. In vitro incubations revealed that, among all the tested potential electron acceptors, only the addition of oxygen enhanced the rates of methane oxidation. An equally pronounced stimulation was also observed when the anoxic water samples were incubated in the light. Our combined results from molecular, biogeochemical and single-cell analyses indicate that methane removal at the anoxic chemocline of Lago di Cadagno is due to true aerobic oxidation of methane fuelled by in situ oxygen production by photosynthetic algae. A similar mechanism could be active in seasonally stratified lakes and marine basins such as the Black Sea, where light penetrates to the anoxic chemocline. Given the widespread occurrence of seasonally stratified anoxic lakes, aerobic methane oxidation coupled to oxygenic photosynthesis might have an important but so far neglected role in methane emissions from lakes.

  14. Biomimetic methane oxidation

    SciTech Connect

    Watkins, B.E.; Droege, M.W.; Taylor, R.T.; Satcher, J.H.

    1992-06-12

    Methane monooxygenase (MMO) is an enzyme found in methanotrophs that catalyses the selective oxidation of methane to methanol. MMO is protein complex one component of which is a binuclear metal center containing oxygenase. We have completed one round of a design/synthesis/evaluation cycle in the development of coordination complexes that mimic the structure/function of the MMO active site. One of these, a binuclear, coordinately-asymmetric copper complex, is capable of oxidizing cyclohexane to a mixture of cyclohexanol and cyclohexanone in the presence of hydrogen peroxide.

  15. [Research progress in microbial methane oxidation coupled to denitrification].

    PubMed

    Zhu, Jing; Yuan, Meng-Dong; Liu, Jing-Jing; Huang, Xiao-Xiao; Wu, Wei-Xiang

    2013-12-01

    Methane oxidation coupled to denitrification is an essential bond to connect carbon- and nitrogen cycling. To deeply research this process will improve our understanding on the biochemical cycling of global carbon and nitrogen. As an exogenous gaseous carbon source of denitrification, methane can both regulate the balance of atmospheric methane to effectively mitigate the greenhouse effect caused by methane, and reduce the cost of exogenous carbon source input in traditional wastewater denitrification treatment process. As a result, great attention has being paid to the mechanical study of the process. This paper mainly discussed the two types of methane oxidation coupled to denitrification, i. e., aerobic methane oxidation coupled to denitrification (AME-D) and anaerobic methane oxidation coupled to denitrification (ANME-D), with the focus on the microbiological coupling mechanisms and related affecting factors. The existing problems in the engineering application of methane oxidation coupled to denitrification were pointed out, and the application prospects were approached. PMID:24697087

  16. [Research progress in microbial methane oxidation coupled to denitrification].

    PubMed

    Zhu, Jing; Yuan, Meng-Dong; Liu, Jing-Jing; Huang, Xiao-Xiao; Wu, Wei-Xiang

    2013-12-01

    Methane oxidation coupled to denitrification is an essential bond to connect carbon- and nitrogen cycling. To deeply research this process will improve our understanding on the biochemical cycling of global carbon and nitrogen. As an exogenous gaseous carbon source of denitrification, methane can both regulate the balance of atmospheric methane to effectively mitigate the greenhouse effect caused by methane, and reduce the cost of exogenous carbon source input in traditional wastewater denitrification treatment process. As a result, great attention has being paid to the mechanical study of the process. This paper mainly discussed the two types of methane oxidation coupled to denitrification, i. e., aerobic methane oxidation coupled to denitrification (AME-D) and anaerobic methane oxidation coupled to denitrification (ANME-D), with the focus on the microbiological coupling mechanisms and related affecting factors. The existing problems in the engineering application of methane oxidation coupled to denitrification were pointed out, and the application prospects were approached.

  17. Regulation of Methane Oxidation in a Freshwater Wetland by Water Table Changes and Anoxia

    NASA Technical Reports Server (NTRS)

    Roslev, Peter; King, Gary M.

    1996-01-01

    The effects of water table fluctuations and anoxia on methane emission and methane oxidation were studied in a freshwater marsh. Seasonal aerobic methane oxidation rates varied between 15% and 76% of the potential diffusive methane flux (diffusive flux in the absence of aerobic oxidation). On an annual basis, approximately 43% of the methane diffusing into the oxic zone was oxidized before reaching the atmosphere. The highest methane oxidation was observed when the water table was below the peat surface. This was confirmed in laboratory experiments where short-term decreases in water table levels increased methane oxidation but also net methane emission. Although methane emission was generally not observed during the winter, stems of soft rush (Juncus effusus) emitted methane when the marsh was ice covered. Indigenous methanotrophic bacteria from the wetiand studied were relatively anoxia tolerant. Surface peat incubated under anoxic conditions maintained 30% of the initial methane oxidation capacity after 32 days of anoxia. Methanotrophs from anoxic peat initiated aerobic methane oxidation relatively quickly after oxygen addition (1-7 hours). These results were supported by culture experiments with the methanotroph Methylosinus trichosporium OB3b. This organism maintained a greater capacity for aerobic methane oxidation when starved under anoxic compared to oxic conditions. Anoxic incubation of M. trichosporium OB3b in the presence of sulfide (2 mM) and a low redox potential (-110 mV) did not decrease the capacity for methane oxidation relative to anoxic cultures incubated without sulfide. The results suggest that aerobic methane oxidation was a major regulator of seasonal methane emission front the investigated wetland. The observed water table fluctuations affected net methane oxidation presumably due to associated changes in oxygen gradients. However, changes from oxic to anoxic conditions in situ had relatively little effect on survival of the methanotrophic

  18. Aerobic methane emissions from stinkweed (Thlaspi arvense) capsules

    PubMed Central

    Qaderi, Mirwais M; Reid, David M

    2014-01-01

    Aerobic methane (CH4) emission from plant vegetative parts has been confirmed by many studies. However, the origin of aerobic CH4 from plants and its emission from reproductive parts have not been well documented. We determined the effects of developmental stages (early, mid, late) and incubation conditions (darkness, dim light, bright light) on CH4 emissions from stinkweed (Thlaspi arvense) capsules. We found that CH4 emissions from capsules varied with developmental stage and incubation light. Methane emission was highest for the late harvested capsules and for those incubated under lower (dim) light condition. Our results also showed a significant negative correlation between CH4 emission and capsule moisture content. We conclude that CH4 emissions vary with capsule age and diurnal light environment. PMID:25482797

  19. Potential methane production and methane oxidation rates in peatland ecosystems of the Appalachian Mountains, United States

    SciTech Connect

    Yavitt, J.B.; Lang, G.E.; Downey, D.M. )

    1988-09-01

    Potential rates of methane production and carbon dioxide production were measured on 11 dates in 1986 in peat from six plant communities typical of moss-dominated peatlands in the Appalachian Mountains. Annual methane production ranged from 2.7 to 17.5 mol/sq m, and annual carbon dioxide production ranged from 30.6 to 79.0 mol/sq m. The wide range in methane production values among the communities found within a single peatland indicates that obtaining one production value for a peatland may not be appropriate. Low temperature constrained the potential for methane production in winter, while the chemical quality of the peat substrate appears to control methane production in the summer. Methane oxidation was measured throughout the peat profile to a depth of 30 cm. Values for methane oxidation ranged from 0.08 to 18.7 microM/hr among the six plant communities. Aerobic methane-oxidizing bacteria probably mediated most of the activity. On a daily basis during the summer, between 11 and 100% of the methane produced is susceptible to oxidation within the peat column. Pools of dissolved methane and dissolved carbon dioxide in pore waters were less than 0.2 and less than 1.0 mol/sq m, respectively, indicating that methane does not accumulate in the pore waters. Peatlands have been considered as an important source of biologically produced methane. Despite the high rates of methane production, the high rates of methane oxidation dampen the potential emission of methane to the atmosphere. 41 refs., 7 figs., 4 tabs.

  20. Trichloroethylene Biodegradation by a Methane-Oxidizing Bacterium †

    PubMed Central

    Little, C. Deane; Palumbo, Anthony V.; Herbes, Stephen E.; Lidstrom, Mary E.; Tyndall, Richard L.; Gilmer, Penny J.

    1988-01-01

    Trichloroethylene (TCE), a common groundwater contaminant, is a suspected carcinogen that is highly resistant to aerobic biodegradation. An aerobic, methane-oxidizing bacterium was isolated that degrades TCE in pure culture at concentrations commonly observed in contaminated groundwater. Strain 46-1, a type I methanotrophic bacterium, degraded TCE if grown on methane or methanol, producing CO2 and water-soluble products. Gas chromatography and 14C radiotracer techniques were used to determine the rate, methane dependence, and mechanism of TCE biodegradation. TCE biodegradation by strain 46-1 appears to be a cometabolic process that occurs when the organism is actively metabolizing a suitable growth substrate such as methane or methanol. It is proposed that TCE biodegradation by methanotrophs occurs by formation of TCE epoxide, which breaks down spontaneously in water to form dichloroacetic and glyoxylic acids and one-carbon products. Images PMID:16347616

  1. Assessing the Efficacy of the Aerobic Methanotrophic Biofilter in Methane Hydrate Environments

    SciTech Connect

    Valentine, David

    2012-09-30

    In October 2008 the University of California at Santa Barbara (UCSB) initiated investigations of water column methane oxidation in methane hydrate environments, through a project funded by the National Energy Technology Laboratory (NETL) entitled: assessing the efficacy of the aerobic methanotrophic biofilter in methane hydrate environments. This Final Report describes the scientific advances and discoveries made under this award as well as the importance of these discoveries in the broader context of the research area. Benthic microbial mats inhabit the sea floor in areas where reduced chemicals such as sulfide reach the more oxidizing water that overlies the sediment. We set out to investigate the role that methanotrophs play in such mats at locations where methane reaches the sea floor along with sulfide. Mats were sampled from several seep environments and multiple sets were grown in-situ at a hydrocarbon seep in the Santa Barbara Basin. Mats grown in-situ were returned to the laboratory and used to perform stable isotope probing experiments in which they were treated with 13C-enriched methane. The microbial community was analyzed, demonstrating that three or more microbial groups became enriched in methane?s carbon: methanotrophs that presumably utilize methane directly, methylotrophs that presumably consume methanol excreted by the methanotrophs, and sulfide oxidizers that presumably consume carbon dioxide released by the methanotrophs and methylotrophs. Methanotrophs reached high relative abundance in mats grown on methane, but other bacterial processes include sulfide oxidation appeared to dominate mats, indicating that methanotrophy is not a dominant process in sustaining these benthic mats, but rather a secondary function modulated by methane availability. Methane that escapes the sediment in the deep ocean typically dissolved into the overlying water where it is available to methanotrophic bacteria. We set out to better understand the efficacy of this

  2. Controlling the catalytic aerobic oxidation of phenols.

    PubMed

    Esguerra, Kenneth Virgel N; Fall, Yacoub; Petitjean, Laurène; Lumb, Jean-Philip

    2014-05-28

    The oxidation of phenols is the subject of extensive investigation, but there are few catalytic aerobic examples that are chemo- and regioselective. Here we describe conditions for the ortho-oxygenation or oxidative coupling of phenols under copper (Cu)-catalyzed aerobic conditions that give rise to ortho-quinones, biphenols or benzoxepines. We demonstrate that each product class can be accessed selectively by the appropriate choice of Cu(I) salt, amine ligand, desiccant and reaction temperature. In addition, we evaluate the effects of substituents on the phenol and demonstrate their influence on selectivity between ortho-oxygenation and oxidative coupling pathways. These results create an important precedent of catalyst control in the catalytic aerobic oxidation of phenols and set the stage for future development of catalytic systems and mechanistic investigations. PMID:24784319

  3. Methane formation and methane oxidation by methanogenic bacteria.

    PubMed Central

    Zehnder, A J; Brock, T D

    1979-01-01

    Methanogenic bacteria were found to form and oxidize methane at the same time. As compared to the quantity of methane formed, the amount of methane simultaneously oxidized varied between 0.3 and 0.001%, depending on the strain used. All the nine tested strains of methane producers (Methanobacterium ruminantium, Methanobacterium strain M.o.H., M. formicicum, M. thermoautotrophicum, M. arbophilicum, Methanobacterium strain AZ, Methanosarcina barkeri, Methanospirillum hungatii, and the "acetate organism") reoxidized methane to carbon dioxide. In addition, they assimilated a small part of the methane supplied into cell material. Methanol and acetate also occurred as oxidation products in M. barkeri cultures. Acetate was also formed by the "acetate organism," a methane bacterium unable to use methanogenic substrates other than acetate. Methane was the precursor of the methyl group of the acetate synthesized in the course of methane oxidation. Methane formation and its oxidation were inhibited equally by 2-bromoethanesulfonic acid. Short-term labeling experiments with M. thermoautotrophicum and M. hungatii clearly suggest that the pathway of methane oxidation is not identical with a simple back reaction of the methane formation process. Images PMID:762019

  4. Molecular and isotopic insights into methane oxidation in Lake Kivu

    NASA Astrophysics Data System (ADS)

    Zigah, P. K.; Wehrli, B.; Schubert, C. J.

    2013-12-01

    Lake Kivu is a meromictic lake in the East African Rift Valley, located between the Republic of Rwanda and the Democratic Republic of Congo. The hypolimnion is permanently stratified and contain an unusually high amount of dissolved methane (CH4; ~ 60 km3) and carbon dioxide (CO2; ~300 km3) at standard temperature and pressure. While microbial-mediated methane oxidation is an important sink of methane in the lake, little is known about the distribution of microbes involved in the methane oxidation. To provide insights into methanotrophy in the lake, we analyzed depth profile of CH4, δ13C-CH4 and δ13C-DIC, δ13C-POC and the biomarkers of methanotrophic archaea and bacteria and their stable carbon isotopic composition from suspended particulate matter isolated from the lake water column. Our preliminary data show enhanced methane oxidation in oxic-anoxic transition zone in the water column. Depth distribution of diagnostic methanotrophic archaeal biomarkers such as archaeol and hydroxyarchaeol suggest archaea might be involved in anaerobic methane oxidation. Phospholipid fatty acids and diplopterol distribution and carbon isotopic signatures indicate bacteria-mediated anaerobic (and aerobic) methane oxidation in the lake.

  5. Anaerobic Methane Oxidation: Occurrence and Ecology

    PubMed Central

    Zehnder, Alexander J. B.; Brock, Thomas D.

    1980-01-01

    Anoxic sediments and digested sewage sludge anaerobically oxidized methane to carbon dioxide while producing methane. This strictly anaerobic process showed a temperature optimum between 25 and 37°C, indicating an active microbial participation in this reaction. Methane oxidation in these anaerobic habitats was inhibited by oxygen. The rate of the oxidation followed the rate of methane production. The observed anoxic methane oxidation in Lake Mendota and digested sewage sludge was more sensitive to 2-bromoethanesulfonic acid than the simultaneous methane formation. Sulfate diminished methane formation as well as methane oxidation. However, in the presence of iron and sulfate the ratio of methane oxidized to methane formed increased markedly. Manganese dioxide and higher partial pressures of methane also stimulated the oxidation. The rate of methane oxidation in untreated samples was approximately 2% of the CH4 production rate in Lake Mendota sediments and 8% of that in digested sludge. This percentage could be increased up to 90% in sludge in the presence of 10 mM ferrous sulfate and at a partial pressure of methane of 20 atm (2,027 kPa). PMID:16345488

  6. Microbial Methane Oxidation Rates in Guandu Wetland of northern Taiwan

    NASA Astrophysics Data System (ADS)

    Yu, Zih-Huei; Wang, Pei-Ling; Lin, Li-Hung

    2016-04-01

    Wetland is one of the major sources of atmospheric methane. The exact magnitude of methane emission is essentially controlled by microbial processes. Besides of methanogenesis, methanotrophy oxidizes methane with the reduction of various electron acceptors under oxic or anoxic conditions. The interplay of these microbial activities determines the final methane flux under different circumstances. In a tidal wetland, the cyclic flooding and recession of tide render oxygen and sulfate the dominant electron acceptors for methane oxidation. However, the details have not been fully examined, especially for the linkage between potential methane oxidation rates and in situ condition. In this study, a sub-tropical wetland in northern Taiwan, Guandu, was chosen to examine the tidal effect on microbial methane regulation. Several sediment cores were retrieved during high tide and low tide period and their geochemical profiles were characterized to demonstrate in situ microbial activities. Incubation experiments were conducted to estimate potential aerobic and anaerobic methane oxidation rates in surface and core sediments. Sediment cores collected in high tide and low tide period showed different geochemical characteristics, owning to tidal inundation. Chloride and sulfate concentration were lower during low tide period. A spike of enhanced sulfate at middle depth intervals was sandwiched by two sulfate depleted zones above and underneath. Methane was accumulated significantly with two methane depletion zones nearly mirroring the sulfate spike zone identified. During the high tide period, sulfate decreased slightly with depth with methane production inhibited at shallow depths. However, a methane consumption zone still occurred near the surface. Potential aerobic methane oxidation rates were estimated between 0.7 to 1.1 μmole/g/d, showing no difference between the samples collected at high tide or low tide period. However, a lag phase was widely observed and the lag phase

  7. Anaerobic methane oxidation coupled to denitrification is the dominant methane sink in a deep lake

    PubMed Central

    Deutzmann, Joerg S.; Stief, Peter; Brandes, Josephin; Schink, Bernhard

    2014-01-01

    Anaerobic methane oxidation coupled to denitrification, also known as “nitrate/nitrite-dependent anaerobic methane oxidation” (n-damo), was discovered in 2006. Since then, only a few studies have identified this process and the associated microorganisms in natural environments. In aquatic sediments, the close proximity of oxygen- and nitrate-consumption zones can mask n-damo as aerobic methane oxidation. We therefore investigated the vertical distribution and the abundance of denitrifying methanotrophs related to Candidatus Methylomirabilis oxyfera with cultivation-independent molecular techniques in the sediments of Lake Constance. Additionally, the vertical distribution of methane oxidation and nitrate consumption zones was inferred from high-resolution microsensor profiles in undisturbed sediment cores. M. oxyfera-like bacteria were virtually absent at shallow-water sites (littoral sediment) and were very abundant at deep-water sites (profundal sediment). In profundal sediment, the vertical distribution of M. oxyfera-like bacteria showed a distinct peak in anoxic layers that coincided with the zone of methane oxidation and nitrate consumption, a strong indication for n-damo carried out by M. oxyfera-like bacteria. Both potential n-damo rates calculated from cell densities (660–4,890 µmol CH4⋅m−2⋅d−1) and actual rates calculated from microsensor profiles (31–437 µmol CH4⋅m−2⋅d−1) were sufficiently high to prevent methane release from profundal sediment solely by this process. Additionally, when nitrate was added to sediment cores exposed to anoxic conditions, the n-damo zone reestablished well below the sediment surface, completely preventing methane release from the sediment. We conclude that the previously overlooked n-damo process can be the major methane sink in stable freshwater environments if nitrate is available in anoxic zones. PMID:25472842

  8. Aerobic methane production in surface waters of the Gulf of Mexico

    NASA Astrophysics Data System (ADS)

    Finke, N.; Crespo-Medina, M.; Schweers, J.; Joye, S. B.

    2011-12-01

    Near surface water of the global oceans often show elevated methane concentrations compared to the water column below with concentrations in supersaturation in regard to the atmosphere (Lamontagne et al. 1973), resulting in a source of this potent greenhouse gas to the atmosphere. The mechanisms leading to methane supersaturation in surface waters remains unclear. Incubations with Trichodesmium-containing Pacific surface water suggested methylphosphonate as potential methane precursor under phosphate limiting conditions (Karl et al. 2008), whereas in phosphate rich Arctic surface waters, DMSP addition stimulated methane production (Damm et al. 2010). Surface waters of the Gulf of Mexico typically exhibit a methane maximum that is conincident with the deep chlorophyll maximum, below the depths where Trichodesmium is abundant. Addition of methylphosphonate, dimethylsulfoniopropionate (DMSP) or methane thiol (MeSH), the proposed methane precursor in DMSP conversion to methane, to oxic sea water did not affect methane production within the chlorophyll maximum at most stations, whereas methyl phosphonate addition stimulated methane production in the surface water and proposed deep Trichodesmium horizon. Pre-filtration of the water through a 10 μm sieve, which eliminated Trichodesmium, or through a 1.2 μm filter, which eliminated additional cyanobacteria such as Synechococcus, did not reduce methane production. Under dark oxic and dark anoxic conditions, however, methane production was reduced 5 and 7-20 fold, respectively, indicating that anerobic methane production in anoxic microniches is not responsible for the methane production. The reduction of methane production under dark conditions suggests that methane production is, in some yet unrecognized way, linked to phototrophic metabolism. Cyanobacteria are likely not responsible for the observed aerobic methane production in the surface waters of the Gulf of Mexico and while methylphosphonate is a potential

  9. Microbial production and oxidation of methane in deep subsurface

    NASA Astrophysics Data System (ADS)

    Kotelnikova, Svetlana

    2002-10-01

    microbially to carbon dioxide. Microbial methane oxidation is a biogeochemical process that limits the release of methane, a greenhouse gas from anaerobic environments. Anaerobic methane oxidation plays an important role in marine sediments. Similar processes may take place in deep subsurface and thus fuel the deep microbial community. Organisms or consortia responsible for anaerobic methane oxidation have not yet been cultured, although diverse aerobic methanotrophs have been isolated from a variety of underground niches. The presence of aerobic methanotrophs in the anoxic subsurface remains to be explained. The presence of methane in the deep subsurface have been shown all over the world. The flux of gases between the deep subsurface and the atmosphere is driven by the concentration gradient from depth to the atmosphere. However, methane is consumed by methanotrophs on the way of its evolution in oxidized environments and is transformed to organic form, available for further microbial processing. When the impact of subsurface environments to global warming is estimated, it is necessary to take into account the activity of methane-producing Archaea and methane-oxidizing biofilters in groundwater. Microbial production and oxidation of methane is involved in the carbon cycle in the deep subsurface environments.

  10. Inhibition Experiments on Anaerobic Methane Oxidation

    PubMed Central

    Alperin, Marc J.; Reeburgh, William S.

    1985-01-01

    Anaerobic methane oxidation is a general process important in controlling fluxes of methane from anoxic marine sediments. The responsible organism has not been isolated, and little is known about the electron acceptors and substrates involved in the process. Laboratory evidence indicates that sulfate reducers and methanogens are able to oxidize small quantities of methane. Field evidence suggests anaerobic methane oxidation may be linked to sulfate reduction. Experiments with specific inhibitors for sulfate reduction (molybdate), methanogenesis (2-bromoethanesulfonic acid), and acetate utilization (fluoroacetate) were performed on marine sediments from the zone of methane oxidation to determine whether sulfate-reducing bacteria or methanogenic bacteria are responsible for methane oxidation. The inhibition experiment results suggest that methane oxidation in anoxic marine sediments is not directly mediated by sulfate-reducing bacteria or methanogenic bacteria. Our results are consistent with two possibilities: anaerobic methane oxidation may be mediated by an unknown organism or a consortium involving an unknown methane oxidizer and sulfate-reducing bacteria. PMID:16346921

  11. Nitrate-dependent anaerobic methane oxidation in a freshwater sediment

    NASA Astrophysics Data System (ADS)

    Norði, Katrin á.; Thamdrup, Bo

    2014-05-01

    Anaerobic oxidation of methane coupled to denitrification (DAOM) is a novel process of potential importance to the regulation of methane emissions from freshwater environments. We established nitrate-enriched microcosms of sediment from a freshwater pond in order to quantify the role of this process in a simulated natural redox zonation. The microcosms were allowed to acclimate to nitrate levels of 1-2 mmol L-1 in the overlying water for 16 months leading to a nitrate penetration of 4 cm. The nitrate enrichment significantly stimulated AOM relative to controls, and based on the similar concentrations of sulfate and reactive Fe(III) in the control sediment we conclude that the observed AOM was coupled to denitrification. DAOM occurred at rates that were two orders of magnitude lower than aerobic methane oxidation rates reported in freshwater sediments, and the process appeared to be limited by nitrate or nitrite even at millimolar nitrate concentrations. By contrast, ammonium was efficiently consumed at the base of the nitrate zone, presumably by the anammox process. Although DAOM was stimulated by nitrate enrichment, there were no significant differences between the methane emission from the control and nitrate-enriched microcosms. Our results provide the first experimental evaluation of the kinetics of DAOM in whole sediment cores and indicate that AOM coupled to denitrification can consume a substantial part of the methane flux in nitrate-rich environments. Because it is much less efficient in scavenging methane than its aerobic counterpart, the anaerobic process will, however, mainly be of significance in the regulation of methane emission from oxygen-depleted systems.

  12. Anaerobic oxidation of methane: an "active" microbial process.

    PubMed

    Cui, Mengmeng; Ma, Anzhou; Qi, Hongyan; Zhuang, Xuliang; Zhuang, Guoqiang

    2015-02-01

    The anaerobic oxidation of methane (AOM) is an important sink of methane that plays a significant role in global warming. AOM was first found to be coupled with sulfate reduction and mediated by anaerobic methanotrophic archaea (ANME) and sulfate-reducing bacteria (SRB). ANME, often forming consortia with SRB, are phylogenetically related to methanogenic archaea. ANME-1 is even able to produce methane. Subsequently, it has been found that AOM can also be coupled with denitrification. The known microbes responsible for this process are Candidatus Methylomirabilis oxyfera (M. oxyfera) and Candidatus Methanoperedens nitroreducens (M. nitroreducens). Candidatus Methylomirabilis oxyfera belongs to the NC10 bacteria, can catalyze nitrite reduction through an "intra-aerobic" pathway, and may catalyze AOM through an aerobic methane oxidation pathway. However, M. nitroreducens, which is affiliated with ANME-2d archaea, may be able to catalyze AOM through the reverse methanogenesis pathway. Moreover, manganese (Mn(4+) ) and iron (Fe(3+) ) can also be used as electron acceptors of AOM. This review summarizes the mechanisms and associated microbes of AOM. It also discusses recent progress in some unclear key issues about AOM, including ANME-1 in hypersaline environments, the effect of oxygen on M. oxyfera, and the relationship of M. nitroreducens with ANME. PMID:25530008

  13. [Copper in methane oxidation: a review].

    PubMed

    Su, Yao; Kong, Jiao-Yan; Zhang, Xuan; Xia, Fang-Fang; He, Ruo

    2014-04-01

    Methane bio-oxidation plays an important role in the global methane balance and warming mitigation, while copper has a crucial function in methane bio-oxidation. On one side, copper is known to be a key factor in regulating the expression of the genes encoding the two forms of methane monooxygenases (MMOs) and is the essential metal element of the particulate methane monooxygenase (pMMO). On the other side, the content and fractionation of copper in the environment have great effects on the distribution of methanotrophs and their metabolic capability of methane and non-methane organic compounds, as well as on the copper-specific uptake systems in methanotrophs. Thus, it is meaningful to know the role of copper in methane bio-oxidation for comprehensive understanding of this process and is valuable for guiding the application of methanotrophs in greenhouse gas removal and pollution remediation. In this paper, the roles of copper in methane oxidation were reviewed, including the effect of copper on methanotrophic community structure and activity, the expression and activity of MMOs as well as the copper uptake systems in methanotrophs. The future studies of copper and methane oxidation were also discussed.

  14. Methane oxidation linked to chlorite dismutation

    PubMed Central

    Miller, Laurence G.; Baesman, Shaun M.; Carlström, Charlotte I.; Coates, John D.; Oremland, Ronald S.

    2014-01-01

    We examined the potential for CH4 oxidation to be coupled with oxygen derived from the dissimilatory reduction of perchlorate, chlorate, or via chlorite (ClO−2) dismutation. Although dissimilatory reduction of ClO−4 and ClO−3 could be inferred from the accumulation of chloride ions either in spent media or in soil slurries prepared from exposed freshwater lake sediment, neither of these oxyanions evoked methane oxidation when added to either anaerobic mixed cultures or soil enriched in methanotrophs. In contrast, ClO−2 amendment elicited such activity. Methane (0.2 kPa) was completely removed within several days from the headspace of cell suspensions of Dechloromonas agitata CKB incubated with either Methylococcus capsulatus Bath or Methylomicrobium album BG8 in the presence of 5 mM ClO−2. We also observed complete removal of 0.2 kPa CH4 in bottles containing soil enriched in methanotrophs when co-incubated with D. agitata CKB and 10 mM ClO−2. However, to be effective these experiments required physical separation of soil from D. agitata CKB to allow for the partitioning of O2 liberated from chlorite dismutation into the shared headspace. Although a link between ClO−2 and CH4 consumption was established in soils and cultures, no upstream connection with either ClO−4 or ClO−3 was discerned. This result suggests that the release of O2 during enzymatic perchlorate reduction was negligible, and that the oxygen produced was unavailable to the aerobic methanotrophs. PMID:24987389

  15. Methane oxidation linked to chlorite dismutation

    USGS Publications Warehouse

    Miller, Laurence G.; Baesman, Shaun M.; Carlström, Charlotte I.; Coates, John D.; Oremland, Ronald S.

    2014-01-01

    We examined the potential for CH4 oxidation to be coupled with oxygen derived from the dissimilatory reduction of perchlorate, chlorate, or via chlorite (ClO−2) dismutation. Although dissimilatory reduction of ClO−4 and ClO−3 could be inferred from the accumulation of chloride ions either in spent media or in soil slurries prepared from exposed freshwater lake sediment, neither of these oxyanions evoked methane oxidation when added to either anaerobic mixed cultures or soil enriched in methanotrophs. In contrast, ClO−2 amendment elicited such activity. Methane (0.2 kPa) was completely removed within several days from the headspace of cell suspensions of Dechloromonas agitata CKB incubated with either Methylococcus capsulatus Bath or Methylomicrobium album BG8 in the presence of 5 mM ClO−2. We also observed complete removal of 0.2 kPa CH4 in bottles containing soil enriched in methanotrophs when co-incubated with D. agitata CKB and 10 mM ClO−2. However, to be effective these experiments required physical separation of soil from D. agitata CKB to allow for the partitioning of O2 liberated from chlorite dismutation into the shared headspace. Although a link between ClO−2 and CH4 consumption was established in soils and cultures, no upstream connection with either ClO−4 or ClO−3 was discerned. This result suggests that the release of O2 during enzymatic perchlorate reduction was negligible, and that the oxygen produced was unavailable to the aerobic methanotrophs.

  16. Carbon and hydrogen isotope fractionation during nitrite-dependent anaerobic methane oxidation by Methylomirabilis oxyfera

    NASA Astrophysics Data System (ADS)

    Rasigraf, Olivia; Vogt, Carsten; Richnow, Hans-Hermann; Jetten, Mike S. M.; Ettwig, Katharina F.

    2012-07-01

    Anaerobic oxidation of methane coupled to nitrite reduction is a recently discovered methane sink of as yet unknown global significance. The bacteria that have been identified to carry out this process, Candidatus Methylomirabilis oxyfera, oxidize methane via the known aerobic pathway involving the monooxygenase reaction. In contrast to aerobic methanotrophs, oxygen is produced intracellularly and used for the activation of methane by a phylogenetically distinct particulate methane monooxygenase (pMMO). Here we report the fractionation factors for carbon and hydrogen during methane oxidation by an enrichment culture of M. oxyfera bacteria. In two separate batch incubation experiments with different absolute biomass and methane contents, the specific methanotrophic activity was similar and the progressive isotope enrichment identical. Headspace methane was consumed up to 98% with rates showing typical first order reaction kinetics. The enrichment factors determined by Rayleigh equations were -29.2 ± 2.6‰ for δ13C (εC) and -227.6 ± 13.5‰ for δ2H (εH), respectively. These enrichment factors were in the upper range of values reported so far for aerobic methanotrophs. In addition, two-dimensional specific isotope analysis (Λ = ( α H - 1 - 1)/( α C - 1 - 1)) was performed and also the determined Λ value of 9.8 was within the range determined for other aerobic and anaerobic methanotrophs. The results showed that in contrast to abiotic processes biological methane oxidation exhibits a narrow range of fractionation factors for carbon and hydrogen irrespective of the underlying biochemical mechanisms. This work will therefore facilitate the correct interpretation of isotopic composition of atmospheric methane with implications for modeling of global carbon fluxes.

  17. Comparison of Two Techniques to Calculate Methane Oxidation rates in Samples Obtained From the Hudson Canyon Seep Field in the North Atlantic

    NASA Astrophysics Data System (ADS)

    Leonte, M.; Kessler, J. D.; Chepigin, A.; Kellermann, M. Y.; Arrington, E.; Valentine, D. L.; Sylva, S.

    2014-12-01

    Aerobic methane oxidation, or methanotrophy, is the dominant process by which methane is removed from the water column in oceanic environments. Therefore, accurately quantifying methane oxidation rates is crucial when constructing methane budgets on a local or global scale. Here we present a comparison of two techniques used to determine methane oxidation rates based on samples obtained over the Hudson Canyon seep field in the North Atlantic. Traditional methane oxidation rate measurements require inoculation of water samples with isotopically labeled methane and tracking the changes to methane concentrations and isotopes as the samples are incubated. However, the addition of methane above background levels is thought to increase the potential for methane oxidation in the sample. A new technique to calculate methane oxidation rates is based on kinetic isotope models and incorporates direct measurements of methane concentrations, methane 13C isotopes, and water current velocity. Acoustic instrumentation (ADCP) aboard the R/V Endeavor was used to obtain water current velocity data while water samples were collected for methane concentration and isotopic ratio analysis. Methane δ13C measurements allow us to attribute changes in methane concentration to either water dispersion or bacterial methane oxidation. The data obtained from this cruise will tell us a comprehensive story of methane removal processes from this active seep field. The kinetic isotope models will allow us to estimate the total flux of methane from the seep site and calculate methane oxidation rates at different depths and locations away from seafloor plumes.

  18. Surface Structure of Aerobically Oxidized Diamond Nanocrystals

    PubMed Central

    2015-01-01

    We investigate the aerobic oxidation of high-pressure, high-temperature nanodiamonds (5–50 nm dimensions) using a combination of carbon and oxygen K-edge X-ray absorption, wavelength-dependent X-ray photoelectron, and vibrational spectroscopies. Oxidation at 575 °C for 2 h eliminates graphitic carbon contamination (>98%) and produces nanocrystals with hydroxyl functionalized surfaces as well as a minor component (<5%) of carboxylic anhydrides. The low graphitic carbon content and the high crystallinity of HPHT are evident from Raman spectra acquired using visible wavelength excitation (λexcit = 633 nm) as well as carbon K-edge X-ray absorption spectra where the signature of a core–hole exciton is observed. Both spectroscopic features are similar to those of chemical vapor deposited (CVD) diamond but differ significantly from the spectra of detonation nanodiamond. The importance of these findings to the functionalization of nanodiamond surfaces for biological labeling applications is discussed. PMID:25436035

  19. Methane oxidation and methanotrophs: resistance and resilience against model perturbations

    NASA Astrophysics Data System (ADS)

    Ho, A.; Frenzel, P.

    2009-04-01

    Biodiversity is claimed to be essential for ecosystem functioning. However, most experiments on biodiversity and ecosystem functioning (BEF) have been made on higher plants, while only few studies have dealt with microbial communities. Overall microbial diversity may be very high, and general functions like aerobic carbon mineralization are assumed to be supported by highly redundant communities. Therefore, we focused on methane oxidation, a microbial process of global importance mitigating methane emissions from wetland, rice fields, and landfills. We used a rice paddy as our model system, where >90% of potentially emitted methane may be oxidized in the oxic surface layer. This community is presumed to consist of 10-20 taxa more or less equivalent to species. We focused on the ability of methanotrophs to recover from a disturbance causing a significant die-off of all microbial populations. This was simulated by mixing native with sterile soil in two ratios (1:4 and 1:40). Microcosms were incubated and the temporal shift of the methanotrophic communities was followed by pmoA-based Terminal Restriction Length Polymorphism (T-RFLP), qPCR, and a pmoA-based diagnostic microarray. We consistently observed distinctive temporal shifts between Methylocystaceaea and Methylococcacea, a rapid population growth leading to the same or even higher cell numbers as in microcosms made from native soil alone, but no effect on the amount of methane oxidized. The ratio of different methanotrophs changed with treatment, while the number of taxa stayed nearly the same. Overall, methanotrophs showed a remarkable resilience compensating for die-offs. It has to be noted, however, that our experiment focused on methanotrophs adapted to and living at high methane fluxes. Quite different, methanotrophs living in upland soils do not mitigate methane emissions, but are the only biological sink to atmospheric methane. These microbes are severely substrate limited, and will be much more

  20. Anaerobic oxidation of methane in grassland soils used for cattle husbandry

    NASA Astrophysics Data System (ADS)

    Bannert, A.; Bogen, C.; Esperschütz, J.; Koubová, A.; Buegger, F.; Fischer, D.; Radl, V.; Fuß, R.; Chroňáková, A.; Elhottová, D.; Šimek, M.; Schloter, M.

    2012-04-01

    While the importance of anaerobic methane oxidation has been reported for marine ecosystems, the role of this process in soils is still questionable. Grasslands used as pastures for cattle-overwintering show an increase in anaerobic soil micro-sites caused by animal treading and excrement deposition. Therefore anaerobic potential methane oxidation activity of severely impacted soil from a cattle winter pasture was investigated in an incubation experiment under anaerobic conditions using 13C-labeled methane. We were able to detect a high microbial activity utilizing CH4 as nutrient source shown by the respiration of 13CO2. Measurements of possible terminal electron acceptors for anaerobic oxidation of methane were carried out. Soil sulfate concentrations were too low to explain the oxidation of the amount of methane added, but enough nitrate and iron(III) were detected. However, only nitrate was consumed during the experiment. 13C-PLFA analyses clearly showed the utilization of CH4 as nutrient source mainly by organisms harbouring 16:1ω7 PLFAs. These lipids were found in Gram-negative microorganisms and anaerobes. The fact that these lipids are also typical for type I methanotrophs, known as aerobic methane oxidizers, might indicate a link between aerobic and anaerobic methane oxidation.

  1. Thermophilic methane production and oxidation in compost.

    PubMed

    Jäckel, Udo; Thummes, Kathrin; Kämpfer, Peter

    2005-04-01

    Methane cycling within compost heaps has not yet been investigated in detail. We show that thermophilic methane oxidation occurred after a lag phase of up to one day in 4-week old, 8-week old and mature (>10-week old) compost material. The potential rate of methane oxidation was between 2.6 and 4.1 micromol CH4(gdw)(-1)h(-1). Profiles of methane concentrations within heaps of different ages indicated that 46-98% of the methane produced was oxidised by methanotrophic bacteria. The population size of thermophilic methanotrophs was estimated at 10(9) cells (gdw)(-1), based on methane oxidation rates. A methanotroph (strain KTM-1) was isolated from the highest positive step of a serial dilution series. This strain belonged to the genus Methylocaldum, which contains thermotolerant and thermophilic methanotrophs. The closest relative organism on the basis of 16S rRNA gene sequence identity was M. szegediense (>99%), a species originally isolated from hot springs. The temperature optimum (45-55 degrees C) for methane oxidation within the compost material was identical to that of strain KTM-1, suggesting that this strain was well adapted to the conditions in the compost material. The temperatures measured in the upper layer (0-40 cm) of the compost heaps were also in this range, so we assume that these organisms are capable of effectively reducing the potential methane emissions from compost.

  2. Anaerobic methane oxidation on the Amazon shelf

    SciTech Connect

    Blair, N.E.; Aller, R.C.

    1995-09-01

    Anaerobic methane oxidation on the Amazon shelf is strongly controlled by dynamic physical sedimentation processes. Rapidly accumulating, physically reworked deltaic sediments characteristic of much of the shelf typically support what appear to be low rates of steady state anaerobic methane oxidation at depths of 5-8 m below the sediment-water interface. Methane oxidation in these cases is responsible for < {approximately}10% of the {Sigma}CO{sub 2} inventory in the oxidation zone and is limited largely by the steady-state diffusive flux of methane into the overlying sulfate reduction zone. In contrast, a large area of the shelf has been extensively eroded, reexposing once deeply buried (>10 m) methane-charged sediment directly to seawater. In this nonsteady-state situation, methane is a major source of recently produced {Sigma}CO{sub 2} and an important reductant for sulfate. These observations suggest that authigenic sedimentary carbonates derived from anaerobic methane oxidation may sometimes reflect physically enhanced nonsteady-state exposure of methane to sulfate in otherwise biogeochemically unreactive deposits. The concentration profiles of CH{sub 4}, SO{sub 4}{sup =}, and {Sigma}CO{sub 2} in the eroded deposit were reproduced by a coupled reaction-transport model. This area of the shelf was reexposed to seawater approximately 5-10 years ago based on the model results and the assumption that the erosion of the deposit occurred as a single event that has now ceased. The necessary second order rate constant for anaerobic methane oxidation was {le}0.1 mM{sup -1} d{sup -1}.

  3. Anaerobic oxidation of methane: progress with an unknown process.

    PubMed

    Knittel, Katrin; Boetius, Antje

    2009-01-01

    Methane is the most abundant hydrocarbon in the atmosphere, and it is an important greenhouse gas, which has so far contributed an estimated 20% of postindustrial global warming. A great deal of biogeochemical research has focused on the causes and effects of the variation in global fluxes of methane throughout earth's history, but the underlying microbial processes and their key agents remain poorly understood. This is a disturbing knowledge gap because 85% of the annual global methane production and about 60% of its consumption are based on microbial processes. Only three key functional groups of microorganisms of limited diversity regulate the fluxes of methane on earth, namely the aerobic methanotrophic bacteria, the methanogenic archaea, and their close relatives, the anaerobic methanotrophic archaea (ANME). The ANME represent special lines of descent within the Euryarchaeota and appear to gain energy exclusively from the anaerobic oxidation of methane (AOM), with sulfate as the final electron acceptor according to the net reaction: CH(4) + SO(42-) ---> HCO(3-) + HS(-) + H(2)O. This review summarizes what is known and unknown about AOM on earth and its key catalysts, the ANME clades and their bacterial partners.

  4. Anaerobic oxidation of methane: an “active” microbial process

    PubMed Central

    Cui, Mengmeng; Ma, Anzhou; Qi, Hongyan; Zhuang, Xuliang; Zhuang, Guoqiang

    2015-01-01

    The anaerobic oxidation of methane (AOM) is an important sink of methane that plays a significant role in global warming. AOM was first found to be coupled with sulfate reduction and mediated by anaerobic methanotrophic archaea (ANME) and sulfate-reducing bacteria (SRB). ANME, often forming consortia with SRB, are phylogenetically related to methanogenic archaea. ANME-1 is even able to produce methane. Subsequently, it has been found that AOM can also be coupled with denitrification. The known microbes responsible for this process are Candidatus Methylomirabilis oxyfera (M. oxyfera) and Candidatus Methanoperedens nitroreducens (M. nitroreducens). Candidatus Methylomirabilis oxyfera belongs to the NC10 bacteria, can catalyze nitrite reduction through an “intra-aerobic” pathway, and may catalyze AOM through an aerobic methane oxidation pathway. However, M. nitroreducens, which is affiliated with ANME-2d archaea, may be able to catalyze AOM through the reverse methanogenesis pathway. Moreover, manganese (Mn4+) and iron (Fe3+) can also be used as electron acceptors of AOM. This review summarizes the mechanisms and associated microbes of AOM. It also discusses recent progress in some unclear key issues about AOM, including ANME-1 in hypersaline environments, the effect of oxygen on M. oxyfera, and the relationship of M. nitroreducens with ANME. PMID:25530008

  5. News from the "blowout", a man-made methane pockmark in the North Sea: chemosynthetic communities and microbial methane oxidation

    NASA Astrophysics Data System (ADS)

    Steinle, Lea I.; Wilfert, Philipp; Schmidt, Mark; Bryant, Lee; Haeckel, Matthias; Lehmann, Moritz F.; Linke, Peter; Sommer, Stefan; Treude, Tina; Niemann, Helge

    2013-04-01

    The accidental penetration of a base-Quaternary shallow gas pocket by a drilling rig in 1990 caused a "blowout" in the British sector of the North Sea (57°55.29' N, 01°37.86' E). Large quantities of methane have been seeping out of this man-made pockmark ever since. As the onset of gas seepage is well constrained, this site can be used as a natural laboratory to gain information on the development of methane oxidizing microbial communities at cold seeps. During an expedition with the R/V Celtic Explorer in July and August 2012, we collected sediments by video-guided push-coring with an ROV (Kiel 6000) along a gradient from inside the crater (close to where a jet of methane bubbles enters the water column) outwards. We also sampled the water column in a grid above the blowout at three different depths. In this presentation, we provide evidence for the establishment of methanotrophic communities in the sediment (AOM communities) on a time scale of decades. Furthermore, we will report data on methane concentrations and anaerobic methane oxidation rates in the sediment. Finally, we will also discuss the spatial distribution of methane and aerobic methane oxidation rates in the water column.

  6. Surface Structure of Aerobically Oxidized Diamond Nanocrystals

    SciTech Connect

    Wolcott, Abraham; Schiros, Theanne; Trusheim, Matthew E.; Chen, Edward H.; Nordlund, Dennis; Diaz, Rosa E.; Gaaton, Ophir; Englund, Dirk; Owen, Jonathan S.

    2014-10-27

    Here we investigate the aerobic oxidation of high-pressure, high-temperature nanodiamonds (5–50 nm dimensions) using a combination of carbon and oxygen K-edge X-ray absorption, wavelength-dependent X-ray photoelectron, and vibrational spectroscopies. Oxidation at 575 °C for 2 h eliminates graphitic carbon contamination (>98%) and produces nanocrystals with hydroxyl functionalized surfaces as well as a minor component (<5%) of carboxylic anhydrides. The low graphitic carbon content and the high crystallinity of HPHT are evident from Raman spectra acquired using visible wavelength excitation (λexcit = 633 nm) as well as carbon K-edge X-ray absorption spectra where the signature of a core–hole exciton is observed. Both spectroscopic features are similar to those of chemical vapor deposited (CVD) diamond but differ significantly from the spectra of detonation nanodiamond. Lastly, we discuss the importance of these findings to the functionalization of nanodiamond surfaces for biological labeling applications.

  7. Surface Structure of Aerobically Oxidized Diamond Nanocrystals

    DOE PAGES

    Wolcott, Abraham; Schiros, Theanne; Trusheim, Matthew E.; Chen, Edward H.; Nordlund, Dennis; Diaz, Rosa E.; Gaaton, Ophir; Englund, Dirk; Owen, Jonathan S.

    2014-10-27

    Here we investigate the aerobic oxidation of high-pressure, high-temperature nanodiamonds (5–50 nm dimensions) using a combination of carbon and oxygen K-edge X-ray absorption, wavelength-dependent X-ray photoelectron, and vibrational spectroscopies. Oxidation at 575 °C for 2 h eliminates graphitic carbon contamination (>98%) and produces nanocrystals with hydroxyl functionalized surfaces as well as a minor component (<5%) of carboxylic anhydrides. The low graphitic carbon content and the high crystallinity of HPHT are evident from Raman spectra acquired using visible wavelength excitation (λexcit = 633 nm) as well as carbon K-edge X-ray absorption spectra where the signature of a core–hole exciton is observed.more » Both spectroscopic features are similar to those of chemical vapor deposited (CVD) diamond but differ significantly from the spectra of detonation nanodiamond. Lastly, we discuss the importance of these findings to the functionalization of nanodiamond surfaces for biological labeling applications.« less

  8. Growth of nitrite-oxidizing bacteria by aerobic hydrogen oxidation.

    PubMed

    Koch, Hanna; Galushko, Alexander; Albertsen, Mads; Schintlmeister, Arno; Gruber-Dorninger, Christiane; Lücker, Sebastian; Pelletier, Eric; Le Paslier, Denis; Spieck, Eva; Richter, Andreas; Nielsen, Per H; Wagner, Michael; Daims, Holger

    2014-08-29

    The bacterial oxidation of nitrite to nitrate is a key process of the biogeochemical nitrogen cycle. Nitrite-oxidizing bacteria are considered a highly specialized functional group, which depends on the supply of nitrite from other microorganisms and whose distribution strictly correlates with nitrification in the environment and in wastewater treatment plants. On the basis of genomics, physiological experiments, and single-cell analyses, we show that Nitrospira moscoviensis, which represents a widely distributed lineage of nitrite-oxidizing bacteria, has the genetic inventory to utilize hydrogen (H2) as an alternative energy source for aerobic respiration and grows on H2 without nitrite. CO2 fixation occurred with H2 as the sole electron donor. Our results demonstrate a chemolithoautotrophic lifestyle of nitrite-oxidizing bacteria outside the nitrogen cycle, suggesting greater ecological flexibility than previously assumed.

  9. Inhibitory effects of sulfur compounds on methane oxidation by a methane-oxidizing consortium.

    PubMed

    Lee, Eun-Hee; Moon, Kyung-Eun; Kim, Tae Gwan; Lee, Sang-Don; Cho, Kyung-Suk

    2015-12-01

    Kinetic and enzymatic inhibition experiments were performed to investigate the effects of methanethiol (MT) and hydrogen sulfide (H2S) on methane oxidation by a methane-oxidizing consortium. In the coexistence of MT and H2S, the oxidation of methane was delayed until MT and H2S were completely degraded. MT and H2S could be degraded, both with and without methane. The kinetic analysis revealed that the methane-oxidizing consortium showed a maximum methane oxidation rate (Vmax) of 3.7 mmol g-dry cell weight (DCW)(-1) h(-1) and a saturation constant (Km) of 184.1 μM. MT and H2S show competitive inhibition on methane oxidation, with inhibition values (Ki) of 1504.8 and 359.8 μM, respectively. MT was primary removed by particulate methane monooxygenases (pMMO) of the consortium, while H2S was degraded by the other microorganisms or enzymes in the consortium. DNA and mRNA transcript levels of the pmoA gene expressions were decreased to ∼10(6) and 10(3)pmoA gene copy number g-DCW(-1) after MT and H2S degradation, respectively; however, both the amount of the DNA and mRNA transcript recovered their initial levels of ∼10(7) and 10(5)pmoA gene copy number g-DCW(-1) after methane oxidation, respectively. The gene expression results indicate that the pmoA gene could be rapidly reproducible after methane oxidation. This study provides comprehensive information of kinetic interactions between methane and sulfur compounds. PMID:26143035

  10. Inhibitory effects of sulfur compounds on methane oxidation by a methane-oxidizing consortium.

    PubMed

    Lee, Eun-Hee; Moon, Kyung-Eun; Kim, Tae Gwan; Lee, Sang-Don; Cho, Kyung-Suk

    2015-12-01

    Kinetic and enzymatic inhibition experiments were performed to investigate the effects of methanethiol (MT) and hydrogen sulfide (H2S) on methane oxidation by a methane-oxidizing consortium. In the coexistence of MT and H2S, the oxidation of methane was delayed until MT and H2S were completely degraded. MT and H2S could be degraded, both with and without methane. The kinetic analysis revealed that the methane-oxidizing consortium showed a maximum methane oxidation rate (Vmax) of 3.7 mmol g-dry cell weight (DCW)(-1) h(-1) and a saturation constant (Km) of 184.1 μM. MT and H2S show competitive inhibition on methane oxidation, with inhibition values (Ki) of 1504.8 and 359.8 μM, respectively. MT was primary removed by particulate methane monooxygenases (pMMO) of the consortium, while H2S was degraded by the other microorganisms or enzymes in the consortium. DNA and mRNA transcript levels of the pmoA gene expressions were decreased to ∼10(6) and 10(3)pmoA gene copy number g-DCW(-1) after MT and H2S degradation, respectively; however, both the amount of the DNA and mRNA transcript recovered their initial levels of ∼10(7) and 10(5)pmoA gene copy number g-DCW(-1) after methane oxidation, respectively. The gene expression results indicate that the pmoA gene could be rapidly reproducible after methane oxidation. This study provides comprehensive information of kinetic interactions between methane and sulfur compounds.

  11. Oxidative conversion of methane to higher hydrocarbons

    SciTech Connect

    Sofranko, J.A.; Leonard, J.J.; Jones, C.A.

    1987-02-01

    Many transition metal oxides have been evaluated as oxidative coupling catalysts for converting methane to C/sub 2/ and higher hydrocarbons. Reactions were done in a cyclic redox mode in which oxidized catalyst was reacted with methane in the absence of oxygen to form coupling products and reduced catalyst which was reoxidized with air in a separate step. Manganese, indium, germanium, antimony, tin, bismuth, and lead oxides were found to be effective coupling catalysts, giving 10 to 50% selectivity to higher hydrocarbons. Silica is a superior support compared to alumina. Mechanistic studies with manganese oxide on silica indicate that the initial coupling product is ethane which is formed via dimerization of a CH/sub 3/ radical-like species. The ethane is oxidatively dehydrogenated to ethylene which may react with CH/sub 3/ to give propylene. The major path for combustion involves sequential oxidation of products.

  12. Methane Oxidation in Termite Hindguts: Absence of Evidence and Evidence of Absence▿

    PubMed Central

    Pester, Michael; Tholen, Anne; Friedrich, Michael W.; Brune, Andreas

    2007-01-01

    A steep oxygen gradient and the presence of methane render the hindgut internal periphery of termites a potential habitat for aerobic methane-oxidizing bacteria. However, methane emissions of various termites increased, if at all, only slightly when termites were exposed to an anoxic (nitrogen) atmosphere, and 14CH4 added to the air headspace over live termites was not converted to 14CO2. Evidence for the absence of methane oxidation in living termites was corroborated by the failure to detect pmoA, the marker gene for particulate methane monooxygenase, in hindgut DNA extracts of all termites investigated. This adds robustness to our concept of the degradation network in the termite hindgut and eliminates the gut itself as a potential sink of this important greenhouse gas. PMID:17261514

  13. Seasonal Oxygen Dynamics in a Thermokarst Bog in Interior Alaska: Implications for Rates of Methane Oxidation

    NASA Astrophysics Data System (ADS)

    Neumann, R. B.; Moorberg, C.; Wong, A.; Waldrop, M. P.; Turetsky, M. R.

    2015-12-01

    Methane is a potent greenhouse gas, and wetlands represent the largest natural source of methane to the atmosphere. However, much of the methane generated in anoxic wetlands never gets emitted to the atmosphere; up to >90% of generated methane can get oxidized to carbon dioxide. Thus, oxidation is an important methane sink and changes in the rate of methane oxidation can affect wetland methane emissions. Most methane is aerobically oxidized at oxic-anoxic interfaces where rates of oxidation strongly depend on methane and oxygen concentrations. In wetlands, oxygen is often the limiting substrate. To improve understanding of belowground oxygen dynamics and its impact on methane oxidation, we deployed two planar optical oxygen sensors in a thermokarst bog in interior Alaska. Previous work at this site indicated that, similar to other sites, rates of methane oxidation decrease over the growing season. We used the sensors to track spatial and temporal patterns of oxygen concentrations over the growing season. We coupled these in-situ oxygen measurements with periodic oxygen injection experiments performed against the sensor to quantify belowground rates of oxygen consumption. We found that over the season, the thickness of the oxygenated water layer at the peatland surface decreased. Previous research has indicated that in sphagnum-dominated peatlands, like the one studied here, rates of methane oxidation are highest at or slightly below the water table. It is in these saturated but oxygenated locations that both methane and oxygen are available. Thus, a seasonal reduction in the thickness of the oxygenated water layer could restrict methane oxidation. The decrease in thickness of the oxygenated layer coincided with an increase in the rate of oxygen consumption during our oxygen injection experiments. The increase in oxygen consumption was not explained by temperature; we infer it was due to an increase in substrate availability for oxygen consuming reactions and

  14. Effects of exogenous aerobic bacteria on methane production and biodegradation of municipal solid waste in bioreactors.

    PubMed

    Ge, Sai; Liu, Lei; Xue, Qiang; Yuan, Zhiming

    2016-09-01

    Landfill is the most common and efficient ways of municipal solid waste (MSW) disposal and the landfill biogas, mostly methane, is currently utilized to generate electricity and heat. The aim of this work is to study the effects and the role of exogenous aerobic bacteria mixture (EABM) on methane production and biodegradation of MSW in bioreactors. The results showed that the addition of EABM could effectively enhance hydrolysis and acidogenesis processes of MSW degradation, resulting in 63.95% reduction of volatile solid (VS), the highest methane production rate (89.83Lkg(-1) organic matter) ever recorded and a threefold increase in accumulative methane production (362.9L) than the control (127.1L). In addition, it is demonstrated that white-rot fungi (WRF) might further promote the methane production through highly decomposing lignin, but the lower pH value in leachate and longer acidogenesis duration may cause methane production reduced. The data demonstrated that methane production and biodegradation of MSW in bioreactors could be significantly enhanced by EABM via enhanced hydrolysis and acidogenesis processes, and the results are of great economic importance for the future design and management of landfill. PMID:26601890

  15. Effects of exogenous aerobic bacteria on methane production and biodegradation of municipal solid waste in bioreactors.

    PubMed

    Ge, Sai; Liu, Lei; Xue, Qiang; Yuan, Zhiming

    2016-09-01

    Landfill is the most common and efficient ways of municipal solid waste (MSW) disposal and the landfill biogas, mostly methane, is currently utilized to generate electricity and heat. The aim of this work is to study the effects and the role of exogenous aerobic bacteria mixture (EABM) on methane production and biodegradation of MSW in bioreactors. The results showed that the addition of EABM could effectively enhance hydrolysis and acidogenesis processes of MSW degradation, resulting in 63.95% reduction of volatile solid (VS), the highest methane production rate (89.83Lkg(-1) organic matter) ever recorded and a threefold increase in accumulative methane production (362.9L) than the control (127.1L). In addition, it is demonstrated that white-rot fungi (WRF) might further promote the methane production through highly decomposing lignin, but the lower pH value in leachate and longer acidogenesis duration may cause methane production reduced. The data demonstrated that methane production and biodegradation of MSW in bioreactors could be significantly enhanced by EABM via enhanced hydrolysis and acidogenesis processes, and the results are of great economic importance for the future design and management of landfill.

  16. Photocatalytic oxidation of methane over silver decorated zinc oxide nanocatalysts.

    PubMed

    Chen, Xuxing; Li, Yunpeng; Pan, Xiaoyang; Cortie, David; Huang, Xintang; Yi, Zhiguo

    2016-01-01

    The search for active catalysts that efficiently oxidize methane under ambient conditions remains a challenging task for both C1 utilization and atmospheric cleansing. Here, we show that when the particle size of zinc oxide is reduced down to the nanoscale, it exhibits high activity for methane oxidation under simulated sunlight illumination, and nano silver decoration further enhances the photo-activity via the surface plasmon resonance. The high quantum yield of 8% at wavelengths <400 nm and over 0.1% at wavelengths ∼470 nm achieved on the silver decorated zinc oxide nanostructures shows great promise for atmospheric methane oxidation. Moreover, the nano-particulate composites can efficiently photo-oxidize other small molecular hydrocarbons such as ethane, propane and ethylene, and in particular, can dehydrogenize methane to generate ethane, ethylene and so on. On the basis of the experimental results, a two-step photocatalytic reaction process is suggested to account for the methane photo-oxidation. PMID:27435112

  17. Photocatalytic oxidation of methane over silver decorated zinc oxide nanocatalysts

    PubMed Central

    Chen, Xuxing; Li, Yunpeng; Pan, Xiaoyang; Cortie, David; Huang, Xintang; Yi, Zhiguo

    2016-01-01

    The search for active catalysts that efficiently oxidize methane under ambient conditions remains a challenging task for both C1 utilization and atmospheric cleansing. Here, we show that when the particle size of zinc oxide is reduced down to the nanoscale, it exhibits high activity for methane oxidation under simulated sunlight illumination, and nano silver decoration further enhances the photo-activity via the surface plasmon resonance. The high quantum yield of 8% at wavelengths <400 nm and over 0.1% at wavelengths ∼470 nm achieved on the silver decorated zinc oxide nanostructures shows great promise for atmospheric methane oxidation. Moreover, the nano-particulate composites can efficiently photo-oxidize other small molecular hydrocarbons such as ethane, propane and ethylene, and in particular, can dehydrogenize methane to generate ethane, ethylene and so on. On the basis of the experimental results, a two-step photocatalytic reaction process is suggested to account for the methane photo-oxidation. PMID:27435112

  18. Field assessment of semi-aerobic condition and the methane correction factor for the semi-aerobic landfills provided by IPCC guidelines

    SciTech Connect

    Jeong, Sangjae; Nam, Anwoo; Yi, Seung-Muk; Kim, Jae Young

    2015-02-15

    Highlights: • CH{sub 4}/CO{sub 2} and CH{sub 4} + CO{sub 2}% are proposed as indices to evaluate semi-aerobic landfills. • A landfill which CH{sub 4}/CO{sub 2} > 1.0 is difficult to be categorized as semi-aerobic landfill. • Field conditions should be carefully investigated to determine landfill types. • The MCF default value for semi-aerobic landfills underestimates the methane emissions. - Abstract: According to IPCC guidelines, a semi-aerobic landfill site produces one-half of the amount of CH{sub 4} produced by an equally-sized anaerobic landfill site. Therefore categorizing the landfill type is important on greenhouse gas inventories. In order to assess semi-aerobic condition in the sites and the MCF value for semi-aerobic landfill, landfill gas has been measured from vent pipes in five semi-aerobically designed landfills in South Korea. All of the five sites satisfied requirements of semi-aerobic landfills in 2006 IPCC guidelines. However, the ends of leachate collection pipes which are main entrance of air in the semi-aerobic landfill were closed in all five sites. The CH{sub 4}/CO{sub 2} ratio in landfill gas, indicator of aerobic and anaerobic decomposition, ranged from 1.08 to 1.46 which is higher than the values (0.3–1.0) reported for semi-aerobic landfill sites and is rather close to those (1.0–2.0) for anaerobic landfill sites. The low CH{sub 4} + CO{sub 2}% in landfill gas implied air intrusion into the landfill. However, there was no evidence that air intrusion has caused by semi-aerobic design and operation. Therefore, the landfills investigated in this study are difficult to be classified as semi-aerobic landfills. Also MCF of 0.5 may significantly underestimate methane emissions compared to other researches. According to the carbon mass balance analyses, the higher MCF needs to be proposed for semi-aerobic landfills. Consequently, methane emission estimate should be based on field evaluation for the semi-aerobically designed landfills.

  19. Crystal structure of methane oxidation enzyme determined

    SciTech Connect

    Baum, R.

    1994-01-10

    A team of chemists has determined to 2.2-[angstrom] resolution the crystal structure of the hydroxylase protein of methane monooxygenase, the enzyme system responsible for the biological oxidation of methane. The hydroxylase, at a molecular weight of 251,000 daltons, if by far the largest component of methane monooxygenase. Although the crystal structure of the hydroxylase did not reveal any startling surprises about the enzyme-many features of the hydroxylase had been inferred previously from modeling and spectroscopic studies -- obtaining it is a significant achievement. For one thing, the crystal structure unambiguously confirms aspects of the enzyme structure that been at least somewhat speculative. The three-dimensional structure of the enzyme, the chemist say, also provides important insight into biological methane oxidation, including how methane, a relatively inert gas, might diffuse to and bind near the active site of the enzyme. The structure points to particular amino acid residues that are likely to participate in catalysis, and clarifies the structure of the dinuclear iron core of the enzyme.

  20. Oxidation of ammonia and methane in an alkaline, saline lake

    USGS Publications Warehouse

    Joye, S.B.; Connell, T.L.; Miller, L.G.; Oremland, R.S.; Jellison, R.S.

    1999-01-01

    The oxidation of ammonia (NH3) and methane (CH4) was investigated in an alkaline saline lake, Mono Lake, California (U.S.A.). Ammonia oxidation was examined in April and July 1995 by comparing dark 14CO2 fixation rates in the presence or absence of methyl fluoride (MeF), an inhibitor of NH3 oxidation. Ammonia oxidizer-mediated dark 14CO2 fixation rates were similar in surface (5-7 m) and oxycline (11-15 m) waters, ranging between 70-340 and 89-186 nM d-1, respectively, or 1-7% of primary production by phytoplankton. Ammonia oxidation rates ranged between 580-2,830 nM d-1 in surface waters and 732-1,548 nM d-1 in oxycline waters. Methane oxidation was examined using a 14CH4 tracer technique in July 1994, April 1995, and July 1995. Methane oxidation rates were consistently higher in July, and rates in oxycline and anaerobic bottom waters (0.5-37 and 7-48 nM d-1, respectively) were 10-fold higher than those in aerobic surface waters (0.04-3.8 nM d-1). The majority of CH4 oxidation, in terms of integrated activity, occurred within anoxic bottom waters. Water column oxidation reduced the potential lake-atmosphere CH4 flux by a factor of two to three. Measured oxidation rates and water column concentrations were used to estimate the biological turnover times of NH3 and CH4. The NH3 pool turns over rapidly, on time scales of 0.8 d in surface waters and 10 d within the oxycline, while CH4 is cycled on 103-d time scales in surface waters and 102-d time scales within oxycline and bottom waters. Our data suggest an important role for NH3 oxidation in alkaline, saline lakes since the process converts volatile NH3 to soluble NO2-, thereby reducing loss via lake-atmosphere exchange and maintaining nitrogen in a form that is readily available to phytoplankton.

  1. Methane-Oxidizing Enzymes: An Upstream Problem in Biological Gas-to-Liquids Conversion.

    PubMed

    Lawton, Thomas J; Rosenzweig, Amy C

    2016-08-01

    Biological conversion of natural gas to liquids (Bio-GTL) represents an immense economic opportunity. In nature, aerobic methanotrophic bacteria and anaerobic archaea are able to selectively oxidize methane using methane monooxygenase (MMO) and methyl coenzyme M reductase (MCR) enzymes. Although significant progress has been made toward genetically manipulating these organisms for biotechnological applications, the enzymes themselves are slow, complex, and not recombinantly tractable in traditional industrial hosts. With turnover numbers of 0.16-13 s(-1), these enzymes pose a considerable upstream problem in the biological production of fuels or chemicals from methane. Methane oxidation enzymes will need to be engineered to be faster to enable high volumetric productivities; however, efforts to do so and to engineer simpler enzymes have been minimally successful. Moreover, known methane-oxidizing enzymes have different expression levels, carbon and energy efficiencies, require auxiliary systems for biosynthesis and function, and vary considerably in terms of complexity and reductant requirements. The pros and cons of using each methane-oxidizing enzyme for Bio-GTL are considered in detail. The future for these enzymes is bright, but a renewed focus on studying them will be critical to the successful development of biological processes that utilize methane as a feedstock. PMID:27366961

  2. Methane oxidation and molecular characterization of methanotrophs from a former mercury mine impoundment

    USGS Publications Warehouse

    Baesman, Shaun; Miller, Laurence G.; Wei, Jeremy H.; Cho, Yirang; Matys, Emily D.; Summons, Roger E.; Welander, Paula V.; Oremland, Ronald S.

    2015-01-01

    The Herman Pit, once a mercury mine, is an impoundment located in an active geothermal area. Its acidic waters are permeated by hundreds of gas seeps. One seep was sampled and found to be composed of mostly CO2 with some CH4 present. The δ13CH4 value suggested a complex origin for the methane: i.e., a thermogenic component plus a biological methanogenic portion. The relatively 12C-enriched CO2 suggested a reworking of the ebullitive methane by methanotrophic bacteria. Therefore, we tested bottom sediments for their ability to consume methane by conducting aerobic incubations of slurried materials. Methane was removed from the headspace of live slurries, and subsequent additions of methane resulted in faster removal rates. This activity could be transferred to an artificial, acidic medium, indicating the presence of acidophilic or acid-tolerant methanotrophs, the latter reinforced by the observation of maximum activity at pH = 4.5 with incubated slurries. A successful extraction of sterol and hopanoid lipids characteristic of methanotrophs was achieved, and their abundances greatly increased with increased sediment methane consumption. DNA extracted from methane-oxidizing enrichment cultures was amplified and sequenced for pmoA genes that aligned with methanotrophic members of the Gammaproteobacteria. An enrichment culture was established that grew in an acidic (pH 4.5) medium via methane oxidation.

  3. Methane Oxidation and Molecular Characterization of Methanotrophs from a Former Mercury Mine Impoundment

    PubMed Central

    Baesman, Shaun M.; Miller, Laurence G.; Wei, Jeremy H.; Cho, Yirang; Matys, Emily D.; Summons, Roger E.; Welander, Paula V.; Oremland, Ronald S.

    2015-01-01

    The Herman Pit, once a mercury mine, is an impoundment located in an active geothermal area. Its acidic waters are permeated by hundreds of gas seeps. One seep was sampled and found to be composed of mostly CO2 with some CH4 present. The δ13CH4 value suggested a complex origin for the methane: i.e., a thermogenic component plus a biological methanogenic portion. The relatively 12C-enriched CO2 suggested a reworking of the ebullitive methane by methanotrophic bacteria. Therefore, we tested bottom sediments for their ability to consume methane by conducting aerobic incubations of slurried materials. Methane was removed from the headspace of live slurries, and subsequent additions of methane resulted in faster removal rates. This activity could be transferred to an artificial, acidic medium, indicating the presence of acidophilic or acid-tolerant methanotrophs, the latter reinforced by the observation of maximum activity at pH = 4.5 with incubated slurries. A successful extraction of sterol and hopanoid lipids characteristic of methanotrophs was achieved, and their abundances greatly increased with increased sediment methane consumption. DNA extracted from methane-oxidizing enrichment cultures was amplified and sequenced for pmoA genes that aligned with methanotrophic members of the Gammaproteobacteria. An enrichment culture was established that grew in an acidic (pH 4.5) medium via methane oxidation.

  4. Methane Oxidation and Molecular Characterization of Methanotrophs from a Former Mercury Mine Impoundment

    PubMed Central

    Baesman, Shaun M.; Miller, Laurence G.; Wei, Jeremy H.; Cho, Yirang; Matys, Emily D.; Summons, Roger E.; Welander, Paula V.; Oremland, Ronald S.

    2015-01-01

    The Herman Pit, once a mercury mine, is an impoundment located in an active geothermal area. Its acidic waters are permeated by hundreds of gas seeps. One seep was sampled and found to be composed of mostly CO2 with some CH4 present. The δ13CH4 value suggested a complex origin for the methane: i.e., a thermogenic component plus a biological methanogenic portion. The relatively 12C-enriched CO2 suggested a reworking of the ebullitive methane by methanotrophic bacteria. Therefore, we tested bottom sediments for their ability to consume methane by conducting aerobic incubations of slurried materials. Methane was removed from the headspace of live slurries, and subsequent additions of methane resulted in faster removal rates. This activity could be transferred to an artificial, acidic medium, indicating the presence of acidophilic or acid-tolerant methanotrophs, the latter reinforced by the observation of maximum activity at pH = 4.5 with incubated slurries. A successful extraction of sterol and hopanoid lipids characteristic of methanotrophs was achieved, and their abundances greatly increased with increased sediment methane consumption. DNA extracted from methane-oxidizing enrichment cultures was amplified and sequenced for pmoA genes that aligned with methanotrophic members of the Gammaproteobacteria. An enrichment culture was established that grew in an acidic (pH 4.5) medium via methane oxidation. PMID:27682090

  5. Metal enzymes in "impossible" microorganisms catalyzing the anaerobic oxidation of ammonium and methane.

    PubMed

    Reimann, Joachim; Jetten, Mike S M; Keltjens, Jan T

    2015-01-01

    Ammonium and methane are inert molecules and dedicated enzymes are required to break up the N-H and C-H bonds. Until recently, only aerobic microorganisms were known to grow by the oxidation of ammonium or methane. Apart from respiration, oxygen was specifically utilized to activate the inert substrates. The presumed obligatory need for oxygen may have resisted the search for microorganisms that are capable of the anaerobic oxidation of ammonium and of methane. However extremely slowly growing, these "impossible" organisms exist and they found other means to tackle ammonium and methane. Anaerobic ammonium-oxidizing (anammox) bacteria use the oxidative power of nitric oxide (NO) by forging this molecule to ammonium, thereby making hydrazine (N2H4). Nitrite-dependent anaerobic methane oxidizers (N-DAMO) again take advantage of NO, but now apparently disproportionating the compound into dinitrogen and dioxygen gas. This intracellularly produced dioxygen enables N-DAMO bacteria to adopt an aerobic mechanism for methane oxidation.Although our understanding is only emerging how hydrazine synthase and the NO dismutase act, it seems clear that reactions fully rely on metal-based catalyses known from other enzymes. Metal-dependent conversions not only hold for these key enzymes, but for most other reactions in the central catabolic pathways, again supported by well-studied enzymes from model organisms, but adapted to own specific needs. Remarkably, those accessory catabolic enzymes are not unique for anammox bacteria and N-DAMO. Close homologs are found in protein databases where those homologs derive from (partly) known, but in most cases unknown species that together comprise an only poorly comprehended microbial world. PMID:25707470

  6. Metal enzymes in "impossible" microorganisms catalyzing the anaerobic oxidation of ammonium and methane.

    PubMed

    Reimann, Joachim; Jetten, Mike S M; Keltjens, Jan T

    2015-01-01

    Ammonium and methane are inert molecules and dedicated enzymes are required to break up the N-H and C-H bonds. Until recently, only aerobic microorganisms were known to grow by the oxidation of ammonium or methane. Apart from respiration, oxygen was specifically utilized to activate the inert substrates. The presumed obligatory need for oxygen may have resisted the search for microorganisms that are capable of the anaerobic oxidation of ammonium and of methane. However extremely slowly growing, these "impossible" organisms exist and they found other means to tackle ammonium and methane. Anaerobic ammonium-oxidizing (anammox) bacteria use the oxidative power of nitric oxide (NO) by forging this molecule to ammonium, thereby making hydrazine (N2H4). Nitrite-dependent anaerobic methane oxidizers (N-DAMO) again take advantage of NO, but now apparently disproportionating the compound into dinitrogen and dioxygen gas. This intracellularly produced dioxygen enables N-DAMO bacteria to adopt an aerobic mechanism for methane oxidation.Although our understanding is only emerging how hydrazine synthase and the NO dismutase act, it seems clear that reactions fully rely on metal-based catalyses known from other enzymes. Metal-dependent conversions not only hold for these key enzymes, but for most other reactions in the central catabolic pathways, again supported by well-studied enzymes from model organisms, but adapted to own specific needs. Remarkably, those accessory catabolic enzymes are not unique for anammox bacteria and N-DAMO. Close homologs are found in protein databases where those homologs derive from (partly) known, but in most cases unknown species that together comprise an only poorly comprehended microbial world.

  7. Aerobic sulfur-oxidizing bacteria: Environmental selection and diversification

    NASA Technical Reports Server (NTRS)

    Caldwell, D.

    1985-01-01

    Sulfur-oxidizing bacteria oxidize reduced inorganic compounds to sulfuric acid. Lithotrophic sulfur oxidizer use the energy obtained from oxidation for microbial growth. Heterotrophic sulfur oxidizers obtain energy from the oxidation of organic compounds. In sulfur-oxidizing mixotrophs energy are derived either from the oxidation of inorganic or organic compounds. Sulfur-oxidizing bacteria are usually located within the sulfide/oxygen interfaces of springs, sediments, soil microenvironments, and the hypolimnion. Colonization of the interface is necessary since sulfide auto-oxidizes and because both oxygen and sulfide are needed for growth. The environmental stresses associated with the colonization of these interfaces resulted in the evolution of morphologically diverse and unique aerobic sulfur oxidizers.

  8. Nitric oxide reburning with methane

    SciTech Connect

    Kumpaty, S.K.; Subramanian, K.

    1996-12-31

    This paper deals with initial findings from the ongoing, three-year DOE program that began on 02/01/1995. The program involves computer simulation studies to aid in planning and conducting a series of experiments that will extend the knowledge of reburning process. The objective of this work is to find nitric oxide reduction effectiveness for various reburning fuels and identify both homogeneous and heterogeneous reaction mechanisms characterizing NO reduction.

  9. [Effect of temperature on methane production and oxidation in soils].

    PubMed

    Ding, Weixin; Cai, Zucong

    2003-04-01

    The influence of temperature and its mechanism on methane production and oxidation in soils were reviewed in this paper. Temperature can alter the soil ability to produce methane through changing types of dominant methanogens in archaeal community. Dominant methanogen is Methanosarcinaceae at higher temperature which can utilize both H2/CO2 and acetate as the precursor to produce methane, while Methanosaetaceae at lower temperature which only use acetate as the precursor and produce far less methane than do Methanosarcinaceae. Increasing soil temperature apparently raises soil ability to produce methane, which is called temperature effectiveness and expressed as Q10 with a range from 1.5 to 28 and an average of 4.1. There is an obviously positive correlation between temperature effectiveness (Q10) on methane production and substrate content. As compared to methane production, effect of temperature on methane oxidation is lower, which may be related to the strong affinity of methanotrophs for methane.

  10. Anaerobic Methane Oxidation in Soils - revealed using 13C-labelled methane tracers

    NASA Astrophysics Data System (ADS)

    Riekie, G. J.; Baggs, E. M.; Killham, K. S.; Smith, J. U.

    2008-12-01

    In marine sediments, anaerobic methane oxidation is a significant biogeochemical process limiting methane flux from ocean to atmosphere. To date, evidence for anaerobic methane oxidation in terrestrial environments has proved elusive, and its significance is uncertain. In this study, an isotope dilution method specifically designed to detect the process of anaerobic methane oxidation in methanogenic wetland soils is applied. Methane emissions of soils from three contrasting permanently waterlogged sites in Scotland are investigated in strictly anoxic microcosms to which 13C- labelled methane is added, and changes in the concentration and 12C/13C isotope ratios of methane and carbon dioxide are subsequently measured and used to calculate separate the separate components of the methane flux. The method used takes into account the 13C-methane associated with methanogenesis, and the amount of methane dissolved in the soil. The calculations make no prior assumptions about the kinetics of methane production or oxidation. The results indicate that methane oxidation can take place in anoxic soil environments. The clearest evidence for anaerobic methane oxidation is provided by soils from a minerotrophic fen site (pH 6.0) in Bin Forest underlain by ultra-basic and serpentine till. In the fresh soil anoxic microcosms, net consumption methane was observed, and the amount of headspace 13C-CO2 increased at a greater rate than the 12+13C-CO2, further proof of methane oxidation. A net increase in methane was measured in microcosms of soil from Murder Moss, an alkaline site, pH 6.5, with a strong calcareous influence. However, the 13C-CH4 data provided evidence of methane oxidation, both in the disappearance of C- CH4 and appearance of smaller quantities of 13C-CO2. The least alkaline (pH 5.5) microcosms, of Gateside Farm soil - a granitic till - exhibited net methanogenesis and the changes in 13C-CH4 and 13C-CO2 here followed the pattern expected if no methane is consumed

  11. Inhibition of Methane Oxidation by Methylococcus capsulatus with Hydrochlorofluorocarbons and Fluorinated Methanes

    PubMed Central

    Matheson, L. J.; Jahnke, L. L.; Oremland, R. S.

    1997-01-01

    The inhibition of methane oxidation by cell suspensions of Methylococcus capsulatus (Bath) exposed to hydrochlorofluorocarbon 21 (HCFC-21; difluorochloromethane [CHF(inf2)Cl]), HCFC-22 (fluorodichloromethane [CHFCl(inf2)]), and various fluorinated methanes was investigated. HCFC-21 inhibited methane oxidation to a greater extent than HCFC-22, for both the particulate and soluble methane monooxygenases. Among the fluorinated methanes, both methyl fluoride (CH(inf3)F) and difluoromethane (CH(inf2)F(inf2)) were inhibitory while fluoroform (CHF(inf3)) and carbon tetrafluoride (CF(inf4)) were not. The inhibition of methane oxidation by HCFC-21 and HCFC-22 was irreversible, while that by methyl fluoride was reversible. The HCFCs also proved inhibitory to methanol dehydrogenase, which suggests that they disrupt other aspects of C(inf1) catabolism in addition to methane monooxygenase activity. PMID:16535662

  12. Combined thermophilic aerobic process and conventional anaerobic digestion: effect on sludge biodegradation and methane production.

    PubMed

    Dumas, C; Perez, S; Paul, E; Lefebvre, X

    2010-04-01

    The efficiency of hyper-thermophilic (65 degrees Celsius) aerobic process coupled with a mesophilic (35 degrees Celsius) digester was evaluated for the activated sludge degradation and was compared to a conventional mesophilic digester. For two Sludge Retention Time (SRT), 21 and 42 days, the Chemical Oxygen Demand (COD) solubilisation and biodegradation processes, the methanisation yield and the aerobic oxidation were investigated during 180 days. The best results were obtained at SRT of 44 days; the COD removal yield was 30% higher with the Mesophilic Anaerobic Digestion/Thermophilic Aerobic Reactor (MAD-TAR) co-treatment. An increase of the sludge intrinsic biodegradability is also observed (20-40%), showing that the unbiodegradable COD in mesophilic conditions becomes bioavailable. However, the methanisation yield was quite similar for both processes at a same SRT. Finally, such a process enables to divide by two the volume of digester with an equivalent efficiency.

  13. Aerobic Denitrifying Bacteria That Produce Low Levels of Nitrous Oxide

    PubMed Central

    Takaya, Naoki; Catalan-Sakairi, Maria Antonina B.; Sakaguchi, Yasushi; Kato, Isao; Zhou, Zhemin; Shoun, Hirofumi

    2003-01-01

    Most denitrifiers produce nitrous oxide (N2O) instead of dinitrogen (N2) under aerobic conditions. We isolated and characterized novel aerobic denitrifiers that produce low levels of N2O under aerobic conditions. We monitored the denitrification activities of two of the isolates, strains TR2 and K50, in batch and continuous cultures. Both strains reduced nitrate (NO3−) to N2 at rates of 0.9 and 0.03 μmol min−1 unit of optical density at 540 nm−1 at dissolved oxygen (O2) (DO) concentrations of 39 and 38 μmol liter−1, respectively. At the same DO level, the typical denitrifier Pseudomonas stutzeri and the previously described aerobic denitrifier Paracoccus denitrificans did not produce N2 but evolved more than 10-fold more N2O than strains TR2 and K50 evolved. The isolates denitrified NO3− with concomitant consumption of O2. These results indicated that strains TR2 and K50 are aerobic denitrifiers. These two isolates were taxonomically placed in the β subclass of the class Proteobacteria and were identified as P. stutzeri TR2 and Pseudomonas sp. strain K50. These strains should be useful for future investigations of the mechanisms of denitrifying bacteria that regulate N2O emission, the single-stage process for nitrogen removal, and microbial N2O emission into the ecosystem. PMID:12788710

  14. Methane oxidation over dual redox catalysts

    SciTech Connect

    Klier, K.; Herman, R.G.; Di Cosimo, J.I.

    1992-02-01

    The effect of doping lanthana-based catalysts with antimony and bismuth on the catalytic behavior toward the selective oxidation of methane has been studied. New catalytic results have been obtained upon doping the Sr/La{sub 2}O{sub 3} catalyst, obtained from AMOCO Oil Co., with the acidic Sb and Fe dopants. Both activity and selectivity of the original Sr/La{sub 2}O{sub 3} catalyst can be modified by introducing small amounts of either dopant. Iron doping lowered selectivity to C{sub 2} products whereas antimony increased the selectivity while decreasing the reaction temperature by 100{degrees}C.

  15. Root-Associated Methane Oxidation and Methanogenesis: Key Determinants of Wetland Methane Emissions

    NASA Technical Reports Server (NTRS)

    King, G. M.

    1997-01-01

    During the award period, we have assessed the extent and controls of methane oxidation in north temperate wetlands. It is evident that wetlands have been a major global source of atmospheric methane in the past, and are so at present. It is also evident that microbial methane oxidation consumes a variable fraction of total wetland methane production, perhaps 10%-90%. Methane oxidation is thus a potentially important control of wetland methane emission. Our efforts have been designed to determine the extent of the process, its controls, and possible relationships to changes that might be expected in wetlands as a consequence of anthropogenic or climate-related disturbances. Current work, has emphasized controls of methane oxidation associated with rooted aquatic plants. As for the sediment-water interface, we have observed that oxygen availability is a primary limiting factor. Our conclusion is based on several different lines of evidence obtained from in vitro and in situ analyses. First, we have measured the kinetics of methane oxidation by intact plant roots harboring methane-oxidizing bacteria, as well as the kinetics of the methanotrophs themselves. Values for the half-saturation constant (apparent K(sub m)) are approximately 5 microns. These values are roughly equivalent to, or much less than porewater methane concentrations, indicating that uptake is likely saturated with respect to methane, and that some other parameter must limit activity. Methane concentrations in the lacunar spaces at the base of plant stems are also comparable to the half-saturation constants (when expressed as equivalent dissolved concentrations), providing further support for limitation of uptake by parameters other than methane.

  16. High rates of anaerobic methane oxidation in freshwater wetlands reduce potential atmospheric methane emissions.

    PubMed

    Segarra, K E A; Schubotz, F; Samarkin, V; Yoshinaga, M Y; Hinrichs, K-U; Joye, S B

    2015-06-30

    The role of anaerobic oxidation of methane (AOM) in wetlands, the largest natural source of atmospheric methane, is poorly constrained. Here we report rates of microbially mediated AOM (average rate=20 nmol cm(-3) per day) in three freshwater wetlands that span multiple biogeographical provinces. The observed AOM rates rival those in marine environments. Most AOM activity may have been coupled to sulphate reduction, but other electron acceptors remain feasible. Lipid biomarkers typically associated with anaerobic methane-oxidizing archaea were more enriched in (13)C than those characteristic of marine systems, potentially due to distinct microbial metabolic pathways or dilution with heterotrophic isotope signals. On the basis of this extensive data set, AOM in freshwater wetlands may consume 200 Tg methane per year, reducing their potential methane emissions by over 50%. These findings challenge precepts surrounding wetland carbon cycling and demonstrate the environmental relevance of an anaerobic methane sink in ecosystems traditionally considered strong methane sources.

  17. Capacity for biodegradation of CFCs and HCFCs in a methane oxidative counter-gradient laboratory system simulating landfill soil covers.

    PubMed

    Scheutz, Charlotte; Kjeldsen, Peter

    2003-11-15

    The attenuation of methane and four chlorofluorocarbons was investigated in a dynamic methane and oxygen counter-gradient system simulating a landfill soil cover. Soil was sampled at Skellingsted Landfill, Denmark. The soil columns showed a high capacity of methane oxidation with oxidation rates of 210 g m(-2) d(-1) corresponding to a removal efficiency of 81%. CFC-11 and to a lesser extent also CFC-12 were degraded in the active soil columns. The average removal efficiency was 90% and 30% for CFC-11 and CFC-12, respectively. Soil gas concentration profiles indicated that the removal was due to anaerobic degradation, which was verified in anaerobic batch experiments where CFC-11 was rapidly degraded. HCFC-21 and HCFC-22 were also degraded in active soil columns (61% and 41%, respectively), but compared to the CFCs, the degradation was located in the upper oxic part of the column with overlapping gradients of methane and oxygen. High oxidation rates of methane and HCFCs were obtained in soil microcosms incubated with methane. When increasing the column inlet flow, the oxidation zone was moved upward in the column, and the removal efficiency of methane and HCFCs decreased. The removal of CFCs was, however, less affected since the anaerobic zone expanded with increasing inlet flow rates. This study demonstrates the complexity of landfill soil cover systems and shows that both anaerobic and aerobic bacteria may play a very important role in reducing the emission of not only methane but also trace components into the atmosphere. PMID:14655700

  18. Explicit Microbial Processes to Simulate Methane Production and Oxidation in Wetlands in the GFDL Land Model

    NASA Astrophysics Data System (ADS)

    Smolander, S.; Sulman, B. N.; Shevliakova, E.

    2015-12-01

    Recent observational studies highlighted the need to include explicit treatment of the soil microbial processes into the next generation of Earth System Models (ESMs). These processes shape most soil biogeochemical cycles and control releases of the most potent greenhouses gases carbon dioxide and methane. Currently global ecosystem models usually parameterize methane production as a fraction of soil heterotrophic respiration. This lumps the pathways of several different functional groups of microbes into one production rate, possibly modified by a number of environmental factor multipliers. Methane oxidation is usually more explicitly modeled by Michaelis-Menten kinetics, but if the maximum rate, before environmental multipliers, is a constant parameter, this essentially implies a constant methanotrophic microbe population size. We present an explicit model for wetland soil microbial processes in an ESM context. We introduce a growth and decomposition model for four functional groups of microbes involved in methane production and oxidation, so microbial populations can grow when conditions are favorable and substrate is available. When soil conditions are anoxic, fermenting microbes transform available soil carbon into intermediate substrates, and two different kinds of methanogenic microbes live on their preferred substrates producing methane. Methane is transported through aerobic layers of the soil column, where methanotrophic microbes oxidize part of the methane, and the rest escapes to the atmosphere. We present initial simulations using the new model in the context of existing measurements of methane emissions and microbial populations at the site level, and discuss the implications of including these processes in an ESM. This explicit process model establishes a foundation for improving dynamic ecosystem-climate feedbacks in ESM simulations, and facilitates more detailed experimental verification of wetland biogeochemical processes.

  19. Transcriptomic evidence for net methane oxidation and net methane production in putative ANaerobic MEthanotrophic (ANME) archaea

    NASA Astrophysics Data System (ADS)

    Lloyd, K. G.; Alperin, M. J.; Teske, A.

    2010-12-01

    Anaerobic methane oxidation regulates methane emissions in marine sediments and is thought to be mediated by uncultured methanogen-like archaea collectively labeled ANME (for ANaerobic MEthanotrophs). ANME archaea are often assumed to be obligate methanotrophs that are incapable of net methanogenesis, and are therefore used as proxies for anaerobic methane oxidation in many environments in spite of uncertainty regarding their metabolic capabilities. We tested this assumption by detecting and quantifying methanogenic gene transcription of ANME archaea across clearly differentiated zones of methane oxidation vs. methane production in sediments from the White Oak River estuary, NC. ANME-1 archaea (a group of putative obligate methanotrophs) consistently transcribe 16S rRNA and mRNA of methyl coenzyme M reductase (mcrA) the key gene for methanogenesis, up to 45 cm into methanogenic sediments. CARD-FISH shows that ANME-1 archaea exist as single rod-shaped cells or pairs of cells, and in very low numbers. Integrating normalized depth-distributions of 16S rDNA and rRNA (measured with qPCR and RT-qPCR, respectively) shows that 26-77 % of the rDNA proxy for ANME-1 cell numbers, and 18-74 % of the rRNA proxy for ANME-1 activity occurs within methane-producing sediments. mRNA transcripts of dissimilatory sulfite reductase (dsrAB) from sulfate reducing bacteria, the putative syntrophic partners of sulfate-dependent methane oxidation, were amplified consistently from methane-oxidizing sediments, and inconsistently from methane-producing sediments. These results change the perspective from ANME-1 archaea as obligate methane oxidizers to methanogens that are also capable of methane oxidation.

  20. A novel thermophilic methane-oxidizing bacteria from thermal springs of Uzon volcano caldera, Kamchatka

    NASA Astrophysics Data System (ADS)

    Dvorianchikova, E.; Kizilova, A.; Kravchenko, I.; Galchenko, V.

    2012-04-01

    Methane is a radiatively active trace gas, contributing significantly to the greenhouse effect. It is 26 times more efficient in absorbing and re-emitting infrared radiation than carbon dioxide. Methanotrophs play an essential role in the global carbon cycle by oxidizing 50-75% of the biologically produced methane in situ, before it reaches the atmosphere. Methane-oxidizing bacteria are isolated from the various ecosystems and described at present. Their biology, processes of methane oxidation in fresh-water, marsh, soil and marine habitats are investigated quite well. Processes of methane oxidation in places with extreme physical and chemical conditions (high or low , salinity and temperature values) are studied in much smaller degree. Such ecosystems occupy a considerable part of the Earth's surface. The existence of aerobic methanotrophs inhabiting extreme environments has been verified so far by cultivation experiments and direct detection of methane monooxygenase genes specific to almost all aerobic methanotrophs. Thermophilic and thermotolerant methanotrophs have been isolated from such extreme environments and consist of the gammaproteobacterial (type I) genera Methylothermus, Methylocaldum, Methylococcus and the verrucomicrobial genus Methylacidiphilum. Uzon volcano caldera is a unique area, where volcanic processes still happen today. Hydrothermal springs of the area are extreme ecosystems which microbial communities represent considerable scientific interest of fundamental and applied character. A thermophilic aerobic methane-oxidising bacterium was isolated from a sediment sample from a hot spring (56.1; 5.3) of Uzon caldera. Strain S21 was isolated using mineral low salt medium. The headspace gas was composed of CH4, Ar, CO2, and O2 (40:40:15:5). The temperature of cultivation was 50, pH 5.5. Cells of strain S21 in exponential and early-stationary phase were coccoid bacilli, about 1 μm in diameter, and motile with a single polar flagellum. PCR and

  1. Kinetics of methane oxidation in selected mineral soils

    NASA Astrophysics Data System (ADS)

    Walkiewicz, A.; Bulak, P.; Brzeziñska, M.; Włodarczyk, T.; Polakowski, C.

    2012-10-01

    The kinetic parameters of methane oxidation in three mineral soils were measured under laboratory conditions. Incubationswere preceded by a 24-day preincubationwith 10%vol. of methane. All soils showed potential to the consumption of added methane. None of the soils, however, consumed atmospheric CH4. Methane oxidation followed the Michaelis-Menten kinetics, with relatively low values of parameters for Eutric Cambisol, while high values for Haplic Podzol, and especially for Mollic Gleysol which showed the highest methanotrophic activity and much lower affinity to methane. The high values of parameters for methane oxidation are typical for organic soils and mineral soils from landfill cover. The possibility of the involvement of nitrifying microorganisms, which inhabit the ammonia-fertilized agricultural soils should be verified.

  2. Methane oxidation over dual redox catalysts

    SciTech Connect

    Klier, K.; Herman, R.G.; Sojka, Z.

    1989-06-01

    The objective of this research is to develop the scientific background for direct catalytic oxidation of methane over oxides that are doubly doped with transition metal ions. The desired process aims at employing of a double redox mechanism, where one redox couple is utilized for activation of oxygen and another for the conversion of CH{sub 3} radicals to carbocations via electron transfer reaction. The latter species can react with surface OH{sup {minus}} groups to form methanol or formaldehyde. To establish the foundations for such a process, two groups of the catalysts, one containing dispersed redox centers (Cu{sup I}/Fe{sup III}/ZnO and Cu{sup I}/Sn{sup IV}/ZnO) and a second of delafossite-type oxides containing concentrated redox centers (CuFeO{sub 2}, CuCoO{sub 2}) were synthesized and chemically analyzed for composition. For the sake of comparison, undoped ZnO treated in the same way as doped zinc oxide catalysts was also prepared. The samples were characterized by X-ray diffraction, BET surface area measurements and preliminarily by scanning electron microscopy. A catalytic testing unit and reactor to study the title reaction were designed and constructed.

  3. Aerobic Oxidation of an Osmium(III) N-Hydroxyguanidine Complex To Give Nitric Oxide.

    PubMed

    Xiang, Jing; Wang, Qian; Yiu, Shek-Man; Man, Wai-Lun; Kwong, Hoi-Ki; Lau, Tai-Chu

    2016-05-16

    The aerobic oxidation of the N-hydroxyguanidinum moiety of N-hydroxyarginine to NO is a key step in the biosynthesis of NO by the enzyme nitric oxide synthase (NOS). So far, there is no chemical system that can efficiently carry out similar aerobic oxidation to give NO. We report here the synthesis and X-ray crystal structure of an osmium(III) N-hydroxyguanidine complex, mer-[Os(III){NH═C(NH2)(NHOH)}(L)(CN)3](-) (OsGOH, HL = 2-(2-hydroxyphenyl)benzoxazole), which to the best of our knowledge is the first example of a transition metal N-hydroxyguanidine complex. More significantly, this complex readily undergoes aerobic oxidation at ambient conditions to generate NO. The oxidation is pH-dependent; at pH 6.8, fac-[Os(NO)(L)(CN)3](-) is formed in which the NO produced is bound to the osmium center. On the other hand, at pH 12, aerobic oxidation of OsGOH results in the formation of the ureato complex [Os(III)(NHCONH2)(L)(CN)3](2-) and free NO. Mechanisms for this aerobic oxidation at different pH values are proposed. PMID:27135258

  4. A four-helix bundle stores copper for methane oxidation.

    PubMed

    Vita, Nicolas; Platsaki, Semeli; Baslé, Arnaud; Allen, Stephen J; Paterson, Neil G; Crombie, Andrew T; Murrell, J Colin; Waldron, Kevin J; Dennison, Christopher

    2015-09-01

    Methane-oxidizing bacteria (methanotrophs) require large quantities of copper for the membrane-bound (particulate) methane monooxygenase. Certain methanotrophs are also able to switch to using the iron-containing soluble methane monooxygenase to catalyse methane oxidation, with this switchover regulated by copper. Methane monooxygenases are nature's primary biological mechanism for suppressing atmospheric levels of methane, a potent greenhouse gas. Furthermore, methanotrophs and methane monooxygenases have enormous potential in bioremediation and for biotransformations producing bulk and fine chemicals, and in bioenergy, particularly considering increased methane availability from renewable sources and hydraulic fracturing of shale rock. Here we discover and characterize a novel copper storage protein (Csp1) from the methanotroph Methylosinus trichosporium OB3b that is exported from the cytosol, and stores copper for particulate methane monooxygenase. Csp1 is a tetramer of four-helix bundles with each monomer binding up to 13 Cu(I) ions in a previously unseen manner via mainly Cys residues that point into the core of the bundle. Csp1 is the first example of a protein that stores a metal within an established protein-folding motif. This work provides a detailed insight into how methanotrophs accumulate copper for the oxidation of methane. Understanding this process is essential if the wide-ranging biotechnological applications of methanotrophs are to be realized. Cytosolic homologues of Csp1 are present in diverse bacteria, thus challenging the dogma that such organisms do not use copper in this location. PMID:26308900

  5. A four-helix bundle stores copper for methane oxidation.

    PubMed

    Vita, Nicolas; Platsaki, Semeli; Baslé, Arnaud; Allen, Stephen J; Paterson, Neil G; Crombie, Andrew T; Murrell, J Colin; Waldron, Kevin J; Dennison, Christopher

    2015-09-01

    Methane-oxidizing bacteria (methanotrophs) require large quantities of copper for the membrane-bound (particulate) methane monooxygenase. Certain methanotrophs are also able to switch to using the iron-containing soluble methane monooxygenase to catalyse methane oxidation, with this switchover regulated by copper. Methane monooxygenases are nature's primary biological mechanism for suppressing atmospheric levels of methane, a potent greenhouse gas. Furthermore, methanotrophs and methane monooxygenases have enormous potential in bioremediation and for biotransformations producing bulk and fine chemicals, and in bioenergy, particularly considering increased methane availability from renewable sources and hydraulic fracturing of shale rock. Here we discover and characterize a novel copper storage protein (Csp1) from the methanotroph Methylosinus trichosporium OB3b that is exported from the cytosol, and stores copper for particulate methane monooxygenase. Csp1 is a tetramer of four-helix bundles with each monomer binding up to 13 Cu(I) ions in a previously unseen manner via mainly Cys residues that point into the core of the bundle. Csp1 is the first example of a protein that stores a metal within an established protein-folding motif. This work provides a detailed insight into how methanotrophs accumulate copper for the oxidation of methane. Understanding this process is essential if the wide-ranging biotechnological applications of methanotrophs are to be realized. Cytosolic homologues of Csp1 are present in diverse bacteria, thus challenging the dogma that such organisms do not use copper in this location.

  6. 2004 Methane and Nitrous Oxide Emissions from Manure Management in South Africa.

    PubMed

    Moeletsi, Mokhele Edmond; Tongwane, Mphethe Isaac

    2015-01-01

    Manure management in livestock makes a significant contribution towards greenhouse gas emissions in the Agriculture; Forestry and Other Land Use category in South Africa. Methane and nitrous oxide emissions are prevalent in contrasting manure management systems; promoting anaerobic and aerobic conditions respectively. In this paper; both Tier 1 and modified Tier 2 approaches of the IPCC guidelines are utilized to estimate the emissions from South African livestock manure management. Activity data (animal population, animal weights, manure management systems, etc.) were sourced from various resources for estimation of both emissions factors and emissions of methane and nitrous oxide. The results show relatively high methane emissions factors from manure management for mature female dairy cattle (40.98 kg/year/animal), sows (25.23 kg/year/animal) and boars (25.23 kg/year/animal). Hence, contributions for pig farming and dairy cattle are the highest at 54.50 Gg and 32.01 Gg respectively, with total emissions of 134.97 Gg (3104 Gg CO₂ Equivalent). Total nitrous oxide emissions are estimated at 7.10 Gg (2272 Gg CO₂ Equivalent) and the three main contributors are commercial beef cattle; poultry and small-scale beef farming at 1.80 Gg; 1.72 Gg and 1.69 Gg respectively. Mitigation options from manure management must be taken with care due to divergent conducive requirements of methane and nitrous oxide emissions requirements. PMID:26479229

  7. Kinetics of microbial landfill methane oxidation in biofilters.

    PubMed

    Gebert, Julia; Groengroeft, Alexander; Miehlich, Guenter

    2003-01-01

    A methane oxidizing biofilter system fitted to the passive venting system of a harbor sludge landfill in Germany was characterized with respect to the the methanotrophic population, methane oxidizing capacity, and reaction kinetics. Methanotrophic cell counts stabilized on a high level with 1.3 x 10(8) to 7.1 x 10(9) cells g dw(-1) about one year after first biofilter operation, and a maximum of 1.2 x 10(11) cells g dw(-1). Potential methane oxidizing activity varied between 5.3 and 10.7 microg h(-1) g dw(-1). Cell numbers correlated well with methane oxidation activities. Extrapolation of potential activities gave methane removal rates between 35 and 109 g CH4 h(-1) m(-3), calculated for 30 degrees C. Optimum temperature was 38 degrees C for freshly sampled biofilter material and 22 degrees C for a methanotrophic enrichment culture grown at 10 degrees C incubation temperature. Substrate kinetics revealed the presence of a low-affinity methane oxidizing community with a high Vmax of 1.78 micromol CH4 h(-1) g ww(-1) and a high K(M) of 15.1 microM. K(MO2) for methane oxidation was 58 microM. No substantial methane oxidizing activity was detected below 1.7-2.6 vol.-% O2 in the gaseous phase. Methane deprivation led to a decrease in methane oxidation activity within 5-9 weeks but could still be detected after 25 weeks of substrate deprivation and was fully restored within 3 weeks of continuous methane supply. Very high salt loads are leached from the novel biofilter material, expanded clay, yielding electric conductivity values of up to 15 mS cm(-1) in the leachate. Values > 6 mS cm(-1) were shown to depress methane consumption. Water retention characteristics of the material proved to be favourable for methane oxidizing systems with a gas permeable volume of 78% of bulk volume at field capacity water content. Correspondingly, no influence of water content on methane oxidation activity could be detected at water contents between 2.5 and 20 vol.-%. PMID:12957156

  8. Non-oxidative conversion of methane with continuous hydorgen removal

    SciTech Connect

    Borry, R.W. III; Iglesia, E.

    1997-12-31

    The objective is to overcome the restrictions of non-oxidative methane pyrolysis and oxidative coupling of methane by transferring hydrogen across a selective inorganic membrane between methane and air streams, without simultaneous transport of hydrocarbon reactants or products. This will make the overall reaction system exothermic, remove the thermodynamic barrier to high conversion, and eliminate the formation of carbon oxides. Our approach is to couple C-H bond activation and hydrogen removal by passage of hydrogen atoms through a dense ceramic membrane. In our membrane reactor, catalytic methane pyrolysis produces C2+ hydrogen carbons and aromatics on the one side of the membrane and hydrogen is removed through an oxide film and combusted with air on the opposite side. This process leads to a net reaction with the stoichiometry and thermodynamic properties of oxidative coupling, but without contact between the carbon atoms and oxygen species.

  9. Artificial electron acceptors decouple archaeal methane oxidation from sulfate reduction.

    PubMed

    Scheller, Silvan; Yu, Hang; Chadwick, Grayson L; McGlynn, Shawn E; Orphan, Victoria J

    2016-02-12

    The oxidation of methane with sulfate is an important microbial metabolism in the global carbon cycle. In marine methane seeps, this process is mediated by consortia of anaerobic methanotrophic archaea (ANME) that live in syntrophy with sulfate-reducing bacteria (SRB). The underlying interdependencies within this uncultured symbiotic partnership are poorly understood. We used a combination of rate measurements and single-cell stable isotope probing to demonstrate that ANME in deep-sea sediments can be catabolically and anabolically decoupled from their syntrophic SRB partners using soluble artificial oxidants. The ANME still sustain high rates of methane oxidation in the absence of sulfate as the terminal oxidant, lending support to the hypothesis that interspecies extracellular electron transfer is the syntrophic mechanism for the anaerobic oxidation of methane.

  10. Methane oxidation in simulated landfill cover soil environments

    SciTech Connect

    Visscher, A. de; Thomas, D.; Boeckx, P.; Cleemput, O. van

    1999-06-01

    Methane is an important greenhouse gas. Its contribution to the enhanced global warming is estimated at 12%. A considerable fraction of the methane that is produced by landfills is oxidized by its covering soil before it can reach the atmosphere. This process was studied in soil columns that simulate landfill cover soil environments. The methane uptake was followed as a function of time. In soils of agricultural origin, a maximum value of 10.7 mol m{sup {minus}2}{sub column} d{sup {minus}1} was observed. Mixing sugar beet leaves with the soil led to a temporary stimulation of the methane oxidation rate, whereas a wheat straw amendment led to permanent stimulation. Soil originating from a real landfill cover oxidized on the order of 15 mol m{sup {minus}2}{sub column} d{sup {minus}1}, the highest value found in the literature to date. The soil gas composition was studied as a function of depth. With a new batch incubation technique, methane oxidation kinetics were determined in samples taken from the soil column. By combining this kinetic data with the soil gas composition data, the actively methane oxidizing zone in the soil column could be determined and an in situ assessment of oxygen limitation could be performed. Methane oxidation takes place mainly in the top 30 cm of the covering soil.

  11. Anaerobic Oxidation of Methane in Sediments of Lake Constance, an Oligotrophic Freshwater Lake▿

    PubMed Central

    Deutzmann, Jörg S.; Schink, Bernhard

    2011-01-01

    Anaerobic oxidation of methane (AOM) with sulfate as terminal electron acceptor has been reported for various environments, including freshwater habitats, and also, nitrate and nitrite were recently shown to act as electron acceptors for methane oxidation in eutrophic freshwater habitats. Radiotracer experiments with sediment material of Lake Constance, an oligotrophic freshwater lake, were performed to follow 14CO2 formation from 14CH4 in sediment incubations in the presence of different electron acceptors, namely, nitrate, nitrite, sulfate, or oxygen. Whereas 14CO2 formation without and with sulfate addition was negligible, addition of nitrate increased 14CO2 formation significantly, suggesting that AOM could be coupled to denitrification. Nonetheless, denitrification-dependent AOM rates remained at least 1 order of magnitude lower than rates of aerobic methane oxidation. Using molecular techniques, putative denitrifying methanotrophs belonging to the NC10 phylum were detected on the basis of the pmoA and 16S rRNA gene sequences. These findings show that sulfate-dependent AOM was insignificant in Lake constant sediments. However, AOM can also be coupled to denitrification in this oligotrophic freshwater habitat, providing first indications that this might be a widespread process that plays an important role in mitigating methane emissions. PMID:21551281

  12. Anaerobic methane oxidation in low-organic content methane seep sediments

    USGS Publications Warehouse

    Pohlman, John W.; Riedel, Michael; Bauer, James E.; Canuel, Elizabeth A.; Paull, Charles K.; Lapham, Laura; Grabowski, Kenneth S.; Coffin, Richard B.; Spence, George D.

    2013-01-01

    Sulfate-dependent anaerobic oxidation of methane (AOM) is the key sedimentary microbial process limiting methane emissions from marine sediments and methane seeps. In this study, we investigate how the presence of low-organic content sediment influences the capacity and efficiency of AOM at Bullseye vent, a gas hydrate-bearing cold seep offshore of Vancouver Island, Canada. The upper 8 m of sediment contains 14C. A fossil origin for the DIC precludes remineralization of non-fossil OM present within the sulfate zone as a significant contributor to pore water DIC, suggesting that nearly all sulfate is available for anaerobic oxidation of fossil seep methane. Methane flux from the SMT to the sediment water interface in a diffusion-dominated flux region of Bullseye vent was, on average, 96% less than at an OM-rich seep in the Gulf of Mexico with a similar methane flux regime. Evidence for enhanced methane oxidation capacity within OM-poor sediments has implications for assessing how climate-sensitive reservoirs of sedimentary methane (e.g., gas hydrate) will respond to ocean warming, particularly along glacially-influenced mid and high latitude continental margins.

  13. Termites Facilitate Methane Oxidation and Shape the Methanotrophic Community

    PubMed Central

    Erens, Hans; Mujinya, Basile Bazirake; Boeckx, Pascal; Baert, Geert; Schneider, Bellinda; Frenzel, Peter; Van Ranst, Eric

    2013-01-01

    Termite-derived methane contributes 3 to 4% to the total methane budget globally. Termites are not known to harbor methane-oxidizing microorganisms (methanotrophs). However, a considerable fraction of the methane produced can be consumed by methanotrophs that inhabit the mound material, yet the methanotroph ecology in these environments is virtually unknown. The potential for methane oxidation was determined using slurry incubations under conditions with high (12%) and in situ (∼0.004%) methane concentrations through a vertical profile of a termite (Macrotermes falciger) mound and a reference soil. Interestingly, the mound material showed higher methanotrophic activity. The methanotroph community structure was determined by means of a pmoA-based diagnostic microarray. Although the methanotrophs in the mound were derived from populations in the reference soil, it appears that termite activity selected for a distinct community. Applying an indicator species analysis revealed that putative atmospheric methane oxidizers (high-indicator-value probes specific for the JR3 cluster) were indicative of the active nest area, whereas methanotrophs belonging to both type I and type II were indicative of the reference soil. We conclude that termites modify their environment, resulting in higher methane oxidation and selecting and/or enriching for a distinct methanotroph population. PMID:24038691

  14. Biomarker evidence for widespread anaerobic methane oxidation in Mediterranean sediments by a consortium of methanogenic archaea and bacteria

    SciTech Connect

    Pancost, R.D.; Damste, J.S.S.; Lint, S. De; Maarel, M.J.E.C. van der; Gottschal, J.C.

    2000-03-01

    Although abundant geochemical data indicate that anaerobic methane oxidation occurs in marine sediments, the linkage to specific microorganisms remains unclear. In order to examine processes of methane consumption and oxidation, sediment samples from mud volcanoes at two distinct sites on the Mediterranean consumption and oxidation, sediment samples from mud volcanoes at two distinct sites on the Mediterranean Ridge were collected via the submersible Nautile. Geochemical data strongly indicate that methane is oxidized under aerobic conditions, and compound-specific carbon isotope analyses indicate that methane is oxidized under anaerobic conditions, and compound-specific carbon isotope analyses indicate that this reaction is facilitated by a consortium of archaea and bacteria. Specifically, these methane-rich sediments contain high abundances of methanogen-specific biomarkers that are significantly depleted in {sup 13}C ({delta}{sup 13}C values are as low as {minus}95%). Biomarkers inferred to derive from sulfate-reducing bacteria and other heterotrophic bacteria are similarly depleted. Consistent with previous work, such depletion can be explained by consumption of {sup 13}C-depleted methane by methanogens operating in reverse and as part a consortium of organisms in which sulfate serves as the terminal electron acceptor. Moreover, their results indicate that this process is widespread in Mediterranean mud volcanoes and in some localized settings in the predominant microbiological process.

  15. Electrochemical and partial oxidation of methane

    NASA Astrophysics Data System (ADS)

    Singh, Rahul

    2008-10-01

    negligible coke formation on the novel fabricated anode by electroless plating process. Hydrogen is an environmentally cleaner source of energy. The recent increase in the demand of hydrogen as fuel for all types of fuel cells and petroleum refining process has boosted the need of production of hydrogen. Methane, a major component of natural gas is the major feedstock for production of hydrogen. The route of partial oxidation of methane to produce syngas (CO + H2) offers significant advantages over commercialized steam reforming process for higher efficiency and lower energy requirements. Partial oxidation of methane was studied by pulsing O2 into a CH4 flow over Rh/Al2O3 in a sequence of in situ infrared (IR) cell and fixed bed reactor at 773 K. The results obtained from the sequence of an IR cell followed by a fixed bed reactor show that (i) adsorbed CO produced possesses a long residence time, indicating that adsorbed oxygen leading to the formation of CO is significantly different from those leading to CO2 and (ii) CO2 is not an intermediate species for the formation of CO. In situ IR of pulse reaction coupled with alternating reactor sequence is an effective approach to study the primary and secondary reactions as well as the nature of their adsorbed species. As reported earlier, hydrogen remains to be the most effective fuel for fuel cells, the production of high purity hydrogen from naturally available resources such as coal, petroleum, and natural gas requires a number of energy-intensive steps, making fuel cell processes for stationary electric power generation prohibitively uneconomic. Direct use of coal or coal gas as the feed is a promising approach for low cost electricity generation. Coal gas solid oxide fuel cell was studied by pyrolyzing Ohio #5 coal to coal gas and transporting to a Cu anode solid oxide fuel cell to generate power. The study of coal-gas solid oxide fuel cell is divided into two sections, i.e., (i) understanding the composition of coal gas by

  16. Mechanism of copper(I)/TEMPO-catalyzed aerobic alcohol oxidation.

    PubMed

    Hoover, Jessica M; Ryland, Bradford L; Stahl, Shannon S

    2013-02-13

    Homogeneous Cu/TEMPO catalyst systems (TEMPO = 2,2,6,6-tetramethylpiperidine-N-oxyl) have emerged as some of the most versatile and practical catalysts for aerobic alcohol oxidation. Recently, we disclosed a (bpy)Cu(I)/TEMPO/NMI catalyst system (NMI = N-methylimidazole) that exhibits fast rates and high selectivities, even with unactivated aliphatic alcohols. Here, we present a mechanistic investigation of this catalyst system, in which we compare the reactivity of benzylic and aliphatic alcohols. This work includes analysis of catalytic rates by gas-uptake and in situ IR kinetic methods and characterization of the catalyst speciation during the reaction by EPR and UV-visible spectroscopic methods. The data support a two-stage catalytic mechanism consisting of (1) "catalyst oxidation" in which Cu(I) and TEMPO-H are oxidized by O(2) via a binuclear Cu(2)O(2) intermediate and (2) "substrate oxidation" mediated by Cu(II) and the nitroxyl radical of TEMPO via a Cu(II)-alkoxide intermediate. Catalytic rate laws, kinetic isotope effects, and spectroscopic data show that reactions of benzylic and aliphatic alcohols have different turnover-limiting steps. Catalyst oxidation by O(2) is turnover limiting with benzylic alcohols, while numerous steps contribute to the turnover rate in the oxidation of aliphatic alcohols.

  17. Mechanism of copper(I)/TEMPO-catalyzed aerobic alcohol oxidation.

    PubMed

    Hoover, Jessica M; Ryland, Bradford L; Stahl, Shannon S

    2013-02-13

    Homogeneous Cu/TEMPO catalyst systems (TEMPO = 2,2,6,6-tetramethylpiperidine-N-oxyl) have emerged as some of the most versatile and practical catalysts for aerobic alcohol oxidation. Recently, we disclosed a (bpy)Cu(I)/TEMPO/NMI catalyst system (NMI = N-methylimidazole) that exhibits fast rates and high selectivities, even with unactivated aliphatic alcohols. Here, we present a mechanistic investigation of this catalyst system, in which we compare the reactivity of benzylic and aliphatic alcohols. This work includes analysis of catalytic rates by gas-uptake and in situ IR kinetic methods and characterization of the catalyst speciation during the reaction by EPR and UV-visible spectroscopic methods. The data support a two-stage catalytic mechanism consisting of (1) "catalyst oxidation" in which Cu(I) and TEMPO-H are oxidized by O(2) via a binuclear Cu(2)O(2) intermediate and (2) "substrate oxidation" mediated by Cu(II) and the nitroxyl radical of TEMPO via a Cu(II)-alkoxide intermediate. Catalytic rate laws, kinetic isotope effects, and spectroscopic data show that reactions of benzylic and aliphatic alcohols have different turnover-limiting steps. Catalyst oxidation by O(2) is turnover limiting with benzylic alcohols, while numerous steps contribute to the turnover rate in the oxidation of aliphatic alcohols. PMID:23317450

  18. Environmental factors affecting methane distribution and bacterial methane oxidation in the German Bight (North Sea)

    NASA Astrophysics Data System (ADS)

    Osudar, Roman; Matoušů, Anna; Alawi, Mashal; Wagner, Dirk; Bussmann, Ingeborg

    2015-07-01

    River estuaries are responsible for high rates of methane emissions to the atmosphere. The complexity and diversity of estuaries require detailed investigation of methane sources and sinks, as well as of their spatial and seasonal variations. The Elbe river estuary and the adjacent North Sea were chosen as the study site for this survey, which was conducted from October 2010 to June 2012. Using gas chromatography and radiotracer techniques, we measured methane concentrations and methane oxidation (MOX) rates along a 60 km long transect from Cuxhaven to Helgoland. Methane distribution was influenced by input from the methane-rich mouth of the Elbe and gradual dilution by methane-depleted sea water. Methane concentrations near the coast were on average 30 ± 13 nmol L-1, while in the open sea, they were 14 ± 6 nmol L-1. Interestingly, the highest methane concentrations were repeatedly detected near Cuxhaven, not in the Elbe River freshwater end-member as previously reported. Though, we did not find clear seasonality we observed temporal methane variations, which depended on temperature and presumably on water discharge from the Elbe River. The highest MOX rates generally coincided with the highest methane concentrations, and varied from 2.6 ± 2.7 near the coast to 0.417 ± 0.529 nmol L-1 d-1 in the open sea. Turnover times varied from 3 to >1000 days. MOX rates were strongly affected by methane concentration, temperature and salinity. We ruled out the supposition that MOX is not an important methane sink in most of the Elbe estuary and adjacent German Bight.

  19. [Activity of methane-oxidizing bacteria in the adsorbed state].

    PubMed

    Nesterov, A I; Nazarenko, A V

    1975-01-01

    Adsorption of pure cultures of methane oxidizing bacteria, Methylosinus trichosporium 20 and Methylococcus ucrainicus 21, on glass and coal was studied; the former strain was sorbed on both sorbents, the latter strain was sorbed on coal but not on glass. The rate of methane oxidation by the cells of adsorbed microorganisms was higher than in the case of free cells, and increased with a decrease in dimensions of the sorbent particles. PMID:1207502

  20. Improvement of methane generation capacity by aerobic pre-treatment of organic waste with a cellulolytic Trichoderma viride culture.

    PubMed

    Wagner, Andreas Otto; Schwarzenauer, Thomas; Illmer, Paul

    2013-11-15

    Trichoderma viride is known as a potent cellulose decomposer and was successfully used to improve and accelerate the decomposition process of aerobic composting. In contrast, the role of fungi as pre-treatment organisms for anaerobic digestion is not clear, since the fast aerobic decomposition is thought to be responsible for a rapid depletion of easily available nutrients, leading to a lack of these for the anaerobic community. In the present study carried out in lab-scale, the application of T. viride for the aerobic pre-incubation of organic matter derived from the inlet port of a 750,000 L anaerobic digester led to an increase in total gas and methane production in a subsequent anaerobic digestion step. A high cellulase activity caused by the addition of T. viride seemed to be responsible for a better nutrient availability for anaerobic microorganisms. Therefore, aerobic pre-incubation of organic residues with T. viride for subsequent anaerobic digestion is a promising approach in order to increase methane yields. PMID:23988521

  1. Improvement of methane generation capacity by aerobic pre-treatment of organic waste with a cellulolytic Trichoderma viride culture.

    PubMed

    Wagner, Andreas Otto; Schwarzenauer, Thomas; Illmer, Paul

    2013-11-15

    Trichoderma viride is known as a potent cellulose decomposer and was successfully used to improve and accelerate the decomposition process of aerobic composting. In contrast, the role of fungi as pre-treatment organisms for anaerobic digestion is not clear, since the fast aerobic decomposition is thought to be responsible for a rapid depletion of easily available nutrients, leading to a lack of these for the anaerobic community. In the present study carried out in lab-scale, the application of T. viride for the aerobic pre-incubation of organic matter derived from the inlet port of a 750,000 L anaerobic digester led to an increase in total gas and methane production in a subsequent anaerobic digestion step. A high cellulase activity caused by the addition of T. viride seemed to be responsible for a better nutrient availability for anaerobic microorganisms. Therefore, aerobic pre-incubation of organic residues with T. viride for subsequent anaerobic digestion is a promising approach in order to increase methane yields.

  2. Anaerobic Oxidation of Methane in Tropical and Boreal Soils: Ecological Significance

    NASA Astrophysics Data System (ADS)

    Blazewicz, S. J.; Petersen, D. G.; Waldrop, M. P.; Firestone, M. K.

    2011-12-01

    Anaerobic oxidation of methane (AOM) is a considerable sink for the greenhouse gas methane (CH4) in marine systems, but the importance of this process in terrestrial systems is less clear. Lowland boreal soils and wet tropical soils are two of the most dynamic terrestrial systems with regard to atmospheric CH4 cycles, yet little work has directly investigated AOM in these systems. We assessed the occurrence and potential importance of AOM in soils from Long Term Ecological Research sites in Alaska and Puerto Rico. Using in vitro techniques, isotope tracers were utilized to enable the simultaneous quantification of CH4 production and consumption without the use of biological inhibitors. Boreal peat soil and tropical mineral soil had the ability to oxidize significant quantities of CH4 to CO2 under anaerobic conditions (p < 0.001). Potential AOM rates were 21 ± 2 nmol gdw-1 d-1 and 2.9 ± 0.5 nmol gdw-1 d-1 for the boreal and tropical soils, respectively. The addition of terminal electron acceptors (NO3-, Fe3+, and SO42-) inhibited AOM and methanogenesis in both soils. In all incubations, CH4 production occurred simultaneously with AOM, and CH4 production rates were always greater than AOM rates. There was a strong correlation between the quantity of CH4 produced and the amount of CH4 oxidized under anaerobic conditions (Pearson's correlation coefficient: Alaska = 0.875, p < 0.0001; Puerto Rico = 0.817, p < 0.0001). Results indicate that CH4 oxidation under anaerobic conditions was biological and likely mediated by methanogenic archaea in both soils. For ecological perspective, we compared and contrasted rates of AOM in our two soils with AOM rates in marine systems and aerobic methane oxidation rates in our systems. While only a small percentage of the total methane produced in our soils was oxidized under anaerobic conditions, this process represents a previously unidentified sink in these soils that warrants further investigation.

  3. Degradation kinetics of chlorinated aliphatic hydrocarbons by methane oxidizers naturally-associated with wetland plant roots.

    PubMed

    Powell, C L; Goltz, M N; Agrawal, A

    2014-12-01

    Chlorinated aliphatic hydrocarbons (CAHs) are common groundwater contaminants that can be removed from the environment by natural attenuation processes. CAH biodegradation can occur in wetland environments by reductive dechlorination as well as oxidation pathways. In particular, CAH oxidation may occur in vegetated wetlands, by microorganisms that are naturally associated with the roots of wetland plants. The main objective of this study was to evaluate the cometabolic degradation kinetics of the CAHs, cis-1,2-dichloroethene (cisDCE), trichloroethene (TCE), and 1,1,1-trichloroethane (1,1,1TCA), by methane-oxidizing bacteria associated with the roots of a typical wetland plant in soil-free system. Laboratory microcosms with washed live roots investigated aerobic, cometabolic degradation of CAHs by the root-associated methane-oxidizing bacteria at initial aqueous [CH4] ~1.9mgL(-1), and initial aqueous [CAH] ~150μgL(-1); cisDCE and TCE (in the presence of 1,1,1TCA) degraded significantly, with a removal efficiency of approximately 90% and 46%, respectively. 1,1,1TCA degradation was not observed in the presence of active methane oxidizers. The pseudo first-order degradation rate-constants of TCE and cisDCE were 0.12±0.01 and 0.59±0.07d(-1), respectively, which are comparable to published values. However, their biomass-normalized degradation rate constants obtained in this study were significantly smaller than pure-culture studies, yet they were comparable to values reported for biofilm systems. The study suggests that CAH removal in wetland plant roots may be comparable to processes within biofilms. This has led us to speculate that the active biomass may be on the root surface as a biofilm. The cisDCE and TCE mass losses due to methane oxidizers in this study offer insight into the role of shallow, vegetated wetlands as an environmental sink for such xenobiotic compounds.

  4. Degradation kinetics of chlorinated aliphatic hydrocarbons by methane oxidizers naturally-associated with wetland plant roots

    NASA Astrophysics Data System (ADS)

    Powell, C. L.; Goltz, M. N.; Agrawal, A.

    2014-12-01

    Chlorinated aliphatic hydrocarbons (CAHs) are common groundwater contaminants that can be removed from the environment by natural attenuation processes. CAH biodegradation can occur in wetland environments by reductive dechlorination as well as oxidation pathways. In particular, CAH oxidation may occur in vegetated wetlands, by microorganisms that are naturally associated with the roots of wetland plants. The main objective of this study was to evaluate the cometabolic degradation kinetics of the CAHs, cis-1,2-dichloroethene (cisDCE), trichloroethene (TCE), and 1,1,1-trichloroethane (1,1,1TCA), by methane-oxidizing bacteria associated with the roots of a typical wetland plant in soil-free system. Laboratory microcosms with washed live roots investigated aerobic, cometabolic degradation of CAHs by the root-associated methane-oxidizing bacteria at initial aqueous [CH4] ~ 1.9 mg L- 1, and initial aqueous [CAH] ~ 150 μg L- 1; cisDCE and TCE (in the presence of 1,1,1TCA) degraded significantly, with a removal efficiency of approximately 90% and 46%, respectively. 1,1,1TCA degradation was not observed in the presence of active methane oxidizers. The pseudo first-order degradation rate-constants of TCE and cisDCE were 0.12 ± 0.01 and 0.59 ± 0.07 d- 1, respectively, which are comparable to published values. However, their biomass-normalized degradation rate constants obtained in this study were significantly smaller than pure-culture studies, yet they were comparable to values reported for biofilm systems. The study suggests that CAH removal in wetland plant roots may be comparable to processes within biofilms. This has led us to speculate that the active biomass may be on the root surface as a biofilm. The cisDCE and TCE mass losses due to methane oxidizers in this study offer insight into the role of shallow, vegetated wetlands as an environmental sink for such xenobiotic compounds.

  5. Atmospheric methane removal by methane-oxidizing bacteria immobilized on porous building materials.

    PubMed

    Ganendra, Giovanni; De Muynck, Willem; Ho, Adrian; Hoefman, Sven; De Vos, Paul; Boeckx, Pascal; Boon, Nico

    2014-04-01

    Biological treatment using methane-oxidizing bacteria (MOB) immobilized on six porous carrier materials have been used to mitigate methane emission. Experiments were performed with different MOB inoculated in building materials at high (~20 % (v/v)) and low (~100 ppmv) methane mixing ratios. Methylocystis parvus in autoclaved aerated concrete (AAC) exhibited the highest methane removal rate at high (28.5 ± 3.8 μg CH₄ g⁻¹ building material h⁻¹) and low (1.7 ± 0.4 μg CH₄ g⁻¹ building material h⁻¹) methane mixing ratio. Due to the higher volume of pores with diameter >5 μm compared to other materials tested, AAC was able to adsorb more bacteria which might explain for the higher methane removal observed. The total methane and carbon dioxide-carbon in the headspace was decreased for 65.2 ± 10.9 % when M. parvus in Ytong was incubated for 100 h. This study showed that immobilized MOB on building materials could be used to remove methane from the air and also act as carbon sink.

  6. Aerobic and anaerobic oxidation of hydrogen by acidophilic bacteria.

    PubMed

    Hedrich, Sabrina; Johnson, D Barrie

    2013-12-01

    While many prokaryotic species are known to use hydrogen as an electron donor to support their growth, this trait has only previously been reported for two acidophilic bacteria, Hydrogenobaculum acidophilum (in the presence of reduced sulfur) and Acidithiobacillus (At.) ferrooxidans. To test the hypothesis that hydrogen may be utilized more widely by acidophilic bacteria, 38 strains of acidophilic bacteria, including representatives of 20 designated and four proposed species, were screened for their abilities to grow via the dissimilatory oxidation of hydrogen. Growth was demonstrated in several species of acidophiles that also use other inorganic electron donors (ferrous iron and sulfur) but in none of the obligately heterotrophic species tested. Strains of At. ferrooxidans, At. ferridurans and At. caldus, grew chemolithotrophically on hydrogen, though those of At. thiooxidans and At. ferrivorans did not. Growth was also observed with Sulfobacillus acidophilus, Sb. benefaciens and Sb. thermosulfidooxidans, though not with other iron-oxidizing Firmicutes. Similarly, Acidimicrobium ferrooxidans grew on hydrogen, closely related acidophilic actinobacteria did not. Growth yields of At. ferrooxidans and At. ferridurans grown aerobically on hydrogen (c. 10(10)  cells mL(-1) ) were far greater than typically obtained using other electron donors. Several species also grew anaerobically by coupling hydrogen oxidation to the reduction of ferric iron.

  7. Compositional and functional stability of aerobic methane consuming communities in drained and rewetted peat meadows.

    PubMed

    Krause, Sascha; Niklaus, Pascal A; Badwan Morcillo, Sara; Meima Franke, Marion; Lüke, Claudia; Reim, Andreas; Bodelier, Paul L E

    2015-11-01

    The restoration of peatlands is an important strategy to counteract subsidence and loss of biodiversity. However, responses of important microbial soil processes are poorly understood. We assessed functioning, diversity and spatial organization of methanotrophic communities in drained and rewetted peat meadows with different water table management and agricultural practice. Results show that the methanotrophic diversity was similar between drained and rewetted sites with a remarkable dominance of the genus Methylocystis. Enzyme kinetics depicted no major differences, indicating flexibility in the methane (CH4) concentrations that can be used by the methanotrophic community. Short-term flooding led to temporary elevated CH4 emission but to neither major changes in abundances of methane-oxidizing bacteria (MOB) nor major changes in CH4 consumption kinetics in drained agriculturally used peat meadows. Radiolabeling and autoradiographic imaging of intact soil cores revealed a markedly different spatial arrangement of the CH4 consuming zone in cores exposed to near-atmospheric and elevated CH4. The observed spatial patterns of CH4 consumption in drained peat meadows with and without short-term flooding highlighted the spatial complexity and responsiveness of the CH4 consuming zone upon environmental change. The methanotrophic microbial community is not generally altered and harbors MOB that can cover a large range of CH4 concentrations offered due to water-table fluctuations, effectively mitigating CH4 emissions.

  8. Phospholipid-Derived Fatty Acids and Their Stable and Radiocarbon Isotope Values as Indicators of Bacterial Methane Oxidation at a Thermogenic Methane Seep

    NASA Astrophysics Data System (ADS)

    Mills, C. T.; Dias, R. F.; Slater, G. F.; Reddy, C. M.; Mandernack, K. W.

    2004-12-01

    The importance of aerobic methanotrophy as a filter for biogenic methane emissions is well documented for environments such as natural wetlands, landfills, and rice paddies, but less is known about methane oxidation in soils overlying thermogenic methane seeps. We are utilizing phospholipid-derived fatty acids (PLFAs) extracted from soils overlying a high-rate, coal-bed methane seep in Southwestern Colorado to investigate the location and extent of bacterial methane consumption within the soil column. PLFAs have been widely used as indicators of both quantities and types of viable bacterial populations. Two specific PLFAs, 16:1ω 8 and 18:1ω 8, appear to be unique to type I and type II methanotrophs, respectively. We have detected higher abundances of these methanotroph biomarkers in surface soils ( ˜0-30 cm) under wetter soil conditions and near the water table ( ˜150 cm) under drier conditions. Maximum concentrations of both type I and type II methanotroph PLFA biomarkers were greatest in the shallow soils during wetter conditions with the type I maximum located just above the type II maximum. This is consistent with pure culture studies that have shown type I methanotrophs to prefer higher oxygen, lower methane conditions and type II methanotrophs to prefer lower oxygen, higher methane conditions. Soil gas methane concentrations during this wetter period were approximately 30% at 20 cm depth and 80% at 100 cm depth. During a drier period a type II methanotroph biomarker maximum was observed near the water table but no type I maximum was observed. Soil gas methane concentrations at this time were less than 1% at 20 cm and 25% at 100 cm. These data suggest that methanotrophs may consume a significant fraction of the methane as it rises through the soil column. Greater saturation of soil pore spaces during wetter conditions may inhibit atmospheric oxygen diffusion into deeper soils forcing methanotrophs to reside in the shallow soils and resulting in larger

  9. Aerobic biotransformation of N-nitrosodimethylamine and N-nitrodimethylamine in methane and benzene amended soil columns.

    PubMed

    Weidhaas, Jennifer; Dupont, R Ryan

    2013-07-01

    Aerobic biotransformation of N-nitrosodimethylamine (NDMA), an emerging contaminant of concern, and its structural analog N-nitrodimethylamine (DMN), was evaluated in benzene and methane amended groundwater passed through laboratory scale soil columns. Competitive inhibition models were used to model the kinetics for NDMA and DMN cometabolism accounting for the concurrent degradation of the growth and cometabolic substrates. Transformation capacities for NDMA and DMN with benzene (13 and 23μg (mgcells)(-1)) and methane (0.14 and 8.4μg (mgcells)(-1)) grown cultures, respectively are comparable to those presented in the literature, as were first order endogenous decay rates estimated to be 2.1×10(-2)±1.7×10(-3)d(-1) and 6.5×10(-1)±7.1×10(-1)d(-1) for the methane and benzene amended cultures, respectively. These studies highlight possible attenuation mechanisms and rates for NDMA and DMN biotransformation in aerobic aquifers undergoing active remediation, natural attenuation or managed aquifer recharge with treated wastewater (i.e., reclaimed water).

  10. Anaerobic Oxidization of Methane in a Minerotrophic Peatland: Enrichment of Nitrite-Dependent Methane-Oxidizing Bacteria

    PubMed Central

    Zhu, Baoli; van Dijk, Gijs; Fritz, Christian; Smolders, Alfons J. P.; Pol, Arjan; Jetten, Mike S. M.

    2012-01-01

    The importance of anaerobic oxidation of methane (AOM) as a methane sink in freshwater systems is largely unexplored, particularly in peat ecosystems. Nitrite-dependent anaerobic methane oxidation (n-damo) was recently discovered and reported to be catalyzed by the bacterium “Candidatus Methylomirabilis oxyfera,” which is affiliated with the NC10 phylum. So far, several “Ca. Methylomirabilis oxyfera” enrichment cultures have been obtained using a limited number of freshwater sediments or wastewater treatment sludge as the inoculum. In this study, using stable isotope measurements and porewater profiles, we investigated the potential of n-damo in a minerotrophic peatland in the south of the Netherlands that is infiltrated by nitrate-rich ground water. Methane and nitrate profiles suggested that all methane produced was oxidized before reaching the oxic layer, and NC10 bacteria could be active in the transition zone where countergradients of methane and nitrate occur. Quantitative PCR showed high NC10 bacterial cell numbers at this methane-nitrate transition zone. This soil section was used to enrich the prevalent NC10 bacteria in a continuous culture supplied with methane and nitrite at an in situ pH of 6.2. An enrichment of nitrite-reducing methanotrophic NC10 bacteria was successfully obtained. Phylogenetic analysis of retrieved 16S rRNA and pmoA genes showed that the enriched bacteria were very similar to the ones found in situ and constituted a new branch of NC10 bacteria with an identity of less than 96 and 90% to the 16S rRNA and pmoA genes of “Ca. Methylomirabilis oxyfera,” respectively. The results of this study expand our knowledge of the diversity and distribution of NC10 bacteria in the environment and highlight their potential contribution to nitrogen and methane cycles. PMID:23042166

  11. Catalytic Aerobic Dehydrogenation of Nitrogen Heterocycles Using Heterogeneous Cobalt Oxide Supported on Nitrogen-Doped Carbon.

    PubMed

    Iosub, Andrei V; Stahl, Shannon S

    2015-09-18

    Dehydrogenation of (partially) saturated heterocycles provides an important route to heteroaromatic compounds. A heterogeneous cobalt oxide catalyst, previously employed for aerobic oxidation of alcohols and amines, is shown to be effective for aerobic dehydrogenation of various 1,2,3,4-tetrahydroquinolines to the corresponding quinolines. The reactions proceed in good yields under mild conditions. Other N-heterocycles are also successfully oxidized to their aromatic counterparts.

  12. Isolation of an aerobic vinyl chloride oxidizer from anaerobic groundwater.

    PubMed

    Fullerton, Heather; Rogers, Rebecca; Freedman, David L; Zinder, Stephen H

    2014-11-01

    Vinyl chloride (VC) is a known human carcinogen and common groundwater contaminant. Reductive dechlorination of VC to non-toxic ethene under anaerobic conditions has been demonstrated at numerous hazardous waste sites. However, VC disappearance without stoichiometric production of ethene has also been observed at some sites and in microcosms. In this study we identify an organism responsible for this observation in presumably anaerobic microcosms and conclude that oxygen was not detectable based on a lack of color change from added resazurin. This organism, a Mycobacterium sp. closely related to known VC oxidizing strains, was present in high numbers in 16S rRNA gene clone libraries from a groundwater microcosm. Although the oxidation/reduction indicator resazurin remained in the clear reduced state in these studies, these results suggest inadvertent oxygen contamination occurred. This study helps to elucidate the dynamic behavior of chlorinated ethenes in contaminated groundwater, through the isolation of a strictly aerobic organism that may be responsible for at least some disappearance of VC without the concomitant production of ethene in groundwater considered anaerobic.

  13. Alpha- and Gammaproteobacterial Methanotrophs Codominate the Active Methane-Oxidizing Communities in an Acidic Boreal Peat Bog

    PubMed Central

    Esson, Kaitlin C.; Lin, Xueju; Kumaresan, Deepak; Chanton, Jeffrey P.; Murrell, J. Colin

    2016-01-01

    The objective of this study was to characterize metabolically active, aerobic methanotrophs in an ombrotrophic peatland in the Marcell Experimental Forest, in Minnesota. Methanotrophs were investigated in the field and in laboratory incubations using DNA-stable isotope probing (SIP), expression studies on particulate methane monooxygenase (pmoA) genes, and amplicon sequencing of 16S rRNA genes. Potential rates of oxidation ranged from 14 to 17 μmol of CH4 g dry weight soil−1 day−1. Within DNA-SIP incubations, the relative abundance of methanotrophs increased from 4% in situ to 25 to 36% after 8 to 14 days. Phylogenetic analysis of the 13C-enriched DNA fractions revealed that the active methanotrophs were dominated by the genera Methylocystis (type II; Alphaproteobacteria), Methylomonas, and Methylovulum (both, type I; Gammaproteobacteria). In field samples, a transcript-to-gene ratio of 1 to 2 was observed for pmoA in surface peat layers, which attenuated rapidly with depth, indicating that the highest methane consumption was associated with a depth of 0 to 10 cm. Metagenomes and sequencing of cDNA pmoA amplicons from field samples confirmed that the dominant active methanotrophs were Methylocystis and Methylomonas. Although type II methanotrophs have long been shown to mediate methane consumption in peatlands, our results indicate that members of the genera Methylomonas and Methylovulum (type I) can significantly contribute to aerobic methane oxidation in these ecosystems. PMID:26873322

  14. Methane oxidation in permeable sediments at hydrocarbon seeps in the Santa Barbara Channel, California

    NASA Astrophysics Data System (ADS)

    Treude, T.; Ziebis, W.

    2010-03-01

    A shallow-water area in the Santa Barbara Channel (California), known collectively as the Coal Oil Point seep field, is one the largest natural submarine oil and gas emission areas in the world. Both gas and oil are seeping constantly through a predominantly sandy seabed into the ocean. This study focused on the methanotrophic activity within the surface sediments (0-15 cm) of the permeable seabed in the so-called Brian Seep area at a water depth ~10 m. Detailed investigations of biogeochemical parameters in the sediment surrounding active gas vents indicated that methane seepage through the permeable seabed induces a convective transport of fluids within the surface sediment layer, which results in a deeper penetration of oxidants (oxygen, sulfate) into the sediment, as well as in a faster removal of potentially inhibiting reduced end products (e.g. hydrogen sulfide). Methanotrophic activity was often found close to the sediment-water interface, indicating the involvement of aerobic bacteria. However, biogeochemical data suggests that the majority of methane is consumed by anaerobic oxidation of methane (AOM) coupled to sulfate reduction below the surface layer (>15 cm), where sulfate is still available in high concentrations. This subsurface maximum of AOM activity in permeable sands is in contrast to known deep-sea seep habitats, where upward fluid advection through more fine-grained sediments leads to an accumulation of AOM activity within the top 10 cm of the sediments, because sulfate is rapidly depleted.

  15. A Metagenomics-Based Metabolic Model of Nitrate-Dependent Anaerobic Oxidation of Methane by Methanoperedens-Like Archaea

    PubMed Central

    Arshad, Arslan; Speth, Daan R.; de Graaf, Rob M.; Op den Camp, Huub J. M.; Jetten, Mike S. M.; Welte, Cornelia U.

    2015-01-01

    Methane oxidation is an important process to mitigate the emission of the greenhouse gas methane and further exacerbating of climate forcing. Both aerobic and anaerobic microorganisms have been reported to catalyze methane oxidation with only a few possible electron acceptors. Recently, new microorganisms were identified that could couple the oxidation of methane to nitrate or nitrite reduction. Here we investigated such an enrichment culture at the (meta) genomic level to establish a metabolic model of nitrate-driven anaerobic oxidation of methane (nitrate-AOM). Nitrate-AOM is catalyzed by an archaeon closely related to (reverse) methanogens that belongs to the ANME-2d clade, tentatively named Methanoperedens nitroreducens. Methane may be activated by methyl-CoM reductase and subsequently undergo full oxidation to carbon dioxide via reverse methanogenesis. All enzymes of this pathway were present and expressed in the investigated culture. The genome of the archaeal enrichment culture encoded a variety of enzymes involved in an electron transport chain similar to those found in Methanosarcina species with additional features not previously found in methane-converting archaea. Nitrate reduction to nitrite seems to be located in the pseudoperiplasm and may be catalyzed by an unusual Nar-like protein complex. A small part of the resulting nitrite is reduced to ammonium which may be catalyzed by a Nrf-type nitrite reductase. One of the key questions is how electrons from cytoplasmically located reverse methanogenesis reach the nitrate reductase in the pseudoperiplasm. Electron transport in M. nitroreducens probably involves cofactor F420 in the cytoplasm, quinones in the cytoplasmic membrane and cytochrome c in the pseudoperiplasm. The membrane-bound electron transport chain includes F420H2 dehydrogenase and an unusual Rieske/cytochrome b complex. Based on genome and transcriptome studies a tentative model of how central energy metabolism of nitrate-AOM could work is

  16. A Metagenomics-Based Metabolic Model of Nitrate-Dependent Anaerobic Oxidation of Methane by Methanoperedens-Like Archaea.

    PubMed

    Arshad, Arslan; Speth, Daan R; de Graaf, Rob M; Op den Camp, Huub J M; Jetten, Mike S M; Welte, Cornelia U

    2015-01-01

    Methane oxidation is an important process to mitigate the emission of the greenhouse gas methane and further exacerbating of climate forcing. Both aerobic and anaerobic microorganisms have been reported to catalyze methane oxidation with only a few possible electron acceptors. Recently, new microorganisms were identified that could couple the oxidation of methane to nitrate or nitrite reduction. Here we investigated such an enrichment culture at the (meta) genomic level to establish a metabolic model of nitrate-driven anaerobic oxidation of methane (nitrate-AOM). Nitrate-AOM is catalyzed by an archaeon closely related to (reverse) methanogens that belongs to the ANME-2d clade, tentatively named Methanoperedens nitroreducens. Methane may be activated by methyl-CoM reductase and subsequently undergo full oxidation to carbon dioxide via reverse methanogenesis. All enzymes of this pathway were present and expressed in the investigated culture. The genome of the archaeal enrichment culture encoded a variety of enzymes involved in an electron transport chain similar to those found in Methanosarcina species with additional features not previously found in methane-converting archaea. Nitrate reduction to nitrite seems to be located in the pseudoperiplasm and may be catalyzed by an unusual Nar-like protein complex. A small part of the resulting nitrite is reduced to ammonium which may be catalyzed by a Nrf-type nitrite reductase. One of the key questions is how electrons from cytoplasmically located reverse methanogenesis reach the nitrate reductase in the pseudoperiplasm. Electron transport in M. nitroreducens probably involves cofactor F420 in the cytoplasm, quinones in the cytoplasmic membrane and cytochrome c in the pseudoperiplasm. The membrane-bound electron transport chain includes F420H2 dehydrogenase and an unusual Rieske/cytochrome b complex. Based on genome and transcriptome studies a tentative model of how central energy metabolism of nitrate-AOM could work is

  17. Optical monitoring of the oxidation of methane in supercritical water

    SciTech Connect

    Steeper, R.R.; Rice, S.F.

    1994-08-01

    Supercritical water oxidation is an emerging technology being developed by many laboratories and industries for the treatment of hazardous wastes. It is appropriate for the destruction of a wide variety of waste streams composed of up to 20% organics in water. Experiments were conducted in a static, high-pressure reactor to investigate the oxidation of methane in supercritical water. Pressures ranged from 138 to 275 bar, temperatures from 380 to 440{degrees}C, and equivalence ratios from 0.2 to 2.0 for initial methane concentrations around 0.1 mole/l. In these experiments, Raman spectroscopy was used as an in-situ diagnostic to monitor the concentrations of methane, oxygen, and carbon dioxide. Over this pressure range the reaction rate of methane with oxygen is unexpectedly observed to decrease with increasing pressure. A non-linear least squares fit was performed to determine four global reaction rate parameters. In contrast to results from experiments at lower initial methane concentrations, the reaction order dependency on methane is found here to be greater than unity. This finding implies that the former results cannot safely extrapolate to concentrations around 0.1 mole/l.

  18. Anaerobic methane oxidation in two tropical freshwater systems

    NASA Astrophysics Data System (ADS)

    Roland, Fleur; Darchambeau, François; Crowe, Sean A.; Borges, Alberto V.

    2014-05-01

    Lake Kivu is one of the East African Great Lakes. It is located at the border between Rwanda and the Democratic Republic of the Congo. It is a deep meromictic lake characterized by huge amounts of methane (CH4) (60 km3 at 0° C and 1 atm) dissolved in its deep waters. Two thirds of the CH4 originates from anoxic bacterial reduction of dissolved carbon dioxide and one third from anaerobic degradation of settling organic material. CH4 then diffuses slowly from the monimolimnion to surface waters where many is oxidised by methanotrophic microorganisms. In Lake Kivu, this biological oxidation of CH4 could occur with different final electron acceptors: oxygen (aerobic oxidation) but also nitrate (NO3-), nitrite, sulfate (SO42-), iron (Fe) or manganese (Mn) in anaerobic conditions. If the anaerobic oxidation of CH4 (AOM) is generally coupled to SO42- reduction in marine waters, electron acceptors of the AOM were rarely investigated in freshwater systems. Five field campaigns were conducted from 2011 to 2013 during periods with contrasted ventilations of the upper water column. The dry season is characterized by a deeper mixing of surface waters ended by a steep gradient of physico-chemical conditions at the redox interface, while during the rainy season the mixed layer is shallower and ended at its deeper part by a NO3- accumulation zone. Sampling was conducted in the main basin of Lake Kivu but also in a particular sub-basin located northeast of the lake, the Kabuno Bay. Both systems are meromictic but differ in terms of morphometry and geochemistry with a shallower permanent chemocline and higher concentrations of CH4, Fe and Mn in the anoxic waters in Kabuno Bay compared to the main lake. Samples were collected for the measurements of CH4 concentrations and the various potential electron acceptors of the AOM. CH4 oxidation rates were measured along vertical profiles at 5 m and 0.5 m depth intervals respectively in the main basin and Kabuno bay water columns. Results

  19. Methane and nitrous oxide in the ice core record.

    PubMed

    Wolff, Eric; Spahni, Renato

    2007-07-15

    Polar ice cores contain, in trapped air bubbles, an archive of the concentrations of stable atmospheric gases. Of the major non-CO2 greenhouse gases, methane is measured quite routinely, while nitrous oxide is more challenging, with some artefacts occurring in the ice and so far limited interpretation. In the recent past, the ice cores provide the only direct measure of the changes that have occurred during the industrial period; they show that the current concentration of methane in the atmosphere is far outside the range experienced in the last 650,000 years; nitrous oxide is also elevated above its natural levels. There is controversy about whether changes in the pre-industrial Holocene are natural or anthropogenic in origin. Changes in wetland emissions are generally cited as the main cause of the large glacial-interglacial change in methane. However, changing sinks must also be considered, and the impact of possible newly described sources evaluated. Recent isotopic data appear to finally rule out any major impact of clathrate releases on methane at these time-scales. Any explanation must take into account that, at the rapid Dansgaard-Oeschger warmings of the last glacial period, methane rose by around half its glacial-interglacial range in only a few decades. The recent EPICA Dome C (Antarctica) record shows that methane tracked climate over the last 650,000 years, with lower methane concentrations in glacials than interglacials, and lower concentrations in cooler interglacials than in warmer ones. Nitrous oxide also shows Dansgaard-Oeschger and glacial-interglacial periodicity, but the pattern is less clear.

  20. 40 CFR Table Hh-4 to Subpart Hh of... - Landfill Methane Oxidation Fractions

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 21 2014-07-01 2014-07-01 false Landfill Methane Oxidation Fractions.... 98, Subpt. HH, Table HH-4 Table HH-4 to Subpart HH of Part 98—Landfill Methane Oxidation Fractions... soil prior to any oxidation and is calculated as follows: ER29NO13.024 Where: MF = Methane flux...

  1. Reduced graphene oxide supported Au nanoparticles as an efficient catalyst for aerobic oxidation of benzyl alcohol

    NASA Astrophysics Data System (ADS)

    Yu, Xianqin; Huo, Yujia; Yang, Jing; Chang, Sujie; Ma, Yunsheng; Huang, Weixin

    2013-09-01

    Various Au/C catalysts were prepared by Au nanoparticels supported on different carbonaceous supports including reduced graphene oxide (RGO), activated carbon (AC) and graphite (GC) using sol-immobilization method. Au/RGO shows a much higher activity than Au/AC and Au/GC in the liquid phase aerobic oxidation of benzyl alcohol. The superior catalytic performance of Au/RGO may be related to the presence of surface O-containing functional groups and moderate graphite character of RGO supports.

  2. Response of Atmospheric-Methane Oxidation to Methane-Flux Manipulation in a Laboratory Soil-Column Experiment

    NASA Astrophysics Data System (ADS)

    Schroth, M. H.; Mignola, I.; Henneberger, R.

    2015-12-01

    Upland soils are an important sink for atmospheric methane (CH4). Uptake of atmospheric CH4 in soils is generally diffusion limited, and is mediated by aerobic CH4 oxidizing bacteria (MOB) that possess a high-affinity form of a key enzyme, allowing CH4 consumption at near-atmospheric concentrations (≤ 1.9 µL/L). As cultivation attempts for these high-affinity MOB have shown little success, there remains much speculation regarding their functioning in different environments. For example, it is frequently assumed that they are highly sensitive to physical disturbance, but their response in activity and abundance to changes in substrate availability remains largely unknown. We present results of a laboratory column experiment conducted to investigate the response in activity and abundance of high-affinity MOB to an increase in CH4 flux. Intact soil cores, collected at a field site where atmospheric CH4 oxidation activity is frequently quantified, were transferred into two 1-m-long, 12-cm-dia. columns. The columns were operated at constant temperature in the dark, their headspace being continuously flushed with air. Diffusive gas-transport conditions were maintained in the reference column, whereas CH4 flux was increased in several steps in the treatment column by inducing advective gas flow using a diaphragm pump. Soil-gas samples periodically collected from ports installed along the length of the columns were analyzed for CH4 content. Together with measurements of soil-water content, atmospheric CH4 oxidation was quantified using the soil-profile method. First results indicate that atmospheric CH4 oxidation activity comparable with the field was maintained in the reference column throughout the experiment. Moreover, high-affinity MOB quickly adjusted to an increase in CH4 flux in the treatment column, efficiently consuming CH4. Quantification of MOB abundance is currently ongoing. Our data provide new insights into controls on atmospheric CH4 oxidation in soils.

  3. Methane oxidation in three Alberta soils: influence of soil parameters and methane flux rates.

    PubMed

    Stein, V B; Hettiaratchi, J P

    2001-01-01

    Current concern over the potentially negative impacts of climate change has brought attention to anthropogenic sources of methane, a primary greenhouse gas. Two such emission sources are methane leakage at heavy oil wells and sanitary landfills. At both of these sources, substantial quantities of methane could potentially be oxidised by methanotrophic microbes living in soils. Optimisation of this phenomenon may serve as an inexpensive technique for reducing methane emissions. Soil column and batch incubation experiments were performed on a landfill loam, an agricultural loam and a sedge peat to gain a better quantitative understanding of the biological and physical processes limiting CH4 oxidation in soils that undergo the freeze-thaw cycles associated with northern climates. Moisture content emerged as a critical variable that can limit a soil's CH4 oxidation potential. For example, the oxidation rate of the agricultural soil was seen to increase by an order of magnitude after increasing its moisture content from 6% to 10% of its dry weight.

  4. Partial oxidation of methane on supported potassium molybdate

    SciTech Connect

    Erdohelyi, A.; Fodor, K.; Solymosi, F.

    1997-03-01

    The partial oxidation of methane to formaldehyde was studied on K{sub 2}MoO{sub 4}, deposited on various supports, in a fixed-bed continuous-flow reactor at 860-923 K using O{sub 2} as oxidant. The catalysts were characterized by Raman and XPS spectroscopies. It was found that the composition of molybdates deposited by impregnation depended sensitively on the pH value of the slurry containing the support. At low pH values a significant amount of K{sub 2}Mo{sub 2}O{sub 7} was formed. The product distribution of the oxidation reaction was markedly influenced by the nature of the support. The highest activity was measured for magnesia-supported catalyst. In this case, however, only the complete oxidation of methane occurred. Formaldehyde, in a larger quantity, was produced on silica-supported catalyst containing a greater amount of K{sub 2}Mo{sub 2}O{sub 7} and on K{sub 2}MoO{sub 4}/ZSM-5. It was observed that at very low oxygen content, {approximately}0.1%, the reaction pathway of methane conversion was basically different: in this case the main hydrocarbon products were ethylene, ethane, and benzene. Formaldehyde was not detected. A possible mechanism for the reaction of methane is discussed. 37 refs., 7 figs., 3 tabs.

  5. Semi-aerobic fermentation as a novel pre-treatment to obtain VFA and increase methane yield from primary sludge.

    PubMed

    Peces, M; Astals, S; Clarke, W P; Jensen, P D

    2016-01-01

    There is a growing trend to consider organic wastes as potential sources of renewable energy and value-add products. Fermentation products have emerged as attractive value-add option due to relative easy production and broad application range. However, pre-fermentation and extraction of soluble products may impact down-stream treatment processes, particularly energy recovery by anaerobic digestion. This paper investigates primary sludge pre-fermentation at different temperatures (20, 37, 55, and 70°C), treatment times (12, 24, 48, and 72h), and oxygen availability (semi-aerobic, anaerobic); and its impact on anaerobic digestion. Pre-fermentation at 20 and 37°C succeeded for VFA production with acetate and propionate being major products. Pre-fermentation at 37, 55, and 70°C resulted in higher solubilisation yield but it reduced sludge methane potential by 20%. Under semi-aerobic conditions, pre-fermentation allowed both VFA recovery (43gCODVFAkg(-1)VS) and improved methane potential. The latter phenomenon was linked to fungi that colonised the sludge top layer during pre-fermentation. PMID:26551651

  6. Nitrogen oxides and methane treatment by non-thermal plasma

    NASA Astrophysics Data System (ADS)

    Alva, E.; Pacheco, M.; Colín, A.; Sánchez, V.; Pacheco, J.; Valdivia, R.; Soria, G.

    2015-03-01

    Non thermal plasma was used to treat nitrogen oxides (NOx) and methane (CH4), since they are important constituents of hydrocarbon combustion emissions processes and, both gases, play a key role in the formation of tropospheric ozone. These gases are involved in environmental problems like acid rain and some diseases such as bronchitis and pneumonia. In the case of methane is widely known its importance in the global climate change, and currently accounts for 30% of global warming. There is a growing concern for methane leaks, associated with a rapid expansion of unconventional oil and gas extraction techniques as well as a large-scale methane release from Arctic because of ice melting and the subsequent methane production of decaying organic matter. Therefore, methane mitigation is a key to avoid dangerous levels of global warming. The research, here reported, deals about the generation of non-thermal plasma with a double dielectric barrier (2DBD) at atmospheric pressure with alternating current (AC) for NOx and CH4 treatment. The degradation efficiencies and their respective power consumption for different reactor configurations (cylindrical and planar) are also reported. Qualitative and quantitative analysis of gases degradation are reported before and after treatment with cold plasma. Experimental and theoretical results are compared obtaining good removal efficiencies, superior to 90% and to 20% respectively for NOx and CH4.

  7. Anaerobic oxidation of methane in the Concepción Methane Seep Area, Chilean continental margin

    NASA Astrophysics Data System (ADS)

    Steeb, P.; Linke, P.; Scholz, F.; Schmidt, M.; Liebetrau, V.; Treude, T.

    2012-04-01

    Within subduction zones of active continental margins, large amounts of methane can be mobilized by dewatering processes and transported to the seafloor along migration pathways. A recently discovered seep area located off Concepción (Chile) at water depth between 600 to 1100 mbsl is characterized by active methane vent sites as well as massive carbonates boulders and plates which probably are related to methane seepage in the past. During the SO210 research expedition "Chiflux" (Sept-Oct 2010), sediment from the Concepción Methane Seep Area (CSMA) at the fore arc of the Chilean margin was sampled to study microbial activity related to methane seepage. We sampled surface sediments (0-30cm) from sulfur bacteria mats, as well as clam, pogonophoran, and tubeworm fields with push cores and a TV-guided multicorer system. Anaerobic oxidation of methane (AOM) and sulfate reduction rates were determined using ex-situ radioisotope tracer techniques. Additionally, porewater chemistry of retrieved cores as well as isotopic composition and age record of surrounding authigenic carbonates were analyzed. The shallowest sulfate-methane-transition zone (SMTZ) was identified at 4 cm sediment depth hinting to locally strong fluid fluxes. However, a lack of Cl- anomalies in porewater profiles indicates a shallow source of these fluids, which is supported by the biogenic origin of the methane (δ13C -70‰ PDB). Sulfide and alkalinity was relatively high (up to 20 mM and 40 mEq, respectively). Rates of AOM and sulfate reduction within this area reached magnitudes typical for seeps with variation between different habitat types, indicating a diverse methane supply, which is affecting the depths of the SMTZ. Rates were highest at sulfur a bacteria mats (20 mmol m-2 d-1) followed by a large field of dead clams, a pogonophoran field, a black sediment spot, and a carbonate rich clam field. Lowest rates (0.2 mmol m-2 d-1) were measured in close vicinity to these hot spots. Abundant massive

  8. Anaerobic oxidation of methane related to methane seepage along the northern US Atlantic margin

    NASA Astrophysics Data System (ADS)

    Treude, T.; Krause, S.; Colwell, F. S.; Graw, M. F.; Pohlman, J.; Ruppel, C. D.

    2015-12-01

    Microbial anaerobic oxidation of methane (AOM), coupled to sulfate reduction, is an important mechanism in marine sediments for reducing methane emissions into the atmosphere. Here we report on AOM and sulfate reduction activity determined from sediments collected at recently-discovered methane seeps along the northern US Atlantic margin (USAM), where more than 550 gas plumes rise from the seafloor. Many of these gas plumes lie within or above the upper limit of gas hydrate stability on the continental slope. Samples were taken by TV-multicorer and a piston corer aboard the R/V Sharp during a September 2015 expedition that was jointly organized by the US Geological Survey, the Oregon State University, GEOMAR, and UCLA. This presentation will display preliminary data of AOM activity from selected seeps at the USAM to discuss (1) the capacity of the methane biofilter in relation to well-known seep sites, (2) its influence on geochemistry (e.g., sulfide accumulation, carbonate formation) and biology (established chemosynthetic communities), and (3) its potential response to recent methane mobilization from dissociating gas hydrates.

  9. The effect of coal bed dewatering and partial oxidation on biogenic methane potential

    USGS Publications Warehouse

    Jones, Elizabeth J.P.; Harris, Steve H.; Barnhart, Elliott P.; Orem, William H.; Clark, Arthur C.; Corum, Margo D.; Kirshtein, Julie D.; Varonka, Matthew S.; Voytek, Mary A.

    2013-01-01

    Coal formation dewatering at a site in the Powder River Basin was associated with enhanced potential for secondary biogenic methane determined by using a bioassay. We hypothesized that dewatering can stimulate microbial activity and increase the bioavailability of coal. We analyzed one dewatered and two water-saturated coals to examine possible ways in which dewatering influences coal bed natural gas biogenesis by looking at differences with respect to the native coal microbial community, coal-methane organic intermediates, and residual coal oxidation potential. Microbial biomass did not increase in response to dewatering. Small Subunit rRNA sequences retrieved from all coals sampled represented members from genera known to be aerobic, anaerobic and facultatively anaerobic. A Bray Curtis similarity analysis indicated that the microbial communities in water-saturated coals were more similar to each other than to the dewatered coal, suggesting an effect of dewatering. There was a higher incidence of long chain and volatile fatty acid intermediates in incubations of the dewatered coal compared to the water-saturated coals, and this could either be due to differences in microbial enzymatic activities or to chemical oxidation of the coal associated with O2 exposure. Dilute H2O2 treatment of two fractions of structural coal (kerogen and bitumen + kerogen) was used as a proxy for chemical oxidation by O2. The dewatered coal had a low residual oxidation potential compared to the water-saturated coals. Oxidation with 5% H2O2 did increase the bioavailability of structural coal, and the increase in residual oxidation potential in the water saturated coals was approximately equivalent to the higher methanogenic potential measured in the dewatered coal. Evidence from this study supports the idea that coal bed dewatering could stimulate biogenic methanogenesis through partial oxidation of the structural organics in coal once anaerobic conditions are restored.

  10. Oxidation of contaminative methane traces with radio-frequency discharge

    NASA Technical Reports Server (NTRS)

    Flamm, D. L.; Wydeven, T. L.

    1976-01-01

    An 11.8 MHz glow discharge was used to oxidize trace levels of methane in oxygen. The concentration of methane can be reduced by three orders of magnitude. The effects of power (0-400 W), flow rate (10-1000 cc-STP/min) and concentration (70-8000 ppm) were investigated at pressures ranging from 50 torr to almost 1 atm. No organic reaction products were detected in the treated gas stream. The process may prove useful for the removal of atmospheric trace contaminants at ambient pressure.

  11. Kinetically driven instabilities and selectivities in methane oxidation

    SciTech Connect

    Park, Y.K.; Vlachos, D.G.

    1997-08-01

    Ignitions, extinctions, and Hopf bifurcations in methane oxidation were studied as a function of pressure and inlet fuel composition. A continuous stirred-tank reactor was modeled with numerical bifurcation techniques, using the 177 reaction/31 species mechanism. Sensitivity and reaction pathway analyses were performed at turning points to identify the most important reactions and reactive species. Then, simulations were compared with experimental data. Multiple ignitions and extinctions as well as oscillations that are purely kinetically driven were found. Ignition to a partially ignited state with considerable reactivity of methane indicates possible narrow operation windows with high selectivities to partial oxidation products. At 0.1 atm, the authors found a selectivity of up to 80% to CO at 70% CH{sub 4} conversion. The ignition to a fully ignited branch is associated with high selectivity to CO{sub 2} and H{sub 2}O. The C2 chemistry inhibits the ignition of methane to the partially ignited branch. The methane ignition temperature exhibits two branches with respect to pressure, with only the low-pressure branch being dominant. Reaction path analysis at ignition conditions shows that the preferred pathway of CH{sub 4} oxidation is to form CO and CO{sub 2} though CH{sub 2}O and CH{sub 2}(s) intermediates. However, at intermediate to high pressures, the recombination of CH{sub 3} to C{sub 2}H{sub 6} also becomes quite significant.

  12. Oxidative coupling of methane with ac and dc corona discharges

    SciTech Connect

    Liu, C.; Marafee, A.; Hill, B.; Xu, G.; Mallinson, R.; Lobban, L.

    1996-10-01

    The oxidative coupling of methane (OCM) is being actively studied for the production of higher hydrocarbons from natural gas. The present study concentrated on the oxidative conversion of methane in an atmospheric pressure, nonthermal plasma formed by ac or dc corona discharges. Methyl radicals are formed by reaction with negatively-charged oxygen species created in the corona discharge. The selectivity to products ethane and ethylene is affected by electrode polarity, frequency, and oxygen partial pressure in the feed. Higher C{sub 2} yields were obtained with the ac corona. All the ac corona discharges are initiated at room temperature (i.e., no oven or other heat source is used), and the temperature increases to 300--500 C due to the exothermic reactions and the discharge itself. The largest C{sub 2} yield is 21% with 43.3% methane conversion and 48.3% C{sub 2} selectivity at a flowrate of 100 cm{sup 3}/min when the ac corona is at 30 Hz, 5 kV (rms) input power was used. The methane conversion may be improved to more than 50% by increasing the residence time, but the C{sub 2} selectivity decreases. A reaction mechanism including the oxidative dehydrogenation (OXD) of ethane to ethylene is presented to explain the observed phenomena. The results suggest that ac and/or dc gas discharge techniques have significant promise for improving the economics of OCM processes.

  13. Importance of methane-oxidizing bacteria in the methane budget as revealed by the use of a specific inhibitor

    USGS Publications Warehouse

    Oremland, R.S.; Culbertson, C.W.

    1992-01-01

    METHANE is a greenhouse gas whose concentration in the atmosphere is increasing1-3 Much of this methane is derived from the metabolism of methane-generating (methanogenic) bacteria4,5, and over the past two decades much has been learned about the ecology of methanogens; specific inhibitors of methanogenesis, such as 2-bromoethanesulphonic acid, have proved useful in this regard6. In contrast, although much is known about the biochemistry of methane-oxidizing (methanotrophic) bacteria7, ecological investigations have been hampered by the lack of an analogous specific inhibitor6. Methanotrophs limit the flux of methane to the atmosphere from sediments8,9 and consume atmospheric methane10, but the quantitative importance of methanotrophy in the global methane budget is not well known5. Methylfluoride (CH3F) is known to inhibit oxygen consumption by Methylococcus capsulatus11, and to inhibit the oxidation of 14CH4 to 14CO2 by endosymbionts in mussel gill tissues12. Here we report that methylfluoride (MF) inhibits the oxidation of methane by methane monooxygenase, and by using methylfluoride in field investigations, we find that methanotrophic bacteria can consume more than 90% of the methane potentially available.

  14. A four-helix bundle stores copper for methane oxidation

    PubMed Central

    Vita, Nicolas; Platsaki, Semeli; Baslé, Arnaud; Allen, Stephen J.; Paterson, Neil G.; Crombie, Andrew T.; Murrell, J. Colin; Waldron, Kevin J.; Dennison, Christopher

    2015-01-01

    Methane-oxidising bacteria (methanotrophs) require large quantities of copper for the membrane-bound (particulate) methane monooxygenase (pMMO)1,2. Certain methanotrophs are also able to switch to using the iron-containing soluble MMO (sMMO) to catalyse methane oxidation, with this switchover regulated by copper3,4. MMOs are Nature’s primary biological mechanism for suppressing atmospheric levels of methane, a potent greenhouse gas. Furthermore, methanotrophs and MMOs have enormous potential in bioremediation and for biotransformations producing bulk and fine chemicals, and in bioenergy, particularly considering increased methane availability from renewable sources and hydraulic fracturing of shale rock5,6. We have discovered and characterised a novel copper storage protein (Csp1) from the methanotroph Methylosinus trichosporium OB3b that is exported from the cytosol, and stores copper for pMMO. Csp1 is a tetramer of 4-helix bundles with each monomer binding up to 13 Cu(I) ions in a previously unseen manner via mainly Cys residues that point into the core of the bundle. Csp1 is the first example of a protein that stores a metal within an established protein-folding motif. This work provides a detailed insight into how methanotrophs accumulate copper for the oxidation of methane. Understanding this process is essential if the wide-ranging biotechnological applications of methanotrophs are to be realised. Cytosolic homologues of Csp1 are present in diverse bacteria thus challenging the dogma that such organisms do not use copper in this location. PMID:26308900

  15. Constraints on methane oxidation in ice-covered boreal lakes

    NASA Astrophysics Data System (ADS)

    Denfeld, Blaize A.; Ricão Canelhas, Monica; Weyhenmeyer, Gesa A.; Bertilsson, Stefan; Eiler, Alexander; Bastviken, David

    2016-07-01

    Boreal lakes can be ice covered for a substantial portion of the year at which time methane (CH4) can accumulate below ice. The amount of CH4 emitted at ice melt is partially determined by the interplay between CH4 production and CH4 oxidation, performed by methane-oxidizing bacteria (MOB). Yet the balance between oxidation and emission and the potential for CH4 oxidation in various lakes during winter is largely unknown. To address this, we performed incubations at 2°C to screen for wintertime CH4 oxidation potential in seven lakes. Results showed that CH4 oxidation was restricted to three lakes, where the phosphate concentrations were highest. Molecular analyses revealed that MOB were initially detected in all lakes, although an increase in type I MOB only occurred in the three lake water incubations where oxidation could be observed. Accordingly, the increase in CO2 was on average 5 times higher in these three lake water incubations. For one lake where no oxidation was measured, we tested if temperature and CH4 availability could trigger CH4 oxidation. However, regardless of incubation temperatures and CH4 concentrations, ranging from 2 to 20°C and 1-500 μM, respectively, no oxidation was observed. Our study indicates that some lakes with active wintertime CH4 oxidation may have low emissions during ice melt, while other and particularly nutrient poor lakes may accumulate large amounts of CH4 below ice that, in the absence of CH4 oxidation, will be emitted following ice melt. This variability in CH4 oxidation rates between lakes needs to be accounted for in large-scale CH4 emission estimates.

  16. Methane Sensitivity to Perturbations in Tropospheric Oxidizing Capacity

    NASA Technical Reports Server (NTRS)

    Yegorova, Elena; Duncan, Bryan

    2011-01-01

    Methane is an important greenhouse gas and has a 25 times greater global warming potential than CO2 on a century timescale. Yet there are considerable uncertainties in the magnitude and variability of its sources and sinks. The response of the coupled non-linear methane-carbon monoxide-hydroxyl radical (OH) system is important in determining the tropospheric oxidizing capacity. Using the NASA Goddard Earth Observing System, Version 5 (GEOS-5) chemistry climate model, we study the response of methane to perturbations of OH and wetland emissions. We use a computationally-efficient option of the GEOS-5 CCM that includes an OH parameterization that accurately represents OH predicted by a full chemical mechanism. The OH parameterization allows for studying non-linear CH4-CO-OH feedbacks in computationally fast sensitivity experiments. We compare our results with surface observations (GMD) and discuss the range of uncertainty in OH and wetland emissions required to bring modeling results in better agreement with surface observations. Our results can be used to improve projections of methane emissions and methane growth.

  17. Anaerobic methane oxidation coupled to nitrite reduction can be a potential methane sink in coastal environments.

    PubMed

    Shen, Li-Dong; Hu, Bao-Lan; Liu, Shuai; Chai, Xiao-Ping; He, Zhan-Fei; Ren, Hong-Xing; Liu, Yan; Geng, Sha; Wang, Wei; Tang, Jing-Liang; Wang, Yi-Ming; Lou, Li-Ping; Xu, Xiang-Yang; Zheng, Ping

    2016-08-01

    In the current study, we investigated nitrite-dependent anaerobic methane oxidation (N-DAMO) as a potential methane sink in the Hangzhou Bay and the adjacent Zhoushan sea area. The potential activity of the N-DAMO process was primarily observed in Hangzhou Bay by means of (13)C-labeling experiments, whereas very low or no potential N-DAMO activity could be detected in the Zhoushan sea area. The measured potential N-DAMO rates ranged from 0.2 to 1.3 nmol (13)CO2 g(-1) (dry sediment) day(-1), and the N-DAMO potentially contributed 2.0-9.4 % to the total microbial methane oxidation in the examined sediments. This indicated that the N-DAMO process may be an alternative pathway in the coastal methane cycle. Phylogenetic analyses confirmed the presence of Candidatus Methylomirabilis oxyfera-like bacteria in all the examined sediments, while the group A members (the dominant bacteria responsible for N-DAMO) were found mainly in Hangzhou Bay. Quantitative PCR showed that the 16S rRNA gene abundance of Candidatus M. oxyfera-like bacteria varied from 5.4 × 10(6) to 5.0 × 10(7) copies g(-1) (dry sediment), with a higher abundance observed in Hangzhou Bay. In addition, the overlying water NO3 (-) concentration and salinity were identified as the most important factors influencing the abundance and potential activity of Candidatus M. oxyfera-like bacteria in the examined sediments. This study showed the evidence of N-DAMO in coastal environments and indicated the importance of N-DAMO as a potential methane sink in coastal environments.

  18. Anaerobic methane oxidation coupled to nitrite reduction can be a potential methane sink in coastal environments.

    PubMed

    Shen, Li-Dong; Hu, Bao-Lan; Liu, Shuai; Chai, Xiao-Ping; He, Zhan-Fei; Ren, Hong-Xing; Liu, Yan; Geng, Sha; Wang, Wei; Tang, Jing-Liang; Wang, Yi-Ming; Lou, Li-Ping; Xu, Xiang-Yang; Zheng, Ping

    2016-08-01

    In the current study, we investigated nitrite-dependent anaerobic methane oxidation (N-DAMO) as a potential methane sink in the Hangzhou Bay and the adjacent Zhoushan sea area. The potential activity of the N-DAMO process was primarily observed in Hangzhou Bay by means of (13)C-labeling experiments, whereas very low or no potential N-DAMO activity could be detected in the Zhoushan sea area. The measured potential N-DAMO rates ranged from 0.2 to 1.3 nmol (13)CO2 g(-1) (dry sediment) day(-1), and the N-DAMO potentially contributed 2.0-9.4 % to the total microbial methane oxidation in the examined sediments. This indicated that the N-DAMO process may be an alternative pathway in the coastal methane cycle. Phylogenetic analyses confirmed the presence of Candidatus Methylomirabilis oxyfera-like bacteria in all the examined sediments, while the group A members (the dominant bacteria responsible for N-DAMO) were found mainly in Hangzhou Bay. Quantitative PCR showed that the 16S rRNA gene abundance of Candidatus M. oxyfera-like bacteria varied from 5.4 × 10(6) to 5.0 × 10(7) copies g(-1) (dry sediment), with a higher abundance observed in Hangzhou Bay. In addition, the overlying water NO3 (-) concentration and salinity were identified as the most important factors influencing the abundance and potential activity of Candidatus M. oxyfera-like bacteria in the examined sediments. This study showed the evidence of N-DAMO in coastal environments and indicated the importance of N-DAMO as a potential methane sink in coastal environments. PMID:27225473

  19. Methane production and oxidation patterns along a hydrological gradient in Luther Bog, Ontario

    NASA Astrophysics Data System (ADS)

    Praetzel, Leandra; Berger, Sina; Blodau, Christian

    2016-04-01

    Methane emissions from natural peatlands contribute significantly to the global budget of atmospheric CH4. In the northern hemisphere, where climate models predict rising temperatures and precipitation rates, these emissions are likely to rise. So far, little is known about the change of processes of methane production and oxidation, which influence the total amount of methane emissions, in peatland soils under warmer and wetter climate conditions. Our work focuses on anaerobic CH4 production and aerobic CH4 oxidation processes along a hydrological gradient in an ombotrophic bog in Ontario, Canada that was induced by creation of a reservoir in 1952. Along this transect, four sites were established differing in hydrologic conditions and vegetation patterns. We examined depth profiles of CO2 and CH4 concentrations and delta 13C isotope ratios in the peat using silicon samplers, dialysis chambers and multi-level piezometers. Chamber flux measurements were used to determine carbon fluxes. Isotope mass balances were calculated based on 13C isotope ratios and concentration profiles. By this approach the contribution of anaerobic CH4 and CO2 production to the total ER flux and the amount of oxidised CH4 can be determined. In addition meteorological data, soil temperatures, moisture and water table levels were recorded. By raising data at different sites and dates and with the help of the additionally recorded parameters, we will be able to make predictions about changing CH4 production and oxidation processes due to changing climate conditions. Preliminary results show that CH4 concentrations in the soil profile are higher at the sites which are exposed to stronger water table fluctuations, whereas CO2 concentration levels are lower at these sites. At all sites, CO2 concentrations in the peat are increasing but CH4 profiles are fairly stable. Moreover, isotopic signatures of 13CH4 indicate that the importance of the production pathway changes with depth from acetoclastic

  20. Base-catalyzed efficient tandem [3 + 3] and [3 + 2 + 1] annulation-aerobic oxidative benzannulations.

    PubMed

    Diallo, Aboubacar; Zhao, Yu-Long; Wang, He; Li, Sha-Sha; Ren, Chuan-Qing; Liu, Qun

    2012-11-16

    An efficient synthesis of substituted benzenes via a base-catalyzed [3 + 3] aerobic oxidative aromatization of α,β-unsaturated carbonyl compounds with dimethyl glutaconate was reported. All the reactions were carried out under mild, metal-free conditions to afford the products in high to excellent yields with molecular oxygen as the sole oxidant and water as the sole byproduct. Furthermore, a more convenient tandem [3 + 2 + 1] aerobic oxidative aromatization reaction was developed through the in situ generation of the α,β-unsaturated carbonyl compounds from aldehydes and ketones.

  1. Formation of Amides from Imines via Cyanide-Mediated Metal-Free Aerobic Oxidation.

    PubMed

    Seo, Hong-Ahn; Cho, Yeon-Ho; Lee, Ye-Sol; Cheon, Cheol-Hong

    2015-12-18

    A new protocol for the direct formation of amides from imines derived from aromatic aldehydes via metal-free aerobic oxidation in the presence of cyanide is described. This protocol was applicable to various aldimines, and the desired amides were obtained in moderate to good yields. Mechanistic studies suggested that this aerobic oxidative amidation might proceed via the addition of cyanide to imines followed by proton transfer from carbon to nitrogen in the original imines, leading to carbanions of α-amino nitriles, which undergo subsequent oxidation with molecular oxygen in air to provide the desired amide compounds.

  2. Oxide ion transport for selective oxidative coupling of methane with new membrane reactor

    SciTech Connect

    Nozaki, Takao; Fujimoto, Kaoru . Dept. of Synthetic Chemistry)

    1994-05-01

    Oxidative coupling of methane was conducted by using membrane reactors. The nonporous membrane film that consisted of PbO modified by alkaline or alkaline earth compound was supported on porous SiO[sub 2]-Al[sub 2]O[sub 3] tube. Higher hydrocarbons were successfully synthesized with high selectivity (about 90%). A kinetic analysis was conducted to clarify whether oxide ion transportation through PbO film participated in the oxidative coupling of methane. The evaluated value of the diffusion coefficient of oxide ion transport based on the methane oxidation agreed well with that of published data. The simulated gradient of the oxide ion concentration through the PbO membrane agreed well with that measured by electron probe X-ray microanalyzer. A transient response simulated by using kinetic parameters evaluated from steady-state analysis also agreed well with the experiment. These results prove the validity of the reaction model that consists of surface reactions of methane with oxide ion which is transferred from inside to outside of the membrane reactor. Alkali modifiers on the PbO membrane surface exhibited a promotional effect on the surface reaction of methane coupling. Another membrane reactor containing Bi[sub 2]O[sub 3] showed higher activity than the PbO membrane.

  3. Identification of Novel Methane-, Ethane-, and Propane-Oxidizing Bacteria at Marine Hydrocarbon Seeps by Stable Isotope Probing ▿ †

    PubMed Central

    Redmond, Molly C.; Valentine, David L.; Sessions, Alex L.

    2010-01-01

    Marine hydrocarbon seeps supply oil and gas to microorganisms in sediments and overlying water. We used stable isotope probing (SIP) to identify aerobic bacteria oxidizing gaseous hydrocarbons in surface sediment from the Coal Oil Point seep field located offshore of Santa Barbara, California. After incubating sediment with 13C-labeled methane, ethane, or propane, we confirmed the incorporation of 13C into fatty acids and DNA. Terminal restriction fragment length polymorphism (T-RFLP) analysis and sequencing of the 16S rRNA and particulate methane monooxygenase (pmoA) genes in 13C-DNA revealed groups of microbes not previously thought to contribute to methane, ethane, or propane oxidation. First, 13C methane was primarily assimilated by Gammaproteobacteria species from the family Methylococcaceae, Gammaproteobacteria related to Methylophaga, and Betaproteobacteria from the family Methylophilaceae. Species of the latter two genera have not been previously shown to oxidize methane and may have been cross-feeding on methanol, but species of both genera were heavily labeled after just 3 days. pmoA sequences were affiliated with species of Methylococcaceae, but most were not closely related to cultured methanotrophs. Second, 13C ethane was consumed by members of a novel group of Methylococcaceae. Growth with ethane as the major carbon source has not previously been observed in members of the Methylococcaceae; a highly divergent pmoA-like gene detected in the 13C-labeled DNA may encode an ethane monooxygenase. Third, 13C propane was consumed by members of a group of unclassified Gammaproteobacteria species not previously linked to propane oxidation. This study identifies several bacterial lineages as participants in the oxidation of gaseous hydrocarbons in marine seeps and supports the idea of an alternate function for some pmoA-like genes. PMID:20675448

  4. Copper N-Heterocyclic Carbene: A Catalyst for Aerobic Oxidation or Reduction Reactions.

    PubMed

    Zhan, Le-Wu; Han, Lei; Xing, Ping; Jiang, Biao

    2015-12-18

    Copper N-heterocyclic carbene complexes can be readily used as catalysts for both aerobic oxidation of alcohols to aldehydes and reduction of imines to amines. Our methodology is universal for aromatic substrates and shows versatile tolerance to potential cascade reactions. A one-pot tandem synthetic strategy could afford useful imines and secondary amines via an oxidation-reduction strategy.

  5. Catalytic Fehling's Reaction: An Efficient Aerobic Oxidation of Aldehyde Catalyzed by Copper in Water.

    PubMed

    Liu, Mingxin; Li, Chao-Jun

    2016-08-26

    The first example of homogeneous copper-catalyzed aerobic oxidation of aldehydes is reported. This method utilizes atmospheric oxygen as the sole oxidant, proceeds under extremely mild aqueous conditions, and covers a wide range of various functionalized aldehydes. Chromatography is generally not necessary for product purification. PMID:27505714

  6. Copper N-Heterocyclic Carbene: A Catalyst for Aerobic Oxidation or Reduction Reactions.

    PubMed

    Zhan, Le-Wu; Han, Lei; Xing, Ping; Jiang, Biao

    2015-12-18

    Copper N-heterocyclic carbene complexes can be readily used as catalysts for both aerobic oxidation of alcohols to aldehydes and reduction of imines to amines. Our methodology is universal for aromatic substrates and shows versatile tolerance to potential cascade reactions. A one-pot tandem synthetic strategy could afford useful imines and secondary amines via an oxidation-reduction strategy. PMID:26633757

  7. Quantifying the flux and fate of methane into the Hudson Canyon at the edge of methane clathrate hydrate stability

    NASA Astrophysics Data System (ADS)

    Kessler, J. D.; Leonte, M.; Garcia-Tigreros Kodovska, F.; Chan, E. W.; Valentine, D. L.; Kellermann, M. Y.; Arrington, E. C.; Navarrete, L. C.; Weinstein, A.; Chepigin, A.; Weber, T.; Ruppel, C. D.; Scranton, M. I.

    2015-12-01

    Methane seeps were investigated in the Hudson Canyon, along the northern US Atlantic Margin on the R/V Endeavor in July 2014. These seeps are located along the upper feather-edge of the methane clathrate hydrate stability zone. Water column samples were collected guided by the acoustic identification of bubble streams in a 32 km2 region. This presentation details the measurements of dissolved methane concentration, natural stable isotopes, potential methane oxidation rates, and current velocity which were used in chemical and isotopic models to quantify (1) the total emission of methane to the water column in this region and (2) the extent of aerobic methane oxidation. In addition, the timing, efficiency, and kinetics of aerobic methane oxidation were investigated with mesocosm incubations of seawater in a unique experimental design that enabled high temporal resolution data acquisition. Finally, the ultimate fate of methane carbon was assessed with high precision measurements of pH.

  8. Identification of Methane, Ethane, and Propane Oxidizing Bacteria at Marine Hydrocarbon Seeps by Stable Isotope Probing

    NASA Astrophysics Data System (ADS)

    Redmond, M.; Ding, H.; Friedrich, M. W.; Valentine, D. L.

    2008-12-01

    Hydrocarbon seeps emit substantial amounts of oil and natural gas into the marine environment, where they can be oxidized by microorganisms in the sediment and water column. Here, we used stable isotope probing of DNA and lipid biomarkers to identify the microorganisms actively consuming 13C-labeled natural gas compounds in seep sediment samples. Surface sediment was collected from the Coal Oil Point seep field (offshore Santa Barbara, California, USA) and incubated under aerobic conditions with 13C labeled methane, ethane, or propane for up to 37 days, with sediment sub-samples taken at 3-4 intermediate time points. DNA was extracted from sediment and separated by CsCl density gradient centrifugation. The microbial community in each fraction was profiled using T-RFLP, and bacterial 16S rRNA gene clone libraries were constructed from un-incubated hydrocarbon seep sediment and selected isotopically 'heavy' (13C) and 'light' (12C) gradient fractions from ethane incubations. All clone libraries were dominated by sequences from members of the family Rhodobacteraceae (>25% of sequences) and a diverse group of Gammaproteobacteria, including sequences related to those of methylotrophs and to those of bacteria known to consume the longer-chain alkanes present in crude oil. After 14 days of incubation, the relative abundance of Rhodobacteraceae was higher in 'heavy' fractions from the 13C-ethane incubation than in 'light' fractions, suggesting incorporation of 13C label. The Rhodobacteraceae are very diverse metabolically, but have often been observed in abundance in oil contaminated seawater. Several members of this group have been shown to oxidize longer chain alkanes (C10 or higher), but none have been previously linked to the consumption of the gaseous alkanes ethane, propane, and butane. For the final time point, 13C content of phospholipid fatty acids (PLFA) were also analyzed, showing substantial incorporation of 13C over 37 days. In the methane incubation

  9. OXIDATIVE COUPLING OF METHANE USING INORGANIC MEMBRANE REACTORS

    SciTech Connect

    Dr. Y.H. Ma; Dr. W.R. Moser; Dr. A.G. Dixon; Dr. A.M. Ramachandra; Dr. Y. Lu; C. Binkerd

    1998-04-01

    The objective of this research is to study the oxidative coupling of methane in catalytic inorganic membrane reactors. A specific target is to achieve conversion of methane to C{sub 2} hydrocarbons at very high selectivity and higher yields than in conventional non-porous, co-feed, fixed bed reactors by controlling the oxygen supply through the membrane. A membrane reactor has the advantage of precisely controlling the rate of delivery of oxygen to the catalyst. This facility permits balancing the rate of oxidation and reduction of the catalyst. In addition, membrane reactors minimize the concentration of gas phase oxygen thus reducing non selective gas phase reactions, which are believed to be a main route for the formation of CO{sub x} products. Such gas phase reactions are a cause of decreased selectivity in the oxidative coupling of methane in conventional flow reactors. Membrane reactors could also produce higher product yields by providing better distribution of the reactant gases over the catalyst than the conventional plug flow reactors. Membrane reactor technology also offers the potential for modifying the membranes both to improve catalytic properties as well as to regulate the rate of the permeation/diffusion of reactants through the membrane to minimize by-product generation. Other benefits also exist with membrane reactors, such as the mitigation of thermal hot-spots for highly exothermic reactions such as the oxidative coupling of methane. The application of catalytically active inorganic membranes has potential for drastically increasing the yield of reactions which are currently limited by either thermodynamic equilibria, product inhibition, or kinetic selectivity.

  10. Microbial oxidation of methane, ethane, propane, and butane in marine gas seeps

    NASA Astrophysics Data System (ADS)

    Kinnaman, F. S.; Valentine, D. L.; Tyler, S.

    2005-12-01

    The microbial consumption of methane (C1), ethane (C2), propane (C3) and n-butane (nC4) in marine gas seeps was investigated using a stable isotope approach. Sediment samples were collected from the shallow hydrocarbon seeps at Coal Oil Point, Santa Barbara, CA and were used to quantify the natural distributions of C1-C4 hydrocarbons (concentrations and 13C) and as inoculum for laboratory experiments designed to quantify stable isotope fractionation associated with microbial C1-C4 consumption. Stable carbon isotope analyses of C1-C4 dissolved in pore fluids display significant enrichments in the 13C content of C1-C4 compared to the seep gas, and are interpreted as an indication of microbial oxidation. Distributions of sulfate in the sediment pore fluids indicate significant advection of pore fluids into the sediments likely driven by bubble flux. The advective flux of seawater into the sediments presumably expands the oxic zone and creates a habitat suitable for the aerobic oxidation of C1-C4. The maximum extent of oxidation was observed at a distance of 4-8 cm from individual gas vents, and at a depth of 6-10cm. Laboratory incubations of seep sediment demonstrate microbial consumption of C1-C4 hydrocarbons. Carbon and hydrogen isotope fractionation factors (ɛc and ɛh) for the aerobic oxidation of C1-C4 were determined as follows: ɛc was -31.4‰ ±1.6 for C1, -8.8‰ ±1.8 for C2, -5.4‰ ±0.7 for C3, and -3.1‰ ±0.7 for nC4; ɛh was -201.9‰ ±33.7, -62.7‰ ±7.4 for C2, and -16.3‰ ±2.0 for C3. Preferential oxidation of higher molecular weight hydrocarbons was noted in mixed gas incubations, along with possible inhibition of methane oxidation by the presence of C2-C4 gases. Application of the isotopic enrichment factors to observed pore water values indicates that as much as 75% of the dissolved hydrocarbons are consumed in the sediment.

  11. Oxidative coupling of methane using inorganic membrane reactor

    SciTech Connect

    Ma, Y.H.; Moser, W.R.; Dixon, A.G.

    1995-12-31

    The goal of this research is to improve the oxidative coupling of methane in a catalytic inorganic membrane reactor. A specific target is to achieve conversion of methane to C{sub 2} hydrocarbons at very high selectivity and relatively higher yields than in fixed bed reactors by controlling the oxygen supply through the membrane. A membrane reactor has the advantage of precisely controlling the rate of delivery of oxygen to the catalyst. This facility permits balancing the rate of oxidation and reduction of the catalyst. In addition, membrane reactors minimize the concentration of gas phase oxygen thus reducing non selective gas phase reactions, which are believed to be a main route for formation of CO{sub x} products. Such gas phase reactions are a cause for decreased selectivity in oxidative coupling of methane in conventional flow reactors. Membrane reactors could also produce higher product yields by providing better distribution of the reactant gases over the catalyst than the conventional plug flow reactors. Modeling work which aimed at predicting the observed experimental trends in porous membrane reactors was also undertaken in this research program.

  12. Oxidative mitigation of aquatic methane emissions in large Amazonian rivers.

    PubMed

    Sawakuchi, Henrique O; Bastviken, David; Sawakuchi, André O; Ward, Nicholas D; Borges, Clovis D; Tsai, Siu M; Richey, Jeffrey E; Ballester, Maria Victoria R; Krusche, Alex V

    2016-03-01

    The flux of methane (CH4 ) from inland waters to the atmosphere has a profound impact on global atmospheric greenhouse gas (GHG) levels, and yet, strikingly little is known about the dynamics controlling sources and sinks of CH4 in the aquatic setting. Here, we examine the cycling and flux of CH4 in six large rivers in the Amazon basin, including the Amazon River. Based on stable isotopic mass balances of CH4 , inputs and outputs to the water column were estimated. We determined that ecosystem methane oxidation (MOX) reduced the diffusive flux of CH4 by approximately 28-96% and varied depending on hydrologic regime and general geochemical characteristics of tributaries of the Amazon River. For example, the relative amount of MOX was maximal during high water in black and white water rivers and minimal in clear water rivers during low water. The abundance of genetic markers for methane-oxidizing bacteria (pmoA) was positively correlated with enhanced signals of oxidation, providing independent support for the detected MOX patterns. The results indicate that MOX in large Amazonian rivers can consume from 0.45 to 2.07 Tg CH4 yr(-1) , representing up to 7% of the estimated global soil sink. Nevertheless, climate change and changes in hydrology, for example, due to construction of dams, can alter this balance, influencing CH4 emissions to atmosphere. PMID:26872424

  13. [The processes of methane formation and oxidation in the soils of the Russian arctic tundra].

    PubMed

    Berestovskaia, Iu Iu; Rusanov, I I; Vasil'eva, L V; Pimenov, N V

    2005-01-01

    Methane emission from the following types of tundra soils was studied: coarse humic gleyey loamy cryo soil, peaty gley soil, and peaty gleyey midloamy cryo soil of the arctic tundra. All the soils studied were found to be potential sources of atmospheric methane. The highest values of methane emission were recorded in August at a soil temperature of 8-10 degrees C. Flooded parcels were the sources of atmospheric methane throughout the observation period. The rates of methane production and oxidation in tundra soils of various types at 5 and 15 degrees C were studied by the radioisotope method. Methane oxidation was found to occur in bog water, in the green part of peat moss, and in all the soil horizons studied. Methane formation was recorded in the horizons of peat, in clay with plant roots, and in peaty moss dust of the bogey parcels. At both temperatures, the methane oxidation rate exceeded the rate of methane formation in all the horizons of the mossy-lichen tundra and of the bumpy sinkhole complex. Methanogenesis prevailed only in a sedge-peat moss bog at 15 degrees C. Enrichment bacterial cultures oxidizing methane at 5 and 15 degrees C were obtained. Different types of methanotrophic bacteria were shown to be responsible for methane oxidation under these conditions. A representative of type I methylotrophs oxidized methane at 5 degrees C, and Methylocella tundrae, a psychroactive representative of an acidophilic methanotrophic genus Methylocella, at 15 degrees C. PMID:15938404

  14. Field-Scale Inhibition and Recovery of Atmospheric-Methane Oxidation in Soil

    NASA Astrophysics Data System (ADS)

    Schroth, M. H.; Dax, A.; Genter, F.; Henneberger, R.

    2015-12-01

    Aerobic methane (CH4) oxidation in upland soils is the only known terrestrial sink for atmospheric CH4. It is mediated by methane-oxidizing bacteria (MOB) that possess a high-affinity form of the enzyme methane monooxygenase (MMO), allowing utilization of CH4 at near-atmospheric, low concentrations (≤ 1.9 µL/L). As cultivation attempts for high-affinity MOB have shown little success to date, there remains much speculation regarding their functioning in different environmental systems. For quantification of microbial functions at the field scale, inhibition experiments are often used as a control and to verify that observed substrate turnover is microbially mediated. Targeting MMO, several compounds have been proposed as inhibitors of CH4 oxidation. However, previous inhibition experiments were mostly conducted in systems dominated by low-affinity MOB, which mediate CH4 oxidation at elevated CH4 concentrations. On the contrary, inhibition experiments targeting high-affinity MOB are scare, particularly at the field scale. We present results of field-scale experiments to investigate effectiveness of and recovery from inhibition of atmospheric CH4 oxidation using the competitive inhibitors CH3F and CH2F2, as well as the non-competitive inhibitor C2H2. The latter is of particular interest, because C2H2 irreversibly binds to MMO, requiring de-novo synthesis of MMO for recovery of CH4 oxidation activity. Experiments were conducted during both winter and summer seasons in a sandy soil. Atmospheric CH4 oxidation was quantified in regular intervals at reference and treatment locations using the soil-profile method with concurrent measurements of soil-water contents and -temperature. Whereas C2H2 inhibition was highly effective in both seasons, the time required for recovery to the level of the reference location was much shorter during the summer experiment (~1 mo compared with 4 mo during winter). Our data provide new insights into the physiology of high-affinity MOB.

  15. Trimetallic Au/Pt/Rh Nanoparticles as Highly Active Catalysts for Aerobic Glucose Oxidation

    NASA Astrophysics Data System (ADS)

    Zhang, Haijun; Cao, Yingnan; Lu, Lilin; Cheng, Zhong; Zhang, Shaowei

    2015-02-01

    This paper reports the findings of an investigation of the correlations between the catalytic activity for aerobic glucose oxidation and the composition of Au/Pt/Rh trimetallic nanoparticles (TNPs) with average diameters of less than 2.0 nm prepared by rapid injection of NaBH4. The prepared TNPs were characterized by UV-Vis, TEM, and HR-TEM. The catalytic activity of the alloy-structured TNPs for aerobic glucose oxidation is several times higher than that of Au monometallic nanoparticles with nearly the same particle size. The catalytic activities of the TNP catalysts were dependent not only on the composition, but also on the electronic structure. The high catalytic activities of the Au/Pt/Rh TNPs can be ascribed to the formed negative-charged Au atoms due to electron donation of Rh neighboring atoms acting as catalytically active sites for aerobic glucose oxidation.

  16. Bioinspired aerobic oxidation of secondary amines and nitrogen heterocycles with a bifunctional quinone catalyst.

    PubMed

    Wendlandt, Alison E; Stahl, Shannon S

    2014-01-01

    Copper amine oxidases are a family of enzymes with quinone cofactors that oxidize primary amines to aldehydes. The native mechanism proceeds via an iminoquinone intermediate that promotes high selectivity for reactions with primary amines, thereby constraining the scope of potential biomimetic synthetic applications. Here we report a novel bioinspired quinone catalyst system consisting of 1,10-phenanthroline-5,6-dione/ZnI2 that bypasses these constraints via an abiological pathway involving a hemiaminal intermediate. Efficient aerobic dehydrogenation of non-native secondary amine substrates, including pharmaceutically relevant nitrogen heterocycles, is demonstrated. The ZnI2 cocatalyst activates the quinone toward amine oxidation and provides a source of iodide, which plays an important redox-mediator role to promote aerobic catalytic turnover. These findings provide a valuable foundation for broader development of aerobic oxidation reactions employing quinone-based catalysts. PMID:24328193

  17. Bioinspired Aerobic Oxidation of Secondary Amines and Nitrogen Heterocycles with a Bifunctional Quinone Catalyst

    PubMed Central

    Wendlandt, Alison E.; Stahl, Shannon S.

    2014-01-01

    Copper amine oxidases are a family of enzymes with quinone cofactors that oxidize primary amines to aldehydes. The native mechanism proceeds via an iminoquinone intermediate that promotes high selectivity for reactions with primary amines, thereby constraining the scope of potential biomimetic synthetic applications. Here, we report a novel bioinspired quinone catalyst system, consisting of 1,10-phenanthroline-5,6-dione/ZnI2, that bypasses these constraints via an abiological pathway involving a hemiaminal intermediate. Efficient aerobic dehydrogenation of non-native secondary amine substrates, including pharmaceutically relevant nitrogen heterocycles, is demonstrated. The ZnI2 cocatalyst activates the quinone toward amine oxidation and provides a source of iodide, which plays an important redox-mediator role to promote aerobic catalytic turnover. These findings provide a valuable foundation for broader development of aerobic oxidation reactions employing quinone-based catalysts. PMID:24328193

  18. Microbial oxidation of methane from old landfills in biofilters

    SciTech Connect

    Streese, J.; Stegmann, R

    2003-07-01

    Landfill gas emissions are among the largest sources of the greenhouse gas methane. For this reason, the possibilities of microbial methane degradation in biofilters were investigated. Different filter materials were tested in two experimental plants, a bench-scale plant (total filter volume 51 l) and a pilot plant (total filter volume 4 m{sup 3}). Three months after the beginning of the experiment, very high degradation rates of up to 63 g CH{sub 4}/(m{sup 3}h) were observed in the bench-scale plant at mean methane concentrations of 2.5% v/v and with fine-grained compost as biofilter material. However, the degradation rates of the compost biofilter decreased in the fifth month of the experiment, probably due to the accumulation of exopolymeric substances formed by the microorganisms. A mixture of compost, peat, and wood fibers showed stable and satisfactory degradation rates around 20 g/(m{sup 3}h) at mean concentrations of 3% v/v over a period of one year. In this material, the wood fibers served as a structural material and prevented clogging of the biofilter. Extrapolation of the experimental data indicates that biofilters for methane oxidation have to be at least 100 times the volume of biofilters for odor control to obtain the same cleaning efficiency per unit volume flow of feed gas.

  19. Microbial oxidation of methane from old landfills in biofilters.

    PubMed

    Streese, J; Stegmann, R

    2003-01-01

    Landfill gas emissions are among the largest sources of the greenhouse gas methane. For this reason, the possibilities of microbial methane degradation in biofilters were investigated. Different filter materials were tested in two experimental plants, a bench-scale plant (total filter volume 51 l) and a pilot plant (total filter volume 4 m3). Three months after the beginning of the experiment, very high degradation rates of up to 63 g CH4/(m3h) were observed in the bench-scale plant at mean methane concentrations of 2.5% v/v and with fine-grained compost as biofilter material. However, the degradation rates of the compost biofilter decreased in the fifth month of the experiment, probably due to the accumulation of exopolymeric substances formed by the microorganisms. A mixture of compost, peat, and wood fibers showed stable and satisfactory degradation rates around 20 g/(m3h) at mean concentrations of 3% v/v over a period of one year. In this material, the wood fibers served as a structural material and prevented clogging of the biofilter. Extrapolation of the experimental data indicates that biofilters for methane oxidation have to be at least 100 times the volume of biofilters for odor control to obtain the same cleaning efficiency per unit volume flow of feed gas. PMID:12957152

  20. Iron oxides stimulate sulfate-driven anaerobic methane oxidation in seeps

    NASA Astrophysics Data System (ADS)

    Sivan, Orit; Antler, Gilad; Turchyn, Alexandra V.; Marlow, Jeffrey J.; Orphan, Victoria J.

    2014-10-01

    Seep sediments are dominated by intensive microbial sulfate reduction coupled to the anaerobic oxidation of methane (AOM). Through geochemical measurements of incubation experiments with methane seep sediments collected from Hydrate Ridge, we provide insight into the role of iron oxides in sulfate-driven AOM. Seep sediments incubated with 13C-labeled methane showed co-occurring sulfate reduction, AOM, and methanogenesis. The isotope fractionation factors for sulfur and oxygen isotopes in sulfate were about 40‰ and 22‰, respectively, reinforcing the difference between microbial sulfate reduction in methane seeps versus other sedimentary environments (for example, sulfur isotope fractionation above 60‰ in sulfate reduction coupled to organic carbon oxidation or in diffusive sedimentary sulfate-methane transition zone). The addition of hematite to these microcosm experiments resulted in significant microbial iron reduction as well as enhancing sulfate-driven AOM. The magnitude of the isotope fractionation of sulfur and oxygen isotopes in sulfate from these incubations was lowered by about 50%, indicating the involvement of iron oxides during sulfate reduction in methane seeps. The similar relative change between the oxygen versus sulfur isotopes of sulfate in all experiments (with and without hematite addition) suggests that oxidized forms of iron, naturally present in the sediment incubations, were involved in sulfate reduction, with hematite addition increasing the sulfate recycling or the activity of sulfur-cycling microorganisms by about 40%. These results highlight a role for natural iron oxides during bacterial sulfate reduction in methane seeps not only as nutrient but also as stimulator of sulfur recycling.

  1. Asymmetric aerobic oxidative NHC-catalysed synthesis of dihydropyranones utilising a system of electron transfer mediators.

    PubMed

    Axelsson, A; Hammarvid, E; Ta, L; Sundén, H

    2016-10-01

    In the context of green chemistry, the replacement of high molecular weight stoichiometric oxidants with O2 is most desirable but difficult. Here, we report the asymmetric aerobic oxidative synthesis of dihydropyranones. The oxidation is aided by a system of electron transfer mediators and is selective toward the homoenolate. The dihydropyranones can be isolated in high to excellent yields, with high ee (up to 95%). PMID:27604573

  2. Copper-catalyzed aerobic oxidative coupling: From ketone and diamine to pyrazine

    PubMed Central

    Wu, Kun; Huang, Zhiliang; Qi, Xiaotian; Li, Yingzi; Zhang, Guanghui; Liu, Chao; Yi, Hong; Meng, Lingkui; Bunel, Emilio E.; Miller, Jeffrey T.; Pao, Chih-Wen; Lee, Jyh-Fu; Lan, Yu; Lei, Aiwen

    2015-01-01

    Copper-catalyzed aerobic oxidative C–H/N–H coupling between simple ketones and diamines was developed toward the synthesis of a variety of pyrazines. Various substituted ketones were compatible for this transformation. Preliminary mechanistic investigations indicated that radical species were involved. X-ray absorption fine structure experiments elucidated that the Cu(II) species 5 coordinated by two N atoms at a distance of 2.04 Å and two O atoms at a shorter distance of 1.98 Å was a reactive one for this aerobic oxidative coupling reaction. Density functional theory calculations suggested that the intramolecular coupling of cationic radicals was favorable in this transformation. PMID:26601302

  3. Cu/Nitroxyl Catalyzed Aerobic Oxidation of Primary Amines into Nitriles at Room Temperature.

    PubMed

    Kim, Jinho; Stahl, Shannon S

    2013-07-01

    An efficient catalytic method has been developed for aerobic oxidation of primary amines to the corresponding nitriles. The reactions proceed at room temperature and employ a catalyst consisting of (4,4'- (t) Bu2bpy)CuI/ABNO (ABNO = 9-azabicyclo[3.3.1]nonan-3-one N-oxyl). The reactions exhibit excellent functional group compatibility and substrate scope, and are effective with benzylic, allylic and aliphatic amines. Preliminary mechanistic studies suggest that aerobic oxidation of the Cu catalyst is the turnover-limiting step of the reaction. PMID:24015373

  4. Detection of chlorinated methanes by tin oxide gas sensors.

    PubMed

    Park, S H; Son, Y C; Shaw, B R; Creasy, K E; Suib, S L

    2001-08-01

    Tin oxide thin films prepared by thermal oxidation of Sn films were used for the detection of chlorinated methanes (CH2Cl2, CHCl3 and CCl4). This resulted in better chemical selectivity, sensitivity, response speed and detection limit than seen with previous detectors. The temperature dependence of the sensing of 1% CCl4 gas was studied and the best sensing behavior was observed at 300 degrees C. The films showed different chemical selectivity in both speed and direction of sensing response to each gas and were stable for more than 3 weeks under operating conditions. The films showed rapid gas sensing (<40 s to reach 90% of full response) and low detection limits (< 4 ppm CCl4). The role of oxygen in the detection of chlorinated methanes and in resistance changes without chlorinated methanes was also studied. The changes at the surface of the film after gas sensing were examined using scanning electron microscopy with energy-dispersive X-ray spectrometry. PMID:11534610

  5. Mechanisms and controlling characteristics of the catalytic oxidation of methane

    SciTech Connect

    Klier, K.; Simmons, G.W.; Herman, R.G.; Miller, A.C.

    1992-01-01

    We have demonstrated in this work (1) that methane is readily activated at mild conditions (100[degree]C, 1 torr) over a relatively noble metal, Pd. This was observed using a stepped and kinked Pd(679) crystal (1), and other crystal faces are now being investigated to establish whether the cracking of the C-H bond of methane on Pd is structure sensitive or structure insensitive. Oxygen chemisorption is extremely structure sensitive: weakly bonded, highly reactive oxygen overlayers form on Pd(100) surface (2), while strongly bonded, moderately reactive oxygen overlayers form on Pd(111) and Pd(679). Reaction of the weakly bonded oxygen with surface carbide gives rise to CO[sub 2] over clean Pd(100) but to CO over halogen-doped Pd(100) (3--5). The effect of halogens is primarily ensemble-controlling, or oxygen-supply restricting, but long range influence of surface Cl on the strength of the Pd-O bond has also been observed (3). Because the overall chemistry of methane activation with the subsequent oxidation gives rise to the very important oxidative reforming CH[sub 4] + 1/2 O[sub 2] [yields][sub Pd/Cl] CO + 2 H[sub 2], Pd/Cl we plan to continue our study of this reaction in detail over Pd(100) (completed), Pd(111) (initiated), Pd(311) (initiated), Pd(110) (to be initiated), and Pd(679) (completed), without and with the halogen modifiers.

  6. Aerobic bacterial pyrite oxidation and acid rock drainage during the Great Oxidation Event.

    PubMed

    Konhauser, Kurt O; Lalonde, Stefan V; Planavsky, Noah J; Pecoits, Ernesto; Lyons, Timothy W; Mojzsis, Stephen J; Rouxel, Olivier J; Barley, Mark E; Rosìere, Carlos; Fralick, Phillip W; Kump, Lee R; Bekker, Andrey

    2011-10-20

    The enrichment of redox-sensitive trace metals in ancient marine sedimentary rocks has been used to determine the timing of the oxidation of the Earth's land surface. Chromium (Cr) is among the emerging proxies for tracking the effects of atmospheric oxygenation on continental weathering; this is because its supply to the oceans is dominated by terrestrial processes that can be recorded in the Cr isotope composition of Precambrian iron formations. However, the factors controlling past and present seawater Cr isotope composition are poorly understood. Here we provide an independent and complementary record of marine Cr supply, in the form of Cr concentrations and authigenic enrichment in iron-rich sedimentary rocks. Our data suggest that Cr was largely immobile on land until around 2.48 Gyr ago, but within the 160 Myr that followed--and synchronous with independent evidence for oxygenation associated with the Great Oxidation Event (see, for example, refs 4-6)--marked excursions in Cr content and Cr/Ti ratios indicate that Cr was solubilized at a scale unrivalled in history. As Cr isotope fractionations at that time were muted, Cr must have been mobilized predominantly in reduced, Cr(III), form. We demonstrate that only the oxidation of an abundant and previously stable crustal pyrite reservoir by aerobic-respiring, chemolithoautotrophic bacteria could have generated the degree of acidity required to solubilize Cr(III) from ultramafic source rocks and residual soils. This profound shift in weathering regimes beginning at 2.48 Gyr ago constitutes the earliest known geochemical evidence for acidophilic aerobes and the resulting acid rock drainage, and accounts for independent evidence of an increased supply of dissolved sulphate and sulphide-hosted trace elements to the oceans around that time. Our model adds to amassing evidence that the Archaean-Palaeoproterozoic boundary was marked by a substantial shift in terrestrial geochemistry and biology. PMID:22012395

  7. Aerobic bacterial pyrite oxidation and acid rock drainage during the Great Oxidation Event.

    PubMed

    Konhauser, Kurt O; Lalonde, Stefan V; Planavsky, Noah J; Pecoits, Ernesto; Lyons, Timothy W; Mojzsis, Stephen J; Rouxel, Olivier J; Barley, Mark E; Rosìere, Carlos; Fralick, Phillip W; Kump, Lee R; Bekker, Andrey

    2011-10-19

    The enrichment of redox-sensitive trace metals in ancient marine sedimentary rocks has been used to determine the timing of the oxidation of the Earth's land surface. Chromium (Cr) is among the emerging proxies for tracking the effects of atmospheric oxygenation on continental weathering; this is because its supply to the oceans is dominated by terrestrial processes that can be recorded in the Cr isotope composition of Precambrian iron formations. However, the factors controlling past and present seawater Cr isotope composition are poorly understood. Here we provide an independent and complementary record of marine Cr supply, in the form of Cr concentrations and authigenic enrichment in iron-rich sedimentary rocks. Our data suggest that Cr was largely immobile on land until around 2.48 Gyr ago, but within the 160 Myr that followed--and synchronous with independent evidence for oxygenation associated with the Great Oxidation Event (see, for example, refs 4-6)--marked excursions in Cr content and Cr/Ti ratios indicate that Cr was solubilized at a scale unrivalled in history. As Cr isotope fractionations at that time were muted, Cr must have been mobilized predominantly in reduced, Cr(III), form. We demonstrate that only the oxidation of an abundant and previously stable crustal pyrite reservoir by aerobic-respiring, chemolithoautotrophic bacteria could have generated the degree of acidity required to solubilize Cr(III) from ultramafic source rocks and residual soils. This profound shift in weathering regimes beginning at 2.48 Gyr ago constitutes the earliest known geochemical evidence for acidophilic aerobes and the resulting acid rock drainage, and accounts for independent evidence of an increased supply of dissolved sulphate and sulphide-hosted trace elements to the oceans around that time. Our model adds to amassing evidence that the Archaean-Palaeoproterozoic boundary was marked by a substantial shift in terrestrial geochemistry and biology.

  8. Dynamics of atmospheric-methane oxidation in glacier-forefield soils

    NASA Astrophysics Data System (ADS)

    Chiri, Eleonora; Nauer, Philipp A.; Rainer, Edda-Marie; Henneberger, Ruth; Zeyer, Josef; Schroth, Martin H.

    2015-04-01

    Mature upland soils are currently considered the sole terrestrial sink for atmospheric methane (CH4). But little is known about CH4 dynamics in young, developing soil ecosystems such as glacier forefields formed by progressive glacial retreat. Glacier forefields are situated on diverse bedrock types, exhibit a continuum of soil age (chronosequence), and are comprised of various geomorphological landforms, which may differ in physicochemical properties. These features may affect activity and community structure of aerobic methane-oxidizing bacteria (MOB) catalyzing atmospheric CH4 oxidation. Moreover, MOB activity and community structure may be affected by environmental parameters subject to seasonal variability such as soil temperature, water content, and nutrient availability. The aim of this study was to assess spatial and seasonal variability in atmospheric CH4 oxidation in glacier-forefield soils derived from siliceous and calcareous bedrock. Specifically, we quantified soil-atmosphere CH4 flux and CH4 oxidation activity using the soil-gas-profile method and static flux chambers in soils of different age and belonging to different landforms. In these soils MOB abundance and variation in community structure were assessed by targeting the functional gene pmoA using quantitative PCR, TRFLP-based cluster analysis, and high-throughput DNA-sequencing technology. Seasonal variability in atmospheric CH4 oxidation was assessed based on the same attributes measured with high temporal resolution throughout one snow-free season. Most glacier-forefield soils acted as a sink for atmospheric CH4 regardless of bedrock type, and CH4 flux (-0.082 to -2.2 mg CH4 m-2 d-1) and MOB abundance (2.4×103 to 5.5×105 pmoA genecopies (g soil w.w.)-1) increased significantly with soil age. Cluster analysis revealed variations in MOB community composition related to bedrock type rather than soil age, suggesting that distinct MOB communities provided a similar ecosystem service in soils on

  9. Iron oxide reduction in deep Baltic Sea sediments: the potential role of anaerobic oxidation of methane

    NASA Astrophysics Data System (ADS)

    Egger, Matthias; Slomp, Caroline P.; Dijkstra, Nikki; Sapart, Célia J.; Risgaard-Petersen, Nils; Kasten, Sabine; Riedinger, Natascha; Barker Jørgensen, Bo

    2015-04-01

    Methane is a powerful greenhouse gas and its emission from marine sediments to the atmosphere is largely controlled by anaerobic oxidation of methane (AOM). Traditionally, sulfate is considered to be the most important electron acceptor for AOM in marine sediments. However, recent studies have shown that AOM may also be coupled to the reduction of iron (Fe) oxides (Beal et al., 2009; Riedinger et al., 2014; Egger et al., 2014). In the Baltic Sea, the transition from the Ancylus freshwater phase to the Littorina brackish/marine phase (A/L-transition) ca. 9-7 ka ago (Zillén et al., 2008) resulted in the accumulation of methanogenic brackish/marine sediments overlying Fe-oxide rich lacustrine deposits. The downward diffusion of methane from the brackish/marine sediments into the lake sediments leads to an ideal diagenetic system to study a potential coupling between Fe oxide reduction and methane oxidation. Here, we use porewater and sediment geochemical data obtained at sites M0063 and M0065 during the IODP Baltic Sea Paleoenvironment Expedition 347 in 2013 to identify the potential mechanisms responsible for the apparent Fe oxide reduction in the non-sulfidic limnic sediments below the A/L transition. In this presentation, we will review the various explanations for the elevated ferrous Fe in the porewater in the lake sediments and we will specifically address the potential role of the reaction of methane with Fe-oxides. References: Beal E. J., House C. H. and Orphan V. J. (2009) Manganese- and iron-dependent marine methane oxidation. Science 325, 184-187. Egger M., Rasigraf O., Sapart C. J., Jilbert T., Jetten M. S. M., Röckmann T., van der Veen C., Banda N., Kartal B., Ettwig K. F. and Slomp C. P. (2014) Iron-mediated anaerobic oxidation of methane in brackish coastal sediments. Environ. Sci. Technol. 49, 277-283. Riedinger N., Formolo M. J., Lyons T. W., Henkel S., Beck A. and Kasten S. (2014) An inorganic geochemical argument for coupled anaerobic oxidation of

  10. The Leeuwenhoek Lecture 2000 The natural and unnatural history of methane-oxidizing bacteria

    PubMed Central

    Dalton, Howard

    2005-01-01

    Methane gas is produced from many natural and anthropogenic sources. As such, methane gas plays a significant role in the Earth's climate, being 25 times more effective as a greenhouse gas than carbon dioxide. As with nearly all other naturally produced organic molecules on Earth, there are also micro-organisms capable of using methane as their sole source of carbon and energy. The microbes responsible (methanotrophs) are ubiquitous and, for the most part, aerobic. Although anaerobic methanotrophs are believed to exist, so far, none have been isolated in pure culture. Methanotrophs have been known to exist for over 100 years; however, it is only in the last 30 years that we have begun to understand their physiology and biochemistry. Their unique ability to use methane for growth is attributed to the presence of a multicomponent enzyme system—methane monooxygenase (MMO)—which has two distinct forms: soluble (sMMO) and membrane-associated (pMMO); however, both convert methane into the readily assimilable product, methanol. Our understanding of how bacteria are capable of effecting one of the most difficult reactions in chemistry—namely, the controlled oxidation of methane to methanol—has been made possible by the isolation, in pure form, of the enzyme components. The mechanism by which methane is activated by sMMO involves abstraction of a hydrogen atom from methane by a high-valence iron species (FeIV or possibly FeV) in the hydroxylase component of the MMO complex to form a methyl radical. The radical combines with a captive oxygen atom from dioxygen to form the reaction product, methanol, which is further metabolized by the cell to produce multicarbon intermediates. Regulation of the sMMO system relies on the remarkable properties of an effector protein, protein B. This protein is capable of facilitating component interactions in the presence of substrate, modifying the redox potential of the diiron species at the active site. These interactions permit

  11. The influence of methane oxidation on the stable isotopic composition of methane emitted from Florida swamp forests

    NASA Astrophysics Data System (ADS)

    Happell, James D.; Chanton, Jeffrey P.; Showers, William S.

    1994-10-01

    This study reports the first measurements of the δ 13C of CH 4 emitted from seasonally flooded swamp forests in the southeastern United States. The seasonally averaged δ 13C of CH 4 emitted from a north Florida swamp forest located in the St. Marks National Wildlife Refuge was -52.7 ± 6.11%. (error is ± one standard deviation throughout, n = 28), a value 13C-enriched, relative to typical wetland emissions. In an Everglades cypress dome, the average δ 13C of emitted CH 4 was -52.5 ± 6.7%.( n = 3). Consistent with attenuation of CH 4 emission by CH 4 oxidation in these environments, CH 4 emitted via diffusion from the St. Marks swamp forest was enriched in 13C by 6.4 ± 5.8%. ( n = 28) and D by 57 ± 36%. ( n = 6) relative to sedimentary CH 4. Methane emitted from the cypress dome had also been altered by oxidation, as it was enriched in 13C by 12.1 ± 4.3%. relative to sedimentary CH 4. Emission experiments, performed in situ with inhibitors of aerobic CH 4 oxidizing bacteria, were used to calculate the fractionation factors (α) for stable carbon and hydrogen isotopes of CH 4 undergoing transport and oxidation. Values ranged from 1.003 to 1.021 and 1.050 to 1.129, respectively. The best estimates for carbon and hydrogen α values were 1.020 and 1.068, respectively. The δ values of produced (sedimentary) CH 4 were relatively constant in the St. Marks subtropical swamp forest. Additionally, because the transport of CH 4 to the atmosphere was dominated by molecular diffusion, variations in the magnitude of CH 4 oxidation appeared to be the primary factor controlling the δ values of emitted CH 4. This contrasts with systems dominated by bubble ebullition, where variations in CH 4 production mechanisms have been hypothesized to be the primary factor controlling the δ values of emitted CH 4.

  12. Partial oxidation of methane by pulsed corona discharges

    NASA Astrophysics Data System (ADS)

    Hoeben, W. F. L. M.; Boekhoven, W.; Beckers, F. J. C. M.; van Heesch, E. J. M.; Pemen, A. J. M.

    2014-09-01

    Pulsed corona-induced partial oxidation of methane in humid oxygen or carbon dioxide atmospheres has been investigated for future fuel synthesis applications. The obtained product spectrum is wide, i.e. saturated, unsaturated and oxygen-functional hydrocarbons. The generally observed methane conversion levels are 6-20% at a conversion efficiency of about 100-250 nmol J-1. The main products are ethane, ethylene and acetylene. Higher saturated hydrocarbons up to C6 have been detected. The observed oxygen-functional hydrocarbons are methanol, ethanol and lower concentrations of aldehydes, ketones, dimethylether and methylformate. Methanol seems to be exclusively produced with CH4/O2 mixtures at a maximum production efficiency of 0.35 nmol J-1. CH4/CO2 mixtures appear to yield higher hydrocarbons. Carboxylic acids appear to be mainly present in the aqueous reactor phase, possibly together with higher molecular weight species.

  13. Thermophilic anaerobic oxidation of methane by marine microbial consortia

    PubMed Central

    Holler, Thomas; Widdel, Friedrich; Knittel, Katrin; Amann, Rudolf; Kellermann, Matthias Y; Hinrichs, Kai-Uwe; Teske, Andreas; Boetius, Antje; Wegener, Gunter

    2011-01-01

    The anaerobic oxidation of methane (AOM) with sulfate controls the emission of the greenhouse gas methane from the ocean floor. AOM is performed by microbial consortia of archaea (ANME) associated with partners related to sulfate-reducing bacteria. In vitro enrichments of AOM were so far only successful at temperatures ⩽25 °C; however, energy gain for growth by AOM with sulfate is in principle also possible at higher temperatures. Sequences of 16S rRNA genes and core lipids characteristic for ANME as well as hints of in situ AOM activity were indeed reported for geothermally heated marine environments, yet no direct evidence for thermophilic growth of marine ANME consortia was obtained to date. To study possible thermophilic AOM, we investigated hydrothermally influenced sediment from the Guaymas Basin. In vitro incubations showed activity of sulfate-dependent methane oxidation between 5 and 70 °C with an apparent optimum between 45 and 60 °C. AOM was absent at temperatures ⩾75 °C. Long-term enrichment of AOM was fastest at 50 °C, yielding a 13-fold increase of methane-dependent sulfate reduction within 250 days, equivalent to an apparent doubling time of 68 days. The enrichments were dominated by novel ANME-1 consortia, mostly associated with bacterial partners of the deltaproteobacterial HotSeep-1 cluster, a deeply branching phylogenetic group previously found in a butane-amended 60 °C-enrichment culture of Guaymas sediments. The closest relatives (Desulfurella spp.; Hippea maritima) are moderately thermophilic sulfur reducers. Results indicate that AOM and ANME archaea could be of biogeochemical relevance not only in cold to moderate but also in hot marine habitats. PMID:21697963

  14. Isolation of an aerobic sulfur oxidizer from the SUP05/Arctic96BD-19 clade.

    PubMed

    Marshall, Katharine T; Morris, Robert M

    2013-02-01

    Bacteria from the uncultured SUP05/Arctic96BD-19 clade of gamma proteobacterial sulfur oxidizers (GSOs) have the genetic potential to oxidize reduced sulfur and fix carbon in the tissues of clams and mussels, in oxygen minimum zones and throughout the deep ocean (>200 m). Here, we report isolation of the first cultured representative from this GSO clade. Closely related cultures were obtained from surface waters in Puget Sound and from the deep chlorophyll maximum in the North Pacific gyre. Pure cultures grow aerobically on natural seawater media, oxidize sulfur, and reach higher final cell densities when glucose and thiosulfate are added to the media. This suggests that aerobic sulfur oxidation enhances organic carbon utilization in the oceans. The first isolate from the SUP05/Arctic96BD-19 clade was given the provisional taxonomic assignment 'Candidatus: Thioglobus singularis', alluding to the clade's known role in sulfur oxidation and the isolate's planktonic lifestyle. PMID:22875135

  15. Highly practical copper(I)/TEMPO catalyst system for chemoselective aerobic oxidation of primary alcohols.

    PubMed

    Hoover, Jessica M; Stahl, Shannon S

    2011-10-26

    Aerobic oxidation reactions have been the focus of considerable attention, but their use in mainstream organic chemistry has been constrained by limitations in their synthetic scope and by practical factors, such as the use of pure O(2) as the oxidant or complex catalyst synthesis. Here, we report a new (bpy)Cu(I)/TEMPO catalyst system that enables efficient and selective aerobic oxidation of a broad range of primary alcohols, including allylic, benzylic, and aliphatic derivatives, to the corresponding aldehydes using readily available reagents, at room temperature with ambient air as the oxidant. The catalyst system is compatible with a wide range of functional groups and the high selectivity for 1° alcohols enables selective oxidation of diols that lack protecting groups. PMID:21861488

  16. Aerobic and Anaerobic Oxidation of Organic Acids in Yellowstone Hot Spring Ecosystems

    NASA Astrophysics Data System (ADS)

    Windman, T. O.; Zolotova, N.; Shock, E.

    2007-12-01

    Thermodynamic analysis of energy supply based on samples collected from continental hot spring ecosystems at Yellowstone show that aerobic reactions yield the greatest energy. In terms of energy per mole of electrons transferred, aerobic oxidation of organic acids rivals or exceeds the energy supply from aerobic oxidation of hydrogen, CO, hydrogen sulfide, pyrite, sulfur or ammonia. This analysis is derived from samples collected where hot spring fluid are in contact with the atmosphere. It is likely that oxygen will be present at lower concentrations deeper in the system, which will place hard constraints on aerobic lifestyles. If so, which metabolisms could be supported deeper in the system? How will other oxidants be used to release energy? What characterizes the transition from aerobic to anaerobic oxidation? To answer these questions, pH, temperature, and alkalinity were measured in the field while measurements of dissolved oxygen and other redox-sensitive species (nitrate, ammonia, ferrous iron, and sulfide) were made with field-portable spectrophotometers and samples were taken for analysis of organic and inorganic ions by ion chromatography. Conditions in the subsurface can be predicted by starting from measured oxygen concentrations and calculating the effect of decreasing the concentration on the overall energetics of the system. Depending on hot spring composition, the amount of energy from aerobic oxidation of organic acid anions like succinate matches that from anaerobic oxidation (by nitrate or sulfate) once the log of the activity of dissolved oxygen drops to -6 to -8. These activities are 1 to 4 orders of magnitude lower that values determined for surface water in the hot springs. At lower oxygen activities aerobic oxidation gives way to anaerobic oxidation, and organic oxidation is more likely to involve nitrate and sulfate. Preliminary estimates indicate that these changes may occur at shallow depths in hot spring sediments (perhaps within the

  17. Oxygen as Intermediate in Anoxic Environments: Nitrite-Dependent Methane Oxidation and Beyond

    NASA Astrophysics Data System (ADS)

    Ettwig, K. F.

    2014-12-01

    In recent years the known diversity of hydrocarbon activation mechanisms under anaerobic conditions has been extended by intra-aerobic denitrification, a process in which oxygen is derived from NO and used for substrate activation. For two phylogenetically unrelated bacterial species, the freshwater NC10 phylum bacterium Methylomirabilis oxyfera [1] and the marine γ-proteobacterial strain HdN1 [2] it has been shown that, under anoxic conditions with nitrate and/or nitrite, mono-oxygenases are used for methane and hexadecane oxidation, respectively. No degradation was observed with nitrous oxide (N2O) only. In the anaerobic methanotroph M. oxyfera, which lacks apparent nitrous oxide reductase in its genome, substrate activation in the presence of nitrite was directly associated with both O2 and N2 formation. These findings strongly argue for the role of nitric oxide (NO), or an oxygen species derived from it, in the activation reaction of methane. Although intracellular oxygen generation has been experimentally documented and elegantly explains the utilization of 'aerobic' pathways under anoxic conditions, research about the underlying molecular mechanism has just started. The proposed candidate enzymes for oxygen (or possibly another another reactive intermediate) production from NO, an NO dismutase (NOD) [3], related to quinol-dependent NO reductases (qNORs), is present and highly expressed in both M. oxyfera and strain HdN1. Besides that, several recently sequenced species from the Cytophaga-Flavobacterium-Bacteroides group harbor Nod/Nor genes, but experimential evidence is needed to show if these have NOD activity, are unusual but functional qNORs, or represent transition states between the two. Additionally, for several anaerobic hydrocarbon-degrading organisms the biochemical mechanism of substrate activation has not been elucidated yet: whereas signature genes of anaerobic degradation are missing, monooxygenase genes are present. Also these microorganisms

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

    NASA Astrophysics Data System (ADS)

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

    2012-06-01

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

  19. Tuning graphitic oxide for initiator- and metal-free aerobic epoxidation of linear alkenes

    NASA Astrophysics Data System (ADS)

    Pattisson, Samuel; Nowicka, Ewa; Gupta, Upendra N.; Shaw, Greg; Jenkins, Robert L.; Morgan, David J.; Knight, David W.; Hutchings, Graham J.

    2016-09-01

    Graphitic oxide has potential as a carbocatalyst for a wide range of reactions. Interest in this material has risen enormously due to it being a precursor to graphene via the chemical oxidation of graphite. Despite some studies suggesting that the chosen method of graphite oxidation can influence the physical properties of the graphitic oxide, the preparation method and extent of oxidation remain unresolved for catalytic applications. Here we show that tuning the graphitic oxide surface can be achieved by varying the amount and type of oxidant. The resulting materials differ in level of oxidation, surface oxygen content and functionality. Most importantly, we show that these graphitic oxide materials are active as unique carbocatalysts for low-temperature aerobic epoxidation of linear alkenes in the absence of initiator or metal. An optimum level of oxidation is necessary and materials produced via conventional permanganate-based methods are far from optimal.

  20. Tuning graphitic oxide for initiator- and metal-free aerobic epoxidation of linear alkenes

    PubMed Central

    Pattisson, Samuel; Nowicka, Ewa; Gupta, Upendra N.; Shaw, Greg; Jenkins, Robert L.; Morgan, David J.; Knight, David W.; Hutchings, Graham J.

    2016-01-01

    Graphitic oxide has potential as a carbocatalyst for a wide range of reactions. Interest in this material has risen enormously due to it being a precursor to graphene via the chemical oxidation of graphite. Despite some studies suggesting that the chosen method of graphite oxidation can influence the physical properties of the graphitic oxide, the preparation method and extent of oxidation remain unresolved for catalytic applications. Here we show that tuning the graphitic oxide surface can be achieved by varying the amount and type of oxidant. The resulting materials differ in level of oxidation, surface oxygen content and functionality. Most importantly, we show that these graphitic oxide materials are active as unique carbocatalysts for low-temperature aerobic epoxidation of linear alkenes in the absence of initiator or metal. An optimum level of oxidation is necessary and materials produced via conventional permanganate-based methods are far from optimal. PMID:27687877

  1. Characterization of Methane Degradation and Methane-Degrading Microbes in Alaska Coastal Water

    SciTech Connect

    Kirchman, David L.

    2012-03-29

    The net flux of methane from methane hydrates and other sources to the atmosphere depends on methane degradation as well as methane production and release from geological sources. The goal of this project was to examine methane-degrading archaea and organic carbon oxidizing bacteria in methane-rich and methane-poor sediments of the Beaufort Sea, Alaska. The Beaufort Sea system was sampled as part of a multi-disciplinary expedition (Methane in the Arctic Shelf or MIDAS) in September 2009. Microbial communities were examined by quantitative PCR analyses of 16S rRNA genes and key methane degradation genes (pmoA and mcrA involved in aerobic and anaerobic methane degradation, respectively), tag pyrosequencing of 16S rRNA genes to determine the taxonomic make up of microbes in these sediments, and sequencing of all microbial genes (metagenomes ). The taxonomic and functional make-up of the microbial communities varied with methane concentrations, with some data suggesting higher abundances of potential methane-oxidizing archaea in methane-rich sediments. Sequence analysis of PCR amplicons revealed that most of the mcrA genes were from the ANME-2 group of methane oxidizers. According to metagenomic data, genes involved in methane degradation and other degradation pathways changed with sediment depth along with sulfate and methane concentrations. Most importantly, sulfate reduction genes decreased with depth while the anaerobic methane degradation gene (mcrA) increased along with methane concentrations. The number of potential methane degradation genes (mcrA) was low and inconsistent with other data indicating the large impact of methane on these sediments. The data can be reconciled if a small number of potential methane-oxidizing archaea mediates a large flux of carbon in these sediments. Our study is the first to report metagenomic data from sediments dominated by ANME-2 archaea and is one of the few to examine the entire microbial assemblage potentially involved in

  2. Treatment of real industrial wastewater using the combined approach of advanced oxidation followed by aerobic oxidation.

    PubMed

    Ramteke, Lokeshkumar P; Gogate, Parag R

    2016-05-01

    Fenton oxidation and ultrasound-based pretreatment have been applied to improve the treatment of real industrial wastewater based on the use of biological oxidation. The effect of operating parameters such as Fe(2+) loading, contact time, initial pH, and hydrogen peroxide loading on the extent of chemical oxygen demand (COD) reduction and change in biochemical oxygen demand (BOD5)/COD ratio has been investigated. The optimum operating conditions established for the pretreatment were initial pH of 3.0, Fe(2+) loading of 2.0, and 2.5 g L(-1) for the US/Fenton/stirring and Fenton approach, respectively, and temperature of 25 °C with initial H2O2 loading of 1.5 g L(-1). The use of pretreatment resulted in a significant increase in the BOD5/COD ratio confirming the production of easily digestible intermediates. The effect of the type of sludge in the aerobic biodegradation was also investigated based on the use of primary activated sludge (PAS), modified activated sludge (MAS), and activated sludge (AS). Enhanced removal of the pollutants as well as higher biomass yield was observed for MAS as compared to PAS and AS. The use of US/Fenton/stirring pretreatment under the optimized conditions followed by biological oxidation using MAS resulted in maximum COD removal at 97.9 %. The required hydraulic retention time for the combined oxidation system was also significantly lower as compared to only biological oxidation operation. Kinetic studies revealed that the reduction in the COD followed a first-order kinetic model for advanced oxidation and pseudo first-order model for biodegradation. The study clearly established the utility of the combined technology for the effective treatment of real industrial wastewater.

  3. Autotrophy as a predominant mode of carbon fixation in anaerobic methane-oxidizing microbial communities

    PubMed Central

    Kellermann, Matthias Y.; Wegener, Gunter; Elvert, Marcus; Yoshinaga, Marcos Yukio; Lin, Yu-Shih; Holler, Thomas; Mollar, Xavier Prieto; Knittel, Katrin; Hinrichs, Kai-Uwe

    2012-01-01

    The methane-rich, hydrothermally heated sediments of the Guaymas Basin are inhabited by thermophilic microorganisms, including anaerobic methane-oxidizing archaea (mainly ANME-1) and sulfate-reducing bacteria (e.g., HotSeep-1 cluster). We studied the microbial carbon flow in ANME-1/ HotSeep-1 enrichments in stable-isotope–probing experiments with and without methane. The relative incorporation of 13C from either dissolved inorganic carbon or methane into lipids revealed that methane-oxidizing archaea assimilated primarily inorganic carbon. This assimilation is strongly accelerated in the presence of methane. Experiments with simultaneous amendments of both 13C-labeled dissolved inorganic carbon and deuterated water provided further insights into production rates of individual lipids derived from members of the methane-oxidizing community as well as their carbon sources used for lipid biosynthesis. In the presence of methane, all prominent lipids carried a dual isotopic signal indicative of their origin from primarily autotrophic microbes. In the absence of methane, archaeal lipid production ceased and bacterial lipid production dropped by 90%; the lipids produced by the residual fraction of the metabolically active bacterial community predominantly carried a heterotrophic signal. Collectively our results strongly suggest that the studied ANME-1 archaea oxidize methane but assimilate inorganic carbon and should thus be classified as methane-oxidizing chemoorganoautotrophs. PMID:23129626

  4. Application of the GRI 1.2 methane oxidation model to methane and methanol oxidation in supercritical water

    SciTech Connect

    Rice, S.F.

    1996-05-01

    The GRI 1.2 mechanism is used to predict the oxidation rates of methane and methanol by oxygen in supercritical water at 250 bar and temperatures ranging from 420--630 C. Using the Chemkin II computational package which assumes an ideal gas equation of state, the GRI model does very well in representing the available experimental results on methane over a wide temperature and concentration rate. However, the model may lack key CH{sub 3}O{sub 2} reactions needed for a complete description in the < 450 C region. The oxidation of methanol and formation of formaldehyde is not well represented by the GRI mechanism when left unchanged. If two important modifications are made to the reactivity of HO{sub 2}, good agreement with the methanol oxidation results is achieved. This paper illustrates that the carefully-assembled GRI 1.2 mechanism, although designed for conventional combustion conditions, can be successfully extended with very little modification to much lower temperature and extreme pressure conditions. The purpose of this study is to understand the operative chemical kinetics of supercritical water oxidation required for the more efficient application of this technology to treatment of hazardous wastes, obsolete munitions, rocket motors, and chemical warfare agents.

  5. Effect of biomass concentration on methane oxidation activity using mature compost and graphite granules as substrata.

    PubMed

    Xie, S; O'Dwyer, T; Freguia, S; Pikaar, I; Clarke, W P

    2016-10-01

    Reported methane oxidation activity (MOA) varies widely for common landfill cover materials. Variation is expected due to differences in surface area, the composition of the substratum and culturing conditions. MOA per methanotrophic cell has been calculated in the study of natural systems such as lake sediments to examine the inherent conditions for methanotrophic activity. In this study, biomass normalised MOA (i.e., MOA per methanotophic cell) was measured on stabilised compost, a commonly used cover in landfills, and on graphite granules, an inert substratum widely used in microbial electrosynthesis studies. After initially enriching methanotrophs on both substrata, biomass normalised MOA was quantified under excess oxygen and limiting methane conditions in 160ml serum vials on both substrata and blends of the substrata. Biomass concentration was measured using the bicinchoninic acid assay for microbial protein. The biomass normalised MOA was consistent across all compost-to-graphite granules blends, but varied with time, reflecting the growth phase of the microorganisms. The biomass normalised MOA ranged from 0.069±0.006μmol CH4/mg dry biomass/h during active growth, to 0.024±0.001μmol CH4/mg dry biomass/h for established biofilms regardless of the substrata employed, indicating the substrata were equally effective in terms of inherent composition. The correlation of MOA with biomass is consistent with studies on methanotrophic activity in natural systems, but biomass normalised MOA varies by over 5 orders of magnitude between studies. This is partially due to different methods being used to quantify biomass, such as pmoA gene quantification and the culture dependent Most Probable Number method, but also indicates that long term exposure of materials to a supply of methane in an aerobic environment, as can occur in natural systems, leads to the enrichment and adaptation of types suitable for those conditions. PMID:27515185

  6. Effects of aerobic training on exercise-related oxidative stress in mitochondrial myopathies.

    PubMed

    Siciliano, Gabriele; Simoncini, Costanza; Lo Gerfo, Annalisa; Orsucci, Daniele; Ricci, Giulia; Mancuso, Michelangelo

    2012-12-01

    In mitochondrial myopathies with respiratory chain deficiency impairment of energy cell production may lead to in excess reactive oxygen species generation with consequent oxidative stress and cell damage. Aerobic training has been showed to increase muscle performance in patients with mitochondrial myopathies. Aim of this study has been to evaluate, in 7 patients (6 F e 1M, mean age 44.9 ± 12.1 years) affected by mitochondrial disease, concomitantly to lactate exercise curve, the occurrence of oxidative stress, as indicated by circulating levels of lipoperoxides, in rest condition and as effect of exercise, and also, to verify if an aerobic training program is able to modify, in these patients, ox-redox balance efficiency. At rest and before training blood level of lipoperoxides was 382.4 ± 37.8 AU, compared to controls (318.7 ± 63.8; P<0.05), this corresponding to a moderate oxidative stress degree according to the adopted scale. During incremental exercise blood level of lipoperoxides did not increase, but maintained significantly higher compared to controls. After an aerobic training of 10 weeks the blood level of lipoperoxides decreased by 13.7% at rest (P<0.01) and 10.4%, 8.6% and 8.5% respectively at the corresponding times during the exercise test (P=0.06). These data indicate that, in mitochondrial patients, oxidative stress occurs and that an aerobic training is useful in partially reverting this condition.

  7. Cu-NHC-TEMPO catalyzed aerobic oxidation of primary alcohols to aldehydes.

    PubMed

    Liu, Xiaolong; Xia, Qinqin; Zhang, Yuejiao; Chen, Congyan; Chen, Wanzhi

    2013-09-01

    Imidazolium salts bearing TEMPO groups react with commercially available copper powder affording Cu-NHC complexes. The in situ generated Cu-NHC-TEMPO complexes are quite efficient catalysts for aerobic oxidation of primary alcohols into aldehydes. The catalyst is easily available, and various primary alcohols were selectively converted to aldehydes in excellent yields. PMID:23944937

  8. Quantum chemical study of the catalytic oxidative coupling of methane

    SciTech Connect

    Onal, I.; Senkan, S.

    1997-10-01

    Oxidative coupling of methane reaction pathways on MgO and lithium-modified MgO were theoretically studied using the semiempirical MNDO-PM3 molecular orbital method. The surface of the MgO catalyst was modeled by a Mg{sub 9}O{sub 9} molecular cluster containing structural defects such as edges and corners. Lithium-promoted magnesia was simulated by isomorphic substitution of Mg{sup 2+} by Li{sup +}; the excess negative charge of the cluster was compensated by a proton connected to a neighboring O{sup 2{minus}} site. Heterolytic adsorption of methane was found to be directly related to the coordination number of both the lattice oxygen and the metal sites. Energetically the most favorable site pair was Mg{sub 3c}-O{sub 3c} with a neighboring Li{sub 4c} site present. Various sequential oxygen and methane adsorption pathways were explored resulting in CH{sub 3}OH formation with lower energy barriers for the Li-modified MgO cluster as compared to unmodified MgO.

  9. Subseafloor Macroscopic Biofilms Involved in Anaerobic Oxidization of Methane

    NASA Astrophysics Data System (ADS)

    Briggs, B. R.; Hieter, J.; Pohlman, J.; Torres, M. E.; Riedel, M.; Rose, K.; Joseph, C.; Colwell, F. S.

    2009-12-01

    The release of methane from seafloor sediments is moderated in part by the anaerobic oxidation of methane (AOM), a process carried out by a consortium of archaea and bacteria within the sulfate methane transition zone (SMTZ). We collected macroscopic biofilms in subseafloor fractures that intersect the SMTZ and, for the first time, have conducted molecular analyses of these biofilms to describe their phylogenetic affiliations. Non-metric multidimensional scaling (NMS) of terminal restriction fragment length polymorphism (t-RFLP) profiles indicate archaea in the biofilm are similar to those present in sediment adjacent to the biofilm. However, cores lacking observable biofilms contained different archaeal taxa. By contrast, NMS also showed the bacterial taxa in the biofilm are distinct from sediment adjacent to the biofilm. Sequencing of 386 bacterial clones indicates a diverse presence of alpha, beta, delta and gammaproteobacteria related to sulfate reducers (52% of clones, 79-89% similarity) and iron reducers (20% of clones, 83-89% similarity,). In addition, 204 archaeal clones were sequenced and the major taxa found are related to ANME-1 (40% of clones, 95% similarity) and archaeoglobus (30% of clones, 93% similarity). Biofilms inhabiting fractures in very fine to fine-grained sediment may play a crucial role in the carbon cycle.

  10. Methane concentrations and oxidation in nearshore waters of the Lena River Delta

    NASA Astrophysics Data System (ADS)

    Joye, S. B.; Samarkin, V.; Shakhova, N. E.; Semiletov, I. P.

    2014-12-01

    The Arctic is warming dramatically, with potentially catastrophic impacts on climate change through rapid mobilization of labile carbon reservoirs sequestered presently in permafrost. Increasingly, Arctic feedbacks are recognized as key contributors to climate change, including cycles associated with the powerful greenhouse gas methane, whose atmospheric concentration has more than doubled since the pre-industrial epoch. Sustained methane release to the atmosphere from thawing Arctic permafrost and delivery to the coastal ocean through groundwater or riverine discharge or expulsion from the seabed is a positive and likely highly significant feedback to climate warming. Microbially-mediated methane oxidation provides a key sink and effective biofilter that can limit methane fluxes from coastal environments to the atmosphere. We examined methane dynamics on the East Siberian Arctic Shelf by determining concentrations and oxidation rates at a series of stations near the Lena River Delta and moving offshore. Methane concentrations and oxidation rates were highly elevated in and near the river mouth compared to offshore waters, except when the offshore waters were impacted by seabed methane seepage. The regulation of methane oxidation in Arctic waters appears two-fold: first, rates are strongly related to methane availability and second, in the presence of methane, nutrient availability strongly regulates methane consumption. Along the Lena river delta, elevated concentrations of both nutrients and methane create ideal conditions to support high rates of pelagic methanotrophy. Offshore, where nutrient concentrations are lower and more limiting, methane oxidation rates are considerably lower. These data suggest that, at present, nearshore waters are fairly efficient methane sinks while in offshore waters, pelagic methanotrophy is inefficient, allowing methane to escape to the atmosphere.

  11. Phylogenetic and enzymatic diversity of deep subseafloor aerobic microorganisms in organics- and methane-rich sediments off Shimokita Peninsula.

    PubMed

    Kobayashi, Tohru; Koide, Osamu; Mori, Kozue; Shimamura, Shigeru; Matsuura, Takae; Miura, Takeshi; Takaki, Yoshihiro; Morono, Yuki; Nunoura, Takuro; Imachi, Hiroyuki; Inagaki, Fumio; Takai, Ken; Horikoshi, Koki

    2008-07-01

    "A meta-enzyme approach" is proposed as an ecological enzymatic method to explore the potential functions of microbial communities in extreme environments such as the deep marine subsurface. We evaluated a variety of extra-cellular enzyme activities of sediment slurries and isolates from a deep subseafloor sediment core. Using the new deep-sea drilling vessel "Chikyu", we obtained 365 m of core sediments that contained approximately 2% organic matter and considerable amounts of methane from offshore the Shimokita Peninsula in Japan at a water depth of 1,180 m. In the extra-sediment fraction of the slurry samples, phosphatase, esterase, and catalase activities were detected consistently throughout the core sediments down to the deepest slurry sample from 342.5 m below seafloor (mbsf). Detectable enzyme activities predicted the existence of a sizable population of viable aerobic microorganisms even in deep subseafloor habitats. The subsequent quantitative cultivation using solid media represented remarkably high numbers of aerobic, heterotrophic microbial populations (e.g., maximally 4.4x10(7) cells cm(-3) at 342.5 mbsf). Analysis of 16S rRNA gene sequences revealed that the predominant cultivated microbial components were affiliated with the genera Bacillus, Shewanella, Pseudoalteromonas, Halomonas, Pseudomonas, Paracoccus, Rhodococcus, Microbacterium, and Flexibacteracea. Many of the predominant and scarce isolates produced a variety of extra-cellular enzymes such as proteases, amylases, lipases, chitinases, phosphatases, and deoxyribonucleases. Our results indicate that microbes in the deep subseafloor environment off Shimokita are metabolically active and that the cultivable populations may have a great potential in biotechnology.

  12. Phylogenetic and enzymatic diversity of deep subseafloor aerobic microorganisms in organics- and methane-rich sediments off Shimokita Peninsula.

    PubMed

    Kobayashi, Tohru; Koide, Osamu; Mori, Kozue; Shimamura, Shigeru; Matsuura, Takae; Miura, Takeshi; Takaki, Yoshihiro; Morono, Yuki; Nunoura, Takuro; Imachi, Hiroyuki; Inagaki, Fumio; Takai, Ken; Horikoshi, Koki

    2008-07-01

    "A meta-enzyme approach" is proposed as an ecological enzymatic method to explore the potential functions of microbial communities in extreme environments such as the deep marine subsurface. We evaluated a variety of extra-cellular enzyme activities of sediment slurries and isolates from a deep subseafloor sediment core. Using the new deep-sea drilling vessel "Chikyu", we obtained 365 m of core sediments that contained approximately 2% organic matter and considerable amounts of methane from offshore the Shimokita Peninsula in Japan at a water depth of 1,180 m. In the extra-sediment fraction of the slurry samples, phosphatase, esterase, and catalase activities were detected consistently throughout the core sediments down to the deepest slurry sample from 342.5 m below seafloor (mbsf). Detectable enzyme activities predicted the existence of a sizable population of viable aerobic microorganisms even in deep subseafloor habitats. The subsequent quantitative cultivation using solid media represented remarkably high numbers of aerobic, heterotrophic microbial populations (e.g., maximally 4.4x10(7) cells cm(-3) at 342.5 mbsf). Analysis of 16S rRNA gene sequences revealed that the predominant cultivated microbial components were affiliated with the genera Bacillus, Shewanella, Pseudoalteromonas, Halomonas, Pseudomonas, Paracoccus, Rhodococcus, Microbacterium, and Flexibacteracea. Many of the predominant and scarce isolates produced a variety of extra-cellular enzymes such as proteases, amylases, lipases, chitinases, phosphatases, and deoxyribonucleases. Our results indicate that microbes in the deep subseafloor environment off Shimokita are metabolically active and that the cultivable populations may have a great potential in biotechnology. PMID:18368287

  13. Understanding complete oxidation of methane on spinel oxides at a molecular level

    SciTech Connect

    Tao, Franklin Feng; Shan, Jun-jun; Nguyen, Luan; Wang, Ziyun; Zhang, Shiran; Zhang, Li; Wu, Zili; Huang, Weixin; Zeng, Shibi; Hu, P.

    2015-08-04

    It is crucial to develop a catalyst made of earth-abundant elements highly active for a complete oxidation of methane at a relatively low temperature. NiCo2O4 consisting of earth-abundant elements which can completely oxidize methane in the temperature range of 350-550 °C. Being a cost-effective catalyst, NiCo2O4 exhibits activity higher than precious-metal-based catalysts. Here we report that the higher catalytic activity at the relatively low temperature results from the integration of nickel cations, cobalt cations and surface lattice oxygen atoms/oxygen vacancies at the atomic scale. Finally, in situ studies of complete oxidation of methane on NiCo2O4 and theoretical simulations show that methane dissociates to methyl on nickel cations and then couple with surface lattice oxygen atoms to form -CH3O with a following dehydrogenation to -CH2O; a following oxidative dehydrogenation forms CHO; CHO is transformed to product molecules through two different sub-pathways including dehydrogenation of OCHO and CO oxidation.

  14. Understanding complete oxidation of methane on spinel oxides at a molecular level

    DOE PAGES

    Tao, Franklin Feng; Shan, Jun-jun; Nguyen, Luan; Wang, Ziyun; Zhang, Shiran; Zhang, Li; Wu, Zili; Huang, Weixin; Zeng, Shibi; Hu, P.

    2015-08-04

    It is crucial to develop a catalyst made of earth-abundant elements highly active for a complete oxidation of methane at a relatively low temperature. NiCo2O4 consisting of earth-abundant elements which can completely oxidize methane in the temperature range of 350-550 °C. Being a cost-effective catalyst, NiCo2O4 exhibits activity higher than precious-metal-based catalysts. Here we report that the higher catalytic activity at the relatively low temperature results from the integration of nickel cations, cobalt cations and surface lattice oxygen atoms/oxygen vacancies at the atomic scale. Finally, in situ studies of complete oxidation of methane on NiCo2O4 and theoretical simulations show thatmore » methane dissociates to methyl on nickel cations and then couple with surface lattice oxygen atoms to form -CH3O with a following dehydrogenation to -CH2O; a following oxidative dehydrogenation forms CHO; CHO is transformed to product molecules through two different sub-pathways including dehydrogenation of OCHO and CO oxidation.« less

  15. Phenazinium salt-catalyzed aerobic oxidative amidation of aromatic aldehydes.

    PubMed

    Leow, Dasheng

    2014-11-01

    Amides are prevalent in organic synthesis. Developing an efficient synthesis that avoids expensive oxidants and heating is highly desirable. Here the oxidative amidation of aromatic aldehydes is reported using an inexpensive metal-free visible light photocatalyst, phenazine ethosulfate, at low catalytic loading (1-2 mol %). The reaction proceeds at ambient temperature and uses air as the sole oxidant. The operationally easy procedure provides an economical, green, and mild alternative for the formation of amide bonds.

  16. Trace Metal Requirements for Microbial Enzymes Involved in the Production and Consumption of Methane and Nitrous Oxide

    PubMed Central

    Glass, Jennifer B.; Orphan, Victoria J.

    2011-01-01

    Fluxes of greenhouse gases to the atmosphere are heavily influenced by microbiological activity. Microbial enzymes involved in the production and consumption of greenhouse gases often contain metal cofactors. While extensive research has examined the influence of Fe bioavailability on microbial CO2 cycling, fewer studies have explored metal requirements for microbial production and consumption of the second- and third-most abundant greenhouse gases, methane (CH4), and nitrous oxide (N2O). Here we review the current state of biochemical, physiological, and environmental research on transition metal requirements for microbial CH4 and N2O cycling. Methanogenic archaea require large amounts of Fe, Ni, and Co (and some Mo/W and Zn). Low bioavailability of Fe, Ni, and Co limits methanogenesis in pure and mixed cultures and environmental studies. Anaerobic methane oxidation by anaerobic methanotrophic archaea (ANME) likely occurs via reverse methanogenesis since ANME possess most of the enzymes in the methanogenic pathway. Aerobic CH4 oxidation uses Cu or Fe for the first step depending on Cu availability, and additional Fe, Cu, and Mo for later steps. N2O production via classical anaerobic denitrification is primarily Fe-based, whereas aerobic pathways (nitrifier denitrification and archaeal ammonia oxidation) require Cu in addition to, or possibly in place of, Fe. Genes encoding the Cu-containing N2O reductase, the only known enzyme capable of microbial N2O conversion to N2, have only been found in classical denitrifiers. Accumulation of N2O due to low Cu has been observed in pure cultures and a lake ecosystem, but not in marine systems. Future research is needed on metalloenzymes involved in the production of N2O by enrichment cultures of ammonia oxidizing archaea, biological mechanisms for scavenging scarce metals, and possible links between metal bioavailability and greenhouse gas fluxes in anaerobic environments where metals may be limiting due to sulfide

  17. Evidence for the cooccurrence of nitrite-dependent anaerobic ammonium and methane oxidation processes in a flooded paddy field.

    PubMed

    Shen, Li-Dong; Liu, Shuai; Huang, Qian; Lian, Xu; He, Zhan-Fei; Geng, Sha; Jin, Ren-Cun; He, Yun-Feng; Lou, Li-Ping; Xu, Xiang-Yang; Zheng, Ping; Hu, Bao-Lan

    2014-12-01

    Anaerobic ammonium oxidation (anammox) and nitrite-dependent anaerobic methane oxidation (n-damo) are two of the most recent discoveries in the microbial nitrogen cycle. In the present study, we provide direct evidence for the cooccurrence of the anammox and n-damo processes in a flooded paddy field in southeastern China. Stable isotope experiments showed that the potential anammox rates ranged from 5.6 to 22.7 nmol N2 g(-1) (dry weight) day(-1) and the potential n-damo rates varied from 0.2 to 2.1 nmol CO2 g(-1) (dry weight) day(-1) in different layers of soil cores. Quantitative PCR showed that the abundance of anammox bacteria ranged from 1.0 × 10(5) to 2.0 × 10(6) copies g(-1) (dry weight) in different layers of soil cores and the abundance of n-damo bacteria varied from 3.8 × 10(5) to 6.1 × 10(6) copies g(-1) (dry weight). Phylogenetic analyses of the recovered 16S rRNA gene sequences showed that anammox bacteria affiliated with "Candidatus Brocadia" and "Candidatus Kuenenia" and n-damo bacteria related to "Candidatus Methylomirabilis oxyfera" were present in the soil cores. It is estimated that a total loss of 50.7 g N m(-2) per year could be linked to the anammox process, which is at intermediate levels for the nitrogen flux ranges of aerobic ammonium oxidation and denitrification reported in wetland soils. In addition, it is estimated that a total of 0.14 g CH4 m(-2) per year could be oxidized via the n-damo process, while this rate is at the lower end of the aerobic methane oxidation rates reported in wetland soils.

  18. Treatment of high salt oxidized modified starch waste water using micro-electrolysis, two-phase anaerobic aerobic and electrolysis for reuse

    NASA Astrophysics Data System (ADS)

    Yi, Xuenong; Wang, Yulin

    2016-08-01

    A combined process of micro-electrolysis, two-phase anaerobic, aerobic and electrolysis was investigated for the treatment of oxidized modified starch wastewater (OMSW). Optimum ranges for important operating variables were experimentally determined and the treated water was tested for reuse in the production process of corn starch. The optimum hydraulic retention time (HRT) of micro-electrolysis, methanation reactor, aerobic process and electrolysis process were 5, 24, 12 and 3 h, respectively. The addition of iron-carbon fillers to the acidification reactor was 200 mg/L while the best current density of electrolysis was 300 A/m2. The biodegradability was improved from 0.12 to 0.34 by micro-electrolysis. The whole treatment was found to be effective with removal of 96 % of the chemical oxygen demand (COD), 0.71 L/day of methane energy recovery. In addition, active chlorine production (15,720 mg/L) was obtained by electrolysis. The advantage of this hybrid process is that, through appropriate control of reaction conditions, effect from high concentration of salt on the treatment was avoided. Moreover, the process also produced the material needed in the production of oxidized starch while remaining emission-free and solved the problem of high process cost.

  19. Iron-mediated anaerobic oxidation of methane in brackish coastal sediments.

    PubMed

    Egger, Matthias; Rasigraf, Olivia; Sapart, Célia J; Jilbert, Tom; Jetten, Mike S M; Röckmann, Thomas; van der Veen, Carina; Bândă, Narcisa; Kartal, Boran; Ettwig, Katharina F; Slomp, Caroline P

    2015-01-01

    Methane is a powerful greenhouse gas and its biological conversion in marine sediments, largely controlled by anaerobic oxidation of methane (AOM), is a crucial part of the global carbon cycle. However, little is known about the role of iron oxides as an oxidant for AOM. Here we provide the first field evidence for iron-dependent AOM in brackish coastal surface sediments and show that methane produced in Bothnian Sea sediments is oxidized in distinct zones of iron- and sulfate-dependent AOM. At our study site, anthropogenic eutrophication over recent decades has led to an upward migration of the sulfate/methane transition zone in the sediment. Abundant iron oxides and high dissolved ferrous iron indicate iron reduction in the methanogenic sediments below the newly established sulfate/methane transition. Laboratory incubation studies of these sediments strongly suggest that the in situ microbial community is capable of linking methane oxidation to iron oxide reduction. Eutrophication of coastal environments may therefore create geochemical conditions favorable for iron-mediated AOM and thus increase the relevance of iron-dependent methane oxidation in the future. Besides its role in mitigating methane emissions, iron-dependent AOM strongly impacts sedimentary iron cycling and related biogeochemical processes through the reduction of large quantities of iron oxides.

  20. The aerobic oxidation of alcohols with a ruthenium porphyrin catalyst in organic and fluorinated solvents.

    PubMed

    Korotchenko, Vasily N; Severin, Kay; Gagné, Michel R

    2008-06-01

    Carbonylruthenium tetrakis(pentafluorophenyl)porphyrin Ru(TPFPP)(CO) was utilized for the aerobic oxidation of alcohols. The in situ activation of the catalyst with mCPBA provided a species capable of catalyzing the oxidation of alcohols with molecular oxygen. The choice of solvent and additive was crucial to obtaining high activity and selectivity. Secondary aromatic alcohols were oxidized in the presence of the ruthenium porphyrin and tetrabutyl ammonium hydroxide in the solvent bromotrichloromethane, enabling high yields to be achieved (up to 99%). Alternatively, alcohols could be oxidized in perfluoro(methyldecalin) with the ruthenium porphyrin at higher temperatures (140 degrees C) and elevated oxygen pressures (50 psi).

  1. NHC-catalysed highly selective aerobic oxidation of nonactivated aldehydes

    PubMed Central

    Möhlmann, Lennart; Ludwig, Stefan

    2013-01-01

    Summary This publication describes a highly selective oxidation of aldehydes to the corresponding acids or esters. The reaction proceeds under metal-free conditions by using N-heterocyclic carbenes as organocatalysts in combination with environmentally friendly oxygen as the terminal oxidation agent. PMID:23616801

  2. Estimation of methane and nitrous oxide emissions from Indian livestock.

    PubMed

    Patra, Amlan K

    2012-10-26

    Greenhouse gas (GHG; methane and nitrous oxide) emissions from enteric fermentation and manure management of Indian livestock were estimated from the last two Indian livestock census datasets (2003 and 2007) using IPCC Tier 2 (2006) guidelines. The total annual GHG emissions from Indian livestock increased in 2007 compared to the year 2003 with an annual growth rate of 1.52% over this period. The contributions of GHG by dairy cattle, non-dairy cattle, buffaloes, goats, sheep and other animals (yak, mithun, horse, donkeys, pigs and poultry) were 30.52, 24.0, 37.7, 4.34, 2.09 and 3.52%, respectively, in 2007. Enteric fermentation was the major source of methane, accounting for 89.2% of the total GHG emissions, followed by manure methane (9.49%). Nitrous oxide emissions accounted for 1.34%. GHG emissions (CO(2)-eq. per kg of fat and protein corrected milk (FPCM)) by female animals were considerably lower for crossbred cows (1161 g), followed by buffaloes (1332 g) and goats (2699 g), and were the highest for indigenous cattle (3261 g) in 2007. There was a decreasing trend in GHG emissions (-1.82% annual growth rate) in relation to milk production from 2003 to 2007 (1818 g and 1689 g CO(2)-eq. per kg FPCM in 2003 and 2007, respectively). This study revealed that GHG emissions (total as well as per unit of products) from dairy and other categories of livestock populations could be reduced substantially through proper dairy herd management without compromising animal production. In conclusion, although the total GHG emissions from Indian livestock increased in 2007, there was a decreasing trend in GHG production per kg of milk production or animal products.

  3. Copper-catalyzed aerobic oxidative C-H functionalizations: trends and mechanistic insights.

    PubMed

    Wendlandt, Alison E; Suess, Alison M; Stahl, Shannon S

    2011-11-18

    The selective oxidation of C-H bonds and the use of O(2) as a stoichiometric oxidant represent two prominent challenges in organic chemistry. Copper(II) is a versatile oxidant, capable of promoting a wide range of oxidative coupling reactions initiated by single-electron transfer (SET) from electron-rich organic molecules. Many of these reactions can be rendered catalytic in Cu by employing molecular oxygen as a stoichiometric oxidant to regenerate the active copper(II) catalyst. Meanwhile, numerous other recently reported Cu-catalyzed C-H oxidation reactions feature substrates that are electron-deficient or appear unlikely to undergo single-electron transfer to copper(II). In some of these cases, evidence has been obtained for the involvement of organocopper(III) intermediates in the reaction mechanism. Organometallic C-H oxidation reactions of this type represent important new opportunities for the field of Cu-catalyzed aerobic oxidations. PMID:22034061

  4. The role of the lattice oxygen of an oxide catalyst in the reaction of oxidative dimerization of methane

    SciTech Connect

    Voskresenskaya, E.N.; Kurteeva, L.I.; Tsygankova, S.I.; Anshits, A.G.

    1993-12-31

    The catalytic oxidative dimerization of methane is described. Catalysts investigated include bismuth oxides with additives of samarium, terbium, and erbium. The main products were ethane and carbon dioxide. The activation energy of formation for the above products is discussed.

  5. High reactivity of nanosized niobium oxide cluster cations in methane activation: A comparison with vanadium oxides.

    PubMed

    Ding, Xun-Lei; Wang, Dan; Wu, Xiao-Nan; Li, Zi-Yu; Zhao, Yan-Xia; He, Sheng-Gui

    2015-09-28

    The reactions between methane and niobium oxide cluster cations were studied and compared to those employing vanadium oxides. Hydrogen atom abstraction (HAA) reactions were identified over stoichiometric (Nb2O5)N(+) clusters for N as large as 14 with a time-of-flight mass spectrometer. The reactivity of (Nb2O5)N(+) clusters decreases as the N increases, and it is higher than that of (V 2O5)N(+) for N ≥ 4. Theoretical studies were conducted on (Nb2O5)N(+) (N = 2-6) by density functional calculations. HAA reactions on these clusters are all favorable thermodynamically and kinetically. The difference of the reactivity with respect to the cluster size and metal type (Nb vs V) was attributed to thermodynamics, kinetics, the electron capture ability, and the distribution of the unpaired spin density. Nanosized Nb oxide clusters show higher HAA reactivity than V oxides, indicating that niobia may serve as promising catalysts for practical methane conversion.

  6. Mechanism of Copper/Azodicarboxylate-Catalyzed Aerobic Alcohol Oxidation: Evidence for Uncooperative Catalysis.

    PubMed

    McCann, Scott D; Stahl, Shannon S

    2016-01-13

    Cooperative catalysis between Cu(II) and redox-active organic cocatalysts is a key feature of important chemical and enzymatic aerobic oxidation reactions, such as alcohol oxidation mediated by Cu/TEMPO and galactose oxidase. Nearly 20 years ago, Markó and co-workers reported that azodicarboxylates, such as di-tert-butyl azodicarboxylate (DBAD), are effective redox-active cocatalysts in Cu-catalyzed aerobic alcohol oxidation reactions [Markó, I. E., et al. Science 1996, 274, 2044], but the nature of the cooperativity between Cu and azodicarboxylates is not well understood. Here, we report a mechanistic study of Cu/DBAD-catalyzed aerobic alcohol oxidation. In situ infrared spectroscopic studies reveal a burst of product formation prior to steady-state catalysis, and gas-uptake measurements show that no O2 is consumed during the burst. Kinetic studies reveal that the anaerobic burst and steady-state turnover have different rate laws. The steady-state rate does not depend on [O2] or [DBAD]. These results, together with other EPR and in situ IR spectroscopic and kinetic isotope effect studies, reveal that the steady-state mechanism consists of two interdependent catalytic cycles that operate in sequence: a fast Cu(II)/DBAD pathway, in which DBAD serves as the oxidant, and a slow Cu(II)-only pathway, in which Cu(II) is the oxidant. This study provides significant insight into the redox cooperativity, or lack thereof, between Cu and redox-active organic cocatalysts in aerobic oxidation reactions. PMID:26694091

  7. Mechanism of Copper/Azodicarboxylate-Catalyzed Aerobic Alcohol Oxidation: Evidence for Uncooperative Catalysis.

    PubMed

    McCann, Scott D; Stahl, Shannon S

    2016-01-13

    Cooperative catalysis between Cu(II) and redox-active organic cocatalysts is a key feature of important chemical and enzymatic aerobic oxidation reactions, such as alcohol oxidation mediated by Cu/TEMPO and galactose oxidase. Nearly 20 years ago, Markó and co-workers reported that azodicarboxylates, such as di-tert-butyl azodicarboxylate (DBAD), are effective redox-active cocatalysts in Cu-catalyzed aerobic alcohol oxidation reactions [Markó, I. E., et al. Science 1996, 274, 2044], but the nature of the cooperativity between Cu and azodicarboxylates is not well understood. Here, we report a mechanistic study of Cu/DBAD-catalyzed aerobic alcohol oxidation. In situ infrared spectroscopic studies reveal a burst of product formation prior to steady-state catalysis, and gas-uptake measurements show that no O2 is consumed during the burst. Kinetic studies reveal that the anaerobic burst and steady-state turnover have different rate laws. The steady-state rate does not depend on [O2] or [DBAD]. These results, together with other EPR and in situ IR spectroscopic and kinetic isotope effect studies, reveal that the steady-state mechanism consists of two interdependent catalytic cycles that operate in sequence: a fast Cu(II)/DBAD pathway, in which DBAD serves as the oxidant, and a slow Cu(II)-only pathway, in which Cu(II) is the oxidant. This study provides significant insight into the redox cooperativity, or lack thereof, between Cu and redox-active organic cocatalysts in aerobic oxidation reactions.

  8. Methane oxidative coupling over nonstoichiometric bismuth -tin pyrochlore catalysts

    SciTech Connect

    Mims, C.A.; Hall, R.B.; Lewandowski, J.T.

    1995-05-01

    A series of expanded pyrochlore oxides Bi{sub 2}Sn{sub 2{minus}x}Bi{sub x}O{sub 7{minus}x/2} (O{le} x {le} 0.86) was synthesized and the influence of their composition on their performance as methane coupling catalysts was examined. A trend to higher selectivity and lower activity accompanies increases in x. However, analysis of the kinetic data by a simple procedure which separates the catalyst activity and selectivity shows that all the catalysts have similar intrinsic surface selectivities, independent of composition. The trend in observed selectivity is an indirect effect of variations in activity. The similarity in surface selectivity is attributed to the formation of a bismuth-oxide-rich surface layer in all materials upon heating to reaction temperatures. 47 refs., 10 figs., 1 tab.

  9. Methane oxidation associated to submerged brown-mosses buffers methane emissions from Siberian polygonal peatlands

    NASA Astrophysics Data System (ADS)

    Liebner, Susanne; Zeyer, Josef; Knoblauch, Christian

    2010-05-01

    Circumpolar peatlands store roughly 18 % of the globally stored carbon in soils [based on 1, 2]. Also, northern wetlands and tundra are a net source of methane (CH4), an effective greenhouse gas (GHG), with an estimated annual CH4 release of 7.2% [3] or 8.1% [4] of the global total CH4 emission. Although it is definite that Arctic tundra significantly contributes to the global methane emissions in general, regional variations in GHG fluxes are enormous. CH4 fluxes of polygonal tundra within the Siberian Lena Delta, for example, were reported to be low [5, 6], particularly at open water polygonal ponds and small lakes [7] which make up around 10 % of the delta's surface. Low methane emissions from polygonal ponds oppose that Arctic permafrost thaw ponds are generally known to emit large amounts of CH4 [8]. Combining tools of biogeochemistry and molecular microbiology, we identified sinks of CH4 in polygonal ponds from the Lena Delta that were not considered so far in GHG studies from Arctic wetlands. Pore water CH4 profiling in polygonal ponds on Samoylov, a small island in the central part of the Lena Delta, revealed a pronounced zone of CH4 oxidation near the vegetation surface in submerged layers of brown-mosses. Here, potential CH4 oxidation was an order of magnitude higher than in non-submerged mosses and in adjacent bulk soil. We could additionally show that this moss associated methane oxidation (MAMO) is hampered when exposure of light is prevented. Shading of plots with submerged Scorpidium scorpioides inhibited MAMO leading to higher CH4 concentrations and an increase in CH4 fluxes by a factor of ~13. Compared to non-submerged mosses, the submerged mosses also showed significantly lower δ13C values indicating that they use carbon dioxide derived from methane oxidation for photosynthesis. Applying stable isotope probing of DNA, type II methanotrophs were identified to be responsible for the oxidation of CH4 in the submerged Scorpidium scorpioides. Our

  10. Does vegetation affect the methane oxidation efficiency of passive biosystems?

    PubMed

    Ndanga, Éliane M; Bradley, Robert L; Cabral, Alexandre R

    2015-04-01

    It is often reported in the technical literature that the presence of vegetation improves the methane oxidation efficiency of biosystems; however, the phenomena involved and biosystem performance results are still poorly documented, particularly in the field. This triggered a study to assess the importance of vegetation in methane oxidation efficiency (MOE). In this study, 4 large scale columns, each filled with sand, topsoil and a mixture of compost and topsoil were tested under controlled conditions in the laboratory and partially controlled conditions in the field. Four series of laboratory tests and two series of field tests were performed. 4 different plant covers were tested for each series: Trifolium repens L. (White clover), Phleum pratense L. (Timothy grass), a mixture of both, and bare soil as the control biosystem. The study results indicated that up to a loading equal to 100 g CH4/m(2)/d, the type of plant cover did not influence the oxidation rates, and the MOE was quite high (⩾ 95%) in all columns. Beyond this point, the oxidation rate continued to increase, reaching 253 and 179 g CH4/m(2)/d in laboratory and field tests respectively. In the end, the bare soil achieved as high or higher MOEs than vegetated biosystems. Despite the fact that the findings of this study cannot be generalized to other types of biosystems and plants and that the vegetation types tested were not fully grown, it was shown that for the short-term tests performed and the types of substrates and plants used herein, vegetation does not seem to be a key factor for enhancing biosystem performance. This key conclusion does not corroborate the conclusion of the relatively few studies published in the technical literature assessing the importance of vegetation in MOE.

  11. Circadian Variability in Methane Oxidation Activity in the Root Zone of Rice Plants

    NASA Astrophysics Data System (ADS)

    Schroth, M. H.; Cho, R.; Zeyer, J.

    2009-12-01

    Methane is an important greenhouse gas with a warming potential about 20 times stronger than that of carbon dioxide. A main source of biogenic methane are rice-paddy soils. Methane is produced in flooded rice fields under anaerobic conditions. Conversely, methanotrophic microorganisms oxidize methane to carbon dioxide in the root zone of rice plants in the presence of molecular oxygen supplied to the roots through the plants’ aerenchyma, thus reducing overall methane emissions to the atmosphere. To quantify methane oxidation we adapted push-pull tests (PPTs), a technique originally developed for aquifer testing, in combination with a suitable microbial inhibitor for application in the root zone of rice plants. During a PPT, 70 ml of a test solution containing dissolved substrates (methane, oxygen), nonreactive tracers (argon, chloride) and the methanogenesis inhibitor 2-Bromoethane sulfonate was injected into the plant’s root zone, and after a rest period of two hours extracted from the same location. Reaction rate constants were calculated from extraction-phase breakthrough curves of substrates and tracers. We conducted a set of three different laboratory PPTs to quantify methane oxidation at day time, directly after dawn, and at night in the root zone of four different potted rice plants each. High diurnal methane oxidation rate constants (up to 23 h-1) were obtained for all rice plants. Methane oxidation potential decreased soon after nightfall. At night, rate constants were usually below 1 h-1. Methane oxidation rates were apparently independent of additional oxygen supplied via the injected test solutions, but strongly dependent on photosynthetically produced oxygen transported to the roots through the plants’ aerenchyma. Additional PPTs utilizing 13C-labeled methane are currently being conducted to corroborate these findings. Ultimately, this novel tool shall support efforts to quantitatively understand the controlling mechanisms of methane turnover in

  12. Performance of green waste biocovers for enhancing methane oxidation.

    PubMed

    Mei, Changgen; Yazdani, Ramin; Han, Byunghyun; Mostafid, M Erfan; Chanton, Jeff; VanderGheynst, Jean; Imhoff, Paul

    2015-05-01

    Green waste aged 2 and 24months, labeled "fresh" and "aged" green waste, respectively, were placed in biocover test cells and evaluated for their ability to oxidize methane (CH4) under high landfill gas loading over a 15-month testing period. These materials are less costly to produce than green waste compost, yet satisfied recommended respiration requirements for landfill compost covers. In field tests employing a novel gas tracer to correct for leakage, both green wastes oxidized CH4 at high rates during the first few months of operation - 140 and 200g/m(2)/day for aged and fresh green waste, respectively. Biocover performance degraded during the winter and spring, with significant CH4 generated from anaerobic regions in the 60-80cm thick biocovers. Concurrently, CH4 oxidation rates decreased. Two previously developed empirical models for moisture and temperature dependency of CH4 oxidation in soils were used to test their applicability to green waste. Models accounted for 68% and 79% of the observed seasonal variations in CH4 oxidation rates for aged green waste. Neither model could describe similar seasonal changes for the less stable fresh green waste. This is the first field application and evaluation of these empirical models using media with high organic matter. Given the difficulty of preventing undesired CH4 generation, green waste may not be a viable biocover material for many climates and landfill conditions. PMID:25792440

  13. Performance of green waste biocovers for enhancing methane oxidation.

    PubMed

    Mei, Changgen; Yazdani, Ramin; Han, Byunghyun; Mostafid, M Erfan; Chanton, Jeff; VanderGheynst, Jean; Imhoff, Paul

    2015-05-01

    Green waste aged 2 and 24months, labeled "fresh" and "aged" green waste, respectively, were placed in biocover test cells and evaluated for their ability to oxidize methane (CH4) under high landfill gas loading over a 15-month testing period. These materials are less costly to produce than green waste compost, yet satisfied recommended respiration requirements for landfill compost covers. In field tests employing a novel gas tracer to correct for leakage, both green wastes oxidized CH4 at high rates during the first few months of operation - 140 and 200g/m(2)/day for aged and fresh green waste, respectively. Biocover performance degraded during the winter and spring, with significant CH4 generated from anaerobic regions in the 60-80cm thick biocovers. Concurrently, CH4 oxidation rates decreased. Two previously developed empirical models for moisture and temperature dependency of CH4 oxidation in soils were used to test their applicability to green waste. Models accounted for 68% and 79% of the observed seasonal variations in CH4 oxidation rates for aged green waste. Neither model could describe similar seasonal changes for the less stable fresh green waste. This is the first field application and evaluation of these empirical models using media with high organic matter. Given the difficulty of preventing undesired CH4 generation, green waste may not be a viable biocover material for many climates and landfill conditions.

  14. Cu-ZSM-5: A biomimetic inorganic model for methane oxidation

    PubMed Central

    Vanelderen, Pieter; Hadt, Ryan G.; Smeets, Pieter J.; Solomon, Edward I.; Schoonheydt, Robert A.; Sels, Bert F.

    2012-01-01

    The present work highlights recent advances in elucidating the methane oxidation mechanism of inorganic Cu-ZSM-5 biomimic and in identifying the reactive intermediates that are involved. Such molecular understanding is important in view of upgrading abundantly available methane, but also to comprehend the working mechanism of genuine Cu-containing oxidation enzymes. PMID:23487537

  15. A field-validated model for landfill methane emissions inclusive of seasonal methane oxidation

    NASA Astrophysics Data System (ADS)

    Bogner, J. E.; Spokas, K.; Chanton, J.

    2010-12-01

    In addition to natural wetlands, atmospheric methane (CH4) has multiple anthropogenic sources with high uncertainties, including rice production, ruminant animals, natural gas leakages, biomass burning, and landfills. For an improved IPCC Tier III methodology for landfill CH4 emissions in California, we have developed a new science-based, field-validated inventory model which decouples emissions from a historical reliance on a theoretical first order kinetic model for CH4 generation potential. The model (CALMIM, CAlifornia Landfill Methane Inventory Model) is a freely-available JAVA tool which estimates net CH4 emissions to the atmosphere for any landfill cover soil over a typical annual cycle, including (1) the effect of engineered gas extraction; (2) the physical effects of daily, intermediate, and final cover materials to retard emissions; and (3) seasonal soil moisture and temperature effects on both gaseous transport and methanotrophic CH4 oxidation. Linking site-specific data with existing globally-validated USDA models for annual climate and soil microclimate (Global TempSim; Global RainSim; Solarcalc; STM2), this model relies on 1-D diffusion as the major driver for emissions. Importantly, unlike current inventory methods based on modeled generation, the driving force for emissions (e.g., the CH4 concentration gradient) can be directly compared to field data. Methane oxidation is scaled to maximum rates over the full range of moisture and temperature conditions based on extensive supporting laboratory studies using California landfill cover soils. Field validation included meteorological data, soil moisture/temperature measurements, and seasonal (wet/dry) CH4 emissions & oxidation measurements for daily, intermediate, and final cover soils over two annual cycles at a northern (Monterey County) and southern California (Los Angeles County) landfill. The model accurately predicted soil temperature and moisture trends for individual cover materials with

  16. Depth profiles of methane oxidation potentials and methanotrophic community in a lab-scale biocover.

    PubMed

    Lee, Eun-Hee; Moon, Kyung-Eun; Kim, Tae Gwan; Cho, Kyung-Suk

    2014-08-20

    The depth profiles of the CH4 oxidation potentials and the methanotrophic community were characterized in a lab-scale soil mixture biocover. The soil mixture samples were collected from the top (0-10cm), middle (10-40cm), and bottom (40-50cm) layers of the biocover where most of methane was oxidized at the top layer due to consumption of O2. Batch tests using serum bottles showed that the middle and bottom samples displayed CH4 oxidation activity under aerobic conditions, and their CH4 oxidation rates were 85 and 71% of the rate of top sample (8.40μmolgdry sample(-1)h(-1)), respectively. The numbers of methanotrophs in the middle and bottom were not significantly different from those in the top sample. There was no statistical difference in the community stability indices (diversity and evenness) among the methanotrophic communities of the three layer samples, even though the community structures were distinguished from each other. Based on microarray analysis, type I and type II methanotrophs were equally present in the top sample, while type I was more dominant than type II in the middle and bottom samples. We suggested that the qualitative difference in the community structures was probably caused by the difference in the depth profiles of the CH4 and O2 concentrations. The results for the CH4 oxidation potential, methanotrophic biomass, and community stability indices in the middle and bottom layer samples indicated that the deeper layer in the methanotrophic biocover serves as a bioresource reservoir for sustainable CH4 mitigation.

  17. Rapid methane oxidation in a landfill cover soil.

    PubMed

    Whalen, S C; Reeburgh, W S; Sandbeck, K A

    1990-11-01

    Methane oxidation rates observed in a topsoil covering a retired landfill are the highest reported (45 g m day) for any environment. This microbial community had the capacity to rapidly oxidize CH(4) at concentrations ranging from <1 ppm (microliters per liter) (first-order rate constant [k] = -0.54 h) to >10 ppm (k = -2.37 h). The physiological characteristics of a methanotroph isolated from the soil (characteristics determined in aqueous medium) and the natural population, however, were similar to those of other natural populations and cultures: the Q(10) and optimum temperature were 1.9 and 31 degrees C, respectively, the apparent half-saturation constant was 2.5 to 9.3 muM, and 19 to 69% of oxidized CH(4) was assimilated into biomass. The CH(4) oxidation rate of this soil under waterlogged (41% [wt/vol] H(2)O) conditions, 6.1 mg liter day, was near rates reported for lake sediment and much lower than the rate of 116 mg liter day in the same soil under moist (11% H(2)O) conditions. Since there are no large physiological differences between this microbial community and other CH(4) oxidizers, we attribute the high CH(4) oxidation rate in moist soil to enhanced CH(4) transport to the microorganisms; gas-phase molecular diffusion is 10-fold faster than aqueous diffusion. These high CH(4) oxidation rates in moist soil have implications that are important in global climate change. Soil CH(4) oxidation could become a negative feedback to atmospheric CH(4) increases (and warming) in areas that are presently waterlogged but are projected to undergo a reduction in summer soil moisture.

  18. Assessment of the methane oxidation capacity of compacted soils intended for use as landfill cover materials

    SciTech Connect

    Rachor, Ingke; Gebert, Julia; Groengroeft, Alexander; Pfeiffer, Eva-Maria

    2011-05-15

    The microbial oxidation of methane in engineered cover soils is considered a potent option for the mitigation of emissions from old landfills or sites containing wastes of low methane generation rates. A laboratory column study was conducted in order to derive design criteria that enable construction of an effective methane oxidising cover from the range of soils that are available to the landfill operator. Therefore, the methane oxidation capacity of different soils was assessed under simulated landfill conditions. Five sandy potential landfill top cover materials with varying contents of silt and clay were investigated with respect to methane oxidation and corresponding soil gas composition over a period of four months. The soils were compacted to 95% of their specific proctor density, resulting in bulk densities of 1.4-1.7 g cm{sup -3}, reflecting considerably unfavourable conditions for methane oxidation due to reduced air-filled porosity. The soil water content was adjusted to field capacity, resulting in water contents ranging from 16.2 to 48.5 vol.%. The investigated inlet fluxes ranged from 25 to about 100 g CH{sub 4} m{sup -2} d{sup -1}, covering the methane load proposed to allow for complete oxidation in landfill covers under Western European climate conditions and hence being suggested as a criterion for release from aftercare. The vertical distribution of gas concentrations, methane flux balances as well as stable carbon isotope studies allowed for clear process identifications. Higher inlet fluxes led to a reduction of the aerated zone, an increase in the absolute methane oxidation rate and a decline of the relative proportion of oxidized methane. For each material, a specific maximum oxidation rate was determined, which varied between 20 and 95 g CH{sub 4} m{sup -2} d{sup -1} and which was positively correlated to the air-filled porosity of the soil. Methane oxidation efficiencies and gas profile data imply a strong link between oxidation capacity

  19. Microbial community structure in a thermophilic aerobic digester used as a sludge pretreatment process for the mesophilic anaerobic digestion and the enhancement of methane production.

    PubMed

    Jang, Hyun Min; Park, Sang Kyu; Ha, Jeong Hyub; Park, Jong Moon

    2013-10-01

    An effective two-stage sewage sludge digestion process, consisting of thermophilic aerobic digestion (TAD) followed by mesophilic anaerobic digestion (MAD), was developed for efficient sludge reduction and methane production. Using TAD as a biological pretreatment, the total volatile suspended solid reduction (VSSR) and methane production rate (MPR) in the MAD reactor were significantly improved. According to denaturing gradient gel electrophoresis (DGGE) analysis, the results indicated that the dominant bacteria species such as Ureibacillus thermophiles and Bacterium thermus in TAD were major routes for enhancing soluble organic matter. TAD pretreatment using a relatively short SRT of 1 day showed highly increased soluble organic products and positively affected an increment of bacteria populations which performed interrelated microbial metabolisms with methanogenic species in the MAD; consequently, a quantitative real-time PCR indicated greatly increased Methanosarcinales (acetate-utilizing methanogens) in the MAD, resulting in enhanced methane production.

  20. Selective aerobic oxidation mediated by TiO(2) photocatalysis.

    PubMed

    Lang, Xianjun; Ma, Wanhong; Chen, Chuncheng; Ji, Hongwei; Zhao, Jincai

    2014-02-18

    TiO2 is one of the most studied metal oxide photocatalysts and has unparal-leled efficiency and stability. This cheap, abundant, and non-toxic material has the potential to address future environmental and energy concerns. Understanding about the photoinduced interfacial redox events on TiO2 could have profound effect on the degradation of organic pollutants, splitting of H2O into H2 and O2, and selective redox organic transformations. Scientists traditionally accept that for a semiconductor photocatalyst such as TiO2 under the illumination of light with energy larger than its band gap, two photocarriers will be created to carry out their independent reduction and oxidation processes. However, our recent discoveries indicate that it is the concerted rather than independent effect of both photocarriers of valence band hole (hvb(+)) and conduction band electron (ecb(-)) that dictate the product formation during interfacial oxidation event mediated by TiO2 photocatalysis. In this Account, we describe our recent findings on the selective oxidation of organic substrates with O2 mediated by TiO2 photocatalysis. The transfer of O-atoms from O2 to the corresponding products dominates the selective oxidation of alcohols, amines, and alkanes mediated by TiO2 photocatalysis. We ascribe this to the concerted effect of both hvb(+) and ecb(-) of TiO2 in contribution to the oxidation products. These findings imply that O2 plays a unique role in its transfer into the products rather than independent role of ecb(-) scavenger. More importantly, ecb(-) plays a crucial role to ensure the high selectivity for the oxygenation of organic substrates. We can also use the half reactions such as those of the conduction band electron of TiO2 for efficient oxidation reactions with O2. To this end, efficient selective oxidation of organic substrates such as alcohols, amines, and aromatic alkanes with O2 mediated by TiO2 photocatalysis under visible light irradiation has been achieved. In

  1. Selective aerobic oxidation mediated by TiO(2) photocatalysis.

    PubMed

    Lang, Xianjun; Ma, Wanhong; Chen, Chuncheng; Ji, Hongwei; Zhao, Jincai

    2014-02-18

    TiO2 is one of the most studied metal oxide photocatalysts and has unparal-leled efficiency and stability. This cheap, abundant, and non-toxic material has the potential to address future environmental and energy concerns. Understanding about the photoinduced interfacial redox events on TiO2 could have profound effect on the degradation of organic pollutants, splitting of H2O into H2 and O2, and selective redox organic transformations. Scientists traditionally accept that for a semiconductor photocatalyst such as TiO2 under the illumination of light with energy larger than its band gap, two photocarriers will be created to carry out their independent reduction and oxidation processes. However, our recent discoveries indicate that it is the concerted rather than independent effect of both photocarriers of valence band hole (hvb(+)) and conduction band electron (ecb(-)) that dictate the product formation during interfacial oxidation event mediated by TiO2 photocatalysis. In this Account, we describe our recent findings on the selective oxidation of organic substrates with O2 mediated by TiO2 photocatalysis. The transfer of O-atoms from O2 to the corresponding products dominates the selective oxidation of alcohols, amines, and alkanes mediated by TiO2 photocatalysis. We ascribe this to the concerted effect of both hvb(+) and ecb(-) of TiO2 in contribution to the oxidation products. These findings imply that O2 plays a unique role in its transfer into the products rather than independent role of ecb(-) scavenger. More importantly, ecb(-) plays a crucial role to ensure the high selectivity for the oxygenation of organic substrates. We can also use the half reactions such as those of the conduction band electron of TiO2 for efficient oxidation reactions with O2. To this end, efficient selective oxidation of organic substrates such as alcohols, amines, and aromatic alkanes with O2 mediated by TiO2 photocatalysis under visible light irradiation has been achieved. In

  2. In situ measurement of methane oxidation in groundwater by using natural-gradient tracer tests

    USGS Publications Warehouse

    Smith, R.L.; Howes, B.L.; Garabedian, S.P.

    1991-01-01

    Methane oxidation was measured in an unconfined sand and gravel aquifer (Cape Cod, Mass.) by using in situ natural-gradient tracer tests at both a pristine, oxygenated site and an anoxic, sewage-contaminated site. The tracer sites were equipped with multilevel sampling devices to create target grids of sampling points; the injectate was prepared with groundwater from the tracer site to maintain the same geochemical conditions. Methane oxidation was calculated from breakthrough curves of methane relative to halide and inert gas (hexafluoroethane) tracers and was confirmed by the appearance of 13C-enriched carbon dioxide in experiments in which 13C-enriched methane was used as the tracer. A V(max) for methane oxidation could be calculated when the methane concentration was sufficiently high to result in zero-order kinetics throughout the entire transport interval. Methane breakthrough curves could be simulated by modifying a one-dimensional advection-dispersion transport model to include a Michaelis-Menten-based consumption term for methane oxidation. The K(m) values for methane oxidation that gave the best match for the breakthrough curve peaks were 6.0 and 9.0 ??M for the uncontaminated and contaminated sites, respectively. Natural-gradient tracer tests are a promising approach for assessing microbial processes and for testing in situ bioremediation potential in groundwater systems.

  3. Fractionation of carbon and hydrogen isotopes by methane-oxidizing bacteria

    USGS Publications Warehouse

    Coleman, D.D.; Risatti, J.B.; Schoell, M.

    1981-01-01

    Carbon isotopic analysis of methane has become a popular technique in the exploration for oil and gas because it can be used to differentiate between thermogenic and microbial gas and can sometimes be used for gas-source rock correlations. Methane-oxidizing bacteria, however, can significantly change the carbon isotopic composition of methane; the origin of gas that has been partially oxidized by these bacteria could therefore be misinterpreted. We cultured methane-oxidizing bacteria at two different temperatures and monitored the carbon and hydrogen isotopic compositions of the residual methane. The residual methane was enriched in both 13C and D. For both isotopic species, the enrichment at equivalent levels of conversion was greater at 26??C than at 11.5??C. The change in ??D relative to the change in ??13C was independent of temperature within the range studied. One culture exhibited a change in the fractionation pattern for carbon (but not for hydrogen) midway through the experiment, suggesting that bacterial oxidation of methane may occur via more than one pathway. The change in the ??D value for the residual methane was from 8 to 14 times greater than the change in the ??13C value, indicating that combined carbon and hydrogen isotopic analysis may be an effective way of identifying methane which has been subjected to partial oxidation by bacteria. ?? 1981.

  4. In situ measurement of methane oxidation in groundwater by using natural-gradient tracer tests.

    PubMed Central

    Smith, R L; Howes, B L; Garabedian, S P

    1991-01-01

    Methane oxidation was measured in an unconfined sand and gravel aquifer (Cape Cod, Mass.) by using in situ natural-gradient tracer tests at both a pristine, oxygenated site and an anoxic, sewage-contaminated site. The tracer sites were equipped with multilevel sampling devices to create target grids of sampling points; the injectate was prepared with groundwater from the tracer site to maintain the same geochemical conditions. Methane oxidation was calculated from breakthrough curves of methane relative to halide and inert gas (hexafluroethane) tracers and was confirmed by the appearance of 13C-enriched carbon dioxide in experiments in which 13C-enriched methane was used as the tracer. A Vmax for methane oxidation could be calculated when the methane concentration was sufficiently high to result in zero-order kinetics throughout the entire transport interval. Methane breakthrough curves could be simulated by modifying a one-dimensional adevection-dispersion transport model to include a Michaelis-Menten-based consumption term for methane oxidation. The Km values for methane oxidation that gave the best match for the breakthrough curve peaks were 6.0 and 9.0 microM for the uncontaminated and contaminated sites, respectively. Natural-gradient tracer tests are a promising approach for assessing microbial processes and for testing in situ bioremediation potential in groundwater systems. PMID:1892389

  5. Modeling sulfate reduction in methane hydrate-bearing continental margin sediments: Does a sulfate-methane transition require anaerobic oxidation of methane?

    USGS Publications Warehouse

    Malinverno, A.; Pohlman, J.W.

    2011-01-01

    The sulfate-methane transition (SMT), a biogeochemical zone where sulfate and methane are metabolized, is commonly observed at shallow depths (1-30 mbsf) in methane-bearing marine sediments. Two processes consume sulfate at and above the SMT, anaerobic oxidation of methane (AOM) and organoclastic sulfate reduction (OSR). Differentiating the relative contribution of each process is critical to estimate methane flux into the SMT, which, in turn, is necessary to predict deeper occurrences of gas hydrates in continental margin sediments. To evaluate the relative importance of these two sulfate reduction pathways, we developed a diagenetic model to compute the pore water concentrations of sulfate, methane, and dissolved inorganic carbon (DIC). By separately tracking DIC containing 12C and 13C, the model also computes ??13C-DIC values. The model reproduces common observations from methane-rich sediments: a well-defined SMT with no methane above and no sulfate below and a ??13C-DIC minimum at the SMT. The model also highlights the role of upward diffusing 13C-enriched DIC in contributing to the carbon isotope mass balance of DIC. A combination of OSR and AOM, each consuming similar amounts of sulfate, matches observations from Site U1325 (Integrated Ocean Drilling Program Expedition 311, northern Cascadia margin). Without AOM, methane diffuses above the SMT, which contradicts existing field data. The modeling results are generalized with a dimensional analysis to the range of SMT depths and sedimentation rates typical of continental margins. The modeling shows that AOM must be active to establish an SMT wherein methane is quantitatively consumed and the ??13C-DIC minimum occurs. The presence of an SMT generally requires active AOM. Copyright 2011 by the American Geophysical Union.

  6. Fe-Catalyzed Aerobic Oxidative C-CN Bond Cleavage of Arylacetonitriles Leading to Various Esters.

    PubMed

    Kong, Weiguang; Li, Bingnan; Xu, Xuezhao; Song, Qiuling

    2016-09-16

    Fe-catalyzed aerobic oxidative esterifications of arylacetonitriles with alcohols, tri alkoxsilanes, silicate esters, or borate esters have been developed. The acyl groups which were in situ generated via chemoselective C(CO)-CN bond cleavage were directly used as electrophiles, leading to corresponding aryl esters in good to excellent yields under molecular oxygen when attacked by alcohols or alcohol surrogates. Dioxygen serves as both oxidant and reactant in this protocol. The reaction has a very broad substrate scope. Cheap starting materials as well as environmentally benign and inexpensive iron catalyst and ideal oxidant O2 feature this transformation and make it a practical and sustainable protocol to afford esters. PMID:27555329

  7. Copper/TEMPO-Catalyzed Aerobic Alcohol Oxidation: Mechanistic Assessment of Different Catalyst Systems

    PubMed Central

    Hoover, Jessica M.; Ryland, Bradford L.; Stahl, Shannon S.

    2013-01-01

    Combinations of homogeneous Cu salts and TEMPO have emerged as practical and efficient catalysts for the aerobic oxidation of alcohols. Several closely related catalyst systems have been reported, which differ in the identity of the solvent, the presence of 2,2′-bipyridine as a ligand, the identity of basic additives, and the oxidation state of the Cu source. These changes have a significant influence on the reaction rates, yields, and substrate scope. In this report, we probe the mechanistic basis for differences among four different Cu/TEMPO catalyst systems and elucidate the features that contribute to efficient oxidation of aliphatic alcohols. PMID:24558634

  8. Iron/ABNO-Catalyzed Aerobic Oxidation of Alcohols to Aldehydes and Ketones under Ambient Atmosphere.

    PubMed

    Wang, Lianyue; Shang, SenSen; Li, Guosong; Ren, Lanhui; Lv, Ying; Gao, Shuang

    2016-03-01

    We report a new Fe(NO3)3·9H2O/9-azabicyclo[3.3.1]nonan-N-oxyl catalyst system that enables efficient aerobic oxidation of a broad range of primary and secondary alcohols to the corresponding aldehydes and ketones at room temperature with ambient air as the oxidant. The catalyst system exhibits excellent activity and selectivity for primary aliphatic alcohol oxidation. This procedure can also be scaled up. Kinetic analysis demonstrates that C-H bond cleavage is the rate-determining step and that cationic species are involved in the reaction. PMID:26859251

  9. Activated carbon for aerobic oxidation: Benign approach toward 2-benzoylbenzimidazoles and 2-benzoylbenzoxazoles synthesis

    PubMed Central

    Bao, Kai; Li, Fuqing; Liu, Hanjing; Wang, Zhiwei; Shen, Qirong; Wang, Jian; Zhang, Weige

    2015-01-01

    A general strategy involving a novel and highly efficient aerobic benzylic oxidation promoted by cheap, reusable activated carbon in water is developed. Application of this method has been demonstrated in the benign synthesis of bioactive 2-benzoylbenzimidazoles and 2-benzoylbenzoxazoles derivatives. Furthermore, the activated carbon catalyst could be recovered and reused at least three times without significantly losing its activity. Preliminary research suggests that the oxidation mechanism may involve intermediate hydroperoxidation and that a portion of the final carbonyl product is obtained through a secondary benzylic alcohol intermediate. Finally, theoretical calculations reveal that the oxidation yield is closely associated with the electric density at the benzylic position of the substrate. PMID:26041483

  10. Copper/TEMPO-Catalyzed Aerobic Alcohol Oxidation: Mechanistic Assessment of Different Catalyst Systems.

    PubMed

    Hoover, Jessica M; Ryland, Bradford L; Stahl, Shannon S

    2013-11-01

    Combinations of homogeneous Cu salts and TEMPO have emerged as practical and efficient catalysts for the aerobic oxidation of alcohols. Several closely related catalyst systems have been reported, which differ in the identity of the solvent, the presence of 2,2'-bipyridine as a ligand, the identity of basic additives, and the oxidation state of the Cu source. These changes have a significant influence on the reaction rates, yields, and substrate scope. In this report, we probe the mechanistic basis for differences among four different Cu/TEMPO catalyst systems and elucidate the features that contribute to efficient oxidation of aliphatic alcohols. PMID:24558634

  11. Selective methane oxidation over promoted oxide catalysts. Quarterly report, March--May 1995

    SciTech Connect

    Klier, K.; Herman, R.G.; Wang, Chaun-Bao; Shi, Chunlei; Sun, Qun

    1995-08-01

    The objective of this research is the selective oxidative coupling of methane to C{sub 2}H{sub 4} hydrocarbons and oxygenates, in particular formaldehyde and methanol. Air, oxygen or carbon dioxide, rather than nitrous oxide will be utilized as the oxidizing gas at high gas hourly space velocity, but mild reaction conditions (500-700 {degrees}C, 1 atm total pressure). All the investigated processes are catalytic, aiming at minimizing gas phase reactions that are difficult to control. The research is divided into the following three tasks: (1) maximizing selective methane oxidation to C{sub 2}H{sub 4} products over promoted Sr/La{sub 2}O{sub 3}; (2) selective methane oxidation to oxygenates; and (3) catalyst characterization and optimization. Task 1 dealt with the preparation, testing, and optimization of acidic promoted lanthana-based catalysts for the synthesis of C{sub 2}H{sub 4} hydrocarbons and is essentially completed. Task 2 aims at the formation and optimization of promoted catalysts for the synthesis of oxygenates, in particular formaldehyde and methanol. Task 3 involves characterization of the most promising catalysts so that optimization can be achieved under Task 2. Accomplishments for this period are presented.

  12. Selective methane oxidation over promoted oxide catalysts. Topical report, September 8, 1992--September 7, 1996

    SciTech Connect

    Klier, K.; Herman, R.G.

    1996-12-31

    The objective of this research was to selectively oxidize methane to C{sub 2} hydrocarbons and to oxygenates, in particular formaldehyde and methanol, in high space time yields using air at the oxidant under milder reaction conditions that heretofore employed over industrially practical oxide catalysts. The research carried out under this US DOE-METC contract was divided into the following three tasks: Task 1, maximizing selective methane oxidation to C{sub 2}{sup +} products over promoted SrO/La{sub 2}O{sub 3} catalysts; Task 2, selective methane oxidation to oxygenates; and Task 3, catalyst characterization and optimization. Principal accomplishments include the following: the 1 wt% SO{sub 4}{sup 2{minus}}/SrO/La{sub 2}O{sub 3} promoted catalyst developed here produced over 2 kg of C{sub 2} hydrocarbons/kg catalyst/hr at 550 C; V{sub 2}O{sub 5}/SiO{sub 2} catalysts have been prepared that produce up to 1.5 kg formaldehyde/kg catalyst/hr at 630 C with low CO{sub 2} selectivities; and a novel dual bed catalyst system has been designed and utilized to produce over 100 g methanol/kg catalyst/hr at 600 C with the presence of steam in the reactant mixture.

  13. Use of 16S rRNA Gene Based Clone Libraries to Assess Microbial Communities Potentially Involved in Anaerobic Methane Oxidation in a Mediterranean Cold Seep

    PubMed Central

    Haese, Ralf R.; van der Wielen, Paul W. J. J.; Forney, Larry J.; van Elsas, Jan Dirk

    2007-01-01

    This study provides data on the diversities of bacterial and archaeal communities in an active methane seep at the Kazan mud volcano in the deep Eastern Mediterranean sea. Layers of varying depths in the Kazan sediments were investigated in terms of (1) chemical parameters and (2) DNA-based microbial population structures. The latter was accomplished by analyzing the sequences of directly amplified 16S rRNA genes, resulting in the phylogenetic analysis of the prokaryotic communities. Sequences of organisms potentially associated with processes such as anaerobic methane oxidation and sulfate reduction were thus identified. Overall, the sediment layers revealed the presence of sequences of quite diverse bacterial and archaeal communities, which varied considerably with depth. Dominant types revealed in these communities are known as key organisms involved in the following processes: (1) anaerobic methane oxidation and sulfate reduction, (2) sulfide oxidation, and (3) a range of (aerobic) heterotrophic processes. In the communities in the lowest sediment layer sampled (22–34 cm), sulfate-reducing bacteria and archaea of the ANME-2 cluster (likely involved in anaerobic methane oxidation) were prevalent, whereas heterotrophic organisms abounded in the top sediment layer (0–6 cm). Communities in the middle layer (6–22 cm) contained organisms that could be linked to either of the aforementioned processes. We discuss how these phylogeny (sequence)-based findings can support the ongoing molecular work aimed at unraveling both the functioning and the functional diversities of the communities under study. PMID:17431711

  14. Temporal resilience and dynamics of anaerobic methane-oxidizing microbial communities to short-term changes in methane partial pressures

    NASA Astrophysics Data System (ADS)

    Klasek, S.; Tiantian, Y.; Torres, M. E.; Colwell, F. S.; Wang, F.; Liang, L.

    2015-12-01

    Marine sediments produce tens to hundreds of teragrams of methane annually, which is released from the seabed at thousands of cold seeps distributed globally along continental margins. Around 80-90% of this methane is consumed in shallower sediment layers before reaching the hydrosphere, in a microbially-mediated process known as anaerobic oxidation of methane (AOM) However, cold seeps appear to exhibit temporal variation in gas flux intensity, and AOM filter efficiency at cold seeps generally decreases with fluid flow rate. To our knowledge, the degree to which temporal heterogeneity in subsurface methane flux stimulates AOM community growth and adaptation to increased methane concentrations has not been investigated. Static high-pressure bioreactors were used to incubate sulfate-methane transition zone (SMTZ) and methanogenic zone sediments underlying a Mediterranean mud volcano gas flare under in situ temperature and pressure at 8 MPa methane. Sulfide production rates of 0.4 μmol/cm3/day in both sediment regimes after 4 months of incubation suggested the resilience of the marine subsurface methane filter may extend well below the SMTZ (40 cm). Similar incubations of SMTZ samples from below a gas flare off Svalbard at saturating (3.8 MPa) and 0.2 MPa methane are being sampled after 1 week, 4 weeks, and 4 months; sulfide production rates of 8-18 nmol/cm3/day were first observed after 4 weeks of incubation. Sediment samples at all specified time points for both sets of incubations were collected for nucleic acid extraction and cell fixation. Anaerobic methanotrophic archaea (ANME) and sulfate-reducing bacteria (SRB) are expected dominant taxa in enriched and non-enriched communities. 16S rDNA community analysis is expected to reveal additional microbial players involved in the short-term adaptation to higher methane partial pressures in the marine subsurface. Increased AOM community activity (RNA/DNA ratio) and copy numbers of methane cycling transcripts (mcr

  15. A fully coupled model for water-gas-heat reactive transport with methane oxidation in landfill covers.

    PubMed

    Ng, C W W; Feng, S; Liu, H W

    2015-03-01

    Methane oxidation in landfill covers is a complex process involving water, gas and heat transfer as well as microbial oxidation. The coupled phenomena of microbial oxidation, water, gas, and heat transfer are not fully understood. In this study, a new model is developed that incorporates water-gas-heat coupled reactive transport in unsaturated soil with methane oxidation. Effects of microbial oxidation-generated water and heat are included. The model is calibrated using published data from a laboratory soil column test. Moreover, a series of parametric studies are carried out to investigate the influence of microbial oxidation-generated water and heat, initial water content on methane oxidation efficiency. Computed and measured results of gas concentration and methane oxidation rate are consistent. It is found that the coupling effects between water-gas-heat transfer and methane oxidation are significant. Ignoring microbial oxidation-generated water and heat can result in a significant difference in methane oxidation efficiency by 100%.

  16. A fully coupled model for water-gas-heat reactive transport with methane oxidation in landfill covers.

    PubMed

    Ng, C W W; Feng, S; Liu, H W

    2015-03-01

    Methane oxidation in landfill covers is a complex process involving water, gas and heat transfer as well as microbial oxidation. The coupled phenomena of microbial oxidation, water, gas, and heat transfer are not fully understood. In this study, a new model is developed that incorporates water-gas-heat coupled reactive transport in unsaturated soil with methane oxidation. Effects of microbial oxidation-generated water and heat are included. The model is calibrated using published data from a laboratory soil column test. Moreover, a series of parametric studies are carried out to investigate the influence of microbial oxidation-generated water and heat, initial water content on methane oxidation efficiency. Computed and measured results of gas concentration and methane oxidation rate are consistent. It is found that the coupling effects between water-gas-heat transfer and methane oxidation are significant. Ignoring microbial oxidation-generated water and heat can result in a significant difference in methane oxidation efficiency by 100%. PMID:25489976

  17. Coupling of nitrous oxide and methane by global atmospheric chemistry.

    PubMed

    Prather, Michael J; Hsu, Juno

    2010-11-12

    Nitrous oxide (N(2)O) and methane (CH(4)) are chemically reactive greenhouse gases with well-documented atmospheric concentration increases that are attributable to anthropogenic activities. We quantified the link between N(2)O and CH(4) emissions through the coupled chemistries of the stratosphere and troposphere. Specifically, we simulated the coupled perturbations of increased N(2)O abundance, leading to stratospheric ozone (O(3)) depletion, altered solar ultraviolet radiation, altered stratosphere-to-troposphere O(3) flux, increased tropospheric hydroxyl radical concentration, and finally lower concentrations of CH(4). The ratio of CH(4) per N(2)O change, -36% by mole fraction, offsets a fraction of the greenhouse effect attributable to N(2)O emissions. These CH(4) decreases are tied to the 108-year chemical mode of N(2)O, which is nine times longer than the residence time of direct CH(4) emissions.

  18. Conventional methanotrophs are responsible for atmospheric methane oxidation in paddy soils

    PubMed Central

    Cai, Yuanfeng; Zheng, Yan; Bodelier, Paul L. E.; Conrad, Ralf; Jia, Zhongjun

    2016-01-01

    Soils serve as the biological sink of the potent greenhouse gas methane with exceptionally low concentrations of ∼1.84 p.p.m.v. in the atmosphere. The as-yet-uncultivated methane-consuming bacteria have long been proposed to be responsible for this ‘high-affinity' methane oxidation (HAMO). Here we show an emerging HAMO activity arising from conventional methanotrophs in paddy soil. HAMO activity was quickly induced during the low-affinity oxidation of high-concentration methane. Activity was lost gradually over 2 weeks, but could be repeatedly regained by flush-feeding the soil with elevated methane. The induction of HAMO activity occurred only after the rapid growth of methanotrophic populations, and a metatranscriptome-wide association study suggests that the concurrent high- and low-affinity methane oxidation was catalysed by known methanotrophs rather than by the proposed novel atmospheric methane oxidizers. These results provide evidence of atmospheric methane uptake in periodically drained ecosystems that are typically considered to be a source of atmospheric methane. PMID:27248847

  19. Conventional methanotrophs are responsible for atmospheric methane oxidation in paddy soils

    NASA Astrophysics Data System (ADS)

    Cai, Yuanfeng; Zheng, Yan; Bodelier, Paul L. E.; Conrad, Ralf; Jia, Zhongjun

    2016-06-01

    Soils serve as the biological sink of the potent greenhouse gas methane with exceptionally low concentrations of ~1.84 p.p.m.v. in the atmosphere. The as-yet-uncultivated methane-consuming bacteria have long been proposed to be responsible for this `high-affinity' methane oxidation (HAMO). Here we show an emerging HAMO activity arising from conventional methanotrophs in paddy soil. HAMO activity was quickly induced during the low-affinity oxidation of high-concentration methane. Activity was lost gradually over 2 weeks, but could be repeatedly regained by flush-feeding the soil with elevated methane. The induction of HAMO activity occurred only after the rapid growth of methanotrophic populations, and a metatranscriptome-wide association study suggests that the concurrent high- and low-affinity methane oxidation was catalysed by known methanotrophs rather than by the proposed novel atmospheric methane oxidizers. These results provide evidence of atmospheric methane uptake in periodically drained ecosystems that are typically considered to be a source of atmospheric methane.

  20. Conventional methanotrophs are responsible for atmospheric methane oxidation in paddy soils.

    PubMed

    Cai, Yuanfeng; Zheng, Yan; Bodelier, Paul L E; Conrad, Ralf; Jia, Zhongjun

    2016-01-01

    Soils serve as the biological sink of the potent greenhouse gas methane with exceptionally low concentrations of ∼1.84 p.p.m.v. in the atmosphere. The as-yet-uncultivated methane-consuming bacteria have long been proposed to be responsible for this 'high-affinity' methane oxidation (HAMO). Here we show an emerging HAMO activity arising from conventional methanotrophs in paddy soil. HAMO activity was quickly induced during the low-affinity oxidation of high-concentration methane. Activity was lost gradually over 2 weeks, but could be repeatedly regained by flush-feeding the soil with elevated methane. The induction of HAMO activity occurred only after the rapid growth of methanotrophic populations, and a metatranscriptome-wide association study suggests that the concurrent high- and low-affinity methane oxidation was catalysed by known methanotrophs rather than by the proposed novel atmospheric methane oxidizers. These results provide evidence of atmospheric methane uptake in periodically drained ecosystems that are typically considered to be a source of atmospheric methane. PMID:27248847

  1. Practical Synthesis of Amides via Copper/ABNO-Catalyzed Aerobic Oxidative Coupling of Alcohols and Amines.

    PubMed

    Zultanski, Susan L; Zhao, Jingyi; Stahl, Shannon S

    2016-05-25

    A modular Cu/ABNO catalyst system has been identified that enables efficient aerobic oxidative coupling of alcohols and amines to amides. All four permutations of benzylic/aliphatic alcohols and primary/secondary amines are viable in this reaction, enabling broad access to secondary and tertiary amides. The reactions exhibit excellent functional group compatibility and are complete within 30 min-3 h at rt. All components of the catalyst system are commercially available. PMID:27171973

  2. Oxidation of methane over palladium catalysts: effect of the support.

    PubMed

    Escandón, Lara S; Ordóñez, Salvador; Vega, Aurelio; Díez, Fernando V

    2005-01-01

    This work is focused on the deep catalytic oxidation of methane over supported palladium catalysts. The influences of the metal loading, oxidation state of palladium, nature of supports, presence of promoters in the supports (for zirconia-based supports), and thermal stability have been studied experimentally. Catalysts were prepared by incipient wetness of commercially available supports with aqueous solutions of palladium nitrate. For gamma-alumina support, it was observed that the optimal amount of palladium is between 0.5% and 2%, with higher amounts leading to a loss in specific activity. Concerning the oxidation state of the catalyst, it is concluded that for all the supports tested in the present work, a reduction of the catalyst is not needed, yielding the same conversion at steady state catalysts reduced and oxidised. The thermal stability of various supported catalysts were also studied, zirconia supports being the most active. These supports, specially Y-modified zirconia support, do not suffer appreciable deactivation below 500 degrees C.

  3. The Aerobic Oxidation of Bromide to Dibromine Catalyzed by Homogeneous Oxidation Catalysts and Initiated by Nitrate in Acetic Acid

    SciTech Connect

    Partenheimer, Walt; Fulton, John L.; Sorensen, Christina M.; Pham, Van Thai; Chen, Yongsheng

    2014-06-01

    A small amount of nitrate, ~0.002 molal, initiates the Co/Mn catalyzed aerobic oxidation of bromide compounds (HBr,NaBr,LiBr) to dibromine in acetic acid at room temperature. At temperatures 40oC or less , the reaction is autocatalytic. Co(II) and Mn(II) themselves and mixed with ionic bromide are known homogeneous oxidation catalysts. The reaction was discovered serendipitously when a Co/Br and Co/Mn/Br catalyst solution was prepared for the aerobic oxidation of methyaromatic compounds and the Co acetate contained a small amount of impurity i.e. nitrate. The reaction was characterized by IR, UV-VIS, MALDI and EXAFS spectroscopies and the coordination chemistry is described. The reaction is inhibited by water and its rate changed by pH. The change in these variables, as well as others, are identical to those observed during homogeneous, aerobic oxidation of akylaromatics. A mechanism is proposed. Accidental addition of a small amount of nitrate compound into a Co/Mn/Br/acetic acid mixture in a large, commercial feedtank is potentially dangerous.

  4. An insight into the mechanism of the aerobic oxidation of aldehydes catalyzed by N-heterocyclic carbenes.

    PubMed

    Bortolini, O; Chiappe, C; Fogagnolo, M; Giovannini, P P; Massi, A; Pomelli, C S; Ragno, D

    2014-02-25

    N-Heterocyclic carbene catalysis for the aerobic oxidation and esterification of aromatic aldehydes was monitored by ESI-MS (MS/MS) and the key intermediates were intercepted and characterized using the charge-tag strategy. PMID:24413829

  5. Low-level 14C methane oxidation rate measurements modified for remote field settings

    NASA Astrophysics Data System (ADS)

    Pack, M. A.; Pohlman, J.; Ruppel, C. D.; Xu, X.

    2012-12-01

    Aerobic methane oxidation limits atmospheric methane emissions from degraded subsea permafrost and dissociated methane hydrates in high latitude oceans. Methane oxidation rate measurements are a crucial tool for investigating the efficacy of this process, but are logistically challenging when working on small research vessels in remote settings. We modified a low-level 14C-CH4 oxidation rate measurement for use in the Beaufort Sea above hydrate bearing sediments during August 2012. Application of the more common 3H-CH4 rate measurement that uses 106 times more radioactivity was not practical because the R/V Ukpik cannot accommodate a radiation van. The low-level 14C measurement does not require a radiation van, but careful isolation of the 14C-label is essential to avoid contaminating natural abundance 14C measurements. We used 14C-CH4 with a total activity of 1.1 μCi, which is far below the 100 μCi permitting level. In addition, we modified field procedures to simplify and shorten sample processing. The original low-level 14C-CH4 method requires 6 steps in the field: (1) collect water samples in glass serum bottles, (2) inject 14C-CH4 into bottles, (3) incubate for 24 hours, (4) filter to separate the methanotrophic bacterial cells from the aqueous sample, (5) kill the filtrate with sodium hydroxide (NaOH), and (6) purge with nitrogen to remove unused 14C-CH4. Onshore, the 14C-CH4 respired to carbon dioxide or incorporated into cell material by methanotrophic bacteria during incubation is quantified by accelerator mass spectrometry (AMS). We conducted an experiment to test the possibility of storing samples for purging and filtering back onshore (steps 4 and 6). We subjected a series of water samples to steps 1-3 & 5, and preserved with mercuric chloride (HgCl2) instead of NaOH because HgCl2 is less likely to break down cell material during storage. The 14C-content of the carbon dioxide in samples preserved with HgCl2 and stored for up to 2 weeks was stable

  6. Role of ammonia-oxidizing bacteria in micropollutant removal from wastewater with aerobic granular sludge.

    PubMed

    Margot, Jonas; Lochmatter, Samuel; Barry, D A; Holliger, Christof

    2016-01-01

    Nitrifying wastewater treatment plants (WWTPs) are more efficient than non-nitrifying WWTPs to remove several micropollutants such as pharmaceuticals and pesticides. This may be related to the activity of nitrifying organisms, such as ammonia-oxidizing bacteria (AOBs), which could possibly co-metabolically oxidize micropollutants with their ammonia monooxygenase (AMO). The role of AOBs in micropollutant removal was investigated with aerobic granular sludge (AGS), a promising technology for municipal WWTPs. Two identical laboratory-scale AGS sequencing batch reactors (AGS-SBRs) were operated with or without nitrification (inhibition of AMOs) to assess their potential for micropollutant removal. Of the 36 micropollutants studied at 1 μg l(-1) in synthetic wastewater, nine were over 80% removed, but 17 were eliminated by less than 20%. Five substances (bisphenol A, naproxen, irgarol, terbutryn and iohexol) were removed better in the reactor with nitrification, probably due to co-oxidation catalysed by AMOs. However, for the removal of all other micropollutants, AOBs did not seem to play a significant role. Many compounds were better removed in aerobic condition, suggesting that aerobic heterotrophic organisms were involved in the degradation. As the AGS-SBRs did not favour the growth of such organisms, their potential for micropollutant removal appeared to be lower than that of conventional nitrifying WWTPs. PMID:26877039

  7. Urban sources and emissions of nitrous oxide and methane in southern California, USA

    NASA Astrophysics Data System (ADS)

    Townsend-Small, A.; Pataki, D.; Tyler, S. C.; Czimczik, C. I.; Xu, X.; Christensen, L. E.

    2012-12-01

    Anthropogenic activities have resulted in increasing levels of greenhouse gases, including carbon dioxide, methane, and nitrous oxide. While global and regional emissions sources of carbon dioxide are relatively well understood, methane and nitrous oxide are less constrained, particularly at regional scales. Here we present the results of an investigation of sources and emissions of methane and nitrous oxide in Los Angeles, California, USA, one of Earth's largest urban areas. The original goal of the project was to determine whether isotopes are useful tracers of agricultural versus urban nitrous oxide and methane sources. For methane, we found that stable isotopes (carbon-13 and deuterium) and radiocarbon are good tracers of biogenic versus fossil fuel sources. High altitude observations of methane concentration, measured continuously using tunable laser spectroscopy, and isotope ratios, measured on discrete flask samples using mass spectrometry, indicate that the predominant methane source in Los Angeles is from fossil fuels, likely from "fugitive" emissions from geologic formations, natural gas pipelines, oil refining, or power plants. We also measured nitrous oxide emissions and isotope ratios from urban (landscaping and wastewater treatment) and agricultural sources (corn and vegetable fields). There was no difference in nitrous oxide isotope ratios between the different types of sources, although stable isotopes did differ between nitrous oxide produced in oxic and anoxic wastewater treatment tanks. Our nitrous oxide flux data indicate that landscaped turfgrass emits nitrous oxide at rates equivalent to agricultural systems, indicating that ornamental soils should not be disregarded in regional nitrous oxide budgets. However, we also showed that wastewater treatment is a much greater source of nitrous oxide than soils regionally. This work shows that global nitrous oxide and methane budgets are not easily downscaled to regional, urban settings, which has

  8. Use of stable isotopes to determine methane oxidation in landfill cover soils

    NASA Astrophysics Data System (ADS)

    Liptay, K.; Chanton, J.; Czepiel, P.; Mosher, B.

    1998-04-01

    The mean isotopic composition of CH4 emitted from six New England (United States) landfills was 13C and D enriched (-48.1 to -50.4‰ and -273 to -281‰) relative to anoxic zone landfill CH4 (mean values of -55.9 to -56.2‰ and -296 to -300‰) owing to the oxidation of methane as it was transported from the landfill to the atmosphere through the soil cap. The fraction of methane oxidized f0 during its passage through the soil cap was calculated from the degree of 13C enrichment in emitted CH4 relative to anoxic zone CH4 in conjunction with values determined for the preference of soil methane oxidizing bacteria for 12CH4 over 13CH4 (α = 1.022 ± 0.008). Mean values for methane oxidation in six landfills were from 24 to 35% of the total flux through the soil during the warm season, depending upon how the data were grouped. Our results bracket recent estimates of methane oxidation of about 30% in the warm summer period produced using a model with the input terms of soil temperature, moisture, depth, and oxygen concentration. Because of variations in the response of methane oxidation to temperature at these New England sites, our study is consistent with the modeling results of Czepiel et al. [1996b] that the best estimate for the annual value for methane oxidation in the landfills considered is about 10%.

  9. Characteristics of methane and nitrous oxide emissions from the wastewater treatment plant.

    PubMed

    Hwang, Kum-Lok; Bang, Cheon-Hee; Zoh, Kyung-Duk

    2016-08-01

    The nitrous oxide (N2O) and methane (CH4) emissions were measured from a municipal wastewater treatment plant (WWTP) using a flux chamber to determine the emission factors. The WWTP treats sewage using both the activated-sludge treatment and anaerobic/anoxic/aerobic (A(2)O) methods. Measurements were performed in the first settling, aeration, and secondary settling basins, as well as in the sludge thickener, sludge digestion tank, and A(2)O basins. The total emission factors of N2O and CH4 from the activated-sludge treatment were 1.256gN2O/kg total nitrogen (TN) and 3.734gCH4/kg biochemical oxygen demand (BOD5), respectively. Those of the advanced treatment (A(2)O) were 1.605gN2O/kg TN and 4.022gCH4/kgBOD5, respectively. These values are applicable as basic data to estimate greenhouse gas emissions. PMID:27237575

  10. Characteristics of methane and nitrous oxide emissions from the wastewater treatment plant.

    PubMed

    Hwang, Kum-Lok; Bang, Cheon-Hee; Zoh, Kyung-Duk

    2016-08-01

    The nitrous oxide (N2O) and methane (CH4) emissions were measured from a municipal wastewater treatment plant (WWTP) using a flux chamber to determine the emission factors. The WWTP treats sewage using both the activated-sludge treatment and anaerobic/anoxic/aerobic (A(2)O) methods. Measurements were performed in the first settling, aeration, and secondary settling basins, as well as in the sludge thickener, sludge digestion tank, and A(2)O basins. The total emission factors of N2O and CH4 from the activated-sludge treatment were 1.256gN2O/kg total nitrogen (TN) and 3.734gCH4/kg biochemical oxygen demand (BOD5), respectively. Those of the advanced treatment (A(2)O) were 1.605gN2O/kg TN and 4.022gCH4/kgBOD5, respectively. These values are applicable as basic data to estimate greenhouse gas emissions.

  11. Inhibition of methane oxidation by nitrogenous fertilizers in a paddy soil

    PubMed Central

    Alam, M. Saiful; Jia, Zhongjun

    2012-01-01

    Nitrogenous fertilizers are generally thought to have an important role in regulating methane oxidation. In this study, the effect of ammonium on methane oxidation activity was investigated in a paddy soil using urea at concentrations of 0, 50, 100, 200, and 400 μg N per gram dry weight soil (N/g.d.w.s) and ammonium sulfate at concentrations of 0, 50, and 200 μg N/g.d.w.s. The results of this study demonstrate that urea concentrations of 200 μg N/g.d.w.s. and above significantly inhibit methane oxidation activity, whereas no statistically significant difference was observed in methane oxidation activity among soil microcosms with urea concentrations of less than 200 μg N/g.d.w.s after incubation for 27 days. Similar results were obtained in a sense that methane oxidation activity was inhibited only when the ammonium sulfate concentration was 200 μg N/g.d.w.s in soil microcosms in this study. Phylogenetic analysis of pmoA genes showed that nitrogen fertilization resulted in apparent changes in the community composition of methane-oxidizing bacteria (MOB). Type I MOB displayed an increased abundance in soil microcosms amended with nitrogenous fertilizers, whereas type II MOB dominated the native soil. Furthermore, although no statistically significant relationship was observed between pmoA gene and amoA gene abundances, methane oxidation activity was significantly negatively correlated with nitrification activity in the presence of urea or ammonium sulfate. Our results indicate that the methane oxidation activity in paddy soils might be inhibited when the concentration of ammonium fertilizers is high and that the interactions between ammonia and methane oxidizers need to be further investigated. PMID:22783249

  12. Supplementation with vitamin A enhances oxidative stress in the lungs of rats submitted to aerobic exercise.

    PubMed

    Gasparotto, Juciano; Petiz, Lyvia Lintzmaier; Girardi, Carolina Saibro; Bortolin, Rafael Calixto; de Vargas, Amanda Rodrigues; Henkin, Bernardo Saldanha; Chaves, Paloma Rodrigues; Roncato, Sabrina; Matté, Cristiane; Zanotto-Filho, Alfeu; Moreira, José Cláudio Fonseca; Gelain, Daniel Pens

    2015-12-01

    Exercise training induces reactive oxygen species production and low levels of oxidative damage, which are required for induction of antioxidant defenses and tissue adaptation. This process is physiological and essential to improve physical conditioning and performance. During exercise, endogenous antioxidants are recruited to prevent excessive oxidative stress, demanding appropriate intake of antioxidants from diet or supplements; in this context, the search for vitamin supplements that enhance the antioxidant defenses and improve exercise performance has been continuously increasing. On the other hand, excess of antioxidants may hinder the pro-oxidant signals necessary for this process of adaptation. The aim of this study was to investigate the effects of vitamin A supplementation (2000 IU/kg, oral) upon oxidative stress and parameters of pro-inflammatory signaling in lungs of rats submitted to aerobic exercise (swimming protocol). When combined with exercise, vitamin A inhibited biochemical parameters of adaptation/conditioning by attenuating exercise-induced antioxidant enzymes (superoxide dismutase and glutathione peroxidase) and decreasing the content of the receptor for advanced glycation end-products. Increased oxidative damage to proteins (carbonylation) and lipids (lipoperoxidation) was also observed in these animals. In sedentary animals, vitamin A decreased superoxide dismutase and increased lipoperoxidation. Vitamin A also enhanced the levels of tumor necrosis factor alpha and decreased interleukin-10, effects partially reversed by aerobic training. Taken together, the results presented herein point to negative effects associated with vitamin A supplementation at the specific dose here used upon oxidative stress and pro-inflammatory cytokines in lung tissues of rats submitted to aerobic exercise.

  13. Global Change Simulations Affect Potential Methane Oxidation in Upland Soils

    NASA Astrophysics Data System (ADS)

    Blankinship, J. C.; Hungate, B. A.

    2004-12-01

    Atmospheric concentrations of methane (CH4) are higher now than they have ever been during the past 420,000 years. However, concentrations have remained stable since 1999. Emissions associated with livestock husbandry are unlikely to have changed, so some combination of reduced production in wetlands, more efficient capture by landfills, or increased consumption by biological CH4 oxidation in upland soils may be responsible. Methane oxidizing bacteria are ubiquitous in upland soils and little is known about how these bacteria respond to anthropogenic global change, and how they will influence - or already are influencing - the radiative balance of the atmosphere. Might ongoing and future global changes increase biological CH4 oxidation? Soils were sampled from two field experiments to assess changes in rates of CH4 oxidation in response to global change simulations. Potential activities of CH4 oxidizing bacterial communities were measured through laboratory incubations under optimal temperature, soil moisture, and atmospheric CH4 concentrations (~18 ppm, or 10x ambient). The ongoing 6-year multifactorial Jasper Ridge Global Change Experiment (JRGCE) simulates warming, elevated precipitation, elevated atmospheric CO2, elevated atmospheric N deposition, and increased wildfire frequency in an annual grassland in a Mediterranean-type climate in central California. The ongoing 1-year multifactorial Merriam Climate Change Experiment (MCCE) simulates warming, elevated precipitation, and reduced precipitation in four different types of ecosystems along an elevational gradient in a semi-arid climate in northern Arizona. The high desert grassland, pinyon-juniper woodland, ponderosa pine forest, and mixed conifer forest ecosystems range in annual precipitation from 100 to 1000 mm yr-1, and from productivity being strongly water limited to strongly temperature limited. Among JRGCE soils, elevated atmospheric CO2 increased potential CH4 oxidation rates (p=0.052) and wildfire

  14. Dissolution of Fe(III)(hydr)oxides by an Aerobic Bacterium

    SciTech Connect

    Maurice, P.

    2004-12-13

    This project investigated the effects of an aerobic Pseudomonas mendocina bacterium on the dissolution of Fe(III)(hydr)oxides. The research is important because metals and radionuclides that adsorb to Fe(III)(hydr)oxides could potentially be remobilized by dissolving bacteria. We showed that P. mendocina is capable of dissolving Fe-bearing minerals by a variety of mechanisms, including production of siderophores, pH changes, and formation of reductants. The production of siderophores by P. mendocina was quantified under a variety of growth conditions. Finally, we demonstrated that microbial siderophores may adsorb to and enhance dissolution of clay minerals.

  15. Methane oxidation in a biofilter (Part 2): A lab-scale experiment for model calibration.

    PubMed

    Amodeo, Corrado; Masi, Salvatore; Van Hulle, Stijn W H; Zirpoli, Pier Francesco; Mancini, Ignazio M; Caniani, Donatella

    2015-01-01

    In this study an experimental study on a biological methane oxidation column presented with the aim to calibrate a mathematical model developed in an earlier study. The column was designed to reproduce at lab-scale a real biofilter trying to consider the more probable landfill boundary conditions. Although the methane oxidation efficiency in the column was lower than the expected (around 35%), an appropriate model implementation showed an acceptable agreement between the outcomes data of the model simulation and the experimental data (with Theil's Inequality Coefficient value of 0.08). A calibrated model allows a better management of the biofilter performance in terms of methane oxidation.

  16. Long-term aerobic exercise increases redox-active iron through nitric oxide in rat hippocampus.

    PubMed

    Chen, Qian; Xiao, De-Sheng

    2014-01-30

    Adult hippocampus is highly vulnerable to iron-induced oxidative stress. Aerobic exercise has been proposed to reduce oxidative stress but the findings in the hippocampus are conflicting. This study aimed to observe the changes of redox-active iron and concomitant regulation of cellular iron homeostasis in the hippocampus by aerobic exercise, and possible regulatory effect of nitric oxide (NO). A randomized controlled study was designed in the rats with swimming exercise treatment (for 3 months) and/or an unselective inhibitor of NO synthase (NOS) (L-NAME) treatment. The results from the bleomycin-detectable iron assay showed additional redox-active iron in the hippocampus by exercise treatment. The results from nonheme iron content assay, combined with the redox-active iron content, showed increased storage iron content by exercise treatment. NOx (nitrate plus nitrite) assay showed increased NOx content by exercise treatment. The results from the Western blot assay showed decreased ferroportin expression, no changes of TfR1 and DMT1 expressions, increased IRP1 and IRP2 expression, increased expressions of eNOS and nNOS rather than iNOS. In these effects of exercise treatment, the increased redox-active iron content, storage iron content, IRP1 and IRP2 expressions were completely reversed by L-NAME treatment, and decreased ferroportin expression was in part reversed by L-NAME. L-NAME treatment completely inhibited increased NOx and both eNOS and nNOS expression in the hippocampus. Our findings suggest that aerobic exercise could increase the redox-active iron in the hippocampus, indicating an increase in the capacity to generate hydroxyl radicals through the Fenton reactions, and aerobic exercise-induced iron accumulation in the hippocampus might mainly result from the role of the endogenous NO.

  17. Anaerobic oxidation of methane in grassland soils used for cattle husbandry

    NASA Astrophysics Data System (ADS)

    Bannert, A.; Bogen, C.; Esperschütz, J.; Koubová, A.; Buegger, F.; Fischer, D.; Radl, V.; Fuß, R.; Chroňáková, A.; Elhottová, D.; Šimek, M.; Schloter, M.

    2012-10-01

    While the importance of anaerobic methane oxidation has been reported for marine ecosystems, the role of this process in soils is still questionable. Grasslands used as pastures for cattle overwintering show an increase in anaerobic soil micro-sites caused by animal treading and excrement deposition. Therefore, anaerobic potential methane oxidation activity of severely impacted soil from a cattle winter pasture was investigated in an incubation experiment under anaerobic conditions using 13C-labelled methane. We were able to detect a high microbial activity utilizing CH4 as nutrient source shown by the respiration of 13CO2. Measurements of possible terminal electron acceptors for anaerobic oxidation of methane were carried out. Soil sulfate concentrations were too low to explain the oxidation of the amount of methane added, but enough nitrate and iron(III) were detected. However, only nitrate was consumed during the experiment. 13C-PLFA analyses clearly showed the utilization of CH4 as nutrient source mainly by organisms harbouring 16:1ω7 PLFAs. These lipids were also found as most 13C-enriched fatty acids by Raghoebarsing et al. (2006) after addition of 13CH4 to an enrichment culture coupling denitrification of nitrate to anaerobic oxidation of methane. This might be an indication for anaerobic oxidation of methane by relatives of "Candidatus Methylomirabilis oxyfera" in the investigated grassland soil under the conditions of the incubation experiment.

  18. Pt{sup +}-catalyzed oxidation of methane: Theory and experiment

    SciTech Connect

    Pavlov, M.; Blomberg, M.R.A.; Siegbahn, P.E.M.; Wesendrup, R.; Heinemann, C.; Schwarz, H.

    1997-02-20

    The oxidation of methane with molecular oxygen using the atomic platinum cation as a catalyst, yielding methanol, formaldehyde, and higher oxidation products, has been studied both computationally and experimentally. The most relevant reaction pathways have been followed in detail. To this end a large number of stationary points, both minima and transition states, have been optimized using a hybrid density functional theory method (B3LYP). At these optimized geometries, energies have been calculated using both an empirical scaling scheme (PCI-80) and the B3LYP method employing extended basis sets with several polarization functions. Good agreement with available experimental data has been obtained. For the parts of the catalytic cycle where detailed experimental results have not been available, the new calculated results have complemented the experimental picture to reach an almost complete understanding of the reaction mechanisms. Spin-orbit effects have been incorporated using an empirical approach, which has lead to improved agreement with experiments. The new FTICR experiments reported in the present study have helped to clarify some of the most complicated reaction sequences. 61 refs., 9 figs., 9 tabs.

  19. Are termite mounds biofilters for methane? - Challenges and new approaches to quantify methane oxidation in termite mounds

    NASA Astrophysics Data System (ADS)

    Nauer, Philipp A.; Hutley, Lindsay B.; Bristow, Mila; Arndt, Stefan K.

    2015-04-01

    Methane emissions from termites contribute around 3% to global methane in the atmosphere, although the total source estimate for termites is the most uncertain among all sources. In tropical regions, the relative source contribution of termites can be far higher due to the high biomass and relative importance of termites in plant decomposition. Past research focused on net emission measurements and their variability, but little is known about underlying processes governing these emissions. In particular, microbial oxidation of methane (MOX) within termite mounds has rarely been investigated. In well-studied ecosystems featuring an oxic matrix above an anoxic methane-producing habitat (e.g. landfills or sediments), the fraction of oxidized methane (fox) can reach up to 90% of gross production. However, conventional mass-balance approaches to apportion production and consumption processes can be challenging to apply in the complex-structured and almost inaccessible environment of a termite mound. In effect, all field-based data on termite-mound MOX is based on one study that measured isotopic shifts in produced and emitted methane. In this study a closed-system isotope fractionation model was applied and estimated fox ranged from 10% to almost 100%. However, it is shown here that by applying an open-system isotope-pool model, the measured isotopic shifts can also be explained by physical transport of methane alone. Different field-based methods to quantify MOX in termite mounds are proposed which do not rely on assumptions of physical gas transport. A simple approach is the use of specific inhibitors for MOX, e.g. difluoromethane (CH2F2), combined with chamber-based flux measurements before and after their application. Data is presented on the suitability of different inhibitors and first results of their application in the field. Alternatively, gas-tracer methods allow the quantification of methane oxidation and reaction kinetics without knowledge of physical gas

  20. Atmospheric methane oxidizers are present and active in Canadian high Arctic soils.

    PubMed

    Martineau, Christine; Pan, Yao; Bodrossy, Levente; Yergeau, Etienne; Whyte, Lyle G; Greer, Charles W

    2014-08-01

    The melting of permafrost and the associated potential for methane emissions to the atmosphere are major concerns in the context of global warming. However, soils can also represent a significant sink for methane through the activity of methane-oxidizing bacteria (MOB). In this study, we looked at the activity, diversity, and community structure of MOB at two sampling depths within the active layer in three soils from the Canadian high Arctic. These soils had the capacity to oxidize methane at low (15 ppm) and high (1000 ppm) methane concentrations, but rates differed greatly depending on the sampling date, depth, and site. The pmoA gene sequences related to two genotypes of uncultured MOB involved in atmospheric methane oxidation, the 'upland soil cluster gamma' and the 'upland soil cluster alpha', were detected in soils with near neutral and acidic pH, respectively. Other groups of MOB, including Type I methanotrophs and the 'Cluster 1' genotype, were also detected, indicating a broader diversity of MOB than previously reported for Arctic soils. Overall, the results reported here showed that methane oxidation at both low and high methane concentrations occurs in high Arctic soils and revealed that different groups of atmospheric MOB inhabit these soils.

  1. Environmental evidence for net methane production and oxidation in putative ANaerobic MEthanotrophic (ANME) archaea.

    PubMed

    Lloyd, Karen G; Alperin, Marc J; Teske, Andreas

    2011-09-01

    Uncultured ANaerobic MEthanotrophic (ANME) archaea are often assumed to be obligate methanotrophs that are incapable of net methanogenesis, and are therefore used as proxies for anaerobic methane oxidation in many environments in spite of uncertainty regarding their metabolic capabilities. Anaerobic methane oxidation regulates methane emissions in marine sediments and appears to occur through a reversal of a methane-producing metabolism. We tested the assumption that ANME are obligate methanotrophs by detecting and quantifying gene transcription of ANME-1 across zones of methane oxidation versus methane production in sediments from the White Oak River estuary, North Carolina. ANME-1 consistently transcribe 16S rRNA and mRNA of methyl coenzyme M reductase (mcrA), the key gene for methanogenesis, up to 45 cm into methanogenic sediments. CARD-FISH shows that ANME-1 exist as single rod-shaped cells or pairs of cells. Integrating normalized depth distributions of 16S rDNA and rRNA (measured with qPCR and RT-qPCR respectively) shows that 26-77% of the rDNA (a proxy for ANME-1 cell numbers), and 18-76% of the rRNA (a proxy for ANME-1 activity) occurs within methane-producing sediments. These results, along with a re-assessment of the published Iiterature, change the perspective to ANME-1 as methanogens that are also capable of methane oxidation.

  2. Field and laboratory studies of methane oxidation in an anoxic marine sediment: Evidence for a methanogen-sulfate reducer consortium

    NASA Astrophysics Data System (ADS)

    Hoehler, Tori M.; Alperin, Marc J.; Albert, Daniel B.; Martens, Christopher S.

    1994-12-01

    Field and laboratory studies of anoxic sediments from Cape Lookout Bight, North Carolina, suggest that anaerobic methane oxidation is mediated by a consortium of methanogenic and sulfate-reducing bacteria. A seasonal survey of methane oxidation and CO2 reduction rates indicates that methane production was confined to sulfate-depleted sediments at all times of year, while methane oxidation occurred in two modes. In the summer, methane oxidation was confined to sulfate-depleted sediments and occurred at rates lower than those of CO2 reduction. In the winter, net methane oxidation occurred in an interval at the base of the sulfate-containing zone. Sediment incubation experiments suggest both methanogens and sulfate reducers were responsible for the observed methane oxidation. In one incubation experiment both modes of oxidation were partially inhibited by 2-bromoethanesulfonic acid (a specific inhibitor of methanogens). This evidence, along with the apparent confinement of methane oxidation to sulfate-depleted sediments in the summer, indicates that methanogenic bacteria are involved in methane oxidation. In a second incubation experiment, net methane oxidation was induced by adding sulfate to homogenized methanogenic sediments, suggesting that sulfate reducers also play a role in the process. We hypothesize that methanogens oxidize methane and produce hydrogen via a reversal of CO2 reduction. The hydrogen is efficiently removed and maintained at low concentrations by sulfate reducers. Pore water H2 concentrations in the sediment incubation experiments (while net methane oxidation was occurring) were low enough that methanogenic bacteria could derive sufficient energy for growth from the oxidation of methane. The methanogen-sulfate reducer consortium is consistent not only with the results of this study, but may also be a feasible mechanism for previously documented anaerobic methane oxidation in both freshwater and marine environments.

  3. Field and laboratory studies of methane oxidation in an anoxic marine sediment: Evidence for a methanogen-sulfate reducer consortium

    SciTech Connect

    Hoehler, T.M.; Alperin, M.J.; Albert, D.B.

    1994-12-01

    Field and laboratory studies of anoxic sediments from Cape Lookout Bight, North Carolina, suggest that anaerobic methane oxidation is mediated by a consortium of methanogenic and sulfate-reducing bacteria. A seasonal survey of methane oxidation and CO{sub 2} reduction rates indicates that methane production was confined to sulfate-depleted sediments at all times of year, while methane oxidation occurred in two modes. In the summer, methane oxidation was confined to sulfate-depleted sediments and occurred at rates lower than those of CO{sub 2} reduction. In the winter, net methane oxidation occurred in an interval at the base of the sulfate-containing zone. Sediment incubation experiments suggest both methanogens and sulfate reducers were responsible for the observed methane oxidation. In one incubation experiment both modes of oxidation were partially inhibited by 2-bromoethanesulfonic acid (a specific inhibitor of methanogens). This evidence, along with the apparent confinement of methane oxidation to sulfate-depleted sediments in the summer, indicates that methanogenic bacteria are involved in methane oxidation. In a second incubation experiment, net methane oxidation was induced by adding sulfate to homogenized methanogenic sediments, suggesting that sulfate reducers also a play a role in the process. We hypothesize that methanogens oxidize methane and produce hydrogen via a reversal of CO{sub 2} reduction. The hydrogen is efficiently removed and maintained at low concentrations by sulfate reducers. Pore water H{sub 2} concentrations in the sediment incubation experiments (while net methane oxidation was occurring) were low enough that methanogenic bacteria could derive sufficient energy for growth from the oxidation of methane. The methanogen-sulfate reducer consortium may also be a feasible mechanism for previously documented anaerobic methane oxidation in both freshwater and marine environments. 63 refs., 6 refs.

  4. Identifying active methane-oxidizers in thawed Arctic permafrost by proteomics

    NASA Astrophysics Data System (ADS)

    Lau, C. M.; Stackhouse, B. T.; Chourey, K.; Hettich, R. L.; Vishnivetskaya, T. A.; Pfiffner, S. M.; Layton, A. C.; Mykytczuk, N. C.; Whyte, L.; Onstott, T. C.

    2012-12-01

    The rate of CH4 release from thawing permafrost in the Arctic has been regarded as one of the determining factors on future global climate. It is uncertain how indigenous microorganisms would interact with such changing environmental conditions and hence their impact on the fate of carbon compounds that are sequestered in the cryosol. Multitudinous studies of pristine surface cryosol (top 5 cm) and microcosm experiments have provided growing evidence of effective methanotrophy. Cryosol samples corresponding to active layer were sampled from a sparsely vegetated, ice-wedge polygon at the McGill Arctic Research Station at Axel Heiberg Island, Nunavut, Canada (N79°24, W90°45) before the onset of annual thaw. Pyrosequencing of 16S rRNA gene indicated the occurrence of methanotroph-containing bacterial families as minor components (~5%) in pristine cryosol including Bradyrhizobiaceae, Methylobacteriaceae and Methylocystaceae within alpha-Proteobacteria, and Methylacidiphilaceae within Verrucomicrobia. The potential of methanotrophy is supported by preliminary analysis of metagenome data, which indicated putative methane monooxygenase gene sequences relating to Bradyrhizobium sp. and Pseudonocardia sp. are present. Proteome profiling in general yielded minute traces of proteins, which likely hints at dormant nature of the soil microbial consortia. The lack of specific protein database for permafrost posted additional challenge to protein identification. Only 35 proteins could be identified in the pristine cryosol and of which 60% belonged to Shewanella sp. Most of the identified proteins are known to be involved in energy metabolism or post-translational modification of proteins. Microcosms amended with sodium acetate exhibited a net methane consumption of ~65 ngC-CH4 per gram (fresh weight) of soil over 16 days of aerobic incubation at room temperature. The pH in microcosm materials remained acidic (decreased from initial 4.7 to 4.5). Protein extraction and

  5. Revealing the halide effect on the kinetics of the aerobic oxidation of Cu(I) to Cu(II)

    SciTech Connect

    Deng, Yi; Zhang, Guanghui; Qi, Xiaotian; Liu, Chao; Miller, Jeffrey T.; Kropf, A. Jeremy; Bunel, Emilio E.; Lan, Yu; Lei, Aiwen

    2015-01-01

    In situ infrared (IR) and X-ray absorption near-edge structure (XANES) spectroscopic investigations reveal that different halide ligands have distinct effects on the aerobic oxidation of Cu(I) to Cu(II) in the presence of TMEDA (tetramethylethylenediamine). The iodide ligand gives the lowest rate and thus leads to the lowest catalytic reaction rate of aerobic oxidation of hydroquinone to benzoquinone. Further DFT calculations suggest that oxidation of CuI–TMEDA involves a side-on transition state, while oxidation of CuCl–TMEDA involves an end-on transition state which has a lower activation energy.

  6. Denitrification and nitric oxide reduction in an aerobic toluene-treating biofilter

    SciTech Connect

    Plessis, C.A. du; Kinney, K.A.; Schroeder, E.D.; Chang, D.P.Y.; Scow, K.M.

    1998-05-20

    The presence of significant denitrification activity in an aerobic toluene-treating biofilter was demonstrated under batch and flow-through conditions. N{sub 2}O concentrations of 9.2 ppm{sub v} were produced by denitrifying bacteria in the presence of 15% acetylene, in a flow-through system with a bulk gas phase O{sub 2} concentration of >17%. The carbon source for denitrification was not toluene but a byproduct or metabolite of toluene catabolism. Denitrification conditions were successfully used for the reduction of 60 ppm{sub v} nitric oxide to 15 ppm{sub v} at a flow rate of 3 L/min (EBRT of 3 min) in a fully aerated, 17%/v/v O{sub 2} (superficially aerobic) biofilter. Higher NO removal efficiency (97%) was obtained by increasing the toluene supply to the biofilter.

  7. Isolation of acidophilic methane-oxidizing bacteria from northern peat wetlands.

    PubMed

    Dedysh, S N; Panikov, N S; Liesack, W; Grosskopf, R; Zhou, J; Tiedje, J M

    1998-10-01

    Acidic northern wetlands are an important source of methane, one of the gases that contributes to global warming. Methane oxidation in the surface of these acidic wetlands can reduce the methane flux to the atmosphere up to 90 percent. Here the isolation of three methanotrophic microorganisms from three boreal forest sites is reported. They are moderately acidophilic organisms and have a soluble methane monooxygenase. In contrast to the known groups of methanotrophs, 16S ribosomal DNA sequence analysis shows that they are affiliated with the acidophilic heterotrophic bacterium Beijerinckia indica subsp. indica.

  8. Isolation of acidophilic methane-oxidizing bacteria from northern peat wetlands.

    PubMed

    Dedysh, S N; Panikov, N S; Liesack, W; Grosskopf, R; Zhou, J; Tiedje, J M

    1998-10-01

    Acidic northern wetlands are an important source of methane, one of the gases that contributes to global warming. Methane oxidation in the surface of these acidic wetlands can reduce the methane flux to the atmosphere up to 90 percent. Here the isolation of three methanotrophic microorganisms from three boreal forest sites is reported. They are moderately acidophilic organisms and have a soluble methane monooxygenase. In contrast to the known groups of methanotrophs, 16S ribosomal DNA sequence analysis shows that they are affiliated with the acidophilic heterotrophic bacterium Beijerinckia indica subsp. indica. PMID:9765151

  9. Modelling of stable isotope fractionation by methane oxidation and diffusion in landfill cover soils

    SciTech Connect

    Mahieu, Koenraad De Visscher, Alex; Vanrolleghem, Peter A.; Van Cleemput, Oswald

    2008-07-01

    A technique to measure biological methane oxidation in landfill cover soils that is gaining increased interest is the measurement of stable isotope fractionation in the methane. Usually to quantify methane oxidation, only fractionation by oxidation is taken into account. Recently it was shown that neglecting the isotope fractionation by diffusion results in underestimation of the methane oxidation. In this study a simulation model was developed that describes gas transport and methane oxidation in landfill cover soils. The model distinguishes between {sup 12}CH{sub 4}, {sup 13}CH{sub 4}, and {sup 12}CH{sub 3}D explicitly, and includes isotope fractionation by diffusion and oxidation. To evaluate the model, the simulations were compared with column experiments from previous studies. The predicted concentration profiles and isotopic profiles match the measured ones very well, with a root mean square deviation (RMSD) of 1.7 vol% in the concentration and a RMSD of 0.8 per mille in the {delta}{sup 13}C value, with {delta}{sup 13}C the relative {sup 13}C abundance as compared to an international standard. Overall, the comparison shows that a model-based isotope approach for the determination of methane oxidation efficiencies is feasible and superior to existing isotope methods.

  10. Anaerobic oxidation of methane in sediments of two boreal lakes

    NASA Astrophysics Data System (ADS)

    Rissanen, Antti J.; Karvinen, Anu; Nykänen, Hannu; Mpamah, Promise; Peura, Sari; Tiirola, Marja; Kankaala, Paula

    2014-05-01

    Anaerobic oxidation of methane (AOM) is a considerable sink for methane (CH4) in marine systems, but very little is known about the occurrence and importance of the process in freshwater systems. In addition, much about the microbial communities involved in AOM is unclear. AOM coupled with sulfate reduction is the dominant AOM process in marine systems but the scarce existing data suggest that, in freshwater systems, AOM coupled with reduction of alternative electron acceptors (nitrate/nitrite, manganese, iron) is more important. In this study, potential for AOM coupled with metal reduction was studied in boreal lake sediments. Slurries of sediment samples collected from two sites in southeastern Finland, i.e. from Lake Orivesi, Heposelkä, an vegetated littoral site, dominated by Phragmites australis (Sample Sa, sediment layer 0 - 25 cm) and from the profundal zone of a mesotrophic Lake Ätäskö (Aa, 0 - 10 cm; Ab, 10 - 30 cm; Ac, 90 - 130 cm), were incubated in laboratory in anaerobic conditions at in situ temperatures for up to 5 months. The samples were amended either 1) with 13CH4, 2) 13CH4 + manganese(II) oxide (MnO) or 3) 13CH4 + iron(III) hydroxide (Fe(OH)3), and the processes were measured by following the 13C transfer to the carbon dioxide (CO2) pool and by concentration measurements of CH4 and CO2. Changes in microbial communities were studied from DNA extracted from sediment samples before and after incubation period by next-generation sequencing (Ion Torrent) of polymerase chain reaction (PCR) - amplified bacterial and archaeal 16S rRNA and methyl coenzyme-M reductase gene (mcrA) amplicons. Increase in 13C of CO2 gas confirmed that AOM took place in sediments of both study lakes. In general, 13CO2 - production was significant both at the beginning (0 - 21 days) and at the end (84 - 151 days) of incubation period. Potential AOM rates (calculated based on 13CO2 - production) varied considerably and were much lower in deep sediment (Sample Ac), 0.1 - 0

  11. Ammonium-oxidizing bacteria facilitate aerobic degradation of sulfanilic acid in activated sludge.

    PubMed

    Chen, Gang; Ginige, Maneesha P; Kaksonen, Anna H; Cheng, Ka Yu

    2014-01-01

    Sulfanilic acid (SA) is a toxic sulfonated aromatic amine commonly found in anaerobically treated azo dye contaminated effluents. Aerobic acclimatization of SA-degrading mixed microbial culture could lead to co-enrichment of ammonium-oxidizing bacteria (AOB) because of the concomitant release of ammonium from SA oxidation. To what extent the co-enriched AOB would affect SA oxidation at various ammonium concentrations was unclear. Here, a series of batch kinetic experiments were conducted to evaluate the effect of AOB on aerobic SA degradation in an acclimatized activated sludge culture capable of oxidizing SA and ammonium simultaneously. To account for the effect of AOB on SA degradation, allylthiourea was used to inhibit AOB activity in the culture. The results indicated that specific SA degradation rate of the mixed culture was negatively correlated with the initial ammonium concentration (0-93 mM, R²= 0.99). The presence of AOB accelerated SA degradation by reducing the inhibitory effect of ammonium (≥ 10 mM). The Haldane substrate inhibition model was used to correlate substrate concentration (SA and ammonium) and oxygen uptake rate. This study revealed, for the first time, that AOB could facilitate SA degradation at high concentration of ammonium (≥ 10 mM) in an enriched activated sludge culture.

  12. Scaling methane oxidation: From laboratory incubation experiments to landfill cover field conditions

    SciTech Connect

    Abichou, Tarek; Mahieu, Koenraad; Chanton, Jeff; Romdhane, Mehrez; Mansouri, Imane

    2011-05-15

    Evaluating field-scale methane oxidation in landfill cover soils using numerical models is gaining interest in the solid waste industry as research has made it clear that methane oxidation in the field is a complex function of climatic conditions, soil type, cover design, and incoming flux of landfill gas from the waste mass. Numerical models can account for these parameters as they change with time and space under field conditions. In this study, we developed temperature, and water content correction factors for methane oxidation parameters. We also introduced a possible correction to account for the different soil structure under field conditions. These parameters were defined in laboratory incubation experiments performed on homogenized soil specimens and were used to predict the actual methane oxidation rates to be expected under field conditions. Water content and temperature corrections factors were obtained for the methane oxidation rate parameter to be used when modeling methane oxidation in the field. To predict in situ measured rates of methane with the model it was necessary to set the half saturation constant of methane and oxygen, K{sub m}, to 5%, approximately five times larger than laboratory measured values. We hypothesize that this discrepancy reflects differences in soil structure between homogenized soil conditions in the lab and actual aggregated soil structure in the field. When all of these correction factors were re-introduced into the oxidation module of our model, it was able to reproduce surface emissions (as measured by static flux chambers) and percent oxidation (as measured by stable isotope techniques) within the range measured in the field.

  13. Sulfur and oxygen isotope fractionation during sulfate reduction coupled to anaerobic oxidation of methane is dependent on methane concentration

    NASA Astrophysics Data System (ADS)

    Deusner, Christian; Holler, Thomas; Arnold, Gail L.; Bernasconi, Stefano M.; Formolo, Michael J.; Brunner, Benjamin

    2014-08-01

    Isotope signatures of sulfur compounds are key tools for studying sulfur cycling in the modern environment and throughout earth's history. However, for meaningful interpretations, the isotope effects of the processes involved must be known. Sulfate reduction coupled to the anaerobic oxidation of methane (AOM-SR) plays a pivotal role in sedimentary sulfur cycling and is the main process responsible for the consumption of methane in marine sediments - thereby efficiently limiting the escape of this potent greenhouse gas from the seabed to the overlying water column and atmosphere. In contrast to classical dissimilatory sulfate reduction (DSR), where sulfur and oxygen isotope effects have been measured in culture studies and a wide range of isotope effects has been observed, the sulfur and oxygen isotope effects by AOM-SR are unknown. This gap in knowledge severely hampers the interpretation of sulfur cycling in methane-bearing sediments, especially because, unlike DSR which is carried out by a single organism, AOM-SR is presumably catalyzed by consortia of archaea and bacteria that both contribute to the reduction of sulfate to sulfide. We studied sulfur and oxygen isotope effects by AOM-SR at various aqueous methane concentrations from 1.4±0.6 mM up to 58.8±10.5 mM in continuous incubation at steady state. Changes in the concentration of methane induced strong changes in sulfur isotope enrichment (εS34) and oxygen isotope exchange between water and sulfate relative to sulfate reduction (θO), as well as sulfate reduction rates (SRR). Smallest εS34 (21.9±1.9‰) and θO (0.5±0.2) as well as highest SRR were observed for the highest methane concentration, whereas highest εS34 (67.3±26.1‰) and θO (2.5±1.5) and lowest SRR were reached at low methane concentration. Our results show that εS34, θO and SRR during AOM-SR are very sensitive to methane concentration and thus also correlate with energy yield. In sulfate-methane transition zones, AOM-SR is likely

  14. Nature of methane activation over oxide centers. Annual report, September 1987-September 1988

    SciTech Connect

    Marcelin, G.; Agarwal, S.K.; Migone, R.A.

    1988-10-01

    The oxidative coupling of methane was studied over alkali-promoted antimony oxide and lead-magnesia catalysts. Reaction studies were used in conjunction with bulk and surface characterization of the catalysts to attempt to characterize the active centers. It was found that both acidity and availability of strong oxidizing sites can influence the selectivities of the various products of the reaction.

  15. Operando XAS study of the influence of CO and NO on methane oxidation by Pd/Al2O3

    NASA Astrophysics Data System (ADS)

    Marchionni, V.; Nachtegaal, M.; Petrov, A.; Kröcher, O.; Ferri, D.

    2016-05-01

    Methane oxidation on Pd/Al2O3 has been investigated using operando X-ray absorption spectroscopy (XAS) at the Pd K-edge. The influence of CO and NO on methane abatement has been addressed performing temperature programmed reaction runs while recording simultaneously XANES spectra. During CO oxidation Pd is reduced while methane conversion is shifted to higher temperature. NO strongly inhibits both CO and CH4 oxidation, despite the higher fraction of oxidized palladium.

  16. Evidence for nitrite-dependent anaerobic methane oxidation as a previously overlooked microbial methane sink in wetlands.

    PubMed

    Hu, Bao-lan; Shen, Li-dong; Lian, Xu; Zhu, Qun; Liu, Shuai; Huang, Qian; He, Zhan-fei; Geng, Sha; Cheng, Dong-qing; Lou, Li-ping; Xu, Xiang-yang; Zheng, Ping; He, Yun-feng

    2014-03-25

    The process of nitrite-dependent anaerobic methane oxidation (n-damo) was recently discovered and shown to be mediated by "Candidatus Methylomirabilis oxyfera" (M. oxyfera). Here, evidence for n-damo in three different freshwater wetlands located in southeastern China was obtained using stable isotope measurements, quantitative PCR assays, and 16S rRNA and particulate methane monooxygenase gene clone library analyses. Stable isotope experiments confirmed the occurrence of n-damo in the examined wetlands, and the potential n-damo rates ranged from 0.31 to 5.43 nmol CO2 per gram of dry soil per day at different depths of soil cores. A combined analysis of 16S rRNA and particulate methane monooxygenase genes demonstrated that M. oxyfera-like bacteria were mainly present in the deep soil with a maximum abundance of 3.2 × 10(7) gene copies per gram of dry soil. It is estimated that ∼0.51 g of CH4 m(-2) per year could be linked to the n-damo process in the examined wetlands based on the measured potential n-damo rates. This study presents previously unidentified confirmation that the n-damo process is a previously overlooked microbial methane sink in wetlands, and n-damo has the potential to be a globally important methane sink due to increasing nitrogen pollution. PMID:24616523

  17. Climatic thresholds for pedogenic iron oxides under aerobic conditions: Processes and their significance in paleoclimate reconstruction

    NASA Astrophysics Data System (ADS)

    Long, Xiaoyong; Ji, Junfeng; Barrón, Vidal; Torrent, José

    2016-10-01

    Iron oxides are widely distributed across the surface of the Earth as a result of the aerobic weathering of primary Fe-bearing minerals. Pedogenic iron oxides which consist mainly of hematite (Hm), goethite (Gt), maghemite (Mgh), are often concentrated synchronously in aerobic soils under low to moderate rainfall regimes. Magnetic susceptibility (χ) and redness, which respectively reflect the content of Mgh and Hm in soils, are considered reasonable pedogenic and climatic indicators in soil taxonomy and paleorainfall reconstruction. However, under high rainfall regimes, the grain growth of Mgh and transformation to Hm, combined with the prior formation of Gt under conditions of high relative humidity (RH), can result in magnetic reduction and dramatic yellowing of soils and sediments, which explains the existence of rainfall thresholds for Mgh and Hm at a large scale even before the pedogenic environment turns anaerobic. In order to capture the rainfall thresholds for Mgh and Hm occurring under aerobic conditions, we explored a tropical transect across a granitic region where the soil color turned from red to yellow under a wide rainfall range of 900-2200 mm/yr and a corresponding mean annual RH range of 77%-85%. We observed a lower rainfall threshold of ∼1500 mm/yr and a corresponding RH ∼80% for Mgh and Hm along this transect, as well as a higher rainfall threshold of ∼1700 mm/yr and a corresponding RH of ∼81% for Gt and total pedogenic iron oxides (citrate/bicarbonate/dithionite-extractable Fe, Fed). Cross-referencing with comparable studies in temperate and subtropical regions, we noted that the rainfall or RH thresholds for Fed and Hm or Mgh likewise increase with temperature. Moreover, the different thresholds for total and individual iron oxide phase indicates that a negative correlation between chemical weathering intensity and redness or χ in sediment sequences can occur under the prevalent climate regime just between their thresholds. Finally

  18. High reactivity of nanosized niobium oxide cluster cations in methane activation: A comparison with vanadium oxides

    SciTech Connect

    Ding, Xun-Lei E-mail: chemzyx@iccas.ac.cn; Wang, Dan; Wu, Xiao-Nan; Li, Zi-Yu; Zhao, Yan-Xia E-mail: chemzyx@iccas.ac.cn; He, Sheng-Gui

    2015-09-28

    The reactions between methane and niobium oxide cluster cations were studied and compared to those employing vanadium oxides. Hydrogen atom abstraction (HAA) reactions were identified over stoichiometric (Nb{sub 2}O{sub 5}){sub N}{sup +} clusters for N as large as 14 with a time-of-flight mass spectrometer. The reactivity of (Nb{sub 2}O{sub 5}){sub N}{sup +} clusters decreases as the N increases, and it is higher than that of (V {sub 2}O{sub 5}){sub N}{sup +} for N ≥ 4. Theoretical studies were conducted on (Nb{sub 2}O{sub 5}){sub N}{sup +} (N = 2–6) by density functional calculations. HAA reactions on these clusters are all favorable thermodynamically and kinetically. The difference of the reactivity with respect to the cluster size and metal type (Nb vs V) was attributed to thermodynamics, kinetics, the electron capture ability, and the distribution of the unpaired spin density. Nanosized Nb oxide clusters show higher HAA reactivity than V oxides, indicating that niobia may serve as promising catalysts for practical methane conversion.

  19. Promotion by tetrachloromethane of the oxidative coupling of methane on silica-supported alkaline earth oxides

    SciTech Connect

    Ahmed, S.; Moffat, J.B. )

    1990-02-01

    The introduction of a small quantity of tetrachloromethane (TEM) into the feed stream has been shown to remarkably enhance the oxidative coupling of methane over alkaline earth oxides supported on silica. That this enhancement, in terms of both selectivity and yield to C{sub 2} hydrocarbons, occurs over a wide range of catalyst loading, feed composition, reaction temperature, and contact time has been illustrated using BaO/SiO{sub 2} as the catalyst. It has been demonstrated that over this catalyst, the coupling and nonselective oxidation processes occur predominantly independently of each other. The high ratio of C{sub 2}H{sub 4}/C{sub 2}H{sub 6} observed in the products is accounted for by the rapid homogeneous oxidative dehydrogenation of C{sub 2}H{sub 6}, a process which is evidently further enhanced by the presence of TCM. It is suggested that TCM promotes the coupling reaction by facilitating the hydrogen abstraction step from methane. Continuous cofeeding of the additive is required to maintain high selectivity and yield of C{sub 2} hydrocarbons in the products.

  20. High reactivity of nanosized niobium oxide cluster cations in methane activation: A comparison with vanadium oxides.

    PubMed

    Ding, Xun-Lei; Wang, Dan; Wu, Xiao-Nan; Li, Zi-Yu; Zhao, Yan-Xia; He, Sheng-Gui

    2015-09-28

    The reactions between methane and niobium oxide cluster cations were studied and compared to those employing vanadium oxides. Hydrogen atom abstraction (HAA) reactions were identified over stoichiometric (Nb2O5)N(+) clusters for N as large as 14 with a time-of-flight mass spectrometer. The reactivity of (Nb2O5)N(+) clusters decreases as the N increases, and it is higher than that of (V 2O5)N(+) for N ≥ 4. Theoretical studies were conducted on (Nb2O5)N(+) (N = 2-6) by density functional calculations. HAA reactions on these clusters are all favorable thermodynamically and kinetically. The difference of the reactivity with respect to the cluster size and metal type (Nb vs V) was attributed to thermodynamics, kinetics, the electron capture ability, and the distribution of the unpaired spin density. Nanosized Nb oxide clusters show higher HAA reactivity than V oxides, indicating that niobia may serve as promising catalysts for practical methane conversion. PMID:26429016

  1. Unexpected Microbial Diversity in Anaerobically Methane-oxidizing Mats of the Black Sea

    NASA Astrophysics Data System (ADS)

    Friedrich, M. W.; Pommerenke, B.; Seifert, R.; Krueger, M.

    2007-12-01

    Sediments of the Black Sea harbour consortia of anaerobically methane-oxidizing microorganisms in dense microbial mats, incrusted in large chimney structures consisting of carbonate precipitate. A number of convincing facts collected previously suggests that anaerobically methane-oxidizing Archaea (ANME) as well as delta- proteobacterial sulphate-reducing bacteria are the key players in anaerobic methane oxidation in Black Sea Mats: their presence has been shown by fluorescent-in-situ hybridization (FISH) with 16S rRNA-targeting probes, lipid biomarkers have typical, low delta13C ratios in archaeal and bacterial lipids, a methyl coenzyme M reductase-like protein was purified from the mat, and mat samples exhibit anaerobic methane oxidation. Here, we show that the diversity of Bacteria in both, pink and black mat samples, is larger than previously known. T-RFLP analysis of 16S rRNA and 16S rRNA genes and cloning and sequencing of randomly selected clones revealed the presence of taxa hitherto unknown to be present in anaerobically methane-oxidizing consortia. Besides the previously known delta-proteobacterial sulphate reducers, clones fell into 7 and 5 different phyla in pink and black coloured mats, respectively. Our findings suggest that the turnover of carbon in anaerobically methane-oxidizing communities might involve a larger diversity of microorganisms than was previously assumed.

  2. Methane and nitrous oxide emissions of China: Sources from agricultural systems and mitigation options

    SciTech Connect

    Lin Erda; Li Yue; Dong Hongmin; Zhou Wennong

    1994-12-31

    This paper reports the estimated results of methane and nitrous oxide emissions from China`s agricultural systems. The results show that the overall methane emissions from paddies and ruminants were 11.335 and 5.796 Tg/y, respectively in 1990. For mitigation options, based on some experiments, a number of options were recommended to reduce methane and nitrous oxide emissions. Several research priority areas were proposed to reduce the uncertainties in estimates they are: (1) improve measurement methods; (2) further identify controlling factors; and (3) develop simulation models.

  3. Modeling of simultaneous anaerobic methane and ammonium oxidation in a membrane biofilm reactor.

    PubMed

    Chen, Xueming; Guo, Jianhua; Shi, Ying; Hu, Shihu; Yuan, Zhiguo; Ni, Bing-Jie

    2014-08-19

    Nitrogen removal by using the synergy of denitrifying anaerobic methane oxidation (DAMO) and anaerobic ammonium oxidation (Anammox) microorganisms in a membrane biofilm reactor (MBfR) has previously been demonstrated experimentally. In this work, a mathematical model is developed to describe the simultaneous anaerobic methane and ammonium oxidation by DAMO and Anammox microorganisms in an MBfR for the first time. In this model, DAMO archaea convert nitrate, both externally fed and/or produced by Anammox, to nitrite, with methane as the electron donor. Anammox and DAMO bacteria jointly remove the nitrite fed/produced, with ammonium and methane as the electron donor, respectively. The model is successfully calibrated and validated using the long-term (over 400 days) dynamic experimental data from the MBfR, as well as two independent batch tests at different operational stages of the MBfR. The model satisfactorily describes the methane oxidation and nitrogen conversion data from the system. Modeling results show the concentration gradients of methane and nitrogen would cause stratification of the biofilm, where Anammox bacteria mainly grow in the biofilm layer close to the bulk liquid and DAMO organisms attach close to the membrane surface. The low surface methane loadings result in a low fraction of DAMO microorganisms, but the high surface methane loadings would lead to overgrowth of DAMO bacteria, which would compete with Anammox for nitrite and decrease the fraction of Anammox bacteria. The results suggest an optimal methane supply under the given condition should be applied not only to benefit the nitrogen removal but also to avoid potential methane emissions. PMID:25055054

  4. Extreme (13)C depletion of carbonates formed during oxidation of biogenic methane in fractured granite.

    PubMed

    Drake, Henrik; Åström, Mats E; Heim, Christine; Broman, Curt; Åström, Jan; Whitehouse, Martin; Ivarsson, Magnus; Siljeström, Sandra; Sjövall, Peter

    2015-01-01

    Precipitation of exceptionally 13C-depleted authigenic carbonate is a result of, and thus a tracer for, sulphate-dependent anaerobic methane oxidation, particularly in marine sediments. Although these carbonates typically are less depleted in 13C than in the source methane, because of incorporation of C also from other sources, they are far more depleted in 13C (δ13C as light as -69‰ V-PDB) than in carbonates formed where no methane is involved. Here we show that oxidation of biogenic methane in carbon-poor deep groundwater in fractured granitoid rocks has resulted in fracture-wall precipitation of the most extremely 13C-depleted carbonates ever reported, δ13C down to -125‰ V-PDB. A microbial consortium of sulphate reducers and methane oxidizers has been involved, as revealed by biomarker signatures in the carbonates and S-isotope compositions of co-genetic sulphide. Methane formed at shallow depths has been oxidized at several hundred metres depth at the transition to a deep-seated sulphate-rich saline water. This process is so far an unrecognized terrestrial sink of methane. PMID:25948095

  5. [Acclimatization and characteristics of microbial community in sulphate-dependent anaerobic methane oxidation].

    PubMed

    Xi, Jing-Ru; Liu, Su-Qin; Li, Lin; Liu, Jun-Xin

    2014-12-01

    The greenhouse effect of methane is 26 times worse than that of carbon dioxide, and wastewater containing high concentrations of sulfate is harmful to water, soil and plants. Therefore, anaerobic oxidation of methane driven by sulfate is one of the effective ways for methane reduction. In this paper, with sulfate as the electron accepter, a microbial consortium capable of oxidating methane under anaerobic condition was cultured. The diversity and characteristics of bacterial and archaeal community were investigated by PCR-DGGE, and phylogenetic analysis of the dominant microorganisms was also carried out. The DGGE fingerprints showed that microbial community structure changed distinctly, and the abundance of methane-oxidizing archea and sulfate-reducing bacteria increased in the acclimatization system added sulfate. After acclimatization, the bacterial diversity increased, while archaea diversity decreased slightly. The representative bands in the DGGE profiles were excised and sequenced. Results indicated that the dominant species in the acclimatization system were Spirochaetes, Desulfuromonadales, Methanosarcinales, Methanosaeta. Methane converted into carbon dioxide while sulfate transformed into hydrogen sulfide and sulfur in the process of anaerobic methane oxidation accompanied by sulphate reduction.

  6. Extreme (13)C depletion of carbonates formed during oxidation of biogenic methane in fractured granite.

    PubMed

    Drake, Henrik; Åström, Mats E; Heim, Christine; Broman, Curt; Åström, Jan; Whitehouse, Martin; Ivarsson, Magnus; Siljeström, Sandra; Sjövall, Peter

    2015-05-07

    Precipitation of exceptionally 13C-depleted authigenic carbonate is a result of, and thus a tracer for, sulphate-dependent anaerobic methane oxidation, particularly in marine sediments. Although these carbonates typically are less depleted in 13C than in the source methane, because of incorporation of C also from other sources, they are far more depleted in 13C (δ13C as light as -69‰ V-PDB) than in carbonates formed where no methane is involved. Here we show that oxidation of biogenic methane in carbon-poor deep groundwater in fractured granitoid rocks has resulted in fracture-wall precipitation of the most extremely 13C-depleted carbonates ever reported, δ13C down to -125‰ V-PDB. A microbial consortium of sulphate reducers and methane oxidizers has been involved, as revealed by biomarker signatures in the carbonates and S-isotope compositions of co-genetic sulphide. Methane formed at shallow depths has been oxidized at several hundred metres depth at the transition to a deep-seated sulphate-rich saline water. This process is so far an unrecognized terrestrial sink of methane.

  7. Extreme 13C depletion of carbonates formed during oxidation of biogenic methane in fractured granite

    PubMed Central

    Drake, Henrik; Åström, Mats E.; Heim, Christine; Broman, Curt; Åström, Jan; Whitehouse, Martin; Ivarsson, Magnus; Siljeström, Sandra; Sjövall, Peter

    2015-01-01

    Precipitation of exceptionally 13C-depleted authigenic carbonate is a result of, and thus a tracer for, sulphate-dependent anaerobic methane oxidation, particularly in marine sediments. Although these carbonates typically are less depleted in 13C than in the source methane, because of incorporation of C also from other sources, they are far more depleted in 13C (δ13C as light as −69‰ V-PDB) than in carbonates formed where no methane is involved. Here we show that oxidation of biogenic methane in carbon-poor deep groundwater in fractured granitoid rocks has resulted in fracture-wall precipitation of the most extremely 13C-depleted carbonates ever reported, δ13C down to −125‰ V-PDB. A microbial consortium of sulphate reducers and methane oxidizers has been involved, as revealed by biomarker signatures in the carbonates and S-isotope compositions of co-genetic sulphide. Methane formed at shallow depths has been oxidized at several hundred metres depth at the transition to a deep-seated sulphate-rich saline water. This process is so far an unrecognized terrestrial sink of methane. PMID:25948095

  8. Uncertainty quantification in the catalytic partial oxidation of methane

    NASA Astrophysics Data System (ADS)

    Navalho, Jorge E. P.; Pereira, José M. C.; Ervilha, Ana R.; Pereira, José C. F.

    2013-12-01

    This work focuses on uncertainty quantification of eight random parameters required as input for 1D modelling of methane catalytic partial oxidation within a highly dense foam reactor. Parameters related to geometrical properties, reactor thermophysics and catalyst loading are taken as uncertain. A widely applied 1D heterogeneous mathematical model that accounts for proper transport and surface chemistry steps is considered for the evaluation of deterministic samples. The non-intrusive spectral projection approach based on polynomial chaos expansion is applied to determine the stochastic temperature and species profiles along the reactor axial direction as well as their ensemble mean and error bars with a confidence interval of 95%. Probability density functions of relevant variables in specific reactor sections are also analysed. A different contribution is noticed from each random input to the total uncertainty range. Porosity, specific surface area and catalyst loading appear as the major sources of uncertainty to bulk gas and surface temperature and species molar profiles. Porosity and the mean pore diameter have an important impact on the pressure drop along the whole reactor as expected. It is also concluded that any trace of uncertainty in the eight input random variables can be almost dissipated near the catalyst outlet section for a long-enough catalyst, mainly due to the approximation to thermodynamic equilibrium.

  9. Mechanisms and controlling characteristics of the catalytic oxidation of methane

    SciTech Connect

    Klier, K.

    1990-01-01

    Progress has included (1) construction and installation of an ultraviolet photoelectron spectrometer (UPS) with power supply and pumping system that has been added as an attachment to the SCIENTA ESCA-300 instrument, (2) modification of the high resolution electron energy loss spectrometer (HREELS) to produce a stable ultra high vacuum (UHV) environment for initial experiments with a Pd(311) single crystal, (3) construction of a separate high vacuum system for preparation of surface doped model catalysts by chemical vapor deposition and pretreatment of a Pd(100) single crystal in this system, (4) carried out detailed experiments of methane activation and oxidation on Pd(679) using a high pressure reaction cell contained in a third ultra high vacuum system, (5) completion of adsorption/desorption studies of H{sub 2}, CO, and O{sub 2} on Pd(679), (6) utilized angle-resolved XPS to probe the diffraction characteristics and structure of the Pd(100) surface, (7) determination of the electronic surface structure of Pd(100) using angle-resolved UPS, and (8) computational analysis of oxygen overlayers on the PD(100) surface. Each of these is discussed in further detail below.

  10. Nitrous oxide and methane emissions from cryptogamic covers.

    PubMed

    Lenhart, Katharina; Weber, Bettina; Elbert, Wolfgang; Steinkamp, Jörg; Clough, Tim; Crutzen, Paul; Pöschl, Ulrich; Keppler, Frank

    2015-10-01

    Cryptogamic covers, which comprise some of the oldest forms of terrestrial life on Earth (Lenton & Huntingford, ), have recently been found to fix large amounts of nitrogen and carbon dioxide from the atmosphere (Elbert et al., ). Here we show that they are also greenhouse gas sources with large nitrous oxide (N2 O) and small methane (CH4 ) emissions. Whilst N2 O emission rates varied with temperature, humidity, and N deposition, an almost constant ratio with respect to respiratory CO2 emissions was observed for numerous lichens and bryophytes. We employed this ratio together with respiration data to calculate global and regional N2 O emissions. If our laboratory measurements are typical for lichens and bryophytes living on ground and plant surfaces and scaled on a global basis, we estimate a N2 O source strength of 0.32-0.59 Tg year(-1) for the global N2 O emissions from cryptogamic covers. Thus, our emission estimate might account for 4-9% of the global N2 O budget from natural terrestrial sources. In a wide range of arid and forested regions, cryptogamic covers appear to be the dominant source of N2 O. We suggest that greenhouse gas emissions associated with this source might increase in the course of global change due to higher temperatures and enhanced nitrogen deposition.

  11. Nitrous oxide and methane emissions from cryptogamic covers.

    PubMed

    Lenhart, Katharina; Weber, Bettina; Elbert, Wolfgang; Steinkamp, Jörg; Clough, Tim; Crutzen, Paul; Pöschl, Ulrich; Keppler, Frank

    2015-10-01

    Cryptogamic covers, which comprise some of the oldest forms of terrestrial life on Earth (Lenton & Huntingford, ), have recently been found to fix large amounts of nitrogen and carbon dioxide from the atmosphere (Elbert et al., ). Here we show that they are also greenhouse gas sources with large nitrous oxide (N2 O) and small methane (CH4 ) emissions. Whilst N2 O emission rates varied with temperature, humidity, and N deposition, an almost constant ratio with respect to respiratory CO2 emissions was observed for numerous lichens and bryophytes. We employed this ratio together with respiration data to calculate global and regional N2 O emissions. If our laboratory measurements are typical for lichens and bryophytes living on ground and plant surfaces and scaled on a global basis, we estimate a N2 O source strength of 0.32-0.59 Tg year(-1) for the global N2 O emissions from cryptogamic covers. Thus, our emission estimate might account for 4-9% of the global N2 O budget from natural terrestrial sources. In a wide range of arid and forested regions, cryptogamic covers appear to be the dominant source of N2 O. We suggest that greenhouse gas emissions associated with this source might increase in the course of global change due to higher temperatures and enhanced nitrogen deposition. PMID:26152454

  12. Methanobactin and the Link between Copper and Bacterial Methane Oxidation.

    PubMed

    DiSpirito, Alan A; Semrau, Jeremy D; Murrell, J Colin; Gallagher, Warren H; Dennison, Christopher; Vuilleumier, Stéphane

    2016-06-01

    Methanobactins (mbs) are low-molecular-mass (<1,200 Da) copper-binding peptides, or chalkophores, produced by many methane-oxidizing bacteria (methanotrophs). These molecules exhibit similarities to certain iron-binding siderophores but are expressed and secreted in response to copper limitation. Structurally, mbs are characterized by a pair of heterocyclic rings with associated thioamide groups that form the copper coordination site. One of the rings is always an oxazolone and the second ring an oxazolone, an imidazolone, or a pyrazinedione moiety. The mb molecule originates from a peptide precursor that undergoes a series of posttranslational modifications, including (i) ring formation, (ii) cleavage of a leader peptide sequence, and (iii) in some cases, addition of a sulfate group. Functionally, mbs represent the extracellular component of a copper acquisition system. Consistent with this role in copper acquisition, mbs have a high affinity for copper ions. Following binding, mbs rapidly reduce Cu(2+) to Cu(1+). In addition to binding copper, mbs will bind most transition metals and near-transition metals and protect the host methanotroph as well as other bacteria from toxic metals. Several other physiological functions have been assigned to mbs, based primarily on their redox and metal-binding properties. In this review, we examine the current state of knowledge of this novel type of metal-binding peptide. We also explore its potential applications, how mbs may alter the bioavailability of multiple metals, and the many roles mbs may play in the physiology of methanotrophs. PMID:26984926

  13. Effects of 17β-estradiol pollution on water microbial methane oxidation activity.

    PubMed

    Ruan, Aidong; Zong, Fengjiao; Zhao, Ying; Liu, Chenxiao; Chen, Jing

    2014-04-01

    17β-estradiol (17β-E2), a widespread and natural estrogen in the environment, has imposed a serious threat to the safety and function of aquatic ecosystems because of worsening pollution and high potential toxicity. In the present study, the authors focus on the impact of 17β-E2 pollution on water microbial methane oxidation function. The authors investigated the mechanism of its influence on water microbial activity and discuss the growth rate of methane-oxidizing bacteria. The results showed that 17β-E2 could significantly inhibit the function of water microbial methane oxidation. When 17β-E2 concentration was ≥ 5 ng L(-1) , the methane oxidation rate increased with increasing 17β-E2 and finally settled to a constant value. Furthermore, the authors found no significant linear correlation between 17β-E2 concentrations and its methane oxidation rate. However, increasing 17β-E2 dramatically improved water microbial community activity, because a significant or highly significant promotion in the generation rate of CO2 was measured. Moreover, within a certain period of time and at certain concentrations, positive linear correlation existed between water CO2 generation rate and 17β-E2 concentrations. In addition, the growth rate of culturable methane-oxidizing bacteria was promoted when 17β-E2 pollution concentration from 2 ng L(-1) to 20 ng L(-1) . Therefore, 17β-E2 pollution can inhibit microbial methane oxidation function in water, which indirectly promotes the release of water methane and directly contributes to the rate of water-generated and released CO2 . Specifically, 17β-E2 pollution can promote water emissions of greenhouse gases. Environ

  14. Molecular Engineering of Trifunctional Supported Catalysts for the Aerobic Oxidation of Alcohols.

    PubMed

    Fernandes, Antony E; Riant, Olivier; Jensen, Klavs F; Jonas, Alain M

    2016-09-01

    We describe a simple and general method for the preparation and molecular engineering of supported trifunctional catalysts and their application in the representative Cu/TEMPO/NMI-catalyzed aerobic oxidation of benzyl alcohol. The methodology allows in one single step to immobilize, with precise control of surface composition, both pyta, Cu(I) , TEMPO, and NMI sites on azide-functionalized silica particles. To optimize the performance of the heterogeneous trifunctional catalysts, synergistic interactions are finely engineered through modulating the degree of freedom of the imidazole site as well as tuning the relative surface composition, leading to catalysts with an activity significantly superior to the corresponding homogeneous catalytic system.

  15. Molecular Engineering of Trifunctional Supported Catalysts for the Aerobic Oxidation of Alcohols.

    PubMed

    Fernandes, Antony E; Riant, Olivier; Jensen, Klavs F; Jonas, Alain M

    2016-09-01

    We describe a simple and general method for the preparation and molecular engineering of supported trifunctional catalysts and their application in the representative Cu/TEMPO/NMI-catalyzed aerobic oxidation of benzyl alcohol. The methodology allows in one single step to immobilize, with precise control of surface composition, both pyta, Cu(I) , TEMPO, and NMI sites on azide-functionalized silica particles. To optimize the performance of the heterogeneous trifunctional catalysts, synergistic interactions are finely engineered through modulating the degree of freedom of the imidazole site as well as tuning the relative surface composition, leading to catalysts with an activity significantly superior to the corresponding homogeneous catalytic system. PMID:27430481

  16. Oxidative Coupling of Methane over Li/MgO: Catalyst and Nanocatalyst Performance

    NASA Astrophysics Data System (ADS)

    Farsi, Ali; Moradi, Ali; Ghader, Sattar; Shadravan, Vahid

    2011-02-01

    The Li/MgO catalyst and nanocatalyst were prepared by the incipient wetness impregnation and sol-gel method, respectively. The catalytic performance of the Li/MgO catalyst and nanocatalyst on oxidative coupling of methane was compared. The catalysts prepared in two ways were characterized by X-ray powder diffraction, Brunauer-Emmett-Teller surface and transmission electron microscope. The catalyst was tested at temperature of 973-1073 K with constant total pressure of 101 kPa. Experimental results showed that Li/MgO nanocatalyst in the oxidative coupling of methane would result in higher conversion of methane, higher selectivity, and higher yield of main products (ethane and ethylene) compared to ordinary catalyst. The results show the improved influence of nanoscale Li/MgO catalyst performance on oxidative coupling of methane.

  17. Pd/Cu-cocatalyzed aerobic oxidative carbonylative homocoupling of arylboronic acids and CO: a highly selective approach to diaryl ketones.

    PubMed

    Ren, Long; Jiao, Ning

    2014-09-01

    A highly selective Pd/Cu-cocatalyzed aerobic oxidative carbonylative homocoupling of arylboronic acids has been developed. This method employs a simple catalytic system, readily available boronic acids as the substrates, molecular oxygen as the oxidant, and 1 atm of CO/O2 , which makes this method practical for further applications. PMID:24990473

  18. [Effects of methane stress on oxidation rates and microbial community structures in different landfill cover soils].

    PubMed

    He, Ruo; Jiang, Chen-jing; Wang, Jing; Gao, Qing-jun; Shen, Dong-sheng

    2008-12-01

    As compared with the ordinary landfill cover material, clay soil, the effect of methane stress on oxidation rate and microbial community structure was investigated in waste soil (material from biologically treated municipal solid waste). The results showed that the moisture content of the clay soil was low, due to the low water retaining capacity. As environmental temperature and rainfall changed, the clay soil caked and inhibited methanotrophs growth. However, with a high organic matter, water-holding capacity and porosity, the waste soil provided a favor condition for methanotrophs growth and propagation. After exposure to methane flow for 120 days, methane oxidation potential in the middle and bottom layers of the waste soil column increased to 11.25-13.48 micromol/(g x h), which was 10.4-24.5 times higher than that in clay soil column. The topsoils were both found to be dried and inhibit methane oxidation. Methane oxidation (removal) efficiency by the waste soil column reached 48.3% at the end of the experiment, which was 5-6 times higher than that by the clay soil column. The amounts of the phospholipid fatty acid (PLFA) biomarks 16:1 omega 8c and 18:1 omega 8c for Type I and II methanotrophs, respectively, showed that a strong linear relationship was observed between methane oxidation potential and PLFA 18:1 omega 8c content in soil samples. PMID:19256403

  19. Modeling of simultaneous denitrification--anaerobic digestion--organic matter aerobic oxidation and nitrification in an anoxic-anaerobic-aerobic compact filter reactor.

    PubMed

    Moya, Jaime; Huiliñir, César; Peredo, Karol; Aspé, Estrella; Roeckel, Marlene

    2012-08-31

    A mathematical model was developed for a compact anoxic-anaerobic-aerobic filter reactor with liquid recirculation for the treatment of fishing effluents. The model includes denitrification, anaerobic digestion, aerobic carbon oxidation and nitrification steps, as well as an evaluation of the liquid gas mass transfer and pH. The model was calibrated using one experimental condition at a recycling ratio (R)=10, and was validated with R equal to 2 and 0, with an organic concentration of 554±24 mg TOCL(-1), salinity of 24 g L(-1) and hydraulic retention time (HRT) of 2 d. Carbon total removal is higher than 98%, while maximum nitrogen removal is 62% using total nitrification in the aerobic zone, due to a higher quantity of NO(x) produced which were recirculated to the anoxic zone. In the aerobic zone, simultaneous nitrification and denitrification processes occur, because the diffusion limitations cause a low oxygen penetration in the biofilm. In the anoxic-anaerobic zone, denitrification or methanogenesis inhibition by DO (caused by the recycled oxygen) is not observed.

  20. Assessment of methane generation, oxidation, and emission in a subtropical landfill test cell.

    PubMed

    Moreira, João M L; Candiani, Giovano

    2016-08-01

    This paper presents results of a methane balance assessment in a test cell built in a region with a subtropical climate near São Paulo, Brazil. Measurements and calculations were carried out to obtain the total methane emission to the atmosphere, the methane oxidation rate in the cover, and the total methane generation rate in the test cell. The oxidation rate was obtained through a calculation scheme based on a vertical one-dimensional methane transport in the cover region. The measured maximum and mean methane fluxes to the atmosphere were 124.4 and 15.87 g m(-2) d(-1), respectively. The total methane generation rate obtained for the test cell was 0.0380 ± 0.0075 mol s(-1). The results yielded that 69 % of the emitted methane occurred through the central well and 31 % through the cover interface with the atmosphere. The evaluations of the methane oxidation fraction for localized conditions in the lateral embankment of the test cell yielded 0.36 ± 0.11, while for the whole test cell yielded 0.15 ± 0.10. These results conciliate localized and overall evaluations reported in the literature. The specific methane generation rate obtained for the municipal solid waste with an age of 410 days was 317 ± 62 mol year(-1) ton(-1). This result from the subtropical São Paulo region is lower than reported figures for tropical climates and higher than reported figures for temperate climates. PMID:27406209

  1. [Depth Profiles of Methane Oxidation Kinetics and the Related Methanotrophic Community in a Simulated Landfill Cover].

    PubMed

    Xing, Zhi-lin; Zhao, Tian-tao; Gao, Yan-hui; He, Zhi; Yang, Xu; Peng, Xu-ya

    2015-11-01

    Simulated landfill cover with real time online monitoring system was developed using cover soils. Then the system started and the concentrations of bio-gas in various depths were continuously monitored, and it was found that the system ran continually and stably after 2-3 h when methane flux changed. After that, the relationship between regularity of methane oxidation and methane flux in landfill cover was analyzed. The results indicated that concentration of oxygen decreased with increasing methane flux when the depth was deeper than 20 cm, and no obvious correlation between oxygen concentration in landfill cover surface and methane flux, however, methane oxidation rate showed positive correlation with methane flux in various depths (range of R2 was 0.851-0.999). Kinetics of CH4 oxidation in landfill cover was fitted by CH4 -O2 dual-substrate model (range of R2 was 0.902-0.955), the half-saturation constant K(m) increasing with depth was 0.157-0.729 in dynamic condition. Finally, methanotrophs community structure in original cover soil sample and that in simulated landfill cover were investigated by high-throughout sequencing technology, and the statistics indicated that the abundance and species of methanotrophs in simulated landfill cover significantly increased compared with those in original cover soil sample, and type I methanotrophs including Methylobacter and Methylophilaceae and type II methanotrophs Methylocystis were dominant species. PMID:26911022

  2. [Depth Profiles of Methane Oxidation Kinetics and the Related Methanotrophic Community in a Simulated Landfill Cover].

    PubMed

    Xing, Zhi-lin; Zhao, Tian-tao; Gao, Yan-hui; He, Zhi; Yang, Xu; Peng, Xu-ya

    2015-11-01

    Simulated landfill cover with real time online monitoring system was developed using cover soils. Then the system started and the concentrations of bio-gas in various depths were continuously monitored, and it was found that the system ran continually and stably after 2-3 h when methane flux changed. After that, the relationship between regularity of methane oxidation and methane flux in landfill cover was analyzed. The results indicated that concentration of oxygen decreased with increasing methane flux when the depth was deeper than 20 cm, and no obvious correlation between oxygen concentration in landfill cover surface and methane flux, however, methane oxidation rate showed positive correlation with methane flux in various depths (range of R2 was 0.851-0.999). Kinetics of CH4 oxidation in landfill cover was fitted by CH4 -O2 dual-substrate model (range of R2 was 0.902-0.955), the half-saturation constant K(m) increasing with depth was 0.157-0.729 in dynamic condition. Finally, methanotrophs community structure in original cover soil sample and that in simulated landfill cover were investigated by high-throughout sequencing technology, and the statistics indicated that the abundance and species of methanotrophs in simulated landfill cover significantly increased compared with those in original cover soil sample, and type I methanotrophs including Methylobacter and Methylophilaceae and type II methanotrophs Methylocystis were dominant species.

  3. Remarkable recovery and colonization behaviour of methane oxidizing bacteria in soil after disturbance is controlled by methane source only.

    PubMed

    Pan, Yao; Abell, Guy C J; Bodelier, Paul L E; Meima-Franke, Marion; Sessitsch, Angela; Bodrossy, Levente

    2014-08-01

    Little is understood about the relationship between microbial assemblage history, the composition and function of specific functional guilds and the ecosystem functions they provide. To learn more about this relationship we used methane oxidizing bacteria (MOB) as model organisms and performed soil microcosm experiments comprised of identical soil substrates, hosting distinct overall microbial diversities(i.e., full, reduced and zero total microbial and MOB diversities). After inoculation with undisturbed soil, the recovery of MOB activity, MOB diversity and total bacterial diversity were followed over 3 months by methane oxidation potential measurements and analyses targeting pmoA and 16S rRNA genes. Measurement of methane oxidation potential demonstrated different recovery rates across the different treatments. Despite different starting microbial diversities, the recovery and succession of the MOB communities followed a similar pattern across the different treatment microcosms. In this study we found that edaphic parameters were the dominant factor shaping microbial communities over time and that the starting microbial community played only a minor role in shaping MOB microbial community.

  4. Anaerobic oxidation of methane associated with sulfate reduction in a natural freshwater gas source

    PubMed Central

    Timmers, Peer HA; Suarez-Zuluaga, Diego A; van Rossem, Minke; Diender, Martijn; Stams, Alfons JM; Plugge, Caroline M

    2016-01-01

    The occurrence of anaerobic oxidation of methane (AOM) and trace methane oxidation (TMO) was investigated in a freshwater natural gas source. Sediment samples were taken and analyzed for potential electron acceptors coupled to AOM. Long-term incubations with 13C-labeled CH4 (13CH4) and different electron acceptors showed that both AOM and TMO occurred. In most conditions, 13C-labeled CO2 (13CO2) simultaneously increased with methane formation, which is typical for TMO. In the presence of nitrate, neither methane formation nor methane oxidation occurred. Net AOM was measured only with sulfate as electron acceptor. Here, sulfide production occurred simultaneously with 13CO2 production and no methanogenesis occurred, excluding TMO as a possible source for 13CO2 production from 13CH4. Archaeal 16S rRNA gene analysis showed the highest presence of ANME-2a/b (ANaerobic MEthane oxidizing archaea) and AAA (AOM Associated Archaea) sequences in the incubations with methane and sulfate as compared with only methane addition. Higher abundance of ANME-2a/b in incubations with methane and sulfate as compared with only sulfate addition was shown by qPCR analysis. Bacterial 16S rRNA gene analysis showed the presence of sulfate-reducing bacteria belonging to SEEP-SRB1. This is the first report that explicitly shows that AOM is associated with sulfate reduction in an enrichment culture of ANME-2a/b and AAA methanotrophs and SEEP-SRB1 sulfate reducers from a low-saline environment. PMID:26636551

  5. Anaerobic oxidation of methane associated with sulfate reduction in a natural freshwater gas source.

    PubMed

    Timmers, Peer Ha; Suarez-Zuluaga, Diego A; van Rossem, Minke; Diender, Martijn; Stams, Alfons Jm; Plugge, Caroline M

    2016-06-01

    The occurrence of anaerobic oxidation of methane (AOM) and trace methane oxidation (TMO) was investigated in a freshwater natural gas source. Sediment samples were taken and analyzed for potential electron acceptors coupled to AOM. Long-term incubations with (13)C-labeled CH4 ((13)CH4) and different electron acceptors showed that both AOM and TMO occurred. In most conditions, (13)C-labeled CO2 ((13)CO2) simultaneously increased with methane formation, which is typical for TMO. In the presence of nitrate, neither methane formation nor methane oxidation occurred. Net AOM was measured only with sulfate as electron acceptor. Here, sulfide production occurred simultaneously with (13)CO2 production and no methanogenesis occurred, excluding TMO as a possible source for (13)CO2 production from (13)CH4. Archaeal 16S rRNA gene analysis showed the highest presence of ANME-2a/b (ANaerobic MEthane oxidizing archaea) and AAA (AOM Associated Archaea) sequences in the incubations with methane and sulfate as compared with only methane addition. Higher abundance of ANME-2a/b in incubations with methane and sulfate as compared with only sulfate addition was shown by qPCR analysis. Bacterial 16S rRNA gene analysis showed the presence of sulfate-reducing bacteria belonging to SEEP-SRB1. This is the first report that explicitly shows that AOM is associated with sulfate reduction in an enrichment culture of ANME-2a/b and AAA methanotrophs and SEEP-SRB1 sulfate reducers from a low-saline environment. PMID:26636551

  6. Methane oxidation in landfill cover soils, is a 10% default value reasonable?

    PubMed

    Chanton, Jeffrey P; Powelson, David K; Green, Roger B

    2009-01-01

    We reviewed literature results from 42 determinations of the fraction of methane oxidized and 30 determinations of methane oxidation rate in a variety of soil types and landfill covers. Both column measurements and in situ field measurements were included. The means for the fraction of methane oxidized on transit across the soil covers ranged from 22 to 55% from clayey to sandy material. Mean values for oxidation rate ranged from 3.7 to 6.4 mol m(-2) d(-1) (52-102 g m(-2) d(-1)) for the different soil types. The overall mean fraction oxidized across all studies was 36% with a standard error of 6%. The overall mean oxidation rate across all studies was 4.5 mol m(-2) d(-1) +/- 1.0 (72 +/- 16 g m(-2)d(-1)). For the subset of 15 studies conducted over an annual cycle the fraction of methane oxidized ranged from 11 to 89% with a mean value of 35 +/- 6%, nearly identical to the overall mean. Nine of these studies were conducted in north Florida at 30 degrees N latitude and had a fraction oxidized of 27 +/- 4%. Five studies were conducted in northern Europe ( approximately 50-55 degrees N) and exhibited an average of 54 +/- 14%. One study, conducted in New Hampshire, had a value of 10%. The results indicate that the fraction of methane oxidized in landfill greater than the default value of 10%. Of the 42 determinations of methane oxidation reported, only four report values of 10% or less.

  7. Methane and nitrous oxide exchange over a managed hay meadow

    NASA Astrophysics Data System (ADS)

    Hörtnagl, L.; Wohlfahrt, G.

    2014-12-01

    The methane (CH4) and nitrous oxide (N2O) exchange of a temperate mountain grassland near Neustift, Austria, was measured during 2010-2012 over a time period of 22 months using the eddy covariance method. Exchange rates of both compounds at the site were low, with 97% of all half-hourly CH4 and N2O fluxes ranging between ±200 and ±50 ng m-2 s-1, respectively. The meadow acted as a sink for both compounds during certain time periods, but was a clear source of CH4 and N2O on an annual timescale. Therefore, both gases contributed to an increase of the global warming potential (GWP), effectively reducing the sink strength in terms of CO2 equivalents of the investigated grassland site. In 2011, our best guess estimate showed a net greenhouse gas (GHG) sink of -32 g CO2 equ. m-2 yr-1 for the meadow, whereby 55% of the CO2 sink strength of -71 g CO2 m-2 yr-1 was offset by CH4 (N2O) emissions of 7 (32) g CO2 equ. m-2 yr-1. When all data were pooled, the ancillary parameters explained 27 (42)% of observed CH4 (N2O) flux variability, and up to 62 (76)% on shorter timescales in-between management dates. In the case of N2O fluxes, we found the highest emissions at intermediate soil water contents and at soil temperatures close to 0 or above 14 °C. In comparison to CO2, H2O and energy fluxes, the interpretation of CH4 and N2O exchange was challenging due to footprint heterogeneity regarding their sources and sinks, uncertainties regarding post-processing and quality control. Our results emphasize that CH4 and N2O fluxes over supposedly well-aerated and moderately fertilized soils cannot be neglected when evaluating the GHG impact of temperate managed grasslands.

  8. Oxidation-reduction processes in ice swimmers after ice-cold water bath and aerobic exercise.

    PubMed

    Sutkowy, Paweł; Woźniak, Alina; Boraczyński, Tomasz; Boraczyński, Michał; Mila-Kierzenkowska, Celestyna

    2015-06-01

    The effect of an ice-cold water (ICW) bath as a recovery intervention from aerobic exercise on the oxidant-antioxidant balance in healthy ice swimmers was determined. Twenty ice swimmers aged 31.2 ± 6.3 years performed a 30-min cycloergometer exercise test at room temperature (20°C, RT), followed by recovery at RT or in a pool of ice-cold water (ICW bath, 3°C, 5 min). Blood for laboratory assays was collected from the basilic vein two times: before the exercise (baseline) and 40 min after the RT or ICW recovery. The concentrations of plasma and erythrocytic thiobarbituric acid reactive substances (plTBARS and erTBARS, respectively), serum concentrations of 8-iso-prostaglandin F2α, 4-hydroxynonenal and malondialdehyde, along with the erythrocytic activities of catalase (CAT) and superoxide dismutase (SOD), as well as the serum level of total antioxidant capacity, were assessed. No statistically significant changes were observed. However, a statistically significant negative linear correlation between the erTBARS concentration and the SOD activity was found 40 min after the combination of exercise/RT recovery (r=-0.571, P<0.01). The baseline CAT and SOD activities were also linearly correlated (r=0.469, P<0.05). Both the 5-min ICW bath and the 30-min aerobic exercise have practically no impact on the oxidant-antioxidant balance in healthy ice swimmers.

  9. Oxidation-reduction processes in ice swimmers after ice-cold water bath and aerobic exercise.

    PubMed

    Sutkowy, Paweł; Woźniak, Alina; Boraczyński, Tomasz; Boraczyński, Michał; Mila-Kierzenkowska, Celestyna

    2015-06-01

    The effect of an ice-cold water (ICW) bath as a recovery intervention from aerobic exercise on the oxidant-antioxidant balance in healthy ice swimmers was determined. Twenty ice swimmers aged 31.2 ± 6.3 years performed a 30-min cycloergometer exercise test at room temperature (20°C, RT), followed by recovery at RT or in a pool of ice-cold water (ICW bath, 3°C, 5 min). Blood for laboratory assays was collected from the basilic vein two times: before the exercise (baseline) and 40 min after the RT or ICW recovery. The concentrations of plasma and erythrocytic thiobarbituric acid reactive substances (plTBARS and erTBARS, respectively), serum concentrations of 8-iso-prostaglandin F2α, 4-hydroxynonenal and malondialdehyde, along with the erythrocytic activities of catalase (CAT) and superoxide dismutase (SOD), as well as the serum level of total antioxidant capacity, were assessed. No statistically significant changes were observed. However, a statistically significant negative linear correlation between the erTBARS concentration and the SOD activity was found 40 min after the combination of exercise/RT recovery (r=-0.571, P<0.01). The baseline CAT and SOD activities were also linearly correlated (r=0.469, P<0.05). Both the 5-min ICW bath and the 30-min aerobic exercise have practically no impact on the oxidant-antioxidant balance in healthy ice swimmers. PMID:25910677

  10. Closing the Gaps in the Budgets of Methane and Nitrous Oxide

    SciTech Connect

    Khalil, Aslam; Rice, Andrew; Rasmussen, Reinhold

    2013-11-22

    Together methane and nitrous oxide contribute almost 40% of the estimated increase in radiative forcing caused by the buildup of greenhouse gases during the last 250 years (IPCC, 2007). These increases are attributed to human activities. Since the emissions of these gases are from biogenic sources and closely associated with living things in the major terrestrial ecosystems of the world, climate change is expected to cause feedbacks that may further increase emissions even from systems normally classified as natural. Our results support the idea that while past increases of methane were driven by direct emissions from human activities, some of these have reached their limits and that the future of methane changes may be determined by feedbacks from warming temperatures. The greatly increased current focus on the arctic and the fate of the carbon frozen in its permafrost is an example of such a feedback that could exceed the direct increases caused by future human activities (Zimov et al. 2006). Our research was aimed at three broad areas to address open questions about the global budgets of methane and nitrous oxide. These areas of inquiry were: The processes by which methane and nitrous oxide are emitted, new sources such as trees and plants, and integration of results to refine the global budgets both at present and of the past decades. For the process studies the main research was to quantify the effect of changes in the ambient temperature on the emissions of methane and nitrous oxide from rice agriculture. Additionally, the emissions of methane and nitrous oxide under present conditions were estimated using the experimental data on how fertilizer applications and water management affect emissions. Rice was chosen for detailed study because it is a prototype system of the wider terrestrial source, its role in methane emissions is well established, it is easy to cultivate and it represents a major anthropogenic source. Here we will discuss the highlights of the

  11. Growth and Methane Oxidation Rates of Anaerobic Methanotrophic Archaea in a Continuous-Flow Bioreactor

    PubMed Central

    Girguis, Peter R.; Orphan, Victoria J.; Hallam, Steven J.; DeLong, Edward F.

    2003-01-01

    Anaerobic methanotrophic archaea have recently been identified in anoxic marine sediments, but have not yet been recovered in pure culture. Physiological studies on freshly collected samples containing archaea and their sulfate-reducing syntrophic partners have been conducted, but sample availability and viability can limit the scope of these experiments. To better study microbial anaerobic methane oxidation, we developed a novel continuous-flow anaerobic methane incubation system (AMIS) that simulates the majority of in situ conditions and supports the metabolism and growth of anaerobic methanotrophic archaea. We incubated sediments collected from within and outside a methane cold seep in Monterey Canyon, Calif., for 24 weeks on the AMIS system. Anaerobic methane oxidation was measured in all sediments after incubation on AMIS, and quantitative molecular techniques verified the increases in methane-oxidizing archaeal populations in both seep and nonseep sediments. Our results demonstrate that the AMIS system stimulated the maintenance and growth of anaerobic methanotrophic archaea, and possibly their syntrophic, sulfate-reducing partners. Our data demonstrate the utility of combining physiological and molecular techniques to quantify the growth and metabolic activity of anaerobic microbial consortia. Further experiments with the AMIS system should provide a better understanding of the biological mechanisms of methane oxidation in anoxic marine environments. The AMIS may also enable the enrichment, purification, and isolation of methanotrophic archaea as pure cultures or defined syntrophic consortia. PMID:12957936

  12. Survey on Atmospheric Methane Oxidation in Young Glacier-Forefield Soils

    NASA Astrophysics Data System (ADS)

    Schroth, M. H.; Nauer, P.; Zeyer, J. A.

    2010-12-01

    The capacity of soils to act as a sink for atmospheric methane has been observed in a variety of environments. Atmospheric methane oxidation is mediated by thus far uncultivated methanotrophic bacteria, commonly termed “high-affinity” methanotrophs. Despite their ubiquity, relatively little is known about their activity and abundance in pioneer ecosystems and their role in primary succession. In alpine environments, receding glaciers provide a unique opportunity to investigate soil development and establishment of microbial communities. In a field survey we assayed the forefields of several Swiss glaciers for activity and abundance of high-affinity methanotrophs. The forefields differed in exposition, altitude, local climate and specific physical and geochemical parameters. At each forefield, sampling was performed at locations without vegetation cover where glacier retreat occurred less than 20 years ago. At each location we obtained a soil-air profile and collected soil for molecular-biological and chemical analyses. In addition, we quantified soil bulk density and water content to estimate the effective gas-diffusion coefficient of methane. Using this value we quantified rate coefficients of methane oxidation by fitting a diffusion-consumption model to soil-methane concentration data. At selected locations, we applied surface gas push-pull tests (GPPTs) to independently estimate first-order rate coefficients of methane oxidation. A top-closed steel cylinder previously emplaced in the soil was employed to allow for sufficiently long reaction times during GPPTs. To further increase the GPPTs’ sensitivity at locations with low activity, we injected 13C-methane and measured the evolution of δ13C of extracted carbon dioxide. We will present results from soil-methane concentration profiles and GPPTs, which indicated little methane oxidation activity in forefields on siliceous bedrock, but generally higher activity in forefields on calcareous bedrock, as well as

  13. Anaerobic Oxidation of Methane in Sediments of Two Boreal Lakes

    NASA Astrophysics Data System (ADS)

    Tiirola, M. A.; Rissanen, A. J.; Karvinen, A.; Nykänen, H.; Mpamah, P.; Peura, S.; Kankaala, P.

    2014-12-01

    In this study, potential for Anaerobic oxidation of methane (AOM) coupled with metal reduction was studied in boreal lake sediments. Slurries of sediment samples collected from two sites in southeastern Finland, i.e. from Lake Orivesi, Heposelkä, an vegetated littoral site, dominated by Phragmites australis (Sample Sa, sediment layer 0 - 25 cm) and from the profundal zone of a mesotrophic Lake Ätäskö (Aa, 0 - 10 cm; Ab, 10 - 30 cm; Ac, 90 - 130 cm), were incubated in laboratory in anaerobic conditions at in situ temperatures for up to 5 months. The samples were amended either 1) with 13CH4, 2) 13CH4 + manganese(IV) oxide (MnO2) or 3) 13CH4 + iron(III) hydroxide (Fe(OH)3), and the processes were measured by following the 13C transfer to the carbon dioxide (CO2) pool and by concentration measurements of CH4 and CO2. Changes in microbial communities were studied from DNA extracted from sediment samples before and after incubation period by next-generation sequencing (Ion Torrent) of polymerase chain reaction (PCR) - amplified bacterial and archaeal 16S rRNA and methyl coenzyme-M reductase gene (mcrA) amplicons. AOM took place in every sample except in deepest sample (Ac) with potential rates up to 2.1 nmol CH4 d-1 g-1wetsedim (~2 nmol d-1 cm-3) which are considerably lower than previously reported metal-driven AOM in marine sediments (10-40 nmol d-1 cm-3) but within a range of NO3- -driven AOM in an oligotrophic lake (0.6-3.6 nmol d-1 cm-3). AOM took place without metal additions but addition of Mn4+ increased the potential rates and this increase was especially high in 10-30 cm layer (Ab) of the profundal site (5-fold increase). The structure of the bacterial and archaeal communities changed considerably during incubation. Communities incubated with Mn4+ were especially different from those incubated with Fe3+ or without metals which were more similar with each other. Surprisingly, anaerobic methanotrophic archaea detected, ANME-2D and AOM-associated archaea (AAA

  14. Impact of oxidative stress defense on bacterial survival and morphological change in Campylobacter jejuni under aerobic conditions.

    PubMed

    Oh, Euna; McMullen, Lynn; Jeon, Byeonghwa

    2015-01-01

    Campylobacter jejuni, a microaerophilic foodborne pathogen, inescapably faces high oxygen tension during its transmission to humans. Thus, the ability of C. jejuni to survive under oxygen-rich conditions may significantly impact C. jejuni viability in food and food safety as well. In this study, we investigated the impact of oxidative stress resistance on the survival of C. jejuni under aerobic conditions by examining three mutants defective in key antioxidant genes, including ahpC, katA, and sodB. All the three mutants exhibited growth reduction under aerobic conditions compared to the wild-type (WT), and the ahpC mutant showed the most significant growth defect. The CFU reduction in the mutants was recovered to the WT level by complementation. Higher levels of reactive oxygen species were accumulated in C. jejuni under aerobic conditions than microaerobic conditions, and supplementation of culture media with an antioxidant recovered the growth of C. jejuni. The levels of lipid peroxidation and protein oxidation were significantly increased in the mutants compared to WT. Additionally, the mutants exhibited different morphological changes under aerobic conditions. The ahpC and katA mutants developed coccoid morphology by aeration, whereas the sodB mutant established elongated cellular morphology. Compared to microaerobic conditions, interestingly, aerobic culture conditions substantially induced the formation of coccoidal cells, and antioxidant treatment reduced the emergence of coccoid forms under aerobic conditions. The ATP concentrations and PMA-qPCR analysis supported that oxidative stress is a factor that induces the development of a viable-but-non-culturable state in C. jejuni. The findings in this study clearly demonstrated that oxidative stress resistance plays an important role in the survival and morphological changes of C. jejuni under aerobic conditions. PMID:25914692

  15. Soil fluxes of methane, nitrous oxide, and nitric oxide from aggrading forests in coastal Oregon

    USGS Publications Warehouse

    Erickson, Heather E.; Perakis, Steven S.

    2014-01-01

    Soil exchanges of greenhouse and other gases are poorly known for Pacific Northwest forests where gradients in nutrient availability and soil moisture may contribute to large variations in fluxes. Here we report fluxes of methane (CH4), nitrous oxide (N2O), and nitric oxide (NO) over multiple seasons from three naturally N-rich, aggrading forests of coastal Oregon, USA. Mean methane uptake rates (3.2 mg CH4 m−2 d−1) were high compared with forests globally, negatively related to water-filled pore space (WFPS), but unrelated to N availability or temperature. Emissions of NO (6.0 μg NO–N m−2 h−1) exceeded N2O (1.4 μg N2O–N m−2 h−1), except when WFPS surpassed 55%. Spatial variation in NO fluxes correlated positively with soil nitrate concentrations (which generally exceeded ammonium concentrations, indicating the overall high N status for the sites) and negatively with soil pH, and at one site increased with basal area of N2-fixing red alder. Combined NO and N2O emissions were greatest from the site with highest annual net N mineralization and lowest needle litterfall C/N. Our findings of high CH4 uptake and NO/N2O ratios generally >1 most likely reflect the high porosity of the andic soils underlying the widespread regenerating forests in this seasonally wet region.

  16. Antibacterial Action of Nitric Oxide-Releasing Chitosan Oligosaccharides against Pseudomonas aeruginosa under Aerobic and Anaerobic Conditions

    PubMed Central

    Reighard, Katelyn P.

    2015-01-01

    Chitosan oligosaccharides were modified with N-diazeniumdiolates to yield biocompatible nitric oxide (NO) donor scaffolds. The minimum bactericidal concentrations and MICs of the NO donors against Pseudomonas aeruginosa were compared under aerobic and anaerobic conditions. Differential antibacterial activities were primarily the result of NO scavenging by oxygen under aerobic environments and not changes in bacterial physiology. Bacterial killing was also tested against nonmucoid and mucoid biofilms and compared to that of tobramycin. Smaller NO payloads were required to eradicate P. aeruginosa biofilms under anaerobic versus aerobic conditions. Under oxygen-free environments, the NO treatment was 10-fold more effective at killing biofilms than tobramycin. These results demonstrate the potential utility of NO-releasing chitosan oligosaccharides under both aerobic and anaerobic environments. PMID:26239983

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

    PubMed

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

    2015-11-01

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

  18. Osmium(ii) complexes for light-driven aerobic oxidation of amines to imines.

    PubMed

    Li, Yong-Hui; Liu, Xiao-Le; Yu, Zhen-Tao; Li, Zhao-Sheng; Yan, Shi-Cheng; Chen, Guang-Hui; Zou, Zhi-Gang

    2016-08-01

    Herein, we describe the synthesis and characterization of three Os(ii) complexes (i.e., [Os(fptz)2(PPhMe2)2] (1, fptzH = 3-trifluoromethyl-5-pyridyl-1,2,4-triazole), [Os(fptz)2(CO)(L1)] (2, L1 = PPh3; 3, L1 = pyridine)) that have been successfully utilized as good photocatalysts to promote aerobic oxidative coupling of amines to imines with molecular oxygen in air as a green oxidant. Complex 1 is the most effective catalyst for the oxidative coupling of benzylamine with molecular O2 (air) as the oxidant because of the complex's strong absorption of visible light and long-lived triplet state. The application of a low catalyst loading (0.06 mol%) of complex 1 to the oxidative coupling of a wide range of amines affords the corresponding imines efficiently and selectively in most cases. The reaction mechanism was investigated via relevant control and quenching experiments. The results indicated that the reaction occurs via an active (1)O2-involved pathway. The (1)O2-generating ability of complex 1 as a photosensitizer was evaluated using 9,10-dimethylanthracene (DMA) as a chemical trap for (1)O2. PMID:27431765

  19. Steam Methane Reformation Testing for Air-Independent Solid Oxide Fuel Cell Systems

    NASA Technical Reports Server (NTRS)

    Mwara, Kamwana N.

    2015-01-01

    Recently, NASA has been looking into utilizing landers that can be propelled by LOX-CH (sub 4), to be used for long duration missions. Using landers that utilize such propellants, also provides the opportunity to use solid oxide fuel cells as a power option, especially since they are able to process methane into a reactant through fuel reformation. One type of reformation, called steam methane reformation, is a process to reform methane into a hydrogen-rich product by reacting methane and steam (fuel cell exhaust) over a catalyst. A steam methane reformation system could potentially use the fuel cell's own exhaust to create a reactant stream that is hydrogen-rich, and requires less internal reforming of the incoming methane. Also, steam reformation may hold some advantages over other types of reforming, such as partial oxidation (PROX) reformation. Steam reformation does not require oxygen, while up to 25 percent can be lost in PROX reformation due to unusable CO (sub 2) reformation. NASA's Johnson Space Center has conducted various phases of steam methane reformation testing, as a viable solution for in-space reformation. This has included using two different types of catalysts, developing a custom reformer, and optimizing the test system to find the optimal performance parameters and operating conditions.

  20. Methane Oxidation in Arctic Soils from High- and Flat-Centered Polygons

    NASA Astrophysics Data System (ADS)

    Zheng, J.; Roy Chowdhury, T.; Yang, Z.; Gu, B.; Wullschleger, S. D.; Graham, D. E.

    2015-12-01

    The premise of global warming will cause deeper permafrost thawing, followed by increased carbon mineralization and CH4 formation in saturated tundra soils. Arctic tundra soils also serve as potential sinks for CH4 in response to warming temperature, which might be a key process in the global CH4 budget. Quantification of methane oxidation potential of Arctic tundra is an important component to constrain models assessing the Carbon-climate feedback from high latitude soils. The signature polygonal ground of Arctic tundra generates high level of heterogeneity in soil hydrology and soil thermal regime. Thus, two distinct polygonal features were investigated in this study to evaluate CH4 oxidation potentials under multiple biogeochemical controls. The rates, drivers, and temperature sensitivity of methane oxidation were compared between High- and Flat-Centered Polygons (HCP and FCP, respectively). A significant lag period of CO2 production was observed in soil microcosms from HCP center, which might be attributed to microbial biomass limitations and the slow growth of anaerobic microbial populations that were sensitive to freezing. Prolonged thawing significantly accelerated carbon mineralization and CH4 oxidation rates measured via methane oxidation assays (MOA) from both active and permafrost organic layers of HCP. Soil microcosms from FCP showed higher CO2 production and CH4 oxidation rates in the active organic layer, but not permafrost layer, which might be explained by the anoxic/oxic interface identified by Fe(II) content in active layer. MOAs with temperature manipulation demonstrated high temperature dependence of methane oxidation activity, mediated primarily by soluble methane monooxygenase based upon metagenomic analysis and PCR quantification. Future work will identify key variables controlling methane oxidation rate and develop parameterization that can be incorporated into Arctic terrestrial ecosystem models.

  1. Biogeochemical and Molecular Signatures of Anaerobic Methane Oxidation in a Marine Sediment

    PubMed Central

    Thomsen, Trine R.; Finster, Kai; Ramsing, Niels B.

    2001-01-01

    Anaerobic methane oxidation was investigated in 6-m-long cores of marine sediment from Aarhus Bay, Denmark. Measured concentration profiles for methane and sulfate, as well as in situ rates determined with isotope tracers, indicated that there was a narrow zone of anaerobic methane oxidation about 150 cm below the sediment surface. Methane could account for 52% of the electron donor requirement for the peak sulfate reduction rate detected in the sulfate-methane transition zone. Molecular signatures of organisms present in the transition zone were detected by using selective PCR primers for sulfate-reducing bacteria and for Archaea. One primer pair amplified the dissimilatory sulfite reductase (DSR) gene of sulfate-reducing bacteria, whereas another primer (ANME) was designed to amplify archaeal sequences found in a recent study of sediments from the Eel River Basin, as these bacteria have been suggested to be anaerobic methane oxidizers (K. U. Hinrichs, J. M. Hayes, S. P. Sylva, P. G. Brewer, and E. F. DeLong, Nature 398:802–805, 1999). Amplification with the primer pairs produced more amplificate of both target genes with samples from the sulfate-methane transition zone than with samples from the surrounding sediment. Phylogenetic analysis of the DSR gene sequences retrieved from the transition zone revealed that they all belonged to a novel deeply branching lineage of diverse DSR gene sequences not related to any previously described DSR gene sequence. In contrast, DSR gene sequences found in the top sediment were related to environmental sequences from other estuarine sediments and to sequences of members of the genera Desulfonema, Desulfococcus, and Desulfosarcina. Phylogenetic analysis of 16S rRNA sequences obtained with the primers targeting the archaeal group of possible anaerobic methane oxidizers revealed two clusters of ANME sequences, both of which were affiliated with sequences from the Eel River Basin. PMID:11282617

  2. Effect of acetylene and ammonia as reburn fuel additions to methane in nitric oxide reburning

    SciTech Connect

    Kumpaty, S.K.; Nokku, V.P.; Subramanian, K.

    1996-12-31

    Presented in this paper are the computational results of NO reburning with (a) a combination of methane and acetylene and (b) a combination of methane and ammonia. An updated reaction mechanism that was more comprehensive in terms of predicting the ammonia and isocyanic acid oxidation chemistry was employed to run the CKINTERP program. Using the binary file created by executing the above program and the input stoichiometric ratio conditions, the CHEMKIN package predicted the exit concentrations of various species involved in NO reburning.

  3. Thermodynamic Study of Transformation of Methane to Synthesis Gas Over Metal Oxides

    NASA Astrophysics Data System (ADS)

    Roohi, P.; Alizadeh, R.; Fatehifar, E.

    2015-01-01

    A metal oxide reduction-water splitting cycle is a new developing method to produce synthesis gas without using a catalyst. In the reduction stage, metal oxide reduction and methane activation are combined in an efficient and energy-saving process using methane as a reducing agent. In this study, the effect of temperature and reductant (oxidant) amount on the equilibrium composition of products, graphitic carbon formation, yield of synthesis gas (water splitting stage), and produced ratio are thermodynamically investigated. This investigation includes metal oxides of zinc, tin, cobalt, and nickel. The results show that the synthesis gas is produced simultaneously with gaseous zinc, molten tin, solid cobalt, and solid nickel for those metal oxides in the reduction process. In the case of tin oxide, the feasibility of the graphitic carbon formation is less than the other oxides. The maximum yield of synthesis gas occurs in the stoichiometric molar ratio of methanothermal reduction reactions. From the methane consumption point of view, zinc oxide has a much higher synthesis gas yield. Finally, it is proposed that cobalt and nickel oxides can be used only in the reduction stage to produce synthesis gas and reduced metals due to low equilibrium conversion in the water splitting stage. The metal oxide reduction-water splitting cycle can be developed as an environmentally friendly technology for synthesis gas production over metal oxides.

  4. Anaerobic Oxidation of Methane at a Marine Methane Seep in a Forearc Sediment Basin off Sumatra, Indian Ocean

    PubMed Central

    Siegert, Michael; Krüger, Martin; Teichert, Barbara; Wiedicke, Michael; Schippers, Axel

    2011-01-01

    A cold methane seep was discovered in a forearc sediment basin off the island Sumatra, exhibiting a methane-seep adapted microbial community. A defined seep center of activity, like in mud volcanoes, was not discovered. The seep area was rather characterized by a patchy distribution of active spots. The relevance of anaerobic oxidation of methane (AOM) was reflected by 13C-depleted isotopic signatures of dissolved inorganic carbon. The anaerobic conversion of methane to CO2 was confirmed in a 13C-labeling experiment. Methane fueled a vital microbial community with cell numbers of up to 4 × 109 cells cm−3 sediment. The microbial community was analyzed by total cell counting, catalyzed reporter deposition–fluorescence in situ hybridization (CARD–FISH), quantitative real-time PCR (qPCR), and denaturing gradient gel electrophoresis (DGGE). CARD–FISH cell counts and qPCR measurements showed the presence of Bacteria and Archaea, but only small numbers of Eukarya. The archaeal community comprised largely members of ANME-1 and ANME-2. Furthermore, members of the Crenarchaeota were frequently detected in the DGGE analysis. Three major bacterial phylogenetic groups (δ-Proteobacteria, candidate division OP9, and Anaerolineaceae) were abundant across the study area. Several of these sequences were closely related to the genus Desulfococcus of the family Desulfobacteraceae, which is in good agreement with previously described AOM sites. In conclusion, the majority of the microbial community at the seep consisted of AOM-related microorganisms, while the relevance of higher hydrocarbons as microbial substrates was negligible. PMID:22207865

  5. KetoABNO/NOx Cocatalytic Aerobic Oxidation of Aldehydes to Carboxylic Acids and Access to α-Chiral Carboxylic Acids via Sequential Asymmetric Hydroformylation/Oxidation.

    PubMed

    Miles, Kelsey C; Abrams, M Leigh; Landis, Clark R; Stahl, Shannon S

    2016-08-01

    A method for aerobic oxidation of aldehydes to carboxylic acids has been developed using organic nitroxyl and NOx cocatalysts. KetoABNO (9-azabicyclo[3.3.1]nonan-3-one N-oxyl) and NaNO2 were identified as the optimal nitroxyl and NOx sources, respectively. The mildness of the reaction conditions enables sequential asymmetric hydroformylation of alkenes/aerobic aldehyde oxidation to access α-chiral carboxylic acids without racemization. The scope, utility, and limitations of the oxidation method are further evaluated with a series of achiral aldehydes bearing diverse functional groups.

  6. Aerobic addition of secondary phosphine oxides to vinyl sulfides: a shortcut to 1-hydroxy-2-(organosulfanyl)ethyl(diorganyl)phosphine oxides

    PubMed Central

    Malysheva, Svetlana F; Artem’ev, Alexander V; Gusarova, Nina K; Belogorlova, Nataliya A; Albanov, Alexander I; Liu, C W

    2015-01-01

    Summary Secondary phosphine oxides react with vinyl sulfides (both alkyl- and aryl-substituted sulfides) under aerobic and solvent-free conditions (80 °C, air, 7–30 h) to afford 1-hydroxy-2-(organosulfanyl)ethyl(diorganyl)phosphine oxides in 70–93% yields. PMID:26664618

  7. Effect of trichloroethylene and tetrachloroethylene on methane oxidation and community structure of methanotrophic consortium.

    PubMed

    Choi, Sun-Ah; Lee, Eun-Hee; Cho, Kyung-Suk

    2013-01-01

    The methane oxidation rate and community structure of a methanotrophic consortium were analyzed to determine the effects of trichloroethylene (TCE) and tetrachloroethylene (PCE) on methane oxidation. The maximum methane oxidation rate (Vmax ) of the consortium was 326.8 μmol·g-dry biomass(-1)·h(-1), and it had a half-saturation constant (Km ) of 143.8 μM. The addition of TCE or PCE resulted in decreased methane oxidation rates, which were decreased from 101.73 to 5.47-24.64 μmol·g-dry biomass(-1)·h(-1) with an increase in the TCE-to-methane ratio, and to 61.95-67.43 μmol·g-dry biomass(-1)·h(-1) with an increase in the PCE-to-methane ratio. TCE and PCE were non-competitive inhibitors for methane oxidation, and their inhibition constants (Ki ) were 33.4 and 132.0 μM, respectively. When the methanotrophic community was analyzed based on pmoA using quantitative real-time PCR (qRT-PCR), the pmoA gene copy numbers were shown to decrease from 7.3 ± 0.7 × 10(8) to 2.1-5.0 × 10(7) pmoA gene copy number · g-dry biomass(-1) with an increase in the TCE-to-methane ratio and to 2.5-7.0 × 10(7) pmoA gene copy number · g-dry biomass(-1) with an increase in the PCE-to-methane ratio. Community analysis by microarray demonstrated that Methylocystis (type II methanotrophs) were the most abundant in the methanotrophic community composition in the presence of TCE. These results suggest that toxic effects caused by TCE and PCE change not only methane oxidation rates but also the community structure of the methanotrophic consortium.

  8. Methane and nitrous oxide exchange over a managed hay meadow

    PubMed Central

    Hörtnagl, L.; Wohlfahrt, G.

    2015-01-01

    The methane (CH4) and nitrous oxide (N2O) exchange of a temperate mountain grassland near Neustift, Austria, was measured during 2010–2012 over a time period of 22 months using the eddy covariance method. Exchange rates of both compounds at the site were low, with 97% of all half-hourly CH4 and N2O fluxes ranging between ±200 and ±50 ng m−2 s−1, respectively. The meadow acted as a sink for both compounds during certain time periods, but was a clear source of CH4 and N2O on an annual timescale. Therefore, both gases contributed to an increase of the global warming potential (GWP), effectively reducing the sink strength in terms of CO2 equivalents of the investigated grassland site. In 2011, our best guess estimate showed a net greenhouse gas (GHG) sink of −32 g CO2 equ. m−2 yr−1 for the meadow, whereby 55% of the CO2 sink strength of −71 g CO2m−2 yr−1 was offset by CH4 (N2O) emissions of 7 (32) g CO2 equ. m−2 yr−1. When all data were pooled, the ancillary parameters explained 27 (42)% of observed CH4 (N2O) flux variability, and up to 62 (76)% on shorter timescales in-between management dates. In the case of N2O fluxes, we found the highest emissions at intermediate soil water contents and at soil temperatures close to 0 or above 14 °C. In comparison to CO2, H2O and energy fluxes, the interpretation of CH4 and N2O exchange was challenging due to footprint heterogeneity regarding their sources and sinks, uncertainties regarding post-processing and quality control. Our results emphasize that CH4 and N2O fluxes over supposedly well-aerated and moderately fertilized soils cannot be neglected when evaluating the GHG impact of temperate managed grasslands. PMID:25821473

  9. Methane and nitrous oxide exchange over a managed hay meadow

    NASA Astrophysics Data System (ADS)

    Hörtnagl, L.; Wohlfahrt, G.

    2014-06-01

    The methane (CH4) and nitrous oxide (N2O) exchange of a temperate mountain grassland near Neustift, Austria, was measured during 2010-2012 over a time period of 22 months using the eddy covariance method. Exchange rates of both compounds at the site were low, with more than 95% of the half-hourly fluxes of CH4 and N2O ranging between ±10 and ±1 nmol m-2 s-1, respectively. The meadow acted as a sink for both compounds during certain time periods, but was a clear source of CH4 and N2O on an annual time scale. Therefore, both gases contributed to an increase of the global warming potential (GWP), effectively reducing the sink strength in terms of CO2-equivalents of the investigated grassland site. In 2011, our best guess estimate showed a net GHG sink of -32 g CO2-equ. m-2 yr-1 for the meadow, whereby 55% of the CO2 sink strength of -71 g CO2 m-2 yr-1 was offset by CH4/N2O emissions of 7/32 g CO2-equ. m-2 yr-1. When all data were pooled, the ancillary parameters explained 26/38% of observed CH4/N2O flux variability, and up to 62/75% on shorter time scales in-between management dates. In case of N2O fluxes, we found highest emissions at intermediate soil water contents and at soil temperatures close to zero or above 14 °C. In comparison to CO2, H2O and energy fluxes, the interpretation of CH4 and N2O exchange was challenging due to footprint heterogeneity regarding their sources and sinks, uncertainties regarding post-processing and quality control. Our results emphasize that CH4 and N2O fluxes over supposedly well-aerated and moderately fertilized soils cannot be neglected when evaluating the GHG impact of temperate managed grasslands.

  10. Ammonia-oxidizing archaea use the most energy-efficient aerobic pathway for CO2 fixation.

    PubMed

    Könneke, Martin; Schubert, Daniel M; Brown, Philip C; Hügler, Michael; Standfest, Sonja; Schwander, Thomas; Schada von Borzyskowski, Lennart; Erb, Tobias J; Stahl, David A; Berg, Ivan A

    2014-06-01

    Archaea of the phylum Thaumarchaeota are among the most abundant prokaryotes on Earth and are widely distributed in marine, terrestrial, and geothermal environments. All studied Thaumarchaeota couple the oxidation of ammonia at extremely low concentrations with carbon fixation. As the predominant nitrifiers in the ocean and in various soils, ammonia-oxidizing archaea contribute significantly to the global nitrogen and carbon cycles. Here we provide biochemical evidence that thaumarchaeal ammonia oxidizers assimilate inorganic carbon via a modified version of the autotrophic hydroxypropionate/hydroxybutyrate cycle of Crenarchaeota that is far more energy efficient than any other aerobic autotrophic pathway. The identified genes of this cycle were found in the genomes of all sequenced representatives of the phylum Thaumarchaeota, indicating the environmental significance of this efficient CO2-fixation pathway. Comparative phylogenetic analysis of proteins of this pathway suggests that the hydroxypropionate/hydroxybutyrate cycle emerged independently in Crenarchaeota and Thaumarchaeota, thus supporting the hypothesis of an early evolutionary separation of both archaeal phyla. We conclude that high efficiency of anabolism exemplified by this autotrophic cycle perfectly suits the lifestyle of ammonia-oxidizing archaea, which thrive at a constantly low energy supply, thus offering a biochemical explanation for their ecological success in nutrient-limited environments.

  11. Ammonia-oxidizing archaea use the most energy-efficient aerobic pathway for CO2 fixation.

    PubMed

    Könneke, Martin; Schubert, Daniel M; Brown, Philip C; Hügler, Michael; Standfest, Sonja; Schwander, Thomas; Schada von Borzyskowski, Lennart; Erb, Tobias J; Stahl, David A; Berg, Ivan A

    2014-06-01

    Archaea of the phylum Thaumarchaeota are among the most abundant prokaryotes on Earth and are widely distributed in marine, terrestrial, and geothermal environments. All studied Thaumarchaeota couple the oxidation of ammonia at extremely low concentrations with carbon fixation. As the predominant nitrifiers in the ocean and in various soils, ammonia-oxidizing archaea contribute significantly to the global nitrogen and carbon cycles. Here we provide biochemical evidence that thaumarchaeal ammonia oxidizers assimilate inorganic carbon via a modified version of the autotrophic hydroxypropionate/hydroxybutyrate cycle of Crenarchaeota that is far more energy efficient than any other aerobic autotrophic pathway. The identified genes of this cycle were found in the genomes of all sequenced representatives of the phylum Thaumarchaeota, indicating the environmental significance of this efficient CO2-fixation pathway. Comparative phylogenetic analysis of proteins of this pathway suggests that the hydroxypropionate/hydroxybutyrate cycle emerged independently in Crenarchaeota and Thaumarchaeota, thus supporting the hypothesis of an early evolutionary separation of both archaeal phyla. We conclude that high efficiency of anabolism exemplified by this autotrophic cycle perfectly suits the lifestyle of ammonia-oxidizing archaea, which thrive at a constantly low energy supply, thus offering a biochemical explanation for their ecological success in nutrient-limited environments. PMID:24843170

  12. Aerobic exercise improves oxidant-antioxidant balance in patients with rheumatoid arthritis.

    PubMed

    Tuna, Zeynep; Duger, Tulin; Atalay-Guzel, Nevin; Aral, Arzu; Basturk, Bilkay; Haznedaroglu, Seminur; Goker, Berna

    2015-04-01

    [Purpose] Although oxidative stress is known to be present in rheumatoid arthritis (RA), the effects of exercise on oxidative parameters are unknown. The aim of this study was to investigate the effects of acute aerobic exercise on serum oxidant and antioxidant levels in patients with RA. [Subjects and Methods] Sixteen patients with RA and 10 age-matched healthy volunteers participated in this study. All participants wore polar telemeters and walked on a treadmill for 30 minutes at a speed eliciting 60-75% of maximal heart rates. Blood samples were obtained before, immediately and 24 hours after exercise and malondialdehyde (MDA) and total sulfhydrile group (RSH) levels were measured. [Results] Both groups had similar heart rates during the test but the treadmill speed of the RA patients was significantly lower than that of the healthy volunteers. Serum MDA levels were lower than in both groups immediately after exercise, with greater decrements in the RA patients than controls. MDA levels returned to baseline 24 hours after the exercise only in the controls; they remained low in the RA patients. There was a slight increase in serum RSH levels after exercise compared to baseline in both groups. [Conclusion] Moderate intensity treadmill exercise did not have any adverse effect on the oxidant-antioxidant balance. The results suggest that such an exercise may be safely added to the rehabilitation program of RA for additional antioxidant effects. Morever, this antioxidant environment is maintained longer in RA patients.

  13. Metabolic reprogramming during neuronal differentiation from aerobic glycolysis to neuronal oxidative phosphorylation

    PubMed Central

    Zheng, Xinde; Boyer, Leah; Jin, Mingji; Mertens, Jerome; Kim, Yongsung; Ma, Li; Ma, Li; Hamm, Michael; Gage, Fred H; Hunter, Tony

    2016-01-01

    How metabolism is reprogrammed during neuronal differentiation is unknown. We found that the loss of hexokinase (HK2) and lactate dehydrogenase (LDHA) expression, together with a switch in pyruvate kinase gene splicing from PKM2 to PKM1, marks the transition from aerobic glycolysis in neural progenitor cells (NPC) to neuronal oxidative phosphorylation. The protein levels of c-MYC and N-MYC, transcriptional activators of the HK2 and LDHA genes, decrease dramatically. Constitutive expression of HK2 and LDHA during differentiation leads to neuronal cell death, indicating that the shut-off aerobic glycolysis is essential for neuronal survival. The metabolic regulators PGC-1α and ERRγ increase significantly upon neuronal differentiation to sustain the transcription of metabolic and mitochondrial genes, whose levels are unchanged compared to NPCs, revealing distinct transcriptional regulation of metabolic genes in the proliferation and post-mitotic differentiation states. Mitochondrial mass increases proportionally with neuronal mass growth, indicating an unknown mechanism linking mitochondrial biogenesis to cell size. DOI: http://dx.doi.org/10.7554/eLife.13374.001 PMID:27282387

  14. Severe acute oxidant exposure: morphological damage and aerobic metabolism in the lung

    SciTech Connect

    Montgomery, M.R.; Teuscher, F.; LaSota, I.; Niewoehner, D.E.

    1986-09-01

    Groups of male rats were exposed to acute doses of oxygen, ozone, or paraquat which produced equivalent mortality (25-30%) over a 28 day post-exposure period. Quantitative evaluation of morphological changes indicated the primary response to be edema and inflammation with only slight fibrosis being apparent by the end of the observation period. Aerobic pulmonary metabolism was inhibited in lungs from animals exposed to oxygen and ozone as evidenced by decreased oxygen consumption; however, this was transient and O/sub 2/ consumption returned to normal within 24 hours after removal from the exposure chamber. Conversely, treatment with paraquat caused an immediate, transient stimulation of O/sub 2/ consumption. Glucose metabolism was unaltered by the gas exposures and, as previously reported, was initially stimulated by paraquat treatment. In vitro, only paraquat altered both O/sub 2/ consumption and glucose metabolism when added to lung slice preparations; ozone had no effect. Oxygen did not alter O/sub 2/ consumption but caused a slight biphasic response in glucose metabolism. Aerobic metabolism is relatively unchanged by these doses of oxygen and ozone which result in the death of 25-30% of all treated animals. Even though paraquat produces similar morphologic changes, it may represent a more severe metabolic insult than ''equivalent'' doses of oxygen or ozone. Also, if interstitial pulmonary fibrosis is a desired result of experimental exposure, rats may not be a suitable model for oxidant induced lung injury.

  15. Impact of aerobic and anaerobic exercise training on oxidative stress and antioxidant defense in athletes.

    PubMed

    Park, Song-Young; Kwak, Yi-Sub

    2016-04-01

    Exercise mediates an excessive free radical production leading to oxidative stress (OS). The body has natural antioxidant systems that help decrease OS, and these systems may be enhanced with exercise training. However, only a few studies have investigated the differences in resting OS and antioxidant capacity (AOC) between aerobically trained athletes (ET), anaerobically trained athletes (RT), and untrained individuals (UT). Therefore, this study sought to investigate the resting and postexercise OS and AOC in ET, RT, and UT. Sixty healthy young males (26.6±0.8 yr) participated in this study. Subjects were divided into three groups, ET, RT, and UT by distinct training background. Resting plasma malondialdehyde (MDA) and protein carbonyls (PC) were not significantly different in ET, RT, and UT. However, MDA and PC were significantly increased following a graded exercise test (GXT) in UT but not in ET and RT. Resting total antioxidant capacity (TAC) levels and TAC were not different in ET, RT, and UT. Interestingly, TAC levels significantly decreased after the GXT in all groups. Additionally, UT showed lower post-exercise TAC levels compared to ET and RT. These results showed that ET, RT, and UT have similar OS and AOC at rest. However, both ET and RT have greater AOC against exercise mediated OS compared to UT. These findings may explain, at least in part, why both aerobic and anaerobic types of exercise training improve redox balance. However, it appears there is no specific exercise type effect in terms of redox balance.

  16. Impact of aerobic and anaerobic exercise training on oxidative stress and antioxidant defense in athletes.

    PubMed

    Park, Song-Young; Kwak, Yi-Sub

    2016-04-01

    Exercise mediates an excessive free radical production leading to oxidative stress (OS). The body has natural antioxidant systems that help decrease OS, and these systems may be enhanced with exercise training. However, only a few studies have investigated the differences in resting OS and antioxidant capacity (AOC) between aerobically trained athletes (ET), anaerobically trained athletes (RT), and untrained individuals (UT). Therefore, this study sought to investigate the resting and postexercise OS and AOC in ET, RT, and UT. Sixty healthy young males (26.6±0.8 yr) participated in this study. Subjects were divided into three groups, ET, RT, and UT by distinct training background. Resting plasma malondialdehyde (MDA) and protein carbonyls (PC) were not significantly different in ET, RT, and UT. However, MDA and PC were significantly increased following a graded exercise test (GXT) in UT but not in ET and RT. Resting total antioxidant capacity (TAC) levels and TAC were not different in ET, RT, and UT. Interestingly, TAC levels significantly decreased after the GXT in all groups. Additionally, UT showed lower post-exercise TAC levels compared to ET and RT. These results showed that ET, RT, and UT have similar OS and AOC at rest. However, both ET and RT have greater AOC against exercise mediated OS compared to UT. These findings may explain, at least in part, why both aerobic and anaerobic types of exercise training improve redox balance. However, it appears there is no specific exercise type effect in terms of redox balance. PMID:27162773

  17. Anaerobic nitrite-dependent methane-oxidizing bacteria - novel participants in methane cycling of drained peatlands ecosystems

    NASA Astrophysics Data System (ADS)

    Kravchenko, Irina; Sukhacheva, Marina; Menko, Ekaterina; Sirin, Andrey

    2014-05-01

    Northern peatlands are one of the key sources of atmospheric methane. Process-based studies of methane dynamic are based on the hypothesis of the balance between microbial methane production and oxidation, but this doesn't explain all variations in and constraints on peatland CH4 emissions. One of the reasons for this discrepancy could be anaerobic methane oxidation (AOM) - the process which is still poorly studied and remained controversial. Very little is known about AOM in peatlands, where it could work as an important 'internal' sink for CH4. This lack of knowledge primarily originated from researchers who generally consider AOM quantitatively insignificant or even non-existent in northern peatland ecosystems. But not far ago, Smemo and Yavitt (2007) presented evidence for AOM in freshwater peatlands used indirect techniques including isotope dilution assays and selective methanogenic inhibitors. Nitrite-dependent anaerobic methane oxidation NC10 group bacteria (n-damo) were detected in a minerotrophic peatland in the Netherlands that is infiltrated by nitrate-rich ground water (Zhu et al., 2012). Present study represents the first, to our knowledge, characterization of AOM in human disturbed peatlands, including hydrological elements of artificial drainage network. The experiments were conducted with samples of peat from drained peatlands, as well as of water and bottom sediments of ditches from drained Dubnensky mire massif, Moscow region (Chistotin et al., 2006; Sirin et al., 2012). This is the key testing area of our research group in European part of Russia for the long-term greenhouse gases fluxes measurements supported by testing physicochemical parameters, intensity and genomic diversity of CH4-cycling microbial communities. Only in sediments of drainage ditches the transition anaerobic zone was found, where methane and nitrate occurred, suggested the possible ecological niche for n-damo bacteria. The NC10 group methanotrophs were analyzed by PCR

  18. Quantification of methane and nitrous oxide emissions from various waste treatment facilities by tracer dilution method

    NASA Astrophysics Data System (ADS)

    Mønster, Jacob; Rella, Chris; Jacobson, Gloria; Kjeldsen, Peter; Scheutz, Charlotte

    2013-04-01

    Urban activities generate solid and liquid waste, and the handling and aftercare of the waste results in the emission of various compounds into the surrounding environment. Some of these compounds are emitted as gasses into the atmosphere, including methane and nitrous oxide. Methane and nitrous oxide are strong greenhouse gases and are considered to have 25 and 298 times the greenhouse gas potential of carbon dioxide on a hundred years term (Solomon et al. 2007). Global observations of both gasses have shown increasing concentrations that significantly contribute to the greenhouse gas effect. Methane and nitrous oxide are emitted from both natural and anthropogenic sources and inventories of source specific fugitive emissions from the anthropogenic sources of methane and nitrous oxide of are often estimated on the basis of modeling and mass balance. Though these methods are well-developed, actual measurements for quantification of the emissions is a very useful tool for verifying the modeling and mass balance as well as for validation initiatives done for lowering the emissions of methane and nitrous oxide. One approach to performing such measurements is the tracer dilution method (Galle et al. 2001, Scheutz et al. 2011), where the exact location of the source is located and a tracer gas is released at this source location at a known flow. The ratio of downwind concentrations of the tracer gas and the methane and nitrous oxide gives the emissions rates of the greenhouse gases. This tracer dilution method can be performed using both stationary and mobile measurements and in both cases, real-time measurements of both tracer and quantified gas are required, placing high demands on the analytical detection method. To perform the methane and nitrous oxide measurements, two robust instruments capable of real-time measurements were used, based on cavity ring-down spectroscopy and operating in the near-infrared spectral region. One instrument measured the methane and

  19. Surface and bulk properties of stoichiometric and nonstoichiometric strontium hydroxyapatite and the oxidation of methane

    SciTech Connect

    Sugiyama, Shigeru; Minami, Toshimitsu; Hayashi, Hiromu

    1996-11-01

    The oxidation of methane on near-stoichiometric strontium hydroxyapatites pretreated at 873, 1048 and 1123 K in O{sub 2} has been examined in the presence and absence of tetrachloromethane (TCM) as a gas-phase additive at 973 K. Under these conditions, strontium hydroxyapatite, regardless of its stoichiometry, is converted, at least in part, to Sr{sub 3}(PO{sub 4}){sub 2}. On introduction of TCM to the feedstream, the selectivities to carbon monoxide, ethane, and ethylene are increased while the conversion of methane is decreased. Qualitatively similar effects of TCM on the oxidation were observed on Sr{sub 3}(PO{sub 4}){sub 2} prepared by an independent procedure. Strontium chlorapatite, formed from the apatites and phosphate during the oxidation in the presence of TCM, as shown from XRD, contributes to the increased selectivity to CO and decreased conversion of methane.

  20. Methane and nitrous oxide (N{sub 2}O) emission characteristics from automobiles

    SciTech Connect

    Koike, Noriyuki; Odaka, Matsuo

    1996-09-01

    Exhaust gases discharged from automobiles are noticed as one of the reasons for recent increase in atmospheric methane and nitrous oxide concentration, which have been considered as greenhouse gases. In order to make an accurate estimation of methane and nitrous oxide discharged from automobiles, measurement methods were experimentally developed and emissions were measured for different kinds of automobiles under various driving conditions. Then, the authors have tried to estimate the annual global emissions from automobiles using these measurement results and statistical data such as the number of automobiles, the total annual mileage, and the total annual fuel consumption, etc. The emissions from passenger vehicles which have been estimated from the global number of automobiles were 477.263 t/year for methane and 313.472 t/year for nitrous oxide. These numbers are higher than what had been estimated.

  1. Partial oxidation and dry reforming of methane over Ca/Ni/K(Na) catalysts

    SciTech Connect

    Shamsi, Abolghasem

    2006-07-01

    Partial oxidation and dry reforming of methane to synthesis gas over Ca/Ni/K(Na) catalysts have been studied. Effects of temperature, pressure, and oxygen/methane ratios on catalytic activity, selectivity, and carbon formation have been determined. Also reforming of 13CH4 in the presence of CO2 and Temperature-Programmed Oxidation (TPO) of deposited carbon after the reaction indicated that both methane and CO2 contribute to carbon formation. The TPO of deposited carbon on Ca/Ni/K catalyst showed that the catalyst consumed a significant amount of oxygen, only a fraction of which was consumed by carbon species on the surface, indicating that the surface oxygen plays a significant role in oxidizing and removing carbon species from the catalyst surfaces.

  2. Effect of Co/Ni ratios in cobalt nickel mixed oxide catalysts on methane combustion

    SciTech Connect

    Lim, Tae Hwan; Cho, Sung June; Yang, Hee Sung; Engelhard, Mark H.; Kim, Do Heui

    2015-07-31

    A series of cobalt nickel mixed oxide catalysts with the varying ratios of Co to Ni, prepared by co-precipitation method, were applied to methane combustion. Among the various ratios, cobalt nickel mixed oxides having the ratios of Co to Ni of (50:50) and (67:33) demonstrate the highest activity for methane combustion. Structural analysis obtained from X-ray diffraction (XRD) and extended X-ray absorption fine structure (EXAFS) evidently demonstrates that CoNi (50:50) and (67:33) samples consist of NiCo2O4and NiO phase and, more importantly, NiCo2O4spinel structure is largely distorted, which is attributed to the insertion of Ni2+ions into octahedral sites in Co3O4spinel structure. Such structural dis-order results in the enhanced portion of surface oxygen species, thus leading to the improved reducibility of the catalysts in the low temperature region as evidenced by temperature programmed reduction by hydrogen (H2TPR) and X-ray photoelectron spectroscopy (XPS) O 1s results. They prove that structural disorder in cobalt nickel mixed oxides enhances the catalytic performance for methane combustion. Thus, it is concluded that a strong relationship between structural property and activity in cobalt nickel mixed oxide for methane combustion exists and, more importantly, distorted NiCo2O4spinel structure is found to be an active site for methane combustion.

  3. Conversion of methane to methanol: nickel, palladium, and platinum (d9) cations as catalysts for the oxidation of methane by ozone at room temperature.

    PubMed

    Božović, Andrea; Feil, Stefan; Koyanagi, Gregory K; Viggiano, Albert A; Zhang, Xinhao; Schlangen, Maria; Schwarz, Helmut; Bohme, Diethard K

    2010-10-11

    The room-temperature chemical kinetics has been measured for the catalytic activity of Group 10 atomic cations in the oxidation of methane to methanol by ozone. Ni(+) is observed to be the most efficient catalyst. The complete catalytic cycle with Ni(+) is interpreted with a computed potential energy landscape and, in principle, has an infinite turnover number for the oxidation of methane, without poisoning side reactions. The somewhat lower catalytic activity of Pd(+) is reported for the first time and also explored with DFT calculations. Pt(+) is seen to be ineffective as a catalyst because of the observed failure of PtO(+) to convert methane to methanol. PMID:20827690

  4. Methane oxidation in Swedish landfills quantified with the stable carbon isotope technique in combination with an optical method for emitted methane.

    PubMed

    Börjesson, Gunnar; Samuelsson, Jerker; Chanton, Jeffrey

    2007-10-01

    Methane budgets (production = emissions + oxidation + recovery) were estimated for six landfill sites in Sweden. Methane oxidation was measured in downwind plumes with a stable isotope technique (Chanton, J. P., et al., Environ. Sci Technol. 1999, 33, 3755-3760.) Positions in plumes for isotope sampling as well as methane emissions were determined with an optical instrument (Fourier Transform InfraRed) in combination with N20 as tracer gas (Galle, B., et al., Environ. Sci Technol. 2001, 35, 21-25.) Two landfills had been closed for years prior to the measurements, while four were active. Measurements at comparable soil temperatures showed that the two closed landfills had a significantly higher fraction of oxidized methane (38-42% of emission) relative to the four active landfills (4.6-15% of emission). These results highlight the importance of installing and maintaining effective landfill covers and also indicate that substantial amounts of methane escape from active landfills. Based on these results we recommend that the IPCC default values for methane oxidation in managed landfills could be set to 10% for active sites and 20% for closed sites. Gas recovery was found to be highly variable at the different sites, with values from 14% up to 65% of total methane production. The variance can be attributed to different waste management practices. PMID:17969681

  5. Assessment of nitrous oxide and methane emissions for California agriculture

    NASA Astrophysics Data System (ADS)

    Horwath, W. R.; Burger, M.; Assa, Y.; Wilson, T. J.

    2012-12-01

    The California Global Warming Solutions Act of 2006 (AB 32) mandates comprehensive strategies to reduce nitrous oxide (N2O) and methane (CH4) emissions. In agriculture crop production, sources of N2O are related to nitrogen fertilization while CH4 emission is associated with rice production. More than half the GHG emissions from agriculture are attributed to N2O production. Currently, baseline N2O emission data for most cropping systems in the State is lacking. Estimates of CH4 emission in rice have been established from previous studies, but a lack of information exists for its expansion into the San Joaquin Delta to address subsidence issues. The paucity of N2O emission data has hampered biogeochemical modeling efforts. The objectives of this assessment are to (1) measure annual N2O and CH4 emissions for major California crops (vineyards, almonds, tomato, wheat, alfalfa, lettuce, and rice) under typical management practices, (2) characterize the effects of environmental factors on the temporal profile of N2O and CH4 emissions, and (3) determine N2O emission factors. The growth of rice in Delta peat soils produced highly variable CH4 emissions depending on tillage intensity. In 2010, standard tillage produced 184 kg CH4-C/ha while in 2011 after deep plowing placing rice residue deeper into the soil, only 26 kg CH4-C/ha was observed. In processing tomato systems, an average 2.5 kg N2O-N/ha was emitted with standard fertilization (160 kg N / ha), similar to background emissions and those from a drip irrigated system, while 4.0 to 5.8 kg N2O-N /ha y-1 was emitted at fertilizer rates of 225 and 300 kg N /ha (see Fig. 1 for example of temporal sources of emissions). About half the annual emissions were emitted within 3 d after the first seasonal rainfall event. In other tomato studies, estimated losses of fertilizer N as N2O were 0.38 ± 0.03 kg/ha y-1 in a drip irrigated system and 1.79 ± 0.21 kg/ha y-1 in furrow irrigated system, which was equivalent to 0.19% and 0

  6. Microcosm Approach to Understanding Methane-oxidizing Communities and the Role of Nitrogen Sources

    NASA Astrophysics Data System (ADS)

    Chistoserdova, L.; Hernandez, M. E.; Oshkin, I.

    2014-12-01

    We will report our observations on the dynamics of bacterial communities in response to methane and nitrate stimuli in laboratory microcosm incubations prepared with Lake Washington sediment samples. The experiments were designed to test our hypothesis of methane oxidation as a communal function, with the specific contents of the communities being determined by environmental factors such as oxygen concentration and the nature of the nitrogen source. We first measure taxonomic compositions of long-term oxygenated enrichment cultures and determine that, while dominated by Methylococcaceae bacteria, these cultures also contain accompanying types belonging to a limited number of bacterial taxa, both methylotrophs and non-methylotrophs. We then follow with the short-term community dynamics, under different oxygen tension regimens ('high' to 'low'), different nitrogen source regimens (added nitrate versus no nitrate) and different temperature ranges (10 to 30 oC). We observe rapid loss of species diversity in all incubations, but the composition of the communities depends on the specific environmental factors. Methylobacter represents the major methane-oxidizing partner in the communities incubated at low temperatures while Methylomonas and Methylocystis are more competitive at higher temperatures. All methanotrophs respond positively to nitrate. The non-methanotroph members of the communities reveal different trajectories in response to different oxygen tensions over time, with Methylotenera species persisting under 'low' and Methylophilus species persisting under 'high' oxygen tensions. Metagenomic sequencing reveals successions of different types of the major methane-oxidizing species as well as accompanying species. These types differ in their physiological details such as central carbon meand nitrate metabolism. A broad range of denitrifying capabilities in the organisms forming these stable methane-oxidizing communities is evident from genomic analysis. Our results

  7. Atmospheric oxygen levels, anaerobic methane oxidation, and the coupling of the global COS cycles by sulfate reduction

    NASA Astrophysics Data System (ADS)

    Wortmann, U. G.; Chernyavsky, B. M.

    2007-12-01

    Changes in the partitioning between the reduced and oxidized reservoirs of carbon and sulfur are the dominant control on atmospheric oxygen levels, and the partitioning itself depends to a large degree on microbial redox processes remineralizing organic matter (OM). However, the controls of organic matter preservation in marine sediments are one of the most complex and controversial issues in contemporary biochemistry. Knowledge how the transition from one electron acceptor to another affects OM remineralization rates is scant even for the transition from aerobic to anaerobic respiration. Much less is known about the transition from anaerobic respiration to fermentation. Although the individual pathways of methane generation are known, our understanding of the complex interactions between different bacterial groups remains limited, resulting in considerable difficulties to resolve these questions in microcosm experiments. Here we show that a dramatic drop in seawater sulfate concentrations during the Early Cretaceous (Wortmann & Chernyavsky, Nature 2007) resulted in a global breakdown of microbial sulfate reduction in the marine subsurface biosphere. This event resulted in a positive excursion of the global δ13C-value, suggesting that organic matter remineralization rates dropped by more than 50%. This implies that the methanogenic microbial community was unable to increase their metabolic rates, despite the increased supply of organic matter. the reduced availability of sulfate for anaerobic methane oxidation did not increase the flux of isotopically light carbon into the ocean/atmosphere system. We therefore speculate that the capacity of marine methanogenic ecosystems to synthesize extracellular enzymes to hydrolyze organic matter is specific to the prevailing type of organic matter. This results in a positive coupling of the metabolic activity of both ecosystems, which in turn is a necessary prerequisite to decouple reduced carbon and sulfur burial, a key

  8. Kinetics of biological methane oxidation in the presence of non-methane organic compounds in landfill bio-covers

    SciTech Connect

    Albanna, Muna; Warith, Mostafa; Fernandes, Leta

    2010-02-15

    In this experimental program, the effects of non-methane organic compounds (NMOCs) on the biological methane (CH{sub 4}) oxidation process were examined. The investigation was performed on compost experiments incubated with CH{sub 4} and selected NMOCs under different environmental conditions. The selected NMOCs had different concentrations and their effects were tested as single compounds and mixtures of compounds. The results from all experimental sets showed a decrease in CH{sub 4} oxidation capacity of the landfill bio-cover with the increase in NMOCs concentrations. For example, in the experiment using compost with 100% moisture content at 35 deg. C without any NMOCs the V{sub max} value was 35.0 mug CH{sub 4}h{sup -1}g{sub wetwt}{sup -1}. This value was reduced to 19.1 mug CH{sub 4}h{sup -1}g{sub wetwt}{sup -1} when mixed NMOCs were present in the batch reactors under the same environmental conditions. The experimental oxidation rates of CH{sub 4} in the presence of single and mixed NMOCs were modeled using the uncompetitive inhibition model and kinetic parameters, including the dissociation constants, were obtained. Additionally, the degradation rates of the NMOCs and co-metabolic abilities of methanotrophic bacteria were estimated.

  9. Aerobic and Anaerobic Thiosulfate Oxidation by a Cold-Adapted, Subglacial Chemoautotroph

    PubMed Central

    Harrold, Zoë R.; Skidmore, Mark L.; Hamilton, Trinity L.; Desch, Libby; Amada, Kirina; van Gelder, Will; Glover, Kevin; Roden, Eric E.

    2015-01-01

    Geochemical data indicate that protons released during pyrite (FeS2) oxidation are important drivers of mineral weathering in oxic and anoxic zones of many aquatic environments, including those beneath glaciers. Oxidation of FeS2 under oxic, circumneutral conditions proceeds through the metastable intermediate thiosulfate (S2O32−), which represents an electron donor capable of supporting microbial metabolism. Subglacial meltwaters sampled from Robertson Glacier (RG), Canada, over a seasonal melt cycle revealed concentrations of S2O32− that were typically below the limit of detection, despite the presence of available pyrite and concentrations of the FeS2 oxidation product sulfate (SO42−) several orders of magnitude higher than those of S2O32−. Here we report on the physiological and genomic characterization of the chemolithoautotrophic facultative anaerobe Thiobacillus sp. strain RG5 isolated from the subglacial environment at RG. The RG5 genome encodes genes involved with pathways for the complete oxidation of S2O32−, CO2 fixation, and aerobic and anaerobic respiration with nitrite or nitrate. Growth experiments indicated that the energy required to synthesize a cell under oxygen- or nitrate-reducing conditions with S2O32− as the electron donor was lower at 5.1°C than 14.4°C, indicating that this organism is cold adapted. RG sediment-associated transcripts of soxB, which encodes a component of the S2O32−-oxidizing complex, were closely affiliated with soxB from RG5. Collectively, these results suggest an active sulfur cycle in the subglacial environment at RG mediated in part by populations closely affiliated with RG5. The consumption of S2O32− by RG5-like populations may accelerate abiotic FeS2 oxidation, thereby enhancing mineral weathering in the subglacial environment. PMID:26712544

  10. Aerobic and Anaerobic Thiosulfate Oxidation by a Cold-Adapted, Subglacial Chemoautotroph.

    PubMed

    Harrold, Zoë R; Skidmore, Mark L; Hamilton, Trinity L; Desch, Libby; Amada, Kirina; van Gelder, Will; Glover, Kevin; Roden, Eric E; Boyd, Eric S

    2016-03-01

    Geochemical data indicate that protons released during pyrite (FeS2) oxidation are important drivers of mineral weathering in oxic and anoxic zones of many aquatic environments, including those beneath glaciers. Oxidation of FeS2 under oxic, circumneutral conditions proceeds through the metastable intermediate thiosulfate (S2O3 (2-)), which represents an electron donor capable of supporting microbial metabolism. Subglacial meltwaters sampled from Robertson Glacier (RG), Canada, over a seasonal melt cycle revealed concentrations of S2O3 (2-) that were typically below the limit of detection, despite the presence of available pyrite and concentrations of the FeS2 oxidation product sulfate (SO4 (2-)) several orders of magnitude higher than those of S2O3 (2-). Here we report on the physiological and genomic characterization of the chemolithoautotrophic facultative anaerobe Thiobacillus sp. strain RG5 isolated from the subglacial environment at RG. The RG5 genome encodes genes involved with pathways for the complete oxidation of S2O3 (2-), CO2 fixation, and aerobic and anaerobic respiration with nitrite or nitrate. Growth experiments indicated that the energy required to synthesize a cell under oxygen- or nitrate-reducing conditions with S2O3 (2-) as the electron donor was lower at 5.1°C than 14.4°C, indicating that this organism is cold adapted. RG sediment-associated transcripts of soxB, which encodes a component of the S2O3 (2-)-oxidizing complex, were closely affiliated with soxB from RG5. Collectively, these results suggest an active sulfur cycle in the subglacial environment at RG mediated in part by populations closely affiliated with RG5. The consumption of S2O3 (2-) by RG5-like populations may accelerate abiotic FeS2 oxidation, thereby enhancing mineral weathering in the subglacial environment. PMID:26712544

  11. Aerobic and Anaerobic Thiosulfate Oxidation by a Cold-Adapted, Subglacial Chemoautotroph.

    PubMed

    Harrold, Zoë R; Skidmore, Mark L; Hamilton, Trinity L; Desch, Libby; Amada, Kirina; van Gelder, Will; Glover, Kevin; Roden, Eric E; Boyd, Eric S

    2015-12-28

    Geochemical data indicate that protons released during pyrite (FeS2) oxidation are important drivers of mineral weathering in oxic and anoxic zones of many aquatic environments, including those beneath glaciers. Oxidation of FeS2 under oxic, circumneutral conditions proceeds through the metastable intermediate thiosulfate (S2O3 (2-)), which represents an electron donor capable of supporting microbial metabolism. Subglacial meltwaters sampled from Robertson Glacier (RG), Canada, over a seasonal melt cycle revealed concentrations of S2O3 (2-) that were typically below the limit of detection, despite the presence of available pyrite and concentrations of the FeS2 oxidation product sulfate (SO4 (2-)) several orders of magnitude higher than those of S2O3 (2-). Here we report on the physiological and genomic characterization of the chemolithoautotrophic facultative anaerobe Thiobacillus sp. strain RG5 isolated from the subglacial environment at RG. The RG5 genome encodes genes involved with pathways for the complete oxidation of S2O3 (2-), CO2 fixation, and aerobic and anaerobic respiration with nitrite or nitrate. Growth experiments indicated that the energy required to synthesize a cell under oxygen- or nitrate-reducing conditions with S2O3 (2-) as the electron donor was lower at 5.1°C than 14.4°C, indicating that this organism is cold adapted. RG sediment-associated transcripts of soxB, which encodes a component of the S2O3 (2-)-oxidizing complex, were closely affiliated with soxB from RG5. Collectively, these results suggest an active sulfur cycle in the subglacial environment at RG mediated in part by populations closely affiliated with RG5. The consumption of S2O3 (2-) by RG5-like populations may accelerate abiotic FeS2 oxidation, thereby enhancing mineral weathering in the subglacial environment.

  12. Methane-induced Activation Mechanism of Fused Ferric Oxide-Alumina Catalysts during Methane Decomposition.

    PubMed

    Reddy Enakonda, Linga; Zhou, Lu; Saih, Youssef; Ould-Chikh, Samy; Lopatin, Sergei; Gary, Daniel; Del-Gallo, Pascal; Basset, Jean-Marie

    2016-08-01

    Activation of Fe2 O3 -Al2 O3 with CH4 (instead of H2 ) is a meaningful method to achieve catalytic methane decomposition (CMD). This reaction of CMD is more economic and simple against commercial methane steam reforming (MSR) as it produces COx -free H2 . In this study, for the first time, structure changes of the catalyst were screened during CH4 reduction with time on stream. The aim was to optimize the pretreatment conditions through understanding the activation mechanism. Based on results from various characterization techniques, reduction of Fe2 O3 by CH4 proceeds in three steps: Fe2 O3 →Fe3 O4 →FeO→Fe0. Once Fe0 is formed, it decomposes CH4 with formation of Fe3 C, which is the crucial initiation step in the CMD process to initiate formation of multiwall carbon nanotubes. PMID:27345621

  13. Soluble porous coordination polymers by mechanochemistry: from metal-containing films/membranes to active catalysts for aerobic oxidation.

    PubMed

    Zhang, Pengfei; Li, Haiying; Veith, Gabriel M; Dai, Sheng

    2015-01-14

    Soluble porous coordination polymers from mechanochemical synthesis are presented through a coordination polymerization between highly contorted, rigid tetraphenol and a broad variety of transition metal ions. These polymers can be easily cast as metal-containing films or freestanding membranes. Importantly, as-made coordination polymers are highly active and stable in the aerobic oxidation of allylic C-H bonds. PMID:25389070

  14. Cu(II)-catalyzed esterification reaction via aerobic oxidative cleavage of C(CO)-C(alkyl) bonds.

    PubMed

    Ma, Ran; He, Liang-Nian; Liu, An-Hua; Song, Qing-Wen

    2016-02-01

    A novel Cu(II)-catalyzed aerobic oxidative esterification of simple ketones for the synthesis of esters has been developed with wide functional group tolerance. This process is assumed to go through a tandem sequence consisting of α-oxygenation/esterification/nucleophilic addition/C-C bond cleavage and carbon dioxide is released as the only byproduct.

  15. A template-free solvent-mediated synthesis of high surface area boron nitride nanosheets for aerobic oxidative desulfurization.

    PubMed

    Wu, Peiwen; Zhu, Wenshuai; Chao, Yanhong; Zhang, Jinshui; Zhang, Pengfei; Zhu, Huiyuan; Li, Changfeng; Chen, Zhigang; Li, Huaming; Dai, Sheng

    2016-01-01

    Hexagonal boron nitride nanosheets (h-BNNs) with rather high specific surface area (SSA) are important two-dimensional layer-structured materials. Here, a solvent-mediated synthesis of h-BNNs revealed a template-free lattice plane control strategy that induced high SSA nanoporous structured h-BNNs with outstanding aerobic oxidative desulfurization performance. PMID:26502800

  16. Oxidative stress in response to aerobic and anaerobic power testing: influence of exercise training and carnitine supplementation.

    PubMed

    Bloomer, Richard J; Smith, Webb A

    2009-01-01

    The purpose of this study is to compare the oxidative stress response to aerobic and anaerobic power testing, and to determine the impact of exercise training with or without glycine propionyl-L-carnitine (GPLC) in attenuating the oxidative stress response. Thirty-two subjects were assigned (double blind) to placebo, GPLC-1 (1g PLC/d), GPLC-3 (3g PLC/d) for 8 weeks, plus aerobic exercise. Aerobic (graded exercise test: GXT) and anaerobic (Wingate cycle) power tests were performed before and following the intervention. Blood was taken before and immediately following exercise tests and analyzed for malondialdehyde (MDA), hydrogen peroxide (H2O2), and xanthine oxidase activity (XO). No interaction effects were noted. MDA was minimally effected by exercise but lower at rest for both GPLC groups following the intervention (p = 0.044). A time main effect was noted for H2O2 (p = 0.05) and XO (p = 0.003), with values increasing from pre- to postexercise. Both aerobic and anaerobic power testing increase oxidative stress to a similar extent. Exercise training plus GPLC can decrease resting MDA, but it has little impact on exercise-induced oxidative stress biomarkers.

  17. Methane oxidation following submarine permafrost degradation: Measurements from a central Laptev Sea shelf borehole

    NASA Astrophysics Data System (ADS)

    Overduin, Pier Paul; Liebner, Susanne; Knoblauch, Christian; Günther, Frank; Wetterich, Sebastian; Schirrmeister, Lutz; Hubberten, Hans-Wolfgang; Grigoriev, Mikhail N.

    2015-05-01

    Submarine permafrost degradation has been invoked as a cause for recent observations of methane emissions from the seabed to the water column and atmosphere of the East Siberian shelf. Sediment drilled 52 m down from the sea ice in Buor Khaya Bay, central Laptev Sea revealed unfrozen sediment overlying ice-bonded permafrost. Methane concentrations in the overlying unfrozen sediment were low (mean 20 µM) but higher in the underlying ice-bonded submarine permafrost (mean 380 µM). In contrast, sulfate concentrations were substantially higher in the unfrozen sediment (mean 2.5 mM) than in the underlying submarine permafrost (mean 0.1 mM). Using deduced permafrost degradation rates, we calculate potential mean methane efflux from degrading permafrost of 120 mg m-2 yr-1 at this site. However, a drop of methane concentrations from 190 µM to 19 µM and a concomitant increase of methane δ13C from -63‰ to -35‰ directly above the ice-bonded permafrost suggest that methane is effectively oxidized within the overlying unfrozen sediment before it reaches the water column. High rates of methane ebullition into the water column observed elsewhere are thus unlikely to have ice-bonded permafrost as their source.

  18. Stimulation by ammonium-based fertilizers of methane oxidation in soil around rice roots.

    PubMed

    Bodelier, P L; Roslev, P; Henckel, T; Frenzel, P

    2000-01-27

    Methane is involved in a number of chemical and physical processes in the Earth's atmosphere, including global warming. Atmospheric methane originates mainly from biogenic sources, such as rice paddies and natural wetlands; the former account for at least 30% of the global annual emission of methane to the atmosphere. As an increase of rice production by 60% is the most appropriate way to sustain the estimated increase of the human population during the next three decades, intensified global fertilizer application will be necessary: but it is known that an increase of the commonly used ammonium-based fertilizers can enhance methane emission from rice agriculture. Approximately 10-30% of the methane produced by methanogens in rice paddies is consumed by methane-oxidizing bacteria associated with the roots of rice; these bacteria are generally thought to be inhibited by ammonium-based fertilizers, as was demonstrated for soils and sediments. In contrast, we show here that the activity and growth of such bacteria in the root zone of rice plants are stimulated after fertilization. Using a combination of radioactive fingerprinting and molecular biology techniques, we identify the bacteria responsible for this effect. We expect that our results will make necessary a re-evaluation of the link between fertilizer use and methane emissions, with effects on global warming studies.

  19. Biogeochemical Evidence that Thermophilic Archaea Mediate the Anaerobic Oxidation of Methane

    PubMed Central

    Schouten, Stefan; Wakeham, Stuart G.; Hopmans, Ellen C.; Sinninghe Damsté, Jaap S.

    2003-01-01

    Distributions and isotopic analyses of lipids from sediment cores at a hydrothermally active site in the Guaymas Basin with a steep sedimentary temperature gradient revealed the presence of archaea that oxidize methane anaerobically. The presence of strongly 13C-depleted lipids at greater depths in the sediments suggests that microbes involved in anaerobic oxidation of methane are present and presumably active at environmental temperatures of >30°C, indicating that this process can occur not only at cold seeps but also at hydrothermal sites. The distribution of the membrane tetraether lipids of the methanotrophic archaea shows that these organisms have adapted their membrane composition to these high environmental temperatures. PMID:12620859

  20. Oxidation of fugitive methane in ground water linked to bacterial sulfate reduction.

    PubMed

    Van Stempvoort, Dale; Maathuis, Harm; Jaworski, Ed; Mayer, Bernhard; Rich, Kathleen

    2005-01-01

    When fugitive methane migrates upward along boreholes of oil and gas wells, it may migrate into shallow ground water or pass through overlying soil to the atmosphere. Prior to this study, there was little information on the fate of fugitive methane that migrates into ground water. In a field study near Lloydminster, Alberta, Canada, we found hydrogeochemical evidence that fugitive methane from an oil well migrated into a shallow aquifer but has been attenuated by dissimilatory bacterial sulfate reduction at low temperature ( approximately 5 degrees C) under anaerobic conditions. Evidence includes spatial and temporal trends in concentrations of methane and sulfate in ground water and associated trends in concentrations of bicarbonate and sulfide. Within 10 m of the oil well, sulfate concentrations were low, and sulfate was enriched in both 34S and 18O. Sulfate concentrations had a strong positive correlation with delta13C values of bicarbonate, and sulfide was depleted in 34S compared to sulfate. These data indicate that bacterial sulfate reduction occurred near the production well. Near the oil well, elevated concentrations of bicarbonate were observed, and the bicarbonate was depleted in 13C. Modeling indicates that the main source of this excess 13C-depleted bicarbonate is oxidized methane. In concert with the sulfate concentration and isotope data, these results support an interpretation that in situ bacterial oxidation of methane has occurred, linked to bacterial sulfate reduction. Bacterial sulfate reduction may play a major role in bioattenuation of fugitive natural gas in ground water in western Canada. PMID:15819940

  1. The effect of aerobic exercise on hepatotoxicity induced by intratracheal instillation of iron oxide nanoparticles in Wistar rats.

    PubMed

    Vasili, Azadeh; Sharifi, Gholamreza; Faramarzi, Mohammad; Noori, Ali; Yazdanshenas, Shora

    2016-01-01

    Iron oxide nanoparticles (IONPs) can cause significant health problems due to their unique physicochemical properties and environmental characteristics. They are found as ultrafine particles in ambient air. After inhalation, these particles move from the lung to phagocytosis tissues, especially the liver. The aim of present study was to investigate the effect of concurrent aerobic exercise and IONPs on liver enzymes and histological hepatic appearance. 48 rats were divided into six groups: experimental 1 (aerobic exercise), experimental 2 (nanoparticle, anesthesia), experimental 3 (aerobic exercise, nanoparticles, anesthesia), placebo 4 (distilled water, anesthesia), placebo 5 (aerobic exercise, anesthesia), and control group. In groups 2 and 3, 40 mg/kg/b.w. of IONPs was injected via intratracheal installation every other day for 14 days. Groups 1, 3, and 5 [corrected] run on treadmill for 30 minutes with the intensity of 35-40% VO2max (maximal oxygen consumption) every day. ALT was increased in group 1 but decreased in groups 2 and 3. AST was not significant in any of the groups, while ALP was reduced significantly in groups 2 and 3 (p < 0.05). Histological examination of the liver showed that, in groups 2 and 3, hepatic cells were damaged and also the congestion, inflammation, mononuclear cell infiltration, and ballooning degeneration were occurred. Tissue injuries in group 3 were less than those of group 2. These findings indicated that hepatotoxicity was caused by iron oxide nanoparticles; however, low-intensity aerobic exercise could decrease the damage somewhat. PMID:26492071

  2. BOREAS TGB-6 Soil Methane Oxidation and Production from NSA BP and Fen Sites

    NASA Technical Reports Server (NTRS)

    Deck, Bruce; Wahlen, Martin; Hall, Forrest G. (Editor); Conrad, Sara K. (Editor)

    2000-01-01

    The BOReal Ecosystem-Atmosphere Study Trace Gas Biogeochemistry (BOREAS TGB-6) team collected soil methane measurements at several sites in the Southern Study Area (SSA) and Northern Study Area (NSA). This data set contains soil methane consumption (bacterial CH4 oxidation) and associated C-13 fractionation effects in samples that were collected at various sites in 1994 and 1996 from enclosures (chambers). Methane C-13 data in soil gas samples from the NSA Young Jack Pine (YJP) and Old Jack Pine (OJP) sites for 1994 and 1996 are also given. Additional data on the isotopic composition of methane (carbon and hydrogen isotopes) produced in the NSA beaver ponds and fen bog in 1993 and 1994 are given as well. The data are stored in tabular ASCII files.

  3. Oxidation of aquatic pollutants by ferrous-oxalate complexes under dark aerobic conditions.

    PubMed

    Lee, Jaesang; Kim, Jungwon; Choi, Wonyong

    2014-06-15

    This study evaluates the ability of Fe(II)-oxalate complexes for the generation of OH through oxygen reduction and the oxidative degradation of aquatic pollutants under dark aerobic conditions (i.e., with oxygen but without light). The degradation of 4-chlorophenol (4-CP) was rapid in the mixture of Fe(2+) and oxalate prepared using ultrapure water, but was absent without either Fe(2+) or oxalate. The formation of Fe(II)-oxalate complexes enables two-electron reduction of oxygen to generate H2O2 and subsequent production of OH. The significant inhibition of 4-CP degradation in the presence of H2O2 and OH scavenger confirms such mechanisms. The degradation experiments with varying [Fe(2+)], [oxalate], and initial pH demonstrated that the degradation rate depends on [Fe(II)(Ox)2(2-)], but the degree of degradation is primarily determined by [Fe(II)(Ox)2(2-)]+[Fe(II)(Ox)(0)]. Efficient degradation of diverse aquatic pollutants, especially phenolic pollutants, was observed in the Fe(II)-oxalate complexes system, wherein the oxidation efficacy was primarily correlated with the reaction rate constant between pollutant and OH. The effect of various organic ligands (oxalate, citrate, EDTA, malonate, and acetate) on the degradation kinetics of 4-CP was investigated. The highest efficiency of oxalate for the oxidative degradation is attributed to its high capability to enhance the reducing power and low reactivity with OH.

  4. Microsensor Measurements of Sulfate Reduction and Sulfide Oxidation in Compact Microbial Communities of Aerobic Biofilms

    PubMed Central

    Kühl, Michael; Jørgensen, Bo Barker

    1992-01-01

    The microzonation of O2 respiration, H2S oxidation, and SO42- reduction in aerobic trickling-filter biofilms was studied by measuring concentration profiles at high spatial resolution (25 to 100 μm) with microsensors for O2, S2-, and pH. Specific reaction rates were calculated from measured concentration profiles by using a simple one-dimensional diffusion reaction model. The importance of electron acceptor and electron donor availability for the microzonation of respiratory processes and their reaction rates was investigated. Oxygen respiration was found in the upper 0.2 to 0.4 mm of the biofilm, whereas sulfate reduction occurred in deeper, anoxic parts of the biofilm. Sulfate reduction accounted for up to 50% of the total mineralization of organic carbon in the biofilms. All H2S produced from sulfate reduction was reoxidized by O2 in a narrow reaction zone, and no H2S escaped to the overlying water. Turnover times of H2S and O2 in the reaction zone were only a few seconds owing to rapid bacterial H2S oxidation. Anaerobic H2S oxidation with NO3- could be induced by addition of nitrate to the medium. Total sulfate reduction rates increased when the availability of SO42- or organic substrate increased as a result of deepening of the sulfate reduction zone or an increase in the sulfate reduction intensity, respectively. PMID:16348687

  5. Oxidative stability of pork emulsion containing tomato products and pink guava pulp during refrigerated aerobic storage.

    PubMed

    Joseph, Serlene; Chatli, Manish K; Biswas, Ashim K; Sahoo, Jhari

    2014-11-01

    Lipid oxidation-induced quality problems can be minimized with the use of natural antioxidants. Antioxidant potential of tomato puree (10 %; T-1), tomato pulp (12.5 %; T-2), lyophilized tomato peel (6 %; T-3), and pink guava pulp (10 %; T-4) was evaluated in raw pork emulsion during refrigerated storage for 9 days under aerobic packaging. The lycopene and β-carotene content varied in pork emulsion as T-3 > T-1 > T-2 > T-4 and decreased (P < 0.05) during storage. The surface redness (a* value) increased (P < 0.05) with the incorporation of tomato products and pink guava pulp. Furthermore, metmyoglobin formation and lipid oxidation were lower (P < 0.05) in tomato- and guava-treated emulsions than in control. Overall, incorporation of tomato products and pink guava pulp improved the visual colour and odour scores of raw pork emulsion. These results indicated that tomato products and guava pulp can be utilized as sources of natural antioxidants in raw pork products to minimize lipid oxidation, off-odour development, and surface discolouration. PMID:26396313

  6. Anaerobic oxidation of methane by sulfate in hypersaline groundwater of the Dead Sea aquifer.

    PubMed

    Avrahamov, N; Antler, G; Yechieli, Y; Gavrieli, I; Joye, S B; Saxton, M; Turchyn, A V; Sivan, O

    2014-11-01

    Geochemical and microbial evidence points to anaerobic oxidation of methane (AOM) likely coupled with bacterial sulfate reduction in the hypersaline groundwater of the Dead Sea (DS) alluvial aquifer. Groundwater was sampled from nine boreholes drilled along the Arugot alluvial fan next to the DS. The groundwater samples were highly saline (up to 6300 mm chlorine), anoxic, and contained methane. A mass balance calculation demonstrates that the very low δ(13) CDIC in this groundwater is due to anaerobic methane oxidation. Sulfate depletion coincident with isotope enrichment of sulfur and oxygen isotopes in the sulfate suggests that sulfate reduction is associated with this AOM. DNA extraction and 16S amplicon sequencing were used to explore the microbial community present and were found to be microbial composition indicative of bacterial sulfate reducers associated with anaerobic methanotrophic archaea (ANME) driving AOM. The net sulfate reduction seems to be primarily controlled by the salinity and the available methane and is substantially lower as salinity increases (2.5 mm sulfate removal at 3000 mm chlorine but only 0.5 mm sulfate removal at 6300 mm chlorine). Low overall sulfur isotope fractionation observed ((34) ε = 17 ± 3.5‰) hints at high rates of sulfate reduction, as has been previously suggested for sulfate reduction coupled with methane oxidation. The new results demonstrate the presence of sulfate-driven AOM in terrestrial hypersaline systems and expand our understanding of how microbial life is sustained under the challenging conditions of an extremely hypersaline environment. PMID:25039851

  7. Anaerobic oxidation of methane by sulfate in hypersaline groundwater of the Dead Sea aquifer.

    PubMed

    Avrahamov, N; Antler, G; Yechieli, Y; Gavrieli, I; Joye, S B; Saxton, M; Turchyn, A V; Sivan, O

    2014-11-01

    Geochemical and microbial evidence points to anaerobic oxidation of methane (AOM) likely coupled with bacterial sulfate reduction in the hypersaline groundwater of the Dead Sea (DS) alluvial aquifer. Groundwater was sampled from nine boreholes drilled along the Arugot alluvial fan next to the DS. The groundwater samples were highly saline (up to 6300 mm chlorine), anoxic, and contained methane. A mass balance calculation demonstrates that the very low δ(13) CDIC in this groundwater is due to anaerobic methane oxidation. Sulfate depletion coincident with isotope enrichment of sulfur and oxygen isotopes in the sulfate suggests that sulfate reduction is associated with this AOM. DNA extraction and 16S amplicon sequencing were used to explore the microbial community present and were found to be microbial composition indicative of bacterial sulfate reducers associated with anaerobic methanotrophic archaea (ANME) driving AOM. The net sulfate reduction seems to be primarily controlled by the salinity and the available methane and is substantially lower as salinity increases (2.5 mm sulfate removal at 3000 mm chlorine but only 0.5 mm sulfate removal at 6300 mm chlorine). Low overall sulfur isotope fractionation observed ((34) ε = 17 ± 3.5‰) hints at high rates of sulfate reduction, as has been previously suggested for sulfate reduction coupled with methane oxidation. The new results demonstrate the presence of sulfate-driven AOM in terrestrial hypersaline systems and expand our understanding of how microbial life is sustained under the challenging conditions of an extremely hypersaline environment.

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

    PubMed Central

    2015-01-01

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

  9. Depth-related coupling relation between methane-oxidizing bacteria (MOBs) and sulfate-reducing bacteria (SRBs) in a marine sediment core from the Dongsha region, the South China Sea.

    PubMed

    Xu, Xiao-Ming; Fu, Shao-Ying; Zhu, Qing; Xiao, Xi; Yuan, Jian-Ping; Peng, Juan; Wu, Chou-Fei; Wang, Jiang-Hai

    2014-12-01

    The vertical distributions of methane-oxidizing bacteria (MOBs) and sulfate-reducing bacteria (SRBs) in the marine sediment core of DH-CL14 from the Dongsha region, the South China Sea, were investigated. To enumerate MOBs and SRBs, their specific genes of pmoA and apsA were quantified by a culture-independent molecular biological technique, real-time polymerase chain reaction (RT-PCR). The result shows that the pmoA gene copies per gram of sediments reached the maximum of 1,118,679 at the depth of 140-160 cm. Overall considering the detection precision, sample amount, measurement cost, and sensitivity to the seepage of methane from the oil/gas reservoirs or gas hydrates, we suggest that the depth of 140-160 cm may be the optimal sampling position for the marine microbial exploration of oils, gases, and gas hydrates in the Dongsha region. The data of the pmoA and apsA gene copies exhibit an evident coupling relation between MOBs and SRBs as illustrated in their vertical distributions in this sediment core, which may well be interpreted by a high sulfate concentration inhibiting methane production and further leading to the reduction of MOBs. In comparison with the numbers of the pmoA and apsA copies at the same sediment depth, we find out that there were two methane-oxidizing mechanisms of aerobic and anaerobic oxidation in this sediment core, i.e., the aerobic oxidation with free oxygen dominantly occurred above the depth of 210-230 cm, while the anaerobic oxidation with the other electron acceptors such as sulfates and manganese-iron oxides happened below the depth of 210-230 cm.

  10. Depth-related coupling relation between methane-oxidizing bacteria (MOBs) and sulfate-reducing bacteria (SRBs) in a marine sediment core from the Dongsha region, the South China Sea.

    PubMed

    Xu, Xiao-Ming; Fu, Shao-Ying; Zhu, Qing; Xiao, Xi; Yuan, Jian-Ping; Peng, Juan; Wu, Chou-Fei; Wang, Jiang-Hai

    2014-12-01

    The vertical distributions of methane-oxidizing bacteria (MOBs) and sulfate-reducing bacteria (SRBs) in the marine sediment core of DH-CL14 from the Dongsha region, the South China Sea, were investigated. To enumerate MOBs and SRBs, their specific genes of pmoA and apsA were quantified by a culture-independent molecular biological technique, real-time polymerase chain reaction (RT-PCR). The result shows that the pmoA gene copies per gram of sediments reached the maximum of 1,118,679 at the depth of 140-160 cm. Overall considering the detection precision, sample amount, measurement cost, and sensitivity to the seepage of methane from the oil/gas reservoirs or gas hydrates, we suggest that the depth of 140-160 cm may be the optimal sampling position for the marine microbial exploration of oils, gases, and gas hydrates in the Dongsha region. The data of the pmoA and apsA gene copies exhibit an evident coupling relation between MOBs and SRBs as illustrated in their vertical distributions in this sediment core, which may well be interpreted by a high sulfate concentration inhibiting methane production and further leading to the reduction of MOBs. In comparison with the numbers of the pmoA and apsA copies at the same sediment depth, we find out that there were two methane-oxidizing mechanisms of aerobic and anaerobic oxidation in this sediment core, i.e., the aerobic oxidation with free oxygen dominantly occurred above the depth of 210-230 cm, while the anaerobic oxidation with the other electron acceptors such as sulfates and manganese-iron oxides happened below the depth of 210-230 cm. PMID:25064353

  11. A Bioinspired Catalytic Aerobic Oxidative C–H Functionalization of Primary Aliphatic Amines: Synthesis of 1,2-Disubstituted Benzimidazoles

    PubMed Central

    Nguyen, Khac Minh Huy; Largeron, Martine

    2015-01-01

    Aerobic oxidative C–H functionalization of primary aliphatic amines has been accomplished with a biomimetic cooperative catalytic system to furnish 1,2-disubstituted benzimidazoles that play an important role as drug discovery targets. This one-pot atom-economical multistep process, which proceeds under mild conditions, with ambient air and equimolar amounts of each coupling partner, constitutes a convenient environmentally friendly strategy to functionalize non-activated aliphatic amines that remain challenging substrates for non-enzymatic catalytic aerobic systems. PMID:26206475

  12. Activity and distribution of methane-oxidizing bacteria in flooded rice soil microcosms and in rice plants (Oryza sativa)

    SciTech Connect

    Bosse, U.; Frenzel, P.

    1997-04-01

    Methane is an important greenhouse gas, and its atmospheric concentration has been increasing for decades. Flooded rice fields are one of the major sources of methane emissions to the atmosphere. These emissions are the net result of methane production by methanogenic bacteria in anoxic environments and methane oxidation by methane oxidizing bacteria in oxic environments. This study describes both the activity and distribution of methane oxidizing bacteria in microcosms used as a model for flooded rice fields. Then the process was characterized and localized, and finally the distribution of these organisms on the roots and culm, the size of the rhizosphere and the changes associated with plant age were examined. 59 refs., 8 figs., 2 tabs.

  13. Competitive interactions between methane- and ammonia-oxidizing bacteria modulate carbon and nitrogen cycling in paddy soil

    NASA Astrophysics Data System (ADS)

    Zheng, Y.; Huang, R.; Wang, B. Z.; Bodelier, P. L. E.; Jia, Z. J.

    2014-06-01

    Pure culture studies have demonstrated that methanotrophs and ammonia oxidizers can both carry out the oxidation of methane and ammonia. However, the expected interactions resulting from these similarities are poorly understood, especially in complex, natural environments. Using DNA-based stable isotope probing and pyrosequencing of 16S rRNA and functional genes, we report on biogeochemical and molecular evidence for growth stimulation of methanotrophic communities by ammonium fertilization, and that methane modulates nitrogen cycling by competitive inhibition of nitrifying communities in a rice paddy soil. Pairwise comparison between microcosms amended with CH4, CH4+Urea, and Urea indicated that urea fertilization stimulated methane oxidation activity 6-fold during a 19-day incubation period, while ammonia oxidation activity was significantly suppressed in the presence of CH4. Pyrosequencing of the total 16S rRNA genes revealed that urea amendment resulted in rapid growth of Methylosarcina-like MOB, and nitrifying communities appeared to be partially inhibited by methane. High-throughput sequencing of the 13C-labeled DNA further revealed that methane amendment resulted in clear growth of Methylosarcina-related MOB while methane plus urea led to an equal increase in Methylosarcina and Methylobacter-related type Ia MOB, indicating the differential growth requirements of representatives of these genera. An increase in 13C assimilation by microorganisms related to methanol oxidizers clearly indicated carbon transfer from methane oxidation to other soil microbes, which was enhanced by urea addition. The active growth of type Ia methanotrops was significantly stimulated by urea amendment, and the pronounced growth of methanol-oxidizing bacteria occurred in CH4-treated microcosms only upon urea amendment. Methane addition partially inhibited the growth of Nitrosospira and Nitrosomonas in urea-amended microcosms, as well as growth of nitrite-oxidizing bacteria. These

  14. Methane conversion

    SciTech Connect

    Jones, C.A.; Leonard, J.J.; Sofranko, J.A.

    1984-04-17

    Another version of Arco's process for reforming methane or natural gas into a synthesis gas uses bismuth oxide as the reforming agent; it also requires no nickel or noble metal catalyst. The methane-containing gas contacts bismuth oxide at temperatures of 900/sup 0/-1560/sup 0/F. The oxide is reduced by methane and easily regenerated with an oxygen-containing gas. The oxide Bi/sub 2/O/sub 3/ is a particularly effective synthesizing agent.

  15. Organometallic Complexes Anchored to Conductive Carbon for Electrocatalytic Oxidation of Methane at Low Temperature.

    PubMed

    Joglekar, Madhura; Nguyen, Vinh; Pylypenko, Svitlana; Ngo, Chilan; Li, Quanning; O'Reilly, Matthew E; Gray, Tristan S; Hubbard, William A; Gunnoe, T Brent; Herring, Andrew M; Trewyn, Brian G

    2016-01-13

    Low-temperature direct methane fuel cells (DMEFCs) offer the opportunity to substantially improve the efficiency of energy production from natural gas. This study focuses on the development of well-defined platinum organometallic complexes covalently anchored to ordered mesoporous carbon (OMC) for electrochemical oxidation of methane in a proton exchange membrane fuel cell at 80 °C. A maximum normalized power of 403 μW/mg Pt was obtained, which was 5 times higher than the power obtained from a modern commercial catalyst and 2 orders of magnitude greater than that from a Pt black catalyst. The observed differences in catalytic activities for oxidation of methane are linked to the chemistry of the tethered catalysts, determined by X-ray photoelectron spectroscopy. The chemistry/activity relationships demonstrate a tangible path for the design of electrocatalytic systems for C-H bond activation that afford superior performance in DMEFC for potential commercial applications. PMID:26492385

  16. The role of molecular hydrogen and methane oxidation in the water vapour budget of the stratosphere

    NASA Technical Reports Server (NTRS)

    Le Texier, H.; Solomon, S.; Garcia, R. R.

    1988-01-01

    The detailed photochemistry of methane oxidation has been studied in a coupled chemical/dynamical model of the middle atmosphere. The photochemistry of formaldehyde plays an important role in determining the production of water vapor from methane oxidation. At high latitudes, the production and transport of molecular hydrogen is particularly important in determining the water vapor distribution. It is shown that the ratio of the methane vertical gradient to the water vapor vertical gradient at any particular latitude should not be expected to be precisely 2, due both to photochemical and dynamical effects. Modeled H2O profiles are compared with measurements from the Limb Infrared Monitor of the Stratosphere (LIMS) experiment at various latitudes. Molecular hydrogen is shown to be responsible for the formation of a secondary maximum displayed by the model water vapor profiles in high latitude summer, a feature also found in the LIMS data.

  17. Organometallic Complexes Anchored to Conductive Carbon for Electrocatalytic Oxidation of Methane at Low Temperature.

    PubMed

    Joglekar, Madhura; Nguyen, Vinh; Pylypenko, Svitlana; Ngo, Chilan; Li, Quanning; O'Reilly, Matthew E; Gray, Tristan S; Hubbard, William A; Gunnoe, T Brent; Herring, Andrew M; Trewyn, Brian G

    2016-01-13

    Low-temperature direct methane fuel cells (DMEFCs) offer the opportunity to substantially improve the efficiency of energy production from natural gas. This study focuses on the development of well-defined platinum organometallic complexes covalently anchored to ordered mesoporous carbon (OMC) for electrochemical oxidation of methane in a proton exchange membrane fuel cell at 80 °C. A maximum normalized power of 403 μW/mg Pt was obtained, which was 5 times higher than the power obtained from a modern commercial catalyst and 2 orders of magnitude greater than that from a Pt black catalyst. The observed differences in catalytic activities for oxidation of methane are linked to the chemistry of the tethered catalysts, determined by X-ray photoelectron spectroscopy. The chemistry/activity relationships demonstrate a tangible path for the design of electrocatalytic systems for C-H bond activation that afford superior performance in DMEFC for potential commercial applications.

  18. Mechanisms and controlling characteristics of the oxidation of methane. Progress report

    SciTech Connect

    Klier, K.; Simmons, G.W.

    1985-02-13

    The research aims at the scientific foundations for processes dealing with selective oxidation of methane to methanol and formaldehyde. Progress has been achieved in two major areas: (a) Catalytic oxidation of methane to formaldehyde by molecular oxygen over molybdena-based catalysts at subatmospheric pressures; the catalysts have been characterized by laser Raman microprobe, electron microscopy, EPR, and ESCA/Auger spectroscopy; (b) Surface science of adsorbates in the palladium-oxygen-dichloromethane-methane system. A combined LEED/Auger/Mass Spectrometer apparatus dedicated to this project has been constructed and is in operation. The structures, energetics, and desorption patterns of oxygen and dichloromethane overlayers have been determined on the Pd(100) crystal surface. An interesting exclusion of dichloromethane chemisorption by preadsorbed oxygen and the occurrence of oxygen chemisorption into the dichloromethane overlayer indicate a reaction pattern that will be very sensitive to the gas phase oxygen-to-dichloromethane concentration ratio.

  19. Growth of Anaerobic Methane-Oxidizing Archaea and Sulfate-Reducing Bacteria in a High-Pressure Membrane Capsule Bioreactor

    PubMed Central

    Gieteling, Jarno; Widjaja-Greefkes, H. C. Aura; Plugge, Caroline M.; Stams, Alfons J. M.; Lens, Piet N. L.; Meulepas, Roel J. W.

    2014-01-01

    Communities of anaerobic methane-oxidizing archaea (ANME) and sulfate-reducing bacteria (SRB) grow slowly, which limits the ability to perform physiological studies. High methane partial pressure was previously successfully applied to stimulate growth, but it is not clear how different ANME subtypes and associated SRB are affected by it. Here, we report on the growth of ANME-SRB in a membrane capsule bioreactor inoculated with Eckernförde Bay sediment that combines high-pressure incubation (10.1 MPa methane) and thorough mixing (100 rpm) with complete cell retention by a 0.2-μm-pore-size membrane. The results were compared to previously obtained data from an ambient-pressure (0.101 MPa methane) bioreactor inoculated with the same sediment. The rates of oxidation of labeled methane were not higher at 10.1 MPa, likely because measurements were done at ambient pressure. The subtype ANME-2a/b was abundant in both reactors, but subtype ANME-2c was enriched only at 10.1 MPa. SRB at 10.1 MPa mainly belonged to the SEEP-SRB2 and Eel-1 groups and the Desulfuromonadales and not to the typically found SEEP-SRB1 group. The increase of ANME-2a/b occurred in parallel with the increase of SEEP-SRB2, which was previously found to be associated only with ANME-2c. Our results imply that the syntrophic association is flexible and that methane pressure and sulfide concentration influence the growth of different ANME-SRB consortia. We also studied the effect of elevated methane pressure on methane production and oxidation by a mixture of methanogenic and sulfate-reducing sludge. Here, methane oxidation rates decreased and were not coupled to sulfide production, indicating trace methane oxidation during net methanogenesis and not anaerobic methane oxidation, even at a high methane partial pressure. PMID:25501484

  20. Growth of anaerobic methane-oxidizing archaea and sulfate-reducing bacteria in a high-pressure membrane capsule bioreactor.

    PubMed

    Timmers, Peer H A; Gieteling, Jarno; Widjaja-Greefkes, H C Aura; Plugge, Caroline M; Stams, Alfons J M; Lens, Piet N L; Meulepas, Roel J W

    2015-02-01

    Communities of anaerobic methane-oxidizing archaea (ANME) and sulfate-reducing bacteria (SRB) grow slowly, which limits the ability to perform physiological studies. High methane partial pressure was previously successfully applied to stimulate growth, but it is not clear how different ANME subtypes and associated SRB are affected by it. Here, we report on the growth of ANME-SRB in a membrane capsule bioreactor inoculated with Eckernförde Bay sediment that combines high-pressure incubation (10.1 MPa methane) and thorough mixing (100 rpm) with complete cell retention by a 0.2-m-pore-size membrane. The results were compared to previously obtained data from an ambient-pressure (0.101 MPa methane) bioreactor inoculated with the same sediment. The rates of oxidation of labeled methane were not higher at 10.1 MPa, likely because measurements were done at ambient pressure. The subtype ANME-2a/b was abundant in both reactors, but subtype ANME-2c was enriched only at 10.1 MPa. SRB at 10.1 MPa mainly belonged to the SEEP-SRB2 and Eel-1 groups and the Desulfuromonadales and not to the typically found SEEP-SRB1 group. The increase of ANME-2a/b occurred in parallel with the increase of SEEP-SRB2, which was previously found to be associated only with ANME-2c. Our results imply that the syntrophic association is flexible and that methane pressure and sulfide concentration influence the growth of different ANME-SRB consortia. We also studied the effect of elevated methane pressure on methane production and oxidation by a mixture of methanogenic and sulfate-reducing sludge. Here, methane oxidation rates decreased and were not coupled to sulfide production, indicating trace methane oxidation during net methanogenesis and not anaerobic methane oxidation, even at a high methane partial pressure.

  1. Dynamics of Gross Methane Production and Oxidation in a Peatland Soil

    NASA Astrophysics Data System (ADS)

    McNicol, G.; Yang, W. H.; Teh, Y.; Silver, W. L.

    2012-12-01

    Globally, peatlands are major sources of the potent greenhouse gas methane (CH4) that is implicated in 20% of the post-industrial increase in radiative forcing. Many temperate peatlands have been drained for alternative land-use and are characterized by a layer of unsaturated soil overlying the remnant organic histosol. Drained soil layers may attenuate surface CH4 emissions from deeper, flooded peat layers via microbial CH4 consumption. We measured gross rates of CH4 production and oxidation seasonally across a range of topographic landforms in a partially drained peatland on Sherman Island, California. Net CH4 fluxes across the soil-atmosphere interface ranged from -7.4 to 1096 mg-C m-2 d-1 across all landforms. Fluxes were highest in May and in irrigation ditches (date, p < 0.001; landform, p < 0.001; n = 55). Gross CH4 production rates ranged from 0-1461 mg-C m-2 d-1 and oxidation rates ranged from 0-40 mg-C m-2 d-1. Excluding the irrigation ditches, gross fluxes did not vary seasonally. Gross CH4 fluxes were significantly higher in the hollow/hummock than in the slope. We subsequently selected the hollow/hummock based upon the observation of a strong redox gradient with depth and characterized gross fluxes of CH4 both in the field and in laboratory incubations of four soil depth increments (0-10 cm, 10-30 cm, 30-60 cm, 60-80 cm). The laboratory incubation consisted of 3 separate gross flux experiments: the first using fresh soil under ambient headspace, the second after incubation in an N2 headspace, and the third after incubation in an ambient headspace. Gross CH4 fluxes in the field varied from a slight sink (-0.11 mg-C m-2 d-1) to a large source (23.9 mg-C m-2 d-1). In 3 plots net fluxes were reduced by competing CH4 oxidation. In the depth profile experiment, production and consumption were observed in the fresh soil, but without a clear depth trend. In contrast, we found that consumption rates increased with depth following the aerobic incubation and

  2. Nitrous oxide emission and nutrient removal in aerobic granular sludge sequencing batch reactors.

    PubMed

    Quan, Xiangchun; Zhang, Mingchuan; Lawlor, Peadar G; Yang, Zhifeng; Zhan, Xinmin

    2012-10-15

    Application of aerobic granular sludge into wastewater treatment is promising due to its excellent settling ability and high microbial concentrations. However, its spatial structure could induce incomplete denitrification, leading to generation of nitrous oxide (N(2)O) - a potent greenhouse gas. Under the temperature of 14 ± 4 °C, three identical laboratory-scale aerobic granular sludge sequencing batch reactors (SBRs) were established to treat synthetic wastewater simulating a mixture of liquid pig manure digestate and municipal wastewater at three aeration rates (0.2, 0.6 and 1.0 L air/min) and three COD:N ratios (1:0.22, 1:0.15 and 1:0.11). The studies show the proportions of N(2)O emission to the influent nitrogen loading rate at the aeration rates of 0.2, 0.6 and 1.0 L air/min were 8.2%, 6.1% and 3.8% at a COD:N ratio of 1:0.22; 7.0%, 5.1% and 3.5% at a COD:N ratio of 1:0.15; and 4.4%, 2.9% and 2.2% at a COD:N ratio of 1:0.11, respectively. With NO(2)(-) as the only nitrogen source in the liquid phase, the specific N(2)O generation rates via denitrification were 1.7, 1.6 and 1.3 μg N(2)O/(g SS· min) at the aeration rates of 0.2, 0.6 and 1.0 L air/min, respectively, which were 40.9%, 44.8%, 39.9% higher than those with NO(3)(-) as the only nitrogen source, respectively. N(2)O generation by aerobic granular sludge due to NH(4)(+)-N nitrification was not sensitive to the aeration rate, and the average specific N(2)O generation rate was 0.8 ± 0.02 μg N(2)O/(g SS· min).

  3. Emissions of methane and nitrous oxide from outdoor-stored broiler litter using tunable-diode laser spectroscopy

    NASA Astrophysics Data System (ADS)

    de Wit, William Harrison

    Handling and storage of a variety of types of agricultural wastes results in the formation and release of nitrous oxide (N2O) and methane (CH4) gases to the atmosphere. These gases contribute to climate change through the greenhouse effect. Few studies have examined evolution of these gases from stored poultry litter in North America. Although N 2O is a by-product of nitrification, it is largely produced as an intermediate product of denitrification and is produced most intensely when both aerobic and anaerobic conditions are present. CH4 emissions, however, are typically associated with anaerobic reactions. Outdoor storage of broiler litter provides an excellent media for which both aerobic and anaerobic zones can coexist, particularly when the litter is of varying ages from multiple broiler flocks (cycles). It provides a large amount of nitrogen for bacterial nitrification/denitrification processes as well as Carbon to support anaerobic bacterial fermentation. The objective of the study was to quantify N 2O and CH4 emissions for broiler litter stored in an uncovered, outdoor bunker by conducting small-scale dynamic flux chamber studies and full-scale field experiments. The field experiments used a modified micrometeorological mass balance approach to monitor emissions from stored broiler litter in a three-walled concrete bunker. Atmospheric concentrations of N2O and CH4 were measured using tunable-diode laser spectroscopy. Field experiments over the course of approximately four months yielded average emission rates of 14+/-17mug m-2 s -1 and 84+/-61 mug m-2 s-1 for N2O and CH4 respectively that agreed well with the trends of emission rates observed in the dynamic flux chamber experiments. The primary drivers of emissions of both CH4 and N2O appeared to be temperature and moisture content while organic carbon and organic nitrogen (loss on ignition, nitrate concentrations) contents were also important factors.

  4. Continuous Flow Aerobic Alcohol Oxidation Reactions Using a Heterogeneous Ru(OH)x/Al2O3 Catalyst

    PubMed Central

    2015-01-01

    Ru(OH)x/Al2O3 is among the more versatile catalysts for aerobic alcohol oxidation and dehydrogenation of nitrogen heterocycles. Here, we describe the translation of batch reactions to a continuous-flow method that enables high steady-state conversion and single-pass yields in the oxidation of benzylic alcohols and dehydrogenation of indoline. A dilute source of O2 (8% in N2) was used to ensure that the reaction mixture, which employs toluene as the solvent, is nonflammable throughout the process. A packed bed reactor was operated isothermally in an up-flow orientation, allowing good liquid–solid contact. Deactivation of the catalyst during the reaction was modeled empirically, and this model was used to achieve high conversion and yield during extended operation in the aerobic oxidation of 2-thiophene methanol (99+% continuous yield over 72 h). PMID:25620869

  5. Copper(I)/ABNO-catalyzed aerobic alcohol oxidation: alleviating steric and electronic constraints of Cu/TEMPO catalyst systems.

    PubMed

    Steves, Janelle E; Stahl, Shannon S

    2013-10-23

    Cu/TEMPO catalyst systems promote efficient aerobic oxidation of sterically unhindered primary alcohols and electronically activated substrates, but they show reduced reactivity with aliphatic and secondary alcohols. Here, we report a catalyst system, consisting of ((MeO)bpy)Cu(I)(OTf) and ABNO ((MeO)bpy = 4,4'-dimethoxy-2,2'-bipyridine; ABNO = 9-azabicyclo[3.3.1]nonane N-oxyl), that mediates aerobic oxidation of all classes of alcohols, including primary and secondary allylic, benzylic, and aliphatic alcohols with nearly equal efficiency. The catalyst exhibits broad functional group compatibility, and most reactions are complete within 1 h at room temperature using ambient air as the source of oxidant. PMID:24128057

  6. Mitigation of methane and nitrous oxide emissions from animal operations: A review of manure management options

    Technology Transfer Automated Retrieval System (TEKTRAN)

    This review analyzes published data on manure management practices used to mitigate methane (CH4) and nitrous oxide (N2O) emissions from animal operations. This is the second in a series of reports commissioned by the Food and Agriculture Organization of the United Nations to evaluate mitigation pra...

  7. Contemporary and projected biogenic fluxes of methane and nitrous oxide in North American terrestrial ecosystems

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The importance of methane (CH4) and nitrous oxide (N2O) in determining global climate change has been increasingly recognized, but terrestrial CH4 and N2O budgets and the underlying mechanisms remain far from certain. Accurate estimation of terrestrial CH4 and N2O budgets would be a critical step fo...

  8. Real time chemical imaging of a working catalytic membrane reactor during oxidative coupling of methane.

    PubMed

    Vamvakeros, A; Jacques, S D M; Middelkoop, V; Di Michiel, M; Egan, C K; Ismagilov, I Z; Vaughan, G B M; Gallucci, F; van Sint Annaland, M; Shearing, P R; Cernik, R J; Beale, A M

    2015-08-18

    We report the results from an operando XRD-CT study of a working catalytic membrane reactor for the oxidative coupling of methane. These results reveal the importance of the evolving solid state chemistry during catalytic reaction, particularly the chemical interaction between the catalyst and the oxygen transport membrane.

  9. Learning the Fundamentals of Kinetics and Reaction Engineering with the Catalytic Oxidation of Methane

    ERIC Educational Resources Information Center

    Cybulskis, Viktor J.; Smeltz, Andrew D.; Zvinevich, Yury; Gounder, Rajamani; Delgass, W. Nicholas; Ribeiro, Fabio H.

    2016-01-01

    Understanding catalytic chemistry, collecting and interpreting kinetic data, and operating chemical reactors are critical skills for chemical engineers. This laboratory experiment provides students with a hands-on supplement to a course in chemical kinetics and reaction engineering. The oxidation of methane with a palladium catalyst supported on…

  10. [Physicochemical and biological factors affecting atmospheric methane oxidation in gray forest soils].

    PubMed

    Kravchenko, I K; Semenov, V M; Kuznetsova, T V; Bykova, S A; Dulov, L E; Pardini, G; Gispert, M; Boeckx, P; Van Cleemput, O; Gal'chenko, V F

    2005-01-01

    The decline of methane oxidizing activities in gray forest soil upon its conversion into arable land was shown to be caused by major changes in biotic and physicochemical properties of soil. Using the method of immune serums, methane-oxidizing bacteria were detected in both forest and agricultural soils, but their populations differed significantly in both abundance and composition. In the forest soil, the number of methanotrophs was an order of magnitude higher than in arable soil, amounting to 3.5 x 10(8) and 0.24 x 10(8) cells/g soil, respectively. All methane-oxidizing bacteria identified in the forest soil belonged to the genus Methylocystis, and 94% of these were represented by a single species, M. parvus. The arable soil was dominated by type I methanotrophs (Methylobacter and Methylomonas, 67.6%), occurring along with bacteria of the genus Methylocystis. In addition, arable soil is characterized by a low content of microbial biomass, lower porosity and water permeability of soil aggregates, and the predominance of nitrogen mineralization processes over those of nitrogen immobilization. These factors can also contribute to lower rates of methane oxidation in arable soil as compared to forest soil.

  11. Environmental detection of octahaem cytochrome c hydroxylamine/hydrazine oxidoreductase genes of aerobic and anaerobic ammonium-oxidizing bacteria.

    PubMed

    Schmid, Markus C; Hooper, Alan B; Klotz, Martin G; Woebken, Dagmar; Lam, Phyllis; Kuypers, Marcel M M; Pommerening-Roeser, Andreas; Op den Camp, Huub J M; Jetten, Mike S M

    2008-11-01

    Bacterial aerobic ammonium oxidation and anaerobic ammonium oxidation (anammox) are important processes in the global nitrogen cycle. Key enzymes in both processes are the octahaem cytochrome c (OCC) proteins, hydroxylamine oxidoreductase (HAO) of aerobic ammonium-oxidizing bacteria (AOB), which catalyses the oxidation of hydroxylamine to nitrite, and hydrazine oxidoreductase (HZO) of anammox bacteria, which converts hydrazine to N(2). While the genomes of AOB encode up to three nearly identical copies of hao operons, genome analysis of Candidatus'Kuenenia stuttgartiensis' showed eight highly divergent octahaem protein coding regions as possible candidates for the HZO. Based on their phylogenetic relationship and biochemical characteristics, the sequences of these eight gene products grouped in three clusters. Degenerate primers were designed on the basis of available gene sequences with the aim to detect hao and hzo genes in various ecosystems. The hao primer pairs amplified gene fragments from 738 to 1172 bp and the hzo primer pairs amplified gene fragments from 289 to 876 bp in length, when tested on genomic DNA isolated from a variety of AOB and anammox bacteria. A selection of these primer pairs was also used successfully to amplify and analyse the hao and hzo genes in community DNA isolated from different ecosystems harbouring both AOB and anammox bacteria. We propose that OCC protein-encoding genes are suitable targets for molecular ecological studies on both aerobic and anaerobic ammonium-oxidizing bacteria.

  12. Doped graphene as a metal-free carbocatalyst for the selective aerobic oxidation of benzylic hydrocarbons, cyclooctane and styrene.

    PubMed

    Dhakshinamoorthy, Amarajothi; Primo, Ana; Concepcion, Patricia; Alvaro, Mercedes; Garcia, Hermenegildo

    2013-06-01

    Nitrogen (N)-, boron (B)-, and boron,nitrogen (B,N)-doped graphene (G) act as carbocatalysts, promoting the aerobic oxidation of the benzylic positions of aromatic hydrocarbons and cyclooctane to the corresponding alcohol/ketone mixture with more than 90 % selectivity. The most active material was the co-doped (B,N)G, which, in the absence of solvent and with a substrate/(B,N)G ratio of 200, achieved 50 % tetralin conversion in 24 h with a alcohol/ketone selectivity of 80 %. An FT-Raman spectroscopic study of a sample of (B,N)G heated at 100 °C in the presence of oxygen revealed new bands that disappeared upon evacuation and that have been attributed to hydroperoxide-like species formed on the G sheet based on the isotopic shift of the peak from 819 to 779 cm(-1) when (18)O2 was used as the oxidizing reagent. Furthermore, (B)G and (N)G exhibited high catalytic activity in the aerobic oxidation of styrene to benzaldehyde (BA) in 4 h. However, the product distribution changed over time and after 10 h a significant percentage of styrene oxide (SO) was observed under the same conditions. The use of doped G as catalyst appears to offer broad scope for the aerobic oxidation of benzylic compounds and styrene, for which low catalyst loading, mild reaction temperatures, and no additional solvents are required.

  13. Release of ANP and fat oxidation in overweight persons during aerobic exercise in water.

    PubMed

    Fenzl, M; Schnizer, W; Aebli, N; Schlegel, C; Villiger, B; Disch, A; Gredig, J; Zaugg, T; Krebs, J

    2013-09-01

    Exercise in water compared to land-based exercise (LE) results in a higher release of natriuretic peptides, which are involved in the regulation of exercise-induced adipose tissue lipolysis. The present study was performed to compare the release of atrial natriuretic peptide (ANP) and free fatty acids (FFA) during prolonged aerobic water-based exercise (WE) with the release after an identical LE. 14 untrained overweight subjects performed 2 steady state workload tests on the same ergometer in water and on land. Before and after exercise, venous blood samples were collected for measuring ANP, FFA, epinephrine, norepinephrine, insulin and glucose. The respiratory exchange ratio (RER) was determined for fat oxidation.The exercises resulted in a significant increase in ANP in LE (61%) and in WE (177%), and FFA increased about 3-fold in LE and WE with no significant difference between the groups. Epinephrine increased, while insulin decreased similarly in both groups. The RER values decreased during the exercises, but there was no significant difference between LE and WE. In conclusion, the higher ANP concentrations in WE had no additional effect on lipid mobilization, FFA release and fat oxidation. Moderate-intensity exercises in water offer no benefit regarding adipose tissue lipolysis in comparison to LE.

  14. Evidence for microbial methane oxidation at cold seeps along the main active fault in the Marmara Sea

    NASA Astrophysics Data System (ADS)

    Chevalier, Nicolas; Birgel, Daniel; Lopez-Garcia, Purificacion; Taphanel, Marie-Helene; Bouloubassi, Ioanna

    2010-05-01

    The North Anatolian Fault in the Marmara Sea is a spectacular example of a seismically active fault where, in recent years, numerous sites of active fluid venting have been discovered and explored. During the MARNAUT cruise (2007), multidisciplinary sampling was carried out with the Nautile submersible in order to investigate biogeochemical and hydrogeological processes taking place at these newly discovered cold seeps. We have studied short sediment cores (< 20 cm) and authigenic carbonate crusts retrieved with the Nautile submersible from sub-basins of the Marmara Sea, aiming at gaining insight into microbial processes and assemblages in this recently discovered methane-rich setting and at comparing it with previously studied cold seeps. To do so, we investigated diagnostic microbial lipids and their carbon isotope composition, and, in selected sediment samples, we carried out cloning and sequencing of 16S rRNA genes. The sediment core retrieved from the southern slope of the Çinarcik Basin, in an area of black patches, bacterial mats and polychaetes, contained abundant and strongly 13C-depleted archaeal and bacterial lipids. Archaeal lipids consisted mainly of archaeol, sn-2-hydroxyarchaeol, crocetane, and unsaturated PMIs, and showed δ13C values as low as -125 per mille. Concurrently, bacterial lipids (e.g. cyclopropyl-C17:0, C16:1?5, i-/ai-C15:0, and non-isoprenoidal glycerol monoethers), previously assigned to sulphate reducing bacteria (SRB), were identified with low δ13C values (-55 to -115 per mille). The structural and isotopic features of microbial lipids provided compelling evidence for anaerobic oxidation of methane (AOM) taking place within the upper 17 cm of the sediment core, mediated by methanotrophic archaea (ANME) and sulphate reducing bacteria. No biomarker evidence for aerobic oxidation of methane was found. Depth profiles of microbial lipids revealed the vertical zonation of AOM and associated microbial biomass, and implied that AOM is

  15. [Potential activity of methane and ammonia oxidation by methanotropic communities from soda lakes of the southern Transbaikal].

    PubMed

    Khmelenina, V N; Eshinimaev, B Ts; Kaliuzhnaia, M G; Trotsenko, Iu A

    2000-01-01

    Radioisotopic measurements of the methane consumption by mud samples taken from nine Southern Transbaikal soda lakes (pH 9.5-10.6) showed an intense oxidation of methane in the muds of lakes Khuzhirta, Bumalai Nur, Gorbunka, and Suduntuiskii Torom, with the maximum oxidation rate in the mud of lakes Khuzhirta (33.2 nmol/(ml day)). The incorporation rate of the radioactive label from 14CH4 into 14CO2 was higher than into acid-stable metabolites. Optimum pH values for methane oxidation in water samples were 7-8, whereas mud samples exhibited two peaks of methane oxidation activity (at pH 8.15-9.4 and 5.8-7.0). The majority of samples could oxidize ammonium to nitrites; the oxidation was inhibited by methane. The PCR amplification analysis of samples revealed the presence of genes encoding soluble and particulate methane monooxygenase and methanol dehydrogenase. Three alkaliphilic methanotrophic bacteria of morphotype I were isolated from mud samples in pure cultures, one of which, B5, was able to oxidize ammonium to nitrites at pH 7-11. The data obtained suggest that methanotrophs are widely spread in the soda lakes of Southern Transbaikal, where they actively oxidize methane and ammonium. PMID:11008692

  16. The variations of Oxidation-Reduction Potential in paddy soil and effects on the methane emission from a periodically irrigated paddy field.

    NASA Astrophysics Data System (ADS)

    Yagi, K.; Iwata, T.; Wakikuromaru, N.

    2014-12-01

    Paddy fields are one of the most important eco-system in monsoon Asia and one of the largest source of CH4 emission. CH4 has significant contribution to the global warming next to CO2 and its greenhouse effect is about 21 times as large as same amount of CO2. CH4 is generated by decomposition of organic matter in soil under anaerobic condition. Oxidation-Reduction Potential (ORP) is the most suitable index representing soil aerobic condition. Or, CH4 is more generated under lower ORP conditions. In this study, ORP in paddy soil was measured during rice cultivated season at a periodically irrigated paddy field, and some effects on the methane flux from the paddy soil was investigated. 3-days flood and 4-days drained condition were regularly repeated at the site from late-June to early October. ORP under flooded condition was measured during irrigated term in 2013 at two mode; regular interval measurement every 2 weeks and intensive measurements during two flooded periods. Methane flux was also measured by the aerodynamic gradient technique. ORP showed rapid decrease when irrigation water was introduced in the paddy field, and lower ORP was shown under the longer flooded condition. From the seasonal-term point of view, lower ORP was shown in later rice season. ORP was suitably modeled as a function of irrigation time. During an irrigation period for four days, higher methane emissions were shown under lower OPR conditions as shown in Fig.1. From the seasonal-term point of view, however, no significant relationship between ORP and methane fluxes. Rapid rise of CH4 flux in early August and gradual decrease between late August and September were shown. It is suggested that seasonal change of methane flux is affected by seasonal changes of soil temperature or the growth level of rice plants.

  17. Analytical study of mechanisms for nitric oxide formation during combustion of methane in a jet-stirred combustor

    NASA Technical Reports Server (NTRS)

    Jachimowski, C. J.

    1975-01-01

    The role of chemical kinetics in the formation of nitric oxide during the combustion of methane was examined analytically by means of a detailed chemical mechanism for the oxidation of methane, for the reaction between hydrocarbon fragments, and for the formation of nitric oxide. By comparing predicted nitric oxide levels with values reported in the literature from jet-stirred combuster experiments, it was determined that the nitric oxide levels observed in fuel-rich flames cannot be described by a mechanism in which the rate of nitric oxide formation is controlled solely by the kinetics of oxygen atom formation. A proposed mechanism for the formation of nitric oxide in methane-rich flames reproduces the observed levels. The oxidation of hydrogen cyanide appears to be an important factor in nitric oxide formation.

  18. Microsensor measurements of sulfate reduction and sulfide oxidation in compact microbial communities of aerobic biofilms

    SciTech Connect

    Kuehl, M.; Joergensen, B.B. )

    1992-04-01

    The microzonation of O{sub 2} respiration, H{sub 2}S oxidation, and SO{sub 4}{sup 2{minus}} reduction in aerobic trickling-filter biofilms was studied by measuring concentration profiles at high spatial resolution (25 to 100 {mu}m) with microsensors for O{sub 2}, S{sup 2{minus}}, and pH. Specific reaction rates were calculated from measured concentration profiles by using a simple one-dimensional diffusion reaction model. The importance of electron acceptor and electron donor availability for the microzonation of respiratory processes and their reaction rates was investigated. Oxygen respiration was found in the upper 0.2 to 0.4 mm of the biofilm, whereas sulfate reduction occurred in deeper, anoxic parts of the biofilm. Sulfate reduction accounted for up to 50% of the total mineralization of organic carbon in the biofilms. All H{sub 2}S produced from sulfate reduction was reoxidized by O{sub 2} in a narrow reaction zone, and no H{sub 2}S escaped to the overlying water. Turnover times of H{sub 2}S and O{sub 2} in the reaction zone were only a few seconds owing to rapid bacterial H{sub 2}S oxidation. Anaerobic H{sub 2}S oxidation with NO{sub 3}{sup {minus}} could be induced by addition of nitrate to the medium. Total sulfate reduction rates increased when the availability of SO{sub 4}{sup 2{minus}} or organic substrate increased as a result of deepening of the sulfate reduction zone or an increase in the sulfate reduction intensity, respectively.

  19. Plutonium Oxidation State Distribution under Aerobic and Anaerobic Subsurface Conditions for Metal-Reducing Bacteria

    NASA Astrophysics Data System (ADS)

    Reed, D. T.; Swanson, J.; Khaing, H.; Deo, R.; Rittmann, B.

    2009-12-01

    The fate and potential mobility of plutonium in the subsurface is receiving increased attention as the DOE looks to cleanup the many legacy nuclear waste sites and associated subsurface contamination. Plutonium is the near-surface contaminant of concern at several DOE sites and continues to be the contaminant of concern for the permanent disposal of nuclear waste. The mobility of plutonium is highly dependent on its redox distribution at its contamination source and along its potential migration pathways. This redox distribution is often controlled, especially in the near-surface where organic/inorganic contaminants often coexist, by the direct and indirect effects of microbial activity. The redox distribution of plutonium in the presence of facultative metal reducing bacteria (specifically Shewanella and Geobacter species) was established in a concurrent experimental and modeling study under aerobic and anaerobic conditions. Pu(VI), although relatively soluble under oxidizing conditions at near-neutral pH, does not persist under a wide range of the oxic and anoxic conditions investigated in microbiologically active systems. Pu(V) complexes, which exhibit high chemical toxicity towards microorganisms, are relatively stable under oxic conditions but are reduced by metal reducing bacteria under anaerobic conditions. These facultative metal-reducing bacteria led to the rapid reduction of higher valent plutonium to form Pu(III/IV) species depending on nature of the starting plutonium species and chelating agents present in solution. Redox cycling of these lower oxidation states is likely a critical step in the formation of pseudo colloids that may lead to long-range subsurface transport. The CCBATCH biogeochemical model is used to explain the redox mechanisms and final speciation of the plutonium oxidation state distributions observed. These results for microbiologically active systems are interpreted in the context of their importance in defining the overall migration

  20. Radioactive fingerprinting of microorganisms that oxidize atmospheric methane in different soils.

    PubMed

    Roslev, P; Iversen, N

    1999-09-01

    Microorganisms that oxidize atmospheric methane in soils were characterized by radioactive labelling with (14)CH(4) followed by analysis of radiolabelled phospholipid ester-linked fatty acids ((14)C-PLFAs). The radioactive fingerprinting technique was used to compare active methanotrophs in soil samples from Greenland, Denmark, the United States, and Brazil. The (14)C-PLFA fingerprints indicated that closely related methanotrophic bacteria were responsible for the oxidation of atmospheric methane in the soils. Significant amounts of labelled PLFAs produced by the unknown soil methanotrophs coeluted with a group of fatty acids that included i17:0, a17:0, and 17:1omega8c (up to 9.0% of the total (14)C-PLFAs). These PLFAs are not known to be significant constituents of methanotrophic bacteria. The major PLFAs of the soil methanotrophs (73.5 to 89.0% of the total PLFAs) coeluted with 18:1 and 18:0 fatty acids (e.g., 18:1omega9, 18:1omega7, and 18:0). The (14)C-PLFAs fingerprints of the soil methanotrophs that oxidized atmospheric methane did not change after long-term methane enrichment at 170 ppm CH(4). The (14)C-PLFA fingerprints of the soil methanotrophs were different from the PLFA profiles of type I and type II methanotrophic bacteria described previously. Some similarity at the PLFA level was observed between the unknown soil methanotrophs and the PLFA phenotype of the type II methanotrophs. Methanotrophs in Arctic, temperate, and tropical regions assimilated between 20 and 54% of the atmospheric methane that was metabolized. The lowest relative assimilation (percent) was observed for methanotrophs in agricultural soil, whereas the highest assimilation was observed for methanotrophs in rain forest soil. The results suggest that methanotrophs with relatively high carbon conversion efficiencies and very similar PLFA compositions dominate atmospheric methane metabolism in different soils. The characteristics of the methane metabolism and the (14)C-PLFA fingerprints

  1. Anaerobic Oxidation of Methane Coupled to Nitrite Reduction by Halophilic Marine NC10 Bacteria.

    PubMed

    He, Zhanfei; Geng, Sha; Cai, Chaoyang; Liu, Shuai; Liu, Yan; Pan, Yawei; Lou, Liping; Zheng, Ping; Xu, Xinhua; Hu, Baolan

    2015-08-15

    Anaerobic oxidation of methane (AOM) coupled to nitrite reduction is a novel AOM process that is mediated by denitrifying methanotrophs. To date, enrichments of these denitrifying methanotrophs have been confined to freshwater systems; however, the recent findings of 16S rRNA and pmoA gene sequences in marine sediments suggest a possible occurrence of AOM coupled to nitrite reduction in marine systems. In this research, a marine denitrifying methanotrophic culture was obtained after 20 months of enrichment. Activity testing and quantitative PCR (qPCR) analysis were then conducted and showed that the methane oxidation activity and the number of NC10 bacteria increased correlatively during the enrichment period. 16S rRNA gene sequencing indicated that only bacteria in group A of the NC10 phylum were enriched and responsible for the resulting methane oxidation activity, although a diverse community of NC10 bacteria was harbored in the inoculum. Fluorescence in situ hybridization showed that NC10 bacteria were dominant in the enrichment culture after 20 months. The effect of salinity on the marine denitrifying methanotrophic culture was investigated, and the apparent optimal salinity was 20.5‰, which suggested that halophilic bacterial AOM coupled to nitrite reduction was obtained. Moreover, the apparent substrate affinity coefficients of the halophilic denitrifying methanotrophs were determined to be 9.8 ± 2.2 μM for methane and 8.7 ± 1.5 μM for nitrite.

  2. Radioactive fingerprinting of microorganisms that oxidize atmospheric methane in different soils

    SciTech Connect

    Roslev, P.; Iversen, N.

    1999-09-01

    Microorganisms that oxidize atmospheric methane in soils were characterized by radioactive labeling with {sup 14}CH{sub 4} followed by analysis of radiolabelled phospholipid ester-linked fatty acids ({sup 14}C-PLFAs). The radioactive fingerprinting technique was used to compare active methanotrophs in soil samples from Greenland, Denmark, the United States, and Brazil. The {sup 14}C-PLFA fingerprints indicated that closely related methanotrophic bacteria were responsible for the oxidation of atmospheric methane in the soils. Significant amounts of labeled PLFAs produced by the unknown soil methanotrophs coeluted with a group of fatty acids that included i17:0, a17:0, and 17:1{omega}8c. These PLFAs are not known to be significant constituents of methanotrophic bacteria. The major PLFAs of the soil methanotrophs coeluted with 18:1 and 18:0 fatty acids. The {sup 14}C-PLFAs fingerprints of the soil methanotrophs that oxidized atmospheric methane did not change after long-term methane enrichment at 170 ppm CH{sub 4}. The {sup 14}C-PLFA fingerprints of the soil methanotrophs were different from the PLFA profiles of type 1 and type 2 methanotrophic bacteria described previously. Some similarity at the PLFA level was observed between the unknown soil methanotrophs and the PLFA phenotype of the type 2 methanotrophs.

  3. Carbon isotope fractionation by methane-oxidizing bacteria intropical rain forest soils

    SciTech Connect

    Teh, Yit Arn; Silver, Whendee L.; Conrad, Mark E.; Borglin,Sharon E.; Carlson, Charlotte M.

    2005-05-12

    Humid tropical forests have the potential to be significantsources or sinks of atmospheric methane (CH4), a radiatively importanttrace gas. Methane oxidation can consume a large fraction of the CH4produced in tropical soils, although controls on this process are poorlyunderstood. Using soil incubation experiments, we investigated theeffects of CH4 and oxygen (O2) concentrations on C isotope fractionationand CH4 oxidation in tropical rain forest soils. We also explored theeffects of these environmental variables on the isotope fractionationfactor for CH4 oxidation (alpha), which is widely used to evaluate therelative contributions of CH4 production and oxidation to the atmosphericCH4 pool. Methane oxidation was sensitive to CH4 at lower CH4concentrations (<850 ppmv) and insensitive to O2 concentrationsbetween 3 and 21 percent. Maximum rates of CH4 oxidation were between 8.2+- 1.2 and 11.3 +- 1.5 nmol CH4 hour-1 g dry soil-1. Measured values foralpha were sensitive to both CH4 oxidation rate and CH4 concentration.Alpha was inversely proportional to CH4 oxidation rate (r2 = 0.86, P<0.001) and positively correlated with CH4 concentration (r2 = 0.52, P<0.01). A multiple regression model that included CH4 oxidation rate,CH4 concentration, and the interaction of the two terms explained a highproportion of the variability in alpha (r2 = 0.94, P<0.0001). Thesedata suggest that it is possible to accurately determine alpha, allowingfor more precise estimates of CH4 oxidation by isotope massbalance.

  4. Competitive interactions between methane- and ammonia-oxidizing bacteria modulate carbon and nitrogen cycling in paddy soil

    NASA Astrophysics Data System (ADS)

    Zheng, Y.; Huang, R.; Wang, B. Z.; Bodelier, P. L. E.; Jia, Z. J.

    2014-03-01

    Pure culture studies have demonstrated that methanotrophs and ammonia oxidizers can both carry out the oxidation of methane and ammonia. However, the expected interactions resulting from these similarities are poorly understood, especially in complex, natural environments. Using DNA-based stable isotope probing and pyrosequencing of 16S rRNA and pmoA genes, we report on biogeochemical and molecular evidence for growth stimulation of methanotrophic communities by ammonium fertilization, and that methane modulates nitrogen cycling by competitive inhibition of nitrifying communities in a rice paddy soil. Pairwise comparison between microcosms amended with CH4, CH4+Urea, and Urea indicated that urea fertilization stimulated methane oxidation activity by 6-fold during a 19 day incubation period, while ammonia oxidation activity was significantly inhibited in the presence of CH4. Pyrosequencing of the total 16S rRNA genes revealed that urea amendment resulted in rapid growth of Methylosarcina-like type Ia MOB, and nitrifying communities appeared to be suppressed by methane. High-throughput sequencing of the 13C-labeled DNA further revealed that methane amendment resulted in clear growth of Methylosarcina-related MOB while methane plus urea led to equal increase in Methylosarcina and Methylobacter-related MOB, indicating the differential growth requirements of representatives of these genera. Strikingly, type Ib MOB did not respond to methane nor to urea. Increase in 13C-assimilation by microorganisms related to methanol oxidizers clearly indicated carbon transfer from methane oxidation to other soil microbes, which was enhanced by urea addition. The active growth of type Ia methanotrops was significantly stimulated by urea amendment, and the pronounced growth of methanol-oxidizing bacteria occurred in CH4-treated microcosms only upon urea amendment. Methane addition inhibited the growth of Nitrosospira and Nitrosomonas in urea-amended microcosms, in addition of nitrite-oxidizing

  5. Remediation of a winery wastewater combining aerobic biological oxidation and electrochemical advanced oxidation processes.

    PubMed

    Moreira, Francisca C; Boaventura, Rui A R; Brillas, Enric; Vilar, Vítor J P

    2015-05-15

    Apart from a high biodegradable fraction consisting of organic acids, sugars and alcohols, winery wastewaters exhibit a recalcitrant fraction containing high-molecular-weight compounds as polyphenols, tannins and lignins. In this context, a winery wastewater was firstly subjected to a biological oxidation to mineralize the biodegradable fraction and afterwards an electrochemical advanced oxidation process (EAOP) was applied in order to mineralize the refractory molecules or transform them into simpler ones that can be further biodegraded. The biological oxidation led to above 97% removals of dissolved organic carbon (DOC), chemical oxygen demand (COD) and 5-day biochemical oxygen demand (BOD5), but was inefficient on the degradation of a bioresistant fraction corresponding to 130 mg L(-1) of DOC, 380 mg O2 L(-1) of COD and 8.2 mg caffeic acid equivalent L(-1) of total dissolved polyphenols. Various EAOPs such as anodic oxidation with electrogenerated H2O2 (AO-H2O2), electro-Fenton (EF), UVA photoelectro-Fenton (PEF) and solar PEF (SPEF) were then applied to the recalcitrant effluent fraction using a 2.2 L lab-scale flow plant containing an electrochemical cell equipped with a boron-doped diamond (BDD) anode and a carbon-PTFE air-diffusion cathode and coupled to a photoreactor with compound parabolic collectors (CPCs). The influence of initial Fe(2+) concentration and current density on the PEF process was evaluated. The relative oxidative ability of EAOPs increased in the order AO-H2O2 < EF < PEF ≤ SPEF. The SPEF process using an initial Fe(2+) concentration of 35 mg L(-1), current density of 25 mA cm(-2), pH of 2.8 and 25 °C reached removals of 86% on DOC and 68% on COD after 240 min, regarding the biologically treated effluent, along with energy consumptions of 45 kWh (kg DOC)(-1) and 5.1 kWh m(-3). After this coupled treatment, color, odor, COD, BOD5, NH4(+), NO3(-) and SO4(2-) parameters complied with the legislation targets and, in addition, a total

  6. Remediation of a winery wastewater combining aerobic biological oxidation and electrochemical advanced oxidation processes.

    PubMed

    Moreira, Francisca C; Boaventura, Rui A R; Brillas, Enric; Vilar, Vítor J P

    2015-05-15

    Apart from a high biodegradable fraction consisting of organic acids, sugars and alcohols, winery wastewaters exhibit a recalcitrant fraction containing high-molecular-weight compounds as polyphenols, tannins and lignins. In this context, a winery wastewater was firstly subjected to a biological oxidation to mineralize the biodegradable fraction and afterwards an electrochemical advanced oxidation process (EAOP) was applied in order to mineralize the refractory molecules or transform them into simpler ones that can be further biodegraded. The biological oxidation led to above 97% removals of dissolved organic carbon (DOC), chemical oxygen demand (COD) and 5-day biochemical oxygen demand (BOD5), but was inefficient on the degradation of a bioresistant fraction corresponding to 130 mg L(-1) of DOC, 380 mg O2 L(-1) of COD and 8.2 mg caffeic acid equivalent L(-1) of total dissolved polyphenols. Various EAOPs such as anodic oxidation with electrogenerated H2O2 (AO-H2O2), electro-Fenton (EF), UVA photoelectro-Fenton (PEF) and solar PEF (SPEF) were then applied to the recalcitrant effluent fraction using a 2.2 L lab-scale flow plant containing an electrochemical cell equipped with a boron-doped diamond (BDD) anode and a carbon-PTFE air-diffusion cathode and coupled to a photoreactor with compound parabolic collectors (CPCs). The influence of initial Fe(2+) concentration and current density on the PEF process was evaluated. The relative oxidative ability of EAOPs increased in the order AO-H2O2 < EF < PEF ≤ SPEF. The SPEF process using an initial Fe(2+) concentration of 35 mg L(-1), current density of 25 mA cm(-2), pH of 2.8 and 25 °C reached removals of 86% on DOC and 68% on COD after 240 min, regarding the biologically treated effluent, along with energy consumptions of 45 kWh (kg DOC)(-1) and 5.1 kWh m(-3). After this coupled treatment, color, odor, COD, BOD5, NH4(+), NO3(-) and SO4(2-) parameters complied with the legislation targets and, in addition, a total

  7. The Apparent Involvement of ANMEs in Mineral Dependent Methane Oxidation, as an Analog for Possible Martian Methanotrophy.

    PubMed

    House, Christopher H; Beal, Emily J; Orphan, Victoria J

    2011-11-18

    On Earth, marine anaerobic methane oxidation (AOM) can be driven by the microbial reduction of sulfate, iron, and manganese. Here, we have further characterized marine sediment incubations to determine if the mineral dependent methane oxidation involves similar microorganisms to those found for sulfate-dependent methane oxidation. Through FISH and FISH-SIMS analyses using 13C and 15N labeled substrates, we find that the most active cells during manganese dependent AOM are primarily mixed and mixed-cluster aggregates of archaea and bacteria. Overall, our control experiment using sulfate showed two active bacterial clusters, two active shell aggregates, one active mixed aggregate, and an active archaeal sarcina, the last of which appeared to take up methane in the absence of a closely-associated bacterial partner. A single example of a shell aggregate appeared to be active in the manganese incubation, along with three mixed aggregates and an archaeal sarcina. These results suggest that the microorganisms (e.g., ANME-2) found active in the manganese-dependent incubations are likely capable of sulfate-dependent AOM. Similar metabolic flexibility for Martian methanotrophs would mean that the same microbial groups could inhabit a diverse set of Martian mineralogical crustal environments. The recently discovered seasonal Martian plumes of methane outgassing could be coupled to the reduction of abundant surface sulfates and extensive metal oxides, providing a feasible metabolism for present and past Mars. In an optimistic scenario Martian methanotrophy consumes much of the periodic methane released supporting on the order of 10,000 microbial cells per cm2 of Martian surface. Alternatively, most of the methane released each year could be oxidized through an abiotic process requiring biological methane oxidation to be more limited. If under this scenario, 1% of this methane flux were oxidized by biology in surface soils or in subsurface aquifers (prior to release), a total

  8. The Apparent Involvement of ANMEs in Mineral Dependent Methane Oxidation, as an Analog for Possible Martian Methanotrophy

    PubMed Central

    House, Christopher H.; Beal, Emily J.; Orphan, Victoria J.

    2011-01-01

    On Earth, marine anaerobic methane oxidation (AOM) can be driven by the microbial reduction of sulfate, iron, and manganese. Here, we have further characterized marine sediment incubations to determine if the mineral dependent methane oxidation involves similar microorganisms to those found for sulfate-dependent methane oxidation. Through FISH and FISH-SIMS analyses using 13C and 15N labeled substrates, we find that the most active cells during manganese dependent AOM are primarily mixed and mixed-cluster aggregates of archaea and bacteria. Overall, our control experiment using sulfate showed two active bacterial clusters, two active shell aggregates, one active mixed aggregate, and an active archaeal sarcina, the last of which appeared to take up methane in the absence of a closely-associated bacterial partner. A single example of a shell aggregate appeared to be active in the manganese incubation, along with three mixed aggregates and an archaeal sarcina. These results suggest that the microorganisms (e.g., ANME-2) found active in the manganese-dependent incubations are likely capable of sulfate-dependent AOM. Similar metabolic flexibility for Martian methanotrophs would mean that the same microbial groups could inhabit a diverse set of Martian mineralogical crustal environments. The recently discovered seasonal Martian plumes of methane outgassing could be coupled to the reduction of abundant surface sulfates and extensive metal oxides, providing a feasible metabolism for present and past Mars. In an optimistic scenario Martian methanotrophy consumes much of the periodic methane released supporting on the order of 10,000 microbial cells per cm2 of Martian surface. Alternatively, most of the methane released each year could be oxidized through an abiotic process requiring biological methane oxidation to be more limited. If under this scenario, 1% of this methane flux were oxidized by biology in surface soils or in subsurface aquifers (prior to release), a total

  9. The Apparent Involvement of ANMEs in Mineral Dependent Methane Oxidation, as an Analog for Possible Martian Methanotrophy

    NASA Astrophysics Data System (ADS)

    House, Christopher H.; Beal, Emily J.; Orphan, Victoria J.

    2011-11-01

    On Earth, marine anaerobic methane oxidation (AOM) can be driven by the microbial reduction of sulfate, iron, and manganese. Here, we have further characterized marine sediment incubations to determine if the mineral dependent methane oxidation involves similar microorganisms to those found for sulfate-dependent methane oxidation. Through FISH and FISH-SIMS analyses using 13C and 15N labeled substrates, we find that the most active cells during manganese dependent AOM are primarily mixed and mixed-cluster aggregates of archaea and bacteria. Overall, our control experiment using sulfate showed two active bacterial clusters, two active shell aggregates, one active mixed aggregate, and an active archaeal sarcina, the last of which appeared to take up methane in the absence of a closely-associated bacterial partner. A single example of a shell aggregate appeared to be active in the manganese incubation, along with three mixed aggregates and an archaeal sarcina. These results suggest that the microorganisms (e.g., ANME-2) found active in the manganese-dependent incubations are likely capable of sulfate-dependent AOM. Similar metabolic flexibility for Martian methanotrophs would mean that the same microbial groups could inhabit a diverse set of Martian mineralogical crustal environments. The recently discovered seasonal Martian plumes of methane outgassing could be coupled to the reduction of abundant surface sulfates and extensive metal oxides, providing a feasible metabolism for present and past Mars. In an optimistic scenario Martian methanotrophy consumes much of the periodic methane released supporting on the order of 10,000 microbial cells per cm2 of Martian surface. Alternatively, most of the methane released each year could be oxidized through an abiotic process requiring biological methane oxidation to be more limited. If under this scenario, 1% of this methane flux were oxidized by biology in surface soils or in subsurface aquifers (prior to release), a total

  10. Development of Vanadium Phosphaate Catalysts for Methanol Production by Selective Oxidation of Methane.

    SciTech Connect

    McCormick, R.L.

    1997-10-01

    This DOE sponsored study of methane partial oxidation was initiated at Amax Research and Development in Golden, CO in October of 1993. Shortly thereafter the management of Amax closed this R&D facility and the PI moved to the Colorado School of Mines. The project was begun again after contract transfer via a novation agreement. Experimental work began with testing of vandyl pyrophosphate (VPO), a well known alkane selective oxidation catalyst. It was found that VPO was not a selective catalyst for methane conversion yielding primarily CO. However, promotion of VPO with Fe, Cr, and other first row transition metals led to measurable yields for formaldehyde, as noted in the summary table. Catalyst characterization studies indicated that the role of promoters was to stabilize some of the vanadium in the V{sup 5+} oxidation state rather than the V{sup 4+} state formally expected for (VO){sub 2}P{sub 2}O{sub 7}.

  11. Bacterial methane oxidation in the region of shallow-water gas hydrotherms of the western part of the Pacific Ocean

    SciTech Connect

    Namsaraev, B.B.; Kachalkin, V.I.; Dulov, L.E.; Obzhirov, A.I.

    1995-01-01

    Methane content and rates of its oxidation in near-bottom water and bottom sediments were studied in the regions of submarine volcano Epi (New Hebrides Islands), Matupy Harbor (New Britain Island), and Kraternaya Bay (Yankich Island, Kurile Islands). The rate of methane oxidation ranged from 0.0001 to 2.097 {mu}/(1 day) in near-bottom water and from 0.0004 to 37.73 {mu}l/(kg day) in sediments. High concentrations of methane and high temperatures characteristic of the studied ecosystems favor the active process of CH{sub 4} oxidation. 9 refs., 2 figs., 5 tabs.

  12. A methane-driven microbial food web in a wetland rice soil.

    PubMed

    Murase, Jun; Frenzel, Peter

    2007-12-01

    Methane oxidation is a key process controlling methane emission from anoxic habitats into the atmosphere. Methanotrophs, responsible for aerobic methane oxidation, do not only oxidize but also assimilate methane. Once assimilated, methane carbon may be utilized by other organisms. Here we report on a microbial food web in a rice field soil driven by methane. A thin layer of water-saturated rice field soil was incubated under opposing gradients of oxygen and (13)C-labelled methane. Bacterial and eukaryotic communities incorporating methane carbon were analysed by RNA-stable isotope probing (SIP). Terminal restriction fragment length polymorphism (T-RFLP) and cloning showed that methanotrophs were the most prominent group of bacteria incorporating methane carbon. In addition, a few Myxobacteria-related sequences were obtained from the 'heavy' rRNA fraction. Denaturing gradient gel electrophoresis (DGGE) targeting 18S rRNA detected various groups of protists in the 'heavy' rRNA fraction including naked amoeba (Lobosea and Heterolobosea), ciliates (Colpodea) and flagellates (Cercozoa). Incubation of soil under different methane concentrations in air resulted in the development of distinct protozoan communities. These results suggest that methane carbon is incorporated into non-methanotrophic pro- and microeukaryotes probably via grazing, and that methane oxidation is a shaping force of the microeukaryotic community depending on methane availability.

  13. Aerobic oxidation of alkylaromatics using a lipophilic N-hydroxyphthalimide: overcoming the industrial limit of catalyst solubility.

    PubMed

    Petroselli, Manuel; Franchi, Paola; Lucarini, Marco; Punta, Carlo; Melone, Lucio

    2014-09-01

    4,4'-(4,4'-Isopropylidenediphenoxy)bis(N-hydroxyphthalimide), which is a new lipophilic analogue of N-hydroxyphthalimide, can act as an effective catalyst in the aerobic oxidation of alkylaromatics under reduced amounts of polar cosolvent. The catalyst was selected on the basis of an in-depth study of the influence that substituents on the aromatic ring of N-hydroxyphthalimide exert on determining the NO-H bond dissociation energy (BDE). BDE values for a range of model molecules are calculated by DFT and measured by EPR spectroscopy. The new catalyst can be successfully employed in the aerobic oxidation of cumene, ethylbenzene, and cyclohexylbenzene, affording, in all cases, good conversions and high selectivity for the corresponding hydroperoxide. The effect of solvent, catalyst, and temperature has also been investigated.

  14. Development of vanadium-phosphate catalysts for methanol production by selective oxidation of methane

    SciTech Connect

    McCormick, R.L.

    1995-12-31

    The United States has vast natural gas reserves which could contribute significantly to our energy security if economical technologies for conversion to liquid fuels and chemicals were developed. Many of these reserves are small scale or in remote locations and of little value unless they can be transported to consumers. Transportation is economically performed via pipeline, but this route is usually unavailable in remote locations. Another option is to convert the methane in the gas to liquid hydrocarbons, such as methanol, which can easily and economically be transported by truck. Therefore, the conversion of methane to liquid hydrocarbons has the potential to decrease our dependence upon oil imports by opening new markets for natural gas and increasing its use in the transportation and chemical sectors of the economy. In this project, we are attempting to develop, and explore new catalysts capable of direct oxidation of methane to methanol. The specific objectives of this work are discussed.

  15. Subtropical freshwater storages: a major source of nitrous oxide and methane?

    NASA Astrophysics Data System (ADS)

    Sturm, Katrin; Grinham, Alistair; Yuan, Zhiguo

    2013-04-01

    Studies of greenhouse gas cycling in subtropical water bodies, particularly in the Southern Hemisphere, are very limited. This represents an important gap in our understanding of global emissions as the higher temperatures experienced in the subtropics will likely accelerate greenhouse gas production and consumption. Critical to understanding the net impact of these accelerated rates are detailed studies of representative systems within this region. In this paper we present a model artificial freshwater storage: Gold Creek Dam in South East Queensland, Australia. Freshwater storages are commonplace for drinking water and irrigation purposes in Australia as unpredictable rainfall patterns make river and ground water sources unreliable. Over 85 % of Australian rivers are modified with weirs and dams providing permanent inundation of previously terrestrial environments. The higher temperatures experienced at these latitudes drive thermal stratification of these systems as well as rapidly deoxygenate bottom waters. High organic matter availability in the sediment zone as well as the anoxic overlying water provide ideal conditions for reduced products (including methane and ammonia) from microbial processing to be formed and diffuse into bottom waters. A mid-water metalimnion is generally associated with large gradients in dissolved oxygen availability and reduced metabolites undergo oxidation prior to their emission from water surface. An intensive field study was undertaken to improve understanding of production and transformation rates of methane and nitrous oxide from the sediments, through the water column and to the atmosphere. Sediment nutrient (ammonia, nitrite/nitrate and filterable reactive phosphorus) and greenhouse gas (methane and nitrous oxide) porewater samples were collected at selected sites. To determine the magnitude of the benthic sediment contribution of methane and nitrous oxide to the water column sediment incubations were conducted in the

  16. Potential methane production and oxidation in soil reclamation covers of an oil sands mining site in Alberta, Canada

    NASA Astrophysics Data System (ADS)

    Pum, Lisa; Reichenauer, Thomas; Germida, Jim

    2015-04-01

    Anthropogenic activities create a number of significant greenhouse gases and thus potentially contribute to global warming. Methane production is significant in some agricultural production systems and from wetlands. In soil, methane can be oxidised by methanotrophic bacteria. However, little is known about methane production and oxidation in oil sand reclamation covers. The purpose of this study was to investigate methane production and oxidation potential of tailing sands and six different reclamation layers of oil sands mining sites in Alberta, Canada. Methane production and oxidation potential were investigated in laboratory scale microcosms through continuous headspace analysis using gas chromatography. Samples from a reclamation layer were collected at the Canadian Natural Resources Limited (CNRL) reclamation site at depths of 0-10 cm, 10-20 cm and 20-40 cm in October 2014. In addition, tailing sands provided by Suncor Energy Inc. and soil from a CNRL wetland were studied for methane production. Samples were dried, crushed and sieved to 4 mm, packed into serum bottle microcosms and monitored for eight weeks. Methane production potential was assessed by providing an anoxic environment and by adjusting the samples to a moisture holding capacity of 100 %. Methane oxidation potential was examined by an initial application of 2 vol % methane to the microcosms and by adjusting the samples to a moisture holding capacity of 50 %. Microcosm headspace gas was analysed for methane, carbon dioxide, nitrous oxide and oxygen. All experiments were carried out in triplicates, including controls. SF6 and Helium were used as internal standards to detect potential leaks. Our results show differences for methane production potential between the soil depths, tailing sands and wetlands. Moreover, there were differences in the methane oxidation potential of substrate from the three depths investigated and between the reclamation layers. In conclusion, the present study shows that

  17. [Enhanced Resistance of Pea Plants to Oxidative: Stress Caused by Paraquat during Colonization by Aerobic Methylobacteria].

    PubMed

    Agafonova, N V; Doronina, N Y; Trotsenko, Yu A

    2016-01-01

    The influence of colonization of the pea (Pisum sativum L.) by aerobic methylobacteria of five different species (Methylophilus flavus Ship, Methylobacterium extorquens G10, Methylobacillus arboreus Iva, Methylopila musalis MUSA, Methylopila turkiensis Sidel) on plant resistance to paraquat-induced stresses has been studied. The normal conditions of pea colonization by methylobacteria were characterized by a decrease in the activity of antioxidant enzymes (superoxide dismutase, catalase, and peroxidases) and in the concentrations of endogenous H2O2, proline, and malonic dialdehyde, which is a product of lipid peroxidation and indicator of damage to plant cell membranes, and an increase in the activity of the photosynthetic apparatus (the content of chlorophylls a, b and carotenoids). In the presence of paraquat, the colonized plants had higher activities of antioxidant enzymes, stable photosynthetic indices, and a less intensive accumulation of the products of lipid peroxidation as compared to noncolonized plants. Thus, colonization by methylobacteria considerably increased the adaptive protection of pea plants to the paraquat-induced oxidative stress.

  18. Praseodymium incorporated AIPO-5 molecular sieves for aerobic oxidation of ethylbenzene.

    PubMed

    Sundaravel, B; Babu, C M; Palanisamy, B; Palanichamy, M; Shanthi, K; Murugesan, V

    2013-04-01

    PrAlPO-5 with (Al + P)/Pr ratios of 25, 50, 75 and 100 molecular sieves were successfully synthesized by hydrothermal method. These molecular sieves were characterised using XPS, TPD-NH3, ex-situ pyridine adsorbed IR, TPR, TGA, 27Al and 31P MAS-NMR and ESR studies. The incorporation of praseodymium in the framework of AlPO-5 was confirmed by XRD, DRS UV-vis and 27Al and 31P MAS-NMR analysis. ESR spectrum showed the presence of adsorbed oxygen. The nature and strength of acid sites were identified by ex-situ pyridine adsorbed IR and TPD-NH3. The BET surface area was found to be in the range of 238-272 m2 g(-1). The catalytic activity of the molecular sieves was tested for the liquid phase aerobic oxidation of ethylbenzene. Acetophenone was found to be the major product with more than 90% ethylbenzene conversion. ICP-OES analysis revealed the presence of praseodymium intact in the framework of AlPO-5 up to five cycles.

  19. [Enhanced Resistance of Pea Plants to Oxidative: Stress Caused by Paraquat during Colonization by Aerobic Methylobacteria].

    PubMed

    Agafonova, N V; Doronina, N Y; Trotsenko, Yu A

    2016-01-01

    The influence of colonization of the pea (Pisum sativum L.) by aerobic methylobacteria of five different species (Methylophilus flavus Ship, Methylobacterium extorquens G10, Methylobacillus arboreus Iva, Methylopila musalis MUSA, Methylopila turkiensis Sidel) on plant resistance to paraquat-induced stresses has been studied. The normal conditions of pea colonization by methylobacteria were characterized by a decrease in the activity of antioxidant enzymes (superoxide dismutase, catalase, and peroxidases) and in the concentrations of endogenous H2O2, proline, and malonic dialdehyde, which is a product of lipid peroxidation and indicator of damage to plant cell membranes, and an increase in the activity of the photosynthetic apparatus (the content of chlorophylls a, b and carotenoids). In the presence of paraquat, the colonized plants had higher activities of antioxidant enzymes, stable photosynthetic indices, and a less intensive accumulation of the products of lipid peroxidation as compared to noncolonized plants. Thus, colonization by methylobacteria considerably increased the adaptive protection of pea plants to the paraquat-induced oxidative stress. PMID:27266250

  20. Mechanisms and controlling characteristics of the catalytic oxidation of methane

    SciTech Connect

    Klier, Kamil; Simmons, Gary W.; Herman, Richard G.; Park, Kenneth T.; Hess, James S.; Hunsicker, Robert A.

    1999-07-01

    Methane dissociation and oxygen activation have been found to be structure sensitive on different single crystal palladium surfaces. Geometrically restricted surfaces on Pd single crystal and polycrystalline surfaces using tetrachloroethylene and pentamethylcyclopentasiloxane have been formed and compared with surface structures formed using dichloromethane and chlorine. The adsorption and activation of O{sub 2}, CO, and H{sub 2}O on clean Pd surfaces and those containing the surface ensembles have also been investigated. To interpret high-resolution angle-resolved x-ray photoelectron spectra (HR AR-XPS), a new self-modeling method of resolving HR-XPS spectra was developed and applied to the experimental spectra. The effects of electron-accepting Cl, O{sub 2}, and H{sub 2}O adsobated on Cs/MoS{sub 2} were determined.

  1. Anaerobic oxidation of methane alters sediment records of sulfur, iron and phosphorus in the Black Sea

    NASA Astrophysics Data System (ADS)

    Egger, Matthias; Kraal, Peter; Jilbert, Tom; Sulu-Gambari, Fatimah; Sapart, Célia J.; Röckmann, Thomas; Slomp, Caroline P.

    2016-09-01

    The surface sediments in the Black Sea are underlain by extensive deposits of iron (Fe)-oxide-rich lake sediments that were deposited prior to the inflow of marine Mediterranean Sea waters ca. 9000 years ago. The subsequent downward diffusion of marine sulfate into the methane-bearing lake sediments has led to a multitude of diagenetic reactions in the sulfate-methane transition zone (SMTZ), including anaerobic oxidation of methane (AOM) with sulfate. While the sedimentary cycles of sulfur (S), methane and Fe in the SMTZ have been extensively studied, relatively little is known about the diagenetic alterations of the sediment record occurring below the SMTZ.Here we combine detailed geochemical analyses of the sediment and porewater with multicomponent diagenetic modeling to study the diagenetic alterations below the SMTZ at two sites in the western Black Sea. We focus on the dynamics of Fe, S and phosphorus (P), and demonstrate that diagenesis has strongly overprinted the sedimentary burial records of these elements. In line with previous studies in the Black Sea, we show that sulfate-mediated AOM substantially enhances the downward diffusive flux of sulfide into the deep limnic deposits. During this downward sulfidization, Fe oxides, Fe carbonates and Fe phosphates (e.g., vivianite) are converted to sulfide phases, leading to an enrichment in solid-phase S and the release of phosphate to the porewater. Below the sulfidization front, high concentrations of dissolved ferrous Fe (Fe2+) lead to sequestration of downward-diffusing phosphate as authigenic vivianite, resulting in a transient accumulation of total P directly below the sulfidization front.Our model results further demonstrate that downward-migrating sulfide becomes partly re-oxidized to sulfate due to reactions with oxidized Fe minerals, fueling a cryptic S cycle and thus stimulating slow rates of sulfate-driven AOM ( ˜ 1-100 pmol cm-3 d-1) in the sulfate-depleted limnic deposits. However, this process is

  2. Aerobic oxidation of diverse primary alcohols to methyl esters with a readily accessible heterogeneous Pd/Bi/Te catalyst.

    PubMed

    Powell, Adam B; Stahl, Shannon S

    2013-10-01

    Efficient aerobic oxidative methyl esterification of primary alcohols has been achieved with a heterogeneous catalyst consisting of 1 mol % Pd/charcoal (5 wt %) in combination with bismuth(III) nitrate and tellurium metal. The Bi and Te additives significantly increase the reaction rate, selectivity, and overall product yields. This readily accessible catalyst system exhibits a broad substrate scope and is effective with both activated (benzylic) and unactivated (aliphatic) alcohols bearing diverse functional groups. PMID:24050194

  3. Differential methane oxidation activity and microbial community composition at cold seeps in the Arctic off western Svalbard

    NASA Astrophysics Data System (ADS)

    Gründger, Friederike; Svenning, Mette M.; Niemann, Helge; Silyakova, Anna; Serov, Pavel; Li Hong, Wei; Wegener, Gunter; Panieri, Giuliana; Carroll, JoLynn

    2016-04-01

    Most models considering climate change related bottom water warming suggest that gas hydrates may become destabilized, leading to the mobilization of methane into seabed and water column ecosystems, and, eventually, into the atmosphere. However, the capacity of methanotrophic microbes retaining methane in sediments and the hydrosphere is not well constrained. Here, we investigate the microbial utilization of methane in sediments and the water column, focusing on cold seeps discovered at the arctic continental margin of western Svalbard. We measured ex situ rates of methane oxidation and sulfate reduction in two active gas flare sites with different geological settings at the Vestnesa Ridge (1204 m water depth) and within a pingolike feature area southwest off Svalbard (PLF; 380 m water depth). Our results show contrarily situations at our two sampling sites: At Vestnesa Ridge we find high methane oxidation rates with values up to 2055 nmol cm-3 d-1 at the sediment surface where the sediments are oversaturated with methane. Whereas, methane concentration and oxidation rates are low in the overlying water column (2 pmol cm-3 d-1). In contrast, at the sediment surface at PLF methane concentration and oxidation rates are considerably lower (up to 1.8 nmol cm-3 d-1). While the overlying bottom water contains high concentration of methane and shows oxidation rates with values of up to 3.8 nmol cm-3 d-1. The data on methane oxidation and sulfate reduction activity are compared to the sediment geochemistry and to data from metagenomic analysis identifying the methanotrophic community composition. These results provide unique insight into the dynamic responses of the seabed biological filter at cold seeps in the Arctic off western Svalbard. This study is part of the Centre for Arctic Gas Hydrate, Environment and Climate and was supported by the Research Council of Norway through its Centres of Excellence funding scheme grant No. 223259.

  4. Selective methane oxidation over promoted oxide catalysts. Quarterly technical progress report, September 8, 1992--November 30, 1992

    SciTech Connect

    Klier, K.; Herman, R.G.; Sun, Q.; Sarkany, J.

    1993-01-01

    Support effects on catalytic reactions, especially of highly exothermic oxidation reactions, can be very significant. Since we had shown that a MoO{sub 3}/SiO{sub 2} catalyst, especially when used in a double bed configuration with a Sr/La{sub 2}O{sub 3} catalyst, can selectively oxidize methane to formaldehyde, the role of the SiO{sub 2} support was investigated. Therefore, partial oxidation of methane by oxygen to form formaldehyde, carbon oxides, and C{sub 2} products (ethane and ethene) has been studied over silica catalyst supports (fumed Cabosil and Grace 636 silica gel) in the 630-780{degrees}C temperature range under ambient pressure. When relatively high gas hourly space velocities (GHSV) were utilized, the silica catalysts exhibit high space time yields (at low conversions) for methane partial oxidation to formaldehyde, and the C{sub 2} hydrocarbons were found to be parallel products with formaldehyde. In general, the selectivities toward CO were high while those toward CO{sub 2} were low. Based on the present results obtained by a double catalyst bed experiment, the observations of product composition dependence on the variation of GHSV (i.e. gas residence time), and differences in apparent activation energies of formation of C{sub 2}H{sub 6}, and CH{sub 2}O, a reaction mechanism is proposed for the activation of methane over the silica surface. This mechanism can explain the observed product distribution patterns (specifically the parallel formation of formaldehyde and C{sub 2} hydrocarbons).

  5. Influence of heavy metals on methane oxidation in tropical rice soils.

    PubMed

    Mohanty, S R; Bharati, K; Deepa, N; Rao, V R; Adhya, T K

    2000-11-01

    In a laboratory incubation study, the effect of select heavy metals on methane (CH4) oxidation in two rice soils was investigated under two moisture regimes. Heavy metals differed in their effect on CH4 oxidation in both soils under the two water regimes. Cr significantly inhibited CH4 oxidation in the alluvial soil at 60% moisture holding capacity, while Cu stimulated the process. On the contrary, Zn inhibited CH4 oxidation in both alluvial and laterite soils only under flooded conditions. Application of rice straw alleviated the inhibitory effect of heavy metals on CH4 oxidation and CO2 production. Inhibition of CH4 oxidation in the alluvial soil was related to the methanotrophic bacterial population in Cr- and Zn-amended alluvial soil. PMID:11139181

  6. Influence of heavy metals on methane oxidation in tropical rice soils.

    PubMed

    Mohanty, S R; Bharati, K; Deepa, N; Rao, V R; Adhya, T K

    2000-11-01

    In a laboratory incubation study, the effect of select heavy metals on methane (CH4) oxidation in two rice soils was investigated under two moisture regimes. Heavy metals differed in their effect on CH4 oxidation in both soils under the two water regimes. Cr significantly inhibited CH4 oxidation in the alluvial soil at 60% moisture holding capacity, while Cu stimulated the process. On the contrary, Zn inhibited CH4 oxidation in both alluvial and laterite soils only under flooded conditions. Application of rice straw alleviated the inhibitory effect of heavy metals on CH4 oxidation and CO2 production. Inhibition of CH4 oxidation in the alluvial soil was related to the methanotrophic bacterial population in Cr- and Zn-amended alluvial soil.

  7. Permafrost Thaw Induces Methane Oxidation in Transitional Thaw Stages in a Subarctic Peatland

    NASA Astrophysics Data System (ADS)

    Perryman, C. R.; Kashi, N. N.; Malhotra, A.; McCalley, C. K.; Varner, R. K.

    2015-12-01

    Rising temperatures in the subarctic are accelerating permafrost thaw and increasing methane (CH4) emissions from subarctic peatlands. Methanotrophs in these peatlands can consume/oxidize CH4, potentially mitigating CH4 emissions in these peatlands. Oxidation rates can exceed 90% of CH4 production in some settings, depending on O2 and CH4 availability and environmental conditions. Malhotra and Roulet identified 10 thaw stages in Stordalen Mire near Abisko, Sweden (68°21'N,18°49'E ) with variable vegetation, environmental conditions, and associated CH4 emissions. We investigated potential methane oxidation rates across these thaw stages. Peat cores were extracted from two depths at each stage and incubated in 350ml glass jars at in situ temperatures and CH4 concentrations. Headspace samples were collected from each incubation jar over a 48-hour period and analyzed for CH4 concentration using flame ionization detection gas chromatography (GC-FID). Oxidation rates ranged from <0.1 to 17 μg of CH4 per gram of dry biomass per day. Water table depth and pore water pH were the strongest environmental correlates of oxidation (sample size = 56, p < 0.001). The highest potential oxidation rates were observed in collapsing palsa sites and recently collapsed sedge-dominated open water sites near palsa mounds. Our results suggest that permafrost thaw induces high CH4 oxidation rates by creating conditions ideal for both methanogenic and methanotrophic microbial communities. Our results also reinforce the importance of incorporating transitional thaw stages in landscape level carbon budgets of thawing peatlands emphasized by Malhotra and Roulet. Forthcoming microbial analysis and stable isotope analysis will further elucidate the factors controlling methane oxidation rates at Stordalen Mire.

  8. Anaerobic oxidation of methane by sulfate in hypersaline groundwater of the Dead Sea aquifer

    PubMed Central

    Avrahamov, N; Antler, G; Yechieli, Y; Gavrieli, I; Joye, S B; Saxton, M; Turchyn, A V; Sivan, O

    2014-01-01

    Geochemical and microbial evidence points to anaerobic oxidation of methane (AOM) likely coupled with bacterial sulfate reduction in the hypersaline groundwater of the Dead Sea (DS) alluvial aquifer. Groundwater was sampled from nine boreholes drilled along the Arugot alluvial fan next to the DS. The groundwater samples were highly saline (up to 6300 mm chlorine), anoxic, and contained methane. A mass balance calculation demonstrates that the very low δ13CDIC in this groundwater is due to anaerobic methane oxidation. Sulfate depletion coincident with isotope enrichment of sulfur and oxygen isotopes in the sulfate suggests that sulfate reduction is associated with this AOM. DNA extraction and 16S amplicon sequencing were used to explore the microbial community present and were found to be microbial composition indicative of bacterial sulfate reducers associated with anaerobic methanotrophic archaea (ANME) driving AOM. The net sulfate reduction seems to be primarily controlled by the salinity and the available methane and is substantially lower as salinity increases (2.5 mm sulfate removal at 3000 mm chlorine but only 0.5 mm sulfate removal at 6300 mm chlorine). Low overall sulfur isotope fractionation observed (34ε = 17 ± 3.5‰) hints at high rates of sulfate reduction, as has been previously suggested for sulfate reduction coupled with methane oxidation. The new results demonstrate the presence of sulfate-driven AOM in terrestrial hypersaline systems and expand our understanding of how microbial life is sustained under the challenging conditions of an extremely hypersaline environment. PMID:25039851

  9. Carbon and hydrogen isotope fractionation by microbial methane oxidation: Improved determination

    SciTech Connect

    Mahieu, Koenraad . E-mail: Koenraad.Mahieu@Ugent.be; Visscher, Alex De; Vanrolleghem, Peter A.; Cleemput, Oswald Van

    2006-07-01

    Isotope fractionation is a promising tool for quantifying methane oxidation in landfill cover soils. For good quantification an accurate determination of the isotope fractionation factor ({alpha}) of methane oxidation based on independent batch experiments with soil samples from the landfill cover is required. Most studies so far used data analysis methods based on approximations of the Rayleigh model to determine {alpha}. In this study, the two most common approximations were tested, the simplified Rayleigh approach and the Coleman method. To do this, the original model of Rayleigh was described in measurable variables, methane concentration and isotopic abundances, and fitted to batch oxidation data by means of a weighted non-linear errors-in-variables regression technique. The results of this technique were used as a benchmark to which the results of the two conventional approximations were compared. Three types of batch data were used: simulated data, data obtained from the literature, and data obtained from new batch experiments conducted in our laboratory. The Coleman approximation was shown to be acceptable but not recommended for carbon fractionation (error on {alpha} - 1 up to 5%) and unacceptable for hydrogen fractionation (error up to 20%). The difference between the simplified Rayleigh approach and the exact Rayleigh model is much smaller for both carbon and hydrogen fractionation (error on {alpha} - 1 < 0.05%). There is also a small difference when errors in both variables (methane concentration and isotope abundance) are accounted for instead of assuming an error-free independent variable. By means of theoretical calculations general criteria, not limited to methane, {sup 13}C, or D, were developed for the validity of the simplified Rayleigh approach when using labelled compounds.

  10. Temperature response of methane oxidation and production potentials in peatland ecosystems across Finland

    NASA Astrophysics Data System (ADS)

    Welti, Nina; Korrensalo, Aino; Kerttula, Johanna; Maljanen, Marja; Uljas, Salli; Lohila, Annalea; Laine, Anna; Vesala, Timo; Elliott, David; Tuittila, Eeva-Stiina

    2016-04-01

    It has been suggested that the ecosystems located in the high latitudes are especially sensitive to warming. Therefore, we compared 14 peatland systems throughout Finland along a latitudinal gradient from 69°N to 61°N to examine the response of methane production and methane oxidation with warming climate. Peat samples were taken at the height of the growing season in 2015 from 0 - 10cm below the water table depth. The plant communities in sampling locations were described by estimating cover of each plant species and pH of water was measured. Upon return to the lab, we made two parallel treatments, under anoxic and oxic conditions in order to calculate the CH4 production and consumption potentials of the peat and used three temperatures, 4°C, 17.5°C, and 30°C to examine the temperature effect on the potentials. We hypothesized that there will be an observable response curve in CH4 production and oxidation relative to temperature with a greater response with increasing latitude. In general, increasing temperature increased the potential for CH4 production and oxidation, at some sites, the potential was highest at 17.5°C, indicating that there is an optimum temperature threshold for the in situ methane producing and oxidizing microbial communities. Above this threshold, the peat microbial communities are not able to cope with increasing temperature. This is especially noticeable for methane oxidation at sites above 62°N. As countries are being expected to adequately account for their greenhouse gas budgets with increasing temperature models, knowing where the temperature threshold exists is of critical importance.

  11. Species and temperature measurements of methane oxidation in a nanosecond repetitively pulsed discharge.

    PubMed

    Lefkowitz, Joseph K; Guo, Peng; Rousso, Aric; Ju, Yiguang

    2015-08-13

    Speciation and temperature measurements of methane oxidation during a nanosecond repetitively pulsed discharge in a low-temperature flow reactor have been performed. Measurements of temperature and formaldehyde during a burst of pulses were made on a time-dependent basis using tunable diode laser absorption spectroscopy, and measurements of all other major stable species were made downstream of a continuously pulsed discharge using gas chromatography. The major species for a stoichiometric methane/oxygen/helium mixture with 75% dilution are H(2)O, CO, CO(2), H(2), CH(2)O, CH(3)OH, C(2)H(6), C(2)H(4) and C(2)H(2). A modelling tool to simulate homogeneous plasma combustion kinetics is assembled by combining the ZDPlasKin and CHEMKIN codes. In addition, a kinetic model for plasma-assisted combustion (HP-Mech/plasma) of methane, oxygen and helium mixtures has been assembled to simulate the measurements. Predictions can accurately capture reactant consumption as well as production of the major product species. However, significant disagreement is found for minor species, particularly CH(2)O and CH(3)OH. Further analysis revealed that the plasma-activated low-temperature oxidation pathways, particularly those involving CH(3)O(2) radical reactions and methane reactions with O((1)D), are responsible for this disagreement. PMID:26170433

  12. New insights into the physiology of the anaerobic oxidation of methane

    NASA Astrophysics Data System (ADS)

    Krüger, M.; Nauhaus, K.; Treude, T.; Boetius, A.; Widdel, F.

    2003-04-01

    During the last decades the anaerobic oxidation of methane (AOM) has been intensively studied using numerous different approaches. Biomarker and molecular 16S rRNA-targeting studies showed for the study site at Hydrate Ridge that a consortium of sulfate-reducing bacteria and ANME-II-archaea is mediating this globally important process. So far, any attempt to isolate the microorganisms involved has not been successful. However, we could confirm under laboratory conditions the 1 to 1 stoichiometry of sulfate to methane in environmental samples from Hydrate Ridge. An incubation temperature between 4--15 degrees C, high methane partial pressures, and sulfate concentrations close to those in seawater were optimal for AOM activity. The application of inhibitors of sulfate reduction or methanogenesis stopped AOM. The addition of hydrogen, formate, or acetate -- as potential intermediates -- instead of methane did not result in sulfate reduction. Also, known electron shuttles, like AQDS, humic acids or different phenazines, did not lead to a stimluation of AOM. At Hydrate Ridge, AOM appeared to be exclusively coupled to the use of sulfate as terminal electron acceptor. Other alternative electron acceptors, including nitrate, ferric iron, sulphur, fumarate, or manganese oxide, were reduced, but this was not coupled to AOM.

  13. Diversity and methane oxidation of active epibiotic methanotrophs on live Shinkaia crosnieri

    PubMed Central

    Watsuji, Tomo-o; Yamamoto, Asami; Takaki, Yoshihiro; Ueda, Kenji; Kawagucci, Shinsuke; Takai, Ken

    2014-01-01

    Shinkaia crosnieri is a galatheid crab that predominantly dwells in deep-sea hydrothermal systems in the Okinawa Trough, Japan. In this study, the phylogenetic diversity of active methanotrophs in the epibiotic microbial community on the setae of S. crosnieri was characterized by reverse transcription-polymerase chain reaction (RT-PCR) of a functional gene (pmoA) encoding a subunit of particulate methane monooxygenase. Phylogenetic analysis of pmoA transcript sequences revealed that the active epibiotic methanotrophs on S. crosnieri setae consisted of gammaproteobacterial type Ia and Ib methanotrophs. The effect of different RNA stabilization procedures on the abundance of pmoA and 16S rRNA transcripts in the epibiotic community was estimated by quantitative RT-PCR. Our novel RNA fixation method performed immediately after sampling effectively preserved cellular RNA assemblages, particularly labile mRNA populations, including pmoA mRNA. Methane consumption in live S. crosnieri was also estimated by continuous-flow incubation under atmospheric and in situ hydrostatic pressures, and provided a c