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Sample records for aerobic ch4 oxidation

  1. Using carbon isotope fractionation for an improved quantification of CH4 oxidation efficiency in Arctic peatlands

    NASA Astrophysics Data System (ADS)

    Preuss, I.; Knoblauch, C.; Gebert, J.; Pfeiffer, E.-M.

    2012-04-01

    Much research effort is focused on identifying global CH4 sources and sinks to estimate their current and potential strength in response to land-use change and global warming. Aerobic CH4 oxidation is regarded as the key process reducing the strength of CH4 emissions in wetlands, but is hitherto difficult to quantify. Recent studies quantify the efficiency of CH4 oxidation based on CH4 stable isotope signatures. The approach utilizes the fact that a significant isotope fractionation occurs when CH4 is oxidized. Moreover, it also considers isotope fractionation by diffusion. For field applications the 'open-system equation' is applied to determine the CH4 oxidation efficiency: fox = (δE - δP)/ (αox - αtrans) where fox is the fraction of CH4 oxidized; δE is δ13C of emitted CH4; δP is δ13C of produced CH4; αox is the isotopic fractionation factor of oxidation; αtrans is the isotopic fractionation factor of transport. We quantified CH4 oxidation in polygonal tundra soils of Russia's Lena River Delta analyzing depth profiles of CH4 concentrations and stable isotope signatures. Therefore, both fractionation factors αox and αtrans were determined for three polygon centers with differing water table positions and a polygon rim. While most previous studies on landfill cover soils have assumed a gas transport dominated by advection (αtrans = 1), other CH4 transport mechanisms as diffusion have to be considered in peatlands and αtrans exceeds a value of 1. At our study we determined αtrans = 1.013 ± 0.003 for CH4 when diffusion is the predominant transport mechanism. Furthermore, results showed that αox differs widely between sites and horizons (αox = 1.013 ± 0.012) and has to be determined for each case. The impact of both fractionation factors on the quantification of CH4 oxidation was estimated by considering both the potential diffusion rate at different water contents and potential oxidation rates. Calculations for a water saturated tundra soil

  2. Improved quantification of microbial CH4 oxidation efficiency in arctic wetland soils using carbon isotope fractionation

    NASA Astrophysics Data System (ADS)

    Preuss, I.; Knoblauch, C.; Gebert, J.; Pfeiffer, E.-M.

    2013-04-01

    Permafrost-affected tundra soils are significant sources of the climate-relevant trace gas methane (CH4). The observed accelerated warming of the arctic will cause deeper permafrost thawing, followed by increased carbon mineralization and CH4 formation in water-saturated tundra soils, thus creating a positive feedback to climate change. Aerobic CH4 oxidation is regarded as the key process reducing CH4 emissions from wetlands, but quantification of turnover rates has remained difficult so far. The application of carbon stable isotope fractionation enables the in situ quantification of CH4 oxidation efficiency in arctic wetland soils. The aim of the current study is to quantify CH4 oxidation efficiency in permafrost-affected tundra soils in Russia's Lena River delta based on stable isotope signatures of CH4. Therefore, depth profiles of CH4 concentrations and δ13CH4 signatures were measured and the fractionation factors for the processes of oxidation (αox) and diffusion (αdiff) were determined. Most previous studies employing stable isotope fractionation for the quantification of CH4 oxidation in soils of other habitats (such as landfill cover soils) have assumed a gas transport dominated by advection (αtrans = 1). In tundra soils, however, diffusion is the main gas transport mechanism and diffusive stable isotope fractionation should be considered alongside oxidative fractionation. For the first time, the stable isotope fractionation of CH4 diffusion through water-saturated soils was determined with an αdiff = 1.001 ± 0.000 (n = 3). CH4 stable isotope fractionation during diffusion through air-filled pores of the investigated polygonal tundra soils was αdiff = 1.013 ± 0.003 (n = 18). Furthermore, it was found that αox differs widely between sites and horizons (mean αox = 1.017 ± 0.009) and needs to be determined on a case by case basis. The impact of both fractionation factors on the quantification of CH4 oxidation was analyzed by considering both the

  3. Improved quantification of microbial CH4 oxidation efficiency in Arctic wetland soils using carbon isotope fractionation

    NASA Astrophysics Data System (ADS)

    Preuss, I.; Knoblauch, C.; Gebert, J.; Pfeiffer, E.-M.

    2012-12-01

    Permafrost-affected tundra soils are significant sources of the climate-relevant trace gas methane (CH4). The observed accelerated warming of the Arctic will cause a deeper permafrost thawing followed by increased carbon mineralization and CH4 formation in water saturated tundra soils which might cause a positive feedback to climate change. Aerobic CH4 oxidation is regarded as the key process reducing CH4 emissions from wetlands, but quantification of turnover rates has remained difficult so far. The application of carbon stable isotope fractionation enables the in situ quantification of CH4 oxidation efficiency in arctic wetland soils. The aim of the current study is to quantify CH4 oxidation efficiency in permafrost-affected tundra soils in Russia's Lena River Delta based on stable isotope signatures of CH4. Therefore, depth profiles of CH4 concentrations and δ13CH4-signatures were measured and the fractionation factors for the processes of oxidation (αox) and diffusion (αdiff) were determined. Most previous studies employing stable isotope fractionation for the quantification of CH4 oxidation in soils of other habitats (e.g. landfill cover soils) have assumed a gas transport dominated by advection (αtrans = 1). In tundra soils, however, diffusion is the main gas transport mechanism, aside from ebullition. Hence, diffusive stable isotope fractionation has to be considered. For the first time, the stable isotope fractionation of CH4 diffusion through water-saturated soils was determined with an αdiff = 1.001 ± 0.000 (n = 3). CH4 stable isotope fractionation during diffusion through air-filled pores of the investigated polygonal tundra soils was αdiff = 1.013 ± 0.003 (n = 18). Furthermore, it was found that αox differs widely between sites and horizons (mean αox, = 1.017 ± 0.009) and needs to be determined individually. The impact of both fractionation factors on the quantification of CH4 oxidation was analyzed by considering both the potential diffusion

  4. A process-based inventory model for landfill CH4 emissions inclusive of seasonal soil microclimate and CH4 oxidation

    NASA Astrophysics Data System (ADS)

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

    2011-12-01

    We have developed and field-validated an annual inventory model for California landfill CH4 emissions that incorporates both site-specific soil properties and soil microclimate modeling coupled to 0.5° scale global climatic models. Based on 1-D diffusion, CALMIM (California Landfill Methane Inventory Model) is a freely available JAVA tool which models a typical annual cycle for CH4 emissions from site-specific daily, intermediate, and final landfill cover designs. Literature over the last decade has emphasized that the major factors controlling emissions in these highly managed soil systems are the presence or absence of engineered gas extraction, gaseous transport rates as affected by the thickness and physical properties of cover soils, and methanotrophic CH4 oxidation in cover materials as a function of seasonal soil microclimate. Moreover, current IPCC national inventory models for landfill CH4 emissions based on theoretical gas generation have high uncertainties and lack comprehensive field validation. This new approach, which is compliant with IPCC "Tier III" criteria, has been field-validated at two California sites (Monterey County; Los Angeles County), with limited field validation at three additional California sites. CALMIM accurately predicts soil temperature and moisture trends with emission predictions within the same order of magnitude as field measurements, indicating an acceptable initial model comparison in the context of published literature on measured CH4 emissions spanning 7 orders of magnitude. In addition to regional defaults for inventory purposes, CALMIM permits user-selectable parameters and boundary conditions for more rigorous site-specific applications where detailed CH4 emissions, meteorological, and soil microclimate data exist.

  5. Methanogenic Pathway and Fraction of CH4 Oxidized in Paddy Fields: Seasonal Variation and Effect of Water Management in Winter Fallow Season

    PubMed Central

    Zhang, Guangbin; Liu, Gang; Zhang, Yi; Ma, Jing; Xu, Hua; Yagi, Kazuyuki

    2013-01-01

    A 2-year field and incubation experiment was conducted to investigate δ13C during the processes of CH4 emission from the fields subjected to two water managements (flooding and drainage) in the winter fallow season, and further to estimate relative contribution of acetate to total methanogenesis (Fac) and fraction of CH4 oxidized (Fox) based on the isotopic data. Compared with flooding, drainage generally caused CH4, either anaerobically or aerobically produced, depleted in 13C. There was no obvious difference between the two in transport fractionation factor (εtransport) and δ13C-value of emitted CH4. CH4 emission was negatively related to its δ13C-value in seasonal variation (P<0.01). Acetate-dependent methanogenesis in soil was dominant (60–70%) in the late season, while drainage decreased Fac-value by 5–10%. On roots however, CH4 was mostly produced through H2/CO2 reduction (60–100%) over the season. CH4 oxidation mainly occurred in the first half of the season and roughly 10–90% of the CH4 was oxidized in the rhizosphere. Drainage increased Fox-value by 5–15%, which is possibly attributed to a significant decrease in production while no simultaneous decrease in oxidation. Around 30–70% of the CH4 was oxidized at the soil-water interface when CH4 in pore water was released into floodwater, although the amount of CH4 oxidized therein might be negligible relative to that in the rhizosphere. CH4 oxidation was also more important in the first half of the season in lab conditions and about 5–50% of the CH4 was oxidized in soil while almost 100% on roots. Drainage decreased Fox-value on roots by 15% as their CH4 oxidation potential was highly reduced. The findings suggest that water management in the winter fallow season substantially affects Fac in the soil and Fox in the rhizosphere and roots rather than Fac on roots and Fox at the soil-water interface. PMID:24069259

  6. Can soil gas profiles be used to assess microbial CH4 oxidation in landfill covers?

    PubMed

    Gebert, Julia; Röwer, Inga Ute; Scharff, Heijo; Roncato, Camila D L; Cabral, Alexandre R

    2011-05-01

    A method is proposed to estimate CH(4) oxidation efficiency in landfill covers, biowindows or biofilters from soil gas profile data. The approach assumes that the shift in the ratio of CO(2) to CH(4) in the gas profile, compared to the ratio in the raw landfill gas, is a result of the oxidation process and thus allows the calculation of the cumulative share of CH(4) oxidized up to a particular depth. The approach was validated using mass balance data from two independent laboratory column experiments. Values corresponded well over a wide range of oxidation efficiencies from less than 10% to nearly total oxidation. An incubation experiment on 40 samples from the cover soil of an old landfill showed that the share of CO(2) from respiration falls below 10% of the total CO(2) production when the methane oxidation capacity is 3.8 μg CH(4)g(dw)(-1)h(-1) or higher, a rate that is often exceeded in landfill covers and biofilters. The method is mainly suitable in settings where the CO(2) concentrations are not significantly influenced by processes such as respiration or where CH(4) loadings and oxidation rates are high enough so that CO(2) generated from CH(4) oxidation outweighs other sources of CO(2). The latter can be expected for most biofilters, biowindows and biocovers on landfills. This simple method constitutes an inexpensive complementary tool for studies that require an estimation of the CH(4) oxidation efficiency values in methane oxidation systems, such as landfill biocovers and biowindows. PMID:21074981

  7. CH4/CO2 ratios indicate highly efficient methane oxidation by a pumice landfill cover-soil.

    PubMed

    Pratt, Chris; Walcroft, Adrian S; Deslippe, Julie; Tate, Kevin R

    2013-02-01

    Landfills that generate too little biogas for economic energy recovery can potentially offset methane (CH(4)) emissions through biological oxidation by methanotrophic bacteria in cover soils. This study reports on the CH(4) oxidation efficiency of a 10-year old landfill cap comprising a volcanic pumice soil. Surface CH(4) and CO(2) fluxes were measured using field chambers during three sampling intervals over winter and summer. Methane fluxes were temporally and spatially variable (-0.36 to 3044 mgCH(4)m(-2)h(-1)); but were at least 15 times lower than typical literature CH(4) fluxes reported for older landfills in 45 of the 46 chambers tested. Exposure of soil from this landfill cover to variable CH(4) fluxes in laboratory microcosms revealed a very strong correlation between CH(4) oxidation efficiency and CH(4)/CO(2) ratios, confirming the utility of this relationship for approximating CH(4) oxidation efficiency. CH(4)/CO(2) ratios were applied to gas concentrations from the surface flux chambers and indicated a mean CH(4) oxidation efficiency of 72%. To examine CH(4) oxidation with soil depth, we collected 10 soil depth profiles at random locations across the landfill. Seven profiles exhibited CH(4) removal rates of 70-100% at depths <60 cm, supporting the high oxidation rates observed in the chambers. Based on a conservative 70% CH(4) oxidation efficiency occurring at the site, this cover soil is clearly offsetting far greater CH(4) quantities than the 10% default value currently adopted by the IPCC. PMID:23186636

  8. Estimation of mass transport parameters of gases for quantifying CH4 oxidation in landfill soil covers.

    PubMed

    Im, J; Moon, S; Nam, K; Kim, Y-J; Kim, J Y

    2009-02-01

    Methane (CH(4)), which is one of the most abundant anthropogenic greenhouse gases, is produced from landfills. CH(4) is biologically oxidized to carbon dioxide, which has a lower global warming potential than methane, when it passes through a cover soil. In order to quantify the amount of CH(4) oxidized in a landfill cover soil, a soil column test, a diffusion cell test, and a mathematical model analysis were carried out. In the column test, maximum oxidation rates of CH(4) (V(max)) showed higher values in the upper part of the column than those in the lower part caused by the penetration of O(2) from the top. The organic matter content in the upper area was also higher due to the active microbial growth. The dispersion analysis results for O(2) and CH(4) in the column are counter-intuitive. As the upward flow rate of the landfill gas increased, the dispersion coefficient of CH(4) slightly increased, possibly due to the effect of mechanical dispersion. On the other hand, as the upward flow rate of the landfill gas increased, the dispersion coefficient of O(2) decreased. It is possible that the diffusion of gases in porous media is influenced by the counter-directional flow rate. Further analysis of other gases in the column, N(2) and CO(2), may be required to support this hypothesis, but in this paper we propose the possibility that the simulations using the diffusion coefficient of O(2) under the natural condition may overestimate the penetration of O(2) into the soil cover layer and consequently overestimate the oxidation of CH(4). PMID:18804363

  9. A process-based inventory model for landfill CH4 emissions inclusive of seasonal soil microclimate and CH4 oxidation

    Technology Transfer Automated Retrieval System (TEKTRAN)

    We have developed and field-validated an annual inventory model for California landfill CH4 emissions that incorporates both site-specific soil properties and soil microclimate modeling coupled to 0.5o scale global climatic models. Based on 1-D diffusion, CALMIM (California Landfill Methane Inventor...

  10. 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.

  11. Effects of the conversion of cropland to forest on the CH4 oxidation capacity in soils.

    NASA Astrophysics Data System (ADS)

    Bárcena, Teresa G.; D'Imperio, Ludovica; Priemé, Anders; Gundersen, Per; Vesterdal, Lars; Christiansen, Jesper R.

    2013-04-01

    As the second most important greenhouse gas (GHG) in the atmosphere, methane (CH4) plays a central role in global warming. Diverse types of soil have been reported as potential CH4 sinks due to the activity of methane oxidizing bacteria (MOB), underlining the importance of this functional group of microorganisms on a global basis. Agricultural practices are known to negatively affect CH4 oxidation in soil, while afforestation of former agricultural soils has been shown to enhance CH4 oxidation over time. However, knowledge is scarce with regard to the mechanisms driving the process of CH4 oxidation in different land uses. Our aim was to study the changes in CH4 uptake capacity in soils along a land-use change gradient from cropland to forest. We performed an incubation experiment to study the CH4 oxidation capacity of the top mineral soil (0-5 cm and 5-15 cm depth) for sites representing the transition from agriculture to afforestation based on monoculture of three tree species with different stand ages: pedunculate oak (4, 19, 42 and >200 years old), European larch (22 and 41 years old) and Norway spruce (15 and 43 years old). Main soil parameters were also measured to determine differences in soil properties between sites. Methane oxidation rates were related to the abundance of the soil methanotrophic community based on quantitative PCR (qPCR). In addition, we also estimated the abundance of ammonia-oxidizing bacteria (AOB) and archaea (AOA), in order to investigate the link between these two similar functional groups. Although present, the abundance of AOB was under detection limit. The effects and interactions among all measured variables were summarized by Principal Component Analysis (PCA). Along the gradient, CH4 oxidation increased with increasing stand age in both soil layers (ranging from 0-1.3 nmol g-1dw d-1). However, we detected significant differences, in particular between oak and spruce, suggesting a possible tree species effect on the CH4

  12. The incorporation of graphene oxide into polysulfone mixed matrix membrane for CO2/CH4 separation

    NASA Astrophysics Data System (ADS)

    Zahri, K.; Goh, P. S.; Ismail, A. F.

    2016-06-01

    Carbon dioxide (CO2) is often found as the main impurity in natural gas, where methane (CH4) is the major component. The presence of CO2 in natural gas leads to several problems such as reducing the energy content of natural gas and cause pipeline corrosion. Thus it must be removed to meet specifications (CO2 ≤ 2 mol%) before the gas can be delivered to the pipeline. In this work, hollow fiber mixed matrix membrane (MMM) were fabricated by embedding graphene oxide (GO) into a polysulfone (PSf) polymer matrix to improve membrane properties as well as its separation performance towards CO2/CH4 gas. The membrane properties were investigated for pristine membrane and mixed matrix membrane filled with filler loading of 0.25%. The synthesized GO and properties of fabricated membranes were characterized and studied using TEM, AFM, XRD, FTIR and SEM respectively. The permeance of pure gases and ideal selectivity of CO2/CH4 gas were determined using pure gas permeation experiment. GO has affinity towards CO2 gas. The nanosheet structure creates path for small molecule gas and restricted large molecule gas to pass through the membrane. The incorporation of GO in PSf polymer enhanced the permeance of CO 2 and CO2/CH4 separation from 64.47 to 86.80 GPU and from 19 to 25 respectively.

  13. 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.

  14. Air-Independent Solid Oxide Fuel Cells for NASA's LOX-CH4 Landers

    NASA Technical Reports Server (NTRS)

    Ryan, Abigail C.; Araghi, Koorosh R.; Farmer, Serene C.

    2013-01-01

    Gemini, Apollo, and Space Shuttle used fuel cells as main power source for vehicle and water source for life support and thermal PEM (Gemini) and Alkaline (Apollo, Shuttle) fuel cells were used Ideal for short (less than 3 weeks) missions when the required O2 and H2 can be launched with the vehicle. New missions that might require long-duration stays in orbit or at a habitat, cannot rely on the availability of pure reactants but should also aim to be sun-independent - a problem for which Solid Oxide Fuel Cells might be the answer. Recently, NASA has investigated & developed LOX/CH4-propelled landers (Altair, MORPHEUS). In order to preserve mission flexibility, fuel cells are being studied as a potential power source. Much of NASA's fuel cell development has been focused on creating a dead-headed, non-flow through PEM fuel cells which would weigh less and be more reliable than the existing Alkaline and PEM technology; however, LOX/CH4 as a propellant introduces SOFCs as a power option due to their ability to accept those reactants without much reforming.

  15. Nitric Oxide Mediates Biofilm Formation and Symbiosis in Silicibacter sp. Strain TrichCH4B

    PubMed Central

    Rao, Minxi; Smith, Brian C.

    2015-01-01

    ABSTRACT Nitric oxide (NO) plays an important signaling role in all domains of life. Many bacteria contain a heme-nitric oxide/oxygen binding (H-NOX) protein that selectively binds NO. These H-NOX proteins often act as sensors that regulate histidine kinase (HK) activity, forming part of a bacterial two-component signaling system that also involves one or more response regulators. In several organisms, NO binding to the H-NOX protein governs bacterial biofilm formation; however, the source of NO exposure for these bacteria is unknown. In mammals, NO is generated by the enzyme nitric oxide synthase (NOS) and signals through binding the H-NOX domain of soluble guanylate cyclase. Recently, several bacterial NOS proteins have also been reported, but the corresponding bacteria do not also encode an H-NOX protein. Here, we report the first characterization of a bacterium that encodes both a NOS and H-NOX, thus resembling the mammalian system capable of both synthesizing and sensing NO. We characterized the NO signaling pathway of the marine alphaproteobacterium Silicibacter sp. strain TrichCH4B, determining that the NOS is activated by an algal symbiont, Trichodesmium erythraeum. NO signaling through a histidine kinase-response regulator two-component signaling pathway results in increased concentrations of cyclic diguanosine monophosphate, a key bacterial second messenger molecule that controls cellular adhesion and biofilm formation. Silicibacter sp. TrichCH4B biofilm formation, activated by T. erythraeum, may be an important mechanism for symbiosis between the two organisms, revealing that NO plays a previously unknown key role in bacterial communication and symbiosis. PMID:25944856

  16. Revisiting tropospheric yields of CO from CH4 oxidation using EMAC

    NASA Astrophysics Data System (ADS)

    Gromov, Sergey; Taraborrelli, Domenico

    2015-04-01

    Among various sources of tropospheric CO, methane oxidation (MO) is commonly assumed to be least uncertain term due to the fairly well studied kinetics of the reaction of CH4 with OH. Many studies on CO tropospheric budget (including forward and inverse modelling with CTMs and AC-GCMs) employ simplified treatment of MO source in their chemistry schemes, i.e. parameterising the photochemical production of CO using a 'net reaction' that can be written as CH4 + OH → λ CO + (products), where the yield λ approximates the effect of the chemistry regime and removal of intermediates from the CH4 oxidation chain, and is duly used as one of the fitting parameters. The estimates of λ, however, are hitherto inconsistent: Depending on the chemistry and dry/wet deposition schemes used, reckoned average tropospheric λ values vary within 0.6-1, whilst recent model parameterisations tend to favour almost complete conversion of CH4 to CO. The issue of such large uncertainty in CO yield from CH4 is especially important for the SH CO, where more than 50% of its inventory is typically attributed to the MO source in austral summer. In this study we scrutinise the MO source of CO using the ECHAM/MESSy Atmospheric Chemistry (EMAC) model employing elaborate chemistry mechanisms and tools to directly infer the value of λ, which is a diagnosed variable rather than an assumed parameter. Three chemical mechanisms differing in complexity of the MO cycle are used in simulations based on the EMAC evaluation study setup (detailed in Jöckel et al., 2010): (1) The reference (REF) mechanism which represents the 'standard' MO chemistry in EMAC including CH3O2, CH3OH, CH3OOH, HCHO and HCOOH, (2) The extension of REF that resolves CH3 and CH3O intermediates and reactions of CH3O2 with peroxy radicals, foremost HO2 (BASE mechanism), and (3) Further extension of BASE with pathways of MO involving formation and destruction of organic nitrates, plus reactions of CH3O2/CH3/HCHO with Ox and HOx from

  17. Physiology, biochemistry, and specific inhibitors of CH4, NH4+, and CO oxidation by methanotrophs and nitrifiers.

    PubMed Central

    Bédard, C; Knowles, R

    1989-01-01

    Ammonia oxidizers (family Nitrobacteraceae) and methanotrophs (family Methylococcaceae) oxidize CO and CH4 to CO2 and NH4+ to NO2-. However, the relative contributions of the two groups of organisms to the metabolism of CO, CH4, and NH4+ in various environments are not known. In the ammonia oxidizers, ammonia monooxygenase, the enzyme responsible for the conversion of NH4+ to NH2OH, also catalyzes the oxidation of CH4 to CH3OH. Ammonia monooxygenase also mediates the transformation of CH3OH to CO2 and cell carbon, but the pathway by which this is done is not known. At least one species of ammonia oxidizer, Nitrosococcus oceanus, exhibits a Km for CH4 oxidation similar to that of methanotrophs. However, the highest rate of CH4 oxidation recorded in an ammonia oxidizer is still five times lower than rates in methanotrophs, and ammonia oxidizers are apparently unable to grow on CH4. Methanotrophs oxidize NH4+ to NH2OH via methane monooxygenase and NH4+ to NH2OH via methane monooxygenase and NH2OH to NO2- via an NH2OH oxidase which may resemble the enzyme found in ammonia oxidizers. Maximum rates of NH4+ oxidation are considerably lower than in ammonia oxidizers, and the affinity for NH4+ is generally lower than in ammonia oxidizers. NH4+ does not apparently support growth in methanotrophs. Both ammonia monooxygenase and methane monooxygenase oxidize CO to CO2, but CO cannot support growth in either ammonia oxidizers or methanotrophs. These organisms have affinities for CO which are comparable to those for their growth substrates and often higher than those in carboxydobacteria. The methane monooxygenases of methanotrophs exist in two forms: a soluble form and a particulate form. The soluble form is well characterized and appears unrelated to the particulate. Ammonia monooxygenase and the particulate methane monooxygenase share a number of similarities. Both enzymes contain copper and are membrane bound. They oxidize a variety of inorganic and organic compounds, and

  18. 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

  19. Effect of interannual variation in winter vertical mixing on CH4 dynamics in a subtropical reservoir

    NASA Astrophysics Data System (ADS)

    Itoh, Masayuki; Kobayashi, Yuki; Chen, Tzong-Yueh; Tokida, Takeshi; Fukui, Manabu; Kojima, Hisaya; Miki, Takeshi; Tayasu, Ichiro; Shiah, Fuh-Kwo; Okuda, Noboru

    2015-07-01

    Although freshwaters are considered to be substantial natural sources of atmospheric methane (CH4), in situ processes of CH4 production and consumption in freshwater ecosystems are poorly understood, especially in subtropical areas, leading to uncertainties in the estimation of global CH4 emissions. To improve our understanding of physical and biogeochemical factors affecting CH4 dynamics in subtropical lakes, we examined vertical and seasonal profiles of dissolved CH4 and its carbon isotope ratio (δ13C) and conducted incubation experiments to assess CH4 production and oxidation in the deep subtropical Fei-Tsui Reservoir (FTR; Taiwan). The mixing pattern of the FTR is essentially monomixis, but the intensity of winter vertical mixing changes with climatic conditions. In years with incomplete vertical mixing (does not reach the bottom) and subsequent strong thermal stratification resulting in profundal hypoxia, we observed increases in sedimentary CH4 production and thus profundal CH4 storage with the development of reducing conditions. In contrast, in years with strong winter vertical mixing to the bottom of the reservoir, CH4 production was suppressed under NO3--rich conditions, during which denitrifiers have the competitive advantage over methanogens. Diffusive emission from profundal CH4 storage appeared to be negligible due to the efficiency of CH4 oxidation during ascent through methane-oxidizing bacteria (MOB) activity. Most of the profundal CH4 was rapidly oxidized by MOB in both oxic and anoxic layers, as characterized by its carbon isotope signature. In contrast, aerobic CH4 production in the subsurface layer, which may be enhanced under high temperatures in summer, may account for a large portion of atmospheric CH4 emissions from this reservoir. Our CH4 profiling results provide valuable information for future studies predicting CH4 emissions from subtropical lakes with the progress of global warming.

  20. A Year in the Life: Annual Patterns of CO2 and CH4 from a Northern Finland Peatland, Including Anaerobic Methane Oxidation and Summer Ebullition Rates

    NASA Astrophysics Data System (ADS)

    Miller, K.; Lipson, D.; Biasi, C.; Dorodnikov, M.; Männistö, M.; Lai, C. T.

    2014-12-01

    The major ecological controls on methane (CH4) and carbon dioxide (CO2) fluxes in northern wetland systems are well known, yet estimates of source/sink magnitudes are often incongruous with measured rates. This mismatch persists because holistic flux datasets are rare, preventing 'whole picture' determinations of flux controls. To combat this, we measured net CO2 and CH4 fluxes from September 2012-2013 within a peatland in northern Lapland, Finland. In addition, we performed in situ manipulations and in vitro soil incubations to quantify anaerobic methane oxidation and methanogenic rates as they related to alternative electron acceptor availability. Average annual fluxes varied substantially between different depressions within the wetland, a pattern that persisted through all seasons. Season was a strong predictor of both CO2 and CH4 flux rates, yet CH4 rates were not related to melt-season 10cm or 30cm soil temperatures, and only poorly predicted with air temperatures. We found evidence for both autumnal and spring thaw CH4 bursts, collectively accounting for 26% of annual CH4 flux, although the autumnal burst was more than 5 fold larger than the spring burst. CH4 ebullition measured throughout the growing season augmented the CH4 source load by a factor of 1.5, and was linked with fine-scale spatial heterogeneity within the wetland. Surprisingly, CH4 flux rates were insensitive to Fe(III) and humic acid soil amendments, both of which amplified CO2 fluxes. Using in vitro incubations, we determined anaerobic methane oxidation and methanogenesis rates. Measured anaerobic oxidation rates showed potential consumption of between 6-39% of the methane produced, contributing approximately 1% of total carbon dioxide flux. Treatments of nitrate, sulfate and ferric iron showed that nitrate suppressed methanogenesis, but were not associated with anaerobic oxidation rates.

  1. 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.

  2. WETTING STIMULATES ATMOSPHERIC CH4 OXIDATION BY ALPINE SOIL (R823442)

    EPA Science Inventory

    Studies were done to assess the effects of soil moisture manipulations on CH4 oxidation in soils from a dry alpine tundra site. When water was added to these soils there was a stimulation of CH4 oxidation. This stimulation of CH4 oxidation took ti...

  3. CH4/Ar/H2/SF6 Plasma Etching for Surface Oxide Removal of Indium Bumps

    NASA Astrophysics Data System (ADS)

    Huang, Yue; Lin, Chun; Ye, Zhen-Hua; Liao, Qing-Jun; Ding, Rui-Jun

    2015-07-01

    Plasma etching for surface indium oxide removal by methane/argon/hydrogen/sulfur hexafluoride (CH4/Ar/H2/SF6) mixture has been implemented. The morphology of the indium bumps was not deteriorated after the plasma etching. High-resolution O 1 s x-ray photoelectron spectroscopy (XPS) proved that the In-O component decreased from 44.5% for the nonetched sample to 10.8% for the sample after plasma etching. The surface modification of the indium bumps might be in the form of doped fluorine according to the XPS results. The zero-bias resistance derived from current-voltage ( I- V) measurements for plasma-etched infrared detectors was comparable to that for nonetched ones, indicating that such plasma treatment is suitable for processing sensitive materials such as mercury cadmium telluride.

  4. Effect of CH4 and O2 variations on rates of CH4 oxidation and stable isotope fractionation in tropical rain forest soils

    SciTech Connect

    Teh, Yit Arn; Conrad, Mark; Silver, Whendee L.; Carlson, Charlotte M.

    2003-10-01

    Methane-oxidizing bacteria are the primary sink for CH{sub 4} in reduced soils, and account for as much as 90 percent of all CH{sub 4} produced. Methanotrophic bacteria strongly discriminate against the heavy isotopes of carbon, resulting in CH{sub 4} emissions that are significantly more enriched in {sup 13}C than the original source material. Previous studies have used an isotope mass balance approach to quantify CH{sub 4} sources and sinks in the field, based on the assumption that the fractionation factor for CH{sub 4} oxidation is a constant. This study quantifies the effect of systematic variations in CH{sub 4} and O{sub 2} concentrations on rates of CH{sub 4} oxidation and stable isotope fractionation in tropical rain forest soils. Soils were collected from the 0-15 cm depth, and incubated with varying concentrations of CH{sub 4} (100 ppmv, 500 ppmv, 1000 ppmv, and 5000 ppmv) or O{sub 2} (3 percent, 5 percent, 10 percent, and 21 percent). The isotope fractionation factor for CH{sub 4} oxidation was calculated for each incubation using a Rayleigh fractionation model. Rates of CH{sub 4} oxidation varied significantly between CH{sub 4} treatments, with the 100 ppmv CH{sub 4} treatment showing the lowest rate of CH{sub 4} uptake, and the other 3 treatments showing similar rates of CH{sub 4} uptake. Rates of CH{sub 4} oxidation did not vary significantly between the different O{sub 2} treatments. The fractionation factor for CH{sub 4} oxidation varied significantly between the different CH{sub 4} treatments, with the 5000 ppmv CH{sub 4} treatment showing the largest {sup 13}C-enrichment of residual CH{sub 4}. In treatments where CH{sub 4} concentration was not rate-limiting (> 500 ppmv CH{sub 4}), the fractionation factor for CH{sub 4} oxidation was negatively correlated with CH{sub 4} oxidation rate (P < 0.003, r{sup 2} = 0.86). A multiple regression model that included initial CH{sub 4} concentration and CH{sub 4} oxidation rate as independent variables

  5. CO2 and CH4 Production and CH4 Oxidation in Low Temperature Soil Incubations from Flat- and High-Centered Polygons, Barrow, Alaska, 2012

    DOE Data Explorer

    David E. Graham; Jianqiu Zheng; Taniya RoyChowdhury

    2016-08-31

    The dataset consists of respiration and methane production rates and methane oxidation potential obtained from soil microcosm studies carried out under controlled temperature and incubation conditions. Soils cores collected in 2012 represent the flat- and high-centered polygon active layers and permafrost (when present) from the NGEE Arctic Intensive Study Site 1, Barrow, Alaska.

  6. Analysis of the electrochemical performance of MoNi-CeO2 cermet as anode material for solid oxide fuel cell. Part I. H2, CH4 and H2/CH4 mixtures as fuels

    NASA Astrophysics Data System (ADS)

    Escudero, M. J.; Gómez de Parada, I.; Fuerte, A.; Serrano, J. L.

    2014-05-01

    This paper investigates the catalytic activity and the electrochemical performance of bimetallic formulation combining Mo and Ni with CeO2 (MoNi-Ce) in relation its potential use as anode material for SOFC. The catalytic properties were evaluated for methane partial oxidation as function of temperature and the carbon deposition on the anode surface was analysed by TG-MS. A conversion of 12.8% was reached for partial methane oxidation at 850 °C as well as a high coke resistance. The electrochemical performance was studied in a single cell with La0.58Sr0.4Fe0.8Co0.2O3-δ (LSCF) as cathode, La0.9Sr0.1Ga0.8Mg0.2O2.85 (LSGM) as electrolyte and MoNi-Ce as anode. A thin buffer layer of La0.4Ce0.6O4-δ (LCD) between anode and electrolyte was used to avoid possible interfacial reactions. The cell was tested in different humidified fuels (H2, CH4 and H2/CH4 mixtures) and static air at 750, 800 and 850 °C. The electrochemical behaviour was evaluated by current-voltage curves, impedance spectroscopy and load demand. Stability tests were also performed in pure CH4 at each studied temperature in order to assess degradation of the electrochemical cell performance. No significant performance degradation was detected in all studied fuels even pure methane, which suggests that MoNi-Ce is a suitable anode material for direct methane SOFC.

  7. Measurements and Modeling of Nitric Oxide Formation in Counterflow, Premixed CH4/O2/N2 Flames

    NASA Technical Reports Server (NTRS)

    Thomsen, D. Douglas; Laurendeau, Normand M.

    2000-01-01

    Laser-induced fluorescence (LIF) measurements of NO concentration in a variety of CH4/O2/N2 flames are used to evaluate the chemical kinetics of NO formation. The analysis begins with previous measurements in flat, laminar, premixed CH4/O2/N2 flames stabilized on a water-cooled McKenna burner at pressures ranging from 1 to 14.6 atm, equivalence ratios from 0.5 to 1.6, and volumetric nitrogen/oxygen dilution ratios of 2.2, 3.1 and 3.76. These measured results are compared to predictions to determine the capabilities and limitations of the comprehensive kinetic mechanism developed by the Gas Research Institute (GRI), version 2.11. The model is shown to predict well the qualitative trends of NO formation in lean-premixed flames, while quantitatively underpredicting NO concentration by 30-50%. For rich flames, the model is unable to even qualitatively match the experimental results. These flames were found to be limited by low temperatures and an inability to separate the flame from the burner surface. In response to these limitations, a counterflow burner was designed for use in opposed premixed flame studies. A new LIF calibration technique was developed and applied to obtain quantitative measurements of NO concentration in laminar, counterflow premixed, CH4/O2/N2 flames at pressures ranging from 1 to 5.1 atm, equivalence ratios of 0.6 to 1.5, and an N2/O2 dilution ratio of 3.76. The counterflow premixed flame measurements are combined with measurements in burner-stabilized premixed flames and counterflow diffusion flames to build a comprehensive database for analysis of the GRI kinetic mechanism. Pathways, quantitative reaction path and sensitivity analyses are applied to the GRI mechanism for these flame conditions. The prompt NO mechanism is found to severely underpredict the amount of NO formed in rich premixed and nitrogen-diluted diffusion flames. This underprediction is traced to uncertainties in the CH kinetics as well as in the nitrogen oxidation chemistry

  8. 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

  9. Catalytic Partial Oxidation of CH4 over Ni-substituted Barium Hexaaluminate catalysts

    SciTech Connect

    T Gardner; J Spivey; A Campos; J Hissam; E Kugler; A Roy

    2011-12-31

    Ba{sub 0.75}Ni{sub y}Al{sub 12-y}O{sub 19-{delta}} (y = 0.2, 0.4, 0.6, 0.8 and 1.0) catalysts were tested for the partial oxidation of CH{sub 4} at temperatures between 200 and 900 C. Temperature programmed reaction results indicate that light-off for the partial oxidation reaction occurred between 665 and 687 C for all catalysts. Isothermal runs performed at 900 C on the catalysts showed stable reaction product concentrations, consistent with equilibrium. Post-reaction analysis of the used catalysts showed that there are two distinct zones in the catalyst bed. In a short leading edge of the bed, the apparently complete consumption of oxygen leads to a catalyst which XANES analysis shows is primarily Ni-substituted into the hexaaluminate phase. In the downstream portion of the bed, Ni is shown to be present as metallic Ni. This corresponds to a reaction sequence in which the oxidation of CH{sub 4} proceeds at the inlet until all oxygen is reacted, followed by the reaction of CO{sub 2} and H{sub 2}O with unreacted CH{sub 4}, and its derivatives, to produce the final syngas mixture. From the change in the unit-cell dimensions with Ni substitution, there is a clear indication that Ni{sup 2+}, which has a larger ionic radius than aluminum, substitutes for Al{sup 3+} in the hexaaluminate lattice in the synthesis process, and there is no restructuring of the bulk hexaaluminate phase after the Ni is removed from the lattice.

  10. Contribution of Methanotrophic and Nitrifying Bacteria to CH4 and NH4+ Oxidation in the Rhizosphere of Rice Plants as Determined by New Methods of Discrimination

    PubMed Central

    Bodelier, Paul L. E.; Frenzel, Peter

    1999-01-01

    Methanotrophic and nitrifying bacteria are both able to oxidize CH4 as well as NH4+. To date it is not possible to estimate the relative contribution of methanotrophs to nitrification and that of nitrifiers to CH4 oxidation and thus to assess their roles in N and C cycling in soils and sediments. This study presents new options for discrimination between the activities of methanotrophs and nitrifiers, based on the competitive inhibitor CH3F and on recovery after inhibition with C2H2. By using rice plant soil as a model system, it was possible to selectively inactivate methanotrophs in soil slurries at a CH4/CH3F/NH4+ molar ratio of 0.1:1:18. This ratio of CH3F to NH4+ did not affect ammonia oxidation, but methane oxidation was inhibited completely. By using the same model system, it could be shown that after 24 h of exposure to C2H2 (1,000 parts per million volume), methanotrophs recovered within 24 h while nitrifiers stayed inactive for at least 3 days. This gave an “assay window” of 48 h when only methanotrophs were active. Applying both assays to model microcosms planted with rice plants demonstrated a major contribution of methanotrophs to nitrification in the rhizosphere, while the contribution of nitrifiers to CH4 oxidation was insignificant. PMID:10223965

  11. Catalytic Partial Oxidation of CH4 Over Ni-Substituted Hexaaluminate Catalysts

    SciTech Connect

    Gardner, T.H.; Shekhawat, D.; Berry, D.A.; Salazar, M.D.; Smith, M.W.; Kugler, E.L.; Haynes, D.J.; Spivey, J.J.

    2007-06-01

    The catalytic partial oxidation (CPOx) of methane is an attractive source of H2 and CO for fuel cell applications. However, the deposition of carbon onto the surface of the catalyst and the migration and loss of active metals remain the principal issues in the development of a suitable catalyst. The formation of elemental carbon onto the surface of a catalyst has been shown to be related to both the size of the active metal cluster [1] and its coordination [2]. The substitution of a catalytic metal into the lattice of hexaaluminate compounds may serve to reduce the size of active metal clusters and to increase their dispersion thereby reducing their susceptibility toward carbon deposition. Interactions between neighboring substituted metals and the hexaaluminate lattice may serve to suppress active metal mobility. In the present work, a series of barium hexaaluminate catalysts with Ni substituted into the lattice were prepared with the general formula, BaNiyAl12-yO19-δ (y = 0.2, 0.4, 0.6, 0.8 and 1.0). The temperature programmed activity and selectivity for this series were investigated.

  12. Comparison of Landfill Methane Oxidation Measured Using Stable Isotope Analysis and CO2/CH4 Fluxes Measured by the Eddy Covariance Method

    NASA Astrophysics Data System (ADS)

    Xu, L.; Chanton, J.; McDermitt, D. K.; Li, J.; Green, R. B.

    2015-12-01

    Methane plays a critical role in the radiation balance and chemistry of the atmosphere. Globally, landfill methane emission contributes about 10-19% of the anthropogenic methane burden into the atmosphere. In the United States, 18% of annual anthropogenic methane emissions come from landfills, which represent the third largest source of anthropogenic methane emissions, behind enteric fermentation and natural gas and oil production. One uncertainty in estimating landfill methane emissions is the fraction of methane oxidized when methane produced under anaerobic conditions passes through the cover soil. We developed a simple stoichiometric model to estimate methane oxidation fraction when the anaerobic CO2 / CH4 production ratio is known, or can be estimated. The model predicts a linear relationship between CO2 emission rates and CH4 emission rates, where the slope depends on anaerobic CO2 / CH4 production ratio and the fraction of methane oxidized, and the intercept depends on non-methane-dependent oxidation processes. The model was tested using carbon dioxide emission rates (fluxes) and methane emission rates (fluxes) measured using the eddy covariance method over a one year period at the Turkey Run landfill in Georgia, USA. The CO2 / CH4 production ratio was estimated by measuring CO2 and CH4 concentrations in air sampled under anaerobic conditions deep inside the landfill. We also used a mass balance approach to independently estimate fractional oxidation based on stable isotope measurements (δ13C of methane) of gas samples taken from deep inside the landfill and just above the landfill surface. Results from the two independent methods agree well. The model will be described and methane oxidation will be discussed in relation to wind direction, location at the landfill, and age of the deposited refuse.

  13. H 2 production from CH 4 decomposition: Regeneration capability and performance of nickel and rhodium oxide catalysts

    NASA Astrophysics Data System (ADS)

    Rivas, M. E.; Hori, C. E.; Fierro, J. L. G.; Goldwasser, M. R.; Griboval-Constant, A.

    Nickel-lanthanum (LaNiO 3) and nickel-rhodium-lanthanum (LaNi 0.95Rh 0.05O 3) perovskite-type oxide precursors were synthesized by different methodologies (co-precipitation, sol-gel and impregnation). They were reduced in an H 2 atmosphere to produce nickel and rhodium nanoparticles on the La 2O 3 substrate. All samples were tested in the catalytic decomposition of CH 4. Methane decomposed into carbon and H 2 at reaction temperatures as low as 450 °C-no other reaction products were observed. Conversions were in the range of 14-28%, and LaNi 0.95Rh 0.05O 3 synthesized by co-precipitation was the most active catalyst. All catalysts maintained sustained activity even after massive carbon deposition indicating that these deposits are of the nanotube-type, as confirmed by transmission electron microscopy (TEM). The reaction seems to occur in a way that a nickel or rhodium crystal face is always clean enough to expose sufficient active sites to make the catalytic process continue. The samples were subjected to a reduction-oxidation-reduction cycle and in situ analyses confirmed the stability of the perovskite structure. All diffraction patterns showed a phase change around 400 °C, due to reduction of LaNiO 3 to an intermediate La 2Ni 2O 5 structure. When the reduction temperatures reach 600 °C, this structure collapses through the formation of Ni 0 crystallites deposited on the La 2O 3. Under oxidative conditions, the perovskite system is recomposed with nickel re-entering the LaNiO 3 framework structure accounting for the regenerative capability of these solids.

  14. Particle-Scale Modeling of Methane Emission during Pig Manure/Wheat Straw Aerobic Composting.

    PubMed

    Ge, Jinyi; Huang, Guangqun; Huang, Jing; Zeng, Jianfei; Han, Lujia

    2016-04-19

    Inefficient aerobic composting techniques significantly contribute to the atmospheric methane (CH4) levels. Macro-scale models assuming completely aerobic conditions cannot be used to analyze CH4 generation in strictly anaerobic environments. This study presents a particle-scale model for aerobic pig manure/wheat straw composting that incorporates CH4 generation and oxidation kinetics. Parameter estimation revealed that pig manure is characterized by high CH4 yield coefficient (0.6414 mol CH4 mol(-1) Cman) and maximum CH4 oxidation rate (0.0205 mol CH4 kg(-1) VSaero h(-1)). The model accurately predicted CH4 emissions (R(2) = 0.94, RMSE = 2888 ppmv, peak time deviation = 0 h), particularly in the self-heating and cooling phases. During mesophilic and thermophilic stages, a rapid increase of CH4 generation (0.0130 mol CH4 kg(-1) VS h(-1)) and methanotroph inactivation were simulated, implying that additional measures should be performed during these phases to mitigate CH4 emissions. Furthermore, CH4 oxidation efficiency was related to oxygen permeation through the composting particles. Reducing the ambient temperature and extending the aeration duration can decrease CH4 emission, but the threshold temperature is required to trigger the self-heating phase. These findings provide insights into CH4 emission during composting and may inform responsible strategies to counteract climate change. PMID:27045933

  15. Microbial mechanisms to reduce the uncertainties in the CH4 emissions from global rice fields

    NASA Astrophysics Data System (ADS)

    Kamaljit, K.; Tian, H.; Ren, W.; Yang, J.

    2013-12-01

    In terrestrial ecosystems, methane (CH4) uptake or emission represents the net balance between activities of different microbial organisms including anaerobic Methanogens that produce CH4 and Methanotrophs which oxidize CH4 in the aerobic environments. In this way, anaerobic soil environments such as rice fields are major source of terrestrial CH4 emissions. However, large uncertainties in the CH4 emission estimates have been reported from rice fields. The bottom-up and top-down methods showed a wide range of CH4 emissions estimations ranging from 25 to 300 Tg yr-1 from rice fields. The major reason for uncertainties in the CH4 emissions includes the water management that alters the balance of Methanogens and Methanotrophs in the rice fields. Two kinds of water management practices are followed including continuous flooding (CF) which refers to the continuous submergence as well as alternate wetting and drying (AWD) in which the rice fields are drained for several days during the growing season. The AWD provides aeration stress on Methanogens resulting in lower CH4 emissions than CF water management followed in the rice fields. A single aeration during growing season may significantly reduce the CH4 emission from the rice fields. Currently, most of the models structures assume that Methanogens become active once the soil moisture content is raised to saturation. However, several laboratory scale studies have indicated that following aeration the Methanogens don't become fully functional immediately even if the soil moisture content is raised to saturation. In this study, we integrated the aeration stress mechanisms on the Methanogens in the Dynamic Land Ecosystem Model (DLEM). The improved version of DLEM was used to conduct uncertainty analysis on global CH4 emission estimation following CF and AWD water management in the rice fields. Results of this study have shown that inclusion of the aeration stress mechanism on Methanogens in the modeling framework has

  16. 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

  17. 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.

  18. High production of nitrous oxide (N2O), methane (CH4) and dimethylsulphoniopropionate (DMSP) in a massive marine phytoplankton culture

    NASA Astrophysics Data System (ADS)

    Florez-Leiva, L.; Tarifeño, E.; Cornejo, M.; Kiene, R.; Farías, L.

    2010-09-01

    The production of large amounts of algal biomass for different purposes such as aquaculture or biofuels, may cause impacts on the marine environment. One such impact is the production of radiatively active trace gases and aerosols with climate cooling (dimethyl sulfide DMS and its precursor DMSP) and warming (N2O and CH4) effects. Total and dissolved DMSP, N2O and CH4, together with other environmental variables were monitored daily for 46 days within a massive microalgae monoculture of Nannochloris (Chlorophyceae) in an open pond system. The growth of this green microalgae was stimulated by the addition of N- and P-rich salts, resulting in exponential growth (growth phase) during the first 17 days observed by cell abundance (1 × 106 to 4.4 × 106 cell mL-1) and Chl-a levels (from 1.4 to 96 mg Chl-a m-3) followed by a decrease in both Chl-a and cell abundance (senescence phase). Total DMSP (from 6.3 to 142 μmol m-3), dissolved DMSP i.e. 5.8 to 137 μmol m-3 and N2O (from 8 to 600 μmol m-3) abruptly peaked during the senescence phase, whereas CH4 steadily increased between 2 and 10 μmol m-3 during the growth phase. Different ratios between tracers and Chl-a during both phases reveal different biochemical processes involved in the cycling of these gases and tracers. Our results show that despite the consumption of large quantities of CO2 by the massive algal culture, a minor amount of DMS and huge amounts of greenhouse gases were produced, in particular N2O, which has a greater radiative effect per molecule than CO2. These findings have important implications for biogeochemical studies and for environmental management of aquaculture activities.

  19. 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

  20. Effects of simulated spring thaw of permafrost from mineral cryosol on CO2 emissions and atmospheric CH4 uptake

    NASA Astrophysics Data System (ADS)

    Stackhouse, Brandon T.; Vishnivetskaya, Tatiana A.; Layton, Alice; Chauhan, Archana; Pfiffner, Susan; Mykytczuk, Nadia C.; Sanders, Rebecca; Whyte, Lyle G.; Hedin, Lars; Saad, Nabil; Myneni, Satish; Onstott, Tullis C.

    2015-09-01

    Previous studies investigating organic-rich tundra have reported that increasing biodegradation of Arctic tundra soil organic carbon (SOC) under warming climate regimes will cause increasing CO2 and CH4 emissions. Organic-poor, mineral cryosols, which comprise 87% of Arctic tundra, are not as well characterized. This study examined biogeochemical processes of 1 m long intact mineral cryosol cores (1-6% SOC) collected in the Canadian high Arctic. Vertical profiles of gaseous and aqueous chemistry and microbial composition were related to surface CO2 and CH4 fluxes during a simulated spring/summer thaw under light versus dark and in situ versus water saturated treatments. CO2 fluxes attained 0.8 ± 0.4 mmol CO2 m-2 h-1 for in situ treatments, of which 85 ± 11% was produced by aerobic SOC oxidation, consistent with field observations and metagenomic analyses indicating aerobic heterotrophs were the dominant phylotypes. The Q10 values of CO2 emissions ranged from 2 to 4 over the course of thawing. CH4 degassing occurred during initial thaw; however, all cores were CH4 sinks at atmospheric concentration CH4. Atmospheric CH4 uptake rates ranged from -126 ± 77 to -207 ± 7 nmol CH4 m-2 h-1 with CH4 consumed between 0 and 35 cm depth. Metagenomic and gas chemistry analyses revealed that high-affinity Type II methanotrophic sequence abundance and activity were highest between 0 and 35 cm depth. Microbial sulfate reduction dominated the anaerobic processes, outcompeting methanogenesis for H2 and acetate. Fluxes, microbial community composition, and biogeochemical rates indicate that mineral cryosols of Axel Heiberg Island act as net CO2 sources and atmospheric CH4 sinks during summertime thaw under both in situ and water saturated states.

  1. Surface Structure of Aerobically Oxidized Diamond Nanocrystals

    DOE PAGESBeta

    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

  2. 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.

  3. Seasonal, inter-annual and decadal changes of carbon dioxide (CO2), methane (CH4) and nitrous oxide (N2O) in the Scheldt estuary (Belgium, The Netherlands)

    NASA Astrophysics Data System (ADS)

    Borges, Alberto V.; Middelburg, Jack J. B.; Chou, Lei; Kromkamp, Jacco; Houtekamer, Marco; Harlay, Jérôme

    2014-05-01

    We carried out monthly cruises to study the seasonal and spatial variations of the partial pressure of carbon dioxide CO2 (pCO2), methane (CH4) and nitrous oxide (N2O) concentrations in the Scheldt estuary, a strongly human impacted system located in Belgium and the Netherlands. This survey was initiated in 2008 for pCO2, and from 2009 onwards for methane (CH4) and nitrous oxide (N2O). In the lower estuary, pCO2 strongly decreased and oxygen saturation level (%O2) strongly increased during the spring phytoplankton bloom. In the upper estuary, two yearly maxima of pCO2 coinciding with minima of %O2 occurred in spring and fall due to enhanced nitrification and/or net heterotrophy. In the upper estuary, pCO2 decreased in winter due to lower temperature (affecting solubility and inhibiting biological activity). pCO2 also decreased in summer due to increase in primary production and decrease of net heterotrophy. In the upper estuary, maxima of CH4 were observed in winter due to enhanced river inputs (high discharge) while in the lower estuary higher CH4 was observed in summer. This was probably due to inputs of CH4 from inter-tidal areas at the mouth of estuary that increased in summer due to higher temperatures and higher organic matter availability. N2O also showed higher values during winter in the upper estuary, but in summer N2O was low in the lower estuary due to decreased solubility due to higher temperature. During winter 2009, extremely high N2O values were observed in the upper estuary, up to 3257 nM (23738% saturation). This was related to the problems encountered by the Brussels North waste water treatment plant (WWTP) in late 2009. One of the collectors of the station was shut down in 25 November 2009, and by 8 December 2009, the whole WWTP was shut down and the waste-water was delivered directly to the Rupel. Extremely high N2O values were observed in the upper estuary on 7 December 2009, and abnormally high N2O values (compared to other years) persisted

  4. Laboratory measurement of temperature dependent 13C and D kinetic isotope effect in the reaction of CH4 oxidation by O(1D)

    NASA Astrophysics Data System (ADS)

    Shen, Linhan; Bui, Thinh Q.; Chen, Pin; Okumura, Mitchio

    2014-11-01

    Martian atmospheric methane (CH4) concentrations observed from satellite orbiter and Earth based telescopes have shown significant time and spatial variations. Recent MSL measurements observed very low methane concentrations (0.18 ± 0.67 ppbv). In order to reconcile these findings, a search of missing methane sinks is needed. In this study, we investigated the kinetic isotope effect (KIE) of methane oxidation reaction by O(1D) as a function of temperature, which will provide an important constraint to the loss of methane. The KIE of major methane isotopologues (13CH4 and 12CH3D) are measured as a function of temperature. The experiments were carried out by photolyzing a mixture of N2O, isotope enriched methane, and He at 193 nm in a temperature controlled cell between 155 K and 300 K. The N2O molecules were used as an O(1D) source, while He was used to collisionally quench translationally hot O(1D) radicals. The concentrations of all major methane isotopologues before and after photolysis were analyzed using a frequency stabilized cavity ringdown (FS-CRDS) spectrometer. The spectrometer employs coupling of two orthogonally polarized cw lasers into a ringdown cavity for simultaneous spectral measurements over the full wavelength range of 1.45 - 1.65 µm and is capable of measuring isotopes of methane of enriched samples to a very high precision (D < 0.03% and 13C < 0.01%). We measured for the first time the D-KIE and 13C-KIE at temperatures relative to the Martian conditions. Our measurements observed D-KIE(155 K) = 1.133(20), and 13C-KIE(115 K) = 1.149(22).

  5. Microbial CH4 and N2O Consumption in Acidic Wetlands

    PubMed Central

    Kolb, Steffen; Horn, Marcus A.

    2012-01-01

    Acidic wetlands are global sources of the atmospheric greenhouse gases methane (CH4), and nitrous oxide (N2O). Consumption of both atmospheric gases has been observed in various acidic wetlands, but information on the microbial mechanisms underlying these phenomena is scarce. A substantial amount of CH4 is consumed in sub soil by aerobic methanotrophs at anoxic–oxic interfaces (e.g., tissues of Sphagnum mosses, rhizosphere of vascular plant roots). Methylocystis-related species are likely candidates that are involved in the consumption of atmospheric CH4 in acidic wetlands. Oxygen availability regulates the activity of methanotrophs of acidic wetlands. Other parameters impacting on the methanotroph-mediated CH4 consumption have not been systematically evaluated. N2O is produced and consumed by microbial denitrification, thus rendering acidic wetlands as temporary sources or sinks for N2O. Denitrifier communities in such ecosystems are diverse, and largely uncultured and/or new, and environmental factors that control their consumption activity are unresolved. Analyses of the composition of N2O reductase genes in acidic wetlands suggest that acid-tolerant Proteobacteria have the potential to mediate N2O consumption in such soils. Thus, the fragmented current state of knowledge raises open questions concerning methanotrophs and denitrifiers that consume atmospheric CH4 and N2O in acidic wetlands. PMID:22403579

  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. Biogeochemical processes at the fringe of a landfill leachate pollution plume: potential for dissolved organic carbon, Fe(II), Mn(II), NH4, and CH4 oxidation.

    PubMed

    van Breukelen, Boris M; Griffioen, Jasper

    2004-09-01

    Various redox reactions may occur at the fringe of a landfill leachate plume, involving oxidation of dissolved organic carbon (DOC), CH4, Fe(II), Mn(II), and NH4 from leachate and reduction of O2, NO3 and SO4 from pristine groundwater. Knowledge on the relevance of these processes is essential for the simulation and evaluation of natural attenuation (NA) of pollution plumes. The occurrence of such biogeochemical processes was investigated at the top fringe of a landfill leachate plume (Banisveld, the Netherlands). Hydrochemical depth profiles of the top fringe were captured via installation of a series of multi-level samplers at 18, 39 and 58 m downstream from the landfill. Ten-centimeter vertical resolution was necessary to study NA within a fringe as thin as 0.5 m. Bromide appeared an equally well-conservative tracer as chloride to calculate dilution of landfill leachate, and its ratio to chloride was high compared to other possible sources of salt in groundwater. The plume fringe rose steadily from a depth of around 5 m towards the surface with a few meters in the period 1998-2003. The plume uplift may be caused by enhanced exfiltration to a brook downstream from the landfill, due to increased precipitation over this period and an artificial lowering of the water level of the brook. This rise invoked cation exchange including proton buffering, and triggered degassing of methane. The hydrochemical depth profile was simulated in a 1D vertical reactive transport model using PHREEQC-2. Optimization using the nonlinear optimization program PEST brought forward that solid organic carbon and not clay minerals controlled retardation of cations. Cation exchange resulted in spatial separation of Fe(II), Mn(II) and NH4 fronts from the fringe, and thereby prevented possible oxidation of these secondary redox species. Degradation of DOC may happen in the fringe zone. Re-dissolution of methane escaped from the plume and subsequent oxidation is an explanation for absence of

  8. 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.

  9. Simultaneous determination of stable isotopic compositions of nitrous oxide (δ15N and δ18O of N2O) and methane (δ13C of CH4) in nanomolar quantities from a single water sample

    NASA Astrophysics Data System (ADS)

    Hirota, A.; Tsunogai, U.; Komatsu, D. D.; Nakagawa, F.

    2010-12-01

    The stable isotopic compositions of nitrous oxide (δ15N of N2O and δ18O of N2O, respectively) and methane (δ13C of CH4) have provided us with some interesting geochemical insights. We have developed a rapid, sensitive, and automated analytical system to simultaneously determine the concentrations and stable isotopic compositions of nanomolar quantities of N2O and CH4 in the environmental water, by combining continuous-flow isotope-ratio mass spectrometry and a He-sparging system to extract and purify the dissolved gases. Our system, which is composed of a sparging bottle, a chemical trap, four cold traps and a capillary gas chromatograph that use ultra-pure helium as the carrier gas, achieves complete extraction of N2O and CH4 in a water sample and separation among N2O, CH4, and the other component gases. The flow path subsequent to gas chromatograph was periodically changed to pass the gases through the combustion furnace to convert CH4 and the other hydrocarbons into CO2, or to bypass the combustion furnace for the direct introduction of eluted N2O into the mass spectrometer, for determining the stable isotopic compositions through monitoring m/z = 44, 45, and 46, on the bases of CO2+ and N2O+, respectively. The analytical system can be operated automatically with sequential software programmed on a personal computer. The analytical precisions (the standard deviation of a single measurement) were better than 0.2‰ for δ15N of N2O and 0.3‰ for δ18O of N2O, in the case of more than 6.7 nmol N2O injection and better than 1.4‰ for δ15N of N2O and 2.6‰ for δ18O of N2O, in the case of more than 0.2 nmol N2O injection, respectively. Simultaneously, the analytical precisions were better than 0.07‰ for δ13C of CH4, in the case of more than 5.5 nmol CH4 infection and better than 2.1‰ for δ13C of CH4, when more than 0.024 nmol CH4 injection. In this manner, we can simultaneously determine stable isotopic compositions of a 120 mL water sample having

  10. 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

  11. Controls on CH4 flux from an Alaskan boreal wetland

    NASA Astrophysics Data System (ADS)

    Moosavi, Sadredin C.; Crill, Patrick M.; Pullman, Erik R.; Funk, Dale W.; Peterson, Kim M.

    1996-06-01

    Factors controlling the flux of the radiatively important trace gas methane (CH4) from boreal wetlands were examined at three sites along a moisture gradient from a treed low-shrub bog to an open floating graminoid bog in Fairbanks, Alaska. In the summer of 1992 average static chamber flux measurements were -0.02, 71.5, and 289 mg CH4/m2/d in dry, wet, and floating mat communities, respectively. In contrast, the warmer, drier 1993 field season flux measurements were -0.02, 42.9 and 407 mg CH4/m2/d. The data indicate that despite net oxidation of CH4 in the dry regions of the bog, the wetland is a net source of CH4, with fluxes ranging across three orders of magnitude between different plant communities. Comparison with water levels suggests that CH4 flux is turned on and off by changes in site hydrology. In sites where sufficient moisture is present for methanogenesis to occur, CH4 flux appears to be temperature limited, responding exponentially to soil temperature changes. The combined effects of hydrology and temperature create hot spots of CH4 flux within boreal wetlands. The plant communities within Lemeta Bog respond differently to changes in temperature and moisture availability, creating both positive and negative feedbacks to potential global climate change.

  12. Interannual Variability and Trends of CH4, CO and OH Using the Computationally-Efficient CH4-CO-OH (ECCOH) Module

    NASA Technical Reports Server (NTRS)

    Elshorbany, Yasin F.; Duncan, Bryan N.; Strode, Sarah A.; Wang, James S.; Kouatchou, Jules

    2015-01-01

    Methane (CH4) is the second most important anthropogenic greenhouse gas (GHG). Its 100-year global warming potential (GWP) is 34 times larger than that for carbon dioxide. The 100-year integrated GWPof CH4 is sensitive to changes in hydroxyl radical (OH) levels.Oxidation of CH4 and carbon monoxide (CO) by OH is the main loss process, thus affecting the oxidizing capacity of the atmosphere and contributing to the global ozone background. Limitations of using archived, monthly OH fields for studies of methane's and COs evolution are that feedbacks of the CH4-CO-OH system on methane, CO and OH are not captured. In this study, we employ the computationally Efficient CH4-CO-OH (ECCOH) module (Elshorbany et al., 2015) to investigate the nonlinear feedbacks of the CH4-CO-OH system on the interannual variability and trends of the CH4, CO, OH system.

  13. 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

  14. Landscape patterns of CH4 fluxes in an alpine tundra ecosystem

    USGS Publications Warehouse

    West, A.E.; Brooks, P.D.; Fisk, M.C.; Smith, L.K.; Holland, E.A.; Jaeger, C. H., III; Babcock, S.; Lai, R.S.; Schmidt, S.K.

    1999-01-01

    We measured CH4 fluxes from three major plant communities characteristic of alpine tundra in the Colorado Front Range. Plant communities in this ecosystem are determined by soil moisture regimes induced by winter snowpack distribution. Spatial patterns of CH4 flux during the snow-free season corresponded roughly with these plant communities. In Carex-dominated meadows, which receive the most moisture from snowmelt, net CH4 production occurred. However, CH4 production in one Carex site (seasonal mean = +8.45 mg CH4 m-2 d-1) was significantly larger than in the other Carex sites (seasonal means = -0.06 and +0.05 mg CH4 m-2 d-1). This high CH4 flux may have resulted from shallower snowpack during the winter. In Acomastylis meadows, which have an intermediate moisture regime, CH4 oxidation dominated (seasonal mean = -0.43 mg CH4 m-2 d-1). In the windswept Kobresia meadow plant community, which receive the least amount of moisture from snowmelt, only CH4 oxidation was observed (seasonal mean = -0.77 mg CH4 m-2 d-1). Methane fluxes correlated with a different set of environmental factors within each plant community. In the Carex plant community, CH4 emission was limited by soil temperature. In the Acomastylis meadows, CH4 oxidation rates correlated positively with soil temperature and negatively with soil moisture. In the Kobresia community, CH4 oxidation was stimulated by precipitation. Thus, both snow-free season CH4 fluxes and the controls on those CH4 fluxes were related to the plant communities determined by winter snowpack.

  15. Windrow composting mitigated CH4 emissions: characterization of methanogenic and methanotrophic communities in manure management.

    PubMed

    Chen, Ruirui; Wang, Yiming; Wei, Shiping; Wang, Wei; Lin, Xiangui

    2014-12-01

    With increasing livestock breeding, methane (CH4 ) emissions from manure management will increasingly contribute more to atmospheric CH4 concentration. The dynamics of methanogens and methanotrophs have not yet been studied in the manure environment. The current study combines surface CH4 emissions with methanogenic and methanotrophic community analyses from two management practices, windrow composting (WCOM) and solid storage (SSTO). Our results showed that there was an c. 50% reduction of CH4 emissions with WCOM compared with SSTO over a 50-day period. A sharp decrease in the quantities of both methanogens and methanotrophs in WCOM suggested that CH4 mitigation was mainly due to decreased CH4 production rather than increased CH4 oxidation. Pyrosequencing analysis demonstrated that aeration caused a clear shift of dominant methanogens in the manure, with specifically a significant decrease in Methanosarcina and increase in Methanobrevibacter. The composition of methanogenic community was influenced by manure management and regulated CH4 production. A sharp increase in the quantity of methanotrophs in SSTO suggested that microbial CH4 oxidation is an important sink for the CH4 produced. The increased abundance of Methylococcaceae in SSTO suggested that Type I methanotrophs have an advantage in CH4 oxidation in occupying niches under low CH4 and high O2 conditions. PMID:25135448

  16. Effect of sporadic destratification, seasonal overturn, and artificial mixing on CH4 emissions from a subtropical hydroelectric reservoir

    NASA Astrophysics Data System (ADS)

    Guérin, Frédéric; Deshmukh, Chandrashekhar; Labat, David; Pighini, Sylvie; Vongkhamsao, Axay; Guédant, Pierre; Rode, Wanidaporn; Godon, Arnaud; Chanudet, Vincent; Descloux, Stéphane; Serça, Dominique

    2016-06-01

    Inland waters in general and freshwater reservoirs specifically are recognized as a source of CH4 into the atmosphere. Although the diffusion at the air-water interface is the most studied pathway, its spatial and temporal variations are poorly documented. We measured temperature and O2 and CH4 concentrations every 2 weeks for 3.5 years at nine stations in a subtropical monomictic reservoir which was flooded in 2008 (Nam Theun 2 Reservoir, Lao PDR). Based on these results, we quantified CH4 storage in the water column and diffusive fluxes from June 2009 to December 2012. We compared diffusive emissions with ebullition from Deshmukh et al. (2014) and aerobic methane oxidation and downstream emissions from Deshmukh et al. (2016). In this monomictic reservoir, the seasonal variations of CH4 concentration and storage were highly dependent on the thermal stratification. Hypolimnic CH4 concentration and CH4 storage reached their maximum in the warm dry season (WD) when the reservoir was stratified. Concentration and storage decreased during the warm wet (WW) season and reached its minimum after the reservoir overturned in the cool dry (CD) season. The sharp decreases in CH4 storage were concomitant with extreme diffusive fluxes (up to 200 mmol m-2 d-1). These sporadic emissions occurred mostly in the inflow region in the WW season and during overturn in the CD season in the area of the reservoir that has the highest CH4 storage. Although they corresponded to less than 10 % of the observations, these extreme CH4 emissions (> 5 mmol m-2 d-1) contributed up to 50 % of total annual emissions by diffusion. During the transition between the WD and WW seasons, a new emission hotspot was identified upstream of the water intake where diffusive fluxes peaked at 600 mmol m-2 d-1 in 2010 down to 200 mmol m-2 d-1 in 2012. The hotspot was attributed to the mixing induced by the water intakes (artificial mixing). Emissions from this area contributed 15-25 % to total annual emissions

  17. Low methane (CH4) emissions downstream of a monomictic subtropical hydroelectric reservoir (Nam Theun 2, Lao PDR)

    NASA Astrophysics Data System (ADS)

    Deshmukh, C.; Guérin, F.; Pighini, S.; Vongkhamsao, A.; Guédant, P.; Rode, W.; Godon, A.; Chanudet, V.; Descloux, S.; Serça, D.

    2015-07-01

    of the design of the water intake. A significant fraction of the CH4 that should have been transferred and emitted downstream of the powerhouse is emitted at the reservoir surface because of the artificial turbulence generated around the water intake. The positive counterpart of this artificial mixing is that it allows O2 diffusion down to the bottom of the water column enhancing aerobic methane oxidation and it subsequently lowering downstream emissions by at least 40 %.

  18. Low methane (CH4) emissions downstream of a monomictic subtropical hydroelectric reservoir (Nam Theun 2, Lao PDR)

    NASA Astrophysics Data System (ADS)

    Deshmukh, Chandrashekhar; Guérin, Frédéric; Labat, David; Pighini, Sylvie; Vongkhamsao, Axay; Guédant, Pierre; Rode, Wanidaporn; Godon, Arnaud; Chanudet, Vincent; Descloux, Stéphane; Serça, Dominique

    2016-03-01

    of the design of the water intake. A significant fraction of the CH4 that should have been transferred and emitted downstream of the powerhouse is emitted at the reservoir surface because of the artificial turbulence generated around the water intake. The positive counterpart of this artificial mixing is that it allows O2 diffusion down to the bottom of the water column, enhancing aerobic methane oxidation, and it subsequently lowered downstream emissions by at least 40 %.

  19. 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

  20. Oxovanadium complex-catalyzed aerobic oxidation of propargylic alcohols.

    PubMed

    Maeda, Yasunari; Kakiuchi, Nobuyuki; Matsumura, Satoshi; Nishimura, Takahiro; Kawamura, Takashi; Uemura, Sakae

    2002-09-20

    A catalytic system consisting of vanadium oxyacetylacetonate [VO(acac)(2)] and 3 A molecular sieves (MS3A) in acetonitrile works effectively for the aerobic oxidation of propargylic alcohols [R(1)CH(OH)Ctbd1;CR(2)] to the corresponding carbonyl compounds under an atmospheric pressure of molecular oxygen. Although the reactivity of alpha-acetylenic alkanols (R(1) = alkyl) is lower compared to that of the alcohols of R(1) = aryl, alkenyl, and alkynyl, the use of VO(hfac)(2) as a catalyst and the addition of hexafluoroacetylacetone improve the product yield in these cases. A catalytic cycle involving a vanadium(V) alcoholate species and beta-hydrogen elimination from it has been proposed for this oxidation. PMID:12227802

  1. 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.

  2. Mechanism of Copper(I)/TEMPO-Catalyzed Aerobic Alcohol Oxidation

    PubMed Central

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

    2013-01-01

    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)CuI/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 CuI and TEMPO–H are oxidized by O2 via a binuclear Cu2O2 intermediate and (2) “substrate oxidation” mediated by CuII and the nitroxyl radical of TEMPO via a CuII-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 O2 is turnover limiting with benzylic alcohols, while numerous steps contribute to the turnover rate in the oxidation of aliphatic alcohols. PMID:23317450

  3. δ13C-CH4 reveals CH4 variations over oceans from mid-latitudes to the Arctic

    NASA Astrophysics Data System (ADS)

    Yu, Juan; Xie, Zhouqing; Sun, Liguang; Kang, Hui; He, Pengzhen; Xing, Guangxi

    2015-09-01

    The biogeochemical cycles of CH4 over oceans are poorly understood, especially over the Arctic Ocean. Here we report atmospheric CH4 levels together with δ13C-CH4 from offshore China (31°N) to the central Arctic Ocean (up to 87°N) from July to September 2012. CH4 concentrations and δ13C-CH4 displayed temporal and spatial variation ranging from 1.65 to 2.63 ppm, and from -50.34% to -44.94% (mean value: -48.55 ± 0.84%), respectively. Changes in CH4 with latitude were linked to the decreasing input of enriched δ13C and chemical oxidation by both OH and Cl radicals as indicated by variation of δ13C. There were complex mixing sources outside and inside the Arctic Ocean. A keeling plot showed the dominant influence by hydrate gas in the Nordic Sea region, while the long range transport of wetland emissions were one of potentially important sources in the central Arctic Ocean. Experiments comparing sunlight and darkness indicate that microbes may also play an important role in regional variations.

  4. δ13C-CH4 reveals CH4 variations over oceans from mid-latitudes to the Arctic

    PubMed Central

    Yu, Juan; Xie, Zhouqing; Sun, Liguang; Kang, Hui; He, Pengzhen; Xing, Guangxi

    2015-01-01

    The biogeochemical cycles of CH4 over oceans are poorly understood, especially over the Arctic Ocean. Here we report atmospheric CH4 levels together with δ13C-CH4 from offshore China (31°N) to the central Arctic Ocean (up to 87°N) from July to September 2012. CH4 concentrations and δ13C-CH4 displayed temporal and spatial variation ranging from 1.65 to 2.63 ppm, and from −50.34% to −44.94% (mean value: −48.55 ± 0.84%), respectively. Changes in CH4 with latitude were linked to the decreasing input of enriched δ13C and chemical oxidation by both OH and Cl radicals as indicated by variation of δ13C. There were complex mixing sources outside and inside the Arctic Ocean. A keeling plot showed the dominant influence by hydrate gas in the Nordic Sea region, while the long range transport of wetland emissions were one of potentially important sources in the central Arctic Ocean. Experiments comparing sunlight and darkness indicate that microbes may also play an important role in regional variations. PMID:26323236

  5. Chemolithoautotrophic production mediating the cycling of the greenhouse gases N2O and CH4 in an upwelling ecosystem

    NASA Astrophysics Data System (ADS)

    Farías, L.; Fernández, C.; Faúndez, J.; Cornejo, M.; Alcaman, M. E.

    2009-12-01

    The high availability of electron donors occurring in coastal upwelling ecosystems with marked oxyclines favours chemoautotrophy, in turn leading to high N2O and CH4 cycling associated with aerobic NH4+ (AAO) and CH4 oxidation (AMO). This is the case of the highly productive coastal upwelling area off central Chile (36° S), where we evaluated the importance of total chemolithoautotrophic vs. photoautotrophic production, the specific contributions of AAO and AMO to chemosynthesis and their role in gas cycling. Chemolithoautotrophy was studied at a time-series station during monthly (2007-2009) and seasonal cruises (January 2008, September 2008, January 2009) and was assessed in terms of the natural C isotopic ratio of particulate organic carbon (δ13POC), total and specific (associated with AAO and AMO) dark carbon assimilation (CA), and N2O and CH4 cycling experiments. At the oxycline, δ13POC averaged -22.2‰; this was significantly lighter compared to the surface (-19.7‰) and bottom layers (-20.7‰). Total integrated dark CA in the whole water column fluctuated between 19.4 and 2.924 mg C m-2 d-1, was higher during active upwelling, and contributed 0.7 to 49.7% of the total integrated autotrophic CA (photo plus chemoautotrophy), which ranged from 135 to 7.626 mg C m-2 d-1, and averaged 20.3% for the whole sampling period. Dark CA was reduced by 27 to 48% after adding a specific AAO inhibitor (ATU) and by 24 to 76% with GC7, a specific archaea inhibitor. This indicates that AAO and AMO microbes (most of them archaea) were performing dark CA through the oxidation of NH4+ and CH4. Net N2O cycling rates varied between 8.88 and 43 nM d-1, whereas net CH4 cycling rates ranged from -0.41 to -26.8 nM d-1. The addition of both ATU and GC7 reduced N2O accumulation and increased CH4 consumption, suggesting that AAO and AMO were responsible, in part, for the cycling of these gases. These findings show that chemically driven chemolithoautotrophy (with NH4+ and CH4 acting

  6. 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

  7. Above- and belowground fluxes of CH4 from boreal shrubs and Scots pine

    NASA Astrophysics Data System (ADS)

    Halmeenmäki, Elisa; Heinonsalo, Jussi; Santalahti, Minna; Putkinen, Anuliina; Fritze, Hannu; Pihlatie, Mari

    2016-04-01

    Boreal upland forests are considered as an important sink for the greenhouse gas methane (CH4) due to CH4 oxidizing microbes in the soil. However, recent evidence suggests that vegetation can act as a significant source of CH4. Also, preliminary measurements indicate occasional emissions of CH4 above the tree canopies of a boreal forest. Nevertheless, the sources and the mechanisms of the observed CH4 emissions are still mostly unknown. Furthermore, the majority of CH4 flux studies have been conducted with the soil chamber method, thus not considering the role of the vegetation itself. We conducted a laboratory experiment to study separately the above- and belowground CH4 fluxes of bilberry (Vaccinium myrtillus), lingonberry (Vaccinium vitis-idaea), heather (Calluna vulgaris), and Scots pine (Pinus sylvestris), which were grown in microcosms. The above- and belowground fluxes of the plants were measured separately, and these fluxes were compared to fluxes of microcosms containing only humus soil. In addition to the flux measurements, we analysed the CH4 producing archaea (methanogens) and the CH4 consuming bacteria (methanotrophs) with the qPCR method to discover whether these microbes contribute to the CH4 exchange from the plant material and the soil. The results of the flux measurements indicate that the humus soil with roots of lingonberry, heather, and Scots pine consume CH4 compared to bare humus soil. Simultaneously, the shoots of heather and Scots pine emit small amounts of CH4. We did not find detectable amounts of methanogens from any of the samples, suggesting the produced CH4 could be of non-microbial origin, or produced by very small population of methanogens. Based on the first preliminary results, methanotrophs were present in all the studied plant species, and especially in high amounts in the rooted soils, thus implying that the methanotrophs could be responsible of the CH4 uptake in the root-soil systems.

  8. 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.

  9. An analytical model for estimating the reduction of methane emission through landfill cover soils by methane oxidation.

    PubMed

    Yao, Yijun; Su, Yao; Wu, Yun; Liu, Weiping; He, Ruo

    2015-01-01

    Landfill is an important source of atmospheric methane (CH4). In this study, the development and partial validation are presented for an analytical model for predicting the reduction of CH4 emission in landfill cover soils by CH4 oxidation. The model combines an analytic solution of a coupled oxygen (O2) and CH4 soil gas transport in landfill covers with a piecewise first-order aerobic biodegradation, including the influences of environmental factors such as cover soil thickness, CH4 oxidation and CH4 production rate. Comparison of soil gas concentration profiles with a soil column experiment is provided for a partial validation, and then this model is applied to predict the reduction of CH4 emission through landfill covers in several other cases. A discussion is provided to illustrate the roles of soil layer thickness, reaction rate constant for CH4 oxidation and CH4 production rate in determining CH4 emissions. The results suggest that the increase of cover soil thickness cannot always increase CH4 oxidation rates or removal efficiency, which becomes constant if the thickness of landfill cover soil is larger than a limit. PMID:25464331

  10. Effect of sporadic destratification, seasonal overturn and artificial mixing on CH4 emissions at the surface of a subtropical hydroelectric reservoir (Nam Theun 2 Reservoir, Lao PDR)

    NASA Astrophysics Data System (ADS)

    Guérin, F.; Deshmukh, C.; Labat, D.; Pighini, S.; Vongkhamsao, A.; Guédant, P.; Rode, W.; Godon, A.; Chanudet, V.; Descloux, S.; Serça, D.

    2015-07-01

    Inland waters in general and specifically freshwater reservoirs are recognized as source of CH4 to the atmosphere. Although the diffusion at the air-water interface is the most studied pathway, its spatial and temporal variations are poorly documented. We measured fortnightly CH4 concentrations and physico-chemical parameters at nine stations in a subtropical monomictic reservoir which was flooded in 2008 (Nam Theun 2 Reservoir, Lao PDR). Based on these results, we quantified CH4 storage in the water column and diffusive fluxes from June 2009 to December 2012. We also compared emissions with aerobic methane oxidation calculated from Deshmukh et al. (2015). In this monomictic reservoir, the seasonal variations of CH4 concentration and storage were highly dependant of the thermal stratification. Hypolimnic CH4 concentration and CH4 storage reached their maximum in the warm dry season (WD) when the reservoir was stratified. They decreased during the warm wet (WW) season and reached its minimum after the reservoir overturned in the cool dry season (CD). The sharp decreases of the CH4 storage were concomitant with sporadic extreme diffusive fluxes (up to 200 mmol m-2 d-1). These hot moments of emissions occurred mostly in the inflow region in the WW season and during the overturn in the CD season in the area of the reservoir that has the highest CH4 storage. Although they corresponded to less than 10 % of the observations, these CH4 extreme emissions (> 5 mmol m-2 d-1) contributed up to 50 % of total annual emissions by diffusion. Based on our fortnightly monitoring, we determined that accurate estimation of the emissions can be determined from measurements made at least at a monthly frequency. During the transition between the WD and WW seasons, a new hotspot of emissions was identified upstream of the water intake where diffusive fluxes peaked at 600 mmol m-2 d-1 in 2010 down to 200 mmol m-2 d-1 in 2012. In the CD season, diffusive fluxes from this area were the

  11. Chemolithoautotrophic production mediating the cycling of the greenhouses gases N2O and CH4 in an upwelling ecosystem

    NASA Astrophysics Data System (ADS)

    Farías, L.; Fernández, C.; Faúndez, J.; Cornejo, M.; Alcaman, M. E.

    2009-06-01

    Coastal upwelling ecosystems with marked oxyclines (redoxclines) present high availability of electron donors that favour chemoautotrophy, leading in turn to high N2O and CH4 cycling associated with aerobic NH4+ (AAO) and CH4 oxidation (AMO). This is the case of the highly productive coastal upwelling area off Central Chile (36° S), where we evaluated the importance of total chemolithoautotrophic vs. photoautotrophic production, the specific contributions of AAO and AMO to chemosynthesis and their role in gas cycling. Chemoautotrophy (involving bacteria and archaea) was studied at a time-series station during monthly (2002-2009) and seasonal cruises (January 2008, September 2008, January 2009) and was assessed in terms of dark carbon assimilation (CA), N2O and CH4 cycling, and the natural C isotopic ratio of particulate organic carbon (δ13POC). Total Integrated dark CA fluctuated between 19.4 and 2.924 mg C m-2 d-1. It was higher during active upwelling and represented on average 27% of the integrated photoautotrophic production (from 135 to 7.626 mg C m-2d-1). At the oxycline, δ13POC averaged -22.209‰ this was significantly lighter compared to the surface (-19.674‰) and bottom layers (-20.716‰). This pattern, along with low NH4+ content and high accumulations of N2O, NO2- and NO3- within the oxycline indicates that chemolithoautotrophs and specifically AA oxydisers were active. Dark CA was reduced from 27 to 48% after addition of a specific AAO inhibitor (ATU) and from 24 to 76% with GC7, a specific archaea inhibitor, indicating that AAO and maybe AMO microbes (most of them archaea) were performing dark CA through oxidation of NH4+ and CH4. AAO produced N2O at rates from 8.88 to 43 nM d-1 and a fraction of it was effluxed into the atmosphere (up to 42.85 μmol m-2 d-1). AMO on the other hand consumed CH4 at rates between 0.41 and 26.8 nM d-1 therefore preventing its efflux to the atmosphere (up to 18.69 μmol m-2 d-1). These findings show that chemically

  12. Early anthropogenic CH4 emissions and the variation of CH4 and 13CH4 over the last millennium

    NASA Astrophysics Data System (ADS)

    Houweling, S.; van der Werf, G. R.; Klein Goldewijk, K.; RöCkmann, T.; Aben, I.

    2008-03-01

    This study presents a new hypothesis to explain the observed variation of CH4 and δ13C-CH4 over the last millennium. It was originally proposed that the observed minimum of δ13C-CH4 prior to the start of industrialization is caused by a large shift in biomass burning emissions between 1400 and 1700 A.D. According to our new hypothesis, however, the δ13C-CH4 minimum is the first sign of the global rise of anthropogenic CH4 emissions. The main idea is that emissions of isotopically depleted CH4, from, for example, rice cultivation, domestic ruminants, and waste treatment started increasing earlier than the isotopically enriched emissions from fossil fuel, which started with the start of industrialization. However, because the observed increase of atmospheric methane only started around 1750 A.D., these preindustrial anthropogenic emissions must have been accompanied by a net reduction of natural CH4 sources during the Little Ice Age (LIA) compensating for the increase of anthropogenic emissions during that period. Results of transient box model simulations for the last millennium show that under the new hypothesis a close agreement can be obtained between model and measurements. Prior to 1400 A.D., low emissions from anthropogenic biomass burning require a sizable contribution of methane emissions from vegetation to explain the observed high level of δ13C-CH4. During the Little Ice Age, a larger than expected reduction of natural sources is needed, which calls for further verification using a more sophisticated modeling approach and additional constraints from ice core measurements.

  13. High-Frequency, Automated Measurements of CO2, N2O and CH4 from Forested Soils

    NASA Astrophysics Data System (ADS)

    Savage, K. E.; Davidson, E. A.; Phillips, R. L.

    2011-12-01

    Carbon dioxide (CO2), methane (CH4), and nitrous oxide (N2O) are the most important anthropogenic greenhouse gases. Soils are the dominant natural source of N2O, and fertilized agricultural soils are a major source of increasing anthropogenic N2O. Anthropogenic sources of CH4 include rice cultivation, while wetlands are a significant natural source, and upland soils are a natural CH4 sink. While most anthropogenic CO2 is derived from fossil fuel combustion, a significant fraction is from land use change, including a portion from loss of soil carbon. Soils play a central role as sources and sinks of the three most important anthropogenic greenhouse gases of the 21st century, CO2, CH4, and N2O. Variation in soil moisture can be very dynamic, and it is one of the dominant factors controlling soil aeration, and hence the balance between aerobic (CO2 producing) and anaerobic (CH4 producing) respiration. The production and consumption of N2O is also highly dependent on spatial and temporal variation in soil moisture. Although technologies for high frequency, precise measurements of CO2 have been available for years, methods for measuring soil fluxes of CH4 and N2O at high temporal frequency have been hampered by lack of appropriate technology for in situ real-time measurements. We utilized a previously developed automated chamber system for measuring CO2 efflux (Licor 6252 IRGA) from soils, and configured it to run in-line with a new model quantum cascade laser (QCL) system which measures N2O and CH4 (Aerodyne model QC-TILDAS-CS). The QCL is thermoelectrically cooled and uses a 76-meter path length, 0.5 liter volume, and multiple pass absorption cell for sampling. The QCL sampling frequency is 10Hz, and its range is 0.3 to 3000 ppb for N2O with a sensitivity of 0.3 ppb, and 0.5 to 5000 ppb for CH4 with a sensitivity of 0.5 ppb. Six sampling chambers, with corresponding soil water content and soil temperature sensors, were deployed at the Howland Forest ME, in an upland

  14. CO2, CH4, and DOC Flux During Long Term Thaw of High Arctic Tundra

    NASA Astrophysics Data System (ADS)

    Stackhouse, B. T.; Vishnivetskaya, T. A.; Layton, A.; Bennett, P.; Mykytczuk, N.; Lau, C. M.; Whyte, L.; Onstott, T. C.

    2013-12-01

    Arctic regions are expected to experience temperature increases of >4° C by the end of this century. This warming is projected to cause a drastic reduction in the extent of permafrost at high northern latitudes, affecting an estimated 1000 Pg of SOC in the top 3 m. Determining the effects of this temperature change on CO2 and CH4 emissions is critical for defining source constraints to global climate models. To investigate this problem, 18 cores of 1 m length were collected in late spring 2011 before the thawing of the seasonal active layer from an ice-wedge polygon near the McGill Arctic Research Station (MARS) on Axel Heiberg Island, Nunavut, Canada (N79°24, W90°45). Cores were collected from acidic soil (pH 5.5) with low SOC (~1%), summertime active layer depth between 40-70 cm (2010-2013), and sparse vegetation consisting primarily of small shrubs and sedges. Cores were progressively thawed from the surface over the course of 14 weeks to a final temperature of 4.5° C and held at that temperature for 15 months under the following conditions: in situ water saturation conditions versus fully water saturated conditions using artificial rain fall, surface light versus no surface light, cores from the polygon edge, and control cores with a permafrost table maintained at 70 cm depth. Core headspaces were measured weekly for CO2, CH4, H2, CO, and O2 flux during the 18 month thaw experiment. After ~20 weeks of thawing maximum, CO2 flux for the polygon edge and dark treatment cores were 3.0×0.7 and 1.7×0.4 mmol CO2 m-2 hr-1, respectively. The CO2 flux for the control, saturated, and in situ saturation cores reached maximums of 0.6×0.2, 0.9×0.5, and 0.9×0.1 mmol CO2 m-2 hr-1, respectively. Field measurements of CO2 flux from an adjacent polygon during the mid-summer of 2011 to 2013 ranged from 0.3 to 3.7 mmol CO2 m-2 hr-1. Cores from all treatments except water saturated were found to consistently oxidize CH4 at ~atmospheric concentrations (2 ppmv) with a maximum

  15. An Atmospheric CH4 Sink in the High Arctic and its Implication for Global Warming

    NASA Astrophysics Data System (ADS)

    Onstott, T. C.; Lau, C. M.; Stackhouse, B. T.; Medvigy, D.; Chen, Y.; Layton, A.; Vishnivetskaya, T. A.; Pfiffner, S. M.; Whyte, L.; Mykytczuk, N.; Ronholm, J.; Allan, J.; Bennett, P.; Chourey, K.; Hettich, R. L.

    2013-12-01

    Arctic permafrost underlies about 16% of the Earth's surface and contains ~500 Pg of C down to one meter. Organic-rich peatlands (averaging ~4 wt% SOC) comprise 19% of this area, whereas the remaining 81% is permafrost-affected mineral cryosols (0.5-1.5 wt% SOC). Temperatures in the Arctic are predicted to increase ~6°C over the next 100 years which increases the depth of the active layer, the seasonally thawed soil above the permafrost. Thawing permafrost peat deposits (e.g. Stordalen Mire, Sweden) are currently CH4 sources. Field measurements, intact core studies and microcosm experiments performed by us, however, over the past few years on mineral cryosols associated with ice wedge polygons from Axel Heiberg Island (AHI) in the Canadian High Arctic consistently indicate that they are sinks for atmospheric CH4 as well as the CH4 emitted from the underlying permafrost. After 1.5 years of thawing at 4°C, 1 m long intact cores of the active layer and underlying permafrost mineral cryosols collected from ice wedge polygons at AHI continue to exhibit uptake of atmospheric CH4 even for water saturated cores. The measured core fluxes are consistent with flux measurements performed in the field over the past two years, which range from 0.005 to 0.89 mg CH4-C/m2/hr and which have revealed significant differences in the atmospheric CH4 consumption fluxes between the polygon interiors and the polygon troughs. Metagenome and metaproteome analyses of these mineral cryosols indicates that the pmoA genes and proteins are most similar to an uncultured methanotroph type known as USC-α, which is recognized as a high affinity, atmospheric CH4 oxidizer. Our microcosm studies have yielded atmospheric CH4 uptake rates that are consistent with those of published results from high latitude organic-rich soils and temperate forest soils and indicate a temperature dependency for the cellular rate of CH4 oxidization that is approximately twice that reported for methanogenesis. This

  16. 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. PMID:26580330

  17. 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

  18. 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

  19. [Atmospheric CH4 concentrations and the correlation between CH4 and CO concentrations].

    PubMed

    Wei, Xiu-Li; Lu, Yi-Huai; Gao, Min-Guang; Liu, Jian-Guo; Liu, Wen-Qing; Xu, Liang; Zhang, Tian-Shu; Zhu, Jun; Chen, Jun

    2007-04-01

    Methane (CH4) is an important greenhouse gas and a key molecule in tropospheric photochemistry, some more potent than CO2. The remote-sensing experiments of CH4 were carried out in the fall of 2 000 in Beijng. The 6-day records of the atmospheric CH4 concentrations were examined by means of a time-series analysis using a fast Fourier transform with a low-pass filter to elucidate the seasonal cycles and the long-term trends. The variation in the long-time trends of the CH4 concentrations in Beijing may be ascribed to the emission changes in the CH4 sources due to the human activities such as waste dumping and landfills and the emission from motor vehicles. The correlation between the CH4 and CO concentrations was analyzed. PMID:17608171

  20. Respirometric characterization of aerobic sulfide, thiosulfate and elemental sulfur oxidation by S-oxidizing biomass.

    PubMed

    Mora, Mabel; López, Luis R; Lafuente, Javier; Pérez, Julio; Kleerebezem, Robbert; van Loosdrecht, Mark C M; Gamisans, Xavier; Gabriel, David

    2016-02-01

    Respirometry was used to reveal the mechanisms involved in aerobic biological sulfide oxidation and to characterize the kinetics and stoichiometry of a microbial culture obtained from a desulfurizing biotrickling filter. Physical-chemical processes such as stripping and chemical oxidation of hydrogen sulfide were characterized since they contributed significantly to the conversions observed in respirometric tests. Mass transfer coefficient for hydrogen sulfide and the kinetic parameters for chemical oxidation of sulfide with oxygen were estimated. The stoichiometry of the process was determined and the different steps in the sulfide oxidation process were identified. The conversion scheme proposed includes intermediate production of elemental sulfur and thiosulfate and the subsequent oxidation of both compounds to sulfate. A kinetic model describing each of the reactions observed during sulfide oxidation was calibrated and validated. The product selectivity was found to be independent of the dissolved oxygen to hydrogen sulfide concentration ratio in the medium at sulfide concentrations ranging from 3 to 30 mg S L(-1). Sulfide was preferentially consumed (SOURmax = 49.2 mg DO g(-1) VSS min(-1)) and oxidized to elemental sulfur at dissolved oxygen concentrations above 0.8 mg DO L(-1). Substrate inhibition of sulfide oxidation was observed (K(i,S(2-))= 42.4 mg S L(-1)). Intracellular sulfur accumulation also affected negatively the sulfide oxidation rate. The maximum fraction of elemental sulfur accumulated inside cells was estimated (25.6% w/w) and a shrinking particle equation was included in the kinetic model to describe elemental sulfur oxidation. The microbial diversity obtained through pyrosequencing analysis revealed that Thiothrix sp. was the main species present in the culture (>95%). PMID:26704759

  1. 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.

  2. Development of Safe and Scalable Continuous-Flow Methods for Palladium-Catalyzed Aerobic Oxidation Reactions.

    PubMed

    Ye, Xuan; Johnson, Martin D; Diao, Tianning; Yates, Matthew H; Stahl, Shannon S

    2010-01-01

    The synthetic scope and utility of Pd-catalyzed aerobic oxidation reactions has advanced significantly over the past decade, and these reactions have potential to address important green-chemistry challenges in the pharmaceutical industry. This potential has been unrealized, however, because safety concerns and process constraints hinder large-scale applications of this chemistry. These limitations are addressed by the development of a continuous-flow tube reactor, which has been demonstrated on several scales in the aerobic oxidation of alcohols. Use of a dilute oxygen gas source (8% O(2) in N(2)) ensures that the oxygen/organic mixture never enters the explosive regime, and efficient gas-liquid mixing in the reactor minimizes decomposition of the homogeneous catalyst into inactive Pd metal. These results provide the basis for large-scale implementation of palladium-catalyzed (and other) aerobic oxidation reactions for pharmaceutical synthesis. PMID:20694169

  3. 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

  4. 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

  5. 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

  6. 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

  7. Carbon isotope fractionation reveals distinct process of CH4 emission from different compartments of paddy ecosystem

    PubMed Central

    Zhang, Guangbin; Yu, Haiyang; Fan, Xianfang; Ma, Jing; Xu, Hua

    2016-01-01

    Carbon isotopic fractionations in the processes of CH4 emission from paddy field remain poorly understood. The δ13C-values of CH4 in association with production, oxidation and transport of CH4 in different pools of a paddy field were determined, and the stable carbon isotope fractionations were calibrated to assess relative contribution of acetate to CH4 production (fac) and fraction of CH4 oxidized (fox) by different pathways. The apparent isotope fractionation for CO2 conversion to CH4 (αapp) was 1.041–1.056 in the soil and 1.046–1.080 on the roots, indicating that fac was 10–60% and 0–50%, respectively. Isotope fractionation associated with CH4 oxidation (αox) was 1.021 ± 0.007 in the soil and 1.013 ± 0.005 on the roots, and the transport fractionation (εtransport) by rice plants was estimated to be −16.7‰ ~ −11.1‰. Rhizospheric fox was about 30–100%, and it was more important at the beginning but decreased fast towards the end of season. Large value of fox was also observed at the soil-water interface and soil and roots surfaces, respectively. The results demonstrate that carbon isotopic fractionations which might be different in different conditions were sensitive to the estimations of fac and fox in paddy field. PMID:27251886

  8. Carbon isotope fractionation reveals distinct process of CH4 emission from different compartments of paddy ecosystem.

    PubMed

    Zhang, Guangbin; Yu, Haiyang; Fan, Xianfang; Ma, Jing; Xu, Hua

    2016-01-01

    Carbon isotopic fractionations in the processes of CH4 emission from paddy field remain poorly understood. The δ(13)C-values of CH4 in association with production, oxidation and transport of CH4 in different pools of a paddy field were determined, and the stable carbon isotope fractionations were calibrated to assess relative contribution of acetate to CH4 production (fac) and fraction of CH4 oxidized (fox) by different pathways. The apparent isotope fractionation for CO2 conversion to CH4 (αapp) was 1.041-1.056 in the soil and 1.046-1.080 on the roots, indicating that fac was 10-60% and 0-50%, respectively. Isotope fractionation associated with CH4 oxidation (αox) was 1.021 ± 0.007 in the soil and 1.013 ± 0.005 on the roots, and the transport fractionation (εtransport) by rice plants was estimated to be -16.7‰ ~ -11.1‰. Rhizospheric fox was about 30-100%, and it was more important at the beginning but decreased fast towards the end of season. Large value of fox was also observed at the soil-water interface and soil and roots surfaces, respectively. The results demonstrate that carbon isotopic fractionations which might be different in different conditions were sensitive to the estimations of fac and fox in paddy field. PMID:27251886

  9. Carbon isotope fractionation reveals distinct process of CH4 emission from different compartments of paddy ecosystem

    NASA Astrophysics Data System (ADS)

    Zhang, Guangbin; Yu, Haiyang; Fan, Xianfang; Ma, Jing; Xu, Hua

    2016-06-01

    Carbon isotopic fractionations in the processes of CH4 emission from paddy field remain poorly understood. The δ13C-values of CH4 in association with production, oxidation and transport of CH4 in different pools of a paddy field were determined, and the stable carbon isotope fractionations were calibrated to assess relative contribution of acetate to CH4 production (fac) and fraction of CH4 oxidized (fox) by different pathways. The apparent isotope fractionation for CO2 conversion to CH4 (αapp) was 1.041–1.056 in the soil and 1.046–1.080 on the roots, indicating that fac was 10–60% and 0–50%, respectively. Isotope fractionation associated with CH4 oxidation (αox) was 1.021 ± 0.007 in the soil and 1.013 ± 0.005 on the roots, and the transport fractionation (εtransport) by rice plants was estimated to be ‑16.7‰ ~ ‑11.1‰. Rhizospheric fox was about 30–100%, and it was more important at the beginning but decreased fast towards the end of season. Large value of fox was also observed at the soil-water interface and soil and roots surfaces, respectively. The results demonstrate that carbon isotopic fractionations which might be different in different conditions were sensitive to the estimations of fac and fox in paddy field.

  10. 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

  11. Role of plant-mediated gas transport in CH4 emissions from Phragmites-dominated peatlands

    NASA Astrophysics Data System (ADS)

    van den Berg, Merit; Ingwersen, Joachim; van den Elzen, Eva; Lamers, Leon P. M.; Streck, Thilo

    2016-04-01

    A large part of the methane (CH4) produced in peatlands is directly oxidized and the extent of its oxidation depends on the gas transport pathway. In wetland ecosystems, CH4 can be transported from the soil to the atmosphere via diffusion, ebullition and via aerenchyma of roots and stems of vascular plants. Compared to other wetland plants, the very common species Phragmites australis (Common reed) appears to have a high ability to transport gases between the soil and atmosphere. The gas exchange within Phragmites plants takes place via convective flow through the culm, which is believed to be achieved by a humidity-induced pressure gradient and is more than 5-times as efficient as diffusion. By this mechanism, CH4 surpasses the upper (oxic) soil layers and therefore oxidation of CH4 may well be reduced. On the other hand, transport of oxygen in Phragmites plants tends to enhance O2concentration in the rhizosphere, which will foster CH4oxidation in deeper soil layers. It is therefore unknown whether humidity-induced convection leads to higher or lower overall CH4 emission in Phragmites, which is essential to understand their role in the emissions from these very common peatland types. To investigate whether this internal gas transport mechanism of reed promotes or reduces CH4 fluxes to the atmosphere, we conducted manipulative field experiments in a large Phragmites peatland in South-West Germany in October 2014 and July 2015. Using large chambers, we compared CH4 fluxes from intact plots, plots with cut reed, and plots with cut + sealed reed to exclude gas transport through the plants. Additionally, pore water samples from the plots were analyzed for possible changes in soil chemistry due to the change of oxygen transport into the soil by the treatments. Based on our results, we will explain the potential role of rhizosphere oxygenation and convective flow on CH4 emissions from Phragmites-dominated peatlands in relation to other environmental condition.

  12. Identification of functionally active aerobic methanotrophs in sediments from an arctic lake using stable isotope probing

    USGS Publications Warehouse

    He, Ruo; Wooller, Matthew J.; Pohlman, John W.; Catranis, Catharine; Quensen, John; Tiedje, James M.; Leigh, Mary Beth

    2012-01-01

    Arctic lakes are a significant source of the greenhouse gas methane (CH4), but the role that methane oxidizing bacteria (methanotrophs) play in limiting the overall CH4 flux is poorly understood. Here, we used stable isotope probing (SIP) techniques to identify the metabolically active aerobic methanotrophs in upper sediments (0–1 cm) from an arctic lake in northern Alaska sampled during ice-free summer conditions. The highest CH4 oxidation potential was observed in the upper sediment (0–1 cm depth) with 1.59 μmol g wet weight-1 day-1 compared with the deeper sediment samples (1–3 cm, 3–5 cm and 5–10 cm), which exhibited CH4 oxidation potentials below 0.4 μmol g wet weight-1 day-1. Both type I and type II methanotrophs were directly detected in the upper sediment total communities using targeted primer sets based on 16S rRNA genes. Sequencing of 16S rRNA genes and functional genes (pmoA and mxaF) in the 13C-DNA from the upper sediment indicated that type I methanotrophs, mainly Methylobacter, Methylosoma, Methylomonas and Methylovulum miyakonense, dominated the assimilation of CH4. Methylotrophs, including the genera Methylophilus and/or Methylotenera, were also abundant in the 13CDNA. Our results show that a diverse microbial consortium acquired carbon from CH4 in the sediments of this arctic lake.

  13. 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

  14. 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

  15. 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. PMID:26846248

  16. 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

  17. Effects of Aerobic and Microaerobic Conditions on Anaerobic Ammonium-Oxidizing (Anammox) Sludge

    PubMed Central

    Strous, M.; Van Gerven, E.; Kuenen, J. G.; Jetten, M.

    1997-01-01

    The anaerobic ammonium oxidation (Anammox) process is a promising novel option for removing nitrogen from wastewater. In this study it was shown that the Anammox process was inhibited reversibly by the presence of oxygen. Furthermore, aerobic nitrifiers were shown not to play an important role in the Anammox process. PMID:16535633

  18. Aerobic Oxidation in Nanomicelles of Aryl Alkynes, in Water at Room Temperature**

    PubMed Central

    Handa, Sachin; Fennewald, James C.; Rainey, Shane

    2014-01-01

    On the basis of the far higher solubility of oxygen gas inside the hydrocarbon core of nanomicelles, metal and peroxide free aerobic oxidation of aryl alkynes has been achieved in water at room temperature. Many examples are offered that illustrate broad functional group tolerance. The overall process is environmentally friendly, documented by the associated low E Factors. PMID:24616243

  19. CO2 and CH4 isotope compositions and production pathways in a tropical peatland

    NASA Astrophysics Data System (ADS)

    Holmes, M. Elizabeth; Chanton, Jeffrey P.; Tfaily, Malak M.; Ogram, Andrew

    2015-01-01

    While it is widely recognized that peatlands are important in the global carbon cycle, there is limited information on belowground gas production in tropical peatlands. We measured pore water methane (CH4) and carbon dioxide (CO2) concentrations and δ13C isotopic composition and CH4 and CO2 production rates in peat incubations from the Changuinola wetland in Panama. Our most striking finding was that CH4 was depleted in 13C (-94‰ in pore water and produced at -107‰ in incubated peat) relative to CH4 found in most temperate and northern wetlands, potentially impacting the accuracy of approaches that use carbon isotopes to constrain global mass balance estimates. Fractionation factors between CH4 and CO2 showed that hydrogenotrophic methanogenesis was the dominant CH4 production pathway, with up to 100% of the CH4 produced via this route. Far more CO2 than CH4 (7 to 100X) was measured in pore water, due in part to loss of CH4 through ebullition or oxidation and to the production of CO2 from pathways other than methanogenesis. We analyzed data on 58 wetlands from the literature to determine the dominant factors influencing the relative proportions of CH4 produced by hydrogenotrophic and acetoclastic methanogenesis and found that a combination of environmental parameters including pH, vegetation type, nutrient status, and latitude are correlated to the dominant methanogenic pathway. Methane production pathways in tropical peatlands do not correlate with these variables in the same way as their more northerly counterparts and thus may be differently affected by climate change.

  20. Nitrous oxide production by Alcaligenes faecalis under transient and dynamic aerobic and anaerobic conditions

    SciTech Connect

    Otte, S.; Grobben, N.G.; Robertson, L.A.; Jetten, M.S.M.; Kuenen, J.G.

    1996-07-01

    Nitrous oxide production contributes to both greenhouse effect and ozone depletion in the stratosphere. A significant part of the global N2O emission can be attributed to microbial processes, especially nitrification and denitrification, used in biological wastewater treatment systems. This study looks at the efficiency of denitrification and the enzymes involved, with the emphasis on N2O production during the transient phase from aerobic to anaerobic conditions and vice versa. The effect of repetitive changing aerobic-anaerobic conditions on N2O was also studied. Alcaligenes faecalis was used as the model denitrofing organism. 35 refs., 3 figs., 1 tab.

  1. Practical Aerobic Oxidations of Alcohols and Amines with Homogeneous Cu/TEMPO and Related Catalyst Systems

    PubMed Central

    Ryland, Bradford L.; Stahl, Shannon S.

    2014-01-01

    Alcohol and amine oxidations are common reactions in laboratory and industrial synthesis of organic molecules. Aerobic oxidation methods have long been sought for these transformations, but few practical methods exist that offer advantages over traditional oxidation methods. Recently developed homogeneous Cu/TEMPO (TEMPO = 2,2,6,6-tetramethylpiperidinyl-N-oxyl) and related catalyst systems appear to fill this void. The reactions exhibit high levels of chemoselectivity and broad functional-group tolerance, and they often operate efficiently at room temperature with ambient air as the oxidant. These advances, together with their historical context and recent applications, are highlighted in this minireview. PMID:25044821

  2. 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

  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. Responses of methanotrophic activity, community and EPS production to CH4 and O2 concentrations in waste biocover soils.

    PubMed

    Wei, Xiao-Meng; Su, Yao; Zhang, Hong-Tao; Chen, Min; He, Ruo

    2015-08-01

    Biocover soils are known to be a good alternative material to mitigate CH4 emissions from landfills to the atmosphere. In this study, 16 treatments with four O2 concentrations (∼0%, 5%, 10% and 21%) and four CH4 concentrations (i.e. 1%, 10%, 20% and 50%) were conducted to estimate extracellular polymeric substances (EPS) production, methanotrophic activity and community in response to CH4 and O2 concentrations in waste biocover soil (WBS). When the CH4 concentration was saturated for CH4 oxidation in the WBS, the continuous exposure of CH4 above the saturated concentrations could not obviously enhance CH4 oxidation activity. In the WBS, extracellular protein (ECP) production was negatively related with the tested CH4 concentrations, while both ECP and extracellular polysaccharides (ECPS) productions were positively related with the tested O2 concentrations. Cloning and terminal restriction fragment length polymorphism analyses showed that type I methanotrophs (Methylocaldum, Methylococcaceae, Methylomicrobium and Methylobacter) and type II methanotrophs (Methylosinus) dominated in the WBS. Among them, Methylocaldum and/or Methylococcaceae were sensitive to low O2 concentrations of ∼0%. Methylobacter had propensity to grow at low O2 concentrations of ∼0% and 5%, while Methylosinus preferred environments with high concentrations of CH4 (⩾10%) and O2 (21%). In the tested five environmental variables of ECPS, O2, EPS, CH4 and ECP, only ECPS and O2 concentrations had significant effect on the methanotrophic communities. These results suggested that O2 concentration in landfill covers should be paid more attention to optimize and sustain CH4 oxidation for mitigating CH4 emission from landfills. PMID:25921582

  5. Year-round measurements of CH4 exchange in a forested drained peatland using automated chambers

    NASA Astrophysics Data System (ADS)

    Korkiakoski, Mika; Koskinen, Markku; Penttilä, Timo; Arffman, Pentti; Ojanen, Paavo; Minkkinen, Kari; Laurila, Tuomas; Lohila, Annalea

    2016-04-01

    Pristine peatlands are usually carbon accumulating ecosystems and sources of methane (CH4). Draining peatlands for forestry increases the thickness of the oxic layer, thus enhancing CH4 oxidation which leads to decreased CH4 emissions. Closed chambers are commonly used in estimating the greenhouse gas exchange between the soil and the atmosphere. However, the closed chamber technique alters the gas concentration gradient making the concentration development against time non-linear. Selecting the correct fitting method is important as it can be the largest source of uncertainty in flux calculation. We measured CH4 exchange rates and their diurnal and seasonal variations in a nutrient-rich drained peatland located in southern Finland. The original fen was drained for forestry in 1970s and now the tree stand is a mixture of Scots pine, Norway spruce and Downy birch. Our system consisted of six transparent polycarbonate chambers and stainless steel frames, positioned on different types of field and moss layer. During winter, the frame was raised above the snowpack with extension collars and the height of the snowpack inside the chamber was measured regularly. The chambers were closed hourly and the sample gas was sucked into a cavity ring-down spectrometer and analysed for CH4, CO2 and H2O concentration with 5 second time resolution. The concentration change in time in the beginning of a closure was determined with linear and exponential fits. The results show that linear regression systematically underestimated the CH4 flux when compared to exponential regression by 20-50 %. On the other hand, the exponential regression seemed not to work reliably with small fluxes (< 3.5 μg CH4 m-2 h-1): using exponential regression in such cases typically resulted in anomalously large fluxes and high deviation. Due to these facts, we recommend first calculating the flux with the linear regression and, if the flux is high enough, calculate the flux again using the exponential

  6. 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

  7. 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

  8. 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

  9. 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

  10. Field-scale tracking of active methane-oxidizing communities in a landfill cover soil reveals spatial and seasonal variability.

    PubMed

    Henneberger, Ruth; Chiri, Eleonora; Bodelier, Paul E L; Frenzel, Peter; Lüke, Claudia; Schroth, Martin H

    2015-05-01

    Aerobic methane-oxidizing bacteria (MOB) in soils mitigate methane (CH4 ) emissions. We assessed spatial and seasonal differences in active MOB communities in a landfill cover soil characterized by highly variable environmental conditions. Field-based measurements of CH4 oxidation activity and stable-isotope probing of polar lipid-derived fatty acids (PLFA-SIP) were complemented by microarray analysis of pmoA genes and transcripts, linking diversity and function at the field scale. In situ CH4 oxidation rates varied between sites and were generally one order of magnitude lower in winter compared with summer. Results from PLFA-SIP and pmoA transcripts were largely congruent, revealing distinct spatial and seasonal clustering. Overall, active MOB communities were highly diverse. Type Ia MOB, specifically Methylomonas and Methylobacter, were key drivers for CH4 oxidation, particularly at a high-activity site. Type II MOB were mainly active at a site showing substantial fluctuations in CH4 loading and soil moisture content. Notably, Upland Soil Cluster-gamma-related pmoA transcripts were also detected, indicating concurrent oxidation of atmospheric CH4 . Spatial separation was less distinct in winter, with Methylobacter and uncultured MOB mediating CH4 oxidation. We propose that high diversity of active MOB communities in this soil is promoted by high variability in environmental conditions, facilitating substantial removal of CH4 generated in the waste body. PMID:25186436

  11. Recent variation of Siberian CH4 fluxes estimated from atmospheric observations of CH4

    NASA Astrophysics Data System (ADS)

    Kim, H.; Machida, T.; Sasakawa, M.; Belikov, D.; Saeki, T.; Ito, A.; Maksyutov, S.

    2012-12-01

    Siberia is an area of choice for observing the effects of global warming sooner than in other regions. Perceivable changes in ecosystem and cryosphere environment have been reported such as damage to the forest or frequent flood. In this study, we use atmospheric methane observations in Siberia to estimate Siberian CH4 fluxes during 2006-2010 using an inverse model of atmospheric transport and investigate the recent variation of the estimated fluxes. Interseasonally varying CH4 emissions developed in TransCom-CH4 project are used in forward CH4 tracer simulations with NIES transport model including chemical sink rates: wetland and rice paddy emissions simulated with a process-based biogeochemical model (VISIT), biomass burning emissions of GFED v3.1, aseasonal anthropogenic emissions of EDGAR v4.2, and interseasonally repeating termite emissions of GISS. We use flask sampling and continuous measurement data of atmospheric CH4 archived at WDCGG in flux estimates. In addition, atmospheric CH4 observed in Siberia by aircrafts and a tall tower network (JR-STATION: Japan-Russia Siberian Tall Tower Inland Observation Network) are used to optimize Siberian CH4 flux: 1) monthly vertical profiles at Surgut, Novosibirsk and Yakutsk, and 2) continuous measurements at the JR-STATION in Berezorechka, Demyanskoe, Karasevoe, Igrim, Noyabrsk, Savvushka, Vaganovo, and Yakutsk. Annual mean Siberian CH4 flux is estimated to be 21.63 ± 5.25 Tg/yr in 2006-2010, which is 4.3 % to the global total (505.40 Tg/yr). Our Siberian flux estimates present a positive flux anomaly since 2007 and the flux anomaly is defined as the departure from the 2006 flux estimates. In 2007, increased wetland flux is estimated in the north-western Siberia with large wetland area and high summer CH4 concentrations observed at Demyanskoe, Karasevoe and Igrim near extensive wetlands can be explained by the enhanced wetland flux under hot and wet summer. This result is consistent with other studies which

  12. Quantifying (12/13)CH(4) migration and fate following sub-surface release to an agricultural soil.

    PubMed

    Shaw, G; Atkinson, B; Meredith, W; Snape, C; Steven, M; Hoch, A; Lever, D

    2014-07-01

    Following gas generation in a Geological Disposal Facility (GDF), (14)C-containing gases could migrate through the geosphere, eventually diffusing into soils at the Earth's surface. This paper reports summary results from laboratory and field experiments to obtain information on the probable rates of a) diffusive transport and b) oxidation of (12/13)CH(4) (as a surrogate for (14)CH4) in a typical agricultural soil in the UK. Rates of CH(4) oxidation were generally low in the field and undisturbed soil columns, though a re-packed column of homogenised topsoil oxidised ambient atmospheric CH(4) 20× faster than an undisturbed soil column. In contrast to low observed rates of CH(4) oxidation, the effective diffusion of CH(4) through the soil was rapid. Isotopically labelled CH(4) injected at a depth of 45 cm in the field diffused to the surface and exited the soil over a time period ranging from 8 to 24 h. The rate of CH(4) diffusion through the soil was increased by the presence of ryegrass roots which increased soil porosity and decreased water content. δ(13)C values for laboratory column soils after labelled CH(4) injection experiments showed no sign of residual (13)C, despite the extremely high δ(13)C values of the injected (12/13)CH(4). If laboratory observations are confirmed by measurements in field samples it can be concluded that the majority of (14)CH(4) from a GDF which enters a soil with low methanotrophic activity will be lost to the free atmosphere after diffusing rapidly through the soil column. PMID:23958331

  13. Heterogeneous Rhodium-Catalyzed Aerobic Oxidative Dehydrogenative Cross-Coupling: Nonsymmetrical Biaryl Amines.

    PubMed

    Matsumoto, Kenji; Yoshida, Masahiro; Shindo, Mitsuru

    2016-04-18

    The first heterogeneously catalyzed oxidative dehydrogenative cross-coupling of aryl amines is reported herein. 2-Naphthylamine analogues were reacted with various electron-rich arenes using a heterogeneous Rh/C catalyst under mild aerobic conditions, thus affording nonsymmetrical biaryl amines in excellent yields with high selectivities. This reaction provides a mild, operationally simple, and efficient approach for the synthesis of biaryls which are important to pharmaceutical and materials chemistry. PMID:26996772

  14. 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

  15. 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

  16. 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

  17. 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.

  18. CH4 emission and conversion from A2O and SBR processes in full-scale wastewater treatment plants.

    PubMed

    Liu, Yan; Cheng, Xiang; Lun, Xiaoxiu; Sun, Dezhi

    2014-01-01

    Wastewater treatment systems are important anthropogenic sources of CH4 emission. A full-scale experiment was carried out to monitor the CH4 emission from anoxic/anaerobic/oxic process (A20) and sequencing batch reactor (SBR) wastewater treatment plants (WWTPs) for one year from May 2011 to April 2012. The main emission unit of the A2O process was an oxic tank, accounting for 76.2% of CH4 emissions; the main emission unit of the SBR process was the feeding and aeration phase, accounting for 99.5% of CH4 emissions. CH4 can be produced in the anaerobic condition, such as in the primary settling tank and anaerobic tank of the A2O process. While CH4 can be consumed in anoxic denitrification or the aeration condition, such as in the anoxic tank and oxic tank of the A2O process and the feeding and aeration phase of the SBR process. The CH4 emission flux and the dissolved CH4 concentration rapidly decreased in the oxic tank of the A2O process. These metrics increased during the first half of the phase and then decreased during the latter half of the phase in the feeding and aeration phase of the SBR process. The CH4 oxidation rate ranged from 32.47% to 89.52% (mean: 67.96%) in the A2O process and from 12.65% to 88.31% (mean: 47.62%) in the SBR process. The mean CH4 emission factors were 0.182 g/ton of wastewater and 24.75 g CH4/(person x year) for the A2O process, and 0.457 g/ton of wastewater and 36.55 g CH4/(person x year) for the SBR process. PMID:24649710

  19. 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.

  20. Factors affecting variation in CH4 emission from paddy soils grown with different rice cultivars: A pot experiment

    NASA Astrophysics Data System (ADS)

    Watanabe, Akira; Kimura, Makoto

    1998-08-01

    The growth of rice plants greatly influences CH4 emission from paddy fields through the supply of organic materials such as root exudates and sloughed tissues, the release of oxygen to the root environment, and the transfer of CH4 from the rhizosphere into the atmosphere through the aerenchyma. In the present pot experiments, the effects of the release of water-soluble organic substances from roots, the air space in roots, and the CH4-oxidizing capacity of roots on intervarietal differences in CH4 emission were examined using three Japonica type cultivars (Norin 25, Nipponbare, and Aoinokaze), which differ in morphological properties. The CH4 emission rates varied among the cultivars from mid-July (tillering stage) to the beginning of September (heading stage).Total CH4 emission throughout the rice growth period was largest for Norin 25, followed by Nipponbare, and Aoinokaze. In August, the rate of release of water-soluble organic substances from roots was largest for Norin 25. The air space in roots was also largest in Norin 25 and least in Aoinokaze. The stable carbon isotopic ratios (δ13C) of CH4 in roots were 3-10‰ higher than those in soil in August. The difference in δ13C values of CH4 between roots and soil was largest for Aoinokaze and smallest for Norin 25. In September, the difference in δ13C values of CH4 between roots and soil became small (2-3‰). These findings suggest that the proportion of CH4 oxidation in the rhizosphere was largest in the cultivar which emitted the smallest amount of CH4 and that the proportion became smaller with continued plant growth.

  1. Emission of N2O and CH4 from a constructed wetland in southeastern Norway.

    PubMed

    Søvik, A K; Kløve, B

    2007-07-15

    The Skjønhaug constructed wetland (CW) is a free surface water (FSW) wetland polishing chemically treated municipal wastewater in southeastern Norway and consists of three ponds as well as trickling, unsaturated filters with light weight aggregates (LWA). Fluxes of nitrous oxide (N(2)O) and methane (CH(4)) have been measured during the autumn, winter and summer from all three ponds as well as from the unsaturated filters. Physicochemical parameters of the water have been measured at the same localities. The large temporal and spatial variation of N(2)O fluxes was found to cover a range of -0.49 to 110 mg N(2)O-N m(-2) day(-1), while the fluxes of CH(4) was found to cover a range of -1.2 to 1900 mg m(-2) day(-1). Thus, both emission and consumption occurred. Regarding fluxes of N(2)O there was a significant difference between the summer, winter and autumn, with the highest emissions occurring during the autumn. The fluxes of CH(4) were, on the other hand, not significantly different with regard to seasons. Both the emissions of N(2)O and CH(4) were positively influenced by the amount of total organic carbon (TOC). The measured fluxes of N(2)O and CH(4) are in the same range as those reported from other CWs treating wastewater. There was an approximately equal contribution to the global warming potential from N(2)O and CH(4). PMID:17204306

  2. Coupling past climates to wetlands: uncertainties in modelling CH4 fluxes. (Invited)

    NASA Astrophysics Data System (ADS)

    Berrittella, C.; van Huissteden, K. J.; Dolman, H.

    2009-12-01

    The sudden rise of CH4 concentration in the atmosphere has recently become a key topic in the current global warming debate. This phenomenon occurred also during interstadials of the last glacial, when large amounts of CH4 probably were released from northern wetlands within a short time span. Past wetland emission models may help to clarify also present-day processes. Two wetlands CH4 flux models were applied to glacial lowlands in Europe, each coupled to both a hydrological and a paleoclimatic model. The simple model estimates emissions as a fraction of net primary production generated by the BIOME 3.5 global vegetation model. The PEATLAND - VU model includes soil and vegetation processes related to CH4 emission. Validation is provided by the comparison of model results for the present-day climate with field measurements from the literature. The results highlight the uncertainties in modelling of CH4 fluxes. Their results were different, with the sharpest contrast being between stadial and interstadial climate emissions. PEATLAND-VU most interesting result is that interstadial climate emissions were similar to those of present-day wetlands. It is vegetation that mainly contributes to uncertainty in modelling CH4 fluxes, due to parameters related to rates of labile organic matter production, CH4 oxidation, roots and plant transport characteristics. Differences between glacial and present plant species are known from the paleo-botanical record (less Sphagnum mosses in glacial wetlands) and result in difficulties in comparison with current wetlands. Emissions from wetlands on the exposed seafloor are proven to be an important component of glacial CH4 fluxes and compensate for loss of wetlands in glaciated areas.

  3. 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.

  4. Multi-years simulations of atmospheric CH4, δ13C-CH4 and δD-CH4

    NASA Astrophysics Data System (ADS)

    Monteil, Guillaume; Houweling, Sander; Röckmann, Thomas; Vaughn, Bruce H.; Tyler, Stanley C.

    2010-05-01

    The atmospheric concentration of methane has increased by more than a factor of two since the start of the preindustrial era, due to human activities such as fossil fuel usage and intensive agriculture. After a continuous increase during the 20th century, measurements show an almost steady mixing ratio from 1999 to 2006, followed by a new increase since 2007. The main driver of those recent changes is the subject of a scientific debate. Plausible hypothesis have been proposed for the growth-rate slowdown, which however remain difficult to prove. The main obstacle in understanding the observed trend of methane is the lack of accurate estimates of the individual source processes involved in the methane cycle. Moreover, the main sink, the hydroxyl radical, OH, is not directly measurable on a large scale and is therefore poorly constrained. In order to better characterize the methane budget, one possibility is to use isotopic ratios of atmospheric methane, as these ratios carry process specific information. During the last 15 years, isotopic measurements have become more common and we have now a relatively good geographical coverage, of time series spanning several years. We used the global chemistry-transport model TM3 to investigate the constraint imposed by the isotopic measurements. We performed coupled simulations of CH4 and its two most common stable isotopologues, 13C-CH4 and CH3D, using different sources and sink scenarios. The aim is to evaluate the isotopic implications of the different hypothesis explaining the recent methane growth rate variations. We evaluated the probability of those hypotheses by comparison of our results with the available measurements. We will present first results which clearly show that isotopic measurements bring important information, confirming their usefulness, although a better characterizations of the isotopic fractionation factors of the individual process and a larger amount of measurements is needed, in particular for CH3D.

  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. MERLIN Performance Simulation of Global CH4

    NASA Astrophysics Data System (ADS)

    Ehret, G.; Flamant, P.; Kiemle, C.; Quatrevalet, M.; Amediek, A.

    2011-12-01

    Atmospheric methane (CH4) is the second most important anthropogenic greenhouse gas after carbon dioxide that will contribute to global warming, significantly. Large uncertainties exist for example in the estimation of tropical and boreal wetlands which provide a large natural source of atmospheric methane. Particularly sensitive are the northern high latitude regions where permafrost melting and gas hydrate instabilities in ice shelves may drive tomorrow's climate. The overall goal of MERLIN (Methane Remote Lidar Mission) which is the joint Franco-German climate monitoring initiative is to provide better information on methane sources on a global basis during all seasons. This will be achieved by means of inverse modelling using space-based lidar measurements of the column-weighted dry-air mixing ratio of CH4, commonly referred to as XCH4, as input data. The latter is a function of the measured differential-absorption optical depth (DAOD) on one hand, and the calculated path-integrated differential-absorption cross section of the selected on-/off-line wavelengths, commonly referred to as integrated weighting function (IWF), on the other hand. To model the MERLIN measurement precision we assumed statistically independent error sources for both parameters. Based on careful selection of the sounding wavelengths in the near IR around 1.64 μm it is found that the random errors in IWF which stem from uncertainties in the geophysical parameters like surface pressure error or errors in the temperature and humidity profiles remain small compared to those from measurement of DAOD. A total of 177 shot-pairs are averaged, which corresponds to a horizontal resolution of 50 km for each observation, in order to obtain a measurement precision of about 1 %. The surface reflectance in nadir direction, which is a key parameter in the precision analysis, is modelled using MODIS data over land and surface wind speed data over water. Cloud coverage and aerosol/cloud extinction of

  7. 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. PMID:25259503

  8. The Arctic CH4 sink and its implications for the permafrost carbon feedbacks to the global climate system

    NASA Astrophysics Data System (ADS)

    Juncher Jørgensen, Christian; Christiansen, Jesper; Mariager, Tue; Hugelius, Gustaf

    2016-04-01

    Using atmospheric methane (CH4), certain soil microbes are able to sustain their metabolism, and in turn remove this powerful greenhouse gas from the atmosphere. While the process of CH4 oxidation is a common feature in most natural and unmanaged ecosystems in temperate and boreal ecosystems, the interactions between soil physical properties and abiotic process drivers, net landscape exchange and spatial patterns across Arctic drylands remains highly uncertain. Recent works show consistent CH4 comsumption in upland dry tundra soils in Arctic and High Arctic environments (Christiansen et al., 2014, Biogeochemistry 122; Jørgensen et al., 2015, Nature Geoscience 8; Lau et al., 2015, The ISME Journal 9). In these dominantly dry or barren soil ecosystems, CH4 consumption has been observed to significantly exceed the amounts of CH4 emitted from adjacent wetlands. These observations point to a potentially important but largely overlooked component of the global soil-climate system interaction and a counterperspective to the conceptual understanding of the Arctic being a only a source of CH4. However, due to our limited knowledge of spatiotemporal occurrence of CH4 consumption across a wider range of the Arctic landscape we are left with substantial uncertainites and an overall unconstrained range estimate of this terrestrial CH4 sink and its potential effects on permafrost carbon feedback to the atmospheric CH4 concentration. To address this important knowledge gap and identify the most relevant spatial scaling parameters, we studied in situ CH4 net exchange across a large landscape transect on West Greenland. The transect representated soils formed from the dominant geological parent materials of dry upland tundra soils found in the ice-free land areas of Western Greenland, i.e. 1) granitic/gneissic parent material, 2) basaltic parent material and 3) sedimentary deposits. Results show that the dynamic variations in soil physical properties and soil hydrology exerts an

  9. Nanovalved Adsorbents for CH4 Storage.

    PubMed

    Song, Zhuonan; Nambo, Apolo; Tate, Kirby L; Bao, Ainan; Zhu, Minqi; Jasinski, Jacek B; Zhou, Shaojun J; Meyer, Howard S; Carreon, Moises A; Li, Shiguang; Yu, Miao

    2016-05-11

    A novel concept of utilizing nanoporous coatings as effective nanovalves on microporous adsorbents was developed for high capacity natural gas storage at low storage pressure. The work reported here for the first time presents the concept of nanovalved adsorbents capable of sealing high pressure CH4 inside the adsorbents and storing it at low pressure. Traditional natural gas storage tanks are thick and heavy, which makes them expensive to manufacture and highly energy-consuming to carry around. Our design uses unique adsorbent pellets with nanoscale pores surrounded by a coating that functions as a valve to help manage the pressure of the gas and facilitate more efficient storage and transportation. We expect this new concept will result in a lighter, more affordable product with increased storage capacity. The nanovalved adsorbent concept demonstrated here can be potentially extended for the storage of other important gas molecules targeted for diverse relevant functional applications. PMID:27124722

  10. Degraded Land Restoration in Reinstating CH4 Sink.

    PubMed

    Singh, Jay Shankar; Gupta, Vijai K

    2016-01-01

    Methane (CH4), a potent greenhouse gas, contributes about one third to the global green house gas emissions. CH4-assimilating microbes (mostly methanotrophs) in upland soils play very crucial role in mitigating the CH4 release into the atmosphere. Agricultural, environmental, and climatic shifts can alter CH4 sink profiles of soils, likely through shifts in CH4-assimilating microbial community structure and function. Landuse change, as forest and grassland ecosystems altered to agro-ecosystems, has already attenuated the soil CH4 sink potential, and are expected to be continued in the future. We hypothesized that variations in CH4 uptake rates in soils under different landuse practices could be an indicative of alterations in the abundance and/or type of methanotrophic communities in such soils. However, only a few studies have addressed to number and methanotrophs diversity and their correlation with the CH4 sink potential in soils of rehabilitated/restored lands. We focus on landuse practices that can potentially mitigate CH4 gas emissions, the most prominent of which are improved cropland, grazing land management, use of bio-fertilizers, and restoration of degraded lands. In this perspective paper, it is proposed that restoration of degraded lands can contribute considerably to improved soil CH4 sink strength by retrieving/conserving abundance and assortment of efficient methanotrophic communities. We believe that this report can assist in identifying future experimental directions to the relationships between landuse changes, methane-assimilating microbial communities and soil CH4 sinks. The exploitation of microbial communities other than methanotrophs can contribute significantly to the global CH4 sink potential and can add value in mitigating the CH4 problems. PMID:27379053

  11. Degraded Land Restoration in Reinstating CH4 Sink

    PubMed Central

    Singh, Jay Shankar; Gupta, Vijai K.

    2016-01-01

    Methane (CH4), a potent greenhouse gas, contributes about one third to the global green house gas emissions. CH4-assimilating microbes (mostly methanotrophs) in upland soils play very crucial role in mitigating the CH4 release into the atmosphere. Agricultural, environmental, and climatic shifts can alter CH4 sink profiles of soils, likely through shifts in CH4-assimilating microbial community structure and function. Landuse change, as forest and grassland ecosystems altered to agro-ecosystems, has already attenuated the soil CH4 sink potential, and are expected to be continued in the future. We hypothesized that variations in CH4 uptake rates in soils under different landuse practices could be an indicative of alterations in the abundance and/or type of methanotrophic communities in such soils. However, only a few studies have addressed to number and methanotrophs diversity and their correlation with the CH4 sink potential in soils of rehabilitated/restored lands. We focus on landuse practices that can potentially mitigate CH4 gas emissions, the most prominent of which are improved cropland, grazing land management, use of bio-fertilizers, and restoration of degraded lands. In this perspective paper, it is proposed that restoration of degraded lands can contribute considerably to improved soil CH4 sink strength by retrieving/conserving abundance and assortment of efficient methanotrophic communities. We believe that this report can assist in identifying future experimental directions to the relationships between landuse changes, methane-assimilating microbial communities and soil CH4 sinks. The exploitation of microbial communities other than methanotrophs can contribute significantly to the global CH4 sink potential and can add value in mitigating the CH4 problems. PMID:27379053

  12. Identification of key nitrous oxide production pathways in aerobic partial nitrifying granules.

    PubMed

    Ishii, Satoshi; Song, Yanjun; Rathnayake, Lashitha; Tumendelger, Azzaya; Satoh, Hisashi; Toyoda, Sakae; Yoshida, Naohiro; Okabe, Satoshi

    2014-10-01

    The identification of the key nitrous oxide (N2O) production pathways is important to establish a strategy to mitigate N2O emission. In this study, we combined real-time gas-monitoring analysis, (15)N stable isotope analysis, denitrification functional gene transcriptome analysis and microscale N2O concentration measurements to identify the main N2O producers in a partial nitrification (PN) aerobic granule reactor, which was fed with ammonium and acetate. Our results suggest that heterotrophic denitrification was the main contributor to N2O production in our PN aerobic granule reactor. The heterotrophic denitrifiers were probably related to Rhodocyclales bacteria, although different types of bacteria were active in the initial and latter stages of the PN reaction cycles, most likely in response to the presence of acetate. Hydroxylamine oxidation and nitrifier denitrification occurred, but their contribution to N2O emission was relatively small (20-30%) compared with heterotrophic denitrification. Our approach can be useful to quantitatively examine the relative contributions of the three pathways (hydroxylamine oxidation, nitrifier denitrification and heterotrophic denitrification) to N2O emission in mixed microbial populations. PMID:24650173

  13. 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

  14. 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.

  15. Effect of selected monoterpenes on methane oxidation, denitrification, and aerobic metabolism by bacteria in pure culture.

    PubMed

    Amaral, J A; Ekins, A; Richards, S R; Knowles, R

    1998-02-01

    Selected monoterpenes inhibited methane oxidation by methanotrophs (Methylosinus trichosporium OB3b, Methylobacter luteus), denitrification by environmental isolates, and aerobic metabolism by several heterotrophic pure cultures. Inhibition occurred to various extents and was transient. Complete inhibition of methane oxidation by Methylosinus trichosporium OB3b with 1.1 mM (-)-alpha-pinene lasted for more than 2 days with a culture of optical density of 0.05 before activity resumed. Inhibition was greater under conditions under which particulate methane monooxygenase was expressed. No apparent consumption or conversion of monoterpenes by methanotrophs was detected by gas chromatography, and the reason that transient inhibition occurs is not clear. Aerobic metabolism by several heterotrophs was much less sensitive than methanotrophy was; Escherichia coli (optical density, 0.01), for example, was not affected by up to 7.3 mM (-)-alpha-pinene. The degree of inhibition was monoterpene and species dependent. Denitrification by isolates from a polluted sediment was not inhibited by 3.7 mM (-)-alpha-pinene, gamma-terpinene, or beta-myrcene, whereas 50 to 100% inhibition was observed for isolates from a temperate swamp soil. The inhibitory effect of monoterpenes on methane oxidation was greatest with unsaturated, cyclic hydrocarbon forms [e.g., (-)-alpha-pinene, (S)-(-)-limonene, (R)-(+)-limonene, and gamma-terpinene]. Lower levels of inhibition occurred with oxide and alcohol derivatives [(R)-(+)-limonene oxide, alpha-pinene oxide, linalool, alpha-terpineol] and a noncyclic hydrocarbon (beta-myrcene). Isomers of pinene inhibited activity to different extents. Given their natural sources, monoterpenes may be significant factors affecting bacterial activities in nature. PMID:9464387

  16. Diversity of active aerobic methanotrophs along depth profiles of arctic and subarctic lake water column and sediments

    USGS Publications Warehouse

    He, Ruo; Wooller, Matthew J.; Pohlman, John W.; Quensen, John; Tiedje, James M.; Leigh, Mary Beth

    2012-01-01

    Methane (CH4) emitted from high-latitude lakes accounts for 2–6% of the global atmospheric CH4 budget. Methanotrophs in lake sediments and water columns mitigate the amount of CH4 that enters the atmosphere, yet their identity and activity in arctic and subarctic lakes are poorly understood. We used stable isotope probing (SIP), quantitative PCR (Q-PCR), pyrosequencing and enrichment cultures to determine the identity and diversity of active aerobic methanotrophs in the water columns and sediments (0–25 cm) from an arctic tundra lake (Lake Qalluuraq) on the north slope of Alaska and a subarctic taiga lake (Lake Killarney) in Alaska's interior. The water column CH4 oxidation potential for these shallow (~2m deep) lakes was greatest in hypoxic bottom water from the subarctic lake. The type II methanotroph, Methylocystis, was prevalent in enrichment cultures of planktonic methanotrophs from the water columns. In the sediments, type I methanotrophs (Methylobacter, Methylosoma and Methylomonas) at the sediment-water interface (0–1 cm) were most active in assimilating CH4, whereas the type I methanotroph Methylobacter and/or type II methanotroph Methylocystis contributed substantially to carbon acquisition in the deeper (15–20 cm) sediments. In addition to methanotrophs, an unexpectedly high abundance of methylotrophs also actively utilized CH4-derived carbon. This study provides new insight into the identity and activity of methanotrophs in the sediments and water from high-latitude lakes.

  17. Combining two complementary micrometeorological methods to measure CH4 and N2O fluxes over pasture

    NASA Astrophysics Data System (ADS)

    Laubach, J.; Barthel, M.; Fraser, A.; Hunt, J. E.; Griffith, D. W. T.

    2015-09-01

    New Zealand's largest industrial sector is pastoral agriculture, giving rise to a large fraction of the country's emissions of methane (CH4) and nitrous oxide (N2O). We designed a system to continuously measure CH4 and N2O fluxes at the field scale on two adjacent pastures that differed with respect to management. At the core of this system was a closed-cell Fourier-transform infrared spectrometer (FTIR), measuring the mole fractions of CH4, N2O and carbon dioxide (CO2) at two heights at each site. In parallel, CO2 fluxes were measured using eddy-covariance instrumentation. We applied two different micrometeorological ratio methods to infer the CH4 and N2O fluxes from their respective mole fractions and the CO2 fluxes. The first is a variant of the flux-gradient method, where it is assumed that the turbulent diffusivities of CH4 and N2O equal that of CO2. This method was reliable when the CO2 mole-fraction difference between heights was at least 4 times greater than the FTIR's resolution of differences. For the second method, the temporal increases of mole fractions in the stable nocturnal boundary layer, which are correlated for concurrently-emitted gases, are used to infer the unknown fluxes of CH4 and N2O from the known flux of CO2. This method was sensitive to "contamination" from trace gas sources other than the pasture of interest and therefore required careful filtering. With both methods combined, estimates of mean daily CH4 and N2O fluxes were obtained for 60 % of days at one site and 77 % at the other. Both methods indicated both sites as net sources of CH4 and N2O. Mean emission rates for one year at the unfertilised, winter-grazed site were 8.2 (± 0.91) nmol CH4 m-2 s-1 and 0.40 (± 0.018) nmol N2O m-2 s-1. During the same year, mean emission rates at the irrigated, fertilised and rotationally-grazed site were 7.0 (± 0.89) nmol CH4 m-2 s-1 and 0.57 (± 0.019) nmol N2O m-2 s-1. At this site, the N2O emissions amounted to 1.19 (± 0.15) % of the

  18. Combining two complementary micrometeorological methods to measure CH4 and N2O fluxes over pasture

    NASA Astrophysics Data System (ADS)

    Laubach, Johannes; Barthel, Matti; Fraser, Anitra; Hunt, John E.; Griffith, David W. T.

    2016-03-01

    New Zealand's largest industrial sector is pastoral agriculture, giving rise to a large fraction of the country's emissions of methane (CH4) and nitrous oxide (N2O). We designed a system to continuously measure CH4 and N2O fluxes at the field scale on two adjacent pastures that differed with respect to management. At the core of this system was a closed-cell Fourier transform infrared (FTIR) spectrometer, which measured the mole fractions of CH4, N2O and carbon dioxide (CO2) at two heights at each site. In parallel, CO2 fluxes were measured using eddy-covariance instrumentation. We applied two different micrometeorological ratio methods to infer the CH4 and N2O fluxes from their respective mole fractions and the CO2 fluxes. The first is a variant of the flux-gradient method, where it is assumed that the turbulent diffusivities of CH4 and N2O equal that of CO2. This method was reliable when the CO2 mole-fraction difference between heights was at least 4 times greater than the FTIR's resolution of differences. For the second method, the temporal increases of mole fractions in the stable nocturnal boundary layer, which are correlated for concurrently emitted gases, are used to infer the unknown fluxes of CH4 and N2O from the known flux of CO2. This method was sensitive to "contamination" from trace gas sources other than the pasture of interest and therefore required careful filtering. With both methods combined, estimates of mean daily CH4 and N2O fluxes were obtained for 56 % of days at one site and 73 % at the other. Both methods indicated both sites as net sources of CH4 and N2O. Mean emission rates for 1 year at the unfertilised, winter-grazed site were 8.9 (±0.79) nmol CH4 m-2 s-1 and 0.38 (±0.018) nmol N2O m-2 s-1. During the same year, mean emission rates at the irrigated, fertilised and rotationally grazed site were 8.9 (±0.79) nmol CH4 m-2 s-1 and 0.58 (±0.020) nmol N2O m-2 s-1. At this site, the N2O emissions amounted to 1.21 (±0.15) % of the nitrogen

  19. 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

  20. Aerobic oxidation reactions catalyzed by vanadium complexes of bis(phenolate) ligands.

    PubMed

    Zhang, Guoqi; Scott, Brian L; Wu, Ruilian; Silks, L A Pete; Hanson, Susan K

    2012-07-01

    Vanadium(V) complexes of the tridentate bis(phenolate)pyridine ligand H(2)BPP (H(2)BPP = 2,6-(HOC(6)H(2)-2,4-(t)Bu(2))(2)NC(5)H(3)) and the bis(phenolate)amine ligand H(2)BPA (H(2)BPA = N,N-bis(2-hydroxy-4,5-dimethylbenzyl)propylamine) have been synthesized and characterized. The ability of the complexes to mediate the oxidative C-C bond cleavage of pinacol was tested. Reaction of the complex (BPP)V(V)(O)(O(i)Pr) (4) with pinacol afforded the monomeric vanadium(IV) product (BPP)V(IV)(O)(HO(i)Pr) (6) and acetone. Vanadium(IV) complex 6 was oxidized rapidly by air at room temperature in the presence of NEt(3), yielding the vanadium(V) cis-dioxo complex [(BPP)V(V)(O)(2)]HNEt(3). Complex (BPA)V(V)(O)(O(i)Pr) (5) reacted with pinacol at room temperature, to afford acetone and the vanadium(IV) dimer [(BPA)V(IV)(O)(HO(i)Pr)](2). Complexes 4 and 5 were evaluated as catalysts for the aerobic oxidation of 4-methoxybenzyl alcohol and arylglycerol β-aryl ether lignin model compounds. Although both 4 and 5 catalyzed the aerobic oxidation of 4-methoxybenzyl alcohol, complex 4 was found to be a more active and robust catalyst for oxidation of the lignin model compounds. The catalytic activities and selectivities of the bis(phenolate) complexes are compared to previously reported catalysts. PMID:22708725

  1. 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

  2. Ruthenium(salen)-catalyzed aerobic oxidative desymmetrization of meso-diols and its kinetics.

    PubMed

    Shimizu, Hideki; Onitsuka, Satoaki; Egami, Hiromichi; Katsuki, Tsutomu

    2005-04-20

    Chiral (nitrosyl)ruthenium(salen) complexes were found to be efficient catalysts for aerobic oxidative desymmetrization of meso-diols under photoirradiation to give optically active lactols. The scope of the applicability of this reaction ranges widely from acyclic diols to mono-cyclic diols, although fine ligand-tuning of the ruthenium(salen) complexes was required to attain high enantioselectivity (up to 93% ee). In particular, the nature of the apical ligand was found to affect not only enantioselectivity but also kinetics of the desymmetrization reaction. Spectroscopic analysis of the oxidation disclosed that irradiation of visible light is indispensable not only for dissociation of the nitrosyl ligand but also for single electron transfer from the alcohol-bound ruthenium ion to dioxygen. PMID:15826178

  3. 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

  4. 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

  5. CH4 Flux Inversion Studies for Future Active Space CH4 Missions like MERLIN

    NASA Astrophysics Data System (ADS)

    Heimann, M.; Marshall, J.

    2011-12-01

    Space based active sensors such as the planned German-French CH4 DIAL MERLIN mission have a very small footprint and therefore see through moderately small cloud holes. This fact, in addition to being independent of reflected sunlight is expected to provide global coverage with a higher number of observations than heretofore possible with passive sensors. How will this impact our ability to infer the different types of CH4 surface sources? Using a global atmospheric inversion system we quantify the resulting error reduction of inferred CH4 source estimates as a function of spatial and temporal resolution given instrument accuracy and other parameters of potential satellite orbits. The methodology is based on the classical Green's function approach on a monthly global 8°x10° resolution (Houweling et al., 2004) extended by using a nested two-step procedure for the investigation of higher temporal and spatial source resolutions (Rödenbeck et al., 2009). We furthermore employ a nested Lagrangian system at very high resolution (down to 1/8° x 1/12°) to quantify the impact on the detection and quantification of point sources such as power plants, landfills, natural gas pipelines, forest fires, geological seeps, and volcanoes. We demonstrate that the current specification of the MERLIN DIAL mission with a nominal breakthrough instrument precision of 18 ppb and bias of 3 ppb over 50km would lead to a substantial improvement of CH4 source quantification in many regions of the world as compared to what is possible with the currently existing observations from the surface network or passive satellite sensors. Houweling, S, FM Breon, I Aben, C Roedenbeck, M Gloor, M Heimann, and P Ciais. 2004. "Inverse modeling of CO2 sources and sinks using satellite data: a synthetic inter-comparison of measurement techniques and their performance as a function of space and time." Atmospheric Chemistry And Physics 4: 523-538. Roedenbeck, C, C Gerbig, K Trusilova, and M Heimann. 2009. "A

  6. 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

  7. 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

  8. 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

  9. Impact of aerobic and anaerobic exercise training on oxidative stress and antioxidant defense in athletes

    PubMed Central

    Park, Song-Young; Kwak, Yi-Sub

    2016-01-01

    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

  10. 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

  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. Ammonia-oxidizing archaea use the most energy-efficient aerobic pathway for CO2 fixation

    PubMed Central

    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.

    2014-01-01

    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

  13. Supercritical carbon dioxide, a new medium for aerobic alcohol oxidations catalysed by copper-TEMPO.

    PubMed

    Herbert, Matthew; Montilla, Francisco; Galindo, Agustín

    2010-01-21

    The copper catalysed aerobic oxidation of selected alcohol substrates in supercritical carbon dioxide (scCO(2)), employing a range of simple copper(II) catalyst compounds, is here described. The copper acetate complex of polydimethylsiloxane (PDMS) functionalised pyridine (1), compound 2, has previously been synthesised and characterised by us and its solubility in scCO(2) demonstrated. Due to this solubility we anticipated that the selective aerobic oxidation of alcohols to aldehydes could be homogeneously catalysed by this compound in scCO(2) in combination with the co-catalyst 2,2,6,6-tetramethylpiperidin-1-yloxy free radical (TEMPO). Our initial results showed that complete oxidation of 4-nitrobenzyl alcohol was achieved within 4 h of reaction. However, the activities of analogous copper derivatives containing simpler pyridine substituents, [Cu(AcO)(2)(py)](2) and [Cu(AcO)(2)(4VP)](2) (4VP = 4-vinylpyridine), were shown to be similar, in spite of their negligible solubility in scCO(2). When we repeated the reactions in highly non-polar hexane rather than scCO(2) similar observations were made. In both cases, as 2 is soluble and the pyridine analogues are not, a much higher reaction rate was anticipated for 2 as it is the only compound capable of homogeneous catalysis. However, in some cases slightly better activities were observed for [Cu(AcO)(2)(py)](2) rather than for the PDMS functionalised analogue, 2. Thus, despite poor catalyst solubility typically being very inhibitory in this type of catalytic process, in this system solubilisation of the catalyst is not necessary. In continuation the activity of silica supported copper complexes was therefore investigated. Employing such catalysts the 4-nitrobenzyl and benzyl alcohol substrates were completely oxidised to the corresponding aldehydes in scCO(2), this time employing lower catalyst loadings. Other types of alcohol substrate showed more limited conversions however. To conclude, alcohol oxidation in the non

  14. 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.

  15. Emissions of CO2 and CH4 from sludge treatment reed beds depend on system management and sludge loading.

    PubMed

    Olsson, Linda; Dam Larsen, Julie; Ye, Siyuan; Brix, Hans

    2014-08-01

    Sludge treatment reed beds (STRB) are considered as eco-friendly and sustainable alternatives to conventional sludge treatment methods, although little is known about greenhouse gas emissions from such systems. We measured CO2 and CH4 emissions and substrate characteristics in a STRB, an occasionally loaded sludge depot (SD) and a natural reed wetland (NW). The aim was to compare (i) emissions among the sites in relation to substrate characteristics and (ii) emissions before and after sludge loading in the STRB. The STRB emitted twice as much CO2 (1200 mg m(-2) h(-1)) as the SD, whereas the SD emitted four times more CH4 (2 mg m(-2) h(-1)) than the STRB. The NW had the lowest emissions of both gases. The differences in gas emissions among the sites were primarily explained by differences in the availability of oxygen in the substrate. As a consequence of overloading and poor management, the SD had no vegetation and a poor dewatering capacity, which resulted in anaerobic conditions favoring CH4 emission. In contrast, the well-managed STRB had more aerobic conditions in the sludge residue resulting in low CH4 emission rates. We conclude that well-designed and well-managed STRBs have a low climate impact relative to conventional treatment alternatives, but that overloading and poor sludge management enhances the emissions of CH4. PMID:24768834

  16. 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

  17. 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. PMID:26698150

  18. 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

  19. 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

  20. 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

  1. 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

  2. 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

  3. 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

  4. Copper-catalyzed domino synthesis of quinazolinones via Ullmann-type coupling and aerobic oxidative C-H amidation.

    PubMed

    Xu, Wei; Jin, Yibao; Liu, Hongxia; Jiang, Yuyang; Fu, Hua

    2011-03-18

    An efficient copper-catalyzed approach to quinazolinone derivatives has been developed, and the protocol uses cheap and readily available substituted 2-halobenzamides and (aryl)methanamines as the starting materials as well as economical and environmentally friendly air as the oxidant. This can be the first example of constructing N-heterocycles via sequential Ullmann-type coupling under air and aerobic oxidative C-H amidation. PMID:21344914

  5. Isotopomer analysis of production and consumption mechanisms of N2O and CH4 in an advanced wastewater treatment system.

    PubMed

    Toyoda, Sakae; Suzuki, Yuuri; Hattori, Shohei; Yamada, Keita; Fujii, Ayako; Yoshida, Naohiro; Kouno, Rina; Murayama, Kouki; Shiomi, Hiroshi

    2011-02-01

    Wastewater treatment processes are believed to be anthropogenic sources of nitrous oxide (N(2)O) and methane (CH(4)). However, few studies have examined the mechanisms and controlling factors in production of these greenhouse gases in complex bacterial systems. To elucidate production and consumption mechanisms of N(2)O and CH(4) in microbial consortia during wastewater treatment and to characterize human waste sources, we measured their concentrations and isotopomer ratios (elemental isotope ratios and site-specific N isotope ratios in asymmetric molecules of NNO) in water and gas samples collected by an advanced treatment system in Tokyo. Although the estimated emissions of N(2)O and CH(4) from the system were found to be lower than those from the typical treatment systems reported before, water in biological reaction tanks was supersaturated with both gases. The concentration of N(2)O, produced mainly by nitrifier-denitrification as indicated by isotopomer ratios, was highest in the oxic tank (ca. 4000% saturation). The dissolved CH(4) concentration was highest in in-flow water (ca. 3000% saturation). It decreased gradually during treatment. Its carbon isotope ratio indicated that the decrease resulted from bacterial CH(4) oxidation and that microbial CH(4) production can occur in anaerobic and settling tanks. PMID:21171662

  6. Enrichment in 13C of atmospheric CH4 during the Younger Dryas termination

    NASA Astrophysics Data System (ADS)

    Melton, J. R.; Schaefer, H.; Whiticar, M. J.

    2012-07-01

    The abrupt warming across the Younger Dryas termination (~11 600 yr before present) was marked by a large increase in the global atmospheric methane mixing ratio. The debate over sources responsible for the rise in methane centers on the roles of global wetlands, marine gas hydrates, and thermokarst lakes. We present a new, higher-precision methane stable carbon isotope ratio (δ13CH4) dataset from ice sampled at Påkitsoq, Greenland that shows distinct 13C-enrichment associated with this rise. We investigate the validity of this finding in face of known anomalous methane concentrations that occur at Påkitsoq. Comparison with previously published datasets to determine the robustness of our results indicates a similar trend in ice from both an Antarctic ice core and previously published Påkitsoq data measured using four different extraction and analytical techniques. The δ13CH4 trend suggests that 13C-enriched CH4 sources played an important role in the concentration increase. In a first attempt at quantifying the various contributions from our data, we apply a methane triple mass balance of stable carbon and hydrogen isotope ratios and radiocarbon. The mass balance results suggest biomass burning (42-66% of total methane flux increase) and thermokarst lakes (27-59%) as the dominant contributing sources. Given the high uncertainty and low temporal resolution of the 14CH4 dataset used in the triple mass balance, we also performed a mass balance test using just δ13C and δD. These results further support biomass burning as a dominant source, but do not allow distinguishing of thermokarst lake contributions from boreal wetlands, aerobic plant methane, or termites. Our results in both mass balance tests do not suggest as large a role for tropical wetlands or marine gas hydrates as commonly proposed.

  7. Self-assembled dicopper(II) diethanolaminate cores for mild aerobic and peroxidative oxidation of alcohols.

    PubMed

    Figiel, Paweł J; Kirillov, Alexander M; Guedes da Silva, M Fátima C; Lasri, Jamal; Pombeiro, Armando J L

    2010-11-01

    The new dicopper(ii) complexes [Cu(2)(μ-Hmdea)(2)(NCS)(2)] (1) and [Cu(2)(μ-Hedea)(2)(N(3))(2)]·(H(2)O)(0.25) (2) with the {Cu(2)(μ-O)(2)} diethanolaminate cores have been easily generated by aqueous medium self-assembly reactions of copper(ii) nitrate with N-methyl- or N-ethyldiethanolamine (H(2)mdea or H(2)edea, respectively), in the presence of sodium thiocyanate (for 1) or sodium azide (for 2) as ancillary ligands sources. They have been isolated as air-stable crystalline solids and fully characterized by IR and UV-vis spectroscopies, ESI-MS(+), elemental and single-crystal X-ray diffraction analyses. The latter complex also features a fourfold linkage of neighbouring dimeric units via strong intermolecular O-HO hydrogen bonds, giving rise to the formation of tetracopper aggregates. The catalytic activity of compounds 1 and 2 has been studied for the mild (50-80 °C) and selective oxidations of alcohols, namely for (i) the aerobic aqueous medium oxidation of benzyl alcohols to benzaldehydes, mediated by TEMPO radical, and for (ii) the solvent-free oxidation of secondary alcohols to ketones by t-BuOOH under microwave (MW) irradiation. Complex 2 shows the highest efficiency in both oxidation systems, resulting in up to 99% molar yields (based on the alcohol substrate) of products. In addition, remarkably high values of TON (1020) and TOF (4080 h(-1)) have been achieved in the MW-assisted peroxidative oxidation of 1-phenylethanol to acetophenone (model reaction). Attractive green features of these catalytic systems include the operation in aqueous or solvent-free reaction medium, under mild conditions and with high yields and selectivities, using Cu catalyst precursors that are readily available by self-assembly in water of simple chemicals. PMID:20844801

  8. Aerobic training prevents oxidative profile and improves nitric oxide and vascular reactivity in rats with cardiometabolic alteration.

    PubMed

    Medeiros, Renata F; Gaique, Thaiane G; Bento-Bernardes, Thais; Motta, Nádia A V; Brito, Fernanda C F; Fernandes-Santos, Caroline; Castro-Pinheiro, Camila; Oliveira, Karen J; Nóbrega, Antonio C L

    2016-07-01

    Cardiovascular disease is the major cause of death worldwide; therefore it is important to understand the natural history of the pathophysiologic process and develop strategies to halt its progression. Thus this study investigated the protective effect of aerobic training on pathophysiological mechanisms involved in subclinical cardiometabolic alterations in a model with constant exposure to a prejudicial agent. Male Wistar rats were divided into a control group (C), which received drinking water, fructose group (F), which was fed 10% fructose in drinking water for 10 wk, and control training (CT) and fructose training groups (FT), in which moderate aerobic training was added in the last 8 wk of the study. Insulin, triacylglycerol, and isoprostane were higher and superoxide dismutase (SOD) was lower in the F group. There was no difference in thoracic aorta histology, but a decreased vascularization was seen in the F group, avoided by training in left ventricle. Regarding vascular function, the F group exhibited increased vasoconstrictory reactivity to phenylephrine. The F group presented impaired vasodilation to acetylcholine. Regarding endothelial nitric oxide synthase (eNOS), the F group presented a lower expression, and phosphorylated eNOS was higher in the trained groups than in their respective control groups. This same pattern was observed for nitric oxide bioavailability, antioxidant protein expression in aorta, left ventricle, and muscle (catalase, SOD, and glutathione peroxidase), serum SOD activity, and muscle mass. These results suggest that exercise training enhanced the antioxidant pathway and, as a consequence, the eNOS pathway, preventing an impairment in vascular vasodilatory capacity. PMID:27255525

  9. High-pressure LOX/CH4 injector program

    NASA Technical Reports Server (NTRS)

    Wheeler, D. B.; Kirby, F. M.

    1979-01-01

    Two injector types, either coaxial or impinging elements, for high pressure LOX/CH4 operation with an existing 40K chamber are examined. A comparison is presented. The detailed fabrication drawings and supporting analysis are presented.

  10. Vibrational dynamics of the CH4·F- complex.

    PubMed

    Wodraszka, Robert; Palma, Juliana; Manthe, Uwe

    2012-11-26

    Motivated by recent photodetachment experiments studying resonance structures in the transition-state region of the F + CH(4) → HF + CH(3) reaction, the vibrational dynamics of the precursor complex CH(4)·F(-) is investigated. Delocalized vibrational eigenstates of CH(4)·F(-) are computed in full dimensionality employing the multiconfigurational time-dependent Hartree (MCTDH) approach and a recently developed iterative diagonalization approach for general multiwell systems. Different types of stereographic coordinates are used, and a corresponding general N-body kinetic energy operator is given. The calculated tunneling splittings of the ground and the lower vibrational excited states of the CH(4)·F(-) complex do not significantly exceed 1 cm(-1). Comparing the converged MCTDH results for localized vibrational excitations with existing results obtained by normal-mode-based (truncated) vibrational configuration interaction calculations, significantly lower frequencies are found for excitations in the intermolecular modes. PMID:22731911

  11. Microbiology and potential applications of aerobic methane oxidation coupled to denitrification (AME-D) process: A review.

    PubMed

    Zhu, Jing; Wang, Qian; Yuan, Mengdong; Tan, Giin-Yu Amy; Sun, Faqian; Wang, Cheng; Wu, Weixiang; Lee, Po-Heng

    2016-03-01

    Aerobic methane oxidation coupled to denitrification (AME-D) is an important link between the global methane and nitrogen cycles. This mini-review updates discoveries regarding aerobic methanotrophs and denitrifiers, as a prelude to spotlight the microbial mechanism and the potential applications of AME-D. Until recently, AME-D was thought to be accomplished by a microbial consortium where denitrifying bacteria utilize carbon intermediates, which are excreted by aerobic methanotrophs, as energy and carbon sources. Potential carbon intermediates include methanol, citrate and acetate. This mini-review presents microbial thermodynamic estimations and postulates that methanol is the ideal electron donor for denitrification, and may serve as a trophic link between methanotrophic bacteria and denitrifiers. More excitingly, new discoveries have revealed that AME-D is not only confined to the conventional synergism between methanotrophic bacteria and denitrifiers. Specifically, an obligate aerobic methanotrophic bacterium, Methylomonas denitrificans FJG1, has been demonstrated to couple partial denitrification with methane oxidation, under hypoxia conditions, releasing nitrous oxide as a terminal product. This finding not only substantially advances the understanding of AME-D mechanism, but also implies an important but unknown role of aerobic methanotrophs in global climate change through their influence on both the methane and nitrogen cycles in ecosystems. Hence, further investigation on AME-D microbiology and mechanism is essential to better understand global climate issues and to develop niche biotechnological solutions. This mini-review also presents traditional microbial techniques, such as pure cultivation and stable isotope probing, and powerful microbial techniques, such as (meta-) genomics and (meta-) transcriptomics, for deciphering linked methane oxidation and denitrification. Although AME-D has immense potential for nitrogen removal from wastewater, drinking

  12. 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

  13. 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

  14. Highly Dispersed Gold Nanoparticles Supported on SBA-15 for Vapor Phase Aerobic Oxidation of Benzyl Alcohol.

    PubMed

    Kumar, Ashish; Sreedhar, Bojja; Chary, Komandur V R

    2015-02-01

    Gold nanoparticles supported on SBA-15 are prepared by homogenous deposition-precipitation method (HDP) using urea as the precipitating agent. The structural features of the synthesized catalysts were characterized by various techniques such as X-ray diffraction (XRD), transmission electron microscopy (TEM), nitrogen adsorption-desorption (BET), pore size distribution (PSD), CO chemisorption and X-ray photoelectron spectroscopy (XPS). The catalytic activity and stability of the Au/SBA-15 catalysts are investigated during the vapor phase aerobic oxidation of benzyl alcohol. The BJH pore size distribution results of SBA-15 support and Au/SBA-15 catalysts reveals that the formation of mesoporous structure in all the samples. TEM results suggest that Au nanoparticles are highly dispersed over SBA-15 and long range order of hexagonal mesopores of SBA-15 is well retained even after the deposition of Au metallic nanoparticles. XPS study reveals the formation of Au (0) after chemical reduction by NaBH4. The particle size measured from CO-chemisorption and TEM analysis are well correlated with the TOF values of the reaction. Au/SBA-1 5 catalysts are found to show higher activity compare to Au/TiO2 and Au/MgO catalysts during the vapor phase oxidation of benzyl alcohol. The catalytic functionality are well substantiated with particle size measured from TEM. The crystallite size of Au in both fresh and spent catalysts were measured from X-ray diffraction. PMID:26353720

  15. Metal-free aerobic oxidations mediated by N-hydroxyphthalimide. A concise review

    PubMed Central

    Melone, Lucio

    2013-01-01

    Summary Since the beginning of the century, N-hydroxyphthalimide and related compounds have been revealed to be efficient organocatalysts for free-radical processes and have found ample application in promoting the aerobic oxidation of a wide range of organic substrates. When combined with different co-catalysts, they are activated to the corresponding N-oxyl radical species and become able to promote radical chains, involving molecular oxygen, directly or indirectly. Most of the examples reported in the literature describe the use of these N-hydroxy derivatives in the presence of transition-metal complexes. However, eco-friendly standards, including the demand for highly selective transformations, impose the development of metal-free processes, especially for large-scale productions, as in the case of the oxygenation of hydrocarbons. For this reason, many efforts have been devoted in the past decade to the design of new protocols for the activation of N-hydroxy imides in the presence of nonmetal initiators. Herein we provide a concise overview of the most significant and successful examples in this field, with the final aim to furnish a useful instrument for all scientists actively involved in the O2-mediated selective oxidation of organic compounds and looking for environmentally safe alternatives to metal catalysis. PMID:23843925

  16. Seasonal variability of CH4 and N2O fluxes over a managed temperate mountain grassland

    NASA Astrophysics Data System (ADS)

    Hoertnagl, Lukas; Wohlfahrt, Georg

    2013-04-01

    The quantification of greenhouse gas (GHG) budgets on a global scale is an important step in assessing the effect of anthropogenic and biogenic controls on a future climate. In the past, measurements of CO2 fluxes were conducted over a wide array of ecosystems, leading to a better understanding of its exchange patterns on different time scales and more sophisticated models. However, only few studies quantified the fluxes of the other two major GHG, methane (CH4) and nitrous oxide (N2O), mainly due to expensive sensors and their time-consuming maintenance. In addition, early CH4 and N2O measurements mainly focused on ecosystems with presumably high emissions of CH4 (e.g. wetlands) or N2O (e.g. heavily fertilized crops). In recent years, devices for CH4 and N2O measurements became widely available and more studies are conducted over sites that exert small and often close-to-zero fluxes. Despite recent advances in sensor sensitivity and stability, the quantification of CH4 and N2O exchange rates remains challenging. Here we present measurements of CH4 and N2O exchange rates of a temperate mountain grassland managed as a hay meadow near the village Neustift in the Stubai Valley, Austria, that started in April 2010 by means of the eddy covariance method. The three wind components and the speed of sound were acquired at a time resolution of 20 Hz, while CH4 and N2O mixing ratios were recorded at 2 Hz by a quantum cascade laser absorption spectrometer (QCL-AS). Fluxes of both compounds were calculated using the virtual disjunct eddy covariance method (vDEC). For better comparability fluxes of N2O and CH4 were also converted to g CO2-equivalents and compared to the CO2 exchange at the same site. In addition to exchange rates, challenges regarding the calculation of GHG fluxes at the investigated grassland site will also be discussed. In 2011, deposition of CH4 was recorded on 9 days with average uptake rates of -0.6 nmol m-2 s-1. Peak emissions of up to 12.9 nmol m-2 s-1

  17. Mechanistic insight into aerobic alcohol oxidation using NOx-nitroxide catalysis based on catalyst structure-activity relationships.

    PubMed

    Shibuya, Masatoshi; Nagasawa, Shota; Osada, Yuji; Iwabuchi, Yoshiharu

    2014-11-01

    The mechanism of an NOx-assisted, nitroxide(nitroxyl radical)-catalyzed aerobic oxidation of alcohols was investigated using a set of sterically and electronically modified nitroxides (i.e., TEMPO, AZADO (1), 5-F-AZADO (2), 5,7-DiF-AZADO (3), 5-MeO-AZADO (4), 5,7-DiMeO-AZADO (5), oxa-AZADO (6), TsN-AZADO (7), and DiAZADO (8)). The motivation for the present study stemmed from our previous observation that the introduction of an F atom at a remote position from the nitroxyl radical moiety on the azaadamantane nucleus effectively enhanced the catalytic activity under typical NOx-mediated aerobic-oxidation conditions. The kinetic profiles of the azaadamantane-N-oxyl-[AZADO (1)-, 5-F-AZADO (2)-, and 5,7-DiF-AZADO (3)]-catalyzed aerobic oxidations were closely investigated, revealing that AZADO (1) showed a high initial reaction rate compared to 5-F-AZADO (2) and 5,7-DiF-AZADO (3); however, AZADO-catalyzed oxidation exhibited a marked slowdown, resulting in ∼90% conversion, whereas 5-F-AZADO-catalyzed oxidation smoothly reached completion without a marked slowdown. The reasons for the marked slowdown and the role of the fluoro group are discussed. Oxa-AZADO (6), TsN-AZADO (7), and DiAZADO (8) were designed and synthesized to confirm their comparable catalytic efficiency to that of 5-F-AZADO (2), providing supporting evidence for the electronic effect on the catalytic efficiency of the heteroatoms under NOx-assisted aerobic-oxidation conditions. PMID:25286356

  18. CH4 production via CO2 reduction in a temperate bog - A source of (C-13)-depleted CH4

    NASA Technical Reports Server (NTRS)

    Lansdown, J. M.; Quay, P. D.; King, S. L.

    1992-01-01

    The paper reports measurements, taken over two annual cycles, of the flux and delta(C-13) of CH4 released from an acidic peat bog located in the foothills of the Cascade Range in Washington state, U.S. Measurements of the rate of aceticlastic methanogenesis and CO2 reduction in peat soil, using (C-14)-labeled acetate and sodium bicarbonate, show that acetate was not an important CH4 precursor and that CO2 reduction could account for all of the CH4 production. The in situ kinetic isotope effect for CO2 reduction, calculated using the delta-(C-13) of soil water CO2 and CH4 flux, was 0.932 +/- 0.007.

  19. Techno-economic evaluation of the application of ozone-oxidation in a full-scale aerobic digestion plant.

    PubMed

    Chiavola, Agostina; D'Amato, Emilio; Gori, Riccardo; Lubello, Claudio; Sirini, Piero

    2013-04-01

    This paper deals with the application of the ozone-oxidation in a full scale aerobic sludge digester. Ozonation was applied continuously to a fraction of the biological sludge extracted from the digestion unit; the ozonated sludge was then recirculated to the same digester. Three different ozone flow rates were tested (60,500 and 670g O3 h(-1)) and their effects evaluated in terms of variation of the total and soluble fractions of COD, nitrogen and phosphorous, of total and volatile suspended solids concentrations and Sludge Volume Index in the aerobic digestion unit. During the 7-month operation of the ozonation process, it was observed an appreciable improvement of the aerobic digestion efficiency (up to about 20% under the optimal conditions) and of the sludge settleability properties. These results determined an average reduction of about 60% in the biological sludge extracted from the plant and delivered to final disposal. A thorough economic analysis showed that this reduction allowed to achieve a significant cost saving for the plant with respect to the previous years operated without ozonation. Furthermore, it was determined the threshold disposal cost above which implementation of the ozone oxidation in the aerobic digestion units of similar WWTPs becomes economically convenient (about 60€t(-1) of sludge). PMID:23384542

  20. BOREAS TF-1 SSA-OA Weekly Tower CH4 and N2O Flux

    NASA Technical Reports Server (NTRS)

    Thurtell, George; Edwards, Grant; Simpson, George; Hall, Forrest G. (Editor); Huemmrich, Karl (Editor)

    2000-01-01

    The BOREAS TF-1 team collected various trace gas and energy flux data in its efforts to characterize the temporal energy and gas exchanges that occurred over the SSA-OA site. This data set contains methane (CH4) and nitrous oxide (N2O) fluxes that were measured at the BOREAS SSA-OA site. These fluxes were measured from 16-Apr to 16-Sep-1994. The data were averaged to weekly values and are available in tabular ASCII files.

  1. 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

  2. A multi-scale approach to characterize pure CH4, CF4, and CH4/CF4 mixtures

    NASA Astrophysics Data System (ADS)

    Chattoraj, Joyjit; Risthaus, Tobias; Rubner, Oliver; Heuer, Andreas; Grimme, Stefan

    2015-04-01

    In this study, we develop three intermolecular potentials for methane (CH4), tetrafluoromethane (CF4), and CH4/CF4 dimers using a novel ab initio method. The ultimate goal is to understand microscopically the phase-separation in CH4/CF4 systems, which takes place in the liquid states near their freezing points. Monte-Carlo (MC) simulations of the pure CH4 system are performed using the ab initio energies to verify the potential. The simulations reproduce quite well the experimentally known liquid densities, the internal energies, the second virial coefficients, and the radial distribution function. The essentially six-dimensional (6D) ab initio potential is then reduced to a one-dimensional (1D) effective potential using the inverse Monte-Carlo technique. This potential, too, successfully reproduces the experimental results. Interestingly, the MC study cannot be extended to the pure CF4 system and the CH4/CF4 mixed system because the two respective ab initio potentials present very rough potential landscapes. This renders the interpolation of energies for the MC simulations and thus the multi-scale approach unreliable. It suggests, however, a possible driving force for the experimentally observed phase separation of the CH4/CF4 system at low temperatures. Furthermore, we carefully study the determination of 1D effective potentials via inverse MC techniques. We argue that to a good approximation the temperature dependence of the 1D potentials can be estimated via reweighting techniques for a fixed temperature.

  3. Effects of natural and anthropogenic CH4 sources on variations of atmospheric CH4 over western Siberia identified by its carbon and hydrogen stable isotopes

    NASA Astrophysics Data System (ADS)

    Umezawa, T.; Machida, T.; Aoki, S.; Nakazawa, T.

    2010-12-01

    Western Siberia is thought to be important for the global CH4 budget due to the presence of large natural and anthropogenic CH4 sources. We have conducted aircraft observations of CH4 concentration at altitudes of 0.5-7 km over the region once a month since 1993. Deviations of the CH4 concentration from the best-fit curves obtained at the respective altitudes indicated that the lowest layer below 2 km was generally influenced by the local sources. In order to examine effects of the sources on the observed CH4 variations, measurements of carbon and hydrogen stable isotopic ratios of atmospheric CH4 (δ13CH4 and δD-CH4) at altitudes of 1 and 2 km were also made during 2005-2009. In most observation flights, the CH4 concentration was higher at 1 km than that at 2 km with lower δ13CH4 and δD-CH4 values. These vertical gradients, which were pronounced in summer, imply the presence of strong CH4 sources at the ground surface with low δ13CH4 and δD-CH4 values. δ13CH4 at 1 km showed its seasonal minimum in late summer, while the CH4 concentration and δD-CH4 did not show such clear seasonality, because they were masked by large variability. By inspecting relationships between the CH4 concentration and δ13CH4 (δD-CH4) (Miller/Tans plot), we examined the CH4 sources influencing on atmospheric CH4 variations in various timescales. δ13CH4 and δD-CH4 values of the CH4 source in winter (December-April) were estimated to be -41.2±1.8‰ and -187±18‰, respectively, while those in summer (June-October) to be -65.0±2.5‰ and -282±25‰. Since these isotopic values for respective seasons were consistent with those of CH4 originated from fossil and biogenic sources, fossil fuel and wetlands would be the primary CH4 sources in winter and summer, respectively. It was also indicated from various Miller/Tans plots that fossil source brought relatively short-term variations of atmospheric CH4 while wetlands did long-term variations, which might be explained by spot

  4. CH4 continuous measurements in the upper Spanish plateau.

    PubMed

    Sánchez, M Luisa; García, M Ángeles; Pérez, Isidro A; Pardo, Nuria

    2014-05-01

    Continuous methane, CH4, concentrations were measured in a rural area of the upper Spanish plateau from June 2010 to May 2012 by cavity ring-down spectroscopy technique. The results obtained have proven the local impact of anthropogenic nearby sources on CH4 concentrations, and evidence a significant influence on the overall mean, averaged daily and seasonal patterns recorded at the measuring site. The positive anomalies in CH4 concentrations, statistically significant at 95 %, in the southeast sector, defined here as ESE, SE, SSE and S sectors, have been attributed to the contribution of the Valladolid urban plume and the urban landfill. Based on this finding, CH4 background levels were associated to the concentrations recorded in the remaining un-disturbed sectors. CH4 means of the overall data set, the southeast sector and background sectors yielded average means of 1,894.1, 1,927.9 and 1,887.1 ppb, respectively. The diurnal and seasonal patterns of the overall data set and background concentrations have shown that CH4 concentrations are mainly dominated by its reaction with OH radicals. Maximum hourly concentrations were reached during night-time and early morning, 5-7 h, whereas minimum concentrations were recorded at 16 h. Maximum and minimum monthly means were recorded in January and July, respectively. The diurnal and seasonal amplitudes, namely, peak-to-peak means, of background concentrations were 25.1 and 48.1 ppb, respectively. These values were significantly lower than those obtained for the overall data set, 42.9 and 58.1 ppb, revealing the significant role of local influences on CH4 concentrations despite the low frequency of southeast winds recorded at the measuring site, 16.9 %. PMID:24366818

  5. 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

  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. Selective aerobic oxidation of HMF to 2,5-diformylfuran on covalent triazine frameworks-supported Ru catalysts.

    PubMed

    Artz, Jens; Mallmann, Sabrina; Palkovits, Regina

    2015-02-01

    The selective aerobic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-diformylfuran has been performed under mild conditions at 80 °C and 20 bar of synthetic air in methyl t-butyl ether. Ru clusters supported on covalent triazine frameworks (CTFs) allowed excellent selectivity and superior catalytic activity compared to other support materials such as activated carbon, γ-Al2 O3 , hydrotalcite, or MgO. CTFs with varying pore size, specific surface area, and N content could be prepared from different monomers. The structural properties of the CTF materials influence the catalytic activity of Ru/CTF significantly in the aerobic oxidation of HMF, which emphasizes the superior activity of mesoporous CTFs. Recycling of the catalysts is challenging, but promising methods to maintain high catalytic activity were developed that facilitate only minor deactivation in five consecutive recycling experiments. PMID:25586312

  8. Effects of Long-Term CO2 Enrichment on Soil-Atmosphere CH4 Fluxes and the Spatial Micro-Distribution of Methanotrophic Bacteria

    PubMed Central

    Karbin, Saeed; Guillet, Cécile; Kammann, Claudia I.; Niklaus, Pascal A.

    2015-01-01

    Background Effects of elevated atmospheric CO2 concentrations on plant growth and associated C cycling have intensively been studied, but less is known about effects on the fluxes of radiatively active trace gases other than CO2. Net soil-atmosphere CH4 fluxes are determined by the balance of soil microbially-driven methane (CH4) oxidation and methanogenesis, and both might change under elevated CO2. Methods and Results Here, we studied CH4 dynamics in a permanent grassland exposed to elevated CO2 for 14 years. Soil-atmosphere fluxes of CH4 were measured using large static chambers, over a period of four years. The ecosystem was a net sink for atmospheric CH4 for most of the time except summer to fall when net CH4 emissions occurred. We did not detect any elevated CO2 effects on CH4 fluxes, but emissions were difficult to quantify due to their discontinuous nature, most likely because of ebullition from the saturated zone. Potential methanotrophic activity, determined by incubation of fresh sieved soil under standardized conditions, also did not reveal any effect of the CO2 treatment. Finally, we determined the spatial micro-distribution of methanotrophic activity at less than 5× atmospheric (10 ppm) and elevated (10000 ppm) CH4 concentrations, using a novel auto-radiographic technique. These analyses indicated that domains of net CH4 assimilation were distributed throughout the analyzed top 15 cm of soils, with no dependence on CH4 concentration or CO2 treatment. Conclusions Our investigations suggest that elevated CO2 exerts no or only minor effects on CH4 fluxes in the type of ecosystem we studied, at least as long as soil moisture differences are small or absent as was the case here. The autoradiographic analyses further indicate that the spatial niche of CH4 oxidation does not shift in response to CO2 enrichment or CH4 concentration, and that the same type of methanotrophs may oxidize CH4 from atmospheric and soil-internal sources. PMID:26147694

  9. [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

  10. Central release of nitric oxide mediates antinociception induced by aerobic exercise.

    PubMed

    Galdino, G S; Duarte, I D; Perez, A C

    2015-09-01

    Nitric oxide (NO) is a soluble gas that participates in important functions of the central nervous system, such as cognitive function, maintenance of synaptic plasticity for the control of sleep, appetite, body temperature, neurosecretion, and antinociception. Furthermore, during exercise large amounts of NO are released that contribute to maintaining body homeostasis. Besides NO production, physical exercise has been shown to induce antinociception. Thus, the present study aimed to investigate the central involvement of NO in exercise-induced antinociception. In both mechanical and thermal nociceptive tests, central [intrathecal (it) and intracerebroventricular (icv)] pretreatment with inhibitors of the NO/cGMP/KATP pathway (L-NOArg, ODQ, and glybenclamide) prevented the antinociceptive effect induced by aerobic exercise (AE). Furthermore, pretreatment (it, icv) with specific NO synthase inhibitors (L-NIO, aminoguanidine, and L-NPA) also prevented this effect. Supporting the hypothesis of the central involvement of NO in exercise-induced antinociception, nitrite levels in the cerebrospinal fluid increased immediately after AE. Therefore, the present study suggests that, during exercise, the NO released centrally induced antinociception. PMID:25517916

  11. Rh- and Cu-Cocatalyzed Aerobic Oxidative Approach to Quinazolines via [4 + 2] C-H Annulation with Alkyl Azides.

    PubMed

    Wang, Xiaoyang; Jiao, Ning

    2016-05-01

    A novel and efficient rhodium- and copper-co-catalyzed C-H bond activation and annulation for the construction of bioactively important quinazolines has been developed. This [4 + 2] annulation strategy utilizing alkyl azides as the carbon-heteroatom synthons shows high efficiency in the synthesis of six-membered benzoheterocycles containing two heteroatoms. This aerobic oxidative protocol provides a useful application of simple alkyl azides in N-heterocycle synthesis with N2 and H2O as byproducts. PMID:27081916

  12. TEMPO-catalyzed aerobic oxidation of alcohols to aldehydes and ketones in ionic liquid [bmim][PF6].

    PubMed

    Ansari, Imtiaz A; Gree, Rene

    2002-05-01

    [reaction: see text]. A simple and mild TEMPO-CuCl catalyzed aerobic oxidation of primary and secondary alcohols to the corresponding aldehydes and ketones in ionic liquid [bmim][PF6] with no trace of overoxidation to carboxylic acids has been developed. The product can be isolated by a simple extraction with organic solvent, and the ionic liquid can be recycled or reused. PMID:11975615

  13. The Drivers of the CH4 Seasonal Cycle in the Arctic and What Long-Term Observations of CH4 Imply About Trends in Arctic CH4 Fluxes

    NASA Astrophysics Data System (ADS)

    Sweeney, C.; Karion, A.; Bruhwiler, L.; Miller, J. B.; Wofsy, S. C.; Miller, C. E.; Chang, R. Y.; Dlugokencky, E. J.; Daube, B.; Pittman, J. V.; Dinardo, S. J.

    2012-12-01

    The large seasonal change in the atmospheric column for CH4 in the Arctic is driven by two dominant processes: transport of CH4 from low latitudes and surface emissions throughout the Arctic region. The NOAA ESRL Carbon Cycle Group Aircraft Program along with the NASA funded Carbon in Arctic Reservoirs Vulnerability Experiment (CARVE) have initiated an effort to better understand the factors controlling the seasonal changes in the mole fraction of CH4 in the Arctic with a multi-scale aircraft observing network in Alaska. The backbone of this network is multi-species flask sampling from 500 to 8000 masl that has been conducted every two weeks for the last 10 years over Poker Flat, AK. In addition regular profiles at the interior Alaska site at Poker Flat, NOAA has teamed up with the United States Coast Guard to make profiling flights with continuous observations of CO2, CO, CH4 and Ozone between Kodiak and Barrow every 2 weeks. More recently, CARVE has significantly added to this observational network with targeted flights focused on exploring the variability of CO2, CH4 and CO in the boundary layer both in the interior and the North Slope regions of Alaska. Taken together with the profiling of HIAPER Pole-to-Pole Observations (HIPPO), ground sites at Barrow and a new CARVE interior Alaska surface site just north of Fairbanks, AK, we now have the ability to investigate the full evolution of the seasonal cycle in the Arctic using both the multi-scale sampling offered by the different aircraft platforms as well as the multi-species sampling offered by in-situ and flask sampling. The flasks also provide a valuable tie-point between different platforms so that spatial and temporal gradients can be properly interpreted. In the context of the seasonal cycle observed by the aircraft platforms we will look at long term ground observations over the last 20 years to assess changes in Arctic CH4 emissions which have occurred as a result of 0.6C/decade changes in mean surface

  14. Aerobic nitrous oxide production through N-nitrosating hybrid formation in ammonia-oxidizing archaea.

    PubMed

    Stieglmeier, Michaela; Mooshammer, Maria; Kitzler, Barbara; Wanek, Wolfgang; Zechmeister-Boltenstern, Sophie; Richter, Andreas; Schleper, Christa

    2014-05-01

    Soil emissions are largely responsible for the increase of the potent greenhouse gas nitrous oxide (N2O) in the atmosphere and are generally attributed to the activity of nitrifying and denitrifying bacteria. However, the contribution of the recently discovered ammonia-oxidizing archaea (AOA) to N2O production from soil is unclear as is the mechanism by which they produce it. Here we investigate the potential of Nitrososphaera viennensis, the first pure culture of AOA from soil, to produce N2O and compare its activity with that of a marine AOA and an ammonia-oxidizing bacterium (AOB) from soil. N. viennensis produced N2O at a maximum yield of 0.09% N2O per molecule of nitrite under oxic growth conditions. N2O production rates of 4.6±0.6 amol N2O cell(-1) h(-1) and nitrification rates of 2.6±0.5 fmol NO2(-) cell(-1) h(-1) were in the same range as those of the AOB Nitrosospira multiformis and the marine AOA Nitrosopumilus maritimus grown under comparable conditions. In contrast to AOB, however, N2O production of the two archaeal strains did not increase when the oxygen concentration was reduced, suggesting that they are not capable of denitrification. In (15)N-labeling experiments we provide evidence that both ammonium and nitrite contribute equally via hybrid N2O formation to the N2O produced by N. viennensis under all conditions tested. Our results suggest that archaea may contribute to N2O production in terrestrial ecosystems, however, they are not capable of nitrifier-denitrification and thus do not produce increasing amounts of the greenhouse gas when oxygen becomes limiting. PMID:24401864

  15. Methanotrophic N2-Fixation in Boreal Peatlands: Master Regulation of Newly Fixed N and Moderation of CH4 Fluxes to the Atmosphere

    NASA Astrophysics Data System (ADS)

    Schlesinger, M.; Fillingim, H. M.; Wieder, R. K.; Vile, M. A.

    2015-12-01

    Boreal peatlands are important to global carbon (C) and nitrogen (N) cycling. While they cover only 3-4% of the terrestrial surface, they account for 25-30% and 9-15% of the world's soil C and N, respectively. Globally, peatlands function as a net sink for atmospheric CO2, but also act as a net source of CH4. In peatlands of Alberta, Canada, rates of atmospheric N deposition are low: ~1 kg·ha-1·yr-1, however, NPP of Sphagnum mosses is surprisingly high. Sphagnum mosses are able to maintain high levels of NPP due to their symbiotic relationship with N2-fixing methanotrophs. Annually, rates of N2-fixation typically provide between 10-30 kg of newly fixed N per ha, while also oxidizing CH4. CH4 fluxes from boreal peatlands in Canada are typically quite low, however, fluxes also can be high during rare episodic ebullition events. CH4 accumulation and storage is substantial, especially at depth as CH4 concentrations in peat pore water typically exceed 1000 μM at 1-m below the peat surface. Given that CH4 fluxes are typically low, we wanted to examine the importance of CH4 oxidation in these same peats. We hypothesized that methanotrophic N2-fixation may be important not only in providing inputs of newly fixed N, but also in regulating CH4 emissions from peatlands. We measured concentrations of CH4 in peat porewaters, CH4 flux rates, CH4 oxidation rates, biological N2-fixation rates. Porewater CH4 concentrations were highest at depth and decreased to negligible amounts closer to the surface of the water table. CH4 flux rates were low and ranged from -2.6 to +8.7 μmol·m-2·min-1 (negative values indicate net CH4 consumption). In Sphagnum incubations, rates of CH4 oxidation (0.6-10.2 mmol·m-2·min-1) were ~2-3 orders of magnitude higher than CH4 flux rates. Additionally, N2-fixation rates in paired cores ranged from 11.7-63.3 kg·ha-1·yr-1; CH4 oxidation rates in these same units ranged from ~3.1-622 kg·CH4 oxidized ha-1·yr-1. Additionally, we confirmed that N2

  16. 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

  17. Vibrational transition moments of CH4 from first principles

    NASA Astrophysics Data System (ADS)

    Yurchenko, Sergei N.; Tennyson, Jonathan; Barber, Robert J.; Thiel, Walter

    2013-09-01

    New nine-dimensional (9D), ab initio electric dipole moment surfaces (DMSs) of methane in its ground electronic state are presented. The DMSs are computed using an explicitly correlated coupled cluster CCSD(T)-F12 method in conjunction with an F12-optimized correlation consistent basis set of the TZ-family. A symmetrized molecular bond representation is used to parameterise these 9D DMSs in terms of sixth-order polynomials. Vibrational transition moments as well as band intensities for a large number of IR-active vibrational bands of 12CH4 are computed by vibrationally averaging the ab initio dipole moment components. The vibrational wavefunctions required for these averages are computed variationally using the program TROVE and a new ‘spectroscopic’ 12CH4 potential energy surface. The new DMSs will be used to produce a hot line list for 12CH4.

  18. Greenhouse warming by CH4 in the atmosphere of early Earth.

    PubMed

    Pavlov, A A; Kasting, J F; Brown, L L; Rages, K A; Freedman, R

    2000-05-25

    Earth appears to have been warm during its early history despite the faintness of the young Sun. Greenhouse warming by gaseous CO2 and H2O by itself is in conflict with constraints on atmospheric CO2 levels derived from paleosols for early Earth. Here we explore whether greenhouse warming by methane could have been important. We find that a CH4 mixing ratio of 10(-4) (100 ppmv) or more in Earth's early atmosphere would provide agreement with the paleosol data from 2.8 Ga. Such a CH4 concentration could have been readily maintained by methanogenic bacteria, which are thought to have been an important component of the biota at that time. Elimination of the methane component of the greenhouse by oxidation of the atmosphere at about 2.3-2.4 Ga could have triggered the Earth's first widespread glaciation. PMID:11543544

  19. Structural response of Ni/ZrO2 to feed modulations during CH4 reforming reactions

    NASA Astrophysics Data System (ADS)

    Steib, M.; Jentys, A.; Lercher, J. A.

    2016-05-01

    Time resolved oxidation and reduction cycles of ZrO2-supported Ni catalysts for dry reforming of CH4 (CO2 + CH4 ↔ 2 CO + 2 H2) during feed modulations have been studied. Under reaction conditions (1073 K) Ni remains fully reduced, whereas switching the feed gas to pure CO2 results in a slow (25 sec) formation of a stable NiO phase. When switching back to reaction conditions the NiO phase is rapidly reduced (∼ 1 sec) to metallic Ni. In the context of this study, a novel capillary cell has been built, allowing the parallel treatment of 5 catalyst samples with different gas compositions and different pressures. A comparison of the capillary cell to conventional systems regarding the spectral quality and the kinetic data shows that the capillary cell can be used to obtain identical kinetic data and high quality X-ray absorption spectra.

  20. A high level computational study of the CH4/CF4 dimer: how does it compare with the CH4/CH4 and CF4/CF4 dimers?

    NASA Astrophysics Data System (ADS)

    Biller, Matthew J.; Mecozzi, Sandro

    2012-04-01

    The interaction within the methane-methane (CH4/CH4), perfluoromethane-perfluoromethane (CF4/CF4) methane-perfluoromethane dimers (CH4/CF4) was calculated using the Hartree-Fock (HF) method, multiple orders of Møller-Plesset perturbation theory [MP2, MP3, MP4(DQ), MP4(SDQ), MP4(SDTQ)], and coupled cluster theory [CCSD, CCSD(T)], as well as the PW91, B97D, and M06-2X density functional theory (DFT) functionals. The basis sets of Dunning and coworkers (aug-cc-pVxZ, x = D, T, Q), Krishnan and coworkers [6-311++G(d,p), 6-311++G(2d,2p)], and Tsuzuki and coworkers [aug(df, pd)-6-311G(d,p)] were used. Basis set superposition error (BSSE) was corrected via the counterpoise method in all cases. Interaction energies obtained with the MP2 method do not fit with the experimental finding that the methane-perfluoromethane system phase separates at 94.5 K. It was not until the CCSD(T) method was considered that the interaction energy of the methane-perfluoromethane dimer (-0.69 kcal mol-1) was found to be intermediate between the methane (-0.51 kcal mol-1) and perfluoromethane (-0.78 kcal mol-1) dimers. This suggests that a perfluoromethane molecule interacts preferentially with another perfluoromethane (by about 0.09 kcal mol-1) than with a methane molecule. At temperatures much lower than the CH4/CF4 critical solution temperature of 94.5 K, this energy difference becomes significant and leads perfluoromethane molecules to associate with themselves, forming a phase separation. The DFT functionals yielded erratic results for the three dimers. Further development of DFT is needed in order to model dispersion interactions in hydrocarbon/perfluorocarbon systems.

  1. Joint CO2 and CH4 accountability for global warming

    PubMed Central

    Smith, Kirk R.; Desai, Manish A.; Rogers, Jamesine V.; Houghton, Richard A.

    2013-01-01

    We propose a transparent climate debt index incorporating both methane (CH4) and carbon dioxide (CO2) emissions. We develop national historic emissions databases for both greenhouse gases to 2005, justifying 1950 as the starting point for global perspectives. We include CO2 emissions from fossil sources [CO2(f)], as well as, in a separate analysis, land use change and forestry. We calculate the CO2(f) and CH4 remaining in the atmosphere in 2005 from 205 countries using the Intergovernmental Panel on Climate Change’s Fourth Assessment Report impulse response functions. We use these calculations to estimate the fraction of remaining global emissions due to each country, which is applied to total radiative forcing in 2005 to determine the combined climate debt from both greenhouse gases in units of milliwatts per square meter per country or microwatts per square meter per person, a metric we term international natural debt (IND). Australia becomes the most indebted large country per capita because of high CH4 emissions, overtaking the United States, which is highest for CO2(f). The differences between the INDs of developing and developed countries decline but remain large. We use IND to assess the relative reduction in IND from choosing between CO2(f) and CH4`control measures and to contrast the imposed versus experienced health impacts from climate change. Based on 2005 emissions, the same hypothetical impact on world 2050 IND could be achieved by decreasing CH4 emissions by 46% as stopping CO2 emissions entirely, but with substantial differences among countries, implying differential optimal strategies. Adding CH4 shifts the basic narrative about differential international accountability for climate change. PMID:23847202

  2. Joint CO2 and CH4 accountability for global warming.

    PubMed

    Smith, Kirk R; Desai, Manish A; Rogers, Jamesine V; Houghton, Richard A

    2013-07-30

    We propose a transparent climate debt index incorporating both methane (CH4) and carbon dioxide (CO2) emissions. We develop national historic emissions databases for both greenhouse gases to 2005, justifying 1950 as the starting point for global perspectives. We include CO2 emissions from fossil sources [CO2(f)], as well as, in a separate analysis, land use change and forestry. We calculate the CO2(f) and CH4 remaining in the atmosphere in 2005 from 205 countries using the Intergovernmental Panel on Climate Change's Fourth Assessment Report impulse response functions. We use these calculations to estimate the fraction of remaining global emissions due to each country, which is applied to total radiative forcing in 2005 to determine the combined climate debt from both greenhouse gases in units of milliwatts per square meter per country or microwatts per square meter per person, a metric we term international natural debt (IND). Australia becomes the most indebted large country per capita because of high CH4 emissions, overtaking the United States, which is highest for CO2(f). The differences between the INDs of developing and developed countries decline but remain large. We use IND to assess the relative reduction in IND from choosing between CO2(f) and CH4`control measures and to contrast the imposed versus experienced health impacts from climate change. Based on 2005 emissions, the same hypothetical impact on world 2050 IND could be achieved by decreasing CH4 emissions by 46% as stopping CO2 emissions entirely, but with substantial differences among countries, implying differential optimal strategies. Adding CH4 shifts the basic narrative about differential international accountability for climate change. PMID:23847202

  3. Sensitivity of optimized high-resolution North American CH4 emissions to regional CH4 boundary conditions

    NASA Astrophysics Data System (ADS)

    Stanevich, Ilya; Strong, Kimberly; Jones, Dylan; Lin, John; Wecht, Kevin; Andrews, Arlyn; Worthy, Doug; Wennberg, Paul; Wunch, Debra; Roehl, Coleen

    2016-04-01

    Constraining CH4 emissions at subcontinental scales is of great value, especially for quantifying local anthropogenic emissions. However, high-resolution emission estimates are more uncertain, particularly due to their relatively weak signature in the atmosphere and the uncertainty of the CH4 measurements used to infer the emissions. In this work, we investigate the robustness of high-resolution North American emission estimates. We perform regional inversion analyses over North America using the Stochastic Time-Inverted Lagrangian Transport (STILT) model, with initial and boundary conditions imposed from the GEOS-Chem global chemical transport model, constrained by NOAA and Environment Canada CH4 flask measurements and CH4 columns measured using Fourier transform spectrometers at the University of Toronto Atmospheric Observatory and at the Total Carbon Column Observing Network (TCCON) Lamont station. We also perform STILT and GEOS-Chem inversions with pseudo in situ- and satellite-like measurements, respectively, to assess the seasonal sensitivity of optimized emissions to uncorrected biases in CH4 boundary conditions. We show that, depending on the season, the sensitivity of the emissions to the biases varies by up to 40%.

  4. Interactions of CH4 and CO in the earth's atmosphere

    NASA Technical Reports Server (NTRS)

    Wofsy, S. C.

    1976-01-01

    Global distributions, sources, and sinks of methane and carbon monoxide in upper and lower levels of the earth's atmosphere, and the global budgets of methane and carbon monoxide, are studied, with emphasis on cumulative pollution. Stratospheric contents, vertical profiles of concentrations, simulation of vertical transport through the atmosphere, and latitudinal distributions are examined. Diffuse and localized (urban) concentrations of CO as pollutant are studied, and anthropogenic sources and sinks for CH4 and CO are considered. Perturbation of the CH4-CO-CO2 cycle, crucial to self-cleansing mechanisms of the troposphere, by anthropogenic CO emissions, and the effect of CO long life as global pollutant, are investigated.

  5. Rotational excitation of CH4 by He atoms

    NASA Astrophysics Data System (ADS)

    Yanga, B. H.; Stancil, P. C.

    2008-10-01

    Quantum close-coupling and coupled-state approximation scattering calculations for rotational energy transfer of rotationally excited CH4 due to collisions with He are presented for collision energies between 10-7 and 3000 cm-1 using the MP4 potential of Calderoni et al. [J. Chem. Phys. 121, 8261 (2004)]. State-to-state cross sections and rate coefficients from selected initial rotational states of CH4 in symmetries A, E, and F are studied from the ultra-cold to the thermal regime. Comparison of the cross sections with available theoretical results and experimental data show good agreement. Applications to astrophysics and cold laboratory environments are briefly addressed.

  6. 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

  7. Unexpected copper-catalyzed aerobic oxidative cleavage of C(sp3)-C(sp3) bond of glycol ethers.

    PubMed

    Liu, Zhong-Quan; Zhao, Lixing; Shang, Xiaojie; Cui, Zili

    2012-06-15

    An unexpected Cu-catalyzed oxidative cleavage of the C(sp(3))-C(sp(3)) bond in glycol ethers by using air or molecular oxygen as the terminal stoichiometric oxidant is demonstrated. As a result, the corresponding α-acyloxy ethers and formates of 1,2-ethanediol are formed by direct coupling of carboxylic acids and aldehydes with glycol ethers under the reaction conditions. This method represents the first example of Cu-catalyzed aerobic cleavage of saturated C-C bond in ethers. PMID:22668348

  8. Methylmercury decomposition in sediments and bacterial cultures: Involvement of methanogens and sulfate reducers in oxidative demethylation

    USGS Publications Warehouse

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

    1991-01-01

    Demethylation of monomethylmercury in freshwater and estuarine sediments and in bacterial cultures was investigated with 14CH3HgI. Under anaerobiosis, results with inhibitors indicated partial involvement of both sulfate reducers and methanogens, the former dominating estuarine sediments, while both were active in freshwaters. Aerobes were the most significant demethylators in estuarine sediments, but were unimportant in freshwater sediments. Products of anaerobic demethylation were mainly 14CO2 as well as lesser amounts of 14CH4. Acetogenic activity resulted in fixation of some 14CO2 produced from 14CH3HgI into acetate. Aerobic demethylation in estuarine sediments produced only 14CH4, while aerobic demethylation in freshwater sediments produced small amounts of both 14CH4 and 14CO2. Two species of Desulfovibrio produced only traces of 14CH4 from 14CH3HgI, while a culture of a methylotrophic methanogen formed traces of 14CO2 and 14CH4 when grown on trimethylamine in the presence of the 14CH3HgI. These results indicate that both aerobes and anaerobes demethylate mercury in sediments, but that either group may dominate in a particular sediment type. Aerobic demethylation in the estuarine sediments appeared to proceed by the previously characterized organomercurial-lyase pathway, because methane was the sole product. However, aerobic demethylation in freshwater sediments as well as anaerobic demethylation in all sediments studied produced primarily carbon dioxide. This indicates the presence of an oxidative pathway, possibly one in which methylmercury serves as an analog of one-carbon substrates.

  9. The effects of climate changes on soil methane oxidation in a dry Arctic tundra

    NASA Astrophysics Data System (ADS)

    D'Imperio, Ludovica

    2014-05-01

    The effects of climate changes on soil methane oxidation in a dry Arctic tundra. Ludovica D'Imperio1, Anders Michelsen1, Christian J. Jørgensen1, Bo Elberling1 1Center for Permafrost (CENPERM), Department of Geosciences and Natural Resource Management, University of Copenhagen, Denmark At Northern latitudes climatic changes are predicted to be most pronounced resulting in increasing active layer depth and changes in growing season length, vegetation cover and nutrient cycling. As a consequence of increased temperature, large stocks of carbon stored in the permafrost-affected soils could become available for microbial transformations and under anoxic conditions result in increasing methane production affecting net methane (CH4) budget. Arctic tundra soils also serves as an important sink of atmospheric CH4 by microbial oxidation under aerobic conditions. While several process studies have documented the mechanisms behind both production and emissions of CH4 in arctic ecosystems, an important knowledge gap exists with respect to the in situ dynamics of microbial-driven uptake of CH4 in arctic dry lands which may be enhanced as a consequence of global warming and thereby counterbalancing CH4 emissions from Arctic wetlands. In-situ methane measurements were made in a dry Arctic tundra in Disko Island, Western Greenland, during the summer 2013 to assess the role of seasonal and inter-annual variations in temperatures and snow cover. The experimental set-up included snow fences installed in 2012, allowed investigations of the emissions of GHGs from soil under increased winter snow deposition and ambient field conditions. The soil fluxes of CH4 and CO2 were measured using closed chambers in manipulated plots with increased summer temperatures and shrub removal with or without increased winter precipitation. At the control plots, the averaged seasonal CH4 oxidation rates ranged between -0.05 mg CH4 m-2 hr-1 (end of August) and -0.32 mg CH4 m-2 hr-1 (end of June). In the

  10. High-Potential Electrocatalytic O2 Reduction with Nitroxyl / NOx Mediators: Implications for Fuel Cells and Aerobic Oxidation Catalysis

    SciTech Connect

    Gerken, James B.; Stahl, Shannon S.

    2015-07-15

    Efficient reduction of O2 to water is a central challenge in energy conversion and aerobic oxidation catalysis. In the present study, we investigate the electrochemical reduction of O2 with soluble organic nitroxyl and nitrogen oxide (NOx) mediators. When used alone, neither organic nitroxyls, such as TEMPO (2,2,6,6-tetramethyl-1-piperidinyl-N-oxyl), nor NOx species, such as sodium nitrite, are effective mediators of electrochemical O2 reduction. The combination of nitroxyl/NOx species, however, mediates sustained O2 reduction at electrochemical potentials of 0.19–0.33 V (vs. Fc/Fc+) in acetonitrile containing trifluoroacetic acid. Mechanistic analysis of the coupled redox reactions supports a process in which the nitrogen oxide catalyst drives aerobic oxidation of a nitroxyl mediator to an oxoammonium species, which then is reduced back to the nitroxyl at the cathode. The electrolysis potential is dictated by the oxoammonium/nitroxyl reduction potential. The high potentials observed with this ORR system benefit from the mechanism-based specificity for four-electron reduction of oxygen to water mediated by NOx species, together with kinetically efficient reduction of oxidized NOx species by TEMPO and other organic nitroxyls. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center, funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences.

  11. High-Potential Electrocatalytic O2 Reduction with Nitroxyl/NOx Mediators: Implications for Fuel Cells and Aerobic Oxidation Catalysis

    PubMed Central

    2015-01-01

    Efficient reduction of O2 to water is a central challenge in energy conversion and many aerobic oxidation reactions. Here, we show that the electrochemical oxygen reduction reaction (ORR) can be achieved at high potentials by using soluble organic nitroxyl and nitrogen oxide (NOx) mediators. When used alone, neither organic nitroxyls, such as 2,2,6,6-tetramethyl-1-piperidinyl-N-oxyl (TEMPO), nor NOx species, such as sodium nitrite, are effective ORR mediators. The combination of nitroxyl/NOx species, however, mediates sustained O2 reduction with overpotentials as low as 300 mV in acetonitrile containing trifluoroacetic acid. Mechanistic analysis of the coupled redox reactions supports a process in which the nitrogen oxide catalyst drives aerobic oxidation of a nitroxyl mediator to an oxoammonium species, which then is reduced back to the nitroxyl at the cathode. The electrolysis potential is dictated by the oxoammonium/nitroxyl reduction potential. The overpotentials accessible with this ORR system are significantly lower than widely studied molecular metal-macrocycle ORR catalysts and benefit from the mechanism-based specificity for four-electron reduction of oxygen to water mediated by NOx species, together with kinetically efficient reduction of oxidized NOx species by TEMPO and other organic nitroxyls. PMID:27162977

  12. A snapshot of CO2 and CH4 evolution in a thermokarst pond near Igarka, northern Siberia

    NASA Astrophysics Data System (ADS)

    Blodau, Christian; Rees, Rainer; Flessa, Heiner; Rodionov, Andrej; Guggenberger, Georg; Knorr, Klaus-Holger; Shibistova, Olga; Zrazhevskaya, Galina; Mikheeva, Natalia; Kasansky, Oleg A.

    2008-09-01

    Thermokarst wetlands and ponds in the subarctic, which are located in land surface depressions resulting from permafrost melt, are strong sources of CH4, but little is known about respiration processes supporting these emissions. We determined CH4 fluxes and concentration profiles of dissolved gases and anions and some δ13C ratios of CO2 and CH4 in a thermokarst pond and adjacent smaller thermokarst depressions in the forest tundra near Igarka, northern Siberia in August 2006. Methane was emitted at 110-170 mg m-2 d-1 and produced mostly by CO2 reduction, which also provided high Gibbs free energies on the order of 50-70 KJ mol-1 H2 due to high H2 concentrations. The diffusive flux calculated from CH4 gradients in the floating mat contributed <2% to emissions. CH4 was apparently not oxidized deeper than 20 cm into the floating mat and the water body below. Anaerobic respiration required to reproduce nonsteady state CO2 concentration maxima in the floating mat above the water body was 30-80 nmol cm-3 d-1 or 250 mg m-2 d-1 and thus on a similar order of magnitude as CH4 fluxes. The results suggest that floating mat-covered thermokarst ponds located in northern Siberian bogs effectively convert recently fixed carbon into CH4 and thus allow for emissions independently from the finite, bog-derived carbon source. The relative contribution of recently fixed and old bog-derived carbon to C fluxes requires further investigation, however.

  13. Airborne measurements of CO2, CH4 and HCN in boreal biomass burning plumes

    NASA Astrophysics Data System (ADS)

    O'Shea, Sebastian J.; Bauguitte, Stephane; Muller, Jennifer B. A.; Le Breton, Michael; Archibald, Alex; Gallagher, Martin W.; Allen, Grant; Percival, Carl J.

    2013-04-01

    Biomass burning plays an important role in the budgets of a variety of atmospheric trace gases and particles. For example, fires in boreal Russia have been linked with large growths in the global concentrations of trace gases such as CO2, CH4 and CO (Langenfelds et al., 2002; Simpson et al., 2006). High resolution airborne measurements of CO2, CH4 and HCN were made over Eastern Canada onboard the UK Atmospheric Research Aircraft FAAM BAe-146 from 12 July to 4 August 2011. These observations were made as part of the BORTAS project (Quantifying the impact of BOReal forest fires on Tropospheric oxidants over the Atlantic using Aircraft and Satellites). Flights were aimed at transecting and sampling the outflow from the commonly occurring North American boreal forest fires during the summer months and to investigate and identify the chemical composition and evolution of these plumes. CO2 and CH4 dry air mole fractions were determined using an adapted system based on a Fast Greenhouse Gas Analyser (FGGA, Model RMT-200) from Los Gatos Research Inc, which uses the cavity enhanced absorption spectroscopy technique. In-flight calibrations revealed a mean accuracy of 0.57 ppmv and 2.31 ppbv for 1 Hz observations of CO2 and CH4, respectively, during the BORTAS project. During these flights a number of fresh and photochemically-aged plumes were identified using simultaneous HCN measurements. HCN is a distinctive and useful marker for forest fire emissions and it was detected using chemical ionisation mass spectrometry (CIMS). In the freshest plumes, strong relationships were found between CH4, CO2 and other tracers for biomass burning. From this we were able to estimate that 8.5 ± 0.9 g of CH4 and 1512 ± 185 g of CO2 were released into the atmosphere per kg of dry matter burnt. These emission factors are in good agreement with estimates from previous studies and can be used to calculate budgets for the region. However for aged plumes the correlations between CH4 and other

  14. 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

  15. Six weeks of aerobic dance exercise improves blood oxidative stress status and increases interleukin-2 in previously sedentary women.

    PubMed

    Leelarungrayub, Donrawee; Saidee, Kunteera; Pothongsunun, Prapas; Pratanaphon, Sainetee; YanKai, Araya; Bloomer, Richard J

    2011-07-01

    This study evaluated the change in blood oxidative stress, blood interleukin-2, and physical performance following 6 weeks of moderate intensity and duration aerobic dance exercise in 24 sedentary women. Blood samples were collected at rest twice before (baseline) and after the 6-week intervention for analysis of protein hydroperoxide (PrOOH), malondialdehyde (MDA), total anti-oxidant capacity (TAC), and interleukin-2 (IL-2) levels. Maximal treadmill run time (Time(max)) and maximal oxygen consumption (VO(2max)) were also measured. All variables were statistically analyzed with a repeated measurement ANOVA and Tukey post hoc. No differences were noted in any variable during the baseline period (p > 0.05). After aerobic dance exercise, VO(2max), Time(max), TAC and IL-2 were significantly increased, whereas MDA levels were decreased significantly (p < 0.05). PrOOH did not change either between baseline measures or after exercise. It can be concluded that aerobic dance exercise at a moderate intensity and duration can improve physical fitness, decrease MDA, and increase TAC and IL-2 in previously sedentary women. PMID:21665113

  16. Silver(I) as a widely applicable, homogeneous catalyst for aerobic oxidation of aldehydes toward carboxylic acids in water—“silver mirror”: From stoichiometric to catalytic

    PubMed Central

    Liu, Mingxin; Wang, Haining; Zeng, Huiying; Li, Chao-Jun

    2015-01-01

    The first example of a homogeneous silver(I)-catalyzed aerobic oxidation of aldehydes in water is reported. More than 50 examples of different aliphatic and aromatic aldehydes, including natural products, were tested, and all of them successfully underwent aerobic oxidation to give the corresponding carboxylic acids in extremely high yields. The reaction conditions are very mild and greener, requiring only a very low silver(I) catalyst loading, using atmospheric oxygen as the oxidant and water as the solvent, and allowing gram-scale oxidation with only 2 mg of our catalyst. Chromatography is completely unnecessary for purification in most cases. PMID:26601150

  17. Experimental simulations of CH4 evaporation on Titan

    NASA Astrophysics Data System (ADS)

    Luspay-Kuti, A.; Chevrier, V. F.; Wasiak, F. C.; Roe, L. A.; Welivitiya, W. D. D. P.; Cornet, T.; Singh, S.; Rivera-Valentin, E. G.

    2012-12-01

    We present the first experimental results on the evaporation of liquid CH4 under simulated Titan surface conditions similar to those observed at the Huygens landing site. An average evaporation rate of (3.1 ± 0.6) × 10-4 kg s-1 m-2 at 94 K and 1.5 bar was measured. While our results are generally higher than previous models based on energy balance, they show an excellent match with a theoretical mass transfer approach. Indeed, we find that evaporation in the Titan environmental chamber is predominantly diffusion driven and affected by the buoyancy of lighter CH4 in the heavier N2 atmosphere. After correcting for the difference in gravity of Earth and Titan, the resulting evaporation rate is (1.6 ± 0.3) × 10-4 kg s-1m-2 (or 1.13 ± 0.3 mm hr-1). Using our experimental evaporation rates, we determine that the low-latitude storm recently observed by Cassini ISS would have resulted in a maximum evaporated mass of (5.4 ± 1.2) × 1010 kg of CH4 equivalent to a 2.4 ± 0.5 m thick layer over 80 days. Based on our results, a sufficient amount of CH4 can accumulate in the otherwise arid equatorial regions to produce transient ponds and liquid flows.

  18. Natural evidence for rapid abiogenic hydrothermal generation of CH 4

    NASA Astrophysics Data System (ADS)

    Fiebig, Jens; Woodland, Alan B.; Spangenberg, Jorge; Oschmann, Wolfgang

    2007-06-01

    Although recent hydrothermal experiments imply that abiogenic methane (CH 4) generation from hydrothermal reduction of CO 2 can occur, evidence from natural systems was still lacking. Based on the chemical and isotopic equilibrium signatures of low-temperature fumarolic gas discharges, we are able to provide hard evidence for its natural occurrence, namely in three subduction-related bi-phase hydrothermal systems of the Mediterranean, whose temperatures range from 260 to 470 °C. The attainment of equilibrium and the time spans of recent volcanic dormancy allowed us to calculate minimum rates for chemical and isotopic equilibration. These are significantly higher than those previously reported and might be due to the presence of a saturated water vapor phase in the investigated systems. The fact that nature provides conditions enabling relatively fast production of hydrocarbons from CO 2 strongly supports the concerns that were recently raised from laboratory experiments. These address the use of the carbon isotope composition of reduced carbon in Archean sediments as a tracer of early life and the occurrence of CH 4 on extraterrestrial planets as a bioindicator. In view of the potential role of abiogenic CH 4 as a precursor of life, we also present an estimate of abiogenic hydrothermal CH 4 fluxes throughout the Archean. It is not expected that these fluxes exceeded 80 Mt/yr during the past 4.0 Ga. This, however, would have been enough to facilitate HCN production on the prebiotic Earth.

  19. Climate change reduces the net sink of CH4 and N2O in a semiarid grassland

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Methane (CH4) and nitrous oxide (N2O) are potent greenhouse gases; their concentrations in the atmosphere have increased because of human activity. Soils are important sources and sinks of both gases where their production and consumption are largely regulated by biological processes. Climate change...

  20. Solvent-free aerobic oxidation of hydrocarbons and alcohols with Pd@N-doped carbon from glucose.

    PubMed

    Zhang, Pengfei; Gong, Yutong; Li, Haoran; Chen, Zhirong; Wang, Yong

    2013-01-01

    The development of efficient systems for selective aerobic oxidation of hydrocarbons and alcohols to produce more functional compounds (aldehydes, ketones, acids or esters) with atmospheric air or molecular oxygen is a grand challenge for the chemical industry. Here we report the synthesis of palladium nanoparticles supported on novel nanoporous nitrogen-doped carbon, and their impressive performance in the controlled oxidation of hydrocarbons and alcohols with air. In terms of catalytic activity, these catalysts afford much higher turnover frequencies (up to 863 turnovers per hour for hydrocarbon oxidation and up to ~210,000 turnovers per hour for alcohol oxidation) than most reported palladium catalysts under the same reaction conditions. This work provides great potential for the application of ambient air and recyclable palladium catalysts in fine-chemical production with high activity. PMID:23481401

  1. Soil microorganisms as controllers of atmospheric trace gases (H2, CO, CH4, OCS, N2O, and NO).

    PubMed

    Conrad, R

    1996-12-01

    Production and consumption processes in soils contribute to the global cycles of many trace gases (CH4, CO, OCS, H2, N2O, and NO) that are relevant for atmospheric chemistry and climate. Soil microbial processes contribute substantially to the budgets of atmospheric trace gases. The flux of trace gases between soil and atmosphere is usually the result of simultaneously operating production and consumption processes in soil: The relevant processes are not yet proven with absolute certainty, but the following are likely for trace gas consumption: H2 oxidation by abiontic soil enzymes; CO cooxidation by the ammonium monooxygenase of nitrifying bacteria; CH4 oxidation by unknown methanotrophic bacteria that utilize CH4 for growth; OCS hydrolysis by bacteria containing carbonic anhydrase; N2O reduction to N2 by denitrifying bacteria; NO consumption by either reduction to N2O in denitrifiers or oxidation to nitrate in heterotrophic bacteria. Wetland soils, in contrast to upland soils are generally anoxic and thus support the production of trace gases (H2, CO, CH4, N2O, and NO) by anaerobic bacteria such as fermenters, methanogens, acetogens, sulfate reducers, and denitrifiers. Methane is the dominant gaseous product of anaerobic degradation of organic matter and is released into the atmosphere, whereas the other trace gases are only intermediates, which are mostly cycled within the anoxic habitat. A significant percentage of the produced methane is oxidized by methanotrophic bacteria at anoxic-oxic interfaces such as the soil surface and the root surface of aquatic plants that serve as conduits for O2 transport into and CH4 transport out of the wetland soils. The dominant production processes in upland soils are different from those in wetland soils and include H2 production by biological N2 fixation, CO production by chemical decomposition of soil organic matter, and NO and N2O production by nitrification and denitrification. The processes responsible for CH4 production

  2. Soil microorganisms as controllers of atmospheric trace gases (H2, CO, CH4, OCS, N2O, and NO).

    PubMed Central

    Conrad, R

    1996-01-01

    Production and consumption processes in soils contribute to the global cycles of many trace gases (CH4, CO, OCS, H2, N2O, and NO) that are relevant for atmospheric chemistry and climate. Soil microbial processes contribute substantially to the budgets of atmospheric trace gases. The flux of trace gases between soil and atmosphere is usually the result of simultaneously operating production and consumption processes in soil: The relevant processes are not yet proven with absolute certainty, but the following are likely for trace gas consumption: H2 oxidation by abiontic soil enzymes; CO cooxidation by the ammonium monooxygenase of nitrifying bacteria; CH4 oxidation by unknown methanotrophic bacteria that utilize CH4 for growth; OCS hydrolysis by bacteria containing carbonic anhydrase; N2O reduction to N2 by denitrifying bacteria; NO consumption by either reduction to N2O in denitrifiers or oxidation to nitrate in heterotrophic bacteria. Wetland soils, in contrast to upland soils are generally anoxic and thus support the production of trace gases (H2, CO, CH4, N2O, and NO) by anaerobic bacteria such as fermenters, methanogens, acetogens, sulfate reducers, and denitrifiers. Methane is the dominant gaseous product of anaerobic degradation of organic matter and is released into the atmosphere, whereas the other trace gases are only intermediates, which are mostly cycled within the anoxic habitat. A significant percentage of the produced methane is oxidized by methanotrophic bacteria at anoxic-oxic interfaces such as the soil surface and the root surface of aquatic plants that serve as conduits for O2 transport into and CH4 transport out of the wetland soils. The dominant production processes in upland soils are different from those in wetland soils and include H2 production by biological N2 fixation, CO production by chemical decomposition of soil organic matter, and NO and N2O production by nitrification and denitrification. The processes responsible for CH4 production

  3. Soil CO2 constrain and distinction of root respiration and microbial activity by soil CO2 and CH4 profile

    NASA Astrophysics Data System (ADS)

    Ji, S.; Breecker, D.; Nie, J.

    2015-12-01

    Profiles of soil pore space CO2 and CH4 concentrations are rarely reported, especially from the same soils, yet are important for a number of applications. First, quantifying the component of respired CO2 in the soil pore spaces improves paleosol-based paleo-atmospheric CO2 estimates. Second, profiles can be used to estimate the average depth of biological activity (e.g. respiration and CH4 oxidation). Third, CH4 profiles, by identifying microbial activity, may help distinguish root/rhizosphere respiration from microbial decomposition. Here, we report soil CO2 and CH4 profiles measured at the Semi-Arid Climate Observatory and Laboratory (SACOL) on the Chinese Loess Plateau (CLP) at Lanzhou University, Gansu, China. Soil parent material on the site is mainly Quaternary aeolian loess and classifies as an Entisol. Soil respired CO2 (S(z) = soil CO2 - atmospheric CO2) is the most uncertain variable required to reconstruct ancient atmospheric CO2 concentrations from paleosol carbonates. Our direct soil pore space CO2 measurements show that S(z) values varied from ~100ppmV during the spring to ~2200ppmV during the summer. S(z) average 390 ± 30ppmV during May before the summer monsoon begins when soil temperature is increasing, soil water content is at a minimum and pedogenic carbonate may be forming. This value lies in the range of S(z) values previously estimated for surface Inceptisols (300 ± 100ppmV, Breecker 2013) and is lower than Pleistocene CLP paleosols (Da et al.,2015) in similar parent material. Our direct measurements of soil pore space CO2 thus support these previous independent S(z) estimates. We also investigate the average depth of CH4 oxidation and soil respiration, which range from 3-10cm and at least 20cm, respectively, using the shapes of soil gas profiles. Fitting observed soil CO2 and CH4 profiles with a production-diffusion model show that the average depth of CH4 oxidation was always at least 10 cm shallower than the average depth of respiration

  4. Large contribution to inland water CO2 and CH4 emissions from very small ponds

    NASA Astrophysics Data System (ADS)

    Holgerson, Meredith A.; Raymond, Peter A.

    2016-03-01

    Inland waters are an important component of the global carbon cycle. Although they contribute to greenhouse gas emissions, estimates of carbon processing in these waters are uncertain. The global extent of very small ponds, with surface areas of less than 0.001 km2, is particularly difficult to map, resulting in their exclusion from greenhouse gas budget estimates. Here we combine estimates of the lake and pond global size distribution, gas exchange rates, and measurements of carbon dioxide and methane concentrations from 427 lakes and ponds ranging in surface area from 2.5 m2 to 674 km2. We estimate that non-running inland waters release 0.583 Pg C yr-1. Very small ponds comprise 8.6% of lakes and ponds by area globally, but account for 15.1% of CO2 emissions and 40.6% of diffusive CH4 emissions. In terms of CO2 equivalence, the ratio of CO2 to CH4 flux increases with surface area, from about 1.5 in very small ponds to about 19 in large lakes. The high fluxes from very small ponds probably result from shallow waters, high sediment and edge to water volume ratios, and frequent mixing. These attributes increase CO2 and CH4 supersaturation in the water and limit efficient methane oxidation. We conclude that very small ponds represent an important inland water carbon flux.

  5. Kinetic conversion of CO to CH4 in the Solar System

    NASA Technical Reports Server (NTRS)

    Yung, Y. L.; Allen, M.; Pinto, J. P.

    1991-01-01

    Some of the most interesting chemistry in the Solar System involves changes in the oxidation state of the simple carbon species. The chemical pathways for the conversion of CH4 to CO and CO2 are for the most part known. The reverse process, the reduction of CO to CH4, is, however, poorly understood. This is surprising in view of the importance of the reduction process in the chemistry of the Solar System. Recently we investigated the chemical kinetics of a hitherto unsuspected reaction. It is argued that the formation of the methoxy radical (CH3O) from H+H2CO may play an essential role in the reduction of CO to CH4. The rate coefficient for this reaction has been estimated using the approximate theory of J. Troe and transition state theory. We will discuss the implications of this reaction for the chemistry of CO on Jupiter, in the solar nebula, for interpreting the laboratory experiments of A. Bar-Nun and A. Shaviv and A. Bar-Nun and S. Chang, and for organic synthesis in the prebiotic terrestrial atmosphere. The possible relation of CO reduction in the solar nebula and polyoxymethylene observed in comet Halley will be discussed.

  6. Carbonate control of H2 and CH4 production in serpentinization systems at elevated P-Ts

    USGS Publications Warehouse

    Jones, L. Camille; Rosenbauer, Robert; Goldsmith, Jonas I.; Oze, Christopher

    2010-01-01

    Serpentinization of forsteritic olivine results in the inorganic synthesis of molecular hydrogen (H2) in ultramafic hydrothermal systems (e.g., mid-ocean ridge and forearc environments). Inorganic carbon in those hydrothermal systems may react with H2 to produce methane (CH4) and other hydrocarbons or react with dissolved metal ions to form carbonate minerals. Here, we report serpentinization experiments at 200°C and 300 bar demonstrating Fe2+ being incorporated into carbonates more rapidly than Fe2+ oxidation (and concomitant H2 formation) leading to diminished yields of H2 and H2-dependent CH4. In addition, carbonate formation is temporally fast in carbonate oversaturated fluids. Our results demonstrate that carbonate chemistry ultimately modulates the abiotic synthesis of both H2 and CH4 in hydrothermal ultramafic systems and that ultramafic systems present great potential for CO2-mineral sequestration.

  7. Whole-Genome Transcriptional Analysis of Chemolithoautotrophic Thiosulfate Oxidation by Thiobacillus denitrificans Under Aerobic vs. Denitrifying Conditions

    SciTech Connect

    Beller, H R; Letain, T E; Chakicherla, A; Kane, S R; Legler, T C; Coleman, M A

    2006-04-22

    Thiobacillus denitrificans is one of the few known obligate chemolithoautotrophic bacteria capable of energetically coupling thiosulfate oxidation to denitrification as well as aerobic respiration. As very little is known about the differential expression of genes associated with ke chemolithoautotrophic functions (such as sulfur-compound oxidation and CO2 fixation) under aerobic versus denitrifying conditions, we conducted whole-genome, cDNA microarray studies to explore this topic systematically. The microarrays identified 277 genes (approximately ten percent of the genome) as differentially expressed using Robust Multi-array Average statistical analysis and a 2-fold cutoff. Genes upregulated (ca. 6- to 150-fold) under aerobic conditions included a cluster of genes associated with iron acquisition (e.g., siderophore-related genes), a cluster of cytochrome cbb3 oxidase genes, cbbL and cbbS (encoding the large and small subunits of form I ribulose 1,5-bisphosphate carboxylase/oxygenase, or RubisCO), and multiple molecular chaperone genes. Genes upregulated (ca. 4- to 95-fold) under denitrifying conditions included nar, nir, and nor genes (associated respectively with nitrate reductase, nitrite reductase, and nitric oxide reductase, which catalyze successive steps of denitrification), cbbM (encoding form II RubisCO), and genes involved with sulfur-compound oxidation (including two physically separated but highly similar copies of sulfide:quinone oxidoreductase and of dsrC, associated with dissimilatory sulfite reductase). Among genes associated with denitrification, relative expression levels (i.e., degree of upregulation with nitrate) tended to decrease in the order nar > nir > nor > nos. Reverse transcription, quantitative PCR analysis was used to validate these trends.

  8. Development and Comparison of the Substrate Scope of Pd-Catalysts for the Aerobic Oxidation of Alcohols

    PubMed Central

    Schultz, Mitchell J.; Hamilton, Steven S.; Jensen, David R.; Sigman, Matthew S.

    2009-01-01

    Three catalysts for aerobic oxidation of alcohols are discussed and the effectiveness of each is evaluated for allylic, benzylic, aliphatic, and functionalized alcohols. Additionally, chiral nonracemic substrates as well as chemoselective and diastereoselective oxidations are investigated. In this study, the most convenient system for the Pd-catalyzed aerobic oxidation of alcohols is Pd(OAc)2 in combination with triethylamine. This system functions effectively for the majority of alcohols tested and uses mild conditions (3 to 5 mol % of catalyst, room temperature). Pd(IiPr)(OAc)2(H2O) (1) also successfully oxidizes the majority of alcohols evaluated. This system has the advantage of significantly lowering catalyst loadings but requires higher temperatures (0.1 to 1 mol % of catalyst, 60 °C). A new catalyst is also disclosed, Pd(IiPr)(OPiv)2 (2). This catalyst operates under very mild conditions (1 mol %, room temperature, and air as the O2 source) but with a more limited substrate scope. PMID:15844968

  9. Chiral N-salicylidene vanadyl carboxylate-catalyzed enantioselective aerobic oxidation of α-hydroxy esters and amides

    PubMed Central

    Weng, Shiue-Shien; Shen, Mei-Wen; Kao, Jun-Qi; Munot, Yogesh S.; Chen, Chien-Tien

    2006-01-01

    A series of chiral vanadyl carboxylates derived from N-salicylidene-l-α-amino acids and vanadyl sulfate has been developed. These configurationally well defined complexes were examined for the kinetic resolution of double- and mono-activated 2° alcohols. The best chiral templates involve the combination of l-tert-leucine and 3,5-di-t-butyl-, 3,5-diphenyl-, or 3,4-dibromo-salicylaldehyde. The resulting vanadyl(V)-methoxide complexes after recrystallization from air-saturated methanol serve as highly enantioselective catalysts for asymmetric aerobic oxidation of α-hydroxyl-esters and amides with a diverse array of α-, O-, and N-substituents at ambient temperature in toluene. The asymmetric inductions of the oxidation process are in the range of 10 to >100 in terms of selectivity factors (krel) in most instances. The previously undescribed aerobic oxidation protocol is also applicable to the kinetic resolution of C-13 taxol side chain with high selectivity factor (krel = 35). X-ray crystallographic analysis of an adduct between a given vanadyl complex and N-benzyl-mandelamide allows for probing the stereochemical origin of the nearly exclusive asymmetric control in the oxidation process. PMID:16501046

  10. Spatial variability of CH 4 and N 2 O fluxes in alpine ecosystems on the Qinghai-Tibetan Plateau

    NASA Astrophysics Data System (ADS)

    Kato, Tomomichi; Hirota, Mitsuru; Tang, Yanhong; Wada, Eitaro

    2011-10-01

    The intra- and inter-site spatial variability of methane (CH 4) and nitrous oxide (N 2O) fluxes were investigated in three alpine ecosystems at Haibei station on the Qinghai-Tibetan Plateau (QTP) in summer 2005 and in sixteen alpine ecosystems with various vegetations across the QTP in summer 2006, respectively. The magnitude of average CH 4 emissions from wetlands was at least 100 times larger than average CH 4 uptake by grassland, suggesting that the entire QTP is likely to be a source of methane in summertime because of a significant fractional area of wetlands (˜ 2.2%) on the plateau. Intra-site investigation, with sixteen chambers, revealed a significant negative relationship of CH 4 emissions with the C/N ratio of aboveground biomass and soil pH in the alpine wetland when all chambers were considered. Moreover, soil oxidation-reduction potential (ORP) had a remarkably strong influence on CH 4 emissions for nine chambers above the water level, resulting in a negative exponential relationship. For N 2O flux in alpine meadows, a negative relationship with both soil pH and livestock dung biomass was observed. Aboveground plant biomass and soil pH were important variables overall in wetlands. Inter-site investigation found positive and negative relationships between CH 4 flux and soil biomass to 5 cm depth in nine grassland and seven wetland sites, respectively. N 2O flux showed a moderately strong negative exponential relationship with the C/N ratio of surface soil in the grassland sites. In the wetlands, soil pH was negatively correlated with N 2O flux, perhaps due to both reduced N 2O release from suppressed nitrification and denitrification.

  11. Self-catalysed aerobic oxidization of organic linker in porous crystal for on-demand regulation of sorption behaviours

    NASA Astrophysics Data System (ADS)

    Liao, Pei-Qin; Zhu, Ai-Xin; Zhang, Wei-Xiong; Zhang, Jie-Peng; Chen, Xiao-Ming

    2015-02-01

    Control over the structure and property of synthetic materials is crucial for practical applications. Here we report a facile, green and controllable solid-gas reaction strategy for on-demand modification of porous coordination polymer. Copper(I) and a methylene-bridged bis-triazolate ligand are combined to construct a porous crystal consisting of both enzyme-like O2-activation site and oxidizable organic substrate. Thermogravimetry, single-crystal X-ray diffraction, electron paramagnetic resonance and infrared spectroscopy showed that the methylene groups can be oxidized by O2/air even at room temperature via formation of the highly active Cu(II)-O2˙- intermediate, to form carbonyl groups with enhance rigidity and polarity, without destroying the copper(I) triazolate framework. Since the oxidation degree or reaction progress can be easily monitored by the change of sample weight, gas sorption property of the crystal can be continuously and drastically (up to 4 orders of magnitude) tuned to give very high and even invertible selectivity for CO2, CH4 and C2H6.

  12. A comparative study of silver-graphene oxide nanocomposites as a recyclable catalyst for the aerobic oxidation of benzyl alcohol: Support effect

    NASA Astrophysics Data System (ADS)

    Zahed, Bahareh; Hosseini-Monfared, Hassan

    2015-02-01

    Three different nanocomposites of silver and graphene oxide, namely silver nanoparticles (AgNPs) immobilized on reduced graphene oxide (AgNPs/rGO), partially reduced graphene oxide (AgNPs/GO) and thiolated partially reduced graphene oxide (AgNPs/GOSH), were synthesized in order to compare their properties. Characterizations were carried out by infrared and UV-Vis and Raman spectroscopy, ICP, X-ray diffraction, SEM and TEM, confirming both the targeted chemical modification and the composite formation. The nanocomposites were successfully employed in the aerobic oxidation of benzyl alcohol at atmospheric pressure. AgNPs/GOSH is stable and recyclable catalyst which showed the highest activity in the aerobic oxidation of benzyl alcohol in the presence of N-hydroxyphthalimide (NHPI) to give benzaldehyde with 58% selectivity in 24 h at 61% conversion. The favorite properties of AgNPs/GOSH are reasonably attributed to the stable and well distributed AgNPs over GOSH due to strong adhesion between AgNPs and GOSH.

  13. Complete Genome Sequence of the Aerobic CO-Oxidizing Thermophile Thermomicrobium roseum

    PubMed Central

    Wu, Dongying; Raymond, Jason; Wu, Martin; Chatterji, Sourav; Ren, Qinghu; Graham, Joel E.; Bryant, Donald A.; Robb, Frank; Colman, Albert; Tallon, Luke J.; Badger, Jonathan H.; Madupu, Ramana; Ward, Naomi L.; Eisen, Jonathan A.

    2009-01-01

    In order to enrich the phylogenetic diversity represented in the available sequenced bacterial genomes and as part of an “Assembling the Tree of Life” project, we determined the genome sequence of Thermomicrobium roseum DSM 5159. T. roseum DSM 5159 is a red-pigmented, rod-shaped, Gram-negative extreme thermophile isolated from a hot spring that possesses both an atypical cell wall composition and an unusual cell membrane that is composed entirely of long-chain 1,2-diols. Its genome is composed of two circular DNA elements, one of 2,006,217 bp (referred to as the chromosome) and one of 919,596 bp (referred to as the megaplasmid). Strikingly, though few standard housekeeping genes are found on the megaplasmid, it does encode a complete system for chemotaxis including both chemosensory components and an entire flagellar apparatus. This is the first known example of a complete flagellar system being encoded on a plasmid and suggests a straightforward means for lateral transfer of flagellum-based motility. Phylogenomic analyses support the recent rRNA-based analyses that led to T. roseum being removed from the phylum Thermomicrobia and assigned to the phylum Chloroflexi. Because T. roseum is a deep-branching member of this phylum, analysis of its genome provides insights into the evolution of the Chloroflexi. In addition, even though this species is not photosynthetic, analysis of the genome provides some insight into the origins of photosynthesis in the Chloroflexi. Metabolic pathway reconstructions and experimental studies revealed new aspects of the biology of this species. For example, we present evidence that T. roseum oxidizes CO aerobically, making it the first thermophile known to do so. In addition, we propose that glycosylation of its carotenoids plays a crucial role in the adaptation of the cell membrane to this bacterium's thermophilic lifestyle. Analyses of published metagenomic sequences from two hot springs similar to the one from which this strain

  14. Cu-Catalyzed Consecutive Hydroxylation and Aerobic Oxidative Cycloetherification under Microwave Conditions: Entry to 2-Arylbenzofuran-3-carboxylic Acids.

    PubMed

    Xu, Tianlong; Zhang, Ensheng; Wang, Dejian; Wang, Yan; Zou, Yong

    2015-05-01

    A convenient one-pot synthesis of 2-arylbenzofuran-3-carboxylic acids from (E)-2-(2-bromophenyl)-3-phenylacrylic acids via Cu-catalyzed consecutive hydroxylation and aerobic oxidative cycloetherification under microwave conditions has been developed. This protocol employed the reagent combination of Cu(OAc)2, 1,10-phen, and KOH in DMSO/H2O (1:1), all of which are cost-effective, readily available, and easily removable from the reaction mixture. Utilizing this synthetic protocol, various 2-arylbenzofuran-3-carboxylic acids as well as the natural product moracin M have been synthesized in satisfactory yields under mild conditions. PMID:25836742

  15. Stable TEMPO and ABNO Catalyst Solutions for User-Friendly (bpy)Cu/Nitroxyl-Catalyzed Aerobic Alcohol Oxidation.

    PubMed

    Steves, Janelle E; Stahl, Shannon S

    2015-11-01

    Two solutions, one consisting of bpy/TEMPO/NMI and the other bpy/ABNO/NMI (bpy =2,2'-bipyridyl; TEMPO = 2,2,6,6-tetramethylpiperidine N-oxyl, ABNO = 9-azabicyclo[3.3.1]nonane N-oxyl; NMI = N-methylimidazole), in acetonitrile are shown to have good long-term stability (≥1 year) under air at 5 °C. The solutions may be combined in appropriate quantities with commercially available [Cu(MeCN)4]OTf to provide a convenient catalyst system for the aerobic oxidation of primary and secondary alcohols. PMID:26457658

  16. Experimental Limiting Oxygen Concentrations for Nine Organic Solvents at Temperatures and Pressures Relevant to Aerobic Oxidations in the Pharmaceutical Industry

    PubMed Central

    2015-01-01

    Applications of aerobic oxidation methods in pharmaceutical manufacturing are limited in part because mixtures of oxygen gas and organic solvents often create the potential for a flammable atmosphere. To address this issue, limiting oxygen concentration (LOC) values, which define the minimum partial pressure of oxygen that supports a combustible mixture, have been measured for nine commonly used organic solvents at elevated temperatures and pressures. The solvents include acetic acid, N-methylpyrrolidone, dimethyl sulfoxide, tert-amyl alcohol, ethyl acetate, 2-methyltetrahydrofuran, methanol, acetonitrile, and toluene. The data obtained from these studies help define safe operating conditions for the use of oxygen with organic solvents. PMID:26622165

  17. Mechanistic study of copper-catalyzed aerobic oxidative coupling of arylboronic esters and methanol: insights into an organometallic oxidase reaction.

    PubMed

    King, Amanda E; Brunold, Thomas C; Stahl, Shannon S

    2009-04-15

    Copper-catalyzed aerobic oxidative coupling of arylboronic acid derivatives and heteroatom nucleophiles is a highly useful method for the formation of aryl-heteroatom bonds. Mechanistic studies reveal that this reaction proceeds via an "oxidase"-style mechanism. Kinetic and spectroscopic studies establish that transmetalation of the aryl group from boron to Cu(II) is the turnover-limiting step and reoxidation of the reduced catalyst by O(2) is rapid. Further mechanistic analysis implicates the involvement of an aryl-copper(III) intermediate that undergoes facile C-O bond formation. PMID:19309072

  18. Spatial patterns of methane oxidation and methanotrophic diversity in landfill cover soils of southern China.

    PubMed

    Chi, Zi-Fang; Lu, Wen-Jing; Wang, Hong-Tao

    2015-04-01

    Aerobic CH4 oxidation is an important CH4 sink in landfills. To investigate the distribution and community diversity of methanotrophs and link with soil characteristics and operational parameters (e.g., concentrations of O2, CH4), cover soil samples were collected at different locations and depths from the Mengzi semi-aerobic landfill (SAL) in Yunnan Province of southern China. Specific PCR followed by denaturing gradient gel electrophoresis and realtime PCR were used to examine methanotrophs in the landfill cover soils. The results showed that different locations did harbor distinct methanotroph communities. Methanotrophs were more abundant in areas near the venting pipes because of the higher O2 concentrations. The depth of 20-25 cm, where the ratio of the CH4 to O2 was within the range from 1.3 to 8.6, was more conducive to the growth of CH4-oxidizing bacteria. Type II methanotrophs dominated in all samples compared with Type I methanotrophs, as evidenced by the high ratio of Type II to Type I methanotrophic copy numbers (from 1.76 to 11.60). The total copy numbers of methanotrophs detected were similar to other ecosystems, although the CH4 concentration was much higher in SAL cover soil. Methylobacter and Methylocystis were the most abundant Type I and Type II methanotrophs genera, respectively, in the Mengzi SAL. The results suggested that SALs could provide a special environment with both high concentrations of CH4 and O2 for methanotrophs, especially around the vertical venting pipes. PMID:25341468

  19. Linking methane oxidation with perchlorate reduction: a microbial base for possible Martian life

    NASA Astrophysics Data System (ADS)

    Miller, L. G.; Carlstrom, C.; Baesman, S. M.; Coates, J. D.; Oremland, R. S.

    2011-12-01

    Recent observations of methane (CH4) and perchlorate (ClO4-) within the atmosphere and surface of Mars, respectively, provide impetus for establishing a metabolic linkage between these compounds whereby CH4 acts as an electron donor and perchlorate acts as an electron acceptor. Direct linkage through anaerobic oxidation of methane (AOM) has not been observed. However, indirect syntrophic oxygenase-dependent oxidation of CH4 with an aerobic methane oxidizer is feasible. The pathway for anaerobic dissimilatory perchlorate reduction includes 3 steps. The first 2 are sequential reductions of (1) perchlorate to chlorate and (2) chlorate to chlorite, mediated by perchlorate reductase. The third step is disproportionation of chlorite to chloride and molecular oxygen, mediated by chlorite dismutase. Utilization of thusly derived oxygen by hydrocarbon-degrading organisms in anoxic environments was first demonstrated by Coates et. al. (1998)1, however the link to aerobic methane oxidation was not examined at that time. Here, we systematically explore the potential for several species of aerobic methanotrophs to couple with chlorite during dissimilatory perchlorate reduction. In one experiment, 0.5 kPa CH4 was completely removed in one day from the headspace of combined cell suspensions of Dechloromonas agitata strain CKB and Methylococcus capsulatus in the presence of 5 mM chlorite. Oxidation of labeled 14CH4 to 14CO2 under similar conditions was later confirmed. Another experiment demonstrated complete removal of 0.2 kPa CH4 over several days by Methylobacter albus strain BG8 with strain CKB in the presence of 5 mM chlorite. Finally, we observed complete removal of 0.2 kPa CH4 in bottles containing natural soil (enriched in methanotrophs by CH4 additions over several weeks) and strain CKB and in the presence of 10 mM chlorite. This soil, collected from a pristine lake shoreline, demonstrated endogenous methane, perchlorate, chlorate and chlorite uptake. Other soil and

  20. Long-term data on δ13C-CH4 emissions elucidate drivers of CH4 metabolism in temperate and northern wetlands

    NASA Astrophysics Data System (ADS)

    McCalley, C. K.; Shorter, J. H.; Crill, P. M.; Hodgkins, S. B.; Chanton, J.; Saleska, S. R.; Varner, R. K.

    2015-12-01

    Methane flux from wetlands is both a critical component of the global CH4 budget, and highly sensitive to global climate change. Gaps in our knowledge of the biological processes that underlie CH4 fluxes from natural ecosystems limit our ability to scale flux estimates as well as predict future emissions. To address these gaps, we used quantum cascade laser technology linked to automated chambers to quantify the isotopic composition of CH4 fluxes from a high latitude (68° N) wetland underlain by discontinuous permafrost (Stordalen Mire, Sweden) and a temperate wetland (43° N) undergoing shrub encroachment (Sallie's Fen, NH). Changes in plant communities and hydrology during permafrost thaw result in both large increases in CH4 emissions as well as shifts in the CH4 production pathway, from hydrogenotrophic to increasingly acetoclastic mechanisms. In contrast, shrub encroachment that replaces sedge species in the temperate wetland reduces CH4 emissions, but doesn't effect δ 13C-CH4, with predominantly acetoclastic production occurring across plant communities. Multi-year data sets identify temperature and hydrologic variability as key contributors to annual and interannual patterns in δ 13C-CH4. Fully-thawed fens at Stordalen had consistent δ13C-CH4 across years, with an annual pattern suggestive of more hydrogenotrophic production early and late in the growing season. In contrast, intermediate-thaw sites, where the water table was more dynamic, had large variations in δ13C-CH4 across years. At Sallie's Fen, patterns in δ13C-CH4 suggest an abrupt shift in CH4 transport and metabolism at the beginning of the growing season and then more stable δ13C-CH4 during the growing season. Together these results provide insights into how plant communities and variable environmental conditions interact to influence the microbial metabolisms that drive CH4 production and consumption in diverse wetland ecosystems.

  1. New products of GOSAT/TANSO-FTS TIR CO2 and CH4 profiles: Algorithm and initial validation results

    NASA Astrophysics Data System (ADS)

    Saitoh, N.; Imasu, R.; Sugita, T.; Hayashida, S.; Shiomi, K.; Kawakami, S.; Machida, T.; Sawa, Y.; Matsueda, H.; Terao, Y.

    2013-12-01

    The Thermal and Near-infrared Sensor for Carbon Observation Fourier Transform Spectrometer (TANSO-FTS) on board the Greenhouse Gases Observing Satellite (GO-SAT) simultaneously observes column abundances and profiles of CO2 and CH4 in the same field of view, from the shortwave infrared (SWIR) and thermal infrared (TIR) bands, respectively. The latest version of the GOSAT Level 1B (L1B) radiance spectra, the version 160.160, is improved compared to the previous versions, but still has a bias judging from comparisons with spectral data of other coincident instruments. The bias is largest at around 14-15 micron band that includes carbon dioxide strong absorption lines [Kataoka et al., 2013]; it probably causes a high bias in mid-tropospheric carbon dioxide concentration of the current released V00.01 TIR products. Besides, relatively low sig-nal-to-noise ratio (SNR) less than 100 at around 7-8 micron band makes CH4 retrieval unstable. We have improved an algorithm for retrieving CO2 and CH4 profiles in order to overcome the spectral bias and low SNR problems. In our new algorithm, we treated surface temperature and surface emissivity as correction parameters for radi-ance-independent and radiance-dependent spectral biases, respectively, and retrieved them simultaneously with gas retrieval. We used 7-8 micron band (1140-1370 wave-number) for methane retrieval and 10 and 14-15 micron bands (930-990, 1040-1090, 690-750, and 790-795 wavenumber) for carbon dioxide retrieval. Temperature, water vapor, ozone, and nitrous oxide were retrieved simultaneously other than CO2 and CH4. CO2 profiles retrieved using our new algorithm have no clear bias in mid-troposphere compared to the previous V00.01 CO2 product. New retrieved CH4 profiles show better agreement with aircraft CH4 profiles than the a priori profiles.

  2. Temporal changes in soil water repellency linked to the soil respiration and CH4 and CO2 fluxes

    NASA Astrophysics Data System (ADS)

    Qassem, Khalid; Urbanek, Emilia; van Keulen, Geertje

    2014-05-01

    Soil water repellency (SWR) is known to be a spatially and temporally variable phenomenon. The seasonal changes in soil moisture lead to development of soil water repellency, which in consequence may affect the microbial activity and in consequence alter the CO2 and CH4 fluxes from soils. Soil microbial activity is strongly linked to the temperature and moisture status of the soil. In terms of CO2 flux intermediate moisture contents are most favourable for the optimal microbial activity and highest CO2 fluxes. Methanogenesis occurs primarily in anaerobic water-logged habitats while methanotrophy is a strictly aerobic process. In the study we hypothesise that the changes in CO2 and CH4 fluxes are closely linked to critical moisture thresholds for soil water repellency. This research project aims to adopt a multi-disciplinary approach to comprehensively determine the effect of SWR on CO2 and CH4 fluxes. Research is conducted in situ at four sites exhibiting SWR in the southern UK. Flux measurements are carried out concomitant with meteorological and SWR observations Field observations are supported by laboratory measurements carried out on intact soil samples collected at the above identified field sites. The laboratory analyses are conducted under constant temperatures with controlled changes of soil moisture content. Methanogenic and Methanotrophic microbial populations are being analysed at different SWR and moisture contents using the latest metagenomic and metatranscriptomic approaches. Currently available data show that greenhouse gas flux are closely linked with soil moisture thresholds for SWR development.

  3. Aerobic oxidation of starch catalyzed by isopolyoxovanadate Na4Co(H2O)6V10O28.

    PubMed

    Chen, Xiaoli; Yan, Siqi; Wang, Hang; Hu, Zhiyun; Wang, Xiaohong; Huo, Mingxin

    2015-03-01

    The partial oxidation of starch was achieved in the presence of oxygen with Na4Co(H2O)6V10O28·18H2O (abbreviated as CoV10) as catalyst. The oxidation degree of starch was determined by FT-IR, XRD and SEM measurements, which indicated that the aerobic oxidation of starch was promoted by oxidative catalyst CoV10. The application of CoV10 could give a high oxidation degree (DO) of 1.35 COOH/100 GU and 2.07 CO/100 GU with 86 wt.% yield of solid starch under mild reaction conditions (pH=6; reaction time, 8 h; temperature, 50 °C; catalyst amount, 8 mg, when 1.5 g starch was used as substrate; atmospheric pressure). Among some vanadium compounds, CoV10 exhibited 4-fold activity higher than orthovanadate due to its coordination effect of cobalt and V10O28. Meanwhile, CoV10 could be recycled for six times with only a slight decrease in activity. Thus, CoV10/O2 is one of the most efficient systems for partial oxidation of starch reported so far. PMID:25498687

  4. P-Doped Porous Carbon as Metal Free Catalysts for Selective Aerobic Oxidation with an Unexpected Mechanism.

    PubMed

    Patel, Mehulkumar A; Luo, Feixiang; Khoshi, M Reza; Rabie, Emann; Zhang, Qing; Flach, Carol R; Mendelsohn, Richard; Garfunkel, Eric; Szostak, Michal; He, Huixin

    2016-02-23

    An extremely simple and rapid (seconds) approach is reported to directly synthesize gram quantities of P-doped graphitic porous carbon materials with controlled P bond configuration. For the first time, it is demonstrated that the P-doped carbon materials can be used as a selective metal free catalyst for aerobic oxidation reactions. The work function of P-doped carbon materials, its connectivity to the P bond configuration, and the correlation with its catalytic efficiency are studied and established. In direct contrast to N-doped graphene, the P-doped carbon materials with higher work function show high activity in catalytic aerobic oxidation. The selectivity trend for the electron donating and withdrawing properties of the functional groups attached to the aromatic ring of benzyl alcohols is also different from other metal free carbon based catalysts. A unique catalytic mechanism is demonstrated, which differs from both GO and N-doped graphene obtained by high temperature nitrification. The unique and unexpected catalytic pathway endows the P-doped materials with not only good catalytic efficiency but also recyclability. This, combined with a rapid, energy saving approach that permits fabrication on a large scale, suggests that the P-doped porous materials are promising materials for "green catalysis" due to their higher theoretical surface area, sustainability, environmental friendliness, and low cost. PMID:26751165

  5. The synthesis of a bifunctional copper metal organic framework and its application in the aerobic oxidation/Knoevenagel condensation sequential reaction.

    PubMed

    Miao, Zongcheng; Luan, Yi; Qi, Chao; Ramella, Daniele

    2016-09-21

    A novel one-pot aerobic oxidation/Knoevenagel condensation reaction system was developed employing a Cu(ii)/amine bifunctional, basic metal-organic framework (MOF) as the catalyst. The sequential aerobic alcohol oxidation/Knoevenagel condensation reaction was efficiently promoted by the Cu3TATAT MOF catalyst in the absence of basic additives. The benzylidenemalononitrile product was produced in high yield and selectivity from an inexpensive benzyl alcohol starting material under an oxygen atmosphere. The role of the basic functionality was studied to demonstrate its role in the aerobic oxidation and Knoevenagel condensation reactions. The reaction progress was monitored in order to identify the reaction intermediate and follow the accumulation of the desired product. Lastly, results showed that the yield was not significantly compromised by the reuse of a batch of catalyst, even after more than five cycles. PMID:27523776

  6. Mapping pan-Arctic CH4 emissions using an adjoint method by integrating process-based wetland and lake biogeochemical models and atmospheric CH4 concentrations

    NASA Astrophysics Data System (ADS)

    Tan, Z.; Zhuang, Q.; Henze, D. K.; Frankenberg, C.; Dlugokencky, E. J.; Sweeney, C.; Turner, A. J.

    2015-12-01

    Understanding CH4 emissions from wetlands and lakes are critical for the estimation of Arctic carbon balance under fast warming climatic conditions. To date, our knowledge about these two CH4 sources is almost solely built on the upscaling of discontinuous measurements in limited areas to the whole region. Many studies indicated that, the controls of CH4 emissions from wetlands and lakes including soil moisture, lake morphology and substrate content and quality are notoriously heterogeneous, thus the accuracy of those simple estimates could be questionable. Here we apply a high spatial resolution atmospheric inverse model (nested-grid GEOS-Chem Adjoint) over the Arctic by integrating SCIAMACHY and NOAA/ESRL CH4 measurements to constrain the CH4 emissions estimated with process-based wetland and lake biogeochemical models. Our modeling experiments using different wetland CH4 emission schemes and satellite and surface measurements show that the total amount of CH4 emitted from the Arctic wetlands is well constrained, but the spatial distribution of CH4 emissions is sensitive to priors. For CH4 emissions from lakes, our high-resolution inversion shows that the models overestimate CH4 emissions in Alaskan costal lowlands and East Siberian lowlands. Our study also indicates that the precision and coverage of measurements need to be improved to achieve more accurate high-resolution estimates.

  7. Origin and transport of CH4 in two maar lakes fed by mantle-derived volatiles (Mt. Vulture volcano, Italy)

    NASA Astrophysics Data System (ADS)

    Caracausi, Antonio; Cosenza, Paolo; Favara, Rocco; Foresta Martin, Luigi; Galli, Nunzio; Grassa, Fausto; Nuccio, Pasquale Mario; Paternoster, Michele; Riccobono, Giuseppe

    2014-05-01

    from previous limnological-geochemical investigations has been joined with isotope signature of gas (CH4 and CO2) collected from sediments at the bottom of LPM, by means of a specially designed robot called "Muddy". Muddy is also able to perform vertical profiles both of pH and of temperature in the water column and in the sediments as well. The obtained results lead us: 1) to assess the production ratio of CH4 through acetoclastic methanogenesis and CO2 reduction in the sediments; 2) to determinate CH4 oxidation; 3) to detect the origin of CO2 involved in methanogenic processes, evaluating the contribution organic-CO2 and the sink of mantle-derived CO2.;4) to discuss the differences in CH4 sources in the water and sediments; 5) to properly define gas hazards assessment. A. Caracausi, M. Nicolosi, P.M. Nuccio, R. Favara, M. Paternoster, A. Rosciglione (2013) Geochemical insight into differences in the physical structures and dynamics of two adjacent maar lakes at Mt. Vulture volcano (southern Italy), G. Cubed, doi: 10.1002/ggge.2011

  8. Design of Highly Selective Platinum Nanoparticle Catalysts for the Aerobic Oxidation of KA-Oil using Continuous-Flow Chemistry.

    PubMed

    Gill, Arran M; Hinde, Christopher S; Leary, Rowan K; Potter, Matthew E; Jouve, Andrea; Wells, Peter P; Midgley, Paul A; Thomas, John M; Raja, Robert

    2016-03-01

    Highly active and selective aerobic oxidation of KA-oil to cyclohexanone (precursor for adipic acid and ɛ-caprolactam) has been achieved in high yields using continuous-flow chemistry by utilizing uncapped noble-metal (Au, Pt & Pd) nanoparticle catalysts. These are prepared using a one-step in situ methodology, within three-dimensional porous molecular architectures, to afford robust heterogeneous catalysts. Detailed spectroscopic characterization of the nature of the active sites at the molecular level, coupled with aberration-corrected scanning transmission electron microscopy, reveals that the synthetic methodology and associated activation procedures play a vital role in regulating the morphology, shape and size of the metal nanoparticles. These active centers have a profound influence on the activation of molecular oxygen for selective catalytic oxidations. PMID:26833972

  9. Airborne measurements of HCN, CO2 and CH4 associated with emissions from boreal biomass burning

    NASA Astrophysics Data System (ADS)

    Muller, J. B. A.; Le Breton, M.; O'Shea, S.; Bauguitte, S.; Gallagher, M. W.; Bacak, A.; Percival, C. J.

    2012-04-01

    High resolution measurements of hydrogen cyanide (HCN), carbon dioxide (CO2) and methane (CH4) were made over Canada onboard the UK Atmospheric Research Aircraft FAAM BAe-146 from 12 July to 4 August 2011. The observations were made as part of the international BORTAS project which aims to quantify the impact of BOReal forest fires on Tropospheric oxidants over the Atlantic using Aircraft and Satellites. The sorties were aimed at transecting and sampling the outflow from the commonly occurring North American boreal forest fires during the summer months and to investigate and identify the chemical composition and evolution of these plumes. HCN is a distinctive and useful marker for forest fire emissions and it was detected using chemical ionisation mass spectrometry (CIMS). The ionisation scheme employed I- ions which form an adduct with HCN and typical sensitivities of 0.6 counts/ppt have been achieved for sampling at 1 Hz. Elevated CO2 and CH4 are also commonly associated with forest fire emissions and they were measured using the Fast Greenhouse Gas Analyser (FGGA) by Los Gatos Research. This near-IR off-axis integrated cavity output spectroscopy system allowed detection and sampling at 10 Hz. In-flight calibrations revealed a mean accuracy of -0.02 ppmv ± 0.57 ppmv (1σ precision) for CO2 and a mean accuracy of 0.08 ppbv ± 2.31 ppbv (1σ precision) for CH4 for 1Hz observations during the BORTAS campaign. During the 10 flights over the Eastern Canada region (Nova Scotia, New Brunswick, Newfoundland, Ontario and Quebec) several biomass burning plumes were sampled and enhancements in levels of HCN, CO2 and CH4 within these plumes were evident. The observed HCN enhancements inside the plume compared to outside the plume reached up to factor of about 10. For the majority of plumes, a good positive correlation with CO was seen, and in some plumes, CO was observed whilst no HCN was detected, indicating possibly emission sources of anthropogenic activity rather than

  10. Effect of chemical functionalization groups on Zr6-AzoBDC to enhance H2, CH4 storage and CO2 capture: a theoretical investigation

    NASA Astrophysics Data System (ADS)

    Trang, Khung M.; Pham, Hung Q.; Pham-Tran, Nguyen-Nguyen

    2015-09-01

    Grand canonical Monte Carlo (GCMC) simulation combined with the ideal adsorbed solution theory (IAST) and a statistical method were utilized to investigate the effect of functional groups on zirconium oxide based metal-organic frameworks (MOFs) Zr6-AzoBDC (Zr6A) for the gases (H2, CH4) adsorption property and CO2/CH4 selectivity under low pressure. The results showed that phenyl groups containing nitrogen (pyridine, pyrimidine) and thiophene group enhance the gas affinity with MOFs, therefore increasing both gravimetric and volumetric uptake. In addition, this behavior can also cause significantly improved selective capture of CO2 from CO2/CH4 gas mixtures. Among functional groups studied, the sulfonic acid group can potentially improve CH4, CO2 uptake and H2 isosteric heat of adsorption. These findings would play a vital role in designing new materials toward gas adsorption properties.

  11. Palladium-Catalyzed Aerobic Oxidative Dehydrogenation of Cyclohexenes to Substituted Arene Derivatives

    PubMed Central

    Iosub, Andrei V.; Stahl, Shannon S.

    2015-01-01

    A palladium(II) catalyst system has been identified for aerobic dehydrogenation of substituted cyclohexenes to the corresponding arene derivatives. Use of sodium anthraquinone-2-sulfonate (AMS) as a co-catalyst enhances the product yields. A wide range of functional groups are tolerated in the reactions, and the scope and limitations of the method are described. The catalytic dehydrogenation of cyclohexenes is showcased in an efficient route to a phthalimide-based TRPA1 activity modulator. PMID:25734414

  12. Mechanistic studies on a Cu-catalyzed aerobic oxidative coupling reaction with N-phenyl tetrahydroisoquinoline: structure of intermediates and the role of methanol as a solvent.

    PubMed

    Boess, Esther; Sureshkumar, Devarajulu; Sud, Abhishek; Wirtz, Cornelia; Farès, Christophe; Klussmann, Martin

    2011-06-01

    The mechanism of an aerobic copper-catalyzed oxidative coupling reaction with N-phenyl tetrahydroisoquinoline was investigated. The oxidized species formed from the reaction of the amine with the copper catalyst were analyzed by NMR-spectroscopy. An iminium dichlorocuprate was found to be the reactive intermediate and could be structurally characterized by X-ray crystallography. The effect of methanol to effectively stabilize the iminium ion was investigated and shown to be beneficial in an oxidative allylation reaction. PMID:21561084

  13. Long-term measurements of atmospheric trace gases (CO2, CH4, N2O, SF6, CO, H2), O2, and δ13CH4 isotopes at Weybourne Atmospheric Observatory, UK: past, present and future

    NASA Astrophysics Data System (ADS)

    Manning, Andrew C.; Forster, Grant L.; Oram, David E.; Reeves, Claire E.; Pickers, Penelope A.; Barningham, S. Thomas; Sturges, William T.; Bandy, Brian; Nisbet, Euan G.; Lowry, David; Fisher, Rebecca; Fleming, Zoe

    2016-04-01

    The Weybourne Atmospheric Observatory (WAO) is situated on the north Norfolk Coast (52.95°N, 1.13°E) in the United Kingdom and is run by the University of East Anglia (UEA), with support from the UK National Centre for Atmospheric Science (NCAS). In 2016, the WAO became a UK-ICOS (Integrated Carbon Observing System) monitoring station. Since 2008, we have been collecting high-precision long-term in situ measurements of atmospheric carbon dioxide (CO2), oxygen (O2), carbon monoxide (CO) and molecular hydrogen (H2), as well as regular bag sampling for δ13CH4. In early 2013, the measurement of atmospheric methane (CH4) commenced, and nitrous oxide (N2O) and sulphur hexafluoride (SF6) began in 2014. We summarise the CO2, O2, CH4, N2O, SF6, CO, H2 and δ13CH4 measurements made to date and highlight some key features observed (e.g. seasonal cycles, long-term trends, pollution events and deposition events). We summarise how the long-term measurements fit into other broader projects which have helped to support the long term time-series at WAO over the years, and highlight how we contribute to broader global atmospheric observation networks.

  14. Salinity-induced hydrate dissociation: A mechanism for recent CH4 release on Mars

    SciTech Connect

    Madden, Megan Elwood; Ulrich, Shannon M; Onstott, Tullis; Phelps, Tommy Joe

    2007-01-01

    Recent observations of CH4 in the Martian atmosphere suggest that CH4 has been added relatively recently. Several mechanisms for recent CH4 release have been proposed including subsurface biological methanogenesis, abiogenic hydrothermal and/or volcanic activity, dissociation of CH4 hydrates, atmospheric photolysis, or addition of organics via bolide impact. This study examines the effects of increasing salinity on gas hydrate stability and compares estimates of the Martian geothermal gradient to CH4 and CO2 hydrate stability fields in the presence of high salinity brines. The results demonstrate that salinity increases alone result in a significant decrease in the predicted hydrate stability zone within the Martian subsurface and may be a driving force in CH4 hydrate destabilization. Active thermal and/or pressure fluctuations are not required in order for CH4 hydrates to be the source of atmospheric CH4.

  15. Carbon kinetic isotope effect in the reaction of CH4 with Cl atoms

    NASA Astrophysics Data System (ADS)

    Saueressig, G.; Bergamaschi, P.; Crowley, J. N.; Fischer, H.; Harris, G. W.

    1995-05-01

    The carbon kinetic isotope effect in the reaction between Cl and CH4 (KIE(sub Cl)) has been measured using tunable diode laser absorption spectroscopy to determine (13)CH4/(12)CH4 ratios. Cl atoms were generated by the irradition of Cl2 in static mixtures of Cl2/CH4/N2 or Cl2/CH4/N2/O2. Both methods resulted in a (KIE(sub Cl)) of 1.066 +/- 0.002 at 297 K. The KIE(sub Cl) displayed a slight temperature dependence, increasing to 1.075 +/- 0.005 at 223 K. This result suggests a significant influence of the title reaction on the stratospheric CH4 isotopic composition and may help to resolve discrepancies between measurements of stratospheric (13)CH4/(12)CH4 profiles and laboratory measurements of KIE(sub OH).

  16. Divergent role of nitric oxide in insulin-stimulated aortic vasorelaxation between low- and high-intrinsic aerobic capacity rats.

    PubMed

    Crissey, Jacqueline M; Padilla, Jaume; Vieira-Potter, Victoria J; Thorne, Pamela K; Koch, Lauren G; Britton, Steven L; Thyfault, John P; Laughlin, M Harold

    2015-07-01

    Low-intrinsic aerobic capacity is associated with increased risk for cardiovascular and metabolic diseases and is a strong predictor of early mortality. The effects of intrinsic aerobic capacity on the vascular response to insulin are largely unknown. We tested the hypothesis that rats selectively bred for a low capacity to run (LCR) exhibit vascular dysfunction and impaired vascular reactivity to insulin compared to high capacity running (HCR) rats. Mature female LCR (n = 21) and HCR (n = 17) rats were maintained under sedentary conditions, and in vitro thoracic aortic vascular function was assessed. LCR exhibited greater body mass (13%), body fat (35%), and subcutaneous, perigonadal, and retroperitoneal adipose tissue mass, than HCR. During an intraperitoneal glucose tolerance test, glucose area under the curve (AUC) was not different but insulin AUC was 2-fold greater in LCR than HCR. Acetylcholine and insulin-stimulated aortic vasorelaxation was significantly greater in LCR (65.2 ± 3.8%, and 32.7 ± 4.1%) than HCR (55.0 ± 3.3%, and 16.7 ± 2.8%). Inhibition of nitric oxide synthase (NOS) with L-NAME entirely abolished insulin-mediated vasorelaxation in the aorta of LCR, with no effect in HCR. LCR rats exhibited greater expression of Insulin Receptor protein, lower Endothelin Receptor-A protein, a down-regulation of transcripts for markers of immune cell infiltration (CD11C, CD4, and F4/80) and up-regulation of pro-atherogenic inflammatory genes (VCAM-1 and MCP-1) in the aorta wall. Contrary to our hypothesis, low-aerobic capacity was associated with enhanced aortic endothelial function and NO-mediated reactivity to insulin, despite increased adiposity and evidence of whole body insulin resistance. PMID:26197933

  17. Ultrafine MnO2 nanoparticles decorated on graphene oxide as a highly efficient and recyclable catalyst for aerobic oxidation of benzyl alcohol.

    PubMed

    Hu, Zonggao; Zhao, Yafei; Liu, Jindun; Wang, Jingtao; Zhang, Bing; Xiang, Xu

    2016-12-01

    The highly active and selective aerobic oxidation of aromatic alcohols over earth-abundant, inexpensive and recyclable catalysts is highly desirable. We fabricated herein MnO2/graphene oxide (GO) composites by a facile in-situ growth approach at room temperature and used them in selective aerobic oxidation of benzyl alcohol to benzaldehyde. TEM, XRD, FTIR, XPS and N2 adsorption/desorption analysis were employed to systematically investigate the morphology, particle size, structure and surface properties of the catalysts. The 96.8% benzyl alcohol conversion and 100% benzaldehyde selectivity over the MnO2/GO (10/100) catalyst with well dispersive ultrafine MnO2 nanoparticles (ca. 3nm) can be obtained within 3h under 383K. Simultaneously, no appreciable loss of activity and selectivity occurred after recycling use up to six times. Due to their significant low cost, excellent catalytic performance, the MnO2/GO composites have huge application prospect in organic synthesis. PMID:27544446

  18. Methanogenic Conversion of CO2 Into CH4

    SciTech Connect

    Stevens, S.H., Ferry, J.G., Schoell, M.

    2012-05-06

    This SBIR project evaluated the potential to remediate geologic CO2 sequestration sites into useful methane gas fields by application of methanogenic bacteria. Such methanogens are present in a wide variety of natural environments, converting CO2 into CH4 under natural conditions. We conclude that the process is generally feasible to apply within many of the proposed CO2 storage reservoir settings. However, extensive further basic R&D still is needed to define the precise species, environments, nutrient growth accelerants, and economics of the methanogenic process. Consequently, the study team does not recommend Phase III commercial application of the technology at this early phase.

  19. Large-scale synthesis of ultrathin tungsten oxide nanowire networks: an efficient catalyst for aerobic oxidation of toluene to benzaldehyde under visible light.

    PubMed

    Bai, Hua; Yi, Wencai; Liu, Jingyao; Lv, Qing; Zhang, Qing; Ma, Qiang; Yang, Haifeng; Xi, Guangcheng

    2016-07-14

    As a very important chemical raw material, the selective formation of benzaldehyde from toluene at preparative or industrial levels requires the use of highly corrosive chlorine and high reaction temperatures, which severely corrodes equipment, pollutes the environment, and consumes a lot of energy. Herein, we report a robust and highly active catalyst for the benzaldehyde evolution reaction that is constructed by the surfactant-free growth of oxygen vacancy-rich W18O49 ultrathin nanowire networks. Under atmospheric pressure and visible-light irradiation, the new catalyst can selectively (92% selectivity) catalyze the aerobic oxidation of toluene to benzaldehyde with yields of above 95%. PMID:27357748

  20. Consequence of forest-to-pasture conversion on CH4 fluxes in the Brazilian Amazon Basin

    NASA Astrophysics Data System (ADS)

    Steudler, Paul A.; Melillo, Jerry M.; Feigl, Brigitte J.; Neill, Christopher; Piccolo, Marisa C.; Cerri, Carlos C.

    1996-08-01

    Methane (CH4) fluxes between soils and the atmosphere were measured in two tropical forest-to-pasture chronosequences in the state of Rondônia, Brazil. Forest soils always consumed atmospheric CH4 with maximum uptake rates in the dry season. Pasture soils consumed atmospheric CH4 during the dry season, but at lower rates than those in the forests. When soil moisture increased in the pasture soils, they became a source of CH4 to the atmosphere. Integrated over the year, forest soils were a net sink of approximately 470 mg CH4-C/m2, while pastures were a net source of about 270 mg CH4-C/m2. Thus forest-to-pasture conversion resulted in a net source of CH4 from the soil of about 1 g CH4/m2/yr. The total pasture-related CH4 release for the entire Brazilian Amazon increased from 0.8 Tg CH4 in 1970 to about 2.5 Tg CH4 in 1990, with a maximum of 3.1 Tg CH4/yr in 1988. Soils accounted for a small part (about 5%) of the total CH4 release from the basin, while biomass burning and cattle emissions accounted for 95%. The average rate of increase in CH4 emission from pastures was about 0.2 Tg CH4/yr between 1975 and 1988. This represents between 12% and 14% of the global average rate of change in tropospheric CH4 content for this time period.

  1. Regional Variation of CH4 and N2 Production Processes in the Deep Aquifers of an Accretionary Prism

    PubMed Central

    Matsushita, Makoto; Ishikawa, Shugo; Nagai, Kazushige; Hirata, Yuichiro; Ozawa, Kunio; Mitsunobu, Satoshi; Kimura, Hiroyuki

    2016-01-01

    Accretionary prisms are mainly composed of ancient marine sediment scraped from the subducting oceanic plate at a convergent plate boundary. Large amounts of anaerobic groundwater and natural gas, mainly methane (CH4) and nitrogen gas (N2), are present in the deep aquifers associated with an accretionary prism; however, the origins of these gases are poorly understood. We herein revealed regional variations in CH4 and N2 production processes in deep aquifers in the accretionary prism in Southwest Japan, known as the Shimanto Belt. Stable carbon isotopic and microbiological analyses suggested that CH4 is produced through the non-biological thermal decomposition of organic matter in the deep aquifers in the coastal area near the convergent plate boundary, whereas a syntrophic consortium of hydrogen (H2)-producing fermentative bacteria and H2-utilizing methanogens contributes to the significant production of CH4 observed in deep aquifers in midland and mountainous areas associated with the accretionary prism. Our results also demonstrated that N2 production through the anaerobic oxidation of organic matter by denitrifying bacteria is particularly prevalent in deep aquifers in mountainous areas in which groundwater is affected by rainfall. PMID:27592518

  2. Uncertainties in modelling CH4 emissions from northern wetlands in glacial climates: effect of hydrological model and CH4 model structure

    NASA Astrophysics Data System (ADS)

    Berrittella, C.; van Huissteden, J.

    2009-07-01

    Methane (CH4) fluxes from northern wetlands may have influenced atmospheric CH4 concentrations at climate warming phases during the last 800 000 years and during the present global warming. Including these CH4 fluxes in earth system models is essential to understand feedbacks between climate and atmospheric composition. Attempts to model CH4 fluxes from wetlands have previously been undertaken using various approaches. Here, we test a process-based wetland CH4 flux model (PEATLAND-VU) which includes details of soil-atmosphere CH4 transport. The model has been used to simulate CH4 emissions from continental Europe in previous glacial climates and the current climate. This paper presents results regarding the sensitivity of modeling glacial terrestrial CH4 fluxes to (a) basic tuning parameters of the model, (b) different approaches in modeling of the water table, and (c) model structure. In order to test the model structure, PEATLAND-VU was compared to a simpler modeling approach based on wetland primary production estimated from a vegetation model (BIOME 3.5). The tuning parameters are the CH4 production rate from labile organic carbon and its temperature sensitivity. The modelled fluxes prove comparatively insensitive to hydrology representation, while sensitive to microbial parameters and model structure. Glacial climate emissions are also highly sensitive to assumptions about the extent of ice cover and exposed seafloor. Wetland expansion over low relief exposed seafloor areas have compensated for a decrease of wetland area due to continental ice cover.

  3. Uncertainties in modeling CH4 emissions from northern wetlands in glacial climates: effect of hydrological model and CH4 model structure

    NASA Astrophysics Data System (ADS)

    Berrittella, C.; van Huissteden, J.

    2009-03-01

    Methane (CH4) fluxes from northern wetlands may have influenced atmospheric CH4 concentrations at climate warming phases during the 800 000 years and at present global warming. Including these CH4 fluxes in earth system models is essential to understand feedbacks between climate and atmospheric composition. Attempts to model CH4 fluxes from wetlands have been undertaken previously using various approaches. Here, we test a process-based wetland CH4 flux model (PEATLAND-VU) which includes details of soil-atmosphere CH4 transport. The model has been used to simulate CH4 emissions from continental Europe in different glacial climates and the present climate. This paper displays results on the sensitivity of modeling glacial terrestrial CH4 fluxes to basic tuning parameters of the model, to different approaches in modeling of the water table, and to model structure. For testing the model structure, PEATLAND-VU has been compared to a simpler modeling approach based on wetland primary production estimated from a vegetation model (BIOME). The tuning parameters are the CH4 production rate from labile organic carbon and its temperature sensitivity. The modelled fluxes prove comparatively insensitive to hydrology representation, and sensitive to microbial parameters and model structure. Glacial climate emissions are also highly sensitive to assumptions on the extent of ice cover and exposed seafloors. Wetland expansion on low relief exposed seafloor areas, may have compensated for a decrease of wetland area due to continental ice cover.

  4. Metallic Sn spheres and SnO2@C core-shells by anaerobic and aerobic catalytic ethanol and CO oxidation reactions over SnO2 nanoparticles

    PubMed Central

    Kim, Won Joo; Lee, Sung Woo; Sohn, Youngku

    2015-01-01

    SnO2 has been studied intensely for applications to sensors, Li-ion batteries and solar cells. Despite this, comparatively little attention has been paid to the changes in morphology and crystal phase that occur on the metal oxide surface during chemical reactions. This paper reports anaerobic and aerobic ethanol and CO oxidation reactions over SnO2 nanoparticles (NPs), as well as the subsequent changes in the nature of the NPs. Uniform SnO2@C core-shells (10 nm) were formed by an aerobic ethanol oxidation reaction over SnO2 NPs. On the other hand, metallic Sn spheres were produced by an anaerobic ethanol oxidation reaction at 450 °C, which is significantly lower than that (1200 °C) used in industrial Sn production. Anaerobic and aerobic CO oxidation reactions were also examined. The novelty of the methods for the production of metallic Sn and SnO2@C core-shells including other anaerobic and aerobic reactions will contribute significantly to Sn and SnO2-based applications. PMID:26300041

  5. Organization of the Escherichia coli aerobic enzyme complexes of oxidative phosphorylation in dynamic domains within the cytoplasmic membrane

    PubMed Central

    Erhardt, Heiko; Dempwolff, Felix; Pfreundschuh, Moritz; Riehle, Marc; Schäfer, Caspar; Pohl, Thomas; Graumann, Peter; Friedrich, Thorsten

    2014-01-01

    The Escherichia coli cytoplasmic membrane contains the enzyme complexes of oxidative phosphorylation (OXPHOS). Not much is known about their supramolecular organization and their dynamics within the membrane in this model organism. In mitochondria and other bacteria, it was demonstrated by nondenaturing electrophoretic methods and electron microscopy that the OXPHOS complexes are organized in so-called supercomplexes, stable assemblies with a defined number of the individual enzyme complexes. To investigate the organization of the E. coli enzyme complexes of aerobic OXPHOS in vivo, we established fluorescent protein fusions of the NADH:ubiquinone oxidoreductase, the succinate:ubiquinone oxidoreductase, the cytochrome bd-I, and the cytochrome bo3 terminal oxidases, and the FoF1 ATP-synthase. The fusions were integrated in the chromosome to prevent artifacts caused by protein overproduction. Biochemical analysis revealed that all modified complexes were fully assembled, active, and stable. The distribution of the OXPHOS complexes in living cells was determined using total internal reflection fluorescence microscopy. The dynamics within the membrane were detected by fluorescence recovery after photobleaching. All aerobic OXPHOS complexes showed an uneven distribution in large mobile patches within the E. coli cytoplasmic membrane. It is discussed whether the individual OXPHOS complexes are organized as clustered individual complexes, here called “segrazones.” PMID:24729508

  6. Mechanically-biologically treated municipal solid waste as a support medium for microbial methane oxidation to mitigate landfill greenhouse emissions.

    PubMed

    Einola, Juha-Kalle M; Karhu, A Elina; Rintala, Jukka A

    2008-01-01

    The residual fraction of mechanically-biologically treated municipal solid waste (MBT residual) was studied in the laboratory to evaluate its suitability and environmental compatibility as a support medium in methane (CH(4)) oxidative biocovers for the mitigation of greenhouse gas emissions from landfills. Two MBT residuals with 5 and 12 months total (aerobic) biological stabilisation times were used in the study. MBT residual appeared to be a favourable medium for CH(4) oxidation as indicated by its area-based CH(4) oxidation rates (12.2-82.3 g CH(4) m(-2) d(-1) at 2-25 degrees C; determined in CH(4)-sparged columns). The CH(4) oxidation potential (determined in batch assays) of the MBT residuals increased during the 124 d column experiment, from <1.6 to a maximum of 104 microg CH(4) g(dw)(-1) h(-1) (dw=dry weight) at 5 degrees C and 578 microg CH(4) g(dw)(-1) h(-1) at 23 degrees C. Nitrous oxide (N(2)O) production in MBT residual (<15 microg N(2)O kg(dw)(-1) d(-1) in the CH(4) oxidative columns) was at the lower end of the range of N(2)O emissions reported for landfills and non-landfill soils, and insignificant as a greenhouse gas source. Also, anaerobic gas production (25.6 l kg(dw)(-1) during 217 d) in batch assays was low, indicating biological stability of the MBT residual. The electrical conductivities (140-250 mS m(-1)), as well as the concentrations of zinc (3.0 mg l(-1)), copper (0.5 mg l(-1)), arsenic (0.3 mg l(-1)), nickel (0.1 mg l(-1)) and lead (0.1 mg l(-1)) in MBT residual eluates from a leaching test (EN-12457-4) with a liquid/solid (L/S) ratio of 10:1, suggest a potential for leachate pollutant emissions which should be considered in plans to utilise MBT residual. In conclusion, the laboratory experiments suggest that MBT residual can be utilised as a support medium for CH(4) oxidation, even at low temperatures, to mitigate greenhouse gas emissions from landfills. PMID:17360174

  7. Site Specific Landfill CH4 Emissions: Shortcomings of National GHG Inventory Guidelines and a New Process-Based Approach Linked to Climate and Soil Microclimate

    NASA Astrophysics Data System (ADS)

    Bogner, J. E.; Spokas, K.; Corcoran, M.

    2012-12-01

    Current (2006) IPCC national GHG inventory guidelines for landfill CH4, which estimate CH4 generation from the mass of waste in place, have high uncertainties, cannot be reliably related to measured emissions at specific sites, and lack comprehensive field validation. Moreover, measured landfill CH4 emissions vary over a wide range from >1000 g/m2/d down to negative values (uptake of atmospheric CH4). Literature over the last decade has emphasized that the major factors controlling emissions in these highly managed soil systems are gaseous transport rates as affected by the thickness and physical properties of cover soils, methanotrophic CH4 oxidation in cover materials as a function of seasonal soil microclimate. and the presence or absence of engineered gas extraction. Thus we developed and field validated a new site specific annual inventory model that incorporates specific soil profile properties and soil microclimate modeling coupled to 0.5° scale global climatic models. Based on 1D diffusion, CALMIM (California Landfill Methane Inventory Model) is a freely available JAVA tool which models a typical annual cycle for CH4 emissions from site specific daily, intermediate, and final landfill cover designs. This new approach, which is compliant with IPCC Tier III criteria, was originally field validated at two California sites (Monterey County; Los Angeles County), with limited field validation at three additional California sites. In addition to regional defaults for inventory purposes, CALMIM permits user selectable parameters and boundary conditions for more rigorous site specific applications where detailed CH4 emissions, meteorological, and soil microclimate data exist. We report here on improvements and expanded international field validation for CALMIM 5.2 in collaboration with research groups in the U.S., Europe, Africa, Asia, and Australia.odeled and measured annual cycle of landfill CH4 emissions for Austrian site. Cover consists of 50 cm sand & gravel

  8. Observations of middle atmospheric CH4 and N2O vertical distributions by the Spacelab 1 grille spectrometer

    NASA Astrophysics Data System (ADS)

    Muller, C.; Vercheval, J.; Ackerman, M.; Lippens, C.; Laurent, J.

    1985-10-01

    Methane and nitrous oxide have been observed by limb absorption spectrometry using the Spacelab One grille spectrometer. The CH4 nu3 band is observed with a 0.1/cm resolution up to 80 km while N2O can be seen up to 52 km in strong lines of its nu3 band. The values are compared, where possible, with previous observations and are in agreement with rocket determinations.

  9. Aqueous aerobic oxidation of alkyl arenes and alcohols catalyzed by copper(II) phthalocyanine supported on three-dimensional nitrogen-doped graphene at room temperature.

    PubMed

    Mahyari, Mojtaba; Laeini, Mohammad Sadegh; Shaabani, Ahmad

    2014-07-25

    Copper(ii) tetrasulfophthalocyanine supported on three-dimensional nitrogen-doped graphene-based frameworks was synthesized and introduced as a bifunctional catalyst for selective aerobic oxidation of alkyl arenes and alcohols to the corresponding carbonyl compounds. The ease of catalyst separation, high turnover, low catalyst loading and recyclability could potentially render it applicable in industrial setting. PMID:24912023

  10. One-pot synthesis of amides by aerobic oxidative coupling of alcohols or aldehydes with amines using supported gold and base as catalysts.

    PubMed

    Kegnæs, Søren; Mielby, Jerrik; Mentzel, Uffe V; Jensen, Thomas; Fristrup, Peter; Riisager, Anders

    2012-02-28

    Synthesis of amides by aerobic oxidative coupling of alcohols or aldehydes with amines via intermediate formation of methyl esters is highly efficient and selective when using a catalytic system comprised of supported gold nanoparticles and added base in methanol. PMID:22274843

  11. Large-scale synthesis of ultrathin tungsten oxide nanowire networks: an efficient catalyst for aerobic oxidation of toluene to benzaldehyde under visible light

    NASA Astrophysics Data System (ADS)

    Bai, Hua; Yi, Wencai; Liu, Jingyao; Lv, Qing; Zhang, Qing; Ma, Qiang; Yang, Haifeng; Xi, Guangcheng

    2016-07-01

    As a very important chemical raw material, the selective formation of benzaldehyde from toluene at preparative or industrial levels requires the use of highly corrosive chlorine and high reaction temperatures, which severely corrodes equipment, pollutes the environment, and consumes a lot of energy. Herein, we report a robust and highly active catalyst for the benzaldehyde evolution reaction that is constructed by the surfactant-free growth of oxygen vacancy-rich W18O49 ultrathin nanowire networks. Under atmospheric pressure and visible-light irradiation, the new catalyst can selectively (92% selectivity) catalyze the aerobic oxidation of toluene to benzaldehyde with yields of above 95%.As a very important chemical raw material, the selective formation of benzaldehyde from toluene at preparative or industrial levels requires the use of highly corrosive chlorine and high reaction temperatures, which severely corrodes equipment, pollutes the environment, and consumes a lot of energy. Herein, we report a robust and highly active catalyst for the benzaldehyde evolution reaction that is constructed by the surfactant-free growth of oxygen vacancy-rich W18O49 ultrathin nanowire networks. Under atmospheric pressure and visible-light irradiation, the new catalyst can selectively (92% selectivity) catalyze the aerobic oxidation of toluene to benzaldehyde with yields of above 95%. Electronic supplementary information (ESI) available: Experimental procedure, XRD patterns, TEM and HRTEM images, energy-dispersive X-ray spectra, UV-vis spectra, X-ray photoelectron spectroscopy (XPS), and EDS. See DOI: 10.1039/c6nr02949c

  12. Isolating wetland CH4 emissions using the additional constraints of δ13CH4, and C2H6 in a inverse modeling framework

    NASA Astrophysics Data System (ADS)

    Guillermo Nuñez Ramirez, Tonatiuh; Marshall, Julia; Houweling, Sander; Dlugokencky, Edward J.; Worthy, Douglas E. J.; Vaughn, Bruce; Simpson, Isobel; White, James; Brand, Willi A.; Sasakawa, Motoki; Nichol, Silvia; Ramonet, Michel; Tyler, Stanley C.; Hueber, Jacques; Helmig, Detlev; Read, Katie; Punjabi, Schalini; Vanni Gatti, Luciana; Krummel, Paul; Heimann, Martin

    2015-04-01

    Wetlands are the largest single source of atmospheric methane (CH_4). However, estimates of their relative contribution to the atmospheric CH4 budget are highly uncertain. Models of CH4 fluxes from wetlands, which reflect our understanding of the processes driving these fluxes, disagree strongly in their estimates of the total contribution of wetlands to the CH4 budget and in the variability of the fluxes in space and time. Atmospheric CH4 observations can provide a top-down constraint on wetland CH4 flux estimates. Results from atmospheric inverse modeling studies highlight the importance of tropical wetlands in driving interannual variability of atmospheric CH_4. Nevertheless, atmospheric observations in the tropics are scarce, with large areas of strong emissions not covered by the atmospheric observation network. Furthermore, the Bayesian framework, often used in atmospheric inverse modeling, preferentially projects signals onto spatiotemporal regions with large a-priori uncertainty, which is the case of tropical wetlands. Since a large lack of knowledge exists as well for other non-wetland sources of atmospheric CH_4, signals from these could be wrongly allocated to tropical wetlands. The CH4 stable carbon isotope signal (δ13CH_4) and co-emitted species such as ethane (C_2H_6) can provide additional constraints which may be use to discriminate wetland from non-wetland CH4 emissions. We describe the set-up of an inverse modeling framework based on the Jena Inversion System and the TM3 transport model that optimizes CH4 fluxes to fit the observed atmospheric CH_4, δ13CH_4, and C_2H6 signals. The fluxes are optimized with the constraint that each source process was assigned a characteristic range of δ13CH4 signals and methane-to-ethane ratios (MERs). An additional characteristic of our set-up is that no seasonal or interannual variability was included in the wetland a-priori estimate to ensure that all variability is derived exclusively from observations. A

  13. New evidence for Cu-decorated binary-oxides mediating bacterial inactivation/mineralization in aerobic media.

    PubMed

    Rtimi, S; Pulgarin, C; Bensimon, M; Kiwi, J

    2016-08-01

    Binary oxide semiconductors TiO2-ZrO2 and Cu-decorated TiO2-ZrO2 (TiO2-ZrO2-Cu) uniform films were sputtered on polyester (PES). These films were irradiated under low intensity solar simulated light and led to bacterial inactivation in aerobic and anaerobic media as evaluated by CFU-plate counting. But bacterial mineralization was only induced by TiO2-ZrO2-Cu in aerobic media. The highly oxidative radicals generated on the films surface under light were identified by the use of appropriate scavengers. The hole generated on the TiO2-ZrO2 films is shown to be the main specie leading to bacterial inactivation. TiO2-ZrO2 and Cu-decorated TiO2-ZrO2 films release Zr and Ti <1ppb and Cu 4.6ppb/cm(2) as determined by inductively coupled plasma mass spectrometry (ICP-MS) This level is far below the citotoxicity permitted level allowed for mammalian cells suggesting that bacterial disinfection proceeds through an oligodynamic effect. By Fourier transform attenuated infrared spectroscopy (ATR-FTIR) the systematic shift of the predominating νs(CH2) vibrational-rotational peak making up most of the bacterial cell-wall content in C was monitored. Based on this evidence a mechanism suggested leading to CH bond stretching followed by cell lysis and cell death. Bacterial inactivation cycling was observed on TiO2-ZrO2-Cu showing the stability of these films leading to bacterial inactivation. PMID:27088192

  14. Seasonal CH4 and N2O emissions and plant growth characteristics of several cultivars in direct seeded rice systems

    NASA Astrophysics Data System (ADS)

    Simmonds, M.; Anders, M. M.; Adviento-Borbe, M. A.; Van Kessel, C.; McClung, A.; Linquist, B.

    2014-12-01

    Understanding cultivar effects on field greenhouse gas (GHG) emissions in rice (Oryza sativa L.) systems is needed to improve the accuracy of predictive models used for estimating GHG emissions, and to determine to what extent choice of cultivar may have on GHG mitigation. We compared CH4 and N2O emissions, global warming potential (GWP = N2O + CH4), yield-scaled GWP (GWPY = GWP Mg-1 grain), and plant growth characteristics of 8 cultivars within 4 study sites in California and Arkansas. Seasonal CH4 emissions differed between cultivars by a factor of 2.1 and 1.3 at one California and one Arkansas site, respectively. Nitrous oxide emissions were negligible, comprised <10% of GWP, and were not different among cultivars. When sites and cultivars were pooled, and data were normalized to site averages, there was a positive correlation (r = 0.33) between root biomass at heading and seasonal CH4 emissions, but no correlation with shoot biomass at heading, or grain or straw biomass at maturity. Although differences in GWP and GWPY were observed, the consistency of some of the trends was variable across sites, indicating the importance of the genotype x environment interaction. While no high-yielding and low CH4-emitting cultivars were identified at the California sites, among the Southern varieties tested at the Arkansas site, the lowest emitting cultivar had the highest yield. This highlights the potential for breeding high-yielding varieties with low GWP, the ideal scenario to achieve low GWPY due to simultaneously mitigating GHG emissions and improving global food security.

  15. Combining Microbial Enzyme Kinetics Models with Light Use Efficiency Models to Predict CO2 and CH4 Ecosystem Exchange from Flooded and Drained Peatland Systems

    NASA Astrophysics Data System (ADS)

    Oikawa, P. Y.; Jenerette, D.; Knox, S. H.; Sturtevant, C. S.; Verfaillie, J. G.; Baldocchi, D. D.

    2014-12-01

    Under California's Cap-and-Trade program, companies are looking to invest in land-use practices that will reduce greenhouse gas (GHG) emissions. The Sacramento-San Joaquin River Delta is a drained cultivated peatland system and a large source of CO2. To slow soil subsidence and reduce CO2 emissions, there is growing interest in converting drained peatlands to wetlands. However, wetlands are large sources of CH4 that could offset CO2-based GHG reductions. The goal of our research is to provide accurate measurements and model predictions of the changes in GHG budgets that occur when drained peatlands are restored to wetland conditions. We have installed a network of eddy covariance towers across multiple land use types in the Delta and have been measuring CO2 and CH4 ecosystem exchange for multiple years. In order to upscale these measurements through space and time we are using these data to parameterize and validate a process-based biogeochemical model. To predict gross primary productivity (GPP), we are using a simple light use efficiency (LUE) model which requires estimates of light, leaf area index and air temperature and can explain 90% of the observed variation in GPP in a mature wetland. To predict ecosystem respiration we have adapted the Dual Arrhenius Michaelis-Menten (DAMM) model. The LUE-DAMM model allows accurate simulation of half-hourly net ecosystem exchange (NEE) in a mature wetland (r2=0.85). We are working to expand the model to pasture, rice and alfalfa systems in the Delta. To predict methanogenesis, we again apply a modified DAMM model, using simple enzyme kinetics. However CH4 exchange is complex and we have thus expanded the model to predict not only microbial CH4 production, but also CH4 oxidation, CH4 storage and the physical processes regulating the release of CH4 to the atmosphere. The CH4-DAMM model allows accurate simulation of daily CH4 ecosystem exchange in a mature wetland (r2=0.55) and robust estimates of annual CH4 budgets. The LUE

  16. Annual Greenhouse Gas (CO2, CH4, and N2O) Fluxes Via Ebullition from a Temperate Emergent Wetland

    NASA Astrophysics Data System (ADS)

    Mcnicol, G.; Sturtevant, C. S.; Knox, S. H.; Baldocchi, D. D.; Silver, W. L.

    2014-12-01

    Quantifying wetland greenhouse gas exchange is necessary to evaluate their potential for mitigating climate change via carbon sequestration. However measuring greenhouse gas fluxes of carbon dioxide (CO2), methane (CH4), and nitrous oxide (N2O) in wetlands is difficult due to high spatial and temporal variability, and multiple transport pathways of emission. Transport of biogenic soil gas via highly sporadic ebullition (bubbling) events is often ignored or quantified poorly in wetland greenhouse gas budgets, but can rapidly release large volumes of gas to the atmosphere. To quantify a robust annual ebullition flux we measured rates continuously for a year (2013-2014) using custom-built chambers deployed in a restored emergent wetland located in the Sacramento-San Joaquin Delta, CA. We combined ebullition flux rates with observations of gas concentrations to estimate annual ebullition emissions of CO2, CH4, and N2O and compare flux rates to whole-ecosystem exchange of CO2 and CH4 measured simultaneously by eddy covariance.Mean ebullition flux rates were 18.3 ± 5.6 L m-2 yr-1. Ebullition CH4 concentrations were very high and ranged from 23-76 % with a mean of 47 ± 2.9 %; CO2 concentrations were lower and ranged from 0.7-6.6 % with a mean of 2.8 ± 0.3 %; N2O concentrations were below atmospheric concentrations and ranged from 130-389 ppb(v) with a mean of 257 ± 13 ppb(v). We calculated well-constrained annual ebullition fluxes of: 6.2 ± 1.9 g CH4 m-2 yr-1, 1.0 ± 0.3 g CO2 m-2 yr-1 and 9.3 ± 2.8 mg N2O m-2 yr-1. Methane emissions via ebullition were very large, representing 15-25 % of total wetland CH4 emissions measured at this site, whereas ebullition released only relatively small quantities of CO2 and N2O. Our results demonstrate that large releases of CH4 via ebullition from open water surfaces can be a significant component of restored wetland greenhouse gas budgets.

  17. Temporal and spatial variations of soil CO2, CH4 and N2O fluxes at three differently managed grasslands

    NASA Astrophysics Data System (ADS)

    Imer, D.; Merbold, L.; Eugster, W.; Buchmann, N.

    2013-09-01

    A profound understanding of temporal and spatial variabilities of soil carbon dioxide (CO2), methane (CH4) and nitrous oxide (N2O) fluxes between terrestrial ecosystems and the atmosphere is needed to reliably quantify these fluxes and to develop future mitigation strategies. For managed grassland ecosystems, temporal and spatial variabilities of these three soil greenhouse gas (GHG) fluxes occur due to changes in environmental drivers as well as fertilizer applications, harvests and grazing. To assess how such changes affect soil GHG fluxes at Swiss grassland sites, we studied three sites along an altitudinal gradient that corresponds to a management gradient: from 400 m a.s.l. (intensively managed) to 1000 m a.s.l. (moderately intensive managed) to 2000 m a.s.l. (extensively managed). The alpine grassland was included to study both effects of extensive management on CH4 and N2O fluxes and the different climate regime occurring at this altitude. Temporal and spatial variabilities of soil GHG fluxes and environmental drivers on various timescales were determined along transects of 16 static soil chambers at each site. All three grasslands were N2O sources, with mean annual soil fluxes ranging from 0.15 to 1.28 nmol m-2 s-1. Contrastingly, all sites were weak CH4 sinks, with soil uptake rates ranging from -0.56 to -0.15 nmol m-2 s-1. Mean annual soil and plant respiration losses of CO2, measured with opaque chambers, ranged from 5.2 to 6.5 μmol m-2 s-1. While the environmental drivers and their respective explanatory power for soil N2O emissions differed considerably among the three grasslands (adjusted r2 ranging from 0.19 to 0.42), CH4 and CO2 soil fluxes were much better constrained (adjusted r2 ranging from 0.46 to 0.80) by soil water content and air temperature, respectively. Throughout the year, spatial heterogeneity was particularly high for soil N2O and CH4 fluxes. We found permanent hot spots for soil N2O emissions as well as locations of permanently lower

  18. Investigation of oxidative phosphorylation in continuous cultures. A non-equilibrium thermodynamic approach to energy transduction for Escherichia coli in aerobic condition

    NASA Astrophysics Data System (ADS)

    Ghafuri, Mohazabeh; Nosrati, Mohsen; Hosseinkhani, Saman

    2015-03-01

    Adenosine triphosphate (ATP) production in living cells is very important. Different researches have shown that in terms of mathematical modeling, the domain of these investigations is essentially restricted. Recently the thermodynamic models have been suggested for calculation of the efficiency of oxidative phosphorylation process and rate of energy loss in animal cells using chemiosmotic theory and non-equilibrium thermodynamics equations. In our previous work, we developed a mathematical model for mitochondria of animal cells. In this research, according to similarities between oxidative phosphorylation process in microorganisms and animal cells, Golfar's model was developed to predict the non-equilibrium thermodynamic behavior of the oxidative phosphorylation process for bacteria in aerobic condition. With this model the rate of energy loss, P/O ratio, and efficiency of oxidative phosphorylation were calculated for Escherichia coli in aerobic condition. The results then were compared with experimental data given by other authors. The thermodynamic model had an acceptable agreement with the experimental data.

  19. Derivation of tropospheric methane from TCCON CH4 and HF total column observations

    NASA Astrophysics Data System (ADS)

    Saad, K. M.; Wunch, D.; Toon, G. C.; Bernath, P.; Boone, C.; Connor, B.; Deutscher, N. M.; Griffith, D. W. T.; Kivi, R.; Notholt, J.; Roehl, C.; Schneider, M.; Sherlock, V.; Wennberg, P. O.

    2014-09-01

    The Total Carbon Column Observing Network (TCCON) is a global ground-based network of Fourier transform spectrometers that produce precise measurements of column-averaged dry-air mole fractions of atmospheric methane (CH4). Temporal variability in the total column of CH4 due to stratospheric dynamics obscures fluctuations and trends driven by tropospheric transport and local surface fluxes that are critical for understanding CH4 sources and sinks. We reduce the contribution of stratospheric variability from the total column average by subtracting an estimate of the stratospheric CH4 derived from simultaneous measurements of hydrogen fluoride (HF). HF provides a proxy for stratospheric CH4 because it is strongly correlated to CH4 in the stratosphere, has an accurately known tropospheric abundance (of zero), and is measured at most TCCON stations. The stratospheric partial column of CH4 is calculated as a function of the zonal and annual trends in the relationship between CH4 and HF in the stratosphere, which we determine from ACE-FTS satellite data. We also explicitly take into account the CH4 column averaging kernel to estimate the contribution of stratospheric CH4 to the total column. The resulting tropospheric CH4 columns are consistent with in situ aircraft measurements and augment existing observations in the troposphere.

  20. Search of CH4 around the mud volcanism areas on Mars

    NASA Astrophysics Data System (ADS)

    Aoki, Shohei

    2012-06-01

    We propose the first measurement of CH4 specialized in the mud volcanism areas on Mars. Although the small amount of CH4 in the Martian atmosphere is remarkable because its source is potentially geological (or biological) activity, it is still open question. The high spectral and spatial resolution with high sensitivity and wide spectral coverage of IRCS/Subaru enable us the first mapping of CH4 on the localized mud volcanism areas. In the terrestrial case, mud volcanism vents about 25% of CH4 released from geological sources to the atmosphere. In such locations, CH4 can potentially combine with the infiltrated H2O and generate CH4-hydrate. While in the Martian case, the mud volcanism is expected the mounds in Acidalia Planitia and the Utopia/Isidis pitted cones. However, the releases of CH4 on these locations have not been discovered yet. Since the CH4-hydrate suggests the correlation of CH4 and H2O, high spatial resolution with simultaneous measurements of CH4 and H2O lines are essential. IRCS/Subaru can provide this opportunity. In addition, our observation will override the past one with CSHELL/IRTF in the following aspects, (1) less uncertainty by simultaneous measurement of multiple CH4 lines with wider spectral coverage, and (2) better spatial resolution.

  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. How well can we assess impacts of agricultural land management changes on the total greenhouse gas balance (CO2, CH4 and N2O) of tropical rice-cropping systems with biogeochemical models?

    NASA Astrophysics Data System (ADS)

    Kraus, David; Weller, Sebastian; Janz, Baldur; Klatt, Steffen; Santabárbara, Ignacio; Haas, Edwin; Werner, Christian; Wassmann, Reiner; Kiese, Ralf; Butterbach-Bahl, Klaus

    2016-04-01

    Paddy rice cultivation is increasingly challenged by physical and economic irrigation water scarcity. This already results in the trend of converting paddy rice to upland crop cultivation (e.g., maize, aerobic rice) in large parts of South East Asia. Such land management change from flooded lowland systems to well-aerated upland systems drastically affects soil C and N cycling and related emissions of greenhouse gases. Emissions of methane (CH4) are expected to decrease, while emissions of nitrous oxide (N2O) will most likely increase. In addition to such fast evolving 'pollution swapping' it is expected that on longer time scales significant amounts of soil organic carbon (SOC) stocks will be lost in form of carbon dioxide (CO2). Within the DFG-funded research unit ICON (Introducing non-flooded crops in rice-dominated landscapes: Impact on carbon, nitrogen and water cycles), we investigated environmental impacts of land management change from historical paddy rice cultivation to the upland crops maize and aerobic rice at experimental sites at the International Rice Research Institute (IRRI), the Philippines. To present, more than three years of continuous measurement data of CH4 and N2O emissions under different fertilization regimes have been collected. In addition, measurements of SOC contents and bulk densities in different soil horizons allow for an overall very good characterization of the environmental impacts of mentioned land management change. In this contribution we will show how well mentioned land management change effects in tropical agricultural systems can be represented and thus better understood by the help of process-based biogeochemical models. Seasonal emissions of CH4 and N2O are simulated with r2 values of 0.85 and 0.78 and average underestimations of 15 and 14 %, respectively. These underestimations predominantly originate from treatments in which no fertilizer is applied (CH4) as well as uncertainties of soil hydrology (N2O). Long

  3. Copper-catalyzed aerobic oxidation and cleavage/formation of C-S bond: a novel synthesis of aryl methyl sulfones from aryl halides and DMSO.

    PubMed

    Yuan, Gaoqing; Zheng, Junhua; Gao, Xiaofang; Li, Xianwei; Huang, Liangbin; Chen, Huoji; Jiang, Huanfeng

    2012-08-01

    With atmospheric oxygen as the oxidant, a novel copper(I)-catalyzed synthesis of aryl methyl sulfones from aryl halides and widely available DMSO is described. The procedure tolerates aryl halides with various functional groups (such as methoxy, acetyl, chloro, fluoro and nitro groups), which could afford aryl methyl sulfones in moderate to high yields. The copper-catalyzed aerobic oxidation and the cleavage/formation of C-S bond are the key steps for this transformation. PMID:22728918

  4. Implications of the large carbon kinetic isotope effect in the reaction CH4 + Cl for the 13C/12C ratio of stratospheric CH4

    NASA Astrophysics Data System (ADS)

    Bergamaschi, P.; Brühl, C.; Brenninkmeijer, C. A. M.; Saueressig, G.; Crowley, J. N.; Grooß, J. U.; Fischer, H.; Crutzen, P. J.

    Recent investigations of the carbon kinetic isotope effect (KIE) of the reaction CH4 + Cl yielded KIECl = 1.066±0.002 at 297 K (increasing to 1.075±0.005 at 223 K) [Saueressig et al., 1995]. In order to assess the effect of the exceptionally large KIEcl on δ13C of stratospheric CH4 we applied a two-dimensional, time dependent chemical transport model. The model results demonstrate the strong influence of the CH4 + Cl reaction on δ13CH4 in particular in the middle and upper stratosphere, where this reaction contributes several tens of percent to the total CH4 sink. The Cl sink helps to explain the relatively large overall isotope fractionation of 1.010-1.012 observed in the lower stratosphere [Brenninkmeijer et al., 1995; Brenninkmeijer et al., 1996], even though the model results predict a smaller effect than observed.

  5. Biogeochemical processes involving dissolved CO2 and CH4 at Albano, Averno, and Monticchio meromictic volcanic lakes (Central-Southern Italy)

    NASA Astrophysics Data System (ADS)

    Cabassi, Jacopo; Tassi, Franco; Vaselli, Orlando; Fiebig, Jens; Nocentini, Matteo; Capecchiacci, Francesco; Rouwet, Dmitri; Bicocchi, Gabriele

    2013-01-01

    measured δ13CTDIC values are not consistent, indicating that CO2 and the main carbon-bearing ion species (HCO3 -) are not in isotopic equilibrium, likely due to the fast kinetics of biochemical processes involving both CO2 and CH4. This study demonstrates that the vertical patterns of the CO2/CH4 ratio and of δ13C-CO2 and δ13C-CH4 are to be regarded as promising tools to detect perturbations, related to different causes, such as changes in the CO2 input from sublacustrine springs, that may affect aerobic and anaerobic layers of meromictic volcanic lakes.

  6. Biofilter for removal of nitrogen oxides from contaminated gases under aerobic conditions

    DOEpatents

    Apel, W.A.

    1998-08-18

    A biofilter is described for reducing concentrations of gaseous nitrogen oxides in a polluted gas comprises a porous organic filter bed medium disposed in a housing, the filter bed medium including a mixed culture of naturally occurring denitrifying bacteria for converting the nitrogen oxides to nitrogen gas, carbon dioxide, and water. A method is described of reducing concentrations of nitrogen oxides in polluted gas comprises conducting the polluted gas through the biofilter so that the denitrifying bacteria can degrade the nitrogen oxides. A preferred filter medium is wood compost, however composts of other organic materials are functional. Regulation of pH, moisture content, exogenous carbon sources, and temperature are described. 6 figs.

  7. Biofilter for removal of nitrogen oxides from contaminated gases under aerobic conditions

    DOEpatents

    Apel, William A.

    1998-01-01

    A biofilter for reducing concentrations of gaseous nitrogen oxides in a polluted gas comprises a porous organic filter bed medium disposed in a housing, the filter bed medium including a mixed culture of naturally occurring denitrifying bacteria for converting the nitrogen oxides to nitrogen gas, carbon dioxide, and water. A method of reducing concentrations of nitrogen oxides in polluted gas comprises conducting the polluted gas through the biofilter so that the denitrifying bacteria can degrade the nitrogen oxides. A preferred filter medium is wood compost, however composts of other organic materials are functional. Regulation of pH, moisture content, exogenous carbon sources, and temperature are described.

  8. Stratospheric aerosols from CH4 photochemistry on Neptune

    NASA Technical Reports Server (NTRS)

    Romani, Paul N.; Atreya, Sushil K.

    1989-01-01

    A combined photochemical-condensation model has been used to study hydrocarbon ices produced from CH4 photolysis in the stratosphere of Neptune. A total stratospheric haze production rate of 4.2 x 10 to the -15th g/sq cm/s. The total production rate is insensitive to within a factor of two to order of magnitude changes in the eddy diffusion coefficient and methane mixing ratio, which is within the present estimate of uncertainty for this number. The condensation temperatures are 97 K for C4H2, 71 K for C2H2, and 64 K for C2H6. Voyager 2 images of Neptune will be able to confirm the presence of stratospheric aerosols and provide constraints on their production rate and location.

  9. 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.

  10. Aerobic oxidation of lignin models using a base metal vanadium catalyst.

    PubMed

    Hanson, Susan K; Baker, R Tom; Gordon, John C; Scott, Brian L; Thorn, David L

    2010-06-21

    Dipicolinate vanadium(V) complexes oxidize lignin model complexes pinacol monomethyl ether (A), 2-phenoxyethanol (B), 1-phenyl-2-phenoxyethanol (C), and 1,2-diphenyl-2-methoxyethanol (D). With substrates having C-H bonds adjacent to the alcohol moiety (B-D), the C-H bond is broken in pyridine-d(5) solvent, yielding 2-phenoxyacetaldehyde from B, 2-phenoxyacetophenone from C, and benzoin methyl ether from D. In DMSO-d(6) solvent the reaction is slower, and both C-H and C-C bond cleavage products are observed for D. The vanadium(IV) products of these reactions have been identified and characterized. Catalytic oxidation of C and D has been demonstrated using air and (dipic)V(O)O(i)Pr. For both substrates, the C-C bond between the alcohol and ether groups is broken in the catalytic oxidation. 1-Phenyl-2-phenoxyethanol is oxidized to a mixture of phenol, formic acid, benzoic acid, and 2-methoxyacetophenone. The products of oxidation of 1,2-diphenyl-2-methoxyethanol depend on the solvent; in DMSO benzaldehyde and methanol are the major products, while benzoic acid and methyl benzoate are the major products obtained in pyridine solvent. Phenyl substituents on the model complex facilitate the oxidation, with relative rates of oxidation D > C > B. PMID:20491453

  11. Characterization and validation of CH4 profiles derived from the GOSAT thermal infrared band

    NASA Astrophysics Data System (ADS)

    Tanaka, T.

    2015-12-01

    Methane (CH4) is one of most effective greenhouse gases which is responsible for global warming since pre-industrial time. CH4 emitted from anthropogenic and natural sources can be identified but poorly quantified in the local scale. Vertical profiles of CH4 are retrieved from the Greenhouse gases Observing SATellite (GOSAT) Thermal InfraRed (TIR) band, and the evaluation of the GOSAT TIR CH4 profile is being conducted. Here we show the results of the comparison of GOSAT TIR and the aircraft CH4 in-situ profiles measured by the National Oceanic and Atmospheric Administration (NOAA) and the Alpha Jet Atmospheric eXperiment (AJAX). We compare the TIR CH4 with the aircraft profiles from 15 NOAA sites and Railroad valley measured by AJAX. GOSAT TIR CH4 profiles are collected under conditions within 200 km and ±12 hours from the aircraft measurements at each observation site. The TIR CH4 profiles agree well with aircraft profiles and average differences have slightly negative biases (-3 to -6 ppb) in both the boundary layer and the free troposphere.Satellite based CH4 measurements can provide the large spatial and temporal that improve the understanding of CH4 transport, surface emissions and chemical loss.

  12. Selective aerobic alcohol oxidation method for conversion of lignin into simple aromatic compounds

    DOEpatents

    Stahl, Shannon S; Rahimi, Alireza

    2015-03-03

    Described is a method to oxidize lignin or lignin sub-units. The method includes oxidation of secondary benzylic alcohol in the lignin or lignin sub-unit to a corresponding ketone in the presence of unprotected primarily aliphatic alcohol in the lignin or lignin sub-unit. The optimal catalyst system consists of HNO.sub.3 in combination with another Bronsted acid, in the absence of a metal-containing catalyst, thereby yielding a selectively oxidized lignin or lignin sub-unit. The method may be carried out in the presence or absence of additional reagents including TEMPO and TEMPO derivatives.

  13. Shock tube measurements of specific reaction rates in the branched chain CH4-CO-O2 system

    NASA Technical Reports Server (NTRS)

    Brabbs, T. A.; Brokaw, R. S.

    1975-01-01

    Growth constants, obtained by measuring the blue CO flame band emission behind incident shock waves, were obtained for two elementary bimolecular reactions involved in the oxidation of methane. Gas mixtures containing small amounts of CH4 with varying amounts of CO, O2, and in one case CO2, diluted with argon, were investigated, and exponential growth constants were derived from plots of the logarithm of observed light intensity versus gas time. The rate constant for the reaction O + CH4 yields CH3 + OH was found to be 1.9 times 10 to the 14th exp(-5900/T) cu cm per mole per sec in the range 1300-2000 K; for the reaction CH3 + O2 yields CH3O + O, the rate constant was determined to be 2.4 times 10 to the 13th exp(-14,500/T) cu cm per mole per sec in the range 1200 to 1900 K.

  14. Potential application of aerobic denitrifying bacterium Pseudomonas aeruginosa PCN-2 in nitrogen oxides (NOx) removal from flue gas.

    PubMed

    Zheng, Maosheng; Li, Can; Liu, Shufeng; Gui, Mengyao; Ni, Jinren

    2016-11-15

    Conventional biological removal of nitrogen oxides (NOx) from flue gas has been severely restricted by the presence of oxygen. This paper presents an efficient alternative for NOx removal at varying oxygen levels using the newly isolated bacterial strain Pseudomonas aeruginosa PCN-2 which was capable of aerobic and anoxic denitrification. Interestingly, nitric oxide (NO), as the obligatory intermediate, was negligibly accumulated during nitrate and nitrite reduction. Moreover, normal nitrate reduction with decreasing NO accumulation was realized under O2 concentration ranging from 0 to 100%. Reverse transcription and real-time quantitative polymerase chain reaction (RT-qPCR) analysis revealed that high efficient NO removal was attributed to the coordinate regulation of gene expressions including napA (for periplasmic nitrate reductase), nirS (for cytochrome cd1 nitrite reductase) and cnorB (for NO reductase). Further batch experiments demonstrated the immobilized strain PCN-2 possessed high capability of removing NO and nitrogen dioxide (NO2) at O2 concentration of 0-10%. A biotrickling filter established with present strain achieved high NOx removal efficiencies of 91.94-96.74% at inlet NO concentration of 100-500ppm and O2 concentration of 0-10%, which implied promising potential applications in purifying NOx contaminated flue gas. PMID:27469045

  15. Iron Catalysis for Room-Temperature Aerobic Oxidation of Alcohols to Carboxylic Acids.

    PubMed

    Jiang, Xingguo; Zhang, Jiasheng; Ma, Shengming

    2016-07-13

    Oxidation from alcohols to carboxylic acids, a class of essential chemicals in daily life, academic laboratories, and industry, is a fundamental reaction, usually using at least a stoichiometric amount of an expensive and toxic oxidant. Here, an efficient and practical sustainable oxidation technology of alcohols to carboxylic acids using pure O2 or even O2 in air as the oxidant has been developed: utilizing a catalytic amount each of Fe(NO3)3·9H2O/TEMPO/MCl, a series of carboxylic acids were obtained from alcohols (also aldehydes) in high yields at room temperature. A 55 g-scale reaction was demonstrated using air. As a synthetic application, the first total synthesis of a naturally occurring allene, i.e., phlomic acid, was accomplished. PMID:27304226

  16. Basin scale controls on CO2 and CH4 emissions from the Upper Mississippi River

    NASA Astrophysics Data System (ADS)

    Crawford, John T.; Loken, Luke C.; Stanley, Emily H.; Stets, Edward G.; Dornblaser, Mark M.; Striegl, Robert G.

    2016-03-01

    The Upper Mississippi River, engineered for river navigation in the 1930s, includes a series of low-head dams and navigation pools receiving elevated sediment and nutrient loads from the mostly agricultural basin. Using high-resolution, spatially resolved water quality sensor measurements along 1385 river kilometers, we show that primary productivity and organic matter accumulation affect river carbon dioxide and methane emissions to the atmosphere. Phytoplankton drive CO2 to near or below atmospheric equilibrium during the growing season, while anaerobic carbon oxidation supports a large proportion of the CO2 and CH4 production. Reductions of suspended sediment load, absent of dramatic reductions in nutrients, will likely further reduce net CO2 emissions from the river. Large river pools, like Lake Pepin, which removes the majority of upstream sediments, and large agricultural tributaries downstream that deliver significant quantities of sediments and nutrients, are likely to persist as major geographical drivers of greenhouse gas emissions.

  17. Summertime N2O, CH4 and CO2 exchanges from a tundra marsh and an upland tundra in maritime Antarctica

    NASA Astrophysics Data System (ADS)

    Zhu, Renbin; Ma, Dawei; Xu, Hua

    2014-02-01

    This study provides the first concurrent measurements of nitrous oxide (N2O), methane (CH4) and carbon dioxide (CO2) fluxes from a tundra marsh and an upland tundra in maritime Antarctica over the summers of 2007/2008 and 2011/2012. Tundra N2O and CH4 fluxes showed large spatial variations depending on local hydrological regimes. N2O sinks generally occurred at waterlogged marsh sites (-3.0 to 27.5 μg N2O m-2 h-1) whereas relatively dry and mesic sites presented weak or strong N2O sources (2.2-41.6 μg N2O m-2 h-1). Upland tundra sites showed negligible N2O emissions due to low soil TN and NH4+-N contents. Dry/upland tundra sites showed weak to strong CH4 uptake (-4.5 to -85.8 μg CH4 m-2 h-1). The waterlogged sites showed weak to strong CH4 emissions (29.8 μg CH4 m-2 h-1-2.4 mg CH4 m-2 h-1). Both tundra marsh and upland tundra experienced a large net CO2 uptake with the greatest mean CO2 uptake rate (-92.1 mg CO2 m-2 h-1) at dry marsh sites. Mean ecosystem respiration (ER) ranged between 82.5 ± 13.2 and 174.9 ± 25.7 mg CO2 m-2 h-1 at all the sites, and showed a strong exponential correlation (P < 0.001) with 0-10 cm soil temperature. Gross photosynthesis (Pg) was more than two times higher in tundra marsh than in upland tundra due to the difference of vegetation coverage. N2O flux showed a strong negative correlation (P < 0.01) with 0-10 cm soil temperature at the marsh sites, and significant or weak positive correlations with total daily radiation (TDR) and sunlight time (ST). No significant correlation was obtained between CH4 fluxes and environmental variables at tundra marsh and upland tundra sites. There was a significant negative correlation (P < 0.01) between NEE and 0-10 cm mean soil temperature, total daily radiation. Our results indicated that the lowering of water table significantly increased N2O emissions and CH4 consumption, but decreased C loss from the tundra marsh. In the future, the combination of climate warming and frequent precipitation

  18. Thermodynamic and hydrochemical controls on CH4 in a coal seam gas and overlying alluvial aquifer: new insights into CH4 origins.

    PubMed

    Owen, D Des R; Shouakar-Stash, O; Morgenstern, U; Aravena, R

    2016-01-01

    Using a comprehensive data set (dissolved CH4, δ(13)C-CH4, δ(2)H-CH4, δ(13)C-DIC, δ(37)Cl, δ(2)H-H2O, δ(18)O-H2O, Na, K, Ca, Mg, HCO3, Cl, Br, SO4, NO3 and DO), in combination with a novel application of isometric log ratios, this study describes hydrochemical and thermodynamic controls on dissolved CH4 from a coal seam gas reservoir and an alluvial aquifer in the Condamine catchment, eastern Surat/north-western Clarence-Moreton basins, Australia. δ(13)C-CH4 data in the gas reservoir (-58‰ to -49‰) and shallow coal measures underlying the alluvium (-80‰ to -65‰) are distinct. CO2 reduction is the dominant methanogenic pathway in all aquifers, and it is controlled by SO4 concentrations and competition for reactants such as H2. At isolated, brackish sites in the shallow coal measures and alluvium, highly depleted δ(2)H-CH4 (<310‰) indicate acetoclastic methanogenesis where SO4 concentrations inhibit CO2 reduction. Evidence of CH4 migration from the deep gas reservoir (200-500 m) to the shallow coal measures (<200 m) or the alluvium was not observed. The study demonstrates the importance of understanding CH4 at different depth profiles within and between aquifers. Further research, including culturing studies of microbial consortia, will improve our understanding of the occurrence of CH4 within and between aquifers in these basins. PMID:27578542

  19. Thermodynamic and hydrochemical controls on CH4 in a coal seam gas and overlying alluvial aquifer: new insights into CH4 origins

    PubMed Central

    Owen, D. Des. R.; Shouakar-Stash, O.; Morgenstern, U.; Aravena, R.

    2016-01-01

    Using a comprehensive data set (dissolved CH4, δ13C-CH4, δ2H-CH4, δ13C-DIC, δ37Cl, δ2H-H2O, δ18O-H2O, Na, K, Ca, Mg, HCO3, Cl, Br, SO4, NO3 and DO), in combination with a novel application of isometric log ratios, this study describes hydrochemical and thermodynamic controls on dissolved CH4 from a coal seam gas reservoir and an alluvial aquifer in the Condamine catchment, eastern Surat/north-western Clarence-Moreton basins, Australia. δ13C-CH4 data in the gas reservoir (−58‰ to −49‰) and shallow coal measures underlying the alluvium (−80‰ to −65‰) are distinct. CO2 reduction is the dominant methanogenic pathway in all aquifers, and it is controlled by SO4 concentrations and competition for reactants such as H2. At isolated, brackish sites in the shallow coal measures and alluvium, highly depleted δ2H-CH4 (<310‰) indicate acetoclastic methanogenesis where SO4 concentrations inhibit CO2 reduction. Evidence of CH4 migration from the deep gas reservoir (200–500 m) to the shallow coal measures (<200 m) or the alluvium was not observed. The study demonstrates the importance of understanding CH4 at different depth profiles within and between aquifers. Further research, including culturing studies of microbial consortia, will improve our understanding of the occurrence of CH4 within and between aquifers in these basins. PMID:27578542

  20. Effects of plant species on soil microbial processes and CH4 emission from constructed wetlands.

    PubMed

    Wang, Yanhua; Yang, Hao; Ye, Chun; Chen, Xia; Xie, Biao; Huang, Changchun; Zhang, Jixiang; Xu, Meina

    2013-03-01

    Methane (CH(4)) emission from constructed wetland has raised environmental concern. This study evaluated the influence of mono and polyculture constructed wetland and seasonal variation on CH(4) fluxes. Methane emission data showed large temporal variation ranging from 0 to 249.29 mg CH(4) m(-2) h(-1). Results indicated that the highest CH(4) flux was obtained in the polyculture system, planted with Phragmites australis, Zizania latifolia and Typha latifolia, reflecting polyculture system could stimulate CH(4) emission. FISH analysis showed the higher amount of methanotrophs in the profile of Z. latifolia in both mono and polyculture systems. The highest methanogens amount and relatively lower methanotrophs amount in the profile of polyculture system were obtained. The results support the characteristics of CH(4) fluxes. The polyculture constructed wetland has the higher potential of global warming. PMID:23291006

  1. Systemic oxidative-nitrosative-inflammatory stress during acute exercise in hypoxia; implications for microvascular oxygenation and aerobic capacity.

    PubMed

    Woodside, John D S; Gutowski, Mariusz; Fall, Lewis; James, Philip E; McEneny, Jane; Young, Ian S; Ogoh, Shigehiko; Bailey, Damian M

    2014-12-01

    Exercise performance in hypoxia may be limited by a critical reduction in cerebral and skeletal tissue oxygenation, although the underlying mechanisms remain unclear. We examined whether increased systemic free radical accumulation during hypoxia would be associated with elevated microvascular deoxygenation and reduced maximal aerobic capacity (V̇O2 max ). Eleven healthy men were randomly assigned single-blind to an incremental semi-recumbent cycling test to determine V̇O2 max in both normoxia (21% O2) and hypoxia (12% O2) separated by a week. Continuous-wave near-infrared spectroscopy was employed to monitor concentration changes in oxy- and deoxyhaemoglobin in the left vastus lateralis muscle and frontal cerebral cortex. Antecubital venous blood samples were obtained at rest and at V̇O2 max to determine oxidative (ascorbate radical by electron paramagnetic resonance spectroscopy), nitrosative (nitric oxide metabolites by ozone-based chemiluminescence and 3-nitrotyrosine by enzyme-linked immunosorbent assay) and inflammatory stress biomarkers (soluble intercellular/vascular cell adhesion 1 molecules by enzyme-linked immunosorbent assay). Hypoxia was associated with increased cerebral and muscle tissue deoxygenation and lower V̇O2 max (P < 0.05 versus normoxia). Despite an exercise-induced increase in oxidative-nitrosative-inflammatory stress, hypoxia per se did not have an additive effect (P > 0.05 versus normoxia). Consequently, we failed to observe correlations between any metabolic, haemodynamic and cardiorespiratory parameters (P > 0.05). Collectively, these findings suggest that altered free radical metabolism cannot explain the elevated microvascular deoxygenation and corresponding lower V̇O2 max in hypoxia. Further research is required to determine whether free radicals when present in excess do indeed contribute to the premature termination of exercise in hypoxia. PMID:25344270

  2. Aerobic exercise training improves oxidative stress and ubiquitin proteasome system activity in heart of spontaneously hypertensive rats.

    PubMed

    de Andrade, Luiz Henrique Soares; de Moraes, Wilson Max Almeida Monteiro; Matsuo Junior, Eduardo Hiroshi; de Orleans Carvalho de Moura, Elizabeth; Antunes, Hanna Karen Moreira; Montemor, Jairo; Antonio, Ednei Luiz; Bocalini, Danilo Sales; Serra, Andrey Jorge; Tucci, Paulo José Ferreira; Brum, Patricia Chakur; Medeiros, Alessandra

    2015-04-01

    The activity of the ubiquitin proteasome system (UPS) and the level of oxidative stress contribute to the transition from compensated cardiac hypertrophy to heart failure in hypertension. Moreover, aerobic exercise training (AET) is an important therapy for the treatment of hypertension, but its effects on the UPS are not completely known. The aim of this study was to evaluate the effect of AET on UPS's activity and oxidative stress level in heart of spontaneously hypertensive rats (SHR). A total of 53 Wistar and SHR rats were randomly divided into sedentary and trained groups. The AET protocol was 5×/week in treadmill for 13 weeks. Exercise tolerance test, non-invasive blood pressure measurement, echocardiographic analyses, and left ventricle hemodynamics were performed during experimental period. The expression of ubiquitinated proteins, 4-hydroxynonenal (4-HNE), Akt, phospho-Akt(ser473), GSK3β, and phospho-GSK3β(ser9) were analyzed by western blotting. The evaluation of lipid hydroperoxide concentration was performed using the xylenol orange method, and the proteasomal chymotrypsin-like activity was measured by fluorimetric assay. Sedentary hypertensive group presented cardiac hypertrophy, unaltered expression of total Akt, phospho-Akt, total GSK3β and phospho-GSK3β, UPS hyperactivity, increased lipid hydroperoxidation as well as elevated expression of 4-HNE but normal cardiac function. In contrast, AET significantly increased exercise tolerance, decreased resting systolic blood pressure and heart rate in hypertensive animals. In addition, the AET increased phospho-Akt expression, decreased phospho-GSK3β, and did not alter the expression of total Akt, total GSK3β, and ubiquitinated proteins, however, significantly attenuated 4-HNE levels, lipid hydroperoxidation, and UPS's activity toward normotensive group levels. Our results provide evidence for the main effect of AET on attenuating cardiac ubiquitin proteasome hyperactivity and oxidative stress in SHR

  3. Uniform distributions of glucose oxidation and oxygen extraction in gray matter of normal human brain: No evidence of regional differences of aerobic glycolysis.

    PubMed

    Hyder, Fahmeed; Herman, Peter; Bailey, Christopher J; Møller, Arne; Globinsky, Ronen; Fulbright, Robert K; Rothman, Douglas L; Gjedde, Albert

    2016-05-01

    Regionally variable rates of aerobic glycolysis in brain networks identified by resting-state functional magnetic resonance imaging (R-fMRI) imply regionally variable adenosine triphosphate (ATP) regeneration. When regional glucose utilization is not matched to oxygen delivery, affected regions have correspondingly variable rates of ATP and lactate production. We tested the extent to which aerobic glycolysis and oxidative phosphorylation power R-fMRI networks by measuring quantitative differences between the oxygen to glucose index (OGI) and the oxygen extraction fraction (OEF) as measured by positron emission tomography (PET) in normal human brain (resting awake, eyes closed). Regionally uniform and correlated OEF and OGI estimates prevailed, with network values that matched the gray matter means, regardless of size, location, and origin. The spatial agreement between oxygen delivery (OEF≈0.4) and glucose oxidation (OGI ≈ 5.3) suggests that no specific regions have preferentially high aerobic glycolysis and low oxidative phosphorylation rates, with globally optimal maximum ATP turnover rates (VATP ≈ 9.4 µmol/g/min), in good agreement with (31)P and (13)C magnetic resonance spectroscopy measurements. These results imply that the intrinsic network activity in healthy human brain powers the entire gray matter with ubiquitously high rates of glucose oxidation. Reports of departures from normal brain-wide homogeny of oxygen extraction fraction and oxygen to glucose index may be due to normalization artefacts from relative PET measurements. PMID:26755443

  4. The emissions and soil concentrations of N2O and CH4 from natural soil temperature gradients in a volcanic area in southwest Iceland

    NASA Astrophysics Data System (ADS)

    Maljanen, Marja; Yli-Moijala, Heli; Leblans, Niki I. W.; De Boeck, Hans J.; Bjarnadóttir, Brynhildur; Sigurdsson, Bjarni D.

    2016-04-01

    We studied nitrous oxide (N2O) and methane (CH4) emissions along three natural geothermal soil temperature (Ts) gradients in a volcanic area in southwest Iceland. Two of the gradients (on a grassland and a forest site, respectively) were recently formed (in May 2008). The third gradient, a grassland site, had been subjected to long-term soil warming (over 30 years, and probably centuries). Nitrous oxide and methane emissions were measured along the temperature gradients using the static chamber method and also soil gas concentrations were studied. With a moderate soil temperature increase (up to +5 °C) there were no significant increase in gas flux rates in any of the sites but an increase of 20 to 45 °C induced an increase in both N2O and CH4 emissions. The measured N2O emissions (up to 2600 μg N2O m-2 h-1) from the warmest plots were about two magnitudes higher compared with the coolest plots (less than 20 μg N2O m-2 h-1). While a net uptake of CH4 was measured in the coolest plots (up to -0.15 mg CH4 m-2 h-1), a net emission of CH4 was measured from the warmest plots (up to 1.3 mg CH4 m-2 h-1). Soil CH4 concentrations decreased first with a moderate (up to +5 °C) increase in Ts, but above that threshold increased significantly. The soil N2O concentration at depths from 5 to 20 cm increased with increasing Ts, indicating enhanced N-turnover. Further, there was a clear decrease in soil organic matter (SOM), C- and N concentration with increasing Ts at all sites. One should note, however, that a part of the N2O emitted from the warmest plots may be partly geothermally derived, as was revealed by 15N2O isotope studies. These natural Ts gradients show that the emission of N2O and CH4 can increase significantly when Ts increases considerably. This implies that these geothermally active sites can act as local hot spots for CH4 and N2O emissions.

  5. Nitrite-driven nitrous oxide production under aerobic soil conditions: Kinetics and biochemical controls

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Nitrite (NO2-) can accumulate during nitrification in soil following fertilizer application. While the role of NO2- as a substrate regulating nitrous oxide (N2O) production is recognized, kinetic data are not available that allow for estimating N2O production or soil-to-atmosphere fluxes as a functi...

  6. Nitrite-Driven Nitrous Oxide Production Under Aerobic Soil Conditions: Kinetics and Biochemical Controls

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Nitrite (NO2-) can accumulate during nitrification in soil following fertilizer application. While the role of NO2- as a substrate regulating nitrous oxide (N2O) production is recognized, kinetic data are not available that allow for estimating N2O production or soil-to-atmosphere fluxes as a functi...

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

    PubMed

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

    2016-01-01

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

  8. Confined iron nanowires enhance the catalytic activity of carbon nanotubes in the aerobic oxidation of cyclohexane.

    PubMed

    Yang, Xixian; Yu, Hao; Peng, Feng; Wang, Hongjuan

    2012-07-01

    Inside job: New applications of carbon materials pave the way towards greener chemical syntheses. The encapsulation of metallic Fe within CNTs improves electron transfer between the metal and the CNTs. The resulting material offers a high catalytic activity and easy magnetic separation of catalyst in the heterogeneous selective oxidation of cyclohexane. PMID:22488987

  9. Selective Aerobic Oxidation of 5-(Hydroxymethyl)furfural to 5-Formyl-2-furancarboxylic Acid in Water.

    PubMed

    Ventura, Maria; Aresta, Michele; Dibenedetto, Angela

    2016-05-23

    A simple, cheap, and selective catalyst based on copper/cerium oxides is described for the oxidation of 5-(hydroxymethyl)furfural (5-HMF) in water. An almost quantitative conversion (99 %) with excellent (90 %) selectivity towards the formation of 5-formyl-2-furancarboxylic acid, a platform molecule for other high value chemicals, is observed. The catalyst does not require any pretreatment or additives, such as bases, to obtain high yield and selectivity in water as solvent and using oxygen as oxidant. When a physical mixture of the oxides is used, low conversion and selectivity are observed. Air can be used instead of oxygen, but a lower conversion rate is observed if the same overall pressure is used, and the selectivity remains high. The catalyst can be recovered almost quantitatively and reused. Deactivation of the catalyst, observed in repeated runs, is due to the deposition of humins on its surface. Upon calcination the catalyst almost completely recovers its activity and selectivity, proving that the catalyst is robust. PMID:27101568

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

    PubMed Central

    Damirchi, Arsalan; Farjaminezhad, Manoochehr

    2016-01-01

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

  11. Analysis of High Resolution Spectra of Eris: Possible Evidence for Cold Phase CH4 Ice

    NASA Astrophysics Data System (ADS)

    Cook, J.; Mastrapa, R. M.; Cruikshank, D. P.; Alvarez-Candal, A.; Pinilla-Alonso, N.

    2011-10-01

    We examined the spectrum of Eris by isolating the 1.67 and 1.72 μm CH4 bands and comparing these to Hapke models. These bands are chosen because (i) CH4(II) is more distinguished from CH4(I) at these wavelengths and (ii) the SNR of the observationswere higher than the bands longward of 1.8 μm. At the time of writing this abstract, the analysis was performed using optical constants for pure CH4 because of the lack of optical constants for CH4 diluted in N2 between 15 and 30 K.We assume the spectrum of Eris is a spectral blend of both CH4 phases. To model the spectrum, we used the CH4 optical constants from (11). CH4(II) ice is represented by their 20 K measurements, while optical constants for the CH4(I) ice is estimated from a linear interpolation between measurements at T > 30 K, or a second order extrapolation of the data at T > 30 to estimate the optical constants at 20.4 < T < 30 K. Each component is allowed to shift in wavelength.

  12. Method for Indirect Quantification of CH4 Production via H2O Production Using Hydrogenotrophic Methanogens.

    PubMed

    Taubner, Ruth-Sophie; Rittmann, Simon K-M R

    2016-01-01

    Hydrogenotrophic methanogens are an intriguing group of microorganisms from the domain Archaea. Methanogens exhibit extraordinary ecological, biochemical, and physiological characteristics and possess a huge biotechnological potential. Yet, the only possibility to assess the methane (CH4) production potential of hydrogenotrophic methanogens is to apply gas chromatographic quantification of CH4. In order to be able to effectively screen pure cultures of hydrogenotrophic methanogens regarding their CH4 production potential we developed a novel method for indirect quantification of the volumetric CH4 production rate by measuring the volumetric water production rate. This method was established in serum bottles for cultivation of methanogens in closed batch cultivation mode. Water production was estimated by determining the difference in mass increase in a quasi-isobaric setting. This novel CH4 quantification method is an accurate and precise analytical technique, which can be used to rapidly screen pure cultures of methanogens regarding their volumetric CH4 evolution rate. It is a cost effective alternative determining CH4 production of methanogens over CH4 quantification by using gas chromatography, especially if applied as a high throughput quantification method. Eventually, the method can be universally applied for quantification of CH4 production from psychrophilic, thermophilic and hyperthermophilic hydrogenotrophic methanogens. PMID:27199898

  13. Method for Indirect Quantification of CH4 Production via H2O Production Using Hydrogenotrophic Methanogens

    PubMed Central

    Taubner, Ruth-Sophie; Rittmann, Simon K.-M. R.

    2016-01-01

    Hydrogenotrophic methanogens are an intriguing group of microorganisms from the domain Archaea. Methanogens exhibit extraordinary ecological, biochemical, and physiological characteristics and possess a huge biotechnological potential. Yet, the only possibility to assess the methane (CH4) production potential of hydrogenotrophic methanogens is to apply gas chromatographic quantification of CH4. In order to be able to effectively screen pure cultures of hydrogenotrophic methanogens regarding their CH4 production potential we developed a novel method for indirect quantification of the volumetric CH4 production rate by measuring the volumetric water production rate. This method was established in serum bottles for cultivation of methanogens in closed batch cultivation mode. Water production was estimated by determining the difference in mass increase in a quasi-isobaric setting. This novel CH4 quantification method is an accurate and precise analytical technique, which can be used to rapidly screen pure cultures of methanogens regarding their volumetric CH4 evolution rate. It is a cost effective alternative determining CH4 production of methanogens over CH4 quantification by using gas chromatography, especially if applied as a high throughput quantification method. Eventually, the method can be universally applied for quantification of CH4 production from psychrophilic, thermophilic and hyperthermophilic hydrogenotrophic methanogens. PMID:27199898

  14. Understanding effect of structure and stability on transformation of CH4 hydrate to CO2 hydrate

    NASA Astrophysics Data System (ADS)

    Liu, Jinxiang; Yan, Yujie; Liu, Haiying; Xu, Jiafang; Zhang, Jun; Chen, Gang

    2016-03-01

    Understanding the transformation process of CH4 hydrate to CO2 hydrate is crucial to develop the CH4sbnd CO2 replacement technique for CH4 production and CO2 sequestration. Ab initio calculations show that the transformation will slightly distort the host lattice and decrease the binding strength of guest molecules, but it is a thermodynamically spontaneous process dominated by the entropic contribution. Moreover, ab initio molecular dynamics simulations suggest that the dynamics of the host lattice is independent on the guest molecules, while CO2 in hydrate exhibits slower translational and rotational motion than CH4 in hydrate.

  15. The Unique Gas-Phase Chemistry of the [AuO](+) /CH4 Couple: Selective Oxygen-Atom Transfer to, Rather than Hydrogen-Atom Abstraction from, Methane.

    PubMed

    Zhou, Shaodong; Li, Jilai; Schlangen, Maria; Schwarz, Helmut

    2016-08-26

    The thermal reaction of [AuO](+) with methane has been explored using FT-ICR mass spectrometry complemented by high-level quantum chemical calculations. In contrast to the previously studied congener [CuO](+) , and to [AgO](+) , [AuO](+) reacts with CH4 exclusively via oxygen-atom transfer to form CH3 OH, and a novel mechanistic scenario for this selective oxidation process has been revealed. Also, the origin of the inertness of the [AgO](+) /CH4 couple has been addressed computationally. PMID:27390885

  16. Constraining anthropogenic CH4 emissions in Nanjing and the Yangtze River Delta, China, using atmospheric CO2 and CH4 mixing ratios

    NASA Astrophysics Data System (ADS)

    Shen, Shuanghe; Yang, Dong; Xiao, Wei; Liu, Shoudong; Lee, Xuhui

    2014-11-01

    Methane (CH4) emissions estimated with the Intergovernmental Panel on Climate Change (IPCC) inventory method at the city and regional scale are subject to large uncertainties. In this study, we determined the CH4:CO2 emissions ratio for both Nanjing and the Yangtze River Delta (YRD), using the atmospheric CH4 and CO2 concentrations measured at a suburban site in Nanjing in the winter. The atmospheric estimate of the CH4:CO2 emissions ratio was in reasonable agreement with that calculated using the IPCC method for the YRD (within 20%), but was 200% greater for the municipality of Nanjing. The most likely reason for the discrepancy is that emissions from unmanaged landfills are omitted from the official statistics on garbage production.

  17. The description and validation of a computationally-Efficient CH4-CO-OH (ECCOHv1.01) chemistry module for 3-D model applications

    NASA Astrophysics Data System (ADS)

    Elshorbany, Y. F.; Duncan, B. N.; Strode, S. A.; Wang, J. S.; Kouatchou, J.

    2015-11-01

    We present the Efficient CH4-CO-OH chemistry module (ECCOH) that allows for the simulation of the methane, carbon monoxide and hydroxyl radical (CH4-CO-OH) system, within a chemistry climate model, carbon cycle model, or earth system model. The computational efficiency of the module allows many multi-decadal sensitivity simulations of the CH4-CO-OH system, which primarily determines the global atmospheric oxidizing capacity. This capability is important for capturing the nonlinear feedbacks of the CH4-CO-OH system and understanding the perturbations to methane, CO and OH and the concomitant impacts on climate. We implemented the ECCOH chemistry module into the NASA GEOS-5 Atmospheric Global Circulation Model (AGCM), performed multiple sensitivity simulations of the CH4-CO-OH system over two decades, and evaluated the model output with surface and satellite datasets of methane and CO. The favorable comparison of output from the ECCOH chemistry module (as configured in the GEOS-5 AGCM) with observations demonstrates the fidelity of the module for use in scientific research.

  18. The description and validation of the computationally Efficient CH4-CO-OH (ECCOHv1.01) chemistry module for 3-D model applications

    NASA Astrophysics Data System (ADS)

    Elshorbany, Yasin F.; Duncan, Bryan N.; Strode, Sarah A.; Wang, James S.; Kouatchou, Jules

    2016-02-01

    We present the Efficient CH4-CO-OH (ECCOH) chemistry module that allows for the simulation of the methane, carbon monoxide, and hydroxyl radical (CH4-CO-OH) system, within a chemistry climate model, carbon cycle model, or Earth system model. The computational efficiency of the module allows many multi-decadal sensitivity simulations of the CH4-CO-OH system, which primarily determines the global atmospheric oxidizing capacity. This capability is important for capturing the nonlinear feedbacks of the CH4-CO-OH system and understanding the perturbations to methane, CO, and OH, and the concomitant impacts on climate. We implemented the ECCOH chemistry module in the NASA GEOS-5 atmospheric global circulation model (AGCM), performed multiple sensitivity simulations of the CH4-CO-OH system over 2 decades, and evaluated the model output with surface and satellite data sets of methane and CO. The favorable comparison of output from the ECCOH chemistry module (as configured in the GEOS-5 AGCM) with observations demonstrates the fidelity of the module for use in scientific research.

  19. Temperature Effects on Microbial CH4 and CO2 Production in Permafrost-Affected Soils From the Barrow Environmental Observatory

    NASA Astrophysics Data System (ADS)

    Graham, D. E.; Roy Chowdhury, T.; Zheng, J.; Moon, J. W.; Yang, Z.; Gu, B.; Wullschleger, S. D.

    2015-12-01

    Warmer Arctic temperatures are increasing the annual soil thaw depth and prolonging the thaw season in Alaskan permafrost zones. This change exposes organic matter buried in the soils and permafrost to microbial degradation and mineralization to form CO2 and CH4. The proportion and fluxes of these greenhouse gases released into the atmosphere control the global feedback on warming. To improve representations of these biogeochemical processes in terrestrial ecosystem models we compared soil properties and microbial activities in core samples of polygonal tundra from the Barrow Environmental Observatory. Measurements of soil water potential through the soil column characterized water binding to the organic and mineral components. This suction combines with temperature to control freezing, gas diffusion and microbial activity. The temperature-dependence of CO2 and CH4 production from anoxic soil incubations at -2, +4 or +8 °C identified a significant lag in methanogenesis relative to CO2 production by anaerobic respiration and fermentation. Changes in the abundance of methanogen signature genes during incubations indicate that microbial population shifts caused by thawing and warmer temperatures drive changes in the mixtures of soil carbon degradation products. Comparisons of samples collected across the microtopographic features of ice-wedge polygons address the impacts of water saturation, iron reduction and organic matter content on CH4 production and oxidation. These combined measurements build process understanding that can be applied across scales to constrain key response factors in models that address Arctic soil warming.

  20. Nanoscaled copper metal-organic framework (MOF) based on carboxylate ligands as an efficient heterogeneous catalyst for aerobic epoxidation of olefins and oxidation of benzylic and allylic alcohols.

    PubMed

    Qi, Yue; Luan, Yi; Yu, Jie; Peng, Xiong; Wang, Ge

    2015-01-19

    Aerobic epoxidation of olefins at a mild reaction temperature has been carried out by using nanomorphology of [Cu3(BTC)2] (BTC = 1,3,5-benzenetricarboxylate) as a high-performance catalyst through a simple synthetic strategy. An aromatic carboxylate ligand was employed to furnish a heterogeneous copper catalyst and also serves as the ligand for enhanced catalytic activities in the catalytic reaction. The utilization of a copper metal-organic framework catalyst was further extended to the aerobic oxidation of aromatic alcohols. The shape and size selectivity of the catalyst in olefin epoxidation and alcohol oxidation was investigated. Furthermore, the as-synthesized copper catalyst can be easily recovered and reused several times without leaching of active species or significant loss of activity. PMID:25430789

  1. Fluxes of CO2, CH4 and N2O at two European beech forests: linking soil gas production profiles with soil and stem fluxes

    NASA Astrophysics Data System (ADS)

    Maier, Martin; Machacova, Katerina; Halaburt, Ellen; Haddad, Sally; Urban, Otmar; Lang, Friederike

    2016-04-01

    Soil and plant surfaces are known to exchange greenhouse gases with the atmosphere. Some gases like nitrous oxide (N2O) and methane (CH4) can be produced and re-consumed in different soil depths and soil compartments, so that elevated concentrations of CH4 or N2O in the soil do not necessarily mean a net efflux from the soil into the atmosphere. Soil aeration, and thus the oxygen status can underlay a large spatial variability within the soil on the plot and profile scale, but also within soil aggregates. Thus, conditions suitable for production and consumption of CH4 and N2O can vary on different scales in the soil. Plant surfaces can also emit or take up CH4 and N2O, and these fluxes can significantly contribute to the net ecosystem exchange. Since roots usually have large intercellular spaces or aerenchyma they may represent preferential transport ways for soil gases, linking possibly elevated soil gas concentrations in the subsoil in a "shortcut" to the atmosphere. We tested the hypothesis that the spatial variability of the soil-atmosphere fluxes of CO2, CH4 and N2O is caused by the heterogeneity in soil properties. Therefore, we measured soil-atmosphere gas fluxes, soil gas concentrations and soil diffusivity profiles and did a small scale field assessment of soil profiles on the measurments plots. We further tried to link vertical profiles of soil gas concentrations and diffusivity to derive the production and consumption profiles, and to link these profiles to the stem-atmosphere flux rates of individual trees. Measurements were conducted in two mountain beech forests with different geographical and climatic conditions (White Carpathians, Czech Republic; Black Forest, Germany). Gas fluxes at stem and soil levels were measured simultaneously using static chamber systems and chromatographic and continuous laser analyses. Monitoring simultaneously vertical soil gas profiles allowed to assess the within-soil gas fluxes, and thus to localize the production and

  2. Greenhouse gas budget (CO2, CH4 and N2O) of intensively managed grassland following restoration

    NASA Astrophysics Data System (ADS)

    Merbold, Lutz; Eugster, Werner; Stieger, Jacqueline; Zahniser, Mark; Nelson, David; Buchmann, Nina

    2014-05-01

    The first full greenhouse gas (GHG) flux budget of an intensively managed grassland in Switzerland (Chamau) is presented. The three major trace gases, carbon dioxide (CO2), methane (CH4) and nitrous oxide (N2O) were measured with the eddy covariance (EC) technique. For CO2 concentrations, an open-path infrared gas analyzer was used, while N2O and CH4 concentrations were measured with a recently developed continuous-wave quantum cascade laser absorption spectrometer (QCLAS). We investigated the magnitude of these trace gas emissions after grassland restoration, including ploughing, harrowing, sowing and fertilization with inorganic and organic fertilizers in 2012. Large peaks of N2O fluxes (20 - 50 nmol m-2 s-1 compared to a < 5 nmol m-2 s-1 background) were observed during thawing of the soil after the winter period and after mineral fertilizer application followed by re-sowing in the beginning of the summer season. N2O fluxes were controlled by nitrogen input, plant productivity, soil water content and temperature. Management activities led to increased variations of N2O fluxes up to 14 days after the management event as compared to background fluxes measured during periods without management (< 5nmol m-2 s-1). Fluxes of CO2 remained small until full plant development in early summer 2012. In contrast methane emissions showed only minor variations over time. The annual GHG flux budget was dominated by N2O (48 % contribution) and CO2 emissions (44 %). CH4 flux contribution to the annual budget was only minor (8 %). We conclude that recently developed multi-species QCLAS in an EC system open new opportunities to determine the temporal variation of N2O and CH4 fluxes, which further allow to quantify annual emissions. With respect to grassland restoration, our study emphasizes the key role of N2O and CO2 losses after ploughing, changing a permanent grassland from a carbon sink to a significant carbon source.

  3. N 2O emissions at municipal solid waste landfill sites: Effects of CH 4 emissions and cover soil

    NASA Astrophysics Data System (ADS)

    Zhang, Houhu; He, Pinjing; Shao, Liming

    Municipal solid waste landfills are the significant anthropogenic sources of N 2O due to the cooxidation of ammonia by methane-oxidizing bacteria in cover soils. Such bacteria could be developed through CH 4 fumigation, as evidenced by both laboratory incubation and field measurement. During a 10-day incubation with leachate addition, the average N 2O fluxes in the soil samples, collected from the three selected landfill covers, were multiplied by 1.75 ( p < 0.01), 3.56 ( p < 0.01), and 2.12 ( p < 0.01) from the soil samples preincubated with 5% CH 4 for three months when compared with the control, respectively. Among the three selected landfill sites, N 2O fluxes in two landfill sites were significantly correlated with the variations of the CH 4 emissions without landfill gas recovery ( p < 0.001). N 2O fluxes were also elevated by the increase of the CH 4 emissions with landfill gas recovery in another landfill site ( p > 0.05). The annual average N 2O flux was 176 ± 566 μg N 2O-N m -2 h -1 ( p < 0.01) from sandy soil-covered landfill site, which was 72% ( p < 0.05) and 173% ( p < 0.01) lower than the other two clay soil covered landfill sites, respectively. The magnitude order of N 2O emissions in three landfill sites was also coincident by the results of laboratory incubation, suggesting the sandy soil cover could mitigate landfill N 2O emissions.

  4. Preparation and Catalytic Activity for Aerobic Glucose Oxidation of Crown Jewel Structured Pt/Au Bimetallic Nanoclusters

    NASA Astrophysics Data System (ADS)

    Zhang, Haijun; Wang, Liqiong; Lu, Lilin; Toshima, Naoki

    2016-08-01

    Understanding of the “structure-activity” relations for catalysts at an atomic level has been regarded as one of the most important objectives in catalysis studies. Bimetallic nanoclusters (NCs) in its many types, such as core/shell, random alloy, cluster-in-cluster, bi-hemisphere, and crown jewel (one kind of atom locating at the top position of another kind of NC), attract significant attention owing to their excellent optical, electronic, and catalytic properties. PVP-protected crown jewel-structured Pt/Au (CJ-Pt/Au) bimetallic nanoclusters (BNCs) with Au atoms located at active top sites were synthesized via a replacement reaction using 1.4-nm Pt NCs as mother clusters even considering the fact that the replacement reaction between Pt and Au3+ ions is difficult to be occurred. The prepared CJ-Pt/Au colloidal catalysts characterized by UV-Vis, TEM, HR-TEM and HAADF-STEM-EELS showed a high catalytic activity for aerobic glucose oxidation, and the top Au atoms decorating the Pt NCs were about 15 times more active than the Au atoms of Au NCs with similar particle size.

  5. Copper(II) complexes as catalyst for the aerobic oxidation of o-phenylenediamine to 2,3-diaminophenazine

    NASA Astrophysics Data System (ADS)

    Khattar, Raghvi; Yadav, Anjana; Mathur, Pavan

    2015-05-01

    Two new mononuclear copper(II) complexes [Cu (L) (NO3)2] (1) and [Cu (L) Br2] (2) where (L = bis(1-(pyridin-2-ylmethyl)-benzimidazol-2-ylmethyl)ether) are synthesized and characterized by single-crystal X-ray diffraction analysis, elemental analysis, UV-Visible, IR spectroscopy, EPR and cyclic voltammetry. The complexes exhibit different coordination structures; the E1/2 value of the complex (1) is found to be relatively more cathodic than that of complex (2). X-band EPR spectra at low temperature in DMF supports a tetragonally distorted complex (1) while complex (2) shows three different g values suggesting a rhombic geometry. These complexes were utilized as a catalyst for the aerobic oxidation of o-phenylenediamine to 2,3-diaminophenazine assisted by molecular oxygen. The initial rate of reaction is dependent on the concentration of Cu(II) complex as well as substrate, and was found to be higher for the nitrate bound complex, while presence of acetate anion acts as a mild inhibitor of the reaction, as it is likely to pick up protons generated during the course of reaction. The inhibition suggests that the generated protons are further required in another important catalytic step.

  6. Preparation and Catalytic Activity for Aerobic Glucose Oxidation of Crown Jewel Structured Pt/Au Bimetallic Nanoclusters

    PubMed Central

    Zhang, Haijun; Wang, Liqiong; Lu, Lilin; Toshima, Naoki

    2016-01-01

    Understanding of the “structure-activity” relations for catalysts at an atomic level has been regarded as one of the most important objectives in catalysis studies. Bimetallic nanoclusters (NCs) in its many types, such as core/shell, random alloy, cluster-in-cluster, bi-hemisphere, and crown jewel (one kind of atom locating at the top position of another kind of NC), attract significant attention owing to their excellent optical, electronic, and catalytic properties. PVP-protected crown jewel-structured Pt/Au (CJ-Pt/Au) bimetallic nanoclusters (BNCs) with Au atoms located at active top sites were synthesized via a replacement reaction using 1.4-nm Pt NCs as mother clusters even considering the fact that the replacement reaction between Pt and Au3+ ions is difficult to be occurred. The prepared CJ-Pt/Au colloidal catalysts characterized by UV-Vis, TEM, HR-TEM and HAADF-STEM-EELS showed a high catalytic activity for aerobic glucose oxidation, and the top Au atoms decorating the Pt NCs were about 15 times more active than the Au atoms of Au NCs with similar particle size. PMID:27476577

  7. Preparation and Catalytic Activity for Aerobic Glucose Oxidation of Crown Jewel Structured Pt/Au Bimetallic Nanoclusters.

    PubMed

    Zhang, Haijun; Wang, Liqiong; Lu, Lilin; Toshima, Naoki

    2016-01-01

    Understanding of the "structure-activity" relations for catalysts at an atomic level has been regarded as one of the most important objectives in catalysis studies. Bimetallic nanoclusters (NCs) in its many types, such as core/shell, random alloy, cluster-in-cluster, bi-hemisphere, and crown jewel (one kind of atom locating at the top position of another kind of NC), attract significant attention owing to their excellent optical, electronic, and catalytic properties. PVP-protected crown jewel-structured Pt/Au (CJ-Pt/Au) bimetallic nanoclusters (BNCs) with Au atoms located at active top sites were synthesized via a replacement reaction using 1.4-nm Pt NCs as mother clusters even considering the fact that the replacement reaction between Pt and Au(3+) ions is difficult to be occurred. The prepared CJ-Pt/Au colloidal catalysts characterized by UV-Vis, TEM, HR-TEM and HAADF-STEM-EELS showed a high catalytic activity for aerobic glucose oxidation, and the top Au atoms decorating the Pt NCs were about 15 times more active than the Au atoms of Au NCs with similar particle size. PMID:27476577

  8. Special role of corn flour as an ideal carbon source for aerobic denitrification with minimized nitrous oxide emission.

    PubMed

    Zhu, Shuangyue; Zheng, Maosheng; Li, Can; Gui, Mengyao; Chen, Qian; Ni, Jinren

    2015-06-01

    Much effort has been made for reducing nitrous oxide (N2O) emission in wastewater treatment processes. This paper presents an interesting way to minimize N2O in aerobic denitrification by strain Pseudomonas stutzeri PCN-1 with help of corn flour as cheaper additional carbon source. Experimental results showed that maximal N2O accumulation by strain PCN-1 was only 0.02% of removed nitrogen if corn flour was used as sole carbon source, which was significantly reduced by 52.07-99.81% comparing with others such as succinate, glucose, acetate and citrate. Sustained release of reducing sugar from starch and continuous expression of nosZ coding for N2O reductase contributed to the special role of corn flour as the ideal carbon source for strain PCN-1. Further experiments in sequencing batch reactors (SBRs) demonstrated similarly efficient nitrogen removal with much less N2O emission due to synergy of the novel strain and activated sludge, which was then confirmed by quantitative PCR analysis. PMID:25802047

  9. Selective aerobic oxidation of 1,3-propanediol to 3-hydroxypropanoic acid using hydrotalcite supported bimetallic gold nanoparticle catalyst in water

    NASA Astrophysics Data System (ADS)

    Mohammad, Mujahid; Nishimura, Shun; Ebitani, Kohki

    2015-02-01

    Selective oxidation of 1,3-propanediol (1,3-PD) to 3-hydroxypropanoic acid (3-HPA), an important industrial building block, was successfully achieved using hydrotalcite-supported bimetallic Au nanoparticle catalysts in water at 343 K under aerobic and base-free conditions. The highest yield of 42% with 73% selectivity towards 3-HPA was afforded by 1wt% Au0.8Pd0.2-PVP/HT catalyst.

  10. (E)-α,β-unsaturated amides from tertiary amines, olefins and CO via Pd/Cu-catalyzed aerobic oxidative N-dealkylation.

    PubMed

    Shi, Renyi; Zhang, Hua; Lu, Lijun; Gan, Pei; Sha, Yuchen; Zhang, Heng; Liu, Qiang; Beller, Matthias; Lei, Aiwen

    2015-02-21

    A novel Pd/Cu-catalyzed chemoselective aerobic oxidative N-dealkylation/carbonylation reaction has been developed. Tertiary amines are utilized as a "reservoir" of "active" secondary amines in this transformation, which inhibits the formation of undesired by-products and the deactivation of the catalysts. This protocol allows for an efficient and straightforward construction of synthetically useful and bioactive (E)-α,β-unsaturated amide derivatives from easily available tertiary amines, olefins and CO. PMID:25610923

  11. Organocatalytic Aerobic Oxidation of Benzylic sp(3) C-H Bonds of Ethers and Alkylarenes Promoted by a Recyclable TEMPO Catalyst.

    PubMed

    Zhang, Zhiguang; Gao, Yuan; Liu, Yuan; Li, Jianjun; Xie, Hexin; Li, Hao; Wang, Wei

    2015-11-01

    An entirely metal-free catalyst system consisting of an easily prepared recyclable new TEMPO derived sulfonic salt catalyst, and mineral acids (NaNO2 and HCl) has been developed for selective aerobic oxidation of structurally diverse benzylic sp(3) C-H bonds of ethers and alkylarenes. The mild reaction conditions allow for the generation of synthetically and biologically valued isochromanones and xanthones from readily accessible alkyl aromatic precursors in good yields. PMID:26513695

  12. Multi-regional input-output analysis for China's regional CH4 emissions

    NASA Astrophysics Data System (ADS)

    Zhang, Bo; Li, Jiashuo; Peng, Beihua

    2014-03-01

    China is the largest CH4 emitter in the world. Given the importance of CH4 in greenhouse gas emission inventories, the characteristics of China's CH4 emissions at different scales deserve to be fully understood. Presented in this paper is an interprovincial input-output embodiment analysis of China's regional CH4 emissions in 2007, based on the most recently available multi-regional input-output table, and relevant CH4 emissions data. The results show that the eastern, central and western areas contribute to 48.2%, 28.6%, and 23.3% of the national total embodied emissions, respectively. Guangdong has the highest level of embodied CH4 emissions among all of the 30 regions. The Agriculture sector produces the most embodied CH4 emissions in final demand, followed by the Construction, Food Production and Tobacco Processing, and Other Service Activities sectors. Significant net transfers of embodied CH4 emission flows are identified from the central and western areas to the eastern area via interregional trade. Shanxi is the largest interregional exporter of embodied CH4 emissions. In contrast, Guangdong is the largest interregional importer. Energy activities, agricultural activities, and waste management comprise 65.6%, 30.7%, and 3.7% of the total embodied CH4 emissions in interregional trade, respectively. By using consumption-based accounting principles, the emission magnitudes, per capita emissions, and emission intensities of most eastern regions increase remarkably, while those of some central and western regions decrease largely. To achieve regional CH4 emission mitigation, comprehensive mitigation measures should be designed under consideration of regional transfer of emission responsibility.

  13. Similar response in δD(CH4) during Holocene, Eem, MIS 11 and antecedent terminations

    NASA Astrophysics Data System (ADS)

    Bock, M.; Schmitt, J.; Fischer, H.

    2012-04-01

    Methane (CH4) is the third most important greenhouse gas after water vapour and carbon dioxide (CO2). Since the industrial revolution the mixing ratio of CH4 in the atmosphere rose to ~1800 ppb, a value never reached within the last 800 000 years. Nowadays, CH4 contributes ~20% to the total radiative forcing from all of the long-lived greenhouse gases. This CH4 increase can only be assessed compared to its natural changes in the past. Firn air and air enclosures in polar ice cores represent the only direct paleoatmospheric archive. The latter show that atmospheric CH4 concentrations changed in concert with northern hemisphere temperature during both glacial/interglacial transitions as well as rapid climate changes (Dansgaard-Oeschger events). Since the different sources of atmospheric methane exhibit distinct carbon and hydrogen isotopic composition (δ13CH4 and δD(CH4)) reconstructions of these parameters on ice cores allow to constrain individual CH4 source/sink changes. δD(CH4) also reflects water cycle changes as hydrogen of precipitation is traced into methane produced from wetland/thermokarst/permafrost systems (Bock et al. 2010, Science). Using an improved technique (GC/P/irmMS) for analysis of δD(CH4) based on earlier developments (Bock et al. 2010, RCM) we produced high precision records for the penultimate termination and interglacial (marine isotope stages (MIS) 6 to 5) from the EDML (European Project for Ice Coring in Antarctica, Dronning Maud Land) ice core and for MIS 11 from the EDC ice core (European Project for Ice Coring in Antarctica, Dome Concordia). We compare our data sets with the last termination and the Holocene by means of own measurements and published records (Sowers 2006, 2010). The principle response of δD(CH4) is similar for the three investigated time periods which allows to identify main natural drivers.

  14. Rotational study of the CH4-CO complex: Millimeter-wave measurements and ab initio calculations.

    PubMed

    Surin, L A; Tarabukin, I V; Panfilov, V A; Schlemmer, S; Kalugina, Y N; Faure, A; Rist, C; van der Avoird, A

    2015-10-21

    The rotational spectrum of the van der Waals complex CH4-CO has been measured with the intracavity OROTRON jet spectrometer in the frequency range of 110-145 GHz. Newly observed and assigned transitions belong to the K = 2-1 subband correlating with the rotationless jCH4 = 0 ground state and the K = 2-1 and K = 0-1 subbands correlating with the jCH4 = 2 excited state of free methane. The (approximate) quantum number K is the projection of the total angular momentum J on the intermolecular axis. The new data were analyzed together with the known millimeter-wave and microwave transitions in order to determine the molecular parameters of the CH4-CO complex. Accompanying ab initio calculations of the intermolecular potential energy surface (PES) of CH4-CO have been carried out at the explicitly correlated coupled cluster level of theory with single, double, and perturbative triple excitations [CCSD(T)-F12a] and an augmented correlation-consistent triple zeta (aVTZ) basis set. The global minimum of the five-dimensional PES corresponds to an approximately T-shaped structure with the CH4 face closest to the CO subunit and binding energy De = 177.82 cm(-1). The bound rovibrational levels of the CH4-CO complex were calculated for total angular momentum J = 0-6 on this intermolecular potential surface and compared with the experimental results. The calculated dissociation energies D0 are 91.32, 94.46, and 104.21 cm(-1) for A (jCH4 = 0), F (jCH4 = 1), and E (jCH4 = 2) nuclear spin modifications of CH4-CO, respectively. PMID:26493903

  15. High fat intake lowers hepatic fatty acid synthesis and raises fatty acid oxidation in aerobic muscle in Shetland ponies.

    PubMed

    Geelen, S N; Blázquez, C; Geelen, M J; Sloet van Oldruitenborgh-Oosterbaan, M M; Beynen, A C

    2001-07-01

    The metabolic effects of feeding soyabean oil instead of an isoenergetic amount of maize starch plus glucose were studied in ponies. Twelve adult Shetland ponies were given a control diet (15 g fat/kg DM) or a high-fat diet (118 g fat/kg DM) according to a parallel design. The diets were fed for 45 d. Plasma triacylglycerol (TAG) concentrations decreased by 55 % following fat supplementation. Fat feeding also reduced glycogen concentrations significantly by up to 65 % in masseter, gluteus and semitendinosus muscles (P < 0.05 and P < 0.01 and P < 0.01 respectively). The high-fat diet significantly increased the TAG content of semitendinosus muscle by 80 % (P < 0.05). Hepatic acetyl-CoA carboxylase and fatty acid synthase activities were 53 % (P < 0.01) and 56 % (P < 0.01) lower respectively in the high-fat group, but diacylglycerol acyltransferase activity was unaffected. Although carnitine palmitoyltransferase-I (CPT-I) activity in liver mitochondria was not influenced, fat supplementation did render CPT-I less sensitive to inhibition by malonyl-CoA. There was no significant effect of diet on the activity of phosphofructokinase in the different muscles. The activity of citrate synthase was raised significantly (by 25 %; P < 0.05) in the masseter muscle of fat-fed ponies, as was CPT-I activity (by 46 %; P < 0.01). We conclude that fat feeding enhances both the transport of fatty acids through the mitochondrial inner membrane and the oxidative capacity of highly-aerobic muscles. The higher oxidative ability together with the depressed rate of de novo fatty acid synthesis in liver may contribute to the dietary fat-induced decrease in plasma TAG concentrations in equines. PMID:11432762

  16. Catalytic Amine Oxidation under Ambient Aerobic Conditions: Mimicry of Monoamine Oxidase B.

    PubMed

    Murray, Alexander T; Dowley, Myles J H; Pradaux-Caggiano, Fabienne; Baldansuren, Amgalanbaatar; Fielding, Alistair J; Tuna, Floriana; Hendon, Christopher H; Walsh, Aron; Lloyd-Jones, Guy C; John, Matthew P; Carbery, David R

    2015-07-27

    The flavoenzyme monoamine oxidase (MAO) regulates mammalian behavioral patterns by modulating neurotransmitters such as adrenaline and serotonin. The mechanistic basis which underpins this enzyme is far from agreed upon. Reported herein is that the combination of a synthetic flavin and alloxan generates a catalyst system which facilitates biomimetic amine oxidation. Mechanistic and electron paramagnetic (EPR) spectroscopic data supports the conclusion that the reaction proceeds through a radical manifold. This data provides the first example of a biorelevant synthetic model for monoamine oxidase B activity. PMID:26087676

  17. 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

  18. Use of Advanced Oxidation and Aerobic Degradation for Remediation of Various Hydrocarbon Contaminates

    SciTech Connect

    Paul Fallgren

    2009-03-06

    Western Research Institute in conjunction with Sierra West Consultants, Inc., Tetra Tech, Inc., and the U.S. Department of Energy conducted laboratory and field studies to test different approaches to enhance degradation of hydrocarbons and associated contaminants. WRI in conjunction with Sierra West Consultants, Inc., conducted a laboratory and field study for using ozone to treat a site contaminated with MTBE and other hydrocarbons. Results from this study demonstrate that a TOD test can be used to resolve the O{sub 3} dosage problem by establishing a site-specific benchmark dosage for field ozone applications. The follow-up testing of the laboratory samples provided indications that intrinsic biodegradation could be stimulated by adding oxygen. Laboratory studies also suggests that O3 dosage in the full-scale field implementation could be dialed lower than stoichiometrically designed to eliminate the formation of Cr(VI). WRI conducted a study involving a series of different ISCO oxidant applications to diesel-contaminated soil and determined the effects on enhancing biodegradation to degrade the residual hydrocarbons. Soils treated with permanganate followed by nutrients and with persulfate followed by nutrients resulted in the largest decrease in TPH. The possible intermediates and conditions formed from NOM and TPH oxidation by permanganate and activated persulfate favors microbial TPH degrading activity. A 'passive-oxidation' method using microbial fuel cell (MFC) technology was conducted by WRI in conjunction with Tetra Tech, Inc., to degrade MTBE in groundwater. These experiments have demonstrated that a working MFC (i.e., one generating power) could be established in the laboratory using contaminated site water or buffered media inoculated with site water and spiked with MTBE, benzene, or toluene. Electrochemical methods were studied by WRI with goal of utilizing low voltage and amperage electrical sources for 'geo-oxidation' of organic contaminants. The

  19. Effects of oxidation reduction potential in the bypass micro-aerobic sludge zone on sludge reduction for a modified oxic-settling-anaerobic process.

    PubMed

    Li, Kexun; Wang, Yi; Zhang, Zhongpin; Liu, Dongfang

    2014-01-01

    Batch experiments were conducted to determine the effect of oxidation reduction potential (ORP) on sludge reduction in a bypass micro-aerobic sludge reduction system. The system was composed of a modified oxic-settling-anaerobic process with a sludge holding tank in the sludge recycle loop. The ORPs in the micro-aerobic tanks were set at approximately +350, -90, -150, -200 and -250 mV, by varying the length of aeration time for the tanks. The results show that lower ORP result in greater sludge volume reduction, and the sludge production was reduced by 60% at the lowest ORP. In addition, low ORP caused extracellular polymer substances dissociation and slightly reduced sludge activity. Comparing the sludge backflow characteristics of the micro-aerobic tank's ORP controlled at -250 mV with that of +350 mV, the average soluble chemical oxygen (SCOD), TN and TP increased by 7, 0.4 and 2 times, median particle diameter decreased by 8.5 μm and the specific oxygen uptake rate (SOUR) decreased by 0.0043 milligram O2 per gram suspended solids per minute. For the effluent, SCOD and TN and TP fluctuated around 30, 8.7 and 0.66 mg/L, respectively. Therefore, the effective assignment of ORP in the micro-aerobic tank can remarkably reduce sludge volume and does not affect final effluent quality. PMID:24845332

  20. Field and experimental evidence for low-O2 affinity of aerobic methane oxidizers in coastal waters

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

    The coastal ocean accounts for more than 75 % of the global oceanic methane emissions. An important process in mitigating methane emissions from the seawater to the atmosphere is aerobic methane oxidation (MOx). 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. We conducted a two-year time-series study of MOx measurements 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, 28 m water depth; www.bokniseck.de). Physicochemical parameters at this station have been monitored since 1957. Seasonal stratification during summer/autumn leads to intermittent oxygen depletion (hypoxic to anoxic) in bottom waters in the later part of the stratification period. The duration of these low-oxygen events increased since the 1970s (Lennartz et al., 2014). Furthermore, the organic-rich seafloor continuously produces methane, which leads to gas ebullition followed by accumulation of dissolved methane in bottom waters (up to 470 nM) and supersaturation (with respect to the atmospheric equilibrium) in surface waters (up to 27 nM). MOx communities were most active in bottom waters (1-5 nM/day), which usually contain the lowest oxygen concentrations (sometimes below the in situ detection limit of ~1 µM). In order to better understand the effect of low oxygen concentrations, and thus of hypoxic and suboxic events, on MOx in coastal systems, we conducted lab-based experiments, during which we adjusted oxygen concentrations to values between 0.2 - 220 µM in methane-rich (~100 nM) Eckernförde Bay waters. These samples were then incubated with trace amounts of tritium-labeled methane to assess first order rate constants of methane oxidation. Highest MOx rates were detected at oxygen concentrations of ~0.5 µM (considerably higher than at

  1. From California dreaming to California data: Challenging historic models for landfill CH4 emissions

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Improved quantification of diverse CH4 sources at the urban scale is needed to guide local greenhouse gas (GHG) mitigation strategies in the Anthropocene. Herein, we focus on landfill CH4 emissions in California, challenging the current IPCC methodology which focuses on a climate dependency for land...

  2. Kinetics of the CI(2PJ) + CH4 Reaction: Effects of Secondary Chemistry Below 300k

    NASA Technical Reports Server (NTRS)

    Keyser, L.; Wang, J.

    1999-01-01

    Because of the relatively large disagreement among earlier measurements at low temperatures, the results were examined for possible effects of non-Boltzmann spin distribution and vibrational excitation of CH4, secondary chemistry of CH3 radicals,and impuities in the CH4 source.

  3. Ice core δD(CH4) record precludes marine hydrate CH4 emissions at the onset of Dansgaard-Oeschger events

    NASA Astrophysics Data System (ADS)

    Bock, M.; Schmitt, J.; Möller, L.; Spahni, R.; Blunier, T.; Fischer, H.

    2010-12-01

    Air enclosures in polar ice cores represent the only direct paleoatmospheric archive (besides firn air) and show that atmospheric CH4 concentrations changed in concert with northern hemisphere temperature during both glacial/interglacial transitions as well as rapid climate changes (Dansgaard-Oeschger events). For stadials and interstadials during Marine Isotope Stage 3 concentration jumps of 100 - 200 ppbv within a few decades are observed. A concentration gradient with higher values in the northern versus the southern hemisphere during warm stages was reconstructed from ice core methane data from Greenland and Antarctica. This gradient indicates additional methane emissions during warm periods located in the northern hemisphere. However, the underlying processes for these changes are still not well understood. With tropical and boreal wetlands, biomass burning, thermokarst lakes, ruminants, termites, UV-induced emissions from organic matter and marine gas hydrates all contributing to the natural atmospheric CH4 level, an unambiguous source attribution remains difficult. Also changes in the methane sinks can modify the tropospheric CH4 budget, as trace gases like volatile organic compounds are competing for the major reactant - the OH radical. Additionally, the changing global atmospheric methane concentration itself feeds back on its lifetime. Together with the CH4 interhemispheric gradient, stable hydrogen and carbon isotopic studies on methane (δD(CH4) and δ13CH4) in ice cores allow to constrain individual CH4 source/sink changes. Here we present clear evidence from the North Greenland Ice Core Project ice core based on the hydrogen isotopic composition of methane δD(CH4) that clathrates did not cause atmospheric methane concentration to rise at the onset of Dansgaard-Oeschger (DO) events 7 and 8 (34 - 41 kilo years before present), however, we can not exclude that they played a minor role during and at the end of an interstadial. Box modeling supports

  4. Copper(II)-Mediated Aerobic Oxidation of Benzylimidates: Synthesis of Primary α-Ketoamides.

    PubMed

    Kumar, Yogesh; Shaw, Mukta; Thakur, Rima; Kumar, Amit

    2016-08-01

    A simple and straightforward method for the synthesis of primary α-ketoamides has been discovered. The reaction represents the first example of benzylimidates directly converting to primary α-ketoamides by using sustainable molecular oxygen as an oxidant. This reaction proceeds in the presence of copper(II) salt via cleavage of benzylic C-H and C-O bonds of the benzylimidates with liberation of alcohols as the only byproduct. A wide substrate scope, operationally mild conditions, the use of single substrates, and a reaction scaled up to grams make this strategy very attractive and practical. Furthermore, mechanistic studies illustrate that the imidate group adjacent to the benzylic position plays crucial role in facilitating this chemical process. PMID:27347744

  5. Megafauna and frozen soil: the drivers of atmospheric CH4 dynamics

    NASA Astrophysics Data System (ADS)

    Zimov, N.; Zimov, S. A.

    2010-12-01

    During the last deglaciation (LD) a strong increase in atmospheric methane (CH4) concentrations occurred simultaneously with a rise in Greenland temperatures indicating that in the north, during this time period, strong CH4 sources “awakened”, as additionally documented by the appearance of a strong gradient between northern (Greenland) and southern (Antarctica) hemisphere atmospheric CH4 concentrations. This rise could not be caused by wetland expansion. A reconstruction of peatland formation dynamics has indicated that wetlands on Earth were few in LD and only actively expanded 10,000 yr BP, after atmospheric CH4 concentrations began to decline. Destabilization of methane clathrates also could not be the source for atmospheric CH4 increase. Geological CH4 (including methane clathrates) has the highest deuterium content (δD) among all of the known sources of CH4 while atmospheric CH4 δD values determined for the LD were record low. To explain recorded atmospheric CH4 and its isotopic dynamics required a strong northern source, which was active only during the LD and that provided very low δD CH4 values. Such a source is permafrost thawing under anaerobic conditions (or better stated soils of mammoth steppe-tundra ecosystems). Permafrost thawing is the strongest, among known, wetland sources (usually over 100g CH4/m2yr) and has a unique isotopic signature (δD = -400 per mil (-338 to -479 per mil), δ13C = -73 per mil (-58 to -99 per mil)). The main sources of atmospheric CH4 have different isotopic signatures (δ13C, δD). The isotopic content of atmospheric CH4 is a simple function of the weight average for all of the sources. Inclusion of permafrost source into a budget model of the atmospheric methane and its isotopes allowed us to reconstruct the dynamics of methane’s main sources. Model indicated geological source to be negligible as in LGM so and in LD and Holocene. During the glaciation, the largest methane source was megafauna, whose 1

  6. Copper(II)-catalyzed room temperature aerobic oxidation of hydroxamic acids and hydrazides to acyl-nitroso and azo intermediates, and their Diels-Alder trapping.

    PubMed

    Chaiyaveij, Duangduan; Cleary, Leah; Batsanov, Andrei S; Marder, Todd B; Shea, Kenneth J; Whiting, Andrew

    2011-07-01

    CuCl(2), in the presence of a 2-ethyl-2-oxazoline ligand, is an effective catalyst for the room temperature, aerobic oxidation of hydroxamic acids and hydrazides, to acyl-nitroso and azo dienophiles respectively, which are efficiently trapped in situ via both inter- and intramolecular hetero-Diels-Alder reactions with dienes. Both inter- and intramolecular variants of the Diels-Alder reaction are suitable under the reaction conditions using a variety of solvents. Under the same conditions, an acyl hydrazide was also oxidized to give an acyl-azo dienophile which was trapped intramolecularly by a diene. PMID:21644530

  7. CarbonTracker-CH4: an assimilation system for estimating emissions of atmospheric methane

    NASA Astrophysics Data System (ADS)

    Bruhwiler, L.; Dlugokencky, E.; Masarie, K.; Ishizawa, M.; Andrews, A.; Miller, J.; Sweeney, C.; Tans, P.; Worthy, D.

    2014-08-01

    We describe an assimilation system for atmospheric methane (CH4), CarbonTracker-CH4, and demonstrate the diagnostic value of global or zonally averaged CH4 abundances for evaluating the results. We show that CarbonTracker-CH4 is able to simulate the observed zonal average mole fractions and capture inter-annual variability in emissions quite well at high northern latitudes (53-90° N). In contrast, CarbonTracker-CH4 is less successful in the tropics where there are few observations and therefore misses significant variability and is more influenced by prior flux estimates. CarbonTracker-CH4 estimates of total fluxes at high northern latitudes are about 81 ± 7 Tg CH4 yr-1, about 12 Tg CH4 yr-1 (13%) lower than prior estimates, a result that is consistent with other atmospheric inversions. Emissions from European wetlands are decreased by 30%, a result consistent with previous work by Bergamaschi et al. (2005); however, unlike their results, emissions from wetlands in boreal Eurasia are increased relative to the prior estimate. Although CarbonTracker-CH4 does not estimate an increasing trend in emissions from high northern latitudes for 2000 through 2010, significant inter-annual variability in high northern latitude fluxes is recovered. Exceptionally warm growing season temperatures in the Arctic occurred in 2007, a year that was also anonymously wet. Estimated emissions from natural sources were greater than the decadal average by 4.4 ± 3.8 Tg CH4 yr-1 in 2007. CarbonTracker-CH4 estimates for temperate latitudes are only slightly increased over prior estimates, but about 10 Tg CH4 yr-1 is redistributed from Asia to North America. This difference exceeds the estimated uncertainty for North America (±3.5 Tg CH4 yr-1). We used time invariant prior flux estimates, so for the period from 2000 to 2006, when the growth rate of global atmospheric CH4 was very small, the assimilation does not produce increases in natural or anthropogenic emissions in contrast to bottom

  8. 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.

  9. 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.

  10. Carbon nanotube-supported Au-Pd alloy with cooperative effect of metal nanoparticles and organic ketone/quinone groups as a highly efficient catalyst for aerobic oxidation of amines.

    PubMed

    Deng, Weiping; Chen, Jiashu; Kang, Jincan; Zhang, Qinghong; Wang, Ye

    2016-05-21

    Functionalised carbon nanotube (CNT)-supported Au-Pd alloy nanoparticles were highly efficient catalysts for the aerobic oxidation of amines. We achieved the highest turnover frequencies (>1000 h(-1)) for the oxidative homocoupling of benzylamine and the oxidative dehydrogenation of dibenzylamine. We discovered a cooperative effect between Au-Pd nanoparticles and ketone/quinone groups on CNTs. PMID:27125360

  11. [Distribution of CH4 in the suburb of Changsha City, China].

    PubMed

    Liu, Lu-Ning; Wang, Ying-Hong; Xu, Xiao-Juan; Wang, Wei-Dong; Wang, Yue-Si

    2013-11-01

    To study the variation of atmospheric CH4 concentration in the Yangtze River region, air samples which collected weekly using flasks from the suburb of Changsha City from 2007 to 2011 and the CH4 concentration was measured by gas chromatography. CH4 concentrations were analyzed combined with ground meteorological elements and backward trajectories to explore the CH4 concentration variations with source-sink relationships. The results showed that during the observation period, the annual mean concentration of CH4 was in the range 2012 x 10(-9) - 2075 x 10(-9) (volume mixing ratio, the same below). The difference between the maximum and minimum monthly mean of CH4 concentrations was 152 x 10(-9), with the highest concentration observed in autumn and the lowest in spring. Analysis of the surface wind showed that the concentration of CH4 was controlled by northwest wind and southerly winds alternately, and the contribution rate was 41.1% and 20.4%, respectively. Surface winds causing CH4 concentration uplift included W-WNW-NW in all four seasons, ESE-SE in summer and S in winter; while S in spring and summer have resulted in the decrease of CH4 concentration. Analysis of the air mass transport showed that the concentration of CH4 in the suburb of Changsha was significantly contributed by air masses from rice-producing areas in summer and high energy consumption areas in winter, and was cleared by air masses of long-distance transport from southern district. PMID:24455920

  12. Characteristics of atmospheric CO2 and CH4 at the Shangdianzi regional background station in China

    NASA Astrophysics Data System (ADS)

    Fang, Shuang-xi; Tans, Pieter P.; Dong, Fan; Zhou, Huaigang; Luan, Tian

    2016-04-01

    Atmospheric CO2 and CH4 have been continuously measured at the Shangdianzi regional background station (SDZ) in China from 2009 to 2013. Based on the influences of local surface wind and long-distance transport, the observed records were flagged into locally influenced, Beijing-Tianjin-Hebei (BTH) influenced, and Russia, Mongolia, and Inner Mongolia autonomous region influenced (RMI). ∼ 81.4% of CO2 and ∼75.6% of CH4 mole fractions were flagged as locally representative, indicating that the atmospheric CO2 and CH4 at SDZ were strongly influenced by local sources and sinks. Cluster analysis of back trajectories proved that the atmospheric CO2 and CH4 were influenced by air masses from northwest (RMI) or from south and southeast (BTH). The CO2 and CH4 mole fractions in BTH are always higher than in RMI, with the largest difference of 11.5 ± 0.3 ppm for CO2 and 102 ± 1 ppb for CH4 in July. The annual growth rates of CO2 and CH4 in BTH are 3.8 ± 0.01 ppm yr-1 and 10 ± 0.1 ppb yr-1, respectively, which are apparently higher than those of the RMI and the global means. The long-term trends of CO2 and CH4 in BTH are deviating from those in RMI, with ratios of ∼1.0 ppm yr-1 for CO2 and ∼2 ppb yr-1 for CH4, indicating the strengths of CO2 and CH4 emission in Beijing-Tianjin-Hebei plain increased more than 20% every year.

  13. Potential of nitrous oxide recovery from an aerobic/oxic/anoxic SBR process.

    PubMed

    Zhao, Jianqiang; Huang, Nan; Hu, Bo; Jia, Luwei; Ge, Guanghuan

    2016-01-01

    A single sequencing batch reactor (SBR) with an operating mode of anaerobic/oxic/anoxic (A/O/A) was developed to determine a simpler process to recover nitrous oxide (N2O) from synthetic wastewater containing ammonia and glucose. This SBR system was initiated in A/O mode to implement nitritation (ammonia to nitrite) and then switched to A/O/A mode. Using measurements of the dissolved N2O concentration and release rate, the total production and conversion rate of N2O were calculated to reveal the potential of producing and recovering N2O in the extended anoxic phase. Results showed that the A/O/A SBR could convert the majority of the nitrite available in the system into N2O by heterotrophic denitritation over longer anoxic periods, and a conversion rate of 77% could be achieved. As a consequence, the A/O/A SBR presents potential ability to produce and recover N2O from wastewater containing ammonia and organic carbon. PMID:26942527

  14. High-Potential Electrocatalytic O2 Reduction with Nitroxyl/NO x Mediators: Implications for Fuel Cells and Aerobic Oxidation Catalysis.

    PubMed

    Gerken, James B; Stahl, Shannon S

    2015-08-26

    Efficient reduction of O2 to water is a central challenge in energy conversion and many aerobic oxidation reactions. Here, we show that the electrochemical oxygen reduction reaction (ORR) can be achieved at high potentials by using soluble organic nitroxyl and nitrogen oxide (NO x ) mediators. When used alone, neither organic nitroxyls, such as 2,2,6,6-tetramethyl-1-piperidinyl-N-oxyl (TEMPO), nor NO x species, such as sodium nitrite, are effective ORR mediators. The combination of nitroxyl/NO x species, however, mediates sustained O2 reduction with overpotentials as low as 300 mV in acetonitrile containing trifluoroacetic acid. Mechanistic analysis of the coupled redox reactions supports a process in which the nitrogen oxide catalyst drives aerobic oxidation of a nitroxyl mediator to an oxoammonium species, which then is reduced back to the nitroxyl at the cathode. The electrolysis potential is dictated by the oxoammonium/nitroxyl reduction potential. The overpotentials accessible with this ORR system are significantly lower than widely studied molecular metal-macrocycle ORR catalysts and benefit from the mechanism-based specificity for four-electron reduction of oxygen to water mediated by NO x species, together with kinetically efficient reduction of oxidized NO x species by TEMPO and other organic nitroxyls. PMID:27162977

  15. 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.

  16. Reducing Uncertainty in Life Cycle CH4 Emissions from Natural Gas using Atmospheric Inversions

    NASA Astrophysics Data System (ADS)

    Schwietzke, S.; Griffin, W.; Matthews, H.; Bruhwiler, L.

    2013-12-01

    Rising interest in natural gas (NG) as a potentially cleaner alternative to coal and successful tapping of unconventional resources in North America, particularly shale gas, have led to numerous life cycle assessment (LCA) studies revisiting NG leakage rates, i.e., the fraction of produced NG, mostly methane, emitted to the atmosphere, intentionally or unintentionally. Accurately quantifying leakage rates of the full NG life cycle - extraction, processing, transport, and distribution - is challenging due to the size and complexity of the NG industry. Recent U.S. LCA estimates suggest that current NG leakage could be as high as 8% and 6%, from shale and conventional NG, respectively, compared to less than 2% in the latest EPA GHG emission inventory. Reducing uncertainty in the NG leakage rate is important for assessing potential climate benefits of NG over coal, and for understanding the global CH4 budget. The objective of this research is to analyze which ranges of the global average NG leakage rate are reasonable given existing atmospheric observations. We establish detailed prior global CH4 and C2H6 emission inventory scenarios for NG, oil, and coal using emissions data from the LCA literature including uncertainty estimates. Global CH4 and C2H6 inverse box-modeling is used to test the above hypotheses of various global NG leakage rates over the period 1984-2011. Forward simulations with NOAA's CarbonTracker-CH4 (CT-CH4) model provide additional spatial and seasonal information about CH4 atmospheric distribution. Box model inversion results indicate worst-case scenarios of current (2010) global average NG leakage rates of 7% (128 Tg CH4/yr) and 5% (92 Tg CH4/yr) based on CH4 isotope and C2H6 observations, respectively, as well as available raw gas composition data. Worst-case assumptions include upper bound estimates of the global CH4 and C2H6 budget, lower bound literature estimates of all CH4 and C2H6 sources other than NG simultaneously, and absence of a

  17. Airborne measurements of CO2 and CH4 onboard the UK FAAM research aircraft using a, Los Gatos Research Inc, cavity enhanced absorption spectrometer

    NASA Astrophysics Data System (ADS)

    O'Shea, S.; Bauguitte, S.; Muller, J. B.; Le Breton, M.; Gallagher, M. W.; Allen, G.; Percival, C. J.

    2012-12-01

    Airborne measurements of CO2 and CH4 have been made using the UK Facility for Airborne Atmospheric Measurements (FAAM) BAe-146 research aircraft since spring 2011.The measurement system uses a commercially available analyser, based on the off-axis integrated cavity output spectroscopy technique, from Los Gatos Research Inc (FGGA, Model RMT-200). During the first year of operation (29 flights), 1 Hz measurements were found to be accurate to 0.07 ± 2.48ppbv for CH4 and -0.06± 0.66ppmv for CO2. In summer 2011, as part of the BORTAS project (Quantifying the impact of BOReal forest fires on Tropospheric oxidants over the Atlantic using Aircraft and Satellites), outflow from boreal forest fires was measured in Eastern Canada. A number of fresh and photochemically-aged plumes were identified using simultaneous HCN measurements, a widely used tracer for biomass burning. In the freshest plumes, strong relationships were found between CH4, CO2 and other tracers for biomass burning. From this we were able to estimate that 6.9±0.8 g of CH4 and 1551±213 g of CO2 were released into the atmosphere per kg of dry matter burnt. These emission factors are in good agreement with estimates from previous studies in boreal regions. However for aged plumes the correlations between CH4 and other biomass burning tracers were not as robust, most likely due to mixing from other CH4 emission sources, such as the wetland regions. The role of additional emission sources will be investigated using the UK Met Office NAME atmospheric dispersion model and the HYSPLIT trajectory model. Using tailored back trajectory analysis, we will present an interpretation of this new dataset in the context of air mass/fire origin, relating this to MODIS fire maps and source strength.

  18. Emissions of CH4 and N2O under Different Tillage Systems from Double-Cropped Paddy Fields in Southern China

    PubMed Central

    Zhang, Hai-Lin; Bai, Xiao-Lin; Xue, Jian-Fu; Chen, Zhong-Du; Tang, Hai-Ming; Chen, Fu

    2013-01-01

    Understanding greenhouse gases (GHG) emissions is becoming increasingly important with the climate change. Most previous studies have focused on the assessment of soil organic carbon (SOC) sequestration potential and GHG emissions from agriculture. However, specific experiments assessing tillage impacts on GHG emission from double-cropped paddy fields in Southern China are relatively scarce. Therefore, the objective of this study was to assess the effects of tillage systems on methane (CH4) and nitrous oxide (N2O) emission in a double rice (Oryza sativa L.) cropping system. The experiment was established in 2005 in Hunan Province, China. Three tillage treatments were laid out in a randomized complete block design: conventional tillage (CT), rotary tillage (RT) and no-till (NT). Fluxes of CH4 from different tillage treatments followed a similar trend during the two years, with a single peak emission for the early rice season and a double peak emission for the late rice season. Compared with other treatments, NT significantly reduced CH4 emission among the rice growing seasons (P<0.05). However, much higher variations in N2O emission were observed across the rice growing seasons due to the vulnerability of N2O to external influences. The amount of CH4 emission in paddy fields was much higher relative to N2O emission. Conversion of CT to NT significantly reduced the cumulative CH4 emission for both rice seasons compared with other treatments (P<0.05). The mean value of global warming potentials (GWPs) of CH4 and N2O emissions over 100 years was in the order of NT

  19. CH4 and N2O emissions from China's beef feedlots with ad libitum and restricted feeding in fall and spring seasons.

    PubMed

    Lin, Zhi; Liao, Wenhua; Yang, Yuanyuan; Gao, Zhiling; Ma, Wenqi; Wang, Dianwu; Cao, Yufeng; Li, Jianguo; Cai, Zhenjiang

    2015-04-01

    Accurately quantifying methane (CH4) and nitrous oxide (N2O) emissions from beef operations in China is necessary to evaluate the contribution of beef cattle to greenhouse gas budgets at the national and global level. Methane and N2O emissions from two intensive beef feedlots in the North China Plain, one with a restricted feeding strategy and high manure collection frequency and the other with an ad libitum feeding strategy and low manure collection frequency, were quantified in the fall and spring seasons using an inverse dispersion technique. The diel pattern of CH4 from the beef feedlot with an ad libitum feed strategy (single peak during a day) differed from that under a restricted feeding condition (multiple peaks during a day), but little difference in the diel pattern of N2O emissions between two feeding strategies was observed. The two-season average CH4 emission rates of the two intensive feedlots were 230 and 198gCH4animal(-1)d(-1) and accounted for 6.7% and 6.8% of the gross energy intake, respectively, indicating little impact of the feeding strategy and manure collection frequency on the CH4 conversion factor at the feedlot level. However, the average N2O emission rates (21.2g N2Oanimal(-1)d(-1)) and conversion factor (8.5%) of the feedlot with low manure collection frequency were approximately 131% and 174% greater, respectively, than the feedlot under high frequency conditions, which had a N2O emission rate and conversion factor of 9.2g N2Oanimal(-1)d(-1) and 3.1%, respectively, indicating that increasing manure collection frequency played an important role in reducing N2O emissions from beef feedlots. In addition, comparison indicated that China's beef and dairy cattle in feedlots appeared to have similar CH4 conversion factors. PMID:25769128

  20. Osmium(0) nanoclusters stabilized by zeolite framework; highly active catalyst in the aerobic oxidation of alcohols under mild conditions.

    PubMed

    Zahmakiran, Mehmet; Akbayrak, Serdar; Kodaira, Tetsuya; Ozkar, Saim

    2010-08-28

    Osmium(0) nanoclusters stabilized by zeolite-Y framework were reproducibly prepared by a simple two step procedure involving the incorporation of osmium(III) cations into the zeolite matrix by ion-exchange, followed by their reduction within the cavities of zeolite with sodium borohydride in aqueous solution all at room temperature. The composition and morphology of osmium(0) nanoclusters stabilized by zeolite framework, as well as the integrity and crystallinity of the host material were investigated by using ICP-OES, XRD, XPS, SEM, TEM, HRTEM, TEM/EDX, mid-IR, far-IR spectroscopies, and N(2)-adsorption/desorption technique. The results of the multiprong analysis reveal the formation of osmium(0) nanoclusters within the cavities of zeolite-Y without causing alteration in the framework lattice, formation of mesopores, or loss in the crystallinity of the host material. More importantly, far-IR studies showed that after the reduction of Os(3+) cations by sodium borohydride the Na(+) cations reoccupy their authentic cation sites restoring the integrity of zeolite-Y. The catalytic activity of osmium(0) nanoclusters stabilized by zeolite framework was tested in the aerobic oxidation of activated, unactivated and heteroatom containing alcohols to carbonyl compounds and was found to provide high activity and selectivity even under mild conditions (80 degrees C and 1 atm O(2) or air). Moreover, they were found to be stable enough to be isolated and bottled as solid material, which can be reused as active catalyst under the identical conditions of the first run. PMID:20614055

  1. Continuous Aerobic Training in Individualized Intensity Avoids Spontaneous Physical Activity Decline and Improves MCT1 Expression in Oxidative Muscle of Swimming Rats

    PubMed Central

    Scariot, Pedro P. M.; Manchado-Gobatto, Fúlvia de Barros; Torsoni, Adriana S.; dos Reis, Ivan G. M.; Beck, Wladimir R.; Gobatto, Claudio A.

    2016-01-01

    Although aerobic training has been shown to affect the lactate transport of skeletal muscle, there is no information concerning the effect of continuous aerobic training on spontaneous physical activity (SPA). Because every movement in daily life (i.e., SPA) is generated by skeletal muscle, we think that it is possible that an improvement of SPA could affect the physiological properties of muscle with regard to lactate transport. The aim of this study was to evaluate the effect of 12 weeks of continuous aerobic training in individualized intensity on SPA of rats and their gene expressions of monocarboxylate transporters (MCT) 1 and 4 in soleus (oxidative) and white gastrocnemius (glycolytic) muscles. We also analyzed the effect of continuous aerobic training on aerobic and anaerobic parameters using the lactate minimum test (LMT). Sixty-day-old rats were randomly divided into three groups: a baseline group in which rats were evaluated prior to initiation of the study; a control group (Co) in which rats were kept without any treatment during 12 weeks; and a chronic exercise group (Tr) in which rats swam for 40 min/day, 5 days/week at 80% of anaerobic threshold during 12 weeks. After the experimental period, SPA of rats was measured using a gravimetric method. Rats had their expression of MCTs determined by RT-PCR analysis. In essence, aerobic training is effective in maintaining SPA, but did not prevent the decline of aerobic capacity and anaerobic performance, leading us to propose that the decline of SPA is not fully attributed to a deterioration of physical properties. Changes in SPA were concomitant with changes in MCT1 expression in the soleus muscle of trained rats, suggestive of an additional adaptive response toward increased lactate clearance. This result is in line with our observation showing a better equilibrium on lactate production-remotion during the continuous exercise (LMT). We propose an approach to combat the decline of SPA of rats in their home

  2. Continuous Aerobic Training in Individualized Intensity Avoids Spontaneous Physical Activity Decline and Improves MCT1 Expression in Oxidative Muscle of Swimming Rats.

    PubMed

    Scariot, Pedro P M; Manchado-Gobatto, Fúlvia de Barros; Torsoni, Adriana S; Dos Reis, Ivan G M; Beck, Wladimir R; Gobatto, Claudio A

    2016-01-01

    Although aerobic training has been shown to affect the lactate transport of skeletal muscle, there is no information concerning the effect of continuous aerobic training on spontaneous physical activity (SPA). Because every movement in daily life (i.e., SPA) is generated by skeletal muscle, we think that it is possible that an improvement of SPA could affect the physiological properties of muscle with regard to lactate transport. The aim of this study was to evaluate the effect of 12 weeks of continuous aerobic training in individualized intensity on SPA of rats and their gene expressions of monocarboxylate transporters (MCT) 1 and 4 in soleus (oxidative) and white gastrocnemius (glycolytic) muscles. We also analyzed the effect of continuous aerobic training on aerobic and anaerobic parameters using the lactate minimum test (LMT). Sixty-day-old rats were randomly divided into three groups: a baseline group in which rats were evaluated prior to initiation of the study; a control group (Co) in which rats were kept without any treatment during 12 weeks; and a chronic exercise group (Tr) in which rats swam for 40 min/day, 5 days/week at 80% of anaerobic threshold during 12 weeks. After the experimental period, SPA of rats was measured using a gravimetric method. Rats had their expression of MCTs determined by RT-PCR analysis. In essence, aerobic training is effective in maintaining SPA, but did not prevent the decline of aerobic capacity and anaerobic performance, leading us to propose that the decline of SPA is not fully attributed to a deterioration of physical properties. Changes in SPA were concomitant with changes in MCT1 expression in the soleus muscle of trained rats, suggestive of an additional adaptive response toward increased lactate clearance. This result is in line with our observation showing a better equilibrium on lactate production-remotion during the continuous exercise (LMT). We propose an approach to combat the decline of SPA of rats in their home

  3. The effect of low-level laser therapy on oxidative stress and functional fitness in aged rats subjected to swimming: an aerobic exercise.

    PubMed

    Guaraldo, Simone A; Serra, Andrey Jorge; Amadio, Eliane Martins; Antônio, Ednei Luis; Silva, Flávio; Portes, Leslie Andrews; Tucci, Paulo José Ferreira; Leal-Junior, Ernesto Cesar Pinto; de Carvalho, Paulo de Tarso Camillo

    2016-07-01

    The aim of the present study was to determine whether low-level laser therapy (LLLT) in conjunction with aerobic training interferes with oxidative stress, thereby influencing the performance of old rats participating in swimming. Thirty Wistar rats (Norvegicus albinus) (24 aged and six young) were tested. The older animals were randomly divided into aged-control, aged-exercise, aged-LLLT, aged-LLLT/exercise, and young-control. Aerobic capacity (VO2max(0.75)) was analyzed before and after the training period. The exercise groups were trained for 6 weeks, and the LLLT was applied at 808 nm and 4 J energy. The rats were euthanized, and muscle tissue was collected to analyze the index of lipid peroxidation thiobarbituric acid reactive substances (TBARS), glutathione (GSH), superoxide dismutase (SOD), and catalase (CAT) activities. VO2 (0.75)max values in the aged-LLLT/exercise group were significantly higher from those in the baseline older group (p <0.01) and the LLLT and exercise group (p <0.05). The results indicate that the activities of CAT, SOD, and GPx were higher and statistically significant (p <0.05) in the LLLT/exercise group than those in the LLLT and exercise groups. Young animals presented lesser and statistically significant activities of antioxidant enzymes compared to the aged group. The LLLT/exercise group and the LLLT and exercise group could also mitigate the concentration of TBARS (p > 0.05). Laser therapy in conjunction with aerobic training may reduce oxidative stress, as well as increase VO2 (0.75)max, indicating that an aerobic exercise such as swimming increases speed and improves performance in aged animals treated with LLLT. PMID:26861983

  4. CH4 emission from various rice fields in P.R. China

    NASA Astrophysics Data System (ADS)

    Wang, M.-X.; Shangguan, X.-J.

    1996-03-01

    The CH4 emission rates from Chinese rice fields have been measured in five typical areas representing all of the five major rice culture regions in People's Republic of China (P.R. China). Four types of diurnal variations (afternoon peak, night peak, afternoon-night double peaks and random pattern) of CH4 emission rates have been found. The first pattern was normally found in clear weather, the second and the third types were only found occasionally in particular place, while the fourth were found in cloudy or rainy weather. Due to the irregular pattern of the methane production observed in the morning-afternoon comparison experiment, the transport pathway influenced by certain factors, may be the major factor governing the diurnal variation of CH4 emission. Seasonal variation patterns of CH4 emission differ slightly with different field locations, where climate system, cropping system and other factors are different. Two and three emission peaks were generally found during single and early rice vegetation periods, with the peak magnitude and time of appearance differing to small degree in individual sites. A decreasing trend of seasonal variation was always observed in late rice season. A combination of seasonal change of transport efficiency and that of CH4 production rate in the paddy soil explains well the CH4 emission. The role of rice plant in transporting CH4 varied over a large range in different rice growing stages. The reasons for internnual changes of CH4 flux are not yet clear. Great spatial variation of the CH4 emission has been found, which can be attributed to the differences in soil type and soil properties, local climate condition, rice species, fertilizer and water treatment. Experiments showed that while the application of some mineral fertilizers will reduce the CH4 emission and CH4 production in the soil, the application of organic manure will enhance CH4 emission and CH4 production in the soil. Any measures which can get off easily decomposed

  5. CarbonTracker-CH4: an assimilation system for estimating emissions of atmospheric methane

    NASA Astrophysics Data System (ADS)

    Bruhwiler, L. M.; Dlugokencky, E.; Masarie, K.; Ishizawa, M.; Andrews, A.; Miller, J.; Sweeney, C.; Tans, P.; Worthy, D.

    2014-01-01

    We describe an assimilation system for atmospheric methane (CH4), CarbonTracker-CH4, and demonstrate the diagnostic value of global or zonally averaged CH4 abundances for evaluating the results. We show that CarbonTracker-CH4 is able to simulate the observed zonal average mole fractions and capture inter-annual variability in emissions quite well at high northern latitudes (53-90° N). CarbonTracker-CH4 estimates of total fluxes at high northern latitudes are about 81 Tg CH4 yr-1, about 12 Tg CH4 yr-1 (13%) lower than prior estimates, a result that is consistent with other atmospheric inversions. Emissions from European wetlands are decreased by 30%, a result consistent with previous; however, emissions from wetlands in Boreal Eurasia are increased relative to the prior estimate. Although CarbonTracker-CH4 does not estimate increases in emissions from high northern latitudes for 2000 through 2010, significant inter-annual variability in high northern latitude fluxes is recovered. During the exceptionally warm Arctic summer of 2007, estimated emissions were greater than the decadal average by 4.4 Tg CH4 yr-1. In 2008, temperatures returned to more normal values over Arctic North America while they stayed above normal over Arctic Eurasia. CarbonTracker-CH4 estimates were 2.4 Tg CH4 yr-1 higher than the decadal average, and the anomalous emissions occurred over Arctic Eurasia, suggesting that the data allow discrimination between these two source regions. Also, the emission estimates respond to climate variability without having the system constrained by climate parameters. CarbonTracker-CH4 estimates for temperate latitudes are only slightly increased over prior estimates, but about 10 Tg CH4 yr-1 is redistributed from Asia to North America. We used time invariant prior flux estimates, so for the period from 2000 to 2006, when the growth rate of global atmospheric CH4 was very small, the assimilation does not produce increases in natural or anthropogenic emissions in

  6. Long-term Variations of Atmospheric CH4 Concentration over Siberia Derived from Aircraft Observation.

    NASA Astrophysics Data System (ADS)

    Sasakawa, M.; Machida, T.; Ito, A.; Tsuda, N.; Arshinov, M.; Davydov, D.; Fofonov, A.; Krasnov, O.; Patra, P. K.; Ishijima, K.

    2015-12-01

    We have been carrying out monthly flask sampling over 3 Siberian sites (Surgut, Novosibirsk, and Yakutsk) using aircraft and obtained the vertical profile of CH4 concentration up to 7 km since 1993. Temporal variation at each altitude exhibited increasing trend as observed globally (Figure). Seasonal variation at Yakutsk in East Siberia showed expected summer minimum, as seen at remote sites in northern mid to high latitudes, although no clear seasonality was observed at West Siberian sites (Surgut and Novosibirsk). Large CH4 emissions from West Siberian Lowlands (WSL) might compensate CH4 loss by reaction with OH radical during summer. The vertical gradient in CH4 concentration was larger in Surgut and Novosibirsk than in Yakutsk, which suggests a strong CH4 emission from WSL as well. However, the vertical gradient at Surgut was obviously decreasing; the annual mean difference between 5.5 km and 1.0 km decreased from 62-76 ppb during 1994-1996 to 33-49 ppb during 2012-2014. Chemical transport model reproduced this decrease tendency and suggested that global CH4 emissions have increased, but the contribution from WSL and Europe have decreased in this decade. Figure. Temporal variations in CH4 concentration observed at 1000 and 5500 km altitude over Surgut in West Siberia. Dot color and error bar indicates the number of samples in the same altitude and the range of measured concentration, respectively. The curved line shows fitting line.

  7. Indirect Estimation of CH4 from Livestock Feeds through TOCs Evaluation.

    PubMed

    Kim, M J; Lee, J S; Kumar, S; Rahman, M M; Shin, J S; Ra, C S

    2012-04-01

    Thirty-five available feeds were fermented in vitro in order to investigate their soluble total organic carbon (TOCs) and methane (CH4) production rate. A fermentation reactor was designed to capture the CH4 gas emitted and to collect liquor from the reactor during in vitro fermentation. The results showed that CH4 production rate greatly varied among feeds with different ingredients. The lowest CH4-producing feeds were corn gluten feed, brewer's grain, and orchard grass among the energy, protein, and forage feed groups, respectively. Significant differences (p<0.05) were found in digestibility, soluble total organic carbon (TOCs), and CH4 emissions among feeds, during 48 h of in vitro fermentation. Digestibility and TOCs was not found to be related due to different fermentation pattern of each but TOCs production was directly proportional to CH4 production (y = 0.0076x, r(2) = 0.83). From this in vitro study, TOCs production could be used as an indirect index for estimation of CH4 emission from feed ingredients. PMID:25049590

  8. SAPO-34 Membranes for N-2/CH4 separation: Preparation, characterization, separation performance and economic evaluation

    SciTech Connect

    Li, SG; Zong, ZW; Zhou, SJ; Huang, Y; Song, ZN; Feng, XH; Zhou, RF; Meyer, HS; Yu, M; Carreon, MA

    2015-08-01

    SAPO-34 membranes were synthesized by several routes towards N-2/CH4 separation. Membrane synthesis parameters including water content in the gel, crystallization time, support pore size, and aluminum source were investigated. High performance N-2-selective membranes were obtained on 100-nm-pore alumina tubes by using Al(i-C3H7O)(3) as aluminum source with a crystallization time of 6 h. These membranes separated N-2 from CH, with N-2 permeance as high as 500 GPU with separation selectivity of 8 at 24 degrees C. for a 50/50 N-2/CH4 mixture. Nitrogen and CH, adsorption isotherms were measured on SAPO-34 crystals. The N-2 and CH, heats of adsorption were 11 and 15 kJ/mol, respectively, which lead to a preferential adsorption of CE-H-4 over N-2 in the N-2/CH4 mixture. Despite this, the SAPO-34 membranes were selective for N-2 over CH4 in the mixture because N-2 diffuses much faster than CH4 and differences in diffusivity played a more critical role than the competitive adsorption. Preliminary economic evaluation indicates that the required N-2/CH4 selectivity would be 15 in order to maintain a CH4 loss below 10%. For small nitrogen-contaminated gas wells, our current SAPO-34 membranes have potential to compete with the benchmark technology cryogenic distillation for N-2 rejection. (C) 2015 Elsevier B.V. All rights reserved,

  9. Indirect Estimation of CH4 from Livestock Feeds through TOCs Evaluation

    PubMed Central

    Kim, M. J.; Lee, J. S.; Kumar, S.; Rahman, M. M.; Shin, J. S.; Ra, C. S.

    2012-01-01

    Thirty-five available feeds were fermented in vitro in order to investigate their soluble total organic carbon (TOCs) and methane (CH4) production rate. A fermentation reactor was designed to capture the CH4 gas emitted and to collect liquor from the reactor during in vitro fermentation. The results showed that CH4 production rate greatly varied among feeds with different ingredients. The lowest CH4-producing feeds were corn gluten feed, brewer’s grain, and orchard grass among the energy, protein, and forage feed groups, respectively. Significant differences (p<0.05) were found in digestibility, soluble total organic carbon (TOCs), and CH4 emissions among feeds, during 48 h of in vitro fermentation. Digestibility and TOCs was not found to be related due to different fermentation pattern of each but TOCs production was directly proportional to CH4 production (y = 0.0076x, r2 = 0.83). From this in vitro study, TOCs production could be used as an indirect index for estimation of CH4 emission from feed ingredients. PMID:25049590

  10. Quasi-Bound States of the F·CH4 Complex.

    PubMed

    Schäpers, Daniela; Manthe, Uwe

    2016-05-19

    The F + CH4 → HF + CH3 reaction is an intensively studied prototypical example of a polyatomic reaction showing an early transition state. Prereactive complexes are assumed to play an important role in the dynamics of the reaction. In this work, the long-living resonance states resulting from the formation of a metastable F·CH4 complex are investigated in detail. Full-dimensional quantum dynamics calculations employing the multiconfigurational time-dependent Hartree (MCTDH) approach and a single adiabatic potential energy surface are used to study the low-lying quasi-bound states of the F·CH4 complex for vanishing total (nuclear) angular momentum. The computed dissociation energy of the F·CH4 complex with respect to the reactant asymptote is 170 cm(-1). About 60 resonance states with energies below the reactant asymptote are found. A detailed analysis of the computed wave function of the low-lying states shows an almost free relative rotation of F and CH4 and an approximately separable F-CH4 stretching vibration. The present results are compared with transition state spectroscopy experiments which study the photodetachment spectrum of the CH4F(-) anion. PMID:26730978

  11. A factorial randomized controlled trial to evaluate the effect of micronutrients supplementation and regular aerobic exercise on maternal endothelium-dependent vasodilatation and oxidative stress of the newborn

    PubMed Central

    2011-01-01

    Background Many studies have suggested a relationship between metabolic abnormalities and impaired fetal growth with the development of non-transmissible chronic diseases in the adulthood. Moreover, it has been proposed that maternal factors such as endothelial function and oxidative stress are key mechanisms of both fetal metabolic alterations and subsequent development of non-transmissible chronic diseases. The objective of this project is to evaluate the effect of micronutrient supplementation and regular aerobic exercise on endothelium-dependent vasodilation maternal and stress oxidative of the newborn. Methods and design 320 pregnant women attending to usual prenatal care in Cali, Colombia will be included in a factorial randomized controlled trial. Women will be assigned to the following intervention groups: 1. Control group: usual prenatal care (PC) and placebo (maltodextrine). 2. Exercise group: PC, placebo and aerobic physical exercise. 3. Micronutrients group: PC and a micronutrients capsule consisting of zinc (30 mg), selenium (70 μg), vitamin A (400 μg), alphatocopherol (30 mg), vitamin C (200 mg), and niacin (100 mg). 4. Combined interventions Group: PC, supplementation of micronutrients, and aerobic physical exercise. Anthropometric measures will be taken at the start and at the end of the interventions. Discussion Since in previous studies has been showed that the maternal endothelial function and oxidative stress are related to oxidative stress of the newborn, this study proposes that complementation with micronutrients during pregnancy and/or regular physical exercise can be an early and innovative alternative to strengthen the prevention of chronic diseases in the population. Trial registration NCT00872365. PMID:21356082

  12. Local- and regional-scale measurements of CH4, δ13CH4, and C2H6 in the Uintah Basin using a mobile stable isotope analyzer

    NASA Astrophysics Data System (ADS)

    Rella, C. W.; Hoffnagle, J.; He, Y.; Tajima, S.

    2015-10-01

    In this paper, we present an innovative CH4, δ13CH4, and C2H6 instrument based on cavity ring-down spectroscopy (CRDS). The design and performance of the analyzer is presented in detail. The instrument is capable of precision of less than 1 ‰ on δ13CH4 with 1 in. of averaging and about 0.1 ‰ in an hour. Using this instrument, we present a comprehensive approach to atmospheric methane emissions attribution. Field measurements were performed in the Uintah Basin (Utah, USA) in the winter of 2013, using a mobile lab equipped with the CRDS analyzer, a high-accuracy GPS, a sonic anemometer, and an onboard gas storage and playback system. With a small population and almost no other sources of methane and ethane other than oil and gas extraction activities, the Uintah Basin represents an ideal location to investigate and validate new measurement methods of atmospheric methane and ethane. We present the results of measurements of the individual fugitive emissions from 23 natural gas wells and six oil wells in the region. The δ13CH4 and C2H6 signatures that we observe are consistent with the signatures of the gases found in the wells. Furthermore, regional measurements of the atmospheric CH4, δ13CH4, and C2H6 signatures throughout the basin have been made, using continuous sampling into a 450 m long tube and laboratory reanalysis with the CRDS instrument. These measurements suggest that 85 ± 7 % of the total emissions in the basin are from natural gas production.

  13. N2O and CH4 emissions from a Chinese wheat-rice cropping system under different tillage practices during the wheat-growing season

    NASA Astrophysics Data System (ADS)

    Zhang, Y.

    2015-12-01

    The annual wheat (Triticum aestivum L.)-rice (Oryza sativa L.) cropping system is the most important cereal production system in the Yangtze River Valley of China, in which various tillage systems are currently implemented during the wheat-growing season. The emissions of nitrous oxide (N2O) and methane (CH4) from the different tillage systems in this system remain unclear. We conducted a 3-year field experiment in a wheat-rice cropping system in a silt clay loam soil to investigate the effects of the type of tillage employed during the wheat-growing season (no-tillage (NT), reduced tillage (RT) or conventional tillage (CT)) on the emissions of N2O and CH4 using the static chamber method over three annual rotation cycles from the 2008 wheat season to the 2011 rice season. The results revealed that the adoption of an NT system during the wheat-growing season significantly increased CH4 emissions during both the wheat-growing season and the following rice-growing season. Over the three annual rotation cycles studied, the annual N2O emissions from the NT (2.24 kg N2O-N ha-1) and CT (2.01 kg N2O-N ha-1) treatments were similar to each other and significantly higher than those from the RT treatment (1.73 kg N2O-N ha-1); the annual CH4 emissions were significantly higher from the NT (100.1 kg CH4-C ha-1) than the CT (83.7 kg CH4-C ha-1) and RT (73.9 kg CH4-C ha-1) systems. The overall results regarding the net global warming potential associated with annual N2O and CH4 emissions indicate that the conversion of conventional tillage to no-tillage systems during the wheat-growing season would intensify the radiative forcing in wheat-rice cropping systems in China.

  14. Fluxes of CH4, CO2, and N2O in hydroelectric reservoirs Lokka and Porttipahta in the northern boreal zone in Finland

    NASA Astrophysics Data System (ADS)

    Huttunen, Jari T.; Väisänen, Tero S.; Hellsten, Seppo K.; Heikkinen, Mirja; Nykänen, Hannu; Jungner, Högne; Niskanen, Arto; Virtanen, Markku O.; Lindqvist, Ossi V.; Nenonen, Olli S.; Martikainen, Pertti J.

    2002-01-01

    Concentrations and fluxes of greenhouse gases methane (CH4), carbon dioxide (CO2), and nitrous oxide (N2O) were measured during open water conditions in two hydroelectric reservoirs, Lokka and Porttipahta, in the northern boreal zone in Finland. These reservoirs were located on peat and forest soils and were built in 1967 and 1970, respectively. Over 20 years after their flooding, the reservoirs were still largely supersaturated with dissolved CH4 and CO2. Measured with floating static chambers, the stations in Lokka released more CH4 (means of 5.3-119 mg m-2 d-1) during the open water periods in 1994 and 1995 than the stations in Porttipahta (means of 2.5-4.8 mg m-2 d-1), measured in 1995. The mean CO2 emission rates in Lokka (21-133 mg m-2 h-1) and Porttipahta (36-95 mg CO2 m-2 h-1) were more similar. The chamber measurements could not detect episodic CH4 ebullition in Lokka Reservoir, indicated by generally higher CH4 fluxes (means of 2.6-660 mg m-2 d-1) obtained with bubble gas collectors than with the chambers. The seasonal mean N2O fluxes were generally low, ranging from -89 to 270 μg m-2 d-1. There was no clear association between the CH4 emissions and the bottom type, including mineral soils and old peat deposits. The flooded vegetation, higher nutrient content, and primary production in the water column rather than old peat could account for the higher CH4 emissions from the stations in Lokka. This conclusion is supported by the high content of modern carbon (C) in methane (percent modern C of 92-104%) that was extracted from the sediment of Lokka. The results suggested that if there is a good long-term availability of phosphorus and nitrogen, the intensive internal C cycle associated with the primary production could maintain high CH4 and CO2 production for decades, similar to the situation in eutrophied natural lakes.

  15. Effect of ammonium-based, non-sulfate fertilizers on CH 4 emissions from a paddy field with a typical Chinese water management regime

    NASA Astrophysics Data System (ADS)

    Dong, Haibo; Yao, Zhisheng; Zheng, Xunhua; Mei, Baoling; Xie, Baohua; Wang, Rui; Deng, Jia; Cui, Feng; Zhu, Jianguo

    2011-02-01

    The effects of ammonium-based, non-sulfate fertilizers, such as urea and/or ammonium phosphate (NH 4H 2PO 4), on methane (CH 4) emissions from paddy rice fields deserve attention, as they are being used increasingly for rice cultivation. A four-year field campaign was conducted in the Yangtze River Delta from 2004 to 2007 to assess the effects of different application rates of urea plus NH 4H 2PO 4 on the CH 4 emissions from a paddy rice field. The experimental field was under a typical Chinese water regime that follows a flooding-midseason drainage-reflooding-moist irrigation mode. Over the course of four years, the mean cumulative CH 4 emissions during the rice seasons were 221, 136 and 112 kg C ha -1 for nitrogen addition rates of 0, 150 and 250 kg N ha -1, respectively. Compared to the treatment without nitrogen amendments, the 150 kg N ha -1 decreased the CH 4 emissions by 6-59% ( P < 0.01 in one year, but not statistically significant in the others). When the addition rate was further increased to 250 kg N ha -1, the CH 4 emissions were significantly reduced by 35-53% ( P < 0.01) compared to the no-nitrogen treatment. Thus, an addition rate of 250 kg N ha -1, which has been commonly adopted in the delta region in the past two decades, can be regarded as an effective management measure as regards increasing rice yields while reducing CH 4 emissions. Considering that doses of ammonium-based, non-sulfate fertilizers higher than 250 kg N ha -1 currently are, and most likely will continue to be, commonly applied for paddy rice cultivation in the Yangtze River Delta and other parts of China, the inhibitory effects on CH 4 emissions from rice production are expected to be pronounced at the regional scale. However, further studies are required to provide more concrete evidence about this issue. Moreover, further research is needed to determine whether N management measures are also effective in view of net greenhouse gas fluxes (including CH 4, nitrous oxide, ammonia

  16. Hydrothermal plumes in the Gulf of Aden, as characterized by light transmission, Mn, Fe, CH4 and δ13C-CH4 anomalies

    NASA Astrophysics Data System (ADS)

    Gamo, Toshitaka; Okamura, Kei; Hatanaka, Hiroshi; Hasumoto, Hiroshi; Komatsu, Daisuke; Chinen, Masakazu; Mori, Mutsumi; Tanaka, Junya; Hirota, Akinari; Tsunogai, Urumu; Tamaki, Kensaku

    2015-11-01

    We conducted water column surveys to search for hydrothermal plumes over the spreading axes in the Gulf of Aden between 45°35‧E and 52°42‧E. We measured light transmission and chemical tracers Mn, Fe, CH4 and δ13C of CH4 in seawater taken using a CTD-Carrousel multi-sampling system at 12 locations including a control station in the Arabian Sea. We recognized three types of hydrothermal plumes at depths of ~650 to ~900 m (shallow plumes), ~1000 to ~1200 m (intermediate plumes), and >1500 m (deep plumes). The shallow plumes were apparently originated from newly discovered twin seamounts (12°03-06‧N and 45°35-41‧E) at the westernmost survey area, where two-dimensional distributions of light transmission and Mn were mapped by tow-yo observations of the CTD-sampling system with an in situ auto-analyzer GAMOS. The maximum concentrations of Mn, Fe, and CH4 of 46 nM, 251 nM, and 15 nM, respectively, were observed for collected seawater within the shallow plumes. The intermediate plumes were characterized by anomalies of light transmission, Mn, Fe, and δ13C of CH4, but by little CH4 anomalies, suggesting that CH4 had been consumed down to the background level during the aging of the plumes. Anomalies of δ3He already reported by the World Ocean Circulation Experiment (WOCE) program exhibited a hydrothermal plume-like peak at ~2000 m depth in the Gulf of Aden, which seems to coincide with the deep plumes observed in this study. The endmember δ13C-CH4 values for the shallow and the deep plumes were estimated to be in a range between -10‰ and -15‰, demonstrating that the sources of CH4 are not biogenic but magmatic as similarly observed at sediment-starved mid-oceanic ridges.

  17. VizieR Online Data Catalog: Empirical methane (CH4) line list (Hargreaves+,

    NASA Astrophysics Data System (ADS)

    Hargreaves, R. J.; Bernath, P. F.; Bailey, J.; Dulick, M.

    2016-02-01

    Nine CH4 transmittance spectra have been acquired betwee temperature (i.e., 23°C) and 200°C-900°C in 100°C intervals. For each transmittance spectrum, four individual spectra are required to correct for the emission of CH4 and the cell. A total of 36 spectra were acquired and the four resultant spectra at 700°C are illustrated in Figure 1. The 2600-5000/cm (2.0-3.8um) spectral range has been covered and includes pentad and octad regions of the CH4 infrared spectrum. (2 data files).

  18. BOREAS TGB-1 CH4 Concentration and Flux Data from NSA Tower Sites

    NASA Technical Reports Server (NTRS)

    Hall, Forrest G. (Editor); Conrad, Sara K. (Editor); Crill, Patrick; Varner, Ruth K.

    2000-01-01

    The BOREAS TGB-1 team made numerous measurements of trace gas concentrations and fluxes at various NSA sites. This data set contains half-hourly averages of ambient methane (CH4) measurements and calculated fluxes for the NSA-Fen in 1996 and the NSA-BP and NSA-OJP tower sites in 1994. The purpose of this study was to determine the CH4 flux from the study area by measuring ambient CH 4 concentrations. This flux can then be compared to the chamber flux measurements taken at the same sites. The data are provided in tabular ASCII files.

  19. BOREAS TGB-1 Soil CH4 and CO2 Profile Data from NSA Tower Sites

    NASA Technical Reports Server (NTRS)

    Crill, Patrick; Varner, Ruth K.; Hall, Forrest G. (Editor); Conrad, Sara K. (Editor)

    2000-01-01

    The BOREAS TGB-1 team made numerous measurements of trace gas concentrations and fluxes at various NSA sites. This data set contains methane (CH4) and carbon dioxide (CO2) concentrations in soil profiles from the NSA-OJP, NSA-OBS, NSA-YJP, and NSA-BP sites during the period of 23-May to 20-Sep-1994. The soil gas sampling profiles of CH 4 and CO 2 were completed to quantify controls on CO2 and CH4 fluxes in the boreal forest. The data are provided in tabular ASCII files.

  20. Dissociation of CH4 at high pressures and temperatures: diamond formation in giant planet interiors?

    PubMed

    Benedetti, L R; Nguyen, J H; Caldwell, W A; Liu, H; Kruger, M; Jeanloz, R

    1999-10-01

    Experiments using laser-heated diamond anvil cells show that methane (CH4) breaks down to form diamond at pressures between 10 and 50 gigapascals and temperatures of about 2000 to 3000 kelvin. Infrared absorption and Raman spectroscopy, along with x-ray diffraction, indicate the presence of polymeric hydrocarbons in addition to the diamond, which is in agreement with theoretical predictions. Dissociation of CH4 at high pressures and temperatures can influence the energy budgets of planets containing substantial amounts of CH4, water, and ammonia, such as Uranus and Neptune. PMID:10506552

  1. Post pyrolysis trapping of molecular hydrogen improves precision for δD(CH4) analysis

    NASA Astrophysics Data System (ADS)

    Bock, M.; Schmitt, J.; Schneider, R.; Fischer, H.

    2012-04-01

    Methane (CH4) is the third most important greenhouse gas after water vapour and carbon dioxide (CO2). Since the industrial revolution the mixing ratio of CH4 in the atmosphere rose to ~1800 ppb, a value never reached within the last 800 000 years. This CH4 increase can only be assessed compared to its natural changes in the past. Firn air and air enclosures in polar ice cores represent the only direct paleoatmospheric archive. The latter show that atmospheric CH4 concentrations changed in concert with northern hemisphere temperature during both glacial/interglacial transitions as well as rapid climate changes (Dansgaard-Oeschger events). Since the different sources of atmospheric methane exhibit distinct carbon and hydrogen isotopic composition (δ13CH4 and δD(CH4)) reconstructions of these parameters on ice cores allow to constrain individual CH4 source/sink changes. δD(CH4) also reflects water cycle changes as hydrogen of precipitation is traced into methane produced from wetland/thermokarst/permafrost systems (Bock et al. 2010, Science). Here we present an updated high precision on line gas chromatography pyrolysis isotope ratio monitoring mass spectrometry technique (GC/P/irmMS) for analysis of δD(CH4) extracted from ice cores. It is based on earlier developments (Bock et al. 2010, RCM) and is improved concerning sample size and precision. The main achievement is post pyrolysis trapping (PPT) of molecular hydrogen after the high temperature conversion of methane leading to a better signal to noise ratio. Air from only 350 g of ice with CH4 concentrations as low as 350 ppb can now be measured with a precision of ~2‰. Such ice samples contain only approximately 30 mL of air and less than 1 nmol CH4. The new method was applied on ice samples from the EDML and EDC ice cores (European Project for Ice Coring in Antarctica, Dronning Maud Land, Dome Concordia). We present the first δD(CH4) records covering the penultimate termination and interglacial from EDML

  2. Anaerobic Metabolism: Linkages to Trace Gases and Aerobic Processes

    NASA Astrophysics Data System (ADS)

    Megonigal, J. P.; Hines, M. E.; Visscher, P. T.

    2003-12-01

    's surface area, they have a profound influence on the biogeochemistry of the planet. This is evident from the observation that the O2 and CH4 content of Earth's atmosphere are in extreme disequilibrium (Sagan et al., 1993). The combination of high aerobic primary production and anoxic sediments provided the large deposits of fossil fuels that have become vital and contentious sources of energy for modern industrialized societies. Anaerobic metabolism is responsible for the abundance of N2 in the atmosphere; otherwise N2-fixing bacteria would have consumed most of the N2 pool long ago (Schlesinger, 1997). Anaerobic microorganisms are common symbionts of termites, cattle, and many other animals, where they aid digestion. Nutrient and pollutant chemistry are strongly modified by the reduced conditions that prevail in wetland and aquatic ecosystems.This review of anaerobic metabolism emphasizes aerobic oxidation, because the two processes cannot be separated in a complete treatment of the topic. It is process oriented and highlights the fascinating microorganisms that mediate anaerobic biogeochemistry. We begin this review with a brief discussion of CO2 assimilation by autotrophs, the source of most of the reducing power on Earth, and then consider the biological processes that harness this potential energy. Energy liberation begins with the decomposition of organic macromolecules to relatively simple compounds, which are simplified further by fermentation. Methanogenesis is considered next because CH4 is a product of acetate fermentation, and thus completes the catabolism of organic matter, particularly in the absence of inorganic electron acceptors. Finally, the organisms that use nitrogen, manganese, iron, and sulfur for terminal electron acceptors are considered in order of decreasing free-energy yield of the reactions.

  3. Observations on the methane oxidation capacity of landfill soils.

    PubMed

    Chanton, Jeffrey; Abichou, Tarek; Langford, Claire; Spokas, Kurt; Hater, Gary; Green, Roger; Goldsmith, Doug; Barlaz, Morton A

    2011-05-01

    The objective of this study was to determine the role of CH(4) loading to a landfill cover in the control of CH(4) oxidation rate (gCH(4)m(-2)d(-1)) and CH(4) oxidation efficiency (% CH(4) oxidation) in a field setting. Specifically, we wanted to assess how much CH(4) a cover soil could handle. To achieve this objective we conducted synoptic measurements of landfill CH(4) emission and CH(4) oxidation in a single season at two Southeastern USA landfills. We hypothesized that percent oxidation would be greatest at sites of low CH(4) emission and would decrease as CH(4) emission rates increased. The trends in the experimental results were then compared to the predictions of two differing numerical models designed to simulate gas transport in landfill covers, one by modeling transport by diffusion only and the second allowing both advection and diffusion. In both field measurements and in modeling, we found that percent oxidation is a decreasing exponential function of the total CH(4) flux rate (CH(4) loading) into the cover. When CH(4) is supplied, a cover's rate of CH(4) uptake (gCH(4)m(-2)d(-2)) is linear to a point, after which the system becomes saturated. Both field data and modeling results indicate that percent oxidation should not be considered as a constant value. Percent oxidation is a changing quantity and is a function of cover type, climatic conditions and CH(4) loading to the bottom of the cover. The data indicate that an effective way to increase the % oxidation of a landfill cover is to limit the amount of CH(4) delivered to it. PMID:20889326

  4. Greenhouse gas budget (CO2, CH4 and N2O) of intensively managed grassland following restoration.

    PubMed

    Merbold, Lutz; Eugster, Werner; Stieger, Jacqueline; Zahniser, Mark; Nelson, David; Buchmann, Nina

    2014-06-01

    The first full greenhouse gas (GHG) flux budget of an intensively managed grassland in Switzerland (Chamau) is presented. The three major trace gases, carbon dioxide (CO2), methane (CH4), and nitrous oxide (N2O) were measured with the eddy covariance (EC) technique. For CO2 concentrations, an open-path infrared gas analyzer was used, while N2O and CH4 concentrations were measured with a recently developed continuous-wave quantum cascade laser absorption spectrometer (QCLAS). We investigated the magnitude of these trace gas emissions after grassland restoration, including ploughing, harrowing, sowing, and fertilization with inorganic and organic fertilizers in 2012. Large peaks of N2O fluxes (20-50 nmol m(-2) s(-1) compared with a <5 nmol m(-2) s(-1) background) were observed during thawing of the soil after the winter period and after mineral fertilizer application followed by re-sowing in the beginning of the summer season. Nitrous oxide (N2O) fluxes were controlled by nitrogen input, plant productivity, soil water content and temperature. Management activities led to increased variations of N2O fluxes up to 14 days after the management event as compared with background fluxes measured during periods without management (<5 nmol m(-2) s(-1)). Fluxes of CO2 remained small until full plant development in early summer 2012. In contrast, methane emissions showed only minor variations over time. The annual GHG flux budget was dominated by N2O (48% contribution) and CO2 emissions (44%). CH4 flux contribution to the annual budget was only minor (8%). We conclude that recently developed multi-species QCLAS in an EC system open new opportunities to determine the temporal variation of N2O and CH4 fluxes, which further allow to quantify annual emissions. With respect to grassland restoration, our study emphasizes the key role of N2O and CO2 losses after ploughing, changing a permanent grassland from a carbon sink to a significant carbon source. PMID:24395474

  5. Vertical distribution of methane oxidation and methanotrophic response to elevated methane concentrations in stratified waters of the Arctic fjord Storfjorden (Svalbard, Norway)

    NASA Astrophysics Data System (ADS)

    Mau, S.; Blees, J.; Helmke, E.; Niemann, H.; Damm, E.

    2013-10-01

    The bacterially mediated aerobic methane oxidation (MOx) is a key mechanism in controlling methane (CH4) emissions from the world's oceans to the atmosphere. In this study, we investigated MOx in the Arctic fjord Storfjorden (Svalbard) by applying a combination of radio-tracer-based incubation assays (3H-CH4 and 14C-CH4), stable C-CH4 isotope measurements, and molecular tools (16S rRNA gene Denaturing Gradient Gel Electrophoresis (DGGE) fingerprinting, pmoA- and mxaF gene analyses). Storfjorden is stratified in the summertime with melt water (MW) in the upper 60 m of the water column, Arctic water (ArW) between 60 and 100 m, and brine-enriched shelf water (BSW) down to 140 m. CH4 concentrations were supersaturated with respect to the atmospheric equilibrium (about 3-4 nM) throughout the water column, increasing from ∼20 nM at the surface to a maximum of 72 nM at 60 m and decreasing below. MOx rate measurements at near in situ CH4 concentrations (here measured with 3H-CH4 raising the ambient CH4 pool by <2 nM) showed a similar trend: low rates at the sea surface, increasing to a maximum of ∼2.3 nM day-1 at 60 m, followed by a decrease in the deeper ArW/BSW. In contrast, rate measurements with 14C-CH4 (incubations were spiked with ∼450 nM of 14C-CH4, providing an estimate of the CH4 oxidation at elevated concentration) showed comparably low turnover rates (<1 nM day-1) at 60 m, and peak rates were found in ArW/BSW at ∼100 m water depth, concomitant with increasing 13C values in the residual CH4 pool. Our results indicate that the MOx community in the surface MW is adapted to relatively low CH4 concentrations. In contrast, the activity of the deep-water MOx community is relatively low at the ambient, summertime CH4 concentrations but has the potential to increase rapidly in response to CH4 availability. A similar distinction between surface and deep-water MOx is also suggested by our molecular analyses. The DGGE banding patterns of 16S rRNA gene

  6. Missing aerobic-phase nitrogen: The potential for heterotrophic reduction of autotrophically generated nitrous oxide in a sequencing batch reactor wastewater treatment system.

    PubMed

    Shiskowskii, D M; Mavinic, D S

    2005-08-01

    Several biochemical pathways can induce nitrogen loss from aerated, aerobic wastewater treatment bioreactors. These pathways include "traditional" simultaneous nitrification-denitrification (SND) (i.e. autotrophic nitrification - heterotrophic denitrification), autotrophic denitrification, and anaerobic ammonia oxidation. An oxygen limitation, often expressed in terms of low dissolved oxygen (DO) concentration, is a common element of these pathways. The presented research investigated the effect of mixed liquor DO concentration and biomass slowly degradable carbon (SDC) utilization rate on the heterotrophic nitrous oxide (N2O) reduction rate, for biomass cultured in an anoxic/aerobic wastewater treatment bioreactor. Biomass oxygen and SDC availability-limitation, expressed in terms of DO concentration and SDC ultilization rate, respectively, were found to significantly impact the observed heterotrophic N2O reduction rate. The findings support the hypothesis that nitrogen lost from the mixed liquor of an aerobic bioreactor could result from simultaneous autotrophic N2O generation (i.e. autotrophic denitrification) and heterotrophic N2O reduction. The results also support the idea that autotrophic N2O generation could be occurring in a bioreactor, although N2O may not be measurable in the reactor off-gas. Therefore, this autotrophic N2O generation - heterotrophic N2O reduction mechanism provides an alternative explanation to nitrogen loss, when compared to "conventional" SND, where heterotrophic organisms are assumed to reduce autotrophically generated nitrite and nitrate to dinitrogen (N2). In addition, nitrogen loss speculatively attributed to N2 formation via anaerobic ammonia oxidation in oxygen-limited environments, again because of the absence of measurable N2O, may in fact be due to the autotrophic N2O generation - heterotrophic N2O reduction mechanism. PMID:16128383

  7. Functionalized poly(ethylene glycol)-stabilized water-soluble palladium nanoparticles: property/activity relationship for the aerobic alcohol oxidation in water.

    PubMed

    Feng, Bo; Hou, Zhenshan; Yang, Hanmin; Wang, Xiangrui; Hu, Yu; Li, Huan; Qiao, Yunxiang; Zhao, Xiuge; Huang, Qingfa

    2010-02-16

    The preparation, characterization, and catalytic properties of water-soluble palladium nanoparticles stabilized by the functionalized-poly(ethylene glycol) as a protective ligand were demonstrated for aerobic oxidation of alcohols in aqueous phase. UV/vis spectra and X-ray photoelectron spectroscopy (XPS) proved that there was an electronic interaction between the bidentate nitrogen ligand and palladium atoms. Transmission electron microscopy and XPS analysis showed that the particle size and surface properties of the generated palladium nanoparticles can be controlled by varying the amount of protective ligand and the kinds of reducing agents. It was found that both the size and surface properties of palladium nanoparticles played very important roles in affecting catalytic performance. The stabilized metallic palladium nanoparticles were proven to be the active centers for benzyl alcohol oxidation in the present system, and the water-soluble Pd nanocatalysts can also be extended to the selective oxidation of various alcohols. PMID:20039597

  8. CH4-CO2 reforming over Ni-substituted barium hexaaluminate catalysts

    SciTech Connect

    Gardner, Todd H.; Spivey, James J.; Kugler, Edwin L.; Pakhare, Devendra

    2013-01-01

    A series of Ni-substituted barium hexaaluminate catalysts, Ba0.75NiyAl12−yO19−ı (y = 0.4, 0.6 and 1.0), were tested for CO2 reforming of CH4 at temperatures between 200 and 900 ◦C. Temperature programmed surface reaction results show that the reaction lights-off in a temperature range between 448 and 503 ◦C with a consistent decrease in light-off temperature with increasing Ni substitution. Isothermal runs performed at 900 ◦C show near equilibrium conversion and stable product concentrations for 18 h on all catalysts. Temperature programmed oxidation of the used catalysts show that the amount of carbon deposited on the catalyst increases with Ni substitution. High resolution XRD of the used Ba0.75Ni0.4Al11.6O19−ı catalyst shows a statistically significant contraction of the unit cell which is the result of NiO reduction from the lattice. XRD of the used catalyst also confirms the presence of graphitic carbon. XPS and ICP measurements of the as prepared catalysts show that lower levels of Ni substitution result in an increasing proportion of Ba at the surface.

  9. Emissions of N2O, CH4 and CO2 from tropical forest soils

    NASA Technical Reports Server (NTRS)

    Keller, Michael; Kaplan, Warren A.; Wofsy, Steven C.

    1986-01-01

    Emissions of nitrous oxide, methane, and carbon dioxide were measured at diverse locations in tropical forests of Brazil, Ecuador, and Puerto Rico using a static open chamber technique. Mean fluxes to the atmosphere were 1.7 x 10 to the 10th, -0.7 x 10 to the 10th, and 1.5 x 10 to the 14th molecules/sq cm per s for N2O, CH4, and CO2, respectively. The data indicate that tropical forests contribute a significant fraction of the global source for atmospheric N2O, about 40 percent of the current source, and possibly 75 percent of the preindustrial source. Methane is consumed by soils on average, but the sink is an insignificant part (less than 5 percent) of the atmospheric cycle for the gas. Emissions of CO2 from forest soils are higher at equatorial sites than at middle or high latitudes, as expected from ecological considerations. Soils emit CO2 at rates more than twice as large as the rate of carbon infall in litter; hence much of the emitted CO2 must arise from root metabolism.

  10. Surface Forcing from CH4 at the North Slope of Alaska and Southern Great Plains Sites

    NASA Astrophysics Data System (ADS)

    Collins, W.; Feldman, D.; Turner, D. D.

    2014-12-01

    Recent increases in atmospheric CH4 have been spatially heterogeneous as indicated by in situ flask measurements and space-borne remote-sensing retrievals from the AIRS instrument, potentially leading to increased radiative forcing. We present detailed, specialized measurements at the DOE ARM North Slope of Alaska (NSA) and Southern Great Plains (SGP) sites to derive the time-series of both CH4 atmospheric concentrations and associated radiative implications at highly-contrasting natural and anthropogenic sources. Using a combination of spectroscopic measurements, in situ observations, and ancillary data for the atmospheric thermodynamic state from radiosondes and cloud-clearing from active sounders, we can separate out the contribution of CH4 to clear-sky downwelling radiance spectra and its infrared surface forcing. The time-series indicates year-to-year variation in shoulder season increases of CH4 concentration and forcing at NSA and large signals from anthropogenic activity at SGP.

  11. Theoretical model of vertical distributions of CO and CH4 in the mesosphere and upper stratosphere.

    NASA Technical Reports Server (NTRS)

    Shimazaki, T.; Cadle, R. D.

    1973-01-01

    Carbon compounds (CO and CO2) and methane are added to an existing computer program (Shimazaki and Laird, 1970, 1972), which calculates diurnal variations in density distributions of pure oxygen compounds, hydrogen compounds, and nitrogen compounds. For the present model calculations, the original program was modified to calculate the steady-state profiles for all constituents, and then these solutions were used as the initial condition for solving the time-dependent equations. The effects of chemical reactions and vertical eddy diffusion transport on the CH4 and CO concentrations above 40 km, where one-dimensional treatment may not be too inappropriate, are discussed. Some of the 15 constituents included in the computer program interact with CO and CH4 chemically, and CH4 is more sensitive to the eddy diffusion coefficient than any other constituent. Therefore it is easier to determine the most appropriate profile of the eddy diffusion coefficient by comparing the model profile with the observations for CH4.

  12. Space-based remote imaging spectroscopy of the Aliso Canyon CH4 superemitter

    NASA Astrophysics Data System (ADS)

    Thompson, D. R.; Thorpe, A. K.; Frankenberg, C.; Green, R. O.; Duren, R.; Guanter, L.; Hollstein, A.; Middleton, E.; Ong, L.; Ungar, S.

    2016-06-01

    The Aliso Canyon gas storage facility near Porter Ranch, California, produced a large accidental CH4 release from October 2015 to February 2016. The Hyperion imaging spectrometer on board the EO-1 satellite successfully detected this event, achieving the first orbital attribution of CH4 to a single anthropogenic superemitter. Hyperion measured shortwave infrared signatures of CH4 near 2.3 μm at 0.01 μm spectral resolution and 30 m spatial resolution. It detected the plume on three overpasses, mapping its magnitude and morphology. These orbital observations were consistent with measurements by airborne instruments. We evaluate Hyperion instrument performance, draw implications for future orbital instruments, and extrapolate the potential for a global survey of CH4 superemitters.

  13. Reducing Uncertainty in Life Cycle CH4 Emissions from Natural Gas using Atmospheric Inversions

    NASA Astrophysics Data System (ADS)

    Schwietzke, S.; Griffin, W.; Matthews, S.

    2012-12-01

    Methane emissions associated with the production and use of natural gas (NG) are highly uncertain because of challenges to accurately measure fugitive CH4 emissions from NG leaks and venting throughout a large and complex industry. Better understanding the CH4 emissions from the NG life cycle is important for two reasons. First, the rising interest in NG use associated with the recent development of unconventional sources, such as shale gas, may cause a shift in the future energy system from coal towards more NG. Given its relatively high greenhouse gas potency, fugitive CH4 emissions from the NG life cycle have the potential to outweigh lower CO2 emissions compared to coal use in terms of their climate impacts over the next few decades. Second, worldwide NG related CH4 emissions play a key role in understanding the global CH4 budget. According to current atmospheric inversion studies, NG and oil production account for about 12% of global CH4 emissions. However, these results largely depend on prior emissions estimates whose uncertainties are poorly documented. The objective of this research is to analyze which ranges of global fugitive CH4 emissions from the NG life cycle are reasonable given atmospheric observations as a constraint. We establish a prior global CH4 inventory for NG, oil, and coal using emissions data from the life cycle assessment (LCA) literature. This inventory includes uncertainty estimates for different fuels, world regions, and time periods based on LCA literature, which existing inventories do not account for. Furthermore, global CH4 inversion modeling will be used to test bottom-up hypotheses of high NG leakage and venting associated with the upper bound of the prior inventory. Given the use of detailed LCA emissions factors, we will test bottom-up scenarios regarding management and technology improvements over time. The emissions inventory will be established for the past decade, and inversion modeling will be carried out using NOAA

  14. D/H kinetic isotope effect in the reaction CH4+Cl

    NASA Astrophysics Data System (ADS)

    Saueressig, G.; Bergamaschi, P.; Crowley, J. N.; Fischer, H.; Harris, G. W.

    The D/H kinetic isotope effect (KIEClD) in the reaction of CH4 with Cl has been investigated using a tunable diode laser absorption spectrometer (TDLAS) to measure 12CH3D/12CH4 ratios. A KIEClD of 1.508±0.041 was obtained at room temperature (296 K). Experiments employing Fourier transform infrared measurements of 12CH3D/12CH4 ratios confirmed this result. An investigation of the temperature dependence showed an increase of KIEClD (1.592±0.057 at 223 K) with decreasing temperature. This very large D/H fractionation effect affects the overall isotope fractionation in the middle and upper stratosphere, where Cl contributes substantially to the total removal of CH4.

  15. Theoretical collision-induced rototranslational absorption spectra for the outer planets - H2-CH4 pairs

    NASA Astrophysics Data System (ADS)

    Borysow, A.; Frommhold, L.

    1986-05-01

    Computations of the rototranslational absorption spectra of H2-CH4 molecular complexes are presented which are based on the classical multipole expansion; spectral profiles are obtained from an exact quantum formalism. The interaction potential is based on laboratory measurements of H2-CH4 pairs at 195 and 297K. The computed spectra provide the most reliable temperature dependence of the absorption coefficient as a function of frequency that can be made under the present circumstances. A theoretical description of the H2CH4 dimer features is given in the isotropic potential approximation. This work is significant for the modeling of the far-infrared absorption of the outer planets' atmospheres, where H2 and CH4 are present.

  16. Experimental warming of a mountain tundra increases soil CO2 effluxes and enhances CH4 and N2O uptake at Changbai Mountain, China

    PubMed Central

    Zhou, Yumei; Hagedorn, Frank; Zhou, Chunliang; Jiang, Xiaojie; Wang, Xiuxiu; Li, Mai-He

    2016-01-01

    Climatic warming is expected to particularly alter greenhouse gas (GHG) emissions from soils in cold ecosystems such as tundra. We used 1 m2 open-top chambers (OTCs) during three growing seasons to examine how warming (+0.8–1.2 °C) affects the fluxes of carbon dioxide (CO2), methane (CH4) and nitrous oxide (N2O) from alpine tundra soils. Results showed that OTC warming increased soil CO2 efflux by 141% in the first growing season and by 45% in the second and third growing season. The mean CH4 flux of the three growing seasons was −27.6 and −16.7 μg CH4-C m−2h−1 in the warmed and control treatment, respectively. Fluxes of N2O switched between net uptake and emission. Warming didn’t significantly affect N2O emission during the first and the second growing season, but stimulated N2O uptake in the third growing season. The global warming potential of GHG was clearly dominated by soil CO2 effluxes (>99%) and was increased by the OTC warming. In conclusion, soil temperature is the main controlling factor for soil respiration in this tundra. Climate warming will lead to higher soil CO2 emissions but also to an enhanced CH4 uptake with an overall increase of the global warming potential for tundra. PMID:26880107

  17. Experimental warming of a mountain tundra increases soil CO2 effluxes and enhances CH4 and N2O uptake at Changbai Mountain, China

    NASA Astrophysics Data System (ADS)

    Zhou, Yumei; Hagedorn, Frank; Zhou, Chunliang; Jiang, Xiaojie; Wang, Xiuxiu; Li, Mai-He

    2016-02-01

    Climatic warming is expected to particularly alter greenhouse gas (GHG) emissions from soils in cold ecosystems such as tundra. We used 1 m2 open-top chambers (OTCs) during three growing seasons to examine how warming (+0.8-1.2 °C) affects the fluxes of carbon dioxide (CO2), methane (CH4) and nitrous oxide (N2O) from alpine tundra soils. Results showed that OTC warming increased soil CO2 efflux by 141% in the first growing season and by 45% in the second and third growing season. The mean CH4 flux of the three growing seasons was -27.6 and -16.7 μg CH4-C m-2h-1 in the warmed and control treatment, respectively. Fluxes of N2O switched between net uptake and emission. Warming didn’t significantly affect N2O emission during the first and the second growing season, but stimulated N2O uptake in the third growing season. The global warming potential of GHG was clearly dominated by soil CO2 effluxes (>99%) and was increased by the OTC warming. In conclusion, soil temperature is the main controlling factor for soil respiration in this tundra. Climate warming will lead to higher soil CO2 emissions but also to an enhanced CH4 uptake with an overall increase of the global warming potential for tundra.

  18. Stabilization of fine fraction from landfill mining in anaerobic and aerobic laboratory leach bed reactors.

    PubMed

    Mönkäre, Tiina J; Palmroth, Marja R T; Rintala, Jukka A

    2015-11-01

    Fine fraction (FF, <20 mm) from mined landfill was stabilized in four laboratory-scale leach bed reactors (LBR) over 180 days. The aim was to study feasibility of biotechnological methods to treat FF and if further stabilization of FF is possible. Four different stabilization methods were compared and their effects upon quality of FF were evaluated. Also during the stabilization experiment, leachate quality as well as gas composition and quantity were analyzed. The methods studied included three anaerobic LBRs (one without water addition, one with water addition, and one with leachate recirculation) and one aerobic LBR (with water addition). During the experiment, the most methane was produced in anaerobic LBR without water addition (18.0 L CH4/kg VS), while water addition and leachate recirculation depressed methane production slightly, to 16.1 and 16.4 L CH4/kg VS, respectively. Organic matter was also removed via the leachate and was measured as chemical oxygen demand (COD). Calculated removal of organic matter in gas and leachate was highest in LBR with water addition (59 g COD/kg VS), compared with LBR without water addition or with leachate recirculation (51 g COD/kg VS). Concentrations of COD, ammonium nitrogen and anions in leachate decreased during the experiment, indicating washout mechanism caused by water additions. Aeration increased sulfate and nitrate concentrations in leachate due to oxidized sulfide and ammonium. Molecular weight distributions of leachates showed that all the size categories decreased, especially low molecular weight compounds, which were reduced the most. Aerobic stabilization resulted in the lowest final VS/TS (13.1%), lowest respiration activity (0.9-1.2 mg O2/g TS), and lowest methane production after treatment (0.0-0.8 L CH4/kg VS), with 29% of VS being removed from FF. Anaerobic stabilization methods also reduced organic matter by 9-20% compared with the initial amount. Stabilization reduced the quantity of soluble nitrogen

  19. Pd-catalyzed intramolecular aerobic oxidative C-H amination of 2-aryl-3-(arylamino)quinazolinones: synthesis of fluorescent indazolo[3,2-b]quinazolinones.

    PubMed

    Yang, Weiguang; Chen, Jiuxi; Huang, Xiaobo; Ding, Jinchang; Liu, Miaochang; Wu, Huayue

    2014-10-17

    A palladium-catalyzed intramolecular aerobic oxidative C-H amination of 2-aryl-3-(arylamino)quinazolinones has been developed, providing a variety of substituted indazolo[3,2-b]quinazolinone derivatives in moderate to excellent yields. Preliminary mechanistic studies suggested that a palladacycle dimer could be the key intermediate, which underwent a cascade "rollover" cyclometalation and C-H amination sequence. Furthermore, the potential utility of these products has been demonstrated as a new class of blue fluorophores for fluorescent materials. PMID:25290066

  20. CuBr catalyzed aerobic oxidative coupling of 2-aminopyridines with cinnamaldehydes: direct access to 3-formyl-2-phenyl-imidazo[1,2-a]pyridines.

    PubMed

    Bharate, Jaideep B; Abbat, Sheenu; Bharatam, Prasad V; Vishwakarma, Ram A; Bharate, Sandip B

    2015-07-28

    Copper bromide catalyzed aerobic oxidative coupling of 2-aminopyridines with cinnamaldehydes directly led to the formation of 3-formyl-2-phenyl-imidazo[1,2-a]pyridines. The quantum chemical calculations were performed to trace the reaction mechanism and get insights into the possible reaction pathway. 2-Aminopyridines on coupling with cinnamaldehyde generate (E)-3-phenyl-3-(pyridin-2-ylamino)acrylaldehyde IV as a key intermediate, which undergoes C-N bond formation reaction to produce 3-formyl-2-phenyl-imidazo[1,2-a]pyridines. PMID:26103156

  1. Theoretical study on the catalytic reactivity of N-hydroxyphthalimide tuned by different heterocyclic substitutions on its phenyl ring for aerobic oxidation

    NASA Astrophysics Data System (ADS)

    Chen, Kexian; Xie, Haiying; Jiang, Kezhi; Mao, Jianyong

    2016-07-01

    The structure-reactivity relationship of new hydroxyimide organocatalysts based on the heterocyclic replacements of the phenyl ring of N-hydroxyphthalimide (NHPI) has been theoretically investigated to gain a mature understanding of this particular catalysis for aerobic oxidation. We find that the reactivity of catalysts with the common five-member aromatic rings is lower than that of NHPI. The catalyst with the recyclable structure of imidazolium ionic liquid may serve as a novel model catalyst for further improvements due to its reactivity comparable to that of NHPI. The catalytic reactivity of multi-nitroxyl catalysts is theoretically more fascinating than that of the highly efficient N,N-dihydroxypyromellitimide.

  2. Theagalloflavic Acid, a New Pigment Derived from Hexahydroxydiphenoyl Group, and Lignan Oxidation Products Produced by Aerobic Microbial Fermentation of Green Tea.

    PubMed

    Matsuo, Yosuke; Matsuda, Tomoko; Sugihara, Keisuke; Saito, Yoshinori; Zhang, Ying-Jun; Yang, Chong-Ren; Tanaka, Takashi

    2016-01-01

    Chinese ripe pu-erh tea is produced by aerobic microbial fermentation of green tea. To clarify the microbial degradation of tea polyphenols, Japanese commercial green tea was mixed with Chinese ripe pu-erh tea, which retains microorganisms, and fermented for 5 d. Chromatographic separation yielded a novel water-soluble yellow pigment termed theagalloflavic acid. Spectroscopic and chemical evidence suggested that this pigment was produced by oxidative ring cleavage of hexahydroxydiphenoyl esters. In addition, two new oxygenated lignin metabolites, (+)-5,5'-dihydroxypinoresinol and 5-hydroxydihydrodehydrodiconiferyl alcohol, were also isolated together with known degradation products of quercetin and tea catechins. PMID:27373646

  3. From ketones to esters by a Cu-catalyzed highly selective C(CO)-C(alkyl) bond cleavage: aerobic oxidation and oxygenation with air.

    PubMed

    Huang, Xiaoqiang; Li, Xinyao; Zou, Miancheng; Song, Song; Tang, Conghui; Yuan, Yizhi; Jiao, Ning

    2014-10-22

    The Cu-catalyzed aerobic oxidative esterification of simple ketones via C-C bond cleavage has been developed. Varieties of common ketones, even inactive aryl long-chain alkyl ketones, are selectively converted into esters. The reaction tolerates a wide range of alcohols, including primary and secondary alcohols, chiral alcohols with retention of the configuration, electron-deficient phenols, as well as various natural alcohols. The usage of inexpensive copper catalyst, broad substrate scope, and neutral and open air conditions make this protocol very practical. (18)O labeling experiments reveal that oxygenation occurs during this transformation. Preliminary mechanism studies indicate that two novel pathways are mainly involved in this process. PMID:25251943

  4. A pan-Arctic synthesis of CH4 and CO2 production from anoxic soil incubations

    USGS Publications Warehouse

    Treat, C.C.; Natali, S.M.; Ernakovich, Jessica; Iverson, Colleen M.; Lupasco, Massimo; McGuire, Anthony; Norby, Richard J.; Roy Chowdhury, Taniya; Richter, Andreas; Šantrůčková, Hana; Schädel, C.; Schuur, Edward A.G.; Sloan, Victoria L.; Turetsky, Merritt R.; Waldrop, Mark P.

    2015-01-01

    Permafrost thaw can alter the soil environment through changes in soil moisture, frequently resulting in soil saturation, a shift to anaerobic decomposition, and changes in the plant community. These changes, along with thawing of previously frozen organic material, can alter the form and magnitude of greenhouse gas production from permafrost ecosystems. We synthesized existing methane (CH4) and carbon dioxide (CO2) production measurements from anaerobic incubations of boreal and tundra soils from the geographic permafrost region to evaluate large-scale controls of anaerobic CO2 and CH4 production and compare the relative importance of landscape-level factors (e.g., vegetation type and landscape position), soil properties (e.g., pH, depth, and soil type), and soil environmental conditions (e.g., temperature and relative water table position). We found fivefold higher maximum CH4 production per gram soil carbon from organic soils than mineral soils. Maximum CH4 production from soils in the active layer (ground that thaws and refreezes annually) was nearly four times that of permafrost per gram soil carbon, and CH4 production per gram soil carbon was two times greater from sites without permafrost than sites with permafrost. Maximum CH4 and median anaerobic CO2 production decreased with depth, while CO2:CH4 production increased with depth. Maximum CH4 production was highest in soils with herbaceous vegetation and soils that were either consistently or periodically inundated. This synthesis identifies the need to consider biome, landscape position, and vascular/moss vegetation types when modeling CH4 production in permafrost ecosystems and suggests the need for longer-term anaerobic incubations to fully capture CH4 dynamics. Our results demonstrate that as climate warms in arctic and boreal regions, rates of anaerobic CO2 and CH4 production will increase, not only as a result of increased temperature, but also from shifts in vegetation and increased

  5. BOREAS TF-4 CO2 and CH4 Chamber Flux Data from the SSA

    NASA Technical Reports Server (NTRS)

    Anderson, Dean; Striegl, Robert; Wickland, Kimberly; Hall, Forrest G. (Editor); Conrad, Sara (Editor)

    2000-01-01

    The BOREAS TF-4 team measured fluxes of CO2 and CH4 across the soil-air interface in four ages of jack pine forest at the BOREAS SSA during August 1993 to March 1995. Gross and net flux of CO2 and flux of CH4 between soil and air are presented for 24 chamber sites in mature jack pine forest, 20-year-old, 4-year-old, and clear cut areas. The data are stored in tabular ASCII files.

  6. Reticular Synthesis of HKUST-like tbo-MOFs with Enhanced CH4 Storage.

    PubMed

    Spanopoulos, Ioannis; Tsangarakis, Constantinos; Klontzas, Emmanuel; Tylianakis, Emmanuel; Froudakis, George; Adil, Karim; Belmabkhout, Youssef; Eddaoudi, Mohamed; Trikalitis, Pantelis N

    2016-02-10

    Successful implementation of reticular chemistry using a judiciously designed rigid octatopic carboxylate organic linker allowed the construction of expanded HKUST-1-like tbo-MOF series with intrinsic strong CH4 adsorption sites. The Cu-analogue displayed a concomitant enhancement of the gravimetric and volumetric surface area with the highest reported CH4 uptake among the tbo family, comparable to the best performing metal organic frameworks (MOFs) for CH4 storage. The corresponding gravimetric (BET) and volumetric surface areas of 3971 m(2) g(-1) and 2363 m(2) cm(-3) represent an increase of 115% and 47%, respectively, in comparison to the corresponding values for the prototypical HKUST-1 (tbo-MOF-1), and are 42% and 20% higher than that of tbo-MOF-2. High-pressure methane adsorption isotherms revealed a high total gravimetric and volumetric CH4 uptakes, reaching 372 cm(3) (STP) g(-1) and 221 cm(3) (STP) cm(-3), respectively, at 85 bar and 298 K. The corresponding working capacities between 5 and 80 bar were found to be 294 cm(3) (STP) g(-1) and 175 cm(3) (STP) cm(-3) and are placed among the best performing MOFs for CH4 storage particularly at relatively low temperature. To gain insight on the mechanism accounting for the resultant enhanced CH4 storage capacity, molecular simulation study was performed and revealed the presence of very strong CH4 adsorption sites near the organic linker with similar adsorption energetics as the open metal sites. The present findings support the potential of tbo-MOFs based on the supermolecular building layer (SBL) approach as an ideal platform to further enhance the CH4 storage capacity via expansion and functionalization of the quadrangular pillars. PMID:26694977

  7. Long Path Quantum Cascade Laser Based Sensor for Environment Sensing/Ambient Detection of CH4 and N2O

    NASA Astrophysics Data System (ADS)

    Castillo, P. C.; Sydoryk, I.; Gross, B.; Moshary, F.

    2013-12-01

    Methane (CH4) and Nitrous Oxide (N2O) are long-lived greenhouse gases in the atmosphere with significant global warming effects. These gases also are known to be produced in a number of anthropogenic settings such as manure management systems, which releases substantial GHGs and is mandated by the EPA to provide continuous monitoring. In addition, natural gas leaks in urban areas is another source of strong spatially inhomogeneous methane emissions Most open path methods for quantitative detection of trace gases utilize either Fourier Transform Spectrometer (FTIR) or near-IR differential optical absorption spectroscopy (DOAS). Although, FTIR is suitable for ambient air monitoring measurement of more abundant gases such as CO2 and H20 etc., the lack of spectral resolution makes the retrieval of weaker absorbing features such as N20 more difficult. On the other hand, conventional DOAS systems can be large and impractical. As an alternative, we illustrate a robust portable quantum cascade laser (QCL) approach for simultaneous detection of CH4 and N2O. In particular, gas spectra were recorded by ultrafast pulse intensity (thermal) chirp tuning over the 1299 - 1300cm-1 spectral window. Etalon measurements insure stable tuning was obtained. To deal with multiple species, a LSQ spectral fitting approach was used which accounted for both the overlapping trace gases , background water vapor as well as detector drift and calibration. In summary, ambient concentrations of CH4 with and N2O with accuracy < 1% was obtained on the order of 5ms using optical paths of 500 m path length. In addition, unattended long term operation was demonstrated and validations using other sensors when possible were shown to be consistent. The system accuracy is limited by systemic errors, which are still being explored.

  8. Zoom in new insights of potential microbial control of N and CH4 gaseous losses induced by different agricultural practices in temperate paddy soils

    NASA Astrophysics Data System (ADS)

    Cucu, Maria Alexandra; Bardi, Laura; Said-Pullicino, Daniel; Sacco, Dario; Celi, Luisella; Gorra, Roberta

    2016-04-01

    that the assimilation of N contributes to the last step of archaeal denitrification. In a field experiment a high abundance of aerobic ammonia oxidizers suggested nitrification as proxy for complete denitrification, highlighting the importance of the latter in mitigating N2O emission from rice ecosystem. As a new insight for temperate rice paddies, our data indicated a high abundance of Anammox bacteria, suggesting this process to be very important in controlling N losses independently of water and rice straw management. Characteristic treatment interactions and cooperation were shown between aerobic and anaerobic ammonia oxidizers. Rice straw incorporation and the increased rice biomass due to N fertilization supported the methanogenesis. In this regard, a high abundance of mcrA gene was shown in situ level. Our findings highlighted the possibility of microorganisms niche differentiation not only driven by differential responses to NH4+ concentration, but also through different organic C substrates derived from more or less labile pools, and the contrasting straw C/N ratios in different treatments. The results provide novel insights into the influence of paddy soil management on microbial communities dynamics, with important implications on their potential functionality. These studies are a step forward in understanding the overall microbial control in N and CH4 gaseous losses mitigation from rice fields.

  9. Atmospheric radon, CO2 and CH4 dynamics in an Australian coal seam gas field

    NASA Astrophysics Data System (ADS)

    Tait, D. R.; Santos, I. R.; Maher, D. T.

    2013-12-01

    Atmospheric radon (222Rn), carbon dioxide (CO2), and methane concentrations (CH4) as well as carbon stable isotope ratios (δ13C) were used to gain insight into atmospheric chemistry within an Australian coal seam gas (CSG) field (Surat Basin, Tara region, Queensland). A˜3 fold increase in maximum 222Rn concentration was observed inside the gas field compared to outside of it. There was a significant relationship between maximum and average 222Rn concentrations and the number of gas wells within a 2 km to 4 km radius of the sampling sites (n = 5 stations; p < 0.05). We hypothesize that the radon relationship was a response to enhanced emissions within the gas field related to point sources (well heads, pipelines, etc.) and diffse soil sources due to changes in the soil structural and hydrological characteristics. A rapid qualitative assessment of CH4 and CO2 concentration, and carbon isotopes using a mobile cavity ring-down spectrometer system showed a widespread enrichment of both CH4 and CO2 within the production gas field. Concentrations of CH4 and CO2 were as high as 6.89 ppm and 541 ppm respectively compared average concentrations of 1.78 ppm (CH4) and 388 ppm (CO2) outside the gas field. The δ13C values showed distinct differences between areas inside and outside the production field with the δ13C value of the CH4 source within the field matching that of the methane in the CSG.

  10. New constraints on the CH4 vertical profile in Uranus and Neptune from Herschel observations

    NASA Astrophysics Data System (ADS)

    Lellouch, E.; Moreno, R.; Orton, G. S.; Feuchtgruber, H.; Cavalié, T.; Moses, J. I.; Hartogh, P.; Jarchow, C.; Sagawa, H.

    2015-07-01

    Dedicated line observations of CH4 rotational lines performed with Herschel/PACS and HIFI in 2009-2011 provide new inferences of the mean methane profile in the upper tropospheres and stratospheres of Uranus and Neptune. At Uranus, CH4 is found to be near saturation, with a ~9 × 10-4 tropopause/lower stratosphere mole fraction. This is nominally six times larger than inferred from Spitzer in 2007, although reconciliation may be possible if the CH4 abundance decreases sharply from ~100 to 2 mbar. This unexpected situation might reflect heterogeneous conditions in Uranus' stratosphere, with local CH4 depletions and heating associated with downwelling motions. Higher CH4 abundances compared to values inferred under solstitial conditions by Voyager in 1989 suggest that atmospheric mixing is effectively subdued at high latitudes and/or is time-variable. At Neptune, the mid-stratosphere CH4 abundance is (1.15 ± 0.10) × 10-3, in agreement with earlier determinations and indicative of either leakage through a warmer polar region or upwelling at low or middle latitudes. On both planets, spatially resolved observations of temperature and methane in the stratosphere are needed to further identify the physical processes at work. Herschel is an ESA space observatory with science instruments provided by European-led Principal Investigator consortia and with important participation from NASA.

  11. The Campylobacter jejuni MarR-like transcriptional regulators RrpA and RrpB both influence bacterial responses to oxidative and aerobic stresses

    PubMed Central

    Gundogdu, Ozan; da Silva, Daiani T.; Mohammad, Banaz; Elmi, Abdi; Mills, Dominic C.; Wren, Brendan W.; Dorrell, Nick

    2015-01-01

    The ability of the human intestinal pathogen Campylobacter jejuni to respond to oxidative stress is central to bacterial survival both in vivo during infection and in the environment. Re-annotation of the C. jejuni NCTC11168 genome revealed the presence of two MarR-type transcriptional regulators Cj1546 and Cj1556, originally annotated as hypothetical proteins, which we have designated RrpA and RrpB (regulator of response to peroxide) respectively. Previously we demonstrated a role for RrpB in both oxidative and aerobic (O2) stress and that RrpB was a DNA binding protein with auto-regulatory activity, typical of MarR-type transcriptional regulators. In this study, we show that RrpA is also a DNA binding protein and that a rrpA mutant in strain 11168H exhibits increased sensitivity to hydrogen peroxide oxidative stress. Mutation of either rrpA or rrpB reduces catalase (KatA) expression. However, a rrpAB double mutant exhibits higher levels of resistance to hydrogen peroxide oxidative stress, with levels of KatA expression similar to the wild-type strain. Mutation of either rrpA or rrpB also results in a reduction in the level of katA expression, but this reduction was not observed in the rrpAB double mutant. Neither the rrpA nor rrpB mutant exhibits any significant difference in sensitivity to either cumene hydroperoxide or menadione oxidative stresses, but both mutants exhibit a reduced ability to survive aerobic (O2) stress, enhanced biofilm formation and reduced virulence in the Galleria mellonella infection model. The rrpAB double mutant exhibits wild-type levels of biofilm formation and wild-type levels of virulence in the G mellonella infection model. Together these data indicate a role for both RrpA and RrpB in the C. jejuni peroxide oxidative and aerobic (O2) stress responses, enhancing bacterial survival in vivo and in the environment. PMID:26257713

  12. Soil trace gas emissions (CH4 and N2O) offset the CO2 uptake in poplar short rotation coppice

    NASA Astrophysics Data System (ADS)

    Zenone, Terenzio; Zona, Donatella; Gelfand, Iya; Gielen, Bert; camino serrano, Marta; Ceulemans, Reinhart

    2015-04-01

    The need for renewable energy sources will lead to a considerable expansion in the planting of dedicated fast-growing biomass crops across Europe. Among them poplar (Populus spp) is the most widely planted as short rotation coppice (SRC) and an increase in the surface area of large-scale SRC poplar plantations might thus be expected. In this study we report the greenhouse gas fluxes (GHG) of carbon dioxide (CO2), methane (CH4), and nitrous oxide (N2O) measured using the eddy covariance technique in a SRC plantation for bioenergy production during the period 2010-2013. The plantation was established in April 2010 on 18.4 ha of former agricultural land with a density of 8000 plants ha-1; the above-ground biomass was harvested on February 2012 and 2014.The whole GHG balance of the four years of the study was 1.90 (± 1.37) Mg CO2eq ha-1; this indicated that soil trace gas emissions offset the CO2 uptake by the plantation. CH4 and N2O almost equally contributed to offset the CO2 uptake of -5.28 (±0.67) Mg CO2eq ha-1 with an overall emission of 3.56 (± 0.35) Mg CO2eq ha-1 of N2O and of 3.53 (± 0.85) Mg CO2eq ha-1 of CH4. N2O emissions mostly occurred during a single peak a few months after the site was converted into SRC and represented 44% of the entire N2O loss during the entire study. Accurately capturing these emission events proved to be critical for correct estimates of the GHG balance. The self-organizing map (SOM) technique graphically showed the relationship between the CO2 fluxes and the principal environmental variables but failed to explain the variability of the soil trace gas emissions. The nitrogen content in the soil and the water table depth were the two drivers that best explained the variability in N2O and CH4 respectively. This study underlines the importance of the "non-CO2 GHG" on the overall balance as well as the impact of the harvest on the CO2 uptake rate. Further long-term investigations of soil trace gas emissions should also monitor the N

  13. Factors Contributing to High CH4 and CO2 Efflux Rates from Thermokarst Lakes in the Rapidly Warming Hudson Bay Region

    NASA Astrophysics Data System (ADS)

    Matveev, A.; Vincent, W. F.; Laurion, I.

    2014-12-01

    Thermokarst lakes and ponds that form on thawing permafrost landscapes have long been recognized as biogeochemical reactors that emit significant amounts of CH4 and CO2. However, there is considerable uncertainty in the exact contribution of these water bodies to the global carbon cycle, in large part because of the paucity of observations from different ecosystem types across the circumpolar North, and the incomplete understanding of factors that control the balance between methane production (methanogenesis) and loss (methanotrophy). The aim of our research was to address these gaps by focusing on thermokarst lakes in subarctic Canada (eastern Hudson Bay), primarily at the southern limit of permafrost that is experiencing rapid warming, but where limnological changes have received little attention to date. Thermokarst lakes were sampled at five geographical locations that differed in their degree of permafrost degradation, as well as in carbon content and lability. All sampled lakes were supersaturated with CH4, with epilimnetic concentrations varying from CO2 undersaturation in turbid mineral (lithalsa) lakes of the continuous and discontinuous permafrost landscapes, to oversaturation by several orders of magnitude of both CO2 and CH4 in the organic-rich (palsa) lakes, especially in the areas of highly degraded permafrost at its southern limit. Concentrations and fluxes of CH4 and CO2 in these palsa lakes were at or above the highest values reported for thermokarst waters elsewhere. In addition, methane oxidation experiments showed high rates of methanotrophy that substantially reduced the net emission of CH4 from both lithalsa and palsa lake types. Our results imply that subarctic thermokarst lakes, especially those at the northward migrating permafrost margin, may be a major source of greenhouse gases as the circumpolar North continues to warm.

  14. Segregation of biomass in cyclic anaerobic/aerobic granular sludge allows the enrichment of anaerobic ammonium oxidizing bacteria at low temperatures.

    PubMed

    Winkler, Mari K H; Kleerebezem, Robbert; Kuenen, J Gijs; Yang, Jingjing; van Loosdrecht, Mark C M

    2011-09-01

    A cyclic anaerobic/aerobic bubble column reactor was run for 420 days to study the competition for nitrite between nitrite oxidizing bacteria (NOB) and anaerobic ammonium oxidizing bacteria (Anammox) at low temperatures. An anaerobic feeding period with nitrite and ammonium in the influent followed by an aerated period was applied resulting in a biomass specific conversion rate of 0.18 ± 0.02 [gN(2) - N · gVSS(-1)· day(-1)] when the dissolved oxygen concentration was maintained at 1.0 mgO(2) · L(-1). An increase in white granules was observed in the reactor which were mainly located at the top of the settled sludge bed, whereas red granules were located at the bottom. FISH, activity tests, and qPCR techniques revealed that red biomass was dominated by Anammox bacteria and white granules by NOB. Granules from the top of the sludge bed were smaller and therefore had a higher aerobic volume fraction, a lower density, and consequently a slower settling rate. Sludge was manually removed from the top of the settled sludge bed to selectively remove NOB which resulted in an increased overall biomass specific N-conversion rate of 0.32 ± 0.02 [gN(2) - N · gVSS(-1) · day(-1)]. Biomass segregation in granular sludge reactors gives an extra opportunity to select for specific microbial groups by applying a different SRT for different microbial groups. PMID:21744798

  15. C3N4-H5PMo10V2O40: a dual-catalysis system for reductant-free aerobic oxidation of benzene to phenol

    PubMed Central

    Long, Zhouyang; Zhou, Yu; Chen, Guojian; Ge, Weilin; Wang, Jun

    2014-01-01

    Hydroxylation of benzene is a widely studied atom economical and environmental benign reaction for producing phenol, aiming to replace the existing three-step cumene process. Aerobic oxidation of benzene with O2 is an ideal and dream process, but benzene and O2 are so inert that current systems either require expensive noble metal catalysts or wasteful sacrificial reducing agents; otherwise, phenol yields are extremely low. Here we report a dual-catalysis non-noble metal system by simultaneously using graphitic carbon nitride (C3N4) and Keggin-type polyoxometalate H5PMo10V2O40 (PMoV2) as catalysts, showing an exceptional activity for reductant-free aerobic oxidation of benzene to phenol. The dual-catalysis mechanism results in an unusual route to create phenol, in which benzene is activated on the melem unit of C3N4 and O2 by the V-O-V structure of PMoV2. This system is simple, highly efficient and thus may lead the one-step production of phenol from benzene to a more practical pathway. PMID:24413448

  16. Chiral tetranuclear and dinuclear copper(ii) complexes for TEMPO-mediated aerobic oxidation of alcohols: are four metal centres better than two?

    PubMed

    Zhang, Guoqi; Proni, Gloria; Zhao, Sherry; Constable, Edwin C; Housecroft, Catherine E; Neuburger, Markus; Zampese, Jennifer A

    2014-08-28

    The one-pot reaction of 3,5-di-tert-butyl-2-hydroxybenzaldehyde, (R)-2-aminoglycinol and Cu(OAc)2·2H2O in a 1 : 1 : 1 ratio in the presence of triethylamine led to the isolation of X-ray quality crystals of the chiral complex (R)- in high yield. The single crystal structure of (R)- reveals a tetranuclear copper(ii) complex that contains a {Cu4(μ-O)2(μ3-O)2N4O4} core. A reaction using (1S,2R)-2-amino-1,2-diphenylethanol as precursor under the same conditions generated the chiral complex (S,R)-; its structure was determined by single crystal X-ray crystallography and was found to contain a {Cu2(μ-O)2N2O2} core. Both (R)- and (S,R)- have been used for catalytic aerobic oxidation of benzylic alcohols in combination with the TEMPO (2,2,6,6-tetramethylpiperidinyl-1-oxyl) radical. (R)- selectively catalyses the conversion of various aromatic primary alcohols to the corresponding aldehydes with high yields (99%) and TONs (770) in the air, while (S,R)- exhibits less promising catalytic performance under the same reaction conditions. The role of the cluster structures in (R)- and (S,R)- in controlling the reactivity towards aerobic oxidation reactions is discussed. PMID:24986135

  17. Non-equilibrium simulation of CH4 production through the depressurization method from gas hydrate reservoirs

    NASA Astrophysics Data System (ADS)

    Qorbani, Khadijeh; Kvamme, Bjørn

    2016-04-01

    Natural gas hydrates (NGHs) in nature are formed from various hydrate formers (i.e. aqueous, gas, and adsorbed phases). As a result, due to Gibbs phase rule and the combined first and second laws of thermodynamics CH4-hydrate cannot reach thermodynamic equilibrium in real reservoir conditions. CH4 is the dominant component in NGH reservoirs. It is formed as a result of biogenic degradation of biological material in the upper few hundred meters of subsurface. It has been estimated that the amount of fuel-gas reserve in NGHs exceed the total amount of fossil fuel explored until today. Thus, these reservoirs have the potential to satisfy the energy requirements of the future. However, released CH4 from dissociated NGHs could find its way to the atmosphere and it is a far more aggressive greenhouse gas than CO2, even though its life-time is shorter. Lack of reliable field data makes it difficult to predict the production potential, as well as safety of CH4 production from NGHs. Computer simulations can be used as a tool to investigate CH4 production through different scenarios. Most hydrate simulators within academia and industry treat hydrate phase transitions as an equilibrium process and those which employ the kinetic approach utilize simple laboratory data in their models. Furthermore, it is typical to utilize a limited thermodynamic description where only temperature and pressure projections are considered. Another widely used simplification is to assume only a single route for the hydrate phase transitions. The non-equilibrium nature of hydrate indicates a need for proper kinetic models to describe hydrate dissociation and reformation in the reservoir with respect to thermodynamics variables, CH4 mole-fraction, pressure and temperature. The RetrasoCodeBright (RCB) hydrate simulator has previously been extended to model CH4-hydrate dissociation towards CH4 gas and water. CH4-hydrate is added to the RCB data-base as a pseudo mineral. Phase transitions are treated

  18. Seasonal study of dissolved CH 4, CO 2 and N 2O in a shallow tidal system of the bay of Cádiz (SW Spain)

    NASA Astrophysics Data System (ADS)

    Ferrón, S.; Ortega, T.; Gómez-Parra, A.; Forja, J. M.

    2007-06-01

    During 2004, 10 samplings were performed in order to measure dissolved methane (CH 4), carbon dioxide (CO 2) and nitrous oxide (N 2O) in the surface waters of Río San Pedro, a tidal creek in the salt marsh area of the Bay of Cádiz (SW Spain). The inner partvs of the creek is affected by the inputs coming from an intensive fish farm and the drainage of an extensive salt marsh area. Dissolved CH 4, CO 2 and N 2O concentrations ranged from 11 to 88 nM, 36 to 108 μM and 14 to 50 nM, respectively. Surface waters were in all cases oversaturated with respect to the atmosphere, reaching values of up to 5000% for CH 4, 1240% for CO 2 and 840% for N 2O. Dissolved CH 4, CO 2 and N 2O showed a significant tidal and seasonal variability. Over a tidal cycle, concentrations were always highest during low tide, which points to the influence of the inputs from the fish farm effluent and the drainage of the adjacent salt marsh area, as well as in situ production within the system. Dissolved CH 4, CO 2 and N 2O seasonal patterns were similar and showed maximum concentrations in summer conditions. Using four different parameterizations to calculate the gas transfer coefficients [Liss, P.S. and Merlivat, L., 1986. Air-sea exchange rates: introduction and synthesis. In P. Buat-Ménard (Ed.), The Role of Air-Sea Exchanges in Geochemical Cycling. Reidel, Dordrecht, The Netherlands, p. 113-127.; Clark, J.F., Schlosser, P., Simpson, H.J., Stute, M., Wanninkhof, R., and Ho, D.T., 1995. Relationship between gas transfer velocities and wind speeds in the tidal Hudson River determined by the dual tracer technique. In: B. Jähne and E. Monahan (Eds.), Air-Water Gas Transfer: AEON Verlag and Studio, Hanau, Germany, pp. 785-800.; Carini, S., Weston, N., Hopkinson, G., Tucker, J., Giblin, A. and Vallino, J., 1996. Gas exchanges rates in the Parker River estuary, Massachusetts. Biol. Bull., 191: 333-334.; Kremer, J.N., Reischauer, A. and D'Avanzo, C., 2003. Estuary-specific variation in the air

  19. Porous Au-embedded WO3 Nanowire Structure for Efficient Detection of CH4 and H2S

    PubMed Central

    Minh Vuong, Nguyen; Kim, Dojin; Kim, Hyojin

    2015-01-01

    We developed a facile method to fabricate highly porous Au-embedded WO3 nanowire structures for efficient sensing of CH4 and H2S gases. Highly porous single-wall carbon nanotubes were used as template to fabricate WO3 nanowire structures with high porosity. Gold nanoparticles were decorated on the tungsten nanowires by dipping in HAuCl4 solution, followed by oxidation. The surface morphology, structure, and electrical properties of the fabricated WO3 and Au-embedded WO3 nanowire structures were examined by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and current–voltage measurements. Formation of a nanowire structure resulted in significant enhancement in sensing response to H2S and CH4 gases. Furthermore, Au embedment into the WO3 nanowire structures remarkably improved the performance of the sensors. The increase in response performance of sensors and adsorption–desorption kinetic processes on the sensing layers were discussed in relation with the role of Au embedment. PMID:26087355

  20. Porous Au-embedded WO3 Nanowire Structure for Efficient Detection of CH4 and H2S.

    PubMed

    Vuong, Nguyen Minh; Kim, Dojin; Kim, Hyojin

    2015-01-01

    We developed a facile method to fabricate highly porous Au-embedded WO3 nanowire structures for efficient sensing of CH4 and H2S gases. Highly porous single-wall carbon nanotubes were used as template to fabricate WO3 nanowire structures with high porosity. Gold nanoparticles were decorated on the tungsten nanowires by dipping in HAuCl4 solution, followed by oxidation. The surface morphology, structure, and electrical properties of the fabricated WO3 and Au-embedded WO3 nanowire structures were examined by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and current-voltage measurements. Formation of a nanowire structure resulted in significant enhancement in sensing response to H2S and CH4 gases. Furthermore, Au embedment into the WO3 nanowire structures remarkably improved the performance of the sensors. The increase in response performance of sensors and adsorption-desorption kinetic processes on the sensing layers were discussed in relation with the role of Au embedment. PMID:26087355

  1. Porous Au-embedded WO3 Nanowire Structure for Efficient Detection of CH4 and H2S

    NASA Astrophysics Data System (ADS)

    Minh Vuong, Nguyen; Kim, Dojin; Kim, Hyojin

    2015-06-01

    We developed a facile method to fabricate highly porous Au-embedded WO3 nanowire structures for efficient sensing of CH4 and H2S gases. Highly porous single-wall carbon nanotubes were used as template to fabricate WO3 nanowire structures with high porosity. Gold nanoparticles were decorated on the tungsten nanowires by dipping in HAuCl4 solution, followed by oxidation. The surface morphology, structure, and electrical properties of the fabricated WO3 and Au-embedded WO3 nanowire structures were examined by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and current-voltage measurements. Formation of a nanowire structure resulted in significant enhancement in sensing response to H2S and CH4 gases. Furthermore, Au embedment into the WO3 nanowire structures remarkably improved the performance of the sensors. The increase in response performance of sensors and adsorption-desorption kinetic processes on the sensing layers were discussed in relation with the role of Au embedment.

  2. Investigation of Wyoming Bentonite Hydration in Dry to Water-Saturated Supercritical CH4 and CH4/CO2 Mixtures: Implications for CO2-Enhanced Gas Production

    NASA Astrophysics Data System (ADS)

    Loring, J.

    2015-12-01

    Injection of CO2 into low permeability shale formations leads to additional gas recovery and reduces the flux of CO2 into the atmosphere, thus combining a strong economic incentive with a permanent storage option for CO2. Reduced formation transmissivity due to clay swelling is a concern in CO2-enhanced gas production. Clay minerals partly determine the physical (i.e. permeability, brittleness) and certain chemical properties (i.e. wetting ability, gas adsorption) of shales, and montmorillonites are of particular interest because they swell by the uptake of species in their interlayer. In this study, the hydration and expansion of Na-, Cs-, and NH4+-saturated montmorillonite (Na-, Cs-, and NH4-SWy-2) in high-pressure (90 bar) and moderate temperature (50 °C) methane, carbon dioxide, and CO2/CH4 mixtures (3 and 25 mole% CO2) were investigated using in situ IR spectroscopic titrations, in situ XRD, in situ MAS-NMR, and ab initio electronic structure calculations. The overarching goal was to better understand the hydration/expansion behavior of Na-SWy-2 in CO2/CH4 fluid mixtures by comparison to Cs-, and NH4+-saturated clays. Specific aims were to (1) determine if CH4 intercalates the clays, (2) probe the effects of increasing dissolved CO2 and H2O concentrations, and (3) understand the role of cation solvation by H2O and/or CO2. In pure CH4, no evidence of CH4 intercalation was detected by IR for any of the clays. Similarly, no measurable changes to the basal spacing were observed by XRD in the presence of pure CH4. However, when dry Cs- and NH4-SWy-2 were exposed to dry fluids containing CO2, IR showed maximum CO2 penetrated the interlayer, XRD indicated the clays expanded, and NMR showed evidence for cation solvation by CO2, in line with theoretical predictions. IR titration of these clays with water showed sorbed H2O concentrations decreased with increasing dissolved CO2, suggesting competition for interlayer residency by CO2 and H2O. For Na-SWy-2, on the other

  3. What can we learn about an early human influence on the global methane cycle from bipolar atmospheric CH4, δD(CH4) and δ13CH4 measurements during the Holocene

    NASA Astrophysics Data System (ADS)

    Beck, Jonas; Bock, Michael; Schmitt, Jochen; Seth, Barbara; Blunier, Thomas; Fischer, Hubertus

    2015-04-01

    The past variation of the concentration of atmospheric methane (CH4) is observed to be generally in phase with the northern summer insolation cycle driven by the precession of the rotation axis of the Earth. However, in the mid-Holocene this regularity breaks down, and atmospheric CH4 starts to rise while the northern summer insolation continues to decline. Despite different attempts to explain this feature (e.g. contrasting hypotheses on early human influences or enhanced natural emissions in the southern tropics), an unambiguous explanation of the evolution of the atmospheric methane concentration has not yet been found. In addition to the inter-polar difference (IPD) of methane, allowing us to draw conclusions about the hemispheric imbalance of the source and sink distribution, the isotopic composition (δD and δ13C) of atmospheric CH4 provides further information about the methane cycle. Each source emits methane of a typical isotope signature, and each sink process leads to a certain isotopic fractionation and, thus, influences the isotopic composition of atmospheric methane. To exploit the full parameter set, we measured the methane isotopes on ice cores from both polar regions (NGRIP from Greenland; EDML and Talos Dome from Antarctica) and are able to calculate the inter-polar difference of δD (IPDδD) and δ13C (IPDδ13C) of methane over the Holocene. To avoid systematic errors, the samples from both hemispheres have been measured on the same system and during the same measurement campaign for each parameter. The NGRIP δD data show a clear covariation with the long-term changes in CH4 concentrations during the Holocene. The δD variations of 8-10 o are significantly larger than our measurement error of 2.3 o. However, the resulting IPDδD is constant within the measurement error at approximately -16.5 o (north-south) during the entire Holocene. The δ13C records (with a measurement precision of 0.13 o) show a clear decrease in δ13C of about 1.9 o and an

  4. Direct optical imaging and flux mapping of CH4 in landscapes

    NASA Astrophysics Data System (ADS)

    Gålfalk, M.; Olofsson, G.; Crill, P. M.; Bastviken, D.

    2014-12-01

    Methane (CH4) is a very potent greenhouse gas with many and diverse natural and anthropogenic emission sources such as wetlands, animals, biogas production, waste and sewage management systems. It has increased 2.5-fold since 1750 and is expected to continue to rise, with possible large implications for future climates. Although many individual sources have unknown fluxes, and distributions could be both hotspots or continuous, measurements are mostly made on either a very small scale (chambers or flux towers) with point-like or uncertain footprints, or on the very large scale of satellites with km-sized footprints. There is thus a missing intermediate scale, a scale which would allow both pin-pointing of individual CH4 emission sources and mapping a large enough area to cover a whole landscape. A general such method would be beneficial for connecting scattered local measurements and integrated large scale estimates. Remote sensing is a tool that is often used to map surface materials and the atmosphere from space. This technique, optimized for ground-based or near-ground, sensitive CH4 detection using high spectral resolution, could be a future method for detecting and mapping CH4 sources and fluxes in the environment. We present a new camera system with the ability to both detect and quantify CH4 at low levels in landscapes using remote sensing. Detection is made through thermal infrared (IR) imaging spectroscopy, using the heat radiation of objects in a scene to provide background light (e.g. tree leaves, rocks, grass or the sky). Using spectroscopic and radiative transfer modelling for each pixel (spectrum) in an image, we can calculate a CH4 distribution map from the measured spectra. The system uses imaging at high frequency (hundreds of Hz) to build the spectra - this also enables us to make simultaneous CH4 flux movies that can be used to calculate flows. Our method has broad applications and we will present examples from different environments.

  5. Evaluation of respiration in compost landfill biocovers intended for methane oxidation.

    PubMed

    Scheutz, Charlotte; Pedicone, Alessio; Pedersen, Gitte Bukh; Kjeldsen, Peter

    2011-05-01

    A low-cost alternative approach to reduce landfill gas (LFG) emissions is to integrate compost into the landfill cover design in order to establish a biocover that is optimized for biological oxidation of methane (CH(4)). A laboratory and field investigation was performed to quantify respiration in an experimental compost biocover in terms of oxygen (O(2)) consumption and carbon dioxide (CO(2)) production and emission rates. O(2) consumption and CO(2) production rates were measured in batch and column experiments containing compost sampled from a landfill biowindow at Fakse landfill in Denmark. Column gas concentration profiles were compared to field measurements. Column studies simulating compost respiration in the biowindow showed average CO(2) production and O(2) consumption rates of 107 ± 14 gm(-2)d(-1) and 63 ± 12 gm(-2)d(-1), respectively. Gas profiles from the columns showed elevated CO(2) concentrations throughout the compost layer, and CO(2) concentrations exceeded 20% at a depth of 40 cm below the surface of the biowindow. Overall, the results showed that respiration of compost material placed in biowindows might generate significant CO(2) emissions. In landfill compost covers, methanotrophs carrying out CH(4) oxidation will compete for O(2) with other aerobic microorganisms. If the compost is not mature, a significant portion of the O(2) diffusing into the compost layer will be consumed by non-methanotrophs, thereby limiting CH(4) oxidation. The results of this study however also suggest that the consumption of O(2) in the compost due to aerobic respiration might increase over time as a result of the accumulation of biomass in the compost after prolonged exposure to CH(4). PMID:21292472

  6. Riverine GHG emissions: one year of CO2, 13CO2 and CH4 flux measurements on Vistula river in Krakow, southern Poland

    NASA Astrophysics Data System (ADS)

    Jasek, Alina; Wachniew, Przemyslaw; Zimnoch, Miroslaw

    2013-04-01

    Terrestrial surface waters are generally considered to be sources of carbon dioxide and methane, because respiration of organic matter via aerobic and anaerobic pathways causes supersaturation of surface waters with respect to CO2 and CH4, respectively. In rivers, these processes are influenced by such anthropogenic factors as changes of land-use, wastewater and alteration of river channels. The research object is Vistula, the largest Polish river. It has the length of 1047 km and annual runoff of 6.2x1010m3. The urban section of Vistula in Krakow receives large amounts of organic matter from highly urbanized catchment and point discharges of urban waste waters within the city limits. The river was sampled regularly at three points: the entrance to the city, the center and the point where Vistula leaves the agglomeration. A floating chamber coupled with Picarro G2101-i analyzer was applied to quantify CO2, 13CO2 and CH4 fluxes leaving the surface of the river. A floating chamber was equipped with sensors to measure air pressure, temperature and humidity inside the chamber and the temperature of water. The chamber was equipped with a set of floats and an anchor. The measurements started in October 2011, and were repeated with approximately monthly frequency. Physicochemical properties of water (temperature, conductivity, pH, CO2 partial pressure over the water surface and alkalinity) were also measured during each measurement campaign. In addition, at each site short-term variability of the measured fluxes was also investigated. Additionally, short-term variability of the measured fluxes of CO2, 13CO2 and CH4 were performed in all three sites. The results indicate that fluxes of CO2 released from the river are comparable with the soil emissions of this gas measured in Krakow area. The δ13CO2 signature of riverine CO2 flux allowed to identify decomposition of C3 organic matter as the major source of this gas. No distinct seasonal variability of the CO2 emission and

  7. Contribution of grazing to soil atmosphere CH4 exchange during the growing season in a continental steppe

    NASA Astrophysics Data System (ADS)

    Tang, Shiming; Wang, Chengjie; Wilkes, Andreas; Zhou, Pei; Jiang, Yuanyuan; Han, Guodong; Zhao, Mengli; Huang, Ding; Schönbach, Philipp

    2013-03-01

    Degradation of steppes induced by overgrazing may affect the uptake of atmospheric methane (CH4) by soil sinks. However, uncertainty is associated with the very limited knowledge of gas fluxes in rapidly degrading steppe. In this study, we investigated the effects of grazing on CH4 uptake during the growing season in three types of steppe (meadow steppe, typical steppe and desert steppe and) in Inner Mongolia, China, to quantify and compare CH4 uptake in steppe ecosystems under different grazing management conditions. The CH4 fluxes were measured using an automatic cavity ring-down spectrophotometer at three steppe locations that differed primarily in grazing intensity. The results indicated that steppe soils were CH4 sinks throughout the growing season. CH4 uptake at all sites averaged 7.98 kg CH4-C ha-1 yr-1 (ranging from 1.53 to 18.74 kg CH4-C ha-1 yr-1), of which approximately 43.8% occurred in the desert steppe. CH4 uptake in the desert steppe increased 20.4% and 51.2% compared with the typical steppe and meadow steppe, respectively. Light grazing (LG) of steppe did not significantly change CH4 uptake compared with un-grazed (UG) steppe, but moderate and heavy grazing (MG, HG) reduced CH4 uptake significantly (by 6.8-37.9%, P < 0.05). These findings imply that reducing the grazing pressure on steppe would help increase the atmospheric CH4 sinks in steppe soils. Our results suggest that HG exerts a considerable negative impact on CH4 uptake in a continental steppe. Further studies involving year-round, intensive measurements of CH4 uptake are needed.

  8. Stable isotope ratios of atmospheric CO_{2} and CH_{4} over Siberia measured at ZOTTO

    NASA Astrophysics Data System (ADS)

    Timokhina, Anastasiya; Prokushkin, Anatily; Lavric, Jost; Heimann, Martin

    2016-04-01

    The boreal and arctic zones of Siberia housing the large amounts of carbon stored in the living biomass of forests and wetlands, as well as in soils and specifically permafrost, play a crucial role in earth's global carbon cycle. The long-term studies of greenhouse gases (GHG) concentrations are important instruments to analyze the response of these systems to climate warming. In parallel to GHG observations, the measurements of their stable isotopic composition can provide useful information for distinguishing contribution of individual GHG source to their atmospheric variations, since each source has its own isotopic signature. In this study we report first results of laboratory analyses of the CO2 and CH4 concentrations, the stable isotope ratio of δ13C-CO2, δ18O-CO2, δ13C-CH4, δD-CH4 measured in one-liter glass flasks which were obtained from 301 height of ZOTTO (Zotino Tall Tower Observatory, near 60° N, 90° E, about 20 km west of the Yenisei River) during 2008 - 2013 and 2010 - 2013 for stable isotope composition of CO2 and CH4. The magnitudes of δ13C-CO2 and δ18O-CO2 in a seasonal cycle are -1.4±0.1‰ (-7.6 - -9.0‰) and -2.2±0.2‰ (-0.1 - -2.3‰), respectively. The δ13C-CO2 seasonal pattern opposes the CO2 concentrations, with a gradual enrichment in heavy isotope occurring during May - July, reflecting its discrimination in photosynthesis, and further depletion in August - September as photosynthetic activity decreases comparatively to ecosystem respiration. Relationship between the CO2 concentrations and respective δ13C-CO2 (Keeling plot) reveals isotopic source signature for growing season (May - September) -27.3±1.4‰ and -30.4±2.5‰ for winter (January - March). The behavior of δ18O-CO2 associated with both high photosynthetic rate in the June (enrichment of atmospheric CO2 by 18O as consequence of CO2 equilibrium with "heavy" leaf water) and respiratory activity of forest floor in June - October (depletion of respired CO2 by 18O

  9. Atmospheric CO2 and CH4 Measurement Network on Towers in Siberia

    NASA Astrophysics Data System (ADS)

    Shimoyama, K.; Machida, T.; Shinohara, A.; Maksyutov, S.; Arshinov, M.; Davydov, D.; Fofonov, A.; Krasnov, O.; Fedoseev, N.; Belan, B.; Belan, H.; Inoue, G.

    2006-12-01

    In order to estimate CO2 and CH4 fluxes at regional to sub-continental scale by an inverse model, a network of tall towers for atmospheric CO2 and CH4 measurements has been established over a region of thousand square kilometers in west Siberia. In-situ continuous measurements have been conducted at 6 stations: Berezorechka (56.17N, 84.33E) since 2002, Parabel (58.25N, 82.40E) and Igrim (63.20N, 64.48E) since 2004, Demyanskoe (59.78N, 70.87E) and Noyabrsk (63.43N, 76.76E) since 2005, and Yakutsk (62.83N, 129.35E) in east Siberia since 2005. Over next two years, installations of 4 more stations are planned. This study provides some results of observation from this network. Seasonal cycles of CO2 showed quite similar trends in growing season (May to September) among the west Siberian sites. The remarkable decrease of CO2 concentration occurred in early May and the seasonal minimum was observed between July and August. On the other hand, the short-term (from several days to week) variations in CO2 concentrations were quite different among the sites, particularly during the growing season. Rather large variation of more than 25 ppm within a week was observed during winter. The changes in CO2 concentrations at the nearby sites were almost identical. Monthly mean values of CO2 during the growing season were relatively higher at the northern sites than at southern sites. These observational results evidentially reflected the regional characteristics of CO2 flux variation, transportation, and mixing process. Daily cycles of CH4 in summer showed nocturnal increase and diurnal decrease which was due to emission of CH4 from wetland accumulated over night, and diurnal convective mixing. Relatively high concentrations of CH4 were observed in winter and summer. Because there is one of the world's vastest wetland in western Siberia, the peak of CH4 in summer implies the significant role of CH4 emissions from the west Siberian wetland to the atmosphere. On the other hand, an

  10. Using "snapshot" measurements of CH4 fluxes from peatlands to estimate annual budgets: interpolation vs. modelling.

    NASA Astrophysics Data System (ADS)

    Green, Sophie M.; Baird, Andy J.

    2016-04-01

    There is growing interest in estimating annual budgets of peatland-atmosphere carbon dioxide (CO2) and methane (CH4) exchanges. Such budgeting is required for calculating peatland carbon balance and the radiative forcing impact of peatlands on climate. There have been multiple approaches used to estimate CO2 budgets; however, there is a limited literature regarding the modelling of annual CH4 budgets. Using data collected from flux chamber tests in an area of blanket peatland in North Wales, we compared annual estimates of peatland-atmosphere CH4 emissions using an interpolation approach and an additive and multiplicative modelling approach. Flux-chamber measurements represent a snapshot of the conditions on a particular site. In contrast to CO2, most studies that have estimated the time-integrated flux of CH4 have not used models. Typically, linear interpolation is used to estimate CH4 fluxes during the time periods between flux-chamber measurements. It is unclear how much error is involved with such a simple integration method. CH4 fluxes generally show a rise followed by a fall through the growing season that may be captured reasonably well by interpolation, provided there are sufficiently frequent measurements. However, day-to-day and week-to-week variability is also often evident in CH4 flux data, and will not necessarily be properly represented by interpolation. Our fits of the CH4 flux models yielded r2 > 0.5 in 38 of the 48 models constructed, with 55% of these having a weighted rw2 > 0.4. Comparison of annualised CH4 fluxes estimated by interpolation and modelling reveals no correlation between the two data sets; indeed, in some cases even the sign of the flux differs. The difference between the methods seems also to be related to the size of the flux - for modest annual fluxes there is a fairly even scatter of points around the 1:1 line, whereas when the modelled fluxes are high, the corresponding interpolated fluxes tend to be low. We consider the

  11. Unraveling the Complex Drivers of CO2 and CH4 Flux in Permafrost Soils

    NASA Astrophysics Data System (ADS)

    Ernakovich, J. G.; Lynch, L. M.; Calderon, F.; Brewer, P. E.; Wallenstein, M. D.

    2014-12-01

    Permafrost contains large stocks of organic carbon (C) that are vulnerable to decomposition following thaw, which could increase greenhouse gas (GHG) emissions leading to a potential C-climate feedback. Despite their global importance, GHG emissions from thawing permafrost are difficult to predict due to their complex mechanisms. The objective of this study was to determine the mechanisms controlling GHG flux from permafrost soil, comparing CH4 and CO2 production. We simulated permafrost thaw under drained and anoxic conditions at 1 and 15 °C, and measured CH4 and CO2 production. We also measured soil chemical and biological parameters (e.g. mid-infrared spectroscopy, iron speciation, soil redox, and next generation sequencing of the 16S gene). All treatments produced considerable amounts of CO2 (oxic, 15 °C: 0.3-2.0 mg CO2-C gdws-1). CH4 production was highly variable (anoxic, 15 °C: 0.4-67 μg CH4-C gdws-1), which was not explained by soil C content (2-603 μg CH4 g soil C-1). We explored the reasons behind this seemingly random variability in CH4 production, and found that it can be explained by the activity of non-methanogenic anaerobes and substrate supply. For example, we found that the activity of iron reducers improved the fit of CH4 production model, reducing second order bias correction (AICc) from 80 to 38, as did a gross measure of anaerobic activity (AICc reduced from 80 to 60), however neither was statistically significant (p>0.05). In methanogenesis, the lability, rather than the total chemistry of the dissolved organic matter, was important for determining gas production, but the opposite was found to be important for predicting CO2 production. Differences in methanogen populations likely also contributed to the variability in the CH4 production, and further analysis of the 16S gene abundances will elucidate this. In summary, production of CH4 depends not only on the methanogens themselves, but also on the activity of the non

  12. ANAEROBIC VS. AEROBIC PATHWAYS OF CARBONYL AND OXIDANT STRESS IN HUMAN LENS AND SKIN DURING AGING AND IN DIABETES: A COMPARATIVE ANALYSIS

    PubMed Central

    Fan, Xingjun; Sell, David R; Zhang, Jianye; Nemet, Ina; Theves, Mathilde; Lu, Jie; Strauch, Christopher; Halushka, Marc K.; Monnier, Vincent M.

    2010-01-01

    The effects of anaerobic (lens) vs aerobic (skin) environment on carbonyl and oxidant stress are compared using de novo and existing data on advanced glycation and oxidation products in human crystallins and collagen. Almost all modifications increase with age. Methylglyoxal hydroimidazolones (MG-H1), carboxymethyl-lysine (CML), and carboxyethyl-lysine (CEL) are several folds higher in lens than skin, and markedly increase upon incubation of lens crystallins with 5 mM ascorbic acid. Vice-versa, fructose-lysine, glucosepane crosslinks, glyoxal hydroimidazolones (G-H1), metal catalyzed oxidation (allysine) and H2O2 dependent modifications (2-aminoapidic acid and methionine sulfoxide) are markedly elevated in skin, but relatively suppressed in the aging lens. In both tissues ornithine is the dominant modification, implicating arginine residues as the principal target of the Maillard reaction in vivo. Diabetes (here mostly type 2 studied) increases significantly fructose-lysine and glucosepane in both tissues (P<0.001) but has surprisingly little effect on the absolute level of most other advanced glycation end products (AGEs) . However, diabetes strengthens the Spearman correlation coefficients for age-related accumulation of hydrogen peroxide mediated modifications in the lens. Overall, the data suggest oxoaldehyde stress involving methylglyoxal from either glucose or ascorbate is predominant in the aging non-cataractous lens, while aging skin collagen undergoes combined attack by non-oxidative glucose mediated modifications, as well as those from metal catalyzed oxidation and H2O2. PMID:20541005

  13. Monitoring CO2 and CH4 concentrations along an urban-rural transect in London, UK

    NASA Astrophysics Data System (ADS)

    Boon, Alex; Broquet, Gregoire; Clifford, Debbie; Chevallier, Frederic; Butterfield, David

    2013-04-01

    Cities are important sources of carbon dioxide (CO2) and methane (CH4). Anthropogenic CO2 is released in the combustion of fossil fuels for heating, electricity and transport. The major sources of CH4 in city environments are natural gas leakage, landfill sites and transport emissions. Monitoring of urban greenhouse gas concentrations is crucial for cities aiming to reduce emissions through measures such as changes to the transport infrastructure and green planning. We present measurements of CO2 and CH4 concentrations using Cavity Ring-Down Spectroscopy (CRDS) at four sites located in and around London, UK. Two sites were located in the inner city, one in the suburban fringe and the fourth in a rural location close to the city. This study was funded by Astrium Services Ltd as part of a pilot scheme to monitor city-scale GHG emissions and presented a unique opportunity to study changes in greenhouse gas concentrations across an urban to rural 'transect'. The CHIMERE chemistry-transport model is used to estimate CO2 and CH4 concentrations throughout the four month measurement period during the summer of 2012. Comparisons are made between the measured and modelled CO2 and CH4 concentrations and the representativity of the study sites for future urban greenhouse gas monitoring is considered. This study also examines the ability of a variety of measurement and modelling techniques to partition anthropogenic and biogenic CO2 sources.

  14. Insight into CH(4) formation in iron-catalyzed Fischer-Tropsch synthesis.

    PubMed

    Huo, Chun-Fang; Li, Yong-Wang; Wang, Jianguo; Jiao, Haijun

    2009-10-21

    Spin-polarized density functional theory calculations have been performed to investigate the carbon pathways and hydrogenation mechanism for CH(4) formation on Fe(2)C(011), Fe(5)C(2)(010), Fe(3)C(001), and Fe(4)C(100). We find that the surface C atom occupied sites are more active toward CH(4) formation. In Fischer-Tropsch synthesis (FTS), CO direct dissociation is very difficult on perfect Fe(x)C(y) surfaces, while surface C atom hydrogenation could occur easily. With the formation of vacancy sites by C atoms escaping from the Fe(x)C(y) surface, the CO dissociation barrier decreases largely. As a consequence, the active carburized surface is maintained. Based on the calculated reaction energies and effective barriers, CH(4) formation is more favorable on Fe(5)C(2)(010) and Fe(2)C(011), while Fe(4)C(100) and Fe(3)C(001) are inactive toward CH(4) formation. More importantly, it is revealed that the reaction energy and effective barrier of CH(4) formation have a linear relationship with the charge of the surface C atom and the d-band center of the surface, respectively. On the basis of these correlations, one can predict the reactivity of all active surfaces by analyzing their surface properties and further give guides for catalyst design in FTS. PMID:19780531

  15. Two-wavelength single laser CH and CH(4) imaging in a lifted turbulent diffusion flame.

    PubMed

    Namazian, M; Schmitt, R L; Long, M B

    1988-09-01

    A new technique has been developed which allows simultaneous 2-D mapping of CH and CH 4 in a turbulent methane flame. A flashlamp-pumped dye laser using two back mirrors produces output at 431.5 and 444 nm simultaneously. The 431.5-nm line is used to excite the (0, 0) band of the A(2)Delta-X(2)Pi system of CH, and the fluorescence of the (0, 1) transition is observed at 489 nm. Coincidentally, the spontaneous Raman scattering from CH(4) also occurs near 489 nm for a 431.5-nm excitation. To separate the CH(4) and CH contributions, the 444-nm line is used to produce a spontaneous Raman signal from CH(4) that is spectrally separated from the CH fluorescence. Subtraction of the signals generated by the 431.5- and 444-nm wavelength beams yields separate measurements of CH(4) and CH. Raman-scattered light records the instantaneous distribution of the fuel, and simultaneously the CH fluorescence indicates the location of the flame zone. The resulting composite images provide important insight on the interrelationship between fuel-air mixing and subsequent combustion.M. Namazian is with Altex Technologies Corporation, 109 Via De Tesoros, Los Gatos, California 95030; R. L. Schmitt is with Sandia National Laboratories, Combustion Research Facility, Livermore, California 94550; and M. B. Long is with Yale University, Department of Mechanical Engineering, New Haven, Connecticut 06520. PMID:20539426

  16. Estimating CH4 Emissions in California Using Measurements from a Tower Network

    NASA Astrophysics Data System (ADS)

    Jeong, S.; Hsu, Y.; Andrews, A. E.; Bianco, L.; Vaca, P.; Wilczak, J. M.; Fischer, M. L.

    2012-12-01

    We estimate regionally resolved methane (CH4) emissions for California using a Bayesian inverse model driven by CH4 mixing ratios measured at a network of five towers across the Central Valley during 2010 - 2011. The method estimates emissions by comparing measurements with transport model predictions of CH4 signals obtained from two 0.1 degree prior emission maps: 1) seasonally varying "California-specific" emission maps, calibrated to State emission totals, and 2) the EDGAR4.2 static global emission map. Atmospheric transport is calculated from particle trajectories and surface footprints using the Weather Research and Forecasting (WRF) and Stochastic Time-Inverted Lagrangian Transport (STILT) models. Results for the 5-tower CARB-CEC-LBNL-NOAA network show that significant reductions in posterior emissions uncertainty are obtained for regions comprising ~ 90% of California's known CH4 emissions, with annually averaged emissions totaling 1.6+/-0.1 and 2.5+/-0.3 times California's inventory for the California-specific and EDGAR4.2 emissions maps, respectively. Assuming these results apply across California, total CH4 emissions account for approximately 8% - 14% of current state total greenhouse gas emissions. The magnitude and uncertainty of emissions from specific regions and source sectors (e.g., crop agriculture, waste management, livestock, and energy activities) are estimated by comparing region and source sector results obtained with the CA-specific and EDGAR4.2 emission maps.

  17. Stratospheric CH4 and CO2 profiles derived from SCIAMACHY solar occultation measurements

    NASA Astrophysics Data System (ADS)

    Noël, S.; Bramstedt, K.; Hilker, M.; Liebing, P.; Plieninger, J.; Reuter, M.; Rozanov, A.; Bovensmann, H.; Burrows, J. P.

    2015-11-01

    Stratospheric profiles of methane (CH4) and carbon dioxide (CO2) have been derived from solar occultation measurements of the SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY (SCIAMACHY). The retrieval is performed using a method called "Onion Peeling DOAS" (ONPD) which combines an onion peeling approach with a weighting function DOAS (Differential Optical Absorption Spectroscopy) fit. By use of updated pointing information and optimisation of the data selection and of the retrieval approach the altitude range for reasonable CH4 could be extended to about 17 to 45 km. Furthermore, the quality of the derived CO2 has been assessed such that now the first stratospheric profiles of CO2 from SCIAMACHY are available. Comparisons with independent data sets yield an estimated accuracy of the new SCIAMACHY stratospheric profiles of about 5-10 % for CH4 and 2-3 % for CO2. The accuracy of the products is currently mainly restricted by the appearance of unexpected vertical oscillations in the derived profiles which need further investigation. Using the improved ONPD retrieval, CH4 and CO2 stratospheric data sets covering the whole SCIAMACHY time series (August 2002-April 2012) and the latitudinal range between about 50 and 70° N have been derived. Based on these time series, CH4 and CO2 trends have been estimated, which are in reasonable agreement with total column trends for these gases. This shows that the new SCIAMACHY data sets can provide valuable information about the stratosphere.

  18. Reanalysis and New Measurements of N(2) and CH(4) Adsorption on Ice and Snow.

    PubMed

    Dominé; Chaix; Hanot

    2000-07-01

    Numerous literature data indicate that the mean heat of adsorption of a monolayer of N(2) (DeltaQ(N(2))) on ice or snow at 77.15 K, determined by volumetric methods, is highly variable, suggesting that ice surface properties strongly depend on its mode of formation and its thermal history. Less numerous data on CH(4) adsorption show smaller variations of DeltaQ(CH(4)). If such variations are real, the extrapolation to atmospheric chemistry models of adsorption parameters measured on laboratory-made ice may be unwarranted. We have measured CH(4) adsorption on variable amounts of a crushed ice sample, to show that when the total surface area of the sample is below a threshold value, DeltaQ(CH(4)) decreases. We identify the cause of this artifact as an error in the molar budget, because the temperature gradient in the tube connecting the introduction and expansion volumes is not taken into account. Performing an adequate molar budget suppresses this artifact, except for ice samples with very small total surface areas, where the resolution of the manometer becomes a limiting factor and a further decrease in DeltaQ(CH(4)) is observed. Error in DeltaQ(gas) results in large errors in surface area, and we suggest that the value of DeltaQ(gas) obtained can be used to test the reliability of the surface area measurement. Copyright 2000 Academic Press. PMID:10860600

  19. Insights into the structure of mixed CO2/CH4 in gas hydrates

    DOE PAGESBeta

    Everett, S. Michelle; Rawn, Claudia J.; Chakoumakos, Bryan C.; Keffer, David J.; Huq, Ashfia; Phelps, Tommy J.

    2015-05-12

    The exchange of carbon dioxide for methane in natural gas hydrates is an attractive approach to harvesting CH4 for energy production while simultaneously sequestering CO2. In addition to the energy and environmental implications, the solid solution of clathrate hydrate (CH4)1-x(CO2)x·5.75H2O provides a model system to study how the distinct bonding and shapes of CH4 and CO2 influence the structure and properties of the compound. In this paper, high-resolution neutron diffraction was used to examine mixed CO2/CH4 gas hydrates. CO2-rich hydrates had smaller lattice parameters, which were attributed to the higher affinity of the CO2 molecule interacting with H2O molecules thatmore » form the surrounding cages, and resulted in a reduction in the unit-cell volume. Experimental nuclear scattering densities illustrate how the cage occupants and energy landscape change with composition. Finally, these results provide important insights on the impact and mechanisms for the structure of mixed CH4/CO2 gas hydrate.« less

  20. [Effects of organic manures on CO2 and CH4 fluxes of farmland].

    PubMed

    Dong, Yuhong; Ouyang, Zhu