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Sample records for aerobic ch4 oxidation

  1. Variable carbon isotope fractionation expressed by aerobic CH 4-oxidizing bacteria

    NASA Astrophysics Data System (ADS)

    Templeton, Alexis S.; Chu, Kung-Hui; Alvarez-Cohen, Lisa; Conrad, Mark E.

    2006-04-01

    Carbon isotope fractionation factors reported for aerobic bacterial oxidation of CH 4(α) range from 1.003 to 1.039. In a series of experiments designed to monitor changes in the carbon isotopic fractionation of CH 4 by Type I and Type II methanotrophic bacteria, we found that the magnitude of fractionation was largely due to the first oxidation step catalyzed by methane monooxygenase (MMO). The most important factor that modulates the (α) is the fraction of the total CH 4 oxidized per unit time, which strongly correlates to the cell density of the growth cultures under constant flow conditions. At cell densities of less than 0.1 g/L, fractionation factors greater than 1.03 were observed, whereas at cell densities greater than 0.5 g/L the fractionation factors decreased to as low as 1.002. At low cell densities, low concentrations of MMO limit the amount of CH 4 oxidized, while at higher cell densities, the overall rates of CH 4 oxidation increase sufficiently that diffusion of CH 4 from the gaseous to dissolved state and into the cells is likely the rate-determining step. Thus, the residual CH 4 is more fractionated at low cell densities, when only a small fraction of the total CH 4 has been oxidized, than at high cell densities, when up to 40% of the influent CH 4 has been utilized. Therefore, since Rayleigh distillation behavior is not observed, δ 13C values of the residual CH 4 cannot be used to infer the amount oxidized in either laboratory or field-studies. The measured (α) was the same for both Type I and Type II methanotrophs expressing particulate or soluble MMO. However, large differences in the δ 13C values of biomass produced by the two types of methanotrophs were observed. Methylosinus trichosporium OB3b (Type II) produced biomass with δ 13C values about 15‰ higher than the dissimilated CO 2, whereas Methylomonas methanica (Type I) produced biomass with δ 13C values only about 6‰ higher than the CO 2. These effects were independent of the

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

    NASA Astrophysics Data System (ADS)

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

    2016-11-01

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

  3. 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.

  4. The atmospheric CH4 increase since the Last Glacial Maximum. II - Interactions with oxidants

    NASA Technical Reports Server (NTRS)

    Thompson, Anne M.; Chappellaz, Jerome A.; Fung, Inez Y.; Kucsera, T. L.

    1993-01-01

    Results of two studies of the effect of changing CH4 fluxes on global tropospheric oxidant levels, O3, OH, and H2O2, performed with a multibox photochemical model, are presented. A sensitivity study is conducted by scaling back CH4, CO, and NO emissions relative to the present-day budget. When the CH4 ice core record is compared to calculated CH4 abundances, corresponding CH4 fluxes for the preindustrial Holocene (PIH) and Last Glacial Maximum (LGM) are fairly well-constrained: 175-225 Tg CH/4/yr for PIH and 100-130 Tg CH4/yr for LGM. Specific scenarios for CH4/CO/NO are selected to represent sources for the PIH and LGM. The CH4 budget is taken from an evaluation of wetlands and other natural sources.

  5. The Extent of CH4 Emission and Oxidation in Thermogenic and Biogenic Gas Hydrate Environments

    NASA Astrophysics Data System (ADS)

    Kastner, M.; Solem, C.; Bartlett, D.; MacDonald, I.; Valentine, D.

    2003-12-01

    The role of methane hydrate in the global methane budget is poorly understood, because relatively little is known about the transport of gaseous and dissolved methane through the seafloor into the ocean, from the water column into the atmosphere, and the extent of water-column methanotrophy that occurs en route. We characterize the transport and consumption of methane in three distinct gas hydrate environments, spanning the spectrum of thermogenic and biogenic methane occurrences: Bush Hill in the Gulf of Mexico, Eel River off the coast of Northern California, and the Noth and South Hydrate Ridges on the Cascadia Oregon margin. At all the sites studied a significant enrichment in δ 13CH4 with distance along isopycnals away from the methane source is observed, indicative of extensive aerobic bacterial methane oxidation in the water column. The effects of this process are principally pronounced in the mostly biogenic methane setting, with δ 13C-CH4 measured as high as -12 permil (PDB) between North and South Hydrate Ridge. The δ 13C-CH4 values ranged from -12 to -67 permil at Hydrate Ridge, -34 to -52 permil at Eel River, and -41 to -49 permil at Bush Hill. The large variation in methane carbon isotope ranges between the sites suggest that major differences exist in both the rates of aerobic methane oxidation and system openness at the studied locations. A mean kinetic isotope fractionation factor is being determined using a closed-system Rayleigh distillation model. An approximate regional methane flux from the ocean into the atmosphere is being estimated for the Gulf of Mexico, by extrapolation of the flux value from the Bush Hill methane plume over 390 plume locations having persistent oil slicks on the ocean surface, mapped by time series satellite data.

  6. 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

  7. 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...

  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).

  9. 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.

  10. 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.

  11. 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.

  12. 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

  13. Synergetic effect of carbon nanopore size and surface oxidation on CO2 capture from CO2/CH4 mixtures.

    PubMed

    Furmaniak, Sylwester; Kowalczyk, Piotr; Terzyk, Artur P; Gauden, Piotr A; Harris, Peter J F

    2013-05-01

    We have studied the synergetic effect of confinement (carbon nanopore size) and surface chemistry (the number of carbonyl groups) on CO2 capture from its mixtures with CH4 at typical operating conditions for industrial adsorptive separation (298 K and compressed CO2-CH4 mixtures). Although both confinement and surface oxidation have an impact on the efficiency of CO2/CH4 adsorptive separation at thermodynamics equilibrium, we show that surface functionalization is the most important factor in designing an efficient adsorbent for CO2 capture. Systematic Monte Carlo simulations revealed that adsorption of CH4 either pure or mixed with CO2 on oxidized nanoporous carbons is only slightly increased by the presence of functional groups (surface dipoles). In contrast, adsorption of CO2 is very sensitive to the number of carbonyl groups, which can be examined by a strong electric quadrupolar moment of CO2. Interestingly, the adsorbed amount of CH4 is strongly affected by the presence of the co-adsorbed CO2. In contrast, the CO2 uptake does not depend on the molar ratio of CH4 in the bulk mixture. The optimal carbonaceous porous adsorbent used for CO2 capture near ambient conditions should consist of narrow carbon nanopores with oxidized pore walls. Furthermore, the equilibrium separation factor was the greatest for CO2/CH4 mixtures with a low CO2 concentration. The maximum equilibrium separation factor of CO2 over CH4 of ~18-20 is theoretically predicted for strongly oxidized nanoporous carbons. Our findings call for a review of the standard uncharged model of carbonaceous materials used for the modeling of the adsorption separation processes of gas mixtures containing CO2 (and other molecules with strong electric quadrupolar moment or dipole moment).

  14. 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

  15. 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

  16. 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.

  17. Aerobic methane oxidation and methanotroph community composition during seasonal stratification in Mono Lake, California (USA).

    PubMed

    Carini, Stephen; Bano, Nasreen; LeCleir, Gary; Joye, Samantha B

    2005-08-01

    Patterns of aerobic methane (CH4) oxidation and associated methanotroph community composition were investigated during the development of seasonal stratification in Mono Lake, California (USA). CH4 oxidation rates were measured using a tritiated CH4 radiotracer technique. Fluorescence in situ hybridization (FISH), denaturing gradient gel electrophoresis (DGGE) and sequence analysis were used to characterize methanotroph community composition. A temporally shifting zone of elevated CH4 oxidation (59-123 nM day(-1)) was consistently associated with a suboxycline, microaerophilic zone that migrated upwards in the water column as stratification progressed. FISH analysis revealed stable numbers of type I (4.1-9.3 x 10(5) cells ml(-1)) and type II (1.4-3.4 x 10(5) cells ml(-1)) methanotrophs over depth and over time. Denaturing gradient gel electrophoresis and sequence analysis indicated slight shifts in methanotroph community composition despite stable absolute cell numbers. Variable CH4 oxidation rates in the presence of a relatively stable methanotroph population suggested that zones of high CH4 oxidation resulted from an increase in activity of a subset of the existing methanotroph population. These results challenge existing paradigms suggesting that zones of elevated CH4 oxidation activity result from the accumulation of methanotrophic biomass and illustrate that type II methanotrophs may be an important component of the methanotroph population in saline and/or alkaline pelagic environments.

  18. 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...

  19. 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.

  20. 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

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

    SciTech Connect

    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.

  2. 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

  3. Catalytic, oxidative condensation of CH4 to CH3COOH in one step via CH activation.

    PubMed

    Periana, Roy A; Mironov, Oleg; Taube, Doug; Bhalla, Gaurav; Jones, C J

    2003-08-08

    Acetic acid is an important petrochemical that is currently produced from methane (or coal) in a three-step process based on carbonylation of methanol. We report a direct, selective, oxidative condensation of two methane molecules to acetic acid at 180 degrees C in liquid sulfuric acid. Carbon-13 isotopic labeling studies show that both carbons of acetic acid originate from methane. The reaction is catalyzed by palladium, and the results are consistent with the reaction occurring by tandem catalysis, involving methane C-H activation to generate Pd-CH3 species, followed by efficient oxidative carbonylation with methanol, generated in situ from methane, to produce acetic acid.

  4. 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.

  5. 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

  6. Methane oxidation in contrasting soil types: responses to experimental warming with implication for landscape-integrated CH4 budget.

    PubMed

    D'Imperio, Ludovica; Nielsen, Cecilie Skov; Westergaard-Nielsen, Andreas; Michelsen, Anders; Elberling, Bo

    2017-02-01

    Arctic ecosystems are characterized by a wide range of soil moisture conditions and thermal regimes and contribute differently to the net methane (CH4 ) budget. Yet, it is unclear how climate change will affect the capacity of those systems to act as a net source or sink of CH4 . Here, we present results of in situ CH4 flux measurements made during the growing season 2014 on Disko Island (west Greenland) and quantify the contribution of contrasting soil and landscape types to the net CH4 budget and responses to summer warming. We compared gas flux measurements from a bare soil and a dry heath, at ambient conditions and increased air temperature, using open-top chambers (OTCs). Throughout the growing season, bare soil consumed 0.22 ± 0.03 g CH4 -C m(-2) (8.1 ± 1.2 g CO2 -eq m(-2) ) at ambient conditions, while the dry heath consumed 0.10 ± 0.02 g CH4 -C m(-2) (3.9 ± 0.6 g CO2 -eq m(-2) ). These uptake rates were subsequently scaled to the entire study area of 0.15 km(2) , a landscape also consisting of wetlands with a seasonally integrated methane release of 0.10 ± 0.01 g CH4 -C m(-2) (3.7 ± 1.2 g CO2 -eq m(-2) ). The result was a net landscape sink of 12.71 kg CH4 -C (0.48 tonne CO2 -eq) during the growing season. A nonsignificant trend was noticed in seasonal CH4 uptake rates with experimental warming, corresponding to a 2% reduction at the bare soil, and 33% increase at the dry heath. This was due to the indirect effect of OTCs on soil moisture, which exerted the main control on CH4 fluxes. Overall, the net landscape sink of CH4 tended to increase by 20% with OTCs. Bare and dry tundra ecosystems should be considered in the net CH4 budget of the Arctic due to their potential role in counterbalancing CH4 emissions from wetlands - not the least when taking the future climatic scenarios of the Arctic into account.

  7. 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.

  8. Perturbation to global tropospheric oxidizing capacity due to latitudinal redistribution of surface sources of NOx, CH4 and CO

    NASA Astrophysics Data System (ADS)

    Gupta, Mohan L.; Cicerone, Ralph J.; Elliott, Scott

    Economic and social projections indicate that during next several decades there will be major geographical redistribution of surface emissions of O3 precursors, such as NOx, CH4 and CO. A net decrease in their emissions from northern hemispheric mid-latitudes will be accompanied by substantial increases from the tropics. We have investigated a hypothetical scenario of currently underway transition of such emission patterns using a global two-dimensional photochemical model. With overall O3 precursor releases held constant, a simultaneous transfer of their emissions by 25% from the latitude belt 75°N-35°N to 5°S-35°N increases tropospheric oxidizing capacity such that the methane global lifetime and concentrations fall by more than 3%. Seasonally dependent changes in surface O3 concentrations are also calculated. In influencing OH concentration, redistribution of surface NOx emissions is 2-3 orders of magnitude more efficient per unit mass than CO emissions. Shifts in methane sources have insignificant effects on global photochemistry, but lead to a decrease in its interhemispheric gradient.

  9. Consequences of metal-oxide interconversion for C-H bond activation during CH4 reactions on Pd catalysts.

    PubMed

    Chin, Ya-Huei Cathy; Buda, Corneliu; Neurock, Matthew; Iglesia, Enrique

    2013-10-16

    Mechanistic assessments based on kinetic and isotopic methods combined with density functional theory are used to probe the diverse pathways by which C-H bonds in CH4 react on bare Pd clusters, Pd cluster surfaces saturated with chemisorbed oxygen (O*), and PdO clusters. C-H activation routes change from oxidative addition to H-abstraction and then to σ-bond metathesis with increasing O-content, as active sites evolve from metal atom pairs (*-*) to oxygen atom (O*-O*) pairs and ultimately to Pd cation-lattice oxygen pairs (Pd(2+)-O(2-)) in PdO. The charges in the CH3 and H moieties along the reaction coordinate depend on the accessibility and chemical state of the Pd and O centers involved. Homolytic C-H dissociation prevails on bare (*-*) and O*-covered surfaces (O*-O*), while C-H bonds cleave heterolytically on Pd(2+)-O(2-) pairs at PdO surfaces. On bare surfaces, C-H bonds cleave via oxidative addition, involving Pd atom insertion into the C-H bond with electron backdonation from Pd to C-H antibonding states and the formation of tight three-center (H3C···Pd···H)(‡) transition states. On O*-saturated Pd surfaces, C-H bonds cleave homolytically on O*-O* pairs to form radical-like CH3 species and nearly formed O-H bonds at a transition state (O*···CH3(•)···*OH)(‡) that is looser and higher in enthalpy than on bare Pd surfaces. On PdO surfaces, site pairs consisting of exposed Pd(2+) and vicinal O(2-), Pd(ox)-O(ox), cleave C-H bonds heterolytically via σ-bond metathesis, with Pd(2+) adding to the C-H bond, while O(2-) abstracts the H-atom to form a four-center (H3C(δ-)···Pd(ox)···H(δ+)···O(ox))(‡) transition state without detectable Pd(ox) reduction. The latter is much more stable than transition states on *-* and O*-O* pairs and give rise to a large increase in CH4 oxidation turnover rates at oxygen chemical potentials leading to Pd to PdO transitions. These distinct mechanistic pathways for C-H bond activation, inferred from theory

  10. 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.

  11. Effects of nitrogen conversion and environmental factors on landfill CH4 oxidation and N2O emissions in aged refuse.

    PubMed

    Zhang, Houhu; Zhao, Keqiang; Yan, Xiaofei; Sun, Qinfang; Li, Yi; Zhang, Yi; Zun, Zhao; Ke, Fan

    2013-09-15

    We determined the effects of nitrification capacity and environmental factors on landfill methane oxidation potential (MOP) using an aged refuse in laboratory batch assays and compared it with two different types of soils. The nitrogen conversion in the three experimental materials after 120 h incubation yielded first-order reaction kinetics at an initial concentration of 200 mg kg(-1) NH4(+)-N. The net nitrification rate for the aged refuse was 1.50 (p < 0.05) and 2.08 (p < 0.05) times that of the clay soil and the sandy soil, respectively. The net NO3(-)-N generation rate by the aged refuse was 1.93 (p < 0.05) and 2.57 (p < 0.05) times that of the clay soil and the sandy soil, respectively. When facilitated by ammonia-oxidizing bacteria during CH4 co-oxidation, the average value of the MOP in the aged refuse at a temperature range of 4-45 °C was 2.34 (p < 0.01) and 4.71 (p < 0.05) times greater than that of the clay soil and the sandy soil, respectively. When the moisture content ranged from 8 to 32% by mass, the average values for the MOP in the aged refuse were 2.08 (p < 0.01) and 3.15 (p < 0.01) times greater than that of the clay soil and the sandy soil, respectively. The N2O fluxes in the aged refuse at 32% moisture content were 5.33 (p < 0.05) and 12.00 (p < 0.05) times more than in the clay and the sandy soil, respectively. The increase in N2O emissions from a municipal solid waste landfill can be neglected after applying an aged refuse bio-cover because of the much higher MOP in the aged refuse. The calculated maximum MOP value in the aged refuse was 12.45 μmol g(-1) d.w. h(-1), which was much higher than the documented data.

  12. The influence of hydrogen-containing molybdenum and tungsten bronzes on the catalytic activity of palladium composite catalysts for the oxidation of H2, CO, and CH4

    NASA Astrophysics Data System (ADS)

    Lesnyak, V. V.; Yatsimirskii, V. K.; Gut, I. N.; Boldyreva, O. Yu.

    2008-09-01

    The influence of hydrogen-containing molybdenum and tungsten bronzes on the catalytic activity of palladium composite catalysts for the oxidation of H2, CO, and CH4 was studied. It was found that the composite catalysts containing H x MO3 phases (M = W or Mo), which were formed by the reduction of MoO3 and WO3 oxides with hydrogen in the presence of deposited Pd, showed higher catalytic activity in the oxidation of small molecules (H2, CO, and CH4) with excess oxygen than the traditional Pd/Al2O3 deposited catalyst with the same content of the deposited metal. It was shown that the thermal stability of the H x MO3 phases was the limiting factor influencing the activity of these composite catalysts.

  13. Using reduced catalysts for oxidation reactions: mechanistic studies of the "Periana-Catalytica" system for CH4 oxidation.

    PubMed

    Mironov, Oleg A; Bischof, Steven M; Konnick, Michael M; Hashiguchi, Brian G; Ziatdinov, Vadim R; Goddard, William A; Ahlquist, Mårten; Periana, Roy A

    2013-10-02

    Designing oxidation catalysts based on CH activation with reduced, low oxidation state species is a seeming dilemma given the proclivity for catalyst deactivation by overoxidation. This dilemma has been recognized in the Shilov system where reduced Pt(II) is used to catalyze methane functionalization. Thus, it is generally accepted that key to replacing Pt(IV) in that system with more practical oxidants is ensuring that the oxidant does not over-oxidize the reduced Pt(II) species. The "Periana-Catalytica" system, which utilizes (bpym)Pt(II)Cl2 in concentrated sulfuric acid solvent at 200 °C, is a highly stable catalyst for the selective, high yield oxy-functionalization of methane. In lieu of the over-oxidation dilemma, the high stability and observed rapid oxidation of (bpym)Pt(II)Cl2 to Pt(IV) in the absence of methane would seem to contradict the originally proposed mechanism involving CH activation by a reduced Pt(II) species. Mechanistic studies show that the originally proposed mechanism is incomplete and that while CH activation does proceed with Pt(II) there is a solution to the over-oxidation dilemma. Importantly, contrary to the accepted view to minimize Pt(II) overoxidation, these studies also show that increasing that rate could increase the rate of catalysis and catalyst stability. The mechanistic basis for this counterintuitive prediction could help to guide the design of new catalysts for alkane oxidation that operate by CH activation.

  14. 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.

  15. 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.

  16. Surface Structure of Aerobically Oxidized Diamond Nanocrystals

    DTIC Science & Technology

    2014-10-27

    distribution is unlimited. Surface Structure of Aerobically Oxidized Diamond Nanocrystals The views, opinions and/or findings contained in this report...2211 diamond nanocrystals, REPORT DOCUMENTATION PAGE 11. SPONSOR/MONITOR’S REPORT NUMBER(S) 10. SPONSOR/MONITOR’S ACRONYM(S) ARO 8. PERFORMING...Room 254, Mail Code 8725 New York, NY 10027 -7922 ABSTRACT Surface Structure of Aerobically Oxidized Diamond Nanocrystals Report Title We investigate

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

    NASA Astrophysics Data System (ADS)

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

    2013-12-01

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

  18. 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.

  19. Evaluation of Methyl Fluoride and Dimethyl Ether as Inhibitors of Aerobic Methane Oxidation

    PubMed Central

    Oremland, Ronald S.; Culbertson, Charles 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. PMID:16348771

  20. Surface Structure of Aerobically Oxidized Diamond Nanocrystals.

    PubMed

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

    2014-11-20

    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.

  1. 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

  2. Simulating CO2 and CH4 production and consumption from incubated permafrost soils: how important are the microbial mechanisms

    NASA Astrophysics Data System (ADS)

    Xu, X.; Elias, D. A.; Graham, D. E.; Phelps, T. J.; Thornton, P. E.

    2012-12-01

    An incubation experiment was conducted to examine the production and consumption of the greenhouse gases CO2 and CH4 in soils of the top layer, active layer, and permafrost layer under various moisture and temperature conditions using soil cores extracted from the Alaskan permafrost region. The incubation results confirmed the production of hydrogen gas and acetic acid resulting in a decreased soil pH. Three key mechanisms for production and consumption of CH4 are suspected; CH4 production from acetic acid and H2 and CO2, and aerobic CH4 oxidation. We translated these mechanisms into a subroutine program which was then combined with decomposition subroutines in the community land model (CLM4) to evaluate the performance of these mechanisms in simulating CO2 and CH4 production and consumption from the incubated permafrost soils. Two guilds of microorganisms for methanogenesis and one group for methanotrophy were simulated. The simulation results confirmed that microbial mechanisms are critically important in reconstructing the observed changes in temporal CO¬2 and CH4 concentrations. There are large variations in CO2 and CH4 production and consumption among the different soil layers. Acetic acid production caused the observed drop in soil pH, which in turn exerted a substantial effect on CO2 and CH4 dynamics. The moisture and temperature had significant effects on microbial mechanisms and further on CO2 and CH4 production and consumption. Further efforts will be incorporating microbial dynamics and these mechanisms into the Community Earth System Model for a global scale investigation.onceptural diagram showing the mechanisms incorporated in the improved module

  3. 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

  4. 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.

  5. Surface Structure of Aerobically Oxidized Diamond Nanocrystals

    DOE PAGES

    Wolcott, Abraham; Schiros, Theanne; Trusheim, Matthew E.; ...

    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

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

    PubMed

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

    2014-08-29

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

  7. CH4 and CO2 flux observations in northeast Siberian tundra and its implications for modelling of CH4 fluxes

    NASA Astrophysics Data System (ADS)

    van Huissteden, K. J.; Parmentier, F.; Petrescu, R.; van Beek, L. P.; Karsanaev, S.; Maximov, T.; van der Molen, M.; Dolman, H.

    2009-12-01

    Six years of data on CO2 and CH4 fluxes are available from the tundra research site Kytalyk in the northeast Siberian tundra. The site covers a frequently flooded floodplain area dominated by grasses and Carex/Eriphorum vegetation, and a non-flooded tundra area with more oligotrophic Sphagnum-rich vegetation. CO2 fluxes are related to variations in gross primary productivity. The tundra part of the site is a small net sink for CO2 and total greenhouse gases in summer. The spatial variability of the CH4 fluxes is large. With similar water table, Sphagnum-rich tundra surfaces show low fluxes, while the river floodplain emits high amounts of CH4. The CH4 flux in the river floodplain is sensitive to river discharge, being highest in wet years with flooding. This has implications for large-scale modelling of CH4 fluxes. Sub-grid variation in vegetation variability and in the extent and duration of flooding have to be taken into account. We used a coupled hydrological/CH4 flux model (PCR-GLOBWB global hydrology and PEATLAND-VU CH4) dealing with some of these aspects. Our results show considerable year-to-year variation due to variation in floodplain hydrology and to a lesser degree in wetland extent. Also vegetation variability contributes to uncertainty in modelling fluxes, as shown by model sensitivity to parameters governing within-plant transport and oxidation of CH4.

  8. Processes and emissions of CH4 and CO2 from subarctic and arctic thaw ponds: Insights from stable isotopes

    NASA Astrophysics Data System (ADS)

    Laurion, I.; Negandhi, K.; Whiticar, M. J.

    2011-12-01

    The expansion of permafrost thaw ponds, a widespread feature of Canadian arctic sedimentary basins, is accelerating due to climate change. Permafrost soils store half of the global below ground organic carbon stock, which is now being mobilized as peat soils thaw and erode. Thaw ponds are large emitters of methane and carbon dioxide. Our studies of organic-rich thaw ponds in the Canadian Arctic (Bylot Island, north Baffin Island) and Subarctic (Kuujjuarapik, Quebec) reveal substantial fluxes to the atmosphere of CO2 (up to 326 mmol CO2 m-2 d-1) and CH4 (up to 15 mmol CH4 m-2 d-1) in summer, using wind-based model estimations (excluding ebullition). Carbon and hydrogen isotopes indicate that acetoclastic fermentation is the dominant methanogenic pathway in these ponds (e.g., δ13CH4 ca. -55 to -75 %; δD-CH4 ca. -350 %). In contrast with many peatland sites, methanogenesis in thaw ponds does not transition to the hydrogenotrophic pathway. In one type of arctic ponds colonized with thick cyanobacterial mats, active photosynthesis during summer drags down atmospheric CO2 (negative flux down to -18 mmol CO2 m-2 d-1) and potentially influences the δ13CH4. Trends in the isotope data, in concert with O2, confirm the importance and variability of aerobic methane oxidation on dissolved methane concentrations in the ponds. The combined mechanisms of methanogenesis and methylotrophy modulate the release of important greenhouse gases from these environments.

  9. 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.

  10. Martian CH(4): sources, flux, and detection.

    PubMed

    Onstott, T C; McGown, D; Kessler, J; Lollar, B Sherwood; Lehmann, K K; Clifford, S M

    2006-04-01

    Recent observations have detected trace amounts of CH(4) heterogeneously distributed in the martian atmosphere, which indicated a subsurface CH(4) flux of ~2 x 10(5) to 2 x 10(9) cm(2) s(1). Four different origins for this CH(4) were considered: (1) volcanogenic; (2) sublimation of hydrate- rich ice; (3) diffusive transport through hydrate-saturated cryosphere; and (4) microbial CH(4) generation above the cryosphere. A diffusive flux model of the martian crust for He, H(2), and CH(4) was developed based upon measurements of deep fracture water samples from South Africa. This model distinguishes between abiogenic and microbial CH(4) sources based upon their isotopic composition, and couples microbial CH(4) production to H(2) generation by H(2)O radiolysis. For a He flux of approximately 10(5) cm(2) s(1) this model yields an abiogenic CH(4) flux and a microbial CH(4) flux of approximately 10(6) and approximately 10(9) cm(2) s(1), respectively. This flux will only reach the martian surface if CH(4) hydrate is saturated in the cryosphere; otherwise it will be captured within the cryosphere. The sublimation of a hydrate-rich cryosphere could generate the observed CH(4) flux, whereas microbial CH(4) production in a hypersaline environment above the hydrate stability zone only seems capable of supplying approximately 10(5) cm(2) s(1) of CH(4). The model predicts that He/H(2)/CH(4)/C(2)H(6) abundances and the C and H isotopic values of CH(4) and the C isotopic composition of C(2)H(6) could reveal the different sources. Cavity ring-down spectrometers represent the instrument type that would be most capable of performing the C and H measurements of CH(4) on near future rover missions and pinpointing the cause and source of the CH(4) emissions.

  11. 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.

  12. 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.; 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.

  13. 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.

  14. Methane Emission From the Congo Deep Sea Fan and Subsequent Aerobic Oxidation in the Quaternary Tropical Atlantic

    NASA Astrophysics Data System (ADS)

    Handley, L.; Cooke, M. P.; Talbot, H. M.; Wagner, T.

    2008-12-01

    The Congo Fan is a well-documented region of important methane (CH4) storage and gas seepage: gas hydrates abound at and just below the sediment surface as do large deeply-buried reservoirs of thermogenic methane linked with hydrocarbon source rocks. In the Congo Fan, both sources of methane are intimately connected through a complex network of faults, structuring this massive sediment wedge in a unique way. Methane release from both reservoirs has the potential to drive or respond to changes in local and global climate, thus causing changes in ocean chemical properties and biotic responses. Understanding these poorly-constrained mechanisms of methane emission and reconstructing the history of past emissions in the ocean is the main focus of our study. The ultimate fate of CH4 is, typically, its oxidation to CO2; this process can occur aerobically and anaerobically. Compared to anaerobic processes, aerobic methane oxidation, and its underlying mechanisms and possible feedbacks for the ocean-climate system, has received little attention. Here we present molecular evidence from Congo Fan sediments for aerobic methane oxidation and highlight how the process may play a previously unrecognised role in carbon cycling and oxygen availability in the water column. Bacteriohopanepolyols (BHPs) are lipid membrane constituents and occur with a wide range of structural and functional variability in many bacteria. Amino-BHPs are produced in large abundances by methane-oxidising bacteria and the 35-aminobacteriohopane-30,31,32,33,34-pentol (aminopentol) is a highly specific biomarker for aerobic methane oxidation. The Congo Fan record (ODP Leg 175, Site 1075; 2996 m depth) spans the last 1 Myr and reveals remarkable organic biomarker preservation, with a suite of 13 different BHPs identified in most sediment horizons, including aminopentol. Aminopentol abundance varies widely throughout the section and appears to do so cyclically, with markedly greater concentrations between ca

  15. 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

  16. 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 %.

  17. 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

  18. δ(13)C-CH4 reveals CH4 variations over oceans from mid-latitudes to the Arctic.

    PubMed

    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 δ(13)C-CH4 from offshore China (31°N) to the central Arctic Ocean (up to 87°N) from July to September 2012. CH4 concentrations and δ(13)C-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 δ(13)C and chemical oxidation by both OH and Cl radicals as indicated by variation of δ(13)C. 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.

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

    PubMed

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

    2011-06-01

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

  20. 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.

  1. 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

  2. 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.

  3. Land-atmosphere exchange of CH4 in Barrow, Alaska: Contributions of Methanogens and Methanotrophy

    NASA Astrophysics Data System (ADS)

    Xu, X.; Thornton, P. E.; Graham, D. E.; Elias, D. A.; Phelps, T. J.; Wullschleger, S. D.

    2013-12-01

    Accurate prediction of climate-biogeochemistry requires a good understanding and explicit microbial mechanisms being incorporated. A microbial functional group-based module has been developed to simulate the production and consumption of the methane (CH4), a potent greenhouse gas along soil profile. The developed module in stand-along version has been tested and validated against our previous incubation results. The module was then incorporated into the Community Land Model 4.5 (CLM4.5), the land component of the Community Earth system model. After parameterization with literature-derived data, we use the CLM4.5 model with multiple soil layers version to simulate CH4 processes at Barrow, Alaska and compare with the field observational data from the Next-Generation Ecosystem Experiment (NGEE Arctic). The relative contributions of four microbial functional groups, acetotrophic methanogens, hydrogenotrophic methanogens, aerobic methanotrophs, and anaerobic methanotrophs, to the CH4 flux were quantified and evaluated. The tested model was used for regional estimation of CH4 fluxes. The sensitivity analysis identifies that acetate acid production has a substantial effect on CH4 production. The simulation results confirmed that microbial mechanisms are critically important for simulating CH4 fluxes. The acetotrophic methanogens play a dominant contribution while hydrogenotrophic methanogens have minor contribution to CH4 production; aerobic methanotrophs have predominated contribution to methane consumption. The anaerobic methanotrophs are important for CH4 consumption in the northern permafrost region due to long-term anaerobic condition in the Arctic region that normally induces large population of anaerobic methanotrophs. The vertical distribution of microbial contribution to the CH4 process is largely different across microbial functional groups and environmental condition. This microbial functional group-based biogeochemistry module is among the first attempts to

  4. Co(salophen)-Catalyzed Aerobic Oxidation of p-Hydroquinone: Mechanism and Implications for Aerobic Oxidation Catalysis

    SciTech Connect

    Anson, Colin W.; Ghosh, Soumya; Hammes-Schiffer, Sharon; Stahl, Shannon S.

    2016-03-30

    Macrocyclic metal complexes and p-benzoquinones are commonly used as co-catalytic redox mediators in aerobic oxidation reactions. In an effort to gain insight into the mechanism and energetic efficiency of these reactions, we investigated Co(salophen)-catalyzed aerobic oxidation of p-hydroquinone. Kinetic and spectroscopic data suggest that the catalyst resting-state consists of an equilibrium between a CoII(salophen) complex, a CoIII-superoxide adduct, and a hydrogen-bonded adduct between the hydroquinone and the CoIII–O2 species. The kinetic data, together with density functional theory data, suggest that the turnover-limiting step features proton-coupled electron transfer from a semi-hydroquinone species and a CoIII-hydroperoxide intermediate. Additional experimental and computational data suggest that a coordinated H2O2 intermediate oxidizes a second equivalent of hydroquinone. 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. The NSF provided partial support for the EPR instrumentation (NSF CHE-0741901).

  5. 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.

  6. 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

  7. 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

  8. 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

  9. 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.

  10. Warming Early Mars With CH4

    NASA Astrophysics Data System (ADS)

    Justh, H. L.; Kasting, J. F.

    2002-12-01

    The nature of the ancient climate of Mars remains one of the fundamental unresolved problems in martian research. While the present environment is hostile to life, images from the Mariner, Viking and Mars Global Surveyor missions, have shown geologic features on the martian surface that seem to indicate an earlier period of hydrologic activity. The fact that ancient valley networks and degraded craters have been seen on the martian surface indicates that the early martian climate may have been more Earth-like, with a warmer surface temperature. The presence of liquid water would require a greenhouse effect much larger than needed at present, as the solar constant, S0, was 25% lower 3.8 billion years ago when the channels are thought to have formed (1,2). Previous calculations have shown that gaseous CO2 and H2O alone could not have warmed the martian surface to the temperature needed to account for the presence of liquid water (3). It has been hypothesized that a CO2-H2O atmosphere could keep early Mars warm if it was filled with CO2 ice clouds in the upper martian troposphere (4). Obtaining mean martian surface temperatures above 273 K would require nearly 100% cloud cover, a condition that is unrealistic for condensation clouds on early Mars. Any reduction in cloud cover makes it difficult to achieve warm martian surface temperatures except at high pressures and CO2 clouds could cool the martian surface if they were low and optically thick (5). CO2 and CH4 have been suggested as important greenhouse gases on the early Earth. Our research focuses on the effects of increased concentrations of atmospheric greenhouse gases on the surface temperature of early Mars, with emphasis on the reduced greenhouse gas, CH4. To investigate the possible warming effect of CH4, we modified a one-dimensional, radiative-convective climate model used in previous studies of the early martian climate (5). New cloud-free temperature profiles for various surface pressures and CH4 mixing

  11. 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.

  12. 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

  13. 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.

  14. Synthesis of Tungsten Carbides by Temperature-Programmed Reaction with CH 4-H 2 Mixtures. Influence of the CH 4 and Hydrogen Content in the Carburizing Mixture

    NASA Astrophysics Data System (ADS)

    Giraudon, J.-M.; Devassine, P.; Lamonier, J.-F.; Delannoy, L.; Leclercq, L.; Leclercq, G.

    2000-11-01

    The influence of the composition of a carburizing CH4-H2 gas mixture on the process of reduction-carburization over WO3 has been studied. Bulk tungsten carbide synthesis has been carried out from WO3 in different CH4-H2 mixtures (CH4-H2=1/1-3/1; CH4-N2=1/1; pure CH4) at atmospheric pressure by temperature-programmed reduction-carburization (TPRC). The composition of the reaction products has been monitored and quantified by gas chromatography analysis (GCA) and the results have been compared to those obtained for a reference sample WC20 (CH4-H2=1/4). The solids have been characterized by elemental analysis, XRD, XPS, and BET surface area measurements. The overall process is complex. Considering first the reduction, both H2 and CH4 act as oxides reducing agents and are converted respectively into H2O, CO, and to a less extent CO2. If the reduction steps follow the same sequence observed under pure H2, WO3→W20O58→WO2→W, with the strong difference that W metal is detected only at the surface to be rapidly carburized, the overall reduction process can be accomplished under CH4-H2 mixtures at temperatures all the lower than PCH4/PH2 increases. Prereduction of WO3 into bulk WO2 allows an easier reduction in practically pure CH4 (95% (v/v) CH4-H2) as reduction with CH4 increases the rate of the WO2→W transformation. Studies of the carburization suggest that CH4 decomposes on a metallic surface into C (or CHx) species before bulk WO2 reduction followed by surface carburization. Then carbon diffuses into the bulk of the solid to give first α-W2C whose formation occurs rapidly. α-W2C transformation into WC is slower and seems to be very much influenced by the ratio PCH4/PH2 which controls the rate of carbon deposit at the surface of the solid. The best surface area carbide of 27 m2.g-1 consisting of a core of α-W2C covered with α-WC has been obtained by using WO2 as starting material.

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

    PubMed

    Iosub, Andrei V; Stahl, Shannon S

    2015-09-18

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

  16. 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.

  17. 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

  18. Electron Impact Fragmentation of CH4 Molecules

    NASA Astrophysics Data System (ADS)

    Suzuki, Ryoji; Oguri, Kazuhiro; Makochekanwa, Casten; Kitajima, Masashi; Tanaka, Hiroshi

    2004-09-01

    Absolute electron-molecule impact dissociation cross sections are of interest in many fields of physics and chemistry, plasma etching of microelectronic devices and other industrial applications. However, experimental data on these cross sections is scarce mainly because of the difficulties involved in measuring neutral fragments [1]. Electron impact dissociation of CH4 molecules into the CH3 radicals have been investigated over the energy range 15.0 to 37.0 eV. The experimental procedure involves a dual-electron-beam in a two-stage collision system in conjunction with a quadrupole mass spectrometer (QMS). This is similar to the threshold-ionization mass spectrometry method [2]. Significant differences, in magnitude up to four times at 100 eV, exist between the only available absolute measurements by Sugai et al. [2] and Moore et al. [3]. Our data shows very close agreement with the Moore et al. data, which which show reasonable consistency with the available CH4 total dissociation data by Winters [3]. [1] L. S. Polak and D. I. Slovetsky, Int. J. Rad. Phys. Chem. 8, 257 (1976). [2] H. Sugai, H. Toyoda and T. Nakano, Jpn. J. Appl. Phys. 30, 2912 (1991). [3] H. F. Winters, J. Chem. Phys. 63, 3462 (1975).

  19. Comparison Between Dust Particle Generation In CH4 or CH4/N2 Mixing RF Plasmas

    SciTech Connect

    Pereira, Jeremy; Massereau-Guilbaud, Veronique; Geraud-Grenier, Isabelle; Plain, Andre

    2005-10-31

    Dust particles have been spontaneously generated either in pure CH4 or in CH4/N2 r.f. plasmas. The dust particle formation results from homogeneous nucleation in the plasma and is detected by laser light scattering (Ar+, {lambda} = 514.5 nm). The temporal and spatial behaviour of dust particles is studied. In pure methane gas, particles are trapped in well defined clouds at the plasma sheath boundaries. In a CH4/N2 mixture, the nitrogen addition leads to an expansion of the clouds. For nitrogen contents higher than 50%, the space between the electrodes is nearly completely filled with dust particles leading to plasma instabilities and a void appears in the center of the discharge. The particles are spherical with diameters in the range 0.8-2 {mu}m. For nitrogen-rich plasmas, the particles growth is improved and leads to a rough shape with an orange-peel-type surface texture.

  20. Mitigation of nitrous oxide (N2 O) emission from swine wastewater treatment in an aerobic bioreactor packed with carbon fibers.

    PubMed

    Yamashita, Takahiro; Yamamoto-Ikemoto, Ryoko; Yokoyama, Hiroshi; Kawahara, Hirofumi; Ogino, Akifumi; Osada, Takashi

    2015-03-01

    Mitigation of nitrous oxide (N2 O) emission from swine wastewater treatment was demonstrated in an aerobic bioreactor packed with carbon fibers (CF reactor). The CF reactor had a demonstrated advantage in mitigating N2 O emission and avoiding NOx (NO3  + NO2 ) accumulation. The N2 O emission factor was 0.0003 g N2 O-N/gTN-load in the CF bioreactor compared to 0.03 gN2 O-N/gTN-load in an activated sludge reactor (AS reactor). N2 O and CH4 emissions from the CF reactor were 42 g-CO2 eq/m(3) /day, while those from the AS reactor were 725 g-CO2 eq/m(3) /day. The dissolved inorganic nitrogen (DIN) in the CF reactor removed an average of 156 mg/L of the NH4 -N, and accumulated an average of 14 mg/L of the NO3 -N. In contrast, the DIN in the AS reactor removed an average 144 mg/L of the NH4 -N and accumulated an average 183 mg/L of the NO3 -N. NO2 -N was almost undetectable in both reactors.

  1. Combustion of CH4/H2/air mixtures in catalytic microreactors.

    PubMed

    Specchia, Stefania; Vella, Luigi D; Burelli, Sara; Saracco, Guido; Specchia, Vito

    2009-03-23

    The combustion of CH(4)/H(2)/HC mixtures in a very small space represents an alternative, innovative way to produce thermal/electrical energy. Pd/NiCrO(4) catalysts are lined on SiC monoliths via in situ solution combustion synthesis (SCS), and the monoliths are then tested by feeding CH(4), H(2), and lean CH(4)/H(2) mixtures into a lab-scale test rig at an output thermal power of 7.6 MW(th) m(-3). In all cases, the combustion temperature shifts to values lower than those observed in non-catalytic combustion. When the power density is kept constant (by adding H(2) to the gas mixture), the value of CH(4)-T(50) (the half-conversion temperature of CH(4)) decreases relative to that of pure CH(4), and the slope of the conversion curve becomes steeper. The higher the H(2) concentration is, the higher the reactivity of the mixture towards CH(4) oxidation-probably due to a higher production of H(2) reactive radicals (OH).

  2. Study of the characteristics of CH4 and N2O emission and methods of controlling their emission in the soil-trench wastewater treatment process.

    PubMed

    Kong, Hai Nan; Kimochi, Yuzuru; Mizuochi, Motoyuki; Inamori, Ryuhei; Inamori, Yuhei

    2002-05-06

    In recent years, worldwide concern over global warming has been expressed. It has been reported that domestic wastewater and its treatment processes are sources of CH4 and N2O, designated as greenhouse gases, the reduction of which was noted to be extremely important at the Third Conference of the Framework Convention on Climate Change (Conference Of the Parties; COP3). Here we report a study of a field that has been unexplored until now: analytical evaluation of the properties of the emission of CH4 and N2O and methods of restricting their emission in soil-trench wastewater treatment processes, the use of which is spreading, mainly in developing nations. The results have provided the following information. A field fact-finding survey has confirmed that soil trenches emit 9.3-13.9 g CH4 m(-3) and 8.2-12.2 gN2O m(-3) in Japan, and 3.0-4.5 g CH4 m(-3) and 3.3-5.0 g N2O m(-3) in China. The emission properties widely vary according to the structure of the treatment system. The conversion ratio for nitrogen in the wastewater influent to N2O by a soil trench is between 2 and a maximum of 8%, and ranges from a few- to several 10-fold as much as that with the activated sludge method, suggesting that this can be a large source of N2O emission. It has also clearly been shown that the aerobic-anaerobic state inside the treatment system is closely related to its CH4 and N2O emission characteristics. By performing ventilation to maintain the oxidation-reduction potential (ORP) near the trench at an aerobic condition of +200 mV or more, the quantities of CH4 and N2O emitted can be reduced by as much as 50% from the levels without this ventilation, and that this can make a large contribution.

  3. A mild oxidative aryl radical addition into alkenes by aerobic oxidation of arylhydrazines.

    PubMed

    Taniguchi, Tsuyoshi; Zaimoku, Hisaaki; Ishibashi, Hiroyuki

    2011-04-04

    A mild and practical oxyarylation of alkenes by oxidative radical addition has been developed by using aerobic oxidation of hydrazine compounds. The use of a catalytic amount of potassium ferrocyanide trihydrate (K(4)[Fe(CN)(6)]⋅3H(2)O) and water accelerated this radical reaction to give peroxides or alcohols from simple alkenes in good yields. The environmentally friendly and economical radical reactions were achieved at room temperature in the presence of iron catalyst, oxygen gas, and water. A method involving aniline as a radical precursor is also described.

  4. 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

  5. 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

  6. 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.

  7. CH4 and N2O dynamics in the boreal forest-mire ecotone

    NASA Astrophysics Data System (ADS)

    Tupek, B.; Minkkinen, K.; Pumpanen, J.; Vesala, T.; Nikinmaa, E.

    2014-06-01

    In spite of advances in greenhouse gas research, the spatio-temporal CH4 and N2O dynamics of boreal landscape remain challenging, e.g. we need clarification of whether the forest-mire transitions are occasional hotspots of landscape CH4 and N2O emissions during exceptionally high and low ground water level events. In our study, we tested the differences and drivers of CH4 and N2O dynamics of forest/mire types in field conditions along the soil moisture gradient of the forest-mire ecotone. Soils changed from podzols to histosols and ground water rose downslope from the depth of 10 m in upland sites to 0.1 m in mires. Yearly meteorological conditions changed from being exceptionally wet to typical and exceptionally dry for the local climate. The median fluxes measured with a static chamber technique varied from -51 to 586 μg m-2 h-1 for CH4 and from 0 to 6 μg m-2 h-1 for N2O between forest/mire types throughout the entire wet-dry period. In spite of the highly dynamic soil water fluctuations in carbon rich soils in forest-mire transitions, there were no large peak emissions in CH4 and N2O fluxes and the flux rates changed minimally between years. Methane oxidations were significantly lower in poorly drained transitions than in the well-drained uplands. Water saturated mires showed large CH4 emissions, which were reduced entirely during the exceptional summer drought period. Near zero N2O fluxes did not differ significantly between the forest/mire types probably due to their low nitrification potential. When up scaling boreal landscapes, pristine forest-mire transitions should be categorized as CH4 oxidation types and background N2O emission types instead of CH4 and N2O emission hotspots.

  8. Aerobic condition increases carotenoid production associated with oxidative stress tolerance in Enterococcus gilvus.

    PubMed

    Hagi, Tatsuro; Kobayashi, Miho; Nomura, Masaru

    2014-01-01

    Although it is known that a part of lactic acid bacteria can produce carotenoid, little is known about the regulation of carotenoid production. The objective of this study was to determine whether aerobic growth condition influences carotenoid production in carotenoid-producing Enterococcus gilvus. Enterococcus gilvus was grown under aerobic and anaerobic conditions. Its growth was slower under aerobic than under anaerobic conditions. The decrease in pH levels and production of lactic acid were also lower under aerobic than under anaerobic conditions. In contrast, the amount of carotenoid pigments produced by E. gilvus was significantly higher under aerobic than under anaerobic conditions. Further, real-time quantitative reverse transcription PCR revealed that the expression level of carotenoid biosynthesis genes crtN and crtM when E. gilvus was grown under aerobic conditions was 2.55-5.86-fold higher than when it was grown under anaerobic conditions. Moreover, after exposure to 16- and 32-mM H2O2, the survival rate of E. gilvus grown under aerobic conditions was 61.5- and 72.5-fold higher, respectively, than when it was grown under anaerobic conditions. Aerobic growth conditions significantly induced carotenoid production and the expression of carotenoid biosynthesis genes in E. gilvus, resulting in increased oxidative stress tolerance.

  9. Aerobic organocatalytic oxidation of aryl aldehydes: flavin catalyst turnover by Hantzsch's ester.

    PubMed

    Chen, Shuai; Foss, Frank W

    2012-10-05

    The first Dakin oxidation fueled by molecular oxygen as the terminal oxidant is reported. Flavin and NAD(P)H coenzymes, from natural enzymatic redox systems, inspired the use of flavin organocatalysts and a Hantzsch ester to perform transition-metal-free, aerobic oxidations. Catechols and electron-rich phenols are achieved with as low as a 0.1 mol % catalyst loading, 1 equiv of Hantzsch ester, and O(2) or air as the stoichiometric oxidant source.

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

    PubMed

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

    2012-11-16

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

  11. Reaction-driven surface restructuring and selectivity control in allylic alcohol catalytic aerobic oxidation over Pd.

    PubMed

    Lee, Adam F; Ellis, Christine V; Naughton, James N; Newton, Mark A; Parlett, Christopher M A; Wilson, Karen

    2011-04-20

    Synchronous, time-resolved DRIFTS/MS/XAS cycling studies of the vapor-phase selective aerobic oxidation of crotyl alcohol over nanoparticulate Pd have revealed surface oxide as the desired catalytically active phase, with dynamic, reaction-induced Pd redox processes controlling selective versus combustion pathways.

  12. Contrasting wetland CH4 emission responses to simulated glacial atmospheric CO2 in temperate bogs and fens.

    PubMed

    Boardman, Carl P; Gauci, Vincent; Watson, Jonathan S; Blake, Stephen; Beerling, David J

    2011-12-01

    Wetlands were the largest source of atmospheric methane (CH(4) ) during the Last Glacial Maximum (LGM), but the sensitivity of this source to exceptionally low atmospheric CO(2) concentration ([CO(2) ]) at the time has not been examined experimentally. We tested the hypothesis that LGM atmospheric [CO(2) ] reduced CH(4) emissions as a consequence of decreased photosynthate allocation to the rhizosphere. We exposed minerotrophic fen and ombrotrophic bog peatland mesocosms to simulated LGM (c. 200 ppm) or ambient (c. 400 ppm) [CO(2) ] over 21 months (n = 8 per treatment) and measured gaseous CH(4) flux, pore water dissolved CH(4) and volatile fatty acid (VFA; an indicator of plant carbon supply to the rhizosphere) concentrations. Cumulative CH(4) flux from fen mesocosms was suppressed by 29% (P < 0.05) and rhizosphere pore water [CH(4) ] by c. 50% (P < 0.01) in the LGM [CO(2) ], variables that remained unaffected in bog mesocosms. VFA analysis indicated that changes in plant root exudates were not the driving mechanism behind these results. Our data suggest that the LGM [CO(2) ] suppression of wetland CH(4) emissions is contingent on trophic status. The heterogeneous response may be attributable to differences in species assemblage that influence the dominant CH(4) production pathway, rhizosphere supplemented photosynthesis and CH(4) oxidation.

  13. 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

  14. 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%).

  15. On the escape of CH4 from Pluto's atmosphere

    NASA Astrophysics Data System (ADS)

    Koskinen, T. T.; Erwin, J. T.; Yelle, R. V.

    2015-09-01

    We adapted a multispecies escape model, developed for close-in extrasolar planets, to calculate the escape rates of CH4 and N2 from Pluto. In the absence of escape, CH4 should overtake N2 as the dominant species below the exobase. The CH4 profile depends strongly on the escape rate, however, and the typical escape rates predicted for Pluto lead to a nearly constant mixing ratio of less than 1% below the exobase. In this case the CH4 escape rate is only 5-10% of the N2 escape rate. Observations of the CH4 profile by the New Horizons/ALICE spectrograph can constrain the CH4 escape rate and provide a unique test for escape models.

  16. Importance of vegetation classes in modeling CH4 emissions from boreal and subarctic wetlands in Finland.

    PubMed

    Li, Tingting; Raivonen, Maarit; Alekseychik, Pavel; Aurela, Mika; Lohila, Annalea; Zheng, Xunhua; Zhang, Qing; Wang, Guocheng; Mammarella, Ivan; Rinne, Janne; Yu, Lijun; Xie, Baohua; Vesala, Timo; Zhang, Wen

    2016-12-01

    Boreal/arctic wetlands are dominated by diverse plant species, which vary in their contribution to CH4 production, oxidation and transport processes. Earlier studies have often lumped the processes all together, which may induce large uncertainties into the results. We present a novel model, which includes three vegetation classes and can be used to simulate CH4 emissions from boreal and arctic treeless wetlands. The model is based on an earlier biogeophysical model, CH4MODwetland. We grouped the vegetation as graminoids, shrubs and Sphagnum and recalibrated the vegetation parameters according to their different CH4 production, oxidation and transport capacities. Then, we used eddy-covariance-based CH4 flux observations from a boreal (Siikaneva) and a subarctic fen (Lompolojänkkä) in Finland to validate the model. The results showed that the recalibrated model could generally simulate the seasonal patterns of the Finnish wetlands with different plant communities. The comparison between the simulated and measured daily CH4 fluxes resulted in a correlation coefficient (R(2)) of 0.82 with a slope of 1.0 and an intercept of -0.1mgm(-2)h(-1) for the Siikaneva site (n=2249, p<0.001) and an R(2) of 0.82 with a slope of 1.0 and an intercept of 0.0mgm(-2)h(-1) for the Lompolojänkkä site (n=1826, p<0.001). Compared with the original model, the recalibrated model in this study significantly improved the model efficiency (EF), from -5.5 to 0.8 at the Siikaneva site and from -0.4 to 0.8 at the Lompolojänkkä site. The simulated annual CH4 emissions ranged from 7 to 24gm(-2)yr(-1), which was consistent with the observations (7-22gm(-2)yr(-1)). However, there are some discrepancies between the simulated and observed daily CH4 fluxes for the Siikaneva site (RMSE=50.0%) and the Lompolojänkkä site (RMSE=47.9%). Model sensitivity analysis showed that increasing the proportion of the graminoids would significantly increase the CH4 emission levels. Our study demonstrated that

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

    PubMed Central

    Wendlandt, Alison E.; Stahl, Shannon S.

    2014-01-01

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

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

    PubMed Central

    Ye, Xuan; Diao, Tianning

    2010-01-01

    Summary 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% O2 in N2) 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

  19. Unusual reaction paths of SN2 nucleophile substitution reactions CH4 + H- → CH4 + H- and CH4 + F- → CH3F + H-: Quantum chemical calculations

    NASA Astrophysics Data System (ADS)

    Minyaev, Ruslan M.; Quapp, Wolfgang; Schmidt, Benjamin; Getmanskii, Ilya V.; Koval, Vitaliy V.

    2013-11-01

    Quantum chemical (CCSD(full)/6-311++G(3df,3pd), CCSD(T)(full)/6-311++G(3df,3pd)) and density function theory (B3LYP/6-311++G(3df,3pd)) calculations were performed for the SN2 nucleophile substitution reactions CH4 + H- → CH4 + H- and CH4 + F- → CH3F + H-. The calculated gradient reaction pathways for both reactions have an unusual behavior. An unusual stationary point of index 2 lies on the gradient reaction path. Using Newton trajectories for the reaction path, we can detect VRI point at which the reaction path branches.

  20. 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

  1. 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

  2. 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

  3. 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.

  4. Combination of ozonation with conventional aerobic oxidation for distillery wastewater treatment.

    PubMed

    Sangave, Preeti C; Gogate, Parag R; Pandit, Aniruddha B

    2007-05-01

    Laboratory-scale experiments were conducted in order to investigate the effect of ozone as pre-aerobic treatment and post-aerobic treatment for the treatment of the distillery wastewater. The degradation of the pollutants present in distillery spent wash was carried out by ozonation, aerobic biological degradation processes alone and by using the combinations of these two processes to investigate the synergism between the two modes of wastewater treatment and with the aim of reducing the overall treatment costs. Pollutant removal efficiency was followed by means of global parameters directly related to the concentration of organic compounds in those effluents: chemical oxygen demand (COD) and the color removal efficiency in terms of absorbance of the sample at 254 nm. Ozone was found to be effective in bringing down the COD (up to 27%) during the pretreatment step itself. In the combined process, pretreatment of the effluent led to enhanced rates of subsequent biological oxidation step, almost 2.5 times increase in the initial oxidation rate has been observed. Post-aerobic treatment with ozone led to further removal of COD along with the complete discoloration of the effluent. The integrated process (ozone-aerobic oxidation-ozone) achieved approximately 79% COD reduction along with discoloration of the effluent sample as compared to 34.9% COD reduction for non-ozonated sample, over a similar treatment period.

  5. 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

  6. 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

  7. Microwave Plasma Assisted Combustion of Premixed Ar/CH4 and He/CH4 Gases at Atmospheric Pressure

    NASA Astrophysics Data System (ADS)

    Wang, Chuji; Srivastava, Nimisha; Malik Kaya, Burak

    2010-11-01

    Low-temperature nonthermal plasma assisted combustion is of growing interest due to potential applications in the improvement of combustion efficiency, reduction of ignition delay time, fuel reforming, etc. A 2.45 GHz microwave plasma source was used to study the microwave plasma enhanced flame of premixed Ar/CH4 and He/CH4 gases at atmospheric pressure. We present the visual observations of the plasma-assisted flames sustained at different mixing ratios of Ar/CH4 and He/CH4 gases. Optical emission spectroscopy (OES) was employed to study the reactive species generated from plasma flame. Visual imaging clearly showed the effect of microwave power and difference in flame shapes created in the Ar/CH4 and He/CH4 combustion: for Ar/CH4 continuous flames were observed; for He/CH4 floating flames (flames sustained with an air-gap from the plasma orifice) were observed at low plasma powers and some particular gas mixing ratios of He/CH4. Measured flame temperatures were much higher than plasma gas temperatures. Reactive species, such as OH, NO, N2, and C2, were observed using OES. Effect of various gas mixing ratios, flow rates, and plasma powers on flame shape and flame temperature were also studied.

  8. A TEMPO-free copper-catalyzed aerobic oxidation of alcohols.

    PubMed

    Xu, Boran; Lumb, Jean-Philip; Arndtsen, Bruce A

    2015-03-27

    The copper-catalyzed aerobic oxidation of primary and secondary alcohols without an external N-oxide co-oxidant is described. The catalyst system is composed of a Cu/diamine complex inspired by the enzyme tyrosinase, along with dimethylaminopyridine (DMAP) or N-methylimidazole (NMI). The Cu catalyst system works without 2,2,6,6-tetramethyl-l-piperidinoxyl (TEMPO) at ambient pressure and temperature, and displays activity for un-activated secondary alcohols, which remain a challenging substrate for catalytic aerobic systems. Our work underscores the importance of finding alternative mechanistic pathways for alcohol oxidation, which complement Cu/TEMPO systems, and demonstrate, in this case, a preference for the oxidation of activated secondary over primary alcohols.

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

    PubMed

    Marshall, Katharine T; Morris, Robert M

    2013-02-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

  11. Challenges in polyoxometalate-mediated aerobic oxidation catalysis: catalyst development meets reactor design.

    PubMed

    Lechner, Manuel; Güttel, Robert; Streb, Carsten

    2016-11-14

    Selective catalytic oxidation is one of the most widely used chemical processes. Ideally, highly active and selective catalysts are used in combination with molecular oxygen as oxidant, leading to clean, environmentally friendly process conditions. For homogeneous oxidation catalysis, molecular metal oxide anions, so-called polyoxometalates (POMs) are ideal prototypes which combine high reactivity and stability with chemical tunability on the molecular level. Typically, POM-mediated aerobic oxidations are biphasic, using gaseous O2 and liquid reaction mixtures. Therefore, the overall efficiency of the reaction is not only dependent on the chemical components, but requires chemical engineering insight to design reactors with optimized productivity. This Perspective shows that POM-mediated aerobic liquid-phase oxidations are ideal reactions to be carried out in microstructured flow reactors as they enable facile mass and energy transfer, provide large gas-liquid interfaces and can be easily upscaled. Recent advances in POM-mediated aerobic catalytic oxidations are therefore summarized with a focus on technological importance and mechanistic insight. The principles of reactor design are discussed from a chemical engineering point of view with a focus on homogeneous oxidation catalysis using O2 in microfluidic systems. Further, current limitations to catalytic activity are identified and future directions based on combined chemistry and chemical engineering approaches are discussed to show that this approach could lead to sustainable production methods in industrial chemistry based on alternative energy sources and chemical feedstocks.

  12. 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

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

    PubMed Central

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

    2016-01-01

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

  14. 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.

  15. High Resolution CH4 Emissions and Dissolved CH4 Measurements Elucidate Surface Gas Exchange Processes in Toolik Lake, Arctic Alaska

    NASA Astrophysics Data System (ADS)

    Del Sontro, T.; Sollberger, S.; Kling, G. W.; Shaver, G. R.; Eugster, W.

    2013-12-01

    Approximately 14% of the Alaskan North Slope is covered in lakes of various sizes and depths. Diffusive carbon emissions (CH4 and CO2) from these lakes offset the tundra sink by ~20 %, but the offset would substantially increase if ebullitive CH4 emissions were also considered. Ultimately, arctic lake CH4 emissions are not insignificant in the global CH4 budget and their contribution is bound to increase due to impacts from climate change. Here we present high resolution CH4 emission data as measured via eddy covariance and a Los Gatos gas analyzer during the ice free period from Toolik Lake, a deep (20 m) Arctic lake located on the Alaskan North Slope, over the last few summers. Emissions are relatively low (< 25 mg CH4 m-2 d-1) with little variation over the summer. Diurnal variations regularly occur, however, with up to 3 times higher fluxes at night. Gas exchange is a relatively difficult process to estimate, but is normally done so as the product of the CH4 gradient across the air-water interface and the gas transfer velocity, k. Typically, k is determined based on the turbulence on the water side of the interface, which is most commonly approximated by wind speed; however, it has become increasingly apparent that this assumption does not remain valid across all water bodies. Dissolved CH4 profiles in Toolik revealed a subsurface peak in CH4 at the thermocline of up to 3 times as much CH4 as in the surface water. We hypothesize that convective mixing at night due to cooling surface waters brings the subsurface CH4 to the surface and causes the higher night fluxes. In addition to high resolution flux emission estimates, we also acquired high resolution data for dissolved CH4 in surface waters of Toolik Lake during the last two summers using a CH4 equilibrator system connected to a Los Gatos gas analyzer. Thus, having both the flux and the CH4 gradient across the air-water interface measured directly, we can calculate k and investigate the processes influencing

  16. The H2/CH4 ratio during serpentinization cannot reliably identify biological signatures

    NASA Astrophysics Data System (ADS)

    Huang, Ruifang; Sun, Weidong; Liu, Jinzhong; Ding, Xing; Peng, Shaobang; Zhan, Wenhuan

    2016-09-01

    Serpentinization potentially contributes to the origin and evolution of life during early history of the Earth. Serpentinization produces molecular hydrogen (H2) that can be utilized by microorganisms to gain metabolic energy. Methane can be formed through reactions between molecular hydrogen and oxidized carbon (e.g., carbon dioxide) or through biotic processes. A simple criterion, the H2/CH4 ratio, has been proposed to differentiate abiotic from biotic methane, with values approximately larger than 40 for abiotic methane and values of <40 for biotic methane. The definition of the criterion was based on two serpentinization experiments at 200 °C and 0.3 kbar. However, it is not clear whether the criterion is applicable at a wider range of temperatures. In this study, we performed sixteen experiments at 311–500 °C and 3.0 kbar using natural ground peridotite. Our results demonstrate that the H2/CH4 ratios strongly depend on temperature. At 311 °C and 3.0 kbar, the H2/CH4 ratios ranged from 58 to 2,120, much greater than the critical value of 40. By contrast, at 400–500 °C, the H2/CH4 ratios were much lower, ranging from 0.1 to 8.2. The results of this study suggest that the H2/CH4 ratios cannot reliably discriminate abiotic from biotic methane.

  17. The H2/CH4 ratio during serpentinization cannot reliably identify biological signatures

    PubMed Central

    Huang, Ruifang; Sun, Weidong; Liu, Jinzhong; Ding, Xing; Peng, Shaobang; Zhan, Wenhuan

    2016-01-01

    Serpentinization potentially contributes to the origin and evolution of life during early history of the Earth. Serpentinization produces molecular hydrogen (H2) that can be utilized by microorganisms to gain metabolic energy. Methane can be formed through reactions between molecular hydrogen and oxidized carbon (e.g., carbon dioxide) or through biotic processes. A simple criterion, the H2/CH4 ratio, has been proposed to differentiate abiotic from biotic methane, with values approximately larger than 40 for abiotic methane and values of <40 for biotic methane. The definition of the criterion was based on two serpentinization experiments at 200 °C and 0.3 kbar. However, it is not clear whether the criterion is applicable at a wider range of temperatures. In this study, we performed sixteen experiments at 311–500 °C and 3.0 kbar using natural ground peridotite. Our results demonstrate that the H2/CH4 ratios strongly depend on temperature. At 311 °C and 3.0 kbar, the H2/CH4 ratios ranged from 58 to 2,120, much greater than the critical value of 40. By contrast, at 400–500 °C, the H2/CH4 ratios were much lower, ranging from 0.1 to 8.2. The results of this study suggest that the H2/CH4 ratios cannot reliably discriminate abiotic from biotic methane. PMID:27666288

  18. The H2/CH4 ratio during serpentinization cannot reliably identify biological signatures.

    PubMed

    Huang, Ruifang; Sun, Weidong; Liu, Jinzhong; Ding, Xing; Peng, Shaobang; Zhan, Wenhuan

    2016-09-26

    Serpentinization potentially contributes to the origin and evolution of life during early history of the Earth. Serpentinization produces molecular hydrogen (H2) that can be utilized by microorganisms to gain metabolic energy. Methane can be formed through reactions between molecular hydrogen and oxidized carbon (e.g., carbon dioxide) or through biotic processes. A simple criterion, the H2/CH4 ratio, has been proposed to differentiate abiotic from biotic methane, with values approximately larger than 40 for abiotic methane and values of <40 for biotic methane. The definition of the criterion was based on two serpentinization experiments at 200 °C and 0.3 kbar. However, it is not clear whether the criterion is applicable at a wider range of temperatures. In this study, we performed sixteen experiments at 311-500 °C and 3.0 kbar using natural ground peridotite. Our results demonstrate that the H2/CH4 ratios strongly depend on temperature. At 311 °C and 3.0 kbar, the H2/CH4 ratios ranged from 58 to 2,120, much greater than the critical value of 40. By contrast, at 400-500 °C, the H2/CH4 ratios were much lower, ranging from 0.1 to 8.2. The results of this study suggest that the H2/CH4 ratios cannot reliably discriminate abiotic from biotic methane.

  19. Trace metal pyritization variability in response to mangrove soil aerobic and anaerobic oxidation processes.

    PubMed

    Machado, W; Borrelli, N L; Ferreira, T O; Marques, A G B; Osterrieth, M; Guizan, C

    2014-02-15

    The degree of iron pyritization (DOP) and degree of trace metal pyritization (DTMP) were evaluated in mangrove soil profiles from an estuarine area located in Rio de Janeiro (SE Brazil). The soil pH was negatively correlated with redox potential (Eh) and positively correlated with DOP and DTMP of some elements (Mn, Cu and Pb), suggesting that pyrite oxidation generated acidity and can affect the importance of pyrite as a trace metal-binding phase, mainly in response to spatial variability in tidal flooding. Besides these aerobic oxidation effects, results from a sequential extraction analyses of reactive phases evidenced that Mn oxidized phase consumption in reaction with pyrite can be also important to determine the pyritization of trace elements. Cumulative effects of these aerobic and anaerobic oxidation processes were evidenced as factors affecting the capacity of mangrove soils to act as a sink for trace metals through pyritization processes.

  20. 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

  1. An ab initio electronic density study of the CH4-Ar, CH4-Xe, CH4-H2O and CH4-H2S complexes: insights into the nature of the intermolecular interaction

    NASA Astrophysics Data System (ADS)

    Bartocci, Alessio; Frati, Federica; Roncaratti, Luiz F.; Cappelletti, David; Tarantelli, Francesco; Belpassi, Leonardo; Pirani, Fernando

    2015-12-01

    The main point of this paper concerns the theoretical characterisation of the effects induced by the intermolecular interaction on the electron density upon the formation of CH4-H2X (X=O,S) and CH4-Ng (Ng=Ar,Xe) complexes. The work has been stimulated by recent molecular scattering beams experiments, which point out differences in both strength and anisotropy of the intermolecular potential between CH4-H2X respect to reference CH4-Ng systems. Herein, attention is focused on the electronic charge polarisation and particularly charge transfer (CT) effects between involved partners, directly related to the topology of the full potential energy surface. The modification of electron density and the occurrence of CT have been evaluated via the charge displacement function worked out by high level ab initio calculations. Moreover, in the case of a specific configuration of CH4-H2O system, we define the leading interaction components, including their relative stabilising role and test our intermolecular potential model with reference to ab initio calculations. The results obtained indicate that CT clearly affects the strength and the anisotropy of CH4-H2O complex, and covers a minor and negligible role for CH4-H2S and the noble gas complexes, respectively.

  2. 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.

  3. 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.

  4. Marine hypoxia/anoxia as a source of CH4 and N2O

    NASA Astrophysics Data System (ADS)

    Naqvi, S. W. A.; Bange, H. W.; Farías, L.; Monteiro, P. M. S.; Scranton, M. I.; Zhang, J.

    2010-07-01

    We review here the available information on methane (CH4) and nitrous oxide (N2O) from major marine, mostly coastal, oxygen (O2)-deficient zones formed both naturally and as a result of human activities (mainly eutrophication). Concentrations of both gases in subsurface waters are affected by ambient O2 levels to varying degrees. Organic matter supply to seafloor appears to be the primary factor controlling CH4 production in sediments and its supply to (and concentration in) overlying waters, with bottom-water O2-deficiency exerting only a modulating effect. High (micromolar level) CH4 accumulation occurs in anoxic (sulphidic) waters of silled basins, such as the Black Sea and Cariaco Basin, and over the highly productive Namibian shelf. In other regions experiencing various degrees of O2-deficiency (hypoxia to anoxia), CH4 concentrations vary from a few to hundreds of nanomolar levels. Since coastal O2-deficient zones are generally very productive and are sometimes located close to river mouths and submarine hydrocarbon seeps, it is difficult to differentiate any O2-deficiency-induced enhancement from in situ production of CH4 in the water column and its inputs through freshwater runoff or seepage from sediments. While the role of bottom-water O2-deficiency in CH4 formation appears to be secondary, even when CH4 accumulates in O2-deficient subsurface waters, methanotrophic activity severely restricts its diffusive efflux to the atmosphere. As a result, an intensification or expansion of coastal O2-deficient zones will probably not drastically change the present status where emission from the ocean as a whole forms an insignificant term in the atmospheric CH4 budget. The situation is different for N2O, the production of which is greatly enhanced in low-O2 waters, and although it is lost through denitrification in most suboxic and anoxic environments, the peripheries of such environments offer most suitable conditions for its production, with the exception of

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

    PubMed

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

    2014-02-18

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

  6. Atmospheric methane /CH4/ - Trends and seasonal cycles

    NASA Technical Reports Server (NTRS)

    Rasmussen, R. A.; Khalil, M. A. K.

    1981-01-01

    On the basis of 22 months of almost continuous automated, GC/FID measurements of atmospheric CH4 and Cape Meares (45 deg N), it is shown that the concentration of CH4 is increasing at about 2% per yr (+ or - 0.5%/yr). The data also revealed stable seasonal cycles with peak concentrations in October and minimum concentrations in July. The magnitude of the seasonal variations during these months is about + or - 20 ppby from the average (+ or - 1.2%). If the current trend continues, the increased CH4 concentration may result in a 0.2 K to 0.4 K average increase in earth's surface temperature over the next 40 years or so (based on calculations of Wang et al. (1976)). The coupling of CH4 to tropospheric and stratospheric chemical processes is discussed.

  7. Combination of aerobic and vacuum packaging to control lipid oxidation and off-odor volatiles of irradiated raw turkey breast.

    PubMed

    Nam, K C; Ahn, D U

    2003-03-01

    Effects of the combination of aerobic and anaerobic packaging on color, lipid oxidation, and volatile production were determined to establish a modified packaging method to control quality changes in irradiated raw turkey meat. Lipid oxidation was the major problem with aerobically packaged irradiated turkey breast, while retaining characteristic irradiation off-odor volatiles such as dimethyl sulfide, dimethyl disulfide, and dimethyl trisulfide was the concern for vacuum-packaged breast during the 10-day refrigerated storage. Vacuum packaging of aerobically packaged irradiated turkey breast meat at 1 or 3 days of storage lowered the amounts of S-volatiles and lipid oxidation products compared with vacuum- and aerobically packaged meats, respectively. Irradiation increased the a-value of raw turkey breast, but exposing the irradiated meat to aerobic conditions alleviated the intensity of redness.

  8. 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.

  9. Factors Related with CH4 and N2O Emissions from a Paddy Field: Clues for Management implications

    PubMed Central

    Wang, Chun; Lai, Derrick Y. F.; Sardans, Jordi; Wang, Weiqi; Zeng, Congsheng; Peñuelas, Josep

    2017-01-01

    Paddy fields are major sources of global atmospheric greenhouse gases, including methane (CH4) and nitrous oxide (N2O). The different phases previous to emission (production, transport, diffusion, dissolution in pore water and ebullition) despite well-established have rarely been measured in field conditions. We examined them and their relationships with temperature, soil traits and plant biomass in a paddy field in Fujian, southeastern China. CH4 emission was positively correlated with CH4 production, plant-mediated transport, ebullition, diffusion, and concentration of dissolved CH4 in porewater and negatively correlated with sulfate concentration, suggesting the potential use of sulfate fertilizers to mitigate CH4 release. Air temperature and humidity, plant stem biomass, and concentrations of soil sulfate, available N, and DOC together accounted for 92% of the variance in CH4 emission, and Eh, pH, and the concentrations of available N and Fe3+, leaf biomass, and air temperature 95% of the N2O emission. Given the positive correlations between CH4 emission and DOC content and plant biomass, reduce the addition of a carbon substrate such as straw and the development of smaller but higher yielding rice genotypes could be viable options for reducing the release of greenhouse gases from paddy fields to the atmosphere. PMID:28081161

  10. 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.

  11. Direct Measurements of Leaf Level CH4 and CO2 Exchange in a Boreal Forest

    NASA Astrophysics Data System (ADS)

    Crill, P.; Lindroth, A.; Vestin, P.; Båth, A.

    2008-12-01

    Reports of aerobic CH4 sources from leaves and litter of a variety of forests and plant functional types have added a potential mystery to our understanding of CH4 dynamics especially if these sources contribute enough to have a significant impact on the global budget. We have made direct measurements of leaf level CH4 and CO2 exchange using a quartz branch cuvette in a boreal forest in Norunda, Sweden since August of this year. The cuvette was temperature controlled and was designed to close for 5 minutes every 30 minutes. Air was circulated to a Los Gatos CH4/CO2 infrared absorption laser spectrometer. Air and cuvette temperatures, PAR and UV radiation (Kipp and Zonen, CUV4; spectral range 300-380 nm) were measured at the branch chamber. The study was made in the Norunda 100 years old stand consisting of a mixture of Scots pine (Pinus sylvestris L.) , Birch (Betula sp.) and Norway spruce (Picea abies (L.) Karst.). The cuvette was moved between trees at roughly 5 day intervals. A null empty cuvette period was included in the rotation. The initial data show the expected CO2 uptake correlated with incident PAR and low rates of emission at night. However, there was no clear pattern of emissions detectable in the CH4. We estimate that we should be able to resolve a change of 0.5 ppbv CH4 min- 1 with our analytical setup. Both the daytime (1000-1600) and nighttime (2200-0400) averages were less than our detection. Even on very sunny days with high PAR and UV flux values, no consistent pattern was detectable. The lack of a distinct signal may be due to the fact that the past month has been very rainy, it is late in the growth season at these latitudes and sun angles are increasing quickly. The trees were at the northern edge of a clearing and we were also measuring mid height (2-3 m) leaves and branches of young trees. The branch cuvette design can also be optimized to improve its sensitivity.

  12. Termite mound emissions of CH4 and CO2 are primarily determined by seasonal changes in termite biomass and behaviour.

    PubMed

    Jamali, Hizbullah; Livesley, Stephen J; Dawes, Tracy Z; Hutley, Lindsay B; Arndt, Stefan K

    2011-10-01

    Termites are a highly uncertain component in the global source budgets of CH(4) and CO(2). Large seasonal variations in termite mound fluxes of CH(4) and CO(2) have been reported in tropical savannas but the reason for this is largely unknown. This paper investigated the processes that govern these seasonal variations in CH(4) and CO(2) fluxes from the mounds of Microcerotermes nervosus Hill (Termitidae), a common termite species in Australian tropical savannas. Fluxes of CH(4) and CO(2) of termite mounds were 3.5-fold greater in the wet season as compared to the dry season and were a direct function of termite biomass. Termite biomass in mound samples was tenfold greater in the wet season compared to the dry season. When expressed per unit termite biomass, termite fluxes were only 1.2 (CH(4)) and 1.4 (CO(2))-fold greater in the wet season as compared to the dry season and could not explain the large seasonal variations in mound fluxes of CH(4) and CO(2). Seasonal variation in both gas diffusivity through mound walls and CH(4) oxidation by mound material was negligible. These results highlight for the first time that seasonal termite population dynamics are the main driver for the observed seasonal differences in mound fluxes of CH(4) and CO(2). These findings highlight the need to combine measurements of gas fluxes from termite mounds with detailed studies of termite population dynamics to reduce the uncertainty in quantifying seasonal variations in termite mound fluxes of CH(4) and CO(2).

  13. Palladium nanoparticles in ionic liquids: reusable catalysts for aerobic oxidation of alcohols

    NASA Astrophysics Data System (ADS)

    Mondal, Arijit; Das, Amit; Adhikary, Bibhutosh; Mukherjee, Deb Kumar

    2014-04-01

    The search for more efficient catalytic systems that might combine the advantages of both homogenous (catalyst modulation) and heterogenous catalysis (catalyst recycling) is still the challenge of modern chemistry. With the advent of nanochemistry, it has been possible to prepare soluble analogues of heterogenous catalysts. These nanoparticles are generally stabilized against aggregation into larger less active particles by electrostatic or steric protection. In the present case, we demonstrate the use of room temperature ionic liquids (ILs) as effective agents of dispersion of palladium nanoparticles (prepared from palladium chloride with 5 ± 0.5 nm size distribution) that are recyclable catalysts for aerobic oxidation of alcohols under mild conditions. The particles suspended in ILs show no metal agglomeration or loss of catalytic activity even on prolonged use. An attempt has been made to elucidate the reaction mechanism of aerobic alcohol oxidation using a soluble palladium catalyst.

  14. 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.

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

    PubMed

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

    2015-04-28

    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.

  16. 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.

  17. Using δ13C-CH4 and δD-CH4 to constrain Arctic methane emissions

    NASA Astrophysics Data System (ADS)

    Warwick, Nicola J.; Cain, Michelle L.; Fisher, Rebecca; France, James L.; Lowry, David; Michel, Sylvia E.; Nisbet, Euan G.; Vaughn, Bruce H.; White, James W. C.; Pyle, John A.

    2016-12-01

    We present a global methane modelling study assessing the sensitivity of Arctic atmospheric CH4 mole fractions, δ13C-CH4 and δD-CH4 to uncertainties in Arctic methane sources. Model simulations include methane tracers tagged by source and isotopic composition and are compared with atmospheric data at four northern high-latitude measurement sites. We find the model's ability to capture the magnitude and phase of observed seasonal cycles of CH4 mixing ratios, δ13C-CH4 and δD-CH4 at northern high latitudes is much improved using a later spring kick-off and autumn decline in northern high-latitude wetland emissions than predicted by most process models. Results from our model simulations indicate that recent predictions of large methane emissions from thawing submarine permafrost in the East Siberian Arctic Shelf region could only be reconciled with global-scale atmospheric observations by making large adjustments to high-latitude anthropogenic or wetland emission inventories.

  18. Temperature and peat type control CO2 and CH4 production in Alaskan permafrost peats.

    PubMed

    Treat, C C; Wollheim, W M; Varner, R K; Grandy, A S; Talbot, J; Frolking, S

    2014-08-01

    Controls on the fate of ~277 Pg of soil organic carbon (C) stored in permafrost peatland soils remain poorly understood despite the potential for a significant positive feedback to climate change. Our objective was to quantify the temperature, moisture, organic matter, and microbial controls on soil organic carbon (SOC) losses following permafrost thaw in peat soils across Alaska. We compared the carbon dioxide (CO2 ) and methane (CH4 ) emissions from peat samples collected at active layer and permafrost depths when incubated aerobically and anaerobically at -5, -0.5, +4, and +20 °C. Temperature had a strong, positive effect on C emissions; global warming potential (GWP) was >3× larger at 20 °C than at 4 °C. Anaerobic conditions significantly reduced CO2 emissions and GWP by 47% at 20 °C but did not have a significant effect at -0.5 °C. Net anaerobic CH4 production over 30 days was 7.1 ± 2.8 μg CH4 -C gC(-1) at 20 °C. Cumulative CO2 emissions were related to organic matter chemistry and best predicted by the relative abundance of polysaccharides and proteins (R(2) = 0.81) in SOC. Carbon emissions (CO2 -C + CH4 -C) from the active layer depth peat ranged from 77% larger to not significantly different than permafrost depths and varied depending on the peat type and peat decomposition stage rather than thermal state. Potential SOC losses with warming depend not only on the magnitude of temperature increase and hydrology but also organic matter quality, permafrost history, and vegetation dynamics, which will ultimately determine net radiative forcing due to permafrost thaw.

  19. 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.

  20. Highly diastereoselective and regioselective copper-catalyzed nitrosoformate dearomatization reaction under aerobic-oxidation conditions.

    PubMed

    Yang, Weibo; Huang, Long; Yu, Yang; Pflästerer, Daniel; Rominger, Frank; Hashmi, A Stephen K

    2014-04-01

    An unprecedented copper-catalyzed acylnitroso dearomatization reaction, which expands the traditional acylnitroso ene reaction and acylnitroso Diels-Alder reaction to a new type of transformation, has been developed under aerobic oxidation. Intermolecular and intra-/intermolecular reaction modes demonstrate an entirely different N- or O-acylnitroso selectivity. Hence, we can utilize this reaction as a highly diastereoselective access to a series of new pyrroloindoline derivatives, which are important structural motifs for natural-product synthesis.

  1. 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 %.

  2. 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.

  3. 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.

  4. Micrometeorological measurements of N2O and CH4 emissions from a municipal solid waste landfill.

    PubMed

    McBain, Matthew C; Warland, Jon S; McBride, Raymond A; Wagner-Riddle, Claudia

    2005-10-01

    Micrometeorological measurements of methane (CH4) and nitrous oxide (N2O) emissions were made at the decommissioned Park Road Landfill in Grimsby, Ontario, Canada between June and August 2002. The influence of precipitation, air temperature, wind speed and barometric pressure on the temporal variability of landfill biogas emissions was assessed. Gas flux measurements were obtained using a micrometeorological mass balance measurement technique [integrated horizontal flux (IHF)] in conjunction with two tunable diode laser trace gas analyser (TDLTGA) systems. This method allows for continuous, non-intrusive measurements of gas flux at high temporal resolution. Mean fluxes of N2O were negligible over the duration of the study (-0.23 to 0.02 microg m(-2) s(-1)). In contrast, mean emissions of CH4 were much greater (80.4 to 450.8 microg m(-2) s(-1)) and varied both spatially and temporally. Spatial variations in CH4 fluxes were observed between grass kill areas (biogas 'hot spots') and the densely grass-covered areas of the landfill. Temporal variations in CH4 fluxes were also observed, due at least in part to barometric pressure, wind speed and precipitation effects.

  5. NO(y) Correlation with N2O and CH4 in the Midlatitude Stratosphere

    NASA Technical Reports Server (NTRS)

    Kondo, Y.; Schmidt, U.; Sugita, T.; Engel, A.; Koike, M.; Aimedieu, P.; Gunson, M. R.; Rodriguez, J.

    1996-01-01

    Total reactive nitrogen (NO(y)), nitrous oxide (NO2), methane (CH4), and ozone (03) were measured on board a balloon launched from Aire sur l'Adour (44 deg N, 0 deg W), France on October 12, 1994. Generally, NO(y) was highly anti-correlated with N2O and CH4 at altitudes between 15 and 32 km. The linear NO(y) - N2O and NO(y) - CH4 relationships obtained by the present observations are very similar to those obtained on board ER-2 and DC-8 aircraft previously at altitude below 20 km in the northern hemisphere. They also agree well with the data obtained by the Atmospheric Trace Molecule Spectroscopy (ATMOS) instrument at 41 deg N in November 1994. Slight departures from linear correlations occurred around 29 km, where N2O and CH4 mixing ratios were larger than typical midlatitude values, suggesting horizontal transport of tropical airmasses to northern midlatitudes in a confined altitude region.

  6. 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.

  7. 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

  8. Methane concentration and isotopic composition (δ13C-CH4) in the Nerja Cave system (South Spain)

    NASA Astrophysics Data System (ADS)

    Vadillo, Iñaki; Etiope, Giuseppe; Benavente, José; Ojeda, Lucia; Liñán, Cristina; Carrasco, Francisco

    2016-04-01

    Air in underground caves often has methane (CH4) concentrations below the atmospheric level, due to methanotrophic or other unkown CH4 consuming processes. Caves are thus considered a potential sink for atmospheric methane. If globally important, this underground CH4 oxidation should be taken into account in the atmospheric methane budget, in addition to the known soil methanotrophy and tropospheric/stratospheric sinks. A large set of data is however necessary to understand how and how much methane from external atmospheric air is consumed in the caves. While methane concentration data are available for several caves worldwide, its isotopic composition and variations in space and time are poorly documented. We measured methane concentration and stable C isotope composition (δ13C) in the Nerja cave (Southern Spain) air during two surveys in March and April 2015. CH4 concentration decreases progressively from the more external cave rooms, with atmospheric levels of 1.9 ppmv, to the more internal and isolated rooms down to 0.5 ppmv. δ13C increases correspondingly from -47 ‰ to -41 ‰ (VPDB). CH4 is systematically 13C-enriched (δ13C > -45) in areas of the cave where the concentration is below 1.4 ppmv. This combination of concentration decrease and 13C-enrichment towards the more internal and isolated zones of the cave confirms the importance of CH4 oxidation, likely driven by methanotrophic bacteria. Further data, including stable H isotope composition of sub-atmospheric CH4 concentrations, CO2 and microbial analyses, shall be acquired over time to assess the actual role of methanotrophic bacteria and seasonal controls in the CH4 consumption process.

  9. 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

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

    PubMed

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

    2015-12-01

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

  11. Catalyst-Controlled Regioselectivity in the Synthesis of Branched Conjugated Dienes via Aerobic Oxidative Heck Reactions

    PubMed Central

    Zheng, Changwu; Wang, Dian; Stahl, Shannon S.

    2012-01-01

    Pd-catalyzed aerobic oxidative coupling of vinylboronic acids and electronically unbiased alkyl olefins provides regioselective access to 1,3-disubstituted conjugated dienes. Catalyst-controlled regioselectivity is achieved by using 2,9-dimethylphenanthroline as a ligand. The observed regioselectivity is opposite to that observed from a traditional (non-oxidative) Heck reaction between a vinyl bromide and an alkene. DFT computational studies reveal that steric effects of the 2,9-dimethylphenanthroline ligand promote C–C bond-formation at the internal position of the alkene. PMID:22998540

  12. 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.

  13. Shipboard measurements and modeling of the distribution of CH4 and 13CH4 in the western Pacific

    NASA Astrophysics Data System (ADS)

    Bromley, T.; Allan, W.; Martin, R.; Mikaloff Fletcher, S. E.; Lowe, D. C.; Struthers, H.; Moss, R.

    2012-02-01

    We present observations of methane (CH4) mixing ratio and 13C/12C isotopic ratios in CH4 (δ13C) data from a collaborative shipboard project using bulk carrier ships sailing between Nelson, New Zealand, and Osaka, Japan, in the western Pacific Ocean. Measurements of the CH4 mixing ratio and δ13C in CH4were obtained from large clean-air samples collected in each 2.5° to 5° of latitude between 30°S and 30°N on eight voyages from 2004 to 2007. The data show large variations in CH4 mixing ratio in the tropical western Pacific, and data analysis suggests that these large variations are related to the positions and strengths of the South Pacific Convergence Zone and the Intertropical Convergence Zone, with variability in the sources playing a much smaller role. These measurements are compared with results from a modified version of the Unified Model (UMeth) general circulation model along two transects, one similar to the ship transects and another 18.75° to the east. Although UMeth was run to a steady state with the same sources and sinks each year, the gradient structures varied considerably from year to year, supporting our conclusion that variability in transport is a major driver for the observed variations in CH4. Simulations forced with an idealized representation of the El Niño-Southern Oscillation (ENSO) suggest that a large component of the observed variability in latitudinal gradients of CH4 and its δ13C arises from intrinsic variability in the climate system that does not occur on ENSO time scales.

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

    PubMed

    Chen, Qian; Xiao, De-Sheng

    2014-01-30

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

  15. 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.

  16. A new intra-aerobic metabolism in the nitrite-dependent anaerobic methane-oxidizing bacterium Candidatus 'Methylomirabilis oxyfera'.

    PubMed

    Wu, Ming L; Ettwig, Katharina F; Jetten, Mike S M; Strous, Marc; Keltjens, Jan T; van Niftrik, Laura

    2011-01-01

    Biological methane oxidation proceeds either through aerobic or anaerobic pathways. The newly discovered bacterium Candidatus 'Methylomirabilis oxyfera' challenges this dichotomy. This bacterium performs anaerobic methane oxidation coupled to denitrification, but does so in a peculiar way. Instead of scavenging oxygen from the environment, like the aerobic methanotrophs, or driving methane oxidation by reverse methanogenesis, like the methanogenic archaea in sulfate-reducing systems, it produces its own supply of oxygen by metabolizing nitrite via nitric oxide into oxygen and dinitrogen gas. The intracellularly produced oxygen is then used for the oxidation of methane by the classical aerobic methane oxidation pathway involving methane mono-oxygenase. The present mini-review summarizes the current knowledge about this process and the micro-organism responsible for it.

  17. 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.

  18. 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.

  19. 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

  20. 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.

  1. Harmonisation and diagnostics of MIPAS ESA CH4 and N2O profiles using data assimilation

    NASA Astrophysics Data System (ADS)

    Errera, Quentin; Ceccherini, Simone; Christophe, Yves; Chabrillat, Simon; Hegglin, Michaela I.; Lambert, Alyn; Ménard, Richard; Raspollini, Piera; Skachko, Sergey; van Weele, Michiel; Walker, Kaley A.

    2016-12-01

    This paper discusses assimilation experiments of methane (CH4) and nitrous oxide (N2O) profiles retrieved from the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS). Here we focus on data versions 6 and 7 provided by the ESA processor. These data sets have been assimilated by the Belgian Assimilation System for Chemical ObsErvations (BASCOE). The CH4 and N2O retrieved profiles can oscillate, especially in the tropical lower stratosphere. Using the averaging kernels of the observations and a background error covariance matrix, which has previously been calibrated, allows the system to partly remedy this issue and provide assimilated fields that are more regular vertically. In general, there is a good agreement between the BASCOE analyses and independent observations from ACE-FTS (CH4 and N2O) and MLS (N2O), demonstrating the general good quality of CH4 and N2O retrievals provided by MIPAS ESA. Nevertheless, this study also identifies two issues in these data sets. First, time series of the observations show unexpected discontinuities due to an abrupt change in the gain of MIPAS band B, generally occurring after the instrument decontamination. Since the calibration is performed weekly, the abrupt change in the gain affects the measurements until the subsequent calibration is performed. Second, the correlations between BASCOE analyses and independent observations are poor in the lower stratosphere, especially in the tropics, probably due to the presence of outliers in the assimilated data. In this region, we recommend using MIPAS CH4 and N2O retrievals with caution.

  2. Selective inhibition of nitrite oxidation by chlorate dosing in aerobic granules.

    PubMed

    Xu, Guangjing; Xu, Xiaochen; Yang, Fenglin; Liu, Sitong

    2011-01-15

    Partial nitrification was successfully achieved with addition of 5mM KClO(3) in the aerobic granules system. Batch tests demonstrated that KClO(3) selectively inhibited nitrite-oxidizing bacteria (NOB) but not ammonia-oxidizing bacteria (AOB). During stable partial nitrification, the influent pH was kept at 7.8-8.2, while the DO and temperature were not controlled in the SBR. When the NH(4)-N and COD levels were kept at 100mg/l and 400mg/l in the influent, the NH(4)-N and COD removal efficiencies reached 98.93% and 78.65%, respectively. The NO(2)-N accounted for 92.95% of the NO(χ)-N (NO(2)-N+NO(3)-N) in the effluent. Furthermore, about 90% of the chlorate was reduced to nontoxic chloride, thus it would not cause environmental problem. SEM showed that the main composition of the aerobic granules was bacilli and coccus bacteria. FISH analysis revealed that AOB became the dominant nitrifying bacteria, whereas NOB were detected only in low abundance. Chlorate could be used to control the development and maintenance of aerobic granules sludge for partial nitrification.

  3. Low-Altitude CH4 and δ13CH4 spatial Heterogeneity over the Northern Slope of Alaska

    NASA Astrophysics Data System (ADS)

    Healy, C. E.; Sayres, D. S.; Munster, J. B.; Dumas, E. J.; Dobosy, R.; Kochendorfer, J.; Wilkerson, J.; Baker, B.; Heuer, M.; Meyers, T. P.; Dubey, M. K.; Anderson, J. G.

    2014-12-01

    Increased methane emissions from arctic environments due to amplified polar warming have long been postulated as a potent positive feedback mechanism for climate change. However, measuring methane in the Arctic for the purpose of monitoring the feedback presents a daunting observational challenge since techniques must ideally be able distinguish between biological and anthropogenic methane sources, have the ability to cover large spatial ranges, and have the sensitivity to distinguish changes from season to season, and year to year. The FOCAL platform has been engineered to address this niche and help bridge the gap in spatial coverage between ground based and inverse modelling studies. It consists of a small aircraft equipped with the best atmospheric turbulence (BAT) probe, and gas sensors for in situ measurements of CH4, CO2, δ13CH4, δ13CO2 to make regional scale surface eddy-covariance flux measurements of methane and carbon dioxide as well as their stable isotopologues to gain mechanisitic insight and assist in source determination. The initial FOCAL flight series in August 2013 based out of Deadhorse, AK was a low altitude (<50m) survey mission to observe spatial and temporal variability of CH4 and CO2 over the Northern Slope. We will present the CH4 concentration and δ13CH4 data, and discuss some of the possible drivers behind their observed spatial heterogeneity.

  4. Climate relevant trace gases (N2O and CH4) in the Eurasian Basin (Arctic Ocean)

    NASA Astrophysics Data System (ADS)

    Verdugo, Josefa; Damm, Ellen; Snoeijs, Pauline; Díez, Beatriz; Farías, Laura

    2016-11-01

    The concentration of greenhouse gases, including nitrous oxide (N2O), methane (CH4), and compounds such as total dimethylsulfoniopropionate (DMSPt), along with other oceanographic variables were measured in the ice-covered Arctic Ocean within the Eurasian Basin (EAB). The EAB is affected by the perennial ice-pack and has seasonal microalgal blooms, which in turn may stimulate microbes involved in trace gas cycling. Data collection was carried out on board the LOMROG III cruise during the boreal summer of 2012. Water samples were collected from the surface to the bottom layer (reaching 4300 m depth) along a South-North transect (SNT), from 82.19°N, 8.75°E to 89.26°N, 58.84°W, crossing the EAB through the Nansen and Amundsen Basins. The Polar Mixed Layer and halocline waters along the SNT showed a heterogeneous distribution of N2O, CH4 and DMSPt, fluctuating between 42-111 and 27-649% saturation for N2O and CH4, respectively; and from 3.5 to 58.9 nmol L-1 for DMSPt. Spatial patterns revealed that while CH4 and DMSPt peaked in the Nansen Basin, N2O was higher in the Amundsen Basin. In the Atlantic Intermediate Water and Arctic Deep Water N2O and CH4 distributions were also heterogeneous with saturations between 52% and 106% and 28% and 340%, respectively. Remarkably, the Amundsen Basin contained less CH4 than the Nansen Basin and while both basins were mostly under-saturated in N2O. We propose that part of the CH4 and N2O may be microbiologically consumed via methanotrophy, denitrification, or even diazotrophy, as intermediate and deep waters move throughout EAB associated with the overturning water mass circulation. This study contributes to baseline information on gas distribution in a region that is increasingly subject to rapid environmental changes, and that has an important role on global ocean circulation and climate regulation.

  5. Macromolecule simulation and CH4 adsorption mechanism of coal vitrinite

    NASA Astrophysics Data System (ADS)

    Yu, Song; Yan-ming, Zhu; Wu, Li

    2017-02-01

    The microscopic mechanism of interactions between CH4 and coal macromolecules is of significant practical and theoretical importance in CBM development and methane storage. Under periodic boundary conditions, the optimal energy configuration of coal vitrinite, which has a higher torsion degree and tighter arrangement, can be determined by the calculation of molecular mechanics (MM) and molecular dynamics (MD), and annealing kinetics simulation based on ultimate analysis, 13C NMR, FT IR and HRTEM. Macromolecular stabilization is primarily due to the van der Waals energy and covalent bond energy, mainly consisting of bond torsion energy and bond angle energy. Using the optimal configuration as the adsorbent, GCMC simulation of vitrinite adsorption of CH4 is conducted. A saturated state is reached after absorbing 17 CH4s per coal vitrinite molecule. CH4 is preferentially adsorbed on the edge, and inclined to gathering around the branched chains of the inner vitrinite sites. Finally, the adsorption parameters are calculated through first principle DFT. The adsorbability order is as follows: aromatic structure> heteroatom rings > oxygen functional groups. The adsorption energy order is as follows: Top < Bond < Center, Up < Down. The order of average RDF better reflects the adsorption ability and that of [-COOH] is lower than those of [sbnd Cdbnd O] and [Csbnd Osbnd C]. CH4 distributed in the distance of 0.99-16 Å to functional groups in the type of monolayer adsorption and the average distance order manifest as [sbnd Cdbnd O] (1.64 Å) < [Csbnd Osbnd C] (1.89 Å) < [sbnd COOH] (3.78 Å) < [-CH3] (4.11 Å) according to the average RDF curves. CH4 enriches around [sbnd Cdbnd O] and [Csbnd O-C] whereas is rather dispersed about [-COOH] and [CH3]. Simulation and experiment data are both in strong agreement with the Langmuir and D-A isothermal adsorption model and the D-A model fit better than Langmuir model. Preferential adsorption sites and orientations in vitrinite are

  6. 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.

  7. 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.

  8. Novel stable isotope laser spectrometry elucidates changing mechanisms of CH4 production and consumption across a climate change sequence in an arctic wetland

    NASA Astrophysics Data System (ADS)

    McCalley, C. K.; Wehr, R.; Crill, P. M.; Chanton, J.; Hodgkins, S. B.; Nelson, D. D.; McManus, J. B.; Zahniser, M. S.; Rich, V.; Tyson, G.; Mondav, R.; Frolking, S.; Li, C.; Saleska, S. R.

    2011-12-01

    Methane flux from high latitude wetlands is both a critical component of the global CH4 budget, and highly sensitive to global climate change, with expected increases in emissions as permafrost thaws. Gaps in our understanding of the mechanisms driving changing CH4 production and consumption dynamics under permafrost thaw, however, limit our ability to predict the magnitude of this response under future climate conditions. To address these gaps, we quantified the isotopic composition of carbon gas fluxes (δ13C of CH4 and CO2) from a high latitude (68° N) wetland in Sweden (Stordalen Mire) to partition net CH4 emissions into its component parts, methanogenesis (including both acetoclastic, and CO2-reductive pathways) and methanotrophy (which consumes CH4 primarily via aerobic metabolism). We used newly developed quantum cascade laser technology, linked to automated chambers, to quantify isotopes at high frequency. Our measurements across a permafrost thaw gradient, going from permafrost-dominated, well-drained palsas to intermediate permafrost sites dominated by Sphagnum spp. to wet sites with no underlying permafrost, dominated by Eriophorum angustifolium, show both large increases in productivity and CH4 emissions as well as shifts in the CH4 production pathway. Across this permafrost thaw gradient the isotopic composition of CH4 becomes 13C enriched, due to increased acetoclastic CH4 production. While the palsa sites have no detectable CH4 emissions, fluxes in the Sphagnum site have an average isotopic composition of -79%, a value indicative of CH4 production dominated by CO2 reduction, in contrast the isotopic composition of CH4 produced in the Eriophorum sites ranged from -71 to -57%, showing increased CH4 production via the acetate pathway. We also observed an increase in acetoclastic methanogenesis as the growing season progressed. Together, these initial results suggest that thaw induced changes in hydrology and plant community composition increase peat

  9. Induction of E. coli oh8Gua endonuclease by oxidative stress: its significance in aerobic life.

    PubMed

    Kim, H S; Park, Y W; Kasai, H; Nishimura, S; Park, C W; Choi, K H; Chung, M H

    1996-06-12

    The induction of 8-hydroxyguanine (oh8Gua) endonuclease, a DNA repair enzyme for an oxidatively modified guanine, oh8Gua was studied in various growth conditions in Escherichia coli (AB1157). Anaerobically grown E. coli were found to have a very low activity of this enzyme while aerobically grown cells showed activity about 20 times that of the anaerobic level. Under the same condition, superoxide dismutase (SOD) showed about 6-fold increase in activity. A shift in growth conditions from anaerobic to aerobic resulted in rapid induction of this enzyme, and this induction was blocked (but not completely) by chloramphenicol. It is indicated that molecular oxygen is an effective stimulator to the induction of this enzyme and its induction depends partly on protein synthesis. Superoxide-producing compounds such as paraquat and menadione also increased the activity of endonuclease as well as SOD, but H2O2 showed no effect. Thus, superoxides are also implied as a stimulator. In contrast, hyperoxia induced only SOD not the endonuclease. This induction of the endonuclease by hyperoxia was only observed in a SOD-deficient strain (QC774). The aerobic activity of the endonuclease in QC774 was the same as that of wild types (AB1157, GC4468). It is implied that the responsiveness of oh8Gua endonuclease to superoxides is less sensitive than that of SOD. The endonuclease was also induced by a temperature shift from 30 to 43 degrees C and treatment with nalidixic acid. Among the stimuli used, molecular oxygen seems to be most effective for its induction. The inducible nature of this enzyme will serve as an important mechanism for the protection of oxidative DNA damage in the aerobic environment.

  10. Nitrous oxide emissions from an aerobic granular sludge system treating low-strength ammonium wastewater.

    PubMed

    Gao, Mingming; Yang, Sen; Wang, Mingyu; Wang, Xin-Hua

    2016-11-01

    Aerobic granular sludge is a promising technology in wastewater treatment process. Its special microorganism structure could make the emissions of greenhouse gas nitrous oxide (N2O) more complicated. This study investigated the N2O emissions from a batch-fed aerobic granular sludge system during nitrification of low-strength synthetic ammonium wastewater. The N2O emission was 2.72 ± 0.52% of the oxidized ammonium during the whole anoxic-oxic sequencing batch reactor (SBR) cycle. Under nitrification batch test with sole ammonium substrate (50 mg N/L), N2O emission factor was 1.82% (N2ON/NH4(+)-Nox) and ammonia-oxidizing bacteria (AOB) was the responsible microorganism. The presence of high ammonium concentration (or high ammonium oxidation rate (AOR)) and accumulation of nitrite would lead to significant N2O emissions. AOB denitrification pathway was speculated to contribute more to the N2O emissions under nitrification conditions. While under simultaneous nitrification and denitrification condition with carbon source of 500 mg COD/L, the N2O emission factor increased to 2.76%. Both AOB and heterotrophic denitrifiers were responsible for N2O emission and heterotrophic denitrification enhances N2O emission. Step feeding of organic carbon source declined N2O emission factor to 1.60%, which underlined the role of storage substance consumption in N2O generation during denitrification.

  11. Effects of acute aerobic and anaerobic exercise on blood markers of oxidative stress.

    PubMed

    Bloomer, Richard J; Goldfarb, Allan H; Wideman, Laurie; McKenzie, Michael J; Consitt, Leslie A

    2005-05-01

    The purpose of this study was to compare oxidative modification of blood proteins, lipids, DNA, and glutathione in the 24 hours following aerobic and anaerobic exercise using similar muscle groups. Ten cross-trained men (24.3 +/- 3.8 years, [mean +/- SEM]) performed in random order 30 minutes of continuous cycling at 70% of Vo(2)max and intermittent dumbbell squatting at 70% of 1 repetition maximum (1RM), separated by 1-2 weeks, in a crossover design. Blood samples taken before, and immediately, 1, 6, and 24 hours postexercise were analyzed for plasma protein carbonyls (PC), plasma malondialdehyde (MDA), and whole-blood total (TGSH), oxidized (GSSG), and reduced (GSH) glutathione. Blood samples taken before and 24 hours postexercise were analyzed for serum 8-hydroxy-2'-deoxyguanosine (8-OHdG). PC values were greater at 6 and 24 hours postexercise compared with pre-exercise for squatting, with greater PC values at 24 hours postexercise for squatting compared with cycling (0.634 +/- 0.053 vs. 0.359 +/- 0.018 nM.mg protein(-1)). There was no significant interaction or main effects for MDA or 8-OHdG. GSSG experienced a short-lived increase and GSH a transient decrease immediately following both exercise modes. These data suggest that 30 minutes of aerobic and anaerobic exercise performed by young, cross-trained men (a) can increase certain biomarkers of oxidative stress in blood, (b) differentially affect oxidative stress biomarkers, and (c) result in a different magnitude of oxidation based on the macromolecule studied. Practical applications: While protein and glutathione oxidation was increased following acute exercise as performed in this study, future research may investigate methods of reducing macromolecule oxidation, possibly through the use of antioxidant therapy.

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

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

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

  13. 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.

  14. 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.

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

    NASA Astrophysics Data System (ADS)

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

    1994-10-01

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

  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. Separation of CO2-CH4 mixtures on defective single walled carbon nanohorns--tip does matter.

    PubMed

    Furmaniak, Sylwester; Terzyk, Artur P; Kowalczyk, Piotr; Kaneko, Katsumi; Gauden, Piotr A

    2013-10-21

    Using realistic models of single-walled carbon nanohorns and their single-walled carbon nanotube counterparts, we study the equilibrium separation of CO2-CH4 mixtures near ambient operating conditions by using molecular simulations. We show that regardless of the studied operating conditions (i.e., total CO2-CH4 mixture pressures and mole fractions of mixture components in the bulk phase), single-walled carbon nanohorns maximize the CO2-CH4 equilibrium separation factor. Optimized samples of single-walled carbon nanohorns consisting of narrow tubular parts capped with horn-shaped tips show highly selective adsorption of CO2 over the CH4 mixture component, with the CO2-CH4 equilibrium separation factor of ~8-12. A large surface-to-volume ratio (i.e., enhanced surface forces) and unique defective morphology (i.e., packing of adsorbed molecules in quasi-one/quasi-zero dimensional nanospaces) of single-walled carbon nanohorns are their key structural properties responsible for the excellent separation performance. Our theoretical simulation results are in quantitative agreement with a recent experimental/theoretical study of the CO2-CH4 adsorption and separation on oxidized single-walled carbon nanohorns [Ohba et al., Chem. Lett., 40, 2011, 1089]. Both experiment and theory showed that the CO2-CH4 equilibrium separation factor of oxidized samples of single-walled nanohorns measured near ambient operating conditions is ~2-5. This reduction in the separation efficiency as compared to optimized samples of single-walled carbon nanohorns is theoretically justified by their lower surface-to-volume ratio (i.e., larger diameters of tubular parts and horn-shaped tips).

  18. GENERAL CH4 OXIDATION MODEL AND COMPARISONS OF CH4 OXIDATION IN NATURAL AND MANAGED SYSTEMS. (R824993)

    EPA Science Inventory

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  19. 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.

  20. 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.

  1. Modeling of simultaneous denitrification--anaerobic digestion--organic matter aerobic oxidation and nitrification in an anoxic-anaerobic-aerobic compact filter reactor.

    PubMed

    Moya, Jaime; Huiliñir, César; Peredo, Karol; Aspé, Estrella; Roeckel, Marlene

    2012-08-31

    A mathematical model was developed for a compact anoxic-anaerobic-aerobic filter reactor with liquid recirculation for the treatment of fishing effluents. The model includes denitrification, anaerobic digestion, aerobic carbon oxidation and nitrification steps, as well as an evaluation of the liquid gas mass transfer and pH. The model was calibrated using one experimental condition at a recycling ratio (R)=10, and was validated with R equal to 2 and 0, with an organic concentration of 554±24 mg TOCL(-1), salinity of 24 g L(-1) and hydraulic retention time (HRT) of 2 d. Carbon total removal is higher than 98%, while maximum nitrogen removal is 62% using total nitrification in the aerobic zone, due to a higher quantity of NO(x) produced which were recirculated to the anoxic zone. In the aerobic zone, simultaneous nitrification and denitrification processes occur, because the diffusion limitations cause a low oxygen penetration in the biofilm. In the anoxic-anaerobic zone, denitrification or methanogenesis inhibition by DO (caused by the recycled oxygen) is not observed.

  2. 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

  3. 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

  4. 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

  5. Ion irradiation of CH 4-containing icy mixtures

    NASA Astrophysics Data System (ADS)

    Baratta, G. A.; Domingo, M.; Ferini, G.; Leto, G.; Palumbo, M. E.; Satorre, M. A.; Strazzulla, G.

    2003-08-01

    We have studied by infrared absorption spectroscopy the effects of ion irradiation with 60 keV Ar 2+ ions on pure methane (CH 4) ice at 12 K and mixtures with water (H 2O) and nitrogen (N 2). Ion irradiation, among other effects, causes the rupture of original molecular bonds and the formation of molecular species not present in the initial ice. Here we present the experimental results and discuss their astrophysical relevance.

  6. Global inverse modeling of CH4 sources and sinks: an overview of methods

    NASA Astrophysics Data System (ADS)

    Houweling, Sander; Bergamaschi, Peter; Chevallier, Frederic; Heimann, Martin; Kaminski, Thomas; Krol, Maarten; Michalak, Anna M.; Patra, Prabir

    2017-01-01

    The aim of this paper is to present an overview of inverse modeling methods that have been developed over the years for estimating the global sources and sinks of CH4. It provides insight into how techniques and estimates have evolved over time and what the remaining shortcomings are. As such, it serves a didactical purpose of introducing apprentices to the field, but it also takes stock of developments so far and reflects on promising new directions. The main focus is on methodological aspects that are particularly relevant for CH4, such as its atmospheric oxidation, the use of methane isotopologues, and specific challenges in atmospheric transport modeling of CH4. The use of satellite retrievals receives special attention as it is an active field of methodological development, with special requirements on the sampling of the model and the treatment of data uncertainty. Regional scale flux estimation and attribution is still a grand challenge, which calls for new methods capable of combining information from multiple data streams of different measured parameters. A process model representation of sources and sinks in atmospheric transport inversion schemes allows the integrated use of such data. These new developments are needed not only to improve our understanding of the main processes driving the observed global trend but also to support international efforts to reduce greenhouse gas emissions.

  7. 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.

  8. 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.

  9. Cobalt nanoparticles as recyclable catalyst for aerobic oxidation of alcohols in liquid phase

    NASA Astrophysics Data System (ADS)

    Mondal, Arijit; Mukherjee, Debkumar; Adhikary, Bibhutosh; Ahmed, Md Azharuddin

    2016-05-01

    Cobalt nanoparticles prepared at room temperature from cobalt sulphate and tetrabutyl ammonium bromide as surfactant have been found to be effective oxidation catalysts. Palladium and platinum nanoparticles (average size 4-6 nm) can also be prepared from PdCl2 and K2PtCl4, respectively, using the same surfactant but require high temperature ( 120 °C) and much longer preparation time. Agglomeration of nanoparticles prepared from metals like palladium and platinum in common solvents, however, restricts their use as catalysts. It is therefore our endeavour to find the right combination of catalyst and solvent that will be beneficial from industrial point of view. Magnetic property measurement of cobalt nanoclusters was made using SQUID to identify their reusability nature. Herein, we report the use of cobalt nanoparticles (average size 90-95 nm) in dichloromethane solvent as effective reusable catalysts for aerobic oxidation of a variety of alcohols.

  10. Methane Production Pathways in a California Rice Paddy: Isotopic Evidence for Substantial CO2 Reduction as Cause for Isotopically Light Emitted CH4 Carbon

    NASA Astrophysics Data System (ADS)

    Tyler, S. C.; McMillan, A. M.; Bearden, K.; Chidthaisong, A.; Macalady, J.

    2003-12-01

    We report measurements of δ 13C of emitted CH4 and sediment CH4 and CO2 during the 1999 rice-growing season near Maxwell, CA. Two treatments, one with rice straw incorporated from the previous season and one without rice straw were studied. The δ 13C value of emitted CH4 was consistently lighter isotopically (-67‰ to -83‰ throughout the season) in both straw incorporated and straw removed (burned) plots than in fields we have studied in Texas, Kenya, and Japan. Measured isotopic values of the production zone CH4 were compared to a two-point mixing curve representative of isotopic CH4 produced from either pure methyl-group fermentation or CO2 reduction pathways to partition the production pathways and to track seasonal changes in the production processes. Our sediment CH4 and CO2 isotope data indicate that fermentation was rarely the dominant methanogenic pathway - on the contrary CO2 reduction with H2 was more prevalent than fermentation methanogenesis throughout most of the season. The relatively isotopically light CH4 emitted by the paddy fields is also a product of oxidation and stem-transport processes which have isotopic effects of their own. These effects are discussed in context with the methanogenic isotope effects to provide a complete picture of the paddy field CH4 carbon isotope system.

  11. 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

  12. 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...

  13. 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

  14. 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

  15. 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

  16. Approach to construct polysubstituted 1,2-dihydronaphtho[2,1-b]furans and their aerobic oxidative aromatization.

    PubMed

    Huo, Congde; Xu, Xiaolan; An, Jinzhu; Jia, Xiaodong; Wang, Xicun; Wang, Cheng

    2012-09-21

    Triarylaminium salt was disclosed as an efficient initiator for the novel Friedel-Crafts alkylation/annulation cascade reaction between chalcone epoxides and 2-naphthols to construct polysubstituted 1,2-dihydronaphtho[2,1-b]furans. The DDQ/NaNO(2)/O(2) catalytic system was first applied to the aerobic oxidative aromatization of heterocycles, and a simple and efficient one-pot tandem FC alkylation/annulation/aerobic oxidative aromatization procedure was also developed for the synthesis of complex naphtho[2,1-b]furans.

  17. Combined Fenton oxidation and aerobic biological processes for treating a surfactant wastewater containing abundant sulfate.

    PubMed

    Wang, Xiao-Jun; Song, Yang; Mai, Jun-Sheng

    2008-12-30

    The present study is to investigate the treatment of a surfactant wastewater containing abundant sulfate by Fenton oxidation and aerobic biological processes. The operating conditions have been optimized. Working at an initial pH value of 8, a Fe2+ dosage of 600mgL(-1) and a H2O2 dosage of 120mgL(-1), the chemical oxidation demand (COD) and linear alkylbenzene sulfonate (LAS) were decreased from 1500 and 490mgL(-1) to 230 and 23mgL(-1) after 40min of Fenton oxidation, respectively. Advanced oxidation pretreatment using Fenton reagent was very effective at enhancing the biodegradability of this kind of wastewater. The wastewater was further treated by a bio-chemical treatment process based on an immobilized biomass reactor with a hydraulic detention time (HRT) of 20h after Fenton oxidation pretreatment under the optimal operating conditions. It was found that the COD and LAS of the final effluent were less than 100 and 5mgL(-1), corresponding to a removal efficiencies of over 94% and 99%, respectively.

  18. CH4 sources estimated from atmospheric observations of CH4 and its 13C/12C isotopic ratios: 1. Inverse modeling of source processes

    NASA Astrophysics Data System (ADS)

    Mikaloff Fletcher, Sara E.; Tans, Pieter P.; Bruhwiler, Lori M.; Miller, John B.; Heimann, Martin

    2004-12-01

    A time-dependent inverse modeling approach that estimates the global magnitude of atmospheric methane sources from the observed spatiotemporal distribution of atmospheric CH4, 13C/12C isotopic ratios, and a priori estimates of the source strengths is presented. Relative to the a priori source estimates, the inverse model calls for increased CH4 flux from sources with strong spatial footprints in the tropics and Southern Hemisphere and decreases in sources in the Northern Hemisphere. The CH4 and 13C/12C isotopic ratio observations suggest an unusually high CH4 flux from swamps (˜200 ± 44 Tg CH4/yr) and biomass burning (88 ± 18 Tg CH4/yr) with relatively low estimates of emissions from bogs (˜20 ± 14 Tg CH4/yr), and landfills (35 ± 14 Tg CH4/yr). The model results support the hypothesis that the 1998 CH4 growth rate anomaly was caused in part by a large increase in CH4 production from wetlands, and indicate that wetland sources were about 40 Tg CH4/yr higher in 1998 than 1999.

  19. 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.

  20. Characterization of THGEM coupled to submillimetric induction gaps in Ne/CH4 and Ar/CH4 mixtures

    NASA Astrophysics Data System (ADS)

    Coimbra, A. E. C.; Henriques, C. A. O.; Israelashvili, I.; Mir, J. A.; dos Santos, J. M. F.

    2017-01-01

    The coupling of a THGEM to an induction region having a thickness below 1 mm allows the application of intense induction electric fields, resulting in a more efficient extraction of the avalanche electrons into the anode electrode and the extension of the charge avalanche amplification into the induction region. In the present work, we investigate the performance of such configuration, operating in Ne-5% CH4 and Ar-20% CH4 mixtures, in terms of gain characteristics and energy resolution for 5.9 keV X-rays. Gains above 105 can be achieved in both mixtures without jeopardizing the energy resolution for induction gaps of 0.8 and 0.5 mm, while applying lower biasing voltages to the THGEM. We have demonstrated that it is possible to implement gas electron multiplier configurations having an effective reduction of its thickness and that high gains can be achieved in Ar-based mixtures having CH4 concentrations as high as 20%. Ar based mixtures present higher ionization yields and lower electron diffusion coefficients, when compared to Ne-based ones.

  1. Emission and oxidation of methane in a meromictic, eutrophic and temperate lake (Dendre, Belgium).

    PubMed

    Roland, Fleur A E; Darchambeau, François; Morana, Cédric; Bouillon, Steven; Borges, Alberto V

    2017-02-01

    We sampled the water column of the Dendre stone pit lake (Belgium) in spring, summer, autumn and winter. Depth profiles of several physico-chemical variables, nutrients, dissolved gases (CO2, CH4, N2O), sulfate, sulfide, iron and manganese concentrations and δ(13)C-CH4 were determined. We performed incubation experiments to quantify CH4 oxidation rates, with a focus on anaerobic CH4 oxidation (AOM), without and with an inhibitor of sulfate reduction (molybdate). The evolution of nitrate and sulfate concentrations during the incubations was monitored. The water column was anoxic below 20 m throughout the year, and was thermally stratified in summer and autumn. High partial pressure of CO2 and CH4 and high concentrations of ammonium and phosphate were observed in anoxic waters. Important nitrous oxide and nitrate concentration maxima were also observed (up to 440 nmol L(-1) and 80 μmol L(-1), respectively). Vertical profiles of δ(13)C-CH4 unambiguously showed the occurrence of AOM. Important AOM rates (up to 14 μmol L(-1) d(-1)) were observed and often co-occurred with nitrate consumption peaks, suggesting the occurrence of AOM coupled with nitrate reduction. AOM coupled with sulfate reduction also occurred, since AOM rates tended to be lower when molybdate was added. CH4 oxidation was mostly aerobic (∼80% of total oxidation) in spring and winter, and almost exclusively anaerobic in summer and autumn. Despite important CH4 oxidation rates, the estimated CH4 fluxes from the water surface to the atmosphere were high (mean of 732 μmol m(-2) d(-1) in spring, summer and autumn, and up to 12,482 μmol m(-2) d(-1) in winter).

  2. 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.

  3. Effects of land use conversion and fertilization on CH4 and N2O fluxes from typical hilly red soil.

    PubMed

    Liu, Huifeng; Liu, Guohua; Li, Ya; Wu, Xing; Liu, Dan; Dai, Xiaoqin; Xu, Ming; Yang, Fengting

    2016-10-01

    Land use conversion and fertilization have been widely reported to be important managements affecting the exchanges of greenhouse gases between soil and atmosphere. For comprehensive assessment of methane (CH4) and nitrous oxide (N2O) fluxes from hilly red soil induced by land use conversion and fertilization, a 14-month continuous field measurement was conducted on the newly converted citrus orchard plots with fertilization (OF) and without fertilization (ONF) and the conventional paddy plots with fertilization (PF) and without fertilization (PNF). Our results showed that land use conversion from paddy to orchard reduced the CH4 fluxes at the expense of increasing the N2O fluxes. Furthermore, fertilization significantly decreased the CH4 fluxes from paddy soils in the second stage after conversion, but it failed to affect the CH4 fluxes from orchard soils, whereas fertilizer applied to orchard and paddy increased soil N2O emissions by 68 and 113.9 %, respectively. Thus, cumulative CH4 emissions from the OF were 100 % lower, and N2O emissions were 421 % higher than those from the PF. Although cumulative N2O emissions were stimulated in the newly converted orchard, the strong reduction of CH4 led to lower global warming potentials (GWPs) as compared to the paddy. Besides, fertilization in orchard increased GWPs but decreased GWPs of paddy soils. In addition, measurement of soil moisture, temperature, dissolved carbon contents (DOCs), and ammonia (NH4(+)-N) and nitrate (NO3(-)-N) contents indicated a significant variation in soil properties and contributed to variations in soil CH4 and N2O fluxes. Results of this study suggest that land use conversion from paddy to orchard would benefit for reconciling greenhouse gas mitigation and citrus orchard cultivation would be a better agricultural system in the hilly red soils in terms of greenhouse gas emission. Moreover, selected fertilizer rate applied to paddy would lead to lower GWPs of CH4 and N2O. Nevertheless, more

  4. 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

    2014-06-03

    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.

  5. Oxidative stress and inflammation response following aerobic exercise: role of ethnicity.

    PubMed

    McKenzie, M J; Goldfarb, A; Garten, R S; Vervaecke, L

    2014-09-01

    African-Americans are at a significantly greater risk for developing several diseases and conditions. These conditions often have underlying oxidative stress mechanisms. Therefore the purpose of this investigation was to ascertain the post-exercise oxidative response to a single bout of aerobic exercise in African-American and Caucasian college-age females. A total of 10 African-American and 10 Caucasian females completed the study. Each subject had her VO2 max measured while exercising on a treadmill. A week later, each subject returned to the laboratory and performed a 30-min run at 70% of her VO2max. Blood samples were taken immediately prior to and following exercise for analysis. Lipid hydroperoxides, protein carbonyls, malondialdehyde, xanthine oxidase, glutathione in the reduced (GSH) and oxidized (GSSG) forms, TNFα and interleukin 6 were measured from blood taken before and after exercise. Significance was set at p≤0.05 a priori. Xanthine oxidase was the only measure that did not significantly increase following exercise. All other markers showed a significant elevation in response to the exercise bout with no difference between groups except that the Caucasian group had significantly higher malondialdehyde post-exercise compared to the African-American group. This cohort of college-age African-American and Caucasian females showed little difference in their response to a single 30-min run at 70% of their max in the markers of oxidative stress within the blood.

  6. 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

  7. 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

  8. Comparison of static chambers to measure N2O and CH4 fluxes from soils

    NASA Astrophysics Data System (ADS)

    Pihlatie, M.

    2009-04-01

    Soil fluxes of the greenhouse gases (GHG) nitrous oxide (N2O), methane (CH4) and carbon dioxide (CO2) are often measured by closed static chambers. During a chamber enclosure the concentration of the target gas changes in the headspace of the chamber. This changes the concentration difference between the soil and the atmosphere and hence also the fluxes from the soil. We hypothesize that the magnitude how much a chamber affects the gas fluxes from the soil is chamber design specific. In addition, the use of inappropriate flux calculation methods can further lead to uncertainties in the flux estimates. To test different types of static chambers for N2O and CH4 flux measurements a chamber calibration campaign was organized at Hyytiälä Forestry Field Station in Southern Finland during August-October 2008. The overall aims of the campaign were to quantitatively assess the uncertainties and errors related to static chamber measurements. Overall 17 different static chambers were tested for five different N2O and CH4 flux levels with three different soil conditions (different moisture and porosity) in the chamber calibration system described by Pumpanen et al. (2004). Preliminary results show that most of the static chambers either over- or underestimated the N2O and CH4 fluxes. This chamber specific over- or underestimation remained near constant with different flux levels. However, the deviation varied greatly with different soil porosities. Here we will show the main results of the measurement campaign and give preliminary suggestions for ideal chamber designs, gas sampling protocol and flux calculation methods for N2O and CH4 flux measurements. References: Pumpanen, J., Kolari, P., Ilvesniemi, H., Minkkinen, K., Vesala, T., Niinistö, S., Lohila, A., Larmola, T., Morero, M., Pihlatie, M., Janssens, I., Curiel Yuste, J., Grünzweig, J. M., Reth, S., Subke, J.-A., Savage, K., Kutsch, W., Østreng, G., Ziegler, W., Anthoni, P., Lindroth, A. & Hari, P. 2004. Comparison

  9. 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.

  10. Tests of MULTIMODE calculations of rovibrational energies of CH 4

    NASA Astrophysics Data System (ADS)

    Wu, Jiayan; Huang, Xinchuan; Carter, Stuart; Bowman, Joel M.

    2006-08-01

    We report variational calculations of rovibrational energies of CH 4 using the code MULTIMODE and an ab initio force field of Schwenke and Partridge. The systematic convergence of the energies with respect to the level of mode coupling is presented. Converged vibrational energies calculated using the five-mode representation of the potential for zero total angular momentum are compared with previous, benchmark calculations based on Radau coordinates using this force field for zero total angular momentum and for J = 1. Very good agreement with the previous benchmark calculations is found.

  11. 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.

  12. 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

  13. Aerobic and Anaerobic Thiosulfate Oxidation by a Cold-Adapted, Subglacial Chemoautotroph.

    PubMed

    Harrold, Zoë R; Skidmore, Mark L; Hamilton, Trinity L; Desch, Libby; Amada, Kirina; van Gelder, Will; Glover, Kevin; Roden, Eric E; Boyd, Eric S

    2015-12-28

    Geochemical data indicate that protons released during pyrite (FeS2) oxidation are important drivers of mineral weathering in oxic and anoxic zones of many aquatic environments, including those beneath glaciers. Oxidation of FeS2 under oxic, circumneutral conditions proceeds through the metastable intermediate thiosulfate (S2O3 (2-)), which represents an electron donor capable of supporting microbial metabolism. Subglacial meltwaters sampled from Robertson Glacier (RG), Canada, over a seasonal melt cycle revealed concentrations of S2O3 (2-) that were typically below the limit of detection, despite the presence of available pyrite and concentrations of the FeS2 oxidation product sulfate (SO4 (2-)) several orders of magnitude higher than those of S2O3 (2-). Here we report on the physiological and genomic characterization of the chemolithoautotrophic facultative anaerobe Thiobacillus sp. strain RG5 isolated from the subglacial environment at RG. The RG5 genome encodes genes involved with pathways for the complete oxidation of S2O3 (2-), CO2 fixation, and aerobic and anaerobic respiration with nitrite or nitrate. Growth experiments indicated that the energy required to synthesize a cell under oxygen- or nitrate-reducing conditions with S2O3 (2-) as the electron donor was lower at 5.1°C than 14.4°C, indicating that this organism is cold adapted. RG sediment-associated transcripts of soxB, which encodes a component of the S2O3 (2-)-oxidizing complex, were closely affiliated with soxB from RG5. Collectively, these results suggest an active sulfur cycle in the subglacial environment at RG mediated in part by populations closely affiliated with RG5. The consumption of S2O3 (2-) by RG5-like populations may accelerate abiotic FeS2 oxidation, thereby enhancing mineral weathering in the subglacial environment.

  14. 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

    2016-01-04

    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.

  15. Complete genome sequence of Methylocystis sp. strain SC2, an aerobic methanotroph with high-affinity methane oxidation potential.

    PubMed

    Dam, Bomba; Dam, Somasri; Kube, Michael; Reinhardt, Richard; Liesack, Werner

    2012-11-01

    Methylocystis sp. strain SC2 is an aerobic type II methanotroph isolated from a highly polluted aquifer in Germany. A specific trait of the SC2 strain is the expression of two isozymes of particulate methane monooxygenase with different methane oxidation kinetics. Here we report the complete genome sequence of this methanotroph that contains not only a circular chromosome but also two large plasmids.

  16. Reactivity of chemisorbed oxygen atoms and their catalytic consequences during CH4-O2 catalysis on supported Pt clusters.

    PubMed

    Chin, Ya-Huei Cathy; Buda, Corneliu; Neurock, Matthew; Iglesia, Enrique

    2011-10-12

    Kinetic and isotopic data and density functional theory treatments provide evidence for the elementary steps and the active site requirements involved in the four distinct kinetic regimes observed during CH(4) oxidation reactions using O(2), H(2)O, or CO(2) as oxidants on Pt clusters. These four regimes exhibit distinct rate equations because of the involvement of different kinetically relevant steps, predominant adsorbed species, and rate and equilibrium constants for different elementary steps. Transitions among regimes occur as chemisorbed oxygen (O*) coverages change on Pt clusters. O* coverages are given, in turn, by a virtual O(2) pressure, which represents the pressure that would give the prevalent steady-state O* coverages if their adsorption-desorption equilibrium was maintained. The virtual O(2) pressure acts as a surrogate for oxygen chemical potentials at catalytic surfaces and reflects the kinetic coupling between C-H and O═O activation steps. O* coverages and virtual pressures depend on O(2) pressure when O(2) activation is equilibrated and on O(2)/CH(4) ratios when this step becomes irreversible as a result of fast scavenging of O* by CH(4)-derived intermediates. In three of these kinetic regimes, C-H bond activation is the sole kinetically relevant step, but occurs on different active sites, which evolve from oxygen-oxygen (O*-O*), to oxygen-oxygen vacancy (O*-*), and to vacancy-vacancy (*-*) site pairs as O* coverages decrease. On O*-saturated cluster surfaces, O*-O* site pairs activate C-H bonds in CH(4) via homolytic hydrogen abstraction steps that form CH(3) groups with significant radical character and weak interactions with the surface at the transition state. In this regime, rates depend linearly on CH(4) pressure but are independent of O(2) pressure. The observed normal CH(4)/CD(4) kinetic isotope effects are consistent with the kinetic-relevance of C-H bond activation; identical (16)O(2)-(18)O(2) isotopic exchange rates in the presence or

  17. 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.

  18. 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

  19. Cu-catalyzed aerobic oxidative three-component coupling route to N-sulfonyl amidines via an ynamine intermediate.

    PubMed

    Kim, Jinho; Stahl, Shannon S

    2015-02-20

    Cu-catalyzed aerobic oxidative three-component coupling of a terminal alkyne, secondary amine, and sulfonamide enables efficient synthesis of amidines. The use of Cu(OTf)2 (5 mol %) produces amidines selectively without Glaser-Hay alkyne homocoupling products. Preliminary studies suggest that the reaction pathway involves initial oxidative coupling of the terminal alkyne with the secondary amine, followed by hydroamidation of the ynamine intermediate with the sulfonamide.

  20. Transport and transformation of soil-derived CO2, CH4 and DOC sustain CO2 supersaturation in small boreal streams.

    PubMed

    Rasilo, Terhi; Hutchins, Ryan H S; Ruiz-González, Clara; Del Giorgio, Paul A

    2017-02-01

    Streams are typically supersaturated in carbon dioxide (CO2) and methane (CH4), and are recognized as important components of regional carbon (C) emissions in northern landscapes. Whereas there is consensus that in most of the systems the CO2 emitted by streams represents C fixed in the terrestrial ecosystem, the pathways delivering this C to streams are still not well understood. We assessed the contribution of direct soil CO2 injection versus the oxidation of soil-derived dissolved organic C (DOC) and CH4 in supporting CO2 supersaturation in boreal streams in Québec. We measured the concentrations of CO2, CH4 and DOC in 43 streams and adjacent soil waters during summer base-flow period. A mass balance approach revealed that all three pathways are significant, and that the mineralization of soil-derived DOC and CH4 accounted for most of the estimated stream CO2 emissions (average 75% and 10%, respectively), and that these estimated contributions did not change significantly between the studied low order (≤3) streams. Whereas some of these transformations take place in the channel proper, our results suggest that they mainly occur in the hyporheic zones of the streams. Our results further show that stream CH4 emissions can be fully explained by soil CH4 inputs. This study confirms that these boreal streams, and in particular their hyporheic zones, are extremely active processors of soil derived DOC and CH4, not just vents for soil produced CO2.

  1. A Bioinspired Catalytic Aerobic Oxidative C–H Functionalization of Primary Aliphatic Amines: Synthesis of 1,2-Disubstituted Benzimidazoles

    PubMed Central

    Nguyen, Khac Minh Huy; Largeron, Martine

    2015-01-01

    Aerobic oxidative C–H functionalization of primary aliphatic amines has been accomplished with a biomimetic cooperative catalytic system to furnish 1,2-disubstituted benzimidazoles that play an important role as drug discovery targets. This one-pot atom-economical multistep process, which proceeds under mild conditions, with ambient air and equimolar amounts of each coupling partner, constitutes a convenient environmentally friendly strategy to functionalize non-activated aliphatic amines that remain challenging substrates for non-enzymatic catalytic aerobic systems. PMID:26206475

  2. 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.

  3. 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

  4. 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.

  5. Stratospheric aerosols from CH4 photochemistry on Neptune

    NASA Astrophysics Data System (ADS)

    Romani, P. N.; Atreya, S. K.

    1989-08-01

    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.

  6. An improved treatment of spectator mode vibrations in reduced dimensional quantum dynamics: application to the hydrogen abstraction reactions mu + CH4, H + CH4, D + CH4, and CH3 + CH4.

    PubMed

    Banks, Simon T; Tautermann, Christofer S; Remmert, Sarah M; Clary, David C

    2009-07-28

    A method for projecting chemical reaction surface coordinates from a Hessian in curvilinear internal coordinates has recently been developed. Here we introduce a modification to this approach which allows for analytical evaluation of the necessary coordinate derivatives, thus reducing the number of ab initio calculations required. We apply this method to the determination of spectator mode frequencies and zero-point energies for the series of hydrogen abstraction reactions X + CH(4) --> XH + CH(3), X = muonium (mu), H, D, CH(3). Comparison of these frequencies with those obtained using rectilinear coordinates allows us to examine how the mass of X affects the coordinate sensitivity of the spectator modes. We carry out two-dimensional quantum reactive scattering calculations for these reactions to highlight instances where the choice of coordinates may have a significant impact on the evaluated thermal rate constants.

  7. 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.

  8. 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.

  9. N2O, NO and CH4 exchange, and microbial N turnover over a Mediterranean pine forest soil

    NASA Astrophysics Data System (ADS)

    Rosenkranz, P.; Brüggemann, N.; Papen, H.; Xu, Z.; Seufert, G.; Butterbach-Bahl, K.

    2006-03-01

    Trace gas exchange of N2O, NO/NO2 and CH4 between soil and the atmosphere was measured in a typical Mediterranean pine (Pinus pinaster) forest during two intensive field campaigns in spring and autumn 2003. Furthermore, gross and net turnover rates of N mineralization and nitrification as well as soil profiles of N2O and CH4 concentrations were determined. For both seasons a weak but significant N2O uptake from the atmosphere into the soil was observed. During the unusually dry and hot spring mean N2O uptake was -4.32 µg N m-2 h-1, whereas during the wet and mild autumn mean N2O uptake was -7.85 µg N m-2 h-1. The observed N2O uptake into the soil was linked to the very low availability of inorganic nitrogen at the study site. Organic layer gross N mineralization decreased from 5.06 mg N kg-1 SDW d-1 in springtime to 2.68 mg N kg-1 SDW d-1 in autumn. Mean NO emission rates were significantly higher in springtime (9.94 µg N m-2 h-1) than in autumn (1.43 µg N m-2 h-1). A significant positive correlation between NO emission rates and gross N mineralization as well as nitrification rates was found. The negative correlation between NO emissions and soil moisture was explained with a stimulation of aerobic NO uptake under N limiting conditions. Since NO2 deposition was continuously higher than NO emission rates the examined forest soil functioned as a net NOx sink. Observed mean net CH4 uptake rates were in spring significantly higher (-73.34 µg C m-2 h-1) than in autumn (-59.67 µg C m-2 h-1). Changes in CH4 uptake rates were strongly negatively correlated with changes in soil moisture. The N2O and CH4 concentrations in different soil depths revealed the organic layer and the upper 0.1 m of mineral soil as the most important soil horizons for N2O and CH4 consumption.

  10. Release of ANP and fat oxidation in overweight persons during aerobic exercise in water.

    PubMed

    Fenzl, M; Schnizer, W; Aebli, N; Schlegel, C; Villiger, B; Disch, A; Gredig, J; Zaugg, T; Krebs, J

    2013-09-01

    Exercise in water compared to land-based exercise (LE) results in a higher release of natriuretic peptides, which are involved in the regulation of exercise-induced adipose tissue lipolysis. The present study was performed to compare the release of atrial natriuretic peptide (ANP) and free fatty acids (FFA) during prolonged aerobic water-based exercise (WE) with the release after an identical LE. 14 untrained overweight subjects performed 2 steady state workload tests on the same ergometer in water and on land. Before and after exercise, venous blood samples were collected for measuring ANP, FFA, epinephrine, norepinephrine, insulin and glucose. The respiratory exchange ratio (RER) was determined for fat oxidation.The exercises resulted in a significant increase in ANP in LE (61%) and in WE (177%), and FFA increased about 3-fold in LE and WE with no significant difference between the groups. Epinephrine increased, while insulin decreased similarly in both groups. The RER values decreased during the exercises, but there was no significant difference between LE and WE. In conclusion, the higher ANP concentrations in WE had no additional effect on lipid mobilization, FFA release and fat oxidation. Moderate-intensity exercises in water offer no benefit regarding adipose tissue lipolysis in comparison to LE.

  11. Treatment of leather industry wastewater by aerobic biological and Fenton oxidation process.

    PubMed

    Mandal, Tamal; Dasgupta, Dalia; Mandal, Subhasis; Datta, Siddhartha

    2010-08-15

    Degradation of leather industry wastewater by sole aerobic treatment incorporating Thiobacillus ferrooxidans, Fenton's reagents, and combined treatment was investigated in this study. The sole treatment by Fenton's oxidation involving the introduction of 6g FeSO(4) and 266 g H(2)O(2) in a liter of wastewater at pH of 3.5 and 30 degrees C for 30 min at batch conditions reduced COD, BOD(5), sulfide, total chromium and color up to 69%, 72%, 88%, 5%, 100% and T. ferrooxidans alone showed maximum reduction to an extent of 77, 80, 85, 52, 89, respectively, in 21 d treatment at pH 2.5, FeSO(4) 16 g/L and temperature of 30 degrees C. The combined treatment at batch conditions involving 30 min chemical treatment by Fenton's oxidation followed by 72 h biochemical treatment by T. ferrooxidans at batch conditions gave rise up to 93%, 98%, 72%, 62% and 100% removal efficiencies of COD, BOD, sulfide, chromium and color at pH of 2.5 and 30 degrees C. Decrease in photo absorption of the Fenton's reagent treated samples, as compared to the banks, at 280, 350 and 470 nm wave lengths was observed. This may be the key factor for stimulating the biodegradation by T. ferrooxidans.

  12. Onset of the aerobic nitrogen cycle during the Great Oxidation Event

    NASA Astrophysics Data System (ADS)

    Zerkle, Aubrey L.; Poulton, Simon W.; Newton, Robert J.; Mettam, Colin; Claire, Mark W.; Bekker, Andrey; Junium, Christopher K.

    2017-02-01

    The rise of oxygen on the early Earth (about 2.4 billion years ago) caused a reorganization of marine nutrient cycles, including that of nitrogen, which is important for controlling global primary productivity. However, current geochemical records lack the temporal resolution to address the nature and timing of the biogeochemical response to oxygenation directly. Here we couple records of ocean redox chemistry with nitrogen isotope (15N/14N) values from approximately 2.31-billion-year-old shales of the Rooihoogte and Timeball Hill formations in South Africa, deposited during the early stages of the first rise in atmospheric oxygen on the Earth (the Great Oxidation Event). Our data fill a gap of about 400 million years in the temporal 15N/14N record and provide evidence for the emergence of a pervasive aerobic marine nitrogen cycle. The interpretation of our nitrogen isotope data in the context of iron speciation and carbon isotope data suggests biogeochemical cycling across a dynamic redox boundary, with primary productivity fuelled by chemoautotrophic production and a nitrogen cycle dominated by nitrogen loss processes using newly available marine oxidants. This chemostratigraphic trend constrains the onset of widespread nitrate availability associated with ocean oxygenation. The rise of marine nitrate could have allowed for the rapid diversification and proliferation of nitrate-using cyanobacteria and, potentially, eukaryotic phytoplankton.

  13. Onset of the aerobic nitrogen cycle during the Great Oxidation Event.

    PubMed

    Zerkle, Aubrey L; Poulton, Simon W; Newton, Robert J; Mettam, Colin; Claire, Mark W; Bekker, Andrey; Junium, Christopher K

    2017-02-23

    The rise of oxygen on the early Earth (about 2.4 billion years ago) caused a reorganization of marine nutrient cycles, including that of nitrogen, which is important for controlling global primary productivity. However, current geochemical records lack the temporal resolution to address the nature and timing of the biogeochemical response to oxygenation directly. Here we couple records of ocean redox chemistry with nitrogen isotope ((15)N/(14)N) values from approximately 2.31-billion-year-old shales of the Rooihoogte and Timeball Hill formations in South Africa, deposited during the early stages of the first rise in atmospheric oxygen on the Earth (the Great Oxidation Event). Our data fill a gap of about 400 million years in the temporal (15)N/(14)N record and provide evidence for the emergence of a pervasive aerobic marine nitrogen cycle. The interpretation of our nitrogen isotope data in the context of iron speciation and carbon isotope data suggests biogeochemical cycling across a dynamic redox boundary, with primary productivity fuelled by chemoautotrophic production and a nitrogen cycle dominated by nitrogen loss processes using newly available marine oxidants. This chemostratigraphic trend constrains the onset of widespread nitrate availability associated with ocean oxygenation. The rise of marine nitrate could have allowed for the rapid diversification and proliferation of nitrate-using cyanobacteria and, potentially, eukaryotic phytoplankton.

  14. [Effects of temperature on CH4 emission from subtropical common tree species leaves].

    PubMed

    Yang, Yan-Hua; Yi, Li-Ming; Xie, Jin-Sheng; Yang, Zhi-Jie; Jiang, Jun; Xu, Chao; Yang, Yu-Sheng

    2013-06-01

    Laboratory incubation test was conducted to study the effects of temperature on the CH4 emission from the leaves of subtropical common tree species Castanopsis carlesii, Schima superb, Cinnamomum chekiangense, Castsanopsis fabri, Cunninghamia lanceolata, and Citrus reticulata. Among the six tree species, only S. superb, C. reticulate, and C. fabri emitted CH4 at 10 degrees C. At above 20 degrees C, all the six species emitted CH4, and the average CH4 emission rate at above 30 degrees C (1.010 ng CH4 x g(-1) DM x h(-1)) was 2.96 times higher than that at 10-30 degrees C (0.255 ng CH4 x g(-1) DM x h(-1)). Moreover, increasing temperature had much more effects on the CH4 emission rate of C. reticulata and C. lanceolata than on that of the other four tree species. Incubation time affected the CH4 emission rate of all test tree species significantly, suggesting that the effects of temperature stress on the CH4 emission could be controlled by plant activity. Dry leaves could not emit CH4 no matter the temperature was very high or low. It was suggested that high temperature stress had important effects on the CH4 emission from subtropical tree leaves, and global warming could increase the CH4 emission from plants.

  15. Eddy Covariance and Autochamber Measurements of Methane Isotopologues Using a Novel 13CH4 and 12CH4 Quantum Cascade Laser Spectrometer

    NASA Astrophysics Data System (ADS)

    Santoni, G. W.; Lee, B. H.; Goodrich, J. P.; Varner, R. K.; Crill, P. M.; McManus, J. B.; Nelson, D. D.; Zahniser, M. S.; Wofsy, S. C.

    2010-12-01

    Sources of atmospheric methane (CH4) remain poorly constrained largely due to fundamental uncertainties in the processes controlling methanogenesis. Measurements of the isotopes of CH4 can help identify sources and underlying processes, but these measurements have historically been costly and time-consuming. The development of high-power mid-infrared continuous wave quantum cascade lasers (CW-QCL) provides a means to perform fast-response (~1 Hz) spectroscopy of the 12C and 13C isotopologues of CH4 at ambient concentrations with precisions approaching those of traditional Isotope Ratio Mass-Spectrometry (IRMS) methods. This technique involves independent measurement of spectral absorption lines for 13CH4 and 12CH4 which are expressed as a ratio (in ‰) relative to an international standard. Such measurements enable the use of eddy covariance (EC) techniques to measure both the fluxes and isofluxes of CH4, which can be used to derive the isotopic source distribution, δ13Cch4NEE. Two days of EC measurements were carried out at Sallies Fen, a mineral poor fen in Barrington, NH, and compared to measurements taken with ten autochambers. An additional eight days of measurements were taken by subsampling the autochamber system. Long-term measurements of CH4 flux at this fen enable us to put our isotopic data into context. The average EC CH4 flux and the mean of all autochamber CH4 fluxes taken over the same 2-day period are statistically indistinguishable, as are the isotopic composition of the CH4 source derived from eddy isofluxes and from individual keeling regressions of autochamber data. The isotopic composition of ebullitive fluxes, captured predominately at nighttime during auto-chamber sampling, was also measured. This work highlights the potential uses of such fast-response CH4 isotope instrumentation to better understand processes controlling methanogenesis.

  16. Influence of O2 exposure on the interaction between CH4 and amorphous AlYB14

    NASA Astrophysics Data System (ADS)

    Hunold, Oliver; Wiesing, Martin; de los Arcos, Teresa; Music, Denis; Grundmeier, Guido; Schneider, Jochen M.

    2017-01-01

    The influence of surface oxidation on the interaction between CH4 and amorphous AlYB14 (a-AlYB14) has been studied theoretically by using density functional theory and experimentally by ultra-high vacuum atomic force microscopy (UHV-AFM). CH4 mimics the -CH3 termination and aliphatic subunits of a polymer chain. Low-energy ion scattering measurements of magnetron sputtered thin films suggest that the bonding at the surfaces of pristine a-AlYB14 and O2 exposed a-AlYB14 (O2//a-AlYB14) is metal-boron and metal-oxygen dominated, respectively. Based on the ab initio calculations the adsorption energies of CH4 on a-AlYB14 and O2//a-AlYB14 decreases from -0.07 to -0.30 eV, respectively. This trend is consistent with experimental data obtained by colloidal probe UHV-AFM studies with a polyethylene sphere, where larger adhesion forces for the O2 exposed surface as compared to the pristine a-AlYB14 surface were measured. No charge transfer takes place between CH4 and the pristine as well as the O2 exposed a-AlYB14. Oxygen chemisorption induces changes in surface bonding. States at the Fermi level are depleted upon oxidation, hence the surface bonding becomes more semiconducting causing a charge redistribution within the adsorbed CH4 molecule. Hence, these data serve as proof of concept for exploring the effect of O2 exposure on the interaction between aliphatic polymers and a-AlYB14 using a correlative experimental and theoretical research approach.

  17. 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.

  18. 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

  19. 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

  20. 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).

  1. New Constraints on Methane Emissions from 1978 to 1999 Using δ13C-CH4 and δD-CH4 From Cape Meares, Oregon Archived Air

    NASA Astrophysics Data System (ADS)

    Roeger, F. H.; Butenhoff, C. L.; Rice, A. L.; Teama, D. G.

    2012-12-01

    Having the second largest radiative forcing of all anthropogenic greenhouse gases, methane (CH4) plays a crucial role in climate change and efforts at mitigation. Recently, the stable carbon and hydrogen isotopic ratios of methane ( δ13C and δD) have been measured from archived air sampled at a marine Northern Hemisphere mid-latitude site (Cape Meares, Oregon, 45°N, 124°W) spanning the years 1978 to 1999. These new measurements, available at roughly monthly resolution, provide us with a unique new insight into the behavior of atmospheric CH4 during this important period when the growth rate of CH4 began a two-decade long decline for reasons that are not completely certain. Competing theories for the decline include changes in emissions from fossil fuel production, agriculture, and a return to steady state. We use the global 3D Chemistry Transport Model GEOS-Chem to simulate CH4, δ13C-CH4, and δD-CH4 under different source history scenarios and place new constraints on emissions during the period 1978-1999. We also test the degree to which a widely used history of CH4 emissions (EDGAR4, EDGAR-HYDE) can simultaneously reproduce the measured dual CH4 isotope record during this time.

  2. 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

  3. 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.

  4. Water table control of CH4 emission enhancement by vascular plants in boreal peatlands

    NASA Astrophysics Data System (ADS)

    Waddington, J. M.; Roulet, N. T.; Swanson, R. V.

    1996-10-01

    Removal of the vascular vegetation (Eriophorum vaginatum) at two sites in a Swedish boreal peatland decreased the seasonal CH4 flux by 55 to 85%, while the daily CH4 flux at a Canadian boreal peatland with Carex rostrata removed decreased by over 30%. Dissolved CH4 pore water concentrations in the rooting zone were 1.2 to 2.5 times greater than the storage at similar sites where vegetation was removed by clipping, suggesting that the removal of vascular vegetation decreased CH4 production. Moreover, nighttime CH4 flux enhancement was coincident with the diurnal peak in dissolved CH4 pore water concentration. A positive correlation between mean daily net ecosystem production and mean daily CH4 flux (r2 = 0.655, n = 8) at lawn sites with sedge vegetation suggests that sites with greater CO2 fixation had a higher CH4 flux, likely through enhanced methanogenesis and transport. The degree of vascular vegetation CH4 flux enhancement, however, changed throughout the growing season and was correlated to the position of the water table. Under low water table conditions the presence of vascular plant cover has a lesser effect in enhancing CH4 emissions, indicating that CH4 and net ecosystem exchange coupling is limited to vascular plants and only to sites that remain wet with the water table near the surface.

  5. Remediation of a winery wastewater combining aerobic biological oxidation and electrochemical advanced oxidation processes.

    PubMed

    Moreira, Francisca C; Boaventura, Rui A R; Brillas, Enric; Vilar, Vítor J P

    2015-05-15

    Apart from a high biodegradable fraction consisting of organic acids, sugars and alcohols, winery wastewaters exhibit a recalcitrant fraction containing high-molecular-weight compounds as polyphenols, tannins and lignins. In this context, a winery wastewater was firstly subjected to a biological oxidation to mineralize the biodegradable fraction and afterwards an electrochemical advanced oxidation process (EAOP) was applied in order to mineralize the refractory molecules or transform them into simpler ones that can be further biodegraded. The biological oxidation led to above 97% removals of dissolved organic carbon (DOC), chemical oxygen demand (COD) and 5-day biochemical oxygen demand (BOD5), but was inefficient on the degradation of a bioresistant fraction corresponding to 130 mg L(-1) of DOC, 380 mg O2 L(-1) of COD and 8.2 mg caffeic acid equivalent L(-1) of total dissolved polyphenols. Various EAOPs such as anodic oxidation with electrogenerated H2O2 (AO-H2O2), electro-Fenton (EF), UVA photoelectro-Fenton (PEF) and solar PEF (SPEF) were then applied to the recalcitrant effluent fraction using a 2.2 L lab-scale flow plant containing an electrochemical cell equipped with a boron-doped diamond (BDD) anode and a carbon-PTFE air-diffusion cathode and coupled to a photoreactor with compound parabolic collectors (CPCs). The influence of initial Fe(2+) concentration and current density on the PEF process was evaluated. The relative oxidative ability of EAOPs increased in the order AO-H2O2 < EF < PEF ≤ SPEF. The SPEF process using an initial Fe(2+) concentration of 35 mg L(-1), current density of 25 mA cm(-2), pH of 2.8 and 25 °C reached removals of 86% on DOC and 68% on COD after 240 min, regarding the biologically treated effluent, along with energy consumptions of 45 kWh (kg DOC)(-1) and 5.1 kWh m(-3). After this coupled treatment, color, odor, COD, BOD5, NH4(+), NO3(-) and SO4(2-) parameters complied with the legislation targets and, in addition, a total

  6. 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

  7. [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.

  8. Praseodymium incorporated AIPO-5 molecular sieves for aerobic oxidation of ethylbenzene.

    PubMed

    Sundaravel, B; Babu, C M; Palanisamy, B; Palanichamy, M; Shanthi, K; Murugesan, V

    2013-04-01

    PrAlPO-5 with (Al + P)/Pr ratios of 25, 50, 75 and 100 molecular sieves were successfully synthesized by hydrothermal method. These molecular sieves were characterised using XPS, TPD-NH3, ex-situ pyridine adsorbed IR, TPR, TGA, 27Al and 31P MAS-NMR and ESR studies. The incorporation of praseodymium in the framework of AlPO-5 was confirmed by XRD, DRS UV-vis and 27Al and 31P MAS-NMR analysis. ESR spectrum showed the presence of adsorbed oxygen. The nature and strength of acid sites were identified by ex-situ pyridine adsorbed IR and TPD-NH3. The BET surface area was found to be in the range of 238-272 m2 g(-1). The catalytic activity of the molecular sieves was tested for the liquid phase aerobic oxidation of ethylbenzene. Acetophenone was found to be the major product with more than 90% ethylbenzene conversion. ICP-OES analysis revealed the presence of praseodymium intact in the framework of AlPO-5 up to five cycles.

  9. 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.

  10. Impacts of global emissions of CO, NO x , and CH4 on China tropospheric hydroxyl free radicals

    NASA Astrophysics Data System (ADS)

    Su, Mingfeng; Lin, Yunping; Fan, Xinqiang; Peng, Li; Zhao, Chunsheng

    2012-07-01

    Using the global chemistry and transport model MOZART, the simulated distributions of tropospheric hydroxyl free radicals (OH) over China and its sensitivities to global emissions of carbon monoxide (CO), nitrogen oxide (NO x ), and methane (CH4) were investigated in this study. Due to various distributions of OH sources and sinks, the concentrations of tropospheric OH in east China are much greater than in west China. The contribution of NO + perhydroxyl radical (HO2) reaction to OH production in east China is more pronounced than that in west China, and because of the higher reaction activity of non-methane volatile organic compounds (NMVOCs), the contributions to OH loss by NMVOCs exceed those of CO and take the dominant position in summer. The results of the sensitivity runs show a significant increase of tropospheric OH in east China from 1990 to 2000, and the trend continues. The positive effect of double emissions of NO x on OH is partly offset by the contrary effect of increased CO and CH4 emissions: the double emissions of NO x will cause an increase of OH of 18.1%-30.1%, while the increases of CO and CH4 will cause a decrease of OH of 12.2%-20.8% and 0.3%-3.0%, respectively. In turn, the lifetimes of CH4, CO, and NO x will increase by 0.3%-3.1% with regard to double emissions of CH4, 13.9%-26.3% to double emissions of CO and decrease by 15.3%-23.2% to double emissions of NO x .

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

  12. Flexible bacterial strains that oxidize arsenite in anoxic or aerobic conditions and utilize hydrogen or acetate as alternative electron donors.

    PubMed

    Rodríguez-Freire, Lucía; Sun, Wenjie; Sierra-Alvarez, Reyes; Field, Jim A

    2012-02-01

    Arsenic is a carcinogenic compound widely distributed in the groundwater around the world. The fate of arsenic in groundwater depends on the activity of microorganisms either by oxidizing arsenite (As(III)), or by reducing arsenate (As(V)). Because of the higher toxicity and mobility of As(III) compared to As(V), microbial-catalyzed oxidation of As(III) to As(V) can lower the environmental impact of arsenic. Although aerobic As(III)-oxidizing bacteria are well known, anoxic oxidation of As(III) with nitrate as electron acceptor has also been shown to occur. In this study, three As(III)-oxidizing bacterial strains, Azoarcus sp. strain EC1-pb1, Azoarcus sp. strain EC3-pb1 and Diaphorobacter sp. strain MC-pb1, have been characterized. Each strain was tested for its ability to oxidize As(III) with four different electron acceptors, nitrate, nitrite, chlorate and oxygen. Complete As(III) oxidation was achieved with both nitrate and oxygen, demonstrating the novel ability of these bacterial strains to oxidize As(III) in either anoxic or aerobic conditions. Nitrate was only reduced to nitrite. Different electron donors were used to study their suitability in supporting nitrate reduction. Hydrogen and acetate were readily utilized by all the cultures. The flexibility of these As(III)-oxidizing bacteria to use oxygen and nitrate to oxidize As(III) as well as organic and inorganic substrates as alternative electron donors explains their presence in non-arsenic-contaminated environments. The findings suggest that at least some As(III)-oxidizing bacteria are flexible with respect to electron-acceptors and electron-donors and that they are potentially widespread in low arsenic concentration environments.

  13. 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.

  14. Simulated nitrogen deposition reduces CH4 uptake and increases N2O emission from a subtropical plantation forest soil in southern China.

    PubMed

    Wang, Yongsheng; Cheng, Shulan; Fang, Huajun; Yu, Guirui; Xu, Minjie; Dang, Xusheng; Li, Linsen; Wang, Lei

    2014-01-01

    To date, few studies are conducted to quantify the effects of reduced ammonium (NH4+) and oxidized nitrate (NO3-) on soil CH4 uptake and N2O emission in the subtropical forests. In this study, NH4Cl and NaNO3 fertilizers were applied at three rates: 0, 40 and 120 kg N ha(-1) yr(-1). Soil CH4 and N2O fluxes were determined twice a week using the static chamber technique and gas chromatography. Soil temperature and moisture were simultaneously measured. Soil dissolved N concentration in 0-20 cm depth was measured weekly to examine the regulation to soil CH4 and N2O fluxes. Our results showed that one year of N addition did not affect soil temperature, soil moisture, soil total dissolved N (TDN) and NH4+-N concentrations, but high levels of applied NH4Cl and NaNO3 fertilizers significantly increased soil NO3(-)-N concentration by 124% and 157%, respectively. Nitrogen addition tended to inhibit soil CH4 uptake, but significantly promoted soil N2O emission by 403% to 762%. Furthermore, NH4+-N fertilizer application had a stronger inhibition to soil CH4 uptake and a stronger promotion to soil N2O emission than NO3(-)-N application. Also, both soil CH4 and N2O fluxes were driven by soil temperature and moisture, but soil inorganic N availability was a key integrator of soil CH4 uptake and N2O emission. These results suggest that the subtropical plantation soil sensitively responses to atmospheric N deposition, and inorganic N rather than organic N is the regulator to soil CH4 uptake and N2O emission.

  15. Simulated Nitrogen Deposition Reduces CH4 Uptake and Increases N2O Emission from a Subtropical Plantation Forest Soil in Southern China

    PubMed Central

    Wang, Yongsheng; Cheng, Shulan; Fang, Huajun; Yu, Guirui; Xu, Minjie; Dang, Xusheng; Li, Linsen; Wang, Lei

    2014-01-01

    To date, few studies are conducted to quantify the effects of reduced ammonium (NH4+) and oxidized nitrate (NO3−) on soil CH4 uptake and N2O emission in the subtropical forests. In this study, NH4Cl and NaNO3 fertilizers were applied at three rates: 0, 40 and 120 kg N ha−1 yr−1. Soil CH4 and N2O fluxes were determined twice a week using the static chamber technique and gas chromatography. Soil temperature and moisture were simultaneously measured. Soil dissolved N concentration in 0–20 cm depth was measured weekly to examine the regulation to soil CH4 and N2O fluxes. Our results showed that one year of N addition did not affect soil temperature, soil moisture, soil total dissolved N (TDN) and NH4+-N concentrations, but high levels of applied NH4Cl and NaNO3 fertilizers significantly increased soil NO3−-N concentration by 124% and 157%, respectively. Nitrogen addition tended to inhibit soil CH4 uptake, but significantly promoted soil N2O emission by 403% to 762%. Furthermore, NH4+-N fertilizer application had a stronger inhibition to soil CH4 uptake and a stronger promotion to soil N2O emission than NO3−-N application. Also, both soil CH4 and N2O fluxes were driven by soil temperature and moisture, but soil inorganic N availability was a key integrator of soil CH4 uptake and N2O emission. These results suggest that the subtropical plantation soil sensitively responses to atmospheric N deposition, and inorganic N rather than organic N is the regulator to soil CH4 uptake and N2O emission. PMID:24714387

  16. 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

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

    NASA Astrophysics Data System (ADS)

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

    2016-08-01

    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.

  18. Recent trends in global methane emissions inferred from 30-years of surface CH4 and δ13C-CH4 measurements

    NASA Astrophysics Data System (ADS)

    Karmakar, S.; Butenhoff, C. L.; Rice, A. L.; Lofdahl, D. B.; Khalil, A. K.

    2015-12-01

    Methane (CH4) is the second most important greenhouse gas after carbon dioxide. Quantitative understanding of the global CH4 budget is important in order to predict future contributions of global warming and to develop effective strategies for its mitigation. After a decade-long period of decreasing growth rates, atmospheric CH4 concentrations have risen in recent years raising concerns about its long-term stability. Despite much study there is no clear consensus about the causes of this increase. Some bottom-up inventories suggest that fugitive emissions from the fossil fuel industry may be increasing though there are considerable uncertainties in these estimates due in part to the variable nature of this source. To better understand the changing budget of atmospheric CH4, we performed a time-dependent retrieval of CH4 fluxes spanning nearly 30 years using global surface and isotopic CH4 measurements. An earlier inversion from our group suggested that fugitive fossil fuel emissions increased from 2000-2008, contributing to the recent rise. Here we extend this study to year 2015 using the most recent NOAA Global Monitoring Division (GMD) CH4 measurements and available δ13C -CH4 data along with a higher resolution version of the chemical transport model GEOS-Chem (2ox2.5o). The higher resolution grid allowed us to extract more information from the observations due to the improved ability of the model to simulate CH4 at each station and the decreased need to aggregate neighboring stations. This in turn increased the error reduction between the a priori and posterior emissions leading to more accurate estimates of the retrieved fluxes and improved understanding of the drivers underlying the current atmospheric record.

  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. 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.

  1. N2O, NO and CH4 exchange, and microbial N turnover over a Mediterranean pine forest soil

    NASA Astrophysics Data System (ADS)

    Rosenkranz, P.; Brüggemann, N.; Papen, H.; Xu, Z.; Seufert, G.; Butterbach-Bahl, K.

    2005-06-01

    Trace gas exchange of N2O, NO/NO2 and CH4 between soil and the atmosphere was measured in a typical Mediterranean pine (Pinus pinaster) forest during two intensive field campaigns in spring and autumn 2003. Furthermore, gross and net turnover rates of N mineralization and nitrification as well as soil profiles of N2O and CH4 concentrations were determined. For both seasons a weak but significant N2O uptake from the atmosphere into the soil was observed. During the unusually dry and hot spring mean N2O uptake was -4.32 µg N m-2 h-1, whereas during the wet and mild autumn mean N2O uptake was -7.8 µg N m-2 h-1. The observed N2O uptake into the soil was linked to the very low availability of inorganic nitrogen at the study site. Organic layer gross N mineralization decreased from 5.06 mg N kg-1 SDW d-1 in springtime to 2.68 mg N kg-1 SDW d-1 in autumn. Mean NO emission rates were significantly higher in springtime (9.9 µ N m-2 h-1 than in autumn (1.4 µg N m-2 h-1. A significant positive correlation between NO emission rates and gross N mineralization as well as nitrification rates was found. The negative correlation between NO emissions and soil moisture was explained with a stimulation of aerobic NO uptake under N limiting conditions. Since NO2 deposition was continuously higher than NO emission rates the examined forest soil did function as a net NOx sink. Observed mean net CH4 uptake rates were in spring significantly higher (-73.34 µg C m-2 h-1 than in autumn (-59.67 µg C m-2 h-1. Changes in CH2 uptake rates were strongly negatively correlated with changes in soil moisture. The N2O and CH4 concentrations in different soil depths revealed the organic layer and the upper 10 cm of mineral soil as the most important soil horizons for N2O and CH4 consumption.

  2. 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.

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

    USGS Publications Warehouse

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

    2016-01-01

    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 CO2to 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 CO2emissions 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.

  4. 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

  5. Stable isotope ratios in atmospheric CH4: Implications for seasonal sources and sinks

    NASA Astrophysics Data System (ADS)

    Tyler, Stanley C.; Rice, Andrew L.; Ajie, Henry O.

    2007-02-01

    We report δD and δ13C measurements of atmospheric CH4 from air samples collected from two locations in the United States. They are the mid continental site Niwot Ridge, Colorado (40°N, 105°W), and a Pacific coastal site receiving strong westerlies, Montaña de Oro, California (35°N, 121°W). Data from multiyear approximately bimonthly sampling provide information relating seasonal cycling of CH4 sources and sinks in background air, record long-term trends in CH4 mixing and isotope ratio related to the atmospheric CH4 loading, and may indicate regional CH4 sources. At Niwot Ridge, δD-CH4 averaged -93.1 ± 3.0‰ from 1999 to 2001, while δ13C-CH4 averaged -47.22 ± 0.13‰ from 1995 to 2001 with distinct seasonal cycles in both isotope ratios. At Montaña de Oro, atmospheric CH4 was observed to be more depleted in 13C and D: Measured δD-CH4 averaged -97.3 ± 3.7‰ from 2000 to 2001, while δ13C-CH4 averaged -47.26 ± 0.17‰ from 1996 to 2001, and seasonal cycles were larger than those observed at Niwot Ridge. Mixing ratios observed at Montaña de Oro were higher on average than at Niwot Ridge. At both sites, δ13C-CH4 was found to correlate poorly with mixing ratio, an indication that varying CH4 sources are partly responsible for the δ13C-CH4 seasonal signal. In contrast, a strong anticorrelation exists between δD-CH4 and mixing ratio, with maxima and minima approximately 6 months out of phase, indicating a sensitivity of δD to sink processes. The dual isotopic constraint to atmospheric CH4 seasonality implies that these midlatitude sites are annually influenced by a 13C-enriched CH4 source(s) seasonally increasing in late spring and a 13C-depleted CH4 source(s) seasonally increasing in late summer or early fall.

  6. 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.

  7. 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

  8. Microbial Removal of Atmospheric Carbon Tetrachloride in Bulk Aerobic Soils▿

    PubMed Central

    Mendoza, Y.; Goodwin, K. D.; Happell, J. D.

    2011-01-01

    Atmospheric concentrations of carbon tetrachloride (CCl4) were removed by bulk aerobic soils from tropical, subtropical, and boreal environments. Removal was observed in all tested soil types, indicating that the process was widespread. The flux measured in field chamber experiments was 0.24 ± 0.10 nmol CCl4 (m2 day)−1 (average ± standard deviation [SD]; n = 282). Removal of CCl4 and removal of methane (CH4) were compared to explore whether the two processes were linked. Removal of both gases was halted in laboratory samples that were autoclaved, dry heated, or incubated in the presence of mercuric chloride (HgCl2). In marl soils, treatment with antibiotics such as tetracycline and streptomycin caused partial inhibition of CCl4 (50%) and CH4 (76%) removal, but removal was not affected in soils treated with nystatin or myxothiazol. These data indicated that bacteria contributed to the soil removal of CCl4 and that microeukaryotes may not have played a significant role. Amendments of methanol, acetate, and succinate to soil samples enhanced CCl4 removal by 59%, 293%, and 72%, respectively. Additions of a variety of inhibitors and substrates indicated that nitrification, methanogenesis, or biological reduction of nitrate, nitrous oxide, or sulfate (e.g., occurring in possible anoxic microzones) did not play a significant role in the removal of CCl4. Methyl fluoride inhibited removal of CH4 but not CCl4, indicating that CH4 and CCl4 removals were not directly linked. Furthermore, CCl4 removal was not affected in soils amended with copper sulfate or methane, supporting the results with MeF and suggesting that the observed CCl4 removal was not significantly mediated by methanotrophs. PMID:21724884

  9. Amine-Appended Hierarchical Ca-A Zeolite for Enhancing CO2 /CH4 Selectivity of Mixed-Matrix Membranes.

    PubMed

    Nguyen, Tien Hoa; Gong, Heqing; Lee, Siew Siang; Bae, Tae-Hyun

    2016-10-18

    An amine-appended hierarchical Ca-A zeolite that can selectively capture CO2 was synthesized and incorporated into inexpensive membrane polymers, in particular polyethylene oxide and Matrimid, to design mixed-matrix membranes with high CO2 /CH4 selectivities. Binary mixture permeation testing reveals that amine-appended mesoporous Ca-A is highly effective in improving CO2 /CH4 selectivity of polymeric membranes. In particular, the CO2 /CH4 selectivity of the polyethylene oxide membrane increases from 15 to 23 by incorporating 20 wt % amine-appended Ca-A zeolite. Furthermore, the formation of filler/polymer interfacial defects, which is typically found in glassy polymer-zeolite pairs, is inhibited owing to the interaction between the amine groups on the external surface of zeolites and polymer chains. Our results suggest that the amine-appended hierarchial Ca-A, which was utilized in membrane fabrication for the first time, is a good filler material for fabricating a CO2 -selective mixed-matrix membrane with defect-free morphology.

  10. 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.

  11. The case for human causes of increased atmospheric CH 4 over the last 5000 years

    NASA Astrophysics Data System (ADS)

    Ruddiman, William F.; Thomson, Jonathan S.

    2001-12-01

    We propose that humans significantly altered atmospheric CH 4 levels after 5000 years BP and that anthropogenic inputs just prior to the industrial revolution accounted for up to 25% of the CH 4 level of 725 ppb (parts per billion). We base this hypothesis on three arguments: (1) the 100 ppb increase in atmospheric CH 4 that occurred after 5000 years BP follows a pattern unprecedented in any prior orbitally driven change in the ice-core record; (2) non-anthropogenic explanations for this increase (expansion of boreal peat lands or tropical wetlands) are inconsistent with existing evidence; and (3) inefficient early rice farming is a quantitatively plausible means of producing anomalously large CH 4 inputs to the atmosphere prior to the industrial revolution. If the areas flooded for farming harbored abundant CH 4-producing weeds, disproportionately large amounts of CH 4 would have been produced in feeding relatively small pre-industrial populations.

  12. 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.

  13. 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.

  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. Uncertainty and dynamics of natural wetland CH4 release in China: Research status and priorities

    NASA Astrophysics Data System (ADS)

    Wei, Da; Wang, Xiaodan

    2017-04-01

    Natural wetlands represent the largest single source of methane (CH4), a potent greenhouse gas. China is home to the world's fourth largest wetland area, and it is facing intense climate- and human-related impacts. The scientific community in China has invested considerable effort into investigating wetland CH4 release and its dynamics. Static chamber and eddy covariance observations have verified the temperature, water regime and air pressure as factors that regulate the diurnal and seasonal variation of CH4 release. Non-growing seasons, especially freezing-thawing cycles, play a role in CH4 release. However, a knowledge gap still exists with respect to the inter-annual variability of CH4 release. Observations also suggest that water and temperature regimes control the micro- and macro-scale spatial pattern of CH4 release, respectively. Recent bookkeeping surveys, biogeochemical model simulations, and chemical transport model inversions, have narrowed the uncertainty range of national CH4 release to 2.46-3.20, 2.77-4.95 and 2.38-4.91 Tg CH4 yr-1, respectively. Wetland loss (especially cropland conversion in Northeast China), despite climate changes, decreased CH4 release by 45.2%-52.2% from the 1950s-2000s, and by 13.2%-15.4% from the 1980s-2000s. However, future warmer temperatures and rising CO2 are predicted to strengthen national CH4 release by 32% (RCP2.6), 55% (RCP4.5) and 91% (RCP8.5) by the 2080s, albeit without the variation in wetland extent having been considered. Furthermore, future research should emphasize the mechanisms involved in CH4 release during freezing-thawing cycles and interannual variability. Model-data fusion of eddy covariance and manipulative experiments, especially warming and CO2 enrichment, would benefit estimations and projections of CH4 release.

  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. Copper(II)-Catalyzed Benzylic C(sp(3))-H Aerobic Oxidation of (Hetero)Aryl Acetimidates: Synthesis of Aryl-α-ketoesters.

    PubMed

    Kumar, Yogesh; Jaiswal, Yogesh; Kumar, Amit

    2016-12-16

    A straightforward method is developed in this paper for the synthesis of α-ketoesters through copper-catalyzed aerobic oxidation of (hetero)aryl acetimidates using molecular oxygen as a sustainable oxidant. The reaction represents the first example of the direct synthesis of aryl-α-ketoesters from arylacetimidates through the aerobic oxidation of a benzylic C(sp3)-H (C═O) bond in moderate to good yield. This transformation occurs under mild reaction conditions with a wide range of substrates and utilizes a readily available oxidant and catalyst. The synthetic utility of this transformation is demonstrated through scaled-up synthesis. A plausible reaction mechanism is also proposed.

  18. The atmospheric CH4 increase since the Last Glacial Maximum. I - Source estimates

    NASA Technical Reports Server (NTRS)

    Chappellaz, Jerome A.; Fung, Inez Y.; Thompson, Anne M.

    1993-01-01

    An estimate of the distribution of wetland area and associated CH4 emission is presented for the Last Glacial Maximum (LGM, 18 kyr BP, kiloyear Before Present) and the Pre-Industrial Holocene (PIH, 9000-200 years BP). The wetland source, combined with estimates of the other biogenic sources and sink, yields total source strengths of 120 and 180 Tg CH4/yr for LGM and PIH respectively. These source strengths are shown to be consistent with source estimates inferred from a photochemical model, and point to changes in wetland CH4 source as a major factor driving the atmospheric CH4 increase from LGM to PIH.

  19. Gas-phase synthesis and characterization of CH4-loaded hydroquinone clathrates.

    PubMed

    Lee, Jong-Won; Lee, Yongjae; Takeya, Satoshi; Kawamura, Taro; Yamamoto, Yoshitaka; Lee, Yun-Je; Yoon, Ji-Ho

    2010-03-11

    A CH(4)-loaded hydroquinone (HQ) clathrate was synthesized via a gas-phase reaction using the alpha-form of crystalline HQ and CH(4) gas at 12 MPa and room temperature. Solid-state (13)C cross-polarization/magic angle spinning (CP/MAS) NMR and Raman spectroscopic measurements confirm the incorporation of CH(4) molecules into the cages of the HQ clathrate framework. The chemical analysis indicates that about 69% of the cages are filled by CH(4) molecules, that is, 0.69 CH(4) per three HQ molecules. Rietveld refinement using synchrotron X-ray powder diffraction (XRD) data shows that the CH(4)-loaded HQ clathrate adopts the beta-form of HQ clathrate in a hexagonal space group R3 with lattice parameters of a = 16.6191 A and c = 5.5038 A. Time-resolved synchrotron XRD and quadrupole mass spectroscopic measurements show that the CH(4)-loaded HQ clathrate is stable up to 368 K and gradually transforms to the alpha-form by releasing the confined CH(4) gases between 368-378 K. Using solid-state (13)C CP/MAS NMR, the reaction kinetics between the alpha-form HQ and CH(4) gas is qualitatively described in terms of the particle size of the crystalline HQ.

  20. Spatial and seasonal variability of CH4 in the eastern Gulf of Cadiz (SW Iberian Peninsula).

    PubMed

    Sierra, A; Jiménez-López, D; Ortega, T; Ponce, R; Bellanco, M J; Sánchez-Leal, R; Gómez-Parra, A; Forja, J

    2017-03-10

    Methane (CH4) concentrations were measured along three sections of the eastern Gulf of Cadiz (designated "Guadalquivir", "Sancti Petri" and "Trafalgar") during eight cruises in 2014 and 2015. The concentration of CH4 varied from 3.6 to 19.7nmolkg(-1) (CH4 saturation percent of 122 and 916%), showing seasonal variation. The highest values were found in December 2014 and November 2015. In most of the sampling area the highest concentration of CH4 was found in subsurface waters at depths close to the thermocline, and in the bottom waters near the coast. The seawater-air flux of CH4 ranged between 0.8 and 59.7μmolm(-2)d(-1), showing seasonal variation in function of the temperature of the surface water. In the "Guadalquivir" and "Sancti Petri" sections, the CH4 fluxes increased with proximity to the coast; this may be a result of continental inputs and CH4 emissions from sediments. The whole study area behaves as a source of CH4 to the atmosphere with mean values of 0.5 and 0.6GgCH4yr(-1) in 2014 and 2015, respectively.

  1. 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

  2. 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.

  3. Warburg Meets Autophagy: Cancer-Associated Fibroblasts Accelerate Tumor Growth and Metastasis via Oxidative Stress, Mitophagy, and Aerobic Glycolysis

    PubMed Central

    Pavlides, Stephanos; Vera, Iset; Gandara, Ricardo; Sneddon, Sharon; Pestell, Richard G.; Mercier, Isabelle; Martinez-Outschoorn, Ubaldo E.; Whitaker-Menezes, Diana; Howell, Anthony

    2012-01-01

    Abstract Significance: Here, we review certain recent advances in oxidative stress and tumor metabolism, which are related to understanding the contributions of the microenvironment in promoting tumor growth and metastasis. In the early 1920s, Otto Warburg, a Nobel Laureate, formulated a hypothesis to explain the “fundamental basis” of cancer, based on his observations that tumors displayed a metabolic shift toward glycolysis. In 1963, Christian de Duve, another Nobel Laureate, first coined the phrase auto-phagy, derived from the Greek words “auto” and “phagy,” meaning “self” and “eating.” Recent Advances: Now, we see that these two ideas (autophagy and aerobic glycolysis) physically converge in the tumor stroma. First, cancer cells secrete hydrogen peroxide. Then, as a consequence, oxidative stress in cancer-associated fibroblasts drives autophagy, mitophagy, and aerobic glycolysis. Critical Issues: This “parasitic” metabolic coupling converts the stroma into a “factory” for the local production of recycled and high-energy nutrients (such as L-lactate)—to fuel oxidative mitochondrial metabolism in cancer cells. We believe that Warburg and de Duve would be pleased with this new two-compartment model for understanding tumor metabolism. It adds a novel stromal twist to two very well-established cancer paradigms: aerobic glycolysis and autophagy. Future Directions: Undoubtedly, these new metabolic models will foster the development of novel biomarkers, and corresponding therapies, to achieve the goal of personalized cancer medicine. Given the central role that oxidative stress plays in this process, new powerful antioxidants should be developed in the fight against cancer. Antioxid. Redox Signal. 16, 1264–1284. PMID:21883043

  4. 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.

  5. Seasonal variation of N2O and CH4 fluxes in differently managed arable soils in southern Germany

    NASA Astrophysics Data System (ADS)

    Flessa, H.; DöRsch, P.; Beese, F.

    1995-11-01

    Agricultural practices are assumed to contribute significantly to the increase in atmospheric nitrous oxide (N2O) concentrations observed in the last decades, and they might influence the consumption of atmospheric methane (CH4) by soil. The aim of this study was to quantify the effects of management intensity, soil type, and frost periods on the emission of N2O and the consumption of CH4 in rotations in southern Germany. Fluxes of N2O and CH4 were monitored over 12 months, using a closed chamber technique. The extensively managed system was cropped to sunflower and fertilized with farmyard manure (12 t ha-1). The intensively managed field was planted with spring wheat and fertilized with a total of 190 kg N ha-1 given as calcium ammonium nitrate (30 kg N) and urea-NH4NO3 solution (160 kg N). Variation in the N2O emissions with time was extremely high, with flux rates ranging from 0 to 2700 μg m-2 h-1. The N2O fluxes were influenced by soil properties, management practices, and weather. The highest release rates were measured in the winter during thawing of the frozen soil. During the growing season, N2O emission was highest after heavy precipitation. No strong relationship was found between N2O emission rates and soil factors such as soil temperature, soil moisture, and soil nitrate content. Annual fluxes of N2O from the extensively managed field were 9.4 and 12.9 kg N2O-N ha-1 yr-1 for a sandy soil and a clay soil, respectively. Total N2O-N losses from the intensively fertilized field amounted to 9.6 kg ha-1 yr-1 for a silty soil with a tendency to waterlogging during wintertime and to 16.8 kg ha yr-1 for a loamy colluvial soil. Up to 46% of the annual N2O evolution was emitted during December and January when frost/thaw cycles induced extremely high N2O production. The application of urea-NH4NO3 solution significantly increased N2O emission rates. Of the 160 kg N applied, 2.9 kg N or 1.8% was lost as N2O within a period of 8 weeks. Rates of CH4-C uptake varied

  6. 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

  7. 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.

  8. A pan-Arctic synthesis of CH4 and CO2 production from anoxic soil incubations.

    PubMed

    Treat, Claire C; Natali, Susan M; Ernakovich, Jessica; Iversen, Colleen M; Lupascu, Massimo; McGuire, Anthony David; Norby, Richard J; Roy Chowdhury, Taniya; Richter, Andreas; Šantrůčková, Hana; Schädel, Christina; Schuur, Edward A G; Sloan, Victoria L; Turetsky, Merritt R; Waldrop, Mark P

    2015-01-24

    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 ground

  9. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2015-10-01

    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.

  11. 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

  12. 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

  13. 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.

  14. 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.

  15. 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...

  16. 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.

  17. Mn-Catalyzed Highly Efficient Aerobic Oxidative Hydroxyazidation of Olefins: A Direct Approach to β-Azido Alcohols.

    PubMed

    Sun, Xiang; Li, Xinyao; Song, Song; Zhu, Yuchao; Liang, Yu-Feng; Jiao, Ning

    2015-05-13

    An efficient Mn-catalyzed aerobic oxidative hydroxyazidation of olefins for synthesis of β-azido alcohols has been developed. The aerobic oxidative generation of azido radical employing air as the terminal oxidant is disclosed as the key process for this transformation. The reaction is appreciated by its broad substrate scope, inexpensive Mn-catalyst, high efficiency, easy operation under air, and mild conditions at room temperature. This chemistry provides a novel approach to high value-added β-azido alcohols, which are useful precursors of aziridines, β-amino alcohols, and other important N- and O-containing heterocyclic compounds. This chemistry also provides an unexpected approach to azido substituted cyclic peroxy alcohol esters. A DFT calculation indicates that Mn catalyst plays key dual roles as an efficient catalyst for the generation of azido radical and a stabilizer for peroxyl radical intermediate. Further calculation reasonably explains the proposed mechanism for the control of C-C bond cleavage or for the formation of β-azido alcohols.

  18. Metabolic engineering of Escherichia coli for 1-butanol biosynthesis through the inverted aerobic fatty acid β-oxidation pathway.

    PubMed

    Gulevich, Andrey Yu; Skorokhodova, Alexandra Yu; Sukhozhenko, Alexey V; Shakulov, Rustem S; Debabov, Vladimir G

    2012-03-01

    The basic reactions of the clostridial 1-butanol biosynthesis pathway can be regarded to be the inverted reactions of the fatty acid β-oxidation pathway. A pathway for the biosynthesis of fuels and chemicals was recently engineered by combining enzymes from both aerobic and anaerobic fatty acid β-oxidation as well as enzymes from other metabolic pathways. In the current study, we demonstrate the inversion of the entire aerobic fatty acid β-oxidation cycle for 1-butanol biosynthesis. The constructed markerless and plasmidless Escherichia coli strain BOX-3 (MG1655 lacI(Q) attB-P(trc-ideal-4)-SD(φ10)-adhE(Glu568Lys) attB-P(trc-ideal-4)-SD(φ10)-atoB attB-P(trc-ideal-4)-SD(φ10)-fadB attB-P(trc-ideal-4)-SD(φ10)-fadE) synthesises 0.3-1 mg 1-butanol/l in the presence of the specific inducer. No 1-butanol production was detected in the absence of the inducer.

  19. Photopromoted Ru-catalyzed asymmetric aerobic sulfide oxidation and epoxidation using water as a proton transfer mediator.

    PubMed

    Tanaka, Haruna; Nishikawa, Hiroaki; Uchida, Tatsuya; Katsuki, Tsutomu

    2010-09-01

    Ru(NO)-salen complexes were found to catalyze asymmetric aerobic oxygen atom transfer reactions such as sulfide oxidation and epoxidation in the presence of water under visible light irradiation at room temperature. Oxidation of sulfides including alkyl aryl sulfides and 2-substituted 1,3-dithianes using complex 2 as the catalyst proceeded with moderate to high enantioselectivity of up to 98% ee, and epoxidation of conjugated olefins using complex 3 as the catalyst proceeded with good to high enantioselectivity of 76-92% ee. Unlike biological oxygen atom transfer reactions that need a proton and electron transfer system, this aerobic oxygen atom transfer reaction requires neither such a system nor a sacrificial reductant. Although the mechanism of this oxidation has not been completely clarified, some experimental results support the notion that an aqua ligand coordinated with the ruthenium ion serves as a proton transfer agent for the oxygen activation process, and it is recycled and used as the proton transfer mediator during the process. Thus, we have achieved catalytic asymmetric oxygen atom transfer reaction using molecular oxygen that can be carried out under ambient conditions.

  20. Disproportionation and Thermochemical Sulfate Reduction Reactions in S-H2O-CH4 and S-D2O-CH4 Systems from 200 to 340 °C at Elevated Pressures

    NASA Astrophysics Data System (ADS)

    Chou, I.; Yuan, S.; Burruss, R. C.

    2010-12-01

    Elemental sulfur plays significant roles in thermochemical sulfate reduction (TSR) reactions as a transient intermediate oxidation state compound, by-product, or catalyst. However, the mechanisms of the reactions in S-H2O-hydrocarbon systems are not clear. To improve our understanding of reaction mechanisms, we conducted a series of experiments between 200 and 340 °C for S-H2O-CH4, S-D2O-CH4, and S-CH4-1m ZnBr2 systems in fused silica capillary capsules. After a heating period ranging from one to 90 days, the quenched samples were analyzed by Raman spectroscopy. Our results showed that the disproportionation of sulfur in the S-H2O-CH4 system occurred at temperatures above 200 °C and produced H2S, SO42-, and HSO4-. We also observed that the amounts of SO42- and HSO4- decreased for the samples quenched from 250 and 340 °C, and at the same time the amounts of CO2 and H2S increased. To demonstrate that the observed consumption of SO42- and HSO4- in the S-H2O-CH4 system at 300 °C was due to TSR instead of the back reaction between SO42- (or HSO4-) and H2S to form S during and after quench, we introduced 1m ZnBr2 to remove H2S as a ZnS precipitate, as soon as it formed. In these experiments sulfate species decreased and CO2 and H2S increased consistent with TSR and no back reaction. When compared with previously published experiments, our temperatures between 250 and 340 °C are much closer to natural systems (<200 °C) with documented TSR. Also, to demonstrate the relationship between disproportionation and TSR reactions in the S-H2O-CH4 system, we conducted experiments in the S-D2O-CH4 system at 250 and 300 °C. Only small Raman signals for CO2 and no signals for H2S and D2S were detected in the sample quenched from 250 °C, indicating that both the disproportionation reaction and the TSR reaction were very slow at this temperature. After heating at 300 °C for 40 h, Raman signals of the quenched sample indicated significant amount of D2S was produced through the

  1. 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

  2. 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

  3. Surface Tension of Mixtures of Molecular Fluids: Comparison between the Experimental and Theoretical Study of CH4 + Kr, Kr + NO, and CH4 + NO

    PubMed

    Calado; Mendonca; Saramago; Soares

    1997-01-01

    We report a study of the surface tension of three binary liquid mixtures of molecular fluids. A microscopic mean field theory (MFT) has been used to calculate the theoretical results enabling the comparison with the experimental data. The mean field theory has been successfully used in the prediction of the surface properties of simple systems composed by quasi-spherical molecules. In the present study the MFT was able to reproduce the essential features of the interfacial properties of the systems CH4 + Kr, Kr + NO and CH4 + NO. The pure components were modeled by Lennard-Jones potentials with a set of intermolecular parameters taken from the literature for Kr and calculated from the fitting of the energy parameters (epsilon) to the surface tension, for CH4 and NO. In the case of the mixtures, it was found that reasonable agreement with experiment can only be obtained by allowing deviations from the Lorentz-Berthelot combining rules. For the CH4 + Kr system we used the binary energy parameter xi obtained through a fitting to the bulk properties; for the Kr + NO and CH4 + NO systems the binary parameter was adjusted to the interfacial properties.

  4. Hydrogen isotope systematics of H2-H2O-CH4 during hydrogenotrophic methanogenesis

    NASA Astrophysics Data System (ADS)

    Kobayashi, M.; Kawagucci, S.; Hattori, S.; Yamada, K.; Ueno, Y.; Takai, K.; Yoshida, N.

    2011-12-01

    Hydrogen and carbon isotopes of CH4 have been utilized to trace microbial processes. The isotope fractionations during hydrogenotrophic methanogenesis, one of the major processes of environmental CH4, have been studied by several laboratory incubations. For the carbon isotope, H2 concentration is thought to be the major parameter controlling the carbon isotope fractionation by hydrogenotrophic methanogenesis. For the hydrogen, on the other hand, factors controlling isotope fractionation remain poorly understood, although H2 concentration is suggested to be important. This uncertainty prevents us to utilize δD-CH4 value as the tracer. The most important and principal question is whether all hydrogen atoms in microbially-generated CH4 come from environmental H2O or not. To answer the question, we investigated the D/H systematics of H2-H2O-CH4 during hydrogenotrophic methanogenesis by pure culture incubation with softly deuterium-enriched H2 and/or H2O. Our results demonstrate that δD-CH4 value produced by hydrogenotrophic methanogens depends not only on δD-H2O value but also on δD-H2 value. We observed constant correlation between δD-H2 and δD-CH4 values as well as between δD-H2O and δD-CH4 values, which suggests that hydrogen (/deuterium) atom of substrate H2 is also transferred to the product CH4. This implies that the range of δD-CH4 value produced by hydrogenotrophic methanogenesis should be re-evaluated considering the distribution of δD-H2 and δD-H2O values in natural environments.

  5. [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.

  6. The Description and Validation of a Computationally-Efficient CH4-CO-OH (ECCOH) Module for 3D Model Applications

    NASA Technical Reports Server (NTRS)

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

    2015-01-01

    We present the Efficient CH4-CO-OH Module (ECCOH) that allows for the simulation of the methane, carbon monoxide and hydroxyl radical (CH4-CO-OH cycle, 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 cycle, which primarily determines the global tropospheric oxidizing capacity. This capability is important for capturing the nonlinear feedbacks of the CH4-CO-OH system and understanding the perturbations to relatively long-lived methane and the concomitant impacts on climate. We implemented the ECCOH 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 module (as configured in the GEOS-5 AGCM) with observations demonstrates the fidelity of the module for use in scientific research.

  7. The Description and Validation of a Computationally-Efficient CH4-CO-OH (ECCOHv1.01) Chemistry Module for 3D Model Applications

    NASA Technical Reports Server (NTRS)

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

    2016-01-01

    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.

  8. 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.

  9. 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

  10. 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

  11. 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.

  12. SBA-15-functionalized 3-oxo-ABNO as recyclable catalyst for aerobic oxidation of alcohols under metal-free conditions.

    PubMed

    Karimi, Babak; Farhangi, Elham; Vali, Hojatollah; Vahdati, Saleh

    2014-09-01

    The nitroxyl radical 3-oxo-9-azabicyclo [3.3.1]nonane-N-oxyl (3-oxo-ABNO) has been prepared using a simple protocol. This organocatalyst is found to be an efficient catalyst for the aerobic oxidation of a wide variety of alcohols under metal-free conditions. In addition, the preparation and characterization of a supported version of 3-oxo-ABNO on ordered mesoporous silica SBA-15 (SABNO) is described for the first time. The catalyst has been characterized using several techniques including simultaneous thermal analysis (STA), transmission electron microscopy (TEM), and nitrogen sorption analysis. This catalyst exhibits catalytic performance comparable to its homogeneous analogue and much superior catalytic activity in comparison with (2,2,6,6-tetramethylpiperidin-1-yl)oxy (TEMPO) for the aerobic oxidation of almost the same range of alcohols under identical reaction conditions. It is also found that SABNO can be conveniently recovered and reused at least 12 times without significant effect on its catalytic efficiency.

  13. Aerobic oxidation of methanol to formic acid on Au20-: a theoretical study on the reaction mechanism.

    PubMed

    Bobuatong, Karan; Karanjit, Sangita; Fukuda, Ryoichi; Ehara, Masahiro; Sakurai, Hidehiro

    2012-03-07

    The aerobic oxidation of methanol to formic acid catalyzed by Au(20)(-) has been investigated quantum chemically using density functional theory with the M06 functional. Possible reaction pathways are examined taking account of full structure relaxation of the Au(20)(-) cluster. The proposed reaction mechanism consists of three elementary steps: (1) formation of formaldehyde from methoxy species activated by a superoxo-like anion on the gold cluster; (2) nucleophilic addition by the hydroxyl group of a hydroperoxyl-like complex to formaldehyde resulting in a hemiacetal intermediate; and (3) formation of formic acid by hydrogen transfer from the hemiacetal intermediate to atomic oxygen attached to the gold cluster. A comparison of the computed energetics of various elementary steps indicates that C-H bond dissociation of the methoxy species leading to formation of formaldehyde is the rate-determining step. A possible reaction pathway involving single-step hydrogen abstraction, a concerted mechanism, is also discussed. The stabilities of reactants, intermediates and transition state structures are governed by the coordination number of the gold atoms, charge distribution, cooperative effect and structural distortion, which are the key parameters for understanding the relationship between the structure of the gold cluster and catalytic activity in the aerobic oxidation of alcohols.

  14. 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.

  15. Variation of CH Stretch Frequencies with CH_4 Orientation in the CH_4 - F^- Complex: Multiple Resonances as Vibrational Conical Intersections

    NASA Astrophysics Data System (ADS)

    Thapaliya, Bishnu P.; Perry, David S.

    2016-06-01

    In the CH_4 - F^- complex, an adiabatic separation of the CH stretch frequencies from the CH_4 orientational coordinates allows the calculation of the four adiabatic CH stretch surfaces. These ab initio calculations reveal (i) a large variation of CH stretch frequencies (> 100 wn) in the orientational space and (ii) the existence of four symmetrically equivalent sets of vibrational conical intersections (CIs). Two sets of symmetry-allowed CIs are identified in addition to the symmetry-required CIs at the front- and back-side C3v geometries. These results have implications for the evolution of excited CH vibrations in methane during its approach to a potentially reactive surface.

  16. 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

  17. Seismic characteristics and strain of coal during the sorption of CO2 and CH4

    NASA Astrophysics Data System (ADS)

    Iyengar, Padmavathi

    Coal has been studied for its extensive capability of adsorbing CO2 in exchange for coalbed CH4. Various sorption models have been developed and enhanced in order to precisely understand the implications of carbon sequestration and enhanced coalbed CH4 recovery processes. Our study aims at analyzing the characteristic behavior of a bituminous coal in various CO2 and CH4 pressure environments through seismic waveform and strain analyses. Laboratory-scale geophysical investigation of a coal specimen was performed under pressures of up to 1000 psi for CH 4 and up to 700 psi for CO2. The results show that the coal specimen has a significantly higher rate of swelling from CO2 injection than CH4. The coal specimen shows instability to reach equilibrium at higher CO2 pressure level; micro-bedding layers of the coal specimen exhibit high seismic impedance at atmospheric pressure, which decreases concurrently as CO2/CH4 pressure increases. The results also show that the coal experiences different rates of swelling and shrinkage for CO2 and CH4 in a confined pressure environment, after a given time interval.

  18. Outgassing from the Congo River Basin: a Major Source of Atmospheric CH4

    NASA Astrophysics Data System (ADS)

    Salter, M. E.; Mann, P. J.; Dinga, B.; Poulsen, J.; Barnes, J.; Fiske, G.; Upstill-Goddard, R. C.; Holmes, R. M.

    2011-12-01

    Methane (CH4) is a major greenhouse gas and although its production by human activities now exceeds that by natural sources, the single largest source in the global CH4 budget is natural production in wetlands. Recent studies have highlighted the potential importance of tropical regions as a significant source of tropospheric CH4 although large uncertainties remain. A major part of the uncertainty is that many important source regions remain at best only poorly investigated. One such region is the Congo River basin. Although recent satellite-derived measurements have highlighted the potentially large contribution of the Congo basin (25.7 ± 1.7 Tg CH4 y-1) to overall wetland emissions, political instability and limited infrastructure have severely inhibited in situ sampling of this region. Here we report surface water measurements of dissolved methane from a range of streams and rivers throughout a ˜ 260,600 km2 quadrant of the low-gradient central Congo basin collected in November 2010 and August 2011. We estimated regional CH4 emissions by partitioning the basin into distinct landcover types using satellite-derived estimates of seasonal water coverage and land-cover type. Scaling-up these estimates, we demonstrate that the Congo River basin, and in particular its wetland regions, are a globally significant atmospheric source of CH4. These wetland regions are now under threat from deforestation and degradation, highlighting the critical need for improved regional CH4 budgets to inform future policy decisions within the region.

  19. 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,

  20. A method for on-line measurement of wastewater organic substrate oxidation level during aerobic heterotrophic respiration.

    PubMed

    Rudelle, E A; Vollertsen, J; Hvitved-Jacobsen, T; Nielsen, A H

    2013-01-01

    A method for on-line measurement of the organic carbon oxidation level (OXC) during aerobic heterotrophic respiration in domestic wastewater was developed and tested. The method is based on batch incubation of sewer wastewater in an intermittently aerated respirometric reactor. Between aeration cycles, measured pH, dissolved oxygen (DO) and dissolved carbon dioxide (CO2) were used to calculate electron flow accepted by DO and the resulting production of dissolved inorganic carbon (DIC). The CO2 production was measured using a novel fiber-optic sensor based on luminescence quenching. The method was tested on domestic wastewater with a relatively high pH and alkalinity. From the DO and DIC measurements, it was possible to evaluate substrate oxidation levels with a temporal resolution of less than an hour. Addition of organic substrates during the experiments confirmed the method's applicability. The substrates tested included ethanol (OXC = -2), glucose (OXC = 0) and oxalic acid (OXC = 3).

  1. Surface-active ionic liquids in catalysis: Impact of structure and concentration on the aerobic oxidation of octanol in water.

    PubMed

    Cognigni, Alice; Kampichler, Sebastian; Bica, Katharina

    2017-04-15

    We present design and synthesis of surface-active ionic liquids for the application in micellar catalysis. A series of 1-methyl-3-dodecylimidazolium based ionic liquids with variable core structures including dicationic and zwitterionic ones was synthesized and characterized. These surface-active ionic liquids where applied in the aerobic oxidation of aliphatic alcohols to carbonyl compounds. A strong dependence on the ionic liquid concentration and structure was identified, which is in accordance with the concepts of micellar catalysis. Optimum conditions for the oxidation of 1-octanol could be identified, and the use of surface-active ionic liquids strongly improved the reaction performance compared to pure water. Under optimized conditions, it was possible to isolate up to 75% of octanoic acid using only small amounts of surface-active ionic liquid in a 0.05mM solution in water without further ligands.

  2. 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.

  3. 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.

  4. 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.

  5. 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).

  6. Measurement and analysis of the far infrared absorption spectrum of the gaseous mixture H2-CH4

    NASA Technical Reports Server (NTRS)

    Birnbaum, George; Borysow, Aleksandra; Sutter, Herbert G.

    1987-01-01

    The collision-induced absorption of H2-CH4 mixtures was measured from 20 to 900/cm at 195 and 297 K. By subtracting the absorption due to H2-H2 and CH4-CH4 collisions from that of the mixture, the absorption due to H2-CH4 collisions was obtained. This spectrum was analyzed using the BC model line shape to provide a way of estimating the far-IR spectrum of H2-CH4 for various concentrations of H2 and CH4. Theoretical spectral moments were computed with different potential functions and compared with experimental values.

  7. A 3D microporous covalent organic framework with exceedingly high C3H8/CH4 and C2 hydrocarbon/CH4 selectivity.

    PubMed

    Ma, Heping; Ren, Hao; Meng, Shuang; Yan, Zhuojun; Zhao, Huanyu; Sun, Fuxing; Zhu, Guangshan

    2013-10-28

    Here we present a new 3D microporous COF with a uniform pore size (0.64 nm). MCOF-1 exhibits high adsorption selectivity towards C3H8, C2H6 and C2H4 over CH4 owing to the pore size and preferential adsorption.

  8. 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.; Thompson, C.; Ilton, E. S.; McGrail, B. P.; Schaef, T.

    2014-12-01

    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 a Na-saturated montmorillonite (Na-SWy-2) in high-pressure (90 bar) and moderate temperature (50 °C) methane and mixtures of methane and carbon dioxide were investigated usingCH4 IR spectroscopic titrations andCH4 XRD. The goals were to (1) determine if the hydration/expansion behavior of the clay in supercritical methane is different than in supercritical CO2, (2) determine if methane intercalates the clay, and (3) probe the effects of increasing CO2 concentrations. IR spectra were collected as Na-SWy-2 was titrated with water under several fluid exposures: pure methane, 25, 50, and 75 mole% CO2 in methane, and pure CO2. ComplementaryCH4 XRD experiments were conducted in the same fluids at discrete dissolved water concentrations to measure the d001 values of the clay and thus its volume change on hydration and CH4 and/or CO2 intercalation. In pure methane, no direct evidence of CH4 intercalation was detected in CH bending or stretching regions of the IR spectra. Similarly, in situ XRD indicated the montmorillonite structure was stable in the presence of CH4 and no measurable changes to the basal spacing were observed. However, under low water conditions where the montmorillonite structure was partially expanded (~sub 1W), the IR data indicated a rapid intercalation of CO2 into the interlayer, even with fluid mixtures containing the

  9. 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.

  10. 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.

  11. 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

  12. 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.

  13. 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.

  14. Comparison of in situ N2O and CH4 measurements in the upper troposphere and lower stratosphere during STRAT and POLARIS

    NASA Astrophysics Data System (ADS)

    Hurst, D. F.; Dutton, G. S.; Romashkin, P. A.; Elkins, J. W.; Herman, R. L.; Moyer, E. J.; Scott, D. C.; May, R. D.; Webster, C. R.; Grecu, J.; Loewenstein, M.; Podolske, J. R.

    2000-08-01

    Nitrous oxide (N2O) and methane (CH4) were measured in the upper troposphere and lower stratosphere by multiple instruments aboard the NASA ER-2 aircraft during the 1995-1996 Stratospheric Tracers of Atmospheric Transport (STRAT) and 1997 Photochemistry of Ozone Loss in the Arctic Region in Summer (POLARIS) campaigns. Differences between coincidental, in situ measurements are examined to evaluate the agreement and variability in the agreement between these instruments during each flight. Mean N2O measurement differences for each flight were much smaller than limits calculated from quoted values of N2O measurement accuracy and for all but two flights were ≤8.7 ppb (3.5%). Mean CH4 measurement differences for flights were similarly much smaller than calculated limits and for all but three flights were ≤65 ppb (4.4%). Typical agreement between instruments during flights averaged 6.2 ppb (2.5%) for N2O and 43 ppb (2.9%) for CH4. In contrast, for about half of the flights, the variability of N2O and CH4 measurement differences exceeded limits calculated from quoted values of measurement precision. The typical measurement difference variability (1σ) during a flight averaged ±8.0 ppb (3.2%) for N2O and ±43 ppb (2.9%) for CH4. For some flights, large differences or variations in differences are attributable to the poor measurement accuracy or precision of one instrument. It is demonstrated that small offsets between the computer clocks of these instruments can result in significant differences between their "coincidental" N2O and CH4 data, especially when there is high spatial variability in tracer abundance along a flight track.

  15. Valorization of CH4 emissions into high-added-value products: Assessing the production of ectoine coupled with CH4 abatement.

    PubMed

    Cantera, Sara; Lebrero, Raquel; Sadornil, Lidia; García-Encina, Pedro A; Muñoz, Raúl

    2016-11-01

    This study assessed an innovative strategy for the valorization of dilute methane emissions based on the bio-conversion of CH4 (the second most important greenhouse gas (GHG)) into ectoine by the methanotrophic ectoine-producing strain Methylomicrobium alcaliphilum 20 Z. The influence of CH4 (2-20%), Cu(2+) (0.05-50 μM) and NaCl (0-9%) concentration as well as temperature (25-35 °C) on ectoine synthesis and specific CH4 biodegradation rate was evaluated for the first time. Concentrations of 20% CH4 (at 3% NaCl, 0.05 μM Cu(2+), 25 °C) and 6% NaCl (at 4% CH4, 0.05 μM Cu(2+), 25 °C) supported the maximum intra-cellular ectoine production yield (31.0 ±1.7 and 66.9 ±4.2 mg g biomass(-1), respectively). On the other hand, extra-cellular ectoine concentrations of up to 4.7 ± 0.1 mg L(-1) were detected at high Cu(2+)concentrations (50 μM), despite this methanotroph has not been previously classified as an ectoine-excreting strain. This research demonstrated the feasibility of the bio-conversion of dilute emissions of methane into high-added value products in an attempt to develop a sustainable GHG bioeconomy.

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

    NASA Astrophysics Data System (ADS)

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

    2015-08-01

    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.

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

    PubMed

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

    2015-08-24

    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.

  18. 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

  19. A pan-Arctic synthesis of CH4 and CO2 production from anoxic soil incubations

    USGS Publications Warehouse

    Treat, C.C.; Natali, Susan 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

  20. CH4 and N2O dynamics in the boreal forest-mire ecotone

    NASA Astrophysics Data System (ADS)

    Tupek, B.; Minkkinen, K.; Pumpanen, J.; Vesala, T.; Nikinmaa, E.

    2015-01-01

    In spite of advances in greenhouse gas research, the spatiotemporal CH4 and N2O dynamics of boreal landscapes remain challenging, e.g., we need clarification of whether forest-mire transitions are occasional hotspots of landscape CH4 and N2O emissions during exceptionally high and low ground water level events. In our study, we tested the differences and drivers of CH4 and N2O dynamics of forest/mire types in field conditions along the soil moisture gradient of the forest-mire ecotone. Soils changed from Podzols to Histosols and ground water rose downslope from a depth of 10 m in upland sites to 0.1 m in mires. Yearly meteorological conditions changed from being exceptionally wet to typical and exceptionally dry for the local climate. The median fluxes measured with a static chamber technique varied from -51 to 586 μg m-2 h-1 for CH4 and from 0 to 6 μg m-2 h-1 for N2O between forest and mire types throughout the entire wet-dry period. In spite of the highly dynamic soil water fluctuations in carbon rich soils in forest-mire transitions, there were no large peak emissions in CH4 and N2O fluxes and the flux rates changed minimally between years. Methane uptake was significantly lower in poorly drained transitions than in the well-drained uplands. Water-saturated mires showed large CH4 emissions, which were reduced entirely during the exceptional summer drought period. Near-zero N2O fluxes did not differ significantly between the forest and mire types probably due to their low nitrification potential. When upscaling boreal landscapes, pristine forest-mire transitions should be regarded as CH4 sinks and minor N2O sources instead of CH4 and N2O emission hotspots.

  1. 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.

  2. Ozone oxidation and aerobic biodegradation with spent mushroom compost for detoxification and benzo(a)pyrene removal from contaminated soil.

    PubMed

    Russo, Lara; Rizzo, Luigi; Belgiorno, Vincenzo

    2012-05-01

    The combination of ozonation and spent mushroom compost (SMC)-mediated aerobic biological treatment was investigated in the removal of benzo(a)pyrene from contaminated soil. The performances of the process alone and combined were evaluated in terms of benzo(a)pyrene removal efficiency, mineralization efficiency (as total organic carbon removal), and soil residual toxicity (phytotoxicity to Lepidium Sativum and toxicity to Vibrio fischeri). In spite of the removal efficiency (35%) obtained by SMC-mediated biological process as a stand-alone treatment, the combined process showed a benzo(a)pyrene concentration reduction higher than 75%; the best removal (82%) was observed after 10 min pre-ozonation treatment. In particular, ozonation improved the biodegradability of the contaminant, as confirmed by the increase of CO(2) production (close to 70% compared to the control), mineralization (greater than 60%) and bacterial density (which increased by two orders of magnitude). Moreover, according to phytotoxicity tests on L. Sativum, the aerobic biological process of pre-ozonated soil decreased toxicity. According to the results achieved in the present study, ozonation pre-treatment showed an high potential to overcome the limitation of bioremediation of recalcitrant compound, but it should be carefully operated in order to maximize PAH removal efficiency as well as to minimize soil residual toxicity which can result from the formation of the oxidation intermediates.

  3. 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

  4. Evaluation of origins of CH4 carbon emitted from rice paddies

    NASA Astrophysics Data System (ADS)

    Watanabe, Akira; Takeda, Takuya; Kimura, Makoto

    1999-10-01

    Possible carbon sources for CH4 emitted from rice paddies are organic matter applied to the fields, such as rice straw (RS), soil organic matter (SOM), and carbon supplied from rice plants (RP), such as exudates and sloughed tissues. To estimate the contribution of each carbon source to CH4 emission, a pot experiment was conducted using 13C-enriched soil sample and 13C-enriched RS as tracers. The percentage contribution of RP carbon was estimated by subtraction. When RS was applied at a rate corresponding to 6 t ha-1, the percentage contributions of RS, SOM, and RP carbon to CH4 emission throughout the period of rice growth were 42%, 18-21%, and 37-40%, respectively. The values for SOM and RP carbon for the treatment in which RS was not applied were 15-20% and 80-85%, respectively. Seasonal variations in the percentage contribution of soil organic carbon to CH4 emission were small in the range between 13% and 30% for the pots with RS and between 15% and 24% for the pots without RS. In the RS-applied treatment, RS and SOM accounted for almost 100% of the CH4 carbon early in the period of rice growth, while 65-70% of the CH4 emission in the milky stage was derived from RP carbon.

  5. Hotspots of N2O and CH4 emissions in tropical ecosystems

    NASA Astrophysics Data System (ADS)

    Castaldi, Simona; Bertolini, Teresa; Santini, Monia; Thongo M'Bou, Armel; De Grandcourt, Agnes; Nicolini, Giacomo; Valentini, Riccardo

    2013-04-01

    At global level, tropics represent the strongest biogenic source of N2O and CH4, with natural ecosystems having a comparable or even dominant role, in terms of source strength, respect to agro-ecosystems. The uncertainty related to both sources is very high, due to the paucity of data and small frequency of sampling in tropical studies. We present data of ongoing measurements of N2O and CH4 fluxes from tropical areas of the African continent spanning from savannas to humid forests and ephemeral wetlands. Natural and managed sites are also compared. A budget at African continental level is presented based on empirical relationships derived from a reanalysis of experimental published studies. Data show that humid tropical forests are the strongest N2O terrestrial source. Both spatial and temporal variability seem to be mainly driven by organic matter inputs. At Regional level annual N2O production follows a sigmoid distribution with rainfall, a key drivers of NPP. In presence of land conversion, agro-ecosystems are significant sources of N2O in the first year following deforestation, but after 10-15 years they strongly reduce their emissions compared with primary forests. Wetlands are the strongest source of CH4 but humid forests, when analysed at landscape level, present lowland hotspots of CH4 emissions which counterbalance the CH4 sink of upland areas. Also the CH4 sink from seasonally dry areas seems weaker than previous estimates.

  6. Column Averaged CO2, CH4, and CO Mixing Ratios at ARM-SGP

    NASA Astrophysics Data System (ADS)

    Fischer, M. L.; Wunch, D.; Biraud, S.; Abshire, J. B.; Blavier, J. L.; Keppel-Aleks, G.; Kulawik, S. S.; Miller, C. E.; Roehl, C. M.; Payne, V.; Sweeney, C.; Smith, J.; Toon, G. C.; Torn, M. S.; Wennberg, P. O.

    2009-12-01

    We report column-averaged measurements of CO2, CH4, and CO made at the ARM Climate Research Facility in the Southern Great Plains (36.6053 N, 97.4891 W), near Lamont, Oklahoma, USA. Data include multi-year records of midday near-surface (60 m) CO2 and CO mixing ratios, periodic continuous CO2, and flask CO2, CH4, and CO profiles (to ~ 5 km) from a small aircraft, a limited number of flask profiles (to ~ 12 km) from a NASA Lear 25, column CO2, CH4, and CO retrievals made with a sun-tracking Fourier transform spectrometer (FTS) deployed at the SGP site, and estimates of CO2, CH4, and CO from the Tropospheric Emission Spectrometer (TES) on the NASA Aura spacecraft. We compare aircraft measurements with prototype TES retrievals of CO2, TES representative tropospheric values of CH4, and TES CO profile values. We then compare the column-average mixing ratios with the FTS retrievals, and examine the differences in each comparison for seasonality. These results provide an initial evaluation of the TES and FTS retrievals at the ARM-SGP and prepare for future evaluation of CO2 and CH4 retrievals from future satellite missions including GOSAT.

  7. Relationship between environmental variables and CH4 fluxes in sub-Boreal peatlands

    NASA Astrophysics Data System (ADS)

    Pypker, T. G.; Moore, P. A.; Waddington, J. M.; Chimner, R. A.; Hribljan, J. A.

    2012-12-01

    Peatlands are a critical component in the global carbon (C) cycle because they have been slowly sequestering atmospheric greenhouse gases as peat since the last glaciation. Today, soil C stocks in peatlands are estimated to represent 224 to 455 Pg, equal to 12-30% of the global soil C pool. At present, peatlands are estimated to sequester 76 Tg C yr-1. The flux of C from peatlands is likely to respond to climate change, thereby influencing atmospheric C concentrations. We explored the relationship between ecosystem CO2 exchange, CH4 emissions and weather from May to November 2011 using the eddy covariance method. The peatland was located in the Seney National Wildlife Refuge in the Upper Peninsula of Michigan. During the study period, CO2 and CH4 fluxes ranged between -7.7 to 3.44 g CO2 m-2 d-1 and 0.01 to 0.21 nmol CH4 m-2 d-1, respectively. Both CO2 uptake and CH4 losses peaked in early July and were lowest in early May and late September. To better understand the environmental mechanisms controlling CH4 emissions, changes in CH4 fluxes were related to changes in temperature, precipitation, water table height and CO2 uptake.

  8. 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.

  9. CH4 combustion cycles at Pd/Al2O3--important role of support and oxygen access.

    PubMed

    Czekaj, Izabela; Kacprzak, Katarzyna A; Mantzaras, John

    2013-07-21

    This research is focused on the analysis of adsorbed CH4 intermediates at oxidized Pd9 nanoparticles supported on γ-alumina. From first-principle density functional theory calculations, several configurations, charge transfer and electronic density of states have been analyzed in order to determine feasible paths for the oxidation process. Methane oxidation cycles have been considered as a further step at differently oxidized Pd nanoparticles. For low oxidized Pd nanoparticles, activation of methane is observed, whereby hydrogen from methane is adsorbed at one oxygen atom. This reaction is exothermic with adsorption energy equal to -0.38 eV. In a subsequent step, desorption of two water molecules is observed. Additionally, a very interesting structural effect is evident, mainly Pd-carbide formation, which is also an exothermic reaction with an energy of -0.65 eV. Furthermore, oxidation of such carbidized Pd nanoparticles leads to CO2 formation, which is an endothermic reaction. Important result is that the support is involved in CO2 formation. A different mechanism of methane oxidation has been found for highly oxidized Pd nanoparticles. When the Pd nanoparticle is more strongly exposed to oxidative conditions, adsorption of methane is also possible, but it will proceed with carbonic acid production at the interface between Pd nanoparticles and support. However, this step is endothermic.

  10. 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.

  11. 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.

  12. 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

  13. Nickel-Catalyzed Aerobic Oxidative Isocyanide Insertion: Access to Benzimidazoquinazoline Derivatives via a Sequential Double Annulation Cascade (SDAC) Strategy.

    PubMed

    Shinde, Anand H; Arepally, Sagar; Baravkar, Mayur D; Sharada, Duddu S

    2017-01-06

    An efficient protocol for the synthesis of quinazoline derivatives through nickel-catalyzed ligand-/base-free oxidative isocyanide insertion under aerobic conditions with intramolecular bis-amine nucleophiles has been developed. A one-pot sequential double annulation cascade (SDAC) strategy involving an opening of isatoic anhydride and annulation to benzimidazole and further nickel-catalyzed intramolecular isocyanide insertion has also been demonstrated. The method is operationally simple to implement with a wide variety of substrates and represents a new approach for multiple C-N bond formations. The methodology has been successfully applied to the syntheses of hitherto unreported imidazo-fused benzimidazoquinazolines via a deprotection-GBB reaction sequence. Further, a florescence study reveals the potential of the present strategy for the discovery of highly fluorescent probes.

  14. Aerobic Oxidation of Cyclohexane on Catalysts Based on Twinned and Single-Crystal Au75Pd25 Bimetallic Nanocrystals.

    PubMed

    Wang, Liangbing; Zhao, Songtao; Liu, Chenxuan; Li, Chen; Li, Xu; Li, Hongliang; Wang, Youcheng; Ma, Chao; Li, Zhenyu; Zeng, Jie

    2015-05-13

    Bimetallic Au75Pd25 nanocrystals with shapes of icosahedron and octahedron were synthesized by adding different amounts of iodide ions, and were employed as catalysts for solvent-free aerobic oxidation of cyclohexane. Although both icosahedrons and octahedrons were bounded by {111} facets, the turnover frequency number of Au75Pd25 icosahedrons reached 15,106 h(-1), almost three times as high as that of Au75Pd25 octahedrons. The conversion of cyclohexane reached 28.1% after 48 h using Au75Pd25 icosahedrons, with the selectivity of 84.3% to cyclohexanone. Density functional theory calculations along with X-ray photoelectron spectroscopy examinations reveal that the excellent catalytic performance of AuPd icosahedrons could be ascribed to twin-induced strain and highly negative charge density of Au atoms on the surface.

  15. 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

  16. 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

  17. L-Proline: an efficient N,O-bidentate ligand for copper-catalyzed aerobic oxidation of primary and secondary benzylic alcohols at room temperature.

    PubMed

    Zhang, Guofu; Han, Xingwang; Luan, Yuxin; Wang, Yong; Wen, Xin; Ding, Chengrong

    2013-09-18

    A novel and highly practical copper-catalyzed aerobic alcohol oxidation system with L-proline as the ligand at room temperature has been developed. A wide range of primary and secondary benzylic alcohols tested have been smoothly transformed into corresponding aldehydes and ketones with high yields and selectivities.

  18. 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.

  19. 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.

  20. 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.

  1. Highly efficient aerobic oxidation of alcohols by using less-hindered nitroxyl-radical/copper catalysis: optimum catalyst combinations and their substrate scope.

    PubMed

    Sasano, Yusuke; Kogure, Naoki; Nishiyama, Tomohiro; Nagasawa, Shota; Iwabuchi, Yoshiharu

    2015-04-01

    The oxidation of alcohols into their corresponding carbonyl compounds is one of the most fundamental transformations in organic chemistry. In our recent report, 2-azaadamantane N-oxyl (AZADO)/copper catalysis promoted the highly chemoselective aerobic oxidation of unprotected amino alcohols into amino carbonyl compounds. Herein, we investigated the extension of the promising AZADO/copper-catalyzed aerobic oxidation of alcohols to other types of alcohol. During close optimization of the reaction conditions by using various alcohols, we found that the optimum combination of nitroxyl radical, copper salt, and solution concentration was dependent on the type of substrate. Various alcohols, including highly hindered and heteroatom-rich ones, were efficiently oxidized into their corresponding carbonyl compounds under mild conditions with lower amounts of the catalysts.

  2. 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

  3. Version 1.3 AIM SOFIE measured methane (CH4): Validation and seasonal climatology

    NASA Astrophysics Data System (ADS)

    Rong, P. P.; Russell, J. M.; Marshall, B. T.; Siskind, D. E.; Hervig, M. E.; Gordley, L. L.; Bernath, P. F.; Walker, K. A.

    2016-11-01

    The V1.3 methane (CH4) measured by the Aeronomy of Ice in the Mesosphere (AIM) Solar Occultation for Ice Experiment (SOFIE) instrument is validated in the vertical range of 25-70 km. The random error for SOFIE CH4 is 0.1-1% up to 50 km and degrades to 9% at ˜ 70 km. The systematic error remains at 4% throughout the stratosphere and lower mesosphere. Comparisons with CH4 data taken by the SCISAT Atmospheric Chemistry Experiment-Fourier Transform Spectrometer (ACE-FTS) and the Envisat Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) show an agreement within 15% in the altitude range 30-60 km. Below 25 km SOFIE CH4 is systematically higher (≥20%), while above 65 km it is lower by a similar percentage. The sign change from the positive to negative bias occurs between 55 km and 60 km (or 40 km and 45 km) in the Northern (or Southern) Hemisphere. Methane, H2O, and 2CH4 + H2O yearly differences from their values in 2009 are examined using SOFIE and MIPAS CH4 and the Aura Microwave Limb Sounder (MLS) measured H2O. It is concluded that 2CH4 + H2O is conserved with altitude up to an upper limit between 35 km and 50 km depending on the season. In summer this altitude is higher. In the Northern Hemisphere the difference relative to 2009 is the largest in late spring and the established difference prevails throughout summer and fall, suggesting that summer and fall are dynamically quiet. In both hemispheres during winter there are disturbances (with a period of 1 month) that travel downward throughout the stratosphere with a speed similar to the winter descent.

  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. Bottom-up estimates of CH4 emissions from northern thaw lakes: modern and paleo- perspectives

    NASA Astrophysics Data System (ADS)

    Walter, K. M.; Edwards, M.; Zimov, S.; Schuur, T.; Chapin, F.

    2006-12-01

    Here we describe and quantify an important source of atmospheric methane (CH4)— ebullition (bubbling) from northern lakes— that has not been incorporated in previous regional or global CH4 budgets. Using multiple bottom-up approaches we (1) Introduce a new method to quantify the patchiness of ebullition by direct measurement of bubbling point sources and hotspots, thereby increasing previous estimates of CH4 flux from lakes 5-fold in Siberia and 2.5- to 14-fold in Alaska; (2) Weight stable and radiocarbon isotope signatures of different types of ebullition (maximum 14CCH4 age of hotspots 43,000 yrs; whole lake average 16,500 yrs) demonstrating that ebullition patchiness influences estimates of regional isofluxes and that Pleistocene-age organic matter released from thawing permafrost fuels methanogenesis; (3) Use an independent mass-balance approach based on carbon lost from permafrost that thawed beneath lakes to confirm the measured flux estimate in Siberia; and (4) Verify the magnitude of lake CH4 emissions based on CH4 production potentials of organic matter from Pleistocene-aged frozen sediments. Furthermore, we apply these techniques together with a compilation of thaw lake basal ages to show that thaw lake development, a previously unrecognized source, contributed up to 70% of the rapid increase in northern sources of atmospheric CH4 recorded in ice cores during deglaciation. Given the large amount of carbon still present in Siberian permafrost (500 Gt), we predict that tens of thousands of Tg of CH4 will be released in the future from thaw lakes.

  6. CH4 concentrations over the Amazon from GOSAT consistent with in situ vertical profile data

    NASA Astrophysics Data System (ADS)

    Webb, Alex J.; Bösch, Hartmut; Parker, Robert J.; Gatti, Luciana V.; Gloor, Emanuel; Palmer, Paul I.; Basso, Luana S.; Chipperfield, Martyn P.; Correia, Caio S. C.; Domingues, Lucas G.; Feng, Liang; Gonzi, Siegfried; Miller, John B.; Warneke, Thorsten; Wilson, Christopher

    2016-09-01

    The Amazon Basin contains large wetland ecosystems which are important sources of methane (CH4). Spaceborne observations of atmospheric CH4 can provide constraints on emissions from these remote ecosystems, but lack of validation precludes robust estimates. We present the first validation of CH4 columns in the Amazon from the Greenhouse gases Observing SATellite (GOSAT) using aircraft measurements of CH4 over five sites across the Amazon Basin. These aircraft profiles, combined with stratospheric results from the TOMCAT chemical transport model, are vertically integrated allowing direct comparison to the GOSAT XCH4 measurements (the column-averaged dry air mole fraction of CH4). The measurements agree within uncertainties or show no significant difference at three of the aircraft sites, with differences ranging from -1.9 ppb to 6.6 ppb, while at two sites GOSAT XCH4 is shown to be slightly higher than aircraft measurements, by 8.1 ppb and 9.7 ppb. The seasonality in XCH4 seen by the aircraft profiles is also well captured (correlation coefficients from 0.61 to 0.90). GOSAT observes elevated concentrations in the northwest corner of South America in the dry season and enhanced concentrations elsewhere in the Amazon Basin in the wet season, with the strongest seasonal differences coinciding with regions in Bolivia known to contain large wetlands. Our results are encouraging evidence that these GOSAT CH4 columns are generally in good agreement with in situ measurements, and understanding the magnitude of any remaining biases between the two will allow more confidence in the application of XCH4 to constrain Amazonian CH4 fluxes.

  7. 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

    2012-08-04

    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.

  8. 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.

  9. 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.

  10. Experimental warming of a mountain tundra increases soil CO2 effluxes and enhances CH4 and N2O uptake at Changbai Mountain, China.

    PubMed

    Zhou, Yumei; Hagedorn, Frank; Zhou, Chunliang; Jiang, Xiaojie; Wang, Xiuxiu; Li, Mai-He

    2016-02-16

    Climatic warming is expected to particularly alter greenhouse gas (GHG) emissions from soils in cold ecosystems such as tundra. We used 1 m(2) 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(-2)h(-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.

  11. 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.

  12. 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

  13. 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

  14. 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

  15. 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

  16. 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

  17. The history of aerobic ammonia oxidizers: from the first discoveries to today.

    PubMed

    Monteiro, Maria; Séneca, Joana; Magalhães, Catarina

    2014-07-01

    Nitrification, the oxidation of ammonia to nitrite and nitrate, has long been considered a central biological process in the global nitrogen cycle, with its first description dated 133 years ago. Until 2005, bacteria were considered the only organisms capable of nitrification. However, the recent discovery of a chemoautotrophic ammonia-oxidizing archaeon, Nitrosopumilus maritimus, changed our concept of the range of organisms involved in nitrification, highlighting the importance of ammonia-oxidizing archaea (AOA) as potential players in global biogeochemical nitrogen transformations. The uniqueness of these archaea justified the creation of a novel archaeal phylum, Thaumarchaeota. These recent discoveries increased the global scientific interest within the microbial ecology society and have triggered an analysis of the importance of bacterial vs archaeal ammonia oxidation in a wide range of natural ecosystems. In this mini review we provide a chronological perspective of the current knowledge on the ammonia oxidation pathway of nitrification, based on the main physiological, ecological and genomic discoveries.

  18. 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.

  19. 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.

  20. 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.

  1. Multiproperty empirical isotropic interatomic potentials for CH4-inert gas mixtures.

    PubMed

    El-Kader, M S A

    2013-11-01

    An approximate empirical isotropic interatomic potentials for CH4-inert gas mixtures are developed by simultaneously fitting the Exponential-Spline-Morse-Spline-van der Waals (ESMSV) potential form to viscosity, thermal conductivity, thermal diffusion factors, diffusion coefficient, interaction second pressure virial coefficient and scattering cross-section data. Quantum mechanical lineshapes of collision-induced absorption (CIA) at different temperatures for CH4-He and at T = 87 K for CH4-Ar are computed using theoretical values for overlap, octopole and hexadecapole mechanisms and interaction potential as input. Also, the quantum mechanical lineshapes of collision-induced light scattering (CILS) for the mixtures CH4-Ar and CH4-Xe at room temperature are calculated. The spectra of scattering consist essentially of an intense, purely translational component which includes scattering due to free pairs and bound dimers, and the other is due to the induced rotational scattering. These spectra have been interpreted by means of pair-polarizability terms, which arise from a long-range dipole-induced-dipole (DID) with small dispersion corrections and a short-range interaction mechanism involving higher-order dipole-quadrupole A and dipole-octopole E multipole polarizabilities. Good agreement between computed and experimental lineshapes of both absorption and scattering is obtained when the models of potential, interaction-induced dipole and polarizability components are used.

  2. Insights into the structure of mixed CO2/CH4 in gas hydrates

    DOE PAGES

    Everett, S. Michelle; Rawn, Claudia J.; Chakoumakos, Bryan C.; ...

    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

  3. 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.

  4. 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

  5. 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.

  6. Archaea produce lower yields of N2 O than bacteria during aerobic ammonia oxidation in soil.

    PubMed

    Hink, Linda; Nicol, Graeme W; Prosser, James I

    2016-03-11

    Nitrogen fertilisation of agricultural soil contributes significantly to emissions of the potent greenhouse gas nitrous oxide (N2 O), which is generated during denitrification and, in oxic soils, mainly by ammonia oxidisers. Although laboratory cultures of ammonia oxidising bacteria (AOB) and archaea (AOA) produce N2 O, their relative activities in soil are unknown. This work tested the hypothesis that AOB dominate ammonia oxidation and N2 O production under conditions of high inorganic ammonia (NH3 ) input, but result mainly from the activity of AOA when NH3 is derived from mineralisation. 1-octyne, a recently discovered inhibitor of AOB, was used to distinguish N2 O production resulting from archaeal and bacterial ammonia oxidation in soil microcosms, and specifically inhibited AOB growth, activity and N2 O production. In unamended soils, ammonia oxidation and N2 O production were lower and resulted mainly from ammonia oxidation by AOA. The AOA N2 O yield relative to nitrite produced was half that of AOB, likely due to additional enzymatic mechanisms in the latter, but ammonia oxidation and N2 O production were directly linked in all treatments. Relative contributions of AOA and AOB to N2 O production, therefore, reflect their respective contributions to ammonia oxidation. These results suggest potential mitigation strategies for N2 O emissions from fertilised agricultural soils.

  7. CH4 and N2O emissions embodied in international trade of meat

    NASA Astrophysics Data System (ADS)

    Caro, Dario; LoPresti, Anna; Davis, Steven J.; Bastianoni, Simone; Caldeira, Ken

    2014-11-01

    Although previous studies have quantified carbon dioxide emissions embodied in products traded internationally, there has been limited attention to other greenhouse gases such as methane (CH4) and nitrous oxide (N2O). Following IPCC guidelines, we estimate non-CO2 emissions from beef, pork and chicken produced in 237 countries over the period 1990-2010, and assign these emissions to the country where the meat is ultimately consumed. We find that, between 1990 and 2010, an average of 32.8 Mt CO2-eq emissions (using 100 year global warming potentials) are embodied in beef, pork and chicken traded internationally. Further, over the 20 year period, the quantity of CO2-eq emissions embodied in traded meat increased by 19%. The largest trade flows of emissions embodied in meat were from Brazil and Argentina to Russia (2.8 and 1.4 Mt of CO2-eq, respectively). Trade flows within the European region are also substantial: beef and pork exported from France embodied 3.3 Mt and 0.4 Mt of CO2-eq, respectively. Emissions factor of meat production (i.e. CO2-eq emissions per kg of meat) produced depend on ambient temperature, development level, livestock category (e.g. cattle, pork, and chicken) and livestock management practices. Thus, trade may result in an overall increase of GHG emissions when meat-consuming countries import meat from countries with a greater emissions intensity of meat production rather than producing the meat domestically. Comparing the emissions intensity of meat production of trading partners, we assess trade flows according to whether they tend to reduce or increase global emissions from meat production.

  8. Biogeochemical modeling of CO2 and CH4 production in anoxic Arctic soil microcosms

    NASA Astrophysics Data System (ADS)

    Tang, Guoping; Zheng, Jianqiu; Xu, Xiaofeng; Yang, Ziming; Graham, David E.; Gu, Baohua; Painter, Scott L.; Thornton, Peter E.

    2016-09-01

    Soil organic carbon turnover to CO2 and CH4 is sensitive to soil redox potential and pH conditions. However, land surface models do not consider redox and pH in the aqueous phase explicitly, thereby limiting their use for making predictions in anoxic environments. Using recent data from incubations of Arctic soils, we extend the Community Land Model with coupled carbon and nitrogen (CLM-CN) decomposition cascade to include simple organic substrate turnover, fermentation, Fe(III) reduction, and methanogenesis reactions, and assess the efficacy of various temperature and pH response functions. Incorporating the Windermere Humic Aqueous Model (WHAM) enables us to approximately describe the observed pH evolution without additional parameterization. Although Fe(III) reduction is normally assumed to compete with methanogenesis, the model predicts that Fe(III) reduction raises the pH from acidic to neutral, thereby reducing environmental stress to methanogens and accelerating methane production when substrates are not limiting. The equilibrium speciation predicts a substantial increase in CO2 solubility as pH increases, and taking into account CO2 adsorption to surface sites of metal oxides further decreases the predicted headspace gas-phase fraction at low pH. Without adequate representation of these speciation reactions, as well as the impacts of pH, temperature, and pressure, the CO2 production from closed microcosms can be substantially underestimated based on headspace CO2 measurements only. Our results demonstrate the efficacy of geochemical models for simulating soil biogeochemistry and provide predictive understanding and mechanistic representations that can be incorporated into land surface models to improve climate predictions.

  9. Biogeochemical modeling of CO2 and CH4 production in anoxic Arctic soil microcosms

    DOE PAGES

    Tang, Guoping; Zheng, Jianqiu; Xu, Xiaofeng; ...

    2016-09-12

    Soil organic carbon turnover to CO2 and CH4 is sensitive to soil redox potential and pH conditions. However, land surface models do not consider redox and pH in the aqueous phase explicitly, thereby limiting their use for making predictions in anoxic environments. Using recent data from incubations of Arctic soils, we extend the Community Land Model with coupled carbon and nitrogen (CLM-CN) decomposition cascade to include simple organic substrate turnover, fermentation, Fe(III) reduction, and methanogenesis reactions, and assess the efficacy of various temperature and pH response functions. Incorporating the Windermere Humic Aqueous Model (WHAM) enables us to approximately describe themore » observed pH evolution without additional parameterization. Although Fe(III) reduction is normally assumed to compete with methanogenesis, the model predicts that Fe(III) reduction raises the pH from acidic to neutral, thereby reducing environmental stress to methanogens and accelerating methane production when substrates are not limiting. The equilibrium speciation predicts a substantial increase in CO2 solubility as pH increases, and taking into account CO2 adsorption to surface sites of metal oxides further decreases the predicted headspace gas-phase fraction at low pH. Without adequate representation of these speciation reactions, as well as the impacts of pH, temperature, and pressure, the CO2 production from closed microcosms can be substantially underestimated based on headspace CO2 measurements only. Our results demonstrate the efficacy of geochemical models for simulating soil biogeochemistry and provide predictive understanding and mechanistic representations that can be incorporated into land surface models to improve climate predictions.« less

  10. 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.

  11. The effects of periodized concurrent and aerobic training on oxidative stress parameters, endothelial function and immune response in sedentary male individuals of middle age.

    PubMed

    Schaun, Maximiliano Isoppo; Dipp, Thiago; Rossato, Juliane da Silva; Wilhelm, Eurico Nestor; Pinto, Ronei; Rech, Anderson; Plentz, Rodrigo Della Méa; Homem de Bittencourt, Paulo I; Reischak-Oliveira, Alvaro

    2011-10-01

    The vascular endothelium plays a key role in arterial wall homeostasis by preventing atherosclerotic plaque formation. A primary causal factor of endothelial dysfunction is the reactive oxygen species. Aerobic exercise is ascribed as an important adjuvant therapy in endothelium-dependent cardiovascular disease. However, little is known about the effects of concurrent (aerobic + strength) training on that. For a comparison of the effects of aerobic and concurrent physical training on endothelial function, oxidative stress parameters and the immunoinflammatory activity of monocytes/macrophages, 20 adult male volunteers of middle age were divided into a concurrent training (CT) programme group and an aerobic training group. The glutathione disulphide to glutathione ratio (GSSG/GSH) and plasma lipoperoxide (LPO) levels, as well as flow-mediated dilation (FMD), monocyte/macrophage functional activity (zymosan phagocytosis), body lipid profiles, aerobic capacity (maximal oxygen uptake) and strength parameters (one-repetition maximum test), were measured before and after the exercise training programmes. The CT exhibited reduced acute effects of exercise on the GSSG/GSH ratio, plasma LPO levels and zymosan phagocytosis. The CT also displayed improved lipid profiles, glycaemic control, maximal oxygen uptake and one-repetition maximum test values. In both the aerobic training and the CT, training improved the acute responses to exercise, as inferred from a decrease in the GSSG/GSH ratios. The aerobic sessions did not alter basal levels of plasma LPO or macrophage phagocytic activity but improved FMD values as well as lipid profiles and glycaemic control. In summary, both training programmes improve systemic redox status and antioxidant defences. However, the aerobic training was more efficient in improving FMD in the individuals studied.

  12. Influence of Polyoxometalate Protecting Ligands on Catalytic Aerobic Oxidation at the Surfaces of Gold Nanoparticles in Water.

    PubMed

    Zhang, Mingfu; Hao, Jingcheng; Neyman, Alevtina; Wang, Yifeng; Weinstock, Ira A

    2017-03-06

    Metal oxide cluster-anion (polyoxometalate, or POM) protecting ligands, [α-PW11O39](7-) (1), modify the rates at which 14 nm gold nanoparticles (Au NPs) catalyze an important model reaction, the aerobic (O2) oxidation of CO to CO2 in water. At 20 °C and pH 6.2, the following stoichiometry was observed: CO + O2 + H2O = CO2 + H2O2. After control experiments verified that the H2O2 product was sufficiently stable and did not react with 1 under turnover conditions, quantitative analysis of H2O2 was used to monitor the rates of CO oxidation, which increased linearly with the percent coverage of the Au NPs by 1 (0-64% coverage, with the latter value corresponding to 211 ± 19 surface-bound molecules of 1). X-ray photoelectron spectroscopy of Au NPs protected by a series of POM ligands (K(+) salts): 1, the Wells-Dawson ion [α-P2W18O62](6-) (2) and the monodefect Keggin anion [α-SiW11O39](8-) (3) revealed that binding energies of electrons in the Au 4f7/2 and 4f5/2 atomic orbitals decreased as a linear function of the POM charge and percent coverage of Au NPs, providing a direct correlation between the electronic effects of the POMs bound to the surfaces of the Au NPs and the rates of CO oxidation by O2. Additional data show that this effect is not limited to POMs but occurs, albeit to a lesser extent, when common anions capable of binding to Au-NP surfaces, such as citrate or phosphate, are present.

  13. Aerobic Lineage of the Oxidative Stress Response Protein Rubrerythrin Emerged in an Ancient Microaerobic, (Hyper)Thermophilic Environment.

    PubMed

    Cardenas, Juan P; Quatrini, Raquel; Holmes, David S

    2016-01-01

    Rubrerythrins (RBRs) are non-heme di-iron proteins belonging to the ferritin-like superfamily. They are involved in oxidative stress defense as peroxide scavengers in a wide range of organisms. The vast majority of RBRs, including classical forms of this protein, contain a C-terminal rubredoxin-like domain involved in electron transport that is used during catalysis in anaerobic conditions. Rubredoxin is an ancient and large protein family of short length (<100 residues) that contains a Fe-S center involved in electron transfer. However, functional forms of the enzyme lacking the rubredoxin-like domain have been reported (e.g., sulerythrin and ferriperoxin). In this study, phylogenomic evidence is presented that suggests that a complete lineage of rubrerythrins, lacking the rubredoxin-like domain, arose in an ancient microaerobic and (hyper)thermophilic environments in the ancestors of the Archaea Thermoproteales and Sulfolobales. This lineage (termed the "aerobic-type" lineage) subsequently evolved to become adapted to environments with progressively lower temperatures and higher oxygen concentrations via the acquisition of two co-localized genes, termed DUF3501 and RFO, encoding a conserved protein of unknown function and a predicted Fe-S oxidoreductase, respectively. Proposed Horizontal Gene Transfer events from these archaeal ancestors to Bacteria expanded the opportunities for further evolution of this RBR including adaption to lower temperatures. The second lineage (termed the cyanobacterial lineage) is proposed to have evolved in cyanobacterial ancestors, maybe in direct response to the production of oxygen via oxygenic photosynthesis during the Great Oxygen Event (GOE). It is hypothesized that both lineages of RBR emerged in a largely anaerobic world with "whiffs" of oxygen and that their subsequent independent evolutionary trajectories allowed microorganisms to transition from this anaerobic world to an aerobic one.

  14. Aerobic Lineage of the Oxidative Stress Response Protein Rubrerythrin Emerged in an Ancient Microaerobic, (Hyper)Thermophilic Environment

    PubMed Central

    Cardenas, Juan P.; Quatrini, Raquel; Holmes, David S.

    2016-01-01

    Rubrerythrins (RBRs) are non-heme di-iron proteins belonging to the ferritin-like superfamily. They are involved in oxidative stress defense as peroxide scavengers in a wide range of organisms. The vast majority of RBRs, including classical forms of this protein, contain a C-terminal rubredoxin-like domain involved in electron transport that is used during catalysis in anaerobic conditions. Rubredoxin is an ancient and large protein family of short length (<100 residues) that contains a Fe-S center involved in electron transfer. However, functional forms of the enzyme lacking the rubredoxin-like domain have been reported (e.g., sulerythrin and ferriperoxin). In this study, phylogenomic evidence is presented that suggests that a complete lineage of rubrerythrins, lacking the rubredoxin-like domain, arose in an ancient microaerobic and (hyper)thermophilic environments in the ancestors of the Archaea Thermoproteales and Sulfolobales. This lineage (termed the “aerobic-type” lineage) subsequently evolved to become adapted to environments with progressively lower temperatures and higher oxygen concentrations via the acquisition of two co-localized genes, termed DUF3501 and RFO, encoding a conserved protein of unknown function and a predicted Fe-S oxidoreductase, respectively. Proposed Horizontal Gene Transfer events from these archaeal ancestors to Bacteria expanded the opportunities for further evolution of this RBR including adaption to lower temperatures. The second lineage (termed the cyanobacterial lineage) is proposed to have evolved in cyanobacterial ancestors, maybe in direct response to the production of oxygen via oxygenic photosynthesis during the Great Oxygen Event (GOE). It is hypothesized that both lineages of RBR emerged in a largely anaerobic world with “whiffs” of oxygen and that their subsequent independent evolutionary trajectories allowed microorganisms to transition from this anaerobic world to an aerobic one. PMID:27917155

  15. Selective Aerobic Oxidation of Alcohols over Atomically-Dispersed Non-Precious Metal Catalysts

    SciTech Connect

    Xie, Jiahan; Yin, Kehua; Serov, Alexey; Artyushkova, Kateryna; Pham, Hien N.; Sang, Xiahan; Unocic, Raymond R.; Atanassov, Plamen; Datye, Abhaya K.; Davis, Robert J.

    2016-12-15

    Catalytic oxidation of alcohols often requires the presence of expensive transition metals. We show that earth-abundant Fe atoms dispersed throughout a nitrogen-containing carbon matrix catalyze the oxidation of benzyl alcohol and 5-hydroxymethylfurfural by O2 in the aqueous phase. Furthermore, the activity of the catalyst can be regenerated by a mild treatment in H2. An observed kinetic isotope effect indicates that β-H elimination from the alcohol is the kinetically relevant step in the mechanism, which can be accelerated by substituting Fe with Cu. Dispersed Cr, Co, and Ni also convert alcohols, demonstrating the general utility of metal–nitrogen–carbon materials for alcohol oxidation catalysis. Oxidation of aliphatic alcohols is substantially slower than that of aromatic alcohols, but adding 2,2,6,6-tetramethyl-1-piperidinyloxy as a co-catalyst with Fe can significantly improve the reaction rate.

  16. CH4 emissions from two floodplain fens of differing nutrient status

    NASA Astrophysics Data System (ADS)

    Stanley, Kieran; Heppell, Catherine; Belyea, Lisa; Baird, Andrew

    2014-05-01

    Floodplain fens emit large amounts of CH4 in comparison with ombrotrophic bogs. Little is known about the effect of fluvial nitrogen (N) and phosphorus (P) on CH4 dynamics in fens, although N and P affect carbon (C) dynamics indirectly in other environments by controlling plant growth and root exudate release, as well as by altering microbial biomass and decomposition rates. This study aimed to compare CH4 emissions from two floodplain fen sites which differ in nutrient status, Sutton Fen (52°45'N 001°30'E) and Strumpshaw Fen (52°36'N 001°27'E), in the Norfolk Broadland of England. Sutton and Strumpshaw Fen are under conservation management and both sites have water levels that vary within a few decimetres above and below the surface. The sites are dominated by reed (Phragmites australis). Areas within the fens where the reed was cut in 2009 were chosen for this study. Average plant height and mean aboveground biomass were significantly greater at Strumpshaw (107.2 ± 7.8 cm and 1578 ± 169 g m-2, respectively) than Sutton (56.5 ± 5.1 cm and 435 ± 42 g m-2) as were mean foliar N and P contents (21.8 ± 1.5 g kg-1 and 2.0 ± 0.2 g kg-1 at Strumpshaw, versus 16.3 ± 1.5 g kg-1 and 1.1 ± 0.1 g kg-1 at Sutton). Foliar NPK ratios showed Strumpshaw to be N limited, whereas Sutton was both N and P limited, depending on microsite. Surface peat N and P contents were also greater at Strumpshaw (28.3 ± 0.35 g kg-1 and 0.78 ± 0.02 g kg-1, respectively) than Sutton (18.32 ± 0.87 g kg-1 and 0.43 ± 0.1 g kg-1). These results indicate clear differences in nutrient status between the two sites despite their geographical proximity and other similarities. CH4 emissions were monitored monthly between 19th June 2012 and 2nd September 2013 using tall static chambers and glass funnel-traps, the latter for ebullition. Steady fluxes did not follow a clear seasonal pattern; however, emission was greatest in the summer months. Strumpshaw had a greater range in efflux (0.25 to 134

  17. Background CH4 and N2O fluxes in low-input short rotation coppice

    NASA Astrophysics Data System (ADS)

    Görres, Carolyn-Monika; Zenone, Terenzio; Ceulemans, Reinhart

    2016-04-01

    Extensively managed short rotation coppice systems are characterized by low fluxes of CH4 and N2O. However due to the large global warming potential of these trace gases (GWP100: CH4: 34, N2O: 298), such background fluxes can still significantly contribute to offsetting the CO2 uptake of short rotation coppice systems. Recent technological advances in fast-response CH4 and N2O analysers have improved our capability to capture these background fluxes, but their quantification still remains a challenge. As an example, we present here CH4 and N2O fluxes from a short-rotation bioenergy plantation in Belgium. Poplars have been planted in a double-row system on a loamy sand in 2010 and coppiced in the beginning of 2012 and 2014 (two-year rotation system). In 2013 (June - November) and 2014 (April - August), the plantation's CH4 and N2O fluxes were measured in parallel with an eddy covariance tower (EC) and an automated chamber system (AC). The EC had a detection limit of 13.68 and 0.76 μmol m-2 h-1 for CH4 and N2O, respectively. The median detection limit of the AC was 0.38 and 0.08 μmol m-2 h-1 for CH4 and N2O, respectively. The EC picked up a few high CH4 emission events with daily averages >100 μmol m-2 h-1, but a large proportion of the measured fluxes were within the EC's detection limit. The same was true for the EC-derived N2O fluxes where the daily average flux was often close to the detection limit. Sporadically, some negative (uptake) fluxes of N2O were observed. On the basis of the EC data, no clear link was found between CH4 and N2O fluxes and environmental variables. The problem with fluxes within the EC detection limit is that a significant amount of the values can show the opposite sign, thus "mirroring" the true flux. Subsequently, environmental controls of background trace gas fluxes might be disguised in the analysis. As a next step, it will be tested if potential environmental drivers of background CH4 and N2O fluxes at the plantation can be

  18. Recent Development of CO2 Reforming of CH4 by “Arc” Plasma

    NASA Astrophysics Data System (ADS)

    Xu, Yan; Zhang, Xiaoqing; Yang, Chunhui; Zhang, Yanping; Yin, Yongxiang

    2016-10-01

    This paper presents a brief overview of CO2 reforming of CH4 (CRM) by various forms of “arc” plasma, which is more suitable to CRM, and the energy efficiency is used to evaluate different plasma processes specifically. According to the reported results, the arc thermal plasma with binode exhibited better performance. Moreover, the plasma CRM process was compared with the reported plasma steam reforming of CH4 (SRM) process, and the results showed that the former process has advantages on energy efficiency and CH4 consumption. Additionally, it is believed that the plasma CRM process would be competitive with the conventional SRM process in both energy efficiency and CO2 emission once the heat management is emphasized and the renewable power is used. Finally, a concept of plasma reactor for industrial application is proposed. supported by National Natural Science Foundation of China (No. 11375123) and the Research Project of Xuzhou Institute of Technology, China (No. XKY2015308)

  19. A gas filter correlation monitor for CO, CH4, and HCl

    NASA Technical Reports Server (NTRS)

    Sebacher, D. I.

    1977-01-01

    A fast response instrument for monitoring the atmospheric constituents CO, CH4, and HCl, using a modified nondispersive infrared technique, was designed, assembled, and tested. This gas filter correlation method uses a sample of gas to provide a selective filter for radiation absorbed in a gas mixture containing the specified gas. Depending on the spectral line broadening, temperature, and optical depth of the gas selected, exceptionally high spectral resolution may be attained. A description of the single beam rotating cell system and its specific application is presented along with the signal processing circuit. Calibrations of the instrument show that the technique can be used to measure CO, CH4, and HCl concentrations as small as 5 ppm-m. A field version was employed to measure diurnal variations of CO and CH4 and the interfering effects of other atmospheric gases were analyzed.

  20. The Bacteriohopanepolyol Inventory of Novel Aerobic Methane Oxidising Bacteria Reveals New Biomarker Signatures of Aerobic Methanotrophy in Marine Systems.

    PubMed

    Rush, Darci; Osborne, Kate A; Birgel, Daniel; Kappler, Andreas; Hirayama, Hisako; Peckmann, Jörn; Poulton, Simon W; Nickel, Julia C; Mangelsdorf, Kai; Kalyuzhnaya, Marina; Sidgwick, Frances R; Talbot, Helen M

    2016-01-01

    Aerobic methane oxidation (AMO) is one of the primary biologic pathways regulating the amount of methane (CH4) released into the environment. AMO acts as a sink of CH4, converting it into carbon dioxide before it reaches the atmosphere. It is of interest for (paleo)climate and carbon cycling studies to identify lipid biomarkers that can be used to trace AMO events, especially at times when the role of methane in the carbon cycle was more pronounced than today. AMO bacteria are known to synthesise bacteriohopanepolyol (BHP) lipids. Preliminary evidence pointed towards 35-aminobacteriohopane-30,31,32,33,34-pentol (aminopentol) being a characteristic biomarker for Type I methanotrophs. Here, the BHP compositions were examined for species of the recently described novel Type I methanotroph bacterial genera Methylomarinum and Methylomarinovum, as well as for a novel species of a Type I Methylomicrobium. Aminopentol was the most abundant BHP only in Methylomarinovum caldicuralii, while Methylomicrobium did not produce aminopentol at all. In addition to the expected regular aminotriol and aminotetrol BHPs, novel structures tentatively identified as methylcarbamate lipids related to C-35 amino-BHPs (MC-BHPs) were found to be synthesised in significant amounts by some AMO cultures. Subsequently, sediments and authigenic carbonates from methane-influenced marine environments were analysed. Most samples also did not contain significant amounts of aminopentol, indicating that aminopentol is not a useful biomarker for marine aerobic methanotophic bacteria. However, the BHP composition of the marine samples do point toward the novel MC-BHPs components being potential new biomarkers for AMO.

  1. The Bacteriohopanepolyol Inventory of Novel Aerobic Methane Oxidising Bacteria Reveals New Biomarker Signatures of Aerobic Methanotrophy in Marine Systems

    PubMed Central

    Birgel, Daniel; Kappler, Andreas; Hirayama, Hisako; Peckmann, Jörn; Poulton, Simon W.; Nickel, Julia C.; Mangelsdorf, Kai; Kalyuzhnaya, Marina; Sidgwick, Frances R.; Talbot, Helen M.

    2016-01-01

    Aerobic methane oxidation (AMO) is one of the primary biologic pathways regulating the amount of methane (CH4) released into the environment. AMO acts as a sink of CH4, converting it into carbon dioxide before it reaches the atmosphere. It is of interest for (paleo)climate and carbon cycling studies to identify lipid biomarkers that can be used to trace AMO events, especially at times when the role of methane in the carbon cycle was more pronounced than today. AMO bacteria are known to synthesise bacteriohopanepolyol (BHP) lipids. Preliminary evidence pointed towards 35-aminobacteriohopane-30,31,32,33,34-pentol (aminopentol) being a characteristic biomarker for Type I methanotrophs. Here, the BHP compositions were examined for species of the recently described novel Type I methanotroph bacterial genera Methylomarinum and Methylomarinovum, as well as for a novel species of a Type I Methylomicrobium. Aminopentol was the most abundant BHP only in Methylomarinovum caldicuralii, while Methylomicrobium did not produce aminopentol at all. In addition to the expected regular aminotriol and aminotetrol BHPs, novel structures tentatively identified as methylcarbamate lipids related to C-35 amino-BHPs (MC-BHPs) were found to be synthesised in significant amounts by some AMO cultures. Subsequently, sediments and authigenic carbonates from methane-influenced marine environments were analysed. Most samples also did not contain significant amounts of aminopentol, indicating that aminopentol is not a useful biomarker for marine aerobic methanotophic bacteria. However, the BHP composition of the marine samples do point toward the novel MC-BHPs components being potential new biomarkers for AMO. PMID:27824887

  2. Marine animals significantly increase tundra N2O and CH4 emissions in maritime Antarctica

    NASA Astrophysics Data System (ADS)

    Zhu, Renbin; Liu, Yashu; Xu, Hua; Ma, Dawei; Jiang, Shan

    2013-12-01

    studies on greenhouse gas emissions from animals concentrated on domestic animals, with limited data available from wild animals. The number of marine animals is potentially large in coastal Antarctica. In this paper, N2O and CH4 emissions were investigated from a penguin colony, a seal colony, a skua colony, the adjacent animal-lacking tundra, and background tundra sites to test the effects of marine animals on their fluxes in maritime Antarctica. Extremely high N2O emissions occurred in the penguin puddles (mean 392 µg N2O m-2 h-1) and seal wallows (mean 579 µg N2O m-2 h-1). The N2O emissions from animal colony tundra (13-57 µg N2O m-2 h-1) are much higher than those from the animal-lacking tundra, whereas the background tundra showed negligible N2O fluxes. Penguin puddles and seal wallows were stronger CH4 emitters than animal colony tundra soils, while animal-lacking tundra soils were strong CH4 sinks. Overall high N2O and CH4 emissions were modulated by soil physical and chemical processes associated with marine animal activities: sufficient supply of the nutrients NH4+-N and NO3--N, total nitrogen, and total organic carbon from marine animal excreta, animal tramp, and high soil water-filled pore space. Laboratory incubation experiments further confirmed that penguin and seal colony soils produced much higher N2O and CH4 emissions than animal-lacking tundra soils. Our results indicate that marine animal colonies are the hot spots for N2O and CH4 emissions in maritime Antarctica, and even at the global scale, and current climate warming will further increase their emissions.

  3. Influence of atmospheric stability and transport on CH4 concentrations in northern Spain.

    PubMed

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

    2016-04-15

    Continuous methane (CH4) concentrations were measured in Northern Spain over two years (2011-2012) by multi-point sampling at 1.8, 3.7 and 8.3m using a Picarro analyser. The technique is based on cavity ring-down spectroscopy. The contrast in mean concentrations was about 1.2ppb, with 95th percentiles differing by 2.2ppb and mean minimum concentrations proving similar. Temporal variations of CH4 were also analysed, with a similar seasonal variability being found for the three heights. The highest CH4 concentrations were obtained in late autumn and winter and the lowest in summer, yielding a range of 52ppb. This variation may depend on the active photochemical reaction with OH radical during a period of intense solar radiation and changes in soil conditions together with variations in emissions. Peak concentration levels were recorded at night-time, between 5:00-7:00 GMT, with mean values ranging between 1920 and 1923ppb. The lowest value, around 1884ppb, was obtained at 16:00 GMT. This diurnal variation was mainly related to vertical mixing and photochemistry. Therefore, CH4 concentrations were also examined using the bulk Richardson number (RB) as a stability indicator. Four groups were distinguished: unstable cases, situations with pure shear flow, transitional stages and drainage flows. The highest contrast in mean CH4 concentrations between lower and upper heights was obtained for the transition and drainage cases, mainly associated to high concentrations from nearby sources. The impact of long range transport was analysed by means of 3-day isobaric backward air mass trajectories, which were calculated taking into account origins from Europe, Africa, the Atlantic Ocean and Local conditions. Assessment of the results showed the influence of S and SE wind sectors, especially with Local conditions associated with low winds. Finally, an estimation of the background CH4 concentration in the study period provided an average value of about 1892ppb.

  4. Early Mars serpentinization-derived CH4 reservoirs, H2-induced warming and paleopressure evolution

    NASA Astrophysics Data System (ADS)

    Chassefière, E.; Lasue, J.; Langlais, B.; Quesnel, Y.

    2016-11-01

    CH4 has been observed on Mars both by remote sensing and in situ during the past 15 yr. It could have been produced by early Mars serpentinization processes that could also explain the observed Martian remanent magnetic field. Assuming a cold early Mars, a cryosphere could trap such CH4 as clathrates in stable form at depth. The maximum storage capacity of such a clathrate cryosphere has been recently estimated to be 2 × 1019 to 2 × 1020 moles of methane. We estimate how large amounts of serpentinization-derived CH4 stored in the cryosphere have been released into the atmosphere during the Noachian and the early Hesperian. Due to rapid clathrate dissociation and photochemical conversion of CH4 to H2, these episodes of massive CH4 release may have resulted in transient H2-rich atmospheres, at typical levels of 10-20% in a background 1-2 bar CO2 atmosphere. The collision-induced heating effect of H2 present in such an atmosphere has been shown to raise the surface temperature above the water freezing point. We show how local and rapid destabilization of the cryosphere can be induced by large events (such as the Hellas Basin or Tharsis bulge formation) and lead to such releases. Our results show that the early Mars cryosphere had a sufficient CH4 storage capacity to have maintained H2-rich transient atmospheres during a total time period up to several million years or tens of million years, having potentially contributed to the formation of valley networks during the Noachian/early Hesperian.

  5. Influence of Land Cover and Climate on CO2 and CH4 fluxes from Urban Soils

    NASA Astrophysics Data System (ADS)

    Smith, R. M.; Groffman, P. M.; Kaushal, S.; Gold, A.; Cole, J. N.

    2015-12-01

    Soils are important sinks for greenhouse gases globally. Urbanization influences biogeochemical processes and gas fluxes through increased nitrogen deposition, heat island effects, and vegetation management. Previous work at the Baltimore Ecosystem Study LTER site has reported elevated CO2 fluxes and reduced CH4 consumption in urban soils. Differences among soils (urban forest, rural forest, lawns) have been linked to nitrogen cycling and may also be driven by temperature differences between land cover types. A combination of site-specific changes (land cover, nitrogen availability) and climatological (temperature, soil moisture) factors are likely to influence long-term patterns in gas fluxes and therefore carbon storage in growing urban regions. We utilized 15 years of measured gas fluxes and continuous temperature and soil moisture data to model CO2 emissions and CH4 consumption under different vegetation classes. We scaled these fluxes to the metropolitan region using high-resolution spatial, and found that regional CH4 consumption and CO2 fluxes are sensitive to changes in temperature and land cover. For instance, in 2007 land cover in Baltimore City had 21% lawn and 22% forest cover. If all of the lawn area in the city were converted to urban forest, CH4 consumption by urban soils would increase by 70% and CO2 emissions would decrease by 20%. In suburban Baltimore County, lawns and urban forests comprised 35 and 50% of land cover respectively. If all lawns in the county were converted to urban forest, soil CH4 consumption would increase by 55% and soil CO2 flux would decrease by 20%. Soil CO2 fluxes also increase by approximately 0.1g C m-2 d-1 for every 1° C increase across all land cover classes. CH4 consumption increases with temperature in urban and rural forest soils. Our results highlight the interacting effects of land cover change and climate on carbon fluxes from urban soils.

  6. Stratospheric CH4 and CO2 profiles derived from SCIAMACHY solar occultation measurements

    NASA Astrophysics Data System (ADS)

    Noël, Stefan; Bramstedt, Klaus; Hilker, Michael; Liebing, Patricia; Plieninger, Johannes; Reuter, Max; Rozanov, Alexei; Sioris, Christopher E.; Bovensmann, Heinrich; Burrows, John P.

    2016-04-01

    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 in the spectral region between 1559 and 1671 nm. By use of updated pointing information and optimisation of the data selection as well as of the retrieval approach, the altitude range for reasonable CH4 could be broadened from 20 to 40 km to about 17 to 45 km. Furthermore, the quality of the derived CO2 has been assessed such that now the first stratospheric profiles (17-45 km) 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. CH4 trends above about 20 km are not significantly different from zero and the trend at 17 km is about 3 ppbv year-1. The derived CO2 trends show a general decrease with altitude with values of about 1.9 ppmv year-1 at 21 km and about 1.3 ppmv year-1 at 39 km. These results 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.

  7. Response of CH4 and N2O emissions and wheat yields to tillage method changes in the North China plain.

    PubMed

    Tian, Shenzhong; Ning, Tangyuan; Zhao, Hongxiang; Wang, Bingwen; Li, Na; Han, Huifang; Li, Zengjia; Chi, Shuyun

    2012-01-01

    The objective of this study was to quantify soil methane (CH(4)) and nitrous oxide (N(2)O) emissions when converting from minimum and no-tillage systems to subsoiling (tilled soil to a depth of 40 cm to 45 cm) in the North China Plain. The relationships between CH(4) and N(2)O flux and soil temperature, moisture, NH(4) (+)-N, organic carbon (SOC) and pH were investigated over 18 months using a split-plot design. The soil absorption of CH(4) appeared to increase after conversion from no-tillage (NT) to subsoiling (NTS), from harrow tillage (HT) to subsoiling (HTS) and from rotary tillage (RT) to subsoiling (RTS). N(2)O emissions also increased after conversion. Furthermore, after conversion to subsoiling, the combined global warming potential (GWP) of CH(4) and N(2)O increased by approximately 0.05 kg CO(2) ha(-1) for HTS, 0.02 kg CO(2) ha(-1) for RTS and 0.23 kg CO(2) ha(-1) for NTS. Soil temperature, moisture, SOC, NH(4) (+)-N and pH also changed after conversion to subsoiling. These changes were correlated with CH(4) uptake and N(2)O emissions. However, there was no significant correlation between N(2)O emissions and soil temperature in this study. The grain yields of wheat improved after conversion to subsoiling. Under HTS, RTS and NTS, the average grain yield was elevated by approximately 42.5%, 27.8% and 60.3% respectively. Our findings indicate that RTS and HTS would be ideal rotation tillage systems to balance GWP decreases and grain yield improvements in the North China Plain region.

  8. Vibrational energy levels for CH4 from an ab initio potential

    NASA Technical Reports Server (NTRS)

    Schwenke, D. W.; Partridge, H.

    2001-01-01

    Many areas of astronomy and astrophysics require an accurate high temperature spectrum of methane (CH4). The goal of the present research is to determine an accurate ab initio potential energy surface (PES) for CH4. As a first step towards this goal, we have determined a PES including up to octic terms. We compare our results with experiment and to a PES based on a quartic expansion. Our octic PES gives good agreement with experiment for all levels, while the quartic PES only for the lower levels.

  9. Vibrational energy levels for CH4 from an ab initio potential.

    PubMed

    Schwenke, D W; Partridge, H

    2001-03-15

    Many areas of astronomy and astrophysics require an accurate high temperature spectrum of methane (CH4). The goal of the present research is to determine an accurate ab initio potential energy surface (PES) for CH4. As a first step towards this goal, we have determined a PES including up to octic terms. We compare our results with experiment and to a PES based on a quartic expansion. Our octic PES gives good agreement with experiment for all levels, while the quartic PES only for the lower levels.

  10. Argon-broadened line parameters in the ν3 band of 12CH4.

    NASA Astrophysics Data System (ADS)

    Gabard, T.

    1997-02-01

    Prompted by improved measurements of collisional line shapes in the ν3 band P, Q and R branches of 12CH4, The author has performed semi-classical line broadening calculations for methane perturbed by argon. He has used the theoretical approach developed by Robert and Bonamy (1979) as an extension of the well-known Anderson-Tsao-Curnutte theory. The semi-classical theory as reformulated here is shown to fully account for the tetrahedral symmetry of methane type molecules. The variation of argon-broadened linewidth coefficients in the ν3 band of 12CH4 with the branch, J, symmetry and energy level fine structure is discussed.

  11. Aerobic methanotrophy within the pelagic redox-zone of the Gotland Deep (central Baltic Sea)

    NASA Astrophysics Data System (ADS)

    Schmale, O.; Blumenberg, M.; Kießlich, K.; Jakobs, G.; Berndmeyer, C.; Labrenz, M.; Thiel, V.; Rehder, G.

    2012-12-01

    Water column samples taken in summer 2008 from the stratified Gotland Deep (central Baltic Sea) showed a strong gradient in dissolved methane concentrations from high values in the saline deep water (max. 504 nM) to low concentrations in the less dense, brackish surface water (about 4 nM). The steep methane-gradient (between 115 and 135 m water depth) within the redox-zone, which separates the anoxic deep part from the oxygenated surface water (oxygen concentration 0-0.8 mL L-1), implies a methane consumption rate of 0.28 nM d-1. The process of microbial methane oxidation within this zone was evident by a shift of the stable carbon isotope ratio of methane between the bottom water (δ13C CH4 = -82.4‰ and the redox-zone (δ13C CH4 = -38.7‰. Water column samples between 80 and 119 m were studied to identify the microorganisms responsible for the methane turnover in that depth interval. Notably, methane monooxygenase gene expression analyses for water depths covering the whole redox-zone demonstrated that accordant methanotrophic activity was probably due to only one phylotype of the aerobic type I methanotrophic bacteria. An imprint of these organisms on the particular organic matter was revealed by distinctive lipid biomarkers showing bacteriohopanepolyols and lipid fatty acids characteristic for aerobic type I methanotrophs (e.g., 35-aminobacteriohopane-30,31,32,33,34-pentol), corroborating their role in aerobic methane oxidation in the redox-zone of the central Baltic Sea.

  12. Copper-Catalyzed Aerobic Oxidations of Organic Molecules: Pathways for Two-Electron Oxidation with a Four-Electron Oxidant and a One-Electron Redox-Active Catalyst.

    PubMed

    McCann, Scott D; Stahl, Shannon S

    2015-06-16

    Selective oxidation reactions have extraordinary value in organic chemistry, ranging from the conversion of petrochemical feedstocks into industrial chemicals and polymer precursors to the introduction of heteroatom functional groups into pharmaceutical and agrochemical intermediates. Molecular oxygen (O2) would be the ideal oxidant for these transformations. Whereas many commodity-scale oxidations of simple hydrocarbon feedstocks employ O2 as an oxidant, methods for selective oxidation of more complex molecules bearing diverse functional groups are often incompatible with existing aerobic oxidation methods. The latter limitation provides the basis for our interest in the development of new catalytic transformations and the elucidation of mechanistic principles that underlie selective aerobic oxidation reactions. One challenge inherent in such methods is the incommensurate redox stoichiometry associated with the use of O2, a four-electron oxidant, in reactions that achieve two-electron oxidation of organic molecules. This issue is further complicated by the use of first-row transition-metal catalysts, which tend to undergo facile one-electron redox steps. In recent years, we have been investigating Cu-catalyzed aerobic oxidation reactions wherein the complexities just noted are clearly evident. This Account surveys our work in this area, which has emphasized three general classes of reactions: (1) single-electron-transfer reactions for oxidative functionalization of electron-rich substrates, such as arenes and heterocycles; (2) oxidative carbon-heteroatom bond-forming reactions, including C-H oxidations, that proceed via organocopper(III) intermediates; and (3) methods for aerobic oxidation of alcohols and amines that use Cu(II) in combination with an organic redox-active cocatalyst to dehydrogenate the carbon-heteroatom bond. These reaction classes demonstrate three different pathways to achieve two-electron oxidation of organic molecules via the cooperative

  13. Selective Aerobic Oxidation of Alcohols over Atomically-Dispersed Non-Precious Metal Catalysts

    DOE PAGES

    Xie, Jiahan; Yin, Kehua; Serov, Alexey; ...

    2016-12-15

    Catalytic oxidation of alcohols often requires the presence of expensive transition metals. We show that earth-abundant Fe atoms dispersed throughout a nitrogen-containing carbon matrix catalyze the oxidation of benzyl alcohol and 5-hydroxymethylfurfural by O2 in the aqueous phase. Furthermore, the activity of the catalyst can be regenerated by a mild treatment in H2. An observed kinetic isotope effect indicates that β-H elimination from the alcohol is the kinetically relevant step in the mechanism, which can be accelerated by substituting Fe with Cu. Dispersed Cr, Co, and Ni also convert alcohols, demonstrating the general utility of metal–nitrogen–carbon materials for alcohol oxidationmore » catalysis. Oxidation of aliphatic alcohols is substantially slower than that of aromatic alcohols, but adding 2,2,6,6-tetramethyl-1-piperidinyloxy as a co-catalyst with Fe can significantly improve the reaction rate.« less

  14. Seasonal changes in CH4 emissions from an alpine reservoir, Lake Klöntal, Switzerland

    NASA Astrophysics Data System (ADS)

    Sollberger, S.; Eugster, W.; Schubert, C.; Wehrli, B.

    2012-04-01

    Atmospheric methane (CH4) concentration doubled since the pre-industrialized era and its potential as a greenhouse gas is 25 higher than CO2 over a 100-year horizon. Recent studies showed an important contribution of inland waters, including hydropower reservoirs, to the global CH4 cycle. However, the large seasonal and latitudinal variability of emissions reported in the literature highlights the necessity for a better understanding of CH4 emission mechanisms. The aim of this study was to investigate physical factors (water level and temperature) that trigger the seasonal pattern of CH4 emissions in a Swiss alpine reservoir, Lake Klöntal, using multiple methods. Atmospheric CH4 flux was measured using a fast methane analyzer (FMA, Los Gatos Research) and an eddy covariance tower set on a floating platform from April to December 2011 (before ice sets). Emissions were also measured monthly via chambers and calculated from surface water concentrations using Henry's law. Methane ebullition was examined over the lake surface of 5 km2 using a split-beam echosounder. Typical daily variations of CH4 were measured with the eddy covariance setup within the range of 0.23 and 7.4 mg CH4 m-2 d-1 (95% confidence interval) and were mainly related to temperature and solar radiation variability. The seasonal trend shows that average fluxes increase from 3.0 (April) to 3.7 mg CH4 m-2 d-1 in November. Much larger fluctuations can be observed in comparison to the chamber results where the emissions typically increase throughout the day. Furthermore, highest chamber fluxes were measured in July and October, which does not correspond with the FMA results (November). This inconsistency is also observed in the flux estimates calculated from surface concentrations of which the highest fluxes were in September. Ebullition was only observed (Jul., Sep. and Nov.) in a very shallow area where it was not possible to use the echosounder. Hence, our measurements may slightly underestimate the

  15. Aerobic nitric oxide-induced thiol nitrosation in the presence and absence of magnesium cations.

    PubMed

    Kolesnik, Bernd; Heine, Christian L; Schmidt, Renate; Schmidt, Kurt; Mayer, Bernd; Gorren, Antonius C F

    2014-11-01

    Although different routes for the S-nitrosation of cysteinyl residues have been proposed, the main in vivo pathway is unknown. We recently demonstrated that direct (as opposed to autoxidation-mediated) aerobic nitrosation of glutathione is surprisingly efficient, especially in the presence of Mg(2+). In the present study we investigated this reaction in greater detail. From the rates of NO decay and the yields of nitrosoglutathione (GSNO) we estimated values for the apparent rate constants of 8.9 ± 0.4 and 0.55 ± 0.06 M(-1)s(-1) in the presence and absence of Mg(2+). The maximum yield of GSNO was close to 100% in the presence of Mg(2+) but only about half as high in its absence. From this observation we conclude that, in the absence of Mg(2+), nitrosation starts by formation of a complex between NO and O2, which then reacts with the thiol. Omission of superoxide dismutase (SOD) reduced by half the GSNO yield in the absence of Mg(2+), demonstrating O2(-) formation. The reaction in the presence of Mg(2+) seems to involve formation of a Mg(2+)•glutathione (GSH) complex. SOD did not affect Mg(2+)-stimulated nitrosation, suggesting that no O2(-) is formed in that reaction. Replacing GSH with other thiols revealed that reaction rates increased with the pKa of the thiol, suggesting that the nucleophilicity of the thiol is crucial for the reaction, but that the thiol need not be deprotonated. We propose that in cells Mg(2+)-stimulated NO/O2-induced nitrosothiol formation may be a physiologically relevant reaction.

  16. Formation of H2 and CH4 by weathering of olivine at temperatures between 30 and 70°C

    PubMed Central

    2011-01-01

    Hydrocarbons such as CH4 are known to be formed through the Fischer-Tropsch or Sabatier type reactions in hydrothermal systems usually at temperatures above 100°C. Weathering of olivine is sometimes suggested to account for abiotic formation of CH4 through its redox lowering and water splitting properties. Knowledge about the CH4 and H2 formation processes at low temperatures is important for the research about the origin and cause of early Earth and Martian CH4 and for CO2 sequestration. We have conducted a series of low temperature, long-term weathering experiments in which we have tested the CH4 and H2 formation potential of forsteritic olivine. The results show low temperature CH4 production that is probably influenced by chromite and magnetite as catalysts. Extensive analyses of a potential CH4 source trapped in the crystal structure of the olivine showed no signs of incorporated CH4. Also, the available sources of organic carbon were not enough to support the total amount of CH4 detected in our experiments. There was also a linear relationship between silica release into solution and the net CH4 accumulation into the incubation bottle headspaces suggesting that CH4 formation under these conditions could be a qualitative indicator of olivine dissolution. It is likely that minerals such as magnetite, chromite and other metal-rich minerals found on the olivine surface catalyze the formation of CH4, because of the low temperature of the system. This may expand the range of environments plausible for abiotic CH4 formation both on Earth and on other terrestrial bodies. PMID:21707970

  17. Quantitative measurement and mechanisms for CH4 production from hydrates with the injection of liquid CO2.

    PubMed

    Lee, Bo Ram; Koh, Carolyn A; Sum, Amadeu K

    2014-07-28

    The recovery of gas from natural gas hydrates under the permafrost and in oceanic sediments is of particular interest in energy and environmental fields because of the attractive process to release methane gas through the injection of CO2. The sequestration of CO2, a notorious greenhouse gas, in hydrates has the potential to be used in enhanced gas recovery techniques, while simultaneously releasing CH4 locked within the gas bearing hydrates. In this study, we present quantitative experiments to investigate results of possible CH4-CO2 exchange kinetics from injection of liquid CO2 through CH4 hydrates. The experiments performed use CH4 hydrate formed from ice particles (75-90 or 125-150 microns in diameter) at approximately 10.34 MPa and 263 K. In order to reduce unexpected errors, nearly full conversion (>95%) of ice particles to hydrates is achieved. Liquid CO2 is injected into the pressure cell to sweep the residual CH4 atmosphere, ensuring no free CH4 is left in the gas phase. After soaking the hydrate for several hours, CH4 is produced from the hydrates by injecting liquid CO2. The final composition and analysis of the produced CH4 is measured by using in-line gas chromatography. We also measure the CH4 moles after hydrate dissociation to confirm the closure of the total mass balance of the experiment. From these data, we infer the mechanism for CH4 production, identify the penetration depth of the dissociation/exchange on the hydrate particles, and propose physical models describing the mechanism for CH4 production. These experiments are essential in the quantification of the production of CH4 from CH4 hydrates with the injection of CO2.

  18. Riverine GHG emissions: one year of CO2, 13CO2 and CH<