Highly efficient alkane oxidation catalyzed by [Mn(V)(N)(CN)4](2-). Evidence for [Mn(VII)(N)(O)(CN)4](2-) as an active intermediate.

PubMed

Ma, Li; Pan, Yi; Man, Wai-Lun; Kwong, Hoi-Ki; Lam, William W Y; Chen, Gui; Lau, Kai-Chung; Lau, Tai-Chu

2014-05-28

The oxidation of various alkanes catalyzed by [Mn(V)(N)(CN)4](2-) using various terminal oxidants at room temperature has been investigated. Excellent yields of alcohols and ketones (>95%) are obtained using H2O2 as oxidant and CF3CH2OH as solvent. Good yields (>80%) are also obtained using (NH4)2[Ce(NO3)6] in CF3CH2OH/H2O. Kinetic isotope effects (KIEs) are determined by using an equimolar mixture of cyclohexane (c-C6H12) and cyclohexane-d12 (c-C6D12) as substrate. The KIEs are 3.1 ± 0.3 and 3.6 ± 0.2 for oxidation by H2O2 and Ce(IV), respectively. On the other hand, the rate constants for the formation of products using c-C6H12 or c-C6D12 as single substrate are the same. These results are consistent with initial rate-limiting formation of an active intermediate between [Mn(N)(CN)4](2-) and H2O2 or Ce(IV), followed by H-atom abstraction from cyclohexane by the active intermediate. When PhCH2C(CH3)2OOH (MPPH) is used as oxidant for the oxidation of c-C6H12, the major products are c-C6H11OH, c-C6H10O, and PhCH2C(CH3)2OH (MPPOH), suggesting heterolytic cleavage of MPPH to generate a Mn═O intermediate. In the reaction of H2O2 with [Mn(N)(CN)4](2-) in CF3CH2OH, a peak at m/z 628.1 was observed in the electrospray ionization mass spectrometry, which is assigned to the solvated manganese nitrido oxo species, (PPh4)[Mn(N)(O)(CN)4](-)·CF3CH2OH. On the basis of the experimental results the proposed mechanism for catalytic alkane oxidation by [Mn(V)(N)(CN)4](2-)/ROOH involves initial rate-limiting O-atom transfer from ROOH to [Mn(N)(CN)4](2-) to generate a manganese(VII) nitrido oxo active species, [Mn(VII)(N)(O)(CN)4](2-), which then oxidizes alkanes (R'H) via a H-atom abstraction/O-rebound mechanism. The proposed mechanism is also supported by density functional theory calculations.

Enhanced Oxidation Capacity from Photolytic HOx/NOx Recycling: Implications for CH4 Growth

NASA Astrophysics Data System (ADS)

Madronich, S.

2017-12-01

Oxidation by OH radicals converts many emitted compounds (CO, CH4, VOCs as well as NOx, SO2, HCFCs, and others) to more soluble forms that can be removed rapidly from the atmosphere, e.g., by deposition. In a chemically stable atmosphere (without runaway concentration growth) the rate of OH production must generally exceed the emission rates of the reduced compounds, but secondary chemistry complicates OH budgets. If emission rates (e.g., E for CH4) increase, OH concentrations can either decrease or increase depending on NOx conditions, causing a non-linear dependence of CH4 concentrations on its emissions, [CH4] Ef where f, the methane feedback factor, is currently estimated in global 3d models to be 1.3-1.4. This feature is robust among models, and can be reproduced in simpler box models with the canonical Ox-HOx-NOx chemistry, in which global OH is increased by NOx emissions and decreased by CO, CH4, and VOC emissions. Scenarios with lower NOx emissions but higher CH4 emissions point to substantially lower global oxidation capacity in the future. Several newly hypothesized processes have attracted attention in recent years, including the photolytic recycling of OH from biogenic VOCs, and the photolysis of particulate nitrates to regenerate NOx. The latter process could be particularly significant in regions far from NOx emissions, where low NOx levels are more efficient at generating O3 and OH. To the extent that these processes do occur, they may provide some buffering of global OH against CH4 variations (f nearer 1), and more generally against anthropogenic perturbations. However, critical measurements from both lab and field are needed to assess the importance of these proposed processes.

Large fractionations of C and H isotopes related to methane oxidation in Arctic lakes

NASA Astrophysics Data System (ADS)

Cadieux, Sarah B.; White, Jeffrey R.; Sauer, Peter E.; Peng, Yongbo; Goldman, Amy E.; Pratt, Lisa M.

2016-08-01

Microbial oxidation of methane (CH4) plays a central role in carbon cycling in Arctic lakes, reducing potential CH4 emissions associated with warming. Isotopic signatures of CH4 (δ13C and δ2H) are indicators of microbial oxidation, wherein the process strongly enriches 13C and 2H in residual CH4. We present δ13C and δ2H measurements obtained from sampling the water column and sediment for dissolved CH4 from three, small Arctic lakes in western Greenland under both open-water and ice-covered conditions from 2013 to 2014. Despite substantial variations in aquatic chemistry among the lakes, δ13C and δ2H of CH4 suggested that CH4 was produced predominantly by acetoclastic methanogenesis in the littoral sediments and hydrogenotrophic methanogenesis in the profundal sediments in all of the lakes. Surprisingly large variations for both δ13C and δ2H of CH4 were observed, with δ13C extending from -72‰ to +7.4‰ and δ2H from -390‰ to +250‰. The CH4 isotopic values reported here were significantly more enriched (p < 0.0001) in both 13C and 2H than values reported from other Arctic freshwater environments. As is characteristic of methanotrophy, the enrichment in 13C and 2H was associated with low CH4 concentrations. We suggest that the CH4 most enriched in 13C and 2H may reflect unusually efficient methanotrophic communities in Arctic ice-margin lakes. This study provides the first measurement of δ2H for CH4 in an Arctic freshwater environment at concentrations <10 μM. The extreme enrichment of 13C and 2H of CH4 from Arctic methanotrophy has significant implications for interpreting sources and sinks of CH4. Without knowledge of local geology, stable isotope values of CH4 higher than -30‰ for δ13C and -150‰ for δ2H could be misinterpreted as thermogenic, geothermal, or abiogenic origins. Given crystalline bedrock and the strong positive correlation between δ13C and δ2H throughout the water columns in three Arctic lakes confirms that CH4 heavily enriched in 13C and 2H is the result of methanotrophy.

Inhibitory effects of acidic pH and confounding effects of moisture content on methane biofiltration.

PubMed

Barzgar, Sonya; Hettiaratchi, Joseph Patrick; Pearse, Lauretta; Kumar, Sunil

2017-12-01

This study focussed on evaluating the effect of hydrogen sulfide (H 2 S) on biological oxidation of waste methane (CH 4 ) gas in compost biofilters, Batch experiments were conducted to determine the dependency of maximum methane oxidation rate (V max ) on two main factors; pH and moisture content, as well as their interaction effects. The maximum V max was observed at a pH of 7.2 with decreasing V max values observed with decreasing pH, irrespective of moisture content. Flow-through columns operated at a pH of 4.5 oxidized CH 4 at a flux rate of 53g/m 2 /d compared to 146g/m 2 /d in columns operated at neutral pH. No oxidation activity was observed for columns operated at pH 2.5, and DNA sequencing analysis of samples led to the conclusion that highly acidic conditions were responsible for inhibiting the ability of methanotrophs to oxidize CH 4 . Biofilter columns operated at pH 2.5 contained only 2% methanotrophs (type I) out of the total microbial population, compared to 55% in columns operated at pH 7.5. Overall, changes in the population of methanotrophs with acidification within the biofilters compromised its capacity to oxidize CH 4 which demonstrated that a compost biofilter could not operate efficiently in the presence of high levels of H 2 S. Copyright © 2017 Elsevier Ltd. All rights reserved.

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...

Methane oxidation in an intensively cropped tropical rice field soil under long-term application of organic and mineral fertilizers.

PubMed

Nayak, D R; Babu, Y Jagadeesh; Datta, A; Adhya, T K

2007-01-01

Methane (CH4) oxidation is the only known biological sink process for mitigating atmospheric and terrestrial emissions of CH4, a major greenhouse gas. Methane oxidation in an alluvial soil planted to rice (Oryza sativa L.) under long-term application of organic (compost with a C/N ratio of 21.71), and mineral fertilizers was measured in a field-cum-laboratory incubation study. Oxidation rates were quantified in terms of decrease in the concentration of CH4 in the headspace of incubation vessels and expressed as half-life (t(1)2) values. Methane oxidation rates significantly differed among the treatments and growth stages of the rice crop. Methane oxidation rates were high at the maximum tillering and maturity stages, whereas they were low at grain-filling stage. Methane oxidation was low (t(1)2) = 15.76 d) when provided with low concentration of CH4. On the contrary, high concentration of CH4 resulted in faster oxidation (t(1)2) = 6.67 d), suggesting the predominance of "low affinity oxidation" in rice fields. Methane oxidation was stimulated following the application of mineral fertilizers or compost implicating nutrient limitation as one of the factors affecting the process. Combined application of compost and mineral fertilizer, however, inhibited CH4 oxidation probably due to N immobilization by the added compost. The positive effect of mineral fertilizer on CH4 oxidation rate was evident only at high CH4 concentration (t(1)2 = 4.80 d), while at low CH4 concentration their was considerable suppression (t(1) = 17.60 d). Further research may reveal that long-term application of fertilizers, organic or inorganic, may not inhibit CH4 oxidation.

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

Organic acids and ethanol inhibit the oxidation of methane by mire methanotrophs.

PubMed

Wieczorek, Adam S; Drake, Harold L; Kolb, Steffen

2011-07-01

Aerobic methane (CH(4) ) oxidation reduces the emission of CH(4) from mires and is regulated by various environmental factors. Organic acids and alcohols are intermediates of the anaerobic degradation of organic matter or are released by plant roots. Methanotrophs isolated from mires utilize these compounds preferentially to CH(4) . Thus, the effect of organic acids and ethanol on CH(4) oxidation by methanotrophs of a mire was evaluated. Slurries of mire soil oxidized supplemental CH(4) down to subatmospheric concentrations. The dominant pmoA and mmoX genotypes were affiliated with sequences from Methylocystis species capable of utilization of acetate and atmospheric CH(4) . Soil slurries supplemented with acetate, propionate or ethanol had reduced CH(4) oxidation rates compared with unsupplemented or glucose-supplemented controls. Expression of Methylocystis-affiliated pmoA decreased when CH(4) consumption decreased in response to acetate and was enhanced after acetate was consumed, at which time the consumption of CH(4) reached control levels. The inhibition of methanotroph activity might have been due to either toxicity of organic compounds or their preferred utilization. CH(4) oxidation was reduced at 5 and 0.5 mM of supplemental organic compounds. Acetate concentrations may exceed 3 mM in the investigated mire. Thus, the oxidation of CH(4) might decrease in microzones where organic acids occur. © 2011 Federation of European Microbiological Societies. Published by Blackwell Publishing Ltd. All rights reserved.

Effects of prolonged soil drought on CH4 oxidation in a temperate spruce forest

NASA Astrophysics Data System (ADS)

Borken, W.; Brumme, R.; Xu, Y.-J.

2000-03-01

Our objective was to determine potential impacts of changes in rainfall amount and distribution on soil CH4 oxidation in a temperate forest ecosystem. We constructed a roof below the canopy of a 65-year-old Norway spruce forest (Picea abies (L.) Karst.) and simulated two climate change scenarios: (1) an extensively prolonged summer drought of 172 days followed by a rewetting period of 19 days in 1993 and (2) a less intensive summer drought of 108 days followed by a rewetting period of 33 days in 1994. CH4 oxidation, soil matric potential, and soil temperature were measured hourly to daily over a 2-year period. The results showed that annual CH4 oxidation in the drought experiment increased by 102% for the climate change scenario 1 and by 41% for the climate change scenario 2, compared to those of the ambient plot (1.33 kg CH4 ha-1 in 1993 and 1.65 kg CH4 ha-1 in 1994). We tested the relationships between CH4 oxidation rates, water-filled pore space (WFPS), soil matric potential, gas diffusivity, and soil temperature. Temporal variability in the CH4 oxidation rates corresponded most closely to soil matric potential. Employing soil matric potential and soil temperature, we developed a nonlinear model for estimating CH4 oxidation rates. Modeled results were in strong agreement with the measured CH4 oxidation for the ambient (r2 = 0.80) and drought plots (r2 = 0.89) over two experimental years, suggesting that soil matric potential is a highly reliable parameter for modeling CH4 oxidation rate.

Atmospheric CH4 oxidation by Arctic permafrost and mineral cryosols as a function of water saturation and temperature.

PubMed

Stackhouse, B; Lau, M C Y; Vishnivetskaya, T; Burton, N; Wang, R; Southworth, A; Whyte, L; Onstott, T C

2017-01-01

The response of methanotrophic bacteria capable of oxidizing atmospheric CH 4 to climate warming is poorly understood, especially for those present in Arctic mineral cryosols. The atmospheric CH 4 oxidation rates were measured in microcosms incubated at 4 °C and 10 °C along a 1-m depth profile and over a range of water saturation conditions for mineral cryosols containing type I and type II methanotrophs from Axel Heiberg Island (AHI), Nunavut, Canada. The cryosols exhibited net consumption of ~2 ppmv CH 4 under all conditions, including during anaerobic incubations. Methane oxidation rates increased with temperature and decreased with increasing water saturation and depth, exhibiting the highest rates at 10 °C and 33% saturation at 5 cm depth (260 ± 60 pmol CH 4 gdw -1 d -1 ). Extrapolation of the CH 4 oxidation rates to the field yields net CH 4 uptake fluxes ranging from 11 to 73 μmol CH 4  m -2 d -1 , which are comparable to field measurements. Stable isotope mass balance indicates ~50% of the oxidized CH 4 is incorporated into the biomass regardless of temperature or saturation. Future atmospheric CH 4 uptake rates at AHI with increasing temperatures will be determined by the interplay of increasing CH 4 oxidation rates vs. water saturation and the depth to the water table during summer thaw. © 2016 John Wiley & Sons Ltd.

Evaluating the relative contribution of methane oxidation to methane emissions from young floodplain soils under Alternative Irrigation Management

NASA Astrophysics Data System (ADS)

Pierreux, Sofie; Verhoeven, Elizabeth; Akter, Masuda; Sleutel, Steven; Said-Pullicino, Daniel; Romani, Marco; Boeckx, Pascal

2016-04-01

To keep the pace with a yearly growing demand for rice by 1-2%, future rice production must come primarily from high yielding irrigated rice, putting a pressure on fresh water reserves. In this context, water saving Alternative Irrigation Management (AIM) is progressively applied worldwide. By introducing repeated or mid-seasonal drainage, AIM suppresses emission of CH4, otherwise prevalent in continuously flooded rice. However, little is known about the effect of AIM on the balance of CH4 genesis and oxidation in paddy soils. We studied relevant soil parameters and CH4 emissions in continuously flooded (CF) and alternately wetted and dried (AWD) rice paddies. During a field campaign at the Castello d'Agogna experimental station (Pavia, Italy), we measured in situ CH4 oxidation and emission rates using the closed gas chamber technique with or without application of CH2F2 as a selective inhibitor of CH4 oxidation. In addition, we determined potential CH4 oxidation rates using incubated soil slurries originating from the same experimental plots. The dataset was supplemented with depth differentiated monitoring of redox potential, temperature, moisture content and soil solution parameters (DOC, Fe2+, Mn3+, mineral N and dissolved CH4). Peaks in dissolved CH4 manifested at 5 and 12.5cm depth, with much lower and equal levels at 25, 50 and 80cm depth. Also depth distributions of dissolved Fe and Mn followed this pattern, indicating that methanogenic activity was primarily confounded to the topsoil. Seasonal CH4 emissions were about halved by AWD compared to CF management. After a fast decline of in situ oxidation within the AWD treatment at the beginning of the season, CH4 oxidation percentages in CF and AWD increased until the booting stage (67DAS), reaching peak values of 83% and 69% of produced CH4, respectively. CH4 oxidation thereafter gradually declined to nearly 50% in both treatments after the final drainage (103 DAS). Seasonal trends of potential CH4 oxidation rates were alike between CF and AWD fields, except at 52 DAS, when 5cm and 25cm depth CH4 oxidation capacities from CF soil slurries exceeded those under AWD. This could firstly be explained by higher observed soil solution CH4 concentrations of CF paddies, while in mid-season dissolved CH4 was nearly absent in case of AWD. We hypothesize that a larger methanotrophic biomass was present in the CF fields, explaining the higher CH4 oxidation potential, but this requires verification by qPCR. In addition, higher NH4+ concentrations were measured under CF, which as well might have favored methanotrophic activity. Ongoing analysis of stable isotope ratios (12C/13C) in both atmospheric and subsurface gas samples will complement the specific inhibitor-based CH4 oxidation estimates. Currently, the dataset assembled during this field experiment will be used to fine-tune the biogeochemical model 'rice DNDC' (DeNitrification-DeComposition) with specific attention to DNDC's capability to simulate CH4 oxidation and depth profiles . The model revision will take into account the seasonal and depth differentiated behavior of parameters relevant to the processes of CH4 oxidation, production and emission, and hence contribute to a more precise estimation of methane emissions under AIM.

Partial oxidation of methane by pulsed corona discharges

NASA Astrophysics Data System (ADS)

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

2014-09-01

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

Catalytic and electrochemical behaviour of solid oxide fuel cell operated with simulated-biogas mixtures

NASA Astrophysics Data System (ADS)

Dang-Long, T.; Quang-Tuyen, T.; Shiratori, Y.

2016-06-01

Being produced from organic matters of wastes (bio-wastes) through a fermentation process, biogas mainly composed of CH4 and CO2 and can be considered as a secondary energy carrier derived from solar energy. To generate electricity from biogas through the electrochemical process in fuel cells is a state-of-the-art technology possessing higher energy conversion efficiency without harmful emissions compared to combustion process in heat engines. Getting benefits from high operating temperature such as direct internal reforming ability and activation of electrochemical reactions to increase overall system efficiency, solid oxide fuel cell (SOFC) system operated with biogas becomes a promising candidate for distributed power generator for rural applications leading to reductions of environmental issues caused by greenhouse effects and bio-wastes. CO2 reforming of CH4 and electrochemical oxidation of the produced syngas (H2-CO mixture) are two main reaction processes within porous anode material of SOFC. Here catalytic and electrochemical behavior of Ni-ScSZ (scandia stabilized-zirconia) anode in the feed of CH4-CO2 mixtures as simulated-biogas at 800 °C were evaluated. The results showed that CO2 had strong influences on both reaction processes. The increase in CO2 partial pressure resulted in the decrease in anode overvoltage, although open-circuit voltage was dropped. Besides that, the simulation result based on a power-law model for equimolar CH4-CO2 mixture revealed that coking hazard could be suppressed along the fuel flow channel in both open-circuit and closed-circuit conditions.

Oxidative desulfurization of dibenzothiophene with hydrogen peroxide catalyzed by selenium(IV)-containing peroxotungstate.

PubMed

Hu, Yiwen; He, Qihui; Zhang, Zheng; Ding, Naidong; Hu, Baixing

2011-11-28

With stoichiometric H(2)O(2) as oxidant, dibenzothiophene (DBT) is oxidized to its corresponding sulfone with high efficiency, catalyzed by a sub-valence heteronuclear peroxotungstate, [C(18)H(37)N(CH(3))(3)](4)[H(2)Se(IV)(3)W(6)O(34)], under mild biphase conditions and the catalyst shows remarkable selectivity of catalytic oxidation towards DBT, cinnamyl alcohol and quinoline.

Methanol oxidation on stoichiometric and oxygen-rich RuO2(110).

PubMed

Rai, Rahul; Weaver, Jason F

2017-07-26

We used temperature-programmed reaction spectroscopy (TPRS) to investigate the adsorption and oxidation of methanol on stoichiometric and O-rich RuO 2 (110) surfaces. We find that the complete oxidation of CH 3 OH is strongly preferred on stoichiometric RuO 2 (110) during TPRS for initial CH 3 OH coverages below ∼0.33 ML (monolayer), and that partial oxidation to mainly CH 2 O becomes increasingly favored with increasing CH 3 OH coverage from 0.33 to 1.0 ML. We present evidence that an adsorbed CH 2 O 2 species serves as the key intermediate to complete oxidation and that CH 2 O 2 formation is intrinsically facile but becomes limited by the availability of bridging O-atoms on stoichiometric RuO 2 (110) at initial CH 3 OH coverages above 0.33 ML. We show that methanol molecules adsorbed in excess of 0.33 ML dehydrogenate to mainly CH 2 O and desorb during TPRS, with adsorbed CH 3 O groups mediating the evolution of both CH 2 O and CH 3 OH. We find that O-rich RuO 2 (110) surfaces are also highly active toward methanol oxidation and that selectivity toward the complete oxidation of methanol increases markedly with increasing coverage of on-top O-atoms (O ot ) on RuO 2 (110). Our results demonstrate that CH 3 OH species adsorbed within O ot -rich domains react efficiently during TPRS, in parallel with reaction of CH 3 OH adsorbed initially on cus-Ru sites. The data suggests that the facile hydrogenation of O ot atoms and the resulting desorption of H 2 O at low-temperature (<∼400 K) provides an efficient pathway for restoring reactive O-atoms and thereby promoting complete oxidation of methanol on the O-rich RuO 2 (110) surface.

Permafrost Thaw Induces Methane Oxidation in Transitional Thaw Stages in a Subarctic Peatland

NASA Astrophysics Data System (ADS)

Perryman, C. R.; Kashi, N. N.; Malhotra, A.; McCalley, C. K.; Varner, R. K.

2015-12-01

Rising temperatures in the subarctic are accelerating permafrost thaw and increasing methane (CH4) emissions from subarctic peatlands. Methanotrophs in these peatlands can consume/oxidize CH4, potentially mitigating CH4 emissions in these peatlands. Oxidation rates can exceed 90% of CH4 production in some settings, depending on O2 and CH4 availability and environmental conditions. Malhotra and Roulet identified 10 thaw stages in Stordalen Mire near Abisko, Sweden (68°21'N,18°49'E ) with variable vegetation, environmental conditions, and associated CH4 emissions. We investigated potential methane oxidation rates across these thaw stages. Peat cores were extracted from two depths at each stage and incubated in 350ml glass jars at in situ temperatures and CH4 concentrations. Headspace samples were collected from each incubation jar over a 48-hour period and analyzed for CH4 concentration using flame ionization detection gas chromatography (GC-FID). Oxidation rates ranged from <0.1 to 17 μg of CH4 per gram of dry biomass per day. Water table depth and pore water pH were the strongest environmental correlates of oxidation (sample size = 56, p < 0.001). The highest potential oxidation rates were observed in collapsing palsa sites and recently collapsed sedge-dominated open water sites near palsa mounds. Our results suggest that permafrost thaw induces high CH4 oxidation rates by creating conditions ideal for both methanogenic and methanotrophic microbial communities. Our results also reinforce the importance of incorporating transitional thaw stages in landscape level carbon budgets of thawing peatlands emphasized by Malhotra and Roulet. Forthcoming microbial analysis and stable isotope analysis will further elucidate the factors controlling methane oxidation rates at Stordalen Mire.

The Application Of Biofilter System For Reduction Of Methane Emissions From Modern Sanitary Landfills

NASA Astrophysics Data System (ADS)

Sung, K.; Park, S.

2007-12-01

Increased atmospheric concentrations of greenhouse gases (GHG) caused by anthropogenic activities has been related to global climate change. Methane, the second most important GHG after CO2, is 21 times more effective at trapping heat than CO2. Therefore, methane emission control is of utmost importance for global warming reduction. To minimize leachate production and protect groundwater resources, modern sanitary landfills are equipped with composite covers and gas collection systems. Methane from modern sanitary landfills is vented directly to the atmosphere, except for some of the largest landfills where it is recovered as energy and burned at the site. However, the efficiency of energy recovery systems in larger landfills is reduced as the amount of CH4 generated from landfill begins to decrease. In this study, the performance of a lab-scale model biofilter system was investigated to treat CH4 gas emitted from modern sanitary landfills by conducting batch and column experiments using landfill cover soil amended with earthworm cast as the filter bed medium. From the batch experiments to measure the influence of moisture content and temperature of the filter medium on CH4 removal capacity of a biofilter system, the optimum moisture content and temperature were found to be 10-15% by weight and 25-35°C, respectively. The column experiment was conducted to measure the influence of inlet CH4 concentration and CH4 loading rate on CH4 removal capacity of a biofilter system. As the inlet CH4 concentration decreased, the percentage of CH4 oxidized increased. Up to a CH4 loading rate of 2785 g CH4 m3 h- 1 (EBRT = 7.7 min), the CH4 removal efficiency of the biofilter was able to reach 100%. Based on the results of the study, the installation of a properly managed biofilter system should be capable of achieving a reduction in atmospheric CH4 emissions from modern sanitary landfills at low CH4 generation stage.

Landscape patterns of CH4 fluxes in an alpine tundra ecosystem

USGS Publications Warehouse

West, A.E.; Brooks, P.D.; Fisk, M.C.; Smith, Lesley 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.

Pd-Catalyzed C-H activation/oxidative cyclization of acetanilide with norbornene: concise access to functionalized indolines.

PubMed

Gao, Yang; Huang, Yubing; Wu, Wanqing; Huang, Kefan; Jiang, Huanfeng

2014-08-07

An efficient Pd-catalyzed oxidative cyclization reaction for the synthesis of functionalized indolines by direct C-H activation of acetanilide has been developed. The norbornylpalladium species formed via direct ortho C-H activation of acetanilides is supposed to be a key intermediate in this transformation.

Catalytic and electrochemical behaviour of solid oxide fuel cell operated with simulated-biogas mixtures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dang-Long, T., E-mail: 3TE14098G@kyushu-u.ac.jp; Quang-Tuyen, T., E-mail: tran.tuyen.quang.314@m.kyushu-u.ac.jp; Shiratori, Y., E-mail: shiratori.yusuke.500@m.kyushu-u.ac.jp

2016-06-03

Being produced from organic matters of wastes (bio-wastes) through a fermentation process, biogas mainly composed of CH{sub 4} and CO{sub 2} and can be considered as a secondary energy carrier derived from solar energy. To generate electricity from biogas through the electrochemical process in fuel cells is a state-of-the-art technology possessing higher energy conversion efficiency without harmful emissions compared to combustion process in heat engines. Getting benefits from high operating temperature such as direct internal reforming ability and activation of electrochemical reactions to increase overall system efficiency, solid oxide fuel cell (SOFC) system operated with biogas becomes a promising candidatemore » for distributed power generator for rural applications leading to reductions of environmental issues caused by greenhouse effects and bio-wastes. CO{sub 2} reforming of CH{sub 4} and electrochemical oxidation of the produced syngas (H{sub 2}–CO mixture) are two main reaction processes within porous anode material of SOFC. Here catalytic and electrochemical behavior of Ni-ScSZ (scandia stabilized-zirconia) anode in the feed of CH{sub 4}–CO{sub 2} mixtures as simulated-biogas at 800 °C were evaluated. The results showed that CO{sub 2} had strong influences on both reaction processes. The increase in CO{sub 2} partial pressure resulted in the decrease in anode overvoltage, although open-circuit voltage was dropped. Besides that, the simulation result based on a power-law model for equimolar CH{sub 4}−CO{sub 2} mixture revealed that coking hazard could be suppressed along the fuel flow channel in both open-circuit and closed-circuit conditions.« less

Real-time monitoring of methane oxidation in a simulated landfill cover soil and MiSeq pyrosequencing analysis of the related bacterial community structure.

PubMed

Xing, Zhilin; Zhao, Tiantao; Gao, Yanhui; He, Zhi; Zhang, Lijie; Peng, Xuya; Song, Liyan

2017-10-01

Real-time CH 4 oxidation in a landfill cover soil was studied using automated gas sampling that determined biogas (CH 4 and CO 2 ) and O 2 concentrations at various depths in a simulated landfill cover soil (SLCS) column reactor. The real-time monitoring system obtained more than 10,000 biogas (CH 4 and CO 2 ) and O 2 data points covering 32 steady states of CH 4 oxidation with 32 different CH 4 fluxes (0.2-125mol·m -2 ·d -1 ). The kinetics of CH 4 oxidation at different depths (0-20cm, 20-40cm, and 40-60cm) of SLCS were well fit by a CH 4 -O 2 dual-substrate model based on 32 values (averaged, n=5-15) of equilibrated CH 4 concentrations. The quality of the fit (R 2 ranged from 0.90 to 0.96) was higher than those reported in previous studies, which suggests that real time monitoring is beneficial for CH 4 oxidation simulations. MiSeq pyrosequencing indicated that CH 4 flux events changed the bacterial community structure (e.g., increased the abundance of Bacteroidetes and Methanotrophs) and resulted in a relative increase in the amount of type I methanotrophs (Methylobacter and Methylococcales) and a decrease in the amount of type II methanotrophs (Methylocystis). Copyright © 2017 Elsevier Ltd. All rights reserved.

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

DOE PAGES

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

2015-08-04

Methanotrophic bacteria play an important role oxidizing a significant fraction of methane (CH 4) produced in lakes. Aerobic CH 4 oxidation depends mainly on lake CH 4 and oxygen (O 2) 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, CH 4 oxidation is expected to be subject to large seasonal and geographic variations, which have been scarcelymore » reported in the literature. In the present study, we measured CH 4 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 CH 4 and O 2 concentrations. Here, we found that in the winter, aerobic CH 4 oxidation was mainly controlled by the dissolved O 2 concentration, while in the summer it was controlled primarily by the CH 4 concentration, which was scarce compared to dissolved O 2. The permafrost environment of the lakes was identified as another key factor. Thermokarst (thaw) lakes formed in yedoma-type permafrost had significantly higher CH 4 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 CH 4 cycling.« less

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

Methanotrophic bacteria play an important role oxidizing a significant fraction of methane (CH 4) produced in lakes. Aerobic CH 4 oxidation depends mainly on lake CH 4 and oxygen (O 2) 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, CH 4 oxidation is expected to be subject to large seasonal and geographic variations, which have been scarcelymore » reported in the literature. In the present study, we measured CH 4 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 CH 4 and O 2 concentrations. Here, we found that in the winter, aerobic CH 4 oxidation was mainly controlled by the dissolved O 2 concentration, while in the summer it was controlled primarily by the CH 4 concentration, which was scarce compared to dissolved O 2. The permafrost environment of the lakes was identified as another key factor. Thermokarst (thaw) lakes formed in yedoma-type permafrost had significantly higher CH 4 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 CH 4 cycling.« less

Physical and Biological Carbon Isotope Fractionation in Methane During Gas-Push-Pull-Tests

NASA Astrophysics Data System (ADS)

Gonzalez-Gil, G.; Schroth, M. H.; Gomez, K.; Zeyer, J.

2005-12-01

Stable isotope analyses have become a common tool to assess microbially-mediated processes in subsurface environments. We investigated if stable carbon isotope analysis can be used as a tool to complement gas push-pull tests (GPPTs), a novel technique that was recently developed and tested for the in-situ quantification of CH4 oxidation in soils. During a GPPT a gas mixture containing CH4, O2 and nonreactive tracer gases is injected into the soil, where CH4 is oxidized by indigenous microorganisms. Thereafter, a blend of injected gas mixture and soil air is extracted from the same location, and CH4 oxidation is quantified from an analysis of extracted CH4 and tracer gases. To assess the magnitude of physical isotope fractionation due to molecular diffusion during GPPTs, we conducted laboratory experiments in the absence of microbial activity in a 1m-high, 1m-diameter tank filled with dry sand. During the GPPTs' extraction phase, the isotopic composition of methane was analyzed. Results indicated strong carbon isotope fractionation (>20 per mil) during GPPTs. To assess the combined effect of physical and biological isotope fractionation, numerical simulations of GPPTs were conducted in which microbial CH4 isotope fractionation was simulated using first-order rate constants and microbial kinetic isotope fractionation factors previously reported for methane oxidation in landfill environments. Results of these simulations indicated that for small CH4 oxidation rates, overall isotope fractionation in CH4 is dominated by physical fractionation. Conversely, for high CH4 oxidation rates, overall fractionation is dominated by biological fractionation. Thus, CH4 isotope fractionation data alone from a single GPPT cannot be used to assess microbial CH4 oxidation. However, biological fractionation may be quantified if physical fractionation due to diffusion is known. This can be achieved by conducting two sequential GPPTs, with microbial activity being inhibited in the second test.

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 their inhibitor profiles are similar. Inhibitors thought to be specific to ammonia oxidizers have been used in environmental studies of nitrification. However, almost all of the numerous compounds found to inhibit ammonia oxidizers also inhibit methanotrophs, and most of the inhibitors act upon the monooxygenases. Many probably exert their effect by chelating copper, which is essential to the proper functioning of some monooxygenases. The lack of inhibitors specific for one or the other of the two groups of bacteria hampers the determination of their relative roles in nature. PMID:2496288

Heptanuclear CoII5CoIII2 Cluster as Efficient Water Oxidation Catalyst.

PubMed

Xu, Jia-Heng; Guo, Ling-Yu; Su, Hai-Feng; Gao, Xiang; Wu, Xiao-Fan; Wang, Wen-Guang; Tung, Chen-Ho; Sun, Di

2017-02-06

Inspired by the transition-metal-oxo cubical Mn 4 CaO 5 in photosystem II, we herein report a disc-like heptanuclear mixed-valent cobalt cluster, [Co II 5 Co III 2 (mdea) 4 (N 3 ) 2 (CH 3 CN) 6 (OH) 2 (H 2 O) 2 ·4ClO 4 ] (1, H 2 mdea = N-methyldiethanolamine), for photocatalytic oxygen evolution. The topology of the Co 7 core resembles a small piece of cobaltate protected by terminal H 2 O, N 3 - , CH 3 CN, and multidentate N-methyldiethanolamine at the periphery. Under the optimal photocatalytic conditions, 1 exhibits water oxidation activity with a turnover number (TON) of 210 and a turnover frequency (TOF initial ) of 0.23 s -1 . Importantly, electrospray mass spectrometry (ESI-MS) was used to not only identify the possible main active species in the water oxidation reaction but also monitor the evolutions of oxidation states of cobalt during the photocatalytic reactions. These results shed light on the design concept of new water oxidation catalysts and mechanism-related issues such as the key active intermediate and oxidation state evolution in the oxygen evolution process. The magnetic properties of 1 were also discussed in detail.

Choice of precipitant and calcination temperature of precursor for synthesis of NiCo2O4 for control of CO-CH4 emissions from CNG vehicles.

PubMed

Trivedi, Suverna; Prasad, Ram

2018-03-01

Compressed natural gas (CNG) is most appropriate an alternative of conventional fuel for automobiles. However, emissions of carbon-monoxide and methane from such vehicles adversely affect human health and environment. Consequently, to abate emissions from CNG vehicles, development of highly efficient and inexpensive catalysts is necessary. Thus, the present work attempts to scan the effects of precipitants (Na 2 CO 3 , KOH and urea) for nickel cobaltite (NiCo 2 O 4 ) catalysts prepared by co-precipitation from nitrate solutions and calcined in a lean CO-air mixture at 400°C. The catalysts were used for oxidation of a mixture of CO and CH 4 (1:1). The catalysts were characterized by X-ray diffractometer, Brunauer-Emmett-Teller surface-area, X-ray photoelectron spectroscopy; temperature programmed reduction and Scanning electron microscopy coupled with Energy-Dispersive X-Ray Spectroscopy. The Na 2 CO 3 was adjudged as the best precipitant for production of catalyst, which completely oxidized CO-CH 4 mixture at the lowest temperature (T 100 =350°C). Whereas, for catalyst prepared using urea, T 100 =362°C. On the other hand the conversion of CO-CH 4 mixture over the catalyst synthesized by KOH limited to 97% even beyond 400°C. Further, the effect of higher calcination temperatures of 500 and 600°C was examined for the best catalyst. The total oxidation of the mixture was attained at higher temperatures of 375 and 410°C over catalysts calcined at 500 and 600°C respectively. Thus, the best precipitant established was Na 2 CO 3 and the optimum calcination temperature of 400°C was found to synthesize the NiCo 2 O 4 catalyst for the best performance in CO-CH 4 oxidation. Copyright © 2017. Published by Elsevier B.V.

High Temporal and Spatial Variability of Atmospheric-Methane Oxidation in Alpine Glacier Forefield Soils

PubMed Central

Chiri, Eleonora; Nauer, Philipp A.; Rainer, Edda-Marie; Zeyer, Josef

2017-01-01

ABSTRACT Glacier forefield soils can provide a substantial sink for atmospheric CH4, facilitated by aerobic methane-oxidizing bacteria (MOB). However, MOB activity, abundance, and community structure may be affected by soil age, MOB location in different forefield landforms, and temporal fluctuations in soil physical parameters. We assessed the spatial and temporal variability of atmospheric-CH4 oxidation in an Alpine glacier forefield during the snow-free season of 2013. We quantified CH4 flux in soils of increasing age and in different landforms (sandhill, terrace, and floodplain forms) by using soil gas profile and static flux chamber methods. To determine MOB abundance and community structure, we employed pmoA gene-based quantitative PCR and targeted amplicon sequencing. Uptake of CH4 increased in magnitude and decreased in variability with increasing soil age. Sandhill soils exhibited CH4 uptake rates ranging from −3.7 to −0.03 mg CH4 m−2 day−1. Floodplain and terrace soils exhibited lower uptake rates and even intermittent CH4 emissions. Linear mixed-effects models indicated that soil age and landform were the dominating factors shaping CH4 flux, followed by cumulative rainfall (weighted sum ≤4 days prior to sampling). Of 31 MOB operational taxonomic units retrieved, ∼30% were potentially novel, and ∼50% were affiliated with upland soil clusters gamma and alpha. The MOB community structures in floodplain and terrace soils were nearly identical but differed significantly from the highly variable sandhill soil communities. We concluded that soil age and landform modulate the soil CH4 sink strength in glacier forefields and that recent rainfall affects its short-term variability. This should be taken into account when including this environment in future CH4 inventories. IMPORTANCE Oxidation of methane (CH4) in well-drained, “upland” soils is an important mechanism for the removal of this potent greenhouse gas from the atmosphere. It is largely mediated by aerobic, methane-oxidizing bacteria (MOB). Whereas there is abundant information on atmospheric-CH4 oxidation in mature upland soils, little is known about this important function in young, developing soils, such as those found in glacier forefields, where new sediments are continuously exposed to the atmosphere as a result of glacial retreat. In this field-based study, we investigated the spatial and temporal variability of atmospheric-CH4 oxidation and associated MOB communities in Alpine glacier forefield soils, aiming at better understanding the factors that shape the sink for atmospheric CH4 in this young soil ecosystem. This study contributes to the knowledge on the dynamics of atmospheric-CH4 oxidation in developing upland soils and represents a further step toward the inclusion of Alpine glacier forefield soils in global CH4 inventories. PMID:28687652

High temporal and spatial variability of atmospheric-methane oxidation in Alpine glacier-forefield soils.

PubMed

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

2017-07-07

Glacier-forefield soils can provide a substantial sink for atmospheric CH 4 , facilitated by aerobic methane-oxidizing bacteria (MOB). However, MOB activity, abundance, and community structure may be affected by soil age, location in different forefield landforms, and temporal fluctuations in soil-physical parameters. We assessed spatial and temporal variability of atmospheric CH 4 oxidation in an Alpine glacier forefield during the snow-free season 2013. We quantified CH 4 flux in soils of increasing age and in different landforms (sandhill, terrace, floodplain) using soil-gas-profile and static flux-chamber methods. To determine MOB abundance and community structure, we employed pmoA -gene-based quantitative PCR and targeted-amplicon sequencing. Uptake of CH 4 increased in magnitude and decreased in variability with increasing soil age. Sandhill soils exhibited CH 4 uptake ranging from -0.03- -3.7 mg CH 4 m -2 d -1 Floodplain and terrace soils exhibited smaller uptake and even intermittent CH 4 emissions. Linear mixed-effect models indicated that soil age and landform were dominating factors shaping CH 4 flux, followed by cumulative rainfall (weighted sum ≤ 4 d prior to sampling). Of 31 MOB operational taxonomic units retrieved, ∼30% were potentially novel, and ∼50% were affiliated with Upland Soil Clusters gamma and alpha. The MOB community structures in floodplain and terrace soils were nearly identical, but differed significantly from highly variable sandhill-soil communities. We conclude that soil age and landform modulate the soil CH 4 sink strength in glacier forefields, and recent rainfall affects its short-term variability. This should be taken into account when including this environment in future CH 4 inventories. Importance Oxidation of methane (CH 4 ) in well-drained, "upland" soils is an important mechanism for the removal of this potent greenhouse gas from the atmosphere. It is largely mediated by aerobic, methane-oxidizing bacteria (MOB). Whereas there is abundant information on atmospheric CH 4 oxidation in mature upland soils, little is known about this important function in young, developing soils such as those found in glacier forefields, where new sediments are continuously exposed to the atmosphere as a result of glacial retreat.In this field-based study we investigated spatial and temporal variability of atmospheric CH 4 oxidation and associated MOB communities in Alpine glacier-forefield soils, aiming at better understanding factors that shape the sink for atmospheric CH 4 in this young soil ecosystem. The study contributes to the knowledge on the dynamics of atmospheric CH 4 oxidation in developing upland soils, and represents a further step towards the inclusion of Alpine glacier-forefield soils in global CH 4 inventories. Copyright © 2017 American Society for Microbiology.

Assessment of microbial methane oxidation above a petroleum-contaminated aquifer using a combination of in situ techniques

NASA Astrophysics Data System (ADS)

Urmann, Karina; Schroth, Martin H.; Noll, Matthias; Gonzalez-Gil, Graciela; Zeyer, Josef

2008-06-01

Emissions of the greenhouse gas CH4, which is often produced in contaminated aquifers, are reduced or eliminated by microbial CH4 oxidation in the overlying vadose zone. The aim of this field study was to estimate kinetic parameters and isotope fractionation factors for CH4 oxidation in situ in the vadose zone above a methanogenic aquifer in Studen, Switzerland, and to characterize the involved methanotrophic communities. To quantify kinetic parameters, several field tests, so-called gas push-pull tests (GPPTs), with CH4 injection concentrations ranging from 17 to 80 mL L-1 were performed. An apparent Vmax of 0.70 ± 0.15 mmol CH4 (L soil air)-1 h-1 and an apparent Km of 0.28 ± 0.09 mmol CH4 (L soil air)-1 was estimated for CH4 oxidation at 2.7 m depth, close to the groundwater table. At 1.1 m depth, Km (0.13 ± 0.02 mmol CH4 (L soil air)-1) was in a similar range, but Vmax (0.076 ± 0.006 mmol CH4 (L soil air)-1 h-1) was an order of magnitude lower. At 2.7 m, apparent first-order rate constants determined from a CH4 gas profile (1.9 h-1) and from a single GPPT (2.0 ± 0.03 h-1) were in good agreement. Above the groundwater table, a Vmax much higher than the in situ CH4 oxidation rate prior to GPPTs indicated a high buffer capacity for CH4. At both depths, known methanotrophic species affiliated with Methylosarcina and Methylocystis were detected by cloning and sequencing. Apparent stable carbon isotope fractionation factors α for CH4 oxidation determined during GPPTs ranged from 1.006 to 1.032. Variability was likely due to differences in methanotrophic activity and CH4 availability leading to different degrees of mass transfer limitation. This complicates the use of stable isotopes as an independent quantification method.

Effects of alternative electron acceptors on the activity and community structure of methane-producing and consuming microbes in the sediments of two shallow boreal lakes.

PubMed

Rissanen, Antti J; Karvinen, Anu; Nykänen, Hannu; Peura, Sari; Tiirola, Marja; Mäki, Anita; Kankaala, Paula

2017-07-01

The role of anaerobic CH4 oxidation in controlling lake sediment CH4 emissions remains unclear. Therefore, we tested how relevant EAs (SO42-, NO3-, Fe3+, Mn4+, O2) affect CH4 production and oxidation in the sediments of two shallow boreal lakes. The changes induced to microbial communities by the addition of Fe3+ and Mn4+ were studied using next-generation sequencing targeting the 16S rRNA and methyl-coenzyme M reductase (mcrA) genes and mcrA transcripts. Putative anaerobic CH4-oxidizing archaea (ANME-2D) and bacteria (NC 10) were scarce (up to 3.4% and 0.5% of archaeal and bacterial 16S rRNA genes, respectively), likely due to the low environmental stability associated with shallow depths. Consequently, the potential anaerobic CH4 oxidation (0-2.1 nmol g-1dry weight (DW)d-1) was not enhanced by the addition of EAs, nor important in consuming the produced CH4 (0.6-82.5 nmol g-1DWd-1). Instead, the increased EA availability suppressed CH4 production via the outcompetition of methanogens by anaerobically respiring bacteria and via the increased protection of organic matter from microbial degradation induced by Fe3+ and Mn4+. Future studies could particularly assess whether anaerobic CH4 oxidation has any ecological relevance in reducing CH4 emissions from the numerous CH4-emitting shallow lakes in boreal and tundra landscapes. © FEMS 2017. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Culture scale-up and immobilisation of a mixed methanotrophic consortium for methane remediation in pilot-scale bio-filters.

PubMed

Karthikeyan, Obulisamy Parthiba; Saravanan, Nadarajan; Cirés, Samuel; Alvarez-Roa, Carlos; Razaghi, Ali; Chidambarampadmavathy, Karthigeyan; Velu, Chinnathambi; Subashchandrabose, Gobalakrishnan; Heimann, Kirsten

2017-02-01

Robust methanotrophic consortia for methane (CH 4 ) remediation and by-product development are presently not readily available for industrial use. In this study, a mixed methanotrophic consortium (MMC), sequentially enriched from a marine sediment, was assessed for CH 4 removal efficiency and potential biomass-generated by-product development. Suitable packing material for bio-filters to support MMC biofilm establishment and growth was also evaluated. The enriched MMC removed ∼7-13% CH 4 under a very high gas flow rate (2.5 L min -1 ; 20-25% CH 4 ) in continuous-stirred tank reactors (∼10 L working volume) and the biomass contained long-chain fatty acids (i.e. C 16 and C 18 ). Cultivation of the MMC on plastic bio-balls abated ∼95-97% CH 4 in pilot-scale non-sterile outdoor-operated bio-filters (0.1 L min -1 ; 1% CH 4 ). Contamination by cyanobacteria had beneficial effects on treating low-level CH 4 , by providing additional oxygen for methane oxidation by MMC, suggesting that the co-cultivation of MMC with cyanobacterial mats does not interfere with and may actually be beneficial for remediation of CH 4 and CO 2 at industrial scale.

A Methane-Rich Early Mars: Implications for Habitability and the Emergence of Life

NASA Astrophysics Data System (ADS)

Wong, M. L.; Yung, Y. L.; Friedson, A. J.

2016-12-01

High levels of CH4 in Mars's early atmosphere may have played a significant role in determining whether or not the planet was habitable or suitable for the emergence of life. Via the coupling of radiative-convective and photochemical models, we investigate the nature of Mars's 4.0 Ga atmosphere, which is sourced primarily from CH4—not CO2—degassing. This is consistent with a mantle that does not reach the requisite pressure (24 GPa) and temperature (1900 K) for the silicate spinel-to-perovskite transition, which would oxidize the mantle thanks to ferrous iron's tendency to disproportionate to ferric iron in the presence of silicate perovskite (Dale et al., 2012; McCammon, 1997; Wadhwa, 2001; Wood et al., 2006). Impact degassing from chondritic material can also contribute substantial amounts of CH4 to the atmosphere (Schaefer and Fegley, 2007). A terrestrial world whose atmosphere is laden with CH4 would not drive the emergence of life according to the alkaline hydrothermal vent theory (e.g. Martin et al., 2008; Russell et al., 2014, 2010), which relies on the presence of copious CO2. However, CH4 will be oxidized as a result of photochemistry and hydrogen escape; if this process is efficient enough, there will be CO2 aplenty. On the other hand, if CH4 is converted to CO2 too efficiently, then early Mars may lose the greenhouse warming it needs to maintain liquid water at the surface. We use RC1D, a non-gray 1-D radiative-convective equilibrium model, to calculate the atmospheric thermal structure consistent with the radiative heating and cooling associated with the composition computed at each chemical model time step, the Sun's luminosity at that time, and global average insolation conditions. KINETICS, the Caltech/JPL chemistry transport model (e.g. Nair et al., 1994), determines the chemical makeup of the atmosphere, how effectively CH4 can be oxidized to CO2, and evaluate the synthesis of organic molecules in the atmosphere. The atmosphere is in vapor pressure equilibrium with an H2O ocean (Villanueva et al., 2015) or massive glaciation (Fastook and Head, 2015), losing hydrogen to space via hydrodynamic escape, and irradiated by the faint-young Sun. This study is a step towards a grander, more realistic model of early Mars that includes sulfur chemistry, atmospheric dust and haze, and aqueous chemistry.

Nitrogen oxides and methane treatment by non-thermal plasma

NASA Astrophysics Data System (ADS)

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

2015-03-01

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

Estimating Sources and Sinks of Methane from Soils in the Contiguous United States (CONUS)

NASA Astrophysics Data System (ADS)

Shu, S.; Jain, A. K.; Kheshgi, H. S.

2017-12-01

The global methane (CH4) budget estimated based on state-of-the-art models remains highly uncertain. Sources and sinks of CH4 from soils, including wetlands, are the most important source of uncertainty. Soils are estimated to account for about 45% of global CH4 emissions. At the same time oxidation of CH4 by soils is a significant sink, representing about 10% of the total sink. However, most regional and global scale modeling studies of soil CH4 fluxes have ignored the sink through soil oxidation and the source of CH4 emissions from the wet soils with shallow water tables. In this study, we link a bottom-up soil gas diffusion and CH4 biogeochemistry model to a land surface model, ISAM, to calculate the sources, emissions from both wetlands and non-wetlands, and sinks, soil oxidation, of CH4 from soils for the CONUS over the period 1900-2100. The newly developed soil CH4 model framework consists of a gas diffusion module with the vertically resolved soil hydrology (depth up to 3.5 m soil) and soil organic carbon (SOC) and CH4 biogeochemistry module. SOC profile is estimated by modeling vertical soil mixing and thus can represent the deep SOC content and estimate CH4 production from the deep non-wetland soil. For the diffusion calculations, we separately consider both the dissolved and gaseous O2 and CH4 at each soil layer. For CH4 biogeochemistry, we parameterize the production, soil oxidation, ebullition and aerenchyma transportation of CH4 for both seasonal/permanent wetland and wet soil. The SWAMP inundated fraction dataset with 8-day temporal resolution is incorporated to prescribe the extent of permanent and seasonal wetland extent for the recent decade. The model is first evaluated using a compilation of published CH4 site measurement data for CONUS. We then perform two different model experiments: 1) forced by the CRUNCEP climate data from 1900 to 2010 to estimate the contemporary CH4 emission and 2) forced by a climate projection of IPCC's highest representative concentration pathway (RCP8.5) from 2011 to 2100. Our study shows that soil oxidation has an important role attenuating the estimated natural CH4 source. We also find a wetter and warmer climate affects the dry soil CH4 sink and wet soil CH4 emissions and increases the estimated CH4 source over the CONUS.

Selective CO Production by Photoelectrochemical Methane Oxidation on TiO2.

PubMed

Li, Wei; He, Da; Hu, Guoxiang; Li, Xiang; Banerjee, Gourab; Li, Jingyi; Lee, Shin Hee; Dong, Qi; Gao, Tianyue; Brudvig, Gary W; Waegele, Matthias M; Jiang, De-En; Wang, Dunwei

2018-05-23

The inertness of the C-H bond in CH 4 poses significant challenges to selective CH 4 oxidation, which often proceeds all the way to CO 2 once activated. Selective oxidation of CH 4 to high-value industrial chemicals such as CO or CH 3 OH remains a challenge. Presently, the main methods to activate CH 4 oxidation include thermochemical, electrochemical, and photocatalytic reactions. Of them, photocatalytic reactions hold great promise for practical applications but have been poorly studied. Existing demonstrations of photocatalytic CH 4 oxidation exhibit limited control over the product selectivity, with CO 2 as the most common product. The yield of CO or other hydrocarbons is too low to be of any practical value. In this work, we show that highly selective production of CO by CH 4 oxidation can be achieved by a photoelectrochemical (PEC) approach. Under our experimental conditions, the highest yield for CO production was 81.9%. The substrate we used was TiO 2 grown by atomic layer deposition (ALD), which features high concentrations of Ti 3+ species. The selectivity toward CO was found to be highly sensitive to the substrate types, with significantly lower yield on P25 or commercial anatase TiO 2 substrates. Moreover, our results revealed that the selectivity toward CO also depends on the applied potentials. Based on the experimental results, we proposed a reaction mechanism that involves synergistic effects by adjacent Ti sites on TiO 2 . Spectroscopic characterization and computational studies provide critical evidence to support the mechanism. Furthermore, the synergistic effect was found to parallel heterogeneous CO 2 reduction mechanisms. Our results not only present a new route to selective CH 4 oxidation, but also highlight the importance of mechanistic understandings in advancing heterogeneous catalysis.

Stable isotopes as tracers of methane dynamics in Everglades marshes with and without active populations of methane oxidizing bacteria

NASA Technical Reports Server (NTRS)

Happell, James D.; Chanton, Jeffrey P.; Whiting, Gary J.; Showers, William J.

1993-01-01

The stable carbon isotopic composition of CH4 is used to study the processes that affect it during transport through plants from sediment to the atmosphere. The enhancement of CH4 flux from Cladium and Eleocharis over the flux from open water or clipped sites indicated that these plants served as gas conduits between the sediments and the atmosphere. Lowering of the water table below the sediment surface caused an Everglades sawgrass marsh to shift from emission of CH4 to consumption of atmospheric CH4. Cladium transported gases passively mainly via molecular diffusion and/or effusion instead of actively via bulk flow. Stable isotropic data gave no evidence that CH4 oxidation was occurring in the rhizosphere of Cladium. Both CH4 stable carbon isotope and flux data indicated a lack of CH4 oxidation at the sediment-water interface in Everglades marl soils and its presence in peat soils where 40 to 92 percent of the flux across the sediment-water interface was oxidized.

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

PubMed

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

2014-12-01

With increasing livestock breeding, methane (CH4 ) emissions from manure management will increasingly contribute more to atmospheric CH4 concentration. The dynamics of methanogens and methanotrophs have not yet been studied in the manure environment. The current study combines surface CH4 emissions with methanogenic and methanotrophic community analyses from two management practices, windrow composting (WCOM) and solid storage (SSTO). Our results showed that there was an c. 50% reduction of CH4 emissions with WCOM compared with SSTO over a 50-day period. A sharp decrease in the quantities of both methanogens and methanotrophs in WCOM suggested that CH4 mitigation was mainly due to decreased CH4 production rather than increased CH4 oxidation. Pyrosequencing analysis demonstrated that aeration caused a clear shift of dominant methanogens in the manure, with specifically a significant decrease in Methanosarcina and increase in Methanobrevibacter. The composition of methanogenic community was influenced by manure management and regulated CH4 production. A sharp increase in the quantity of methanotrophs in SSTO suggested that microbial CH4 oxidation is an important sink for the CH4 produced. The increased abundance of Methylococcaceae in SSTO suggested that Type I methanotrophs have an advantage in CH4 oxidation in occupying niches under low CH4 and high O2 conditions. © 2014 Federation of European Microbiological Societies. Published by John Wiley & Sons Ltd. All rights reserved.

Chemoselective Aliphatic C-H Bond Oxidation Enabled by Polarity Reversal.

PubMed

Dantignana, Valeria; Milan, Michela; Cussó, Olaf; Company, Anna; Bietti, Massimo; Costas, Miquel

2017-12-27

Methods for selective oxidation of aliphatic C-H bonds are called on to revolutionize organic synthesis by providing novel and more efficient paths. Realization of this goal requires the discovery of mechanisms that can alter in a predictable manner the innate reactivity of these bonds. Ideally, these mechanisms need to make oxidation of aliphatic C-H bonds, which are recognized as relatively inert, compatible with the presence of electron rich functional groups that are highly susceptible to oxidation. Furthermore, predictable modification of the relative reactivity of different C-H bonds within a molecule would enable rapid diversification of the resulting oxidation products. Herein we show that by engaging in hydrogen bonding, fluorinated alcohols exert a polarity reversal on electron rich functional groups, directing iron and manganese catalyzed oxidation toward a priori stronger and unactivated C-H bonds. As a result, selective hydroxylation of methylenic sites in hydrocarbons and remote aliphatic C-H oxidation of otherwise sensitive alcohol, ether, amide, and amine substrates is achieved employing aqueous hydrogen peroxide as oxidant. Oxidations occur in a predictable manner, with outstanding levels of product chemoselectivity, preserving the first-formed hydroxylation product, thus representing an extremely valuable tool for synthetic planning and development.

Stable carbon isotopic evidence of methane consumption and production in three alpine ecosystems on the Qinghai-Tibetan Plateau

NASA Astrophysics Data System (ADS)

Kato, Tomomichi; Yamada, Keita; Tang, Yanhong; Yoshida, Naohiro; Wada, Eitaro

2013-10-01

To understand the mechanisms of soil CH4 consumption and production in alpine ecosystems, we for the first time examined the stable carbon isotope ratio of CH4 (δ13C-CH4) at three major grassland vegetation types, alpine meadow, alpine shrub, and alpine wetland, on the Qinghai-Tibetan Plateau. The alpine meadow and shrub showed net CH4 absorption in their vertical profiles of CH4 concentration in summer, but a difference in their processes. Whereas the alpine shrub was dominated by CH4 consumption in its soil profile, CH4 production in the alpine meadow could slightly cancel consumed CH4 in shallow soil from -0.3 to -0.1 m. This potential CH4 production can be attributed to the relatively wet soil type of that ecosystem, which might allow methanogenesis to act in moist soil lumps in the shallow layer. The alpine wetland differed in methane production, consumption, and transport pathways between hummock and hollow plots. In summer, both plots were enriched in 13C-CH4 in dissolved CH4 in soil pore water, suggesting that CH4 production was conducted mainly by acetate fermentation. In autumn, CH4 production was shifted toward CO2/H2 reduction. Furthermore, in hummocks, plant-mediated transport of CH4 by vascular plants appeared to perform passive CH4 flow from deep soil to atmosphere, which allowed the produced CH4 to bypass the oxidation zone in shallow soil. In hollows, however, CH4 produced in shallow soil was subject to simultaneous oxidation. The fractional oxidation rate on gross CH4 production in hollows was estimated by simple mass balance model at 7-17% in summer and 35-36% in autumn.

Protection of inorganic semiconductors for sustained, efficient photoelectrochemical water oxidation

DOE PAGES

Lichterman, Michael F.; Sun, Ke; Hu, Shu; ...

2015-10-25

Small-band-gap (E g < 2 eV) semiconductors must be stabilized for use in integrated devices that convert solar energy into the bonding energy of a reduced fuel, specifically H 2 (g) or a reduced-carbon species such as CH 3 OH or CH 4 . To sustainably and scalably complete the fuel cycle, electrons must be liberated through the oxidation of water to O 2 (g). Strongly acidic or strongly alkaline electrolytes are needed to enable efficient and intrinsically safe operation of a full solar-driven water-splitting system. But, under water-oxidation conditions, the small-band-gap semiconductors required for efficient cell operation aremore » unstable, either dissolving or forming insulating surface oxides. Here, we describe herein recent progress in the protection of semiconductor photoanodes under such operational conditions. We specifically describe the properties of two protective overlayers, TiO 2 /Ni and NiO x , both of which have demonstrated the ability to protect otherwise unstable semiconductors for > 100 h of continuous solar-driven water oxidation when in contact with a highly alkaline aqueous electrolyte (1.0 M KOH(aq)). Furthermore, the stabilization of various semiconductor photoanodes is reviewed in the context of the electronic characteristics and a mechanistic analysis of the TiO 2 films, along with a discussion of the optical, catalytic, and electronic nature of NiO x films for stabilization of semiconductor photoanodes for water oxidation.« less

Soil Methane Sink Capacity Response to a Long-Term Wildfire Chronosequence in Northern Sweden.

PubMed

McNamara, Niall P; Gregg, Ruth; Oakley, Simon; Stott, Andy; Rahman, Md Tanvir; Murrell, J Colin; Wardle, David A; Bardgett, Richard D; Ostle, Nick J

2015-01-01

Boreal forests occupy nearly one fifth of the terrestrial land surface and are recognised as globally important regulators of carbon (C) cycling and greenhouse gas emissions. Carbon sequestration processes in these forests include assimilation of CO2 into biomass and subsequently into soil organic matter, and soil microbial oxidation of methane (CH4). In this study we explored how ecosystem retrogression, which drives vegetation change, regulates the important process of soil CH4 oxidation in boreal forests. We measured soil CH4 oxidation processes on a group of 30 forested islands in northern Sweden differing greatly in fire history, and collectively representing a retrogressive chronosequence, spanning 5000 years. Across these islands the build-up of soil organic matter was observed to increase with time since fire disturbance, with a significant correlation between greater humus depth and increased net soil CH4 oxidation rates. We suggest that this increase in net CH4 oxidation rates, in the absence of disturbance, results as deeper humus stores accumulate and provide niches for methanotrophs to thrive. By using this gradient we have discovered important regulatory controls on the stability of soil CH4 oxidation processes that could not have not been explored through shorter-term experiments. Our findings indicate that in the absence of human interventions such as fire suppression, and with increased wildfire frequency, the globally important boreal CH4 sink could be diminished.

Soil Methane Sink Capacity Response to a Long-Term Wildfire Chronosequence in Northern Sweden

PubMed Central

McNamara, Niall P.; Gregg, Ruth; Oakley, Simon; Stott, Andy; Rahman, Md. Tanvir; Murrell, J. Colin; Wardle, David A.; Bardgett, Richard D.; Ostle, Nick J.

2015-01-01

Boreal forests occupy nearly one fifth of the terrestrial land surface and are recognised as globally important regulators of carbon (C) cycling and greenhouse gas emissions. Carbon sequestration processes in these forests include assimilation of CO2 into biomass and subsequently into soil organic matter, and soil microbial oxidation of methane (CH4). In this study we explored how ecosystem retrogression, which drives vegetation change, regulates the important process of soil CH4 oxidation in boreal forests. We measured soil CH4 oxidation processes on a group of 30 forested islands in northern Sweden differing greatly in fire history, and collectively representing a retrogressive chronosequence, spanning 5000 years. Across these islands the build-up of soil organic matter was observed to increase with time since fire disturbance, with a significant correlation between greater humus depth and increased net soil CH4 oxidation rates. We suggest that this increase in net CH4 oxidation rates, in the absence of disturbance, results as deeper humus stores accumulate and provide niches for methanotrophs to thrive. By using this gradient we have discovered important regulatory controls on the stability of soil CH4 oxidation processes that could not have not been explored through shorter-term experiments. Our findings indicate that in the absence of human interventions such as fire suppression, and with increased wildfire frequency, the globally important boreal CH4 sink could be diminished. PMID:26372346

Effects of preconditioning the rhizosphere of different plant species on biotic methane oxidation kinetics.

PubMed

Ndanga, Éliane M; Lopera, Carolina B; Bradley, Robert L; Cabral, Alexandre R

2016-09-01

The rhizosphere is known as the most active biogeochemical layer of the soil. Therefore, it could be a beneficial environment for biotic methane oxidation. The aim of this study was to document - by means of batch incubation tests - the kinetics of CH4 oxidation in rhizosphere soils that were previously exposed to methane. Soils from three pre-exposure to CH4 zones were sampled: the never-before pre-exposed (NEX), the moderately pre-exposed (MEX) and the very pre-exposed (VEX). For each pre-exposure zone, the rhizosphere of several plant species was collected, pre-incubated, placed in glass vials and submitted to CH4 concentrations varying from 0.5% to 10%. The time to the beginning of CH4 consumption and the CH4 oxidation rate were recorded. The results showed that the fastest CH4 consumption occurred for the very pre-exposed rhizosphere. Specifically, a statistically significant difference in CH4 oxidation half-life was found between the rhizosphere of the VEX vegetated with a mixture of different plants and the NEX vegetated with ryegrass. This difference was attributed to the combined effect of the preconditioning level and plant species as well as to the organic matter content. Regardless of the preconditioning level, the oxidation rate values obtained in this study were comparable to those reported in the reviewed literature for mature compost. Copyright © 2016 Elsevier Ltd. All rights reserved.

Organic Aerosols in the Presence of CO2 in the Early Earth and Exoplanets: UV-Vis Refractive Indices of Oxidized Tholins

NASA Astrophysics Data System (ADS)

Gavilan, Lisseth; Broch, Laurent; Carrasco, Nathalie; Fleury, Benjamin; Vettier, Ludovic

2017-10-01

In this experimental study we investigate the role of atmospheric CO2 on the optical properties of organic photochemical aerosols. To this end, we add CO2 to a N2:CH4 gas mixture used in a plasma typically used for Titan studies. We produce organic thin films (tholins) in plasmas where the CO2/CH4 ratio is increased from 0 to 4. We measure these films via spectrometric ellipsometry and apply a Tauc-Lorentz model, used for optically transparent materials, to obtain the thickness of the thin film, its optical band gap, and the refractive indices in the UV-visible (270-600 nm). All samples present a significant absorption band in the UV. According to the Tauc-Lorentz model, as the CO2/CH4 ratio is quadrupled, the position of the UV band is shifted from ˜177 nm to 264 nm while its strength is quadrupled. Consequently, we infer that oxidized organic aerosols absorb more efficiently at longer UV wavelengths than reduced aerosols. Our laboratory wavelength-tabulated UV-vis refractive indices provide new constraints to atmospheric models of the early Earth and Earth-like exoplanets including photochemical hazes formed under increasingly oxidizing conditions.

Manganese-catalyzed selective oxidation of aliphatic C-H groups and secondary alcohols to ketones with hydrogen peroxide.

PubMed

Dong, Jia Jia; Unjaroen, Duenpen; Mecozzi, Francesco; Harvey, Emma C; Saisaha, Pattama; Pijper, Dirk; de Boer, Johannes W; Alsters, Paul; Feringa, Ben L; Browne, Wesley R

2013-09-01

An efficient and simple method for selective oxidation of secondary alcohols and oxidation of alkanes to ketones is reported. An in situ prepared catalyst is employed based on manganese(II) salts, pyridine-2-carboxylic acid, and butanedione, which provides good-to-excellent conversions and yields with high turnover numbers (up to 10 000) with H2 O2 as oxidant at ambient temperatures. In substrates bearing multiple alcohol groups, secondary alcohols are converted to ketones selectively and, in general, benzyl C-H oxidation proceeds in preference to aliphatic C-H oxidation. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Methane oxidation in a landfill cover soil reactor: Changing of kinetic parameters and microorganism community structure.

PubMed

Xing, Zhi L; Zhao, Tian T; Gao, Yan H; Yang, Xu; Liu, Shuai; Peng, Xu Y

2017-02-23

Changing of CH 4 oxidation potential and biological characteristics with CH 4 concentration was studied in a landfill cover soil reactor (LCSR). The maximum rate of CH 4 oxidation reached 32.40 mol d -1 m -2 by providing sufficient O 2 in the LCSR. The kinetic parameters of methane oxidation in landfill cover soil were obtained by fitting substrate diffusion and consumption model based on the concentration profile of CH 4 and O 2 . The values of [Formula: see text] (0.93-2.29%) and [Formula: see text] (140-524 nmol kg soil-DW -1 ·s -1 ) increased with CH 4 concentration (9.25-20.30%), while the values of [Formula: see text] (312.9-2.6%) and [Formula: see text] (1.3 × 10 -5 to 9.0 × 10 -3 nmol mL -1 h -1 ) were just the opposite. MiSeq pyrosequencing data revealed that Methylobacter (the relative abundance was decreased with height of LCSR) and Methylococcales_unclassified (the relative abundance was increased expect in H 80) became the key players after incubation with increasing CH 4 concentration. These findings provide information for assessing CH 4 oxidation potential and changing of biological characteristics in landfill cover soil.

Seasonal variation in CH4 emissions and production and oxidation potentials at microsites on an oligotrophic pine fen.

PubMed

Saarnio, S; Alm, Jukka; Silvola, Jouko; Lohila, Annalea; Nykänen, Hannu; Martikainen, Pertti J

1997-04-01

 Temporal and spatial variation in CH 4 emissions was studied at hummock, Eriophorum lawn, flark and Carex lawn microsites in an oligotrophic pine fen over the growing season using a static chamber method, and CH 4 production and oxidation potentials in peat profiles from hummock and flark were determined in laboratory incubation experiments. Emissions were lowest in the hummocks, and decreased with increasing hummock height, while in the lawns and flarks they increased with increasing sedge cover. Statistical response functions with water table and peat temperature as independent variables were calculated in order to reconstruct seasonal CH 4 emissions by reference to the time series for peat temperature and water table specific to each microsite type. Mean CH 4 emissions in the whole area in the snow-free period of 1993, weighted in terms of the proportions of the microsites, were 1.7 mol CH 4 m -2 . Potential CH 4 production and oxidation rates were very low in the hummocks rising above the groundwater table, but were relatively similar when expressed per dry weight of peat both in the hummocks and flarks below the water table. The CH 4 production potential increased in autumn at both microsites and CH 4 oxidation potential seemed to decrease. The decrease in temperature in autumn certainly reduced in situ decomposition processes, possibly leaving unused substrates in the peat, which would explain the increase in CH 4 production potential.

Methane oxidation by termite mounds estimated by the carbon isotopic composition of methane

NASA Astrophysics Data System (ADS)

Sugimoto, Atsuko; Inoue, Tetsushi; Kirtibutr, Nit; Abe, Takuya

1998-12-01

Emission rates and carbon isotope ratios of CH4, emitted by workers of termites, and of CH4, emitted from their mounds, were observed in a dry evergreen forest in Thailand to estimate the proportion of CH4 oxidized during emission through the mound. The δ13C of CH4 emitted from a termite mound (-70.9 to -82.4‰) was higher than that of CH4 emitted by workers in the mound (-85.4 to -97. l‰). Using a fractionation factor (a = 0.987) for oxidation of CH4 which was obtained in the incubation experiment, an emission factor defined as (CH4 emitted from a termite mound/CH4 produced by termites) was calculated. The emission factor obtained in each termite mound was nearly zero for Macrotermes (fungus-growing termites), of which the nest has a thick soil wall and subterrannean termites, and 0.17 to 0.47 for Termitinae (small-mound-making termites). Global CH4 emission by termites was estimated on the basis of the CH4 emission rates by workers and termite biomass with the emission factors. The calculated result was 1.5 to 7.4 Tg/y (0.3 to 1.3% of total source), which is considerably smaller than the estimate by the IPCC [1994].

Biogenic methane, hydrogen escape, and the irreversible oxidation of early Earth.

PubMed

Catling, D C; Zahnle, K J; McKay, C

2001-08-03

The low O2 content of the Archean atmosphere implies that methane should have been present at levels approximately 10(2) to 10(3) parts per million volume (ppmv) (compared with 1.7 ppmv today) given a plausible biogenic source. CH4 is favored as the greenhouse gas that countered the lower luminosity of the early Sun. But abundant CH4 implies that hydrogen escapes to space (upward arrow space) orders of magnitude faster than today. Such reductant loss oxidizes the Earth. Photosynthesis splits water into O2 and H, and methanogenesis transfers the H into CH4. Hydrogen escape after CH4 photolysis, therefore, causes a net gain of oxygen [CO2 + 2H2O --> CH4 + 2O2 --> CO2 + O2 + 4H(upward arrow space)]. Expected irreversible oxidation (approximately 10(12) to 10(13) moles oxygen per year) may help explain how Earth's surface environment became irreversibly oxidized.

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

NASA Astrophysics Data System (ADS)

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

2013-04-01

As the second most important greenhouse gas (GHG) in the atmosphere, methane (CH4) plays a central role in global warming. Diverse types of soil have been reported as potential CH4 sinks due to the activity of methane oxidizing bacteria (MOB), underlining the importance of this functional group of microorganisms on a global basis. Agricultural practices are known to negatively affect CH4 oxidation in soil, while afforestation of former agricultural soils has been shown to enhance CH4 oxidation over time. However, knowledge is scarce with regard to the mechanisms driving the process of CH4 oxidation in different land uses. Our aim was to study the changes in CH4 uptake capacity in soils along a land-use change gradient from cropland to forest. We performed an incubation experiment to study the CH4 oxidation capacity of the top mineral soil (0-5 cm and 5-15 cm depth) for sites representing the transition from agriculture to afforestation based on monoculture of three tree species with different stand ages: pedunculate oak (4, 19, 42 and >200 years old), European larch (22 and 41 years old) and Norway spruce (15 and 43 years old). Main soil parameters were also measured to determine differences in soil properties between sites. Methane oxidation rates were related to the abundance of the soil methanotrophic community based on quantitative PCR (qPCR). In addition, we also estimated the abundance of ammonia-oxidizing bacteria (AOB) and archaea (AOA), in order to investigate the link between these two similar functional groups. Although present, the abundance of AOB was under detection limit. The effects and interactions among all measured variables were summarized by Principal Component Analysis (PCA). Along the gradient, CH4 oxidation increased with increasing stand age in both soil layers (ranging from 0-1.3 nmol g-1dw d-1). However, we detected significant differences, in particular between oak and spruce, suggesting a possible tree species effect on the CH4 oxidation potential. The abundance of MOB also increased with stand age in the top layer (0-5 cm), but this trend was not clear in the 5-15 cm. On the other hand, we found a consistent decrease in the abundance of AOA with increasing stand age. This trend suggests that over time, the environmental niche shared by these microbial populations changes in favour of the MOB, most likely induced by changes in soil parameters, such as bulk density, carbon content and concentration of inorganic forms of nitrogen. In fact, results from the PCA indicated that over time, bulk density and carbon content were the variables that changed the most across the land use gradient, thereby influencing the CH4 oxidation capacity and the presence of the MOB. Our study provides evidence for a positive impact of afforestation of former cropland on CH4 uptake capacity in soils, contributing to mitigate the climatic consequences of this strong GHG in the atmosphere. Keywords: methane oxidation, afforestation, methane oxidizing bacteria (MOB), bulk density.

C-H functionalization of 1,4-naphthoquinone by oxidative coupling with anilines in the presence of a catalytic quantity of copper(II) acetate.

PubMed

Lisboa, Cinthia da S; Santos, Vanessa G; Vaz, Boniek G; de Lucas, Nanci C; Eberlin, Marcos N; Garden, Simon J

2011-07-01

The oxidative addition of anilines (2) with 1,4-naphthoquinone (3) to give N-aryl-2-amino-1,4-naphthoquinones (1) was found to be catalyzed by copper(II) acetate. In the absence of the catalyst, the reactions are slower and give lower yields with the formation of many colateral products. In the presence of 10 mol % hydrated copper(II) acetate, the reactions are generally more efficient in that they are cleaner, higher yielding, and faster.

Single Step Bi-reforming and Oxidative Bi-reforming of Methane (Natural Gas) with Steam and Carbon Dioxide to Metgas (CO-2H2) for Methanol Synthesis: Self-Sufficient Effective and Exclusive Oxygenation of Methane to Methanol with Oxygen.

PubMed

Olah, George A; Goeppert, Alain; Czaun, Miklos; Mathew, Thomas; May, Robert B; Prakash, G K Surya

2015-07-15

Catalysts based on suitable metal oxide supports, such as NiO/MgO and CoO/MgO, were shown to be active for single step bi-reforming, the combined steam and dry reforming of methane or natural gas with H2O and CO2 exclusively to metgas (CO-2H2) for efficient methanol synthesis. Reactions were carried out in a tubular flow reactor under pressures up to 42 bar at 830-910 °C. Using a CH4 to steam to CO2 ratio of ∼3:2:1 in the gas feed, the H2/CO ratio of 2:1 was achieved, which is desired for subsequent methanol synthesis. The needed 2/1 steam/CO2 feed ratio together with the reaction heat for the endothermic bi-reforming can be conveniently obtained by the complete combustion of a quarter part of the overall used methane (natural gas) with oxygen of the air (oxidative bi-reforming). Complete combustion of a part of methane followed by bi-reforming leads to the production of metgas (H2/CO in 2:1 mol ratio) for self-sufficient exclusive methanol synthesis. The long sought after but elusive efficient and selective oxygenation of methane to methanol is thus achieved in an effective and economic way without any oxidation byproduct formation according to CH4 + 1/2O2 → CH3OH.

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 (CO 2 , CH 4 , N 2 O), sulfate, sulfide, iron and manganese concentrations and δ 13 C-CH4 were determined. We performed incubation experiments to quantify CH 4 oxidation rates, with a focus on anaerobic CH 4 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 CO 2 and CH 4 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-CH 4 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. CH 4 oxidation was mostly aerobic (∼80% of total oxidation) in spring and winter, and almost exclusively anaerobic in summer and autumn. Despite important CH 4 oxidation rates, the estimated CH 4 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). Copyright © 2016 Elsevier Ltd. All rights reserved.

Ubiquitous Low-Cost Functionalized Multi-Walled Carbon Nanotube Sensors for Distributed Methane Leak Detection

DOE PAGES

Humayun, Md Tanim; Divan, Ralu; Stan, Liliana; ...

2016-06-16

This paper presents a highly sensitive, energy efficient and low-cost distributed methane (CH 4) sensor system (DMSS) for continuous monitoring, detection, and localization of CH 4 leaks in natural gas infrastructure, such as transmission and distribution pipelines, wells, and production pads. The CH 4 sensing element, a key component of the DMSS, consists of a metal oxide nanocrystal (MONC) functionalized multi-walled carbon nanotube (MWCNT) mesh which, in comparison to existing literature, shows stronger relative resistance change while interacting with lower parts per million (ppm) concentration of CH 4. A Gaussian plume triangulation algorithm has been developed for the DMSS. Givenmore » a geometric model of the surrounding environment the algorithm can precisely detect and localize a CH 4 leak as well as estimate its mass emission rate. A UV-based surface recovery technique making the sensor recover 10 times faster than the reported ones is presented for the DMSS. In conclusion, a control algorithm based on the UV-accelerated recovery is developed which facilitates faster leak detection.« less

Supercritical gasification for the treatment of o-cresol wastewater.

PubMed

Wei, Chao-hai; Hu, Cheng-sheng; Wu, Chao-fei; Yan, Bo

2006-01-01

The supercritical water gasification of phenolic wastewater without oxidant was performed to degrade pollutants and produce hydrogen-enriched gases. The simulated o-cresol wastewater was gasified at 440-650 degrees C and 27.6 MPa in a continuous Inconel 625 reactor with the residence time of 0.42-1.25 min. The influence of the reaction temperature, residence time, pressure, catalyst, oxidant and the pollutant concentration on the gasification efficiency was investigated. Higher temperature and longer residence time enhanced the o-cresol gasification. The TOC removal rate and hydrogen gasification rate were 90.6% and 194.6%, respectively, at the temperature of 650 degrees C and the residence time of 0.83 min. The product gas was mainly composed of H2, CO2, CH4 and CO, among which the total molar percentage of H2 and CH4 was higher than 50%. The gasification efficiency decreased with the pollutant concentration increasing. Both the catalyst and oxidant could accelerate the hydrocarbon gasification at a lower reaction temperature, in which the catalyst promoted H2 production and the oxidant enhanced CO2 generation. The intermediates of liquid effluents were analyzed and phenol was found to be the main composition. The results indicate that the supercritical gasification is a promising way for the treatment of hazardous organic wastewater.

Long-term bio-H2 and bio-CH4 production from food waste in a continuous two-stage system: Energy efficiency and conversion pathways.

PubMed

Algapani, Dalal E; Qiao, Wei; di Pumpo, Francesca; Bianchi, David; Wandera, Simon M; Adani, Fabrizio; Dong, Renjie

2018-01-01

Anaerobic digestion is a well-established technology for treating organic waste, but it is still under challenge for food waste due to process stability problems. In this work, continuous H 2 and CH 4 production from canteen food waste (FW) in a two-stage system were successfully established by optimizing process parameters. The optimal hydraulic retention time was 5d for H 2 and 15d for CH 4 . Overall, around 59% of the total COD in FW was converted into H 2 (4%) and into CH 4 (55%). The fluctuations of FW characteristics did not significantly affect process performance. From the energy point view, the H 2 reactor contributed much less than the methane reactor to total energy balance, but it played a key role in maintaining the stability of anaerobic treatment of food waste. Microbial characterization indicated that methane formation was through syntrophic acetate oxidation combined with hydrogenotrophic methanogenesis pathway. Copyright © 2017. Published by Elsevier Ltd.

Nutrient Controls on Methane Emissions in a Permafrost Thaw Subarctic Peatland

NASA Astrophysics Data System (ADS)

Kashi, N. N.; Perryman, C. R.; Malhotra, A.; Marek, E. A.; Giesler, R.; Varner, R. K.

2015-12-01

Permafrost peatlands in northern latitudes are large reservoirs of sequestered carbon that are vulnerable to climate change. While peatlands account for a small fraction of total global land surfaces, their potential to release sequestered carbon in response to higher temperatures is of concern. Of particular relevance is the conversion of these carbon stores into methane (CH4), a strong greenhouse gas with a global warming potential 20 times greater than that of CO2 over a 100-year time frame. Here, we explore how key nutrients impact the consumption of CH4 at the Stordalen Mire in Abisko, Sweden, a discontinuous permafrost peatland with expanding thaw over the last century. Peatland CH4 emissions are highly spatially variable due to multiple emission pathways and strong dependence on several environmental factors. Among controls on CH4 emissions, such as temperature and water table depth, primary production of wetland vegetation is also a strong factor in the variability of CH4 emissions. Plant community shifts among permafrost thaw stages subsequently change nutrient cycling and availability, which in turn impacts primary production. Early stages of permafrost thaw are mosaicked with a variety of vascular plants and mosses. We analyzed potential enzymatic activities of chitinase, glucosidase, and phosphatase as proxies for organic nitrogen, carbon, and phosphorus cycling, respectively, in tandem with potential CH4 oxidation rates. In addition, stoichiometric ratios of carbon, nitrogen, and phosphorus concentrations are used to illustrate nutrient limitation controls on CH4 oxidation rates. While CH4 emissions are low throughout initial thaw stages, < 7 CH4 mg m-2 day-1, we found they had the highest rates of potential CH4 oxidation. These permafrost thaw-induced CH4 oxidation rates are 5 and 11 times higher, in the surface and depth of the peat profile respectively, than subsequent aerobic permafrost thaw stages. As CH4 emissions are low in intact permafrost peatlands, these high rates of potential CH4 oxidation indicate the importance of plant communities and the methanotrophic microbes they harbor.

OXIDIZING PROTO-ATMOSPHERE ON TITAN: CONSTRAINT FROM N{sub 2} FORMATION BY IMPACT SHOCK

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ishimaru, Ryo; Matsui, Takafumi; Sekine, Yasuhito

2011-11-01

Titan is the only satellite that possesses a thick atmosphere, composed mainly of N{sub 2} and CH{sub 4}. However, its origin and evolution remain largely unknown. Knowledge of the acquirement of a N{sub 2} atmosphere on Titan would provide insights into nitrogen evolution in planetary atmospheres as well as the formation of satellite systems around gas giants. Previous studies have proposed that the atmospheric N{sub 2} would have been converted from NH{sub 3} via shock heating by accreting satellitesimals in the highly reducing proto-atmosphere composed of NH{sub 3} and CH{sub 4}. Nevertheless, the validity of this mechanism strongly depends onmore » both the composition of the proto-atmosphere and kinetics of shock chemistry. Here, we show that a CO{sub 2}-rich oxidizing proto-atmosphere is necessary to form N{sub 2} from NH{sub 3} efficiently by atmospheric shock heating. Efficient shock production of N{sub 2} is inhibited in a reducing proto-atmosphere composed of NH{sub 3} and CH{sub 4}, because CH{sub 4} plays as the coolant gas owing to its large heat capacity. Our calculations show that the amount of N{sub 2} produced in a CO{sub 2}-rich proto-atmosphere could have reached {approx}20 times that on the present Titan. Although further quantitative analysis are required (especially, the occurrence of catalytic reactions), our results imply that the chemical composition of satellitesimals that formed the Saturnian system is required to be oxidizing if the current atmospheric N{sub 2} is derived from the shock heating in the proto-atmosphere during accretion. This supports the formation of regular satellites in an actively supplied circumplanetary disk using CO{sub 2}-rich materials originated from the solar nebula at the final stage of gas giant formation.« less

Efficient photocatalytic selective nitro-reduction and C-H bond oxidation over ultrathin sheet mediated CdS flowers.

PubMed

Pahari, Sandip Kumar; Pal, Provas; Srivastava, Divesh N; Ghosh, Subhash Ch; Panda, Asit Baran

2015-06-28

We report here a visible light driven selective nitro-reduction and oxidation of saturated sp(3) C-H bonds using ultrathin (0.8 nm) sheet mediated uniform CdS flowers as catalyst under a household 40 W CFL lamp and molecular oxygen as oxidant. The CdS flowers were synthesized using a simple surfactant assisted hydrothermal method.

Effect of temperature and oxidation rate on carbon-isotope fractionation during methane oxidation by landfill cover materials.

PubMed

Chanton, Jeffrey P; Powelson, David K; Abichou, Tarek; Fields, Dana; Green, Roger

2008-11-01

The quantification of methane oxidation is one of the major uncertainties in estimating CH4 emissions from landfills. Stable isotope methods provide a useful field approach for the quantification of methane oxidation in landfill cover soils. The approach relies upon the difference between the isotopic composition of oxidized gas at the location of interest and anaerobic zone CH4 and knowledge of alpha(ox), a term that describes the isotopic fractionation of the methanotrophic bacteria in their discrimination against (13)CH4. Natural variability in alpha(0x) in different landfill soils and the effect of temperature and other environmental factors on this parameter are not well defined. Therefore, standard determinations of alpha(ox), batch incubations of landfill cover soils with CH4, were conducted to determine alpha(ox) under a variety of conditions. When these results were combined with those of previous landfill incubation studies, the average alpha(ox) at 25 degrees C was 1.022 +/- 0.0015. alpha(ox) decreased with increasing temperature (-0.00039 alpha(ox) degrees C(-1)) overthe temperature range of 3-35 degrees C. alpha(ox) was found to be higher when determined after CH4-free storage and declined following CH4 pretreatment. alpha(ox) declined nonlinearly with increasing methane oxidation rate, Vmax.

High-Temperature Carbon Deposition on Oxide Surfaces by CO Disproportionation

PubMed Central

2016-01-01

Carbon deposition due to the inverse Boudouard reaction (2CO → CO2 + C) has been studied on yttria-stabilized zirconia (YSZ), Y2O3, and ZrO2 in comparison to CH4 by a variety of different chemical, structural, and spectroscopic characterization techniques, including electrochemical impedance spectroscopy (EIS), Fourier-transform infrared (FT-IR) spectroscopy and imaging, Raman spectroscopy, and electron microscopy. Consentaneously, all experimental methods prove the formation of a more or less conducting carbon layer (depending on the used oxide) of disordered nanocrystalline graphite covering the individual grains of the respective pure oxides after treatment in flowing CO at temperatures above ∼1023 K. All measurements show that during carbon deposition, a more or less substantial surface reduction of the oxides takes place. These results, therefore, reveal that the studied pure oxides can act as efficient nonmetallic substrates for CO-induced growth of highly distorted graphitic carbon with possible important technological implications especially with respect to treatment in pure CO or CO-rich syngas mixtures. Compared to CH4, more carbon is generally deposited in CO under otherwise similar experimental conditions. Although Raman and electron microscopy measurements do not show substantial differences in the structure of the deposited carbon layers, in particular, electrochemical impedance measurements reveal major differences in the dynamic growth process of the carbon layer, eventually leading to less percolated islands and suppressed metallic conductivity in comparison to CH4-induced graphite. PMID:26877828

Performance of green waste biocovers for enhancing methane oxidation.

PubMed

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

2015-05-01

Green waste aged 2 and 24months, labeled "fresh" and "aged" green waste, respectively, were placed in biocover test cells and evaluated for their ability to oxidize methane (CH4) under high landfill gas loading over a 15-month testing period. These materials are less costly to produce than green waste compost, yet satisfied recommended respiration requirements for landfill compost covers. In field tests employing a novel gas tracer to correct for leakage, both green wastes oxidized CH4 at high rates during the first few months of operation - 140 and 200g/m(2)/day for aged and fresh green waste, respectively. Biocover performance degraded during the winter and spring, with significant CH4 generated from anaerobic regions in the 60-80cm thick biocovers. Concurrently, CH4 oxidation rates decreased. Two previously developed empirical models for moisture and temperature dependency of CH4 oxidation in soils were used to test their applicability to green waste. Models accounted for 68% and 79% of the observed seasonal variations in CH4 oxidation rates for aged green waste. Neither model could describe similar seasonal changes for the less stable fresh green waste. This is the first field application and evaluation of these empirical models using media with high organic matter. Given the difficulty of preventing undesired CH4 generation, green waste may not be a viable biocover material for many climates and landfill conditions. Copyright © 2015 Elsevier Ltd. All rights reserved.

Nickel(II) complexes of tripodal 4N ligands as catalysts for alkane oxidation using m-CPBA as oxidant: ligand stereoelectronic effects on catalysis.

PubMed

Balamurugan, Mani; Mayilmurugan, Ramasamy; Suresh, Eringathodi; Palaniandavar, Mallayan

2011-10-07

Several mononuclear Ni(II) complexes of the type [Ni(L)(CH(3)CN)(2)](BPh(4))(2) 1-7, where L is a tetradentate tripodal 4N ligand such as N,N-dimethyl-N',N'-bis(pyrid-2-ylmethyl)ethane-1,2-diamine (L1), N,N-diethyl-N',N'-bis(pyrid-2-ylmethyl)ethane-1,2-diamine (L2), N,N-dimethyl-N'-(1-methyl-1H-imidazol-2-ylmethyl)-N'-(pyrid-2-ylmethyl)ethane-1,2-diamine (L3), N,N-dimethyl-N',N'-bis(1-methyl-1H-imidazol-2-ylmethyl)ethane-1,2-diamine (L4), N,N-dimethyl-N',N'-bis(quinolin-2-ylmethyl)ethane-1,2-diamine (L5), tris(benzimidazol-2-ylmethyl)amine (L6) and tris(pyrid-2-ylmethyl)amine (L7), have been isolated and characterized using CHN analysis, UV-Visible spectroscopy and mass spectrometry. The single-crystal X-ray structures of the complexes [Ni(L1)(CH(3)CN)(H(2)O)](ClO(4))(2) 1a, [Ni(L2)(CH(3)CN)(2)](BPh(4))(2) 2, [Ni(L3)(CH(3)CN)(2)](BPh(4))(2) 3 and [Ni(L4)(CH(3)CN)(2)](BPh(4))(2) 4 have been determined. All these complexes possess a distorted octahedral coordination geometry in which Ni(II) is coordinated to four nitrogen atoms of the tetradentate ligands and two CH(3)CN (2, 3, 4) or one H(2)O and one CH(3)CN (1a) are located in cis positions. The Ni-N(py) bond distances (2.054(2)-2.078(3) Å) in 1a, 2 and 3 are shorter than the Ni-N(amine) bonds (2.127(2)-2.196(3) Å) because of sp(2) and sp(3) hybridizations of the pyridyl and tertiary amine nitrogens respectively. In 3 the Ni-N(im) bond (2.040(5) Å) is shorter than the Ni-N(py) bond (2.074(4) Å) due to the stronger coordination of imidazole compared with the pyridine donor. In dichloromethane/acetonitrile solvent mixture, all the Ni(ii) complexes possess an octahedral coordination geometry, as revealed by the characteristic ligand field bands in the visible region. They efficiently catalyze the hydroxylation of alkanes when m-CPBA is used as oxidant with turnover number (TON) in the range of 340-620 and good alcohol selectivity for cyclohexane (A/K, 5-9). By replacing one of the pyridyl donors in TPA by a weakly coordinating -NMe(2) or -NEt(2) donor nitrogen atom the catalytic activity decreases slightly with no change in the selectivity. In contrast, upon replacing the pyridyl nitrogen donor by the strongly σ-bonding imidazolyl or sterically demanding quinolyl/benzimidazolyl nitrogen donor, both the catalytic activity and selectivity decrease, possibly due to destabilization of the intermediate [(4N)(CH(3)CN)Ni-O˙](+) radical species. Adamantane is selectively (3°/2°, 12-17) oxidized to 1-adamantanol, 2-adamantanol and 2-adamantanone while cumene is selectively oxidized to 2-phenyl-2-propanol. In contrast to cyclohexane oxidation, the incorporation of sterically hindering quinolyl/benzimidazolyl donors around Ni(ii) leads to a high 3°/2° bond selectivity for adamantane oxidation. A linear correlation between the metal-ligand covalency parameter (β) and the turnover number has been observed.

Electrochemical Cobalt-Catalyzed C-H Activation.

PubMed

Sauermann, Nicolas; Meyer, Tjark H; Ackermann, Lutz

2018-06-19

Carbon-heteroatom bonds represent omnipresent structural motifs of the vast majority of functionalized materials and bioactive compounds. C-H activation has emerged as arguably the most efficient strategy to construct C-Het bonds. Despite of major advances, these C-H transformations were largely dominated by precious transition metal catalysts, in combination with stoichiometric, toxic metal oxidants. Herein, we discuss the recent evolution of cobalt-catalyzed C-H activations that enable C-Het formations with electricity as the sole sustainable oxidant until May 2018. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Arctic tundra and mountain landscapes are persistent sinks of atmospheric CH4

NASA Astrophysics Data System (ADS)

Christiansen, Jesper; Winkler, Renato; Juncher Jørgensen, Christian

2017-04-01

Recent studies have shown significant rates of net uptake of atmospheric methane (CH4) in Arctic tundra soils. Oxidation of CH4 in these cold, dry soils in the Arctic region can counteract CH4 emissions from wetlands and play a potential important role for the net Arctic CH4 budget. However, significant knowledge gaps exist on the overall magnitude of the net CH4 sink in these cold, dry systems as the spatial and environmental limits for CH4 oxidation has not been determined. In particular, the extent, magnitude and drivers of CH4 oxidation in mountains and alpine landforms, which occupy large land areas in the Arctic and High Arctic has not yet been investigated leaving a potential vast CH4 sink unquantified with major potential implications for our conceptual view of Arctic CH4 budget in a changing climate. Here we present the results from two expeditions in the summers of 2015 and 2016 from Disko Bay and in the pro-glacial landscape in vicinity of the Russell Glacier, Kangerlussuaq, Greenland, respectively. The aim of our work is to determine the magnitude and extent of net uptake of atmospheric CH4 across a variety of previously unexplored dry tundra and post-glacial landforms in the Arctic, i.e. marginal moraines and other glacial features at the Greenland ice sheet as well as mountain tops and outwash plains. We used high-precision, mobile cavity-ring-down spectrometers (e.g. model G4301 GasScouter, Picarro Inc.) to achieve reliable flux estimates in sub-ambient CH4 concentration levels with a 4-minute enclosure time per chamber measurement. Our results show a persistent net uptake of CH4 uptake in these dry, extreme environments that rival the sink strength observed in temperate forest soils, otherwise considered the primary global terrestrial sink of atmospheric CH4. In this dynamic glacial landscape the magnitude of the net CH4 uptake is mainly constrained by recent landscape evolution along glacier margins and meltwater systems. Utilizing the high mobility and precision of a new generation of greenhouse gas analyzers, like the Picarro GasScouter, we can explore beyond our traditional field scale the spatial drivers of CH4 oxidation in the harsh Arctic landscape. Thus, our measurements highlight the importance of net CH4 uptake in tundra soils for the Arctic CH4 budget.

Effects of compost biocovers on gas flow and methane oxidation in a landfill cover.

PubMed

Abichou, Tarek; Mahieu, Koenraad; Yuan, Lei; Chanton, Jeffery; Hater, Gary

2009-05-01

Previous publications described the performance of biocovers constructed with a compost layer placed on select areas of a landfill surface characterized by high emissions from March 2004 to April 2005. The biocovers reduced CH(4) emissions 10-fold by hydration of underlying clay soils, thus reducing the overall amount of CH(4) entering them from below, and by oxidation of a greater portion of that CH(4). This paper examines in detail the field observations made on a control cell and a biocover cell from January 1, 2005 to December 31, 2005. Field observations were coupled to a numerical model to contrast the transport and attenuation of CH(4) emissions from these two cells. The model partitioned the biocover's attenuation of CH(4) emission into blockage of landfill gas flow from the underlying waste and from biological oxidation of CH(4). Model inputs were daily water content and temperature collected at different depths using thermocouples and calibrated TDR probes. Simulations of CH(4) transport through the two soil columns depicted lower CH(4) emissions from the biocover relative to the control. Simulated CH(4) emissions averaged 0.0gm(-2)d(-1) in the biocover and 10.25gm(-2)d(-1) in the control, while measured values averaged 0.04gm(-2)d(-1) in the biocover and 14gm(-2)d(-1) in the control. The simulated influx of CH(4) into the biocover (2.7gm(-2)d(-1)) was lower than the simulated value passing into the control cell (29.4gm(-2)d(-1)), confirming that lower emissions from the biocover were caused by blockage of the gas stream. The simulated average rate of biological oxidation predicted by the model was 19.2gm(-2)d(-1) for the control cell as compared to 2.7gm(-2)d(-1) biocover. Even though its V(max) was significantly greater, the biocover oxidized less CH(4) than the control cell because less CH(4) was supplied to it.

Greenhouse gas emissions during MSW landfilling in China: influence of waste characteristics and LFG treatment measures.

PubMed

Yang, Na; Zhang, Hua; Shao, Li-Ming; Lü, Fan; He, Pin-Jing

2013-11-15

Reducing greenhouse gas (GHG) emissions from municipal solid waste (MSW) treatment can be highly cost-effective in terms of GHG mitigation. This study investigated GHG emissions during MSW landfilling in China under four existing scenarios and in terms of seven different categories: waste collection and transportation, landfill management, leachate treatment, fugitive CH4 (FM) emissions, substitution of electricity production, carbon sequestration and N2O and CO emissions. GHG emissions from simple sanitary landfilling technology where no landfill gas (LFG) extraction took place (Scenario 1) were higher (641-998 kg CO2-eq·t(-1)ww) than those from open dump (Scenario 0, 480-734 kg CO2-eq·t(-1)ww). This was due to the strictly anaerobic conditions in Scenario 1. LFG collection and treatment reduced GHG emissions to 448-684 kg CO2-eq·t(-1)ww in Scenario 2 (with LFG flare) and 214-277 kg CO2-eq·t(-1)ww in Scenario 3 (using LFG for electricity production). Amongst the seven categories, FM was the predominant contributor to GHG emissions. Global sensitivity analysis demonstrated that the parameters associated with waste characteristics (i.e. CH4 potential and carbon sequestered faction) and LFG management (i.e. LFG collection efficiency and CH4 oxidation efficiency) were of great importance. A further learning on the MSW in China indicated that water content and dry matter content of food waste were the basic factors affecting GHG emissions. Source separation of food waste, as well as increasing the incineration ratio of mixed collected MSW, could effectively mitigate the overall GHG emissions from landfilling in a specific city. To increase the LFG collection and CH4 oxidation efficiencies could considerably reduce GHG emissions on the landfill site level. While, the improvement in the LFG utilization measures had an insignificant impact as long as the LFG is recovered for energy generation. Copyright © 2013 Elsevier Ltd. All rights reserved.

Super-dry reforming of methane intensifies CO2 utilization via Le Chatelier's principle.

PubMed

Buelens, Lukas C; Galvita, Vladimir V; Poelman, Hilde; Detavernier, Christophe; Marin, Guy B

2016-10-28

Efficient CO 2 transformation from a waste product to a carbon source for chemicals and fuels will require reaction conditions that effect its reduction. We developed a "super-dry" CH 4 reforming reaction for enhanced CO production from CH 4 and CO 2 We used Ni/MgAl 2 O 4 as a CH 4 -reforming catalyst, Fe 2 O 3 /MgAl 2 O 4 as a solid oxygen carrier, and CaO/Al 2 O 3 as a CO 2 sorbent. The isothermal coupling of these three different processes resulted in higher CO production as compared with that of conventional dry reforming, by avoiding back reactions with water. The reduction of iron oxide was intensified through CH 4 conversion to syngas over Ni and CO 2 extraction and storage as CaCO 3 CO 2 is then used for iron reoxidation and CO production, exploiting equilibrium shifts effected with inert gas sweeping (Le Chatelier's principle). Super-dry reforming uses up to three CO 2 molecules per CH 4 and offers a high CO space-time yield of 7.5 millimole CO per second per kilogram of iron at 1023 kelvin. Copyright © 2016, American Association for the Advancement of Science.

Scalable and sustainable electrochemical allylic C-H oxidation

NASA Astrophysics Data System (ADS)

Horn, Evan J.; Rosen, Brandon R.; Chen, Yong; Tang, Jiaze; Chen, Ke; Eastgate, Martin D.; Baran, Phil S.

2016-05-01

New methods and strategies for the direct functionalization of C-H bonds are beginning to reshape the field of retrosynthetic analysis, affecting the synthesis of natural products, medicines and materials. The oxidation of allylic systems has played a prominent role in this context as possibly the most widely applied C-H functionalization, owing to the utility of enones and allylic alcohols as versatile intermediates, and their prevalence in natural and unnatural materials. Allylic oxidations have featured in hundreds of syntheses, including some natural product syntheses regarded as “classics”. Despite many attempts to improve the efficiency and practicality of this transformation, the majority of conditions still use highly toxic reagents (based around toxic elements such as chromium or selenium) or expensive catalysts (such as palladium or rhodium). These requirements are problematic in industrial settings; currently, no scalable and sustainable solution to allylic oxidation exists. This oxidation strategy is therefore rarely used for large-scale synthetic applications, limiting the adoption of this retrosynthetic strategy by industrial scientists. Here we describe an electrochemical C-H oxidation strategy that exhibits broad substrate scope, operational simplicity and high chemoselectivity. It uses inexpensive and readily available materials, and represents a scalable allylic C-H oxidation (demonstrated on 100 grams), enabling the adoption of this C-H oxidation strategy in large-scale industrial settings without substantial environmental impact.

A simulation model for methane emissions from landfills with interaction of vegetation and cover soil.

PubMed

Bian, Rongxing; Xin, Danhui; Chai, Xiaoli

2018-01-01

Global climate change and ecological problems brought about by greenhouse gas effect have become a severe threat to humanity in the 21st century. Vegetation plays an important role in methane (CH 4 ) transport, oxidation and emissions from municipal solid waste (MSW) landfills as it modifies the physical and chemical properties of the cover soil, and transports CH 4 to the atmosphere directly via their conduits, which are mainly aerenchymatous structures. In this study, a novel 2-D simulation CH 4 emission model was established, based on an interactive mechanism of cover soil and vegetation, to model CH 4 transport, oxidation and emissions in landfill cover soil. Results of the simulation model showed that the distribution of CH 4 concentration and emission fluxes displayed a significant difference between vegetated and non-vegetated areas. CH 4 emission flux was 1-2 orders of magnitude higher than bare areas in simulation conditions. Vegetation play a negative role in CH 4 emissions from landfill cover soil due to the strong CH 4 transport capacity even though vegetation also promotes CH 4 oxidation via changing properties of cover soil and emitting O 2 via root system. The model will be proposed to allow decision makers to reconsider the actual CH 4 emission from vegetated and non-vegetated covered landfills. Copyright © 2017 Elsevier Ltd. All rights reserved.

Ammonium conversion and its feedback effect on methane oxidation of Methylosinus sporium.

PubMed

He, Ruo; Chen, Min; Ma, Ruo-Chan; Su, Yao; Zhang, Xuan

2017-04-01

Ammonium (NH 4 + ) is not only nitrogen source that can support methanotrophic growth, but also it can inhibit methane (CH 4 ) oxidation by competing with CH 4 for the active site of methane monooxygenase. NH 4 + conversion and its feedback effect on the growth and activity of methanotrophs were evaluated with Methylosinus sporium used as a model methanotroph. Nitrogen sources could affect the CH 4 -derived carbon distribution, which varied with incubation time and nitrogen concentrations. More CH 4 -derived carbon was incorporated into biomass in the media with NH 4 + -N, compared to nitrate-nitrogen (NO 3 - -N), as sole nitrogen source at the nitrogen concentrations of 10-18 mmol L -1 . Although ammonia (NH 3 ) oxidation activity of methanotrophs was considerably lower, only accounting for 0.01-0.06% of CH 4 oxidation activity in the experimental cultures, NH 4 + conversion could lead to the pH decrease and toxic intermediates accumulation in the their habits. Compared with NH 4 + , nitrite (NO 2 - ) accumulation in the NH 4 + conversion of methanotroph had stronger inhibition on its activity, especially the joint inhibition of NO 2 - accumulation and the pH decrease during the NH 4 + -N conversion. These results suggested that more attention should be paid to the feedback effects of NH 4 + conversion by methanotrophs to understand effects of NH 4 + on CH 4 oxidation in the environments. Copyright © 2017 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

Photocatalytic CH activation and oxidative esterification using Pd@g-C3N4

EPA Science Inventory

Graphitic carbon nitride supported palladium nanoparticles, Pd@g-C3N4, have been synthesized and utilized for the direct oxidative esterification of alcohols using atmospheric oxygen as a co-oxidant via photocatalytic CH activation.

Dynamics of Gross Methane Production and Oxidation in a Peatland Soil

NASA Astrophysics Data System (ADS)

McNicol, G.; Yang, W. H.; Teh, Y.; Silver, W. L.

2012-12-01

Globally, peatlands are major sources of the potent greenhouse gas methane (CH4) that is implicated in 20% of the post-industrial increase in radiative forcing. Many temperate peatlands have been drained for alternative land-use and are characterized by a layer of unsaturated soil overlying the remnant organic histosol. Drained soil layers may attenuate surface CH4 emissions from deeper, flooded peat layers via microbial CH4 consumption. We measured gross rates of CH4 production and oxidation seasonally across a range of topographic landforms in a partially drained peatland on Sherman Island, California. Net CH4 fluxes across the soil-atmosphere interface ranged from -7.4 to 1096 mg-C m-2 d-1 across all landforms. Fluxes were highest in May and in irrigation ditches (date, p < 0.001; landform, p < 0.001; n = 55). Gross CH4 production rates ranged from 0-1461 mg-C m-2 d-1 and oxidation rates ranged from 0-40 mg-C m-2 d-1. Excluding the irrigation ditches, gross fluxes did not vary seasonally. Gross CH4 fluxes were significantly higher in the hollow/hummock than in the slope. We subsequently selected the hollow/hummock based upon the observation of a strong redox gradient with depth and characterized gross fluxes of CH4 both in the field and in laboratory incubations of four soil depth increments (0-10 cm, 10-30 cm, 30-60 cm, 60-80 cm). The laboratory incubation consisted of 3 separate gross flux experiments: the first using fresh soil under ambient headspace, the second after incubation in an N2 headspace, and the third after incubation in an ambient headspace. Gross CH4 fluxes in the field varied from a slight sink (-0.11 mg-C m-2 d-1) to a large source (23.9 mg-C m-2 d-1). In 3 plots net fluxes were reduced by competing CH4 oxidation. In the depth profile experiment, production and consumption were observed in the fresh soil, but without a clear depth trend. In contrast, we found that consumption rates increased with depth following the aerobic incubation and production showed the same trend with depth under N2. Our field results demonstrate that flooded drainage ditches can act as CH4 emission hotspots in drained peatlands due to high production rates and low oxidation rates, disproportionately impacting ecosystem CH4 emissions. In contrast CH4 oxidation rates in the drained landforms even led to negative fluxes at times. The depth profile experiment showed that the strongest potential for both production and consumption of CH4 was at depths close to, or below, the water table. Thus despite significant CH4 production potential at depth, drained peatlands may be only minor sources, or even slight sinks, of CH4 if the extent and persistence of flooded landforms is minimal.

Exploring sub-daily to seasonal variations in methane exchange in a single-crop rice paddy in central Japan

NASA Astrophysics Data System (ADS)

Iwata, Hiroki; Mano, Masayoshi; Ono, Keisuke; Tokida, Takeshi; Kawazoe, Takahiro; Kosugi, Yoshiko; Sakabe, Ayaka; Takahashi, Kenshi; Miyata, Akira

2018-04-01

Season-long methane (CH4) exchange was observed in a rice paddy field in central Japan (Kanto Region) using the eddy covariance technique to clarify the variations in environmental controls on CH4 exchange in different stages of cultivation. Before heading of rice plant, the CH4 emission depended on wind speed and soil temperature. The soil temperature dependence can be due to an increase in CH4 production, higher molecular diffusion, and higher conductance within rice plant at higher soil temperature. An occurrence of ebullitive emission was also suggested from the wind speed dependence. After heading was completed, relative humidity and water temperature influenced CH4 emission. The amplitude of the diurnal variation in emission increased from 0.03 μmolm-2s-1 in the late pre-heading stage to 0.13 μmolm-2s-1 in the post-heading stage. Induced convective throughflow within the rice aerenchyma after the change in plant structure was attributable to this variation in environmental controls after the heading. After drainage, CH4 emission was confined to short periods after strong rain events. The water level controlled the timing of emission, most likely by influencing the diffusion efficiency from the anoxic soil to the atmosphere and CH4 oxidation in the surface oxic zone. The variation in the dominant transport pathway needs to be accounted for in terrestrial ecosystem models to accurately predict CH4 emission from rice paddies.

Organic Aerosols in the Presence of CO{sub 2} in the Early Earth and Exoplanets: UV–Vis Refractive Indices of Oxidized Tholins

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gavilan, Lisseth; Carrasco, Nathalie; Vettier, Ludovic

In this experimental study we investigate the role of atmospheric CO{sub 2} on the optical properties of organic photochemical aerosols. To this end, we add CO{sub 2} to a N{sub 2}:CH{sub 4} gas mixture used in a plasma typically used for Titan studies. We produce organic thin films (tholins) in plasmas where the CO{sub 2}/CH{sub 4} ratio is increased from 0 to 4. We measure these films via spectrometric ellipsometry and apply a Tauc–Lorentz model, used for optically transparent materials, to obtain the thickness of the thin film, its optical band gap, and the refractive indices in the UV–visible (270–600more » nm). All samples present a significant absorption band in the UV. According to the Tauc–Lorentz model, as the CO{sub 2}/CH{sub 4} ratio is quadrupled, the position of the UV band is shifted from ∼177 nm to 264 nm while its strength is quadrupled. Consequently, we infer that oxidized organic aerosols absorb more efficiently at longer UV wavelengths than reduced aerosols. Our laboratory wavelength-tabulated UV–vis refractive indices provide new constraints to atmospheric models of the early Earth and Earth-like exoplanets including photochemical hazes formed under increasingly oxidizing conditions.« less

Responses of mixed methanotrophic consortia to variable Cu2+/Fe2+ ratios.

PubMed

Chidambarampadmavathy, Karthigeyan; Karthikeyan, Obulisamy Parthiba; Huerlimann, Roger; Maes, Gregory E; Heimann, Kirsten

2017-07-15

Methane mitigation in landfill top cover soils is mediated by methanotrophs whose optimal methane (CH 4 ) oxidation capacity is governed by environmental and complex microbial community interactions. Optimization of CH 4 remediating bio-filters need to take microbial responses into account. Divalent copper (Cu 2+ ) and iron (Fe 2+ ) are present in landfills at variable ratios and play a vital role in methane oxidation capacity and growth of methanotrophs. This study, as a first of its kind, therefore quantified effects of variable Cu 2+ and Fe 2+ (5:5, 5:25 and 5:50 μM) ratios on mixed methanotrophic communities enriched from landfill top cover (LB) and compost soils (CB). CH 4 oxidation capacity, CH 4 removal efficiencies, fatty acids content/profiles and polyhydroxybutyrate (PHB; a biopolymer) contents were also analysed to quantify performance and potential co-product development. Mixed methanotroph cultures were raised in 10 L continuous stirred tank reactors (CSTRs, Bioflo ® & Celligen ® 310 Fermentor/Bioreactor; John Morris Scientific, Chatswood, NSW, Australia). Community structure was determined by amplifying the V3-V4 region of 16s rRNA gene. Community structure and, consequently, fatty acid-profiles changed significantly with increasing Cu 2+ /Fe 2+ ratios, and responses were different for LB and CB. Effects on methane oxidation capacities and PHB content were similar in the LB- and CB-CSTR, decreasing with increasing Cu 2+ /Fe 2+ ratios, while biomass growth was unaffected. In general, high Fe 2+ concentration favored growth of the type -II methanotroph Methylosinus in the CB-CSTR, but methanotroph abundances decreased in the LB-CSTR. Increase in Cu 2+ /Fe 2+ ratio increased the growth of Sphingopyxis in both systems, while Azospirllum was co-dominant in the LB- but absent in the CB-CSTR. After 13 days, methane oxidation capacities and PHB content decreased by ∼50% and more in response to increasing Fe 2+ concentrations. Although methanotroph abundance was ∼2% in the LB- (compared to >50% in CB-CSTR), methane oxidation capacities were comparable in the two systems, suggesting that methane oxidation capacity was maintained by the dominant Azospirllum and Sphingopyxis in the LB-CSTR. Despite similar methanotroph inoculum community composition and controlled environmental variables, increasing Cu 2+ /Fe 2+ ratios resulted in significantly different microbial community structures in the LB- and CB-CSTR, indicative of complex microbial interactions. In summary, our results suggest that a detailed understanding of allelopathic interactions in mixed methanotrophic consortia is vital for constructing robust bio-filters for CH 4 emission abatement. Copyright © 2017 Elsevier Ltd. All rights reserved.

Chemical and isotope compositions of shallow groundwater in areas impacted by hydraulic fracturing and surface mining in the Central Appalachian Basin, Eastern United States

DOE Office of Scientific and Technical Information (OSTI.GOV)

LeDoux, St. Thomas M.; Szynkiewicz, Anna; Faiia, Anthony M.

Here, hydraulic fracturing of shale deposits has greatly increased the productivity of the natural gas industry by allowing it to exploit previously inaccessible reservoirs. Previous research has demonstrated that this practice has the potential to contaminate shallow aquifers with methane (CH 4) from deeper formations. This study compares concentrations and isotopic compositions of CH 4 sampled from domestic groundwater wells in Letcher County, Eastern Kentucky in order to characterize its occurrence and origins in relation to both neighboring hydraulically fractured natural gas wells and surface coal mines. The studied groundwater showed concentrations of CH 4 ranging from 0.05 mg/L tomore » 10 mg/L, thus, no immediate remediation is required. The δ 13C values of CH 4 ranged from 66‰ to 16‰, and δ 2H values ranged from –286‰ to –86‰, suggesting an immature thermogenic and mixed biogenic/thermogenic origin. The occurrence of CH 4 was not correlated with proximity to hydraulically fractured natural gas wells. Generally, CH 4 occurrence corresponded with groundwater abundant in Na +, Cl –, and HCO 3 – , and with low concentrations of SO 4 –2. The CH 4 and SO 4 –2 concentrations were best predicted by the oxidation/reduction potential of the studied groundwater. CH 4 was abundant in more reducing waters, and SO 4 –2 was abundant in more oxidizing waters. Additionally, groundwater in greater proximity to surface mining was more likely to be oxidized. This, in turn, might have increased the likelihood of CH 4 oxidation in shallow groundwater.« less

Chemical and isotope compositions of shallow groundwater in areas impacted by hydraulic fracturing and surface mining in the Central Appalachian Basin, Eastern United States

DOE PAGES

LeDoux, St. Thomas M.; Szynkiewicz, Anna; Faiia, Anthony M.; ...

2016-05-17

Here, hydraulic fracturing of shale deposits has greatly increased the productivity of the natural gas industry by allowing it to exploit previously inaccessible reservoirs. Previous research has demonstrated that this practice has the potential to contaminate shallow aquifers with methane (CH 4) from deeper formations. This study compares concentrations and isotopic compositions of CH 4 sampled from domestic groundwater wells in Letcher County, Eastern Kentucky in order to characterize its occurrence and origins in relation to both neighboring hydraulically fractured natural gas wells and surface coal mines. The studied groundwater showed concentrations of CH 4 ranging from 0.05 mg/L tomore » 10 mg/L, thus, no immediate remediation is required. The δ 13C values of CH 4 ranged from 66‰ to 16‰, and δ 2H values ranged from –286‰ to –86‰, suggesting an immature thermogenic and mixed biogenic/thermogenic origin. The occurrence of CH 4 was not correlated with proximity to hydraulically fractured natural gas wells. Generally, CH 4 occurrence corresponded with groundwater abundant in Na +, Cl –, and HCO 3 – , and with low concentrations of SO 4 –2. The CH 4 and SO 4 –2 concentrations were best predicted by the oxidation/reduction potential of the studied groundwater. CH 4 was abundant in more reducing waters, and SO 4 –2 was abundant in more oxidizing waters. Additionally, groundwater in greater proximity to surface mining was more likely to be oxidized. This, in turn, might have increased the likelihood of CH 4 oxidation in shallow groundwater.« less

Methane oxidation and abundance of methane oxidizers in tropical agricultural soil (vertisol) in response to CuO and ZnO nanoparticles contamination.

PubMed

Mohanty, Santosh Ranjan; Rajput, Parul; Kollah, Bharati; Chourasiya, Dipanti; Tiwari, Archana; Singh, Muneshwar; Rao, A Subba

2014-06-01

There is worldwide concern over the increase use of nanoparticles (NPs) and their ecotoxicological effect. It is not known if the annual production of tons of industrial nanoparticles (NPs) has the potential to impact terrestrial microbial communities, which are so necessary for ecosystem functioning. Here, we have examined the consequences of adding the NPs particularly the metal oxide (CuO, ZnO) on CH4 oxidation activity in vertisol and the abundance of heterotrophs, methane oxidizers, and ammonium oxidizers. Soil samples collected from the agricultural field located at Madhya Pradesh, India, were incubated with either CuO and ZnO NPs or ionic heavy metals (CuCl2, ZnCl2) separately at 0, 10, and 20 μg g(-1) soil. CH4 oxidation activity in the soil samples was estimated at 60 and 100 % moisture holding capacity (MHC) in order to link soil moisture regime with impact of NPs. NPs amended to soil were highly toxic for the microbial-mediated CH4 oxidation, compared with the ionic form. The trend of inhibition was Zn 20 > Zn 10 > Cu 20 > Cu 10. NPs delayed the lag phase of CH4 oxidation to a maximum of 4-fold and also decreased the apparent rate constant k up to 50 % over control. ANOVA and Pearson correlation analysis (α = 0.01) revealed significant impact of NPs on the CH4 oxidation activity and microbial abundance (p < 0.0001, and high F statistics). Principal component analysis (PCA) revealed that PC1 (metal concentration) rendered 76.06 % of the total variance, while 18.17 % of variance accounted by second component (MHC). Biplot indicated negative impact of NPs on CH4 oxidation and microbial abundance. Our result also confirmed that higher soil moisture regime alleviates toxicity of NPs and opens new avenues of research to manage ecotoxicity and environmental hazard of NPs.

Selective aliphatic carbon-hydrogen bond activation of protected alcohol substrates by cytochrome P450 enzymes.

PubMed

Bell, Stephen G; Spence, Justin T J; Liu, Shenglan; George, Jonathan H; Wong, Luet-Lok

2014-04-21

Protected cyclohexanol and cyclohex-2-enol substrates, containing benzyl ether and benzoate ester moieties, were designed to fit into the active site of the Tyr96Ala mutant of cytochrome P450cam. The protected cyclohexanol substrates were efficiently and selectively hydroxylated by the mutant enzyme at the trans C-H bond of C-4 on the cyclohexyl ring. The selectivity of oxidation of the benzoate ester protected cyclohexanol could be altered by making alternative amino acid substitutions in the P450cam active site. The addition of the double bond in the cyclohexyl ring of the benzoate ester protected cyclohex-2-enol has a debilitative effect on the activity of the Tyr96Ala mutant with this substrate. However, the Phe87Ala/Tyr96Phe double mutant, which introduces space at a different location in the active site than the Tyr96Ala mutant, was able to efficiently hydroxylate the C-H bonds of 1-cyclohex-2-enyl benzoate at the allylic C-4 position. Mutations at Phe87 improved the selectivity of the oxidation of 1-phenyl-1-cyclohexylethylene to trans-4-phenyl-ethenylcyclohexanol (92%) when compared to single mutants at Tyr96 of P450cam.

Oxidation of ammonia and methane in an alkaline, saline lake

USGS Publications Warehouse

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

1999-01-01

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

Potential GHG mitigation options for agriculture in China

DOE Office of Scientific and Technical Information (OSTI.GOV)

Erda, Lin; Yue, Li; Hongmin, Dong

1996-12-31

Agriculture contributes more or less to anthropogenic emissions of carbon dioxide (CO{sub 2}), methane (CH{sub 4}), and nitrous oxide (N{sub 2}O). China`s agriculture accounts for about 5-15% of total emissions for these gases. Land-use changes related to agriculture are not major contributors in China. Mitigation options are available that could result in significant decrease in CH{sub 4} and N{sub 2}O emissions from agricultural systems. If implemented, they are likely to increase crop and animal productivity. Implementation has the potential to decrease CH{sub 4} emissions from rice, ruminants, and animal waste by 4-40%. The key to decreasing N{sub 2}O emissions ismore » improving the efficiency of plant utilization of fertilizer N. This could decrease N{sub 2}O emissions from agriculture by almost 20%. Using animal waste to produce CH{sub 4} for energy and digested manure for fertilizer may at some time be cost effective. Economic analyses of options proposed should show positive economic as well as environmental benefits.« less

Dissolved Organic Carbon: Nitrate Ratios as a Driver of Methane Fluxes in Stream Ecosystems

NASA Astrophysics Data System (ADS)

Sullivan, B. W.; Wymore, A.; Schade, J. D.; McDowell, W. H.

2016-12-01

Fluvial ecosystems are poorly understood components of the global methane (CH4) budget because the ecology of CH4 fluxes in streams has yet to be sufficiently elucidated. Both CH4 production and uptake via oxidation are microbially mediated processes, but it is unclear where in the fluvial environment are the sources and sinks of CH4 and what role terrestrial inputs of carbon (C) and nutrients have on the magnitude and direction of CH4 flux. To address these uncertainties, we measured CH4 fluxes in a laboratory incubation from two temperate headwater streams that differed in ambient dissolved organic carbon (DOC) and nitrate (NO3-) concentrations. We amended stream water and sediment microcosms from each site with labile DOC from senesced leaf litter to assess how DOC concentration and the DOC:NO3- ratio affect proximate controls on CH4 flux. Lastly, we manipulated sediment and water column ratios (0-100%) to estimate sources and fates of CH4 flux within the ecosystem. We measured CH4 fluxes for the first 120 minutes of the incubation to simulate short-term, in stream processes. Initially, streams were a source of methane, but switched to a sink within 120 minutes. Methane fluxes were statistically similar in both stream sediment and water, suggesting that microbial processing of CH4 has similar directionality and magnitude in each environment. Both CH4 oxidation and production were significantly correlated with the DOC: NO3- ratio over the course of the incubation. Early in the incubation, increasing DOC: NO3- increased CH4 flux, but late in the incubation, increasing DOC: NO3- increased CH4 oxidation. Together, our results challenge existing paradigms of CH4 flux in the fluvial environment and identify the DOC:NO3- ratio as a possible mechanism that can explain spatial and temporal CH4 flux patterns in streams.

Fate of methane in aquatic systems dominated by free-floating plants.

PubMed

Kosten, Sarian; Piñeiro, Marcia; de Goede, Eefje; de Klein, Jeroen; Lamers, Leon P M; Ettwig, Katharina

2016-11-01

Worldwide the area of free-floating plants is increasing, which can be expected to alter methane (CH 4 ) emissions from aquatic systems in several ways. A large proportion of the CH 4 produced may become oxidized below the plants due to the accumulation of CH 4 as a result of a decrease in the diffusive water-atmosphere flux and the entrapment of part of the ebullitive CH 4 , in combination with suitable conditions for methane oxidizing (MOX) bacteria in the aerobic rhizosphere. We used a set of essays to test this hypothesis and to explore the effect of different densities for three widespread free-floating species: Azolla filiculoides, Salvinia natans, and Eichhornia crassipes. The gas exchange velocity, proportion of CH 4 bubbles trapped by the plants, occurrence of radial oxygen loss from roots, and MOX rates on the roots were assessed. We subsequently used the outcome of these experiments to parameterize a simple model. With this model we estimated the proportion of the produced CH 4 that is oxidized, for different plant species and different densities. We found that in a shallow (1 m) system up to 70% of the CH 4 produced may become oxidized as a result of a strong decrease in gas exchange combined with high MOX activity of the rhizosphere microbiome. As floating plants also are likely to increase CH 4 production by organic matter production, especially when their presence induces anaerobic conditions, the overall effect on CH 4 emission will strongly depend on local conditions. This explains the contrasting effects of floating plants on CH 4 emissions in literature as reviewed here. As the effect of floating plants on CH 4 emissions, including the high MOX rates we show here, can be substantial, there is an urgent need to consider this impact when assessing greenhouse gas budgets. Copyright © 2016 Elsevier Ltd. All rights reserved.

Methane alleviates copper-induced seed germination inhibition and oxidative stress in Medicago sativa.

PubMed

Samma, Muhammad Kaleem; Zhou, Heng; Cui, Weiti; Zhu, Kaikai; Zhang, Jing; Shen, Wenbiao

2017-02-01

Recent results discovered the protective roles of methane (CH 4 ) against oxidative stress in animals. However, the possible physiological roles of CH 4 in plants are still unknown. By using physiological, histochemical and molecular approaches, the beneficial role of CH 4 in germinating alfalfa seeds upon copper (Cu) stress was evaluated. Endogenous production of CH 4 was significantly increased in Cu-stressed alfalfa seeds, which was mimicked by 0.39 mM CH 4 . The pretreatment with CH 4 significantly alleviated the inhibition of seed germination and seedling growth induced by Cu stress. Cu accumulation was obviously blocked as well. Meanwhile, α/β amylase activities and sugar contents were increased, all of which were consistent with the alleviation of seed germination inhibition triggered by CH 4 . The Cu-triggered oxidative stress was also mitigated, which was confirmed by the decrease of lipid peroxidation and reduction of Cu-induced loss of plasma membrane integrity in CH 4 -pretreated alfalfa seedlings. The results of antioxidant enzymes, including ascorbate peroxidase (APX), superoxide dismutase (SOD), catalase (CAT), and guaiacol peroxidase (POD) total or isozymatic activities, and corresponding transcripts (APX1/2, Cu/Zn SOD and Mn-SOD), indicated that CH 4 reestablished cellular redox homeostasis. Further, Cu-induced proline accumulation was partly impaired by CH 4 , which was supported by the alternation of proline metabolism. Together, these results indicated that CH 4 performs an advantageous effect on the alleviation of seed germination inhibition caused by Cu stress, and reestablishment of redox homeostasis mainly via increasing antioxidant defence.

A Ni(iii) complex stabilized by silica nanoparticles as an efficient nanoheterogeneous catalyst for oxidative C-H fluoroalkylation.

PubMed

Khrizanforov, Mikhail N; Fedorenko, Svetlana V; Strekalova, Sofia O; Kholin, Kirill V; Mustafina, Asiya R; Zhilkin, Mikhail Ye; Khrizanforova, Vera V; Osin, Yuri N; Salnikov, Vadim V; Gryaznova, Tatyana V; Budnikova, Yulia H

2016-07-26

We have developed Ni(III)-doped silica nanoparticles ([(bpy)xNi(III)]@SiO2) as a recyclable, low-leaching, and efficient oxidative functionalization nanocatalyst for aromatic C-H bonds. The catalyst is obtained by doping the complex [(bpy)3Ni(II)] on silica nanoparticles along with its subsequent electrooxidation to [(bpy)xNi(III)] without an additional oxidant. The coupling reaction of arenes with perfluoroheptanoic acid occurs with 100% conversion of reactants in a single step at room temperature under nanoheterogeneous conditions. The catalyst content is only 1% with respect to the substrates under electrochemical regeneration conditions. The catalyst can be easily separated from the reaction mixture and reused a minimum of five times. The results emphasize immobilization on the silica support and the electrochemical regeneration of Ni(III) complexes as a facile route for developing an efficient nanocatalyst for oxidative functionalization.

Highly Cooperative Tetrametallic Ruthenium-μ-Oxo-μ-Hydroxo Catalyst for the Alcohol Oxidation Reaction

PubMed Central

Yi, Chae S.; Zeczycki, Tonya N.; Guzei, Ilia A.

2008-01-01

The tetrametallic ruthenium-oxo-hydroxo-hydride complex {[(PCy3)(CO)RuH]4(μ4-O)(μ3-OH)(μ2-OH)} (1) was synthesized in two steps from the monomeric complex (PCy3)(CO)RuHCl (2). The tetrameric complex 1 was found to be a highly effective catalyst for the transfer dehydrogenation of alcohols. Complex 1 showed a different catalytic activity pattern towards primary and secondary benzyl alcohols, as indicated by the Hammett correlation for the oxidation reaction of p-X-C6H4CH2OH (ρ = −0.45) and p-X-C6H4CH(OH)CH3 (ρ = +0.22) (X = OMe, CH3, H, Cl, CF3). Both a sigmoidal curve from the plot of initial rate vs [PhCH(OH)CH3] (K0.5 = 0.34 M; Hill coefficient, n = 4.2±0.1) and the phosphine inhibition kinetics revealed the highly cooperative nature of the complex for the oxidation of secondary alcohols. PMID:18726005

Evaluating the Classical Versus an Emerging Conceptual Model of Peatland Methane Dynamics

NASA Astrophysics Data System (ADS)

Yang, Wendy H.; McNicol, Gavin; Teh, Yit Arn; Estera-Molina, Katerina; Wood, Tana E.; Silver, Whendee L.

2017-09-01

Methane (CH4) is a potent greenhouse gas that is both produced and consumed in soils by microbially mediated processes sensitive to soil redox. We evaluated the classical conceptual model of peatland CH4 dynamics—in which the water table position determines the vertical distribution of methanogenesis and methanotrophy—versus an emerging model in which methanogenesis and methanotrophy can both occur throughout the soil profile due to spatially heterogeneous redox and anaerobic CH4 oxidation. We simultaneously measured gross CH4 production and oxidation in situ across a microtopographical gradient in a drained temperate peatland and ex situ along the soil profile, giving us novel insight into the component fluxes of landscape-level net CH4 fluxes. Net CH4 fluxes varied among landforms (p < 0.001), ranging from 180.3 ± 81.2 mg C m-2 d-1 in drainage ditches to -0.7 ± 1.2 mg C m-2 d-1 in the highest landform. Contrary to prediction by the classical conceptual model, variability in methanogenesis alone drove the landscape-level net CH4 flux patterns. Consistent with the emerging model, freshly collected soils from above the water table produced CH4 within anaerobic microsites. Even in soil from beneath the water table, gross CH4 production was best predicted by the methanogenic fraction of carbon mineralization, an index of highly reducing microsites. We measured low rates of anaerobic CH4 oxidation, which may have been limited by relatively low in situ CH4 concentrations in the hummock/hollow soil profile. Our study revealed complex CH4 dynamics better represented by the emerging heterogeneous conceptual model than the classical model based on redox strata.

Isotopic insights into methane production, oxidation, and emissions in Arctic polygon tundra.

PubMed

Vaughn, Lydia J S; Conrad, Mark E; Bill, Markus; Torn, Margaret S

2016-10-01

Arctic wetlands are currently net sources of atmospheric CH4 . Due to their complex biogeochemical controls and high spatial and temporal variability, current net CH4 emissions and gross CH4 processes have been difficult to quantify, and their predicted responses to climate change remain uncertain. We investigated CH4 production, oxidation, and surface emissions in Arctic polygon tundra, across a wet-to-dry permafrost degradation gradient from low-centered (intact) to flat- and high-centered (degraded) polygons. From 3 microtopographic positions (polygon centers, rims, and troughs) along the permafrost degradation gradient, we measured surface CH4 and CO2 fluxes, concentrations and stable isotope compositions of CH4 and DIC at three depths in the soil, and soil moisture and temperature. More degraded sites had lower CH4 emissions, a different primary methanogenic pathway, and greater CH4 oxidation than did intact permafrost sites, to a greater degree than soil moisture or temperature could explain. Surface CH4 flux decreased from 64 nmol m(-2)  s(-1) in intact polygons to 7 nmol m(-2)  s(-1) in degraded polygons, and stable isotope signatures of CH4 and DIC showed that acetate cleavage dominated CH4 production in low-centered polygons, while CO2 reduction was the primary pathway in degraded polygons. We see evidence that differences in water flow and vegetation between intact and degraded polygons contributed to these observations. In contrast to many previous studies, these findings document a mechanism whereby permafrost degradation can lead to local decreases in tundra CH4 emissions. © 2016 John Wiley & Sons Ltd.

Oxidative mitigation of aquatic methane emissions in large Amazonian rivers.

PubMed

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

2016-03-01

The flux of methane (CH4 ) from inland waters to the atmosphere has a profound impact on global atmospheric greenhouse gas (GHG) levels, and yet, strikingly little is known about the dynamics controlling sources and sinks of CH4 in the aquatic setting. Here, we examine the cycling and flux of CH4 in six large rivers in the Amazon basin, including the Amazon River. Based on stable isotopic mass balances of CH4 , inputs and outputs to the water column were estimated. We determined that ecosystem methane oxidation (MOX) reduced the diffusive flux of CH4 by approximately 28-96% and varied depending on hydrologic regime and general geochemical characteristics of tributaries of the Amazon River. For example, the relative amount of MOX was maximal during high water in black and white water rivers and minimal in clear water rivers during low water. The abundance of genetic markers for methane-oxidizing bacteria (pmoA) was positively correlated with enhanced signals of oxidation, providing independent support for the detected MOX patterns. The results indicate that MOX in large Amazonian rivers can consume from 0.45 to 2.07 Tg CH4 yr(-1) , representing up to 7% of the estimated global soil sink. Nevertheless, climate change and changes in hydrology, for example, due to construction of dams, can alter this balance, influencing CH4 emissions to atmosphere. © 2015 John Wiley & Sons Ltd.

Investigating the emission, dissolution, and oxidation of CH4 within and around a seep bubble plume in the Gulf of Mexico.

NASA Astrophysics Data System (ADS)

Leonte, M.; Kessler, J. D.; Socolofsky, S. A.

2016-02-01

One of the largest carbon reservoirs on the planet is stored as methane (CH4) in and below the seafloor. However, a large discrepancy exists between estimated fluxes of CH4 into the water column and CH4 fluxes from the sea surface to the atmosphere, suggesting that a significant fraction of CH4 released from seafloor seeps is dissolved and potentially removed through microbial oxidation. Here we present data investigating the fate of CH4 released from the Sleeping Dragon seep site in the Gulf of Mexico. The bubble plume was followed from the seafloor until it fully dissolved using a remotely operated vehicle (ROV). Water samples were collected by the ROV at different depths as well as lateral transects through the bubble plume. These samples were analyzed for dissolved concentrations of methane, ethane, propane, and butane as well as the 13C isotopic ratio of methane. Furthermore, seep bubbles from the seafloor were also collected and analyzed for the same properties. Based on these chemical data, the rate of CH4 emission from the seafloor, oxidation in the water column, and dissolution are investigated.

Acetogenic microbial degradation of vinyl chloride

USGS Publications Warehouse

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

2000-01-01

Under methanogenic conditions, microbial degradation of [1,2-14C]vinyl chloride (VC) resulted in significant (14 ?? 3% maximum recovery) but transient recovery of radioactivity as 14C-acetate. Subsequently, 14C- acetate was degraded to 14CH4 and 14CO2 (18 ?? 2% and 54 ?? 3% final recoveries, respectively). In contrast, under 2-bromoethanesulfonic acid (BES) amended conditions, 14C-acetate recovery remained high (27 ?? 1% maximum recovery) throughout the study, no 14CH4 was produced, and the final recovery of 14CO2 was only 35 ?? 4%. These results demonstrate that oxidative acetogenesis may be an important mechanism for anaerobic VC biodegradation. Moreover, these results (1) demonstrate that microbial degradation of VC to CH4 and CO2 may involve oxidative acetogenesis followed by acetotrophic methanogenesis and (2) suggest that oxidative acetogenesis may be the initial step in the net oxidation of VC to CO2 reported previously under Fe(III)-reducing, SO4-reducing, and humic acids- reducing conditions.Under methanogenic conditions, microbial degradation of [1,2-14C]vinyl chloride (VC) resulted in significant (14 ?? 3% maximum recovery) but transient recovery of radioactivity as 14C-acetate. Subsequently, 14C-acetate was degraded to 14CH4 and 14CO2 (18 ?? 2% and 54 ?? 3% final recoveries respectively). In contrast, under 2-bromoethanesulfonic acid (BES) amended conditions, 14C-acetate recovery remained high (27 ?? 1% maximum recovery) throughout the study, no 14CH4 was produced, and the final recovery of 14CO2 was only 35 ?? 4%. These results demonstrate that oxidative acetogenesis may be an important mechanism for anaerobic VC biodegradation. Moreover, these results (1) demonstrate that microbial degradation of VC to CH4 and CO2 may involve oxidative acetogenesis followed by acetotrophic methanogenesis and (2) suggest that oxidative acetogenesis may be the initial step in the net oxidation of VC to CO2 reported previously under Fe(III)-reducing, SO4-reducing, and humic acids-reducing conditions.

Aerobic Methane Oxidation in Alaskan Lakes Along a Latitudinal Transect

NASA Astrophysics Data System (ADS)

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

2013-12-01

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

Limits and dynamics of methane oxidation in landfill cover soils

USDA-ARS?s Scientific Manuscript database

In order to understand the limits and dynamics of methane (CH4) oxidation in landfill cover soils, we investigated CH4 oxidation in daily, intermediate, and final cover soils from two California landfills as a function of temperature, soil moisture and CO2 concentration. The results indicate a signi...

Pathways and transformations of dissolved methane and dissolved inorganic carbon in Arctic tundra watersheds: Evidence from analysis of stable isotopes

DOE PAGES

Throckmorton, Heather M.; Heikoop, Jeffrey M.; Newman, Brent D.; ...

2015-11-08

Arctic soils contain a large pool of terrestrial C and are of interest due to their potential for releasing significant carbon dioxide (CO 2) and methane (CH 4) to the atmosphere. Due to substantial landscape heterogeneity, predicting ecosystem-scale CH 4 and CO 2 production is challenging. This study assessed dissolved inorganic carbon (DIC = Σ (total) dissolved CO 2) and CH 4 in watershed drainages in Barrow, Alaska as critical convergent zones of regional geochemistry, substrates, and nutrients. In July and September of 2013, surface waters and saturated subsurface pore waters were collected from 17 drainages. Based on simultaneous DICmore » and CH 4 cycling, we synthesized isotopic and geochemical methods to develop a subsurface CH 4 and DIC balance by estimating mechanisms of CH 4 and DIC production and transport pathways and oxidation of subsurface CH 4. We observed a shift from acetoclastic (July) toward hydrogenotropic (September) methanogenesis at sites located toward the end of major freshwater drainages, adjacent to salty estuarine waters, suggesting an interesting landscape-scale effect on CH 4 production mechanism. The majority of subsurface CH 4 was transported upward by plant-mediated transport and ebullition, predominantly bypassing the potential for CH 4 oxidation. Thus, surprisingly, CH 4 oxidation only consumed approximately 2.51± 0.82% (July) and 0.79 ± 0.79% (September) of CH 4 produced at the frost table, contributing to <0.1% of DIC production. DIC was primarily produced from respiration, with iron and organic matter serving as likely e- acceptors. Furthermore, this work highlights the importance of spatial and temporal variability of CH 4 production at the watershed scale and suggests broad scale investigations are required to build better regional or pan-Arctic representations of CH 4 and CO 2 production.« less

Synthetic, structural, and computational investigations of N-alkyl benzo-2,1,3-selenadiazolium iodides and their supramolecular aggregates.

PubMed

Lee, Lucia M; Corless, Victoria B; Tran, Michael; Jenkins, Hilary; Britten, James F; Vargas-Baca, Ignacio

2016-02-28

Despite their versatility, the application of telluradiazoles as supramolecular building blocks is considerably constrained by their sensitivity to moisture. Albeit more robust, their selenium analogues form weaker supramolecular interactions. These, however, are enhanced when one nitrogen atom is bonded to an alkyl group. Here we investigate general methods for the synthesis of such derivatives. Methyl, iso-propyl and tert-butyl benzo-2,1,3-selenadiazolium cations were prepared by direct alkylation or cyclo-condensation of the alkyl-phenylenediamine with selenous acid. While the former reaction only proceeds with the primary and tertiary alkyl iodides, the latter is very efficient. Difficulties reported in earlier literature are attributable to the formation of adducts of benzoselenadiazole with its alkylated cations and side reactions initiated by aerobic oxidation of iodide. However, the cations themselves are resilient to oxidation and stable in acidic to neutral aqueous medium. X-ray crystallography was used in the identification and characterization of the following compounds: [C6H4N2(R)Se](+)X(-), (R = CH(CH3)2, C(CH3)3; X = I(-), I3(-)], [C6H4N2(CH3)Se](+)I(-), and [C6H4N2Se][C6H4N2(CH3)Se]2I2. Formation of SeN secondary bonding interactions (chalcogen bonds) was only observed in the last structure as anion binding to selenium is a strong competitor. The relative strengths of those forces and the structural preferences they enforce were assessed with DFT-D3 calculations supplemented by AIM analysis of the electron density.

An Investigation of Methyl Viologen Functionalized Reduced Graphene Oxide: Chitosan as a Support for Pt Nanoparticles Towards Ethanol Electrooxidation

NASA Astrophysics Data System (ADS)

Ekrami-Kakhki, Mehri-Saddat; Farzaneh, Nahid; Abbasi, Sedigheh; Beitollahi, Hadi; Ekrami-Kakhki, Seyed Ali

2018-05-01

In this research, graphene oxide was prepared by a modified Hummers' method, and then functionalized with 1, 1'-dimethyl-4, 4'-bipyridinium dichloride (MV), and chitosan (CH) to get a MV-RGO-CH support. Pt nanoparticles were prepared on this support to get Pt/MV-RGO-CH catalyst. The morphology and microstructure of Pt/MV-RGO-CH catalyst were characterized with transmission electron microscopy image and X-ray diffraction analysis. The electrocatalytic activity of the prepared catalyst towards ethanol oxidation was investigated by carbon monoxide stripping voltammetry, cyclic voltammetry, and electrochemical impedance spectroscopy techniques. The effects of some experimental parameters such as scan rate, ethanol concentration, and temperature were investigated for ethanol electrooxidation at Pt/MV-RGO-CH catalyst. Durability of the catalyst was also investigated. The electrocatalytic performance of Pt/MV-RGO-CH catalyst for ethanol oxidation was compared with those of Pt/CH and Pt/MV-RGO catalysts. The higher electrocatalytic performance of Pt/MV-RGO-CH than Pt/CH and Pt/MV-RGO catalysts towards ethanol electrooxidation indicated that Pt/MV-RGO-CH could be a promising catalyst for application in direct ethanol fuel cells.

Efficient CH3NH3PbI3 perovskite/fullerene planar heterojunction hybrid solar cells with oxidized Ni/Au/Cu transparent electrode

NASA Astrophysics Data System (ADS)

Lai, Wei-Chih; Lin, Kun-Wei; Guo, Tzung-Fang; Chen, Peter; Liao, Yuan-Yu

2018-02-01

We demonstrated the performance of inverted CH3NH3PbI3 perovskite-based solar cells (SCs) with a thermally oxidized nickel/gold/copper (Ni/Au/Cu) trilayer transparent electrode. Oxidized Ni/Au/Cu is a high transparent layer and has less resistance than the oxidized Ni/Au layer. Like the oxidized Ni/Au layer, oxidized Ni and Cu in oxidized Ni/Au/Cu could perform as a hole transport layer of the perovskite-based SCs. It leads to improved perovskite SC performance on an open circuit voltage of 1.01 V, a short circuit current density of 14.36 mA/cm2, a fill factor of 76.7%, and a power conversion efficiency (η%) of 11.1%. The η% of perovskite SCs with oxidized Ni (10 nm)/Au (6 nm)/Cu (1 nm) improved by approximately 10% compared with that of perovskite SCs with oxidized Ni/Au.

Effect of ammonium and oxygen on methane and nitrous oxide fluxes across sediment-water interface in a eutrophic lake.

PubMed

Liikanen, Anu; Martikainen, Pertti J

2003-09-01

Eutrophication has decreased the O(2) content and increased the NH(4)(+) availability in freshwaters. These changes may affect carbon and nitrogen transformation processes and the production of CH(4) and N(2)O, which are important greenhouse gases. We studied release of CH(4) and N(2)O from a eutrophic lake sediment under varying O(2) and NH(4)(+) conditions. Intact sediment cores were incubated in a laboratory microcosm with a continuous anoxic or oxic water flows containing 0, 50, 500, 5,000, or 15000 microM NH(4)(+). With the anoxic flow, the sediment released CH(4), up to 7.9 mmol m(-2)d(-1). With the oxic flow, the CH(4) emissions were small indicating limited CH(4) production and/or effective CH(4) oxidation. Addition of NH(4)(+) did not affect sediment CH(4) release, evidence that the CH(4) oxidizing bacteria were not disturbed by the extra NH(4)(+). The release of N(2)O from the sediment was highest, up to 7.6 micromol m(-2)d(-1), with the oxic flow without NH(4)(+) addition. Oxygen was the key factor regulating the production of NO(3)(-), which enabled denitrification and production of N(2)O. However, the highest NH(4)(+) addition increased nitrification and associated O(2) consumption causing a decrease in sediment O(2) content and in accumulation of NO(3)(-) and N(2)O, which were effectively reduced to N(2) in denitrification. In summary, sediment CH(4) and N(2)O dynamics are regulated more by the availability of O(2) than extra NH(4)(+). Anoxia in eutrophic lakes favouring the CH(4) production, is the major contributor to the atmospheric consequences of water eutrophication.

Elaboration of copper-oxygen mediated C-H activation chemistry in consideration of future fuel and feedstock generation.

PubMed

Lee, Jung Yoon; Karlin, Kenneth D

2015-04-01

To contribute solutions to current energy concerns, improvements in the efficiency of dioxygen mediated C-H bond cleavage chemistry, for example, selective oxidation of methane to methanol, could minimize losses in natural gas usage or produce feedstocks for fuels. Oxidative C-H activation is also a component of polysaccharide degradation, potentially affording alternative biofuels from abundant biomass. Thus, an understanding of active-site chemistry in copper monooxygenases, those activating strong C-H bonds is briefly reviewed. Then, recent advances in the synthesis-generation and study of various copper-oxygen intermediates are highlighted. Of special interest are cupric-superoxide, Cu-hydroperoxo and Cu-oxy complexes. Such investigations can contribute to an enhanced future application of C-H oxidation or oxygenation processes using air, as concerning societal energy goals. Copyright © 2015 Elsevier Ltd. All rights reserved.

Estimating Landfill Methane Oxidation Using the Information of CO2/CH4 Fluxes Measured By the Eddy Covariance Method

NASA Astrophysics Data System (ADS)

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

2016-12-01

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 the landfill methane oxidation fraction when the anaerobic CO2/CH4 production ratio is known. 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 with eddy covariance CO2 and CH4 emission rates at Bluff Road Landfill in Lincoln Nebraska. It predicted zero oxidation rate in the northern portion of this landfill where a membrane and vents were present. The zero oxidation rate was expected because there would be little opportunity for methane to encounter oxidizing conditions before leaving the vents. We also applied the model at the Turkey Run Landfill in Georgia to estimate the CH4 oxidation rate over a one year period. In contrast to Bluff Road Landfill, the Turkey Run Landfill did not have a membrane or vents. Instead, methane produced in the landfill had to diffuse through a 0.5 m soil cap before release to the atmosphere. We observed evidence for methane oxidation ranging from about 18% to above 60% depending upon the age of deposited waste material. The model will be briefly described, and results from the two contrasting landfills will be discussed in this presentation.

Elaboration of Copper-Oxygen Mediated C–H Activation Chemistry in Consideration of Future Fuel and Feedstock Generation

PubMed Central

Lee, Jung Yoon; Karlin, Kenneth D

2015-01-01

To contribute solutions for current energy concerns, improvements in the efficiency of C-H bond cleavage chemistry, e.g., selective oxidation of methane to methanol, could minimize losses in natural gas usage or produce feedstocks for fuels. Oxidative C-H activation is also a component of polysaccharide degradation, affording alternative biofuels from abundant biomass. Thus, an understanding of active-site chemistry in copper monooxygenases, those activating strong C-H bonds is briefly reviewed. Then, recent advances in the synthesis-generation and study of various copper-oxygen intermediates are highlighted. Of special interest are cupric-superoxide, Cu-hydroperoxo and Cu-oxy complexes. Such investigations can contribute to an enhanced future application of C-H oxidation or oxygenation processes using air, as concerning societal energy goals. PMID:25756327

Anaerobic methane oxidation may be more prevalent in surface soils than was originally thought

NASA Astrophysics Data System (ADS)

Gauthier, Mathieu; Bradley, Robert L.; Šimek, Miloslav

2013-04-01

Anaerobic oxidation of methane (CH4) (AOM) is a process that was first reported to occur in deep anoxic marine sediments. In this environment, CH4 is oxidized with sulphate (SO42-) as the terminal electron acceptor. It is mediated by a syntrophic consortium formed by SO42- reducing bacteria and anaerobic CH4 oxidizing Archaea, or by the latter alone. Since this landmark discovery, AOM was found to occur in other environments including freshwater lake sediments and water columns, mud volcanoes, landfill leachate, deep buried Holocene sediments and hydrocarbon contaminated aquifers. All of these situations are very specific and point to AOM as being primarily occurring in highly reducing conditions. Thus, observations of AOM in surface soils with fluctuating REDOX conditions are relatively scarce, although a few independent studies have reported AOM in surface peatlands as well as in a forest soil. Furthermore, AOM may follow different pathways, such as via the coupled oxidation of CH4 and reduction of manganese (Mn(IV)) or iron (Fe(III)), or by a lone denitrifying species that converts nitrite to nitric oxide in order to generate O2 that is then used internally to oxidize CH4. Thus, the goal of our study was to determine whether AOM is more prevalent than was thought in hydromorphic surface soils across different environments, and whether the addition of NO3- or SO4= as alternative electron acceptors may stimulate the process. We collected samples from 3 peatland soils in Scotland, 2 acid-sulphate soils in Finland, and shore sediments of 15 drained fish ponds in the Czech Republic. Subsamples were incubated in the absence of O2 and amended with either NO3-, SO42-, or left unamended (control). The net flux of CH4 and CO2 were assessed by gas chromatography after 2, 20, 40 and 60 days. We also used a 13C-CH4 isotope dilution technique to determine gross production and consumption rates of CH4. We detected AOM in all of our soils, with oxidation rates ranging between 0.001 and 37.28 nmol g-1 day-1, suggesting that AOM may be more ubiquitous than was originally thought. On the other hand, no clear patterns emerged as to the effects of NO3- or SO42- amendments on this process.

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- and CH4-DAMM models will advance understanding of biogeochemisty and microbial processes in managed peatland systems as well as aid the development of a GHG protocol in the Delta that can provide financial incentive to farmers to reduce GHG emissions under California's Cap and Trade program.

Kinetics of biological methane oxidation in the presence of non-methane organic compounds in landfill bio-covers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Albanna, Muna, E-mail: muna.albanna@gju.edu.j; Warith, Mostafa; Fernandes, Leta

2010-02-15

In this experimental program, the effects of non-methane organic compounds (NMOCs) on the biological methane (CH{sub 4}) oxidation process were examined. The investigation was performed on compost experiments incubated with CH{sub 4} and selected NMOCs under different environmental conditions. The selected NMOCs had different concentrations and their effects were tested as single compounds and mixtures of compounds. The results from all experimental sets showed a decrease in CH{sub 4} oxidation capacity of the landfill bio-cover with the increase in NMOCs concentrations. For example, in the experiment using compost with 100% moisture content at 35 deg. C without any NMOCs themore » V{sub max} value was 35.0 mug CH{sub 4}h{sup -1}g{sub wetwt}{sup -1}. This value was reduced to 19.1 mug CH{sub 4}h{sup -1}g{sub wetwt}{sup -1} when mixed NMOCs were present in the batch reactors under the same environmental conditions. The experimental oxidation rates of CH{sub 4} in the presence of single and mixed NMOCs were modeled using the uncompetitive inhibition model and kinetic parameters, including the dissociation constants, were obtained. Additionally, the degradation rates of the NMOCs and co-metabolic abilities of methanotrophic bacteria were estimated.« less

Effect of selected dimethylaminochalcones on some mitochondrial activities.

PubMed

Vašková, Janka; Reisch, Renáta; Vaško, Ladislav; Poškrobová, Martina; Kron, Ivan; Guzy, Juraj; Perjési, Pál

2013-05-01

Chalcones and their synthetic cyclic analogues have been shown to possess a full scale of biological activities in a variety of experimental systems. They were assessed to be mostly effective in defense against free radicals in the organism, but several compounds exhibited cytotoxic pro-oxidant activities. The respiratory response and antioxidant status in mitochondria were investigated upon addition of 4'-dimethylaminochalcone (1a) and its cyclic analogues, (E)-2-(4'-((CH3)2 N)-benzylidene)-1-indanone (1b), -1-tetralone (1c), and -1-benzosuberone (1d). Selected structures were able to change the respiratory response of mitochondria and showed an ability to modify mitochondrial metabolic and redox efficiency, though they did not indicate redox reactivity towards glutathione in adduct-free incubations. The results of the study indicate that -chalcone and -tetralone derivatives cause suppression of reactive oxygen species affecting mitochondrial respiration by mild uncoupling. In addition, (E)-2-(4'-((CH3)2 N)-indanone (1b), and to a greater extent, -benzosuberone (1d), showed pro-oxidant effects, which partially explain their cytotoxicity.

Efficient H2O2/CH3COOH oxidative desulfurization/denitrification of liquid fuels in sonochemical flow-reactors.

PubMed

Calcio Gaudino, Emanuela; Carnaroglio, Diego; Boffa, Luisa; Cravotto, Giancarlo; Moreira, Elizabeth M; Nunes, Matheus A G; Dressler, Valderi L; Flores, Erico M M

2014-01-01

The oxidative desulfurization/denitrification of liquid fuels has been widely investigated as an alternative or complement to common catalytic hydrorefining. In this process, all oxidation reactions occur in the heterogeneous phase (the oil and the polar phase containing the oxidant) and therefore the optimization of mass and heat transfer is of crucial importance to enhancing the oxidation rate. This goal can be achieved by performing the reaction in suitable ultrasound (US) reactors. In fact, flow and loop US reactors stand out above classic batch US reactors thanks to their greater efficiency and flexibility as well as lower energy consumption. This paper describes an efficient sonochemical oxidation with H2O2/CH3COOH at flow rates ranging from 60 to 800 ml/min of both a model compound, dibenzotiophene (DBT), and of a mild hydro-treated diesel feedstock. Four different commercially available US loop reactors (single and multi-probe) were tested, two of which were developed in the authors' laboratory. Full DBT oxidation and efficient diesel feedstock desulfurization/denitrification were observed after the separation of the polar oxidized S/N-containing compounds (S≤5 ppmw, N≤1 ppmw). Our studies confirm that high-throughput US applications benefit greatly from flow-reactors. Copyright © 2013 Elsevier B.V. All rights reserved.

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.

GO-Cu7S4 catalyzed ortho-aminomethylation of phenol derivatives with N,N-dimethylbenzylamines: site-selective oxidative CDC.

PubMed

Gupta, Sonu; Chandna, Nisha; Dubey, Pooja; Singh, Ajai K; Jain, Nidhi

2018-06-21

Copper chalcogenide nanoparticles (Cu7S4) supported on graphene oxide (GO) have been synthesized for the first time from Cu2S, and used as highly efficient heterogeneous catalysts for oxidative ortho-selective C-H aminomethylation of phenols with N,N-dimethylbenzylamines. The NPs (30-80 nm) have been characterized by HRTEM, SEM-EDX, PXRD, FTIR, Raman, ICP-AES and XPS analyses. The NP catalyzed sp2-sp3 cross dehydrogenative coupling (CDC) features a broad substrate scope, excellent functional group tolerance, high yields, use of an inexpensive and reusable copper catalyst, mild conditions, and no need for pre-functionalization of substrates.

Diversity and Function of Methanotrophic Bacteria in Caves

NASA Astrophysics Data System (ADS)

Webster, K.; Schimmelmann, A.; Lennon, J. T.

2016-12-01

Despite representing the second largest sink for the atmospheric greenhouse gas methane (CH4), the methanotrophic organisms responsible for atmospheric CH4 consumption have eluded cultivation. High-throughput studies of methanotrophic communities present an opportunity to learn novel details about the organisms responsible, yet such studies have rarely been conducted. Recent observations of subatmospheric CH4 concentrations in cave-air have led to the hypothesis that methanotrophs are active over large spatial scales in the subsurface. Karst terrains cover between 10 - 20 % of the terrestrial surface area and offer abundant cave-related methanotrophic habitat due to the exchange of air with the atmosphere. We collected 42 cave soil samples from 20 caves to test the hypothesis that subterranean methanotrophy removes CH4 from cave-air. Methanotrophs were found in 90 % of samples, notably in locations with subatmospheric CH4­ concentrations. Methylocystaceae were present in caves and accounted for 92 % of the methanotrophic community on average (median), however almost all of the observations were of unidentified Methylocystaceae. Abundances of uncultured and unidentified members of the Methylococcales were correlated with cave-air CH4 concentrations suggesting that some Methylococcales may contribute to atmospheric CH4 oxidation. Individual caves had a strong influence on the observed methanotrophic community composition accounting for 77 % of the variance in the assemblage. Nevertheless, cave-air CH4 concentrations were predictive of the methanotrophic community composition accounting for 5 % of the variation. Our findings also are suggestive of CH4-fueled microbial food webs. For example, abundances of known methylotrophic organisms were correlated with cave-air CH4 concentrations. This may suggest that some methylotrophs contribute to atmospheric CH4 oxidation or that molecules produced in the CH4 oxidation pathway, like methanol, are leaked from methanotrophic cells allowing for the growth of methylotrophs. Our results suggest that uncultivated and unidentified methanotrophs are responsible for subatmospheric CH4 concentrations in caves and have secondary influences on the cave-microbial community structure.

Identification of a Methane Oxidation Intermediate on Solid Oxide Fuel Cell Anode Surfaces with Fourier Transform Infrared Emission.

PubMed

Pomfret, Michael B; Steinhurst, Daniel A; Owrutsky, Jeffrey C

2013-04-18

Fuel interactions on solid oxide fuel cell (SOFC) anodes are studied with in situ Fourier transform infrared emission spectroscopy (FTIRES). SOFCs are operated at 800 °C with CH4 as a representative hydrocarbon fuel. IR signatures of gas-phase oxidation products, CO2(g) and CO(g), are observed while cells are under load. A broad feature at 2295 cm(-1) is assigned to CO2 adsorbed on Ni as a CH4 oxidation intermediate during cell operation and while carbon deposits are electrochemically oxidized after CH4 operation. Electrochemical control provides confirmation of the assignment of adsorbed CO2. FTIRES has been demonstrated as a viable technique for the identification of fuel oxidation intermediates and products in working SOFCs, allowing for the elucidation of the mechanisms of fuel chemistry.

Seasonal variations in methane and nitrous oxide emissions factors in northern Australian savanna woodlands

NASA Astrophysics Data System (ADS)

Meyer, C. P.(Mick); Cook, Garry; Reisen, Fabienne; Russell-Smith, Jeremy; Maier, Stefan; Schatz, Jon; Yates, Cameron; Watt, Felicity

2010-05-01

Burning of savannas and grasslands consumes more than one third of the total annual biomass burning globally. In Australia, savanna fires emit annually from 2% to 4% of Australia's greenhouse gas emissions. This has led to efforts to reduce savanna burning emissions through early season prescribed burning. These programs aim to change the fire seasonality from predominantly high intensity late season fires which are characterized by low levels of patchiness and high burning efficiencies to early-season fires characterized by low intensity, a high degree of patchiness and low burning efficiency. The result is a net reduction in fire area and associated carbon emissions. Mitigation of greenhouse gas emissions is predicated on there being little change in methane (CH4) or nitrous oxide (N2O) emission factors (EFs) as the fire season progresses, however, recent analysis of the emission characteristics of African savanna fires by Korontzi et al., indicates CH4-EF, in particular, could decline substantially as the fire season progresses. If this also occurs in Australian savanna woodlands, then the current mitigation strategy could be ineffective. To address the issue a series of field campaigns were undertaken in the savanna woodlands of Western Arnhem land, Australia to quantify the variability in CH4 and N2O EFs throughout the fire season. This study compared CH4 and N2O EFs measured in smoke sampled from prescribed burning in late June/early July with those from late season fires in early October. It concentrated on the two major vegetation classes in Western Arnhemland; eucalypt open woodland, in which the fuel is composed predominantly tree leaf-litter supplemented by senescent native Sorghum, and sandstone heaths which are dominated by Spinifex hummocks. There were no significant differences in CH4 EFs between early or late season fires, however there were substantial differences between vegetation classes. The woodland emitted 0.3% of fuel carbon as CH4 compared to 0.15% in the sandstone heathland and pure Spinifex and Sorghum swords. The lower emission factors from the grasses compared to leaf litter can be entirely explained by higher combustion efficiency of grass fires. Emission of N2O were less dependent on combustion conditions; approximately 0.5% of fuel nitrogen was emitted as N2O, however there were no differences between early and late season fires or between vegetation classes. These results compare favorably with previous studies; the CH4-EF is similar to earlier measurements in open woodland, although the N2O-EF is lower than the value of 0.8% reported in previous work. Therefore we conclude that the proposed mitigation strategy is feasible and but the variation in EF with vegetation class calls for further quantification of EFs across all major vegetation types in the savanna regions.

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

PubMed

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

2015-01-01

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. 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. 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.

Tessellated gold nanostructures from Au144(SCH2CH2Ph)60 molecular precursors and their use in organic solar cell enhancement

NASA Astrophysics Data System (ADS)

Bauld, Reg; Hesari, Mahdi; Workentin, Mark S.; Fanchini, Giovanni

2014-06-01

We report for the first time the fabrication of nanocomposite hole-blocking layers consisting of poly-3,4-ethylene-dioxythiophene:poly-styrene-sulfonate (PEDOT:PSS) thin films incorporating networks of gold nanoparticles assembled from Au144(SCH2CH2Ph)60, a molecular gold precursor. These thin films can be prepared reproducibly on indium tin oxide by spinning on it Au144(SCH2CH2Ph)60 solutions in chlorobenzene, annealing the resulting thin film at 400 °C, and subsequently spinning PEDOT:PSS on top. The use of our nanocomposite hole-blocking layers for enhancing the photoconversion efficiency of bulk heterojunction organic solar cells is demonstrated. By varying the concentration of Au144(SCH2CH2Ph)60 in the starting solution and the annealing time, different gold nanostructures were obtained ranging from individual gold nanoparticles (AuNPs) to tessellated networks of gold nanostructures (Tess-AuNPs). Improvement in organic solar cell efficiencies up to 10% relative to a reference cell is demonstrated with Tess-AuNPs embedded in PEDOT:PSS.

Synthesis of Fe3O4@SiO2@OSi(CH2)3NHRN(CH2PPh2)2PdCl2 type nanocomposite complexes: Highly efficient and magnetically-recoverable catalysts in vitamin K3 synthesis.

PubMed

Uruş, Serhan

2016-12-15

The synthesis of aminomethylphosphine-metal complexes have opened a new perspective to the catalytic applications of organic compounds. Magnetic Fe3O4 nano-core was synthesized using the closed quartz tube with Teflon cover and microwaved 200°C for 1h with power controlled instrument set to max. 600W. Novel nano-composite supported; Fe3O4@SiO2(CH2)3NHArN(CH2PPh2)2 and Fe3O4@SiO2(CH2)3N(CH2PPh2)2 type bis(diphenylphosphinomethyl)amino ligands and their Pd(II) complexes have been synthesized and characterized with FT-IR, SEM, EDX, TEM, UV-Visible, XRD and TG/DTA techniques. All the complexes were used as heterogeneous catalysts in the oxidation of 2-methyl naphthalene (2MN) to 2-methyl-1, 4-naphthoquinone (vitamin K3, menadione, 2MNQ) in the presence of hydrogen peroxide and acetic acid. Selectivity reached about 55-60% with a conversion of 90-96% using the nano-magnetite supported aminomethylphosphine-Pd(II) complexes. The complexes were very active in three times in the catalytic recycling experiments in five catalytic cycles. Copyright © 2016 Elsevier Ltd. All rights reserved.

Activity and diversity of methane-oxidizing bacteria in glacier forefields on siliceous and calcareous bedrock

NASA Astrophysics Data System (ADS)

Nauer, P. A.; Dam, B.; Liesack, W.; Zeyer, J.; Schroth, M. H.

2012-01-01

The global methane (CH4) cycle is largely driven by methanogenic archaea and methane-oxidizing bacteria (MOB), but little is known about their activity and diversity in pioneer ecosystems. We conducted a field survey in forefields of 13 receding Swiss glaciers on both siliceous and calcareous bedrock to investigate and quantify CH4 turnover based on soil-gas CH4 concentration profiles, and to characterize MOB communities using pmoA sequencing and T-RFLP. Methane turnover was fundamentally different in the two bedrock categories. Of the 36 CH4 concentration profiles from siliceous locations, 11 showed atmospheric CH4 consumption at concentrations of ∼1-2 μl l-1 with soil-atmosphere CH4 fluxes of -0.14 to -1.1 mg m-2 d-1. Another 11 profiles showed no apparent activity, while the remaining 14 exhibited slightly increased CH4 concentrations of ∼2-10 μl l-1, most likely due to microsite methanogenesis. In contrast, all profiles from calcareous sites suggested a substantial, yet unknown CH4 source below our sampling zone, with soil-gas CH4 concentrations reaching up to 1400 μl l-1. Remarkably, most soils oxidized ∼90% of the deep-soil CH4, resulting in soil-atmosphere fluxes of 0.12 to 31 mg m-2 d-1. MOB showed limited diversity in both siliceous and calcareous forefields: all identified pmoA sequences formed only 5 OTUs and, with one exception, could be assigned to either Methylocystis or the as-yet-uncultivated Upland Soil Cluster γ (USCγ). The latter dominated T-RFLP patterns of all siliceous and most calcareous samples, while Methylocystis dominated in 4 calcareous samples. As Type I MOB are widespread in cold climate habitats with elevated CH4 concentrations, USCγ might be the corresponding Type I MOBs in habitats exposed to near-atmospheric CH4 concentrations.

Manganese complex-catalyzed oxidation and oxidative kinetic resolution of secondary alcohols by hydrogen peroxide† †Electronic supplementary information (ESI) available: Tables S1–S4 and additional data: NMR spectra of the products, GC and HPLC chromatograms in the OKR of secondary alcohols, key geometric information for DFT, etc. See DOI: 10.1039/c7sc00891k Click here for additional data file.

PubMed Central

Miao, Chengxia; Li, Xiao-Xi; Lee, Yong-Min; Xia, Chungu; Wang, Yong

2017-01-01

The highly efficient catalytic oxidation and oxidative kinetic resolution (OKR) of secondary alcohols has been achieved using a synthetic manganese catalyst with low loading and hydrogen peroxide as an environmentally benign oxidant in the presence of a small amount of sulfuric acid as an additive. The product yields were high (up to 93%) for alcohol oxidation and the enantioselectivity was excellent (>90% ee) for the OKR of secondary alcohols. Mechanistic studies revealed that alcohol oxidation occurs via hydrogen atom (H-atom) abstraction from an α-CH bond of the alcohol substrate and a two-electron process by an electrophilic Mn–oxo species. Density functional theory calculations revealed the difference in reaction energy barriers for H-atom abstraction from the α-CH bonds of R- and S-enantiomers by a chiral high-valent manganese–oxo complex, supporting the experimental result from the OKR of secondary alcohols. PMID:29163900

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lichterman, Michael F.; Sun, Ke; Hu, Shu

Small-band-gap (E g < 2 eV) semiconductors must be stabilized for use in integrated devices that convert solar energy into the bonding energy of a reduced fuel, specifically H 2 (g) or a reduced-carbon species such as CH 3 OH or CH 4 . To sustainably and scalably complete the fuel cycle, electrons must be liberated through the oxidation of water to O 2 (g). Strongly acidic or strongly alkaline electrolytes are needed to enable efficient and intrinsically safe operation of a full solar-driven water-splitting system. But, under water-oxidation conditions, the small-band-gap semiconductors required for efficient cell operation aremore » unstable, either dissolving or forming insulating surface oxides. Here, we describe herein recent progress in the protection of semiconductor photoanodes under such operational conditions. We specifically describe the properties of two protective overlayers, TiO 2 /Ni and NiO x , both of which have demonstrated the ability to protect otherwise unstable semiconductors for > 100 h of continuous solar-driven water oxidation when in contact with a highly alkaline aqueous electrolyte (1.0 M KOH(aq)). Furthermore, the stabilization of various semiconductor photoanodes is reviewed in the context of the electronic characteristics and a mechanistic analysis of the TiO 2 films, along with a discussion of the optical, catalytic, and electronic nature of NiO x films for stabilization of semiconductor photoanodes for water oxidation.« less

Remediation of 1,2,3-trichlorobenzene contaminated soil using a combined thermal desorption-molten salt oxidation reactor system.

PubMed

Li, Jin-hui; Sun, Xiao-fei; Yao, Zhi-tong; Zhao, Xiang-yang

2014-02-01

A combined thermal desorption (TD)-molten salt oxidation (MSO) reactor system was applied to remediate the 1,2,3-trichlorobenzene (1,2,3-TCB) contaminated soil. The TD reactor was used to enrich the contaminant from soil, and its dechlorination of the contaminant was achieved in the MSO reactor. The optimum operating conditions of TD, and the effects of MSO reactor temperatures, additive amounts of the TCB on destruction and removal efficiency (DRE) of TCB and chlorine retention efficiency (CRE) were investigated. The reaction mechanism and pathway were proposed as well. The combined system could remediate the contaminated soil at a large scale of concentration from 5 to 25gkg(-1), and the DRE and CRE reached more than 99% and 95%, respectively, at temperatures above 850°C. The reaction emissions included C6H6, CH4, CO and CO2, and chlorinated species were not detected. It was found that a little increase in the temperature can considerably reduce the emission of C6H6, CH4, and CO, while the CO2 level increased. Copyright © 2014. Published by Elsevier Ltd.

In situ Raman-based measurements of high dissolved methane concentrations in hydrate-rich ocean sediments

NASA Astrophysics Data System (ADS)

Zhang, Xin; Hester, Keith C.; Ussler, William; Walz, Peter M.; Peltzer, Edward T.; Brewer, Peter G.

2011-04-01

Ocean sediment dissolved CH4 concentrations are of interest for possible climate-driven venting from sea floor hydrate decomposition, for supporting the large-scale microbial anaerobic oxidation of CH4 that holds the oceanic CH4 budget in balance, and for environmental issues of the oil and gas industry. Analyses of CH4 from recovered cores near vent locations typically show a maximum of ˜1 mM, close to the 1 atmosphere equilibrium value. We show from novel in situ measurement with a Raman-based probe that geochemically coherent profiles of dissolved CH4 occur rising to 30 mM (pCH4 = 3 MPa) or an excess pressure ˜3× greater than CO2 in a bottle of champagne. Normalization of the CH4 Raman ν1 peak to the ubiquitous water ν2 bending peak provides a fundamental internal calibration. Very large losses of CH4 and fractions of other gases (CO2, H2S) must typically occur from recovered cores at gas rich sites. The new data are consistent with observations of microbial biomass and observed CH4 oxidation rates at hydrate rich sites and support estimates of a greatly expanded near surface oceanic pore water CH4 reservoir.

Modeling the impediment of methane ebullition bubbles by seasonal lake ice

DOE Office of Scientific and Technical Information (OSTI.GOV)

Greene, S.; Walter Anthony, K. M.; Archer, D.

Microbial methane (CH 4) ebullition (bubbling) from anoxic lake sediments comprises a globally significant flux to the atmosphere, but ebullition bubbles in temperate and polar lakes can be trapped by winter ice cover and later released during spring thaw. This "ice-bubble storage" (IBS) constitutes a novel mode of CH 4 emission. Before bubbles are encapsulated by downward-growing ice, some of their CH 4 dissolves into the lake water, where it may be subject to oxidation. We present field characterization and a model of the annual CH 4 cycle in Goldstream Lake, a thermokarst (thaw) lake in interior Alaska. We findmore » that summertime ebullition dominates annual CH 4 emissions to the atmosphere. Eighty percent of CH 4 in bubbles trapped by ice dissolves into the lake water column in winter, and about half of that is oxidized. The ice growth rate and the magnitude of the CH 4 ebullition flux are important controlling factors of bubble dissolution. Seven percent of annual ebullition CH 4 is trapped as IBS and later emitted as ice melts. In a future warmer climate, there will likely be less seasonal ice cover, less IBS, less CH 4 dissolution from trapped bubbles, and greater CH 4 emissions from northern lakes.« less

Modeling the impediment of methane ebullition bubbles by seasonal lake ice

DOE PAGES

Greene, S.; Walter Anthony, K. M.; Archer, D.; ...

2014-12-08

Microbial methane (CH 4) ebullition (bubbling) from anoxic lake sediments comprises a globally significant flux to the atmosphere, but ebullition bubbles in temperate and polar lakes can be trapped by winter ice cover and later released during spring thaw. This "ice-bubble storage" (IBS) constitutes a novel mode of CH 4 emission. Before bubbles are encapsulated by downward-growing ice, some of their CH 4 dissolves into the lake water, where it may be subject to oxidation. We present field characterization and a model of the annual CH 4 cycle in Goldstream Lake, a thermokarst (thaw) lake in interior Alaska. We findmore » that summertime ebullition dominates annual CH 4 emissions to the atmosphere. Eighty percent of CH 4 in bubbles trapped by ice dissolves into the lake water column in winter, and about half of that is oxidized. The ice growth rate and the magnitude of the CH 4 ebullition flux are important controlling factors of bubble dissolution. Seven percent of annual ebullition CH 4 is trapped as IBS and later emitted as ice melts. In a future warmer climate, there will likely be less seasonal ice cover, less IBS, less CH 4 dissolution from trapped bubbles, and greater CH 4 emissions from northern lakes.« less

Global Methane Biogeochemistry

NASA Astrophysics Data System (ADS)

Reeburgh, W. S.

2003-12-01

Methane (CH4) has been studied as an atmospheric constituent for over 200 years. A 1776 letter from Alessandro Volta to Father Campi described the first experiments on flammable "air" released by shallow sediments in Lake Maggiore (Wolfe, 1996; King, 1992). The first quantitative measurements of CH4, both involving combustion and gravimetric determination of trapped oxidation products, were reported in French by Boussingault and Boussingault, 1864 and Gautier (1901), who reported CH4 concentrations of 10 ppmv and 0.28 ppmv (seashore) and 95 ppmv (Paris), respectively. The first modern measurements of atmospheric CH4 were the infrared absorption measurements of Migeotte (1948), who estimated an atmospheric concentration of 2.0 ppmv. Development of gas chromatography and the flame ionization detector in the 1950s led to observations of vertical CH4 distributions in the troposphere and stratosphere, and to establishment of time-series sampling programs in the late 1970s. Results from these sampling programs led to suggestions that the concentration of CH4, as that of CO2, was increasing in the atmosphere. The possible role of CH4 as a greenhouse gas stimulated further research on CH4 sources and sinks. Methane has also been of interest to microbiologists, but findings from microbiology have entered the larger context of the global CH4 budget only recently.Methane is the most abundant hydrocarbon in the atmosphere. It plays important roles in atmospheric chemistry and the radiative balance of the Earth. Stratospheric oxidation of CH4 provides a means of introducing water vapor above the tropopause. Methane reacts with atomic chlorine in the stratosphere, forming HCl, a reservoir species for chlorine. Some 90% of the CH4 entering the atmosphere is oxidized through reactions initiated by the OH radical. These reactions are discussed in more detail by Wofsy (1976) and Cicerone and Oremland (1988), and are important in controlling the oxidation state of the atmosphere. Methane absorbs infrared radiation in the troposphere, as do CO2 and H2O, and is an important greenhouse gas (Lacis et al., 1981; Ramanathan et al., 1985).A number of review articles on atmospheric CH4 have appeared during the last 15 years. Cicerone and Oremland (1988) reviewed evidence for the temporal atmospheric increase, updated source estimates in the global CH4 budget, and placed constraints on the global budget, emphasizing that the total is well constrained, but that the constituent sources may be uncertain by a factor of 2 or more. This paper was part of a special section in Global Biogeochemical Cycles that resulted from a 1987 American Chemical Society Symposium, "Atmospheric Methane: Formation and Fluxes form the Biosphere and Geosphere." Tyler (1991) and Wahlen (1993) emphasized new information on stable isotopes of CH4 and 14CH4, respectively. Several reviews deal with the microbially mediated CH4 oxidation. King (1992) reviewed the ecology of microbial CH4 oxidation, emphasizing the important role of this process in global CH4 dynamics. R. S. Hanson and T. E. Hanson (1996) reviewed the physiology and taxonomy of methylotrophic bacteria, their role in the global carbon cycle, and the ecology of methanotrophic bacteria. Conrad (1996) reviewed the role of soils and soil microbial communities as controllers of CH4 fluxes, as well as those of H2, CO, OCS, N2O, and NO. Two meetings focusing on CH4 biogeochemistry were held in 1991: an NATO Advanced Science Workshop held at Mt. Hood, OR, and the Tenth International Symposium on Environmental Biogeochemistry (ISEB). A dedicated issue of Chemosphere (26(1-4), 1993) contains contributions from the NATO workshop; two additional volumes (Khalil, 1993 and Khalil, 2000) contain a report of the workshop and updates of important topics. Contributions to the ISEB meeting are presented in Oremland (1993). Wuebbles and Hayhoe (2002) reviewed the effects of CH4 on atmospheric chemistry and examined the direct and indirect impact of CH4 on climate. The Intergovernmental Panel on Climate Change (IPCC) has published periodic updates (see, e.g., IPCC, 2001).Substantial advances have resulted from research aimed at understanding the global CH4 mixing ratio increase. Time-series measurements of atmospheric CH4 have continued, new CH4 flux measurements in a range of environments have been reported, and data allowing use of the stable isotope (13C/12C, 2H/1H) composition of CH4 as an independent budget constraint have increased. The importance of microbial oxidation of CH4 has been recognized and modeled; the possible role of CH4 clathrate hydrates in the global budget has been clarified with the introduction of new technology. Studies of CH4 trapped in ice cores from the Greenland and Antarctic ice caps have continued, resulting in higher-resolution records and new interpretations of past conditions. There have been few recent changes in our understanding of the atmospheric chemistry of CH4, and since this is covered in Cicerone and Oremland (1988) it will not be covered here. The aim here is not to repeat information contained in the reviews mentioned above, but to present results that have appeared in the literature since their publication, to outline major questions, and to point to promising new approaches.

Physical and biological controls over patterns of methane flux from wetland soils

NASA Astrophysics Data System (ADS)

Owens, S. M.; von Fischer, J. C.

2006-12-01

While methane (CH4) production and plant-facilitated gas transport both contribute to patterns of CH4 emissions from wetlands, the relative importance of each mechanism is uncertain. In flooded wetland soils, CH4 is produced by anaerobic methanogenic bacteria. In the absence of competing oxidizers (i.e. SO42-, NO3-, O2), CH4 production is limited by the availability of labile carbon, which is supplied from recent plant primary production (e.g. as root exudates) and converted by anaerobic fermenting bacteria into methanogenic substrate (e.g. acetate). Because diffusion of gases through saturated soils is extremely slow, the aerenchymous tissues of wetland plants provide the primary pathway for CH4 emissions in systems dominated by emergent vascular vegetation. Aerenchyma also function to shuttle atmospheric oxygen to belowground plant tissues for respiration. Consequentially, root radial oxygen loss results in an oxidized rhizosphere, which limits CH4 production and provides habitat for aerobic methanotrophic bacteria, potentially reducing CH4 emissions. To test the contribution of recent photosynthates on CH4 emissions, a shading experiment was conducted in a Juncus-dominated wetland in the Colorado Front Range. Shade treatments significantly reduced net ecosystem production (NEE) and gross primary production (GPP) compared to control plots (p=0.0194 and p=0.0551, respectively). While CH4 emissions did not significantly differ between treatments, CH4 flux rates were strongly correlated with NEE (p=0.0063) and GPP (p=0.0020), in support of the hypothesis that labile carbon from recent photosynthesis controls patterns of CH4 emissions. The relative importance of plant gas transport and methane consumption rates on CH4 emissions is not known. Methane flux is more tightly correlated with NEE than GPP, which may be explained by increased CH4 consumption or decreased CH4 production as a result of rhizospheric oxidation. The ability to predict future emissions of this important greenhouse gas will be improved by increased understanding of the controls regulating its emission. Future work will focus on developing a tracer technique using SF6 and 13C-labeled CH4 to determine how plant gas transport properties and CH4 consumption contribute to patterns of methane emissions from wetlands.

Enzyme catalysis: C-H activation is a Reiske business

NASA Astrophysics Data System (ADS)

Bruner, Steven D.

2011-05-01

Enzymes that selectively oxidize unactivated C-H bonds are capable of constructing complex molecules with high efficiency. A new member of this enzyme family is RedG, a Reiske-type oxygenase that catalyses chemically challenging cyclizations in the biosynthesis of prodiginine natural products.

Effects of inorganic electron acceptors on methanogenesis and methanotrophy and on the community structure of bacteria and archaea in sediments of a boreal lake

NASA Astrophysics Data System (ADS)

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

2016-04-01

Lake sediments are globally significant sources of CH4 to the atmosphere, but the factors controlling the production and consumption of CH4 in these systems are understudied. Increasing availability of electron acceptors (EA) (other than CO2) in sediments can decrease or even suppress CH4 production by diverting the electron flow (from H2 and organic substances) from methanogenic to other anaerobic respiration pathways. However, whether these changes in microbial function extend down to changes in the structure of microbial communities is not known. Also anaerobic oxidation of methane (AOM) could be enhanced by increased availability of EAs (SO42-, NO3-, Fe3+ and Mn4+), but information on the role of this process in lake sediments is scarce. We studied the effects of inorganic EAs on the potential for CH4 production and consumption and on the structure of microbial communities in sediments of a boreal lake. Anoxic slurries of sediment samples collected from two depths (0 - 10 cm; 10 - 30 cm) of the profundal zone of a boreal, mesotrophic Lake Ätäskö, were amended with 1) CH4 or with CH4 and either 2) 10 mM Mn4+, 3) 10 mM Fe3+, 4) O2 or 5) CH2F2 (inhibitor of aerobic methane oxidation) and incubated at +10° C for up to 4 months. Furthermore, slurries from the 10 - 30 cm layer were amended with CH4 and either 6) 2 mM NO3- or 7) 2 mM SO42- and incubated at +4 ° C for up to 14 months. The processes were measured using 13C-labelling and by concentration measurements of CH4 and CO2. Effects of treatments 1-3 on microbial communities were also analysed by next-generation sequencing of 16S rRNA, as well as methyl coenzyme-M reductase gene amplicons and mRNA transcripts. CH4 production (max. 83 nmol gdw-1d-1) took place in the anaerobic treatments but was generally decreased by the addition of NO3-, SO42-, Fe3+ and Mn4+. Although the structure of sediment archaeal community was resistant to Fe3+/Mn4+ - additions, slight changes in the structure of bacterial community occurred. Besides decreasing the availability of methanogenic substrates, the Mn4+/Fe3+ - induced changes in the bacterial community also probably decreased the H2:acetate - ratio in the substrate pool. This led to increase in the relative activity (mRNA level) of some operational taxonomic units assigned to aceticlastic Methanosaetaceae and decrease in the relative activity of hydrogenotrophic Methanoregulaceae in the sediment. CH4 oxidation (0.02 - 0.30 nmol gdw-1d-1 in anaerobic and 18 - 73 nmol gdw-1d-1in aerobic treatments) took place without EA additions and was enhanced only by O2. This suggests decoupling of the process from the reduction of other inorganic EAs. The results also indicate that Fe3+/Mn4+ - reduction did not increase CH4 oxidation via increased availability of SO42- by cryptic sulfur cycle or via increased availability of organic EAs. Furthermore, ANME - archaea were only ≤ 3% of sediment archaeal community and their relative activity was decreased during incubations. Thus, EA driving CH4 oxidation in the anoxic sediments of the lake remains unknown or the process was methanogen-driven via trace methane oxidation.

Iron-catalyzed halogenation of alkanes: modeling of nonheme halogenases by experiment and DFT calculations.

PubMed

Comba, Peter; Wunderlich, Steffen

2010-06-25

When the dichloroiron(II) complex of the tetradentate bispidine ligand L=3,7-dimethyl-9-oxo-2,4-bis(2-pyridyl)-3,7-diazabicyclo[3.3.1]nonane-1,5-dicarboxylate methyl ester is oxidized with H(2)O(2), tBuOOH, or iodosylbenzene, the high-valent Fe=O complex efficiently oxidizes and halogenates cyclohexane. Kinetic D isotope effects and the preference for the abstraction of tertiary over secondary carbon-bound hydrogen atoms (quantified in the halogenation of adamantane) indicate that C-H activation is the rate-determining step. The efficiencies (yields in stoichiometric and turnover numbers in catalytic reactions), product ratios (alcohol vs. bromo- vs. chloroalkane), and kinetic isotope effects depend on the oxidant. These results suggest different pathways with different oxidants, and these may include iron(IV)- and iron(V)-oxo complexes as well as oxygen-based radicals.

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

NASA Astrophysics Data System (ADS)

D'Imperio, Ludovica

2014-05-01

The effects of climate changes on soil methane oxidation in a dry Arctic tundra. Ludovica D'Imperio1, Anders Michelsen1, Christian J. Jørgensen1, Bo Elberling1 1Center for Permafrost (CENPERM), Department of Geosciences and Natural Resource Management, University of Copenhagen, Denmark At Northern latitudes climatic changes are predicted to be most pronounced resulting in increasing active layer depth and changes in growing season length, vegetation cover and nutrient cycling. As a consequence of increased temperature, large stocks of carbon stored in the permafrost-affected soils could become available for microbial transformations and under anoxic conditions result in increasing methane production affecting net methane (CH4) budget. Arctic tundra soils also serves as an important sink of atmospheric CH4 by microbial oxidation under aerobic conditions. While several process studies have documented the mechanisms behind both production and emissions of CH4 in arctic ecosystems, an important knowledge gap exists with respect to the in situ dynamics of microbial-driven uptake of CH4 in arctic dry lands which may be enhanced as a consequence of global warming and thereby counterbalancing CH4 emissions from Arctic wetlands. In-situ methane measurements were made in a dry Arctic tundra in Disko Island, Western Greenland, during the summer 2013 to assess the role of seasonal and inter-annual variations in temperatures and snow cover. The experimental set-up included snow fences installed in 2012, allowed investigations of the emissions of GHGs from soil under increased winter snow deposition and ambient field conditions. The soil fluxes of CH4 and CO2 were measured using closed chambers in manipulated plots with increased summer temperatures and shrub removal with or without increased winter precipitation. At the control plots, the averaged seasonal CH4 oxidation rates ranged between -0.05 mg CH4 m-2 hr-1 (end of August) and -0.32 mg CH4 m-2 hr-1 (end of June). In the plots with increased summer temperatures the rates ranged between -0.08 mg CH4 m-2 hr-1 (end of August) and -0.40 mg CH4 m-2 hr-1 (beginning of July). Preliminary results show a significant effect of increased winter precipitation (p<0.01) over the season as well as a significant warming effect (p<0.05) during July and August. These results suggest that in a warmer climate increasing CH4 uptake rates in dry Arctic soils could become an important factor for net CH4 budget.

Supramolecular Recognition Allows Remote, Site-Selective C-H Oxidation of Methylenic Sites in Linear Amines.

PubMed

Olivo, Giorgio; Farinelli, Giulio; Barbieri, Alessia; Lanzalunga, Osvaldo; Di Stefano, Stefano; Costas, Miquel

2017-12-18

Site-selective C-H functionalization of aliphatic alkyl chains is a longstanding challenge in oxidation catalysis, given the comparable relative reactivity of the different methylenes. A supramolecular, bioinspired approach is described to address this challenge. A Mn complex able to catalyze C(sp 3 )-H hydroxylation with H 2 O 2 is equipped with 18-benzocrown-6 ether receptors that bind ammonium substrates via hydrogen bonding. Reversible pre-association of protonated primary aliphatic amines with the crown ether selectively exposes remote positions (C8 and C9) to the oxidizing unit, resulting in a site-selective oxidation. Remarkably, such control of selectivity retains its efficiency for a whole series of linear amines, overriding the intrinsic reactivity of C-H bonds, no matter the chain length. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemical Oxidation of Alkylnitro Compounds PP-1345

DTIC Science & Technology

2004-08-17

to the solution, to deprotonate the methyl group. Figure 22 shows the voltammetric response recorded in a CH3OH /0.2 M Bu4NBF4 solution containing...Voltammogram of Glassy Carbon (GC) Electrode 50 mM TNT/ CH3OH /0.2 M Bu4NBF4/55 mM NaOH 15 The standard redox potential for this reaction was... reaction ). Addition of 100 mM TNT to the basic solution ( CH3OH /0.2 M Bu4NBF4/ 55 mM NaOH) resulted in the appearance of a new oxidation wave with a

Selective photocatalytic reduction of CO2 by H2O/H2 to CH4 and CH3OH over Cu-promoted In2O3/TiO2 nanocatalyst

NASA Astrophysics Data System (ADS)

Tahir, Muhammad; Tahir, Beenish; Saidina Amin, Nor Aishah; Alias, Hajar

2016-12-01

Photocatalytic CO2 reduction by H2O and/or H2 reductant to selective fuels over Cu-promoted In2O3/TiO2 photocatalyst has been investigated. The samples, prepared via a simple and direct sol-gel method, were characterized by XRD, SEM, TEM, XPS, N2 adsorption-desorption, UV-vis diffuse reflectance, Raman and PL spectroscopy. Cu and In loaded into TiO2, oxidized as Cu2+ and In3+, promoted efficient separation of photo-generated electron/hole pairs (e-/h+). The results indicate that the reduction rate of CO2 by H2O to CH4 approached to 181 μmol g-1 h-1 using 0.5% Cu-3% In2O3/TiO2 catalyst, a 1.53 fold higher than the production rate over the 3% In2O3/TiO2 and 5 times the amount produced over the pure TiO2. In addition, Cu was found to promote efficient production of CH3OH and yield rate reached to 68 μmol g-1 h-1 over 1% Cu-3% In2O3/TiO2 catalyst. This improvement was attributed to charge transfer property and suppressed recombination rate by Cu-metal. More importantly, H2 reductant was less favorable for CH4 production, yet a significant amount of CH4 and CH3OH were obtained using a mixture of H2O/H2 reductant. Therefore, Cu-loaded In2O3/TiO2 catalyst has shown to be capable for methanol production, whereas product selectivity was greatly depending on the amount of Cu-loading and the type of reductant. A photocatalytic reaction mechanism was proposed to understand the experimental results over the Cu-loaded In2O3/TiO2 catalyst.

Chirped quantum cascade laser induced rapid passage signatures in an optically thick gas

NASA Astrophysics Data System (ADS)

Northern, J. H.; Ritchie, G. A. D.; Smakman, E. P.; van Helden, J. H.; Walker, R. J.; Duxbury, G.

2011-01-01

We report observations of rapid passage signals induced in samples of N2O and CH4 present in a multipass cell with an optical path length of 5 m. The effect of laser power and chirp rate upon the signals has been studied by utilising two different chirped quantum cascade lasers operating around 8 μm. The rapid passage signals exhibit an increasing delay in the switch from absorption to emission as a function of increased gas pressure (up to 8 Torr of gas). By comparing a selection of transitions in N2O and CH4, we show that, unlike ammonia, this `pressure shift' is independent of the transition dipole moment, spectroscopic branch probed and laser chirp rate. As the transition dipole moment is much larger in nitrous oxide than methane, we believe that this indicates that N2O-N2O collisions are more efficient at removing coherence from the polarised sample than CH4-CH4 collisions. We have also observed this pressure shift in a short path length of 40 cm, although with a much reduced value, indicating that propagation effects are important in this optically thick minimally damped system.

Solid state coordination chemistry: structural consequences of variations in tether length in the oxovanadium-copper-bisterpy-[O3P(CH2)nPO3]4- system, n= 1-6 (bisterpy = 2,2':4',4'':2'',2'''-quarterpyridyl-6',6''-di-2-pyridine).

PubMed

Ouellette, Wayne; Koo, Bon-Kweon; Burkholder, Eric; Golub, Vladimir; O'Connor, C J; Zubieta, Jon

2004-05-21

Hydrothermal reactions of Na3VO4, an appropriate Cu(II) source, bisterpy and an organodiphosphonate, H2O3P(CH2)nPO3H2 (n = 1-6) yielded a family of materials of the type [Cu2(bisterpy)]4+/VxOy(n-)/[O3P(CH2)nPO3]4-. This family of bimetallic oxides is characterized by an unusual structural diversity. The oxides [[Cu2(bisterpy)]V2O4[O3PCH2PO3H]2] (1), [[Cu2(bisterpy)(H2O)]VO2[O3P(CH2)3PO3][HO3P(CH2)3PO3H2

Electrochemical and partial oxidation of methane

NASA Astrophysics Data System (ADS)

Singh, Rahul

2008-10-01

Hydrogen has been the most common fuel used for the fuel cell research but there remains challenging technological hurdles and storage issues with hydrogen fuel. The direct electrochemical oxidation of CH4 (a major component of natural gas) in a solid oxide fuel cell (SOFC) to generate electricity has a potential of commercialization in the area of auxiliary and portable power units and battery chargers. They offer significant advantages over an external reformer based SOFC, namely, (i) simplicity in the overall system architecture and balance of plant, (ii) more efficient and (iii) availability of constant concentration of fuel in the anode compartment of SOFC providing stability factor. The extreme operational temperature of a SOFC at 700-1000°C provides a thermodynamically favorable pathway to deposit carbon on the most commonly used Ni anode from CH4 according to the following reaction (CH4 = C + 2H2), thus deteriorating the cell performance, stability and durability. The coking problem on the anode has been a serious and challenging issue faced by the catalyst research community worldwide. This dissertation presents (i) a novel fabricated bi-metallic Cu-Ni anode by electroless plating of Cu on Ni anode demonstrating significantly reduced or negligible coke deposition on the anode for CH4 and natural gas fuel after long term exposure, (ii) a thorough microstructural examination of Ni and Cu-Ni anode exposed to H2, CH4 and natural gas after long term exposure at 750°C by scanning electron microscopy, energy dispersive X-ray spectroscopy and X-ray diffraction and (iii) in situ electrochemical analysis of Ni and Cu-Ni for H2, CH4 and natural gas during long term exposure at 750°C by impedance spectroscopy. A careful investigation of variation in the microstructure and performance characteristics (voltage-current curve and impedance) of Ni and Cu-Ni anode before and after a long term exposure of CH4 and natural gas would allow us to test the validation of a negligible coke formation on the novel fabricated anode by electroless plating process. Hydrogen is an environmentally cleaner source of energy. The recent increase in the demand of hydrogen as fuel for all types of fuel cells and petroleum refining process has boosted the need of production of hydrogen. Methane, a major component of natural gas is the major feedstock for production of hydrogen. The route of partial oxidation of methane to produce syngas (CO + H2) offers significant advantages over commercialized steam reforming process for higher efficiency and lower energy requirements. Partial oxidation of methane was studied by pulsing O2 into a CH4 flow over Rh/Al2O3 in a sequence of in situ infrared (IR) cell and fixed bed reactor at 773 K. The results obtained from the sequence of an IR cell followed by a fixed bed reactor show that (i) adsorbed CO produced possesses a long residence time, indicating that adsorbed oxygen leading to the formation of CO is significantly different from those leading to CO2 and (ii) CO2 is not an intermediate species for the formation of CO. In situ IR of pulse reaction coupled with alternating reactor sequence is an effective approach to study the primary and secondary reactions as well as the nature of their adsorbed species. As reported earlier, hydrogen remains to be the most effective fuel for fuel cells, the production of high purity hydrogen from naturally available resources such as coal, petroleum, and natural gas requires a number of energy-intensive steps, making fuel cell processes for stationary electric power generation prohibitively uneconomic. Direct use of coal or coal gas as the feed is a promising approach for low cost electricity generation. Coal gas solid oxide fuel cell was studied by pyrolyzing Ohio #5 coal to coal gas and transporting to a Cu anode solid oxide fuel cell to generate power. The study of coal-gas solid oxide fuel cell is divided into two sections, i.e., (i) understanding the composition of coal gas by in situ infrared spectroscopy combined with mass spectrometry and (ii) evaluating the performance of coal gas for power generation based on the composition on a Cu-SOFC. The voltage-current performance curve for coal gas suggests that hydrogen and methane rich coal gas performed better than CO2 or D2O concentrated coal gas. A slow rate of reforming reaction of D2O than CO2 with coal and coal gas was observed during pyrolysis reaction. The coal and coke (by-product of pyrolysis) were characterized by Raman spectrometer to reveal the effect of pyrolysis on the structural properties of coal.

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...

Description of toluene inhibition of methyl bromide biodegradation in seawater and isolation of a marine toluene oxidizer that degrades methyl bromide.

PubMed

Goodwin, Kelly D; Tokarczyk, Ryszard; Stephens, F Carol; Saltzman, Eric S

2005-07-01

Methyl bromide (CH3Br) and methyl chloride (CH3Cl) are important precursors for destruction of stratospheric ozone, and oceanic uptake is an important component of the biogeochemical cycle of these methyl halides. In an effort to identify and characterize the organisms mediating halocarbon biodegradation, we surveyed the effect of potential cometabolic substrates on CH3Br biodegradation using a 13CH3Br incubation technique. Toluene (160 to 200 nM) clearly inhibited CH3Br and CH3Cl degradation in seawater samples from the North Atlantic, North Pacific, and Southern Oceans. Furthermore, a marine bacterium able to co-oxidize CH3Br while growing on toluene was isolated from subtropical Western Atlantic seawater. The bacterium, Oxy6, was also able to oxidize o-xylene and the xylene monooxygenase (XMO) pathway intermediate 3-methylcatechol. Patterns of substrate oxidation, lack of acetylene inhibition, and the inability of the toluene 4-monooxygenase (T4MO)-containing bacterium Pseudomonas mendocina KR1 to degrade CH3Br ruled out participation of the T4MO pathway in Oxy6. Oxy6 also oxidized a variety of toluene (TOL) pathway intermediates such as benzyl alcohol, benzylaldehyde, benzoate, and catechol, but the inability of Pseudomonas putida mt-2 to degrade CH3Br suggested that the TOL pathway might not be responsible for CH3Br biodegradation. Molecular phylogenetic analysis identified Oxy6 to be a member of the family Sphingomonadaceae related to species within the Porphyrobacter genus. Although some Sphingomonadaceae can degrade a variety of xenobiotic compounds, this appears to be the first report of CH3Br degradation for this class of organism. The widespread inhibitory effect of toluene on natural seawater samples and the metabolic capabilities of Oxy6 indicate a possible link between aromatic hydrocarbon utilization and the biogeochemical cycle of methyl halides.

Iron(II) catalysis in oxidation of hydrocarbons with ozone in acetonitrile

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bataineh, Hajem; Pestovsky, Oleg; Bakac, Andreja

Oxidation of alcohols, ethers, and sulfoxides by ozone in acetonitrile is catalyzed by submillimolar concentrations of Fe(CH 3CN) 6 2+. The catalyst provides both rate acceleration and greater selectivity toward the less oxidized products. For example, Fe(CH 3CN) 6 2+-catalyzed oxidation of benzyl alcohol yields benzaldehyde almost exclusively (>95%), whereas the uncatalyzed reaction generates a 1:1 mixture of benzaldehyde and benzoic acid. Similarly, aliphatic alcohols are oxidized to aldehydes/ketones, cyclobutanol to cyclobutanone, and diethyl ether to a 1:1 mixture of ethanol and acetaldehyde. The kinetics of oxidation of alcohols and diethyl ether are first-order in [Fe(CH 3CN) 6 2+] andmore » [O 3] and independent of [substrate] at concentrations greater than ~5 mM. In this regime, the rate constant for all of the alcohols is approximately the same, k cat = (8 ± 1) × 10 4 M –1 s –1, and that for (C 2H 5) 2O is (5 ± 0.5) × 10 4 M –1 s –1. In the absence of substrate, Fe(CH 3CN) 6 2+ reacts with O 3 with k Fe = (9.3 ± 0.3) × 10 4 M –1 s –1. The similarity between the rate constants k Fe and k cat strongly argues for Fe(CH 3CN) 6 2+/O 3 reaction as rate-determining in catalytic oxidation. The active oxidant produced in Fe(CH 3CN) 6 2+/O 3 reaction is suggested to be an Fe(IV) species in analogy with a related intermediate in aqueous solutions. As a result, this assignment is supported by the similarity in kinetic isotope effects and relative reactivities of the two species toward substrates.« less

Iron(II) catalysis in oxidation of hydrocarbons with ozone in acetonitrile

DOE PAGES

Bataineh, Hajem; Pestovsky, Oleg; Bakac, Andreja

2015-02-11

Oxidation of alcohols, ethers, and sulfoxides by ozone in acetonitrile is catalyzed by submillimolar concentrations of Fe(CH 3CN) 6 2+. The catalyst provides both rate acceleration and greater selectivity toward the less oxidized products. For example, Fe(CH 3CN) 6 2+-catalyzed oxidation of benzyl alcohol yields benzaldehyde almost exclusively (>95%), whereas the uncatalyzed reaction generates a 1:1 mixture of benzaldehyde and benzoic acid. Similarly, aliphatic alcohols are oxidized to aldehydes/ketones, cyclobutanol to cyclobutanone, and diethyl ether to a 1:1 mixture of ethanol and acetaldehyde. The kinetics of oxidation of alcohols and diethyl ether are first-order in [Fe(CH 3CN) 6 2+] andmore » [O 3] and independent of [substrate] at concentrations greater than ~5 mM. In this regime, the rate constant for all of the alcohols is approximately the same, k cat = (8 ± 1) × 10 4 M –1 s –1, and that for (C 2H 5) 2O is (5 ± 0.5) × 10 4 M –1 s –1. In the absence of substrate, Fe(CH 3CN) 6 2+ reacts with O 3 with k Fe = (9.3 ± 0.3) × 10 4 M –1 s –1. The similarity between the rate constants k Fe and k cat strongly argues for Fe(CH 3CN) 6 2+/O 3 reaction as rate-determining in catalytic oxidation. The active oxidant produced in Fe(CH 3CN) 6 2+/O 3 reaction is suggested to be an Fe(IV) species in analogy with a related intermediate in aqueous solutions. As a result, this assignment is supported by the similarity in kinetic isotope effects and relative reactivities of the two species toward substrates.« less

Characterization of methane oxidation in a simulated landfill cover system by comparing molecular and stable isotope mass balances.

PubMed

Schulte, Marcel; Jochmann, Maik A; Gehrke, Tobias; Thom, Andrea; Ricken, Tim; Denecke, Martin; Schmidt, Torsten C

2017-11-01

Biological methane oxidation may be regarded as a method of aftercare treatment for landfills to reduce climate relevant methane emissions. It is of social and economic interest to estimate the behavior of bacterial methane oxidation in aged landfill covers due to an adequate long-term treatment of the gas emissions. Different approaches assessing methane oxidation in laboratory column studies have been investigated by other authors recently. However, this work represents the first study in which three independent approaches, ((i) mass balance, (ii) stable isotope analysis, and (iii) stoichiometric balance of product (CO 2 ) and reactant (CH 4 ) by CO 2 /CH 4 -ratio) have been compared for the estimation of the biodegradation by a robust statistical validation on a rectangular, wide soil column. Additionally, an evaluation by thermal imaging as a potential technique for the localization of the active zone of bacterial methane oxidation has been addressed in connection with stable isotope analysis and CO 2 /CH 4 -ratios. Although landfills can be considered as open systems the results for stable isotope analysis based on a closed system correlated better with the mass balance than calculations based on an open system. CO 2 /CH 4 -ratios were also in good agreement with mass balance. In general, highest values for biodegradation were determined from mass balance, followed by CO 2 /CH 4 -ratio, and stable isotope analysis. The investigated topsoil proved to be very suitable as a potential cover layer by removing up to 99% of methane for CH 4 loads of 35-65gm -2 d -1 that are typical in the aftercare phase of landfills. Finally, data from stable isotope analysis and the CO 2 /CH 4 -ratios were used to trace microbial activity within the reactor system. It was shown that methane consumption and temperature increase, as a cause of high microbial activity, correlated very well. Copyright © 2017 Elsevier Ltd. All rights reserved.

Processes controlling the composition of precipitation at a remote southern hemispheric location: Torres del Paine National Park, Chile

NASA Astrophysics Data System (ADS)

Galloway, James N.; Keene, William C.; Likens, Gene E.

1996-03-01

Precipitation composition measured at Torres del Paine National Park, Chile (TdP) (51°10'S, 71°58'W), between 1984 and 1993 was acidic (volume-weighted-average pH of 4.96) with a dilute seawater component. H+ was the dominant non-sea-salt (nss) cation; in decreasing order of abundance, nss anions were HCOO-, Cl-, SO4=, CH3COO-, and NO3-. Relative to lower latitude, remote locations, concentrations and per-event depositions of nss SO4=, NO3-, and NH4+ at TdP were lower; those of HCOOt (HCOO- + HCOOH) and CH3COOHt, (CH3COO- and CH3COOH) were similar; and those of CH3SO3- were higher. Concentrations and deposition fluxes of HCOOt, CH3COOt, nss SO4=, CH3SO3-, and NH4+ varied seasonally with summer maxima and winter minima. Carboxylic acids probably originated from both direct terrestrial emissions and oxidation of hydrocarbons emitted by marine and terrestrial biota. Nss SO4= and CH3SO3- originated primarily from oxidation of biogenic (CH3)2S emitted from the southern Pacific Ocean. Direct emissions of NH3 from upwind terrestrial and marine ecosystems probably accounted for most observed NH4+. NO3- concentrations and depositions were highest during the latter part of austral winter and spring suggesting abiotic controls. Transport of precursors from lightning, biomass burning, and fossil-fuel combustion at lower latitudes and possibly transport of reactive N from the stratosphere apparently contributed oxidized N to the southern Patagonian troposphere. Although the ionic strength of precipitation at TdP is currently among the world's lowest, future changes are likely because of increases in local and regional population and energy and food production.

Mitochondria As Sources and Targets of Methane.

PubMed

Mészáros, András Tamás; Szilágyi, Ágnes Lilla; Juhász, László; Tuboly, Eszter; Érces, Dániel; Varga, Gabriella; Hartmann, Petra

2017-01-01

This review summarizes the current knowledge on the role of mitochondria in the context of hypoxic cell biology, while providing evidence of how these mechanisms are modulated by methane (CH 4 ). Recent studies have unambiguously confirmed CH 4 bioactivity in various in vitro and in vivo experimental models and established the possibility that CH 4 can affect many aspects of mitochondrial physiology. To date, no specific binding of CH 4 to any enzymes or receptors have been reported, and it is probable that many of its effects are related to physico-chemical properties of the non-polar molecule. (i) Mitochondria themselves can be sources of endogenous CH 4 generation under oxido-reductive stress conditions; chemical inhibition of the mitochondrial electron transport chain with site-specific inhibitors leads to increased formation of CH 4 in eukaryote cells, in plants, and in animals. (ii) Conventionally believed as physiologically inert, studies cited in this review demonstrate that exogenous CH 4 modulates key events of inflammation. The anti-apoptotic effects of exogenously administered CH 4 are also recognized, and these properties also suggest that CH 4 -mediated intracellular signaling is closely associated with mitochondria. (iii) Mitochondrial substrate oxidation is coupled with the reduction of molecular oxygen, thus providing energy for cellular metabolism. Interestingly, recent in vivo studies have shown improved basal respiration and modulated mitochondrial oxidative phosphorylation by exogenous CH 4 . Overall, these data suggest that CH 4 liberation and effectiveness in eukaryotes are both linked to hypoxic events and redox regulation and support the notion that CH 4 has therapeutic roles in mammalian pathophysiologies.

Mitochondria As Sources and Targets of Methane

PubMed Central

Mészáros, András Tamás; Szilágyi, Ágnes Lilla; Juhász, László; Tuboly, Eszter; Érces, Dániel; Varga, Gabriella; Hartmann, Petra

2017-01-01

This review summarizes the current knowledge on the role of mitochondria in the context of hypoxic cell biology, while providing evidence of how these mechanisms are modulated by methane (CH4). Recent studies have unambiguously confirmed CH4 bioactivity in various in vitro and in vivo experimental models and established the possibility that CH4 can affect many aspects of mitochondrial physiology. To date, no specific binding of CH4 to any enzymes or receptors have been reported, and it is probable that many of its effects are related to physico-chemical properties of the non-polar molecule. (i) Mitochondria themselves can be sources of endogenous CH4 generation under oxido-reductive stress conditions; chemical inhibition of the mitochondrial electron transport chain with site-specific inhibitors leads to increased formation of CH4 in eukaryote cells, in plants, and in animals. (ii) Conventionally believed as physiologically inert, studies cited in this review demonstrate that exogenous CH4 modulates key events of inflammation. The anti-apoptotic effects of exogenously administered CH4 are also recognized, and these properties also suggest that CH4-mediated intracellular signaling is closely associated with mitochondria. (iii) Mitochondrial substrate oxidation is coupled with the reduction of molecular oxygen, thus providing energy for cellular metabolism. Interestingly, recent in vivo studies have shown improved basal respiration and modulated mitochondrial oxidative phosphorylation by exogenous CH4. Overall, these data suggest that CH4 liberation and effectiveness in eukaryotes are both linked to hypoxic events and redox regulation and support the notion that CH4 has therapeutic roles in mammalian pathophysiologies. PMID:29181377

Activity and diversity of methane-oxidizing bacteria in glacier forefields on siliceous and calcareous bedrock

NASA Astrophysics Data System (ADS)

Nauer, P. A.; Dam, B.; Liesack, W.; Zeyer, J.; Schroth, M. H.

2012-06-01

The global methane (CH4) cycle is largely driven by methanogenic archaea and methane-oxidizing bacteria (MOB), but little is known about their activity and diversity in pioneer ecosystems. We conducted a field survey in forefields of 13 receding Swiss glaciers on both siliceous and calcareous bedrock to investigate and quantify CH4 turnover based on soil-gas CH4 concentration profiles, and to characterize the MOB community by sequencing and terminal restriction fragment length polymorphism (T-RFLP) analysis of pmoA. Methane turnover was fundamentally different in the two bedrock categories. Of the 36 CH4 concentration profiles from siliceous locations, 11 showed atmospheric CH4 consumption at concentrations of ~1-2 μL L-1 with soil-atmosphere CH4 fluxes of -0.14 to -1.1 mg m-2 d-1. Another 11 profiles showed no apparent activity, while the remaining 14 exhibited slightly increased CH4 concentrations of ~2-10 μL L-1 , most likely due to microsite methanogenesis. In contrast, all profiles from calcareous sites suggested a substantial, yet unknown CH4 source below our sampling zone, with soil-gas CH4 concentrations reaching up to 1400 μL L-1. Remarkably, most soils oxidized ~90 % of the deep-soil CH4, resulting in soil-atmosphere fluxes of 0.12 to 31 mg m-2 d-1. MOB showed limited diversity in both siliceous and calcareous forefields: all identified pmoA sequences formed only 5 operational taxonomic units (OTUs) at the species level and, with one exception, could be assigned to either Methylocystis or the as-yet-uncultivated Upland Soil Cluster γ (USCγ). The latter dominated T-RFLP patterns of all siliceous and most calcareous samples, while Methylocystis dominated in 4 calcareous samples. Members of Upland Soil Cluster α (USCα) were not detected. Apparently, USCγ adapted best to the oligotrophic cold climate conditions at the investigated pioneer sites.

The quest for atmospheric methane oxidizers in forest soils.

PubMed

Kolb, Steffen

2009-10-01

Aerobic methanotrophs in forest soils are the largest biological sink for atmospheric methane (CH4 ). Community structures in 53 soils from Europe, Russia, North and South America, Asia and New Zealand located in boreal, temperate and tropical forests were analysed and maximal abundances of 2.1 × 10(7) methanotrophs g(-1)   DW were measured. In acidic soils, the most frequently detected pmoA genotypes were Upland Soil Cluster α (USCα) and Methylocystis spp. Phospholipid fatty acids that were labelled by consumption of (14/13) CH4 suggested the activity of type II methanotrophs. Cluster 1 (Methylocystaceae), USCγ and Methylocystis spp. were frequently detected genotypes in pH-neutral soils. Genotypes with ambiguous functional affiliation were co-detected (Clusters MR1, RA21, 2) and may represent aerobic methanotrophs, ammonia oxidizers or enzymes with an unknown function. The physiological traits of atmospheric CH4 oxidizers are largely unknown because organisms possessing the key forest soil pmoA genotypes (USCα, USCγ, Cluster 1) have not been cultivated. Some methanotrophic strains belonging to the family Methylocystaceae have been shown to oxidize CH4 at atmospheric mixing ratios. Methylocystis strain SC2 was found to have an alternative particulate CH4 monooxygenase responsible for CH4 oxidation at atmospheric mixing ratios. pH, forest type and temperature might be environmental factors that shape methanotrophic communities in forest soils. However, specific effects on individual species are largely unknown, and only a limited number of studies have addressed environmental controls of methanotrophic diversity, pointing to the need for future research in this area. © 2009 Society for Applied Microbiology and Blackwell Publishing Ltd.

Properties of Multiphase Polyurethane Systems.

DTIC Science & Technology

1981-08-01

based on 4,4’-diphenylmethane dilsocyanate (MDI), N -methyl diethanolamine ( MDEA ), and polytetramethylene oxide (PTMO) and were synthesized with four...several levels of ammonium sulfonation (Scheme II) MDI/ MDEA /PTMO Series H04CH2 CH2CH2CH20- H + 0 = C = N -- -CH 2-O- N = C = 0 PTMO MDI 70 C HO OH...catalyst I II11 1 " 0 = C = N "---CH 2 - - N -C-O’-CH 2 CH C2H2 0-4C-’-( >-CH2DMA 1 CH3 70C I * HO - CM2 - CH2 - N - CH2 - CH2 - OH--- MDEA 0 H H 0 CH3H ... H2

Limited role for methane in the mid-Proterozoic greenhouse

PubMed Central

Olson, Stephanie L.; Reinhard, Christopher T.; Lyons, Timothy W.

2016-01-01

Pervasive anoxia in the subsurface ocean during the Proterozoic may have allowed large fluxes of biogenic CH4 to the atmosphere, enhancing the climatic significance of CH4 early in Earth’s history. Indeed, the assumption of elevated pCH4 during the Proterozoic underlies most models for both anomalous climatic stasis during the mid-Proterozoic and extreme climate perturbation during the Neoproterozoic; however, the geologic record cannot directly constrain atmospheric CH4 levels and attendant radiative forcing. Here, we revisit the role of CH4 in Earth’s climate system during Proterozoic time. We use an Earth system model to quantify CH4 fluxes from the marine biosphere and to examine the capacity of biogenic CH4 to compensate for the faint young Sun during the “boring billion” years before the emergence of metazoan life. Our calculations demonstrate that anaerobic oxidation of CH4 coupled to SO42− reduction is a highly effective obstacle to CH4 accumulation in the atmosphere, possibly limiting atmospheric pCH4 to less than 10 ppm by volume for the second half of Earth history regardless of atmospheric pO2. If recent pO2 constraints from Cr isotopes are correct, we predict that reduced UV shielding by O3 should further limit pCH4 to very low levels similar to those seen today. Thus, our model results likely limit the potential climate warming by CH4 for the majority of Earth history—possibly reviving the faint young Sun paradox during Proterozoic time and challenging existing models for the initiation of low-latitude glaciation that depend on the oxidative collapse of a steady-state CH4 greenhouse. PMID:27671638

Oxidative esterification via photocatalytic C-H activation

EPA Science Inventory

Direct oxidative esterification of alcohol via photocatalytic C-H activation has been developed using VO@g-C3N4 catalyst; an expeditious esterification of alcohols occurs under neutral conditions using visible light as the source of energy.

Oxidation-promoted activation of a ferrocene C-H bond by a rhodium complex.

PubMed

Labande, Agnès; Debono, Nathalie; Sournia-Saquet, Alix; Daran, Jean-Claude; Poli, Rinaldo

2013-05-14

The oxidation of a rhodium(I) complex containing a ferrocene-based heterodifunctional phosphine N-heterocyclic carbene (NHC) ligand produces a stable, planar chiral rhodium(III) complex with an unexpected C-H activation on ferrocene. The oxidation of rhodium(I) to rhodium(III) may be accomplished by initial oxidation of ferrocene to ferrocenium and subsequent electron transfer from rhodium to ferrocenium. Preliminary catalytic tests showed that the rhodium(III) complex is active for the Grignard-type arylation of 4-nitrobenzaldehyde via C-H activation of 2-phenylpyridine.

A DFT-Elucidated Comparison of the Solution-Phase and SAM Electrochemical Properties of Short-Chain Mercaptoalkylferrocenes: Synthetic and Spectroscopic Aspects, and the Structure of Fc-CH2CH2-S-S-CH2CH2-Fc.

PubMed

Lewtak, Jan P; Landman, Marilé; Fernández, Israel; Swarts, Jannie C

2016-03-07

Facile synthetic procedures to synthesize a series of difficult-to-obtain mercaptoalkylferrocenes, namely, Fc(CH2)nSH, where n = 1 (1), 2 (2), 3 (3), or 4 (4) and Fc = Fe(η(5)-C5H5)(η(5)-C5H4), are reported. Dimerization of 1-4 to the corresponding disulfides 19-22 was observed in air. Dimer 20 (Z = 2) crystallized in the triclinic space group P1̅. Dimers 20-22 could be reduced back to the original Fc(CH2)nSH derivatives with LiAlH4 in refluxing tetrahydrofuran. Density functional theory (DFT) calculations showed that the highest occupied molecular orbital of 1-4 lies exclusively on the ferrocenyl group implying that the electrochemical oxidation observed at ca. -15 < Epa < 76 mV versus FcH/FcH(+) involves exclusively an Fe(II) to Fe(III) process. Further DFT calculations showed this one-electron oxidation is followed by proton loss on the thiol group to generate a radical, Fc(CH2)nS(•), with spin density mainly located on the sulfur. Rapid exothermic dimerization leads to the observed dimers, Fc(CH2)n-S-S-(CH 2)nFc. Reduction of the ferrocenium groups on the dimer occurs at potentials that still showed the ferrocenyl group ΔE = Epa,monomer - Epc,dimer ≤ 78 mV, indicating that the redox properties of the ferrocenyl group on the mercaptans are very similar to those of the dimer. (1)H NMR measurements showed that, like ferrocenyl oxidation, the resonance position of the sulfhydryl proton, SH, and others, are dependent on -(CH2)n- chain length. Self-assembled monolayers (SAMs) on gold were generated to investigate the electrochemical behavior of 1-4 in the absence of diffusion. Under these conditions, ΔE approached 0 mV for the longer chain derivatives at slow scan rates. The surface-bound ferrocenyl group of the metal-thioether, Fc(CH2)n -S-Au, is oxidized at approximately equal potentials as the equivalent CH2Cl2-dissolved ferrocenyl species 1-4. Surface coverage by the SAMs is dependent on alkyl chain length with the largest coverage obtained for 4, while the rate of heterogeneous electron transfer between SAM substrate and electrode was the fastest for the shortest chain derivative, Fc-CH2-S-Au.

Field application of nitrogen and phenylacetylene to mitigate greenhouse gas emissions from landfill cover soils: effects on microbial community structure.

PubMed

Im, Jeongdae; Lee, Sung-Woo; Bodrossy, Levente; Barcelona, Michael J; Semrau, Jeremy D

2011-01-01

Landfills are large sources of CH(4), but a considerable amount of CH(4) can be removed in situ by methanotrophs if their activity can be stimulated through the addition of nitrogen. Nitrogen can, however, lead to increased N(2)O production. To examine the effects of nitrogen and a selective inhibitor on CH(4) oxidation and N(2)O production in situ, 0.5 M of NH(4)Cl and 0.25 M of KNO(3), with and without 0.01% (w/v) phenylacetylene, were applied to test plots at a landfill in Kalamazoo, MI from 2007 November to 2009 July. Nitrogen amendments stimulated N(2)O production but had no effect on CH(4) oxidation. The addition of phenylacetylene stimulated CH(4) oxidation while reducing N(2)O production. Methanotrophs possessing particulate methane monooxygenase and archaeal ammonia-oxidizers (AOAs) were abundant. The addition of nitrogen reduced methanotrophic diversity, particularly for type I methanotrophs. The simultaneous addition of phenylacetylene increased methanotrophic diversity and the presence of type I methanotrophs. Clone libraries of the archaeal amoA gene showed that the addition of nitrogen increased AOAs affiliated with Crenarchaeal group 1.1b, while they decreased with the simultaneous addition of phenylacetylene. These results suggest that the addition of phenylacetylene with nitrogen reduces N(2)O production by selectively inhibiting AOAs and/or type II methanotrophs.

Electrochemical performance and carbon deposition resistance of M-BaZr0.1Ce0.7Y0.1Yb0.1O3-δ (M = Pd, Cu, Ni or NiCu) anodes for solid oxide fuel cells

PubMed Central

Li, Meng; Hua, Bin; Pu, Jian; Chi, Bo; Jian, Li

2015-01-01

Pd-, Cu-, Ni- and NiCu-BaZr0.1Ce0.7Y0.1Yb0.1O3-δ anodes, designated as M-BZCYYb, were prepared by impregnating M-containing solution into BZCYYb scaffold, and investigated in the aspects of electrocatalytic activity for the reactions of H2 and CH4 oxidation and the resistance to carbon deposition. Impregnation of Pd, Ni or NiCu significantly reduced both the ohmic (RΩ) and polarization (RP) losses of BZCYYb anode exposed to H2 or CH4, while Cu impregnation decreased only RΩ in H2 and the both in CH4. Pd-, Ni- and NiCu-BZCYYb anodes were resistant to carbon deposition in wet (3 mol. % H2O) CH4 at 750°C. Deposited carbon fibers were observed in Pd- and Ni-BZCYYb anodes exposed to dry CH4 at 750°C for 12 h, and not observed in NiCu-BZCYYb exposed to dry CH4 at 750°C for 24 h. The performance of a full cell with NiCu-BZCYYb anode, YSZ electrolyte and La0.6Sr0.4Co0.2Fe0.8O3-δ-Gd doped CeO2 (LSCF-GDC) cathode was stable at 750°C in wet CH4 for 130 h, indicating that NiCu-BZCYYb is a promising anode for direct CH4 solid oxide fuel cells (SOFCs). PMID:25563843

Depth distribution of microbial production and oxidation of methane in northern boreal peatlands.

PubMed

Sundh, I; Nilsson, M; Granberg, G; Svensson, B H

1994-05-01

The depth distributions of anaerobic microbial methane production and potential aerobic microbial methane oxidation were assessed at several sites in both Sphagnum- and sedge-dominated boreal peatlands in Sweden, and compared with net methane emissions from the same sites. Production and oxidation of methane were measured in peat slurries, and emissions were measured with the closed-chamber technique. Over all eleven sites sampled, production was, on average, highest 12 cm below the depth of the average water table. On the other hand, highest potential oxidation of methane coincided with the depth of the average water table. The integrated production rate in the 0-60 cm interval ranged between 0.05 and 1.7 g CH4 m (-2) day(-) and was negatively correlated with the depth of the average water table (linear regression: r (2) = 0.50, P = 0.015). The depth-integrated potential CH4-oxidation rate ranged between 3.0 and 22.1 g CH4 m(-2) day(-1) and was unrelated to the depth of the average water table. A larger fraction of the methane was oxidized at sites with low average water tables; hence, our results show that low net emission rates in these environments are caused not only by lower methane production rates, but also by conditions more favorable for the development of CH4-oxidizing bacteria in these environments.

Mitigation of Methane and Odor using a Pilot-Scale Engineered Biocover at a Landfill, South Korea

NASA Astrophysics Data System (ADS)

Bomin, K.; O, G. C.; Ryu, H. W.; Jeon, J. M.; Cho, K. S.

2016-12-01

Landfill is an important anthropogenic source of methane (CH4) and odorous gases. In South Korea, 37% (0.5 Tg/y) of annual anthropogenic CH4 emissions come from landfills, which represent the third largest source of anthropogenic CH4 emissions. Moreover, civil complaints on landfill odor have been gradually increased. Biocovers have been demonstrated as promising solutions to mitigate CH4 and odors from landfills. The pilot-scale biocover (10 m in length x 5 m in width x 1 m in depth) was constructed at a landfill, Gwangyang, South Korea. The mixture of soil and perlite was used as packing materials, and EG microbial agent was used as an inoculum source. Methane removal efficiencies were 21% 72% from Feburary to May. Based on the dilution-to-threshold ratios derived by the air dilution sensory test, the removal efficiencies for complex odor were ranged from 95% to 99%. The packing materials of biocover were sampled from each of the following depth intervals: 0-15 cm, 15-30 cm, and 30-50 cm, and CH4 and DMS degradation rates were measured in serum bottles experiment. CH4 and DMS average degradation rates were the fastest in the 15-30 cm depth. Average degradation rates of CH4 and DMS in the 15-30 cm depth were 208±2.68 and 82±3.04 μg·g dry soil-1·h-1, respectively. Specific degradation rate were calculated excluding the lag time. CH4 specific degradation rate was the fastest in the 0-15 cm depth (329±14.45 μg·g dry soil-1·h-1), while DMS specific degradation rate was the fastest in the 30-50 cm depth (106±6.93 μg·g dry soil-1·h-1). The filling materials of biocover were sampled during winter, spring and summer. And three samples were examined bacterial communities by 16S rRNA pyrosequencing analysis. In order to clarify the relationship between the community structures and CH4/odor concentration, network analysis using extended local similarity analysis (eLSA) was also conducted. According to a phylogenic analysis, Methylobacter (40.4 42.1%) and Flavobacterium (20.2 38.2%) were the most prevalent species in the pilot-scale biocover. Methylobacter (Methanotrophics of Type I) are responsible for methane oxidation and can be identified in the biocover.

Methane oxidation in anoxic lake waters

NASA Astrophysics Data System (ADS)

Su, Guangyi; Zopfi, Jakob; Niemann, Helge; Lehmann, Moritz

2017-04-01

Freshwater habitats such as lakes are important sources of methante (CH4), however, most studies in lacustrine environments so far provided evidence for aerobic methane oxidation only, and little is known about the importance of anaerobic oxidation of CH4 (AOM) in anoxic lake waters. In marine environments, sulfate reduction coupled to AOM by archaea has been recognized as important sinks of CH4. More recently, the discorvery of anaerobic methane oxidizing denitrifying bacteria represents a novel and possible alternative AOM pathway, involving reactive nitrogen species (e.g., nitrate and nitrite) as electron acceptors in the absence of oxygen. We investigate anaerobic methane oxidation in the water column of two hydrochemically contrasting sites in Lake Lugano, Switzerland. The South Basin displays seasonal stratification, the development of a benthic nepheloid layer and anoxia during summer and fall. The North Basin is permanently stratified with anoxic conditions below 115m water depth. Both Basins accumulate seasonally (South Basin) or permanently (North Basin) large amounts of CH4 in the water column below the chemocline, providing ideal conditions for methanotrophic microorganisms. Previous work revealed a high potential for aerobic methane oxidation within the anoxic water column, but no evidence for true AOM. Here, we show depth distribution data of dissolved CH4, methane oxidation rates and nutrients at both sites. In addition, we performed high resolution phylogenetic analyses of microbial community structures and conducted radio-label incubation experiments with concentrated biomass from anoxic waters and potential alternative electron acceptor additions (nitrate, nitrite and sulfate). First results from the unamended experiments revealed maximum activity of methane oxidation below the redoxcline in both basins. While the incubation experiments neither provided clear evidence for NOx- nor sulfate-dependent AOM, the phylogenetic analysis revealed the presence of members of the Methylomirabiliaceae family (NC10 phylum), known to perform AOM with nitrite as terminal electron acceptor. Interestingly, albeit the similarly favorable conditions in both basins, the South Basin showed nearly two-fold higher CH4 oxidation rates, but the Methylomirabiliaceae abundance appeared to be much higher in the meromictic North Basin. Ongoing work will attempt to verify whether the apparent difference in the abundance of Methylomirabiliaceae is a permanent feature. We will further seek to determine the relative contribution of bacterial nitrite-dependent AOM to total methane oxidation, as well as the environmental controls that may explain the differential importance of Methylomirabiliaceae in the two connected lake basins.

Field-Scale Stable-Isotope Probing of Active Methanotrophs in a Landfill-Cover Soil

NASA Astrophysics Data System (ADS)

Schroth, M. H.; Henneberger, R.; Chiri, E.

2012-12-01

The greenhouse gas methane (CH4) is an important contributor to global climate change. While its atmospheric concentration is increasing, a large portion of produced CH4 never reaches the atmosphere, but is consumed by aerobic methane-oxidizing bacteria (MOB). The latter are ubiquitous in soils and utilize CH4 as sole source of energy and carbon. Among other methods, MOB may be differentiated based on characteristic phospholipid fatty acids (PLFA). Stable-isotope probing (SIP) on PLFA has been widely applied to identify active members of MOB communities in laboratory incubation studies, but results are often difficult to extrapolate to the field. Thus, novel field-scale approaches are needed to link activity and identity of MOB in their natural environment. We present results of field experiments in which we combined PLFA-SIP with gas push-pull tests (GPPTs) to label active MOB at the field-scale while simultaneously quantifying CH4 oxidation activity. During a SIP-GPPT, a mixture of reactive (here 13CH4, O2) and non-reactive tracer gases (e.g., Ar, Ne, He) is injected into the soil at a location of interest. Thereafter, gas flow is reversed and the gas mixture diluted with soil air is extracted from the same location and sampled periodically. Rate constants for CH4 oxidation can be calculated by analyzing breakthrough curves of 13CH4 and a suitable non-reactive tracer gas. SIP-GPPTs were performed in a landfill-cover soil, and feasibility of this novel approach was tested at several locations along a gradient of MOB activity and soil temperature. Soil samples were collected before and after SIP-GPPTs, total PLFA were extracted, and incorporation of 13C in the polar lipid fraction was analyzed. Potential CH4 oxidation rates derived from SIP-GPPTs were similar to those derived from regular GPPTs (using unlabeled CH4) performed at the same locations prior to SIP-GPPTs, indicating that application of 13CH4 did not adversely affect bacterial CH4 oxidation rates. Rates calculated for different locations ranged from 0.2 to 52.8 mmol CH4 (L soil air)-1 d-1. PLFA analyses showed high levels of 13C incorporation into different 14C and 16C fatty acids (FA), typically found in Type I MOB, and 18C FAs, typical for Type II MOB. The amount of 13C incorporated into biomass clearly increased with increasing activity, and δ13C values of >1500 ‰ were observed for selected FAs at high-activity locations. In addition, the range of labeled FAs also changed with activity, and no Type II MOB specific FAs were labeled at the low-activity location. The novel SIP-GPPT approach was shown to be a valuable field-scale method to detect and identify active MOB over a wide range of activities.

Structure and function of methanotrophic communities in a landfill-cover soil.

PubMed

Henneberger, Ruth; Lüke, Claudia; Mosberger, Lona; Schroth, Martin H

2012-07-01

In landfill-cover soils, aerobic methane-oxidizing bacteria (MOB) convert CH(4) to CO(2), mitigating emissions of the greenhouse gas CH(4) to the atmosphere. We investigated overall MOB community structure and assessed spatial differences in MOB diversity, abundance and activity in a Swiss landfill-cover soil. Molecular cloning, terminal restriction-fragment length polymorphism (T-RFLP) and quantitative PCR of pmoA genes were applied to soil collected from 16 locations at three different depths to study MOB community structure, diversity and abundance; MOB activity was measured in the field using gas push-pull tests. The MOB community was highly diverse but dominated by Type Ia MOB, with novel pmoA sequences present. Type II MOB were detected mainly in deeper soil with lower nutrient and higher CH(4) concentrations. Substantial differences in MOB community structure were observed between one high- and one low-activity location. MOB abundance was highly variable across the site [4.0 × 10(4) to 1.1 × 10(7) (g soil dry weight)(-1)]. Potential CH(4) oxidation rates were high [1.8-58.2 mmol CH(4) (L soil air)(-1) day(-1) ] but showed significant lateral variation and were positively correlated with mean CH(4) concentrations (P < 0.01), MOB abundance (P < 0.05) and MOB diversity (weak correlation, P < 0.17). Our findings indicate that Methylosarcina and closely related MOB are key players and that MOB abundance and community structure are driving factors in CH(4) oxidation at this landfill. © 2011 Federation of European Microbiological Societies. Published by Blackwell Publishing Ltd. All rights reserved.

Stability of Fe-Cr alloy interconnects under CH 4-H 2O atmosphere for SOFCs

NASA Astrophysics Data System (ADS)

Horita, Teruhisa; Xiong, Yueping; Yamaji, Katsuhiko; Sakai, Natsuko; Yokokawa, Harumi

The chemical stability of Fe-Cr alloys (ZMG232 and SUS430) was examined under humidified CH 4 gases at 1073 K to simulate the real anode atmosphere in SOFC operation. Surface microstructure change and oxide scale layer formation were observed on the oxidized Fe-Cr alloy surfaces. The main reaction products were Mn-Cr-(Fe) spinels for both alloys. Secondary ion mass spectrometry (SIMS) was applied to measure the elemental distribution of minor and major elements around the oxide scale/alloy interface. A high concentration of Mn on the oxide scale surface suggested the fast diffusion of Mn in the oxide scale to form the spinels. Annealing in CH 4-H 2O made the oxide scale thicker with duration time on the alloy surface. The parabolic growth rates ( kp) of oxide scale layer were evaluated from the thickness of oxide scales by secondary ion mass spectrometry (SIMS) depth profiles, which were calculated to the following: kp=6.25×10 -6 μm 2/s for SUS430 and kp=4.42×10 -6 μm 2/s for ZMG232. The electrical conductivity of oxidized alloys showed the semi-conductor temperature dependence for both alloys. The electrical conductivity of oxidized ZMG232 alloy was higher than that of oxidized SUS430.

More than just one Methane Paradox? - Methane Production in Oxic Waters and Aerobic Methane Oxidation under Oxygen-Depleted Conditions

NASA Astrophysics Data System (ADS)

Lehmann, M. F.; Niemann, H.; Bartosiewicz, M.; Blees, J.; Steinle, L.; Su, G.; Zopfi, J.

2016-12-01

The standing paradigm is that methane (CH4) production through methanogenesis occurs exclusively under anoxic conditions and that at least in freshwater environments most of the biogenic CH4 is oxidized by aerobic methanotrophic bacteria (MOB) under oxic conditions. However, subsurface CH4 accumulation in oxic waters, a phenomenon referred to as the "CH4 paradox", has been observed both in the ocean and in lakes, and suggests in-situ CH4 production or a remarkable tolerance of at least some methanogens to O2. Analogously, MOB seem to thrive also under micro-oxic conditions, i.e., they may be responsible for significant CH4 turnover at extremely low O2 concentrations. O2 availability particularly within the sub-micromolar range is likely one of the key factors controlling the balance between CH4 production and consumption in redox-transition zones of aquatic environments, yet threshold O2 concentrations are poorly constrained. Here we provide multiple lines of evidence for apparent "methanogenesis" in well-oxygenated waters and discuss the potential mechanisms that lead to CH4 accumulation in the oxic epilimnia of two south-alpine lakes. On the other end, we present data from a deep meromictic lake, which indicate aerobic CH4 oxidation (MOx) at O2 concentrations below the detection limit of common O2 sensors. A strong MOx potential throughout the anoxic hyplimnion of the studied lake implies that the MOB community is able to survive prolonged periods of O2 starvation and is capable to rapidly resume microaerobic MOx upon introduction of low levels of O2. This conclusion is qualitatively consistent with field data from a coastal shelf environment in the Baltic Sea, where we observed maximum MOx rates during the summer stratification period when O2 concentrations were lowest, implying that in both environments MOx bacteria are adapted to trace levels of O2. Indeed, laboratory experiments at different manipulated O2 concentration levels suggest a nanomolar O2 optimum for MOx in both environments. The very low O2 requirements may reflect the adaption of water column MOB at the organismic level to O2-limited conditions, with several ecological advantages: it allows them to escape grazing pressure and to avoid the detrimental effects of oxidative stress and/or CH4 starvation in more oxygenated waters.

High-pressure oxidation of ethane

DOE PAGES

Hashemi, Hamid; Jacobsen, Jon G.; Rasmussen, Christian T.; ...

2017-05-02

Here, ethane oxidation at intermediate temperatures and high pressures has been investigated in both a laminar flow reactor and a rapid compression machine (RCM). The flow-reactor measurements at 600–900 K and 20–100 bar showed an onset temperature for oxidation of ethane between 700 and 825 K, depending on pressure, stoichiometry, and residence time. Measured ignition delay times in the RCM at pressures of 10–80 bar and temperatures of 900–1025 K decreased with increasing pressure and/or temperature. A detailed chemical kinetic model was developed with particular attention to the peroxide chemistry. Rate constants for reactions on the C 2H 5O 2more » potential energy surface were adopted from the recent theoretical work of Klippenstein. In the present work, the internal H-abstraction in CH 3CH 2OO to form CH 2CH 2OOH was treated in detail. Modeling predictions were in good agreement with data from the present work as well as results at elevated pressure from literature. The experimental results and the modeling predictions do not support occurrence of NTC behavior in ethane oxidation. Even at the high-pressure conditions of the present work where the C 2H 5 + O 2 reaction yields ethylperoxyl rather than C 2H 4 + HO 2, the chain branching sequence CH 3CH 2OO → CH 2CH 2OOH → +O2 OOCH 2CH 2OOH → branching is not competitive, because the internal H-atom transfer in CH 3CH 2OO to CH 2CH 2OOH is too slow compared to thermal dissociation to C 2H 4 and HO 2.« less

Model Analysis of the Factors Regulating Trends and Variability of Methane, Carbon Monoxide and OH: 1. Model Validation

NASA Technical Reports Server (NTRS)

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

2014-01-01

Methane (CH4) is the second most important anthropogenic greenhouse gas (GHG). Its 100-year global warming potential (GWP) is 25 times larger than that for carbon dioxide. The 100-yr integrated GWP of CH4 is sensitive to changes in OH levels. Methane's atmospheric growth rate was estimated to be more than 10 ppb yr(exp -1) in 1998 but less than zero in 2001, 2004 and 2005 (Kirschke et al., 2013). Since 2006, the CH4 is increasing again. This phenomena is yet not well understood. Oxidation of CH4 by OH is the main loss process, thus affecting the oxidizing capacity of the atmosphere and contributing to the global ozone background. Current models typically use an annual cycle of offline OH fields to simulate CH4. The implemented OH fields in these models are typically tuned so that simulated CH4 growth rates match that measured. For future and climate simulations, the OH tuning technique may not be suitable. In addition, running full chemistry, multi-decadal CH4 simulations is a serious challenge and currently, due to computational intensity, almost impossible.

Low-Concentration Kinetics of Atmospheric CH4 Oxidation in Soil and Mechanism of NH4+ Inhibition

PubMed Central

Gulledge, Jay; Schimel, Joshua P.

1998-01-01

NH4+ inhibition kinetics for CH4 oxidation were examined at near-atmospheric CH4 concentrations in three upland forest soils. Whether NH4+-independent salt effects could be neutralized by adding nonammoniacal salts to control samples in lieu of deionized water was also investigated. Because the levels of exchangeable endogenous NH4+ were very low in the three soils, desorption of endogenous NH4+ was not a significant factor in this study. The Km(app) values for water-treated controls were 9.8, 22, and 57 nM for temperate pine, temperate hardwood, and birch taiga soils, respectively. At CH4 concentrations of ≤15 μl liter−1, oxidation followed first-order kinetics in the fine-textured taiga soil, whereas the coarse-textured temperate soils exhibited Michaelis-Menten kinetics. Compared to water controls, the Km(app) values in the temperate soils increased in the presence of NH4+ salts, whereas the Vmax(app) values decreased substantially, indicating that there was a mixture of competitive and noncompetitive inhibition mechanisms for whole NH4+ salts. Compared to the corresponding K+ salt controls, the Km(app) values for NH4+ salts increased substantially, whereas the Vmax(app) values remained virtually unchanged, indicating that NH4+ acted by competitive inhibition. Nonammoniacal salts caused inhibition to increase with increasing CH4 concentrations in all three soils. In the birch taiga soil, this trend occurred with both NH4+ and K+ salts, and the slope of the increase was not affected by the addition of NH4+. Hence, the increase in inhibition resulted from an NH4+-independent mechanism. These results show that NH4+ inhibition of atmospheric CH4 oxidation resulted from enzymatic substrate competition and that additional inhibition that was not competitive resulted from a general salt effect that was independent of NH4+. PMID:9797279

Comprehensive mechanism and structure-sensitivity of ethanol oxidation on platinum: new transition-state searching method for resolving the complex reaction network.

PubMed

Wang, Hui-Fang; Liu, Zhi-Pan

2008-08-20

Ethanol oxidation on Pt is a typical multistep and multiselectivity heterogeneous catalytic process. A comprehensive understanding of this fundamental reaction would greatly benefit design of catalysts for use in direct ethanol fuel cells and the degradation of biomass-derived oxygenates. In this work, the reaction network of ethanol oxidation on different Pt surfaces, including close-packed Pt{111}, stepped Pt{211}, and open Pt{100}, is explored thoroughly with an efficient reaction path searching method, which integrates our new transition-state searching technique with periodic density functional theory calculations. Our new technique enables the location of the transition state and saddle points for most surface reactions simply and efficiently by optimization of local minima. We show that the selectivity of ethanol oxidation on Pt depends markedly on the surface structure, which can be attributed to the structure-sensitivity of two key reaction steps: (i) the initial dehydrogenation of ethanol and (ii) the oxidation of acetyl (CH3CO). On open surface sites, ethanol prefers C-C bond cleavage via strongly adsorbed intermediates (CH2CO or CHCO), which leads to complete oxidation to CO2. However, only partial oxidizations to CH3CHO and CH3COOH occur on Pt{111}. Our mechanism points out that the open surface Pt{100} is the best facet to fully oxidize ethanol at low coverages, which sheds light on the origin of the remarkable catalytic performance of Pt tetrahexahedra nanocrystals found recently. The physical origin of the structure-selectivity is rationalized in terms of both thermodynamics and kinetics. Two fundamental quantities that dictate the selectivity of ethanol oxidation are identified: (i) the ability of surface metal atoms to bond with unsaturated C-containing fragments and (ii) the relative stability of hydroxyl at surface atop sites with respect to other sites.

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

NASA Astrophysics Data System (ADS)

Watanabe, Akira; Kimura, Makoto

1998-08-01

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

Combination of wet irrigation and nitrification inhibitor reduced nitrous oxide and methane emissions from a rice cropping system.

PubMed

Liu, Gang; Yu, Haiyang; Zhang, Guangbin; Xu, Hua; Ma, Jing

2016-09-01

To conserve water resources and guarantee food security, a new technology termed as "wet irrigation" is developed and practiced in rice fields; thus, its impact on radiative forcing derived from nitrous oxide (N2O) and methane (CH4) emissions merits serious attention. Dicyandiamide (DCD), a kind of nitrification inhibitor, is proposed as a viable means to mitigate greenhouse gas (GHG) emission while enhancing crop productivity. However, little is known about the response of GHG emission and grain yield to DCD application in a rice system under wet irrigation. In these regard, effects of water regime and DCD application on CH4 and N2O emissions, grain yield, global warming potential (GWP), and greenhouse gas intensity (GHGI) from rice fields were studied. For this study, a field experiment, designed: Treatment II (intermittent irrigation), Treatment WI (wet irrigation), Treatment IID (II plus DCD), and Treatment WID (WI plus DCD), was conducted in Jurong, Jiangsu Province, China, from 2011 to 2012. Relative to Treatment II, Treatment WI decreased CH4 emission significantly by 49-71 % while increasing N2O emission by 33-72 %. By integrating CH4 and N2O emissions and grain yield, Treatment WI was 20-28 and 11-15 % lower than Treatment II in GWP and GHGI, respectively. The use of DCD under wet irrigation reduced N2O emission significantly by 25-38 % (p < 0.05) and CH4 emission by 7-8 %, relative to Treatment WI, resulting in a decline of 18-30 % in GWP. Due to the increase in N use efficiency, maximal grain yield (6-7 %) and minimal GHGI (22-34 %) was observed in Treatment WID. These findings indicate that combined application of N fertilizer and DCD is a win-win strategy in water-saving high-yield rice production with less GHG emission.

Highly Efficient Performance and Conversion Pathway of Photocatalytic CH3SH Oxidation on Self-Stabilized Indirect Z-Scheme g-C3N4/I3--BiOI.

PubMed

Hu, Lingling; He, Huanjunwa; Xia, Dehua; Huang, Yajing; Xu, Jiarong; Li, Haoyue; He, Chun; Yang, Wenjing; Shu, Dong; Wong, Po Keung

2018-06-06

A self-stabilized Z-scheme porous g-C 3 N 4 /I 3- -containing BiOI ultrathin nanosheets (g-C 3 N 4 /I 3- -BiOI) heterojunction photocatalyst with I 3 - /I - redox mediator was successfully synthesized by a facile solvothermal method coupling with light illumination. The structure and optical properties of g-C 3 N 4 /I 3- -BiOI composites were systematically characterized by means of X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Fourier transform infrared, X-ray photoelectron spectroscopy, N 2 adsorption/desorption, UV-vis diffuse reflectance spectrum, and photoluminescence. The g-C 3 N 4 /I 3- -BiOI composites, with a heterojunction between porous g-C 3 N 4 and BiOI ultrathin nanosheets, were first applied for the photocatalytic elimination of ppm-leveled CH 3 SH under light-emitting diode visible light illumination. The g-C 3 N 4 /I 3- -BiOI heterojunction with 10% g-C 3 N 4 showed a dramatically enhanced photocatalytic activity in the removal of CH 3 SH compared with pure BiOI and g-C 3 N 4 due to its effective interfacial charge transfer and separation. The adsorption and photocatalytic oxidation of CH 3 SH over g-C 3 N 4 /I 3- -BiOI were deeply explored by in situ diffuse reflectance infrared Fourier transform spectroscopy, and the intermediates and conversion pathways were elucidated and compared. Furthermore, on the basis of reactive species trapping, electron spin resonance and Mott-Schottky experiments, it was revealed that the responsible reactive species for catalytic CH 3 SH composition were h + , • O 2 - , and 1 O 2 ; thus, the g-C 3 N 4 /I 3- -BiOI heterojunction followed an indirect all-solid state Z-scheme charge-transfer mode with self-stabilized I 3 - /I - pairs as redox mediator, which could accelerate the separation of photogenerated charge and enhance the redox reaction power of charged carriers simultaneously.

Oxidative desulfurization of fuels catalyzed by Fenton-like ionic liquids at room temperature.

PubMed

Jiang, Yunqing; Zhu, Wenshuai; Li, Huaming; Yin, Sheng; Liu, Hua; Xie, Qingjie

2011-03-21

Oxidation of the sulfur-containing compounds benzothiophene (BT), dibenzothiophene (DBT), and 4,6-dimethyldibenzothiophene (4,6-DMDBT) has been studied in a desulfurization system composed of model oil, hydrogen peroxide, and different types of ionic liquids [(C(8)H(17))(3)CH(3)N]Cl/FeCl(3), [(C(8)H(17))(3)CH(3)N]Cl/CuCl(2), [(C(8)H(17))(3)CH(3)N]Cl/ZnCl(2), [(C(8)H(17))(3)CH(3)N]Cl/SnCl(2), [(C(4)H(9))(3)CH(3)N]Cl/FeCl(3), [C(10)H(21)(CH(3))(3)N]Cl/FeCl(3), [(C(10)H(21))(2)(CH(3))(2)N]Cl/FeCl(3). Deep desulfurization is achieved in the Fenton-like ionic liquid [(C(8)H(17))(3)CH(3)N]Cl/FeCl(3) at 25 °C for 1 h. The desulfurization of DBT reaches 97.9%, in consuming very low amount of [(C(8)H(17))(3)CH(3)N]Cl/FeCl(3) (only 0.702 mmol). The reaction conditions, for example, the amount of [(C(8)H(17))(3)CH(3)N]Cl/FeCl(3) or H(2)O(2), the temperature, and the molar ratio of FeCl(3) to [(C(8)H(17))(3)CH(3)N]Cl, are investigated for this system. The oxidation reactivity of the different sulfur-containing compounds is found to decrease in the order of DBT>BT>4,6-DMDBT. The desulfurization system can be recycled six times without significant decrease in activity. The sulfur level of FCC gasoline could be reduced from 360 ppm to 110 ppm. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrogenation of organic matter as a terminal electron sink sustains high CO 2 :CH 4 production ratios during anaerobic decomposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wilson, Rachel M.; Tfaily, Malak M.; Rich, Virginia I.

Once inorganic electron acceptors are depleted, organic matter in anoxic environments decomposes by hydrolysis, fermentation, and methanogenesis, requiring syntrophic interactions between microorganisms to achieve energetic favorability. In this classic anaerobic food chain, methanogenesis represents the terminal electron accepting (TEA) process, ultimately producing equimolar CO2 and CH4 for each molecule of organic matter degraded. However, CO2:CH4 production in Sphagnum-derived, mineral-poor, cellulosic peat often substantially exceeds this 1:1 ratio, even in the absence of measureable inorganic TEAs. Since the oxidation state of C in both cellulose-derived organic matter and acetate is 0, and CO2 has an oxidation state of +4, if CH4more » (oxidation state -4) is not produced in equal ratio, then some other compound(s) must balance CO2 production by receiving 4 electrons. Here we present evidence for ubiquitous hydrogenation of diverse unsaturated compounds that appear to serve as organic TEAs in peat, thereby providing the necessary electron balance to sustain CO2:CH4 >1. While organic electron acceptors have previously been proposed to drive microbial respiration of organic matter through the reversible reduction of quinone moieties, the hydrogenation mechanism that we propose, by contrast, reduces C-C double bonds in organic matter thereby serving as 1) a terminal electron sink, 2) a mechanism for degrading complex unsaturated organic molecules, 3) a potential mechanism to regenerate electron-accepting quinones, and, in some cases, 4) a means to alleviate the toxicity of unsaturated aromatic acids. This mechanism for CO2 generation without concomitant CH4 production has the potential to regulate the global warming potential of peatlands by elevating CO2:CH4 production ratios.« less

Evaluation of support matrices for immobilization of anaerobic consortia for efficient carbon cycling in waste regeneration.

PubMed

Chauhan, Ashvini; Ogram, Andrew

2005-02-18

Efficient metabolism of fatty acids during anaerobic waste digestion requires development of consortia that include "fatty acid consuming H(2) producing bacteria" and methanogenic bacteria. The objective of this research was to optimize methanogenesis from fatty acids by evaluating a variety of support matrices for use in maintaining efficient syntrophic-methanogenic consortia. Tested matrices included clays (montmorillonite and bentonite), glass beads (106 and 425-600mum), microcarriers (cytopore, cytodex, cytoline, and cultispher; conventionally employed for cultivation of mammalian cell lines), BioSep beads (powdered activated carbon), and membranes (hydrophilic; nylon, polysulfone, and hydrophobic; teflon, polypropylene). Data obtained from headspace methane (CH(4)) analyses as an indicator of anaerobic carbon cycling efficiency indicated that material surface properties were important in maintenance and functioning of the anaerobic consortia. Cytoline yielded significantly higher CH(4) than other matrices as early as in the first week of incubation. 16S rRNA gene sequence analysis from crushed cytoline matrix showed the presence of Syntrophomonas spp. (butyrate oxidizing syntrophs) and Syntrophobacter spp. (propionate oxidizing syntrophs), with Methanosaeta spp. (acetate utilizing methanogen), and Methanospirillum spp. (hydrogen utilizing methanogen) cells. It is likely that the more hydrophobic surfaces provided a suitable surface for adherence of cells of syntrophic-methanogenic consortia. Cytoline also appeared to protect entrapped consortia from air, resulting in rapid methanogenesis after aerial exposure. Our study suggests that support matrices can be used in anaerobic digestors, pre-seeded with immobilized or entrapped consortia on support matrices, and may be of value as inoculant-adsorbents to rapidly initiate or recover proper system functioning following perturbation.

Quantification of Methane and Nitrous Oxide Emissions from Wastewater Collection Systems (Cincinnati, Ohio, USA)

NASA Astrophysics Data System (ADS)

Fries, A. E.; Townsend-Small, A.; Shuster, W.; Schifman, L. A.

2016-12-01

Greenhouse gas emissions from urban areas is an emerging topic in environmental science, but source apportionment of these emissions, particularly for methane (CH4) and nitrous oxide (N2O), is still underway. Here we present an analysis of CH4 and N2O sources from urban pipelines in Cincinnati, Ohio, USA. Leaks from manholes and sewer grates in Cincinnati are found by using a Bascom Turner Gas Rover to indicate CH4 enhancements, along with spatial data for CH4 enhancements at street level from previously published work. When possible, the atmospheric flux of CH4 and N2O of these leaks are quantified by using a flux chamber method. Source apportionment is determined by using carbon and hydrogen stable isotope ratios (13C and D) and CH4 to N2O ratios. Biogenic CH4 has a δ13C of approximately -55‰ and δD of approximately -270‰, whereas thermogenic CH4 has a δ13C of approximately -45‰ and δD of approximately -150‰. Biogenic CH4 may also co-occur with N2O, whereas thermogenic natural gas does not contain N2O. Contrary to our expectations, we found a portion of CH4 enhancements that are biogenic CH4, presumably from sewer gas, whereas most studies have assumed them to be natural gas leaks. In the future we will be working on determining the exact proportion of biogenic and thermogenic CH4 in street leaks and further quantifying CH4 and N2O emissions throughout Cincinnati. Our work indicates that CH4 leaks in cities may be a mixture of sewer gas and natural gas, especially in cities like Cincinnati where natural gas pipelines have been replaced with less leak-prone pipe materials.

Atmospheric nitrous oxide uptake in boreal spruce forest soil

NASA Astrophysics Data System (ADS)

Siljanen, Henri; Welti, Nina; Heikkinen, Juha; Biasi, Christina; Martikainen, Pertti

2017-04-01

Nitrous oxide (N2O) uptake from the atmosphere has been found in forest soils but environmental factors controlling the uptake and its atmospheric impact are poorly known. We measured N2O fluxes over growing season in a boreal spruce forest having control plots and plots with long nitrogen fertilization history. Also methane (CH4) fluxes were measured to compare the atmospheric impact of N2O and CH4fluxes. Soil chemical and physical characteristics and climatic conditions were measured as background data. Nitrous oxide consumption and uptake mechanisms were measured in complementary laboratory incubation experiments using stable isotope approaches. Gene transcript numbers of nitrous oxide reductase (nosZ) I and II genes were quantified along the incubation with elevated N2O atmosphere. The spruce forests without fertilization history showed highest N2O uptake rates whereas pine forest had low emissions. Nitrous oxide uptake correlated positively with soil moisture, high soil silt content, and low temperature. Nitrous oxide uptake varied seasonally, being highest in spring and autumn when temperature was low and water content was high. The spruce forest was sink for CH4.Methane fluxes were decoupled from the N2O fluxes (i.e. when the N2O uptake was high the CH4 uptake was low). By using GWP approach, the cooling effect of N2O uptake was on average 30% of the cooling effect of CH4 uptake in spruce forest without fertilization. Anoxic conditions promoted higher N2O consumption rates in all soils. Gene transcription of nosZ-I genes were activated at beginning of the incubation. However, atypical/clade-II nosZ was not detected. These results suggests, that also N2O uptake rates have to be considered when accounting for the GHG budget of spruce forests.

Impact of the heatwave in 2003 on the summer CH4 and N2O budget of a spruce forest ecosystem: A four-year comparison

NASA Astrophysics Data System (ADS)

Lamers, M.; Fiedler, S.; Jungkunst, H. F.; Stahr, K.; Streck, T.

2009-04-01

Both CH4 and N2O reduction and oxidation are highly sensitive to variation in soil moisture. Significant changes of net CH4 and total N2O fluxes from soils can therefore be expected to accompany redistribution for precipitation in the course of climate change where more extreme events are predicted for the future. The extreme summer drought in 2003 offered the unique opportunity to study the impact of such events on the emission of greenhouse gases, such as methane or nitrous oxide, under field conditions. The main objective of the present study was to evaluate the impact of the summer drought in 2003 on the net methane and nitrous oxide budget of a spruce forest ecosystem (South-West Germany) with large variation in soil drainage. During the summers of 2000-2004 we measured net CH4 and N2O fluxes (bi)-weekly using the closed-chamber technique for six different soil types ranging from well-aerated Cambisols to poorly drained Gleysols and a wet Histosol. With regard to CH4 the extreme summer draught (1) did not elevate net CH4-sink function of soils, but (2) highly reduced net CH4-source strength and (3) reversed the net CH4 source of the investigated catchment into a sink. In all four summers investigated, net ecosystem exchange of CH4 was found only in the hydromorphic soils but not in the dominant well-aerated soils. This highlighted the key role of hydromorphic soils for the investigated pedodiverse system. With regard to N2O the summer draught in 2003 significantly reduced N2O emissions at least for the Humic Gleysol and the Sapric Histosol and hence markedly reduced the net N2O source strength of the investigated ecosystem.

Adsorption and transport of methane in biochars derived from waste wood.

PubMed

Sadasivam, Bala Yamini; Reddy, Krishna R

2015-09-01

Mitigation of landfill gas (LFG) is among the critical aspects considered in the design of a landfill cover in order to prevent atmospheric pollution and control global warming. In general, landfill cover soils can partially remove methane (CH4) through microbial oxidation carried out by methanotrophic bacteria present within them. The oxidizing capacity of these landfill cover soils may be improved by adding organic materials, such as biochar, which increase adsorption and promote subsequent or simultaneous oxidation of CH4. In this study, seven wood-derived biochars and granular activated carbon (GAC) were characterized for their CH4 adsorption capacity by conducting batch and small-scale column studies. The effects of influential factors, such as exposed CH4 concentration, moisture content and temperature on CH4 adsorption onto biochars, were determined. The CH4 transport was modeled using a 1-D advection-dispersion equation that accounted for sorption. The effects of LFG inflow rates and moisture content on the combined adsorption and transport properties of biochars were determined. The maximum CH4 adsorption capacity of GAC (3.21mol/kg) was significantly higher than that of the biochars (0.05-0.9mol/kg). The CH4 gas dispersion coefficients for all of the biochars ranged from 1×10(-3) to 3×10(-3)m(2)s(-1). The presence of moisture significantly suppressed the extent of methane adsorption onto the biochars and caused the methane to break through within shorter periods of time. Overall, certain biochar types have a high potential to enhance CH4 adsorption and transport properties when used as a cover material in landfills. However, field-scale studies need to be conducted in order to evaluate the performance of biochar-based cover system under a more dynamic field condition that captures the effect of seasonal and temporal changes. Copyright © 2015 Elsevier Ltd. All rights reserved.

Assessing methane oxidation under landfill covers and its contribution to the above atmospheric CO{sub 2} levels: The added value of the isotope ({delta}{sup 13}C and {delta}{sup 18}O CO{sub 2}; {delta}{sup 13}C and {delta}D CH{sub 4}) approach

DOE Office of Scientific and Technical Information (OSTI.GOV)

Widory, D., E-mail: d.widory@brgm.fr; Proust, E.; Bellenfant, G.

2012-09-15

Highlights: Black-Right-Pointing-Pointer Comparison of the isotope and mass balance approaches to evaluate the level of methane oxidation within a landfill. Black-Right-Pointing-Pointer The level of methane oxidation is not homogenous under the landfill cover and is strongly correlated to the methane flux. Black-Right-Pointing-Pointer Isotope tracking of the contribution of the methane oxidation to the CO{sub 2} concentrations in the ambient air. - Abstract: We are presenting here a multi-isotope approach ({delta}{sup 13}C and {delta}{sup 18}O of CO{sub 2}; {delta}{sup 13}C and {delta}D of CH{sub 4}) to assess (i) the level(s) of methane oxidation during waste biodegradation and its migration through amore » landfill cover in Sonzay (France), and (ii) its contribution to the atmospheric CO{sub 2} levels above the surface. The isotope approach is compared to the more conventional mass balance approach. Results from the two techniques are comparable and show that the CH{sub 4} oxidation under the landfill cover is heterogenous, with low oxidation percentages in samples showing high biogas fluxes, which was expected in clay covers presenting fissures, through which CH{sub 4} is rapidly transported. At shallow depth, more immobile biogas pockets show a higher level of CH{sub 4} oxidation by the methanotrophic bacteria. {delta}{sup 13}C of CO{sub 2} samples taken at different heights (from below the cover up to 8 m above the ground level) were also used to identify and assess the relative contributions of its main sources both under the landfill cover and in the surrounding atmosphere.« less

Shifts in identity and activity of methanotrophs in arctic lake sediments in response to temperature changes

USGS Publications Warehouse

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

2012-01-01

Methane (CH4) flux to the atmosphere is mitigated via microbial CH4 oxidation in sediments and water. As arctic temperaturesincrease, understanding the effects of temperature on the activity and identity of methanotrophs in arctic lake sediments is importantto predicting future CH4 emissions. We used DNA-based stable-isotope probing (SIP), quantitative PCR (Q-PCR), andpyrosequencing analyses to identify and characterize methanotrophic communities active at a range of temperatures (4°C, 10°C,and 21°C) in sediments (to a depth of 25 cm) sampled from Lake Qalluuraq on the North Slope of Alaska. CH4 oxidation activitywas measured in microcosm incubations containing sediments at all temperatures, with the highest CH4 oxidation potential of37.5 mol g1 day1 in the uppermost (depth, 0 to 1 cm) sediment at 21°C after 2 to 5 days of incubation. Q-PCR of pmoA and ofthe 16S rRNA genes of type I and type II methanotrophs, and pyrosequencing of 16S rRNA genes in 13C-labeled DNA obtained bySIP demonstrated that the type I methanotrophs Methylobacter, Methylomonas, and Methylosoma dominated carbon acquisitionfrom CH4 in the sediments. The identity and relative abundance of active methanotrophs differed with the incubation temperature.Methylotrophs were also abundant in the microbial community that derived carbon from CH4, especially in the deeper sediments(depth, 15 to 20 cm) at low temperatures (4°C and 10°C), and showed a good linear relationship (R0.82) with the relativeabundances of methanotrophs in pyrosequencing reads. This study describes for the first time how methanotrophiccommunities in arctic lake sediments respond to temperature variations.

QUANTIFICATION OF METHANE EMISSIONS AND DISCUSSON OF NITROUS OXIDE, AND AMMONIA EMISSIONS FROM SEPTIC TANKS, LATRINES, AND STAGNANT OPEN SEWERS OF THE WORLD

EPA Science Inventory

The report gives results of a first attempt to estimate global and country-specific methane (CH4) emissons from sewers and on-site wastewater treatment systems, including latrines and septic sewage tanks. It follows a report that includes CH4 and nitrous oxide (N2O) estimates fro...

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.

Nitrous oxide and methane emissions from different treatment processes in full-scale municipal wastewater treatment plants.

PubMed

Rena, Y G; Wang, J H; Li, H F; Zhang, J; Qi, P Y; Hu, Z

2013-01-01

Nitrous oxide (N2O) and methane (CH4) are two important greenhouse gases (GHG) emitted from biological nutrient removal (BNR) processes in municipal wastewater treatment plants (WWTP). In this study, three typical biological wastewater treatment processes were studied in WWTP of Northern China: pre-anaerobic carrousel oxidation ditch (A+OD) process, pre-anoxic anaerobic-anoxic-oxic (A-A/ A/O) process and reverse anaerobic-anoxic-oxic (r-A/ A/O) process. The N2O and CH4 emissions from these three different processes were measured in every processing unit of each WWTP. Results showed that N2O and CH4 were mainly discharged during the nitrification/denitrification process and the anaerobic/anoxic treatment process, respectively and the amounts of their formation and release were significantly influenced by different BNR processes implemented in these WWTP. The N2O conversion ratio of r-A/ A/O process was the lowest among the three WWTP, which were 10.9% and 18.6% lower than that of A-A/A/O process and A+OD process, respectively. Similarly, the CH4 conversion ratio of r-A/ A/O process was the lowest among the three WWTP, which were 89. I% and 80.8% lower than that of A-A/ A/O process and A+OD process, respectively. The factors influencing N2O and CH4 formation and emission in the three WWTP were investigated to explain the difference between these processes. The nitrite concentration and oxidation-reduction potential (ORP) value were found to be the dominant influencing factors affecting N2O and CH4 production, respectively. The flow-based emission factors of N2O and CH4 of the WWTP were figured out for better quantification of GHG emissions and further technical assessments of mitigation options.

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 absence of CH(4) show that O(2) activation steps are quasi-equilibrated during catalysis. Measured and DFT-derived C-H bond activation barriers are large, because of the weak stabilization of the CH(3) fragments at transition states, but are compensated by the high entropy of these radical-like species. Turnover rates in this regime decrease with increasing Pt dispersion, because low-coordination exposed Pt atoms on small clusters bind O* more strongly than those that reside at low-index facets on large clusters, thus making O* less effective in H-abstraction. As vacancies (*, also exposed Pt atoms) become available on O*-covered surfaces, O*-* site pairs activate C-H bonds via concerted oxidative addition and H-abstraction in transition states effectively stabilized by CH(3) interactions with the vacancies, which lead to much higher turnover rates than on O*-O* pairs. In this regime, O(2) activation becomes irreversible, because fast C-H bond activation steps scavenge O* as it forms. Thus, O* coverages are set by the prevalent O(2)/CH(4) ratios instead of the O(2) pressures. CH(4)/CD(4) kinetic isotope effects are much larger for turnovers mediated by O*-* than by O*-O* site pairs, because C-H (and C-D) activation steps are required to form the * sites involved in C-H bond activation. Turnover rates for CH(4)-O(2) reactions mediated by O*-* pairs decrease with increasing Pt dispersion, as in the case of O*-O* active structures, because stronger O* binding on small clusters leads not only to less reactive O* atoms, but also to lower vacancy concentrations at cluster surfaces. As O(2)/CH(4) ratios and O* coverages become smaller, O(2) activation on bare Pt clusters becomes the sole kinetically relevant step; turnover rates are proportional to O(2) pressures and independent of CH(4) pressure and no CH(4)/CD(4) kinetic isotope effects are observed. In this regime, turnover rates become nearly independent of Pt dispersion, because the O(2) activation step is essentially barrierless. In the absence of O(2), alternate weaker oxidants, such as H(2)O or CO(2), lead to a final kinetic regime in which C-H bond dissociation on *-* pairs at bare cluster surfaces limit CH(4) conversion rates. Rates become first-order in CH(4) and independent of coreactant and normal CH(4)/CD(4) kinetic isotope effects are observed. In this case, turnover rates increase with increasing dispersion, because low-coordination Pt atoms stabilize the C-H bond activation transition states more effectively via stronger binding to CH(3) and H fragments. These findings and their mechanistic interpretations are consistent with all rate and isotopic data and with theoretical estimates of activation barriers and of cluster size effects on transition states. They serve to demonstrate the essential role of the coverage and reactivity of chemisorbed oxygen in determining the type and effectiveness of surface structures in CH(4) oxidation reactions using O(2), H(2)O, or CO(2) as oxidants, as well as the diversity of rate dependencies, activation energies and entropies, and cluster size effects that prevail in these reactions. These results also show how theory and experiments can unravel complex surface chemistries on realistic catalysts under practical conditions and provide through the resulting mechanistic insights specific predictions for the effects of cluster size and surface coordination on turnover rates, the trends and magnitude of which depend sensitively on the nature of the predominant adsorbed intermediates and the kinetically relevant steps.

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

USDA-ARS?s Scientific Manuscript database

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...

Methane evasion and oxidation in the Big Cypress National Preserve—a low relief carbonate wetland

NASA Astrophysics Data System (ADS)

Ward, N. D.; Bianchi, T. S.; Cohen, M. J.; Martin, J. B.; Quintero, C.; Brown, A.; Osborne, T.; Sawakuchi, H. O.

2016-12-01

The Big Cypress National Preserve is a low relief carbonate wetland characterized by unique basin patterning known as "cypress domes." Here we examine the concentration and stable isotopic composition of methane in pore waters, surface waters, and bubbles from the sediment across horizontal gradients in four domes during three sampling campaigns. The proportion of methane oxidized in surface waters was estimated based on isotopic differences between surface water and pore waters/bubbles. Rates of methane evasion from surface waters, soils, and cypress knees to the atmosphere were also measured. Surface water CH4 concentrations ranged from 170 to 4,533 ppm with the highest levels generally being observed during wet periods. Pore water CH4 concentrations ranged from 748 to 75,213 ppm. The concentration of methane in bubbles ranged from 6.5 to 71%. The stable isotopic composition of CH4 ranged from -69.2 to -43.8‰ for all samples and was generally more enriched in surface waters compared to bubbles and porewaters, particularly in the two domes that were persistently inundated throughout the year. Based on these isotopic values, the average percentage of surface water CH4 that was oxidized was 37 ± 16% (maximum of 67%) and 19 ± 4% (maximum of 47%) in the two domes that are persistently inundated versus the two domes that are not inundated during the dry season, respectively. The average rate of CH4 evasion was 3.6 ± 1.6 mmol m-2 d-1 via diffusion, 7.6 ± 4.7 mmol m-2 d-1 via ebullition, 10.9 ± 11.4 mmol m-2 d-1­ from soil surfaces, and 34.3 ± 27.4 mmol m-2 d-1 from cypress knees. These results indicate that CH4 is produced in great quantities in inundated sediments, particularly in the center of the cypress domes. Diffusive fluxes from surface waters are suppressed by microbial oxidation in the water column, whereas ebullition from sediments and evasion through cypress knees, and likely other vascular vegetation, are the primary pathways for CH4 outgassing.

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 overriding control on the net CH4 consumption both within and across these well-aerated soil systems. Quite surprisingly, we found high CH4 sink rates in conditions when soils were both extremely thin (< 10 cm to bedrock), very dry (< 5-10 % soil moisture), weakly developed and exposed to harsh environmental conditions such as mountain tops, alpine tundra and abrasion plateaus, which are historically overlooked "extreme soils" regarding CH4 exchange. The results show that the physical areas and landforms where CH4 oxidation and net CH4 deposition occurs has not been delimited for the Arctic. This calls for a revised understanding of the role of CH4 consumption in natural drylands and extreme environments for the net CH4 budget at the circumpolar scale. In these sensitive regions, changes towards warmer and drier soil conditions in some areas as a consequence of a warming Arctic could favor the activity of the CH4 oxidizing bacteria, leading to future increase in net atmospheric CH4 consumption in dry and barren land areas. This could have far-reaching implications for the permafrost carbon feedback to the global climate system and how we integrate the soil CH4 consumption feedback in Earth Systems Model simulating the Artic CH4 budget.

Pinus sylvestris as a missing source of nitrous oxide and methane in boreal forest.

PubMed

Machacova, Katerina; Bäck, Jaana; Vanhatalo, Anni; Halmeenmäki, Elisa; Kolari, Pasi; Mammarella, Ivan; Pumpanen, Jukka; Acosta, Manuel; Urban, Otmar; Pihlatie, Mari

2016-03-21

Boreal forests comprise 73% of the world's coniferous forests. Based on forest floor measurements, they have been considered a significant natural sink of methane (CH4) and a natural source of nitrous oxide (N2O), both of which are important greenhouse gases. However, the role of trees, especially conifers, in ecosystem N2O and CH4 exchange is only poorly understood. We show for the first time that mature Scots pine (Pinus sylvestris L.) trees consistently emit N2O and CH4 from both stems and shoots. The shoot fluxes of N2O and CH4 exceeded the stem flux rates by 16 and 41 times, respectively. Moreover, higher stem N2O and CH4 fluxes were observed from wet than from dry areas of the forest. The N2O release from boreal pine forests may thus be underestimated and the uptake of CH4 may be overestimated when ecosystem flux calculations are based solely on forest floor measurements. The contribution of pine trees to the N2O and CH4 exchange of the boreal pine forest seems to increase considerably under high soil water content, thus highlighting the urgent need to include tree-emissions in greenhouse gas emission inventories.

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.

Direct Conversion of Methane to Value-Added Chemicals over Heterogeneous Catalysts: Challenges and Prospects.

PubMed

Schwach, Pierre; Pan, Xiulian; Bao, Xinhe

2017-07-12

The quest for an efficient process to convert methane efficiently to fuels and high value-added chemicals such as olefins and aromatics is motivated by their increasing demands and recently discovered large reserves and resources of methane. Direct conversion to these chemicals can be realized either oxidatively via oxidative coupling of methane (OCM) or nonoxidatively via methane dehydroaromatization (MDA), which have been under intensive investigation for decades. While industrial applications are still limited by their low yield (selectivity) and stability issues, innovations in new catalysts and concepts are needed. The newly emerging strategy using iron single sites to catalyze methane conversion to olefins, aromatics, and hydrogen (MTOAH) attracted much attention when it was reported. Because the challenge lies in controlled dehydrogenation of the highly stable CH 4 and selective C-C coupling, we focus mainly on the fundamentals of C-H activation and analyze the reaction pathways toward selective routes of OCM, MDA, and MTOAH. With this, we intend to provide some insights into their reaction mechanisms and implications for future development of highly selective catalysts for direct conversion of methane to high value-added chemicals.

Methane to methanol conversion induced by thorium oxide through the CH3Th(O)H intermediate in solid argon.

PubMed

Gong, Yu; Andrews, Lester; Jackson, Virgil E; Dixon, David A

2012-10-15

Reactions of ThO molecules and CH(4) have been investigated in solid argon near 4 K. The CH(3)Th(O)H molecule is produced when the sample is exposed to UV irradiation. Identification of this new intermediate is substantiated by observation of the Th═O and Th-H stretching vibrational modes with isotopic substitution via matrix infrared spectroscopy, and the assignments are supported by electronic structure frequency calculations. Methanol absorptions increase together with formation of the CH(3)Th(O)H molecule, suggesting a methane to methanol conversion induced by thorium oxide proceeding through the CH(3)Th(O)H intermediate. The formation of CH(3)Th(O)H from ThO + CH(4) is exothermic (ΔH(rxn) = -11 kcal/mol) with an energy barrier of 30 kcal/mol at the CCSD(T)//B3LYP level. Decomposition of this intermediate to form methanol involves spin crossing, and the overall reaction from the intermediate is endothermic by 127 kcal/mol. There is no activation energy for the reaction of thorium atoms with methanol to give CH(3)Th(O)H, as observed in separate experiments with Th and CH(3)OH.

Framework fluxionality of organometallic oxides: synthesis, crystal structure, EXAFS, and DFT studies on [[Ru(eta6-arene)]4Mo4O16] complexes.

PubMed

Laurencin, Danielle; Garcia Fidalgo, Eva; Villanneau, Richard; Villain, Françoise; Herson, Patrick; Pacifico, Jessica; Stoeckli-Evans, Helen; Bénard, Marc; Rohmer, Marie-Madeleine; Süss-Fink, Georg; Proust, Anna

2004-01-05

Reactions of the molybdates Na(2)MoO4.2 H2O and (nBu(4)N)2[Mo2O7] with [[Ru(arene)Cl(2)](2)] (arene=C(6)H5CH3, 1,3,5-C6H3(CH3)(3), 1,2,4,5-C6H2(CH3)4) in water or organic solvents led to formation of the triple-cubane organometallic oxides [[Ru(eta(6)-arene)](4)Mo4O16], whose crystal and molecular structures were determined. Refluxing triple cubane [[Ru(eta(6)-C6H5CH3)](4)Mo4O16] in methanol caused partial isomerization to the windmill form. The two isomers of [[Ru(eta(6)-C6H5CH3)](4)Mo4O16] were characterized by Raman and Mo K-edge X-ray absorption spectroscopy (XAS), both in the solid-state and in solution. This triple-cubane isomer was also used as a spectroscopic model to account for isomerization of the p-cymene windmill [[Ru(eta(6)-1,4-CH3C6H4CH(CH3)2)](4)Mo4O16] in solution. Using both Raman and XAS techniques, we were then able to determine the ratio between the windmill and triple-cubane isomers in dichloromethane and in chloroform. Density functional calculations on [[Ru(eta(6)-arene)](4)Mo4O16] (arene=C6H6, C6H5CH3, 1,3,5-C6H3(CH3)3, 1,4-CH3C6H4CH(CH3)2, C6(CH3)6) suggest that the windmill form is intrinsically more stable, provided the complexes are assumed to be isolated. Intramolecular electrostatic interactions and steric bulk induced by substituted arenes were found to modulate but not to reverse the energy difference between the isomers. The stability of the triple-cubane isomers should therefore be accounted for by effects of the surroundings that induce a shift in the energy balance between both forms.

Magnetic gold nanocatalyst (nanocat-Fe–Au): catalytic applications for the oxidative esterification and hydrogen transfer reactions

EPA Science Inventory

An efficient and sustainable protocol is described for the oxidative esterification of aldehydes and the reduction of aromatic nitro compounds that uses magnetically separable and reusable maghemite-supported gold nanocatalyst (nanocat-Fe-Au) under mild conditions. The complex ch...

Atmospheric chemistry of n-butanol: kinetics, mechanisms, and products of Cl atom and OH radical initiated oxidation in the presence and absence of NO(x).

PubMed

Hurley, M D; Wallington, T J; Laursen, L; Javadi, M S; Nielsen, O J; Yamanaka, T; Kawasaki, M

2009-06-25

Smog chamber/FTIR techniques were used to determine rate constants of k(Cl+n-butanol) = (2.21 +/- 0.38) x 10(-10) and k(OH+n-butanol) = (8.86 +/- 0.85) x 10(-12) cm(3) molecule(-1) s(-1) in 700 Torr of N(2)/O(2) diluent at 296 +/- 2K. The sole primary product identified from the Cl atom initiated oxidation of n-butanol in the absence of NO was butyraldehyde (38 +/- 2%, molar yield). The primary products of the Cl atom initiated oxidation of n-butanol in the presence of NO were (molar yield) butyraldehyde (38 +/- 2%), propionaldehyde (23 +/- 3%), acetaldehyde (12 +/- 4%), and formaldehyde (33 +/- 3%). The substantially lower yields of propionaldehyde, acetaldehyde, and formaldehyde as primary products in experiments conducted in the absence of NO suggests that chemical activation is important in the atmospheric chemistry of CH(3)CH(2)CH(O)CH(2)OH and CH(3)CH(O)CH(2)CH(2)OH alkoxy radicals. The primary products of the OH radical initiated oxidation of n-butanol in the presence of NO were (molar yields) butyraldehyde (44 +/- 4%), propionaldehyde (19 +/- 2%), and acetaldehyde (12 +/- 3%). In all cases, the product yields were independent of oxygen concentration over the partial pressure range of 10-600 Torr. The yields of propionaldehyde, acetaldehyde, and formaldehyde quoted above were not corrected for secondary formation via oxidation of higher aldehydes and should be treated as upper limits. The reactions of Cl atoms and OH radicals with n-butanol proceed 38 +/- 2 and 44 +/- 4%, respectively, via attack on the alpha-position to give an alpha-hydroxy alkyl radical which reacts with O(2) to give butyraldehyde. The results are discussed with respect to the atmospheric chemistry of n-butanol.

Photo reduction of CO2 to CH4 on g-C3N4: The effect of concentrating light and pretreatment

NASA Astrophysics Data System (ADS)

Li, Dong; Fang, Xiaoxiang; Liu, Huayan; Lu, Hanfeng; Zhang, Zekai

2018-06-01

The behavior of CO2 photoreduction to CH4 on the g-C3N4 catalyst was studied in a concentrating light reactor. The g-C3N4 catalysts before and after pretreatment were characterized by FE-SEM, XRD and photoilluminance. It is found that concentrating light increases the CH4 yield on the g-C3N4 by heightening the incident light intensity, and light pretreatment has an excessive effect on the performance. Pretreated by suitable light intensity, air atmosphere and time, the CH4 yield on the g-C3N4 under concentrating light irradiation reached about 3.39 μmol.g-1.h-1, which is about 16 times of that g-C3N4 reacted at nature incident light without pretreatment. The mechanism of pretreatment is considered to be from the surface oxidation state change of the catalyst either from the oxidation of the catalyst surface or the activation of surface oxygen.

Manganese complex-catalyzed oxidation and oxidative kinetic resolution of secondary alcohols by hydrogen peroxide.

PubMed

Miao, Chengxia; Li, Xiao-Xi; Lee, Yong-Min; Xia, Chungu; Wang, Yong; Nam, Wonwoo; Sun, Wei

2017-11-01

The highly efficient catalytic oxidation and oxidative kinetic resolution (OKR) of secondary alcohols has been achieved using a synthetic manganese catalyst with low loading and hydrogen peroxide as an environmentally benign oxidant in the presence of a small amount of sulfuric acid as an additive. The product yields were high (up to 93%) for alcohol oxidation and the enantioselectivity was excellent (>90% ee) for the OKR of secondary alcohols. Mechanistic studies revealed that alcohol oxidation occurs via hydrogen atom (H-atom) abstraction from an α-CH bond of the alcohol substrate and a two-electron process by an electrophilic Mn-oxo species. Density functional theory calculations revealed the difference in reaction energy barriers for H-atom abstraction from the α-CH bonds of R - and S -enantiomers by a chiral high-valent manganese-oxo complex, supporting the experimental result from the OKR of secondary alcohols.

Sunlight stimulates methane uptake and nitrous oxide emission from the High Arctic tundra.

PubMed

Li, Fangfang; Zhu, Renbin; Bao, Tao; Wang, Qing; Xu, Hua

2016-12-01

Many environmental factors affecting methane (CH 4 ) and nitrous oxide (N 2 O) fluxes have been investigated during the processes of carbon and nitrogen transformation in the boreal tundra. However, effects of sunlight on CH 4 and N 2 O fluxes and their budgets were neglected in the boreal tundra. Here, summertime CH 4 and N 2 O fluxes in the presence and total absence of sunlight were investigated at the six tundra sites (DM1-DM6) on Ny-Ålesund in the High Arctic. The mean CH 4 fluxes at the tundra sites ranged from -4.7 to -158.6μg CH 4 m -2 h -1 in the presence of light, indicating that a large CH 4 sink occurred in the tundra soils. However, enhanced CH 4 emission in total absence of light occurred at all the tundra sites. The mean N 2 O fluxes ranged from 7.4 to 14.6μg N 2 O m -2 h -1 in the presence of light, whereas in the absence of light all the tundra sites generally released less N 2 O, and even significant N 2 O uptake occurred there. Soil temperature, chamber temperature and soil moisture showed no significant correlations with tundra CH 4 and N 2 O flux. The presence of sunlight increased tundra CH 4 uptake by 114.2μg CH 4 m -2 h -1 and N 2 O emission by 10.9μg N 2 O m -2 h -1 compared with total absence of light. Overall our results showed that tundra ecosystem switched from CH 4 sink and N 2 O emission source in the presence of light to CH 4 emission source and N 2 O sink in the absence of light. Therefore sunlight had an important effect on CH 4 and N 2 O budgets in the High Arctic tundra. The exclusion of sunlight might overestimate CH 4 budgets, but underestimate N 2 O budgets in the Arctic tundra ecosystem. Copyright © 2016 Elsevier B.V. All rights reserved.

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 accumulation of chloride ions either in spent media or in slurries prepared from Searsville Lake soil, neither of these oxyanions evoked methane oxidation when added to either anaerobic mixed cultures or soils enriched in methanotrophs. This result leads us to surmise that the release of O2 during enzymatic perchlorate reduction was low, and that the oxygen produced was unavailable to the aerobic methanotrophs. This was borne out by patterns of O2 and CO2 production during experiments with lake soil, growth media, and pure cultures of dissimilatory perchlorate reducing bacteria. We observed that O2 release during incubation of D. agitata CKB with 10 mM ClO4- or ClO3- was decoupled from metabolism. More O2 was released during incubations without added acetate than with 10 mM acetate and an even greater amount of O2 was released during incubation with heat-killed cells. This suggests a chemical mechanism of O2 production during reaction with ClO4- and ClO3-. Hence, perchlorate reducing bacteria need not be present to facilitate O2 release from the surface of Mars, in support of recent interpretations of Viking LR and GEx experiments.

Soil methane oxidation in both dry and wet temperate eucalypt forests shows a near-identical relationship with soil air-filled porosity

NASA Astrophysics Data System (ADS)

Fest, Benedikt J.; Hinko-Najera, Nina; Wardlaw, Tim; Griffith, David W. T.; Livesley, Stephen J.; Arndt, Stefan K.

2017-01-01

Well-drained, aerated soils are important sinks for atmospheric methane (CH4) via the process of CH4 oxidation by methane-oxidising bacteria (MOB). This terrestrial CH4 sink may contribute towards climate change mitigation, but the impact of changing soil moisture and temperature regimes on CH4 uptake is not well understood in all ecosystems. Soils in temperate forest ecosystems are the greatest terrestrial CH4 sink globally. Under predicted climate change scenarios, temperate eucalypt forests in south-eastern Australia are predicted to experience rapid and extreme changes in rainfall patterns, temperatures and wild fires. To investigate the influence of environmental drivers on seasonal and inter-annual variation of soil-atmosphere CH4 exchange, we measured soil-atmosphere CH4 exchange at high-temporal resolution (< 2 h) in a dry temperate eucalypt forest in Victoria (Wombat State Forest, precipitation 870 mm yr-1) and in a wet temperature eucalypt forest in Tasmania (Warra Long-Term Ecological Research site, 1700 mm yr-1). Both forest soil systems were continuous CH4 sinks of -1.79 kg CH4 ha-1 yr-1 in Victoria and -3.83 kg CH4 ha-1 yr-1 in Tasmania. Soil CH4 uptake showed substantial temporal variation and was strongly controlled by soil moisture at both forest sites. Soil CH4 uptake increased when soil moisture decreased and this relationship explained up to 90 % of the temporal variability. Furthermore, the relationship between soil moisture and soil CH4 flux was near-identical at both forest sites when soil moisture was expressed as soil air-filled porosity (AFP). Soil temperature only had a minor influence on soil CH4 uptake. Soil nitrogen concentrations were generally low and fluctuations in nitrogen availability did not influence soil CH4 uptake at either forest site. Our data suggest that soil MOB activity in the two forests was similar and that differences in soil CH4 exchange between the two forests were related to differences in soil moisture and thereby soil gas diffusivity. The differences between forest sites and the variation in soil CH4 exchange over time could be explained by soil AFP as an indicator of soil moisture status.

C-H activations at iridium(I) square-planar complexes promoted by a fifth ligand.

PubMed

Martín, Marta; Torres, Olga; Oñate, Enrique; Sola, Eduardo; Oro, Luis A

2005-12-28

In the presence of ligands such as acetonitrile, ethylene, or propylene, the Ir(I) complex [Ir(1,2,5,6-eta-C8H12)(NCMe)(PMe3)]BF4 (1) transforms into the Ir(III) derivatives [Ir(1-kappa-4,5,6-eta-C8H12)(NCMe)(L)(PMe3)]BF4 (L = NCMe, 2; eta2-C2H4, 3; eta2-C3H6, 4), respectively, through a sequence of C-H oxidative addition and insertion elementary steps. The rate of this transformation depends on the nature of L and, in the case of NCMe, the pseudo-first-order rate constants display a dependence upon ligand concentration suggesting the formation of five-coordinate reaction intermediates. A similar reaction between 1 and vinyl acetate affords the Ir(III) complex [Ir(1-kappa-4,5,6-eta-C8H12){kappa-O-eta2-OC(Me)OC2H3}(PMe3)]BF4 (7) via the isolable five-coordinate Ir(I) compound [Ir(1,2,5,6-eta-C8H12){kappa-O-eta2-OC(Me)OC2H3}(PMe3)]BF4 (6). DFT (B3LYP) calculations in model complexes show that reactions initiated by acetonitrile or ethylene five-coordinate adducts involve C-H oxidative addition transition states of lower energy than that found in the absence of these ligands. Key species in these ligand-assisted transformations are the distorted (nonsquare-planar) intermediates preceding the intramolecular C-H oxidative addition step, which are generated after release of one cyclooctadiene double bond from the five-coordinate species. The feasibility of this mechanism is also investigated for complexes [IrCl(L)(PiPr3)2] (L = eta2-C2H4, 27; eta2-C3H6, 28). In the presence of NCMe, these complexes afford the C-H activation products [IrClH(CH=CHR)(NCMe)(PiPr3)2] (R = H, 29; Me, 30) via the common cyclometalated intermediate [IrClH{kappa-P,C-P(iPr)2CH(CH3)CH2}(NCMe)(PiPr3)] (31). The most effective C-H oxidative addition mechanism seems to involve three-coordinate intermediates generated by photochemical release of the alkene ligand. However, in the absence of light, the reaction rates display dependences upon NCMe concentration again indicating the intermediacy of five-coordinate acetonitrile adducts.

Enteric methane production from beef cattle that vary in feed efficiency

USDA-ARS?s Scientific Manuscript database

We hypothesized that CH4 production will decrease with increased feed efficiency. Two experiments were conducted to determine CH4 production of cattle that differed in feed efficiency. Cattle in both studies were selected from larger contemporary groups. Animals furthest from the confidence ellip...

Comprehensive effects of a sedge plant on CH4 and N2O emissions in an estuarine marsh

NASA Astrophysics Data System (ADS)

Li, Yangjie; Wang, Dongqi; Chen, Zhenlou; Hu, Hong

2018-05-01

Although there have been numerous studies focusing on plants' roles in methane (CH4) emissions, the influencing mechanism of wetland plants on nitrous oxide (N2O) emissions has rarely been studied. Here, we test whether wetland plants also play an important role in N2O emissions. Gas fluxes were determined using the in situ static flux chamber technique. We also carried out pore-water extractions, sedge removal experiments and tests of N2O transportation. The brackish marsh acted as a net source of both CH4 and N2O. However, sedge plants played the opposite role in CH4 and N2O emissions. The removal of the sedges led to reduced CH4 emissions and increased accumulation of CH4 inside the sediment. Apart from being a conduit for CH4 transport, the sedges made a greater contribution to CH4 oxidation than CH4 production. The sedges exerted inhibitory effects on the release of N2O. The N2O was barely detectable inside the sediment in both vegetated and vegetation-removed plots. The denitrification measurements and nitrogen addition (the addition rates were equal to 0.028, 0.056 and 0.112 g m-2) experiments suggest that denitrification associated with N2O production occurred mainly in the surface sediment layer. The vascular sedge could transport atmospheric N2O downward into the rhizosphere. The rhizospheric sediment, together with the vascular sedge, became an effective sink of atmospheric N2O.

Portable Cavity Ringdown Spectrometer for Methane Isotope Ratio Measurements

NASA Astrophysics Data System (ADS)

Bostrom, G.; Rice, A.; Atkinson, D.

2008-12-01

Close to 45% (244 Tg/yr) of the methange (CH4) in the atmosphere is produced in anaerobic soil conditions (wetlands and rice paddies). Under aerobic soil conditions, bacteria oxidize CH4 to produce CO2 and H2O. Both production and oxidation rates depend on soil composition, nutrient loadings, water content, and plant conditions, but these dependencies are not well characterized. Measurements of CH4 isotope ratios can provide a better understanding of CH4 processes in natural and man- made ecosystems. Here we present progress on the development of a field deployable instrument capable of making precision 13CH4/12CH4 and CH3D/ CH4 isotope ratio measurements of CH4. Moving the instrument out of the lab and into the field will significantly improve the spatial and temporal resolution of data and enhance the study of plant-soil-atmosphere CH4 source and sink processes. Our instrument is a Near-IR (1280-1340 nm) tunable diode laser Cavity Ringdown Spectroscopy (CRDS) system. CRDS is a technique in which the laser injects energy into a high finesse cavity by tuning to one of the cavity resonant modes, resulting in a buildup of energy. At some threshold intra-cavity intensity the injection is stopped, and the intensity decays exponentially due to losses such as absorption by molecules. If the laser is tuned to an absorption line of a sample gas, the concentration of the molecule is proportional to the decay constant (according to the Beer-Lambert law)--scanning over a frequency range produces an absorption spectrum. Currently our system has a resolution of 150 MHz scanning over a 30 GHz (0.2 nm) region, allowing us to resolve peaks at pressures of 100 torr. Using combinations of CH4 standard (natural isotopic abundance) and a 99% pure 13CH4 standard, we identified several lines in the CH4 HITRAN Database that we attribute to 13CH4. We use these and 12CH4 lines within the same region to measure 13CH4 concentration, 12CH4 concentration, and the isotope ratio (13C/12C and D/H). We present our lab-based prototype system, including our latest isotope ratio performance and measurement precision. In addition, we present the way forward to achieve both our target precision and portability.

Changes in methane oxidation activity and methanotrophic community composition in saline alkaline soils.

PubMed

Serrano-Silva, Nancy; Valenzuela-Encinas, César; Marsch, Rodolfo; Dendooven, Luc; Alcántara-Hernández, Rocio J

2014-05-01

The soil of the former Lake Texcoco is a saline alkaline environment where anthropogenic drainage in some areas has reduced salt content and pH. Potential methane (CH4) consumption rates were measured in three soils of the former Lake Texcoco with different electrolytic conductivity (EC) and pH, i.e. Tex-S1 a >18 years drained soil (EC 0.7 dS m(-1), pH 8.5), Tex-S2 drained for ~10 years (EC 9.0 dS m(-1), pH 10.3) and the undrained Tex-S3 (EC 84.8 dS m(-1), pH 10.3). An arable soil from Alcholoya (EC 0.7 dS m(-1), pH 6.7), located nearby Lake Texcoco was used as control. Methane oxidation in the soil Tex-S1 (lowest EC and pH) was similar to that in the arable soil from Alcholoya (32.5 and 34.7 mg CH4 kg(-1) dry soil day(-1), respectively). Meanwhile, in soils Tex-S2 and Tex-S3, the potential CH4 oxidation rates were only 15.0 and 12.8 mg CH4 kg(-1) dry soil day(-1), respectively. Differences in CH4 oxidation were also related to changes in the methane-oxidizing communities in these soils. Sequence analysis of pmoA gene showed that soils differed in the identity and number of methanotrophic phylotypes. The Alcholoya soil and Tex-S1 contained phylotypes grouped within the upland soil cluster gamma and the Jasper Ridge, California JR-2 clade. In soil Tex-S3, a phylotype related to Methylomicrobium alcaliphilum was detected.

Co-processing CH4 and oxygenates on Mo/H-ZSM-5: 2. CH4-CO2 and CH4-HCOOH mixtures.

PubMed

Bedard, Jeremy; Hong, Do-Young; Bhan, Aditya

2013-08-07

Co-processing of formic acid or carbon dioxide with CH4 (FA/CH4 = 0.01-0.03 and CO2/CH4 = 0.01-0.03) on Mo/H-ZSM-5 catalysts at 950 K with the prospect of kinetically coupling dehydrogenation and deoxygenation cycles results instead in a two-zone, staged bed reactor configuration consisting of upstream oxygenate/CH4 reforming and downstream CH4 dehydroaromatization. The addition of an oxygenate co-feed (oxygenate/CH4 = 0.01-0.03) causes oxidation of the active molybdenum carbide catalyst while producing CO and H2 until completely converted. Forward rates of C6H6 synthesis are unaffected by the introduction of an oxygenate co-feed after rigorously accounting for the thermodynamic reversibility caused by the H2 produced in oxygenate reforming reactions and the fraction of the active catalyst deemed unavailable for CH4 DHA. All effects of co-processing oxygenates with CH4 can be construed in terms of an approach to equilibrium.

Characteristics of greenhouse gas emission in three full-scale wastewater treatment processes.

PubMed

Yan, Xu; Li, Lin; Liu, Junxin

2014-02-01

Three full-scale wastewater treatment processes, Orbal oxidation ditch, anoxic/anaerobic/aerobic (reversed A2O) and anaerobic/anoxic/aerobic (A2O), were selected to investigate the emission characteristics of greenhouse gases (GHG), including carbon dioxide (CO2), methane (CH4) and nitrous oxide (N2O). Results showed that although the processes were different, the units presenting high GHG emission fluxes were remarkably similar, namely the highest CO2 and N2O emission fluxes occurred in the aerobic areas, and the highest CH4 emission fluxes occurred in the grit tanks. The GHG emission amount of each unit can be calculated from its area and GHG emission flux. The calculation results revealed that the maximum emission amounts of CO2, CH4 and N2O in the three wastewater treatment processes appeared in the aerobic areas in all cases. Theoretically, CH4 should be produced in anaerobic conditions, rather than aerobic conditions. However, results in this study showed that the CH4 emission fluxes in the forepart of the aerobic area were distinctly higher than in the anaerobic area. The situation for N2O was similar to that of CH4: the N2O emission flux in the aerobic area was also higher than that in the anoxic area. Through analysis of the GHG mass balance, it was found that the flow of dissolved GHG in the wastewater treatment processes and aerators may be the main reason for this phenomenon. Based on the monitoring and calculation results, GHG emission factors for the three wastewater treatment processes were determined. The A2O process had the highest CO2 emission factor of 319.3 g CO2/kg COD(removed), and the highest CH4 and N2O emission factors of 3.3 g CH4/kg COD(removed) and 3.6 g N2O/kg TN(removed) were observed in the Orbal oxidation ditch process.

Quantitative modeling of the rise in atmospheric oxygen

NASA Astrophysics Data System (ADS)

Claire, Mark W.

The abrupt rise of molecular oxygen in Earth's atmosphere approximately 2.4 billion years ago was perhaps the most profound event in Earth's history after the evolution of life itself. Biogeochemical cycles in Earth's atmosphere, ocean, and crust were completely reorganized and it also likely marked the first moment when our planet could be deemed "inhabited" across interstellar space via identification of biogenically produced O 2 and O 3 in a spectrum of Earth's atmosphere. This dissertation explores the "Great Oxidation Event" via numerical modeling of evolving ancient atmospheres. In creating a self-consistent description of evolving redox fluxes in the Earth system, we reach the following conclusions. After the evolution of oxygenic photosynthesis, the atmosphere has two primary stable states--one is methane- rich and produces mass-independent fractionation of sulfur isotopes (MIF-S), and one is oxygen-rich and does not produce MIF-S. These two stable states are separated by only a few percent in the fluxes of O 2 and CH 4 needed to sustain them. The atmosphere evolves rapidly from one state to the other when the net flux of reductants drops below the net flux of oxidants into the atmosphere. The transition between the two states - "the rise of oxygen" - is only feasible once methane levels drop below ~50 ppm. We show numerically that hydrogen escape can drive irreversible oxidation of Earth's crust, leading to decreasing CH 4 concentrations over long timescales. We argue that the disappearance of the MIF-S signal is better described as recording a collapse of atmospheric CH 4 , rather than the appearance of O 2 . As CH 4 levels decrease, a positive feedback between oxidative weathering, oceanic sulfate concentrations, and the anaerobic oxidation of methane further drives atmospheric instability. Once a critical threshold in CH 4 concentration is overcome, the atmosphere transitions from an anoxic to oxic state on the timescale of 10 3 years. The post-transition levels of O 2 and CH 4 and the global climate are strongly driven by biological forcing. Considering the events of 2.4 Ga as a "Great Collapse of Methane" helps explain the initiation of Snowball Earth, the disappearance of MIF-S, and the rise of oxygen.

Mechanism and stereochemistry for nucleophilic attack at carbon of platinum (iv) alkyls: Model reactions for hydrocarbon oxidation with aqueous platinum chlorides. Technical report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Luinstra, G.A.; Labinger, J.A.; Bercaw, J.E.

1992-10-01

Reactions of PtCl4(2-) with RI (R = CH3, CH2CH2OH) in water yield PtCl5R(2-) which were isolated as their NMe4 salts. They decompose in aqueous chloride solution to give ROH and RCL. erythro- and threo-PtCl5(CHDCHDOH)(2-) are obtained by oxidation of PtCl3(cis- and trans CHD=CHD)(-) respectively. Kinetic rate laws and stereochemistry support SN2 displacement by Cl(-) or H[sub 2]O as the mechanism of the decomposition reactions.

Enhanced ethylene photodegradation performance of g-C3N4-Ag3PO4 composites with direct Z-scheme configuration.

PubMed

Chen, Xuxing; Huang, Xintang; Yi, Zhiguo

2014-12-22

Photocatalytic oxidation of ethylene continues to be a challenge at the frontier of chemistry. In a previous report, a simple Ag3 PO4 semiconductor material was shown to have strong photooxidative properties and efficiently oxidised water and decomposed organics in aqueous solution under visible-light illumination. Herein, its effects on the photo-oxidation of gaseous C2 H4 were investigated by fabricating graphitic C3 N4-Ag3 PO4 composite semiconductors with direct Z-scheme configuration. It was found that both the ethylene photo-oxidative activity and the stability of Ag3 PO4 are considerably improved by fabrication of Z-scheme composites. Moreover, stable C2 H4 photo-oxidation activity could be obtained by treating the composite at 450 °C for 3 h after long-term operation. From the point of view of environmental pollutant cleanup, the present technique avoids the side reaction of oxidising water and will be valuable for further investigations on both Ag3 PO4 and CH degradation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

DOE Data Explorer

David E. Graham; Jianqiu Zheng; Taniya RoyChowdhury

2016-08-31

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

Environmental factors influencing landfill gas biofiltration: Lab scale study on methanotrophic bacteria growth.

PubMed

Amodeo, Corrado; Sofo, Adriano; Tito, Maria Teresa; Scopa, Antonio; Masi, Salvatore; Pascale, Raffaella; Mancini, Ignazio M; Caniani, Donatella

2018-03-29

The post-management of landfills represents an important challenge for landfill gas treatment. Traditional systems (energy recovery, flares, etc.) present technical problems in treating flow with low methane (CH 4 ) concentrations. The objective of this study was to isolate methanotrophic bacteria from a field-scale biofilter in order to study the bacteria in laboratories and evaluate the environmental factors that mostly influence Microbial Aerobic Methane Oxidation (MAMO). The soil considered was sampled from the biofilter located in the landfill of Venosa (Basilicata Region, Italy) and it was mainly composed of wood chips and compost. The results showed that methanotrophic microorganisms are mainly characterized by a slow growth and a significant sensitivity to CH 4 levels. Temperature and nitrogen (N) also have a very important role on their development. On the basis of the results, biofilters for biological CH 4 oxidation can be considered a viable alternative to mitigate CH 4 emissions from landfills.

Anaerobic methane oxidation in two tropical freshwater systems

NASA Astrophysics Data System (ADS)

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

2014-05-01

Lake Kivu is one of the East African Great Lakes. It is located at the border between Rwanda and the Democratic Republic of the Congo. It is a deep meromictic lake characterized by huge amounts of methane (CH4) (60 km3 at 0° C and 1 atm) dissolved in its deep waters. Two thirds of the CH4 originates from anoxic bacterial reduction of dissolved carbon dioxide and one third from anaerobic degradation of settling organic material. CH4 then diffuses slowly from the monimolimnion to surface waters where many is oxidised by methanotrophic microorganisms. In Lake Kivu, this biological oxidation of CH4 could occur with different final electron acceptors: oxygen (aerobic oxidation) but also nitrate (NO3-), nitrite, sulfate (SO42-), iron (Fe) or manganese (Mn) in anaerobic conditions. If the anaerobic oxidation of CH4 (AOM) is generally coupled to SO42- reduction in marine waters, electron acceptors of the AOM were rarely investigated in freshwater systems. Five field campaigns were conducted from 2011 to 2013 during periods with contrasted ventilations of the upper water column. The dry season is characterized by a deeper mixing of surface waters ended by a steep gradient of physico-chemical conditions at the redox interface, while during the rainy season the mixed layer is shallower and ended at its deeper part by a NO3- accumulation zone. Sampling was conducted in the main basin of Lake Kivu but also in a particular sub-basin located northeast of the lake, the Kabuno Bay. Both systems are meromictic but differ in terms of morphometry and geochemistry with a shallower permanent chemocline and higher concentrations of CH4, Fe and Mn in the anoxic waters in Kabuno Bay compared to the main lake. Samples were collected for the measurements of CH4 concentrations and the various potential electron acceptors of the AOM. CH4 oxidation rates were measured along vertical profiles at 5 m and 0.5 m depth intervals respectively in the main basin and Kabuno bay water columns. Results indicate high rates of AOM in both main basin (up to 7 μmol L-1 d-1) and Kabuno bay (up to 16 μmol L-1 d-1). In the main basin, we observed a co-occurrence of the AOM and the SO42- reduction in the dry season. During the rainy season, higher oxidation rates occurred in the NO3- accumulation zone, which is in favour of a coupling between AOM and NO3- reduction. In Kabuno Bay, the higher AOM rates were observed at depths with highest particulate Fe concentrations. Our results suggest that AOM coupled with SO42-reduction may occur during the dry season in the main basin, whereas this oxidation could be coupled with NO3- reduction during the rainy season. In Kabuno Bay, the co-occurrence of the Fe [III] peak with high AOM suggests a coupling between the AOM and Fe reduction.

Can ipids in lake sediments help to reconstruct changes in methane availability and methane fluxes in boreal and temperate lakes?

NASA Astrophysics Data System (ADS)

Stoetter, T.; van Hardenbroek, M.; Rinta, P.; Schilder, J.; Schubert, C. J.; Heiri, O.

2013-12-01

Methane (CH4) is a major greenhouse gas and lakes are an important but poorly studied source of CH4 to the atmosphere. Lipid analysis was used before to identify and quantify CH4 oxidizing bacteria (MOB), giving insight into CH4 oxidation and production in lakes. However, few studies are available that examine how closely the distribution and the carbon isotopic signature (δ13C) of lipids are related to CH4 concentrations and fluxes in different lake ecosystems. In a multi-lake survey we quantified the relationship between lipids, mainly fatty acids (FAs), and CH4 concentrations or fluxes, with the aim of assessing whether FA analysis of lake sediment samples can provide information on past CH4 abundance and production in lakes. The study sites include small lakes in Sweden, Finland, the Netherlands, and Switzerland. Surface sediments collected in the deepest point of the lakes were examined using gas chromatography with flame ionization for determining FA concentrations, gas chromatography mass spectrometry (GC-MS) for identification of individual FAs, and isotope ratio mass spectrometry (IRMS) for determining compound specific δ13C values. Since CH4 is significantly more depleted in 13C than other carbon sources, δ13C is a good tracer for CH4 related processes. The analysis of the acid fraction in the sediments showed that mainly three FAs, identified as C16:1ω7, C16:1ω5 and C18:1ω7, were more depleted in 13C than the others, suggesting that they may originate from MOB. Comparison with literature sources indicated that these FAs are produced by MOB, however, not exclusively. The relative abundance of these depleted FAs showed clear relations to CH4 parameters. For example, increasing abundances were observed with increasing CH4 concentrations in the sediment or with increasing CH4 flux measured at the lake surface. An explanation for these relations would be an increase in MOB biomass with increasing CH4 availability, as they use CH4 as energy and carbon source, which would lead to increasing abundances of MOB produced FAs in the sediment. The presence or absence of oxygen above the sediments seems to have a strong effect on these relationships. In lakes with oxic bottom water, the abundance of depleted FAs shows a stronger rise with increasing CH4 concentrations than in lakes with anoxic bottom waters, suggesting that aerobic CH4 oxidizers are an important source of these depleted FAs. With increasing CH4 concentrations, for example just above the sediment, we find more depleted values in C16:1ω7 and C18:1ω7. This correlation is only strong if we exclude lakes with a strong terrestrial influence. Our preliminary analysis of FAs in surface sediment samples showed clear relations to CH4 parameters measured in the examined lake ecosystems suggesting that it may be possible to use FA analysis of lake sediment records as a proxy for CH4 availability in lakes. However, our results also show that oxygen conditions at the sediment-water interface and organic matter imported from the lake catchment can have a strong effect.

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.

Activity and diversity of methane-oxidizing bacteria along a Norwegian sub-Arctic glacier forefield.

PubMed

Mateos-Rivera, Alejandro; Øvreås, Lise; Wilson, Bryan; Yde, Jacob C; Finster, Kai W

2018-05-01

Methane (CH4) is one of the most abundant greenhouse gases in the atmosphere and identification of its sources and sinks is crucial for the reliability of climate model outputs. Although CH4 production and consumption rates have been reported from a broad spectrum of environments, data obtained from glacier forefields are restricted to a few locations. We report the activities of methanotrophic communities and their diversity along a chronosequence in front of a sub-Arctic glacier using high-throughput sequencing and gas flux measurements. CH4 oxidation rates were measured in the field throughout the growing season during three sampling times at eight different sampling points in combination with laboratory incubation experiments. The overall results showed that the methanotrophic community had similar trends of increased CH4 consumption and increased abundance as a function of soil development and time of year. Sequencing results revealed that the methanotrophic community was dominated by a few OTUs and that a short-term increase in CH4 concentration, as performed in the field measurements, altered slightly the relative abundance of the OTUs.

Clumped isotope effects during OH and Cl oxidation of methane

NASA Astrophysics Data System (ADS)

Whitehill, Andrew R.; Joelsson, Lars Magnus T.; Schmidt, Johan A.; Wang, David T.; Johnson, Matthew S.; Ono, Shuhei

2017-01-01

A series of experiments were carried out to determine the clumped (13CH3D) methane kinetic isotope effects during oxidation of methane by OH and Cl radicals, the major sink reactions for atmospheric methane. Experiments were performed in a 100 L quartz photochemical reactor, in which OH was produced from the reaction of O(1D) (from O3 photolysis) with H2O, and Cl was from photolysis of Cl2. Samples were taken from the reaction cell and analyzed for methane (12CH4, 12CH3D, 13CH4, 13CH3D) isotopologue ratios using tunable infrared laser direct absorption spectroscopy. Measured kinetic isotope effects for singly substituted species were consistent with previous experimental studies. For doubly substituted methane, 13CH3D, the observed kinetic isotope effects closely follow the product of the kinetic isotope effects for the 13C and deuterium substituted species (i.e., 13,2KIE = 13KIE × 2KIE). The deviation from this relationship is 0.3‰ ± 1.2‰ and 3.5‰ ± 0.7‰ for OH and Cl oxidation, respectively. This is consistent with model calculations performed using quantum chemistry and transition state theory. The OH and Cl reactions enrich the residual methane in the clumped isotopologue in open system reactions. In a closed system, however, this effect is overtaken by the large D/H isotope effect, which causes the residual methane to become anti-clumped relative to the initial methane. Based on these results, we demonstrate that oxidation of methane by OH, the predominant oxidant for tropospheric methane, will only have a minor (∼0.3‰) impact on the clumped isotope signature (Δ13CH3D, measured as a deviation from a stochastic distribution of isotopes) of tropospheric methane. This paper shows that Δ13CH3D will provide constraints on methane source strengths, and predicts that Δ12CH2D2 can provide information on methane sink strengths.

Competitive interactions between methane- and ammonia-oxidizing bacteria modulate carbon and nitrogen cycling in paddy soil

NASA Astrophysics Data System (ADS)

Zheng, Y.; Huang, R.; Wang, B. Z.; Bodelier, P. L. E.; Jia, Z. J.

2014-06-01

Pure culture studies have demonstrated that methanotrophs and ammonia oxidizers can both carry out the oxidation of methane and ammonia. However, the expected interactions resulting from these similarities are poorly understood, especially in complex, natural environments. Using DNA-based stable isotope probing and pyrosequencing of 16S rRNA and functional genes, we report on biogeochemical and molecular evidence for growth stimulation of methanotrophic communities by ammonium fertilization, and that methane modulates nitrogen cycling by competitive inhibition of nitrifying communities in a rice paddy soil. Pairwise comparison between microcosms amended with CH4, CH4+Urea, and Urea indicated that urea fertilization stimulated methane oxidation activity 6-fold during a 19-day incubation period, while ammonia oxidation activity was significantly suppressed in the presence of CH4. Pyrosequencing of the total 16S rRNA genes revealed that urea amendment resulted in rapid growth of Methylosarcina-like MOB, and nitrifying communities appeared to be partially inhibited by methane. High-throughput sequencing of the 13C-labeled DNA further revealed that methane amendment resulted in clear growth of Methylosarcina-related MOB while methane plus urea led to an equal increase in Methylosarcina and Methylobacter-related type Ia MOB, indicating the differential growth requirements of representatives of these genera. An increase in 13C assimilation by microorganisms related to methanol oxidizers clearly indicated carbon transfer from methane oxidation to other soil microbes, which was enhanced by urea addition. The active growth of type Ia methanotrops was significantly stimulated by urea amendment, and the pronounced growth of methanol-oxidizing bacteria occurred in CH4-treated microcosms only upon urea amendment. Methane addition partially inhibited the growth of Nitrosospira and Nitrosomonas in urea-amended microcosms, as well as growth of nitrite-oxidizing bacteria. These results suggest that type I methanotrophs can outcompete type II methane oxidizers in nitrogen-rich environments, rendering the interactions among methane and ammonia oxidizers more complicated than previously appreciated.

Thermodynamic and achievable efficiencies for solar-driven electrochemical reduction of carbon dioxide to transportation fuels.

PubMed

Singh, Meenesh R; Clark, Ezra L; Bell, Alexis T

2015-11-10

Thermodynamic, achievable, and realistic efficiency limits of solar-driven electrochemical conversion of water and carbon dioxide to fuels are investigated as functions of light-absorber composition and configuration, and catalyst composition. The maximum thermodynamic efficiency at 1-sun illumination for adiabatic electrochemical synthesis of various solar fuels is in the range of 32-42%. Single-, double-, and triple-junction light absorbers are found to be optimal for electrochemical load ranges of 0-0.9 V, 0.9-1.95 V, and 1.95-3.5 V, respectively. Achievable solar-to-fuel (STF) efficiencies are determined using ideal double- and triple-junction light absorbers and the electrochemical load curves for CO2 reduction on silver and copper cathodes, and water oxidation kinetics over iridium oxide. The maximum achievable STF efficiencies for synthesis gas (H2 and CO) and Hythane (H2 and CH4) are 18.4% and 20.3%, respectively. Whereas the realistic STF efficiency of photoelectrochemical cells (PECs) can be as low as 0.8%, tandem PECs and photovoltaic (PV)-electrolyzers can operate at 7.2% under identical operating conditions. We show that the composition and energy content of solar fuels can also be adjusted by tuning the band-gaps of triple-junction light absorbers and/or the ratio of catalyst-to-PV area, and that the synthesis of liquid products and C2H4 have high profitability indices.

Thermodynamic and achievable efficiencies for solar-driven electrochemical reduction of carbon dioxide to transportation fuels

NASA Astrophysics Data System (ADS)

Singh, Meenesh R.; Clark, Ezra L.; Bell, Alexis T.

2015-11-01

Thermodynamic, achievable, and realistic efficiency limits of solar-driven electrochemical conversion of water and carbon dioxide to fuels are investigated as functions of light-absorber composition and configuration, and catalyst composition. The maximum thermodynamic efficiency at 1-sun illumination for adiabatic electrochemical synthesis of various solar fuels is in the range of 32-42%. Single-, double-, and triple-junction light absorbers are found to be optimal for electrochemical load ranges of 0-0.9 V, 0.9-1.95 V, and 1.95-3.5 V, respectively. Achievable solar-to-fuel (STF) efficiencies are determined using ideal double- and triple-junction light absorbers and the electrochemical load curves for CO2 reduction on silver and copper cathodes, and water oxidation kinetics over iridium oxide. The maximum achievable STF efficiencies for synthesis gas (H2 and CO) and Hythane (H2 and CH4) are 18.4% and 20.3%, respectively. Whereas the realistic STF efficiency of photoelectrochemical cells (PECs) can be as low as 0.8%, tandem PECs and photovoltaic (PV)-electrolyzers can operate at 7.2% under identical operating conditions. We show that the composition and energy content of solar fuels can also be adjusted by tuning the band-gaps of triple-junction light absorbers and/or the ratio of catalyst-to-PV area, and that the synthesis of liquid products and C2H4 have high profitability indices.

Investigating temperature effects on methane production and oxidation in the rice ecosystem using stable carbon and hydrogen isotope ratios

NASA Astrophysics Data System (ADS)

Rice, A. L.; Sithole, A.; Shearer, M. J.; Hanson, E.; Fisher, A.; Khalil, A. K.

2010-12-01

Irrigated rice is a major agricultural source of methane emissions that contributes about 15% of global atmospheric methane (CH4). Our work investigates the relationships between temperature and CH4 production, oxidation, and flux in the rice ecosystem. This is central to understanding the response of the global CH4 emissions from rice under a changing climate. Temperatures were regulated in sixteen rice plots grown in a research greenhouse using four waterbath-temperature control systems held at 20°C, 24°C, 28°C, and 32°C over the course of a growing season. Belowground porewater samples were collected from each treatment weekly and CH4 was extracted into headspace N2 after vigorous shaking. Weekly flux samples were collected using acrylic static flux chambers placed over the rice plots. CH4 concentrations below and aboveground were measured using gas chromatography-flame ionization detection. The carbon (δ13C) and hydrogen (δD) isotopic composition of CH4 was measured using continuous-flow gas chromatography isotope ratio mass spectrometry. Results show that CH4 flux ranged from near zero to 30-60 mg/m2/hr in mid-season corresponding to a rise in porewater CH4 to 8-12 mg/L. Early season CH4 fluxes were larger in elevated temperature treatments but this difference was smaller, or even reversed in some cases, in the late season. Similar trends were observed in CH4 porewater concentration profiles. Results from isotopic measurements show mean belowground δ13C values between -44‰ and -52‰ relative to VPDB and δD values between -290‰ and -320‰ relative to VSMOW. Emitted CH4 had mean δ13C values which ranged from -50‰ to -60‰ VPDB. We integrate these results and interpret them using an empirically-driven concentration and isotope model to understand CH4 dynamics and to examine the effect of temperature on mechanisms that control CH4 emissions.

Plants, microorganisms, and soil temperatures contribute to a decrease in methane fluxes on a drained Arctic floodplain.

PubMed

Kwon, Min Jung; Beulig, Felix; Ilie, Iulia; Wildner, Marcus; Küsel, Kirsten; Merbold, Lutz; Mahecha, Miguel D; Zimov, Nikita; Zimov, Sergey A; Heimann, Martin; Schuur, Edward A G; Kostka, Joel E; Kolle, Olaf; Hilke, Ines; Göckede, Mathias

2017-06-01

As surface temperatures are expected to rise in the future, ice-rich permafrost may thaw, altering soil topography and hydrology and creating a mosaic of wet and dry soil surfaces in the Arctic. Arctic wetlands are large sources of CH 4 , and investigating effects of soil hydrology on CH 4 fluxes is of great importance for predicting ecosystem feedback in response to climate change. In this study, we investigate how a decade-long drying manipulation on an Arctic floodplain influences CH 4 -associated microorganisms, soil thermal regimes, and plant communities. Moreover, we examine how these drainage-induced changes may then modify CH 4 fluxes in the growing and nongrowing seasons. This study shows that drainage substantially lowered the abundance of methanogens along with methanotrophic bacteria, which may have reduced CH 4 cycling. Soil temperatures of the drained areas were lower in deep, anoxic soil layers (below 30 cm), but higher in oxic topsoil layers (0-15 cm) compared to the control wet areas. This pattern of soil temperatures may have reduced the rates of methanogenesis while elevating those of CH 4 oxidation, thereby decreasing net CH 4 fluxes. The abundance of Eriophorum angustifolium, an aerenchymatous plant species, diminished significantly in the drained areas. Due to this decrease, a higher fraction of CH 4 was alternatively emitted to the atmosphere by diffusion, possibly increasing the potential for CH 4 oxidation and leading to a decrease in net CH 4 fluxes compared to a control site. Drainage lowered CH 4 fluxes by a factor of 20 during the growing season, with postdrainage changes in microbial communities, soil temperatures, and plant communities also contributing to this reduction. In contrast, we observed CH 4 emissions increased by 10% in the drained areas during the nongrowing season, although this difference was insignificant given the small magnitudes of fluxes. This study showed that long-term drainage considerably reduced CH 4 fluxes through modified ecosystem properties. © 2016 John Wiley & Sons Ltd.

Partially reduced graphene oxide-gold nanorods composite based bioelectrode of improved sensing performance.

PubMed

Nirala, Narsingh R; Abraham, Shiju; Kumar, Vinod; Pandey, Shobhit A; Yadav, Umakant; Srivastava, Monika; Srivastava, S K; Singh, Vidya Nand; Kayastha, Arvind M; Srivastava, Anchal; Saxena, Preeti S

2015-11-01

The present work proposes partially reduced graphene oxide-gold nanorods supported by chitosan (CH-prGO-AuNRs) as a potential bioelectrode material for enhanced glucose sensing. Developed on ITO substrate by immobilizing glucose oxidase on CH-prGO-AuNRs composite, these CH-prGO-AuNRs/ITO bioelectrodes demonstrate high sensitivity of 3.2 µA/(mg/dL)/cm(2) and linear range of 25-200 mg/dL with an ability to detect as low as 14.5 mg/dL. Further, these CH-prGO-AuNRs/ITO based electrodes attest synergistiacally enhanced sensing properties when compared to simple graphene oxide based CH-GO/ITO electrode. This is evident from one order higher electron transfer rate constant (Ks) value in case of CH-prGO-AuNRs modified electrode (12.4×10(-2) cm/s), in contrast to CH-GO/ITO electrode (6×10(-3) cm/s). Additionally, very low Km value [15.4 mg/dL(0.85 mM)] ensures better binding affinity of enzyme to substrate which is desirable for good biosensor stability and resistance to environmental interferences. Hence, with better loading capacity, kinetics and stability, the proposed CH-prGO-AuNRs composite shows tremendous potential to detect several bio-analytes in the coming future. Copyright © 2015 Elsevier B.V. All rights reserved.

Selective inhibition of ammonium oxidation and nitrification-linked N2O formation by methyl fluoride and dimethyl ether

USGS Publications Warehouse

Miller, L.G.; Coutlakis, M.D.; Oremland, R.S.; Ward, B.B.

1993-01-01

Methyl fluoride (CH3F) and dimethyl ether (DME) inhibited nitrification in washed-cell suspensions of Nitrosomonas europaea and in a variety of oxygenated soils and sediments. Headspace additions of CH3F (10% [vol/vol]) and DME (25% [vol/vol]) fully inhibited NO2- and N2O production from NH4+ in incubations of N. europaea, while lower concentrations of these gases resulted in partial inhibition. Oxidation of hydroxylamine (NH2OH) by N. europaea and oxidation of NO2- by a Nitrobacter sp. were unaffected by CH3F or DME. In nitrifying soils, CH3F and DME inhibited N2O production. In field experiments with surface flux chambers and intact cores, CH3F reduced the release of N2O from soils to the atmosphere by 20- to 30-fold. Inhibition by CH3F also resulted in decreased NO3- + NO2- levels and increased NH4+ levels in soils. CH3F did not affect patterns of dissimilatory nitrate reduction to ammonia in cell suspensions of a nitrate- respiring bacterium, nor did it affect N2O metabolism in denitrifying soils. CH3F and DME will be useful in discriminating N2O production via nitrification and denitrification when both processes occur and in decoupling these processes by blocking NO2- and NO3- production.

The role of forest floor and trees to the ecosystem scale methane budget of boreal forests

NASA Astrophysics Data System (ADS)

Pihlatie, Mari; Halmeenmäki, Elisa; Peltola, Olli; Haikarainen, Iikka; Heinonsalo, Jussi; Santalahti, Minna; Putkinen, Anuliina; Fritze, Hannu; Urban, Otmar; Machacova, Katerina

2016-04-01

Boreal forests are considered as a sink of atmospheric methane (CH4) due to the activity of CH4 oxidizing bacteria (methanotrophs) in the soil. This soil CH4 sink is especially strong for upland forest soils, whereas forests growing on organic soils may act as small sources due to the domination of CH4 production by methanogens in the anaerobic parts of the soil. The role of trees to the ecosystem-scale CH4 fluxes has until recently been neglected due to the perception that trees do not contribute to the CH4 exchange, and also due to difficulties in measuring the CH4 exchange from trees. Findings of aerobic CH4 formation in plants and emissions from tree-stems in temperate and tropical forests during the past decade demonstrate that our understanding of CH4 cycling in forest ecosystems is not complete. Especially the role of forest canopies still remain unresolved, and very little is known of CH4 fluxes from trees in boreal region. We measured the CH4 exchange of tree-stems and tree-canopies from pine (Pinus sylvestris), spruce (Picea abies) and birch (Betula pubescens, Betula pendula) trees growing in Southern Finland (SMEAR II station) on varying soil conditions, from upland mineral soils to paludified soil. We compared the CH4 fluxes from trees to forest-floor CH4 exchange, both measured by static chambers, and to CH4 fluxes measured above the forest canopy by a flux gradient technique. We link the CH4 fluxes from trees and forest floor to physiological activity of the trees, such as transpiration, sap-flow, CO2 net ecosystem exchange (NEE), soil properties such as temperature and moisture, and to the presence of CH4 producing methanogens and CH4 oxidizing methanotrophs in trees or soil. The above canopy CH4 flux measurements show that the whole forest ecosystem was a small source of CH4 over extended periods in the spring and summer 2012, 2014 and 2015. Throughout the 2013-2014 measurements, the forest floor was in total a net sink of CH4, with variation between high CH4 uptake in the dominating dry upland areas and high emissions from the few wet spots of the forest. All the studied tree species emitted small amounts of CH4 from the stems and shoots, with emission rates depending on the season, tree species and soil conditions. Especially, CH4 emissions from birch canopies were high and can therefore contribute significantly to the ecosystem-scale CH4 fluxes. Processes behind the canopy and stem CH4emission remain unresolved, however, ongoing analysis of the methanogens and methanotrophs within the plant-soil systems will reveal whether CH4 production or consumption is of microbial origin. Also, comparison of the CH4 fluxes from trees and forest floor to sap-flow, transpiration, and NEE as well as soil parameters will help to explain the seasonality and mechanisms involved in the CH4 emissions.

Top-down estimates of methane and nitrogen oxide emissions from shale gas production regions using aircraft measurements and a mesoscale Bayesian inversion system together with a flux ratio inversion technique

NASA Astrophysics Data System (ADS)

Cui, Y.; Brioude, J. F.; Angevine, W. M.; McKeen, S. A.; Henze, D. K.; Bousserez, N.; Liu, Z.; McDonald, B.; Peischl, J.; Ryerson, T. B.; Frost, G. J.; Trainer, M.

2016-12-01

Production of unconventional natural gas grew rapidly during the past ten years in the US which led to an increase in emissions of methane (CH4) and, depending on the shale region, nitrogen oxides (NOx). In terms of radiative forcing, CH4 is the second most important greenhouse gas after CO2. NOx is a precursor of ozone (O3) in the troposphere and nitrate particles, both of which are regulated by the US Clean Air Act. Emission estimates of CH4 and NOx from the shale regions are still highly uncertain. We present top-down estimates of CH4 and NOx surface fluxes from the Haynesville and Fayetteville shale production regions using aircraft data collected during the Southeast Nexus of Climate Change and Air Quality (SENEX) field campaign (June-July, 2013) and the Shale Oil and Natural Gas Nexus (SONGNEX) field campaign (March-May, 2015) within a mesoscale inversion framework. The inversion method is based on a mesoscale Bayesian inversion system using multiple transport models. EPA's 2011 National CH4 and NOx Emission Inventories are used as prior information to optimize CH4 and NOx emissions. Furthermore, the posterior CH4 emission estimates are used to constrain NOx emission estimates using a flux ratio inversion technique. Sensitivity of the posterior estimates to the use of off-diagonal terms in the error covariance matrices, the transport models, and prior estimates is discussed. Compared to the ground-based in-situ observations, the optimized CH4 and NOx inventories improve ground level CH4 and O3 concentrations calculated by the Weather Research and Forecasting mesoscale model coupled with chemistry (WRF-Chem).

Metal-free TEMPO-promoted C(sp³)-H amination to afford multisubstituted benzimidazoles.

PubMed

Xue, Ding; Long, Ya-Qiu

2014-05-16

An efficient TEMPO-air/cat. TEMPO-O2 oxidative protocol was developed to synthesize multisubstituted or fused tetracyclic benzimidazoles via a metal-free oxidative C-N coupling between the sp(3) C-H and free N-H of readily available N(1)-benzyl/alkyl-1,2-phenylenediamines.

Equilibrium Acidities and Homolytic Bond Dissociation Enthalpies of the Acidic C-H Bonds in P-(Para-substituted benzyl)triphenylphosphonium Cations and Related Cations.

PubMed

Zhang, Xian-Man; Fry, Albert J.; Bordwell, Frederick G.

1996-06-14

Equilibrium acidities (pK(HA)) of six P-(para-substituted benzyl)triphenylphosphonium (p-GC(6)H(4)CH(2)PPh(3)(+)) cations, P-allyltriphenylphosphonium cation, P-cinnamyltriphenylphosphonium cation, and As-(p-cyanobenzyl)triphenylarsonium cation, together with the oxidation potentials [E(ox)(A(-))] of their conjugate anions (ylides) have been measured in dimethyl sulfoxide (DMSO) solution. The acidifying effects of the alpha-triphenylphosphonium groups on the acidic C-H bonds in toluene and propene were found to be ca 25 pK(HA) units (34 kcal/mol). Introduction of an electron-withdrawing group such as 4-NO(2), 4-CN, or 4-Br into the para position of the benzyl ring in p-GC(6)H(4)CH(2)PPh(3)(+) cations resulted in an additional acidity increase, but introduction of the 4-OEt electron-donating group decreases the acidity. The equilibrium acidities of p-GC(6)H(4)CH(2)PPh(3)(+) cations were nicely linearly correlated with the Hammett sigma(-) constants of the substituents (G) with a slope of 4.78 pK(HA) units (R(2) = 0.992) (Figure 1). Reversible oxidation potentials of the P-(para-substituted benzyl)triphenylphosphonium ylides were obtained by fast scan cyclic voltammetry. The homolytic bond dissociation enthalpies (BDEs) of the acidic C-H bonds in these cations, estimated by combining their equilibrium acidities with the oxidation potentials of their corresponding conjugate anions, showed that the alpha-Ph(3)P(+) groups have negligible stabilizing or destabilizing effects on the adjacent radicals. The equilibrium acidity of As-(p-cyanobenzyl)triphenylarsonium cation is 4 pK(HA) units weaker than that of P-(p-cyanobenzyl)triphenylphosphonium cation, but the BDE of the acidic C-H bond in As-(p-cyanobenzyl)triphenylarsonium cation is ca 2 kcal/mol higher than that in P-(p-cyanobenzyl)triphenylphosphonium cation.

From iron coordination compounds to metal oxide nanoparticles.

PubMed

Iacob, Mihail; Racles, Carmen; Tugui, Codrin; Stiubianu, George; Bele, Adrian; Sacarescu, Liviu; Timpu, Daniel; Cazacu, Maria

2016-01-01

Various types, shapes and sizes of iron oxide nanoparticles were obtained depending on the nature of the precursor, preparation method and reaction conditions. The mixed valence trinuclear iron acetate, [Fe 2 III Fe II O(CH 3 COO) 6 (H 2 O) 3 ]·2H 2 O (FeAc1), μ 3 -oxo trinuclear iron(III) acetate, [Fe 3 O(CH 3 COO) 6 (H 2 O) 3 ]NO 3 ∙4H 2 O (FeAc2), iron furoate, [Fe 3 O(C 4 H 3 OCOO) 6 (CH 3 OH) 3 ]NO 3 ∙2CH 3 OH (FeF), iron chromium furoate, FeCr 2 O(C 4 H 3 OCOO) 6 (CH 3 OH) 3 ]NO 3 ∙2CH 3 OH (FeCrF), and an iron complex with an original macromolecular ligand (FePAZ) were used as precursors for the corresponding oxide nanoparticles. Five series of nanoparticle samples were prepared employing either a classical thermal pathway (i.e., thermal decomposition in solution, solvothermal method, dry thermal decomposition/calcination) or using a nonconventional energy source (i.e., microwave or ultrasonic treatment) to convert precursors into iron oxides. The resulting materials were structurally characterized by wide-angle X-ray diffraction and Fourier transform infrared, Raman, energy-dispersive X-ray, and X-ray fluorescence spectroscopies, as well as thermogravimetric analysis. The morphology was characterized by transmission electron microscopy, atomic force microscopy and dynamic light scattering. The parameters were varied within each route to fine tune the size and shape of the formed nanoparticles.

From iron coordination compounds to metal oxide nanoparticles

PubMed Central

Iacob, Mihail; Racles, Carmen; Tugui, Codrin; Stiubianu, George; Bele, Adrian; Sacarescu, Liviu; Timpu, Daniel

2016-01-01

Various types, shapes and sizes of iron oxide nanoparticles were obtained depending on the nature of the precursor, preparation method and reaction conditions. The mixed valence trinuclear iron acetate, [Fe2 IIIFeIIO(CH3COO)6(H2O)3]·2H2O (FeAc1), μ3-oxo trinuclear iron(III) acetate, [Fe3O(CH3COO)6(H2O)3]NO3∙4H2O (FeAc2), iron furoate, [Fe3O(C4H3OCOO)6(CH3OH)3]NO3∙2CH3OH (FeF), iron chromium furoate, FeCr2O(C4H3OCOO)6(CH3OH)3]NO3∙2CH3OH (FeCrF), and an iron complex with an original macromolecular ligand (FePAZ) were used as precursors for the corresponding oxide nanoparticles. Five series of nanoparticle samples were prepared employing either a classical thermal pathway (i.e., thermal decomposition in solution, solvothermal method, dry thermal decomposition/calcination) or using a nonconventional energy source (i.e., microwave or ultrasonic treatment) to convert precursors into iron oxides. The resulting materials were structurally characterized by wide-angle X-ray diffraction and Fourier transform infrared, Raman, energy-dispersive X-ray, and X-ray fluorescence spectroscopies, as well as thermogravimetric analysis. The morphology was characterized by transmission electron microscopy, atomic force microscopy and dynamic light scattering. The parameters were varied within each route to fine tune the size and shape of the formed nanoparticles. PMID:28144555

Oxidative trifluoromethylation and trifluoromethylthiolation reactions using (trifluoromethyl)trimethylsilane as a nucleophilic CF3 source.

PubMed

Chu, Lingling; Qing, Feng-Ling

2014-05-20

The trifluoromethyl group is widely prevalent in many pharmaceuticals and agrochemicals because its incorporation into drug candidates could enhance chemical and metabolic stability, improve lipophilicity and bioavailability, and increase the protein bind affinity. Consequently, extensive attention has been devoted toward the development of efficient and versatile methods for introducing the CF3 group into various organic molecules. Direct trifluoromethylation reaction has become one of the most efficient and important approaches for constructing carbon-CF3 bonds. Traditionally, the nucleophilic trifluoromethylation reaction involves an electrophile and the CF3 anion, while the electrophilic trifluoromethylation reaction involves a nucleophile and the CF3 cation. In 2010, we proposed the concept of oxidative trifluoromethylation: the reaction of nucleophilic substrates and nucleophilic trifluoromethylation reagents in the presence of oxidants. In this Account, we describe our recent studies of oxidative trifluoromethylation reactions of various nucleophiles with CF3SiMe3 in the presence of oxidants. We have focused most of our efforts on constructing carbon-CF3 bonds via direct trifluoromethylation of various C-H bonds. We have demonstrated copper-mediated or -catalyzed or metal-free oxidative C-H trifluoromethylation of terminal alkynes, tertiary amines, arenes and heteroarenes, and terminal alkenes. Besides various C-H bonds, aryl boronic acids proved to be viable nucleophilic coupling partners for copper-mediated or -catalyzed cross-coupling reactions with CF3SiMe3. To further expand the reaction scope, we also applied H-phosphonates to the oxidative trifluoromethylation system to construct P-CF3 bonds. Most recently, we developed silver-catalyzed hydrotrifluoromethylation of unactivated olefins. These studies explore boronic acids, C-H bonds, and P-H bonds as novel nucleophiles in transition-metal-mediated or -catalyzed cross-coupling reactions with CF3SiMe3, opening new viewpoints for future trifluoromethylation reactions. Furthermore, we also achieved the oxidative trifluoromethylthiolation reactions of aryl boronic acids and terminal alkynes to construct carbon-SCF3 bonds by using CF3SiMe3 and elemental sulfur as the nucleophilic trifluoromethylthiolating reagent. These oxidative trifluoromethylation and trifluoromethylthiolation reactions tolerate a wide range of functional groups, affording a diverse array of CF3- and CF3S-containing compounds with high efficiencies, and provide elegant and complementary alternatives to classical trifluoromethylation and trifluoromethylthiolation reactions. Because of the importance of the CF3 and SCF3 moieties in pharmaceuticals and agrochemicals, these reactions would have potential applications in the life science fields.

Greenhouse gas microbiology in wet and dry straw crust covering pig slurry.

PubMed

Hansen, Rikke R; Nielsen, Daniel Aa; Schramm, Andreas; Nielsen, Lars P; Revsbech, Niels P; Hansen, Martin N

2009-01-01

Liquid manure (slurry) storages are sources of gases such as ammonia (NH(3)) and methane (CH(4)). Danish slurry storages are required to be covered to reduce NH(3) emissions and often a floating crust of straw is applied. This study investigated whether physical properties of the crust or crust microbiology had an effect on the emission of the potent greenhouse gases CH(4) and nitrous oxide (N(2)O) when crust moisture was manipulated ("dry", "moderate", and "wet"). The dry crust had the deepest oxygen penetration (45 mm as compared to 20 mm in the wet treatment) as measured with microsensors, the highest amounts of nitrogen oxides (NO(2)(-) and NO(3)(-)) (up to 36 mumol g(-1) wet weight) and the highest emissions of N(2)O and CH(4). Fluorescent in situ hybridization and gene-specific polymerase chain reaction (PCR) were used to detect occurrence of bacterial groups. Ammonia-oxidizing bacteria (AOB) were abundant in all three crust types, whereas nitrite-oxidizing bacteria (NOB) were undetectable and methane-oxidizing bacteria (MOB) were only sparsely present in the wet treatment. A change to anoxia did not affect the CH(4) emission indicating the virtual absence of aerobic methane oxidation in the investigated 2-mo old crusts. However, an increase in N(2)O emission was observed in all crusted treatments exposed to anoxia, and this was probably a result of denitrification based on NO(x)(-) that had accumulated in the crust during oxic conditions. To reduce overall greenhouse gas emissions, floating crust should be managed to optimize conditions for methanotrophs.

Agriculture's impact on microbial diversity and associated fluxes of carbon dioxide and methane

PubMed Central

Levine, Uri Y; Teal, Tracy K; Robertson, G Philip; Schmidt, Thomas M

2011-01-01

Agriculture has marked impacts on the production of carbon dioxide (CO2) and consumption of methane (CH4) by microbial communities in upland soils—Earth's largest biological sink for atmospheric CH4. To determine whether the diversity of microbes that catalyze the flux of these greenhouse gases is related to the magnitude and stability of these ecosystem-level processes, we conducted molecular surveys of CH4-oxidizing bacteria (methanotrophs) and total bacterial diversity across a range of land uses and measured the in situ flux of CH4 and CO2 at a site in the upper United States Midwest. Conversion of native lands to row-crop agriculture led to a sevenfold reduction in CH4 consumption and a proportionate decrease in methanotroph diversity. Sites with the greatest stability in CH4 consumption harbored the most methanotroph diversity. In fields abandoned from agriculture, the rate of CH4 consumption increased with time along with the diversity of methanotrophs. Conversely, estimates of total bacterial diversity in soil were not related to the rate or stability of CO2 emission. These combined results are consistent with the expectation that microbial diversity is a better predictor of the magnitude and stability of processes catalyzed by organisms with highly specialized metabolisms, like CH4 oxidation, as compared with processes driven by widely distributed metabolic processes, like CO2 production in heterotrophs. The data also suggest that managing lands to conserve or restore methanotroph diversity could mitigate the atmospheric concentrations of this potent greenhouse gas. PMID:21490688

Methanesulfonates of high-valent metals: syntheses and structural features of MoO2(CH3SO3)2, UO2(CH3SO3)2, ReO3(CH3SO3), VO(CH3SO3)2, and V2O3(CH3SO3)4 and their thermal decomposition under N2 and O2 atmosphere.

PubMed

Betke, Ulf; Neuschulz, Kai; Wickleder, Mathias S

2011-11-04

Oxide methanesulfonates of Mo, U, Re, and V have been prepared by reaction of MoO(3), UO(2)(CH(3)COO)(2)·2H(2)O, Re(2)O(7)(H(2)O)(2), and V(2)O(5) with CH(3)SO(3)H or mixtures thereof with its anhydride. These compounds are the first examples of solvent-free oxide methanesulfonates of these elements. MoO(2)(CH(3)SO(3))(2) (Pbca, a=1487.05(4), b=752.55(2), c=1549.61(5) pm, V=1.73414(9) nm(3), Z=8) contains [MoO(2)] moieties connected by [CH(3)SO(3)] ions to form layers parallel to (100). UO(2)(CH(3)SO(3))(2) (P2(1)/c, a=1320.4(1), b=1014.41(6), c=1533.7(1) pm, β=112.80(1)°, V=1.8937(3) nm(3), Z=8) consists of linear UO(2)(2+) ions coordinated by five [CH(3)SO(3)] ions, forming a layer structure. VO(CH(3)SO(3))(2) (P2(1)/c, a=1136.5(1), b=869.87(7), c=915.5(1) pm, β=113.66(1)°, V=0.8290(2) nm(3), Z=4) contains [VO] units connected by methanesulfonate anions to form corrugated layers parallel to (100). In ReO(3)(CH(3)SO(3)) (P1, a=574.0(1), b=1279.6(3), c=1641.9(3) pm, α=102.08(2), β=96.11(2), γ=99.04(2)°, V=1.1523(4) nm(3), Z=8) a chain structure exhibiting infinite O-[ReO(2)]-O-[ReO(2)]-O chains is formed. Each [ReO(2)]-O-[ReO(2)] unit is coordinated by two bidentate [CH(3)SO(3)] ions. V(2)O(3)(CH(3)SO(3))(4) (I2/a, a=1645.2(3), b=583.1(1), c=1670.2(3) pm, β=102.58(3), V=1.5637(5) pm(3), Z=4) adopts a chain structure, too, but contains discrete [VO]-O-[VO] moieties, each coordinated by two bidentate [CH(3)SO(3)] ligands. Additional methanesulfonate ions connect the [V(2)O(3)] groups along [001]. Thermal decomposition of the compounds was monitored under N(2) and O(2) atmosphere by thermogravimetric/differential thermal analysis and XRD measurements. Under N(2) the decomposition proceeds with reduction of the metal leading to the oxides MoO(2), U(3)O(7), V(4)O(7), and VO(2); for MoO(2)(CH(3)SO(3))(2), a small amount of MoS(2) is formed. If the thermal decomposition is carried out in a atmosphere of O(2) the oxides MoO(3) and V(2)O(5) are formed. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Aircraft emissions of methane and nitrous oxide during the alternative aviation fuel experiment.

PubMed

Santoni, Gregory W; Lee, Ben H; Wood, Ezra C; Herndon, Scott C; Miake-Lye, Richard C; Wofsy, Steven C; McManus, J Barry; Nelson, David D; Zahniser, Mark S

2011-08-15

Given the predicted growth of aviation and the recent developments of alternative aviation fuels, quantifying methane (CH(4)) and nitrous oxide (N(2)O) emission ratios for various aircraft engines and fuels can help constrain projected impacts of aviation on the Earth's radiative balance. Fuel-based emission indices for CH(4) and N(2)O were quantified from CFM56-2C1 engines aboard the NASA DC-8 aircraft during the first Alternative Aviation Fuel Experiment (AAFEX-I) in 2009. The measurements of JP-8 fuel combustion products indicate that at low thrust engine states (idle and taxi, or 4% and 7% maximum rated thrusts, respectively) the engines emit both CH(4) and N(2)O at a mean ± 1σ rate of 170 ± 160 mg CH(4) (kg Fuel)(-1) and 110 ± 50 mg N(2)O (kg Fuel)(-1), respectively. At higher thrust levels corresponding to greater fuel flow and higher engine temperatures, CH(4) concentrations in engine exhaust were lower than ambient concentrations. Average emission indices for JP-8 fuel combusted at engine thrusts between 30% and 100% of maximum rating were -54 ± 33 mg CH(4) (kg Fuel)(-1) and 32 ± 18 mg N(2)O (kg Fuel)(-1), where the negative sign indicates consumption of atmospheric CH(4) in the engine. Emission factors for the synthetic Fischer-Tropsch fuels were statistically indistinguishable from those for JP-8.

Effects of ferric iron reduction and regeneration on nitrous oxide and methane emissions in a rice soil.

PubMed

Huang, Bin; Yu, Kewei; Gambrell, Robert P

2009-01-01

A laboratory soil slurry experiment and an outdoor pot experiment were conducted to study effects of ferric iron (Fe(III)) reduction and regeneration on nitrous oxide (N(2)O) and methane (CH(4)) emissions in a rice (Oryza sativa L.) soil. The anoxic slurry experiment showed that enhancing microbial Fe(III) reduction by ferrihydrite amendment (40 mol Fe g(-1)) transitionally stimulated N(2)O production and lowered CH(4) production by 16% during an initial 33-day incubation. Increased regeneration of Fe(III) through a 4-day aeration period in the Fe-amended slurry compared to the control slurry reduced CH(4) emission by 30% in the subsequent 15-day anaerobic incubation. The pot experiment showed that ferrihydrite amendment (63 micromol Fe g(-1)) stimulated N(2)O fluxes in the days following flooding. The Fe amendment suppression on CH(4) emission was obscured in the early season but became significant upon reflooding in the mid- and late-seasons. As a result, seasonal CH(4) emission in Fe-amended pots was 26% lower than the control with a single 2-day drainage and 69% lower with a double 2-day drainage. The reduction in CH(4) emission upon reflooding from the Fe-amended pots was mainly attributed to the increased Fe(III) regeneration during drainage showing a mechanism of Fe(III) regeneration in mitigating CH(4) emission by short-term drainage in flooded soils.

Intensification of oxidation capacity using chloroalkanes as additives in hydrodynamic and acoustic cavitation reactors.

PubMed

Chakinala, Anand G; Gogate, Parag R; Chand, Rashmi; Bremner, David H; Molina, Raúl; Burgess, Arthur E

2008-03-01

The effect of the presence and absence of the chloroalkanes, dichloromethane (CH(2)Cl(2)), chloroform (CHCl(3)) and carbon tetrachloride (CCl(4)) on the extent of oxidation of aqueous I(-) to I(3)(-) has been investigated in (a) a liquid whistle reactor (LWR) generating hydrodynamic cavitation and (b) an ultrasonic probe, which produces acoustic cavitation. The aim has been to examine the intensification achieved in the extent of oxidation due to the generation of additional free radicals/oxidants in the reactor as a result of the presence of chloroalkanes. It has been observed that the extent of increase in the oxidation reaction is strongly dependent on the applied pressure in the case of the LWR. Also, higher volumes of the chloroalkanes favour the intensification and the order of effectiveness is CCl(4)>CHCl(3)>CH(2)Cl(2). However, the results with the ultrasonic probe suggest that an optimum concentration of CH(2)Cl(2) or CHCl(3) exists beyond which there is little increase in the extent of observed intensification. For CCl(4), however, no such optimum concentration was observed and the extent of increase in the rates of oxidation reaction rose with the amount of CCl(4) added. Stage wise addition of the chloroalkanes was found to give marginally better results in the case of the ultrasonic probe as compared to bulk addition at the start of the run. Although CCl(4) is the most effective, its toxicity and carcinogenicity may mean that CH(2)Cl(2) and CHCl(3) offer a safer viable alternative and the present work should be useful in establishing the amount of chloroalkanes required for obtaining a suitable degree of intensification.

Methane oxidation and attenuation of sulphur compounds in landfill top cover systems: Lab-scale tests.

PubMed

Raga, Roberto; Pivato, Alberto; Lavagnolo, Maria Cristina; Megido, Laura; Cossu, Raffaello

2018-03-01

In this study, a top cover system is investigated as a control for emissions during the aftercare of new landfills and for old landfills where biogas energy production might not be profitable. Different materials were studied as landfill cover system in lab-scale columns: mechanical-biological pretreated municipal solid waste (MBP); mechanical-biological pretreated biowaste (PB); fine (PBS f ) and coarse (PBS c ) mechanical-biological pretreated mixtures of biowaste and sewage sludge, and natural soil (NS). The effectiveness of these materials in removing methane and sulphur compounds from a gas stream was tested, even coupled with activated carbon membranes. Concentrations of CO 2 , CH 4 , O 2 , N 2 , H 2 S and mercaptans were analysed at different depths along the columns. Methane degradation was assessed using mass balance and the results were expressed in terms of methane oxidation rate (MOR). The highest maximum and mean MOR were observed for MBP (17.2gCH 4 /m 2 /hr and 10.3gCH 4 /m 2 /hr, respectively). Similar values were obtained with PB and PBS c . The lowest values of MOR were obtained for NS (6.7gCH 4 /m 2 /hr) and PBS f (3.6gCH 4 /m 2 /hr), which may be due to their low organic content and void index, respectively. Activated membranes with high load capacity did not seem to have an influence on the methane oxidation process: MBP coupled with 220g/m 2 and 360g/m 2 membranes gave maximum MOR of 16.5gCH 4 /m 2 /hr and 17.4gCH 4 /m 2 /hr, respectively. Activated carbon membranes proved to be very effective on H 2 S adsorption. Furthermore, carbonyl sulphide, ethyl mercaptan and isopropyl mercaptan seemed to be easily absorbed by the filling materials. Copyright © 2017. Published by Elsevier B.V.

Nitrous oxide and methane in the Atlantic Ocean between 50°N and 52°S: Latitudinal distribution and sea-to-air flux

NASA Astrophysics Data System (ADS)

Forster, Grant; Upstill-Goddard, Rob C.; Gist, Niki; Robinson, Carol; Uher, Gunther; Woodward, E. Malcolm S.

2009-07-01

We discuss nitrous oxide (N 2O) and methane (CH 4) distributions in 49 vertical profiles covering the upper ˜300 m of the water column along two ˜13,500 km transects between ˜50°N and ˜52°S during the Atlantic Meridional Transect (AMT) programme (AMT cruises 12 and 13). Vertical N 2O profiles were amenable to analysis on the basis of common features coincident with Longhurst provinces. In contrast, CH 4 showed no such pattern. The most striking feature of the latitudinal depth distributions was a well-defined "plume" of exceptionally high N 2O concentrations coincident with very low levels of CH 4, located between ˜23.5°N and ˜23.5°S; this feature reflects the upwelling of deep waters containing N 2O derived from nitrification, as identified by an analysis of N 2O, apparent oxygen utilization (AOU) and NO 3-, and presumably depleted in CH 4 by bacterial oxidation. Sea-to-air emissions fluxes for a region equivalent to ˜42% of the Atlantic Ocean surface area were in the range 0.40-0.68 Tg N 2O yr -1 and 0.81-1.43 Tg CH 4 yr -1. Based on contemporary estimates of the global ocean source strengths of atmospheric N 2O and CH 4, the Atlantic Ocean could account for ˜6-15% and 4-13%, respectively, of these source totals. Given that the Atlantic Ocean accounts for around 20% of the global ocean surface, on unit area basis it appears that the Atlantic may be a slightly weaker source of atmospheric N 2O than other ocean regions but it could make a somewhat larger contribution to marine-derived atmospheric CH 4 than previously thought.

Combustion modeling and performance evaluation in a full-scale rotary kiln incinerator.

PubMed

Chen, K S; Hsu, W T; Lin, Y C; Ho, Y T; Wu, C H

2001-06-01

This work summarizes the results of numerical investigations and in situ measurements for turbulent combustion in a full-scale rotary kiln incinerator (RKI). The three-dimensional (3D) governing equations for mass, momentum, energy, and species, together with the kappa - epsilon turbulence model, are formulated and solved using a finite volume method. Volatile gases from solid waste were simulated by gaseous CH4 distributed nonuniformly along the kiln bed. The combustion process was considered to be a two-step stoichiometric reaction for primary air mixed with CH4 gas in the combustion chamber. The mixing-controlled eddy-dissipation model (EDM) was employed to predict the conversion rates of CH4, O2, CO2, and CO. The results of the prediction show that reverse flows occur near the entrance of the first combustion chamber (FCC) and the turning point at the entrance to the second combustion chamber (SCC). Temperature and species are nonuniform and are vertically stratified. Meanwhile, additional mixing in the SCC enhances postflame oxidation. A combustion efficiency of up to 99.96% can be achieved at approximately 150% excess air and 20-30% secondary air. Reasonable agreement is achieved between numerical predictions and in situ measurements.

Radical Cation Salt-initiated Aerobic C-H Phosphorylation of N-Benzylanilines: Synthesis of a-Aminophosphonates.

PubMed

Jia, Xiao Dong; Liu, Xiaofei; Yuan, Yu; Li, Pengfei; Hou, Wentao; He, Kaixuan

2018-06-03

A radical cation salt-initiated phosphorylation of N-benzylanilines was realized through the aerobic oxidation of sp3 C-H bond, providing a series of α-aminophosphonates in high yields. The investigation of the reaction scope revealed that this mild catalyst system is superior in good functional group tolerance and high reaction efficiency. The mechanistic study implied that the cleavage of the sp3 C-H bond was involved in the rate-determining step. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Quantification of atmospheric methane oxidation in glacier forefields: Initial survey results

NASA Astrophysics Data System (ADS)

Nauer, Philipp A.; Schroth, Martin H.; Pinto, Eric A.; Zeyer, Josef

2010-05-01

The oxidation of CH4 by methanotrophic bacteria is the only known terrestrial sink for atmospheric CH4. Aerobic methanotrophs are active in soils and sediments under various environmental conditions. However, little is known about the activity and abundance of methanotrophs in pioneering ecosystems and their role in succession. In alpine environments, receding glaciers pose a unique opportunity to investigate soil development and ecosystem succession. In an initial survey during summer and autumn 2009 we probed several locations in the forefields of four glaciers in the Swiss Alps to quantify the turnover of atmospheric methane in recently exposed soils. Three glacier forefields (the Stein, Steinlimi and Tiefen) are situated on siliceous bedrock, while one (the Griessen) is situated on calcareous bedrock. We sampled soil air from different depths to generate CH4 concentration profiles for qualitative analysis. At selected locations we applied surface Gas Push-Pull Tests (GPPT) to estimate first-order rate coefficients of CH4 oxidation. The test consists of a controlled injection of the reactants CH4 and O2 and the tracer Ar into and out of the soil at the same location. A top-closed steel cylinder previously emplaced in the soil encloses the injected gas mixture to ensure sufficient reaction times. Rate coefficients can be derived from differences of reactant and tracer breakthrough curves. In one GPPT we employed 13C-CH4 and measured the evolution of δ13C of extracted CO2. To confirm rate coefficients obtained by GPPTs we estimated effective soil diffusivity from soil core samples and fitted a diffusion-consumption model to our profile data. A qualitative analysis of the concentration profiles showed little activity in the forefields on siliceous bedrock, with only one out of fifteen locations exhibiting substantially lower CH4 concentrations in the soil compared to the atmosphere. The surface GPPTs with conventional CH4 at the active location were not sensitive enough to derive meaningful first-order rate coefficients of CH4 oxidation. The more sensitive GPPT with 13C-CH4 resulted in a coefficient of 0.025 h-1, close to the value of 0.011 h-1 estimated from the corresponding concentration profile. Activities in the forefield on calcareous bedrock were substantially higher, with decreased CH4 concentrations in the soil at three out of five locations. Estimated first-order rate coefficients from GPPT and profile at one selected location were 0.6 h-1 and 1.3 h-1, respectively, one to two orders of magnitude higher than values from the siliceous forefield. Additional analysis by quantitative PCR revealed substantially lower numbers of pmoA gene copies per g soil at the active location in the siliceous forefield compared to the selected location in the calcareous forefield. Reasons for these differences in activity and abundance are still unknown and will be subject of further investigations in an upcoming field campaign. The GPPT in combination with δ13C analysis of extracted CO2 appeared to be a functioning approach to sensitively quantify low CH4 turnover.

Time-series measurements of methane (CH4) distribution during open water and ice-cover in lakes throughout the Mackenzie River Delta (Canada)

NASA Astrophysics Data System (ADS)

McIntosh, H.; Lapham, L.; Orcutt, B.; Wheat, C. G.; Lesack, L.; Bergstresser, M.; Dallimore, S. R.; MacLeod, R.; Cote, M.

2016-12-01

Arctic lakes are known to emit large amounts of methane to the atmosphere and their importance to the global methane (CH4) cycle has been recognized. It is well known CH4 builds up in Arctic lakes during ice-cover, but the amount of and when the CH4 is released to the atmosphere is not well known. Our preliminary results suggest the largest flux of CH4 from lakes to the atmosphere occurs slightly before complete ice-out; while others have shown the largest flux occurs when lakes overturn in the spring. During ice-out, CH4 can also be oxidized by methane oxidizing bacteria before it can efflux to the atmosphere from the surface water. In order to elucidate the processes contributing to Arctic lake CH4 emissions, continuous, long-term and large scale spatial sampling is required; however it is difficult to achieve in these remote locations. We address this problem using two sampling techniques. 1) We deployed osmotically powered pumps (OsmoSamplers), which were able to autonomously and continuously collect lake bottom water over the course of a year from multiple lakes in the Mackenzie River Delta. OsmoSamplers were placed in four lakes in the mid Delta near Inuvik, Northwest Territories, Canada, two lakes in the outer Delta, and two coastal lakes on Richard's Island in 2015. The dissolved CH4 concentration, stable isotope content of CH4 (δ13C-CH4), and dissolved sulfate concentrations in bottom water from these lakes will be presented to better understand methane dynamics under the ice and over time. 2) Along with the time-series data, we will also present data from discrete samples collected from 40 lakes in the mid Delta during key time periods, before and immediately after the spring ice-out. By determining the CH4 dynamics throughout the year we hope to improve predictions of how CH4 emissions may change in a warming Arctic environment.

Methane and nitrous oxide emissions from livestock agriculture in 16 local administrative districts of Korea.

PubMed

Ji, Eun Sook; Park, Kyu-Hyun

2012-12-01

This study was conducted to evaluate methane (CH4) and nitrous oxide (N2O) emissions from livestock agriculture in 16 local administrative districts of Korea from 1990 to 2030. National Inventory Report used 3 yr averaged livestock population but this study used 1 yr livestock population to find yearly emission fluctuations. Extrapolation of the livestock population from 1990 to 2009 was used to forecast future livestock population from 2010 to 2030. Past (yr 1990 to 2009) and forecasted (yr 2010 to 2030) averaged enteric CH4 emissions and CH4 and N2O emissions from manure treatment were estimated. In the section of enteric fermentation, forecasted average CH4 emissions from 16 local administrative districts were estimated to increase by 4%-114% compared to that of the past except for Daejeon (-63%), Seoul (-36%) and Gyeonggi (-7%). As for manure treatment, forecasted average CH4 emissions from the 16 local administrative districts were estimated to increase by 3%-124% compared to past average except for Daejeon (-77%), Busan (-60%), Gwangju (-48%) and Seoul (-8%). For manure treatment, forecasted average N2O emissions from the 16 local administrative districts were estimated to increase by 10%-153% compared to past average CH4 emissions except for Daejeon (-60%), Seoul (-4.0%), and Gwangju (-0.2%). With the carbon dioxide equivalent emissions (CO2-Eq), forecasted average CO2-Eq from the 16 local administrative districts were estimated to increase by 31%-120% compared to past average CH4 emissions except Daejeon (-65%), Seoul (-24%), Busan (-18%), Gwangju (-8%) and Gyeonggi (-1%). The decreased CO2-Eq from 5 local administrative districts was only 34 kt, which was insignificantly small compared to increase of 2,809 kt from other 11 local administrative districts. Annual growth rates of enteric CH4 emissions, CH4 and N2O emissions from manure management in Korea from 1990 to 2009 were 1.7%, 2.6%, and 3.2%, respectively. The annual growth rate of total CO2-Eq was 2.2%. Efforts by the local administrative offices to improve the accuracy of activity data are essential to improve GHG inventories. Direct measurements of GHG emissions from enteric fermentation and manure treatment systems will further enhance the accuracy of the GHG data. (Key Words: Greenhouse Gas, Methane, Nitrous Oxide, Carbon Dioxide Equivalent Emission, Climate Change).

Effects of aeration method and aeration rate on greenhouse gas emissions during composting of pig feces in pilot scale.

PubMed

Jiang, Tao; Li, Guoxue; Tang, Qiong; Ma, Xuguang; Wang, Gang; Schuchardt, Frank

2015-05-01

The aim of this study was to uncover ways to mitigate greenhouse gas (GHG) emissions and reduce energy consumption during the composting process. We assessed the effects of different aeration rates (0, 0.18, 0.36, and 0.54 L/(kg dry matter (dm)·min)) and methods (continuous and intermittent) on GHG emissions. Pig feces and corn stalks were mixed at a ratio of 7:1. The composting process lasted for 10 weeks, and the compost was turned approximately every 2 weeks. Results showed that both aeration rate and method significantly affected GHG emissions. Higher aeration rates increased NH3 and N2O losses, but reduced CH4 emissions. The exception is that the CH4 emission of the passive aeration treatment was lower than that of the low aeration rate treatment. Without forced aeration, the CH4 diffusion rates in the center of the piles were very low and part of the CH4 was oxidized in the surface layer. Intermittent aeration reduced NH3 and CH4 losses, but significantly increased N2O production during the maturing periods. Intermittent aeration increased the nitrification/denitrification alternation and thus enhanced the N2O production. Forced aeration treatments had higher GHG emission rates than the passive aeration treatment. Forced aeration accelerated the maturing process, but could not improve the quality of the end product. Compared with continuous aeration, intermittent aeration could increase the O2 supply efficiency and reduced the total GHG emission by 17.8%, and this reduction increased to 47.4% when composting was ended after 36 days. Copyright © 2015. Published by Elsevier B.V.

Membrane protein resistance of oligo(ethylene oxide) self-assembled monolayers.

PubMed

Vaish, Amit; Vanderah, David J; Vierling, Ryan; Crawshaw, Fay; Gallagher, D Travis; Walker, Marlon L

2014-10-01

As part of an effort to develop biointerfaces for structure-function studies of integral membrane proteins (IMPs) a series of oligo(ethylene oxide) self-assembled monolayers (OEO-SAMs) were evaluated for their resistance to protein adsorption (RPA) of IMPs on Au and Pt. Spectroscopic ellipsometry (SE) was used to determine SAM thicknesses and compare the RPA of HS(CH2)3O(CH2CH2O)6CH3 (1), HS(CH2)3O(CH2CH2O)6H (2), [HS(CH2)3]2CHO(CH2CH2O)6CH3 (3) and [HS(CH2)3]2CHO(CH2CH2O)6H (4), assembled from water. For both substrates, SAM thicknesses for 1 to 4 were found to be comparable indicating SAMs with similar surface coverages and OEO chain order and packing densities. Fibrinogen (Fb), a soluble plasma protein, and rhodopsin (Rd), an integral membrane G-protein coupled receptor, adsorbed to the SAMs of 1, as expected from previous reports, but not to the hydroxy-terminated SAMs of 2 and 4. The methoxy-terminated SAMs of 3 were resistant to Fb but, surprisingly, not to Rd. The stark difference between the adsorption of Rd to the SAMs of 3 and 4 clearly indicate that a hydroxy-terminus of the OEO chain is essential for high RPA of IMPs. The similar thicknesses and high RPA of the SAMs of 2 and 4 show the conditions of protein resistance (screening the underlying substrate, packing densities, SAM order, and conformational mobility of the OEO chains) defined from previous studies on Au are applicable to Pt. In addition, the SAMs of 4, exhibiting the highest resistance to Fb and Rd, were placed in contact with undiluted fetal bovine serum for 2h. Low protein adsorption (≈12.4ng/cm(2)), obtained under these more challenging conditions, denote a high potential of the SAMs of 4 for various applications requiring the suppression of non-specific protein adsorption. Published by Elsevier B.V.

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

NASA Astrophysics Data System (ADS)

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

2012-12-01

Aerobic methane oxidation limits atmospheric methane emissions from degraded subsea permafrost and dissociated methane hydrates in high latitude oceans. Methane oxidation rate measurements are a crucial tool for investigating the efficacy of this process, but are logistically challenging when working on small research vessels in remote settings. We modified a low-level 14C-CH4 oxidation rate measurement for use in the Beaufort Sea above hydrate bearing sediments during August 2012. Application of the more common 3H-CH4 rate measurement that uses 106 times more radioactivity was not practical because the R/V Ukpik cannot accommodate a radiation van. The low-level 14C measurement does not require a radiation van, but careful isolation of the 14C-label is essential to avoid contaminating natural abundance 14C measurements. We used 14C-CH4 with a total activity of 1.1 μCi, which is far below the 100 μCi permitting level. In addition, we modified field procedures to simplify and shorten sample processing. The original low-level 14C-CH4 method requires 6 steps in the field: (1) collect water samples in glass serum bottles, (2) inject 14C-CH4 into bottles, (3) incubate for 24 hours, (4) filter to separate the methanotrophic bacterial cells from the aqueous sample, (5) kill the filtrate with sodium hydroxide (NaOH), and (6) purge with nitrogen to remove unused 14C-CH4. Onshore, the 14C-CH4 respired to carbon dioxide or incorporated into cell material by methanotrophic bacteria during incubation is quantified by accelerator mass spectrometry (AMS). We conducted an experiment to test the possibility of storing samples for purging and filtering back onshore (steps 4 and 6). We subjected a series of water samples to steps 1-3 & 5, and preserved with mercuric chloride (HgCl2) instead of NaOH because HgCl2 is less likely to break down cell material during storage. The 14C-content of the carbon dioxide in samples preserved with HgCl2 and stored for up to 2 weeks was stable, showing that oxidation of 14C-CH4 did not occur during storage. On the other hand, the 14C-content of the cell material decreased during storage, and the total carbon content of the filtered biomass decreased by 20% in the first 3 days. These results show that: [1] step 6 can be performed onshore because HgCl2 is an effective preservative even when unused 14C-CH4 is not removed, and [2] cell material is not stable in HgCl2 preserved samples, so filtering (step 4) must take place in the field. Next, we attempted to simplify the field filtering procedure by incubating samples in plastic syringes, and then filtering through a luer lock filter holder connected to the syringe. However, syringe incubated samples yielded oxidation rates up to 27 times slower than those in glass bottles, and demonstrated that plastic syringes are not suitable for incubating samples. Thus, we devised a technique to filter directly from sample bottles, through a syringe filter holder, and into an evacuated glass serum bottle in one step. Overall, we were able to simplify the field protocol to work on small vessels in remote field settings without compromising data quality.

Changes in soil moisture drive soil methane uptake along a fire regeneration chronosequence in a eucalypt forest landscape.

PubMed

Fest, Benedikt; Wardlaw, Tim; Livesley, Stephen J; Duff, Thomas J; Arndt, Stefan K

2015-11-01

Disturbance associated with severe wildfires (WF) and WF simulating harvest operations can potentially alter soil methane (CH4 ) oxidation in well-aerated forest soils due to the effect on soil properties linked to diffusivity, methanotrophic activity or changes in methanotrophic bacterial community structure. However, changes in soil CH4 flux related to such disturbances are still rarely studied even though WF frequency is predicted to increase as a consequence of global climate change. We measured in-situ soil-atmosphere CH4 exchange along a wet sclerophyll eucalypt forest regeneration chronosequence in Tasmania, Australia, where the time since the last severe fire or harvesting disturbance ranged from 9 to >200 years. On all sampling occasions, mean CH4 uptake increased from most recently disturbed sites (9 year) to sites at stand 'maturity' (44 and 76 years). In stands >76 years since disturbance, we observed a decrease in soil CH4 uptake. A similar age dependency of potential CH4 oxidation for three soil layers (0.0-0.05, 0.05-0.10, 0.10-0.15 m) could be observed on incubated soils under controlled laboratory conditions. The differences in soil CH4 uptake between forest stands of different age were predominantly driven by differences in soil moisture status, which affected the diffusion of atmospheric CH4 into the soil. The observed soil moisture pattern was likely driven by changes in interception or evapotranspiration with forest age, which have been well described for similar eucalypt forest systems in south-eastern Australia. Our results imply that there is a large amount of variability in CH4 uptake at a landscape scale that can be attributed to stand age and soil moisture differences. An increase in severe WF frequency in response to climate change could potentially increase overall forest soil CH4 sinks. © 2015 John Wiley & Sons Ltd.

Seasonal greenhouse gas emissions (methane, carbon dioxide, nitrous oxide) from engineered landfills: Daily, intermediate, and final California cover soils

USDA-ARS?s Scientific Manuscript database

We quantified the seasonal variability of CH4, CO2, and N2O emissions from fresh refuse and daily, intermediate, and final cover materials at two California landfills. Fresh refuse fluxes (g m-2 d-1) averaged CH4 0.053[+/-0.03], CO2 135[+/-117], and N2O 0.063[+/-0.059]. Average CH4 emissions across ...

Methane production and consumption monitored by stable H and C isotope ratios at a crude oil spill site, Bemidji, Minnesota

USGS Publications Warehouse

Revesz, Kinga; Coplen, Tyler B.; Baedecker, Mary J.; Glynn, Pierre D.

1995-01-01

Stable isotopic ratios of C and H in dissolved CH4 and C in dissolved inorganic C in the ground water of a crude-oil spill near Bemidji, Minnesota, support the concept of CH4production by acetate fermentation with a contemporaneous increase in HCO3−concentration. Methane concentrations in the saturated zone decrease from 20.6 mg L−1 to less than 0.001 mg L−1 along the investigated flow path. Dissolved N2 and Ar concentrations in the ground water below the oil plume are 25 times lower than background; this suggests that gas exsolution is removing dissolved CH4 (along with other dissolved gases) from the ground water. Oxidation of dissolved CH4 along the flow path seems to be minimal because no measurable change in isotopic composition of CH4 occurs with distance from the oil body. However, CH4 is partly oxidized to CO2 as it diffuses upward from the ground water through a 5- to 7-m thick unsaturated zone; theδ13C of the remaining CH4 increases, theδ13C of the CO2 decreases, and the partial pressure of CO2 increases.Calculations of C fluxes in the saturated and unsaturated zones originating from the degradation of the oil plume lead to a minimum estimated life expectancy of 110 years. This is a minimum estimate because the degradation of the oil body should slow down with time as its more volatile and reactive components are leached out and preferentially oxidized. The calculated life expectancy is an order of magnitude estimate because of the uncertainty in the average linear ground-water velocities and because of the factor of 2 uncertainty in the calculation of the effective CO2 diffusion coefficient.

Effects of organic nitrification inhibitors on methane and nitrous oxide emission from tropical rice paddy

NASA Astrophysics Data System (ADS)

Datta, A.; Adhya, T. K.

2014-08-01

We have studied the effects of application of different nitrification inhibitors on methane (CH4) and nitrous oxide (N2O) emissions from rice paddy and associated soil chemical and biological dynamics during wet and dry seasons of rice crop in a tropical climate of eastern India. The experiment consisted of four treatments viz. (i) Prilled urea amended control (ii) urea + Dicyandiamide (DCD), (iii) urea + Nimin and (iv) urea + Karanjin. CH4 emission was significantly higher from the DCD (372.36 kg ha-1) and Karanjin (153.07 kg ha-1) applied plots during the wet and dry season, respectively. N2O emission was significantly inhibited in the Nimin applied plots during both seasons (69% and 85% over control during wet season and dry season respectively). CH4 and N2O emissions per Mg of rice grain yield were lowest from the Nimin applied plots during both seasons. Global warming potential (GWP) of the plot treated with DCD (13.93) was significantly higher during the experimental period. CH4 production potential was significantly higher from the nitrification inhibitor applied plots compared to control. While, CH4 oxidation potential followed the order; urea + Nimin > urea + Karanjin > urea + DCD > control. Application of Nimin significantly increased the methanotrophic bacterial population in the soil during the maximum tillering to flowering stage and may be attributed to low CH4 emission from the plots. Denitrification enzyme activity (DEA) of the soil was significantly low from the Nimin and Karanjin applied plots. Results suggest that apart from being potent nitrification inhibitors, Nimin and Karanjin also have the potential to reduce the denitrification activity in the soil. This in turn, would reduce N2O emission from flooded paddy where both nitrification and denitrification processes causes N2O emission.

Effects of CH3OH Addition on Plasma Electrolytic Oxidation of AZ31 Magnesium Alloys

NASA Astrophysics Data System (ADS)

He, Yongyi; Chen, Li; Yan, Zongcheng; Zhang, Yalei

2015-09-01

Plasma electrolytic oxidation (PEO) films on AZ31 magnesium alloys were prepared in alkaline silicate electrolytes (base electrolyte) with the addition of different volume concentrations of CH3OH, which was used to adjust the thickness of the vapor sheath. The compositions, morphologies, and thicknesses of ceramic layers formed with different CH3OH concentrations were determined via X-ray diffraction (XRD), energy-dispersive spectroscopy (EDS), and scanning electron microscopy (SEM). Corrosion behavior of the oxide films was evaluated in 3.5 wt.% NaCl solution using potentiodynamic polarization tests. PEO coatings mainly comprised Mg, MgO, and Mg2SiO4. The addition of CH3OH in base electrolytes affected the thickness, pores diameter, and Mg2SiO4 content in the films. The films formed in the electrolyte containing 12% CH3OH exhibited the highest thickness. The coatings formed in the electrolyte containing different concentrations of CH3OH exhibited similar corrosion resistance. The energy consumption of PEO markedly decreased upon the addition of CH3OH to the electrolytes. The result is helpful for energy saving in the PEO process. supported by National Natural Science Foundation of China (No. 21376088), the Project of Production, Education and Research, Guangdong Province and Ministry of Education (Nos. 2012B09100063, 2012A090300015), and Guangzhou Science and Technology Plan Projects of China (No. 2014Y2-00042)

Impact of an historic underground gas well blowout on the current methane chemistry in a shallow groundwater system

PubMed Central

Schout, Gilian; Hartog, Niels; Hassanizadeh, S. Majid; Griffioen, Jasper

2018-01-01

Blowouts present a small but genuine risk when drilling into the deep subsurface and can have an immediate and significant impact on the surrounding environment. Nevertheless, studies that document their long-term impact are scarce. In 1965, a catastrophic underground blowout occurred during the drilling of a gas well in The Netherlands, which led to the uncontrolled release of large amounts of natural gas from the reservoir to the surface. In this study, the remaining impact on methane chemistry in the overlying aquifers was investigated. Methane concentrations higher than 10 mg/L (n = 12) were all found to have δ13C-CH4 values larger than −30‰, typical of a thermogenic origin. Both δ13C-CH4 and δD-CH4 correspond to the isotopic composition of the gas reservoir. Based on analysis of local groundwater flow conditions, this methane is not a remnant but most likely the result of ongoing leakage from the reservoir as a result of the blowout. Progressive enrichment of both δ13C-CH4 and δD-CH4 is observed with increasing distance and decreasing methane concentrations. The calculated isotopic fractionation factors of εC = 3 and εD = 54 suggest anaerobic methane oxidation is partly responsible for the observed decrease in concentrations. Elevated dissolved iron and manganese concentrations at the fringe of the methane plume show that oxidation is primarily mediated by the reduction of iron and manganese oxides. Combined, the data reveal the long-term impact that underground gas well blowouts may have on groundwater chemistry, as well as the important role of anaerobic oxidation in controlling the fate of dissolved methane. PMID:29279383

Methane Emissions from Semi-natural, Drained and Re-wetted Peatlands in Germany

NASA Astrophysics Data System (ADS)

Tiemeyer, B.; Bechtold, M.; Albiac Borraz, E.; Augustin, J.; Drösler, M.; Beetz, S.; Beyer, C.; Eickenscheidt, T.; Fiedler, S.; Förster, C.; Giebels, M.; Glatzel, S.; Heinichen, J.; Höper, H.; Leiber-Sauheitl, K.; Peichl-Brak, M.; Rosskopf, N.; Sommer, M.; Zeitz, J.; Freibauer, A.

2014-12-01

Drained peatlands contribute around 5% to the total German greenhouse gas emissions. While these areas are hotspots for carbon dioxide (CO2) and nitrous oxide (N2O) emissions, some re-wetted peatlands may emit large amounts of methane (CH4). To quantify the GHG emission reductions achieved by the re-wetting of peatlands, the reduced CO2 emissions and the potential CH4fluxes need to be balanced. We synthesized methane flux data from 14 peatlands with 122 sites. At each site, methane fluxes were measured for one to three years with static chambers. The sites comprise arable land, intensive and extensive grassland, forest and peat mining areas as well as semi-natural and re-wetted peatlands on both bog peat, fen peat and other soils rich in organic carbon. Besides the groundwater table we consider further potential drivers for the CH4fluxes such as soil properties (carbon, nitrogen, pH, and physical properties), climatic parameters, land use, and vegetation composition. Annual methane fluxes ranged from low uptake rates (around -1 g CH4-C m² a-1) to very high emissions (> 200 g CH4-C m² a-1). Intensively drained sites showed very low emissions, while for annual mean water levels higher than 5-10 cm below ground, elevated emissions of more than 20 g CH4-C may occur. At some re-wetted sites CH4 emissions of more than 100 g CH4-C m² a-1 were measured, which roughly equal the Global Warming Potential of the CO2-emissions from intensively drained agricultural sites. These high fluxes were probably caused by a combination of nutrient-rich conditions, the dieback of poorly adapted plants and a fast accumulation of organic sediments. However, this was the exception and not the rule even for very wet re-wetted sites. Achieving a model efficiency of 0.72 during cross-validation, a boosted regression tree (BRT) model was well able to describe logarithmic CH4-fluxes. Groundwater level, biotope type, soil nitrogen content, and ponding duration during summer were the most important controls. Combining the BRT model with soil, land use, and groundwater table maps as well as weather data, methane fluxes were upscaled for Germany.

Microbial Abundances Predict Methane and Nitrous Oxide Fluxes from a Windrow Composting System

PubMed Central

Li, Shuqing; Song, Lina; Gao, Xiang; Jin, Yaguo; Liu, Shuwei; Shen, Qirong; Zou, Jianwen

2017-01-01

Manure composting is a significant source of atmospheric methane (CH4) and nitrous oxide (N2O) that are two potent greenhouse gases. The CH4 and N2O fluxes are mediated by methanogens and methanotrophs, nitrifying and denitrifying bacteria in composting manure, respectively, while these specific bacterial functional groups may interplay in CH4 and N2O emissions during manure composting. To test the hypothesis that bacterial functional gene abundances regulate greenhouse gas fluxes in windrow composting systems, CH4 and N2O fluxes were simultaneously measured using the chamber method, and molecular techniques were used to quantify the abundances of CH4-related functional genes (mcrA and pmoA genes) and N2O-related functional genes (amoA, narG, nirK, nirS, norB, and nosZ genes). The results indicate that changes in interacting physicochemical parameters in the pile shaped the dynamics of bacterial functional gene abundances. The CH4 and N2O fluxes were correlated with abundances of specific compositional genes in bacterial community. The stepwise regression statistics selected pile temperature, mcrA and NH4+ together as the best predictors for CH4 fluxes, and the model integrating nirK, nosZ with pmoA gene abundances can almost fully explain the dynamics of N2O fluxes over windrow composting. The simulated models were tested against measurements in paddy rice cropping systems, indicating that the models can also be applicable to predicting the response of CH4 and N2O fluxes to elevated atmospheric CO2 concentration and rising temperature. Microbial abundances could be included as indicators in the current carbon and nitrogen biogeochemical models. PMID:28373862

Control of dissolved CH4 in a municipal UASB reactor effluent by means of a desorption - Biofiltration arrangement.

PubMed

Huete, A; de Los Cobos-Vasconcelos, D; Gómez-Borraz, T; Morgan-Sagastume, J M; Noyola, A

2018-06-15

The direct anaerobic treatment of municipal wastewater represents an adapted technology to the conditions of developing countries. In order to get an increased acceptance of this technology, a proper control of dissolved methane in the anaerobic effluents should be considered, as methane is a potent greenhouse gas. In this study, a pilot-scale system was operated for 168 days to recover dissolved methane from an effluent of an upflow anaerobic sludge blanket reactor and then oxidize it in a compost biofilter. The system operated at a constant air (0.9 m 3 /h ±0.09) and two air-to anaerobic effluent ratio (1:1 and 1:2). In both conditions (CH 4 concentration of 2.7 ± 0.87 and 4.3% ± 1.14, respectively) the desorption column recovered 99% of the dissolved CH 4 and approximately 30% ± 8.5 of H 2 S, whose desorption was limited due to the high pH (>8) of the effluent. The biofilter removed 70% ± 8 of the average CH 4 load (60 gCH 4 /m 3 h ± 13) and 100% of the H 2 S load at an empty bed retention time of 23 min. The average temperature inside the biofilter was 42 ± 9 °C due to the CH 4 oxidation reaction, indicating that temperature and moisture control is particularly important for CH 4 removal in compost biofilters. The system may achieve a 54% reduction of greenhouse gas emissions from dissolved CH 4 in this particular case. Copyright © 2017 Elsevier Ltd. All rights reserved.

Indirect effect of changing aerosol concentrations on methane and ozone radiative forcing

NASA Astrophysics Data System (ADS)

Rowlinson, Matthew; Rap, Alexandru; Arnold, Steve; Forster, Piers; Chipperfield, Martyn

2017-04-01

Atmospheric aerosols interact with climate in number of complex ways and quantifying the overall effect remains the dominant uncertainty in estimating anthropogenic climate forcing (IPCC, 2013). The radiative forcing (RF) caused by the direct effect of aerosol interacting with radiation is estimated at -0.35 (-0.85 to +0.15) Wm-2, while cloud-aerosol interactions are estimated at -0.45 (-1.2 to 0.0) Wm-2 (IPCC, 2013). The net impact is a cooling with an effective radiative forcing (ERF) of 0.9 (-1.9 to -0.1) Wm-2 (IPCC, 2013). One effect of aerosols which has not been well evaluated is their effect on atmospheric chemistry. Atmospheric aerosols provide a surface for homogeneous reactions to occur, altering reactions rates and the availability of oxidants, thereby influencing the removal/production of radiatively important species such as methane (CH4) and tropospheric ozone (O3). Oxidants such as the hydroxyl radical (OH) determine the atmospheric lifetime and hence burden of CH4, therefore changes to atmospheric aerosols which impact oxidation chemistry will also influence RF due to CH4. This effect could enhance or offset the negative RF of aerosols, depending on how the individual aerosol changes availability of oxidants. Quantifying the importance of this mechanism for RF is necessary to provide accurate estimates of the effect of aerosols, and assess relative effectiveness of measures to decrease aerosol emissions and precursors. Using a sophisticated aerosol micro-physics model (GLOMAP) coupled to the TOMCAT three-dimensional chemical transport model, we separately simulate changes in atmospheric composition resulting from a 50% decline in anthropogenic emissions of black carbon aerosol (BC), volatile organic compounds (VOCs) and anthropogenic precursors of sulphate and nitrate. The impact of changes to each aerosol on lifetime of CH4 is then calculated to establish the resulting impact on CH4 burden and RF. Cutting global anthropogenic SO2 emissions by 50% decreases atmospheric sulpate concentrations by 44% after 2 years, while increasing global OH concentrations by 0.9%. CH4 lifetime is reduced by approximately 50 days as a result, leading to a decrease in CH4 burden of 38ppb. NOx is anticipated to have a similar but much larger effect (Matsui and Koike 2016). The Edwards and Slingo offline radiation model is also used to calculate changes to direct and indirect aerosol forcing. Presented here is the net RF change following 50% emission decrease of each aerosol or precursors, accounting for the direct and indirect aerosol effect as well as indirect effects via oxidation chemistry on the RF due to CH4 and tropospheric O3.

Optimization of a horizontal-flow biofilm reactor for the removal of methane at low temperatures.

PubMed

Clifford, E; Kennelly, C; Walsh, R; Gerrity, S; Reilly, E O; Collins, G

2012-10-01

Three pilot-scale, horizontal-flow biofilm reactors (HFBRs 1-3) were used to treat methane (CH4)-contaminated air to assess the potential of this technology to manage emissions from agricultural activities, waste and wastewater treatment facilities, and landfills. The study was conducted over two phases (Phase 1, lasting 90 days and Phase 2, lasting 45 days). The reactors were operated at 10 degrees C (typical of ambient air and wastewater temperatures in northern Europe), and were simultaneously dosed with CH4-contaminated air and a synthetic wastewater (SWW). The influent loading rates to the reactors were 8.6 g CH4/m3/hr (4.3 g CH4/m2 TPSA/hr; where TPSA is top plan surface area). Despite the low operating temperatures, an overall average removal of 4.63 g CH4/m3/day was observed during Phase 2. The maximum removal efficiency (RE) for the trial was 88%. Potential (maximum) rates of methane oxidation were measured and indicated that biofilm samples taken from various regions in the HFBRs had mostly equal CH4 removal potential. In situ activity rates were dependent on which part of the reactor samples were obtained. The results indicate the potential of the HFBR, a simple and robust technology, to biologically treat CH4 emissions. The results of this study indicate that the HFBR technology could be effectively applied to the reduction of greenhouse gas emissions from wastewater treatment plants and agricultural facilities at lower temperatures common to northern Europe. This could reduce the carbon footprint of waste treatment and agricultural livestock facilities. Activity tests indicate that methanotrophic communities can be supported at these temperatures. Furthermore, these data can lead to improved reactor design and optimization by allowing conditions to be engineered to allow for improved removal rates, particularly at lower temperatures. The technology is simple to construct and operate, and with some optimization of the liquid phase to improve mass transfer, the HFBR represents a viable, cost-effective solution for these emissions.

Mitigating global warming potentials of methane and nitrous oxide gases from rice paddies under different irrigation regimes.

PubMed

Ali, Muhammad Aslam; Hoque, M Anamul; Kim, Pil Joo

2013-04-01

A field experiment was conducted in Bangladesh Agricultural University Farm to investigate the mitigating effects of soil amendments such as calcium carbide, calcium silicate, phosphogypsum, and biochar with urea fertilizer on global warming potentials (GWPs) of methane (CH4) and nitrous oxide (N2O) gases during rice cultivation under continuous and intermittent irrigations. Among the amendments phosphogypsum and silicate fertilizer, being potential source of electron acceptors, decreased maximum level of seasonal CH4 flux by 25-27 % and 32-38 % in continuous and intermittent irrigations, respectively. Biochar and calcium carbide amendments, acting as nitrification inhibitors, decreased N2O emissions by 36-40 % and 26-30 % under continuous and intermittent irrigations, respectively. The total GWP of CH4 and N2O gases were decreased by 7-27 % and 6-34 % with calcium carbide, phosphogypsum, and silicate fertilizer amendments under continuous and intermittent irrigations, respectively. However, biochar amendments increased overall GWP of CH4 and N2O gases.

Naringin Mitigates Cardiac Hypertrophy by Reducing Oxidative Stress and Inactivating c-Jun Nuclear Kinase-1 Protein in Type I Diabetes.

PubMed

Adebiyi, A Olubunmi; Adebiyi, Oluwafeysetan O; Owira, Peter M O

2016-02-01

Cardiac hypertrophy (CH) in type 1 diabetes mellitus is attributed to increased oxidative stress-associated activation of c-Jun Nuclear Kinase (JNK). We investigated the effects of naringin on hyperglycemia-associated oxidative stress, activation of JNK-1, and CH. Male Sprague-Dawley rats (225-250 g) (n = 7) were divided into 6 groups. Groups I and II were orally treated with distilled water [3.0 mL/kg body weight/day (BW)] and naringin (50 mg/kg BW), respectively. Groups III-VI were rendered diabetic by a single intraperitoneal injection of 65 mg/kg BW of streptozotocin. Groups III, IV, and V were further treated with insulin (4.0 I.U, s.c, twice daily), naringin (50 mg/kg BW), and ramipril (3.0 mg/kg BW), respectively. After 56 days, the animals were sacrificed and then plasma and cardiac tissues obtained for further analysis. Naringin treatment of diabetic rats significantly reversed oxidative stress, lipid peroxidation, proteins oxidation, CH indices, and JNK protein activation compared with untreated diabetic animals. Our results do suggest that naringin mitigates CH by inhibiting oxidative stress leading to inactivation of JNK-1. Naringin supplements could therefore ameliorate CH in diabetic patients.

Methanotrophic communities in aerobic soils with different stages of natural reforestation

NASA Astrophysics Data System (ADS)

Kravchenko, Irina; Sukhacheva, Marina; Kuznetsova, Tatyana

2017-04-01

The land use and management has a significant impact on global biogeochemical cycles of biogenic elements and the Earth's climate. Deforestation is known to change the soil from a net sink for CH4 to a net source as a result of alteration in the activity and composition of the methanotrophic communities. At the same time, the recovery of ecosystems after their withdrawal from agricultural use is poorly understood. Currently, in Russia, the former arable lands occupy about 20% of the territory and more than half of them are not used in agriculture since the early 90-s. Here, soil CH4 oxidation rates and associated methanotrophic communities were examined in a chronosequence of gray forest soils, Moscow region, Russia, consisting of cropland soils, soils at the different stages under postagrogenic forest regenerating, and in a mature native forest. CH4 concentrations were measured by GC and several chemical (pH, total C and N, NH4 -N and NO3 -N) and physical (moisture content, porosity, water-filled pore space and bulk density) soil properties were evaluated. Methane oxidation rates were significantly influenced by reforestation and the regenerating soils have the potential to reach those of the native forest. In fallow, shrublands and young forest soil CH4-oxidation rates were significantly higher as compared with cropland, but not fully stabilized even after 25 years of reforestation. To examine whether changes in CH4-oxidation rate were linked to a shift in the microbial community, we have analyzed soil methanotrophic communities by cloning and sequencing of particulate methane monooxygenase (pmoA) using the primer pair A189-mb650. Based on the relative proportion of the clones it was shown the dominance Type II related and uncultured methanotrophs in forest soils. Both Type I and Type II methanotrophs were found in arable and postagrogenic soils, and the relative abundance of Type II methanotrophs increased with the age of regeneration and recovered after 15-25 years to that close to finding in the native forest. We suggested that the lower CH4- oxidation rates in soils of older reforestation stages is determined by edaphic factors. Our findings may be useful in future prediction of changes in methane emissions resulting from reforestation. The study was partially supported by RFBR research project # 16-04-00136_a.

Bacterial oxidation of dibromomethane and methyl bromide in natural waters and enrichment cultures

USGS Publications Warehouse

Goodwin, K.D.; Schaefer, J.K.; Oremland, R.S.

1998-01-01

Bacterial oxidation of 14CH2Br2 and 14CH3Br was measured in freshwater, estuarine, seawater, and hypersaline-alkaline samples. In general, bacteria from the various sites oxidized similar amounts of 14CH2Br2 and comparatively less 14CH3Br. Bacterial oxidation of 14CH3Br was rapid in freshwater samples compared to bacterial oxidation of 14CH3Br in more saline waters. Freshwater was also the only site in which methyl fluoride-sensitive bacteria (e.g., methanotrophs or nitrifiers) governed brominated methane oxidation. Half-life calculations indicated that bacterial oxidation of CH2Br2 was potentially significant in all of the waters tested. In contrast, only in freshwater was bacterial oxidation of CH3Br as fast as chemical removal. The values calculated for more saline sites suggested that bacterial oxidation of CH3Br was relatively slow compared to chemical and physical loss mechanisms. However, enrichment cultures demonstrated that bacteria in seawater can rapidly oxidize brominated methanes. Two distinct cultures of nonmethanotrophic methylotrophs were recovered; one of these cultures was able to utilize CH2Br2 as a sole carbon source, and the other was able to utilize CH3Br as a sole carbon source.

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

NASA Astrophysics Data System (ADS)

Liebner, Susanne; Zeyer, Josef; Knoblauch, Christian

2010-05-01

Circumpolar peatlands store roughly 18 % of the globally stored carbon in soils [based on 1, 2]. Also, northern wetlands and tundra are a net source of methane (CH4), an effective greenhouse gas (GHG), with an estimated annual CH4 release of 7.2% [3] or 8.1% [4] of the global total CH4 emission. Although it is definite that Arctic tundra significantly contributes to the global methane emissions in general, regional variations in GHG fluxes are enormous. CH4 fluxes of polygonal tundra within the Siberian Lena Delta, for example, were reported to be low [5, 6], particularly at open water polygonal ponds and small lakes [7] which make up around 10 % of the delta's surface. Low methane emissions from polygonal ponds oppose that Arctic permafrost thaw ponds are generally known to emit large amounts of CH4 [8]. Combining tools of biogeochemistry and molecular microbiology, we identified sinks of CH4 in polygonal ponds from the Lena Delta that were not considered so far in GHG studies from Arctic wetlands. Pore water CH4 profiling in polygonal ponds on Samoylov, a small island in the central part of the Lena Delta, revealed a pronounced zone of CH4 oxidation near the vegetation surface in submerged layers of brown-mosses. Here, potential CH4 oxidation was an order of magnitude higher than in non-submerged mosses and in adjacent bulk soil. We could additionally show that this moss associated methane oxidation (MAMO) is hampered when exposure of light is prevented. Shading of plots with submerged Scorpidium scorpioides inhibited MAMO leading to higher CH4 concentrations and an increase in CH4 fluxes by a factor of ~13. Compared to non-submerged mosses, the submerged mosses also showed significantly lower δ13C values indicating that they use carbon dioxide derived from methane oxidation for photosynthesis. Applying stable isotope probing of DNA, type II methanotrophs were identified to be responsible for the oxidation of CH4 in the submerged Scorpidium scorpioides. Our study gives first evidence for MAMO in submerged brown-mosses and in the oligotrophic polygonal peatlands of the Lena Delta. It shows that MAMO might effectively reduce methane fluxes to the atmosphere also in Arctic GHG emission hot spots. References: [1] Zhang, T., Barry, R.G., Knowles, K., Heginbottom, J.A., and Brown, J. (1999) Statistics and characteristics of permafrost and ground-ice distribution in the Northern Hemisphere. Polar Geography 23(2): 132-154 [2] Schuur, E.A.G., Bockheim, J., Candell, J.G., Euskirchen, E., Field, C.B., Goryachkin, S.V., Hagemann, S., Kuhry, P., Lafleur, P.M., Lee, H., Mazhitova, G., Nelson, F.E., Rinke, A., Romanovsky, V., Shiklomanov, N., Tarnocai, C., Venevsky, S., Vogel, J., and Zimov, S. (2008) Vulnerability of Permafrost Carbon to Climate Change: Implications for the Global Carbon Cycle. BioScience 58 (8): 701-714 [3] Denman, K.L., Brasseur G., Chidthaisong A., Ciais, P., Cox, P.M., Dickinson, R.E., Hauglustaine, D., Heinze, C., Holland, E., Jacob, D., Lohmann, U., Ramachandran, S., da Silva Dias, P.L., Wofsy, S.C., and Zhang, X. (2007) Couplings Between Changes in the Climate System and Biogeochemistry. In: Climate Change 2007: The Physical Science Basis. Contribution of Working Group I to the Fourth Assessment Report of the Intergovernmental Panel on Climate Change [Solomon, S., D. Qin, M. Manning, Z. Chen, M. Marquis, K.B. Averyt, M.Tignor and H.L. Miller (eds.)]. Cambridge University Press, Cambridge, United Kingdom and New York, NY, USA [4] Wuebbles, J., and Hayhoe, K. (2002) Atmospheric methane and global change. Earth-Science Reviews 57: 177-210 [5] Sachs, T., Wille, C., Boike, J., and Kutzbach, L. (2008) Environmental controls on ecosystem-scale CH4 emission from polygonal tundra in the Lena River Delta, Siberia. Journal of Geophysical Research 113: G00A03 [6] Wille, C., Kutzbach, L., Sachs, T., Wagner, D., and Pfeiffer, E.M. (2008) Methane emissions from Siberian arctic polygonal tundra: Eddy covariance measurements and modeling. Global Change Biology 14: 1395-1408 [7] Schneider, J., Grosse, G., and Wagner, D. (2009) Land cover classification of tundra environments in the Arctic Lena Delta based on Landsat 7 ETM+ data and its application for upscaling of methane emissions. Remote Sensing of Environment 113: 380-391 [8] Walter, K.M., Edwards, M.E., Grosse, G., Zimov, S.A., and Chapin III, F.S. (2007) Thermokarst Lakes as a Source of Atmospheric CH4 During the Last Deglaciation. Science 318: 633-636

Hydrogenation of Organic Matter as a Terminal Electron Sink Sustains High CO 2 :CH 4 Production Ratios During Anaerobic Decomposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wilson, Rachel M.; Tfaily, Malak M.; Rich, Virginia I.

Once inorganic electron acceptors are depleted, organic matter in anoxic environments decomposes by hydrolysis, fermentation, and methanogenesis, requiring syntrophic interactions between microorganisms to achieve energetic favorability. In this classic anaerobic food chain, methanogenesis represents the terminal electron accepting (TEA) process, ultimately producing equimolar CO 2 and CH 4 for each molecule of organic matter degraded. However, CO 2:CH 4 production in Sphagnum-derived, mineral-poor, cellulosic peat often substantially exceeds this 1:1 ratio, even in the absence of measureable inorganic TEAs. Since the oxidation state of C in both cellulose-derived organic matter and acetate is 0, and CO 2 has an oxidationmore » state of +4, if CH 4 (oxidation state -4) is not produced in equal ratio, then some other compound(s) must balance CO 2 production by receiving 4 electrons. Here we present evidence for ubiquitous hydrogenation of diverse unsaturated compounds that appear to serve as organic TEAs in peat, thereby providing the necessary electron balance to sustain CO 2:CH 4 >1. While organic electron acceptors have previously been proposed to drive microbial respiration of organic matter through the reversible reduction of quinone moieties, the hydrogenation mechanism that we propose, by contrast, reduces C-C double bonds in organic matter thereby serving as 1) a terminal electron sink, 2) a mechanism for degrading complex unsaturated organic molecules, 3) a potential mechanism to regenerate electron-accepting quinones, and, in some cases, 4) a means to alleviate the toxicity of unsaturated aromatic acids. In conclusion, this mechanism for CO 2 generation without concomitant CH 4 production has the potential to regulate the global warming potential of peatlands by elevating CO 2:CH 4 production ratios.« less

Hydrogenation of Organic Matter as a Terminal Electron Sink Sustains High CO 2 :CH 4 Production Ratios During Anaerobic Decomposition

DOE PAGES

Wilson, Rachel M.; Tfaily, Malak M.; Rich, Virginia I.; ...

2017-07-03

Once inorganic electron acceptors are depleted, organic matter in anoxic environments decomposes by hydrolysis, fermentation, and methanogenesis, requiring syntrophic interactions between microorganisms to achieve energetic favorability. In this classic anaerobic food chain, methanogenesis represents the terminal electron accepting (TEA) process, ultimately producing equimolar CO 2 and CH 4 for each molecule of organic matter degraded. However, CO 2:CH 4 production in Sphagnum-derived, mineral-poor, cellulosic peat often substantially exceeds this 1:1 ratio, even in the absence of measureable inorganic TEAs. Since the oxidation state of C in both cellulose-derived organic matter and acetate is 0, and CO 2 has an oxidationmore » state of +4, if CH 4 (oxidation state -4) is not produced in equal ratio, then some other compound(s) must balance CO 2 production by receiving 4 electrons. Here we present evidence for ubiquitous hydrogenation of diverse unsaturated compounds that appear to serve as organic TEAs in peat, thereby providing the necessary electron balance to sustain CO 2:CH 4 >1. While organic electron acceptors have previously been proposed to drive microbial respiration of organic matter through the reversible reduction of quinone moieties, the hydrogenation mechanism that we propose, by contrast, reduces C-C double bonds in organic matter thereby serving as 1) a terminal electron sink, 2) a mechanism for degrading complex unsaturated organic molecules, 3) a potential mechanism to regenerate electron-accepting quinones, and, in some cases, 4) a means to alleviate the toxicity of unsaturated aromatic acids. In conclusion, this mechanism for CO 2 generation without concomitant CH 4 production has the potential to regulate the global warming potential of peatlands by elevating CO 2:CH 4 production ratios.« less

The role of Sphagnum mosses in the methane cycling of a boreal mire.

PubMed

Larmola, Tuula; Tuittila, Eeva-Stiina; Tiirola, Marja; Nykänen, Hannu; Martikainen, Pertti J; Yrjälä, Kim; Tuomivirta, Tero; Fritze, Hannu

2010-08-01

Peatlands are a major natural source of atmospheric methane (CH4). Emissions from Sphagnum-dominated mires are lower than those measured from other mire types. This observation may partly be due to methanotrophic (i.e., methane-consuming) bacteria associated with Sphagnum. Twenty-three of the 41 Sphagnum species in Finland can be found in the peatland at Lakkasuo. To better understand the Sphagnum-methanotroph system, we tested the following hypotheses: (1) all these Sphagnum species support methanotrophic bacteria; (2) water level is the key environmental determinant for differences in methanotrophy across habitats; (3) under dry conditions, Sphagnum species will not host methanotrophic bacteria; and (4) methanotrophs can move from one Sphagnum shoot to another in an aquatic environment. To address hypotheses 1 and 2, we measured the water table and CH4 oxidation for all Sphagnum species at Lakkasuo in 1-5 replicates for each species. Using this systematic approach, we included Sphagnum spp. with narrow and broad ecological tolerances. To estimate the potential contribution of CH4 to moss carbon, we measured the uptake of delta13C supplied as CH4 or as carbon dioxide dissolved in water. To test hypotheses 2-4, we transplanted inactive moss patches to active sites and measured their methanotroph communities before and after transplantation. All 23 Sphagnum species showed methanotrophic activity, confirming hypothesis 1. We found that water level was the key environmental factor regulating methanotrophy in Sphagnum (hypothesis 2). Mosses that previously exhibited no CH4 oxidation became active when transplanted to an environment in which the microbes in the control mosses were actively oxidizing CH4 (hypothesis 4). Newly active transplants possessed a Methylocystis signature also found in the control Sphagnum spp. Inactive transplants also supported a Methylocystis signature in common with active transplants and control mosses, which rejects hypothesis 3. Our results imply a loose symbiosis between Sphagnum spp. and methanotrophic bacteria that accounts for potentially 10-30% of Sphagnum carbon.

Thermodynamic and achievable efficiencies for solar-driven electrochemical reduction of carbon dioxide to transportation fuels

PubMed Central

Singh, Meenesh R.; Clark, Ezra L.; Bell, Alexis T.

2015-01-01

Thermodynamic, achievable, and realistic efficiency limits of solar-driven electrochemical conversion of water and carbon dioxide to fuels are investigated as functions of light-absorber composition and configuration, and catalyst composition. The maximum thermodynamic efficiency at 1-sun illumination for adiabatic electrochemical synthesis of various solar fuels is in the range of 32–42%. Single-, double-, and triple-junction light absorbers are found to be optimal for electrochemical load ranges of 0–0.9 V, 0.9–1.95 V, and 1.95–3.5 V, respectively. Achievable solar-to-fuel (STF) efficiencies are determined using ideal double- and triple-junction light absorbers and the electrochemical load curves for CO2 reduction on silver and copper cathodes, and water oxidation kinetics over iridium oxide. The maximum achievable STF efficiencies for synthesis gas (H2 and CO) and Hythane (H2 and CH4) are 18.4% and 20.3%, respectively. Whereas the realistic STF efficiency of photoelectrochemical cells (PECs) can be as low as 0.8%, tandem PECs and photovoltaic (PV)-electrolyzers can operate at 7.2% under identical operating conditions. We show that the composition and energy content of solar fuels can also be adjusted by tuning the band-gaps of triple-junction light absorbers and/or the ratio of catalyst-to-PV area, and that the synthesis of liquid products and C2H4 have high profitability indices. PMID:26504215

Thermodynamic and achievable efficiencies for solar-driven electrochemical reduction of carbon dioxide to transportation fuels

DOE PAGES

Singh, Meenesh R.; Clark, Ezra L.; Bell, Alexis T.

2015-10-26

Thermodynamic, achievable, and realistic efficiency limits of solar-driven electrochemical conversion of water and carbon dioxide to fuels are investigated as functions of light-absorber composition and configuration, and catalyst composition. The maximum thermodynamic efficiency at 1-sun illumination for adiabatic electrochemical synthesis of various solar fuels is in the range of 32–42%. Single-, double-, and triple-junction light absorbers are found to be optimal for electrochemical load ranges of 0–0.9 V, 0.9–1.95 V, and 1.95–3.5 V, respectively. Achievable solar-to-fuel (STF) efficiencies are determined using ideal double- and triple-junction light absorbers and the electrochemical load curves for CO 2 reduction on silver and coppermore » cathodes, and water oxidation kinetics over iridium oxide. The maximum achievable STF efficiencies for synthesis gas (H 2 and CO) and Hythane (H 2 and CH 4) are 18.4% and 20.3%, respectively. Whereas the realistic STF efficiency of photoelectrochemical cells (PECs) can be as low as 0.8%, tandem PECs and photovoltaic (PV)-electrolyzers can operate at 7.2% under identical operating conditions. Finally, we show that the composition and energy content of solar fuels can also be adjusted by tuning the band-gaps of triple-junction light absorbers and/or the ratio of catalyst-to-PV area, and that the synthesis of liquid products and C 2H 4 have high profitability indices.« less

Synthesis of Polyheteroaromatic Compounds via Rhodium-Catalyzed Multiple C-H Bond Activation and Oxidative Annulation.

PubMed

Peng, Shiyong; Liu, Suna; Zhang, Sai; Cao, Shengyu; Sun, Jiangtao

2015-10-16

Polyheteroaromatic compounds are potential optoelectronic conjugated materials due to their electro- and photochemical properties. Transition-metal-catalyzed multiple C-H activation and sequential oxidative annulation allows rapidly assembling of those compounds from readily available starting materials. A rhodium-catalyzed cascade oxidative annulation of β-enamino esters or 4-aminocoumarins with internal alkynes is described to access those compounds, featuring multiple C-H/N-H bond cleavages and sequential C-C/C-N bond formations in one pot.

A compact QCL based methane and nitrous oxide sensor for environmental and medical applications.

PubMed

Jahjah, Mohammad; Ren, Wei; Stefański, Przemysław; Lewicki, Rafał; Zhang, Jiawei; Jiang, Wenzhe; Tarka, Jan; Tittel, Frank K

2014-05-07

A methane (CH4) and nitrous oxide (N2O) sensor based on a sensitive, selective and well established technique of quartz enhanced photoacoustic spectroscopy (QEPAS) was developed for environmental and biomedical measurements. A thermoelectrically cooled (TEC) distributed feedback quantum cascade laser (DFB-QCL), capable of continuous wave (CW) mode hop free emission in the 7.83 μm wavelength range, was used as an excitation source. For the targeted CH4 and N2O absorption lines located at 1275.04 cm(-1) and 1275.49 cm(-1) detection limits (1σ) of 13 ppbv and 6 ppbv were achieved with a 1 second data acquisition time, respectively. Environmental data of CH4 and N2O mixing ratios acquired using the QEPAS sensor system are also reported.

Methane Cycling in a Warming Wetland

NASA Astrophysics Data System (ADS)

Noyce, G. L.; Megonigal, P.; Rich, R.; Kirwan, M. L.; Herbert, E. R.

2017-12-01

Coastal wetlands are global hotspots of carbon (C) storage, but the future of these systems is uncertain. In June 2016, we initiated an in-situ, active, whole-ecosystem warming experiment in the Smithsonian's Global Change Research Wetland to quantify how warming and elevated CO2 affect the stability of coastal wetland soil C pools and contemporary rates of C sequestration. Transects are located in two plant communities, dominated by C3 sedges or C4 grasses. The experiment has a gradient design with air and soil warming treatments ranging from ambient to +5.1 °C and heated plots consistently maintain their target temperature year-round. In April 2017, an elevated CO2 treatment was crossed with temperature in the C3community. Ongoing measurements include soil elevation, C fluxes, porewater chemistry and redox potential, and above- and below-ground growth and biomass. In both years, warming increased methane (CH4) emissions (measured at 3-4 week intervals) from spring through fall at the C3 site, but had little effect on emissions from the C4 site. Winter (Dec-Mar) emissions showed no treatment effect. Stable isotope analysis of dissolved CH4 and DIC also indicated that warming had differing effects on CH4 pathways in the two vegetation communities. To better understand temperature effects on rates of CH4 production and oxidation, 1 m soil cores were collected from control areas of the marsh in summer 2017 and incubated at temperatures ranging from 4 °C to 35 °C. Warming increased CH4 production and oxidation rates in surface samples and oxidation rates in the rooting zone samples from both sites, but temperature responses in deep (1 m) soil samples were minimal. In the surface and rooting zone samples, production rates were also consistently higher in C3 soils compared to C4 soils, but, contrary to our expectations, the temperature response was stronger in the C4 soils. However, oxidation in C3 rooting zone samples did have a strong temperature response. The ratio of CO2:CH4 decreased with increasing temperature in surface samples from both sites, indicating that anaerobic respiration in surface soil may become increasingly methanogenic with warming. In contrast, the rooting zone and deep soil samples showed the opposite trend, again suggesting that the soil profile will not respond consistently to warming.

Photo-induced CO2 reduction by CH4/H2O to fuels over Cu-modified g-C3N4 nanorods under simulated solar energy

NASA Astrophysics Data System (ADS)

Tahir, Beenish; Tahir, Muhammad; Amin, Nor Aishah Saidina

2017-10-01

Copper modified polymeric graphitic carbon nitride (Cu/g-C3N4) nanorods for photo-induced CO2 conversion with methane (CH4) and water (H2O) as reducing system under simulated solar energy has been investigated. The nanocatalysts, synthesized by pyrolysis and sonication, were characterized by XRD, FTIR, Raman analysis, XPS, SEM, N2 adsorption-desorption and PL spectroscopy. The presence of Cu2+ ions over the g-C3N4 structure inhibited charge carriers recombination process. The results indicated that photo-activity and selectivity of Cu/g-C3N4 photo-catalyst for CO2 reduction greatly dependent on the type of CO2-reduction system. CO2 was efficiently converted to CH4 and CH3OH with traces of C2H4 and C2H6 hydrocarbons in the CO2-water system. The yield of the main product, CH4 over 3 wt.% Cu/g-C3N4 was 109 μmole g-cata.-1 h-1 under visible light irradiation, significantly higher than the pure g-C3N4 catalyst (60 μmole/g.cat). In photo-induced CO2-CH4 reaction, CO and H2 were detected as the main products with smaller amount of hydrocarbons. The highest efficiency was detected over 3 wt.%Cu-loading of g-C3N4 and at optimal CH4/CO2 feed ratio of 1.0. The maximum yield of CO and H2 detected were 142 and 76 μmole g-catal.-1 h-1, respectively at selectivity 66.6% and 32.5%, respectively. Significantly enhanced CO2/CH4 reduction over Cu/g-C3N4 was attributed to its polymeric structure with efficient charge transfer property and inhibited charges recombination rate. A proposed photo-induced reaction mechanism, corroborated with the experimental data, was also deliberated.

Experimental study and detailed modeling of toluene degradation in a low-pressure stoichiometric premixed CH4/O2/N2 flame.

PubMed

Bakali, A El; Dupont, L; Lefort, B; Lamoureux, N; Pauwels, J F; Montero, M

2007-05-17

Temperature and mole fraction profiles have been measured in laminar stoichiometric premixed CH4/O2/N2 and CH4/1.5%C6H5CH3/O2/N2 flames at low pressure (0.0519 bar) by using thermocouple, molecular beam/mass spectrometry (MB/MS), and gas chromatography/mass spectrometry (GC/MS) techniques. The present study completes our previous work performed on the thermal degradation of benzene in CH4/O2/N2 operating at similar conditions. Mole fraction profiles of reactants, final products, and reactive and stable intermediate species have been analyzed. The main intermediate aromatic species analyzed in the methane-toluene flame were benzene, phenol, ethylbenzene, benzylalcohol, styrene, and benzaldehyde. These new experimental results have been modeled with our previous model including submechanisms for aromatics (benzene up to p-xylene) and aliphatic (C1 up to C7) oxidation. Good agreement has been observed for the main species analyzed. The main reaction paths governing the degradation of toluene in the methane flame were identified, and it occurs mainly via the formation of benzene (C6H5CH3 + H = C6H6 + CH3) and benzyl radical (C6H5CH3 + H = C6H5CH2 + H2). Due to the abundance of methyl radicals, it was observed that recombination of benzyl and methyl is responsible for main monosubstitute aromatic species analyzed in the methane-toluene flame. The oxidation of these substitute species led to cyclopentadienyl radical as observed in a methane-benzene flame.

Palladium-catalyzed Kumada coupling reaction of bromoporphyrins with silylmethyl Grignard reagents: preparation of silylmethyl-substituted porphyrins as a multipurpose synthon for fabrication of porphyrin systems.

PubMed

Sugita, Noriaki; Hayashi, Satoshi; Hino, Fumio; Takanami, Toshikatsu

2012-12-07

We have developed an efficient method for preparing silylmethyl-substituted porphyrins via the palladium-catalyzed Kumada cross-coupling reaction of bromoporphyrins with silylmethyl Grignard reagents. We demonstrated the synthetic utility of these silylmethylporphyrins as a multipurpose synthon for fabricating porphyrin derivatives through a variety of transformations of the silylmethyl groups, including the DDQ-promoted oxidative conversion to CHO, CH(2)OH, CH(2)OMe, and CH(2)F functionalities and the fluoride ion-mediated desilylative introduction of carbon-carbon single and double bonds.

C-11 cyanide production system

DOEpatents

Kim, Dohyun; Alexoff, David; Kim, Sung Won; Hooker, Jacob; Ferrieri, Richard A

2015-01-13

A method for providing .sup.11C-labeled cyanides from .sup.11C labeled oxides in a target gas stream retrieved from an irradiated high pressure gaseous target containing O.sub.2 is provided, wherein .sup.11C labeled oxides are reduced with H.sub.2 in the presence of a nickel catalyst under a pressure and a temperature sufficient to form a product stream comprising at least about 95% .sup.11CH.sup.4 , the .sup.11CH.sub.4 is then combined with an excess of NH.sub.3 in a carrier/reaction stream flowing at an accelerated velocity and the combined .sup.11CH4 carrier/reaction stream is then contacted with a platinum (Pt) catalyst particulate supported on a substantially-chemically-nonreactive heat-stable support at a temperature of at least about 900 .degree. C., whereby a product stream comprising at least about 60%H.sup.11CN is provided in less than 10 minutes from retrieval of the .sup.11C labeled oxide.

C-11 cyanide production system

DOEpatents

Kim, Dohyun; Alexoff, David; Kim, Sung Won; Hooker, Jacob M.; Ferrieri, Richard A.

2017-11-21

A method for providing .sup.11C-labeled cyanides from .sup.11C labeled oxides in a target gas stream retrieved from an irradiated high pressure gaseous target containing O.sub.2, wherein .sup.11C labeled oxides are reduced with H.sub.2 in the presence of a nickel catalyst under a pressure and a temperature sufficient to form a product stream comprising at least about 95% .sup.11CH.sub.4, the .sup.11CH.sub.4 is then combined with an excess of NH.sub.3 in a carrier/reaction stream flowing at an accelerated velocity and the combined .sup.11CH4 carrier/reaction stream is then contacted with a platinum (Pt) catalyst particulate supported on a substantially-chemically-nonreactive heat-stable support at a temperature of at least about 900.degree. C., whereby a product stream comprising at least about 60% H.sup.11CN is provided in less than 10 minutes from retrieval of the .sup.11C labeled oxide.

A highly efficient microfluidic nano biochip based on nanostructured nickel oxide.

PubMed

Ali, Md Azahar; Solanki, Pratima R; Patel, Manoj K; Dhayani, Hemant; Agrawal, Ved Varun; John, Renu; Malhotra, Bansi D

2013-04-07

We present results of the studies relating to fabrication of a microfluidic biosensor chip based on nickel oxide nanorods (NRs-NiO) that is capable of directly measuring the concentration of total cholesterol in human blood through electrochemical detection. Using this chip we demonstrate, with high reliability and in a time efficient manner, the detection of cholesterol present in buffer solutions at clinically relevant concentrations. The microfluidic channel has been fabricated onto a nickel oxide nanorod-based electrode co-immobilized with cholesterol esterase (ChEt) and cholesterol oxidase (ChOx) that serves as the working electrode. Bare indium tin oxide served as the counter electrode. A Ag/AgCl wire introduced to the outlet of the microchannel acts as a reference electrode. The fabricated NiO nanorod-based electrode has been characterized using X-ray diffraction, Raman spectroscopy, HR-TEM, FT-IR, UV-visible spectroscopy and electrochemical techniques. The presented NRs-NiO based microfluidic sensor exhibits linearity in the range of 1.5-10.3 mM, a high sensitivity of 0.12 mA mM(-1) cm(-2) and a low value of 0.16 mM of the Michaelis-Menten constant (Km).

Modeling greenhouse gas emissions from dairy farms

USDA-ARS?s Scientific Manuscript database

Dairy farms have been identified as an important source of greenhouse gas emissions. Within the farm, important emissions include enteric methane (CH4) from the animals, CH4 and nitrous oxide (N2O) from manure in housing facilities, during long-term storage and during field application, and N2O from...

Dry Reforming of Methane in a Gliding Arc Plasmatron: Towards a Better Understanding of the Plasma Chemistry.

PubMed

Cleiren, Emelie; Heijkers, Stijn; Ramakers, Marleen; Bogaerts, Annemie

2017-10-23

Dry reforming of methane (DRM) in a gliding arc plasmatron is studied for different CH 4 fractions in the mixture. The CO 2 and CH 4 conversions reach their highest values of approximately 18 and 10 %, respectively, at 25 % CH 4 in the gas mixture, corresponding to an overall energy cost of 10 kJ L -1 (or 2.5 eV per molecule) and an energy efficiency of 66 %. CO and H 2 are the major products, with the formation of smaller fractions of C 2 H x (x=2, 4, or 6) compounds and H 2 O. A chemical kinetics model is used to investigate the underlying chemical processes. The calculated CO 2 and CH 4 conversion and the energy efficiency are in good agreement with the experimental data. The model calculations reveal that the reaction of CO 2 (mainly at vibrationally excited levels) with H radicals is mainly responsible for the CO 2 conversion, especially at higher CH 4 fractions in the mixture, which explains why the CO 2 conversion increases with increasing CH 4 fraction. The main process responsible for CH 4 conversion is the reaction with OH radicals. The excellent energy efficiency can be explained by the non-equilibrium character of the plasma, in which the electrons mainly activate the gas molecules, and by the important role of the vibrational kinetics of CO 2 . The results demonstrate that a gliding arc plasmatron is very promising for DRM. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Redox Potential and C-H Bond Cleaving Properties of a Nonheme FeIV=O Complex in Aqueous Solution

PubMed Central

Wang, Dong; Zhang, Mo; Bühlmann, Philippe; Que, Lawrence

2010-01-01

High-valent iron-oxo intermediates have been identified as the key oxidants in the catalytic cycles of many nonheme enzymes. Among the large number of synthetic FeIV=O complexes characterized to date, [FeIV(O)(N4Py)]2+ (1) exhibits the unique combination of thermodynamic stability, allowing its structural characterization by X-ray crystallography, and oxidative reactivity sufficient to cleave C-H bonds as strong as those in cyclohexane (DC-H = 99.3 kcal mol-1). However, its redox properties are not yet well understood. In this work, the effect of protons on the redox properties of 1 has been investigated electrochemically in nonaqueous and aqueous solutions. While the cyclic voltammetry of 1 in CH3CN is complicated by coupling of several chemical and redox processes, the FeIV/III couple is reversible in aqueous solution with E1/2 = +0.41 V vs. SCE at pH 4 and involves the transfer of one electron and one proton to give the FeIII-OH species. This is in fact the first example of reversible electrochemistry to be observed for this family of nonheme oxoiron(IV) complexes. C-H bond oxidations by 1 have been studied in H2O and found to have reactions rates that depend on the C-H bond strength but not on the solvent. Furthermore, our electrochemical results have allowed a DO-H value of 78(2) kcal mol-1 to be calculated for the FeIII-OH unit derived from 1. Interestingly, although this DO-H value is 6-11 kcal mol-1 lower than those corresponding to oxidants such as [FeIV(O)(TMP)] (TMP = tetramesitylporphinate), [RuIV(O)(bpy)2(py)]2+ (bpy = bipyridine, py = pyridine) and the tert-butylperoxyl radical, the oxidation of dihydroanthracene by 1 occurs at a rate comparable to those for these other oxidants. This comparison suggests that the nonheme N4Py ligand environment confers a kinetic advantage over the others that enhances the C-H bond cleavage ability of 1. PMID:20476758

Uncertainties in modelling CH4 emissions from northern wetlands in glacial climates: the role of vegetation parameters

NASA Astrophysics Data System (ADS)

Berrittella, C.; van Huissteden, J.

2011-10-01

Marine Isotope Stage 3 (MIS 3) interstadials are marked by a sharp increase in the atmospheric methane (CH4) concentration, as recorded in ice cores. Wetlands are assumed to be the major source of this CH4, although several other hypotheses have been advanced. Modelling of CH4 emissions is crucial to quantify CH4 sources for past climates. Vegetation effects are generally highly generalized in modelling past and present-day CH4 fluxes, but should not be neglected. Plants strongly affect the soil-atmosphere exchange of CH4 and the net primary production of the vegetation supplies organic matter as substrate for methanogens. For modelling past CH4 fluxes from northern wetlands, assumptions on vegetation are highly relevant since paleobotanical data indicate large differences in Last Glacial (LG) wetland vegetation composition as compared to modern wetland vegetation. Besides more cold-adapted vegetation, Sphagnum mosses appear to be much less dominant during large parts of the LG than at present, which particularly affects CH4 oxidation and transport. To evaluate the effect of vegetation parameters, we used the PEATLAND-VU wetland CO2/CH4 model to simulate emissions from wetlands in continental Europe during LG and modern climates. We tested the effect of parameters influencing oxidation during plant transport (fox), vegetation net primary production (NPP, parameter symbol Pmax), plant transport rate (Vtransp), maximum rooting depth (Zroot) and root exudation rate (fex). Our model results show that modelled CH4 fluxes are sensitive to fox and Zroot in particular. The effects of Pmax, Vtransp and fex are of lesser relevance. Interactions with water table modelling are significant for Vtransp. We conducted experiments with different wetland vegetation types for Marine Isotope Stage 3 (MIS 3) stadial and interstadial climates and the present-day climate, by coupling PEATLAND-VU to high resolution climate model simulations for Europe. Experiments assuming dominance of one vegetation type (Sphagnum vs. Carex vs. Shrubs) show that Carex-dominated vegetation can increase CH4 emissions by 50% to 78% over Sphagnum-dominated vegetation depending on the modelled climate, while for shrubs this increase ranges from 42% to 72%. Consequently, during the LG northern wetlands may have had CH4 emissions similar to their present-day counterparts, despite a colder climate. Changes in dominant wetland vegetation, therefore, may drive changes in wetland CH4 fluxes, in the past as well as in the future.

Unoccupied Electron States and the Formation of Interface between Films of Dimethyl-Substituted Thiophene-Phenylene Coolygomers and Oxidized Silicon Surface

NASA Astrophysics Data System (ADS)

Komolov, A. S.; Lazneva, E. F.; Gerasimova, N. B.; Panina, Yu. A.; Zashikhin, G. D.; Pshenichnyuk, S. A.; Borshchev, O. V.; Ponomarenko, S. A.; Handke, B.

2018-05-01

The unoccupied electron states and the boundary potential barrier during deposition of ultrathin films of dimethyl-substituted thiophene-phenylene coolygomers of the type of CH3-phenylene-thiophene-thiophene-phenylene-CH3 (CH3-PTTP-CH3) on an oxidized silicon surface have been studied. The electronic characteristics have been measured in the energy range from 5 to 20 eV above the Fermi level using total current spectroscopy (TCS). The structure of the CH3-PTTP-CH3 film surfaces has been studied by atomic force microscopy (AFM), and the atomic compositions of the films have been studied by X-ray photoelectron spectroscopy (XPS). The changes in the maximum intensities measured by the TCS method obtained from the deposited CH3-PTTP-CH3 film and from the substrate during increasing in the organic coating thickness to 6 nm is discussed. The formation of the boundary potential barrier in the n-Si/SiO2/CH3-PTTP-CH3 is accompanied by the decrease in the surface work function from 4.2 ± 0.1 to 4.0 ± 0.1 eV as the organic coating thickness increases to 3 nm. The ratio of atomic concentrations C: S in the CH3-PTTP-CH3 films well corresponds to the chemical formula of CH3-PTTP-CH3 molecules. The roughness of the CH3-PTTP-CH3 coating surface was not higher than 10 nm on the 10 × 10 μm areas as the total CH3-PTTP-CH3-layer thickness was about 100 nm.

Observations and modeling of methane flux in northern wetlands

NASA Astrophysics Data System (ADS)

Futakuchi, Y.; Ueyama, M.; Matsumoto, Y.; Yazaki, T.; Hirano, T.; Kominami, Y.; Harazono, Y.; Igarashi, Y.

2016-12-01

Methane (CH4) budgets in northern wetlands vary greatly with high spatio-temporal heterogeneity. Owing to limited available data, yet, it is difficult to constrain the CH4 emission from northern wetlands. In this context, we continuously measured CH4 fluxes at two northern wetlands. Measured fluxes were used for constraining the new model that empirically partitioned net CH4 fluxes into the processes of production, oxidation, and transport associated with ebullition, diffusion, and plant, based on the optimization technique. This study reveal the important processes related to the seasonal variations in CH4 emission with the continuous observations and inverse model analysis. The measurements have been conducted at a Sphagnum-dominated cool temperate bog (BBY) since April 2015 using the open-path eddy covariance method and a sub-arctic forested bog on permafrost in University of Alaska Fairbanks (UAF) since May 2016 using three automated chambers by a laser-based gas analyzer (FGGA-24r-EP, Los Gatos Research Inc., USA). In BBY, daily CH4 fluxes ranged from 1.9 nmol m-2 s-1 in early spring to 97.9 nmol m-2 s-1 in mid-summer. Growing-season total CH4 flux was 13 g m-2 yr-1 in 2015. In contrast, CH4 flux at the UAF site was small (0.2 to 1.0 nmol m-2 s-1), and hardly increased since start of the observation. This difference could be caused by the difference in the climate and soil conditions; mean air and soil temperature, and presence of permafrost. For BBY, the seasonal variation of CH4 emission was mostly explained by soil temperature, suggesting that the production was the important controlling process. In mid-summer when soil temperature was high, however, decrease in atmospheric pressure and increase in vegetation greenness stimulated CH4 emission probably through plant-mediated transport and form of bubble, suggesting that the transport processes were important. Based on a preliminary results by the model optimization in BBY site, CH4 fluxes were strongly influenced by the processes associated with production, ebullition, and plant-mediated transports rather than the processes associated with oxidation and diffusion. In this presentation, we will show that the new data-model fusion that we developed is the effective tool for evaluating CH4 fluxes and controlling processes at northern wetlands.

Abundances of ethylene oxide and acetaldehyde in hot molecular cloud cores

NASA Technical Reports Server (NTRS)

Nummelin, A.; Dickens, J. E.; Bergman, P.; Hjalmarson, A.; Irvine, W. M.; Ikeda, M.; Ohishi, M.

1998-01-01

We have searched for millimetre-wave line emission from ethylene oxide (c-C2H4O) and its structural isomer acetaldehyde (CH3CHO) in 11 molecular clouds using SEST. Ethylene oxide and acetaldehyde were detected through multiple lines in the hot cores NGC 6334F, G327.3-0.6, G31.41+0.31, and G34.3+0.2. Acetaldehyde was also detected towards G10.47+0.03, G322.2+0.6, and Orion 3'N, and one ethylene oxide line was tentatively detected in G10.47+0.03. Column densities and rotational excitation temperatures were derived using a procedure which fits the observed line intensifies by finding the minimum chi 2-value. The resulting rotational excitation temperatures of ethylene oxide and acetaldehyde are in the range 16-38 K, indicating that these species are excited in the outer, cooler parts of the hot cores or that the excitation is significantly subthermal. For an assumed source size of 20", the deduced column densities are (0.6-1)x10(14) cm-2 for ethylene oxide and (2-5)x10(14) cm-2 for acetaldehyde. The fractional abundances with respect to H2 are X[c-C2H4O]=(2-6)xl0(-10), and X[CH3CHO]=(0.8-3)x10(-9). The ratio X[CH3CHO]/X[c-C2H4O] varies between 2.6 (NGC 6334F) and 8.5 (G327.3-0.6). We also detected and analysed multiple transitions of CH3OH, CH3OCH3, C2H5OH, and HCOOH. The chemical, and possibly evolutionary, states of NGC 6334F, G327.3-0.6, G31.41+0.31, and G34.3+0.2 seem to be very similar.

Adding stable carbon isotopes improves model representation of the role of microbial communities in peatland methane cycling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Deng, Jia; McCalley, Carmody K.; Frolking, Steve

Climate change is expected to have significant and uncertain impacts on methane (CH 4) emissions from northern peatlands. Biogeochemical models can extrapolate site-specific CH 4 measurements to larger scales and predict responses of CH 4 emissions to environmental changes. However, these models include considerable uncertainties and limitations in representing CH4 production, consumption, and transport processes. To improve predictions of CH 4 transformations, we incorporated acetate and stable carbon (C) isotopic dynamics associated with CH 4 cycling into a biogeochemistry model, DNDC. By including these new features, DNDC explicitly simulates acetate dynamics and the relative contribution of acetotrophic and hydrogenotrophic methanogenesismore » (AM and HM) to CH 4 production, and predicts the C isotopic signature (δ 13C) in soil C pools and emitted gases. When tested against biogeochemical and microbial community observations at two sites in a zone of thawing permafrost in a subarctic peatland in Sweden, the new formulation substantially improved agreement with CH 4 production pathways and δ 13C in emitted CH 4 (δ 13C-CH 4), a measure of the integrated effects of microbial production and consumption, and of physical transport. We also investigated the sensitivity of simulated δ 13C-CH 4 to C isotopic composition of substrates and, to fractionation factors for CH4 production (α AM and α HM), CH 4 oxidation (α MO), and plant-mediated CH 4 transport (α TP). The sensitivity analysis indicated that the δ13C-CH 4 is highly sensitive to the factors associated with microbial metabolism (α AM, α HM, and α MO). The model framework simulating stable C isotopic dynamics provides a robust basis for better constraining and testing microbial mechanisms in predicting CH 4 cycling in peatlands.« less

Adding stable carbon isotopes improves model representation of the role of microbial communities in peatland methane cycling

DOE PAGES

Deng, Jia; McCalley, Carmody K.; Frolking, Steve; ...

2017-06-13

Climate change is expected to have significant and uncertain impacts on methane (CH 4) emissions from northern peatlands. Biogeochemical models can extrapolate site-specific CH 4 measurements to larger scales and predict responses of CH 4 emissions to environmental changes. However, these models include considerable uncertainties and limitations in representing CH4 production, consumption, and transport processes. To improve predictions of CH 4 transformations, we incorporated acetate and stable carbon (C) isotopic dynamics associated with CH 4 cycling into a biogeochemistry model, DNDC. By including these new features, DNDC explicitly simulates acetate dynamics and the relative contribution of acetotrophic and hydrogenotrophic methanogenesismore » (AM and HM) to CH 4 production, and predicts the C isotopic signature (δ 13C) in soil C pools and emitted gases. When tested against biogeochemical and microbial community observations at two sites in a zone of thawing permafrost in a subarctic peatland in Sweden, the new formulation substantially improved agreement with CH 4 production pathways and δ 13C in emitted CH 4 (δ 13C-CH 4), a measure of the integrated effects of microbial production and consumption, and of physical transport. We also investigated the sensitivity of simulated δ 13C-CH 4 to C isotopic composition of substrates and, to fractionation factors for CH4 production (α AM and α HM), CH 4 oxidation (α MO), and plant-mediated CH 4 transport (α TP). The sensitivity analysis indicated that the δ13C-CH 4 is highly sensitive to the factors associated with microbial metabolism (α AM, α HM, and α MO). The model framework simulating stable C isotopic dynamics provides a robust basis for better constraining and testing microbial mechanisms in predicting CH 4 cycling in peatlands.« less

Bandgap Engineering of Stable Lead-Free Oxide Double Perovskites for Photovoltaics.

PubMed

Sun, Qingde; Wang, Jing; Yin, Wan-Jian; Yan, Yanfa

2018-04-01

Despite the rapid progress in solar power conversion efficiency of archetype organic-inorganic hybrid perovskite CH 3 NH 3 PbI 3 -based solar cells, the long-term stability and toxicity of Pb remain the main challenges for the industrial deployment, leading to more uncertainties for global commercialization. The poor stabilities of CH 3 NH 3 PbI 3 -based solar cells may not only be attributed to the organic molecules but also the halides themself, most of which exhibit intrinsic instability under moisture and light. As an alternative, the possibility of oxide perovskites for photovoltaic applications is explored here. The class of lead-free stable oxide double perovskites A 2 M(III)M(V)O 6 (A = Ca, Sr, Ba; M(III) = Sb 3+ or Bi 3+ ; M(V) = V 5+ , Nb 5+ , or Ta 5+ ) is comprehensively explored with regard to their stability and their electronic and optical properties. Apart from the strong stability, this class of double perovskites exhibits direct bandgaps ranging from 0.3 to 3.8 eV. With proper B site alloying, the bandgap can be tuned within the range of 1.0-1.6 eV with optical absorptions as strong as CH 3 NH 3 PbI 3 , making them suitable for efficient single-junction thin-film solar cell application. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evidence on Anaerobic Methane Oxidation (AOM) in a boreal cultivated peatland with natural and added electron acceptors

NASA Astrophysics Data System (ADS)

Dorodnikov, Maxim; Silvennoinen, Hanna; Martikainen, Pertti; Dörsch, Peter

2015-04-01

Anaerobic oxidation of methane (AOM) is a process of methane (CH4) consumption under anoxic conditions driven by microorganisms, which oxidize CH4 with various alternate electron acceptors (AEA): sulfate, nitrate, nitrite, metals-(Fe, Mn, Cu), organic compounds. AOM is common in marine ecosystems, where microbial sulfate reduction (SR) consumes most of the CH4 produced in sediments. Despite the global significance of AOM, the exact mechanisms and relevance of the process in terrestrial ecosystems are almost unknown. In the current study the occurrence of AOM was tested for two organic soil horizons (30 and 40 cm depth) and one mineral sub-soil (sand, 50 cm depth) of a cultivated boreal peatland (Linnansuo, Eastern Finland, energy crop Phalaris arundinacea - reed canarygrass) under controlled conditions with the addition of 13C-labeled CH4 and two common AEAs - SO4-2 and Fe+3. Concentrations of CH4, CO2 and O2 were continuously measured during 10 days of incubation and CO2 was sampled periodically under anaerobic conditions for stable 13C analysis. Oxygen dynamics revealed negligible O2 contamination during incubation and its trace amounts (0.05-0.8% from the atmospheric) were accounted in the net CH4 uptake. Application of 13C-enriched CH4 (4.9 atom%) allowed to track the label in CO2 as the end-product of AOM. The highest 13CO2 enrichment (up to 60‰) was observed in mineral sub-soil, however AOM was quantitatively more pronounced in the upper 30 cm horizon (2.1 vs. 0.2 μg CO2 g soil DW-1 in the 50 cm sub-soil). The highest AOM rate of 8.9 ng CO2 g soil DW-1 h-1 was estimated for the control treatment where no AEAs were added indicating sufficient amount of naturally available AEAs, likely organic compounds. This rate was 50 times more intensive (on the C basis) than the CH4 production potential of the same soil. In contrast, external AEAs decreased AOM rates but added Fe+3 stimulated decomposition of native SOM (as seen from the most depleted 13CO2 signatures). Thus, the experiments revealed that this organic soil had capacity for AOM with its natural electron acceptors. Further AOM assessments may change the existing concept of carbon/CH4 cycling in terrestrial ecosystems and will improve current process-based models of regional and global carbon balance.

Understanding methane variability from 1980 - 2015 using inversions of methane, δ13C and ethane

NASA Astrophysics Data System (ADS)

Thompson, Rona; Nisbet, Euan

2017-04-01

Atmospheric methane (CH4) increased globally during the 20th century, from a pre-industrial value of approximately 722 ppb to 1773 ppb in 1999. The upward trend, however, was interrupted between 1999 and 2006, when the atmospheric growth rate of CH4 was close to zero. From 2007, atmospheric CH4 started to increase again and, in 2014, the growth rate was substantially faster (12.5 ppb/y) than in any other year since 2007. Changes in the atmospheric growth rate indicate changes in the balance of CH4 sources and sinks, however, the cause of the 1999-2006 stabilization and subsequent rise in atmospheric CH4, and its attribution to different sources is still not fully resolved. Various explanations have been proposed for the pause in the growth, including a reduction in fossil fuel and wetland emissions, and for its renewed increase, such as increasing emissions from wetlands, enteric fermentation, and fossil fuels, as well as a decline in the OH sink. To better constrain the sources and sinks of CH4, we have performed an inversion using the AGAGE 12-box model of the atmosphere using atmospheric observations of CH4, δ13C, and of ethane. Using observations of these 3 atmospheric tracers simultaneously, a stronger constraint is placed on the different sources, as well as the principal atmospheric sink via oxidation by OH. In the model, we account for all emissions grouped into microbial, fossil fuel, biomass burning, landfill and ocean sources, as well as the soil oxidation sink. We also account for the atmospheric sink of CH4 and ethane via oxidation by OH and Cl radicals. The modelled lifetimes of CH4 and ethane were 8.2 years and 1.3 months, respectively. Inversions were also performed in which the OH sink was optimized simultaneously with the emissions. We find that fossil fuel emissions were underestimated in the northern mid to high latitudes in the 1980s but were overestimated from the mid 1990s onwards with respect to the prior (EDGAR-4.2), and that there is no evidence for a recent increase. For microbial emissions, we find an increase in emissions in the northern low and high latitudes from the early 2000s. The inversion also shifts microbial emissions from the northern to the southern low latitudes with respect to the prior (LPX-Bern for wetlands and EDGAR-4.2 for enteric fermentation). Finally, we do not find any evidence for a recent decrease in the OH sink.

Low-concentration kinetics of atmospheric CH{sub 4} oxidation in soil and mechanism of NH{sub 4}{sup +} inhibition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gulledge, J.; Schimel, J.P.

1998-11-01

NH{sub 4}{sup +} inhibition kinetics for CH{sub 4} oxidation were examined at near-atmospheric CH{sub 4} concentrations in three upland forest soils. Whether NH{sub 4}{sup +}-independent salt effects could be neutralized by adding nonammoniacal salts to control samples in lieu of deionized water was also investigated. Because the levels of exchangeable endogenous NH{sub 4}{sup +} were very low in the three soils, desorption of endogenous NH{sub 4}{sup +} was not a significant factor in this study. The K{sub m(app)} values for water-treated controls were 9.8, 22, and 57 nM for temperate pine, temperate hardwood, and birch taiga soils, respectively. At CH{submore » 4} concentrations of {le}15 {micro}l liter{sup {minus}1}, oxidation followed first-order kinetics in the fine-textured taiga soil, whereas the coarse-textured temperate soils exhibited Michaelis-Menten kinetics. Compared to water controls, the K{sub m(app)} values in the temperate soils increased in the presence of NH{sub 4}{sup +} salts, whereas the V{sub max(app)} values decreased substantially, indicating that there was a mixture of competitive and noncompetitive inhibition mechanisms for whole NH{sub 4}{sup +} salts. Compared to the corresponding K{sup +} salt controls, the K{sub m(app)} values for NH{sub 4}{sup +} salts increased substantially, whereas the V{sub max(app)} values remained virtually unchanged, indicating that NH{sub 4}{sup +} acted by competitive inhibition. Nonammoniacal salts caused inhibition to increase with increasing CH{sub 4} concentrations in all three soils. In the birch taiga soil, this trend occurred with both NH{sub 4}{sup +} and K{sup +} salts, and the slope of the increase was not affected by the addition of NH{sub 4}{sup +}. Hence, the increase in inhibition resulted from an NH{sub 4}{sup +}-independent mechanism.« less

Two-State Reactivity in Low-Valent Iron-Mediated C-H Activation and the Implications for Other First-Row Transition Metals.

PubMed

Sun, Yihua; Tang, Hao; Chen, Kejuan; Hu, Lianrui; Yao, Jiannian; Shaik, Sason; Chen, Hui

2016-03-23

C-H bond activation/functionalization promoted by low-valent iron complexes has recently emerged as a promising approach for the utilization of earth-abundant first-row transition metals to carry out this difficult transformation. Herein we use extensive density functional theory and high-level ab initio coupled cluster calculations to shed light on the mechanism of these intriguing reactions. Our key mechanistic discovery for C-H arylation reactions reveals a two-state reactivity (TSR) scenario in which the low-spin Fe(II) singlet state, which is initially an excited state, crosses over the high-spin ground state and promotes C-H bond cleavage. Subsequently, aryl transmetalation occurs, followed by oxidation of Fe(II) to Fe(III) in a single-electron transfer (SET) step in which dichloroalkane serves as an oxidant, thus promoting the final C-C coupling and finalizing the C-H functionalization. Regeneration of the Fe(II) catalyst for the next round of C-H activation involves SET oxidation of the Fe(I) species generated after the C-C bond coupling. The ligand sphere of iron is found to play a crucial role in the TSR mechanism by stabilization of the reactive low-spin state that mediates the C-H activation. This is the first time that the successful TSR concept conceived for high-valent iron chemistry is shown to successfully rationalize the reactivity for a reaction promoted by low-valent iron complexes. A comparative study involving other divalent middle and late first-row transition metals implicates iron as the optimum metal in this TSR mechanism for C-H activation. It is predicted that stabilization of low-spin Mn(II) using an appropriate ligand sphere should produce another promising candidate for efficient C-H bond activation. This new TSR scenario therefore emerges as a new strategy for using low-valent first-row transition metals for C-H activation reactions.

Methane and nitrous oxide cycling microbial communities in soils above septic leach fields: Abundances with depth and correlations with net surface emissions.

PubMed

Fernández-Baca, Cristina P; Truhlar, Allison M; Omar, Amir-Eldin H; Rahm, Brian G; Walter, M Todd; Richardson, Ruth E

2018-05-31

Onsite septic systems use soil microbial communities to treat wastewater, in the process creating potent greenhouse gases (GHGs): methane (CH 4 ) and nitrous oxide (N 2 O). Subsurface soil dispersal systems of septic tank overflow, known as leach fields, are an important part of wastewater treatment and have the potential to contribute significantly to GHG cycling. This study aimed to characterize soil microbial communities associated with leach field systems and quantify the abundance and distribution of microbial populations involved in CH 4 and N 2 O cycling. Functional genes were used to target populations producing and consuming GHGs, specifically methyl coenzyme M reductase (mcrA) and particulate methane monooxygenase (pmoA) for CH 4 and nitric oxide reductase (cnorB) and nitrous oxide reductase (nosZ) for N 2 O. All biomarker genes were found in all soil samples regardless of treatment (leach field, sand filter, or control) or depth (surface or subsurface). In general, biomarker genes were more abundant in surface soils than subsurface soils suggesting the majority of GHG cycling is occurring in near-surface soils. Ratios of production to consumption gene abundances showed a positive relationship with CH 4 emissions (mcrA:pmoA, p < 0.001) but not with N 2 O emission (cnorB:nosZ, p > 0.05). Of the three measured soil parameters (volumetric water content (VWC), temperature, and conductivity), only VWC was significantly correlated to a biomarker gene, mcrA (p = 0.0398) but not pmoA or either of the N 2 O cycling genes (p > 0.05 for cnorB and nosZ). 16S rRNA amplicon library sequencing results revealed soil VWC, CH 4 flux and N 2 O flux together explained 64% of the microbial community diversity between samples. Sequencing of mcrA and pmoA amplicon libraries revealed treatment had little effect on diversity of CH 4 cycling organisms. Overall, these results suggest GHG cycling occurs in all soils regardless of whether or not they are associated with a leach field system. Copyright © 2018 Elsevier B.V. All rights reserved.

Photomineralization and photomethanification of dissolved organic matter in Saguenay River surface water

NASA Astrophysics Data System (ADS)

Zhang, Y.; Xie, H.

2015-08-01

Rates and apparent quantum yields of photomineralization (AQYDOC) and photomethanification (AQYCH4) of chromophoric dissolved organic matter (CDOM) in Saguenay River surface water were determined at three widely differing dissolved oxygen concentrations ([O2]) (suboxic, air-saturation, and oxygenated) using simulated-solar radiation. Photomineralization increased linearly with CDOM absorbance photobleaching for all three O2 treatments. Whereas the rate of photochemical dissolved organic carbon (DOC) loss increased with increasing [O2], the ratio of fractional DOC loss to fractional absorbance loss showed an inverse trend. CDOM photodegradation led to a nearly complete mineralization under suboxic conditions but to only a partial mineralization under oxic conditions. AQYDOC determined under oxygenated, suboxic, and air-saturated conditions increased, decreased, and remained largely constant with photobleaching, respectively; AQYDOC obtained under air-saturation with short-term irradiations could thus be applied to longer exposures. AQYDOC decreased successively from ultraviolet B (UVB) to ultraviolet A (UVA) to visible (VIS), which, alongside the solar irradiance spectrum, points to VIS and UVA being the primary drivers for photomineralization in the water column. The photomineralization rate in the Saguenay River was estimated to be 2.31 × 108 mol C yr-1, accounting for only 1 % of the annual DOC input into this system. Photoproduction of CH4 occurred under both suboxic and oxic conditions and increased with decreasing [O2], with the rate under suboxic conditions ~ 7-8 times that under oxic conditions. Photoproduction of CH4 under oxic conditions increased linearly with photomineralization and photobleaching. Under air-saturation, 0.00057 % of the photochemical DOC loss was diverted to CH4, giving a photochemical CH4 production rate of 4.36 × 10-6 mol m-2 yr-1 in the Saguenay River and, by extrapolation, of (1.9-8.1) × 108 mol yr-1 in the global ocean. AQYCH4 changed little with photobleaching under air-saturation but increased exponentially under suboxic conditions. Spectrally, AQYCH4 decreased sequentially from UVB to UVA to VIS, with UVB being more efficient under suboxic conditions than under oxic conditions. On a depth-integrated basis, VIS prevailed over UVB in controlling CH4 photoproduction under air-saturation while the opposite held true under O2-deficiency. An addition of micromolar levels of dissolved dimethyl sulfide (DMS) substantially increased CH4 photoproduction, particularly under O2-deficiency; DMS at nanomolar ambient concentrations in surface oceans is, however, unlikely a significant CH4 precursor. Results from this study suggest that CDOM-based CH4 photoproduction only marginally contributes to the CH4 supersaturation in modern surface oceans and to both the modern and Archean atmospheric CH4 budgets, but that the photochemical term can be comparable to microbial CH4 oxidation in modern oxic oceans. Our results also suggest that anoxic microniches in particulate organic matter and phytoplankton cells containing elevated concentrations of precursors of the methyl radical such as DMS may provide potential hotspots for CH4 photoproduction.

Photomineralization and photomethanification of dissolved organic matter in Saguenay River surface water

NASA Astrophysics Data System (ADS)

Zhang, Y.; Xie, H.

2015-11-01

Rates and apparent quantum yields of photomineralization (AQYDOC) and photomethanification (AQYCH4) of chromophoric dissolved organic matter (CDOM) in Saguenay River surface water were determined at three widely differing dissolved oxygen concentrations ([O2]) (suboxic, air saturation, and oxygenated) using simulated-solar radiation. Photomineralization increased linearly with CDOM absorbance photobleaching for all three O2 treatments. Whereas the rate of photochemical dissolved organic carbon (DOC) loss increased with increasing [O2], the ratio of fractional DOC loss to fractional absorbance loss showed an inverse trend. CDOM photodegradation led to a higher degree of mineralization under suboxic conditions than under oxic conditions. AQYDOC determined under oxygenated, suboxic, and air-saturated conditions increased, decreased, and remained largely constant with photobleaching, respectively; AQYDOC obtained under air saturation with short-term irradiations could thus be applied to longer exposures. AQYDOC decreased successively from ultraviolet B (UVB) to ultraviolet A (UVA) to visible (VIS), which, alongside the solar irradiance spectrum, points to VIS and UVA being the primary drivers for photomineralization in the water column. The photomineralization rate in the Saguenay River was estimated to be 2.31 × 108 mol C yr-1, accounting for only 1 % of the annual DOC input into this system. Photoproduction of CH4 occurred under both suboxic and oxic conditions and increased with decreasing [O2], with the rate under suboxic conditions ~ 7-8 times that under oxic conditions. Photoproduction of CH4 under oxic conditions increased linearly with photomineralization and photobleaching. Under air saturation, 0.00057 % of the photochemical DOC loss was diverted to CH4, giving a photochemical CH4 production rate of 4.36 × 10-6 mol m-2 yr-1 in the Saguenay River and, by extrapolation, of (1.9-8.1) × 108 mol yr-1 in the global ocean. AQYCH4 changed little with photobleaching under air saturation but increased exponentially under suboxic conditions. Spectrally, AQYCH4 decreased sequentially from UVB to UVA to VIS, with UVB being more efficient under suboxic conditions than under oxic conditions. On a depth-integrated basis, VIS prevailed over UVB in controlling CH4 photoproduction under air saturation while the opposite held true under O2-deficiency. An addition of micromolar levels of dissolved dimethyl sulfide (DMS) substantially increased CH4 photoproduction, particularly under O2-deficiency; DMS at nanomolar ambient concentrations in surface oceans is, however, unlikely a significant CH4 precursor. Results from this study suggest that CDOM-based CH4 photoproduction only marginally contributes to the CH4 supersaturation in modern surface oceans and to both the modern and Archean atmospheric CH4 budgets, but that the photochemical term can be comparable to microbial CH4 oxidation in modern oxic oceans. Our results also suggest that anoxic microniches in particulate organic matter and phytoplankton cells containing elevated concentrations of precursors of the methyl radical such as DMS may provide potential hotspots for CH4 photoproduction.

The ultrasound-assisted oxidative scission of monoenic fatty acids by ruthenium tetroxide catalysis: influence of the mixture of solvents.

PubMed

Rup, Sandrine; Zimmermann, François; Meux, Eric; Schneider, Michel; Sindt, Michele; Oget, Nicolas

2009-02-01

Carboxylic acids and diacids were synthesized from monoenic fatty acids by using RuO4 catalysis, under ultrasonic irradiation, in various mixtures of solvents. Ultrasound associated with Aliquat 336 have promoted in water, the quantitative oxidative cleavage of the CH=CH bond of oleic acid. A design of experiment (DOE) shows that the optimal mixture of solvents (H2O/MeCN, ratio 1/1, 2.2% RuCl3/4.1 eq. NaIO4) gives 81% azelaic acid and 97% pelargonic acid. With the binary heterogeneous mixture H2O/AcOEt, the oxidation of the oleic acid leads to a third product, the alpha-dione 9,10-dioxostearic acid.

Ice core measurements of 14CH4 show no evidence of methane release to atmosphere from methane hydrates during a large warming event 11,600 years ago

NASA Astrophysics Data System (ADS)

Petrenko, V. V.; Severinghaus, J. P.; Smith, A.; Riedel, K.; Brook, E.; Schaefer, H.; Baggenstos, D.; Harth, C. M.; Hua, Q.; Buizert, C.; Schilt, A.; Fain, X.; Mitchell, L.; Bauska, T. K.; Orsi, A. J.; Weiss, R. F.

2016-12-01

Marine methane hydrate destabilization has been proposed as a potentially large source of methane to the atmosphere in response to both past and future warming. We present new measurements of 14C of paleoatmospheric methane (CH4) over the Younger Dryas - Preboreal (YD - PB) abrupt warming event (≈11,600 years ago) from ancient ice outcropping at Taylor Glacier, Antarctica. The YD - PB abrupt warming was centered in the North Atlantic, occurred partway through the global warming of last deglaciation and was associated with a ≈ 50% increase in atmospheric CH4 concentrations. 14C can unambiguously identify CH4 emissions from "old carbon" sources, such as CH4 hydrates. All samples from before, during and after the abrupt warming and associated CH4 increase yielded 14CH4 values that are consistent with 14C of atmospheric CO2 at that time, indicating a purely contemporaneous methane source. Our results show that neither the abrupt regional warming nor the gradual global warming that preceded it resulted in detectable CH4 release to the atmosphere from CH4 hydrates during the YD - PB transition. Our results are thus consistent with the hypothesis that the vast majority of CH4 that is released from dissociating hydrates or other old-carbon seafloor CH4 sources is oxidized prior to reaching the atmosphere.

Directed C-H Bond Oxidation of (+)-Pleuromutilin.

PubMed

Ma, Xiaoshen; Kucera, Roman; Goethe, Olivia F; Murphy, Stephen K; Herzon, Seth B

2018-05-01

Antibiotics derived from the diterpene fungal metabolite (+)-pleuromutilin (1) are useful agents for the treatment Gram-positive infections in humans and farm animals. Pleuromutilins elicit slow rates of resistance development and minimal cross-resistance with existing antibiotics. Despite efforts aimed at producing new derivatives by semisynthesis, modification of the tricyclic core is underexplored, in part due to a limited number of functional group handles. Herein, we report methods to selectively functionalize the methyl groups of (+)-pleuromutilin (1) by hydroxyl-directed iridium-catalyzed C-H silylation, followed by Tamao-Fleming oxidation. These reactions provided access to C16, C17, and C18 monooxidized products, as well as C15/C16 and C17/C18 dioxidized products. Four new functionalized derivatives were prepared from the protected C17 oxidation product. C6 carboxylic acid, aldehyde, and normethyl derivatives were prepared from the C16 oxidation product. Many of these sequences were executed on gram scales. The efficiency and practicality of these routes provides an easy method to rapidly interrogate structure-activity relationships that were previously beyond reach. This study will inform the design of fully synthetic approaches to novel pleuromutilins and underscores the power of the hydroxyl-directed iridium-catalyzed C-H silylation reaction.

Photo-oxidation of cork manufacturing wastewater.

PubMed

Silva, Carla A; Madeira, Luis M; Boaventura, Rui A; Costa, Carlos A

2004-04-01

Several photo-activated processes have been investigated for oxidation of a cork manufacturing wastewater. A comparative activity study is made between different homogeneous (H2O2/UV-Vis and H2O2/Fe2+/UV-Vis) and heterogeneous (TiO2/UV-Vis and TiO2/H2O2/UV-Vis) systems, with degradation performances being evaluated in terms of total organic carbon (TOC) removal. Results obtained in a batch photo-reactor show that photo-catalysis with TiO2 is not suitable for this kind of wastewater while the H2O2/UV-Vis oxidation process, for which the effect of some operating conditions was investigated, allows to remove 39% of TOC after 4 h of operation (for C(H2O2)=0.59 M, pH=10 and T=35 degrees C). The combined photo-activated process, i.e., using both TiO2 and H2O2, yields an overall TOC decrease of 46% (for C(TiO2)=1.0 gl(-1)). The photo-Fenton process proved to be the most efficient, proceeds at a much higher oxidation rate and allows to achieve 66% mineralization in just 10 min of reaction time (for C(H2O2)=0.31 M, T=30 degrees C, Fe2+:H2O2=0.12 (mol) and pH=3.2).

Methane Transmission and Oxidation throughout the Soil Column from Three Central Florida Sites

NASA Astrophysics Data System (ADS)

Bond-Lamberty, B. P.; Fansler, S.; Becker, K. E.; Hinkle, C. R.; Bailey, V. L.

2015-12-01

When methane (CH4) is generated in anoxic soil sites, it may be subsequently re-oxidized to carbon dioxide (CO2). Understanding the controls on, and magnitudes of, these processes is necessary to accurately represent greenhouse gas production and emission from soils. We used a laboratory incubation to examine the influence of variable conditions on methane transmission and oxidation, and identify critical reaction zones throughout the soil column. Sandy soils were sampled from three different sites at Disney Wilderness Preserve (DWP), Florida, USA: a depression marsh characterized by significant surface organic matter accumulation, a dry pine flatwood site with water intrusion and organic horizon at depth (200+ cm); and an intermediate-drainage site. Contiguous, 30-cm long cores were sampled from N=4 random boreholes at each site, from the surface to the water table (varying from 90 to 240 cm). In the lab, each core was monitored for 50 hours to quantify baseline (pretreatment) gas fluxes before injection with 6 ml CH4 (an amount commensurate with previous field collar measurements) at the base of each core. We then monitored CH4 and CO2 evolution for 100 hours after injection, calculating per-gas and total C evolution. Methane emissions spiked ~10 hours after injection for all cores, peaking at 0.001 μmol/g soil/hr, ~30x larger than pre-injection flux rates. On a C basis, CO2 emissions were orders of magnitude larger, and rose significantly after injection, with elevated rates generally sustained throughout the incubation. Cores from the depression marsh and shallower depths had significantly higher fluxes of both gases. We estimate that 99.1% of the original CH4 injection was oxidized to CO2. These findings suggest either that the methane measured in the field at DWP originates from within a few centimeters of the surface, or that it is produced in much larger quantities deeper in the profile before most is subsequently oxidized. This highlights the need for better understanding and modeling the multiple processes that result in soil-atmosphere CO2 and CH4 fluxes.

Mechanism of the Thermal Decomposition of Ethanethiol and Dimethylsulfide

NASA Astrophysics Data System (ADS)

Melhado, William Francis; Whitman, Jared Connor; Kong, Jessica; Anderson, Daniel Easton; Vasiliou, AnGayle (AJ)

2016-06-01

Combustion of organosulfur contaminants in petroleum-based fuels and biofuels produces sulfur oxides (SO_x). These pollutants are highly regulated by the EPA because they have been linked to poor respiratory health and negative environmental impacts. Therefore much effort has been made to remove sulfur compounds in petroleum-based fuels and biofuels. Currently desulfurization methods used in the fuel industry are costly and inefficient. Research of the thermal decomposition mechanisms of organosulfur species can be implemented via engineering simulations to modify existing refining technologies to design more efficient sulfur removal processes. We have used a resistively-heated SiC tubular reactor to study the thermal decomposition of ethanethiol (CH_3CH_2SH) and dimethylsulfide (CH_3SCH_3). The decomposition products are identified by two independent techniques: 118.2 nm VUV photoionization mass spectroscopy and infrared spectroscopy. The thermal cracking products for CH_3CH_2SH are CH_2CH_2, SH, and H_2S and the thermal cracking products from CH_3SCH_3 are CH_3S, CH_2S, and CH_3.

Investigation of Benthic Foraminiferal Non-Traditional Stable Isotopes to Reconstruct Methane Fluxes in Sedimentary Environments

NASA Technical Reports Server (NTRS)

Borrelli, C.; Gabitov, R. I.; Messenger, S. R.; Nguyen, A. N.; Torres, M. E.; Kessler, J. D.

2015-01-01

Methane (CH4) is an important greenhouse gas, with a global warming potential much higher than carbon dioxide (CO2) on a short time scale. Even if the residence time of CH4 in the atmosphere is relatively short (tens of years), one of the products of CH4 oxidation is CO2, a greenhouse gas with a much longer residence time in the atmosphere (tens to hundreds of years). CH4 has been proposed as one of the trigger mechanisms for rapid global climate change today and in the geological past. With regards to the geological past, numerous studies proposed the benthic foraminiferal carbon isotope ratio (Delta13C) as a tool to reconstruct the impact of marine CH4 on rapid climate changes; however, the investigation of modern benthic foraminiferal Delta13C have produced inconclusive results. CH4 has a distinctive hydrogen isotope (Delta(D)) and Delta13C signature compared to seawater, and sulfate reduction, often coupled to CH4 anaerobic oxidation in sediments, changes the sulfur isotope signature (Delta34S) of the remaining sulfate in porewater. Therefore, we hypothesize that the Delta(D) and Delta34S signature of infaunal benthic foraminiferal species can provide a complementary approach to Delta13C to study CH4 dynamics in sedimentary environments. Here, we present the preliminary results obtained analyzing Uvigerina peregrina Delta(D) and Delta34S from three different locations at Hydrate Ridge, offshore Oregon. Unfortunately, the lack of chemical data related to the moment of foraminiferal calcification makes difficult to build a robust relationship among the U. peregrina stable isotopes and the CH4 fluxes at the sampling sites. However, our results look very promising, as each site is characterized by a different Delta(D) and Delta34S signature. We emphasize that this study represents the first step in the development of new proxies (Delta(D)) and Delta34S), which may complement the more traditional benthic foraminiferal Delta13C values, to reconstruct marine CH4 fluxes in the geological past.

Laboratory-scale measurements of N2O and CH4 emissions from hybrid poplars (Populus deltoides x Populus nigra).

PubMed

McBain, M C; Warland, J S; McBride, R A; Wagner-Riddle, C

2004-12-01

The purpose of this study was to determine whether or not young hybrid poplar (Populus deltoides x Populus nigra) could transport landfill biogas internally from the root zone to the atmosphere, thereby acting as conduits for landfill gas release. Fluxes of methane (CH4) and nitrous oxide (N2O) from the seedlings to the atmosphere were measured under controlled conditions using dynamic flux chambers and a tunable diode laser trace gas analyser (TDLTGA). Nitrous oxide was emitted from the seedlings, but only when extremely high soil N2O concentrations were applied to the root zone. In contrast, no detectable emissions of CH4 were measured in a similar experimental trial. Visible plant morphological responses, characteristic of flood-tolerant trees attempting to cope with the negative effects of soil hypoxia, were observed during the CH4 experiments. Leaf chlorosis, leaf abscission and adventitious roots were all visible plant responses. In addition, seedling survival was observed to be highest in the biogas 'hot spot' areas of a local municipal solid waste landfill involved in this study. Based on the available literature, these observations suggest that CH4 can be transported internally by Populus deltoides x Populus nigra seedlings in trace amounts, although future research is required to fully test this hypothesis.

The geochemistry of methane in Lake Fryxell, an amictic, permanently ice-covered, antarctic lake

USGS Publications Warehouse

Smith, R.L.; Miller, L.G.; Howes, B.L.

1993-01-01

The abundance and distribution of dissolved CH4 were determined from 1987-1990 in Lake Fryxell, Antarctica, an amictic, permanently ice-covered lake in which solute movement is controlled by diffusion. CH4 concentrations were < 1 ??M in the upper oxic waters, but increased below the oxycline to 936 ??M at 18 m. Sediment CH4 was 1100 ??mol (1 sed)-1 in the 0-5 cm zone. Upward flux from the sediment was the source of the CH4, NH4 +, and DOC in the water column; CH4 was 27% of the DOC+CH4 carbon at 18 m. Incubations with surficial sediments indicated that H14CO3 - reduction was 0.4 ??mol (1 sed)-1 day-1 or 4?? the rate of acetate fermentation to CH4. There was no measurable CH4 production in the water column. However, depth profiles of CH4, NH4, and DIC normalized to bottom water concentrations demonstrated that a significant CH4 sink was evident in the anoxic, sulfate-containing zone of the water column (10-18 m). The ??13CH4 in this zone decreased from -72 % at 18 m to -76% at 12 m, indicating that the consumption mechanism did not result in an isotopic enrichment of 13CH4. In contrast, ??13CH4 increased to -55 % at 9 m due to aerobic oxidation, though this was a minor aspect of the CH4 cycle. The water column CH4 profile was modeled by coupling diffusive flux with a first order consumption term; the best-fit rate constant for anaerobic CH4 consumption was 0.012 yr-1. On a total carbon basis, CH4 consumption in the anoxic water column exerted a major effect on the flux of carbonaceous material from the underlying sediments and serves to exemplify the importance of CH4 to carbon cycling in Lake Fryxell. ?? 1993 Kluwer Academic Publishers.

UV radiation and CH4 gas detection with a single ZnO:Pd nanowire

NASA Astrophysics Data System (ADS)

Lupan, O.; Adelung, R.; Postica, V.; Ababii, N.; Chow, L.; Viana, B.; Pauporté, T.

2017-02-01

There is an increasing demand for sensors to monitor environmental levels of ultraviolet (UV) radiation and pollutant gases. In this work, an individual nanowire of Pd modified ZnO nanowire (ZnO:Pd NW) was integrated in a nanosensor device for efficient and fast detection of UV light and CH4 gas at room temperature. Crystalline ZnO:Pd nanowire/nanorod arrays were synthesized onto fluorine doped tin oxide (FTO) substrates by electrochemical deposition (ECD) at relative low-temperatures (90 °C) with different concentrations of PdCl2 in electrolyte solution and investigated by SEM and EDX. Nanodevices were fabricated using dual beam focused electron/ion beam (FIB/SEM) system and showed improved UV radiation response compared to pristine ZnO NW, reported previously by our group. The UV response was increased by one order in magnitude (≈ 11) for ZnO:Pd NW. Gas sensing measurements demonstrated a higher gas response and rapidity to methane (CH4 gas, 100 ppm) at room temperature, showing promising results for multifunctional applications. Also, due to miniature size and ultra-low power consumption of these sensors, it is possible to integrate them into portable devices easily, such as smartphones, digital clock, flame detection, missile lunching and other smart devices.

Greenhouse Gas Emissions from Cotton Field under Different Irrigation Methods and Fertilization Regimes in Arid Northwestern China

PubMed Central

Guo, Wei; Feng, Jinfei; Li, Lanhai; Yang, Haishui; Wang, Xiaohua; Bian, Xinmin

2014-01-01

Drip irrigation is broadly extended in order to save water in the arid cotton production region of China. Biochar is thought to be a useful soil amendment to reduce greenhouse gas (GHG) emissions. Here, a field study was conducted to compare the emissions of nitrous oxide (N2O) and methane (CH4) under different irrigation methods (drip irrigation (D) and furrow irrigation (F)) and fertilization regimes (conventional fertilization (C) and conventional fertilization + biochar (B)) during the cotton growth season. The accumulated N2O emissions were significantly lower with FB, DC, and DB than with FC by 28.8%, 36.1%, and 37.6%, while accumulated CH4 uptake was 264.5%, 226.7%, and 154.2% higher with DC, DB, and FC than that with FB, respectively. Irrigation methods showed a significant effect on total global warming potential (GWP) and yield-scaled GWP (P < 0.01). DC and DB showed higher cotton yield, water use efficiency (WUE), and lower yield-scaled GWP, as compared with FC and FB. This suggests that in northwestern China mulched-drip irrigation should be a better approach to increase cotton yield with depressed GHG. In addition, biochar addition increased CH4 emissions while it decreased N2O emissions. PMID:25133229

Modelling methane emissions from natural wetlands by development and application of the TRIPLEX-GHG model

USGS Publications Warehouse

Zhu, Qing; Liu, Jinxun; Peng, C.; Chen, H.; Fang, X.; Jiang, H.; Yang, G.; Zhu, D.; Wang, W.; Zhou, X.

2014-01-01

A new process-based model TRIPLEX-GHG was developed based on the Integrated Biosphere Simulator (IBIS), coupled with a new methane (CH4) biogeochemistry module (incorporating CH4 production, oxidation, and transportation processes) and a water table module to investigate CH4 emission processes and dynamics that occur in natural wetlands. Sensitivity analysis indicates that the most sensitive parameters to evaluate CH4 emission processes from wetlands are r (defined as the CH4 to CO2 release ratio) and Q10 in the CH4 production process. These two parameters were subsequently calibrated to data obtained from 19 sites collected from approximately 35 studies across different wetlands globally. Being heterogeneously spatially distributed, r ranged from 0.1 to 0.7 with a mean value of 0.23, and the Q10 for CH4 production ranged from 1.6 to 4.5 with a mean value of 2.48. The model performed well when simulating magnitude and capturing temporal patterns in CH4 emissions from natural wetlands. Results suggest that the model is able to be applied to different wetlands under varying conditions and is also applicable for global-scale simulations.

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

USDA-ARS?s Scientific Manuscript database

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...

Diurnal variation in greenhouse fluxes from a feedyard pen surface

USDA-ARS?s Scientific Manuscript database

Accurate estimation of greenhouse gas (GHG) emissions, including nitrous oxide (N2O) and methane (CH4) from open-lot beef cattle feedlots is an increasing concern given the current and potential future reporting requirements for GHG emissions. Research concerning N2O and CH4 emission fluxes from the...

Nitrous oxide and methane dynamics in a coral reef lagoon driven by pore water exchange: Insights from automated high-frequency observations

NASA Astrophysics Data System (ADS)

O'Reilly, Chiara; Santos, Isaac R.; Cyronak, Tyler; McMahon, Ashly; Maher, Damien T.

2015-04-01

Automated cavity ring down spectroscopy was used to make continuous measurements of dissolved methane, nitrous oxide, and carbon dioxide in a coral reef lagoon for 2 weeks (Heron Island, Great Barrier Reef). Radon (222Rn) was used to trace the influence of tidally driven pore water exchange on greenhouse gas dynamics. Clear tidal variation was observed for CH4, which correlated to 222Rn in lagoon waters. N2O correlated to 222Rn during the day only, which appears to be a response to coupled nitrification-denitrification in oxic sediments, fueled by nitrate derived from bird guano. The lagoon was a net source of CH4 and N2O to the atmosphere and a sink for atmospheric CO2. The estimated pore water-derived CH4 and N2O fluxes were 3.2-fold and 24.0-fold greater than the fluxes to the atmosphere. Overall, pore water and/or groundwater exchange were the only important sources of CH4 and major controls of N2O in the coral reef lagoon.

Comparison of partial oxidation and steam-CO{sub 2} mixed reforming of CH{sub 4} to syngas on MgO-supported metals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qin, D.; Lapszewicz, J.; Jiang, X.

1996-03-01

Partial oxidation (POX) and steam-CO{sub 2} mixed reforming of CH{sub 4} on MgO-supported noble metals were investigated at high space velocity (5.5 x 10{sup 5} h{sup -1}). Temperature-programmed reaction (TPR) and isotope transient techniques were used to study the mechanism of POX and mixed reforming. TPR profiles of POX and mixed reforming showed similar ignition reaction behaviors, which implied that there are similar characteristics in their mechanisms. Steam reforming and CO{sub 2} reforming were found to start at the same time in mixed reforming. TPR and CH{sub 4}-D{sub 2} exchange experiments indicated that CH{sub 4} was activated at low temperaturemore » on Rh/MgO. POX showed much higher activity than mixed reforming although their C, H, and O atomic concentrations were the same at the beginning of each reaction. Mechanisms for POX and mixed reforming are suggested and the effect of oxygen-metal bond strength on activity is discussed. 31 refs., 11 figs., 3 tabs.« less

Methane production, oxidation and emission in United Kingdom peatlands and the effect of anions from acid rain

NASA Astrophysics Data System (ADS)

Watson, Andrea

The production, oxidation and emission of methane in UK peatlands was investigated. The main field study site was Ellergower Moss, Dumfriesshire where the peat was characterised by hollows (water-filled depressions) and hummocks (raised vegetative areas). The pathways of carbon flow in peat under hummocks and hollows were determined and compared on a seasonal basis. Methane emissions were significantly greater from hollows than hummocks (0.88 mols and 0.07 mols CH4 m-2 y-1 respectively). Methane emission rates varied seasonally e.g. for hollows were 0.04 mmols CH4 m-2 d-1 for January and 2.3 mmols CH4 m-2 d-1 for June. Methane emissions were modulated by biological methane oxidation by 0% of methane produced in the winter months, increasing during spring until 97% of methane produced was oxidised in the summer months. Both methane oxidation and methanogenesis were strongly temperature dependant with Q10 values of 2.2 and 16, respectively. Rates of methane oxidation potential (MOP) were greatest between 4-8 cm depths below the level of the water table, and were located above the most active zone of methanogenesis (8-16 cm depths below the water table levels). This enabled vertically diffusing methane to be utilised by methanotrophic bacteria, providing a very efficient filter for methane. Methanogenesis was limited by hydrogen availability in the peat, but not by acetate, suggesting that methane was produced by hydrogenophilic methanogenic bacteria (MB), rather than acetate utilising MB. Acid rain pollutants were found to significantly affect carbon flow, with sulphate deposition causing a seasonal inhibition in methanogenesis. Carbon flow predominated through sulphate reduction in the winter and spring months (sulphate reduction to methane production ratio was 1008 and 189, for hummocks and hollows respectively) when sulphate was freely available and when temperatures were low. During the summer when temperatures increased and sulphate became limited carbon flow through methanogenesis predominated (sulphate reduction to methane production ratio 0.39 and 0.07, for hummocks and hollows respectively). The examination of two other peatlands-Great Dun Fell and Caithness which received higher and lower sulphate loadings than Ellergower respectively, did not show a consistent effect of sulphate inhibition on methanogenesis. The methane oxidation kinetics were used in a mathematical model to examine the effect of plant roots on increasing the vertical transport rate of methane out, and oxygen into the peat, by gas phase transport through the roots. (Abstract shortened by UMI.)

Methane and nitrous oxide analyzer comparison and emissions from dairy freestall barns with manure flushing and scraping

NASA Astrophysics Data System (ADS)

Cortus, Erin L.; Jacobson, Larry D.; Hetchler, Brian P.; Heber, Albert J.; Bogan, Bill W.

2015-01-01

Continuous methane (CH4) and nitrous oxide (N2O) emission measurements were conducted at two crossflow-ventilated dairy freestall barns located in the state of Wisconsin, USA during a 19-month period from 2008 to 2010. The two cross-flow mechanically ventilated buildings (275 and 375 cow capacities) were evaluated in the National Air Emissions Monitoring Study. In September of 2008, the barns' manure collection systems were changed from flushing open gutter using manure basin effluent to a tractor scrape. A photoacoustic multi-gas analyzer (PAMGA) and a direct methane/non-methane hydrocarbon analyzer (GC-FID) provided side-by-side measurements of methane (CH4) for 13 months. The PAMGA also measured nitrous oxide (N2O), and a side-by-side comparison was performed with a gas-filter correlation analyzer (GFC) for six months. Barn ventilation rates were measured by recording run times of the 127-cm diameter exhaust fans. All 125 belt-driven exhaust fans were identical, and in situ airflow measurements using the Fan Assessment Numeration System (FANS) were conducted once at the beginning and twice during the test. Daily CH4 and N2O emission rates were calculated over approximately 19 and 6 month periods respectively, on per barn, head, animal unit, floor area space and barn capacity bases. The differences between the analyzers' concentration measurements were compared in conjunction with water vapor and other gases. The analyzer type had a significant impact on the average CH4 emission rate (p < 0.001) and the average N2O emission rate (p < 0.05). Based on the CH4 measurements with the GC-FID, average daily mean CH4 emissions were approximately 290 g AU-1 d-1 (390 g cow-1 d-1) with very limited seasonal effects. Little variation was observed in CH4 emission rates before and after the change in manure collection method, suggesting that most of the CH4 emissions were enteric losses directly from the cows. The average daily mean N2O emission rates based on the GFC were very low, with an approximate rate of only 690 mg AU-1 d-1 (970 mg cow-1 d-1). The change in manure collection had no apparent effect on N2O emission.

Tuning the oxidative power of free iron-sulfur clusters.

PubMed

Lang, Sandra M; Zhou, Shaodong; Schwarz, Helmut

2017-03-15

The gas-phase reactions between a series of di-iron sulfur clusters Fe 2 S x + (x = 1-3) and the small alkenes C 2 H 4 , C 3 H 6 , and C 4 H 8 have been investigated by means of Fourier-transform ion-cyclotron resonance mass spectrometry. For all studied alkenes, the reaction efficiency is found to increase in the order Fe 2 S + < Fe 2 S 2 + < Fe 2 S 3 + . In particular, Fe 2 S + and Fe 2 S 2 + only form simple association products, whereas the sulfur-rich Fe 2 S 3 + is able to dehydrogenate propene and 2-butene via desulfurization of the cluster and formation of H 2 S. This indicates an increased propensity to induce oxidation reactions, i.e. oxidative power, of Fe 2 S 3 + that is attributed to an increased formal oxidation state of the iron atoms. Furthermore, the ability of Fe 2 S 3 + to activate and dissociate the C-H bonds of the alkenes is observed to increase with increasing size of the alkene and thus correlates with the alkene ionization energy.

Formation of a Criegee intermediate in the low-temperature oxidation of dimethyl sulfoxide.

PubMed

Asatryan, Rubik; Bozzelli, Joseph W

2008-04-07

Dimethyl sulfoxide (DMSO) is the major sulfur-containing constituent of the Marine Boundary Layer. It is a significant source of H2SO4 aerosol/particles and methane sulfonic acid via atmospheric oxidation processes, where the mechanism is not established. In this study, several new, low-temperature pathways are revealed in the oxidation of DMSO using CBS-QB3 and G3MP2 multilevel and B3LYP hybrid density functional quantum chemical methods. Unlike analogous hydrocarbon peroxy radicals the chemically activated DMSO peroxy radical, [CH3S(=O)CH2OO*]*, predominantly undergoes simple dissociation to a methylsulfinyl radical CH3S*(=O) and a Criegee intermediate, CH2OO, with the barrier to dissociation 11.3 kcal mol(-1) below the energy of the CH3S(=O)CH2* + O2 reactants. The well depth for addition of O2 to the CH3S(=O)CH2 precursor radical is 29.6 kcal mol(-1) at the CBS-QB3 level of theory. We believe that this reaction may serve an important role in atmospheric photochemical and irradiated biological (oxygen-rich) media where formation of initial radicals is facilitated even at lower temperatures. The Criegee intermediate (carbonyl oxide, peroxymethylene) and sulfinyl radical can further decompose, resulting in additional chain branching. A second reaction channel important for oxidation processes includes formation (via intramolecular H atom transfer) and further decomposition of hydroperoxide methylsulfoxide radical, *CH2S(=O)CH2OOH over a low barrier of activation. The initial H-transfer reaction is similar and common in analogous hydrocarbon radical + O2 reactions; but the subsequent very low (3-6 kcal mol(-1)) barrier (14 kcal mol(-1) below the initial reagents) to beta-scission products is not common in HC systems. The low energy reaction of the hydroperoxide radical is a beta-scission elimination of *CH2S(=O)CH2OOH into the CH2=S=O + CH2O + *OH product set. This beta-scission barrier is low, because of the delocalization of the *CH2 radical center through the -S(=O) group, to the -CH2OOH fragment in the transition state structure. The hydroperoxide methylsulfoxide radical can also decompose via a second reaction channel of intramolecular OH migration, yielding formaldehyde and a sulfur-centered hydroxymethylsulfinyl radical HOCH2S*(=O). The barrier of activation relative to initial reagents is 4.2 kcal mol(-1). Heats of formation for DMSO, DMSO carbon-centered radical and Criegee intermediate are evaluated at 298 K as -35.97 +/- 0.05, 13.0 +/- 0.2 and 25.3 +/- 0.7 kcal mol(-1) respectively using isodesmic reaction analysis. The [CH3S*(=O) + CH2OO] product set is shown to form a van der Waals complex that results in O-atom transfer reaction and the formation of new products CH3SO2* radical and CH2O. Proper orientation of the Criegee intermediate and methylsulfinyl radical, as a pre-stabilized pre-reaction complex, assist the process. The DMSO radical reaction is also compared to that of acetonyl radical.

The C-13/C-12 kinetic isotope effect for soil oxidation of methane at ambient atmospheric concentrations

NASA Technical Reports Server (NTRS)

King, Stagg L.; Quay, Paul D.; Lansdown, John M.

1989-01-01

During a survey of the Alaskan North Slope to estimate the isotopic composition and fluxes of methane (CH4) from the tundra, two sites were encountered that showed net methane consumption within flux chambers. Methane concentrations decreased from ambient (1.78 ppmv) by up to 50 percent, and the delta C-13 increased by up to 10 percent in the two chamber deployments showing CH4 consumption. CH4 consumption rates were measured to be 1.2 and 0.6 mg CH4/sq m per day; the corresponding carbon kinetic isotope effects (k13/k12) were 0.974 and 0.984, respectively.

Consumption of atmospheric methane by desert soils

USGS Publications Warehouse

Striegl, Robert G.; McConnaughey, T.A.; Thorstenson, D.C.; Weeks, E.P.; Woodward, J.C.

1992-01-01

ATMOSPHERIC concentrations of methane, a greenhouse gas, are increasing at a rate of about 1% yr-1 (refs 1-4). Oxidation by methylotrophic bacteria in soil is the largest terrestrial sink for atmospheric CH4, and is estimated to consume about 30?? 1012 g CH4 yr-1 (refs 4-6). Spatial and temporal variability in the rate of soil CH4 consumption are incompletely understood6-19, as are the apparent inhibitory12,13,18 or enhancing20 effects of changes in land use. Dry deserts, which constitute 20% of total land surface, are not currently included in global soil uptake estimates. Here we describe measurements of the rate of uptake of atmospheric CH4 by undisturbed desert soils. We observed rates as great as 4.38 mg CH4 m-2 day-1; 50% of the measured rates were between 0.24 and 0.92 mg CH4 m2 d-1. Uptake of CH4 by desert soil is enhanced by rainfall after an initial soil-drainage period - opposite to the response of temperate forest soils12. Methane is consumed to a depth of about 2 m, allowing for deep removal of atmospheric CH4 if near-surface conditions are unfavourable for consumption. On the basis of an annual average CH4 consumption rate of 0.66 mg CH4 m-2 d-1, we estimate that the global CH4 sink term needs to be increased by about 7 ?? 1012 g yr-1 to account for the contribution of desert soils.

Simultaneous measurement of volatile sulfur compounds using ascorbic acid for oxidant removal and gas chromatography-flame photometric detection.

PubMed

Inomata, Y; Matsunaga, K; Murai, Y; Osada, K; Iwasaka, Y

1999-12-09

A method for the simultaneous measurement of volatile sulfur compounds (COS, H2S, CS2, CH3SH, DMS) is established with preconcentration and GC-flame photometric detection (FPD). Prior to preconcentration of ambient air, it was necessary to remove SO2, water vapor and atmospheric oxidant. SO2 and water vapor were removed using a glass fiber filter and a cooled PTFE water trap loop, respectively. In order to remove atmospheric oxidant, the efficiency of an ascorbic acid scrubber was examined. It was found that an ascorbic acid scrubber enabled measurement of volatile sulfur compounds without adsorption and reaction loss. The detection limits for COS, H2S, CS2, CH3SH and DMS were 20, 34, 35, 263 and 44 pg of S, respectively.

Methane production and consumption in an active volcanic environment of Southern Italy.

PubMed

Castaldi, Simona; Tedesco, Dario

2005-01-01

Methane fluxes were measured, using closed chambers, in the Crater of Solfatara volcano, Campi Flegrei (Southern Italy), along eight transects covering areas of the crater presenting different landscape physiognomies. These included open bare areas, presenting high geothermal fluxes, and areas covered by vegetation, which developed along a gradient from the central open area outwards, in the form of maquis, grassland and woodland. Methane fluxes decreased logarithmically (from 150 to -4.5 mg CH4 m(-2)day(-1)) going from the central part of the crater (fangaia) to the forested edges, similarly to the CO2 fluxes (from 1500 g CO2 m(-2)day(-1) in the centre of the crater to almost zero flux in the woodlands). In areas characterized by high emissions, soil presented elevated temperature (up to 70 degrees C at 0-10 cm depth) and extremely low pH (down to 1.8). Conversely, in woodland areas pH was higher (between 3.7 and 5.1) and soil temperature close to air values. Soil (0-10 cm) was sampled, in two different occasions, along the eight transects, and was tested for methane oxidation capacity in laboratory. Areas covered by vegetation mostly consumed CH4 in the following order woodland>macchia>grassland. Methanotrophic activity was also measured in soil from the open bare area. Oxidation rates were comparable to those measured in the plant covered areas and were significantly correlated with field CH4 emissions. The biological mechanism of uptake was demonstrated by the absence of activity in autoclaved replicates. Thus results suggest the existence of a population of micro-organisms adapted to this extreme environment, which are able to oxidize CH4 and whose activity could be stimulated and supported by elevated concentrations of CH4.

Formaldehyde activation factor, tetrahydromethanopterin, a coenzyme of methanogenesis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Escalante-Semerena, J.C.; Leigh, J.A.; Rinehart, K.L. Jr.

1984-04-01

An oxygen-labile formaldehyde activation factor (FAF) was isolated in highly purified form by use of anoxic fractionation procedures. The molecular weight of FAF was determined to be 776 and that of methanopterin (MPT) 772 by fast-atom-bombardment mass spectrometry (FABMS). High-resolution FABMS measurements on MPT and FAF indicated molecular formulas of C/sub 30/H/sub 41/N/sub 6/O/sub 16/P and C/sub 30/H/sub 45/N/sub 6/O/sub 16/P, respectively. The presence of phosphorus was confirmed by 100-MHz /sup 31/P NMR. The 360-MHz /sup 1/H NMR spectrum of FAF in deuterium oxide was similar to that of MPT. A functional relationship between MPT and FAF was documented; bothmore » compounds stimulated the reductive demethylation of 2-(methylthio)ethanesulfonic acid (CH/sub 3/-S-CoM) to CH/sub 4/ when formaldehyde oxidation provided a source of electrons, and FAF replaced MPT in the CH/sub 3/-S-CoM-stimulated conversion of CO/sub 2/ to CH/sub 4/ under H/sub 2/ (the RPG effect). MPT was enzymically converted to FAF during the reduction of CH/sub 3/-S-CoM, and HCHO to CH/sub 4/ under H/sub 2/. Evidence indicates that FAF is tetrahydromethanopterin. 14 references, 8 figures.« less

Cobalt-Catalyzed C(sp(2))-H Borylation: Mechanistic Insights Inspire Catalyst Design.

PubMed

Obligacion, Jennifer V; Semproni, Scott P; Pappas, Iraklis; Chirik, Paul J

2016-08-24

A comprehensive study into the mechanism of bis(phosphino)pyridine (PNP) cobalt-catalyzed C-H borylation of 2,6-lutidine using B2Pin2 (Pin = pinacolate) has been conducted. The experimentally observed rate law, deuterium kinetic isotope effects, and identification of the catalyst resting state support turnover limiting C-H activation from a fully characterized cobalt(I) boryl intermediate. Monitoring the catalytic reaction as a function of time revealed that borylation of the 4-position of the pincer in the cobalt catalyst was faster than arene borylation. Cyclic voltammetry established the electron withdrawing influence of 4-BPin, which slows the rate of C-H oxidative addition and hence overall catalytic turnover. This mechanistic insight inspired the next generation of 4-substituted PNP cobalt catalysts with electron donating and sterically blocking methyl and pyrrolidinyl substituents that exhibited increased activity for the C-H borylation of unactivated arenes. The rationally designed catalysts promote effective turnover with stoichiometric quantities of arene substrate and B2Pin2. Kinetic studies on the improved catalyst, 4-(H)2BPin, established a change in turnover limiting step from C-H oxidative addition to C-B reductive elimination. The iridium congener of the optimized cobalt catalyst, 6-(H)2BPin, was prepared and crystallographically characterized and proved inactive for C-H borylation, a result of the high kinetic barrier for reductive elimination from octahedral Ir(III) complexes.

Self-sustained operation of a kW e-class kerosene-reforming processor for solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Yoon, Sangho; Bae, Joongmyeon; Kim, Sunyoung; Yoo, Young-Sung

In this paper, fuel-processing technologies are developed for application in residential power generation (RPG) in solid oxide fuel cells (SOFCs). Kerosene is selected as the fuel because of its high hydrogen density and because of the established infrastructure that already exists in South Korea. A kerosene fuel processor with two different reaction stages, autothermal reforming (ATR) and adsorptive desulfurization reactions, is developed for SOFC operations. ATR is suited to the reforming of liquid hydrocarbon fuels because oxygen-aided reactions can break the aromatics in the fuel and steam can suppress carbon deposition during the reforming reaction. ATR can also be implemented as a self-sustaining reactor due to the exothermicity of the reaction. The kW e self-sustained kerosene fuel processor, including the desulfurizer, operates for about 250 h in this study. This fuel processor does not require a heat exchanger between the ATR reactor and the desulfurizer or electric equipment for heat supply and fuel or water vaporization because a suitable temperature of the ATR reformate is reached for H 2S adsorption on the ZnO catalyst beds in desulfurizer. Although the CH 4 concentration in the reformate gas of the fuel processor is higher due to the lower temperature of ATR tail gas, SOFCs can directly use CH 4 as a fuel with the addition of sufficient steam feeds (H 2O/CH 4 ≥ 1.5), in contrast to low-temperature fuel cells. The reforming efficiency of the fuel processor is about 60%, and the desulfurizer removed H 2S to a sufficient level to allow for the operation of SOFCs.

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

DOE PAGES

Tao, Franklin Feng; Shan, Jun-jun; Nguyen, Luan; ...

2015-08-04

It is crucial to develop a catalyst made of earth-abundant elements highly active for a complete oxidation of methane at a relatively low temperature. NiCo 2O 4 consisting of earth-abundant elements which can completely oxidize methane in the temperature range of 350-550 °C. Being a cost-effective catalyst, NiCo 2O 4 exhibits activity higher than precious-metal-based catalysts. Here we report that the higher catalytic activity at the relatively low temperature results from the integration of nickel cations, cobalt cations and surface lattice oxygen atoms/oxygen vacancies at the atomic scale. Finally, in situ studies of complete oxidation of methane on NiCo 2Omore » 4 and theoretical simulations show that methane dissociates to methyl on nickel cations and then couple with surface lattice oxygen atoms to form -CH 3O with a following dehydrogenation to -CH 2O; a following oxidative dehydrogenation forms CHO; CHO is transformed to product molecules through two different sub-pathways including dehydrogenation of OCHO and CO oxidation.« less

Oxidative deterioration of pork during superchilling storage.

PubMed

Pomponio, Luigi; Ruiz-Carrascal, Jorge

2017-12-01

In superchilling (SC), meat is kept at temperatures around 1 °C below its initial freezing point, leading to a significant increase in shelf life. This study aimed to address the oxidative changes taking place in pork loins during prolonged storage at SC temperature. Loins were stored either at chilling (CH) conditions (2-4 °C) for 4 weeks or at SC temperature (around -1 °C) for 12 weeks. Storage at SC temperature diminished the rate of lipid and protein oxidation and discoloration in pork loins, so that final levels of most oxidation products and instrumental color values after 12 weeks of SC storage were similar to those after 4 weeks at CH conditions. However, hexanal content peaked by the end of SC storage, pointing to a potential accumulation of compounds from lipid oxidation during SC storage. SC storage of pork slows down the rate of lipid and protein oxidation. However, accumulation of volatile compounds from lipid oxidation could be a limiting factor for shelf life. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

Methane production by anaerobic digestion of water hyacinth (Eichhornia crassipes)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Klass, D.L.; Ghosh, S.

1980-01-01

Water hyacinth under conventional high-rate digestion conditions exhibited higher CH4 yields and energy recovery efficiencies when grown in sewage-fed lagoons than when grown in a fresh water pond. Mesophilic digestion provided the highest recovery of feed energy in the product gas as CH4, while thermophilic digestion, when operated at sufficiently high loading rates and reduced detention times, gave the highest specific CH4 production rates. CH4 yields, volatile solids reduction, and energy recovery as CH4 from the sewage-grown water hyacinth were in the same range as those observed for other biomass substrates when digested under similar conditions.

Chemical Feedback From Decreasing Carbon Monoxide Emissions

NASA Astrophysics Data System (ADS)

Gaubert, B.; Worden, H. M.; Arellano, A. F. J.; Emmons, L. K.; Tilmes, S.; Barré, J.; Martinez Alonso, S.; Vitt, F.; Anderson, J. L.; Alkemade, F.; Houweling, S.; Edwards, D. P.

2017-10-01

Understanding changes in the burden and growth rate of atmospheric methane (CH4) has been the focus of several recent studies but still lacks scientific consensus. Here we investigate the role of decreasing anthropogenic carbon monoxide (CO) emissions since 2002 on hydroxyl radical (OH) sinks and tropospheric CH4 loss. We quantify this impact by contrasting two model simulations for 2002-2013: (1) a Measurement of the Pollution in the Troposphere (MOPITT) CO reanalysis and (2) a Control-Run without CO assimilation. These simulations are performed with the Community Atmosphere Model with Chemistry of the Community Earth System Model fully coupled chemistry climate model with prescribed CH4 surface concentrations. The assimilation of MOPITT observations constrains the global CO burden, which significantly decreased over this period by 20%. We find that this decrease results to (a) increase in CO chemical production, (b) higher CH4 oxidation by OH, and (c) 8% shorter CH4 lifetime. We elucidate this coupling by a surrogate mechanism for CO-OH-CH4 that is quantified from the full chemistry simulations.

Processing of catalysts by atomic layer epitaxy: modification of supports

NASA Astrophysics Data System (ADS)

Lindblad, Marina; Haukka, Suvi; Kytökivi, Arla; Lakomaa, Eeva-Liisa; Rautiainen, Aimo; Suntola, Tuomo

1997-11-01

Different supports were modified with titania, zirconia and chromia by the atomic layer epitaxy technique (ALE). In ALE, a metal precursor is bound to the support in saturating gas-solid reactions. Surface oxides are grown by alternating reactions of the metal precursor and an oxidizing agent. Growth mechanisms differ depending on the precursor-support pair and the processing conditions. In this work, the influences of the support, precursor and reaction temperature were investigated by comparing the growth of titania from Ti(OCH(CH 3) 2) 4 on silica and alumina, titania from TiCl 4 and Ti(OCH(CH 3) 2) 4 on silica, and zirconia from ZrCl 4 on silica and alumina. The modification of porous oxides supported on metal substrates (monoliths) was demonstrated for the growth of chromia from Cr(acac) 3.

Top-down control of methane emission and nitrogen cycling by waterfowl.

PubMed

Winton, R Scott; Richardson, Curtis J

2017-01-01

Aquatic herbivores impose top-down control on the structure of wetland ecosystems, but the biogeochemical consequences of herbivory on methane (CH 4 ) and nitrogen (N) are poorly known. To investigate the top-down effects of waterfowl on wetland biogeochemistry, we implemented exclosure experiments in a major waterfowl overwintering wetland in the southeastern United States over two growing seasons. We found that herbivory inhibited the oxidation of CH 4 , leading to a mean increase in emission by 230% over control plots, and prevented nitrification, as indicated by low nitrate availability and undetectable emissions of nitrous oxide. Herbivory reduced belowground biomass of macrophytes, retarding the subsequent spring emergence of aerenchymous stems, effectively starving wetland soils of oxygen necessary for CH 4 oxidation and nitrification. The recognition that important populations of aquatic herbivores may influence the capacity for wetlands to emit greenhouse gases and cycle N is particularly salient in the context of climate change and nutrient pollution mitigation goals. For example, our results suggest that (1) annual emissions of 23 Gg CH 4 /yr from ~57 000 ha of publicly owned waterfowl impoundments in the southeastern United States could be tripled by overgrazing and that (2) waterfowl impoundments may export as much N as agricultural fields. We discuss potential implications for habitat management in the context of historic wetland loss and waterfowl population recovery. © 2016 by the Ecological Society of America.

Annual methane and nitrous oxide emissions from rice paddies and inland fish aquaculture wetlands in southeast China

NASA Astrophysics Data System (ADS)

Wu, Shuang; Hu, Zhiqiang; Hu, Tao; Chen, Jie; Yu, Kai; Zou, Jianwen; Liu, Shuwei

2018-02-01

Inland aquaculture ponds have been documented as important sources of atmospheric methane (CH4) and nitrous oxide (N2O), while their regional or global source strength remains unclear due to lack of direct flux measurements by covering more typical habitat-specific aquaculture environments. In this study, we compared the CH4 and N2O fluxes from rice paddies and nearby inland fish aquaculture wetlands that were converted from rice paddies in southeast China. Both CH4 and N2O fluxes were positively related to water temperature and sediment dissolved organic carbon, but negatively related to water dissolved oxygen concentration. More robust response of N2O fluxes to water mineral N was observed than to sediment mineral N. Annual CH4 and N2O fluxes from inland fish aquaculture averaged 0.51 mg m-2 h-1 and 54.78 μg m-2 h-1, amounting to 42.31 kg CH4 ha-1 and 2.99 kg N2O-N ha-1, respectively. The conversion of rice paddies to conventional fish aquaculture significantly reduced CH4 and N2O emissions by 23% and 66%, respectively. The emission factor for N2O was estimated to be 0.46% of total N input in the feed or 1.23 g N2O-N kg-1 aquaculture production. The estimate of sustained-flux global warming potential of annual CH4 and N2O emissions and the net economic profit suggested that such conversion of rice paddies to inland fish aquaculture would help to reconcile the dilemma for simultaneously achieving both low climatic impacts and high economic benefits in China. More solid direct field measurements from inland aquaculture are in urgent need to direct the overall budget of national or global CH4 and N2O fluxes.

Methane and Nitrous Oxide Emissions Reduced Following Conversion of Rice Paddies to Inland Crab-Fish Aquaculture in Southeast China.

PubMed

Liu, Shuwei; Hu, Zhiqiang; Wu, Shuang; Li, Shuqing; Li, Zhaofu; Zou, Jianwen

2016-01-19

Aquaculture is an important source of atmospheric methane (CH4) and nitrous oxide (N2O), while few direct flux measurements are available for their regional and global source strength estimates. A parallel field experiment was performed to measure annual CH4 and N2O fluxes from rice paddies and rice paddy-converted inland crab-fish aquaculture wetlands in southeast China. Besides N2O fluxes dependent on water/sediment mineral N and CH4 fluxes related to water chemical oxygen demand, both CH4 and N2O fluxes from aquaculture were related to water/sediment temperature, sediment dissolved organic carbon, and water dissolved oxygen concentration. Annual CH4 and N2O fluxes from inland aquaculture averaged 0.37 mg m(-2) h(-1) and 48.1 μg m(-2) h(-1), yielding 32.57 kg ha(-1) and 2.69 kg N2O-N ha(-1), respectively. The conversion of rice paddies to aquaculture significantly reduced CH4 and N2O emissions by 48% and 56%, respectively. The emission factor for N2O was estimated to be 0.66% of total N input in the feed or 1.64 g N2O-N kg(-1) aquaculture production in aquaculture. The conversion of rice paddies to inland aquaculture would benefit for reconciling greenhouse gas mitigation and agricultural income increase as far as global warming potentials and net ecosystem economic profits are of concomitant concern. Some agricultural practices such as better aeration and feeding, and fallow season dredging would help to lower CH4 and N2O emissions from inland aquaculture. More field measurements from inland aquaculture are highly needed to gain an insight into national and global accounting of CH4 and N2O emissions.

The Soil Sink for Nitrous Oxide: Trivial Amount but Challenging Question

NASA Astrophysics Data System (ADS)

Davidson, E. A.; Savage, K. E.; Sihi, D.

2015-12-01

Net uptake of atmospheric nitrous oxide (N2O) has been observed sporadically for many years. Such observations have often been discounted as measurement error or noise, but they were reported frequently enough to gain some acceptance as valid. The advent of fast response field instruments with good sensitivity and precision has permitted confirmation that some soils can be small sinks of N2O. With regards to "closing the global N2O budget" the soil sink is trivial, because it is smaller than the error terms of most other budget components. Although not important from a global budget perspective, the existence of a soil sink for atmospheric N2O presents a fascinating challenge for understanding the physical, chemical, and biological processes that explain the sink. Reduction of N2O by classical biological denitrification requires reducing conditions generally found in wet soil, and yet we have measured the N2O sink in well drained soils, where we also simultaneously measure a sink for atmospheric methane (CH4). Co-occurrence of N2O reduction and CH4 oxidation would require a broad range of microsite conditions within the soil, spanning high and low oxygen concentrations. Abiotic sinks for N2O or other biological processes that consume N2O could exist, but have not yet been identified. We are attempting to simulate processes of diffusion of N2O, CH4, and O2 from the atmosphere and within a soil profile to determine if classical biological N2O reduction and CH4 oxidation at rates consistent with measured fluxes are plausible.

Metaproteomic identification of diazotrophic methanotrophs and their localization in root tissues of field-grown rice plants.

PubMed

Bao, Zhihua; Okubo, Takashi; Kubota, Kengo; Kasahara, Yasuhiro; Tsurumaru, Hirohito; Anda, Mizue; Ikeda, Seishi; Minamisawa, Kiwamu

2014-08-01

In a previous study by our group, CH4 oxidation and N2 fixation were simultaneously activated in the roots of wild-type rice plants in a paddy field with no N input; both processes are likely controlled by a rice gene for microbial symbiosis. The present study examined which microorganisms in rice roots were responsible for CH4 oxidation and N2 fixation under the field conditions. Metaproteomic analysis of root-associated bacteria from field-grown rice (Oryza sativa Nipponbare) revealed that nitrogenase complex-containing nitrogenase reductase (NifH) and the alpha subunit (NifD) and beta subunit (NifK) of dinitrogenase were mainly derived from type II methanotrophic bacteria of the family Methylocystaceae, including Methylosinus spp. Minor nitrogenase proteins such as Methylocella, Bradyrhizobium, Rhodopseudomonas, and Anaeromyxobacter were also detected. Methane monooxygenase proteins (PmoCBA and MmoXYZCBG) were detected in the same bacterial group of the Methylocystaceae. Because these results indicated that Methylocystaceae members mediate both CH4 oxidation and N2 fixation, we examined their localization in rice tissues by using catalyzed reporter deposition-fluorescence in situ hybridization (CARD-FISH). The methanotrophs were localized around the epidermal cells and vascular cylinder in the root tissues of the field-grown rice plants. Our metaproteomics and CARD-FISH results suggest that CH4 oxidation and N2 fixation are performed mainly by type II methanotrophs of the Methylocystaceae, including Methylosinus spp., inhabiting the vascular bundles and epidermal cells of rice roots. Copyright © 2014, American Society for Microbiology. All Rights Reserved.

Seasonal variability in methane and nitrous oxide fluxes from tropical peatlands in the western Amazon basin

NASA Astrophysics Data System (ADS)

Arn Teh, Yit; Murphy, Wayne A.; Berrio, Juan-Carlos; Boom, Arnoud; Page, Susan E.

2017-08-01

The Amazon plays a critical role in global atmospheric budgets of methane (CH4) and nitrous oxide (N2O). However, while we have a relatively good understanding of the continental-scale flux of these greenhouse gases (GHGs), one of the key gaps in knowledge is the specific contribution of peatland ecosystems to the regional budgets of these GHGs. Here we report CH4 and N2O fluxes from lowland tropical peatlands in the Pastaza-Marañón foreland basin (PMFB) in Peru, one of the largest peatland complexes in the Amazon basin. The goal of this research was to quantify the range and magnitude of CH4 and N2O fluxes from this region, assess seasonal trends in trace gas exchange, and determine the role of different environmental variables in driving GHG flux. Trace gas fluxes were determined from the most numerically dominant peatland vegetation types in the region: forested vegetation, forested (short pole) vegetation, Mauritia flexuosa-dominated palm swamp, and mixed palm swamp. Data were collected in both wet and dry seasons over the course of four field campaigns from 2012 to 2014. Diffusive CH4 emissions averaged 36.05 ± 3.09 mg CH4-C m-2 day-1 across the entire dataset, with diffusive CH4 flux varying significantly among vegetation types and between seasons. Net ebullition of CH4 averaged 973.3 ± 161.4 mg CH4-C m-2 day-1 and did not vary significantly among vegetation types or between seasons. Diffusive CH4 flux was greatest for mixed palm swamp (52.0 ± 16.0 mg CH4-C m-2 day-1), followed by M. flexuosa palm swamp (36.7 ± 3.9 mg CH4-C m-2 day-1), forested (short pole) vegetation (31.6 ± 6.6 mg CH4-C m-2 day-1), and forested vegetation (29.8 ± 10.0 mg CH4-C m-2 day-1). Diffusive CH4 flux also showed marked seasonality, with divergent seasonal patterns among ecosystems. Forested vegetation and mixed palm swamp showed significantly higher dry season (47.2 ± 5.4 mg CH4-C m-2 day-1 and 85.5 ± 26.4 mg CH4-C m-2 day-1, respectively) compared to wet season emissions (6.8 ± 1.0 mg CH4-C m-2 day-1 and 5.2 ± 2.7 mg CH4-C m-2 day-1, respectively). In contrast, forested (short pole) vegetation and M. flexuosa palm swamp showed the opposite trend, with dry season flux of 9.6 ± 2.6 and 25.5 ± 2.9 mg CH4-C m-2 day-1, respectively, versus wet season flux of 103.4 ± 13.6 and 53.4 ± 9.8 mg CH4-C m-2 day-1, respectively. These divergent seasonal trends may be linked to very high water tables (> 1 m) in forested vegetation and mixed palm swamp during the wet season, which may have constrained CH4 transport across the soil-atmosphere interface. Diffusive N2O flux was very low (0.70 ± 0.34 µg N2O-N m-2 day-1) and did not vary significantly among ecosystems or between seasons. We conclude that peatlands in the PMFB are large and regionally significant sources of atmospheric CH4 that need to be better accounted for in regional emissions inventories. In contrast, N2O flux was negligible, suggesting that this region does not make a significant contribution to regional atmospheric budgets of N2O. The divergent seasonal pattern in CH4 flux among vegetation types challenges our underlying assumptions of the controls on CH4 flux in tropical peatlands and emphasizes the need for more process-based measurements during periods of high water table.

Electroremovable Traceless Hydrazides for Cobalt-Catalyzed Electro-Oxidative C-H/N-H Activation with Internal Alkynes.

PubMed

Mei, Ruhuai; Sauermann, Nicolas; Oliveira, João C A; Ackermann, Lutz

2018-06-27

Electrochemical oxidative C-H/N-H activations have been accomplished with a versatile cobalt catalyst in terms of [4 + 2] annulations of internal alkynes. The electro-oxidative C-H activation manifold proved viable with an undivided cell setup under exceedingly mild reaction conditions at room temperature using earth-abundant cobalt catalysts. The electrochemical cobalt catalysis prevents the use of transition metal oxidants in C-H activation catalysis, generating H 2 as the sole byproduct. Detailed mechanistic studies provided strong support for a facile C-H cobaltation by an initially formed cobalt(III) catalyst. The subsequent alkyne migratory insertion was interrogated by mass spectrometry and DFT calculations, providing strong support for a facile C-H activation and the formation of a key seven-membered cobalta(III) cycle in a regioselective fashion. Key to success for the unprecedented use of internal alkynes in electrochemical C-H/N-H activations was represented by the use of N-2-pyridylhydrazides, for which we developed a traceless electrocleavage strategy by electroreductive samarium catalysis at room temperature.

40 CFR 98.322 - GHGs to report.

Code of Federal Regulations, 2014 CFR

2014-07-01

... this subpart the CO2 emissions from coal mine gas CH4 destruction occurring at the facility, where the gas is not a fuel input for energy generation or use (e.g., flaring and VAM oxidation). (e) You must report under subpart C of this part (General Stationary Fuel Combustion Sources) the CO2, CH4, and N2O...

A record of aerobic methane oxidation in tropical Africa over the last 2.5 Ma

NASA Astrophysics Data System (ADS)

Spencer-Jones, Charlotte L.; Wagner, Thomas; Talbot, Helen M.

2017-12-01

Methane and CO2 are climatically active greenhouse gases (GHG) and are powerful drivers of rapid global warming. Comparable to the Arctic, the tropics store large volumes of labile sedimentary carbon that is vulnerable to climate change. However, little is known about this labile carbon reservoir, in particular the behaviour of high methane-producing environments (e.g. wetlands), and their role in driving or responding to past periods of global climate change. In this study, we use a microbial biomarker approach that traces continental aerobic methane oxidation (AMO) from sedimentary organic matter in deep-sea fan sediments off the Congo River to reconstruct the link between central African methane cycling and continental export during key periods of global Pleistocene warmth. We use 35-amino bacteriohopanepolyols (BHPs), specifically aminobacteriohopane-31,32,33,34-tetrol (aminotetrol) and 35-aminobacteriohopane-30,31,32,33,34-pentol (aminopentol) as diagnostic molecular markers for AMO (CH4 oxidation markers) and the prevalence of continental wetland environments. BHPs were analysed in sediments from the Congo fan (ODP 1075) dated to 2.5 Ma. High resolution studies of key warm marine isotope stages (MIS) 5, 11 and 13 are included to test the relationship between CH4 oxidation markers in sediments at different levels of elevated global atmospheric GHG. This study presents the oldest reported occurrence, to date, of 35-amino BHPs up to 200 m below sea floor (∼2.5 Ma) with no strong degradation signature observed. Low concentrations of CH4 oxidation markers identified between 1.7 Ma and 1 Ma suggest a reduction in wetland extent in tropical Africa in response to more arid environmental conditions. Correlation of high resolution CH4 oxidation marker signatures with global atmospheric GHG concentrations during MIS 5, 11 and 13 further emphasize periods of enhanced tropical C cycling. However, subsequent analysis would be required to further extrapolate the relative importance of tropical methane sources as a driver of global methane concentrations during the Pleistocene.

Linking activity, composition and seasonal dynamics of atmospheric methane oxidizers in a meadow soil

PubMed Central

Shrestha, Pravin Malla; Kammann, Claudia; Lenhart, Katharina; Dam, Bomba; Liesack, Werner

2012-01-01

Microbial oxidation is the only biological sink for atmospheric methane. We assessed seasonal changes in atmospheric methane oxidation and the underlying methanotrophic communities in grassland near Giessen (Germany), along a soil moisture gradient. Soil samples were taken from the surface layer (0–10 cm) of three sites in August 2007, November 2007, February 2008 and May 2008. The sites showed seasonal differences in hydrological parameters. Net uptake rates varied seasonally between 0 and 70 μg CH4 m−2 h−1. Greatest uptake rates coincided with lowest soil moisture in spring and summer. Over all sites and seasons, the methanotrophic communities were dominated by uncultivated methanotrophs. These formed a monophyletic cluster defined by the RA14, MHP and JR1 clades, referred to as upland soil cluster alphaproteobacteria (USCα)-like group. The copy numbers of pmoA genes ranged between 3.8 × 105–1.9 × 106 copies g−1 of soil. Temperature was positively correlated with CH4 uptake rates (P<0.001), but had no effect on methanotrophic population dynamics. The soil moisture was negatively correlated with CH4 uptake rates (P<0.001), but showed a positive correlation with changes in USCα-like diversity (P<0.001) and pmoA gene abundance (P<0.05). These were greatest at low net CH4 uptake rates during winter times and coincided with an overall increase in bacterial 16S rRNA gene abundances (P<0.05). Taken together, soil moisture had a significant but opposed effect on CH4 uptake rates and methanotrophic population dynamics, the latter being increasingly stimulated by soil moisture contents >50 vol% and primarily related to members of the MHP clade. PMID:22189499

Linking activity, composition and seasonal dynamics of atmospheric methane oxidizers in a meadow soil.

PubMed

Shrestha, Pravin Malla; Kammann, Claudia; Lenhart, Katharina; Dam, Bomba; Liesack, Werner

2012-06-01

Microbial oxidation is the only biological sink for atmospheric methane. We assessed seasonal changes in atmospheric methane oxidation and the underlying methanotrophic communities in grassland near Giessen (Germany), along a soil moisture gradient. Soil samples were taken from the surface layer (0-10 cm) of three sites in August 2007, November 2007, February 2008 and May 2008. The sites showed seasonal differences in hydrological parameters. Net uptake rates varied seasonally between 0 and 70 μg CH(4) m(-2) h(-1). Greatest uptake rates coincided with lowest soil moisture in spring and summer. Over all sites and seasons, the methanotrophic communities were dominated by uncultivated methanotrophs. These formed a monophyletic cluster defined by the RA14, MHP and JR1 clades, referred to as upland soil cluster alphaproteobacteria (USCα)-like group. The copy numbers of pmoA genes ranged between 3.8 × 10(5)-1.9 × 10(6) copies g(-1) of soil. Temperature was positively correlated with CH(4) uptake rates (P<0.001), but had no effect on methanotrophic population dynamics. The soil moisture was negatively correlated with CH(4) uptake rates (P<0.001), but showed a positive correlation with changes in USCα-like diversity (P<0.001) and pmoA gene abundance (P<0.05). These were greatest at low net CH(4) uptake rates during winter times and coincided with an overall increase in bacterial 16S rRNA gene abundances (P<0.05). Taken together, soil moisture had a significant but opposed effect on CH(4) uptake rates and methanotrophic population dynamics, the latter being increasingly stimulated by soil moisture contents >50 vol% and primarily related to members of the MHP clade.

The stable carbon isotope composition of methane produced and emitted from northern peatlands

NASA Astrophysics Data System (ADS)

Hornibrook, Edward R. C.

Stable carbon isotope values, pore water concentration, and flux data for methane (CH4) were compiled for 26 peatlands situated in the northern hemisphere to explore relationships between trophic status and CH4 cycling. Methane produced in ombrotrophic bogs has δ13C values that are significantly more negative than CH4 formed in fens apparently because of poor dissociation of acetic acid or an absence of methanogenic archaea capable of metabolizing acetic acid under low pH conditions. The δ 13C values of CH4 in pore water of ombrotrophic and minerotrophic peatlands exhibit the opposite trend: δ13C(CH4) values become more positive with depth in rain-fed bogs and more negative with depth in fens. The key zone for methanogenesis occurs at shallow depths in both types of peatland and consequently, δ13C values of CH4 emitted from ombrotrophic bogs (-74.9 ± 9.8‰ n = 42) are more negative than from fens (-64.8 ± 4.0‰ n = 38). An abundance of graminoids in fens contributes to more positive δ13C(CH4) values in pore water through (1) release of root exudates which promotes aceticlastic methanogenesis, (2) rhizosphere oxidization of CH4 causing localized enrichment of 13CH4, and (3) preferential export of 12CH4 through aerenchyma, which also enriches pore water in 13CH4. Emissions from blanket bogs and raised bogs should be attributed more negative δ13C(CH4) values relative to fens in isotope-weighted mass balance budgets. Further study is needed of bogs that have an apparently low nutrient status but exhibit a pore water distribution of δ13C(CH4) values similar to fens.

A cool-temperate young larch plantation as a net methane source - A 4-year continuous hyperbolic relaxed eddy accumulation and chamber measurements

NASA Astrophysics Data System (ADS)

Ueyama, Masahito; Yoshikawa, Kota; Takagi, Kentaro

2018-07-01

Upland forests are thought to be methane (CH4) sinks due to oxidation by methanotrophs in aerobic soils. However, CH4 budget for upland forests are not well quantified at the ecosystem scale, when possible CH4 sources, such as small wet areas, exists in the ecosystem. Here, we quantified CH4 fluxes in a cool-temperate larch plantation based on four-year continuous measurements using the hyperbolic relaxed eddy accumulation (HREA) method and dynamic closed chambers with a laser-based analyzer. After filling data gaps for half-hourly data using machine-learning-based regressions, we found that the forest acted as a net CH4 source at the canopy scale: 30 ± 11 mg CH4 m-2 yr-1 in 2014, 56 ± 8 mg CH4 m-2 yr-1 in 2015, 154 ± 5 mg CH4 m-2 yr-1 in 2016, and 132 ± 6 mg CH4 m-2 yr-1 in 2017. Hotspot emissions from the edge of the pond could strongly contribute to the canopy-scale emissions. The magnitude of the hotspot emissions was 10-100 times greater than the order of the canopy-scale and chamber-based CH4 fluxes at the dry soils. The high temperatures with wet conditions stimulated the hotspot emissions, and thus induced canopy-scale CH4 emissions in the summer. Understanding and modeling the dynamics of hotspot emissions are important for quantifying CH4 budgets of upland forests. Micrometeorological measurements at various forests are required for revisiting CH4 budget of upland forests.

Methane and nitrous oxide emissions from three paddy rice based cultivation systems in Southwest China

NASA Astrophysics Data System (ADS)

Jiang, Changsheng; Wang, Yuesi; Zheng, Xunhua; Zhu, Bo; Huang, Yao; Hao, Qingju

2006-05-01

To understand methane (CH4) and nitrous oxide (N2O) emissions from permanently flooded rice paddy fields and to develop mitigation options, a field experiment was conducted in situ for two years (from late 2002 to early 2005) in three rice-based cultivation systems, which are a permanently flooded rice field cultivated with a single time and followed by a non-rice season (PF), a rice-wheat rotation system (RW) and a rice-rapeseed rotation system (RR) in a hilly area in Southwest China. The results showed that the total CH4 emissions from PF were 646.3±52.1 and 215.0±45.4 kg CH4 hm-2 during the rice-growing period and non-rice period, respectively. Both values were much lower than many previous reports from similar regions in Southwest China. The CH4 emissions in the rice-growing season were more intensive in PF, as compared to RW and RR. Only 33% of the total annual CH4 emission in PF occurred in the non-rice season, though the duration of this season is two times longer than the rice season. The annual mean N2O flux in PF was 4.5±0.6 kg N2O hm-2 yr-1. The N2O emission in the rice-growing season was also more intensive than in the non-rice season, with only 16% of the total annual emission occurring in the non-rice season. The amounts of N2O emission in PF were ignorable compared to the CH4 emission in terms of the global warming potential (GWP). Changing PF to RW or RR not only eliminated CH4 emissions in the non-rice season, but also substantially reduced the CH4 emission during the following rice-growing period (ca. 58%, P<0.05). However, this change in cultivation system substantially increased N2O emissions, especially in the non-rice season, by a factor of 3.7 to 4.5. On the 100-year horizon, the integrated GWP of total annual CH4 and N2O emissions satisfies PF≫RR≈RW. The GWP of PF is higher than that of RW and RR by a factor of 2.6 and 2.7, respectively. Of the total GWP of CH4 and N2O emissions, CH4 emission contributed to 93%, 65% and 59% in PF, RW and RR, respectively. These results suggest that changing PF to RW and RR can substantially reduce not only CH4 emission but also the total GWP of the CH4 and N2O emissions.

Subsoil methanogenesis as source of stem CH4 emission in upland forest trees: preferential CH4 transport via the root system?

NASA Astrophysics Data System (ADS)

Maier, M.; Machacova, K.; Urban, O.; Friederike, L.

2016-12-01

Quantifying and understanding green house gas fluxes in natural soil-plant-atmosphere systems are crucial to predicting global climate change. Wetland species or trees at waterlogged sites are known to emit large amounts of CH4. Yet upland forest soils are regarded as CH4 sinks and tree species like upland European beech (Fagus sylvatica, L.) are assumed not to emit CH4. We studied the soil-atmosphere and stem-atmosphere fluxes of CH4, and soil gas profiles at two upland beech forest sites in Central Europe. Soil was a net CH4 sink at both. Unusually there was one beech tree with substantial CH4 emissions that were higher than the CH4 sink of the soil. The soil gas profile at this tree indicated CH4 production at a soil depth >0.3 m, despite the net uptake of CH4 observed at the soil surface adjacent to the tree. Field soil assessment showed strong redoximorphic color patterns in the adjacent soil. We think that there is a transport link between the soil and stem via the root system representing a preferential transport mechanism for CH4 despite the fact that beech roots usually do not bear aerenchyma. The gas transport process , either via dissolved CH4 in the xylem water or in the root gas phase, is not yet clear. The observed CH4 stem emissions represent an important CH4flux in this ecosystem, und thus should be considered in future research. AcknowledgementThis research was financially supported by the Czech Academy of Sciences and the German Academic Exchange Service within the project "Methane (CH4) and nitrous oxide (N2O) emissions from Fagus sylvatica trees" (DAAD-15-03), National Programme for Sustainability I (LO1415) and project DFG (MA 5826/2-1). We would like to thank Marek Jakubik, Katerina Svobodova, Sinikka Paulus, Ellen Halaburt and Sally Haddad for technical support.

Transition Metal Catalyzed Hydroarylation of Multiple Bonds: Exploration of Second Generation Ruthenium Catalysts and Extension to Copper Systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

T. Brent Gunnoe

2011-02-17

Catalysts provide foundational technology for the development of new materials and can enhance the efficiency of routes to known materials. New catalyst technologies offer the possibility of reducing energy and raw material consumption as well as enabling chemical processes with a lower environmental impact. The rising demand and expense of fossil resources has strained national and global economies and has increased the importance of accessing more efficient catalytic processes for the conversion of hydrocarbons to useful products. The goals of the research are to develop and understand single-site homogeneous catalysts for the conversion of readily available hydrocarbons into useful materials.more » A detailed understanding of these catalytic reactions could lead to the development of catalysts with improved activity, longevity and selectivity. Such transformations could reduce the environmental impact of hydrocarbon functionalization, conserve energy and valuable fossil resources and provide new technologies for the production of liquid fuels. This project is a collaborative effort that incorporates both experimental and computational studies to understand the details of transition metal catalyzed C-H activation and C-C bond forming reactions with olefins. Accomplishments of the current funding period include: (1) We have completed and published studies of C-H activation and catalytic olefin hydroarylation by TpRu{l_brace}P(pyr){sub 3}{r_brace}(NCMe)R (pyr = N-pyrrolyl) complexes. While these systems efficiently initiate stoichiometric benzene C-H activation, catalytic olefin hydroarylation is hindered by inhibition of olefin coordination, which is a result of the steric bulk of the P(pyr){sub 3} ligand. (2) We have extended our studies of catalytic olefin hydroarylation by TpRu(L)(NCMe)Ph systems to L = P(OCH{sub 2}){sub 3}CEt. Thus, we have now completed detailed mechanistic studies of four systems with L = CO, PMe{sub 3}, P(pyr){sub 3} and P(OCH{sub 2}){sub 3}CEt, which has provided a comprehensive understanding of the impact of steric and electronic parameters of 'L' on the catalytic hydroarylation of olefins. (3) We have completed and published a detailed mechanistic study of stoichiometric aromatic C-H activation by TpRu(L)(NCMe)Ph (L = CO or PMe{sub 3}). These efforts have probed the impact of functionality para to the site of C-H activation for benzene substrates and have allowed us to develop a detailed model of the transition state for the C-H activation process. These results have led us to conclude that the C-H bond cleavage occurs by a {sigma}-bond metathesis process in which the C-H transfer is best viewed as an intramolecular proton transfer. (4) We have completed studies of Ru complexes possessing the N-heterocyclic carbene IMes (IMes = 1,3-bis-(2,4,6-trimethylphenyl)imidazol-2-ylidene). One of these systems is a unique four-coordinate Ru(II) complex that catalyzes the oxidative hydrophenylation of ethylene (in low yields) to produce styrene and ethane (utilizing ethylene as the hydrogen acceptor) as well as the hydrogenation of olefins, aldehydes and ketones. These results provide a map for the preparation of catalysts that are selective for oxidative olefin hydroarylation. (5) The ability of TpRu(PMe{sub 3})(NCMe)R systems to activate sp{sup 3} C-H bonds has been demonstrated including extension to subsequent C-C bond forming steps. These results open the door to the development of catalysts for the functionalization of more inert C-H bonds. (6) We have discovered that Pt(II) complexes supported by simple nitrogen-based ligands serve as catalysts for the hydroarylation of olefins. Given the extensive studies of Pt-based catalytic C-H activation, we believe these results will provide an entry point into an array of possible catalysts for hydrocarbon functionalization.« less

Combustion characteristics of an SI engine fueled with biogas fuel

NASA Astrophysics Data System (ADS)

Chen, Lei; Long, Wuqiang; Song, Peng

2017-04-01

An experimental research of the effect of H2 substitution and CO2 dilution on CH4 combustion has been carried out on a spark ignition engine. The results show that H2 addition could improve BMEP, thermal efficiency, CO and THC emissions. NOX emissions increased for higher low heating value (LHV) of H2 than CH4. CO2 dilution could effective reduce NOX emission of H2-CH4 combustion. Although engine performance, thermal efficiency and exhaust get unacceptable under high fuel dilution ratio (F.D.R.) conditions, it could be solved by decreasing F.D.R. and/or increasing hydrogen substitution ratio (H.S.R.).

Reassessing the stable isotope composition assigned to methane flux from natural wetlands in isotope-constrained budgets

NASA Astrophysics Data System (ADS)

Hornibrook, Edward; Maxfield, Peter; Gauci, Vincent; Stott, Andrew

2013-04-01

Stable isotope ratios in CH4 preserve information about its origin and history, and are commonly used to constrain global CH4 budgets. Wetlands are key contributors to the atmospheric burden of CH4 and typically are assigned a stable carbon isotope composition of ~-60 permil in isotope-weighted stable isotope models despite the considerable range of δ13C(CH4) values (~ -100 to -40 permil) known to occur in these diverse ecosystems. Kinetic isotope effects (KIEs) associated with the metabolism of CH4-producing microorganisms generate much of the natural variation but highly negative and positive δ13C(CH4) values generally result from secondary processes (e.g., diffusive transport or oxidation by soil methanotrophs). Despite these complexities, consistent patterns exist in the isotope composition of wetland CH4 that can be linked conclusively to trophic status and consequently, natural succession or human perturbations that impact nutrient levels. Another challenge for accurate representation of wetlands in carbon cycle models is parameterisation of sporadic CH4 emission events. Abrupt release of large volumes of CH4-rich bubbles in short periods of time can account for a significant proportion of the annual CH4 flux from a wetland but such events are difficult to detect using conventional methods. New infrared spectroscopy techniques capable of high temporal resolution measurements of CH4 concentration and stable isotope composition can readily quantify short-lived CH4 pulses. Moreover, the isotope data can be used conclusively to determine shifts in the mode of CH4 transport and provide the potential to link initiation of abrupt emission events to forcing by internal or external factors.

Near-zero methane emission from an abandoned boreal peatland pasture based on eddy covariance measurements

PubMed Central

Wang, Mei; Luan, Junwei; Lafleur, Peter; Chen, Huai; Zhu, Xinbiao

2017-01-01

Although estimates of the annual methane (CH4) flux from agriculturally managed peatlands exist, knowledge of controls over the variation of CH4 at different time-scales is limited due to the lack of high temporal-resolution data. Here we present CH4 fluxes measured from May 2014 to April 2016 using the eddy covariance technique at an abandoned peatland pasture in western Newfoundland, Canada. The goals of the study were to identify the controls on the seasonal variations in CH4 flux and to quantify the annual CH4 flux. The seasonal variation in daily CH4 flux was not strong in the two study years, however a few periods of pronounced emissions occurred in the late growing season. The daily average CH4 flux was small relative to other studies, ranging from -4.1 to 9.9 nmol m-2 s-1 in 2014–15 and from -7.1 to 12.1 nmol m-2 s-1 in 2015–16. Stepwise multiple regression was used to investigate controls on CH4 flux and this analysis found shifting controls on CH4 flux at different periods of the growing season. During the early growing season CH4 flux was closely related to carbon dioxide fixation rates, suggesting substrate availability was the main control. The peak growing season CH4 flux was principally controlled by the CH4 oxidation in 2014, where the CH4 flux decreased and increased with soil temperature at 50 cm and soil water content at 10 cm, but a contrasting temperature-CH4 relation was found in 2015. The late growing season CH4 flux was found to be regulated by the variation in water table level and air temperature in 2014. The annual CH4 emission was near zero in both study years (0.36 ± 0.30 g CH4 m-2 yr-1 in 2014–15 and 0.13 ± 0.38 g CH4 m-2 yr-1 in 2015–16), but fell within the range of CH4 emissions reported for agriculturally managed peatlands elsewhere. PMID:29252998

Near-zero methane emission from an abandoned boreal peatland pasture based on eddy covariance measurements.

PubMed

Wang, Mei; Wu, Jianghua; Luan, Junwei; Lafleur, Peter; Chen, Huai; Zhu, Xinbiao

2017-01-01

Although estimates of the annual methane (CH4) flux from agriculturally managed peatlands exist, knowledge of controls over the variation of CH4 at different time-scales is limited due to the lack of high temporal-resolution data. Here we present CH4 fluxes measured from May 2014 to April 2016 using the eddy covariance technique at an abandoned peatland pasture in western Newfoundland, Canada. The goals of the study were to identify the controls on the seasonal variations in CH4 flux and to quantify the annual CH4 flux. The seasonal variation in daily CH4 flux was not strong in the two study years, however a few periods of pronounced emissions occurred in the late growing season. The daily average CH4 flux was small relative to other studies, ranging from -4.1 to 9.9 nmol m-2 s-1 in 2014-15 and from -7.1 to 12.1 nmol m-2 s-1 in 2015-16. Stepwise multiple regression was used to investigate controls on CH4 flux and this analysis found shifting controls on CH4 flux at different periods of the growing season. During the early growing season CH4 flux was closely related to carbon dioxide fixation rates, suggesting substrate availability was the main control. The peak growing season CH4 flux was principally controlled by the CH4 oxidation in 2014, where the CH4 flux decreased and increased with soil temperature at 50 cm and soil water content at 10 cm, but a contrasting temperature-CH4 relation was found in 2015. The late growing season CH4 flux was found to be regulated by the variation in water table level and air temperature in 2014. The annual CH4 emission was near zero in both study years (0.36 ± 0.30 g CH4 m-2 yr-1 in 2014-15 and 0.13 ± 0.38 g CH4 m-2 yr-1 in 2015-16), but fell within the range of CH4 emissions reported for agriculturally managed peatlands elsewhere.

Edge effects on N2O, NO and CH4 fluxes in two temperate forests.

PubMed

Remy, Elyn; Gasche, Rainer; Kiese, Ralf; Wuyts, Karen; Verheyen, Kris; Boeckx, Pascal

2017-01-01

Forest ecosystems may act as sinks or sources of nitrogen (N) and carbon (C) compounds, such as the climate relevant trace gases nitrous oxide (N 2 O), nitric oxide (NO) and methane (CH 4 ). Forest edges, which catch more atmospheric deposition, have become important features in European landscapes and elsewhere. Here, we implemented a fully automated measuring system, comprising static and dynamic measuring chambers determining N 2 O, NO and CH 4 fluxes along an edge-to-interior transect in an oak (Q. robur) and a pine (P. nigra) forest in northern Belgium. Each forest was monitored during a 2-week measurement campaign with continuous measurements every 2h. NO emissions were 9-fold higher than N 2 O emissions. The fluxes of NO and CH 4 differed between forest edge and interior, but not for N 2 O. This edge effect was more pronounced in the oak than in the pine forest. In the oak forest, edges emitted less NO (on average 60%) and took up more CH 4 (on average 177%). This suggests that landscape structure can play a role in the atmospheric budgets of these climate relevant trace gases. Soil moisture variation between forest edge and interior was a key variable explaining the magnitude of NO and CH 4 fluxes in our measurement campaign. To better understand the environmental impact of N and C trace gas fluxes from forest edges, additional and long-term measurements in other forest edges are required. Copyright © 2016 Elsevier B.V. All rights reserved.

Production of biogas (methane and hydrogen) from anaerobic digestion of hemicellulosic hydrolysate generated in the oxidative pretreatment of coffee husks.

PubMed

Santos, Lívia Caroline Dos; Adarme, Oscar Fernando Herrera; Baêta, Bruno Eduardo Lobo; Gurgel, Leandro Vinícius Alves; Aquino, Sérgio Francisco de

2018-05-21

Ozone pretreatment of coffee husks (CH) was evaluated to generate hydrolysates for biogas production and to preserve cellulose of the solid phase for 2G ethanol production. Pretreatment variables included liquid-to-solid ratio (LSR), pH and specific applied ozone load (SAOL). Considering single-stage anaerobic digestion (AD), the highest methane production (36 NmL CH 4 /g CH) was achieved with the hydrolysate generated in the experiment using LSR 10 mL/g, pH 11 and SAOL 18.5 mg O 3 /g CH, leading to 0.064 kJ/g CH energy recovery. Due to the presence of toxic compounds in the hydrolysate, the addition of powdered activated carbon (4 g/L) to the reactor enhanced biogas production, leading to 86 NmL CH 4 /g CH yield and 0.58 kJ/g CH energy recovery. When two-stage AD was applied, methane production resulted in 49 NmL CH 4 /g CH, with additional 19 NmL H 2 /g CH production, resulting in a net 0.26 kJ/g CH energy recovery. Copyright © 2018 Elsevier Ltd. All rights reserved.

Graphene Oxide Membranes with Heterogeneous Nanodomains for Efficient CO2 Separations.

PubMed

Wang, Shaofei; Xie, Yu; He, Guangwei; Xin, Qingping; Zhang, Jinhui; Yang, Leixin; Li, Yifan; Wu, Hong; Zhang, Yuzhong; Guiver, Michael D; Jiang, Zhongyi

2017-11-06

Achieving high membrane performance in terms of gas permeance and carbon dioxide selectivity is an important target in carbon capture. Aiming to manipulate the channel affinity towards CO 2 to implement efficient separations, gas separation membranes containing CO 2 -philic and non-CO 2 -philic nanodomains in the interlayer channels of graphene oxide (GO) were formed by intercalating poly(ethylene glycol) diamines (PEGDA). PEGDA reacts with epoxy groups on the GO surface, constructing CO 2 -philic nanodomains and rendering a high sorption capacity, whereas unreacted GO surfaces give non-CO 2 -philic nanodomains, rendering low-friction diffusion. Owing to the orderly stacking of nanochannels through cross-linking and the heterogeneous nanodomains with moderate CO 2 affinity, a GO-PEGDA500 membrane exhibits a high CO 2 permeance of 175.5 GPU and a CO 2 /CH 4 selectivity of 69.5, which is the highest performance reported for dry-state GO-stacking membranes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Oxidized Ni/Au Transparent Electrode in Efficient CH3 NH3 PbI3 Perovskite/Fullerene Planar Heterojunction Hybrid Solar Cells.

PubMed

Lai, Wei-Chih; Lin, Kun-Wei; Wang, Yuan-Ting; Chiang, Tsung-Yu; Chen, Peter; Guo, Tzung-Fang

2016-05-01

The successful application of a Ni/Au transparent electrode for fabricating efficient perovskite-based solar cells is demonstrated. Through interdiffusion of the Ni/Au bilayer, Au forms an interconnected metallic network structure as the transparent electrode. Ni diffuses to the bilayer surface and oxidizes into NiOx becoming an appropriate electrode interlayer. These ITO- and PSS-free devices have potential applications in the design of future cost-effective, low-weight, and stable solar cells. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Product distribution study of the Cl-atom initiated oxidation of ethyl methyl sulfide and diethyl sulfide

NASA Astrophysics Data System (ADS)

Oksdath-Mansilla, Gabriela; Peñéñory, Alicia B.; Barnes, Ian; Wiesen, Peter; Teruel, Mariano A.

2014-03-01

The products formed in the gas-phase reactions of Cl atoms with (CH3CH2)2S and CH3CH2SCH3 have been investigated in a large volume reactor in NOx-free air at atmospheric pressure and (298 ± 2) K using long path “in situ” FTIR spectroscopy for the analysis. HCl, SO2 and CH3CHO were identified as the major products for both reactions. For the Cl + CH3CH2SCH3 reaction HCHO was also identified as a major product. The yields of the products obtained for the reaction of Cl with (CH3CH2)2S were (59 ± 2) %, (52 ± 5) % and (103 ± 4) % for HCl, SO2 and CH3CHO, respectively. For the reaction of Cl with CH3CH2SCH3 yields of (43 ± 5) %, (55 ± 3) %, (58 ± 3) % and (53 ± 5) % were obtained for HCl, SO2, CH3CHO and HCHO, respectively. This is the first products and mechanistic study for the gas-phase Cl-initiated oxidation of non-CH3SCH3 alkyl sulfides. Comparison with previous results for the reaction of Cl with dimethyl sulfide is made and simple atmospheric degradation mechanisms are postulated to explain the formation of the observed products.

Role of atmospheric oxidation in recent methane growth

PubMed Central

Rigby, Matthew; Montzka, Stephen A.; Prinn, Ronald G.; White, James W. C.; Young, Dickon; Lunt, Mark F.; Ganesan, Anita L.; Manning, Alistair J.; Simmonds, Peter G.; Salameh, Peter K.; Harth, Christina M.; Mühle, Jens; Weiss, Ray F.; Fraser, Paul J.; Steele, L. Paul; McCulloch, Archie; Park, Sunyoung

2017-01-01

The growth in global methane (CH4) concentration, which had been ongoing since the industrial revolution, stalled around the year 2000 before resuming globally in 2007. We evaluate the role of the hydroxyl radical (OH), the major CH4 sink, in the recent CH4 growth. We also examine the influence of systematic uncertainties in OH concentrations on CH4 emissions inferred from atmospheric observations. We use observations of 1,1,1-trichloroethane (CH3CCl3), which is lost primarily through reaction with OH, to estimate OH levels as well as CH3CC3 emissions, which have uncertainty that previously limited the accuracy of OH estimates. We find a 64–70% probability that a decline in OH has contributed to the post-2007 methane rise. Our median solution suggests that CH4 emissions increased relatively steadily during the late 1990s and early 2000s, after which growth was more modest. This solution obviates the need for a sudden statistically significant change in total CH4 emissions around the year 2007 to explain the atmospheric observations and can explain some of the decline in the atmospheric 13CH4/12CH4 ratio and the recent growth in C2H6. Our approach indicates that significant OH-related uncertainties in the CH4 budget remain, and we find that it is not possible to implicate, with a high degree of confidence, rapid global CH4 emissions changes as the primary driver of recent trends when our inferred OH trends and these uncertainties are considered. PMID:28416657

Laboratory Studies on the Formation of Three C2H4O Isomers-Acetaldehyde (CH3CHO), Ethylene Oxide (c-C2H4O), and Vinyl Alcohol (CH2CHOH)-in Interstellar and Cometary Ices

NASA Astrophysics Data System (ADS)

Bennett, Chris J.; Osamura, Yoshihiro; Lebar, Matt D.; Kaiser, Ralf I.

2005-11-01

Laboratory experiments were conducted to unravel synthetic routes to form three C2H4O isomers-acetaldehyde (CH3CHO), ethylene oxide (c-C2H4O), and vinyl alcohol (CH2CHOH)-in extraterrestrial ices via electronic energy transfer processes initiated by electrons in the track of MeV ion trajectories. Here we present the results of electron irradiation on a 2:1 mixture of carbon dioxide (CO2) and ethylene (C2H4). Our studies suggest that suprathermal oxygen atoms can add to the carbon-carbon π bond of an ethylene molecule to form initially an oxirene diradical (addition to one carbon atom) and the cyclic ethylene oxide molecule (addition to two carbon atoms) at 10 K. The oxirene diradical can undergo a [1, 2]-H shift to the acetaldehyde molecule. Both the ethylene oxide and the acetaldehyde isomers can be stabilized in the surrounding ice matrix. To a minor amount, suprathermal oxygen atoms can insert into a carbon-hydrogen bond of the ethylene molecule, forming vinyl alcohol. Once these isomers have been synthesized inside the ice layers of the coated grains in cold molecular clouds, the newly formed molecules can sublime as the cloud reaches the hot molecular core stage. These laboratory investigations help to explain astronomical observations by Nummelin et al. and Ikeda et al. toward massive star-forming regions and hot cores, where observed fractional abundances of these isomers are higher than can be accounted for by gas-phase reactions alone. Similar synthetic routes could help explain the formation of acetaldehyde and ethylene oxide in comet C/1995 O1 (Hale-Bopp) and also suggest a presence of both isomers in Titan's atmosphere.

Mitigation of ammonia, nitrous oxide and methane emissions from manure management chains: a meta-analysis and integrated assessment.

PubMed

Hou, Yong; Velthof, Gerard L; Oenema, Oene

2015-03-01

Livestock manure contributes considerably to global emissions of ammonia (NH3 ) and greenhouse gases (GHG), especially methane (CH4 ) and nitrous oxide (N2 O). Various measures have been developed to mitigate these emissions, but most of these focus on one specific gas and/or emission source. Here, we present a meta-analysis and integrated assessment of the effects of mitigation measures on NH3 , CH4 and (direct and indirect) N2 O emissions from the whole manure management chain. We analysed the effects of mitigation technologies on NH3 , CH4 and N2 O emissions from individual sources statistically using results of 126 published studies. Whole-chain effects on NH3 and GHG emissions were assessed through scenario analysis. Significant NH3 reduction efficiencies were observed for (i) housing via lowering the dietary crude protein (CP) content (24-65%, compared to the reference situation), for (ii) external slurry storages via acidification (83%) and covers of straw (78%) or artificial films (98%), for (iii) solid manure storages via compaction and covering (61%, compared to composting), and for (iv) manure application through band spreading (55%, compared to surface application), incorporation (70%) and injection (80%). Acidification decreased CH4 emissions from stored slurry by 87%. Significant increases in N2 O emissions were found for straw-covered slurry storages (by two orders of magnitude) and manure injection (by 26-199%). These side-effects of straw covers and slurry injection on N2 O emission were relatively small when considering the total GHG emissions from the manure chain. Lowering the CP content of feed and acidifying slurry are strategies that consistently reduce NH3 and GHG emissions in the whole chain. Other strategies may reduce emissions of a specific gas or emissions source, by which there is a risk of unwanted trade-offs in the manure management chain. Proper farm-scale combinations of mitigation measures are important to minimize impacts of livestock production on global emissions of NH3 and GHG. © 2014 John Wiley & Sons Ltd.

Primary Volatile Abundances in Comets from Infrared Spectroscopy: Implications for Reactions on Grain Surfaces in the Interstellar/Nebular Environment

NASA Technical Reports Server (NTRS)

DiSanti, M. A.; Bonev, B. P.; Vilanueva, G. L.; Paganini, L.; Radeva, Y. L.; Mumma, M. J.; Gibb, E.; Magee-Sauer, K.

2012-01-01

Comets retain relatively primitive icy material remaining from the epoch of Solar System formation, however the extent to which they are modified from their initial state remains a key question in cometary science. High-resolution lR spectroscopy has emerged as a powerful tool for measuring vibrational emissions from primary volatiles (i.e., those contained in the nuclei of comets). With modern instrumentation, most notably NIRSPEC at the Keck II 10-m telescope, we can quantify species of astrobiological importance (e.g., H20, C2H2, CH4, C2H6, CO, H2CO, CH30H, HCN, NH3). In space environments, compounds of keen interest to astrobiology could originate from HCN and NH3 (leading to amino acids), H2CO (leading to sugars), or C2H6 and CH4 (suggested precursors of ethyl- and methylamine). Measuring the abundances of these precursor molecules (and their variability among comets) is a feasible task that contributes to understanding their delivery to Earth's early biosphere and to the synthesis of more complex pre biotic compounds. Over 20 comets have now been measured with IR spectroscopy, and this sample reveals significant diversity in primary volatile compositions. From this, a taxonomic classification scheme is emerging, presumably reflecting the diverse conditions experienced by pre-cometary grains in interstellar and subsequent nebular environs. The importance of H-atom addition to C2H2 on the surfaces of interstellar grains to produce C2H6 was validated by the discovery of abundant ethane in comet C/1996 B2 (Hyakutake) with C2H6/CH4 well above that achievable by gas-phase chemistry , and then in irradiation experiments on laboratory ices at 10 - 50 K. The large abundance ratios C2H6/CH4 observed universally in comets establish H-atom addition as an important and likely ubiquitous process, and comparing C2H6/C2H2 among comets can provide information on its efficiency. The IR is uniquely capable since symmetric hydrocarbons (e.g., C2H2, CH4, C2H6) have no electric dipole moment and thus no allowed pure rotational transitions. CO should also be hydrogenated on grain surfaces. Irradiation experiments on interstellar ice analogs show this to require very low temperatures, the resulting yields of H2CO and CH30H being highly dependent on temperature in the range approx 10 - 25 K. The relative abundances of these chemically-related molecules in comets provide one measure of the efficiency of H-atom addition to CO Oxidation of CO is also important on grain mantles, as evidenced by the widespread presence of C02 ice towards interstellar sources observed with ISO and in a survey of 17 comets observed with AKARI. H-atom addition to C2H2 produces the vinyl radical, and through subsequent oxidation1reduction reactions can lead to vinyl alcohol, acetaldehyde, and ethanol This may have implications for interpreting observed abundance ratios CO/C2H2. We will discuss possible implications regarding formation conditions in the context of measured primary volatile compositions, emphasizing recently observed comets and published results. These are continually providing new insights regarding our taxonomic scheme and also delivery of pre-biological material to the young Earth.

The CH2O column as a possible constraint on methane oxidation

NASA Astrophysics Data System (ADS)

Valin, L. C.; Fiore, A. M.; Lin, M.

2013-12-01

We explore the potential for space-based measurements of the CH2O column to quantify variations of methane oxidation in the remote atmosphere due to changes in climate (e.g., T, H2O, stratospheric O3) and atmospheric composition (e.g., NOxO, O3, CO, CH4). We investigate the variability of methane oxidation and the formaldehyde column using available global simulations (MOZART-2 chemistry-transport model, GFDL AM3 climate-chemistry model). Over a large region (135° - 175° W; 0° - 16° S), the rate of methane oxidation simulated in the models varies intraseasonally (×10%), seasonally (×20%) and interannually (×5%), and is well correlated with the simulated variability of the CH2O column (R2 = 0.75; ~1x1015 molecules cm-2). The precision of a single space-based measurement is approximately 1×1016 molecules cm-2, an order of magnitude larger than the simulated variability of the CH2O column. However, in a large region such as the tropical Pacific, UV/Vis spectrometers are capable of making thousands of measurements daily, enough sampling to theoretically increase the precision by √N, such that variations on the order of 1×1015 molecules cm-2 should be observable on intraseasonal and interannual timescales.

Gas production, composition and emission at a modern disposal site receiving waste with a low-organic content

DOE Office of Scientific and Technical Information (OSTI.GOV)

Scheutz, Charlotte, E-mail: chs@env.dtu.dk; Fredenslund, Anders M., E-mail: amf@env.dtu.dk; Nedenskov, Jonas, E-mail: jne@amfor.dk

2011-05-15

AV Miljo is a modern waste disposal site receiving non-combustible waste with a low-organic content. The objective of the current project was to determine the gas generation, composition, emission, and oxidation in top covers on selected waste cells as well as the total methane (CH{sub 4}) emission from the disposal site. The investigations focused particularly on three waste disposal cells containing shredder waste (cell 1.5.1), mixed industrial waste (cell 2.2.2), and mixed combustible waste (cell 1.3). Laboratory waste incubation experiments as well as gas modeling showed that significant gas generation was occurring in all three cells. Field analysis showed thatmore » the gas generated in the cell with mixed combustible waste consisted of mainly CH{sub 4} (70%) and carbon dioxide (CO{sub 2}) (29%) whereas the gas generated within the shredder waste, primarily consisted of CH{sub 4} (27%) and nitrogen (N{sub 2}) (71%), containing no CO{sub 2}. The results indicated that the gas composition in the shredder waste was governed by chemical reactions as well as microbial reactions. CH{sub 4} mass balances from three individual waste cells showed that a significant part (between 15% and 67%) of the CH{sub 4} generated in cell 1.3 and 2.2.2 was emitted through leachate collection wells, as a result of the relatively impermeable covers in place at these two cells preventing vertical migration of the gas. At cell 1.5.1, which is un-covered, the CH{sub 4} emission through the leachate system was low due to the high gas permeability of the shredder waste. Instead the gas was emitted through the waste resulting in some hotspot observations on the shredder surface with higher emission rates. The remaining gas that was not emitted through surfaces or the leachate collection system could potentially be oxidized as the measured oxidation capacity exceeded the potential emission rate. The whole CH{sub 4} emission from the disposal site was found to be 820 {+-} 202 kg CH{sub 4} d{sup -1}. The total emission rate through the leachate collection system at AV Miljo was found to be 211 kg CH{sub 4} d{sup -1}. This showed that approximately 1/4 of the emitted gas was emitted through the leachate collections system making the leachate collection system an important source controlling the overall gas migration from the site. The emission pathway for the remaining part of the gas was more uncertain, but emission from open cells where waste is being disposed of or being excavated for incineration, or from horizontal leachate drainage pipes placed in permeable gravel layers in the bottom of empty cells was likely.« less

Influence of transition metal electronegativity on the oxygen storage capacity of perovskite oxides.

PubMed

Liu, Lu; Taylor, Daniel D; Rodriguez, Efrain E; Zachariah, Michael R

2016-08-16

The selection of highly efficient oxygen carriers (OCs) is a key step necessary for the practical development of chemical looping combustion (CLC). In this study, a series of ABO3 perovskites, where A = La, Ba, Sr, Ca and B = Cr, Mn, Fe, Co, Ni, Cu, are synthesized and tested in a fixed bed reactor for reactivity and stability as OCs with CH4 as the fuel. We find that the electronegativity of the transition metal on the B-site (λB), is a convenient descriptor for oxygen storage capacity (OSC) of our perovskite samples. By plotting OSC for total methane oxidation against λB, we observe an inverted volcano plot relationship. These results could provide useful guidelines for perovskite OC design and their other energy related applications.

Impacts of integrated nutrient management on methane emission, global warming potential and carbon storage capacity in rice grown in a northeast India soil.

PubMed

Bharali, Ashmita; Baruah, Kushal Kumar; Baruah, Sunitee Gohain; Bhattacharyya, Pradip

2018-02-01

Rice soil is a source of emission of two major greenhouse gases (methane (CH 4 ) and nitrous oxide (N 2 O)) and a sink of carbon dioxide (CO 2 ). The effect of inorganic fertilizers in combination with various organics (cow dung, green manure (Sesbania aculeata) Azolla compost, rice husk) on CH 4 emission, global warming potential, and soil carbon storage along with crop productivity were studied at university farm under field conditions. The experiment was conducted in a randomized block design for 2 years in a monsoon rice (cv. Ranjit) ecosystem (June-November, 2014 and 2015). Combined application of inorganic (NPK) with Sesbania aculeata resulted in high global warming potential (GWP) of 887.4 kg CO 2 ha -1 and low GWP of 540.6 kg CO 2 ha -1 was recorded from inorganic fertilizer applied field. Irrespective of the type of organic amendments, flag leaf photosynthesis of the rice crop increased over NPK application (control). There was an increase in CH 4 emission from the organic amended fields compared to NPK alone. The combined application of NPK and Azolla compost was effective in the buildup of soil carbon (16.93 g kg -1 ) and capacity of soil carbon storage (28.1 Mg C ha -1 ) with high carbon efficiency ratio (16.9). Azolla compost application along with NPK recorded 15.66% higher CH 4 emission with 27.43% yield increment over control. Azolla compost application significantly enhanced carbon storage of soil and improved the yielding ability of grain (6.55 Mg ha -1 ) over other treatments.

Methylmercury oxidative degradation potentials in contaminated and pristine sediments of the Carson River, Nevada

USGS Publications Warehouse

Oremland, R.S.; Miller, L.G.; Dowdle, P.; Connell, T.; Barkay, T.

1995-01-01

Sediments from mercury-contaminated and uncontaminated reaches of the Carson River, Nevada, were assayed for sulfate reduction, methanogenesis, denitrification, and monomethylmercury (MeHg) degradation. Demethylation of [14C]MeHg was detected at all sites as indicated by the formation of 14CO2 and 14CH4. Oxidative demethylation was indicated by the formation of 14CO2 and was present at significant levels in all samples. Oxidized/reduced demethylation product ratios (i.e., 14CO2/14CH4 ratios) generally ranged from 4.0 in surface layers to as low as 0.5 at depth. Production of 14CO2 was most pronounced at sediment surfaces which were zones of active denitrification and sulfate reduction but was also significant within zones of methanogenesis. In a core taken from an uncontaminated site having a high proportion of oxidized, coarse-grain sediments, sulfate reduction and methanogenic activity levels were very low and 14CO2 accounted for 98% of the product formed from [14C]MeHg. There was no apparent relationship between the degree of mercury contamination of the sediments and the occurrence of oxidative demethylation. However, sediments from Fort Churchill, the most contaminated site, were most active in terms of demethylation potentials. Inhibition of sulfate reduction with molybdate resulted in significantly depressed oxidized/reduced demethylation product ratios, but overall demethylation rates of inhibited and uninhibited samples were comparable. Addition of sulfate to sediment slurries stimulated production of 14CO2 from [14C]MeHg, while 2-bromoethanesulfonic acid blocked production of 14CH4. These results reveal the importance of sulfate-reducing and methanogenic bacteria in oxidative demethylation of MeHg in anoxic environments.

F -state quenching with CH 4 for buffer-gas cooled 171 Y b + frequency standard [Methane (CH4) for quenching the F-state in trapped Yb+ ions].

DOE PAGES

Jau, Y. -Y.; Hunker, J. D.; Schwindt, P. D. D.

2015-11-01

We report that methane, CH 4, can be used as an efficient F-state quenching gas for trapped ytterbium ions. The quenching rate coefficient is measured to be (2.8 ± 0.3) × 10 6 s -1 Torr -1. For applications that use microwave hyperfine transitions of the ground-state 171Y b ions, the CH4 induced frequency shift coefficient and the decoherence rate coefficient are measured as δν/ν = (-3.6 ± 0.1) × 10 -6 Torr -1 and 1/T2 = (1.5 ± 0.2) × 10 5 s -1 Torr -1. In our buffer-gas cooled 171Y b+ microwave clock system, we find that onlymore » ≤10 -8 Torr of CH 4 is required under normal operating conditions to efficiently clear the F-state and maintain ≥85% of trapped ions in the ground state with insignificant pressure shift and collisional decoherence of the clock resonance.« less

Effects of granular activated carbon on methane removal performance and methanotrophic community of a lab-scale bioreactor.

PubMed

Lee, Eun-Hee; Choi, Sun-Ah; Yi, Taewoo; Kim, Tae Gwan; Lee, Sang-Don; Cho, Kyung-Suk

2015-01-01

Two identical lab-scale bioreactor systems were operated to examine the effects of granular activated carbon (GAC) on methane removal performance and methanotrophic community. Both bioreactor systems removed methane completely at a CH4 loading rate of 71.2 g-CH4·d(-1) for 17 days. However, the methane removal efficiency declined to 88% in the bioreactor without GAC, while the bioreactor amended with GAC showed greater methane removal efficiency of 97% at a CH4 loading rate of 107.5 g-CH4·d(-1). Although quantitative real-time PCR showed that methanotrophic populations were similar levels of 5-10 × 10(8) pmoA gene copy number·VSS(-1) in both systems, GAC addition changed the methanotrophic community composition of the bioreactor systems. Microarray assay revealed that GAC enhanced the type I methanotrophic genera including Methylobacter, Methylomicrobium, and Methylomonas of the system, which suggests that GAC probably provided a favorable environment for type I methanotrophs. These results indicated that GAC is a promising support material in bioreactor systems for CH4 mitigation.

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

PubMed

Rao, Minxi; Smith, Brian C; Marletta, Michael A

2015-05-05

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. Bacterial nitric oxide (NO) signaling via heme-nitric oxide/oxygen binding (H-NOX) proteins regulates biofilm formation, playing an important role in protecting bacteria from oxidative stress and other environmental stresses. Biofilms are also an important part of symbiosis, allowing the organism to remain in a nutrient-rich environment. In this study, we show that in Silicibacter sp. strain TrichCH4B, NO mediates symbiosis with the alga Trichodesmium erythraeum, a major marine diazotroph. In addition, Silicibacter sp. TrichCH4B is the first characterized bacteria to harbor both the NOS and H-NOX proteins, making it uniquely capable of both synthesizing and sensing NO, analogous to mammalian NO signaling. Our study expands current understanding of the role of NO in bacterial signaling, providing a novel role for NO in bacterial communication and symbiosis. Copyright © 2015 Rao et al.

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.

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

Effects of Land-Use Conversion from Double Rice Cropping to Vegetables on Methane and Nitrous Oxide Fluxes in Southern China

PubMed Central

Yuan, Ye; Dai, Xiaoqin; Wang, Huimin; Xu, Ming; Fu, Xiaoli; Yang, Fengting

2016-01-01

Compared with CO2, methane (CH4) and nitrous oxide (N2O) are potent greenhouse gases in terms of their global warming potentials. Previous studies have indicated that land-use conversion has a significant impact on greenhouse gas emissions. However, little is known regarding the impact of converting rice (Oryza sativa L.) to vegetable fields, an increasing trend in land-use change in southern China, on CH4 and N2O fluxes. The effects of converting double rice cropping to vegetables on CH4 and N2O fluxes were examined using a static chamber method in southern China from July 2012 to July 2013. The results indicate that CH4 fluxes could reach 31.6 mg C m−2 h−1 under rice before land conversion. The cumulative CH4 emissions for fertilized and unfertilized rice were 348.9 and 321.0 kg C ha−1 yr−1, respectively. After the land conversion, the cumulative CH4 emissions were −0.4 and 1.4 kg C ha−1 yr−1 for the fertilized and unfertilized vegetable fields, respectively. Similarly, the cumulative N2O fluxes under rice were 1.27 and 0.56 kg N ha−1 yr−1 for the fertilized and unfertilized treatments before the land conversion and 19.2 and 8.5 kg N ha−1 yr−1, respectively, after the land conversion. By combining the global warming potentials (GWPs) of both gases, the overall land-use conversion effect was minor (P = 0.36) with fertilization, but the conversion reduced GWP by 63% when rice and vegetables were not fertilized. Increase in CH4 emissions increased GWP under rice compared with vegetables with non-fertilization, but increased N2O emissions compensated for similar GWPs with fertilization under rice and vegetables. PMID:27195497

Effects of Land-Use Conversion from Double Rice Cropping to Vegetables on Methane and Nitrous Oxide Fluxes in Southern China.

PubMed

Yuan, Ye; Dai, Xiaoqin; Wang, Huimin; Xu, Ming; Fu, Xiaoli; Yang, Fengting

2016-01-01

Compared with CO2, methane (CH4) and nitrous oxide (N2O) are potent greenhouse gases in terms of their global warming potentials. Previous studies have indicated that land-use conversion has a significant impact on greenhouse gas emissions. However, little is known regarding the impact of converting rice (Oryza sativa L.) to vegetable fields, an increasing trend in land-use change in southern China, on CH4 and N2O fluxes. The effects of converting double rice cropping to vegetables on CH4 and N2O fluxes were examined using a static chamber method in southern China from July 2012 to July 2013. The results indicate that CH4 fluxes could reach 31.6 mg C m-2 h-1 under rice before land conversion. The cumulative CH4 emissions for fertilized and unfertilized rice were 348.9 and 321.0 kg C ha-1 yr-1, respectively. After the land conversion, the cumulative CH4 emissions were -0.4 and 1.4 kg C ha-1 yr-1 for the fertilized and unfertilized vegetable fields, respectively. Similarly, the cumulative N2O fluxes under rice were 1.27 and 0.56 kg N ha-1 yr-1 for the fertilized and unfertilized treatments before the land conversion and 19.2 and 8.5 kg N ha-1 yr-1, respectively, after the land conversion. By combining the global warming potentials (GWPs) of both gases, the overall land-use conversion effect was minor (P = 0.36) with fertilization, but the conversion reduced GWP by 63% when rice and vegetables were not fertilized. Increase in CH4 emissions increased GWP under rice compared with vegetables with non-fertilization, but increased N2O emissions compensated for similar GWPs with fertilization under rice and vegetables.

Impact of mine wastewaters on greenhouse gas emissions from northern peatlands used for mine water treatment

NASA Astrophysics Data System (ADS)

Palmer, Katharina; Ronkanen, Anna-Kaisa; Klöve, Björn; Hynynen, Jenna; Maljanen, Marja

2015-04-01

The amount of wastewaters generated during mining operations is increasing along with the increasing number of operation mines, which poses great challenges for mine water management and purification. Mine wastewaters contain high concentrations of nitrogen compounds such as nitrate (NO3-) and ammonium (NH4+) originating from remnant explosives as well as sulfate (SO42-) originating from the oxidation of sulfidic ores. At a mine site in Finnish Lapland, two natural peatlands have been used for cost-effective passive wastewater treatment. One peatland have been used for the treatment of drainage waters (TP 1), while the other has been used for the treatment of process-based wastewaters (TP 4). In this study, the impact of mine water derived nitrogen compounds as well as SO42- on the emission of the potent greenhouse gases methane (CH4) and nitrous oxide (N2O) from those treatment peatlands was investigated. Contaminant concentrations in the input and output waters of the treatment peatlands were monitored which allowed for the calculation of contaminant-specific retention efficiencies. Treatment peatlands showed generally good retention efficiencies for metals and metalloids (e.g. nickel, arsenic, antimony, up to 98% reduction in concentration) with rather low input-concentrations (i.e., in the μg/l-range). On the other hand, retention of contaminants with high input-concentrations (i.e., in mg/l-range) such as NO3-, NH4+ and SO42- was much lower (4-41%, 30-60% and -42-30%, respectively), indicating the limited capability of the treatment peatlands to cope with such high input concentrations. NO3- and NH4+ concentrations were determined in surface and pore water from TP 4 in July 2013 as well as in surface water from TP 1 and TP 4 in October 2013. Up to 720 μM NO3- and up to 600 μM NH4+ were detected in surface water of TP 4 in July 2013. NO3- and NH4+ concentrations in surface waters were highest near the mine wastewater distribution ditch and decreased with increasing distances from the ditch. NO3- concentrations were lower in pore water than in surface water, and the peak in NO3- concentration shifted further away from the distribution ditch with increasing depth. On the contrary, NH4+ concentrations were generally higher in pore water than in surface water, and peak concentrations increased with increasing depth. Highest NH4+ concentrations were detected in 30 to 60 cm depth near the outlet at the south end of TP 4. Fluxes of the greenhouse gases CH4 and N2O from 4 sampling points (2 from TP 4, 1 from TP 1, 1 from reference area) were measured on 7 different occasions 2013 and 2014. CH4 emissions were in the same range as measured in other northern pristine peatlands in the reference area, which is not influenced by mine wastewaters. Treatment peatlands showed only very minor CH4 emissions or even CH4 uptake. On the other hand, treatment peatlands showed high N2O emissions, which were in the same range as N2O emissions observed from northern peat soils used for agriculture. Highest emissions were generally observed near the wastewater distribution ditch of TP 4. N2O emissions from the reference area were negligible or even negative. NO3-, NH4+ and SO42- concentrations were determined from surface waters from each sampling point and sampling occasion. N2O emissions were positively correlated with NO3- concentrations, indicating denitrification-derived N2O production in treatment peatlands. On the other hand, CH4 emissions were negatively correlated with SO42- and NO3- concentrations, indicating that the presence of alternative electron acceptors in large amounts suppresses CH4 production in treatment peatlands. In conclusion, the study revealed that (i) treatment peatlands receive high loads of NO3-, NH4+ and SO42- which are not well retained in the peatlands, (ii) mine wastewaters positively and negatively affect N2O and CH4 emissions, respectively, (iii) N2O emissions are positively correlated with NO3- concentrations, and (iv) CH4 emissions are negatively correlated with NO3- and SO42- concentrations. This study thus illustrates the pronounced impacts of mine wastewaters on processes involved in greenhouse gas turnover in peatlands ecosystems.

Methane and nitrous oxide fluxes in native, fertilized and cultivated grasslands

NASA Technical Reports Server (NTRS)

Mosier, A.; Bronson, K.; Schimel, D.; Valentine, D.; Parton, W.

1991-01-01

Measurements of CH4 uptake and N2O emissions in native, nitrogen-fertilized, and wheat-growing prairie soils from spring to late autumn, 1990 are reported. It is found that nitrogen fertilization and cultivation can both decrease CH4 uptake and increase N2O production, thereby contributing to the increasing atmospheric concentrations of these gases.

Synthesis of Bilayer Graphene on 90/10 Copper (Cu)/Nickel (Ni) Alloy and Transfer by Electrochemical Delamination

DTIC Science & Technology

2017-09-01

C) and slow decomposition rate in methane (CH4).11 Cu alone has sometimes been shown to form incomplete bilayers with a significant fraction of...argon BLG bilayer graphene C carbon CH4 methane Cu2O cuprous oxide Cu copper CVD chemical vapor deposition DI deionized FeCl3 iron

Methane and nitrous oxide fluxes in native, fertilized and cultivated grasslands

NASA Astrophysics Data System (ADS)

Mosier, A.; Bronson, K.; Schimel, D.; Valentine, D.; Parton, W.

1991-03-01

Measurements of CH4 uptake and N2O emissions in native, nitrogen-fertilized, and wheat-growing prairie soils from spring to late autumn, 1990 are reported. It is found that nitrogen fertilization and cultivation can both decrease CH4 uptake and increase N2O production, thereby contributing to the increasing atmospheric concentrations of these gases.

Light-trapping in perovskite solar cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Du, Qing Guo; Shen, Guansheng; John, Sajeev

We numerically demonstrate enhanced light harvesting efficiency in both CH 3NH 3PbI 3 and CH(NH 2) 2PbI 3-based perovskite solar cells using inverted verticalcone photonic-crystal nanostructures. For CH 3NH 3PbI 3 perovskite solar cells, the maximum achievable photocurrent density (MAPD) reaches 25.1 mA/cm 2, corresponding to 92% of the total available photocurrent in the absorption range of 300 nm to 800 nm. Our cell shows 6% absorption enhancement compared to the Lambertian limit (23.7 mA/cm 2) and has a projected power conversion efficiency of 12.9%. Excellent solar absorption is numerically demonstrated over a broad angular range from 0 to 60more » degree for both S- and P- polarizations. For the corresponding CH(NH 2) 2PbI 3 based perovskite solar cell, with absorption range of 300 nm to 850 nm, we find a MAPD of 29.1 mA/cm 2, corresponding to 95.4% of the total available photocurrent. Furthermore, the projected power conversion efficiency of the CH(NH 2) 2PbI 3 based photonic crystal solar cell is 23.4%, well above the current world record efficiency of 20.1%.« less

Light-trapping in perovskite solar cells

DOE PAGES

Du, Qing Guo; Shen, Guansheng; John, Sajeev

2016-06-01

We numerically demonstrate enhanced light harvesting efficiency in both CH 3NH 3PbI 3 and CH(NH 2) 2PbI 3-based perovskite solar cells using inverted verticalcone photonic-crystal nanostructures. For CH 3NH 3PbI 3 perovskite solar cells, the maximum achievable photocurrent density (MAPD) reaches 25.1 mA/cm 2, corresponding to 92% of the total available photocurrent in the absorption range of 300 nm to 800 nm. Our cell shows 6% absorption enhancement compared to the Lambertian limit (23.7 mA/cm 2) and has a projected power conversion efficiency of 12.9%. Excellent solar absorption is numerically demonstrated over a broad angular range from 0 to 60more » degree for both S- and P- polarizations. For the corresponding CH(NH 2) 2PbI 3 based perovskite solar cell, with absorption range of 300 nm to 850 nm, we find a MAPD of 29.1 mA/cm 2, corresponding to 95.4% of the total available photocurrent. Furthermore, the projected power conversion efficiency of the CH(NH 2) 2PbI 3 based photonic crystal solar cell is 23.4%, well above the current world record efficiency of 20.1%.« less

Development of methane and nitrous oxide emission factors for the biomass fired circulating fluidized bed combustion power plant.

PubMed

Cho, Chang-Sang; Sa, Jae-Hwan; Lim, Ki-Kyo; Youk, Tae-Mi; Kim, Seung-Jin; Lee, Seul-Ki; Jeon, Eui-Chan

2012-01-01

This study makes use of this distinction to analyze the exhaust gas concentration and fuel of the circulating fluidized bed (CFB) boiler that mainly uses wood biomass, and to develop the emission factors of Methane (CH(4)), Nitrous oxide (N(2)O). The fuels used as energy sources in the subject working sites are Wood Chip Fuel (WCF), RDF and Refused Plastic Fuel (RPF) of which heating values are 11.9 TJ/Gg, 17.1 TJ/Gg, and 31.2 TJ/Gg, respectively. The average concentrations of CH(4) and N(2)O were measured to be 2.78 ppm and 7.68 ppm, respectively. The analyzed values and data collected from the field survey were used to calculate the emission factor of CH(4) and N(2)O exhausted from the CFB boiler. As a result, the emission factors of CH(4) and N(2)O are 1.4 kg/TJ (0.9-1.9 kg/TJ) and 4.0 kg/TJ (2.9-5.3 kg/TJ) within a 95% confidence interval. Biomass combined with the combustion technology for the CFB boiler proved to be more effective in reducing the N(2)O emission, compared to the emission factor of the CFB boiler using fossil fuel.

Synthesis and characterization of metal nanoparticles templated chitosan-SiO2 catalyst for the reduction of nitrophenols and dyes.

PubMed

Ali, Fayaz; Khan, Sher Bahadar; Kamal, Tahseen; Alamry, Khalid A; Bakhsh, Esraa M; Asiri, Abdullah M; Sobahi, Tariq R A

2018-07-15

Different metal nanoparticles (MNPs) templated on chitosan-silica (CH-SiO 2 ) nanocomposite fiber were prepared via simple and fast method of the metal ions uptake by fiber and their subseqent reduction using strong reducing agent. The performance difference of CH-SiO 2 templated with Cu, Co, Ag and Ni nanoparticles for both reduction of 4-nitroaniline (4-NA) and decolorization of congo red (CR) was investigated. The Cu nanoparticles loaded CH-SiO 2 (Cu/CH-SiO 2 ), showed high catalytic efficiencies in the reduction of 4-NA and CR, as compared to other loaded MNP fibers. The apparent rate constants of 6.17 × 10 -3  s -1 and 1.68 × 10 -2  s -1 and turnover frequencies (TOF) of 4.693 h -1 and 3.965 h -1 were observed for the reduction of 4-NA and CR, respectively. In addition, the catalytic activity of Cu/CH-SiO 2 catalyst was also examined and found efficient in the reduction of nitrophenols (2-NP, 3-NP and 4-NP), and other dyes. Thus, Cu/CH-SiO 2 with excellent catalytic activity can also be employed for other applications. Copyright © 2018 Elsevier Ltd. All rights reserved.

Soil fluxes of methane, nitrous oxide, and nitric oxide from aggrading forests in coastal Oregon

USGS Publications Warehouse

Erickson, Heather E.; Perakis, Steven S.

2014-01-01

Soil exchanges of greenhouse and other gases are poorly known for Pacific Northwest forests where gradients in nutrient availability and soil moisture may contribute to large variations in fluxes. Here we report fluxes of methane (CH4), nitrous oxide (N2O), and nitric oxide (NO) over multiple seasons from three naturally N-rich, aggrading forests of coastal Oregon, USA. Mean methane uptake rates (3.2 mg CH4 m−2 d−1) were high compared with forests globally, negatively related to water-filled pore space (WFPS), but unrelated to N availability or temperature. Emissions of NO (6.0 μg NO–N m−2 h−1) exceeded N2O (1.4 μg N2O–N m−2 h−1), except when WFPS surpassed 55%. Spatial variation in NO fluxes correlated positively with soil nitrate concentrations (which generally exceeded ammonium concentrations, indicating the overall high N status for the sites) and negatively with soil pH, and at one site increased with basal area of N2-fixing red alder. Combined NO and N2O emissions were greatest from the site with highest annual net N mineralization and lowest needle litterfall C/N. Our findings of high CH4 uptake and NO/N2O ratios generally >1 most likely reflect the high porosity of the andic soils underlying the widespread regenerating forests in this seasonally wet region.

Does Juncus effusus enhance methane emissions from grazed pastures on peat?

NASA Astrophysics Data System (ADS)

Henneberg, A.; Elsgaard, L.; Sorrell, B. K.; Brix, H.; Petersen, S. O.

2015-06-01

Methane (CH4) emissions from drained organic soils are generally low, but internal gas transport in aerenchymatous plants may result in local emission hotspots. In a paired-sample field study at three different sites we measured fluxes of CH4 with static chambers from adjacent sampling quadrats with and without Juncus effusus during four field campaigns. At all three sites, CH4 was observed in the soil at all sampling depths (5-100 cm), and in most cases both above and below the groundwater table. During spring, local maxima suggested methanogenesis took place above the water table at all three sites. We found significant CH4 emissions at all three sites, but emission controls were clearly different. Across the three sites, average emission rates (±1 SE) for sampling quadrats with and without J. effusus were 1.47 ± 0.28 and 1.37 ± 0.33 mg CH4 m-2 h-1 respectively, with no overall effect of J. effusus on CH4 emissions, but a significant effect at one of the three sites. At this site, local CH4 maxima were closer to the soil surface than at the other sites, and the upper soil layers were dryer. This could have affected both root CH4 accessibility and CH4 oxidation respectively, and together with limited gas diffusivity in the soil column, cause elevated CH4 emissions from J. effusus. We conclude that aerenchymatous plants has the potential to act as point sources of CH4 from drained peatlands, but more studies on the specific conditions under which there is an effect, are needed before the results can be used in modelling of CH4 emissions.

Does uncus effusus enhance methane emissions from grazed pastures on peat?

NASA Astrophysics Data System (ADS)

Henneberg, A.; Elsgaard, L.; Sorrell, B. K.; Brix, H.; Petersen, S. O.

2015-10-01

Methane (CH4) emissions from drained organic soils are generally low, but internal gas transport in aerenchymatous plants may result in local emission hotspots. In a paired-sample field study at three different sites we measured fluxes of CH4 with static chambers from adjacent sampling quadrats with and without Juncus effusus during four field campaigns. At all three sites, CH4 was observed in the soil at all sampling depths (5 to 100 cm), and in most cases both above and below the groundwater table. During spring, local maxima suggested methanogenesis also took place above the water table at all three sites. We found significant CH4 emissions at all three sites, but emission controls were clearly different. Across the three sites, average emission rates (±1 SE) for sampling quadrats with and without J. effusus were 1.47 ± 0.28 and 1.37 ± 0.33 mg CH4 m-2 h-1, respectively, with no overall effect of J. effusus on CH4 emissions. However, a significant effect of J. effusus was seen at one of the three sites. At this site, local CH4 maxima were closer to the soil surface than at the other sites, and the upper soil layers were dryer. This could have affected both root CH4 accessibility and CH4 oxidation respectively, and together with limited gas diffusivity in the soil column, cause elevated CH4 emissions from J. effusus. We conclude that J. effusus has the potential to act as point sources of CH4 from drained peatlands, but more studies on the specific conditions under which there is an effect, are needed before the results can be used in modelling of CH4 emissions.

Chemical Reactivity of Formaldehyde in FeAlP0{sub 4} Sieve

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yeom, Young-Hoon; Ulagappan, Nagappan; Frei, Heinz

2001-03-12

Formaldehyde gas loaded into framework Fe aluminophosphate sieve (FeAlP O4-5) at 250 K was found to react with adsorbed H2O, CH3OH, H2O2, or lattice OH groups to yield the corresponding addition product, namely CH2(OH)2, CH3OCH2OH, HO 2CH2OH, or POCH2OH, respectively. Reactions were monitored in situ by static FT-IR spectroscopy, and assignments are based on experiments with CD2=0 and CD3OD. Most efficient was the reaction with H2O2 as indicated by the fact that HO2CH2OH was formed at the exclusion of CH2(OH)2 and POCH2OH when adsorbing formaldehyde onto a sieve loaded with H2O2 and H2O. Methoxymethanol, methanediol, and POCH2OH were stable atmore » 250 K, but dissociated above 0 degrees C under release of formaldehyde. Hydromethyl hydroperoxide disproportionates to formic acid and water. Under 355 nm irradiation in FeAlPO4 sieve, HO2CH2OH was found to undergo efficient photofragmentation.« less

Reactivity of nitrido complexes of ruthenium(VI), osmium(VI), and manganese(V) bearing Schiff base and simple anionic ligands.

PubMed

Man, Wai-Lun; Lam, William W Y; Lau, Tai-Chu

2014-02-18

Nitrido complexes (M≡N) may be key intermediates in chemical and biological nitrogen fixation and serve as useful reagents for nitrogenation of organic compounds. Osmium(VI) nitrido complexes bearing 2,2':6',2″-terpyridine (terpy), 2,2'-bipyridine (bpy), or hydrotris(1-pyrazolyl)borate anion (Tp) ligands are highly electrophilic: they can react with a variety of nucleophiles to generate novel osmium(IV)/(V) complexes. This Account describes our recent results studying the reactivity of nitridocomplexes of ruthenium(VI), osmium(VI), and manganese(V) that bear Schiff bases and other simple anionic ligands. We demonstrate that these nitrido complexes exhibit rich chemical reactivity. They react with various nucleophiles, activate C-H bonds, undergo N···N coupling, catalyze the oxidation of organic compounds, and show anticancer activities. Ruthenium(VI) nitrido complexes bearing Schiff base ligands, such as [Ru(VI)(N)(salchda)(CH3OH)](+) (salchda = N,N'-bis(salicylidene)o-cyclohexyldiamine dianion), are highly electrophilic. This complex reacts readily at ambient conditions with a variety of nucleophiles at rates that are much faster than similar reactions using Os(VI)≡N. This complex also carries out unique reactions, including the direct aziridination of alkenes, C-H bond activation of alkanes and C-N bond cleavage of anilines. The addition of ligands such as pyridine can enhance the reactivity of [Ru(VI)(N)(salchda)(CH3OH)](+). Therefore researchers can tune the reactivity of Ru≡N by adding a ligand L trans to nitride: L-Ru≡N. Moreover, the addition of various nucleophiles (Nu) to Ru(VI)≡N initially generate the ruthenium(IV) imido species Ru(IV)-N(Nu), a new class of hydrogen-atom transfer (HAT) reagents. Nucleophiles also readily add to coordinated Schiff base ligands in Os(VI)≡N and Ru(VI)≡N complexes. These additions are often stereospecific, suggesting that the nitrido ligand has a directing effect on the incoming nucleophile. M≡N is also a potential platform for the design of new oxidation catalysts. For example, [Os(VI)(N)Cl4](-) catalyzes the oxidation of alkanes by a variety of oxidants, and the addition of Lewis acids greatly accelerates these reactions. [Mn(V)(N)(CN)4]2(-) is another highly efficient oxidation catalyst, which facilitates the epoxidation of alkenes and the oxidation of alcohols to carbonyl compounds using H2O2. Finally, M≡N can potentially bind to and exert various effects on biomolecules. For example, a number of Os(VI)≡N complexes exhibit novel anticancer properties, which may be related to their ability to bind to DNA or other biomolecules.

A two-state computational investigation of methane C--H and ethane C--C oxidative addition to [CpM(PH3)]n+ (M = Co, Rh, Ir; n = 0, 1).

PubMed

Petit, Alban; Richard, Philippe; Cacelli, Ivo; Poli, Rinaldo

2006-01-11

Reductive elimination of methane from methyl hydride half-sandwich phosphane complexes of the Group 9 metals has been investigated by DFT calculations on the model system [CpM(PH(3))(CH(3))(H)] (M = Co, Rh, Ir). For each metal, the unsaturated product has a triplet ground state; thus, spin crossover occurs during the reaction. All relevant stationary points on the two potential energy surfaces (PES) and the minimum energy crossing point (MECP) were optimized. Spin crossover occurs very near the sigma-CH(4) complex local minimum for the Co system, whereas the heavier Rh and Ir systems remain in the singlet state until the CH(4) molecule is almost completely expelled from the metal coordination sphere. No local sigma-CH(4) minimum was found for the Ir system. The energetic profiles agree with the nonexistence of the Co(III) methyl hydride complex and with the greater thermal stability of the Ir complex relative to the Rh complex. Reductive elimination of methane from the related oxidized complexes [CpM(PH(3))(CH(3))(H)](+) (M = Rh, Ir) proceeds entirely on the spin doublet PES, because the 15-electron [CpM(PH(3))](+) products have a doublet ground state. This process is thermodynamically favored by about 25 kcal mol(-1) relative to the corresponding neutral system. It is essentially barrierless for the Rh system and has a relatively small barrier (ca. 7.5 kcal mol(-1)) for the Ir system. In both cases, the reaction involves a sigma-CH(4) intermediate. Reductive elimination of ethane from [CpM(PH(3))(CH(3))(2)](+) (M = Rh, Ir) shows a similar thermodynamic profile, but is kinetically quite different from methane elimination from [CpM(PH(3))(CH(3))(H)](+): the reductive elimination barrier is much greater and does not involve a sigma-complex intermediate. The large difference in the calculated activation barriers (ca. 12.0 and ca. 30.5 kcal mol(-1) for the Rh and Ir systems, respectively) agrees with the experimental observation, for related systems, of oxidatively induced ethane elimination when M = Rh, whereas the related Ir systems prefer to decompose by alternative pathways.

Eosin Y-catalyzed visible-light-mediated aerobic oxidative cyclization of N,N-dimethylanilines with maleimides.

PubMed

Liang, Zhongwei; Xu, Song; Tian, Wenyan; Zhang, Ronghua

2015-01-01

A novel and simple strategy for the efficient synthesis of the corresponding tetrahydroquinolines from N,N-dimethylanilines and maleimides using visible light in an air atmosphere in the presence of Eosin Y as a photocatalyst has been developed. The metal-free protocol involves aerobic oxidative cyclization via sp(3) C-H bond functionalization process to afford good yields in a one-pot procedure under mild conditions.

Reactions of the linear tetranuclear complex Ru sub 4 (CO) sub 10 (CH sub 3 C double bond C(H)C(H) double bond N-i-Pr) sub 2 with oxidizing reagents. Syntheses of halide-bridged (Ru(CO) sub 2 X(CH sub 3 C double bond C(H)C(H) double bond N-i-Pr)) sub 2 and fac-Ru(CO) sub 3 X(CH sub 3 C double bond C(H)C(H) double bond N-i-Pr)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mul, W.P.; Elsevier, C.J.; van Leijen, M.

1991-01-01

The linear tetranuclear complex Ru{sub 4}(CO){sub 10}(CH{sub 3}C{double bond}C(H)C(H){double bond}N-i-Pr){sub 2} (1), containing two {eta}{sup 5}-azaruthenacyclopentadienyl systems, reacts with oxidizing reagents (I{sub 2}, Br{sub 2}, NBS, CCl{sub 4}) at elevated temperatures (40-90C) in heptane or benzene to give the new dimeric halide-bridged organoruthenium(II) complexes (Ru(CO){sub 2}X(CH{sub 3}C{double bond}C(H)C(H){double bond}N-i-Pr)){sub 2} (X = I (3a), X = Br (3b), Cl (3c); yield 30-80%) together with (Ru(CO){sub 3}X{sub 2}){sub 2}. The reactions of 1 with CX{sub 4} (X = I, Br, Cl) are accelerated by CO, probably because Ru{sub 4}(CO){sub 12}(CH{sub 3}C{double bond}C(H)C(H){double bond}N-i-Pr){sub 2} (5), which contains two unbridged metal-metal bonds,more » is formed prior to oxidation. The halide-bridged dimers 3a-c are obtained as mixtures of four isomers, the configurations of which are discussed. Splitting of the halide bridges takes place when a solution of 3a-c is saturated with CO, whereby mononuclear fac-Ru(CO){sub 3}X(CH{sub 3}C{double bond}C(H)C(H){double bond}N-i-Pr) (4a-c) is obtained. This process is reversible; ie., passing a stream of nitrogen through a solution of 4a-c or removal of the solvent under vacuum causes the reverse reaction with reformation of 3a-c. Compounds 3a-c and 4a-c have been characterized by IR (3, 4), FD mass (3), {sup 1}H (3, 4), and {sup 13}C{l brace}H{r brace} NMR (4) spectroscopy and satisfactory elemental analyses have been obtained for 3a-c. Compounds 3 and 4 are suitable precursors for the preparation of new homo- and heteronuclear transition-metal complexes.« less

Theoretical insights into the selective oxidation of methane to methanol in copper-exchanged mordenite

DOE PAGES

Zhao, Zhi -Jian; Kulkarni, Ambarish; Vilella, Laia; ...

2016-05-02

Selective oxidation of methane to methanol is one of the most difficult chemical processes to perform. A potential group of catalysts to achieve CH 4 partial oxidation are Cu-exchanged zeolites mimicking the active structure of the enzyme methane monooxygenase. However, the details of this conversion, including the structure of the active site, are still under debate. In this contribution, periodic density functional theory (DFT) methods were employed to explore the molecular features of the selective oxidation of methane to methanol catalyzed by Cu-exchanged mordenite (Cu-MOR). We focused on two types of previously suggested active species, CuOCu and CuOOCu. Our calculationsmore » indicate that the formation of CuOCu is more feasible than that of CuOOCu. In addition, a much lower C–H dissociation barrier is located on the former active site, indicating that C–H bond activation is easily achieved with CuOCu. We calculated the energy barriers of all elementary steps for the entire process, including catalyst activation, CH 4 activation, and CH 3OH desorption. Finally, our calculations are in agreement with experimental observations and present the first theoretical study examining the entire process of selective oxidation of methane to methanol.« less

Evaluation of constructed wetlands by wastewater purification ability and greenhouse gas emissions.

PubMed

Gui, P; Inamori, R; Matsumura, M; Inamori, Y

2007-01-01

Domestic wastewater is a significant source of nitrogen and phosphorus, which cause lake eutrophication. Among the wastewater treatment technologies, constructed wetlands are a promising low-cost means of treating point and diffuse sources of domestic wastewater in rural areas. However, the sustainable operation of constructed wetland treatment systems depends upon a high rate conversion of organic and nitrogenous loading into their metabolic gaseous end products, such as N2O and CH4. In this study, we examined and compared the performance of three typical types of constructed wetlands: Free Water Surface (FWS), Subsurface Flow (SF) and Vertical Flow (VF) wetlands. Pollutant removal efficiency and N2O and CH4 emissions were assessed as measures of performance. We found that the pollutant removal rates and gas emissions measured in the wetlands exhibited clear seasonal changes, and these changes were closely associated with plant growth. VF wetlands exhibited stable removal of organic pollutants and NH3-N throughout the experiment regardless of season and showed great potential for CH4 adsorption. SF wetlands showed preferable T-N removal performance and a lower risk of greenhouse gas emissions than FWS wetlands. Soil oxidation reduction potential (ORP) analysis revealed that water flow structure and plant growth influenced constructed wetland oxygen transfer, and these variations resulted in seasonal changes of ORP distribution inside wetlands that were accompanied by fluctuations in pollutant removal and greenhouse gas emissions.

Biogas Upgrading via Hydrogenotrophic Methanogenesis in Two-Stage Continuous Stirred Tank Reactors at Mesophilic and Thermophilic Conditions.

PubMed

Bassani, Ilaria; Kougias, Panagiotis G; Treu, Laura; Angelidaki, Irini

2015-10-20

This study proposes an innovative setup composed by two stage reactors to achieve biogas upgrading coupling the CO2 in the biogas with external H2 and subsequent conversion into CH4 by hydrogenotrophic methanogenesis. In this configuration, the biogas produced in the first reactor was transferred to the second one, where H2 was injected. This configuration was tested at both mesophilic and thermophilic conditions. After H2 addition, the produced biogas was upgraded to average CH4 content of 89% in the mesophilic reactor and 85% in the thermophilic. At thermophilic conditions, a higher efficiency of CH4 production and CO2 conversion was recorded. The consequent increase of pH did not inhibit the process indicating adaptation of microorganisms to higher pH levels. The effects of H2 on the microbial community were studied using high-throughput Illumina random sequences and full-length 16S rRNA genes extracted from the total sequences. The relative abundance of archaeal community markedly increased upon H2 addition with Methanoculleus as dominant genus. The increase of hydrogenotrophic methanogens and syntrophic Desulfovibrio and the decrease of aceticlastic methanogens indicate a H2-mediated shift toward the hydrogenotrophic pathway enhancing biogas upgrading. Moreover, Thermoanaerobacteraceae were likely involved in syntrophic acetate oxidation with hydrogenotrophic methanogens in absence of aceticlastic methanogenesis.

Influence of cattle wastes on nitrous oxide and methane fluxes in pasture land

DOE Office of Scientific and Technical Information (OSTI.GOV)

Flessa, H.; Doersch, P.; Beese, F.

1996-11-01

Agricultural practices are assumed to contribute significantly to the increase in atmospheric N{sub 2}O concentrations observed in the last decades, and they might influence the consumption of atmospheric CH{sub 4}. We report on measurements of N{sub 2}O and CH{sub 4} exchange of a pasture soil, as influenced by droppings of a grazing cattle (Bos taurus) herd. Nitrous oxide and methane fluxes in pasture soil were largely determined by the emission rates from cattle excrement with dung patches being hot spots of CH{sub 4} production and urine-affected areas showing extremely high N{sub 2}O release rates. Methane emissions from dung patches (0.778more » g CH{sub 4}-C per animal and day) were insignificant when compared with those from the rumen of the cattle. Total N{sub 2}O-N losses from the droppings were equivalent to 3.2% of the nitrogen excreted. Based on global data of total nitrogen excretion by dairy cattle, non-dairy cattle, buffalo (Syncerus caffer), and bison during grazing, we estimate the global N{sub 2}O emission from this source to be {approximately}1.18 teragrams N{sub 2}O-N per year, indicating that grazing cattle excretory products are one of the most important sources of atmospheric nitrous oxide. Our work suggests that these sources have been drastically underestimated. 27 refs., 2 figs., 2 tabs.« less

Acetate Salts as Nonhalogen Additives To Improve Perovskite Film Morphology for High-Efficiency Solar Cells.

PubMed

Wu, Qiliang; Zhou, Pengcheng; Zhou, Weiran; Wei, Xiangfeng; Chen, Tao; Yang, Shangfeng

2016-06-22

A two-step method has been popularly adopted to fabricate a perovskite film of planar heterojunction organo-lead halide perovskite solar cells (PSCs). However, this method often generates uncontrollable film morphology with poor coverage. Herein, we report a facile method to improve perovskite film morphology by incorporating a small amount of acetate (CH3COO(-), Ac(-)) salts (NH4Ac, NaAc) as nonhalogen additives in CH3NH3I solution used for immersing PbI2 film, resulting in improved CH3NH3PbI3 film morphology. Under the optimized NH4Ac additive concentration of 10 wt %, the best power conversion efficiency (PCE) reaches 17.02%, which is enhanced by ∼23.2% relative to that of the pristine device without additive, whereas the NaAc additive does not lead to an efficiency enhancement despite the improvement of the CH3NH3PbI3 film morphology. SEM study reveals that NH4Ac and NaAc additives can both effectively improve perovskite film morphology by increasing the surface coverage via diminishing pinholes. The improvement on CH3NH3PbI3 film morphology is beneficial for increasing the optical absorption of perovskite film and improving the interfacial contact at the perovskite/spiro-OMeTAD interface, leading to the increase of short-circuit current and consequently efficiency enhancement of the PSC device for NH4Ac additive only.

Amavadin and other vanadium complexes as remarkably efficient catalysts for one-pot conversion of ethane to propionic and acetic acids.

PubMed

Kirillova, Marina V; Kuznetsov, Maxim L; da Silva, José A L; Guedes da Silva, Maria Fátima C; Fraústo da Silva, João J R; Pombeiro, Armando J L

2008-01-01

Synthetic amavadin Ca[V{ON[CH(CH(3))COO](2)}(2)] and its models Ca[V{ON(CH(2)COO)(2)}(2)] and [VO{N(CH(2)CH(2)O)(3)}], in the presence of K(2)S(2)O(8) in trifluoroacetic acid (TFA), exhibit remarkable catalytic activity for the one-pot carboxylation of ethane to propionic and acetic acids with the former as the main product (overall yields up to 93 %, catalyst turnover numbers (TONs) up to 2.0 x 10(4)). The simpler V complexes [VO(CF(3)SO(3))(2)], [VO(acac)(2)] and VOSO(4) are less active. The effects of various factors, namely, C(2)H(6) and CO pressures, time, temperature, and amounts of catalyst, TFA and K(2)S(2)O(8), have been investigated, and this allowed optimisation of the process and control of selectivity. (13)C-labelling experiments indicated that the formation of acetic acid follows two pathways, the dominant one via oxidation of ethane with preservation of the C--C bond, and the other via rupture of this bond and carbonylation of the methyl group by CO; the C--C bond is retained in the formation of propionic acid upon carbonylation of ethane. The reactions proceed via both C- and O-centred radicals, as shown by experiments with radical traps. On the basis of detailed DFT calculations, plausible reaction mechanisms are discussed. The carboxylation of ethane in the presence of CO follows the sequential formation of C(2)H(5) (*), C(2)H(5)CO(*), C(2)H(5)COO(*) and C(2)H(5)COOH. The C(2)H(5)COO(*) radical is easily formed on reaction of C(2)H(5)CO(*) with a peroxo V catalyst via a V{eta(1)-OOC(O)C(2)H(5)} intermediate. In the absence of CO, carboxylation proceeds by reaction of C(2)H(5) (*) with TFA. For the oxidation of ethane to acetic acid, either with preservation or cleavage of the C-C bond, metal-assisted and purely organic pathways are also proposed and discussed.

Infrared absorption of 2-hydroxyethyl (HOCH2CH2) in solid Ar

NASA Astrophysics Data System (ADS)

Kuo, Yu-Ping; Wann, Gwo-Huei; Lee, Yuan-Pern

1993-09-01

An argon matrix containing C2H4 and H2O2 was irradiated at 12 K with the 248 nm emission of a KrF excimer laser; IR spectra were recorded after various periods of photolysis. In addition to lines ascribed to ethylene oxide, acetaldehyde, and vinyl alcohol, absorptions at 2991.0, 2842.7, 1355.4, 1172.5, and 1040.1 cm-1 have been assigned to HOCH2CH2; weaker lines at 3625.8, 2922.4, and 873.9 cm-1 may also be due to HOCH2CH2. Corresponding lines at 2970.6, 2829.3, 1346.5, 1171.3, and 1020.5 (and probably 3625.8, 2915.1, and 860.7) cm-1 were observed for HO13CH2 13CH2. The results are consistent with ab initio calculations.

Influence of water table fluctuations on subsurface methane dynamics and surface fluxes in seasonally flooded subtropical pastures.

NASA Astrophysics Data System (ADS)

Chamberlain, S.; Gomez-Casanovas, N.; Boughton, E.; Keel, E.; Walter, M. T.; Groffman, P. M.; Sparks, J. P.

2015-12-01

Seasonally flooded subtropical pastures are major sources of methane (CH4), and periodic flooding drives complex emission dynamics from these ecosystems. Understanding the mechanisms of belowground CH4 dynamics driving soil surface fluxes is needed to better understand emissions from these systems and their response to environmental change. We investigated subsurface CH4 dynamics in relation to net surface fluxes using laboratory water table manipulations and compared these results to eddy covariance-measured fluxes to link within-soil CH4 dynamics to observed ecosystem fluxes. Pronounced hysteresis was observed in ecosystem CH4 fluxes during precipitation driven flooding events. This dynamic was replicated in mesocosm experiments, with maximum CH4 fluxes observed during periods of water table recession. Hysteresis dynamics were best explained by oxygen dynamics during precipitation recharge events and the oxidation of CH4 produced in organic soil horizons during water table recession. We observed distinct CH4 dynamics between surface organic and deeper mineral soil horizons. In surface organic soil horizons, high levels of CH4 production were temporally linked to observed surface emissions. In contrast, high concentrations of CH4 observed in deeper mineral soils did not contribute to surface fluxes. Methane production potentials in surface organic soils were orders of magnitude higher than in mineral soils, suggesting that over longer flooding regimes CH4 produced in mineral horizons is unlikely to be a significant component of net surface emissions. Our results demonstrate that distinct CH4 dynamics may be stratified by depth, and flooding of the near-surface organic soils drives the high magnitude CH4 fluxes observed from subtropical pastures. These results suggest that relatively small changes in pasture water table dynamics can drive large changes in net CH4 emissions if surface organic soils remain saturated over longer time scales.

Drivers of atmospheric methane uptake by montane forest soils in the southern Peruvian Andes

NASA Astrophysics Data System (ADS)

Jones, Sam P.; Diem, Torsten; Huaraca Quispe, Lidia P.; Cahuana, Adan J.; Reay, Dave S.; Meir, Patrick; Arn Teh, Yit

2016-07-01

The soils of tropical montane forests can act as sources or sinks of atmospheric methane (CH4). Understanding this activity is important in regional atmospheric CH4 budgets given that these ecosystems account for substantial portions of the landscape in mountainous areas like the Andes. We investigated the drivers of net CH4 fluxes from premontane, lower and upper montane forests, experiencing a seasonal climate, in south-eastern Peru. Between February 2011 and June 2013, these soils all functioned as net sinks for atmospheric CH4. Mean (standard error) net CH4 fluxes for the dry and wet season were -1.6 (0.1) and -1.1 (0.1) mg CH4-C m-2 d-1 in the upper montane forest, -1.1 (0.1) and -1.0 (0.1) mg CH4-C m-2 d-1 in the lower montane forest, and -0.2 (0.1) and -0.1 (0.1) mg CH4-C m-2 d-1 in the premontane forest. Seasonality in CH4 exchange varied among forest types with increased dry season CH4 uptake only apparent in the upper montane forest. Variation across these forests was best explained by available nitrate and water-filled pore space indicating that nitrate inhibition of oxidation or diffusional constraints imposed by changes in water-filled pore space on methanotrophic communities may represent important controls on soil-atmosphere CH4 exchange. Net CH4 flux was inversely related to elevation; a pattern that differs to that observed in Ecuador, the only other extant study site of soil-atmosphere CH4 exchange in the tropical Andes. This may result from differences in rainfall patterns between the regions, suggesting that attention should be paid to the role of rainfall and soil moisture dynamics in modulating CH4 uptake by the organic-rich soils typical of high-elevation tropical forests.

Methane Production in Dairy Cows Correlates with Rumen Methanogenic and Bacterial Community Structure.

PubMed

Danielsson, Rebecca; Dicksved, Johan; Sun, Li; Gonda, Horacio; Müller, Bettina; Schnürer, Anna; Bertilsson, Jan

2017-01-01

Methane (CH 4 ) is produced as an end product from feed fermentation in the rumen. Yield of CH 4 varies between individuals despite identical feeding conditions. To get a better understanding of factors behind the individual variation, 73 dairy cows given the same feed but differing in CH 4 emissions were investigated with focus on fiber digestion, fermentation end products and bacterial and archaeal composition. In total 21 cows (12 Holstein, 9 Swedish Red) identified as persistent low, medium or high CH 4 emitters over a 3 month period were furthermore chosen for analysis of microbial community structure in rumen fluid. This was assessed by sequencing the V4 region of 16S rRNA gene and by quantitative qPCR of targeted Methanobrevibacter groups. The results showed a positive correlation between low CH 4 emitters and higher abundance of Methanobrevibacter ruminantium clade. Principal coordinate analysis (PCoA) on operational taxonomic unit (OTU) level of bacteria showed two distinct clusters ( P < 0.01) that were related to CH 4 production. One cluster was associated with low CH 4 production (referred to as cluster L) whereas the other cluster was associated with high CH 4 production (cluster H) and the medium emitters occurred in both clusters. The differences between clusters were primarily linked to differential abundances of certain OTUs belonging to Prevotella . Moreover, several OTUs belonging to the family Succinivibrionaceae were dominant in samples belonging to cluster L. Fermentation pattern of volatile fatty acids showed that proportion of propionate was higher in cluster L, while proportion of butyrate was higher in cluster H. No difference was found in milk production or organic matter digestibility between cows. Cows in cluster L had lower CH 4 /kg energy corrected milk (ECM) compared to cows in cluster H, 8.3 compared to 9.7 g CH 4 /kg ECM, showing that low CH 4 cows utilized the feed more efficient for milk production which might indicate a more efficient microbial population or host genetic differences that is reflected in bacterial and archaeal (or methanogens) populations.

Methane Production in Dairy Cows Correlates with Rumen Methanogenic and Bacterial Community Structure

PubMed Central

Danielsson, Rebecca; Dicksved, Johan; Sun, Li; Gonda, Horacio; Müller, Bettina; Schnürer, Anna; Bertilsson, Jan

2017-01-01

Methane (CH4) is produced as an end product from feed fermentation in the rumen. Yield of CH4 varies between individuals despite identical feeding conditions. To get a better understanding of factors behind the individual variation, 73 dairy cows given the same feed but differing in CH4 emissions were investigated with focus on fiber digestion, fermentation end products and bacterial and archaeal composition. In total 21 cows (12 Holstein, 9 Swedish Red) identified as persistent low, medium or high CH4 emitters over a 3 month period were furthermore chosen for analysis of microbial community structure in rumen fluid. This was assessed by sequencing the V4 region of 16S rRNA gene and by quantitative qPCR of targeted Methanobrevibacter groups. The results showed a positive correlation between low CH4 emitters and higher abundance of Methanobrevibacter ruminantium clade. Principal coordinate analysis (PCoA) on operational taxonomic unit (OTU) level of bacteria showed two distinct clusters (P < 0.01) that were related to CH4 production. One cluster was associated with low CH4 production (referred to as cluster L) whereas the other cluster was associated with high CH4 production (cluster H) and the medium emitters occurred in both clusters. The differences between clusters were primarily linked to differential abundances of certain OTUs belonging to Prevotella. Moreover, several OTUs belonging to the family Succinivibrionaceae were dominant in samples belonging to cluster L. Fermentation pattern of volatile fatty acids showed that proportion of propionate was higher in cluster L, while proportion of butyrate was higher in cluster H. No difference was found in milk production or organic matter digestibility between cows. Cows in cluster L had lower CH4/kg energy corrected milk (ECM) compared to cows in cluster H, 8.3 compared to 9.7 g CH4/kg ECM, showing that low CH4 cows utilized the feed more efficient for milk production which might indicate a more efficient microbial population or host genetic differences that is reflected in bacterial and archaeal (or methanogens) populations. PMID:28261182

Diaminophosphine oxide ligand enabled asymmetric nickel-catalyzed hydrocarbamoylations of alkenes.

PubMed

Donets, Pavel A; Cramer, Nicolai

2013-08-14

Chiral trivalent phosphorus species are the dominant class of ligands and the key controlling element in asymmetric homogeneous transition-metal catalysis. Here, novel chiral diaminophosphine oxide ligands are described. The arising catalyst system with nickel(0) and trimethylaluminum efficiently activates formamide C-H bonds under mild conditions providing pyrrolidones via intramolecular hydrocarbamoylation in a highly enantioselective manner with as little as 0.25% mol catalyst loading. Mechanistically, the secondary phosphine oxides behave as bridging ligands for the nickel center and the Lewis acidic organoaluminum center to give a heterobimetallic catalyst with superior reactivity.

Conductive iron oxides accelerate thermophilic methanogenesis from acetate and propionate.

PubMed

Yamada, Chihaya; Kato, Souichiro; Ueno, Yoshiyuki; Ishii, Masaharu; Igarashi, Yasuo

2015-06-01

Anaerobic digester is one of the attractive technologies for treatment of organic wastes and wastewater, while continuous development and improvements on their stable operation with efficient organic removal are required. Particles of conductive iron oxides (e.g., magnetite) are known to facilitate microbial interspecies electron transfer (termed as electric syntrophy). Electric syntrophy has been reported to enhance methanogenic degradation of organic acids by mesophilic communities in soil and anaerobic digester. Here we investigated the effects of supplementation of conductive iron oxides (magnetite) on thermophilic methanogenic microbial communities derived from a thermophilic anaerobic digester. Supplementation of magnetite accelerated methanogenesis from acetate and propionate under thermophilic conditions, while supplementation of ferrihydrite also accelerated methanogenesis from propionate. Microbial community analysis revealed that supplementation of magnetite drastically changed bacterial populations in the methanogenic acetate-degrading cultures, in which Tepidoanaerobacter sp. and Coprothermobacter sp. dominated. These results suggest that supplementation of magnetite induce electric syntrophy between organic acid-oxidizing bacteria and methanogenic archaea and accelerate methanogenesis even under thermophilic conditions. Findings from this study would provide a possibility for the achievement of stably operating thermophilic anaerobic digestion systems with high efficiency for removal of organics and generation of CH4. Copyright © 2014 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

A mass balance model to estimate the rate of composting, methane oxidation and anaerobic digestion in soil covers and shallow waste layers.

PubMed

Rafiee, Reza; Obersky, Lizanne; Xie, Sihuang; Clarke, William P

2017-05-01

Although CH 4 oxidation in landfill soil covers is widely studied, the extent of composting and CH 4 oxidation in underlying waste layers has been speculated but not measured. The objective of this study was to develop and validate a mass balance model to estimate the simultaneous rates of anaerobic digestion (r AD ), CH 4 oxidation (r OX ) and composting (r COM ) in environments where O 2 penetration is variable and zones of aerobic and anaerobic activity are intermingled. The modelled domain could include, as an example, a soil cover and the underlying shallow waste to a nominated depth. The proposed model was demonstrated on a blend of biogas from three separate known sources of gas representing the three reaction processes: (i) a bottle of laboratory grade 50:50% CH 4 :CO 2 gas representing anaerobic digestion biogas; (ii) an aerated 250mL bottle containing food waste that represented composting activity; and (iii) an aerated 250mL bottle containing non-degradable graphite granules inoculated with methanotrophs and incubated with CH 4 and O 2 to represent methanotrophic activity. CO 2 , CH 4 , O 2 and the stable isotope 13 C-CO 2 were chosen as the components for the mass balance model. The three reaction rates, r (=r AD , r OX , r COM ) were calculated as fitting parameters to the overdetermined set of 4mass balance equations with the net flux of these components from the bottles q (= [Formula: see text] , [Formula: see text] , [Formula: see text] and [Formula: see text] ) as inputs to the model. The coefficient of determination (r 2 ) for observed versus modelled values of r were 1.00, 0.97, 0.98 when the stoichiometry of each reaction was based on gas yields measured in the individual bottles and q was calculated by summing yields from the three bottles. r 2 deteriorated to 0.95, 0.96, 0.87 when using an average stoichiometry from 11 incubations of each of the composting and methane oxidation processes. The significant deterioration in the estimation of r COM showed that this output is highly sensitive to the evaluated stoichiometry coefficients for the reactions. r 2 deteriorated further to 0.86, 0.77, 0.74 when using the average stoichiometry and experimental measurement of the composition and volume of the blended biogas to determine q. This was primarily attributed to average errors of 8%, 7%, 11% and 14% in the measurement of [Formula: see text] , [Formula: see text] , [Formula: see text] and [Formula: see text] relative to the measurement of the same quantities from the individual bottles. Copyright © 2016 Elsevier Ltd. All rights reserved.

Kinetic study on anaerobic oxidation of methane coupled to denitrification.

PubMed

Yu, Hou; Kashima, Hiroyuki; Regan, John M; Hussain, Abid; Elbeshbishy, Elsayed; Lee, Hyung-Sool

2017-09-01

Monod kinetic parameters provide information required for kinetic analysis of anaerobic oxidation of methane coupled to denitrification (AOM-D). This information is critical for engineering AOM-D processes in wastewater treatment facilities. We first experimentally determined Monod kinetic parameters for an AOM-D enriched culture and obtained the following values: maximum specific growth rate (μ max ) 0.121/d, maximum substrate-utilization rate (q max ) 28.8mmol CH 4 /g cells-d, half maximum-rate substrate concentration (K s ) 83μΜ CH 4 , growth yield (Y) 4.76gcells/mol CH 4 , decay coefficient (b) 0.031/d, and threshold substrate concentration (S min ) 28.8μM CH 4 . Clone library analysis of 16S rRNA and mcrA gene fragments suggested that AOM-D reactions might have occurred via the syntrophic interaction between denitrifying bacteria (e.g., Ignavibacterium, Acidovorax, and Pseudomonas spp.) and hydrogenotrophic methanogens (Methanobacterium spp.), supporting reverse methanogenesis-dependent AOM-D in our culture. High μ max and q max , and low K s for the AOM-D enrichment imply that AOM-D could play a significant role in mitigating atmospheric methane efflux. In addition, these high kinetic features suggest that engineered AOM-D systems may provide a sustainable alternative to nitrogen removal in wastewater treatment. Copyright © 2017 Elsevier Inc. All rights reserved.

Soil-atmosphere exchange of nitrous oxide, nitric oxide, and methane under secondary succession of pasture to forest in the Atlantic lowlands of Costa Rica

DOE Office of Scientific and Technical Information (OSTI.GOV)

Keller, M.; Reiners, W.A.

We investigated changes in soil-atmosphere flux of CH{sub 4}, N{sub 2}O, and NO resulting from the succession of pasture to forest in the Atlantic lowlands of Costa Rica. We studied a dozen sites intensively for over one year in order to measure rates and to understand controlling mechanisms for gas exchange. CH{sub 4} flux was controlled primarily by soil moisture content. Soil consumption of atmospheric CH{sub 4} was greatest when soils were relatively dry. Forest soils consumed CH{sub 4} while pasture soils which had poor drainage generally produced CH{sub 4}. The seasonal pattern of N{sub 2}O emissions from forest soilsmore » was related exponentially to soil water-filled pore space. Annual average N{sub 2}O emissions correlated with soil exchangeable NO{sub 3}{sup -} concentrations. Soil-atmosphere NO flux was greatest when soils were relatively dry. We found the largest NO emissions from abandoned pasture sites. Combining these data with those from another study in the Atlantic lowlands of Costa Rica that focused on deforestation, we present a 50-year chronosequence of trace gas emissions that extends from natural conditions, through disturbance and natural recovery. The soil-atmosphere fluxes of CH{sub 4} and N{sub 2}O and NO may be restored to predisturbance rates during secondary succession. The changes in trace gas emissions following deforestation, through pasture use and secondary succession, may be explained conceptually through reference to two major controlling factors, nitrogen availability and soil-atmosphere diffusive exchange of gases as it is influenced by soil moisture content and soil compaction. 59 refs., 6 figs., 3 tabs.« less

A seven-degree-of-freedom, time-dependent quantum dynamics study on the energy efficiency in surmounting the central energy barrier of the OH + CH{sub 3} → O + CH{sub 4} reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yan, Pengxiu; Wang, Yuping; Li, Yida

2015-04-28

A time-dependent, quantum reaction dynamics calculation with seven degrees of freedom was carried out to study the energy efficiency in surmounting the approximate center energy barrier of OH + CH{sub 3}. The calculation shows the OH vibration excitations greatly enhance the reactivity, whereas the vibrational excitations of CH{sub 3} and the rotational excitations hinder the reactivity. On the basis of equal amount of total energy, although this reaction has a slight early barrier, it is the OH vibrational energy that is the dominate force in promoting the reactivity, not the translational energy. The studies on both the forward O +more » CH{sub 4} and reverse OH + CH{sub 3} reactions demonstrate, for these central barrier reactions, a small change of the barrier location can significantly change the energy efficacy roles on the reactivity. The calculated rate constants agree with the experimental data.« less

Differential response of carbon cycling to long-term nutrient input and altered hydrological conditions in a continental Canadian peatland

NASA Astrophysics Data System (ADS)

Berger, Sina; Praetzel, Leandra S. E.; Goebel, Marie; Blodau, Christian; Knorr, Klaus-Holger

2018-02-01

Peatlands play an important role in global carbon cycling, but their responses to long-term anthropogenically changed hydrologic conditions and nutrient infiltration are not well known. While experimental manipulation studies, e.g., fertilization or water table manipulations, exist on the plot scale, only few studies have addressed such factors under in situ conditions. Therefore, an ecological gradient from the center to the periphery of a continental Canadian peatland bordering a eutrophic water reservoir, as reflected by increasing nutrient input, enhanced water level fluctuations, and increasing coverage of vascular plants, was used for a case study of carbon cycling along a sequence of four differently altered sites. We monitored carbon dioxide (CO2) and methane (CH4) surface fluxes and dissolved inorganic carbon (DIC) and CH4 concentrations in peat profiles from April 2014 through September 2015. Moreover, we studied bulk peat and pore-water quality and we applied δ13C-CH4 and δ13C-CO2 stable isotope abundance analyses to examine dominant CH4 production and emission pathways during the growing season of 2015. We observed differential responses of carbon cycling at the four sites, presumably driven by abundances of plant functional types and vicinity to the reservoir. A shrub-dominated site in close vicinity to the reservoir was a comparably weak sink for CO2 (in 1.5 years: -1093 ± 794, in 1 year: +135 ± 281 g CO2 m-2; a net release) as compared to two graminoid-moss-dominated sites and a moss-dominated site (in 1.5 years: -1552 to -2260 g CO2 m-2, in 1 year: -896 to -1282 g CO2 m-2). Also, the shrub-dominated site featured notably low DIC pore-water concentrations and comparably 13C-enriched CH4 (δ13C- CH4: -57.81 ± 7.03 ‰) and depleted CO2 (δ13C-CO2: -15.85 ± 3.61 ‰) in a more decomposed peat, suggesting a higher share of CH4 oxidation and differences in predominant methanogenic pathways. In comparison to all other sites, the graminoid-moss-dominated site in closer vicinity to the reservoir featured a ˜ 30 % higher CH4 emission (in 1.5 years: +61.4 ± 32, in 1 year: +39.86 ± 16.81 g CH4 m-2). Low δ13C-CH4 signatures (-62.30 ± 5.54 ‰) indicated only low mitigation of CH4 emissions by methanotrophic activity here. Pathways of methanogenesis and methanotrophy appeared to be related to the vicinity to the water reservoir: the importance of acetoclastic CH4 production apparently increased toward the reservoir, whereas the importance of CH4 oxidation increased toward the peatland center. Plant-mediated transport was the prevailing CH4 emission pathway at all sites even where graminoids were rare. Our study thus illustrates accelerated carbon cycling in a strongly altered peatland with consequences for CO2 and CH4 budgets. However, our results suggest that long-term excess nutrient input does not necessarily lead to a loss of the peatland carbon sink function.

Methane cycling in alpine wetlands - an interplay of microbial communities and vascular plants

NASA Astrophysics Data System (ADS)

Henneberger, Ruth; Cheema, Simrita; Zeyer, Josef

2014-05-01

Wetland environments play an important role for the global climate, as they represent a major terrestrial carbon store. These environments are potential sinks for atmospheric carbon due to reduced decomposition rates of plant material in the waterlogged, anoxic subsurface. In contrast, wetlands are also a major source of the highly potent greenhouse gas methane (CH4), which is produced in the anoxic zones through methanogenic archaea (methanogens) degrading organic matter. The CH4 emitted into the pore water diffuses upwards towards the surface, and is partially oxidized in the oxic zones by aerobic methanotrophic bacteria (methanotrophs) before reaching the atmosphere. Nonetheless, global emissions of atmospheric CH4 from natural wetlands are estimated to range from 100 to 230 Tg a-1. Natural wetlands can be found around the globe, and are also common in temperate-cold climates in the Northern hemisphere. Methane release from these environments is influenced by many factors (e.g., vegetation, water table, temperature, pH) and shows high seasonal and spatial variability. To comprehend these variations and further predict potential responses to climate change, the biotic and abiotic processes involved in CH4 turnover need to be understood in detail. Many research projects focus on (sub-)arctic wetland areas, while studies on CH4 emissions from alpine wetlands are scarce, despite similar processes occurring in these different regions. Recently, we conducted a survey of 14 wetlands (i.e., fens vegetated with vascular plants) located in the Swiss Alps, showing CH4 emissions between 74 ± 43 and 711 ± 212 mg CH4 m-2 d-1 (Franchini et al., in press). A detailed study of one fen also revealed that CH4 emission was highest immediately after snowmelt, followed by a decrease in CH4 emission throughout the snow-free period (Liebner et al., 2012). Even though the CH4 cycle is largely driven by microbially mediated processes, vascular plants also play a crucial role in CH4 emissions from wetlands, as CH4 generated in the deeper layers can bypass the oxic, methanotrophic zones through the plant aerenchyma. In addition, O2 transported to the root system facilitates CH4 oxidation in the rhizosphere. To further comprehend these complex processes, the present study focused on selected fens dominated by different plants (i.e., Carex spp. or Eriophorum spp.). We combined field-measurements of overall CH4 emissions, CH4 and O2 pore water concentrations and plant-mediated bypass with molecular biological analyses of methanogenic and methanotrophic subpopulations at different soil depths. Methane emissions and pore water concentrations varied with location and dominating plant species. Nevertheless, in all fens we observed the presence of active methanogens and methanotrophs throughout the depth profile, independently of O2 and CH4 concentrations, with active methanogens being highly abundant even in the oxic layers indicating the presence of microniches. The often described spatial separation of methanogenic activity in anoxic zones and methanotrophic activity in oxic zones and oxic-anoxic interfaces could not be observed. The composition of the methanogenic and methanotrophic subpopulations that are active at different depths is currently analyzed in detail, providing new insights into the complex processes involved in CH4 turnover in alpine regions.

Treatment of an actual slaughterhouse wastewater by integration of biological and advanced oxidation processes: Modeling, optimization, and cost-effectiveness analysis.

PubMed

Bustillo-Lecompte, Ciro Fernando; Mehrvar, Mehrab

2016-11-01

Biological and advanced oxidation processes are combined to treat an actual slaughterhouse wastewater (SWW) by a sequence of an anaerobic baffled reactor, an aerobic activated sludge reactor, and a UV/H2O2 photoreactor with recycle in continuous mode at laboratory scale. In the first part of this study, quadratic modeling along with response surface methodology are used for the statistical analysis and optimization of the combined process. The effects of the influent total organic carbon (TOC) concentration, the flow rate, the pH, the inlet H2O2 concentration, and their interaction on the overall treatment efficiency, CH4 yield, and H2O2 residual in the effluent of the photoreactor are investigated. The models are validated at different operating conditions using experimental data. Maximum TOC and total nitrogen (TN) removals of 91.29 and 86.05%, respectively, maximum CH4 yield of 55.72%, and minimum H2O2 residual of 1.45% in the photoreactor effluent were found at optimal operating conditions. In the second part of this study, continuous distribution kinetics is applied to establish a mathematical model for the degradation of SWW as a function of time. The agreement between model predictions and experimental values indicates that the proposed model could describe the performance of the combined anaerobic-aerobic-UV/H2O2 processes for the treatment of SWW. In the final part of the study, the optimized combined anaerobic-aerobic-UV/H2O2 processes with recycle were evaluated using a cost-effectiveness analysis to minimize the retention time, the electrical energy consumption, and the overall incurred treatment costs required for the efficient treatment of slaughterhouse wastewater effluents. Copyright © 2016 Elsevier Ltd. All rights reserved.

Use of wastewater treatment plant biogas for the operation of Solid Oxide Fuel Cells (SOFCs).

PubMed

Lackey, Jillian; Champagne, Pascale; Peppley, Brant

2017-12-01

Solid Oxide Fuel Cells (SOFCs) perform well on light hydrocarbon fuels, and the use of biogas derived from the anaerobic digestion (AD) of municipal wastewater sludges could provide an opportunity for the CH 4 produced to be used as a renewable fuel. Greenhouse gas (GHG), NO x , SO x , and hydrocarbon pollutant emissions would also be reduced. In this study, SOFCs were operated on AD derived biogas. Initially, different H 2 dilutions were tested (N 2 , Ar, CO 2 ) to examine the performance of tubular SOFCs. With inert gases as diluents, a decrease in cell performance was observed, however, the use of CO 2 led to a higher decrease in performance as it promoted the reverse water-gas shift (WGS) reaction, reducing the H 2 partial pressure in the gas mixture. A model was developed to predict system efficiency and GHG emissions. A higher electrical system efficiency was noted for a steam:carbon ratio of 2 compared to 1 due to the increased H 2 partial pressure in the reformate resulting from higher H 2 O concentration. Reductions in GHG emissions were estimated at 2400 tonnes CO 2 , 60 kg CH 4 and 18 kg N 2 O. SOFCs were also tested using a simulated biogas reformate mixture (66.7% H 2 , 16.1% CO, 16.5% CO 2 , 0.7% N 2 , humidified to 2.3 or 20 mol% H 2 O). Higher humidification yielded better performance as the WGS reaction produced more H 2 with additional H 2 O. It was concluded that AD-derived biogas, when cleaned to remove H 2 S, Si compounds, halides and other contaminants, could be reformed to provide a clean, renewable fuel for SOFCs. Copyright © 2016 Elsevier Ltd. All rights reserved.

Control of indium tin oxide anode work function modified using Langmuir-Blodgett monolayer for high-efficiency organic photovoltaics

NASA Astrophysics Data System (ADS)

Yokokura, Yuya; Dogase, Tomomichi; Shinbo, Tatsuki; Nakayashiki, Yuya; Takagi, Yusuke; Ueda, Kazuyoshi; Sarangerel, Khayankhyarvaa; Delgertsetseg, Byambasuren; Ganzorig, Chimed; Sakomura, Masaru

2017-08-01

The use of Langmuir-Blodgett (LB) monolayers to modify the indium tin oxide (ITO) work function and thus improve the performance of zinc phthalocyanine (ZnPc)/fullerene (C60)-based and boron subphthalocyanine chloride (SubPc)/C60-based small molecule organic photovoltaic devices (OPVs) was examined. In general, LB precursor compounds contain one or more long alkyl chain substituents that can act as spacers to prevent electrical contact with adjoining electrode surfaces. As one example of such a compound, arachidic acid (CH3(CH2)18COOH) was inserted in the forms of one-layer, three-layer or five-layer LB films between the anode ITO layer and the p-type layer in ZnPc-C60-based OPVs to investigate the effects of the long alkyl chain group when it acts as an electrically insulating spacer. The short-circuit current density (Jsc) values of the OPVs with the three- and five-layer inserts (1.78 mA.cm-2 and 0.61 mA.cm-2, respectively) were reduced dramatically, whereas the Jsc value for the OPV with the single-layer insertion (2.88 mA.cm-2) was comparable to that of the OPV without any insert (3.14 mA.cm-2). The ITO work function was shifted positively by LB deposition of a surfactant compound, C9F19C2H4-O-C2H4-COOH (PFECA), which contained a fluorinated head group. This positive effect was maintained even after formation of an upper p-type organic layer. The Jsc and open-circuit voltage (Voc) of the SubPc-C60-based OPV with the LB-modified ITO layers were effectively enhanced. As a result, a 42% increase in device efficiency was achieved.

Methane and nitrous oxide exchange over a managed hay meadow

PubMed Central

Hörtnagl, L.; Wohlfahrt, G.

2015-01-01

The methane (CH4) and nitrous oxide (N2O) exchange of a temperate mountain grassland near Neustift, Austria, was measured during 2010–2012 over a time period of 22 months using the eddy covariance method. Exchange rates of both compounds at the site were low, with 97% of all half-hourly CH4 and N2O fluxes ranging between ±200 and ±50 ng m−2 s−1, respectively. The meadow acted as a sink for both compounds during certain time periods, but was a clear source of CH4 and N2O on an annual timescale. Therefore, both gases contributed to an increase of the global warming potential (GWP), effectively reducing the sink strength in terms of CO2 equivalents of the investigated grassland site. In 2011, our best guess estimate showed a net greenhouse gas (GHG) sink of −32 g CO2 equ. m−2 yr−1 for the meadow, whereby 55% of the CO2 sink strength of −71 g CO2m−2 yr−1 was offset by CH4 (N2O) emissions of 7 (32) g CO2 equ. m−2 yr−1. When all data were pooled, the ancillary parameters explained 27 (42)% of observed CH4 (N2O) flux variability, and up to 62 (76)% on shorter timescales in-between management dates. In the case of N2O fluxes, we found the highest emissions at intermediate soil water contents and at soil temperatures close to 0 or above 14 °C. In comparison to CO2, H2O and energy fluxes, the interpretation of CH4 and N2O exchange was challenging due to footprint heterogeneity regarding their sources and sinks, uncertainties regarding post-processing and quality control. Our results emphasize that CH4 and N2O fluxes over supposedly well-aerated and moderately fertilized soils cannot be neglected when evaluating the GHG impact of temperate managed grasslands. PMID:25821473

Thioether-functionalized mesoporous fiber membranes: sol-gel combined electrospun fabrication and their applications for Hg2+ removal.

PubMed

Teng, Minmin; Wang, Hongtao; Li, Fengting; Zhang, Bingru

2011-03-01

Mesoporous polyvinylpyrrolidone (PVP)/SiO(2) composite nanofiber membranes functionalized with thioether groups have been fabricated by a combination method of sol-gel process and electrospinning. The precursor sol was synthesized by one-step co-condensation of tetraethyl orthosilicate (TEOS) and 1,4-bis(triethoxysilyl)propane tetrasulfide (BTESPTS, (CH(3)CH(2)O)(3)Si(CH(2))(3)S-S-S-S(CH(2))(3)Si-(OCH(2)CH(3))(3)), with the triblock copolymer poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (P123, EO(20)PO(70)EO(20)) as template. After the addition of PVP, nanofiber membranes were prepared by electrospinning. The membranes were characterized by scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM) images, X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), N(2) adsorption-desorption isotherms, and an Elementar Vario EL analyzer. The composites were used as highly selective adsorbents for Hg(2+) due to the modification with thioether groups (-S-), and were conveniently separated from the waste water. The composite could be regenerated through acidification. Copyright © 2010 Elsevier Inc. All rights reserved.

Stimulation of methane oxidation potential and effects on vegetation growth by bottom ash addition in a landfill final evapotranspiration cover.

PubMed

Kim, Gil Won; Ho, Adrian; Kim, Pil Joo; Kim, Sang Yoon

2016-09-01

The landfilling of municipal solid waste is a significant source of atmospheric methane (CH4), contributing up to 20% of total anthropogenic CH4 emissions. The evapotranspiration (ET) cover system, an alternative final cover system in waste landfills, has been considered to be a promising way to mitigate CH4 emissions, as well as to prevent water infiltration using vegetation on landfill cover soils. In our previous studies, bottom ash from coal-fired power plants was selected among several industrial residues (blast furnace slag, bottom ash, construction waste, steel manufacture slag, stone powder sludge, and waste gypsum) as the best additive for ET cover systems, with the highest mechanical performance achieved for a 35% (wtwt(-1)) bottom ash content in soil. In this study, to evaluate the field applicability of bottom ash mixed soil as ET cover, four sets of lysimeters (height 1.2m×width 2m×length 6m) were constructed in 2007, and four different treatments were installed: (i) soil+bottom ash (35% wtwt(-1)) (SB); (ii) soil+compost (2% wtwt(-1), approximately corresponding to 40Mgha(-1) in arable field scale) (SC); (iii) soil+bottom ash+compost (SBC); and (iv) soil only as the control (S). The effects of bottom ash mixing in ET cover soil on CH4 oxidation potential and vegetation growth were evaluated in a pilot ET cover system in the 5th year after installation by pilot experiments using the treatments. Our results showed that soil properties were significantly improved by bottom ash mixing, resulting in higher plant growth. Bottom ash addition significantly increased the CH4 oxidation potential of the ET cover soil, mainly due to improved organic matter and available copper concentration, enhancing methanotrophic abundances in soil amended with bottom ash. Conclusively, bottom ash could be a good alternative as a soil additive in the ET cover system to improve vegetation growth and mitigate CH4 emission impact in the waste landfill system. Copyright © 2016 Elsevier Ltd. All rights reserved.

Effect of bio-column composed of aged refuse on methane abatement--a novel configuration of biological oxidation in refuse landfill.

PubMed

Han, Dan; Zhao, Youcai; Xue, Binjie; Chai, Xiaoli

2010-01-01

An experimental bio-column composed of aged refuse was installed around the exhaust pipe as a new way to mitigate methane in refuse landfill. One of the objectives of this work was to assess the effect of aged refuse thickness in bio-column on reducing CH4 emissions. Over the study period, methane oxidation was observed at various thicknesses, 5 cm (small size), 10 cm (middle size) and 15 cm (large size), representing one to three times of pipeline diameters. The middle and large size both showed over 90% methane conversion, and the highest methane conversion rate of above 95% occurred in the middle-size column cell. Michaelis-Menten equation addressed the methanotrophs diffusion in different layers of the bio-columns. Maximum methanotrophic activity (Vmax) measured at the three thicknesses ranged from 6.4 x 10(-3) to 15.6 x 10(-3) units, and the half-saturation value (K(M)) ranged from 0.85% to 1.67%. Both the highest Vmax and K(M) were observed at the middle-size of the bio-column, as well as the largest methanotrophs population, suggesting a significant efficiency of methane mitigation happened in the optimum zone with greatest affinity and methanotrophic bacteria activities. Therefore, bio-column is a potential style for methane abatement in landfill, and the aged refuse both naturally formed and artificially placed in the column plays a critical role in CH4 emission.

Strategic grazing management towards sustainable intensification at tropical pasture-based dairy systems.

PubMed

Congio, Guilhermo F S; Batalha, Camila D A; Chiavegato, Marília B; Berndt, Alexandre; Oliveira, Patrícia P A; Frighetto, Rosa T S; Maxwell, Thomas M R; Gregorini, Pablo; Da Silva, Sila C

2018-05-01

Agricultural systems are responsible for environmental impacts that can be mitigated through the adoption of more sustainable principles. Our objective was to investigate the influence of two pre-grazing targets (95% and maximum canopy light interception during pasture regrowth; LI 95% and LI Max , respectively) on sward structure and herbage nutritive value of elephant grass cv. Cameroon, and dry matter intake (DMI), milk yield, stocking rate, enteric methane (CH 4 ) emissions by Holstein × Jersey dairy cows. We hypothesized that grazing strategies modifying the sward structure of elephant grass (Pennisetum purpureum Schum.) improves nutritive value of herbage, increasing DMI and reducing intensity of enteric CH 4 emissions, providing environmental and productivity benefits to tropical pasture-based dairy systems. Results indicated that pre-sward surface height was greater for LI Max (≈135 cm) than LI 95% (≈100 cm) and can be used as a reliable field guide for monitoring sward structure. Grazing management based on LI 95% criteria improved herbage nutritive value and grazing efficiency, allowing greater DMI, milk yield and stocking rate by dairy cows. Daily enteric CH 4 emission was not affected; however, cows grazing elephant grass at LI 95% were more efficient and emitted 21% less CH 4 /kg of milk yield and 18% less CH 4 /kg of DMI. The 51% increase in milk yield per hectare overcame the 29% increase in enteric CH 4 emissions per hectare in LI 95% grazing management. Thereby the same resource allocation resulted in a 16% mitigation of the main greenhouse gas from pasture-based dairy systems. Overall, strategic grazing management is an environmental friendly practice that improves use efficiency of allocated resources through optimization of processes evolving plant, ruminant and their interface, and enhances milk production efficiency of tropical pasture-based systems. Copyright © 2018 Elsevier B.V. All rights reserved.

The variability of methane, nitrous oxide and sulfur hexafluoride in Northeast India

NASA Astrophysics Data System (ADS)

Ganesan, A. L.; Chatterjee, A.; Prinn, R. G.; Harth, C. M.; Salameh, P. K.; Manning, A. J.; Hall, B. D.; Mühle, J.; Meredith, L. K.; Weiss, R. F.; O'Doherty, S.; Young, D.

2013-06-01

High-frequency atmospheric measurements of methane (CH4), nitrous oxide (N2O) and sulfur hexafluoride (SF6) from Darjeeling, India are presented from December 2011 (CH4)/March 2012 (N2O and SF6) through February 2013. These measurements were made on a gas chromatograph equipped with a flame ionization detector and electron capture detector and were calibrated on the Tohoku University, the Scripps Institution of Oceanography (SIO)-98 and SIO-2005 scales for CH4, N2O and SF6, respectively. The observations show large variability and frequent pollution events in CH4 and N2O mole fractions, suggesting significant sources in the regions sampled by Darjeeling throughout the year. In contrast, SF6 mole fractions show little variability and only occasional pollution episodes, likely due to weak sources in the region. Simulations using the Numerical Atmospheric dispersion Modelling Environment (NAME) particle dispersion model suggest that many of the enhancements in the three gases result from the transport of pollutants from the densely populated Indo-Gangetic plains of India to Darjeeling. The meteorology of the region varies considerably throughout the year from Himalayan flows in the winter to the strong South Asian summer monsoon. The model is consistent in simulating a diurnal cycle in CH4 and N2O mole fractions that is present during the winter but absent in the summer and suggests that the signals measured at Darjeeling are dominated by large scale (~100 km) flows rather than local (<10 km) flows.

The variability of methane, nitrous oxide and sulfur hexafluoride in Northeast India

NASA Astrophysics Data System (ADS)

Ganesan, A. L.; Chatterjee, A.; Prinn, R. G.; Harth, C. M.; Salameh, P. K.; Manning, A. J.; Hall, B. D.; Mühle, J.; Meredith, L. K.; Weiss, R. F.; O'Doherty, S.; Young, D.

2013-11-01

High-frequency atmospheric measurements of methane (CH4), nitrous oxide (N2O) and sulfur hexafluoride (SF6) from Darjeeling, India are presented from December 2011 (CH4)/March 2012 (N2O and SF6) through February 2013. These measurements were made on a gas chromatograph equipped with a flame ionization detector and electron capture detector, and were calibrated on the Tohoku University, the Scripps Institution of Oceanography (SIO)-98 and SIO-2005 scales for CH4, N2O and SF6, respectively. The observations show large variability and frequent pollution events in CH4 and N2O mole fractions, suggesting significant sources in the regions sampled by Darjeeling throughout the year. By contrast, SF6 mole fractions show little variability and only occasional pollution episodes, likely due to weak sources in the region. Simulations using the Numerical Atmospheric dispersion Modelling Environment (NAME) particle dispersion model suggest that many of the enhancements in the three gases result from the transport of pollutants from the densely populated Indo-Gangetic Plains of India to Darjeeling. The meteorology of the region varies considerably throughout the year from Himalayan flows in the winter to the strong south Asian summer monsoon. The model is consistent in simulating a diurnal cycle in CH4 and N2O mole fractions that is present during the winter but absent in the summer and suggests that the signals measured at Darjeeling are dominated by large-scale (~100 km) flows rather than local (<10 km) flows.

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

PubMed

Dijkstra, Feike A; Morgan, Jack A; Follett, Ronald F; Lecain, Daniel R

2013-06-01

Atmospheric concentrations of methane (CH4 ) and nitrous oxide (N2 O) have increased over the last 150 years because of human activity. Soils are important sources and sinks of both potent greenhouse gases where their production and consumption are largely regulated by biological processes. Climate change could alter these processes thereby affecting both rate and direction of their exchange with the atmosphere. We examined how a rise in atmospheric CO2 and temperature affected CH4 and N2 O fluxes in a well-drained upland soil (volumetric water content ranging between 6% and 23%) in a semiarid grassland during five growing seasons. We hypothesized that responses of CH4 and N2 O fluxes to elevated CO2 and warming would be driven primarily by treatment effects on soil moisture. Previously we showed that elevated CO2 increased and warming decreased soil moisture in this grassland. We therefore expected that elevated CO2 and warming would have opposing effects on CH4 and N2 O fluxes. Methane was taken up throughout the growing season in all 5 years. A bell-shaped relationship was observed with soil moisture with highest CH4 uptake at intermediate soil moisture. Both N2 O emission and uptake occurred at our site with some years showing cumulative N2 O emission and other years showing cumulative N2 O uptake. Nitrous oxide exchange switched from net uptake to net emission with increasing soil moisture. In contrast to our hypothesis, both elevated CO2 and warming reduced the sink of CH4 and N2 O expressed in CO2 equivalents (across 5 years by 7% and 11% for elevated CO2 and warming respectively) suggesting that soil moisture changes were not solely responsible for this reduction. We conclude that in a future climate this semiarid grassland may become a smaller sink for atmospheric CH4 and N2 O expressed in CO2 -equivalents. © 2013 Blackwell Publishing Ltd.

Dissolved greenhouse gases (nitrous oxide and methane) associated with the natural iron-fertilized Kerguelen region (KEOPS 2 cruise) in the Southern Ocean

NASA Astrophysics Data System (ADS)

Farías, L.; Florez-Leiva, L.; Besoain, V.; Fernández, C.

2014-08-01

The concentrations of greenhouse gases (GHGs) like nitrous oxide (N2O) and methane (CH4) were measured in the Kerguelen Plateau Region (KPR), an area with annual microalgal bloom caused by natural Fe fertilization, which may stimulate microbes involved in GHG cycling. This study was carried out during the KEOPS 2 cruise during the austral spring of 2011. Two transects were sampled along and across the KRP, the north-south (N-S) transect (46-51° S, 72° E meridian) and the west-east (W-E) transect (66-75° E, 48.3° S latitude), both associated with the presence of a plateau, polar fronts and other mesoscale features. The W-E transect had N2O levels ranging from equilibrium (105%) to light supersaturation (120%) with respect to the atmosphere. CH4 levels fluctuated dramatically, with intense supersaturations (120-970%) in areas close to the coastal waters of Kerguelen Island and in the polar front (PF). There, Fe and nutrient fertilization seem to promote high total chlorophyll a (TChl a) levels. The distribution of both gases was more homogenous in the N-S transect, but CH4 peaked at southeastern stations of the KPR (A3 stations), where phytoplankton bloom was observed. Both gases responded significantly to the patchy distribution of particulate matter as Chl a, stimulated by Fe supply by complex mesoscale circulation. While CH4 appears to be produced mainly at the pycnoclines, N2O seems to be consumed superficially. Air-sea fluxes for N2O (from -10.5 to 8.65, mean 1.71 μmol m-2d-1), and for CH4 (from 0.32 to 38.1, mean 10.07 μmol m-2d-1) reflected sink and source behavior for N2O and source behavior for CH4, with considerable variability associated with a highly fluctuating wind regime and, in the case of CH4, due to its high superficial levels that had not been reported before in the Southern Ocean and may be caused by an intense microbial CH4 cycling.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rachor, Ingke, E-mail: i.rachor@ifb.uni-hamburg.de; Gebert, Julia; Groengroeft, Alexander

2011-05-15

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

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.

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

PubMed

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

2015-11-01

The restoration of peatlands is an important strategy to counteract subsidence and loss of biodiversity. However, responses of important microbial soil processes are poorly understood. We assessed functioning, diversity and spatial organization of methanotrophic communities in drained and rewetted peat meadows with different water table management and agricultural practice. Results show that the methanotrophic diversity was similar between drained and rewetted sites with a remarkable dominance of the genus Methylocystis. Enzyme kinetics depicted no major differences, indicating flexibility in the methane (CH4) concentrations that can be used by the methanotrophic community. Short-term flooding led to temporary elevated CH4 emission but to neither major changes in abundances of methane-oxidizing bacteria (MOB) nor major changes in CH4 consumption kinetics in drained agriculturally used peat meadows. Radiolabeling and autoradiographic imaging of intact soil cores revealed a markedly different spatial arrangement of the CH4 consuming zone in cores exposed to near-atmospheric and elevated CH4. The observed spatial patterns of CH4 consumption in drained peat meadows with and without short-term flooding highlighted the spatial complexity and responsiveness of the CH4 consuming zone upon environmental change. The methanotrophic microbial community is not generally altered and harbors MOB that can cover a large range of CH4 concentrations offered due to water-table fluctuations, effectively mitigating CH4 emissions. © FEMS 2015. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Global Wetland Contribution to 2000-2012 Atmospheric Methane Growth Rate Dynamics

NASA Technical Reports Server (NTRS)

Poulter, Benjamin; Bousquet, Philippe; Canadell, Josep G.; Ciais, Philippe; Peregon, Anna; Saunois, Marielle; Arora, Vivek K.; Beerling, David J.; Brovkin, Victor; Jones, Chris D.;

Effect of irrigation, nitrogen application, and a nitrification inhibitor on nitrous oxide, carbon dioxide and methane emissions from an olive (Olea europaea L.) orchard.

PubMed

Maris, S C; Teira-Esmatges, M R; Arbonés, A; Rufat, J

2015-12-15

Drip irrigation combined with nitrogen (N) fertigation is applied in order to save water and improve nutrient efficiency. Nitrification inhibitors reduce greenhouse gas emissions. A field study was conducted to compare the emissions of nitrous oxide (N2O), carbon dioxide (CO2) and methane (CH4) associated with the application of N fertiliser through fertigation (0 and 50kgNha(-1)), and 50kgNha(-1)+nitrification inhibitor in a high tree density Arbequina olive orchard. Spanish Arbequina is the most suited variety for super intensive olive groves. This system allows reducing production costs and increases crop yield. Moreover its oil has excellent sensorial features. Subsurface drip irrigation markedly reduced N2O and N2O+N2 emissions compared with surface drip irrigation. Fertiliser application significantly increased N2O+N2, but not N2O emissions. Denitrification was the main source of N2O. The N2O losses (calculated as emission factor) ranging from -0.03 to 0.14% of the N applied, were lower than the IPCC (2007) values. The N2O+N2 losses were the largest, equivalent to 1.80% of the N applied, from the 50kgNha(-1)+drip irrigation treatment which resulted in water filled pore space >60% most of the time (high moisture). Nitrogen fertilisation significantly reduced CO2 emissions in 2011, but only for the subsurface drip irrigation strategies in 2012. The olive orchard acted as a net CH4 sink for all the treatments. Applying a nitrification inhibitor (DMPP), the cumulative N2O and N2O+N2 emissions were significantly reduced with respect to the control. The DMPP also inhibited CO2 emissions and significantly increased CH4 oxidation. Considering global warming potential, greenhouse gas intensity, cumulative N2O emissions and oil production, it can be concluded that applying DMPP with 50kgNha(-1)+drip irrigation treatment was the best option combining productivity with keeping greenhouse gas emissions under control. Copyright © 2015 Elsevier B.V. All rights reserved.

Functional disubstituted polyacetylenes: Synthesis, liquid crystallinity, light emission, and fluorescent photopatterning of biphenyl-containing poly(1-phenyl-octyne)s with different functional bridges.

PubMed

Lam, Jacky W Y; Qin, Anjun; Dong, Yuping; Lai, Lo Ming; Häussler, Matthias; Dong, Yongqiang; Tang, Ben Zhong

2006-11-02

Biphenyl (Biph)-containing 1-phenyl-1-octynes and their polymers are synthesized, and the effects of functional bridge groups on the mesomorphic and optical properties of the polymers are studied. The nonmesomorphic disubstituted acetylene monomers (C6H13)C[triple bond]C(C6H4)O(CH2)12O-Biph-OC7H15 (1), (C6H13)C[triple bond]C(C6H4)O(CH2)11OOC-Biph-OC7H15 (2), and (C6H13)C[triple bond]C(C6H4)CO2(CH2)12OOC-Biph-OC7H15 (3) are prepared by multistep reaction routes and converted into their corresponding polymers P1-P3 by a WCl6-Ph4Sn catalyst. The structures and properties of the polymers are characterized and evaluated by NMR, TGA, DSC, POM, XRD, UV, and PL analyses. The mesogenic pendants have endowed the polymers with high thermal stability (> or =400 degrees C). While P1 exhibits no liquid crystallinity, P2 and P3 form enantiotropic S(A) phase with a monolayer structure. Upon photoexcitation, the polymers emit blue and blue-green lights of 460 and 480 nm, respectively, in THF with quantum efficiencies larger than 30%. UV irradiation of a thin film of P2 through a mask oxidizes and quenches the light emission of the exposed regions, generating a two-dimensional luminescent photoimage.

Distinct transport properties of O2 and CH4 across a carbon nanotube

NASA Astrophysics Data System (ADS)

Meng, Xianwen; Wang, Yu; Zhao, Yanjiao; Huang, Jiping

2013-04-01

It is of fundamental importance to investigate either O2 or CH4 molecules across nanochannels in many areas such as breathing or separation. Thus, many researches have focused on such a single type of molecules across nanochannels. However, O2 and CH4 can often appear together and crucially affect human life, say, in a mine. On the basis of molecular dynamics simulations, here we attempt to investigate the mixture of O2 and CH4, in order to identify their different transport properties in a nanochannel. We take a single-walled carbon nanotube (SWCNT) as a model nanochannel, and find that their transport properties are distinctly different. As the concentration of O2 increases up to a high value of 0.8, it is always faster for CH4 molecules to transport across the SWCNT, and the total number of gas molecules transporting across the SWCNT is decreased. Meanwhile, CH4 molecules are always dominant in the SWCNT, and the total number of O2 or CH4 inside the SWCNT is a constant. By calculating the van der Waals interaction between the SWCNT and O2 or CH4, we find that the net interaction between CH4 and the SWCNT is much stronger. Our findings may offer some hints on how to separate CH4 from O2, and/or store CH4 efficiently.

Methane, carbon dioxide, and nitrous oxide emissions from septic tank systems.

PubMed

Diaz-Valbuena, Libia R; Leverenz, Harold L; Cappa, Christopher D; Tchobanoglous, George; Horwath, William R; Darby, Jeannie L

2011-04-01

Emissions of CH4, CO2, and N2O from conventional septic tank systems are known to occur, but there is a dearth of information as to the extent. Mass emission rates of CH4, CO2, and N2O, as measured with a modified flux chamber approach in eight septic tank systems, were determined to be 11, 33.3, and 0.005 g capita(-1) day(-1), respectively, in this research. Existing greenhouse gas (GHG) emission models based on BOD (biochemical oxygen demand) loading have estimated methane emissions to be as high as 27.1 g CH4 capita(-1) day(-1), more than twice the value measured in our study, and concluded that septic tanks are potentially significant sources of GHGs due to the large number of systems currently in use. Based on the measured CH4 emission value, a revised CH4 conversion factor of 0.22 (compared to 0.5) for use in the emissions models is suggested. Emission rates of CH4, CO2, and N2O were also determined from measurements of gas concentrations and flow rates in the septic vent system and were found to be 10.7, 335, and 0.2 g capita(-1)day(-1), respectively. The excellent agreement in the CH4 emission rates between the flux chamber and the vent values indicates the dominant CH4 source is the septic tank.

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.

Function and limits of biofilters for the removal of methane in exhaust gases from the pig industry.

PubMed

Veillette, Marc; Girard, Matthieu; Viens, Pascal; Brzezinski, Ryszard; Heitz, Michèle

2012-05-01

The agricultural sector is responsible for an important part of Canadian greenhouse gas (GHG) emissions, 8 % of the 747 Mt eq. CO(2) emitted each year. The pork industry, a key sector of the agrifood industry, has had a rapid growth in Canada since the middle 1980s. For this industry, slurry storage accounts for the major part of methane (CH(4)) emissions, a GHG 25 times higher than carbon dioxide (CO(2)) on a 100-year time horizon. Intending to reduce these emissions, biofiltration, a process effective to treat CH(4) from landfills and coal mines, could be effective to treat CH(4) from the pig industry. Biofiltration is a complex process that requires the understanding of the biological process of CH(4) oxidation and a control of the engineering parameters (filter bed, temperature, etc.). Some biofiltration studies show that this technology could be used to treat CH(4) at a relatively low cost and with a relatively high purification performance.

Oxidation of Half-Lantern Pt2(II,II) Compounds by Halocarbons. Evidence of Dioxygen Insertion into a Pt(III)-CH3 Bond.

PubMed

Sicilia, V; Baya, M; Borja, P; Martín, A

2015-08-03

The half-lantern compound [{Pt(bzq)(μ-N^S)}2] (1) [bzq = benzo[h]quinoline, HN^S = 2-mercaptopyrimidine (C4H3N2HS)] reacts with CH3I and haloforms CHX3 (X = Cl, Br, I) to give the corresponding oxidized diplatinum(III) derivatives [{Pt(bzq)(μ-N^S)X}2] (X = Cl 2a, Br 2b, I 2c). These compounds exhibit half-lantern structures with short intermetallic distances (∼2.6 Å) due to Pt-Pt bond formation. The halogen abstraction mechanisms from the halocarbon molecules by the Pt2(II,II) compound 1 were investigated. NMR spectroscopic evidence using labeled reagents support that in the case of (13)CH3I the reaction initiates with an oxidative addition through an SN2 mechanism giving rise to the intermediate species [I(bzq)Pt(μ-N^S)2Pt(bzq)((13)CH3)}]. However, with haloforms the reactions proceed through a radical-like mechanism, thermally (CHBr3, CHI3) or photochemically (CHCl3) activated, giving rise to mixtures of species [X(bzq)Pt(μ-N^S)2Pt(bzq)R] (3a-c) and [X(bzq)Pt(μ-N^S)2Pt(bzq)X] (2a-c). In these cases the presence of O2 favors the formation of species 2 over 3. Transformation of 3 into 2 was possible upon irradiation with UV light. In the case of [I(bzq)Pt(μ-N^S)2Pt(bzq)((13)CH3)}] (3d), in the presence of O2 the formation of the unusual methylperoxo derivative [I(bzq)Pt(μ-N^S)2Pt(bzq)(O-O(13)CH3)}] (4d) was detected, which in the presence of (13)CH3I rendered the final product [{Pt(bzq)(μ-N^S)I}2] (2c) and (13)CH3OH.

CO 2 hydrogenation on Pt, Pt/SiO 2 and Pt/TiO 2: Importance of synergy between Pt and oxide support

DOE PAGES

Kattel, Shyam; Yan, Binhang; Chen, Jingguang G.; ...

2016-01-27

In this paper we combined density functional theory (DFT), kinetic Monte Carlo (KMC) simulations and experimental measurements to gain insight into the mechanisms of CO 2 conversion by hydrogen on the Pt nanoparticle (NP). The results show that in spite of the presence of active, low-coordinated sites, Pt NP alone is not able to catalyze the reaction due to the weak CO 2 binding on the catalyst. Once CO 2 is stabilized, the hydrogenation of CO 2 to CO via the reverse-water–gas shift (RWGS) reaction is promoted; in contrast, the enhancement for further *CO hydrogenation to CH 4 is lessmore » significant and no CH 3OH is observed. The selectivity to CO is mainly determined by CO binding energy and the energetics of *CO hydrogenation to *HCO, while that for CH 4 and CH 3OH is determined by the competition between hydrogenation and C–O bond scission reactions of the *H 2COH species. Using SiO 2 and TiO 2 as the support, Pt NP is able to promote the overall CO 2 conversion, while the impact on the selectivity is rather small. The theoretically predicted trend in activity and selectivity is in good agreement with the experimental results. Finally, the enhanced activity of Pt/oxide over Pt is originated from the sites at the Pt–oxide interface, where the synergy between Pt and oxide plays an important role.« less

CO 2 hydrogenation on Pt, Pt/SiO 2 and Pt/TiO 2: Importance of synergy between Pt and oxide support

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kattel, Shyam; Yan, Binhang; Chen, Jingguang G.

In this paper we combined density functional theory (DFT), kinetic Monte Carlo (KMC) simulations and experimental measurements to gain insight into the mechanisms of CO 2 conversion by hydrogen on the Pt nanoparticle (NP). The results show that in spite of the presence of active, low-coordinated sites, Pt NP alone is not able to catalyze the reaction due to the weak CO 2 binding on the catalyst. Once CO 2 is stabilized, the hydrogenation of CO 2 to CO via the reverse-water–gas shift (RWGS) reaction is promoted; in contrast, the enhancement for further *CO hydrogenation to CH 4 is lessmore » significant and no CH 3OH is observed. The selectivity to CO is mainly determined by CO binding energy and the energetics of *CO hydrogenation to *HCO, while that for CH 4 and CH 3OH is determined by the competition between hydrogenation and C–O bond scission reactions of the *H 2COH species. Using SiO 2 and TiO 2 as the support, Pt NP is able to promote the overall CO 2 conversion, while the impact on the selectivity is rather small. The theoretically predicted trend in activity and selectivity is in good agreement with the experimental results. Finally, the enhanced activity of Pt/oxide over Pt is originated from the sites at the Pt–oxide interface, where the synergy between Pt and oxide plays an important role.« less

The Acid-Base Properties, Hydrolytic Mechanism, and Susceptibility to O2 Oxidation of Fe4S4(SR)4-2 Clusters

PubMed Central

Bruice, Thomas C.; Maskiewicz, Richard; Job, Robert

1975-01-01

The iron-sulfur cluster compounds Fe4S4(SR)4-2 [where —SR = —SCH3, —S—C(CH3)3, and —S— CH2—CH(CH3)2] have been found to represent the base species of weak acids of pKa comparable to that of carboxylic acids. The acid species Fe4S4(SR)4H- is most subject to reaction with O2 and to acid-catalyzed solvolysis, while the base species Fe4S4(SR)4-2 most readily undergoes ligand exchange. The kinetics for hydrolysis of the isobutyl mercaptide cluster salt has been investigated in detail and a mechanism involving the stepwise process [Formula: see text] has been proposed. The importance of the acid-base equilibria in determining the reactivity of the iron-sulfur clusters and its possible importance as a factor in the determination of the potentials of ferredoxins and high potential iron protein are discussed. PMID:16592211

Assessing the impact of electronic and steric tuning of the ligand in the spin state and catalytic oxidation ability of the Fe(II)(Pytacn) family of complexes.

PubMed

Prat, Irene; Company, Anna; Corona, Teresa; Parella, Teodor; Ribas, Xavi; Costas, Miquel

2013-08-19

A family of iron complexes with the general formula [Fe(II)((R,R)'Pytacn)(X)2](n+) is described, where (R,R)'Pytacn is the tetradentate ligand 1-[(4-R'-6-R-2-pyridyl)methyl]-4,7-dimethyl-1,4,7-triazacyclononane, R refers to the group at the α-position of the pyridine, R' corresponds to the group at the γ-position, and X denotes CH3CN or CF3SO3. Herein, we study the influence of the pyridine substituents R and R' on the electronic properties of the coordinated iron center by a combination of structural and spectroscopic characterization using X-ray diffraction, (1)H NMR and UV-vis spectroscopies, and magnetic susceptibility measurements. The electronic properties of the substituent in the γ-position of the pyridine ring (R') modulate the strength of the ligand field, as shown by magnetic susceptibility measurements in CD3CN solution, which provide a direct indication of the population of the magnetically active high-spin S = 2 ferrous state. Indeed, a series of complexes [Fe(II)((H,R)'Pytacn)(CD3CN)2](2+) exist as mixtures of high-spin (S = 2) and low-spin (S = 0) complexes, and their effective magnetic moment directly correlates with the electron-releasing ability of R'. On the other hand, the substitution of the hydrogen atom in the α-position of the pyridine by a methyl, chlorine, or fluorine group favors the high-spin state. The whole family of complexes has been assayed in catalytic C-H and C═C oxidation reactions with H2O2. These catalysts exhibit excellent efficiency in the stereospecific hydroxylation of alkanes and in the oxidation of olefins. Remarkably, R'-substituents have little influence on the efficiency and chemoselectivity of the catalytic activity of the complexes, but the selectivity toward olefin cis-dihydroxylation is enhanced for complexes with R = Me, F, or Cl. Isotopic labeling studies in the epoxidation and cis-dihydroxylation reactions show that R has a definitive role in dictating the origin of the oxygen atom that is transferred in the epoxidation reaction.

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

Code of Federal Regulations, 2014 CFR

2014-07-01

... gas sent off-site). If a single monitoring location is used to monitor volumetric flow and CH4... 40 Protection of Environment 21 2014-07-01 2014-07-01 false Landfill Methane Oxidation Fractions... (CONTINUED) AIR PROGRAMS (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Municipal Solid Waste Landfills Pt...

Difluoromethane, a new and improved inhibitor of methanotrophy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miller, L.G.; Sasson, C.; Oremland, R.S.

1998-11-01

Difluoromethane (HFC-32; DFM) is compared to acetylene and methyl fluoride as an inhibitor of methanotrophy in cultures and soils. DFM was found to be a reversible inhibitor of CH{sub 4} oxidation by Methylococcus capsulatus (Bath). Consumption of CH{sub 4} in soil was blocked by additions of low levels of DFM (0.03 kPa), and this inhibition was reversed by DFM removal. Although a small quantity of DFM was consumed during these incubations, its remaining concentration was sufficiently elevated to sustain inhibition. Methanogenesis in anaerobic soil slurries, including acetoclastic methanogenesis, was unaffected by levels of DFM which inhibit methanotrophy. Low levels ofmore » DFM (0.03 kPa) also inhibited nitrification and N{sub 2}O production by soils. DFM is proposed as an improved inhibitor of CH{sub 4} oxidation over acetylene and/or methyl fluoride on the basis of its reversibility, its efficacy at low concentrations, its lack of inhibition of methanogenesis, and its low cost.« less

Gallium oxide thin films from the AACVD of [Ga(NMe2)3]2 and donor functionalised alcohols.

PubMed

Basharat, Siama; Carmalt, Claire J; Binions, Russell; Palgrave, Robert; Parkin, Ivan P

2008-02-07

Thin films of Ga(2)O(3) have been produced from [Ga(NMe(2))(3)](2) and ROH (R = CH(2)CH(2)NMe(2), CH(CH(2)NMe(2))(2), CH(CH(3))CH(2)NMe(2), CH(2)CH(2)OMe and C(CH(3))(2)CH(2)OMe) by aerosol assisted chemical vapour deposition on glass. Transparent, unreflective films were obtained at a deposition temperature of 550 degrees C using toluene as solvent. The gallium oxide films were analyzed by Scanning electron microscopy (SEM), Raman spectroscopy, wavelength dispersive analysis of X-rays (WDX) and X-ray photoelectron spectroscopy (XPS). The gallium oxide films obtained were X-ray amorphous. Gas-sensing experiments indicated that the films showed an n-type response to ethanol at a variety of temperatures.

Effect of pest controlling neem (Azadirachta indica A. Juss) and mata-raton (Gliricidia sepium Jacquin) leaf extracts on emission of green house gases and inorganic-N content in urea-amended soil.

PubMed

Méndez-Bautista, Joaquín; Fernández-Luqueño, Fabián; López-Valdez, Fernando; Mendoza-Cristino, Reyna; Montes-Molina, Joaquín A; Gutierrez-Miceli, F A; Dendooven, L

2009-07-01

Extracts of neem (Azadirachta indica A. Juss.) and Gliricidia sepium Jacquin, locally known as 'mata-raton', are used to control pests of maize. Their application, however, is known to affect soil microorganisms. We investigated if these extracts affected emissions of methane (CH4), carbon dioxide (CO2) and nitrous oxide (N2O), important greenhouse gases, and dynamics of soil inorganic N. Soil was treated with extracts of neem, mata-raton or lambda-cyhalothrin, used as chemical control. The soil was amended with or without urea and incubated at 40% and 100% water holding capacity (WHC). Concentrations of ammonium (NH4+), nitrite (NO2(-)) and nitrate (NO3(-)) and emissions of CH4, CO2 and N2O were monitored for 7d. Treating urea-amended soil with extracts of neem, mata-raton or lambda-cyhalothrin reduced the emission of CO2 significantly compared to the untreated soil with the largest decrease found in the latter. Oxidation of CH4 was inhibited by extracts of neem in the unamended soil, and by neem, mata-raton and lambda-cyhalothrin in the urea-amended soil compared to the untreated soil. Neem, mata-raton and lambda-cyhalothrin reduced the N2O emission from the unamended soil incubated at 40%WHC compared to the untreated soil. Extracts of neem, mata-raton and lambda-cyhalothrin had no significant effect on dynamics of NH4(+), NO2(-) and NO(3)(-). It was found that emission of CO2 and oxidation of CH4 was inhibited in the urea-amended soil treated with extracts of neem, mata-raton and lambda-cyhalothrin, but ammonification, N2O emission and nitrification were not affected.

Mitigating methane emission from paddy soil with rice-straw biochar amendment under projected climate change

PubMed Central

Han, Xingguo; Sun, Xue; Wang, Cheng; Wu, Mengxiong; Dong, Da; Zhong, Ting; Thies, Janice E.; Wu, Weixiang

2016-01-01

Elevated global temperatures and increased concentrations of carbon dioxide (CO2) in the atmosphere associated with climate change will exert profound effects on rice cropping systems, particularly on their greenhouse gas emitting potential. Incorporating biochar into paddy soil has been shown previously to reduce methane (CH4) emission from paddy rice under ambient temperature and CO2. We examined the ability of rice straw-derived biochar to reduce CH4 emission from paddy soil under elevated temperature and CO2 concentrations expected in the future. Adding biochar to paddy soil reduced CH4 emission under ambient conditions and significantly reduced emissions by 39.5% (ranging from 185.4 mg kg−1 dry weight soil, dws season−1 to 112.2 mg kg−1 dws season−1) under simultaneously elevated temperature and CO2. Reduced CH4 release was mainly attributable to the decreased activity of methanogens along with the increased CH4 oxidation activity and pmoA gene abundance of methanotrophs. Our findings highlight the valuable services of biochar amendment for CH4 control from paddy soil in a future that will be shaped by climate change. PMID:27090814

N,B-Bidentate Boryl Ligand-Supported Iridium Catalyst for Efficient Functional-Group-Directed C-H Borylation.

PubMed

Wang, Guanghui; Liu, Li; Wang, Hong; Ding, You-Song; Zhou, Jing; Mao, Shuai; Li, Pengfei

2017-01-11

Convenient silylborane precursors for introducing N,B-bidentate boryl ligands onto transition metals were designed, prepared, and employed in ready formation of irdium(III) complexes via Si-B oxidative addition. A practical, efficient catalytic ortho-borylation reaction of arenes with a broad range of directing groups was developed using an in situ generated catalyst from the silylborane preligand 3c and [IrCl(COD)] 2 .

Selectivity for CO2 over CH4 on a functionalized periodic mesoporous phenylene-silica explained by transition state theory

NASA Astrophysics Data System (ADS)

Kunkel, Christian; Viñes, Francesc; Lourenço, Mirtha A. O.; Ferreira, Paula; Gomes, José R. B.; Illas, Francesc

2017-03-01

Efficient separation of CO2/CH4 is critical in biogas upgrading, requiring highly selective adsorbents. Based on the adsorption energies of -0.30 and -0.14 eV, previously calculated by dispersion corrected density functional theory for adsorption/desorption of CO2 and CH4 on the functionalized periodic mesoporous phenylene-silica material APTMS@Ph-PMO, respectively, transition state theory rates were derived and used to simulate the adsorption/desorption rates of these two gases on APTMS@Ph-PMO. The latter yielded an estimation of initial CO2/CH4 selectivity at various temperatures. At T = 298 K, selectivity of 32.2 agrees to an experimental value of 26.1, which validates the method used for evaluating CO2/CH4 adsorption selectivities.

Functionalized multi-walled carbon nanotube based sensors for distributed methane leak detection

EPA Science Inventory

This paper presents a highly sensitive, energy efficient and low-cost distributed methane (CH4) sensor system (DMSS) for continuous monitoring, detection and localization of CH4 leaks in natural gas infrastructure such as transmission and distribution pipelines, wells, and produc...

Vertical profiles of community abundance and diversity of anaerobic methanotrophic archaea (ANME) and bacteria in a simple waste landfill in north China.

PubMed

Dong, Jun; Ding, Linjie; Wang, Xu; Chi, Zifang; Lei, Jiansen

2015-03-01

Anaerobic methane oxidation (AMO) is considered to be an important sink of CH4 in habitats as marine sediments. But, few studies focused on AMO in landfills which may be an important sink of CH4 derived from waste fermentation. To show evidence of AMO and to uncover function anaerobic methanotroph (ANME) community in landfill, different age waste samples were collected in Jinqianpu landfill located in north China. Through high-throughput sequencing, Methanomicrobiales and Methanosarcinales archaea associated with ANME and reverse methanogenic archaea of Methanosarcina and Methanobacterium were detected. Sulfate-reducing bacteria (SRB) (Desulfobulbus and Desulfococcus) which could couple with ANME-conducting AMO were also found. But, the community structure of ANME had no significant difference with depths. From the results of investigation, we can come to a conclusion that sulfate-dependent anaerobic methane oxidation (SR-DAMO) would be the dominant AMO process in the landfill, while iron-dependent anaerobic methane oxidation (M/IR-DAMO) process was weak though concentration of ferric iron was large in the landfill. Denitrification-dependent anaerobic methane oxidation (NR-DAMO) was negative because of lack of nitrate and relevant function microorganisms in the landfill. Results also indicate that CH4 mitigation would have higher potential by increasing electron acceptor contents and promoting the growth of relevant function microorganisms.

Change of brown coal oxidation kinetic characteristics by promoting additives appending in the form of copper salts

NASA Astrophysics Data System (ADS)

Larionov, K. B.; Mishakov, I. V.; Gromov, A. A.; Zenkov, A. V.

2017-11-01

Process of brown coal oxidation with 5%wt content of copper-salt additives of various nature (Cu (NO3)2, CuSO4 and Cu(CH3COO)2) was studied. The experiment has been performed by thermogravimetric analysis at a heating rate of 2.5°C/min to a maximum temperature of 600°C in the air. Analytical evaluation of oxidation process kinetic characteristics has been conducted based on the results of TGA. It has been established that addition of initiating agents leads to significant reduction in the initial ignition temperature of coal (ΔTi = 15÷40°C), shortening of the sample warm-up time to the ignition point (Δte = 6÷12 min) and reduction of the sample burning time (Δtf = 40÷54 min). The following series of additives activity affecting ignition temperature of coals has been established: Cu(CH3COO)2 > Cu(NO3)2 > CuSO4. Additionally, the opposite can be said about the effect of additives on residence time of the sample in its combustion area (CuSO4 > Cu(NO3)2 > Cu(CH3COO)2). According to mass spectrometric analysis, presence of NOx, SO2, CO2 (intense peaks at 190÷290°C) was recorded in oxidation products of modified samples, which is explained by partial or complete decomposition of salts.

Development of Methane and Nitrous Oxide Emission Factors for the Biomass Fired Circulating Fluidized Bed Combustion Power Plant

PubMed Central

Cho, Chang-Sang; Sa, Jae-Hwan; Lim, Ki-Kyo; Youk, Tae-Mi; Kim, Seung-Jin; Lee, Seul-Ki; Jeon, Eui-Chan

2012-01-01

This study makes use of this distinction to analyze the exhaust gas concentration and fuel of the circulating fluidized bed (CFB) boiler that mainly uses wood biomass, and to develop the emission factors of Methane (CH4), Nitrous oxide (N2O). The fuels used as energy sources in the subject working sites are Wood Chip Fuel (WCF), RDF and Refused Plastic Fuel (RPF) of which heating values are 11.9 TJ/Gg, 17.1 TJ/Gg, and 31.2 TJ/Gg, respectively. The average concentrations of CH4 and N2O were measured to be 2.78 ppm and 7.68 ppm, respectively. The analyzed values and data collected from the field survey were used to calculate the emission factor of CH4 and N2O exhausted from the CFB boiler. As a result, the emission factors of CH4 and N2O are 1.4 kg/TJ (0.9–1.9 kg/TJ) and 4.0 kg/TJ (2.9–5.3 kg/TJ) within a 95% confidence interval. Biomass combined with the combustion technology for the CFB boiler proved to be more effective in reducing the N2O emission, compared to the emission factor of the CFB boiler using fossil fuel. PMID:23365540

Gasification of refinery sludge in an updraft reactor for syngas production

NASA Astrophysics Data System (ADS)

Ahmed, Reem; Sinnathambi, Chandra M.; Eldmerdash, Usama

2014-10-01

The study probes into the investigation on gasification of dry refinery sludge. The details of the study includes; influence of operation time, oxidation temperature and equivalence ratios on carbon gas conversion rate, gasification efficiency, heating value and fuel gas yield are presented. The results show that, the oxidation temperature increased sharply up to 858°C as the operating time increased up to 36 min then bridging occurred at 39 min which cause drop in reaction temperature up to 819 °C. This bridging was found to affect also the syngas compositions, meanwhile as the temperature decreased the CO, H2, CH4 compositions are also found to be decreases. Higher temperature catalyzed the reduction reaction (CO2+ C = 450 2CO ), and accelerated the carbon conversion and gasification efficiencies, resulted in more solid fuel is converted to a high heating value gas fuel. The equivalence ratio of 0.195 was found to be the optimum value for carbon conversion and cold gas efficiencies, high heating value of gas, and fuel gas yield to reach their maximum values of 96.1 % and 53.7 %, 5.42 MJ Nm-3 of, and 2.5 Nm3 kg-1 respectively.

Metabolic and trophic interactions modulate methane production by Arctic peat microbiota in response to warming

PubMed Central

Tveit, Alexander Tøsdal; Urich, Tim; Frenzel, Peter; Svenning, Mette Marianne

2015-01-01

Arctic permafrost soils store large amounts of soil organic carbon (SOC) that could be released into the atmosphere as methane (CH4) in a future warmer climate. How warming affects the complex microbial network decomposing SOC is not understood. We studied CH4 production of Arctic peat soil microbiota in anoxic microcosms over a temperature gradient from 1 to 30 °C, combining metatranscriptomic, metagenomic, and targeted metabolic profiling. The CH4 production rate at 4 °C was 25% of that at 25 °C and increased rapidly with temperature, driven by fast adaptations of microbial community structure, metabolic network of SOC decomposition, and trophic interactions. Below 7 °C, syntrophic propionate oxidation was the rate-limiting step for CH4 production; above this threshold temperature, polysaccharide hydrolysis became rate limiting. This change was associated with a shift within the functional guild for syntrophic propionate oxidation, with Firmicutes being replaced by Bacteroidetes. Correspondingly, there was a shift from the formate- and H2-using Methanobacteriales to Methanomicrobiales and from the acetotrophic Methanosarcinaceae to Methanosaetaceae. Methanogenesis from methylamines, probably stemming from degradation of bacterial cells, became more important with increasing temperature and corresponded with an increased relative abundance of predatory protists of the phylum Cercozoa. We concluded that Arctic peat microbiota responds rapidly to increased temperatures by modulating metabolic and trophic interactions so that CH4 is always highly produced: The microbial community adapts through taxonomic shifts, and cascade effects of substrate availability cause replacement of functional guilds and functional changes within taxa. PMID:25918393

Effect of assessment scale on spatial and temporal variations in CH4, C02, and N20 fluxes in a forested wetland

Treesearch

Zhaohua Dai; Carl Trettin; Changsheng Li; Harbin Li; Ge Sun; Devendra Amatya

2011-01-01

Emissions of methane (CH4), carbon dioxide (CO2), and nitrous oxide (N2O) from a forested watershed (160 ha) in South Carolina, USA, were estimated with a spatially explicit watershed-scale modeling framework that utilizes the spatial variations in physical and biogeochemical characteristics across watersheds. The target watershed (WS80) consisting of wetland (23%) and...

Potential of Svalbard reindeer winter droppings for emission/absorption of methane and nitrous oxide during summer

NASA Astrophysics Data System (ADS)

Hayashi, Kentaro; Cooper, Elisabeth J.; Loonen, Maarten J. J. E.; Kishimoto-Mo, Ayaka W.; Motohka, Takeshi; Uchida, Masaki; Nakatsubo, Takayuki

2014-06-01

Droppings of Svalbard reindeer (Rangifer tarandus platyrhynchus) could affect the carbon and nitrogen cycles in tundra ecosystems. The aim of this study was to evaluate the potential of reindeer droppings originating from the winter diet for emission and/or absorption of methane (CH4) and nitrous oxide (N2O) in summer. An incubation experiment was conducted over 14 days using reindeer droppings and mineral subsoil collected from a mound near Ny-Ålesund, Svalbard, to determine the potential exchanges of CH4 and N2O for combinations of two factors, reindeer droppings (presence or absence) and soil moisture (dry, moderate, or wet). A line transect survey was conducted to determine the distribution density of winter droppings at the study site. The incubation experiment showed a weak absorption of CH4 and a weak emission of N2O. Reindeer droppings originating from the winter diet had a negligible effect on the exchange fluxes of both CH4 and N2O. Although the presence of droppings resulted in a short-lasting increase in N2O emissions on day 1 (24 h from the start) for moderate and wet conditions, the emission rates were still very small, up to 3 μg N2O m-2 h-1.

Dynamic Oxygen on Surface: Catalytic Intermediate and Coking Barrier in the Modeled CO 2 Reforming of CH 4 on Ni (111)

DOE PAGES

Yuan, Kaidi; Zhong, Jian-Qiang; Zhou, Xiong; ...

2016-06-08

We identify Ni-O phases as important intermediates in a model dry (CO 2) reforming of methane catalyzed by Ni (111), based on results from in operando near ambient X-ray photoelectron spectroscopy (NAP-XPS), low energy electron diffraction (LEED) and scanning tunneling microscopy (STM). We find that under a CO 2 or CO 2-CH 4 atmosphere, the Ni-O phases exist as p(2×2) structured chemisorbed oxygen (Chem-O), epitaxial NiO (111), or oxygen-rich Ni xO y (x2O 3), depending on the chemical potential. The growth rates of the Ni-O phases have a negative correlation with temperature from 600 K to 900 K, proving thatmore » their dynamic concentrations in the reaction are not limited by CO 2 activation, but by their thermal stability. Between 300 K and 800 K (1:1 CH 4 and CO 2 mixture), oxidation by CO 2is dominant, resulting in a fully Ni-O covered surface. Between 800 K and 900 K, a partially oxidized Ni (111) exists which could greatly facilitate the effective conversion of CH 4. As CH 4 is activation-limited and dissociates mainly on metallic nickel, the released carbon species can quickly react with the adjacent oxygen (Ni-O phases) to form CO. After combining with carbon and releasing CO molecules, the Ni-O phases can be further regenerated through oxidation by CO 2. In this way, the Ni-O phases participate in the catalytic process, acting as an intermediate in addition to the previously reported Ni-C phases. We also reveal the carbon phobic property of the Ni-O phases, which links to the intrinsic coking resistance of the catalysts. The low dynamic coverage of surface oxygen at higher temperatures (>900 K) is inferred to be an underlying factor causing carbon aggregation. Therefore solutions based on Ni-O stabilization are proposed in developing coking resisting catalysts.« less

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

Degraded Land Restoration in Reinstating CH4 Sink.

PubMed

Singh, Jay Shankar; Gupta, Vijai K

2016-01-01

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

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).

Impact of seabird activity on nitrous oxide and methane fluxes from High Arctic tundra in Svalbard, Norway

NASA Astrophysics Data System (ADS)

Zhu, Renbin; Chen, Qingqing; Ding, Wei; Xu, Hua

2012-12-01

In this study, tundra N2O and CH4 fluxes were measured from one seabird sanctuary (SBT) and two non-seabird colonies (NST-I and NST-II) in Ny-Ålesund (79°55'N, 11°56'E), Svalbard during the summers of 2008 and 2009. N2O and CH4 fluxes from SBT showed large temporal and spatial variations depending on the intensity of seabird activity. High seabird activity sites showed large N2O and CH4 emissions while low N2O and CH4 emissions, even CH4 uptake occurred at medium and low seabird activity sites. Overall the mean fluxes were 18.3 ± 3.6 μg N2O m-2 h-1 and 53.5 ± 20.3 μg CH4 m-2 h-1 from tundra SBT whereas tundra NST-I and NST-II represented a relatively weak N2O source (8.3 ± 13.2 μg N2O m-2 h-1) and strong CH4 sink (-82.8 ± 22.3 μg CH4 m-2 h-1). Seabird activity was the strongest control of N2O and CH4 fluxes compared with soil temperature and moisture, and high N2O and CH4 emissions were created by soil physical and chemical processes (the sufficient supply of nutrients NH4+-N, NO3--N, total nitrogen, total phosphorus and total carbon from seabird guano, seabird tramp and appropriate water content) related to the seabird activity. Our work suggests that tundra ecosystems impacted by seabird activity are the potential "hotspots" for N2O and CH4 emissions although these sources have been largely neglected at present. Furthermore the combination of seabird activity and warming climate will likely further enhance N2O and CH4 emissions from the High Arctic tundra.

Observations on the methane oxidation capacity of landfill soils

USDA-ARS?s Scientific Manuscript database

Field data and two independent models indicate that landfill cover methane (CH4) oxidation should not be considered as a constant 10% or any other single value. Percent oxidation is a decreasing exponential function of the total methane flux rate into the cover and is also dependent on climate and c...

Kinetics of a Criegee intermediate that would survive high humidity and may oxidize atmospheric SO2

PubMed Central

Huang, Hao-Li; Chao, Wen; Lin, Jim Jr-Min

2015-01-01

Criegee intermediates are thought to play a role in atmospheric chemistry, in particular, the oxidation of SO2, which produces SO3 and subsequently H2SO4, an important constituent of aerosols and acid rain. However, the impact of such oxidation reactions is affected by the reactions of Criegee intermediates with water vapor, because of high water concentrations in the troposphere. In this work, the kinetics of the reactions of dimethyl substituted Criegee intermediate (CH3)2COO with water vapor and with SO2 were directly measured via UV absorption of (CH3)2COO under near-atmospheric conditions. The results indicate that (i) the water reaction with (CH3)2COO is not fast enough (kH2O < 1.5 × 10−16 cm3s−1) to consume atmospheric (CH3)2COO significantly and (ii) (CH3)2COO reacts with SO2 at a near–gas-kinetic-limit rate (kSO2 = 1.3 × 10−10 cm3s−1). These observations imply a significant fraction of atmospheric (CH3)2COO may survive under humid conditions and react with SO2, very different from the case of the simplest Criegee intermediate CH2OO, in which the reaction with water dimer predominates in the CH2OO decay under typical tropospheric conditions. In addition, a significant pressure dependence was observed for the reaction of (CH3)2COO with SO2, suggesting the use of low pressure rate may underestimate the impact of this reaction. This work demonstrates that the reactivity of a Criegee intermediate toward water vapor strongly depends on its structure, which will influence the main decay pathways and steady-state concentrations for various Criegee intermediates in the atmosphere. PMID:26283390

Kinetics of a Criegee intermediate that would survive high humidity and may oxidize atmospheric SO2.

PubMed

Huang, Hao-Li; Chao, Wen; Lin, Jim Jr-Min

2015-09-01

Criegee intermediates are thought to play a role in atmospheric chemistry, in particular, the oxidation of SO2, which produces SO3 and subsequently H2SO4, an important constituent of aerosols and acid rain. However, the impact of such oxidation reactions is affected by the reactions of Criegee intermediates with water vapor, because of high water concentrations in the troposphere. In this work, the kinetics of the reactions of dimethyl substituted Criegee intermediate (CH3)2COO with water vapor and with SO2 were directly measured via UV absorption of (CH3)2COO under near-atmospheric conditions. The results indicate that (i) the water reaction with (CH3)2COO is not fast enough (kH2O < 1.5 × 10(-16) cm(3) s(-1)) to consume atmospheric (CH3)2COO significantly and (ii) (CH3)2COO reacts with SO2 at a near-gas-kinetic-limit rate (kSO2 = 1.3 × 10(-10) cm(3) s(-1)). These observations imply a significant fraction of atmospheric (CH3)2COO may survive under humid conditions and react with SO2, very different from the case of the simplest Criegee intermediate CH2OO, in which the reaction with water dimer predominates in the CH2OO decay under typical tropospheric conditions. In addition, a significant pressure dependence was observed for the reaction of (CH3)2COO with SO2, suggesting the use of low pressure rate may underestimate the impact of this reaction. This work demonstrates that the reactivity of a Criegee intermediate toward water vapor strongly depends on its structure, which will influence the main decay pathways and steady-state concentrations for various Criegee intermediates in the atmosphere.

Methanol Oxidation on Pt3Sn(111) for Direct Methanol Fuel Cells: Methanol Decomposition.

PubMed

Lu, Xiaoqing; Deng, Zhigang; Guo, Chen; Wang, Weili; Wei, Shuxian; Ng, Siu-Pang; Chen, Xiangfeng; Ding, Ning; Guo, Wenyue; Wu, Chi-Man Lawrence

2016-05-18

PtSn alloy, which is a potential material for use in direct methanol fuel cells, can efficiently promote methanol oxidation and alleviate the CO poisoning problem. Herein, methanol decomposition on Pt3Sn(111) was systematically investigated using periodic density functional theory and microkinetic modeling. The geometries and energies of all of the involved species were analyzed, and the decomposition network was mapped out to elaborate the reaction mechanisms. Our results indicated that methanol and formaldehyde were weakly adsorbed, and the other derivatives (CHxOHy, x = 1-3, y = 0-1) were strongly adsorbed and preferred decomposition rather than desorption on Pt3Sn(111). The competitive methanol decomposition started with the initial O-H bond scission followed by successive C-H bond scissions, (i.e., CH3OH → CH3O → CH2O → CHO → CO). The Brønsted-Evans-Polanyi relations and energy barrier decomposition analyses identified the C-H and O-H bond scissions as being more competitive than the C-O bond scission. Microkinetic modeling confirmed that the vast majority of the intermediates and products from methanol decomposition would escape from the Pt3Sn(111) surface at a relatively low temperature, and the coverage of the CO residue decreased with an increase in the temperature and decrease in partial methanol pressure.

Controls of Methane Dynamics and Emissions in an Arctic Warming Experiment

NASA Astrophysics Data System (ADS)

Nielsen, C. S.; Elberling, B.; Michelsen, A.; Strobel, B. W.; Wulff, K.; Banyasz, I.

2015-12-01

Climatic changes have resulted in increasing air temperatures across the Arctic. This may increase anaerobic decomposition of soil organic matter to methane (CH4) in wetlands and increase plant growth and thereby production of substrate. Little is known about how seasonal variations in dissolved CH4 in soil water, substrate availability, and the effect of warming affect arctic wetland dynamics of CH4 production and emission. In 2013 we established two experiments in a fen at Disko Island, W Greenland; one with year round warming by open-top chambers and removal of shrubs, and one with removal of the aerenchymatous sedge Carex aquatilis ssp. stans. Throughout the growing season 2014 we measured how the treatments affected CH4 emissions, dissolved CH4 in the soil water, and substrate availability. Ecosystem CH4 emissions peaked at August 5th 2014 (7.5 μmol m-2 h-1) without coinciding with time of highest concentrations of dissolved CH4 or acetate indicating a decoupling between production and emission of CH4. The peak in dissolved CH4 concentration, at ten cm depth (1368 ppm, September 18th 2014), followed the peak in concentration of acetate in the same depth (0.30 ppm, August 30th 2014) highlighting the importance of this substance as a substrate for methanogenesis. C. aquatilis ssp. stans accounted for 60% and 77% of the ecosystem CH4 emissions in areas of the fen with water table above and below soil surface showing the importance of the presence of this species to serve as a pipe for CH4 emission which is bypassing the upper soil zone and potential methane oxidation. Throughout the season, warming increased the air temperature at soil surface by on average 0.89°C and occasionally warming and shrub removal increased soil temperature in 2 and 5 cm depth, but there was no effect of the treatments on the CH4 emissions indicating that this wetland is quite resilient towards future climate change.

A microbial functional group-based module for simulating methane production and consumption: Application to an incubated permafrost soil

DOE PAGES

Xu, Xiaofeng; Elias, Dwayne A.; Graham, David E.; ...

2015-07-23

In this study, accurately estimating methane (CH 4) flux is critically important for investigating and predicting the biogeochemistry-climate feedback. Better simulating CH 4 flux requires explicit representations of microbial processes on CH 4 dynamics because all processes for CH 4 production and consumption are actually carried out by microbes. A microbial functional group based module was developed and tested against an incubation experiment. The module considers four key mechanisms for CH 4 production and consumption: methanogenesis from acetate or single-carbon compounds and CH 4 oxidation using molecular oxygen or other inorganic electron acceptors. These four processes were carried out bymore » four microbial functional groups: acetoclastic methanogens, hydrogenotrophic methanogens, aerobic methanotrophs, and anaerobic methanotrophs. This module was then linked with the decomposition subroutine of the Community Land Model, and was further used to simulate dynamics of carbon dioxide (CO 2) and CH 4 concentrations from an incubation experiment with permafrost soils. The results show that the model could capture the dynamics of CO 2 and CH 4 concentrations in microcosms with top soils, mineral layer soils and permafrost soils under natural and saturated moisture conditions and a temperature gradient of -2°C, 3°C, and 5°C. Sensitivity analysis confirmed the importance of acetic acid's direct contribution as substrate and indirect effects through pH feedback on CO 2 and CH 4 production and consumption. This study suggests that representing the microbial mechanisms is critical for modeling CH 4 production and consumption; it is urgent to incorporate microbial mechanisms into Earth system models for better predicting the behavior of the climate system.« less

Dissolved methane in the Beaufort Sea and the Arctic Ocean, 1992-2009; sources and atmospheric flux

USGS Publications Warehouse

Lorenson, Thomas D.; Greinert, Jens; Coffin, Richard B.

2016-01-01

Methane concentration and isotopic composition was measured in ice-covered and ice-free waters of the Arctic Ocean during eleven surveys spanning the years of 1992-1995 and 2009. During ice-free periods, methane flux from the Beaufort shelf varies from 0.14 to 0.43 mg CH4 m-2 day-1. Maximum fluxes from localized areas of high methane concentration are up to 1.52 mg CH4 m-2 day-1. Seasonal buildup of methane under ice can produce short-term fluxes of methane from the Beaufort shelf that varies from 0.28 to 1.01 to mg CH4 m-2 day-1. Scaled-up estimates of minimum methane flux from the Beaufort Sea and pan-Arctic shelf for both ice-free and ice-covered periods range from 0.02 Tg CH4 yr-1 and 0.30 Tg CH4 yr-1 respectively to maximum fluxes of 0.18 Tg CH4 yr-1 and 2.2 Tg CH4 yr-1 respectively. A methane flux of 0.36 Tg CH4 yr-1from the deep Arctic Ocean was estimated using data from 1993-94. The flux can be as much as 2.35 Tg CH4 yr-1 estimated from maximum methane concentrations and wind speeds of 12 m/s, representing only 0.42% of the annual atmospheric methane budget of ~560 Tg CH4 yr-1. There were no significant changes in methane fluxes during the time period of this study. Microbial methane sources predominate with minor influxes from thermogenic methane offshore Prudhoe Bay and the Mackenzie River delta and may include methane from gas hydrate. Methane oxidation is locally important on the shelf and is a methane sink in the deep Arctic Ocean.

Greenhouse Gas Emission from Beef Cattle Grazing Systems on Temperate Grasslands

NASA Astrophysics Data System (ADS)

Rice, C. W.; Rivera-Zayas, J.

2017-12-01

At a global scale, cattle production is responsible for 65% of GHG emissions. During 2014 cattle management was the largest emitters of methane (CH4) representing a 23.2% of the total CH4 from anthropogenic activities. Since 2014, gas samples have been gathered and analyzed for carbon dioxide (CO2), CH4 and nitrous oxide (N2O) from three grazing areas under three different burning regimes at the temperate grassland of Konza Prairie Biological Station in Kansas. Burning regimes included one site in annually burned, and two sites with patch burned every three years on offset years. Burning regimes showed no effect in N2O emissions (p<0.05). Annual burning lowered CO2 emissions relative to patch burned. There was a significant effect of interaction between emissions and season. Maximum CO2 and CH4 fluxes were gathered during summer and fall; which coincided with high biomass seasons. Weather and edaphological conditions during fall and winter increase N2O emissions. A decrease in CO2 and CH4 fluxes, and N2O and CH4 soil uptake occurred during winter. Data gathered since 2014 implies CH4 and N2O are consumed on grazed grassland soils; with an increase in consumption with patch burning. Results quantify the role of temperate grasslands as a sink of CH4, and a possible sink of N2O. This experiment evidence CO2, CH4 and N2O emissions behavior as a consequence of burning regimes, and quantify the role of temperate grasslands as a sink of CH4 and N2O in order to understand best practice for resilience of beef cattle management.

Studies on the oxidation of hexamethylbenzene 1: Oxidation of hexamethylbenzene with nitric acid

NASA Technical Reports Server (NTRS)

Chiba, K.; Tomura, S.; Mizuno, T.

1986-01-01

The oxidative reaction of hexamethylbenzene (HMB) with nitric acid was studied, and the hitherto unknown polymethylbenzenepolycarboxylic acids were isolated: tetramethylphthalic anhydride, tetramethylisophthalic acid, 1,3,5-, 1,2,4- and 1,2,3-trimethylbenzenetricarboxylic acids. When HMB was warmed with 50% nitric acid at about 80 C, tetramethylphthalic anhydride and tetramethylisophthalic acid were initially produced. The continued reaction led to the production of trimethylbenzenetricarboxylic acids, but only slight amounts of dimethylbenzenetetracarboxylic acids were detected in the reaction mixture. Whereas tetramethylphthalic anydride and tetramethylisophthalic acid were obtained, pentamethylbenzoic acid, a possible precursor of them, was scarcely produced. On the other hand, a yellow material extracted with ether from the initial reaction mixture contained bis-(nitromethyl)prehnitene (CH3)4C6(CH2NO2)2, which was easily converted into the phthalic anhydride.

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.

Energy and exergy analysis of an ethanol reforming process for solid oxide fuel cell applications.

PubMed

Tippawan, Phanicha; Arpornwichanop, Amornchai

2014-04-01

The fuel processor in which hydrogen is produced from fuels is an important unit in a fuel cell system. The aim of this study is to apply a thermodynamic concept to identify a suitable reforming process for an ethanol-fueled solid oxide fuel cell (SOFC). Three different reforming technologies, i.e., steam reforming, partial oxidation and autothermal reforming, are considered. The first and second laws of thermodynamics are employed to determine an energy demand and to describe how efficiently the energy is supplied to the reforming process. Effect of key operating parameters on the distribution of reforming products, such as H2, CO, CO2 and CH4, and the possibility of carbon formation in different ethanol reformings are examined as a function of steam-to-ethanol ratio, oxygen-to-ethanol ratio and temperatures at atmospheric pressure. Energy and exergy analysis are performed to identify the best ethanol reforming process for SOFC applications. Copyright © 2014 Elsevier Ltd. All rights reserved.

Synthesis and characterization of mangenese(III) porphyrin supported on imidazole modified chloromethylated MIL-101(Cr): A heterogeneous and reusable catalyst for oxidation of hydrocarbons with sodium periodate

NASA Astrophysics Data System (ADS)

Zadehahmadi, Farnaz; Tangestaninejad, Shahram; Moghadam, Majid; Mirkhani, Valiollah; Mohammadpoor-Baltork, Iraj; Khosropour, Ahmad R.; Kardanpour, Reihaneh

2014-10-01

In the present work, chloromethylated MIL-101(Cr) modified with imidazole, Im-MIL-101, was applied as a support for immobilizing of tetraphenylporphyrinatomangenese(III) chloride. The imidazole-bound MIL-101, Im-MIL-101, not only used as support for immobilization of manganese porphyrin but also applied as a heterogeneous axial base. The Mn(TPP)Cl@Im-MIL-101 catalyst was characterized by UV-vis, FT-IR, X-ray diffraction (XRD), N2 adsorption, field emission scanning electron microscopy (FE-SEM), energy dispersive X-ray (EDX), elemental analysis and inductively coupled plasma (ICP) methods. The catalytic activity of this new catalytic system was investigated in the alkene epoxidation and alkane hydroxylation using NaIO4 as an oxidant in CH3CN/H2O at room temperature. This heterogeneous catalyst is highly efficient, stable and reusable in the oxidation of hydrocarbons.

Global wetland contribution to 2000–2012 atmospheric methane growth rate dynamics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Poulter, Benjamin; Bousquet, Philippe; Canadell, Josep G.

Increasing atmospheric methane (CH 4) concentrations have contributed to approximately 20% of anthropogenic climate change. Despite the importance of CH 4 as a greenhouse gas, its atmospheric growth rate and dynamics over the past two decades, which include a stabilization period (1999–2006), followed by renewed growth starting in 2007, remain poorly understood. We provide an updated estimate of CH 4 emissions from wetlands, the largest natural global CH 4 source, for 2000–2012 using an ensemble of biogeochemical models constrained with remote sensing surface inundation and inventory-based wetland area data. Between 2000–2012, boreal wetland CH 4 emissions increased by 1.2 Tgmore » yr –1 (–0.2–3.5 Tg yr –1), tropical emissions decreased by 0.9 Tg yr –1 (–3.2–1.1 Tg yr –1), yet globally, emissions remained unchanged at 184 ± 22 Tg yr –1. Changing air temperature was responsible for increasing high-latitude emissions whereas declines in low-latitude wetland area decreased tropical emissions; both dynamics are consistent with features of predicted centennial-scale climate change impacts on wetland CH 4 emissions. Despite uncertainties in wetland area mapping, our study shows that global wetland CH 4 emissions have not contributed significantly to the period of renewed atmospheric CH 4 growth, and is consistent with findings from studies that indicate some combination of increasing fossil fuel and agriculture-related CH 4 emissions, and a decrease in the atmospheric oxidative sink.« less

Global wetland contribution to 2000–2012 atmospheric methane growth rate dynamics

DOE PAGES

Poulter, Benjamin; Bousquet, Philippe; Canadell, Josep G.; ...

2017-09-13

Increasing atmospheric methane (CH 4) concentrations have contributed to approximately 20% of anthropogenic climate change. Despite the importance of CH 4 as a greenhouse gas, its atmospheric growth rate and dynamics over the past two decades, which include a stabilization period (1999–2006), followed by renewed growth starting in 2007, remain poorly understood. We provide an updated estimate of CH 4 emissions from wetlands, the largest natural global CH 4 source, for 2000–2012 using an ensemble of biogeochemical models constrained with remote sensing surface inundation and inventory-based wetland area data. Between 2000–2012, boreal wetland CH 4 emissions increased by 1.2 Tgmore » yr –1 (–0.2–3.5 Tg yr –1), tropical emissions decreased by 0.9 Tg yr –1 (–3.2–1.1 Tg yr –1), yet globally, emissions remained unchanged at 184 ± 22 Tg yr –1. Changing air temperature was responsible for increasing high-latitude emissions whereas declines in low-latitude wetland area decreased tropical emissions; both dynamics are consistent with features of predicted centennial-scale climate change impacts on wetland CH 4 emissions. Despite uncertainties in wetland area mapping, our study shows that global wetland CH 4 emissions have not contributed significantly to the period of renewed atmospheric CH 4 growth, and is consistent with findings from studies that indicate some combination of increasing fossil fuel and agriculture-related CH 4 emissions, and a decrease in the atmospheric oxidative sink.« less

Winter precipitation and snow accumulation drive the methane sink or source strength of Arctic tussock tundra.

PubMed

Blanc-Betes, Elena; Welker, Jeffrey M; Sturchio, Neil C; Chanton, Jeffrey P; Gonzalez-Meler, Miquel A

2016-08-01

Arctic winter precipitation is projected to increase with global warming, but some areas will experience decreases in snow accumulation. Although Arctic CH4 emissions may represent a significant climate forcing feedback, long-term impacts of changes in snow accumulation on CH4 fluxes remain uncertain. We measured ecosystem CH4 fluxes and soil CH4 and CO2 concentrations and (13) C composition to investigate the metabolic pathways and transport mechanisms driving moist acidic tundra CH4 flux over the growing season (Jun-Aug) after 18 years of experimental snow depth increases and decreases. Deeper snow increased soil wetness and warming, reducing soil %O2 levels and increasing thaw depth. Soil moisture, through changes in soil %O2 saturation, determined predominance of methanotrophy or methanogenesis, with soil temperature regulating the ecosystem CH4 sink or source strength. Reduced snow (RS) increased the fraction of oxidized CH4 (Fox) by 75-120% compared to Ambient, switching the system from a small source to a net CH4 sink (21 ± 2 and -31 ± 1 mg CH4  m(-2)  season(-1) at Ambient and RS). Deeper snow reduced Fox by 35-40% and 90-100% in medium- (MS) and high- (HS) snow additions relative to Ambient, contributing to increasing the CH4 source strength of moist acidic tundra (464 ± 15 and 3561 ± 97 mg CH4  m(-2)  season(-1) at MS and HS). Decreases in Fox with deeper snow were partly due to increases in plant-mediated CH4 transport associated with the expansion of tall graminoids. Deeper snow enhanced CH4 production within newly thawed soils, responding mainly to soil warming rather than to increases in acetate fermentation expected from thaw-induced increases in SOC availability. Our results suggest that increased winter precipitation will increase the CH4 source strength of Arctic tundra, but the resulting positive feedback on climate change will depend on the balance between areas with more or less snow accumulation than they are currently facing. © 2016 John Wiley & Sons Ltd.

Isotopic identification of the source of methane in subsurface sediments of an area surrounded by waste disposal facilities

USGS Publications Warehouse

Hackley, Keith C.; Liu, Chao-Li; Trainor, D.

1999-01-01

The major source of methane (CH4) in subsurface sediments on the property of a former hazardous waste treatment facility was determined using isotopic analyses measured on CH4 and associated groundwater. The site, located on an earthen pier built into a shallow wetland lake, has had a history of waste disposal practices and is surrounded by landfills and other waste management facilities. Concentrations of CH4 up to 70% were found in the headspace gases of several piezometers screened at 3 different depths (ranging from 8 to 17 m) in lacustrine and glacial till deposits. Possible sources of the CH4 included a nearby landfill, organic wastes from previous impoundments and microbial gas derived from natural organic matter in the sediments. Isotopic analyses included ??13C, ??D, 14C, and 3H on select CH4 samples and ??D and ??18O on groundwater samples. Methane from the deepest glacial till and intermediate lacustrine deposits had ??13C values from -79 to -82???, typical of natural 'drift gas' generated by microbial CO2-reduction. The CH4 from the shallow lacustrine deposits had ??13C values from -63 to -76???, interpreted as a mixture between CH4 generated by microbial fermentation and the CO2-reduction processes within the subsurface sediments. The ??D values of all the CH4 samples were quite negative ranging from -272 to -299???. Groundwater sampled from the deeper zones also showed quite negative ??D values that explained the light ??D observed for the CH4. Radiocarbon analyses of the CH4 showed decreasing 14C activity with depth, from a high of 58 pMC in the shallow sediments to 2 pMC in the deeper glacial till. The isotopic data indicated the majority of CH4 detected in the fill deposits of this site was microbial CH4 generated from naturally buried organic matter within the subsurface sediments. However, the isotopic data of CH4 from the shallow piezometers was more variable and the possibility of some mixing with oxidized landfill CH4 could not be completely ruled out.

Global methane and nitrous oxide emissions from terrestrial ecosystems due to multiple environmental changes

DOE PAGES

Tian, Hanqin; Chen, Guangsheng; Lu, Chaoqun; ...

2015-03-16

Greenhouse gas (GHG)-induced climate change is among the most pressing sustainability challenges facing humanity today, posing serious risks for ecosystem health. Methane (CH 4) and nitrous oxide (N 2O) are the two most important GHGs after carbon dioxide (CO 2), but their regional and global budgets are not well known. In this paper, we applied a process-based coupled biogeochemical model to concurrently estimate the magnitude and spatial and temporal patterns of CH 4 and N 2O fluxes as driven by multiple environmental changes, including climate variability, rising atmospheric CO 2, increasing nitrogen deposition, tropospheric ozone pollution, land use change, andmore » nitrogen fertilizer use.« less

HIMMELI v1.0: HelsinkI Model of MEthane buiLd-up and emIssion for peatlands

DOE Office of Scientific and Technical Information (OSTI.GOV)

Raivonen, Maarit; Smolander, Sampo; Backman, Leif

Wetlands are one of the most significant natural sources of methane (CH 4) to the atmosphere. They emit CH 4 because decomposition of soil organic matter in waterlogged anoxic conditions produces CH 4, in addition to carbon dioxide (CO 2). Production of CH 4 and how much of it escapes to the atmosphere depend on a multitude of environmental drivers. Models simulating the processes leading to CH 4 emissions are thus needed for upscaling observations to estimate present CH 4 emissions and for producing scenarios of future atmospheric CH 4 concentrations. Aiming at a CH 4 model that can bemore » added to models describing peatland carbon cycling, we composed a model called HIMMELI that describes CH 4 build-up in and emissions from peatland soils. It is not a full peatland carbon cycle model but it requires the rate of anoxic soil respiration as input. Driven by soil temperature, leaf area index (LAI) of aerenchymatous peatland vegetation, and water table depth (WTD), it simulates the concentrations and transport of CH 4, CO 2, and oxygen (O 2) in a layered one-dimensional peat column. Here, we present the HIMMELI model structure and results of tests on the model sensitivity to the input data and to the description of the peat column (peat depth and layer thickness), and demonstrate that HIMMELI outputs realistic fluxes by comparing modeled and measured fluxes at two peatland sites. As HIMMELI describes only the CH 4-related processes, not the full carbon cycle, our analysis revealed mechanisms and dependencies that may remain hidden when testing CH 4 models connected to complete peatland carbon models, which is usually the case. Our results indicated that (1) the model is flexible and robust and thus suitable for different environments; (2) the simulated CH 4 emissions largely depend on the prescribed rate of anoxic respiration; (3) the sensitivity of the total CH 4 emission to other input variables is mainly mediated via the concentrations of dissolved gases, in particular, the O 2 concentrations that affect the CH 4 production and oxidation rates; (4) with given input respiration, the peat column description does not significantly affect the simulated CH 4 emissions in this model version.« less

HIMMELI v1.0: HelsinkI Model of MEthane buiLd-up and emIssion for peatlands

NASA Astrophysics Data System (ADS)

Raivonen, Maarit; Smolander, Sampo; Backman, Leif; Susiluoto, Jouni; Aalto, Tuula; Markkanen, Tiina; Mäkelä, Jarmo; Rinne, Janne; Peltola, Olli; Aurela, Mika; Lohila, Annalea; Tomasic, Marin; Li, Xuefei; Larmola, Tuula; Juutinen, Sari; Tuittila, Eeva-Stiina; Heimann, Martin; Sevanto, Sanna; Kleinen, Thomas; Brovkin, Victor; Vesala, Timo

2017-12-01

Wetlands are one of the most significant natural sources of methane (CH4) to the atmosphere. They emit CH4 because decomposition of soil organic matter in waterlogged anoxic conditions produces CH4, in addition to carbon dioxide (CO2). Production of CH4 and how much of it escapes to the atmosphere depend on a multitude of environmental drivers. Models simulating the processes leading to CH4 emissions are thus needed for upscaling observations to estimate present CH4 emissions and for producing scenarios of future atmospheric CH4 concentrations. Aiming at a CH4 model that can be added to models describing peatland carbon cycling, we composed a model called HIMMELI that describes CH4 build-up in and emissions from peatland soils. It is not a full peatland carbon cycle model but it requires the rate of anoxic soil respiration as input. Driven by soil temperature, leaf area index (LAI) of aerenchymatous peatland vegetation, and water table depth (WTD), it simulates the concentrations and transport of CH4, CO2, and oxygen (O2) in a layered one-dimensional peat column. Here, we present the HIMMELI model structure and results of tests on the model sensitivity to the input data and to the description of the peat column (peat depth and layer thickness), and demonstrate that HIMMELI outputs realistic fluxes by comparing modeled and measured fluxes at two peatland sites. As HIMMELI describes only the CH4-related processes, not the full carbon cycle, our analysis revealed mechanisms and dependencies that may remain hidden when testing CH4 models connected to complete peatland carbon models, which is usually the case. Our results indicated that (1) the model is flexible and robust and thus suitable for different environments; (2) the simulated CH4 emissions largely depend on the prescribed rate of anoxic respiration; (3) the sensitivity of the total CH4 emission to other input variables is mainly mediated via the concentrations of dissolved gases, in particular, the O2 concentrations that affect the CH4 production and oxidation rates; (4) with given input respiration, the peat column description does not significantly affect the simulated CH4 emissions in this model version.

HIMMELI v1.0: HelsinkI Model of MEthane buiLd-up and emIssion for peatlands

DOE PAGES

Raivonen, Maarit; Smolander, Sampo; Backman, Leif; ...

2017-12-22

Wetlands are one of the most significant natural sources of methane (CH 4) to the atmosphere. They emit CH 4 because decomposition of soil organic matter in waterlogged anoxic conditions produces CH 4, in addition to carbon dioxide (CO 2). Production of CH 4 and how much of it escapes to the atmosphere depend on a multitude of environmental drivers. Models simulating the processes leading to CH 4 emissions are thus needed for upscaling observations to estimate present CH 4 emissions and for producing scenarios of future atmospheric CH 4 concentrations. Aiming at a CH 4 model that can bemore » added to models describing peatland carbon cycling, we composed a model called HIMMELI that describes CH 4 build-up in and emissions from peatland soils. It is not a full peatland carbon cycle model but it requires the rate of anoxic soil respiration as input. Driven by soil temperature, leaf area index (LAI) of aerenchymatous peatland vegetation, and water table depth (WTD), it simulates the concentrations and transport of CH 4, CO 2, and oxygen (O 2) in a layered one-dimensional peat column. Here, we present the HIMMELI model structure and results of tests on the model sensitivity to the input data and to the description of the peat column (peat depth and layer thickness), and demonstrate that HIMMELI outputs realistic fluxes by comparing modeled and measured fluxes at two peatland sites. As HIMMELI describes only the CH 4-related processes, not the full carbon cycle, our analysis revealed mechanisms and dependencies that may remain hidden when testing CH 4 models connected to complete peatland carbon models, which is usually the case. Our results indicated that (1) the model is flexible and robust and thus suitable for different environments; (2) the simulated CH 4 emissions largely depend on the prescribed rate of anoxic respiration; (3) the sensitivity of the total CH 4 emission to other input variables is mainly mediated via the concentrations of dissolved gases, in particular, the O 2 concentrations that affect the CH 4 production and oxidation rates; (4) with given input respiration, the peat column description does not significantly affect the simulated CH 4 emissions in this model version.« less

Effect of CH3COOH on Hydrometallurgical Purification of Metallurgical-Grade Silicon Using HCl-HF Leaching

NASA Astrophysics Data System (ADS)

Tian, Chunjin; Lu, Haifei; Wei, Kuixian; Ma, Wenhui; Xie, Keqiang; Wu, Jijun; Lei, Yun; Yang, Bin; Morita, Kazuki

2018-04-01

The present study investigated the effects of adding CH3COOH to HCl and HF used to purify metallurgical-grade Si (MG-Si). After 6 h of leaching MG-Si with an acid mixture consisting of 4 mol L-1 HCl, 3 mol L-1 HF, and 3 mol L-1 CH3COOH at 348 K, the total impurity removal efficiency was 88.5%, exceeding the 81.5% removal efficiency obtained without addition of CH3COOH. The microstructural evolution of Si after etching with the two lixiviants indicated better dissolution of metal impurities in MG-Si when using the HCl-HF-CH3COOH mixture. Furthermore, the leaching kinetics of Fe using the HCl-HF and HCl-HF-CH3COOH mixtures were observed to depend on the interfacial chemical reactions.

Assessing the High Temperature, High Pressure Subsurface for Anaerobic Methane Oxidation

NASA Astrophysics Data System (ADS)

Harris, R. L.; Bartlett, D.; Byrnes, A. W.; Walsh, K. M.; Lau, C. Y. M.; Onstott, T. C.

2017-12-01

The anaerobic oxidation of methane (AOM) is an important sink in the global methane (CH4) budget. ANMEs are known to oxidize CH4 either independently or in consortia with bacteria, coupling the reduction of electron acceptors such as, SO42-, NO2-, NO3-, Mn4+, or Fe3+. To further constrain the contribution of AOM to the global CH4 budget, it is important to assess unexplored environments where AOM is thermodynamically possible such as the high pressure, high temperature deep biosphere. Provided plausible electron acceptor availability, increased temperature and pCH4 yield favorable Gibbs free energies for AOM reactions and the production of ATP (Fig. 1). To date, only sulfate-dependent AOM metabolism has been documented under high temperature conditions (50-72˚C), and AOM has not been assessed above 10.1 MPa. Given that ANMEs share close phylogenetic and metabolic heritage with methanogens and that the most heat-tolerant microorganism known is a barophilic methanogen, there possibly exist thermophilic ANMEs. Here we describe preliminary results from high pressure, high temperature stable isotope tracer incubation experiments on deep biosphere samples. Deep sub-seafloor sediments collected by IODP 370 from the Nankai Trough (257 - 865 m below seafloor) and deep fracture fluid from South Africa (1339 m below land surface) were incubated anaerobically in hydrostatic pressure vessels at 40 MPa in simulated in situ temperatures (40˚ - 80˚C). Sediments and fracture fluid were incubated in sulfate-free artificial seawater, a 2:98 13CH4:N2 headspace, and treated with one of the potential electron acceptors listed above in addition to kill and endogenous activity (i.e. no added electron acceptor) controls. Stable isotope analysis of dissolved inorganic carbon (DIC) suggests that AOM occurred within 60 days of incubation for all investigated electron acceptors and temperatures except 50˚C. Sulfate-dependent AOM rates are consistent with those previously reported in the literature, while the highest rate of AOM was measured in Nankai Trough sediments from 616 m incubated at 70˚C with 10 mM NO2- (0.44 ± .01 µmol 13CO2 day-1 g-1 dry weight sediment). Further analysis is required to investigate the identities and functional adaptations of CH4-cycling organisms active under high pressure and high temperature.

Cycling of greenhouse gases as a function of groundwater level in a floodplain - carbon dioxide, nitrous oxide and methane: Implications for Biogeochemical Change in a Warming World

NASA Astrophysics Data System (ADS)

Bill, M.; Conrad, M. E.; Tokunaga, T. K.; Hobson, C.; Williams, K. H.

2016-12-01

Floodplain sediment-water systems play an important role in carbon dioxide, nitrous oxide and methane greenhouse gas cycling. Changes in temperature and precipitation can alter biogeochemical equilibrium as well as production and consumption of greenhouse gases. We monitored CO2, N2O, CH4 greenhouse gas concentrations and C, O, and N stable isotope variations over a period of 4 years in a cross section of five wells located with increasing distance from the Colorado River. Pore space of partially saturated sediments located above an alluvial aquifer was sampled in vertically resolved profiles from 0.5 m to 3 m depth at a periodicity of one month to 2 weeks. Gas concentrations and stable isotopic signatures show annual-scale fluctuations. From 2013 to 2016 during cold seasons, low δ13C of CO2 ( -24‰) and high δ15N of N2O ( -5‰) and minimum concentrations in CO2 (< 5%v), N2O (< 5ppmv) and CH4 (< 0.5ppmv) coincide with low water table elevation and low temperature. At the beginning of summer, which corresponds to maximum water table elevation, we observed the highest concentrations of N2O ( 50ppmv) and of CO2 ( 5.5%v). Low δ15N ( -16‰) and relatively high δ13C ( -21‰) values were also observed for the summer season. CH4 was observed only in the well closest to the river (7ppmv). The variation of CO2, N2O and CH4 concentrations and δ values suggest changes in reducing/oxidizing microbial activity. Strongest biologically mediated reduction is associated with the highest water table, which typically induces reducing conditions. The maximum water elevation coincides with the annual snowmelt in the Rocky Mountains. Climate change directly impacts on biogeochemical cycling in the floodplain by affecting stream and river water discharge. At local and global scales, a drier and warmer climate will decrease N2O and CH4 production. A wetter climate induces higher stream and river water discharge, which will increase the zone and magnitude of N2O and CH4 production.

CH_{4} production in the deep soil as a source of stem CH_{4} emission in Fagus sylvatica}

NASA Astrophysics Data System (ADS)

Maier, Martin; Machacova, Katerina; Urban, Otmar; Lang, Friederike

2017-04-01

Predicting greenhouse gas (GHG) fluxes on a global scale requires understanding fluxes on the local scale. Understanding GHG processes in soil-plant-atmosphere systems is essential to understand and mitigate GHG fluxes on the local scale. Forests are known to act as carbon sink. Yet, trees at waterlogged sites are known to emit large amounts of CH4, what can offset the positive GHG balance due the CO2 that is sequestered as wood. Generally, upland trees like European beech (Fagus sylvatica L.) are assumed not to emit CH4, and the upland forest soils are regarded as CH4 sinks. Soil-atmosphere fluxes and stem-atmosphere fluxes of CH4 were studied together with soil gas profiles at two upland beech forest sites in Germany and Czech Republic. Soil was a net CH4 sink at both sites. While most trees showed no or low emissions, one beech tree had exorbitant CH4 emissions that were higher than the CH4 sink capacity of the soil. A soil survey showed strong redoximorphic color patterns in the soil adjacent to this tree. Although the soil around the tree was taking up CH4, the soil gas profiles around this tree showed CH4 production at a soil depth >0.3 m. We interpret the coincidence of the production of CH4 in the deep soil below the beech with the large stem emissions as strong hint that there is a transport link between the soil and stem. We think that the root system represents a preferential transport system for CH4 despite the fact that beech roots usually do not have a special gas transport tissue. The observed CH4 stem emissions represent an important CH4 flux in this ecosystem, and, thus, should be considered in future research. Acknowledgement This research was supported by the Czech Academy of Sciences and the German Academic Exchange Service within the project "Methane (CH4) and nitrous oxide (N2O) emissions from Fagus sylvatica trees" (DAAD-15-03), the Czech Science Foundation (17-18112Y), National Programme for Sustainability I (LO1415) and project DFG (MA 5826/2-1). We would like to thank Marek Jakubik, Sinikka Paulus, Ellen Halaburt and Sally Haddad for technical support.

The ecology of methane in streams and rivers: Patterns, controls, and global significance

USGS Publications Warehouse

Stanley, Emily H.; Casson, Nora J.; Christel, Samuel T.; Crawford, John T.; Loken, Luke C.; Oliver, Samantha K.

2016-01-01

Streams and rivers can substantially modify organic carbon (OC) inputs from terrestrial landscapes, and much of this processing is the result of microbial respiration. While carbon dioxide (CO2) is the major end-product of ecosystem respiration, methane (CH4) is also present in many fluvial environments even though methanogenesis typically requires anoxic conditions that may be scarce in these systems. Given recent recognition of the pervasiveness of this greenhouse gas in streams and rivers, we synthesized existing research and data to identify patterns and drivers of CH4, knowledge gaps, and research opportunities. This included examining the history of lotic CH4 research, creating a database of concentrations and fluxes (MethDB) to generate a global-scale estimate of fluvial CH4 efflux, and developing a conceptual framework and using this framework to consider how human activities may modify fluvial CH4 dynamics. Current understanding of CH4 in streams and rivers has been strongly influenced by goals of understanding OC processing and quantifying the contribution of CH4 to ecosystem C fluxes. Less effort has been directed towards investigating processes that dictate in situ CH4 production and loss. CH4 makes a meager contribution to watershed or landscape C budgets, but streams and rivers are often significant CH4 sources to the atmosphere across these same spatial extents. Most fluvial systems are supersaturated with CH4 and we estimate an annual global emission of 26.8 Tg CH4, equivalent to ~15-40% of wetland and lake effluxes, respectively. Less clear is the role of CH4 oxidation, methanogenesis, and total anaerobic respiration to whole ecosystem production and respiration. Controls on CH4 generation and persistence can be viewed in terms of proximate controls that influence methanogenesis (organic matter, temperature, alternative electron acceptors, nutrients) and distal geomorphic and hydrologic drivers. Multiple controls combined with its extreme redox status and low solubility result in high spatial and temporal variance of CH4 in fluvial environments, which presents a substantial challenge for understanding its larger-scale dynamics. Further understanding of CH4 production and consumption, anaerobic metabolism, and ecosystem energetics in streams and rivers can be achieved through more directed studies and comparison with knowledge from terrestrial, wetland, and aquatic disciplines.

Species and temperature measurements of methane oxidation in a nanosecond repetitively pulsed discharge

PubMed Central

Lefkowitz, Joseph K; Guo, Peng; Rousso, Aric; Ju, Yiguang

2015-01-01

Speciation and temperature measurements of methane oxidation during a nanosecond repetitively pulsed discharge in a low-temperature flow reactor have been performed. Measurements of temperature and formaldehyde during a burst of pulses were made on a time-dependent basis using tunable diode laser absorption spectroscopy, and measurements of all other major stable species were made downstream of a continuously pulsed discharge using gas chromatography. The major species for a stoichiometric methane/oxygen/helium mixture with 75% dilution are H2O, CO, CO2, H2, CH2O, CH3OH, C2H6, C2H4 and C2H2. A modelling tool to simulate homogeneous plasma combustion kinetics is assembled by combining the ZDPlasKin and CHEMKIN codes. In addition, a kinetic model for plasma-assisted combustion (HP-Mech/plasma) of methane, oxygen and helium mixtures has been assembled to simulate the measurements. Predictions can accurately capture reactant consumption as well as production of the major product species. However, significant disagreement is found for minor species, particularly CH2O and CH3OH. Further analysis revealed that the plasma-activated low-temperature oxidation pathways, particularly those involving CH3O2 radical reactions and methane reactions with O(1D), are responsible for this disagreement. PMID:26170433

Molecular mechanisms of water table lowering and nitrogen deposition in affecting greenhouse gas emissions from a Tibetan alpine wetland.

PubMed

Wang, Hao; Yu, Lingfei; Zhang, Zhenhua; Liu, Wei; Chen, Litong; Cao, Guangmin; Yue, Haowei; Zhou, Jizhong; Yang, Yunfeng; Tang, Yanhong; He, Jin-Sheng

2017-02-01

Rapid climate change and intensified human activities have resulted in water table lowering (WTL) and enhanced nitrogen (N) deposition in Tibetan alpine wetlands. These changes may alter the magnitude and direction of greenhouse gas (GHG) emissions, affecting the climate impact of these fragile ecosystems. We conducted a mesocosm experiment combined with a metagenomics approach (GeoChip 5.0) to elucidate the effects of WTL (-20 cm relative to control) and N deposition (30 kg N ha -1  yr -1 ) on carbon dioxide (CO 2 ), methane (CH 4 ) and nitrous oxide (N 2 O) fluxes as well as the underlying mechanisms. Our results showed that WTL reduced CH 4 emissions by 57.4% averaged over three growing seasons compared with no-WTL plots, but had no significant effect on net CO 2 uptake or N 2 O flux. N deposition increased net CO 2 uptake by 25.2% in comparison with no-N deposition plots and turned the mesocosms from N 2 O sinks to N 2 O sources, but had little influence on CH 4 emissions. The interactions between WTL and N deposition were not detected in all GHG emissions. As a result, WTL and N deposition both reduced the global warming potential (GWP) of growing season GHG budgets on a 100-year time horizon, but via different mechanisms. WTL reduced GWP from 337.3 to -480.1 g CO 2 -eq m -2 mostly because of decreased CH 4 emissions, while N deposition reduced GWP from 21.0 to -163.8 g CO 2 -eq m -2 , mainly owing to increased net CO 2 uptake. GeoChip analysis revealed that decreased CH 4 production potential, rather than increased CH 4 oxidation potential, may lead to the reduction in net CH 4 emissions, and decreased nitrification potential and increased denitrification potential affected N 2 O fluxes under WTL conditions. Our study highlights the importance of microbial mechanisms in regulating ecosystem-scale GHG responses to environmental changes. © 2016 John Wiley & Sons Ltd.

Comparison of chain sampling plans with single and double sampling plans

NASA Technical Reports Server (NTRS)

Stephens, K. S.; Dodge, H. F.

1976-01-01

The efficiency of chain sampling is examined through matching of operating characteristics (OC) curves of chain sampling plans (ChSP) with single and double sampling plans. In particular, the operating characteristics of some ChSP-0, 3 and 1, 3 as well as ChSP-0, 4 and 1, 4 are presented, where the number pairs represent the first and the second cumulative acceptance numbers. The fact that the ChSP procedure uses cumulative results from two or more samples and that the parameters can be varied to produce a wide variety of operating characteristics raises the question whether it may be possible for such plans to provide a given protection with less inspection than with single or double sampling plans. The operating ratio values reported illustrate the possibilities of matching single and double sampling plans with ChSP. It is shown that chain sampling plans provide improved efficiency over single and double sampling plans having substantially the same operating characteristics.

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.

Study of the acetonitrile poisoning of platinum cathodes on proton exchange membrane fuel cell spatial performance using a segmented cell system

NASA Astrophysics Data System (ADS)

Reshetenko, Tatyana V.; St-Pierre, Jean

2015-10-01

Due to the wide applications of acetonitrile as a solvent in the chemical industry, acetonitrile can be present in the air and should be considered a possible pollutant. In this work, the spatial proton exchange membrane fuel cell performance exposed to air with 20 ppm CH3CN was studied using a segmented cell system. The injection of CH3CN led to performance losses of 380 mV at 0.2 A cm-2 and 290 mV at 1.0 A cm-2 accompanied by a significant change in the current density distribution. The observed local currents behavior is likely attributed to acetonitrile chemisorption and the subsequent two consecutive reduction/oxidation reactions. The hydrolysis of CH3CN and its intermediate imine species resulted in NH4+ formation, which increased the high-frequency resistance of the cell and affected oxygen reduction and performance. Other products of hydrolysis can be oxidized to CO2 under the operating conditions. The reintroduction of pure air completely recovered cell performance within 4 h at 1.0 A cm-2, while at 0.2 A cm-2 the cell recovery was only partial. A detailed analysis of the current density distribution, its correlation with spatial electrochemical impedance spectroscopy data, possible CH3CN oxidation/reduction mechanisms and mitigation strategies are presented and discussed.

Tree CH4 fluxes in forestry drained peatland in southern Finland

NASA Astrophysics Data System (ADS)

Haikarainen, Iikka; Putkinen, Anuliina; Pyykkö, Petteri; Halmeenmäki, Elisa; Pihlatie, Mari

2017-04-01

Methane (CH4) is among the most important greenhouse gases and its atmospheric concentration is increasing. Boreal forests are commonly considered a net sink of atmospheric CH4 due to CH4 consuming bacteria in aerated soil layers. Recent studies have, however, demonstrated that trees are capable of emitting CH4 from their stems and shoots by transporting anaerobically produced CH4 from deeper soil layers to the atmosphere. Furthermore, trees may act as independent sources of CH4. We have measured tree stem CH4 exchange of boreal tree species at Lettosuo, a nutrient rich peatland forest in Tammela, southern Finland (60˚ 38' N, 23˚ 57' E), using the static chamber technique. Three species, downy birch (Betula pubescens), Norway spruce (Picea abies) and Scots pine (Pinus sylvestris), were selected under investigation as they represent common boreal tree species. Fluxes of CH4 were measured during 7.6.2016 - 17.10.2016 from in total 25 sample trees growing on two different plots: a treatment plot where all the pines were removed to raise the water table level (WTL) and a control plot. Three birches from the treatment plot were selected to measure CH4 flux variation within vertical profile of the trees. Characterization of microbial communities, quantification of methanogenic and methanotrophic functional genes, and measurements of potential CH4 production and consumption from peat profile and forest floor moss samples were also carried out to obtain insight to the CH4 flux dynamics at the studied sites. The pine removal treatment did not markedly change the average WTL, but it made the WTL more variable with frequently 10-15 cm closer to soil surface compared to the WTL on the control plot. We found small and variable CH4 emissions from the stems of trees on both of the plots, while occasional consumption of CH4 was also present. Generally the CH4 emissions were higher and more dominant at the treatment plot compared to the control plot, and the fluxes were significantly different between the plots (p < 0.001). The CH4 emission rates from the birches at the treatment plot decreased exponentially in the stem vertical profile. Clear seasonal flux dynamics or significant differences in the CH4 flux between the species were not found at either of the plots. Microbial experiments showed that anaerobic CH4 production, CH4 oxidation potential (under 1000 ppm CH4) and the amount of methanogens were higher in the peat of the treatment site. The difference in the CH4 flux rates between the plots indicates that the WTL is a major regulator of tree CH4 emissions on forestry drained peatlands, supporting our hypothesis that the stem emitted CH4 originates from anaerobic soil conditions. This hypothesis is further supported by the results of the microbial analysis and by the observation that more CH4 is emitting from the lower parts of the stems compared to the upper stem.

Effects of straw incorporation along with microbial inoculant on methane and nitrous oxide emissions from rice fields.

PubMed

Liu, Gang; Yu, Haiyang; Ma, Jing; Xu, Hua; Wu, Qinyan; Yang, Jinghui; Zhuang, Yiqing

2015-06-15

Incorporation of straw together with microbial inoculant (a microorganism agent, accelerating straw decomposition) is being increasingly adopted in rice cultivation, thus its effect on greenhouse gas (GHG) emissions merits serious attention. A 3-year field experiment was conducted from 2010 to 2012 to investigate combined effect of straw and microbial inoculant on methane (CH4) and nitrous oxide (N2O) emissions, global warming potential (GWP) and greenhouse gas intensity (GHGI) in a rice field in Jurong, Jiangsu Province, China. The experiment was designed to have treatment NPK (N, P and K fertilizers only), treatment NPKS (NPK plus wheat straw), treatment NPKSR (NPKS plus Ruilaite microbial inoculant) and treatment NPKSJ (NPKS plus Jinkuizi microbial inoculant). Results show that compared to NPK, NPKS increased seasonal CH4 emission by 280-1370%, while decreasing N2O emission by 7-13%. When compared with NPKS, NPKSR and NPKSJ increased seasonal CH4 emission by 7-13% and 6-12%, respectively, whereas reduced N2O emission by 10-27% and 9-24%, respectively. The higher CH4 emission could be attributed to the higher soil CH4 production potential triggered by the combined application of straw and microbial inoculant, and the lower N2O emission to the decreased inorganic N content. As a whole, the benefit of lower N2O emission was completely offset by increased CH4 emission, resulting in a higher GWP for NPKSR (5-12%) and NPKSJ (5-11%) relative to NPKS. Due to NPKSR and NPKSJ increased rice grain yield by 3-6% and 2-4% compared to NPKS, the GHGI values for NPKS, NPKSR and NPKSJ were comparable. These findings suggest that incorporating straw together with microbial inoculant would not influence the radiative forcing of rice production in the terms of per unit of rice grain yield relative to the incorporation of straw alone. Copyright © 2015 Elsevier B.V. All rights reserved.

Anaerobic oxidation of methane associated with sulfate reduction in a natural freshwater gas source

PubMed Central

Timmers, Peer HA; Suarez-Zuluaga, Diego A; van Rossem, Minke; Diender, Martijn; Stams, Alfons JM; Plugge, Caroline M

2016-01-01

The occurrence of anaerobic oxidation of methane (AOM) and trace methane oxidation (TMO) was investigated in a freshwater natural gas source. Sediment samples were taken and analyzed for potential electron acceptors coupled to AOM. Long-term incubations with 13C-labeled CH4 (13CH4) and different electron acceptors showed that both AOM and TMO occurred. In most conditions, 13C-labeled CO2 (13CO2) simultaneously increased with methane formation, which is typical for TMO. In the presence of nitrate, neither methane formation nor methane oxidation occurred. Net AOM was measured only with sulfate as electron acceptor. Here, sulfide production occurred simultaneously with 13CO2 production and no methanogenesis occurred, excluding TMO as a possible source for 13CO2 production from 13CH4. Archaeal 16S rRNA gene analysis showed the highest presence of ANME-2a/b (ANaerobic MEthane oxidizing archaea) and AAA (AOM Associated Archaea) sequences in the incubations with methane and sulfate as compared with only methane addition. Higher abundance of ANME-2a/b in incubations with methane and sulfate as compared with only sulfate addition was shown by qPCR analysis. Bacterial 16S rRNA gene analysis showed the presence of sulfate-reducing bacteria belonging to SEEP-SRB1. This is the first report that explicitly shows that AOM is associated with sulfate reduction in an enrichment culture of ANME-2a/b and AAA methanotrophs and SEEP-SRB1 sulfate reducers from a low-saline environment. PMID:26636551

Methane hydrates and contemporary climate change

USGS Publications Warehouse

Ruppel, Carolyn D.

2011-01-01

As the evidence for warming climate became better established in the latter part of the 20th century (IPCC 2001), some scientists raised the alarm that large quantities of methane (CH4) might be liberated by widespread destabilization of climate-sensitive gas hydrate deposits trapped in marine and permafrost-associated sediments (Bohannon 2008, Krey et al. 2009, Mascarelli 2009). Even if only a fraction of the liberated CH4 were to reach the atmosphere, the potency of CH4 as a greenhouse gas (GHG) and the persistence of its oxidative product (CO2) heightened concerns that gas hydrate dissociation could represent a slow tipping point (Archer et al. 2009) for Earth's contemporary period of climate change.

Fast Abiotic Production of Methane at Temperatures Below 100°C

NASA Astrophysics Data System (ADS)

Etiope, G.; Ionescu, A.

2015-12-01

Fischer-Tropsch Type (FTT) reactions, e.g., the Sabatier synthesis between H2 and CO2, are considered a main source of abiotic methane on Earth and likely on other planets. Several laboratory FTT experiments demonstrated abiotic CH4 production at temperatures above 200°C, by using Fe, Ni or Cr catalysts, simulating hydrothermal conditions in peridotite-hosted systems in mid-ocean ridges. Nevertheless, at least on laboratory experiment time-scale, Fe-Ni-Cr catalysts do not support CH4 generation at T<100°C, such as those of land-based serpentinization systems. We have recently reported rapid production of considerable amounts of CH4 (>800 ppmv in 155 mL bottles after 1 day) via Sabatier reaction at 90, 50 and 25°C, using small concentrations of non-pretreated ruthenium (Ru) equivalent to those occurring in chromitites in continental ultramafic rocks (Etiope & Ionescu, 2014; Geofluids, doi:10.1111/gfl.12106). We have repeated the experiments by using 13C-enriched CO2 and we confirm fast production of CH4at percentage levels. The experiments performed so far show that: 1. considerable amounts of CH4can be produced in dry conditions below 100°C with small quantities of Ru; 2. under the same experimental conditions (<100°C), Fe, Ni and Cr oxides do not produce CH4; 3. low T Sabatier reaction can produce CH4 with a large C isotope fractionation between CO2 and CH4, leading to relatively " light" (13C-depleted) CH4, resembling microbial gas; 4. the CO2-CH4isotope separation decreases over time and by increasing the temperature; 5. minor amounts of C2-C6hydrocarbons are also generated. Our laboratory data are compatible with the isotopic patterns of CH4 naturally occurring in land-based seeps and springs. Our experiments suggest that Ru-enriched chromitites could potentially generate CH4 at low T. Since Ru is reported in Martian meteorites, low T abiotic CH4 production on Mars via Sabatier reaction cannot be excluded (Etiope et al. 2013, Icarus, 224, 276-285).

Electronically Strongly Coupled Divinylheterocyclic-Bridged Diruthenium Complexes.

PubMed

Pfaff, Ulrike; Hildebrandt, Alexander; Korb, Marcus; Oßwald, Steffen; Linseis, Michael; Schreiter, Katja; Spange, Stefan; Winter, Rainer F; Lang, Heinrich

2016-01-11

Complexes [{Ru(CO)Cl(PiPr3 )2 }2 (μ-2,5-(CH-CH)2 -(c) C4 H2 E] (E=NR; R=C6 H4 -4-NMe2 (10 a), C6 H4 -4-OMe (10 b), C6 H4 -4-Me (10 c), C6 H5 (10 d), C6 H4 -4-CO2 Et (10 e), C6 H4 -4-NO2 (10 f), C6 H3 -3,5-(CF3 )2 (10 g), CH3 (11); E=O (12), S (13)) are discussed. The solid state structures of four alkynes and two complexes are reported. (Spectro)electrochemical studies show a moderate influence of the nature of the heteroatom and the electron-donating or -withdrawing substituents R in 10 a-g on the electrochemical and spectroscopic properties. The CVs display two consecutive one-electron redox events with ΔE°'=350-495 mV. A linear relationship between ΔE°' and the σp Hammett constant for 10 a-f was found. IR, UV/Vis/NIR and EPR studies for 10(+) -13(+) confirm full charge delocalization over the {Ru}CH-CH-heterocycle-CH-CH{Ru} backbone, classifying them as Class III systems according to the Robin and Day classification. DFT-optimized structures of the neutral complexes agree well with the experimental ones and provide insight into the structural consequences of stepwise oxidations. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Formation, Structure and Properties of Boron Nitride Fibers from Polymer Precursors

DTIC Science & Technology

1992-02-25

conversion, have been demonstrated in this study. Poly(ethylene oxide) (PEO), poly(N-vinyl-2-pyrrolidinone) ( PVP ), and poly(methyl methacrylate) (PMMA) were...vinylpyrrolidinone ( PVP , Mw = 360,000). A 100 ml reaction flask with teflon boiling chips and a 100 ml receiving flask were used on a high boiling distilling...CH 3 OBO) 3 : B(OH)3 Predicted 2 Experiment Experiment, 1 wt% PVP 2:1 47.8 mole% CH 3 OH 39.6 mole% CH 3OH 35.2 mole% CH3 OH 3:1 47.8 - 35.5 4:1 47.8