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.

Continuous Measurement of Methane Ebullition Flux from a Northern Peatland using a Fast Methane Analyzer

NASA Astrophysics Data System (ADS)

Zhongjie, Y.; Schafer, K. V.; Slater, L. D.; Varner, R. K.; Amante, J.; Comas, X.; Reeve, A. S.; Alcivar, W.; Gonzalez, D.

2012-12-01

Northern peatlands are an important source of methane (CH4) release to the atmosphere, estimated at between 20 and 50 Tg/yr. Recent work on CH4 emissions from peatlands has demonstrated that ebullition can be a more important emission pathway than previously assumed. However, accurate quantification of the atmospheric CH4 burden due to ebullition is still very limited because ebullition exhibits high spatiotemporal variability such that sudden episodic events are difficult to capture and quantify with existing experimental methods. We have initiated a novel measurement program to better quantify the spatiotemporal variability in CH4 flux in peatlands, and to examine potential effects of vegetation and environmental factors, e.g. atmospheric pressure, water table, etc on these releases. A flow-through system was designed, consisting of a closed static chamber and a fast methane analyzer (FMA) (LI-COR model 7700) that has been employed at both the field and laboratory scale. The CH4 concentration in the air flowing through the chamber is continuously measured by the analyzer and used to reconstruct continuous CH4 emission fluxes. The high sampling rate of the FMA makes it sensitive to both ebullition and diffusion of gaseous CH4, capturing short duration, episodic ebullition fluxes. Non-steady static chamber measurements were also conducted to cross-validate the continuous measurements. Results acquired during summer 2011 show that episodic ebullition occurred more frequently at the pool site where previous studies indicate extensive wood layers at depth and the vegetation was a mix of Sphagnum and wooded heath. During a 3 day period of continuous measurements captured the passage of a tropical storm Irene, where short term episodic releases of CH4, ranging from 113 mg CH4/m2/d to 202 mg CH4/m2/d, were observed at the time of lowest atmospheric pressure, providing new evidence that atmospheric pressure is an important factor to controlling CH4 ebullition from peatlands. While traditional techniques, e.g. static chamber measurement can only occasionally detect the occurrence of ebullition, the continuous measurement by using a flow-through system is able to resolve spatiotemporal complexity of episodic CH4 ebullition events. These continuous CH4 measurements provide new insights into the timing of CH4 ebullition from peatlands to the atmosphere as climate changes and the role of environmental variables in regulating these CH4 releases.

LIF measurements and chemical kinetic analysis of methylidyne formation in high-pressure counter-flow partially premixed and non-premixed flames

NASA Astrophysics Data System (ADS)

Naik, S. V.; Laurendeau, N. M.

2004-11-01

We report quantitative, spatially resolved, linear laser-induced fluorescence (LIF) measurements of methylidyne concentration ([CH]) in laminar, methane air, counter-flow partially premixed and non-premixed flames using excitation near 431.5 nm in the A X (0,0) band. For partially premixed flames, fuel-side equivalence ratios (ϕB) of 1.45, 1.6 and 2.0 are studied at pressures of 1, 3, 6, 9 and 12 atm. For non-premixed flames, the fuel-side mixture consists of 25% CH4 and 75% N2; measurements are obtained at pressures of 1, 2, 3, 4, 5, 6, 9 and 12 atm. The quantitative CH measurements are compared with predictions from an opposed-flow flame code utilizing two GRI chemical kinetic mechanisms (versions 2.11 and 3.0). LIF measurements of [CH] are corrected for variations in the quenching rate coefficient by using major species concentrations and temperatures generated by the code along with suitable quenching cross sections for CH available from the literature. A pathway analysis provides relative contributions from important elementary reactions to the total amount of CH produced at various pressures. Key reactions controlling peak CH concentrations are also identified by using a sensitivity analysis. For the partially premixed flames, measured CH profiles are reproduced reasonably well by GRI 3.0, although some quantitative disagreement exists at all pressures. Two CH radical peaks are observed for ϕB=1.45 and ϕB=1.6 at pressures above 3 atm. Peak CH concentrations for the non-premixed flames are significantly underpredicted by GRI 3.0. The latter agrees with previously reported NO concentrations, which are also underpredicted in these same high-pressure counter-flow diffusion flames.

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.

Kinetics and mechanism studies of switching and association reactions involving Na + -ligand complexes

NASA Astrophysics Data System (ADS)

Yang, X.; Castleman, A. W., Jr.

1990-08-01

The kinetics and mechanisms of the reactions of Na+ṡ(X)n=0-3, X=water, ammonia, and methanol with CH3CN, CH3COCH3, CH3CHO, CH3COOH, CH3COOCH3, NH3, CH3OH, and CH3-O-C2H4-O-CH3(DMOE) were studied at ambient temperature under different pressures. All of the switching (substitution) reactions proceed at near-collision rate and show little dependence on the flow tube pressure, the nature and size of the ligand, or the type of core ions. Interestingly, all of the measured rate constants agree well with predictions based on the parametrized trajectory calculations of Su and Chesnavich [J. Chem. Phys. 76, 5183 (1982)]. The reactions of the bare sodium ion with all neutrals proceed via a three-body association mechanism and the measured rate constants cover a large range from a slow association reaction with NH3, to a near-collision rate with DMOE. The lifetimes and the dissociation rate constants of the intermediate complexes deduced using the parametrized trajectory results, combined with the experimentally determined rates, compare fairly well with predictions based on RRKM theory. The calculations also account for the large isotope effect observed for the clustering of ND3 and NH3 to Na+.

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.

Selective methane chlorination to methyl chloride by zeolite Y-based catalysts

NASA Astrophysics Data System (ADS)

Joo, Hyeonho; Kim, Daeho; Lim, Kwang Soo; Choi, Yong Nam; Na, Kyungsu

2018-03-01

The CH4 chlorination over Y zeolites was investigated to produce CH3Cl in a high yield. Three different catalytic systems based on Y zeolite were tested for enhancement of CH4 conversion and CH3Cl selectivity: (i) HY zeolites in H+-form having various Si/Al ratios, (ii) Pt/HY zeolites supporting Pt metal nanoparticles, (iii) Pt/NaY zeolites in Na+-form supporting Pt metal nanoparticles. The reaction was carried out using the gas mixture of CH4 and Cl2 with the respective flow rates of 15 and 10 mL min-1 at 300-350 °C using a fixed-bed reactor under a continuous gas flow condition (gas hourly space velocity = 3000 mL g-1 h-1). Above the reaction temperature of 300 °C, the CH4 chlorination is spontaneous even in the absence of catalyst, achieving 23.6% of CH4 conversion with 73.4% of CH3Cl selectivity. Under sufficient supplement of thermal energy, Cl2 molecules can be dissociated to two chlorine radicals, which triggered the C-H bond activation of CH4 molecule and thereby various chlorinated methane products (i.e., CH3Cl, CH2Cl2, CHCl3, CCl4) could be produced. When the catalysts were used under the same reaction condition, enhancement in the CH4 conversion was observed. The Pt-free HY zeolite series with varied Si/Al ratios gave around 27% of CH4 conversion, but there was a slight decrease in CH3Cl selectivity with about 64%. Despite the difference in acidity of HY zeolites having different Si/Al ratios, no prominent effect of the Si/Al ratios on the catalytic performance was observed. This suggests that the catalytic contribution of HY zeolites under the present reaction condition is not strong enough to overcome the spontaneous CH4 chlorination. When the Pt/HY zeolite catalysts were used, the CH4 conversion reached further up to 30% but the CH3Cl selectivity decreased to 60%. Such an enhancement of CH4 conversion could be attributed to the strong catalytic activity of HY and Pt/HY zeolite catalysts. However, both catalysts induced the radical cleavage of Cl2 more favorably, which ultimately decreased the CH3Cl selectivity. Such trade-off relationship between CH4 conversion and CH3Cl selectivity can be slightly broken by using Pt/NaY zeolite catalyst that is known to possess Frustrated Lewis Pairs (FLP) that are very useful for ionic cleavage of H2 to H+ and H-. Similarly, in the present work, Pt/NaY(FLP) catalysts enhanced the CH4 conversion while keeping the CH3Cl selectivity as compared to the Pt/HY zeolite catalysts.

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.

Mechanism of high growth rate for diamond-like carbon films synthesized by helicon wave plasma chemical vapor deposition

NASA Astrophysics Data System (ADS)

Peiyu, JI; Jun, YU; Tianyuan, HUANG; Chenggang, JIN; Yan, YANG; Lanjian, ZHUGE; Xuemei, WU

2018-02-01

A high growth rate fabrication of diamond-like carbon (DLC) films at room temperature was achieved by helicon wave plasma chemical vapor deposition (HWP-CVD) using Ar/CH4 gas mixtures. The microstructure and morphology of the films were characterized by Raman spectroscopy and scanning electron microscopy. The diagnosis of plasma excited by a helicon wave was measured by optical emission spectroscopy and a Langmuir probe. The mechanism of high growth rate fabrication for DLC films by HWP-CVD has been discussed. The growth rate of the DLC films reaches a maximum value of 54 μm h-1 at the CH4 flow rate of 85 sccm, which is attributed to the higher plasma density during the helicon wave plasma discharge. The CH and H α radicals play an important role in the growth of DLC films. The results show that the H α radicals are beneficial to the formation and stabilization of C=C bond from sp2 to sp3.

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.

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.

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.

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.

A Pilot Study of Ion - Molecule Reactions at Temperatures Relevant to the Atmosphere of Titan.

PubMed

Zymak, Illia; Žabka, Ján; Polášek, Miroslav; Španěl, Patrik; Smith, David

2016-11-01

Reliable theoretical models of the chemical kinetics of the ionosphere of Saturn's moon, Titan, is highly dependent on the precision of the rates of the reactions of ambient ions with hydrocarbon molecules at relevant temperatures. A Variable Temperature Selected Ions Flow Tube technique, which has been developed primarily to study these reactions at temperatures within the range of 200-330 K, is briefly described. The flow tube temperature regulation system and the thermalisation of ions are also discussed. Preliminary studies of two reactions have been carried out to check the reliability and efficacy of kinetics measurements: (i) Rate constants of the reaction of CH 3 + ions with molecular oxygen were measured at different temperatures, which indicate values in agreement with previous ion cyclotron resonance measurements ostensibly made at 300 K. (ii) Formation of CH 3 + ions in the reaction of N 2 + ions with CH 4 molecules were studied at temperatures within the range 240-310 K which showed a small but statistically significant decrease of the ratio of product CH 3 + ions to reactant N 2 + ions with reaction temperature.

Methane Emissions from the Inland Waters of Alaska

NASA Astrophysics Data System (ADS)

Striegl, R. G.; Butman, D. E.; Stackpoole, S. M.; Dornblaser, M.

2017-12-01

Inland waters at high latitudes generally emit methane (CH4) continuously to the atmosphere during the open water season and build-up CH4 under ice during winter that is released over a short period following ice melt. Landscape position, stream and river size, water source, and turbulence created by water flow largely control CH4 emissions from streams and rivers. Organic carbon sources for CH4 production in lakes vary widely among lakes and landscapes and include hydrologic inputs from terrestrial sources, releases from permafrost thaw (thermokarst), and autochthonous inputs from aquatic macrophytes and algae. Lake emissions are therefore controlled by the balance between within-lake CH4 production and consumption, surface turbulence at the water-air interface, and CH4 ebullition. This creates a complex range of conditions that are difficult to characterize, where dissolved CH4 concentrations may vary by up to 4 orders of magnitude among lakes and/or within a single lake over an annual seasonal cycle. Moreover, large inputs of organic matter from permafrost thaw or other sources commonly result in high rates of bubble production and ebullition from some lakes, while other lakes have negligible ebullition. We quantified water surface areas and estimated CH4 emission rates for lakes, streams and rivers for the six major hydrologic regions of Alaska and determined that they collectively emit about 0.124 Tg C per year as CH4 to the atmosphere. Lake emissions comprise about 75% of the total. When adjusted for total land surface area in Alaska, our lake emission estimate is substantially smaller than previous global estimates for inland waters north of 50 degrees North latitude. We attribute this to incorporation of results that cover a broad range of lake conditions in interior Alaska and to new data from lakes in southwest Alaska that have very low CH4 concentration but very large surface area.

Synergistic effects of plasma-catalyst interactions for CH4 activation.

PubMed

Kim, Jongsik; Go, David B; Hicks, Jason C

2017-05-24

The elucidation of catalyst surface-plasma interactions is a challenging endeavor and therefore requires thorough and rigorous assessment of the reaction dynamics on the catalyst in the plasma environment. The first step in quantifying and defining catalyst-plasma interactions is a detailed kinetic study that can be used to verify appropriate reaction conditions for comparison and to discover any unexpected behavior of plasma-assisted reactions that might prevent direct comparison. In this paper, we provide a kinetic evaluation of CH 4 activation in a dielectric barrier discharge plasma in order to quantify plasma-catalyst interactions via kinetic parameters. The dry reforming of CH 4 with CO 2 was studied as a model reaction using Ni supported on γ-Al 2 O 3 at temperatures of 790-890 K under atmospheric pressure, where the partial pressures of CH 4 (or CO 2 ) were varied over a range of ≤25.3 kPa. Reaction performance was monitored by varying gas hourly space velocity, plasma power, bulk gas temperature, and reactant concentration. After correcting for gas-phase plasma reactions, a linear relationship was observed in the log of the measured rate constant with respect to reciprocal power (1/power). Although thermal catalysis displays typical Arrhenius behavior for this reaction, plasma-assisted catalysis occurs from a complex mixture of sources and shows non-Arrhenius behavior. However, an energy barrier was obtained from the relationship between the reaction rate constant and input power to exhibit ≤∼20 kJ mol -1 (compared to ∼70 kJ mol -1 for thermal catalysis). Of additional importance, the energy barriers measured during plasma-assisted catalysis were relatively consistent with respect to variations in total flow rates, types of diluent, or bulk reaction temperature. These experimental results suggest that plasma-generated vibrationally-excited CH 4 favorably interacts with Ni sites at elevated temperatures, which helps reduce the energy barrier required to activate CH 4 and enhance CH 4 reforming rates.

Assessment of Pneumatic Controller Emission Measurements ...

EPA Pesticide Factsheets

Oil and Natural Gas (ONG) production facilities have the potential to emit greenhouse gases such as methane (CH4) and other hydrocarbons (HCs) to the atmosphere. ONG production sites have multiple emission sources including storage tank venting, enclosed combustion devices, engine exhaust, pneumatic controllers and uncontrolled leaks. Accounting for up to 37.8 percent of CH4 emissions, pneumatic controllers are one of the most significant sources of CH4 in ONG production field operations. Recent measurement studies used the only commercially-available high volume sampling (HVS) technology (Bacharach Hi Flow Sampler, Bacharach, Inc., New Kensington, PA) to quantify CH4 emission rates of pneumatic devices on ONG production pads and compare to inventory estimates. Other studies indicate that this HVS may malfunction, causing underestimates of emissions in certain scenarios encountered in ONG production and should not be used for some sources such as heavy emissions from condensate storage tanks. The HVS malfunction can occur on relatively large emissions, where the measured leak concentrations exceed 5%, and is ascribed to a sensor transition failure in the instrument. The HVS malfunction is believed to be exacerbated by several factors (large emission rates, amount of non-CH4 HCs in the emission stream, non-optimal HVS calibration frequency, firmware, and emission measurement coupling geometries). The degree to which HVS measurements of emissions from pneumatic co

Experimental analysis of thermo-acoustic instabilities in a generic gas turbine combustor by phase-correlated PIV, chemiluminescence, and laser Raman scattering measurements

NASA Astrophysics Data System (ADS)

Arndt, Christoph M.; Severin, Michael; Dem, Claudiu; Stöhr, Michael; Steinberg, Adam M.; Meier, Wolfgang

2015-04-01

A gas turbine model combustor for partially premixed swirl flames was equipped with an optical combustion chamber and operated with CH4 and air at atmospheric pressure. The burner consisted of two concentric nozzles for separately controlled air flows and a ring of holes 12 mm upstream of the nozzle exits for fuel injection. The flame described here had a thermal power of 25 kW, a global equivalence ratio of 0.7, and exhibited thermo-acoustic instabilities at a frequency of approximately 400 Hz. The phase-dependent variations in the flame shape and relative heat release rate were determined by OH* chemiluminescence imaging; the flow velocities by stereoscopic particle image velocimetry (PIV); and the major species concentrations, mixture fraction, and temperature by laser Raman scattering. The PIV measurements showed that the flow field performed a "pumping" mode with varying inflow velocities and extent of the inner recirculation zone, triggered by the pressure variations in the combustion chamber. The flow field oscillations were accompanied by variations in the mixture fraction in the inflow region and at the flame root, which in turn were mainly caused by the variations in the CH4 concentration. The mean phase-dependent changes in the fluxes of CH4 and N2 through cross-sectional planes of the combustion chamber at different heights above the nozzle were estimated by combining the PIV and Raman data. The results revealed a periodic variation in the CH4 flux by more than 150 % in relation to the mean value, due to the combined influence of the oscillating flow velocity, density variations, and CH4 concentration. Based on the experimental results, the feedback mechanism of the thermo-acoustic pulsations could be identified as a periodic fluctuation of the equivalence ratio and fuel mass flow together with a convective delay for the transport of fuel from the fuel injector to the flame zone. The combustor and the measured data are well suited for the validation of numerical combustion simulations.

Diagnostic studies of H2 Ar N2 microwave plasmas containing methane or methanol using tunable infrared diode laser absorption spectroscopy

NASA Astrophysics Data System (ADS)

Hempel, F.; Davies, P. B.; Loffhagen, D.; Mechold, L.; Röpcke, J.

2003-11-01

Tunable infrared diode laser absorption spectroscopy has been used to detect the methyl radical and nine stable molecules, CH4, CH3OH, C2H2, C2H4, C2H6, NH3, HCN, CH2O and C2N2, in H2-Ar-N2 microwave plasmas containing up to 7% of methane or methanol, under both flowing and static conditions. The degree of dissociation of the hydrocarbon precursor molecules varied between 20% and 97%. The methyl radical concentration was found to be in the range 1012-1013 molecules cm-3. By analysing the temporal development of the molecular concentrations under static conditions it was found that HCN and NH3 are the final products of plasma chemical conversion. The fragmentation rates of methane and methanol (RF(CH4) = (2-7) × 1015 molecules J-1, RF(CH3OH) = (6-9) × 1015 molecules J-1) and the respective conversion rates to methane, hydrogen cyanide and ammonia (RCmax(CH4) = 1.2 × 1015 molecules J-1, RCmax(HCN) = 1.3 × 1015 molecules J-1, RCmax(NH3) = 1 × 1014 molecules J-1) have been determined for different hydrogen to nitrogen concentration ratios. An extensive model of the chemical reactions involved in the H2-N2-Ar-CH4 plasma has been developed. Model calculations were performed by including 22 species, 145 chemical reactions and appropriate electron impact dissociation rate coefficients. The results of the model calculations showed satisfactory agreement between calculated and measured concentrations. The most likely main chemical pathways involved in these plasmas are discussed and an appropriate reaction scheme is proposed.

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

Methane fluxes along a salinity gradient on a restored salt marsh, Harpswell, ME

NASA Astrophysics Data System (ADS)

Gunn, Cailene; Johnson, Beverly, ,, Dr.; Dostie, Phil; Bohlen, Curtis; Craig, Matthew

2016-04-01

This study functions as a pilot project to understand the relationship between salinity and methane emissions on a recently restored salt marsh in Casco Bay, Maine. Salt marshes are dynamic and highly productive ecosystems that provide a multitude of ecosystem services including nutrient filtration, storm-water buffering and carbon sequestration. These ecosystems are highly susceptible to anthropogenic alteration. The emplacement of causeways and narrow culverts, restricts tidal flow and leads to loss of healthy salinity gradients. Consequently, numerous salt marshes have experienced increases in freshwater vegetation growth as a result of coastal population expansion. Recent restoration efforts on Long Marsh, Harpswell, ME replaced a severely undersized culvert with a larger one in February, 2014. The salinity gradient has since been restored along much of the marsh, and freshwater vegetation that encroached on the marsh platform has died back. Vegetation and salinity are key indicators and drivers of CH4 emissions on salt marshes. Using static gas chambers, we quantified CH4 fluxes along two transects at five diverse sites ranging from healthy marsh (salinity of 27 to 31 psu) with Spartina vegetation, to regions invaded by Typha and other freshwater vegetation (salinity of 0 to 4 psu). Sampling was executed in the months of July, August and October. CH4 concentrations were determined using a gas chromatograph with a flame-ionization detector. Preliminary findings suggest reintroduction of healthy tidal flows into the marsh inhibits CH4 production, where the lowest fluxes with least variability were observed at the most saline sites with Spartina vegetation. The largest range of CH4 fluxes exhibited emissions from 0.75 μmol CH4/m2/hr to 518.4 μmol CH4/m2/hr at the Typha dominated sites from July to October. Fluxes at the saltwater and brackish regions were far less variable with ranges from 0.94 μmol CH4/m2/hr to 8.2 μmol CH4/m2/hr and 2.6 to 9.5 μmol CH4/m2/hr, respectively. The transitional sites exhibited ranges from 1.2 μmol CH4/m2/hr to 16.8 μmol CH4/m2/hr. For all sites, lowest fluxes were observed during the month of October, suggesting seasonal influence on CH4 emissions. These data will be complimented by sediment analyses at each site providing δC and % organic carbon using isotope-ratio mass spectrometry, as well as bulk density and rates of decomposition using a tea bag index.

Rationale of lymph node dissection for breast cancer--from the viewpoint of analysis of axillary lymphatic flow using activated carbon particle CH40.

PubMed

Sawai, K; Hagiwara, A; Shimotsuma, M; Sakakibara, T; Imanishi, T; Takemoto, Y; Takahashi, T

1996-03-01

In order to rationalize lymph node dissection for breast cancer, we reviewed regional lymphatic flow from the mesial and outer half of the breast using intra-tumoral injection of activated carbon particles (CH40). Seventy patients with breast cancer were included in this study. Cancers were located in the mesial half of the breast in 25 cases and in its outer half in 41 cases. Since regional lymph nodes were blackened by CH40, lymph node dissection was performed easily and small lymph nodes could be readily examined. The average number of resected nodes in each case was 29.4. When CH40 was injected into the mesial half of the breast, the rates of blackened nodes (number of macroscopically blackened lymph nodes/number of total removed lymph nodes) in the stations were 46.6% (No. 1a), 41.4% (No. 1b), 62.1% (No. 1c), 61.8% (No. 2), 69.2.% (No. 2h), and 65.6% (No. 3). When CH40 was injected into outer half of the breast, those were 62.0% (No. 1a), 64.3% (No. 1b), 68.7% (No. 1c), 75.3% (No. 2), and 67.8% (No. 2h). Regardless of tumor location, the rates of blackened nodes were high in each station. In conclusion, regardless of tumor location it is impossible to determine the level of axillary dissection for breast cancer. It should be all or nothing.

Effect of temperature on continuous dry fermentation of swine manure.

PubMed

Deng, Liangwei; Chen, Chuang; Zheng, Dan; Yang, Hongnan; Liu, Yi; Chen, Ziai

2016-07-15

Laboratory-scale experiments were performed on the dry digestion of solid swine manure in a semi-continuous mode using 4.5 L down plug-flow anaerobic reactors with an organic loading rate of 3.46 kg volatile solids (VS) m(-3) d(-1) to evaluate the effects of temperature (15, 25 and 35 °C). At 15 °C, biogas production was the poorest due to organic overload and acidification, with a methane yield of 0.036 L CH4 g(-1) VS added and a volumetric methane production rate of 0.125 L CH4 L(-1) d(-1). The methane yield and volumetric methane production rate at 25 °C (0.226 L CH4 g(-1) VS added and 0.783 L CH4 L(-1) d(-1), respectively) were 6.24 times higher than those at 15 °C. However, the methane yield (0.237 L CH4 g(-1) VS added) and the volumetric methane production rate (0.821 L CH4 L(-1) d(-1)) at 35 °C were only 4.86% higher than those at 25 °C, which indicated similar results were obtained at 25 °C and 35 °C. The lower biogas production at 35 °C in dry digestion compared with that in wet digestion could be attributed to ammonia inhibition. For a single pig farm, digestion of solid manure is accomplished in small-scale domestic or small-farm bioreactors, for which operating temperatures of 35 °C are sometimes difficult to achieve. Considering biogas production, ammonia inhibition and net energy recovery, an optimum temperature for dry digestion of solid swine manure is 25 °C. Copyright © 2016 Elsevier Ltd. All rights reserved.

Interaction with a kinesin-2 tail propels choline acetyltransferase flow towards synapse

PubMed Central

Sadananda, Aparna; Hamid, Runa; Doodhi, Harinath; Ghosal, Debnath; Girotra, Mukul; Jana, Swadhin Chandra; Ray, Krishanu

2012-01-01

Bulk flow constitutes a substantial part of the slow transport of soluble proteins in axons. Though the underlying mechanism is unclear, evidences indicate that intermittent, kinesin based movement of large protein-aggregates aids this process. Choline acetyl-transferase (ChAT), a soluble enzyme catalyzing acetylcholine synthesis, propagates towards synapse at an intermediate, slow rate. The presynaptic enrichment of ChAT requires heterotrimeric kinesin-2, comprising KLP64D, KLP68D and DmKAP, in Drosophila. Here, we show that the bulk flow of a recombinant Green Fluorescent Protein-tagged ChAT (GFP::ChAT), in Drosophila axons, lacks particulate features. It occurs for a brief period during the larval stages. In addition, both the endogenous ChAT and GFP::ChAT directly bind to the KLP64D tail, which is essential for the GFP::ChAT entry and anterograde flow in axon. These evidences suggest that a direct interaction with motor proteins could regulate the bulk flow of soluble proteins, and thus establish their asymmetric distribution. PMID:22486887

Investigating the Hydro-geochemical Impact of Fugitive Methane on Groundwater: The Borden Aquifer Controlled Release Study

NASA Astrophysics Data System (ADS)

Cahill, A. G.; Parker, B. L.; Cherry, J. A.; Mayer, K. U.; Mayer, B.; Ryan, C.

2014-12-01

Shale gas development by hydraulic fracturing is believed by many to have the potential to transform the world's energy economy. The propensity of this technique to cause significant environmental impact is strongly contested and lacks evidence. Fugitive methane (CH4), potentially mobilized during well drilling, the complex extraction process and/or leaking well seals over time is arguably the greatest concern. Advanced understanding of CH4 mobility and fate in the subsurface is needed in order to assess risks, design suitable monitoring systems and gain public trust. Currently knowledge on subsurface CH4 mobilization and migration at scales relevant to shale gas development is lacking. Consequently a shallow aquifer controlled CH4 release experiment is being conducted at the Borden aquifer research facility (an unconfined, unconsolidated silicate sand aquifer) in Ontario, Canada. During the experiment, 100 m3 of gas phase CH4 was injected into the saturated zone over approximately 60 days through 2 inclined sparging wells (4.5 and 9 m depth) at rates relevant to natural gas well casing vent flows. The gas mobility and fate is being comprehensively monitored temporally and spatially in both the saturated and unsaturated zones considering; aqueous chemistry (including stable isotopes), soil gas characterization, surface efflux, geophysics (GPR and ERT), real time sensors (total dissolved gas pressure, soil moisture content, CH4 and CO2), mineralogical and microbiological characterization before, during and after injection. An overview of this unique study will be given including experimental design, monitoring system configuration and preliminary results. This multidisciplinary study will provide important insights regarding the mechanisms and rates for shallow CH4 migration, attenuation and water quality impacts that will inform baseline groundwater monitoring programs and retrospective forensic studies.

Investigating the Hydro-geochemical Impact of Fugitive Methane on Groundwater: The Borden Aquifer Controlled Release Study

NASA Astrophysics Data System (ADS)

Cahill, A. G.; Parker, B. L.; Cherry, J. A.; Mayer, K. U.; Mayer, B.; Ryan, C.

2015-12-01

Shale gas development by hydraulic fracturing is believed by many to have the potential to transform the world's energy economy. The propensity of this technique to cause significant environmental impact is strongly contested and lacks evidence. Fugitive methane (CH4), potentially mobilized during well drilling, the complex extraction process and/or leaking well seals over time is arguably the greatest concern. Advanced understanding of CH4 mobility and fate in the subsurface is needed in order to assess risks, design suitable monitoring systems and gain public trust. Currently knowledge on subsurface CH4 mobilization and migration at scales relevant to shale gas development is lacking. Consequently a shallow aquifer controlled CH4 release experiment is being conducted at the Borden aquifer research facility (an unconfined, unconsolidated silicate sand aquifer) in Ontario, Canada. During the experiment, 100 m3 of gas phase CH4 was injected into the saturated zone over approximately 60 days through 2 inclined sparging wells (4.5 and 9 m depth) at rates relevant to natural gas well casing vent flows. The gas mobility and fate is being comprehensively monitored temporally and spatially in both the saturated and unsaturated zones considering; aqueous chemistry (including stable isotopes), soil gas characterization, surface efflux, geophysics (GPR and ERT), real time sensors (total dissolved gas pressure, soil moisture content, CH4 and CO2), mineralogical and microbiological characterization before, during and after injection. An overview of this unique study will be given including experimental design, monitoring system configuration and preliminary results. This multidisciplinary study will provide important insights regarding the mechanisms and rates for shallow CH4 migration, attenuation and water quality impacts that will inform baseline groundwater monitoring programs and retrospective forensic studies.

Microwave plasma enabled synthesis of free standing carbon nanostructures at atmospheric pressure conditions.

PubMed

Bundaleska, N; Tsyganov, D; Dias, A; Felizardo, E; Henriques, J; Dias, F M; Abrashev, M; Kissovski, J; Tatarova, E

2018-05-23

An experimental and theoretical study on microwave (2.45 GHz) plasma enabled assembly of carbon nanostructures, such as multilayer graphene sheets and nanoparticles, was performed. The carbon nanostructures were fabricated at different Ar-CH4 gas mixture composition and flows at atmospheric pressure conditions. The synthesis method is based on decomposition of the carbon-containing precursor (CH4) in the "hot" microwave plasma environment into carbon atoms and molecules, which are further converted into solid carbon nuclei in the "colder" plasma zones. By tailoring of the plasma environment, a controlled synthesis of graphene sheets and diamond-like nanoparticles was achieved. Selective synthesis of graphene flakes was achieved at a microwave power of 1 kW, Ar and methane flow rates of 600 sccm and 2 sccm respectively, while the predominant synthesis of diamond-like nanoparticles was obtained at the same power, but with higher flow rates, i.e. 1000 and 7.5 sccm, respectively. Optical emission spectroscopy was applied to detect the plasma emission related to carbon species from the 'hot' plasma zone and to determine the main plasma parameters. Raman spectroscopy and scanning electron microscopy have been applied to characterize the synthesized nanostructures. A previously developed theoretical model was further updated and employed to understand the mechanism of CH4 decomposition and formation of the main building units, i.e. C and C2, of the carbon nanostructures. An insight into the physical chemistry of carbon nanostructure formation in a high energy density microwave plasma environment is presented.

Impact of fluid injection velocity on CO2 saturation and pore pressure in porous sandstone

NASA Astrophysics Data System (ADS)

Kitamura, Keigo; Honda, Hiroyuki; Takaki, Shinnosuke; Imasato, Mitsunori; Mitani, Yasuhiro

2017-04-01

The elucidation of CO2 behavior in sandstone is an essential issue to understand the fate of injecting CO2 in reservoirs. Injected CO2 invades pore spaces and replaces with resident brine and forms complex two-phase flow with brine. It is considered that this complex CO2 flow arises CO2 saturation (SCO_2)and pore fluid pressure(Pp) and makes various types of CO2 distribution pattern in pore space. The estimation of SCO_2 in the reservoir is one of important task in CCS projects. Fluid pressure (Pp) is also important to estimate the integrity of CO2 reservoir and overlying cap rocks. Generally, elastic waves are used to monitor the changes of SCO_2. Previous experimental and theoretical studies indicated that SCO_2 and Pp are controlled by the fluid velocity (flow rate) of invaded phase. In this study, we conducted the CO2 injection test for Berea sandstone (φ=18.1{%}) under deep CO2 reservoir conditions (confining pressure: 20MPa; temperature: 40 rC). We try to estimate the changes of SCO_2 and Pp with changing CO2 injection rate (FR) from 10 to 5000 μ l/min for Berea sandstone. P-wave velocities (Vp) are also measured during CO2 injection test and used to investigate the relationships between SCO2 and these geophysical parameters. We set three Vp-measurement channels (ch.1, ch2 and ch.3 from the bottom) monitor the CO2 behavior. The result shows step-wise SCO_2 changes with increasing FR from 9 to 25 {%} in low-FR condition (10-500 μ l/min). Vp also shows step wise change from ch1 to ch.3. The lowermost channel (ch.1) indicates that Vp-reduction stops around 4{%} at 10μ m/min condition. However, ch.3 changes slightly from 4{%} at 10 μ l/min to 5{%} at 100 μ l/min. On the other hand, differential Pp (Δ P) dose not shows obvious changes from 10kPa to 30kPa. Over 1000 μ l/min, SCO_2 increases from 35 to 47 {%}. Vp of all channels show slight reductions and Vp-reductions reach constant values as 8{%}, 6{%} and 8{%}, respectively at 5000{}μ l/min. On the other hand, Δ P shows rapid increasing from 50kPa to 500 kPa. It suggests a drastic change of CO2 behavior with injection rate. CO2 flows gently and enlarges SCO_2up to 25 {%} under low FR conditions without arisen Δ P (

On reaction kinetics and atmospheric lifetimes of CF3CFHCF3 and CF3CH2Br

NASA Technical Reports Server (NTRS)

Nelson, D. D., Jr.; Zahniser, M. S.; Kolb, C. E.

1993-01-01

The rate constants for the reaction of the OH radical with CF3CFHCF3 and with CF3CH2Br have been measured as a function of temperature using the discharge flow technique with laser induced fluorescence detection of the OH radicals. The temperature dependent rate coefficients are well described by a simple Arrhenius expression, k(T) = A exp(E/(RT)). For the reaction of OH with CF3CFHCF3 we find A = 3.7 x 10 exp -13 cu cm/molecules/s and E/R = 1615 K; for the reaction of OH with CF3CH2Br we report A = 1.4 x 10 exp -12 cu cm/molecule/s and E/R = 1350 K. These Arrhenius parameters imply rate coefficients at 277 K of 1.09 x 10 exp -15 cu cm/molecule/s for CF3CFHCF3 and 1.06 x 10 exp -14 cu cm/molecule/s for CF3CH2Br. We find atmospheric lifetimes for CF3CFHCH3 and CF3CH2Br of 42 years and 4.1 years, respectively. We also estimate the steady state ozone depletion potential (ODP) of the brominated species relative to CFCl3 as about 0.84 using a semiempirical model.

Nucleation and growth of single layer graphene on electrodeposited Cu by cold wall chemical vapor deposition

NASA Astrophysics Data System (ADS)

Das, Shantanu; Drucker, Jeff

2017-03-01

The nucleation density and average size of graphene crystallites grown using cold wall chemical vapor deposition (CVD) on 4 μm thick Cu films electrodeposited on W substrates can be tuned by varying growth parameters. Growth at a fixed substrate temperature of 1000 °C and total pressure of 700 Torr using Ar, H2 and CH4 mixtures enabled the contribution of total flow rate, CH4:H2 ratio and dilution of the CH4/H2 mixture by Ar to be identified. The largest variation in nucleation density was obtained by varying the CH4:H2 ratio. The observed morphological changes are analogous to those that would be expected if the deposition rate were varied at fixed substrate temperature for physical deposition using thermal evaporation. The graphene crystallite boundary morphology progresses from irregular/jagged through convex hexagonal to regular hexagonal as the effective C deposition rate decreases. This observation suggests that edge diffusion of C atoms along the crystallite boundaries, in addition to H2 etching, may contribute to shape evolution of the graphene crystallites. These results demonstrate that graphene grown using cold wall CVD follows a nucleation and growth mechanism similar to hot wall CVD. As a consequence, the vast knowledge base relevant to hot wall CVD may be exploited for graphene synthesis by the industrially preferable cold wall method.

Gaseous film cooling investigation in a multi-element splash platelet injector

NASA Astrophysics Data System (ADS)

Yin, Liang; Liu, Weiqiang

2018-03-01

Film cooling is an effective technique that protects chamber walls in rocket combustion against chemical attacks and heat fluxes. This study discusses cooling effect in a multi-element GO2/CH4 splash platelet injector. Influence parameters, such as slot height, slot number, percentage of coolant, and injection position on cooling effect, were investigated. GCH4 with 298.15 K was applied as film coolant. In the first step, slot heights of 0.2 and 0.4 mm were compared by applying a constant film mass flow rate. Temperature, CH4 mole fraction distribution, and flow field structure were obtained. The effects of slot number, percentage of coolant, and injection position on wall temperature distribution were then determined. Finally, the reasons for the low cooling efficiency were analyzed. Improvement in the method is proposed to achieve improved cooling effect for splash platelet injectors.

Tractable Chemical Models for CVD of Silicon and Carbon

NASA Technical Reports Server (NTRS)

Blanquet, E.; Gokoglu, S. A.

1993-01-01

Tractable chemical models are validated for the CVD of silicon and carbon. Dilute silane (SiH4) and methane (CH4) in hydrogen are chosen as gaseous precursors. The chemical mechanism for each systems Si and C is deliberately reduced to three reactions in the models: one in the gas phase and two at the surface. The axial-flow CVD reactor utilized in this study has well-characterized flow and thermal fields and provides variable deposition rates in the axial direction. Comparisons between the experimental and calculated deposition rates are made at different pressures and temperatures.

Gaseous fluxes from subsurface flow constructed wetlands for wastewater treatment.

PubMed

Mander, Ulo; Lõhmus, Krista; Teiter, Sille; Nurk, Kaspar; Mauring, Tõnu; Augustin, Jürgen

2005-01-01

We measured nitrous oxide (N2O), dinitrogen (N2), and methane (CH4) fluxes in two constructed wetlands (CW) in Estonia using the closed chamber method and the He-O method in the period from October 2000 to March 2003. Emission rates of N2O-N, N2-N and CH4-C from both CWs varied significantly on a both spatial and temporal scale, ranging from 1 to 2,600, 170 to 130,000, and -1.7 to 87,200 microg m(-2) h(-1) respectively. The average flux of N2O from the microsites in the Kodijärve horizontal subsurface flow (HSSF) CW and Kõo hybrid CW ranged from 27 to 370 and from 72 to 500 microg N2O-N m(-2) h(-1), respectively, whereas the average dinitrogen flux from the microsites in the HSSF CW in Kodijärve was 2-3 magnitudes higher than the N2O flux, ranging from 19,500 to 33,300 microg N2-N m(-2) h(-1). The average methane emissions from the microsites in the Kodijärve HSSF CW and the Kõo hybrid CW ranged from 31 to 12,100 and from 950 to 5,750 microg CH4-C m(-2) h(-1), respectively. The highest emission values for all three gases were observed in the warm period. There was a significant relationship between emission rates and water table depth: CH4 and N2 emission increased and N2O emission decreased when the water table did rise. Although the emission of N2O and CH4 from CWs was found to be relatively high, their global warming potential (GWP) in the time horizon of 100 years is not significant, ranging from 4.5 to 16.3 tonnes of CO2 equivalents per ha per year in Kodijärve and from 12.1 to 17.3 t CO2 equivalents ha(-1) yr(-1) in Kõo.

Biomethanation of poultry litter leachate in UASB reactor coupled with ammonia stripper for enhancement of overall performance.

PubMed

Gangagni Rao, A; Sasi Kanth Reddy, T; Surya Prakash, S; Vanajakshi, J; Joseph, Johny; Jetty, Annapurna; Rajashekhara Reddy, A; Sarma, P N

2008-12-01

In the present study possibility of coupling stripper to remove ammonia to the UASB reactor treating poultry litter leachate was studied to enhance the overall performance of the reactor. UASB reactor with stripper as ammonia inhibition control mechanism exhibited better performance in terms of COD reduction (96%), methane yield (0.26m(3)CH(4)/kg COD reduced), organic loading rate (OLR) (18.5kg COD m(-3)day(-1)) and Hydraulic residence time (HRT) (12h) compared to the UASB reactor without stripper (COD reduction: 92%; methane yield: 0.21m(3)CH(4)/kg COD reduced; OLR: 13.6kg CODm(-3)day(-1); HRT: 16h). The improved performance was due to the reduction of total ammonia nitrogen (TAN) and free ammonia nitrogen (FAN) in the range of 75-95% and 80-95%, respectively by the use of stripper. G/L (air flow rate/poultry leachate flow rate) in the range of 60-70 and HRT in the range of 7-9min are found to be optimum parameters for the operation of the stripper.

Illuminating Geochemical Controls of Methane Oxidation Along a Gradient of Permafrost Thaw

NASA Astrophysics Data System (ADS)

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

2017-12-01

Increases in annual mean temperature in the subarctic have accelerated the thaw of organic-rich permafrost peatlands, exacerbating methane (CH4) production from microbial decomposition of peat deposits and subsequent CH4 emissions. Methanotrophic bacteria may oxidize/consume upwards of 90% of produced CH4 in some settings, pending substrate availability and environmental conditions. Redox chemistry may also control the rate of CH4 oxidation in thawing permafrost areas, particularly redox potential (Eh) and the availability of oxygen (O2) and other terminal electron receptors. We investigated potential CH4 oxidation rates across a permafrost thaw gradient in Stordalen Mire (68°21'N,18°49'E) near Abisko, Sweden. Methane oxidation rates for sites from thawing and collapsed palsa, semi-wet Sphagnum, and open-water sedge sites were determined through laboratory incubations. Peat cores were extracted from two depths at each site and incubated at in situ temperatures and CH4 concentrations. Headspace samples were collected over a 48-hour period and analyzed for CH4 concentration using flame ionization detection gas chromatography (GC-FID). Dissolved O2, Eh, and dissolved CH4 were measured in sites with porewater. Oxidation rates ranged from <0.1 to 19 μg of CH4 per gram of dry biomass per day. Eh remained positive (41.6 to 316.8 mV) with available dissolved O2 (0.3 - 5.2 mg/L) in all measurement locations down to 20cm, indicating in situ aerobic CH4 oxidation is viable across these environments. Potential CH4 oxidation rates increased with increasing dissolved CH4 concentration. Highest potential CH4 oxidation rates were found in open-water sedge sites. Eh and dissolved O2 were lowest at these sites, suggesting that methanotrophs with low-O2 demand may populate sedge areas. Furthermore, potential CH4 oxidation rates were higher at depth than at the surface in thawing palsa, suggesting CH4 oxidation may mitigate CH4 production triggered by warming in these actively thawing environments. Forthcoming elemental analyses of peat and pore water will further elucidate trends and geochemical controls of CH4 oxidation rates in thawing permafrost areas.

Solid Fuel Burning in Steady, Strained, Premixed Flow Fields: The Graphite/Air/Methane System

NASA Technical Reports Server (NTRS)

Egolfopoulos, Fokion N.; Wu, Ming-Shin (Technical Monitor)

2000-01-01

A detailed numerical investigation was conducted on the simultaneous burning of laminar premixed CH4/air flames and solid graphite in a stagnation flow configuration. The graphite and methane were chosen for this model, given that they are practical fuels and their chemical kinetics are considered as the most reliable ones among solid and hydrocarbon fuels, respectively. The simulation was performed by solving the quasi-one-dimensional equations of mass, momentum, energy, and species. The GRI 2.1 scheme was used for the gas-phase kinetics, while the heterogeneous kinetics were described by a six-step mechanism including stable and radical species. The effects of the graphite surface temperature, the gas-phase equivalence ratio, and the aerodynamic strain rate on the graphite burning rate and NO, production and destruction mechanisms were assessed. Results indicate that as the graphite temperature increases, its burning rate as well as the NO, concentration increase. Furthermore, it was found that by increasing the strain rate, the graphite burning rate increases as a result of the augmented supply of the gas-phase reactants towards the surface, while the NO, concentration decreases as a result of the reduced residence time. The effect of the equivalence ratio on both the graphite burning rate and NO, concentration was found to be non-monotonic and strongly dependent on the graphite temperature. Comparisons between results obtained for a graphite and a chemically inert surface revealed that the chemical activity of the graphite surface can result to the reduction of NO through reactions of the CH3, CH2, CH, and N radicals with NO.

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.

Rate constant for the reaction of atomic chlorine with methane

NASA Technical Reports Server (NTRS)

Lin, C. L.; Leu, M. T.; Demore, W. B.

1978-01-01

The rate constant and temperature dependence of the Cl + CH4 reaction have been investigated by the techniques of competitive chlorination of CH4/C2H6 mixtures and by discharge-flow/mass spectroscopy. The objectives were to determine an accurate value for the rate constant for use in stratospheric modeling, and to clarify discrepancies in results previously obtained by different techniques. The results deduced from the competitive chlorination study are in good agreement with the absolute values measured by the mass spectrometric method, and at temperatures above 300 K are in good agreement with measurements by other techniques based on resonance fluorescence detection of atomic chlorine. However, in the 220-300 K region, the competitive experiments indicate lower rate constants than those obtained by resonance fluorescence methods, and do not reproduce the curved Arrhenius plots seen in some of those studies.

Process contribution evaluation for COD removal and energy production from molasses wastewater in a BioH2-BioCH4-MFC-integrated system.

PubMed

Yun, Jeonghee; Lee, Yun-Yeong; Choi, Hyung Joo; Cho, Kyung-Suk

2017-01-01

In this study, a three-stage-integrated process using the hydrogenic process (BioH 2 ), methanogenic process (BioCH 4 ), and a microbial fuel cell (MFC) was operated using molasses wastewater. The contribution of individual processes to chemical oxygen demand (COD) removal and energy production was evaluated. The three-stage integration system was operated at molasses of 20 g-COD L -1 , and each process achieved hydrogen production rate of 1.1 ± 0.24 L-H 2 L -1 day -1 , methane production rate of 311 ± 18.94 mL-CH 4 L -1 day -1 , and production rate per electrode surface area of 10.8 ± 1.4 g m -2 day -1 . The three-stage integration system generated energy production of 32.32 kJ g-COD -1 and achieved COD removal of 98 %. The contribution of BioH 2 , BioCH 4 , and the MFC reactor was 20.8, 72.2, and, 7.0 % of the total COD removal, and 18.7, 81.2, and 0.16 % of the total energy production, respectively. The continuous stirred-tank reactor BioH 2 at HRT of 1 day, up-flow anaerobic sludge blanket BioCH 4 at HRT of 2 days, and MFC reactor at HRT of 3 days were decided in 1:2:3 ratios of working volume under hydraulic retention time consideration. This integration system can be applied to various configurations depending on target wastewater inputs, and it is expected to enhance energy recovery and reduce environmental impact of the final effluent.

Modern marine sediments as a natural analog to the chemically stressed environment of a landfill

USGS Publications Warehouse

Baedecker, M.J.; Back, W.

1979-01-01

Chemical reactions that occur in landfills are analogous to those reactions that occur in marine sediments. Lateral zonation of C, N, S, O, H, Fe and Mn species in landfills is similar to the vertical zonation of these species in marine sediments and results from the following reaction sequence: (1) oxidation of C, N and S species in the presence of dissolved free oxygen to HCO3-, NO3- and SO2-4; (2) after consumption of molecular oxygen, then NO3- is reduced, and Fe and Mn are solubilized; (3) SO2-4 is reduced to sulfide; and (4) organic compounds become the source of oxygen, and CH4 and NH4+ are formed as fermentation products. In a landfill in Delaware the oxidation potential increases downgradient and the redox zones in the reducing plume are characterized by: CH4, NH4+, Fe2+. Mn2+, HCO3- and NO3-. Lack of SO2-4 at that landfill eliminates the sulfide zone. Although it has not been observed at landfills, mineral alteration should result in precipitation of pyrite and/or siderite downgradient. Controls on the pH of leachate are the relative rates of production of HCO3-, NH4+ and CH4. Production of methane by fermentation at landfills results in 13C isotope fractionation and the accumulation of isotopically heavy ??CO2 (+10 to +18??? PDB). Isotope measurements may be useful to determine the extent of CO2 reduction in landfills and extent of dilution downgradient. The boundaries of reaction zones in stressed aquifers are determined by head distribution and flow velocity. Thus, if the groundwater flow is rapid relative to reaction rates, redox zones will develop downgradient. Where groundwater flow velocities are low the zones will overlap to the extent that they may be indeterminate. ?? 1979.

Effect of plasma treatment (He/CH4) on glass surface for the reduction of powder flux adhesion in the spray drying process

NASA Astrophysics Data System (ADS)

Ramlan, Nadiah; Zamri, Nazirah Wahidah Mohd; Maskat, Mohd Yusof; Hoong, Chin Oi; Theng, Lau Yen; Zubairi, Saiful Irwan

2018-04-01

A 50Hz glow discharge He/CH4 plasma was generated and applied for the modification of glass surface to reduce powder adhesion on the wall of spray dryer. The hydrophobicity of the glass samples determined by the water droplet contact angle and adhesion weight on glass, dependent on the CH4 flow rate and plasma exposure time. There was a peak that appeared at 1470 cm-1 on the surface of treated glass indicating the presence of CH3 groups from ATR-FTIR data. Surface morphology analysis using scanning electron microscopy (SEM) showed changes of roughness in the surface-treated glass. The presence of alkyl group (CH3) that deposited on the glass surface is one of the factors that contribute to the increase in the surface roughness. The surface roughness will reflect the value of contact angle where hydrophobic surface are rougher compared to hydrophilic surface. The plasma treatment could enhance the value of the contact angle and thus reduced the adhesion on the spray dryer glass surface.

Effect of water and heat transport processes on methane emissions from paddy soils: a process-based model analysis

NASA Astrophysics Data System (ADS)

Rizzo, Anacleto; Boano, Fulvio; Revelli, Roberto; Ridolfi, Luca

2013-04-01

High CH4 fluxes are emitted from paddy fields worldwide and represent a considerable issue for the rice production eco-sustainability. Water and heat transport fluxes are known to strongly influence biogeochemical cycles in wetland environments, and therefore also CH4 emissions from paddy soils. Water percolation affects the dynamics of many compounds (e.g. DOC, O2) influencing CH4 fate. On the other hand, heat fluxes strongly influence CH4 production in submerged rice crops, and lowering ponding water temperature (LPWT) can reduce microbial activities and consequently decrease CH4 emissions. Moreover, as long as the optimal temperature range for rice growth is maintained, LPWT can lower CH4 emissions without rice yield limitation. Hence, a process-based model is proposed and applied to investigate the role of water flow on CH4 emissions, and to analyse the efficiency of LPWT as mitigation strategy for CH4 production and release. The process-based model relies on a system of partial differential mass balance equations to describe the vertical dynamics of the chemical compounds leading to CH4 production. Many physico-chemical processes and features characteristic of paddy soil are included: paddy soil stratigraphy; spatio-temporal variations of plant-root compartment; water and heat transport; SOC decomposition; heterotrophic reactions in both aerobic and anaerobic conditions; root radial oxygen loss; root solute uptake; DOC root exudation; plant-mediated, ebullition, and diffusion gas exchange pathways. LPWT is included as a temperature shift subtracted directly to the ponding water temperature. Model results confirm the importance of water flow on CH4 emission, since simulations that do not include water fluxes show a considerable overestimation of CH4 emissions due to a different DOC spatio-temporal dynamics. Particularly, when water fluxes are not modeled the overestimation can reach 67 % of the total CH4 emission over the whole growing season. Moreover, model results also suggest that roots influence CH4 dynamics principally due to their solute uptake, while root effect on advective flow plays a minor role. In addition, the analysis of CH4 transport fluxes show the limiting effect of upward dispersive transport fluxes on the downward CH4 percolation. Finally, LPWT is confirmed to be a valid mitigation strategy for CH4 emissions from paddy soils, since the reduction of CH4 emission reach about -50 % with a LPWT equal to only 2°C over the whole growing season.

Combining CO2 sequestration and CH4 production by means of guest exchange in a gas hydrate reservoir: two pilot scale experiments

NASA Astrophysics Data System (ADS)

Heeschen, Katja U.; Spangenberg, Erik; Schicks, Judith M.; Deusner, Christian; Priegnitz, Mike; Strauch, Bettina; Bigalke, Nikolaus; Luzi-Helbing, Manja; Kossel, Elke; Haeckel, Matthias; Wang, Yi

2017-04-01

Methane (CH4) hydrates are considered as a player in the field of energy supply and - if applied as such - as a possible sink for the greenhouse gas carbon dioxide (CO2). Next to the more conventional production methods depressurization and thermal stimulation, an extraction of CH4 by means of CO2 injection is investigated. The method is based on the chemical potential gradient between the CH4 hydrate phase and the injected CO2 phase. Results from small-scale laboratory experiments on the replacement method indicate recovery ratios of up to 66% CH4 but also encounter major discrepancies in conversion rates. So far it has not been demonstrated with certainty that the process rates are sufficient for an energy and cost effective production of CH4 with a concurrent sequestration of CO2. In a co-operation of GFZ and GEOMAR we used LARS (Large Scale Reservoir Simulator) to investigate the CO2-CH4-replacement method combined with thermal stimulation. LARS accommodates a sample volume of 210 l and allows for the simulation of in situ conditions typically found in gas hydrate reservoirs. Based on the sample size, diverse transport mechanisms could be simulated, which are assumed to significantly alter process yields. Temperature and pressure data complemented by a high resolution electrical resistivity tomography (ERT), gas chromatography, and flow measurements serve to interpret the experiments. In two experiments 50 kg heated CO2 was injected into sediments with CH4 hydrate saturations of 50%. While in the first experiment the CO2 was injected discontinuously in a so called "huff'n puff" manner, the second experiment saw a continuous injection. Conditions within LARS were set to 13 MPa and 8˚ C, which allow for stability of pure CO2 and CH4 hydrates as well as mixed hydrates. The CO2 was heated and entered the sediment sample with temperatures of approximately 30˚ C. In this presentation we will discuss the results from the large-scale experiments and compare them with data from small-scale experiments.

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.

Reaction kinetics of O( 3P) with acrylonitrile and crotononitrile

NASA Astrophysics Data System (ADS)

Upadhyaya, Hari P.; Naik, Prakash D.; Pavanaja, Ubaradka B.; Kumar, Awadhesh; Vatsa, Rajesh K.; Sapre, Avinash V.; Mittal, Jai P.

1997-08-01

The reaction of oxygen atoms O( 3P) with unsaturated nitriles (RCN), viz. acrylonitrile (CH 2=CHCN), and crotononitrile (CH 3CH=CHCN), was studied in a flow discharge tube in the pressure range 1.2-1.7 Torr using the O( 3P) chemiluminescence titration method. The rate constants for the reaction O( 3P) + RCN → products was determined at room temperature to be (4.9 ± 1.0) × 10 -13 and (5.4 ± 0.8) × 10 -13 cm 3 molecule -1 s -1 for acrylonitrile and crotononitrile respectively. The activation energies for the above reactions were estimated using the MNDO method. The formation of a biradical involving the addition of an oxygen atom to the double bond is proposed as the major channel for the reaction.

Dissolution rates of pure methane hydrate and carbon-dioxide hydrate in undersaturated seawater at 1000-m depth

USGS Publications Warehouse

Rehder, G.; Kirby, S.H.; Durham, W.B.; Stern, L.A.; Peltzer, E.T.; Pinkston, J.; Brewer, P.G.

2004-01-01

To help constrain models involving the chemical stability and lifetime of gas clathrate hydrates exposed at the seafloor, dissolution rates of pure methane and carbon-dioxide hydrates were measured directly on the seafloor within the nominal pressure-temperature (P/T) range of the gas hydrate stability zone. Other natural boundary conditions included variable flow velocity and undersaturation of seawater with respect to the hydrate-forming species. Four cylindrical test specimens of pure, polycrystalline CH4 and CO2 hydrate were grown and fully compacted in the laboratory, then transferred by pressure vessel to the seafloor (1028 m depth), exposed to the deep ocean environment, and monitored for 27 hours using time-lapse and HDTV cameras. Video analysis showed diameter reductions at rates between 0.94 and 1.20 ??m/s and between 9.0 and 10.6 ?? 10-2 ??m/s for the CO2 and CH4 hydrates, respectively, corresponding to dissolution rates of 4.15 ?? 0.5 mmol CO2/m2s and 0.37 ?? 0.03 mmol CH4/m2s. The ratio of the dissolution rates fits a diffusive boundary layer model that incorporates relative gas solubilities appropriate to the field site, which implies that the kinetics of the dissolution of both hydrates is diffusion-controlled. The observed dissolution of several mm (CH4) or tens of mm (CO2) of hydrate from the sample surfaces per day has major implications for estimating the longevity of natural gas hydrate outcrops as well as for the possible roles of CO2 hydrates in marine carbon sequestration strategies. ?? 2003 Elsevier Ltd.

40 CFR 98.364 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2014 CFR

2014-07-01

... or operator shall document the procedures used to ensure the accuracy of gas flow rate, gas... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Manure Management § 98.364 Monitoring and QA/QC requirements... fraction of total manure managed in each system component. (c) The CH4 concentration of gas from digesters...

40 CFR 98.364 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2013 CFR

2013-07-01

... or operator shall document the procedures used to ensure the accuracy of gas flow rate, gas... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Manure Management § 98.364 Monitoring and QA/QC requirements... fraction of total manure managed in each system component. (c) The CH4 concentration of gas from digesters...

40 CFR 98.364 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2012 CFR

2012-07-01

... or operator shall document the procedures used to ensure the accuracy of gas flow rate, gas... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Manure Management § 98.364 Monitoring and QA/QC requirements... fraction of total manure managed in each system component. (c) The CH4 concentration of gas from digesters...

Transport of Methane in Trees

NASA Astrophysics Data System (ADS)

Kutschera, E.; Khalil, A. K.; Shearer, M. J.; Rosenstiel, T.; Rice, A. L.

2011-12-01

Although overall methane (CH4) emissions for croplands, wetlands, and forests have been measured, the exact dynamics of CH4 transport through trees is not well understood. What roles transport mechanisms play in emission rates has been thoroughly investigated for rice, but is fairly unknown for trees. Better defined plant transport mechanisms yield more accurate determination of greenhouse gas flux and its variations, contributing to a comprehensive theory quantifying greenhouse gas emissions globally. CH4 emissions from the common wetland tree species black cottonwood (Populus trichocarpa) native to the Pacific Northwest have been measured under hydroponic conditions in order to separate plant transport processes from the influence of soil processes. Canopy emissions of CH4 have been measured via canopy enclosure. Measurements of CH4 flux from each of 16 trees have indicated that emissions are normally constant over the half-hour sampling period. Samples for stable carbon isotope composition have been taken during these experiments and measured on a mass spectrometer. Compared to the isotopic composition of root water CH4, canopy CH4 is depleted in 13C; this indicates that CH4 moving through the tree is not following a bulk flow pathway (where no depletion would occur), but instead moves either diffusively or through other cell or tissue barriers. No correlation was found to exist between leaf area and CH4 emission; this is vital to upscaling tree-level emissions to the global scale since leaf area index (LAI) cannot be treated as an appropriate parameter to upscale flux. Correctly informing global-scale CH4 fluxes from plants requires an association between the role plant physiology plays in the production and transport of CH4 and magnitudes of flux. This research was supported by the Office of Science (BER), U. S. Department of Energy, Grant No. DE-FG02-08ER64515. Supported in part through NASA / Oregon Space Grant Consortium, grant NNG05GJ85H.

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.

A stream-based methane monitoring approach for evaluating groundwater impacts associated with unconventional gas development.

PubMed

Heilweil, Victor M; Stolp, Bert J; Kimball, Briant A; Susong, David D; Marston, Thomas M; Gardner, Philip M

2013-01-01

Gaining streams can provide an integrated signal of relatively large groundwater capture areas. In contrast to the point-specific nature of monitoring wells, gaining streams coalesce multiple flow paths. Impacts on groundwater quality from unconventional gas development may be evaluated at the watershed scale by the sampling of dissolved methane (CH4 ) along such streams. This paper describes a method for using stream CH4 concentrations, along with measurements of groundwater inflow and gas transfer velocity interpreted by 1-D stream transport modeling, to determine groundwater methane fluxes. While dissolved ionic tracers remain in the stream for long distances, the persistence of methane is not well documented. To test this method and evaluate CH4 persistence in a stream, a combined bromide (Br) and CH4 tracer injection was conducted on Nine-Mile Creek, a gaining stream in a gas development area in central Utah. A 35% gain in streamflow was determined from dilution of the Br tracer. The injected CH4 resulted in a fivefold increase in stream CH4 immediately below the injection site. CH4 and δ(13) CCH4 sampling showed it was not immediately lost to the atmosphere, but remained in the stream for more than 2000 m. A 1-D stream transport model simulating the decline in CH4 yielded an apparent gas transfer velocity of 4.5 m/d, describing the rate of loss to the atmosphere (possibly including some microbial consumption). The transport model was then calibrated to background stream CH4 in Nine-Mile Creek (prior to CH4 injection) in order to evaluate groundwater CH4 contributions. The total estimated CH4 load discharging to the stream along the study reach was 190 g/d, although using geochemical fingerprinting to determine its source was beyond the scope of the current study. This demonstrates the utility of stream-gas sampling as a reconnaissance tool for evaluating both natural and anthropogenic CH4 leakage from gas reservoirs into groundwater and surface water. Published 2013. This article is a U.S. Government work and is in the public domain in the USA.

Nitrogen-doped diamond thin films: potential application in Fabry-Pérot interferometer

NASA Astrophysics Data System (ADS)

Kosowska, M.; Majchrowicz, D.; Sankaran, K. J.; Ficek, M.; Jedrzejewska-Szczerska, M.; Haenen, M. K.

2018-04-01

In this paper we present results of preliminary research of using nitrogen-doped diamond (NDD) films as reflective layer in Fabry-Pérot interferometer. NDD films were deposited on Si substrates by Microwave Plasma Enhanced Chemical Vapor Deposition (MPECVD) with the use of CH4, H2 and N2 gas mixtures. During deposition process methane flow rate varied while nitrogen flow was constant. We performed series of measurements which showed that NDD can be used as a mirror in Fabry-Pérot interferometer. The best signal visibility and repeatability of measurements were obtained for sample made with 3 sccm methane flow rate.

Factors Influencing Greenhouse Gas Emissions from Three Gorges Reservoir of China

NASA Astrophysics Data System (ADS)

Zhao, Y.; Zhao, X.; Wu, B.; Zeng, Y.

2013-05-01

Three gorges reservoir (TGR) of China located in a subtropical climate region. It has attracted tremendous attentions on greenhouse gas (GHG) emissions from TGR, including carbon dioxide (CO2), methane (CH4) and nitrous Oxide (N2O). Results on monthly fluxes and their spatial and seasonal variations have been determined by a static chamber method and have published elsewhere recently. Here we made further discussions on the factors influencing GHG emissions from TGR. We conclude that the hydrodynamic situation was the key parameter controlling the fluxes. TGR was a typical valley-type reservoir and with a complex terrain in the surrounding catchment, where almost 94% of the region was occupied by mountainous, this situation made the reservoir had sufficient allochthonous organic carbon input origin from eroded soil. But no significant relationship between organic carbon (both dissolved and particulate form) and GHG fluxes, we thought that TGR was not a carbon-limited reservoir on the GHG issue. In the mainstream of the reservoir, dissolved CO2 and CH4 were supersaturation in the water, the relative high flow together with the narrow-deep channel result in great disturbance, which would promote more dissolved gas escape into the atmosphere. This could also approved by the differences in CO2 and CH4 fluxes in different reach from up to downstream of the reservoir. In the reservoir tail water, the mainstream remained the high flow rate, both CO2 and CH4 fluxes is relative high, while downwards, the fluxes were gradually dropped, as after the impoundment of the reservoir, flow rate have greatly decreased. Another evidence was the relative higher CO2 and CH4 fluxes in the rainy season. As the rainy season approaches, TGR would empty the storage to prepare for retention and mitigation. The interplay between water inflows and outflows produced marked variations in the water residence times. During the rainy season times, this could be as short as 6 days with higher water flow rate which would also cause higher disturbance, while for other periods of a year, the reservoir would act more like a lake and residence times could exceed 30 days. Meanwhile the manipulate of the reservoir made the water column not only well mixed top to bottom for most of the year, but also the complete water column has high dissolved oxygen concentrations (> 6 mg/L). Only in April and May is there substantial temperature stratification in mainstream and tributaries. The high dissolved oxygen concentrations even in the deepest parts of the TGR storage minimize the scope for sediment anoxia and less GHG was produced, especially for CH4. In the tributaries, the totally different hydrodynamic situation made these regions a different GHG emission dynamics. After the impoundment, water velocity had greatly decreased, these regions showed more Limnology characteristics compared to the mainstream. This made the tributaries prone to algal blooms which would great affect the surface GHG fluxes, especially for CO2, which would consume the dissolved CO2 in water and cause the intake of atmospheric CO2.

Observations on the methane oxidation capacity of landfill soils.

PubMed

Chanton, Jeffrey; Abichou, Tarek; Langford, Claire; Spokas, Kurt; Hater, Gary; Green, Roger; Goldsmith, Doug; Barlaz, Morton A

2011-05-01

The objective of this study was to determine the role of CH(4) loading to a landfill cover in the control of CH(4) oxidation rate (gCH(4)m(-2)d(-1)) and CH(4) oxidation efficiency (% CH(4) oxidation) in a field setting. Specifically, we wanted to assess how much CH(4) a cover soil could handle. To achieve this objective we conducted synoptic measurements of landfill CH(4) emission and CH(4) oxidation in a single season at two Southeastern USA landfills. We hypothesized that percent oxidation would be greatest at sites of low CH(4) emission and would decrease as CH(4) emission rates increased. The trends in the experimental results were then compared to the predictions of two differing numerical models designed to simulate gas transport in landfill covers, one by modeling transport by diffusion only and the second allowing both advection and diffusion. In both field measurements and in modeling, we found that percent oxidation is a decreasing exponential function of the total CH(4) flux rate (CH(4) loading) into the cover. When CH(4) is supplied, a cover's rate of CH(4) uptake (gCH(4)m(-2)d(-2)) is linear to a point, after which the system becomes saturated. Both field data and modeling results indicate that percent oxidation should not be considered as a constant value. Percent oxidation is a changing quantity and is a function of cover type, climatic conditions and CH(4) loading to the bottom of the cover. The data indicate that an effective way to increase the % oxidation of a landfill cover is to limit the amount of CH(4) delivered to it. Copyright © 2010 Elsevier Ltd. All rights reserved.

Gas buildup in Lake Nyos, Cameroon: The recharge process and its consequences

USGS Publications Warehouse

Evans, William C.; Kling, G.W.; Tuttle, M.L.; Tanyileke, G.; White, L.D.

1993-01-01

The gases dissolved in Lake Nyos, Cameroon, were quantified recently (December 1989 and September 1990) by two independent techniques: in-situ measurements using a newly designed probe and laboratory analyses of samples collected in pre-evacuated stainless steel cylinders. The highest concentrations of CO2 and CH4 were 0.30 mol/kg and 1.7 mmol/kg, respectively, measured in cylinders collected 1 m above lake bottom. Probe measurements of in-situ gas pressure at three different stations showed that horizontal variations in total dissolved gas were negligible. Total dissolved-gas pressure near the lake bottom is 1.06 MPa (10.5 atm), 50% as high as the hydrostatic pressure of 2.1 MPa (21 atm). Comparing the CO2 profile constructed from the 1990 data to one obtained in May 1987 shows that CO2 concentrations have increased at depths to below 150 m. Based on these profiles, the average rate of CO2 input to bottom waters was 2.6 ?? 108 mol/a. Increased deep-water temperatures require an average heat flow of 0.32 MW into the hypolimnion over the same time period. The transport rates of CO2, heat, and major ions into the hypolimnion suggest that a low-temperature reservoir of free CO2 exists a short distance below lake bottom and that convective cycling of lake water through the sediments is involved in transporting the CO2 into the lake from the underlying diatreme. Increased CH4 concentrations at all depths below the oxycline and a high 14C content (41% modern) in the CH4 4 m above lake bottom show that much of the CH4 is biologically produced within the lake. The CH4 production rate may vary with time, but if the CO2 recharge rate remains constant, CO2 saturation of the entire hypolimnion below 50 m depth would require ???140 a, given present-day concentrations. ?? 1993.

Synthesis of ultrasmooth nanostructured diamond films by microwave plasma chemical vapor deposition using a He/H(2)/CH(4)/N(2) gas mixture.

PubMed

Chowdhury, S; Hillman, Damon A; Catledge, Shane A; Konovalov, Valery V; Vohra, Yogesh K

2006-10-01

Ultrasmooth nanostructured diamond (USND) films were synthesized on Ti-6Al-4V medical grade substrates by adding helium in H(2)/CH(4)/N(2) plasma and changing the N(2)/CH(4) gas flow from 0 to 0.6. We were able to deposit diamond films as smooth as 6 nm (root-mean-square), as measured by an atomic force microscopy (AFM) scan area of 2 μm(2). Grain size was 4-5 nm at 71% He in (H(2) + He) and N(2)/CH(4) gas flow ratio of 0.4 without deteriorating the hardness (~50-60 GPa). The characterization of the films was performed with AFM, scanning electron microscopy, x-ray diffraction (XRD), Raman spectroscopy, and nanoindentation techniques. XRD and Raman results showed the nanocrystalline nature of the diamond films. The plasma species during deposition were monitored by optical emission spectroscopy. With increasing N(2)/CH(4) feedgas ratio (CH(4) was fixed) in He/H(2)/CH(4)/N(2) plasma, a substantial increase of CN radical (normalized by Balmer H(α) line) was observed along with a drop in surface roughness up to a critical N(2)/CH(4) ratio of 0.4. The CN radical concentration in the plasma was thus correlated to the formation of ultrasmooth nanostructured diamond films.

Rate Constant and RRKM Product Study for the Reaction Between CH3 and C2H3 at T = 298K

NASA Technical Reports Server (NTRS)

Thorn, R. Peyton, Jr.; Payne, Walter A., Jr.; Chillier, Xavier D. F.; Stief, Louis J.; Nesbitt, Fred L.; Tardy, D. C.

2000-01-01

The total rate constant k1 has been determined at P = 1 Torr nominal pressure (He) and at T = 298 K for the vinyl-methyl cross-radical reaction CH3 + C2H3 yields products. The measurements were performed in a discharge flow system coupled with collision-free sampling to a mass spectrometer operated at low electron energies. Vinyl and methyl radicals were generated by the reactions of F with C2H4 and CH4, respectively. The kinetic studies were performed by monitoring the decay of C2H3 with methyl in excess, 6 < |CH3|(sub 0)/|C2H3|(sub 0) < 21. The overall rate coefficient was determined to be k1(298 K) = (1.02 +/- 0.53)x10(exp -10) cubic cm/molecule/s with the quoted uncertainty representing total errors. Numerical modeling was required to correct for secondary vinyl consumption by reactions such as C2H3 + H and C2H3 + C2H3. The present result for k1 at T = 298 K is compared to two previous studies at high pressure (100-300 Torr He) and to a very recent study at low pressure (0.9-3.7 Torr He). Comparison is also made with the rate constant for the similar reaction CH3 + C2H5 and with a value for k1 estimated by the geometric mean rule employing values for k(CH3 + CH3) and k(C2H3 + C2H3). Qualitative product studies at T = 298 K and 200 K indicated formation of C3H6, C2H2, and C2H5 as products of the combination-stabilization, disproportionation, and combination-decomposition channels, respectively, of the CH3 + C2H3 reaction. We also observed the secondary C4H8 product of the subsequent reaction of C3H5 with excess CH3; this observation provides convincing evidence for the combination-decomposition channel yielding C3H5 + H. RRKM calculations with helium as the deactivator support the present and very recent experimental observations that allylic C-H bond rupture is an important path in the combination reaction. The pressure and temperature dependencies of the branching fractions are also predicted.

Field Exploration of Methane Seep Near Atqasuk

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

Katey Walter, Dennis Witmer, Gwen Holdmann

2008-12-31

Methane (CH{sub 4}) in natural gas is a major energy source in the U.S., and is used extensively on Alaska's North Slope, including the oilfields in Prudhoe Bay, the community of Barrow, and the National Petroleum Reserve, Alaska (NPRA). Smaller villages, however, are dependent on imported diesel fuel for both power and heating, resulting in some of the highest energy costs in the U.S. and crippling local economies. Numerous CH{sub 4} gas seeps have been observed on wetlands near Atqasuk, Alaska (in the NPRA), and initial measurements have indicated flow rates of 3,000-5,000 ft{sup 3} day{sup -1} (60-100 kg CH{submore » 4} day{sup -1}). Gas samples collected in 1996 indicated biogenic origin, although more recent sampling indicated a mixture of biogenic and thermogenic gas. In this study, we (1) quantified the amount of CH{sub 4} generated by several seeps and evaluated their potential use as an unconventional gas source for the village of Atqasuk; (2) collected gas and analyzed its composition from multiple seeps several miles apart to see if the source is the same, or if gas is being generated locally from isolated biogenic sources; and (3) assessed the potential magnitude of natural CH{sub 4} gas seeps for future use in climate change modeling.« less

Can we explain the observed methane variability after the Mount Pinatubo eruption?

NASA Astrophysics Data System (ADS)

Bândă, N.; Krol, M.; van Weele, M.; van Noije, T.; Le Sager, P.; Röckmann, T.

2015-07-01

The CH4 growth rate in the atmosphere showed large variations after the Pinatubo eruption in June 1991. A decrease of more than 10 ppb yr-1 in the growth rate over the course of 1992 was reported and a partial recovery in the following year. Although several reasons have been proposed to explain the evolution of CH4 after the eruption, their contributions to the observed variations are not yet resolved. CH4 is removed from the atmosphere by the reaction with tropospheric OH, which in turn is produced by O3 photolysis under UV radiation. The CH4 removal after the Pinatubo eruption might have been affected by changes in tropospheric UV levels due to the presence of stratospheric SO2 and sulfate aerosols, and due to enhanced ozone depletion on Pinatubo aerosols. The perturbed climate after the eruption also altered both sources and sinks of atmospheric CH4. Furthermore, CH4 concentrations were influenced by other factors of natural variability in that period, such as ENSO and biomass burning events. Emissions of CO, NOX and NMVOCs also affected CH4 concentrations indirectly by influencing tropospheric OH levels. Potential drivers of CH4 variability are investigated using the TM5 global chemistry model. The contribution that each driver had to the global CH4 variability during the period 1990 to 1995 is quantified. We find that a decrease of 8-10 ppb yr-1 CH4 is explained by a combination of the above processes. However, the timing of the minimum growth rate is found 6-9 months later than observed. The long-term decrease in CH4 growth rate over the period 1990 to 1995 is well captured and can be attributed to an increase in OH concentrations over this time period. Potential uncertainties in our modelled CH4 growth rate include emissions of CH4 from wetlands, biomass burning emissions of CH4 and other compounds, biogenic NMVOC and the sensitivity of OH to NMVOC emission changes. Two inventories are used for CH4 emissions from wetlands, ORCHIDEE and LPJ, to investigate the role of uncertainties in these emissions. Although the higher climate sensitivity of ORCHIDEE improves the simulated CH4 growth rate change after Pinatubo, none of the two inventories properly captures the observed CH4 variability in this period.

Plasma deposited diamondlike carbon on GaAs and InP

NASA Technical Reports Server (NTRS)

Warner, J. D.; Pouch, J. J.; Alterovitz, S. A.; Liu, D. C.; Lanford, W. A.

1984-01-01

The properties of diamond like carbon films grown by RF flow discharge 30 kHz plasma using methane are reported. The Cls XPS line shape of films showed localized hybrid carbon bonds as low as 40 to as high as 95 percent. Infrared spectroscopy and N(15) nuclear reaction profiling data indicated 35 to 42 percent hydrogen, depending inversely on deposition temperature. The deposition rate of films on Si falls off exponentially with substrate temperature, and nucleation does not occur above 200 C on GaAs and InP. Optical data of the films showed bandgap values of 2.0 to 2.4 eV increasing monotonically with CH4 flow rate.

Simultaneous determination of choline and acetylcholine based on a trienzyme chemiluminometric biosensor in a single line flow injection system.

PubMed

Kiba, Nobutoshi; Ito, Seiji; Tachibana, Masaki; Tani, Kazue; Koizumi, Hitoshi

2003-12-01

A detector for the simultaneous determination of choline (Ch) and acetylcholine (ACh) based on a sensitive trienzyme chemiluminometric biosensor in a single line flow injection (FI) system is described. Immobilized choline oxidase (ChOx), immobilized peroxidase (POx), immobilized acetylcholinesterase, and coimmobilized ChOx/POx were packed, in turn, in a transparent ETFE tube (1 mm i.d., 75 cm) and the tube was placed in front of a photomultipier tube as a flow cell. Two-peak response was obtained by one injection of the sample solution. The first and second peaks were dependent on the concentrations of Ch and ACh, respectively. The influence of some experimental parameters such as flow rate, amounts of immobilized enzymes on the behavior of the sensor was studied in order to optimize the sensitivity, sample throughput and resolution. Calibration curves were linear at 1 - 1000 nM for Ch and 3 - 3000 nM for ACh. The sample throughput was 25/h without carryover. The FI system was applied to the simultaneous determination of Ch and ACh in rabbit brain tissue homogenates.

Aerobic Methane Generation From Plants (AMP)? Yes, Mostly!

NASA Astrophysics Data System (ADS)

Whiticar, M. J.; Ednie, A. C.

2007-12-01

In 2006, Keppler et al. (K) published an intriguing and revolutionary idea that aerobic methane is produced in plants (AMP) and released to the atmosphere. Their initial scaling calculations estimated the amount of AMP fluxing from living plants to range from 62-236 Tg/y and 1-7 Tg/y for plant litter. Houweling et al. (2006) (H) refined this flux to ca. 85 Tg/y PIH and 125 Tg/y present day. More recently, Dueck et al. (2007) (D) challenged the claim of AMP from intact plants. Their experiments cited "...No evidence for substantial aerobic methane emission by terrestrial plants..." (max. 0.4 ng/g h-1). Due to the significance of AMP in understanding present and palaeo-atmospheric budgets (e.g., Whiticar and Schaefer, 2007), we conducted a wide range of experiments to confirm or refute the existence and magnitude of AMP. For explanation, experiments of K were time-series batch samples measured by gas chromatography on purged and ambient samples, whereas D used continuous-flow cuvettes and measured by optical PAS with time series single injections. Our longer-term experiments with corn, wheat, tomato, red cedar, chestnut, moss and lichen (3-97 h, 32 °C) used a plant chamber, flow-through system with a GYRO, an optical spectrometer that enables continuous 1 Hz CH4 measurements with a precision of ca. 1 ppbv. We conducted over 100 chamber experiments on sterilized and non-sterilized (Cs-137 radiation) samples of: 1) intact living plants (IP), 2) fresh leaves (FL) and 3) dried leaves (DL); under both 1) high and 2) low light conditions (HL, LL), and with 1) ambient CH4 (AM, ca. 1.92 ppmv) and 2) purged methane (PM, 10 and 96 ppbv) levels. Our results demonstrate that IP-AMs have CH4 flux rates of 0.74-3.48 ng/g h-1. In contrast, IP-PMs show intense CH4 uptake rates of -28.5 to -57.9 ng/g h-1 (substantially different than K's reported emissions of 12-370 ng/g h-1 values). Our FL-AM-LL have CH4 flux rates of 0.36-2.05 ng/g h-1, whereas FL-AM-HL have significant CH4 generation of 0.27 to 12.7 ng/g h-1 (substantially higher than K's max of 3 ng/g h-1). FL-PM emissions are low (ca. 1 ng/g h-1). DL CH4 release is also low ranging from LL of 0.33 to HL of 3.37 ng/g h-1. Interestingly, our Cs-irradiated FL have increasingly higher CH4 emission rates with higher radiation dosages. We do not attempt to extrapolate our AMP laboratory experiments to global scales, nor make any physiological, biochemical or mechanistic claims. However at this point our work does indeed confirm that AMP is indeed operative and significant under certain conditions. The magnitude of our small scale, laboratory, AMP emission experiments is consistent with the earlier claims of K and H. We have, to some degree, emulated the experimental designs of both K and D. We remain intrigued by the findings, yet uncertain, if not puzzled, by the process and the discrepancies between groups.

Testing a biofilter cover design to mitigate dairy effluent pond methane emissions.

PubMed

Pratt, Chris; Deslippe, Julie; Tate, Kevin R

2013-01-02

Biofiltration, whereby CH(4) is oxidized by methanotrophic bacteria, is a potentially effective strategy for mitigating CH(4) emissions from anaerobic dairy effluent lagoons/ponds, which typically produce insufficient biogas for energy recovery. This study reports on the effectiveness of a biofilter cover design at oxidizing CH(4) produced by dairy effluent ponds. Three substrates, a volcanic pumice soil, a garden-waste compost, and a mixture of the two, were tested as media for the biofilters. All substrates were suspended as 5 cm covers overlying simulated dairy effluent ponds. Methane fluxes supplied to the filters were commensurate with emission rates from typical dairy effluent ponds. All substrates oxidized more than 95% of the CH(4) influx (13.9 g CH(4) m(-3) h(-1)) after two months and continued to display high oxidation rates for the remaining one month of the trial. The volcanic soil biofilters exhibited the highest oxidation rates (99% removal). When the influx CH(4) dose was doubled for a month, CH(4) removal rates remained >90% for all substrates (maximum = 98%, for the volcanic soil), suggesting that biofilters have a high capacity to respond to increases in CH(4) loads. Nitrous oxide emissions from the biofilters were negligible (maximum = 19.9 mg N(2)O m(-3) h(-1)) compared with CH(4) oxidation rates, particularly from the volcanic soil that had a much lower microbial-N (75 mg kg(-1)) content than the compost-based filters (>240 mg kg(-1)). The high and sustained CH(4) oxidation rates observed in this laboratory study indicate that a biofilter cover design is a potentially efficient method to mitigate CH(4) emissions from dairy effluent ponds. The design should now be tested under field conditions.

Rate coefficients for the reactions of C2(a(3)Pi(u)) and C2(X(1)Sigma(g)(+)) with various hydrocarbons (CH4, C2H2, C2H4, C2H6, and C3H8): a gas-phase experimental study over the temperature range 24-300 K.

PubMed

Páramo, Alejandra; Canosa, André; Le Picard, Sébastien D; Sims, Ian R

2008-10-02

The kinetics of reactions of C2(a(3)Pi(u)) and C2(X(1)Sigma(g)(+)) with various hydrocarbons (CH4, C2H2, C2H4, C2H6, and C3H8) have been studied in a uniform supersonic flow expansion over the temperature range 24-300 K. Rate coefficients have been obtained by using the pulsed laser photolysis-laser induced fluorescence technique, where both radicals were produced at the same time but detected separately. The reactivity of the triplet state was found to be significantly lower than that of the singlet ground state for all reactants over the whole temperature range of the study. Whereas C2(X(1)Sigma(g)(+)) reacts with a rate coefficient close to the gas kinetic limit with all hydrocarbons studied apart from CH4, C2(a(3)Pi(u)) appears to be more sensitive to the molecular and electronic structure of the reactant partners. The latter reacts at least one order of magnitude faster with unsaturated hydrocarbons than with alkanes, and the rate coefficients increase very significantly with the size of the alkane. Results are briefly discussed in terms of their potential astrophysical impact.

Triton - Stratospheric molecules and organic sediments

NASA Technical Reports Server (NTRS)

Thompson, W. Reid; Singh, Sushil K.; Khare, B. N.; Sagan, Carl

1989-01-01

Continuous-flow plasma discharge techniques show production rates of hydrocarbons and nitriles in N2 + CH4 atmospheres appropriate to the stratosphere of Titan, and indicate that a simple eddy diffusion model together with the observed electron flux quantitatively matches the Voyager IRIS observations for all the hydrocarbons, except for the simplest ones. Charged particle chemistry is very important in Triton's stratosphere. In the more CH4-rich case of Titan, many hydrocarbons and nitriles are produced in high yield. If N2 is present, the CH4 fraction is low, but hydrocarbons and nitriles are produced in fair yield, abundances of HCN and C2H2 in Triton's stratosphere exceed 10 to the 19th molecules/sq cm per sec, and NCCN, C3H4, and other species are predicted to be present. These molecules may be detected by IRIS if the stratosphere is as warm as expected. Both organic haze and condensed gases will provide a substantial UV and visible opacity in Triton's atmosphere.

Methane and Carbon Dioxide Production Rates in Lake Sediments from Sub-Arctic Sweden

NASA Astrophysics Data System (ADS)

DeStasio, J.; Halloran, M.; Erickson, L. M.; Varner, R. K.; Johnson, J. E.; Setera, J.; Prado, M. F.; Wik, M.; Crill, P. M.

2013-12-01

Ecosystems at high latitudes are undergoing rapid change due to amplified arctic warming. Lakes in these regions are sources of both methane (CH4) and carbon dioxide (CO2) to the atmosphere and will likely be impacted by elevated temperatures. Because of the potential increase in the release of organic carbon due to thawing permafrost, it is believed that methanogenesis rates within neighboring fresh water sediments will display a positive feedback response, by increasing CH4 emission to the atmosphere. We studied CH4 production potential of sediments using cores from three lakes in the Stordalen Mire complex in sub-Arctic, Sweden: Inre Harrsjön, Mellan Harrsjön, and Villasjön. Sediment cores were incubated to determine CO2 and CH4 production rates and were analyzed for CH4 concentrations, dissolved inorganic carbon (DIC) concentrations, total organic carbon (TOC) concentrations, as well as carbon, nitrogen and sulfur content. Our results from the Villasjön cores indicate that CH4 production rates were highest at the same sediment depths as peak dissolved CH4 concentrations, with maximum values between depths of approximately 10cm and 30cm. Additionally, the highest observed CH4 production rates were in sediments from areas within Villasjön known to have the highest rates of CH4 ebullition. CO2 production rates were generally highest within surface sediments ranging from about 4cm to 11cm in depth, with production rates displaying a steady decrease below 11cm. Additionally, observed CO2 production rates correlated with total organic carbon (TOC) concentrations with respect to sediment depth, but displayed no relationship with dissolved inorganic carbon (DIC). Further analysis will be conducted to determine how CH4 and CO2 production characteristics vary between sediment core samples, as well as isotopic analysis of select samples taken from each lake.

Can we explain the observed methane variability after the Mount Pinatubo eruption?

NASA Astrophysics Data System (ADS)

Bândă, N.; Krol, M.; van Weele, M.; van Noije, T.; Le Sager, P.; Röckmann, T.

2016-01-01

The CH4 growth rate in the atmosphere showed large variations after the Pinatubo eruption in June 1991. A decrease of more than 10 ppb yr-1 in the growth rate over the course of 1992 was reported, and a partial recovery in the following year. Although several reasons have been proposed to explain the evolution of CH4 after the eruption, their contributions to the observed variations are not yet resolved. CH4 is removed from the atmosphere by the reaction with tropospheric OH, which in turn is produced by O3 photolysis under UV radiation. The CH4 removal after the Pinatubo eruption might have been affected by changes in tropospheric UV levels due to the presence of stratospheric SO2 and sulfate aerosols, and due to enhanced ozone depletion on Pinatubo aerosols. The perturbed climate after the eruption also altered both sources and sinks of atmospheric CH4. Furthermore, CH4 concentrations were influenced by other factors of natural variability in that period, such as El Niño-Southern Oscillation (ENSO) and biomass burning events. Emissions of CO, NOX and non-methane volatile organic compounds (NMVOCs) also affected CH4 concentrations indirectly by influencing tropospheric OH levels.

Potential drivers of CH4 variability are investigated using the TM5 global chemistry model. The contribution that each driver had to the global CH4 variability during the period 1990 to 1995 is quantified. We find that a decrease of 8-10 ppb yr-1 CH4 is explained by a combination of the above processes. However, the timing of the minimum growth rate is found 6&nash;9 months later than observed. The long-term decrease in CH4 growth rate over the period 1990 to 1995 is well captured and can be attributed to an increase in OH concentrations over this time period. Potential uncertainties in our modelled CH4 growth rate include emissions of CH4 from wetlands, biomass burning emissions of CH4 and other compounds, biogenic NMVOC and the sensitivity of OH to NMVOC emission changes. Two inventories are used for CH4 emissions from wetlands, ORCHIDEE and LPJ, to investigate the role of uncertainties in these emissions. Although the higher climate sensitivity of ORCHIDEE improves the simulated CH4 growth rate change after Pinatubo, none of the two inventories properly captures the observed CH4 variability in this period.

Monitoring the evolution and migration of a methane gas plume in an unconfined sandy aquifer using time-lapse GPR and ERT.

PubMed

Steelman, Colby M; Klazinga, Dylan R; Cahill, Aaron G; Endres, Anthony L; Parker, Beth L

2017-10-01

Fugitive methane (CH 4 ) leakage associated with conventional and unconventional petroleum development (e.g., shale gas) may pose significant risks to shallow groundwater. While the potential threat of stray (CH 4 ) gas in aquifers has been acknowledged, few studies have examined the nature of its migration and fate in a shallow groundwater flow system. This study examines the geophysical responses observed from surface during a 72day field-scale simulated CH 4 leak in an unconfined sandy aquifer at Canadian Forces Base Borden, Canada, to better understand the transient behaviour of fugitive CH 4 gas in the subsurface. Time-lapse ground-penetrating radar (GPR) and electrical resistivity tomography (ERT) were used to monitor the distribution and migration of the gas-phase and assess any impacts to groundwater hydrochemistry. Geophysical measurements captured the transient formation of a CH 4 gas plume emanating from the injector, which was accompanied by an increase in total dissolved gas pressure (P TDG ). Subsequent reductions in P TDG were accompanied by reduced bulk resistivity around the injector along with an increase in the GPR reflectivity along horizontal bedding reflectors farther downgradient. Repeat temporal GPR reflection profiling identified three events with major peaks in reflectivity, interpreted to represent episodic lateral CH 4 gas release events into the aquifer. Here, a gradual increase in P TDG near the injector caused a sudden lateral breakthrough of gas in the direction of groundwater flow, causing free-phase CH 4 to migrate much farther than anticipated based on groundwater advection. CH 4 accumulated along subtle permeability boundaries demarcated by grain-scale bedding within the aquifer characteristic of numerous Borden-aquifer multi-phase flow experiments. Diminishing reflectivity over a period of days to weeks suggests buoyancy-driven migration to the vadose zone and/or CH 4 dissolution into groundwater. Lateral and vertical CH 4 migration was primarily governed by subtle, yet measurable heterogeneity and anisotropy in the aquifer. Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.

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.

Effect of CH4 on the CO2 breakthrough pressure and permeability of partially saturated low-permeability sandstone in the Ordos Basin, China

NASA Astrophysics Data System (ADS)

Zhao, Yan; Yu, Qingchun

2018-01-01

The behavior of CO2 that coexists with CH4 and the effect of CH4 on the CO2 stream need to be deeply analyzed and studied, especially in the presence of water. Our previous studies investigated the breakthrough pressure and permeability of pure CO2 in five partially saturated low-permeability sandstone core samples from the Ordos Basin, and we concluded that rocks with a small pore size and low permeability show considerable sealing capacity even under unsaturated conditions. In this paper, we selected three of these samples for CO2-CH4 gas-mixture breakthrough experiments under various degrees of water saturation. The breakthrough experiments were performed by increasing the gas pressure step by step until breakthrough occurred. Then, the effluent gas mixture was collected for chromatographic partitioning analysis. The results indicate that CH4 significantly affects the breakthrough pressure and permeability of CO2. The presence of CH4 in the gas mixture increases the interfacial tension and, thus, the breakthrough pressure. Therefore, the injected gas mixture that contains the highest (lowest) mole fraction of CH4 results in the largest (smallest) breakthrough pressure. The permeability of the gas mixture is greater than that for pure CO2 because of CH4, and the effective permeability decreases with increased breakthrough pressure. Chromatographic partitioning of the effluent mixture gases indicates that CH4 breaks through ahead of CO2 as a result of its weaker solubility in water. Correlations are established between (1) the breakthrough pressure and water saturation, (2) the effective permeability and water saturation, (3) the breakthrough pressure and effective permeability, and (4) the mole fraction of CO2/CH4 in the effluent mixture gases and water saturation. These results deepen our understanding of the multi-phase flow behavior in the porous media under unsaturated conditions, which have implications for formulating emergency response plans for gas leakage into unsaturated zones. Finally, knowing the flow characteristic of gas mixture can guide CO2 storage, CO2-EOR and CO2-ECBM projects. Future studies should pay attention to the effects of saline water with different salt types and concentrations on the multi-phase flow behavior with applications to geological CO2 storage and energy storage using CH4.

Assessing Methane Fluxes in a Small Run-of-River Reservoir: The Importance of Adjacent Marshland

NASA Astrophysics Data System (ADS)

McGinnis, D. F.; Flury, S.; Fietzek, P.; Bilsley, N. A.; Bodmer, P.; Premke, K.; Maeck, A.; Lorke, A.; Schmidt, M.

2013-12-01

We investigate methane (CH4) emissions from a small run-of-river impoundment, the Schwentine River in Kiel, Germany. Small dammed rivers, while important regions for carbon transformation, are presently not considered in the terrestrial carbon budget and are under-represented in CH4 emission studies. Using state-of-the-art monitoring techniques, we determine that 1) the CH4 emissions well-exceed those reported for temperate reservoirs and 2) the hydrodynamic linkage to bordering marshland (consisting of reed belts, sidebays and creeks) is an important CH4 source for Schwentine River CH4. During our study, the Schwentine River discharged into the Kieler Fjord at 3 - 12 m3/s. CH4 measurements included 1) a moored sensor near the dam discharge, 2) discrete water sampling, and 3) real time surface flux measurements with floating chambers. We observed that the CH4 concentration increased nearly linearly from 2.5 km upstream towards the dam. The CH4 concentration near the dam discharge was logged and reported every 30 minutes nearly continuously from 11 July - 28 Sept 2011, and varied from 500 μmol/L to 2,200 μmol/L. Surprisingly, the CH4 mass discharge from the dam - ranging from 4 to 20 kg/day - increased with both temperature and flowrate, suggesting a flow-dependent CH4 source. We found that the bordering and numerous inundated reed belts, sidebays and small creeks, had significantly elevated CH4 concentrations. These marshland regions are relatively productive and quiescent compared to the main river, and trap organic and particulate matter, leading to enhanced CH4 production. As the river flowrate increases, the lateral exchange with these adjacent areas also increases. Using the CH4 concentration time series, measured surface diffusive and ebullition fluxes, and sediment CH4 porewater profiles, we estimate the relative contributions of CH4 in the main branch due to 1) sediment diffusion, 2) dissolution from sediment CH4 bubble release, and 3) lateral fluxes from the marshland. Damming of the rivers potentially creates or increases adjacent marshland, leading to methane production/emission hotspots. Considering only the main branch, the Schwentine River CH4 emission rate is similar to tropical reservoirs. However, including bubble and diffusive emissions from the reed belts and many small side bays and streams could significantly increase this estimate. As millions of such small river impoundments exist worldwide, we discuss the hydrodynamic alterations promoting CH4 production/emission hotspots, illustrate the importance of collecting high-resolution time series data for assessing emissions, and finally estimate the potential contribution of these small aquatic systems to the global terrestrial carbon balance.

Hydraulic and Mechanical Effects from Gas Hydrate Conversion and Secondary Gas Hydrate Formation during Injection of CO2 into CH4-Hydrate-Bearing Sediments

NASA Astrophysics Data System (ADS)

Bigalke, N.; Deusner, C.; Kossel, E.; Schicks, J. M.; Spangenberg, E.; Priegnitz, M.; Heeschen, K. U.; Abendroth, S.; Thaler, J.; Haeckel, M.

2014-12-01

The injection of CO2 into CH4-hydrate-bearing sediments has the potential to drive natural gas production and simultaneously sequester CO2 by hydrate conversion. The process aims at maintaining the in situ hydrate saturation and structure and causing limited impact on soil hydraulic properties and geomechanical stability. However, to increase hydrate conversion yields and rates it must potentially be assisted by thermal stimulation or depressurization. Further, secondary formation of CO2-rich hydrates from pore water and injected CO2 enhances hydrate conversion and CH4 production yields [1]. Technical stimulation and secondary hydrate formation add significant complexity to the bulk conversion process resulting in spatial and temporal effects on hydraulic and geomechanical properties that cannot be predicted by current reservoir simulation codes. In a combined experimental and numerical approach, it is our objective to elucidate both hydraulic and mechanical effects of CO2 injection and CH4-CO2-hydrate conversion in CH4-hydrate bearing soils. For the experimental approach we used various high-pressure flow-through systems equipped with different online and in situ monitoring tools (e.g. Raman microscopy, MRI and ERT). One particular focus was the design of triaxial cell experimental systems, which enable us to study sample behavior even during large deformations and particle flow. We present results from various flow-through high-pressure experimental studies on different scales, which indicate that hydraulic and geomechanical properties of hydrate-bearing sediments are drastically altered during and after injection of CO2. We discuss the results in light of the competing processes of hydrate dissociation, hydrate conversion and secondary hydrate formation. Our results will also contribute to the understanding of effects of temperature and pressure changes leading to dissociation of gas hydrates in ocean and permafrost systems. [1] Deusner C, Bigalke N, Kossel E, Haeckel M. Methane Production from Gas Hydrate Deposits through Injection of Supercritical CO2. Energies 2012:5(7): 2112-2140.

A Posteriori Quantification of Rate-Controlling Effects from High-Intensity Turbulence-Flame Interactions Using 4D Measurements

DTIC Science & Technology

2016-11-22

Unclassified REPORT DOCUMENTATION PAGE Form ApprovedOMB No. 0704-0188 The public reporting burden for this collection of information is estimated to average 1...compact at all conditions tested, as indicated by the overlap of OH and CH2O distributions. 5. We developed analytical techniques for pseudo- Lagrangian ...condition in a constant density flow requires that the flow divergence is zero, ∇ · ~u = 0. Three smoothing schemes were examined, a moving average (i.e

Greenhouse gas emissions from surface flow and subsurface flow constructed wetlands treating dairy wastewater.

PubMed

VanderZaag, A C; Gordon, R J; Burton, D L; Jamieson, R C; Stratton, G W

2010-01-01

Agricultural wastewater treatment is important for protecting water quality in rural ecosystems, and constructed wetlands are an effective treatment option. During treatment, however, some C and N are converted to CH(4), N(2)O, respectively, which are potent greenhouse gases (GHGs). The objective of this study was to assess CH(4), N(2)O, and CO(2) emissions from surface flow (SF) and subsurface flow (SSF) constructed wetlands. Six constructed wetlands (three SF and three SSF; 6.6 m(2) each) were loaded with dairy wastewater in Truro, Nova Scotia, Canada. From August 2005 through September 2006, GHG fluxes were measured continuously using transparent steady-state chambers that encompassed the entire wetlands. Flux densities of all gases were significantly (p < 0.01) different between SF and SSF wetlands changed significantly with time. Overall, SF wetlands had significantly (p < 0.01) higher emissions of CH(4) N(2)O than SSF wetlands and therefore had 180% higher total GHG emissions. The ratio of N(2)O to CH(4) emissions (CO(2)-equivalent) was nearly 1:1 in both wetland types. Emissions of CH(4)-C as a percentage of C removal varied seasonally from 0.2 to 27% were 2 to 3x higher in SF than SSF wetlands. The ratio of N(2)O-N emitted to N removed was between 0.1 and 1.6%, and the difference between wetland types was inconsistent. Thus, N(2)O emissions had a similar contribution to N removal in both wetland types, but SSF wetlands emitted less CH(4) while removing more C from the wastewater than SF wetlands.

High methane emissions from a midlatitude reservoir draining an agricultural watershed.

PubMed

Beaulieu, Jake J; Smolenski, Rebecca L; Nietch, Christopher T; Townsend-Small, Amy; Elovitz, Michael S

2014-10-07

Reservoirs are a globally significant source of methane (CH4), although most measurements have been made in tropical and boreal systems draining undeveloped watersheds. To assess the magnitude of CH4 emissions from reservoirs in midlatitude agricultural regions, we measured CH4 and carbon dioxide (CO2) emission rates from William H. Harsha Lake (Ohio, U.S.A.), an agricultural impacted reservoir, over a 13 month period. The reservoir was a strong source of CH4 throughout the year, emitting on average 176 ± 36 mg C m(-2) d(-1), the highest reservoir CH4 emissions profile documented in the United States to date. Contrary to our initial hypothesis, the largest CH4 emissions were during summer stratified conditions, not during fall turnover. The river-reservoir transition zone emitted CH4 at rates an order of magnitude higher than the rest of the reservoir, and total carbon emissions (i.e., CH4 + CO2) were also greater at the transition zone, indicating that the river delta supported greater carbon mineralization rates than elsewhere. Midlatitude agricultural impacted reservoirs may be a larger source of CH4 to the atmosphere than currently recognized, particularly if river deltas are consistent CH4 hot spots. We estimate that CH4 emissions from agricultural reservoirs could be a significant component of anthropogenic CH4 emissions in the U.S.A.

CH4 dissociation in the early stage of graphene growth on Fe-Cu(100) surface: Theoretical insights

NASA Astrophysics Data System (ADS)

Tian, Baoyang; Liu, Tianhui; Yang, YanYan; Li, Kai; Wu, Zhijian; Wang, Ying

2018-01-01

The mechanism of CH4 dissociation and carbon nucleation process on the Fe doped Cu(100) surface were investigated systematically by using the density functional theory (DFT) calculations and microkinetic model. The activity of the Cu(100) surface was improved by the doped Fe atom and the atomic Fe on the Fe-Cu(100) surface was the reaction center due to the synergistic effect. In the dissociation process of CH4, CH3 → CH2 + H was regarded as the rate-determining step. The results obtained from the microkinetic model showed that the coverage of CHx(x = 1-3) was gradually decreased with the temperature increasing and CH3 was always the major intermediate at the broad range of the temperature (from 1035 to 1080 °C) and the ratio of H2/CH4 (from 0 to 5). It is also found that the reaction rates were increased with the temperature increasing. However, the reaction rates were reduced (or increased) at the range of H2/CH4 = 0-0.2 (or H2/CH4 > 0.2). It is noted that controlling the H2 partial pressure was an effective method to regulate the major intermediates and reaction rates of CH4 dissociation and further influence the growing process of graphene.

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.

Effect of introducing legumes containing condensed tannins in an orchardgrass diet on forage nutritive value and enteric methane output in continuous culture

USDA-ARS?s Scientific Manuscript database

Legumes containing condensed tannins (CT) have been shown to reduce enteric CH4 in ruminants; however, research is lacking on how increased CT levels affect forage nutritive value and CH4 output. A 4-unit, dual-flow continuous culture fermentor system was used to assess CH4 output of CT legumes in a...

Atmospheric methane sources - Alaskan tundra bogs, an alpine fen, and a subarctic boreal marsh

NASA Technical Reports Server (NTRS)

Sebacher, D. I.; Harriss, R. C.; Grice, S. S.; Bartlett, K. B.; Sebacher, S. M.

1986-01-01

Methane (CH4) flux measurements from Alaska tundra bogs, an alpine fen, and a subarctic boreal marsh were obtained at field sites ranging from Prudhoe Bay on the coast of the Arctic Ocean to the Alaskan Range south of Fairbanks during August 1984. In the tundra, average CH4 emission rates varied from 4.9 mg CH4 per sq m per day (moist tundra) to 119 mg CH4 per sq m per day (waterlogged tundra). Fluxes averaged 40 mg CH4 per sq m per day from wet tussock meadows in the Brooks Range and 289 mg Ch4 per sq m per day from an alpine fen in the Alaskan Range. The boreal marsh had an average CH4 emission rate of 106 mg CH4 per sq m per day. Significant emissions were detected in tundra areas where peat temperatures were as low as 4 C, and permafrost was only 25 cm below the ground surface. Emission rates from the 17 sites sampled were found to be logarithmically related to water levels at the sites. Extrapolation of the data to an estimate of the total annual CH4 emission from all arctic and boreal wetlands suggests that these ecosystems are a major source of atmospheric CH4 and could account for up to 23 percent of global CH4 emissions from wetlands.

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.

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.

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.

The Structure of Titan’s N2 and CH4 Coronae

NASA Astrophysics Data System (ADS)

Jiang, Fayu; Cui, Jun; Xu, Jiyao

2017-12-01

In this study, we analyze the structures of Titan’s N2 and CH4 coronae using a large data set acquired by the Ion Neutral Mass Spectrometer (INMS) instrument on board Cassini. The N2 and CH4 densities measured from the exobase up to 2000 km imply a mean exobase temperature of 146 K and 143 K, respectively, which is lower than the mean upper atmospheric temperature by 4 and 7 K. This indicates that on average, Titan possesses a subthermal rather than suprathermal corona. A careful examination reveals that the variability in corona structure is not very likely to be solar driven. Within the framework of the collisionless kinetic model, we investigate how the CH4 energy distribution near the exobase could be constrained if strong CH4 escape occurs on Titan. Several functional forms for the CH4 energy distribution are attempted, assuming two representative CH4 escape rates of 1.2× {10}25 s-1 and 2.2× {10}27 s-1. We find that the double Maxwellian and power-law distributions can reproduce the shape of the CH4 corona structure as well as the imposed CH4 escape rate. In both cases, the escape rate is contributed by a suprathermal CH4 population on the high-energy tail, with a number fraction below 5% and a characteristic energy of 0.1-0.6 eV per suprathermal CH4 molecule. The coexistence of the subthermal CH4 corona revealed by the INMS data and substantial CH4 escape suggested by some previous works could be reconciled by a significant departure in the exobase CH4 energy distribution from ideal Maxwellian that enhances escape and causes a noticeable redistribution of the corona structure.

Purification and characterization of chondroitinase ABC from Acinetobacter sp. C26.

PubMed

Zhu, Changliang; Zhang, Jingliang; Zhang, Jing; Jiang, Yanhui; Shen, Zhaopeng; Guan, Huashi; Jiang, Xiaolu

2017-02-01

An extracellular chondroitinase ABC (ChSase ABC, EC 4.2.2.4) produced by cultivating Acinetobacter sp. C26, was purified to homogeneity from the supernatant by ammonium sulfate fractionation, Q-Sepharose Fast Flow and Sephadex G-100 chromatography. The 76kDa enzyme was purified 48.09-fold to homogeneity with specific activity of 348.64U/mg, Using the chondroitin sulfate A (CS-A) as substrate, the maximal reaction rate (Vmax) and Michaelis-Menten constant (Km) of ChSase ABC were found to be 10.471μmol/min/ml and 0.105mg/ml, respectively. The enzyme showed the highest activity at the optimal conditions of pH 6.0 and 42 ∘C, respectively. This enzyme was stable at pH 5-10, 5-9 and 5-7 at 4°C, 37°C and 42°C, respectively. Investigation about thermal stability of ChSase ABC displayed that it was stable at 37°C. ChSase ABC activity was increased in presence of Na + , K + , Mn 2+ , 1,10-phenanthrolin and strongly inhibited by Cu 2+ , Hg 2+ , Al 3+ and SDS. These properties suggested that ChSase ABC from Acinetobacter sp. C26 bring promising prospects in medical and industry applications. Copyright © 2016 Elsevier B.V. All rights reserved.

Flow immune photoacoustic sensor for real-time and fast sampling of trace gases

NASA Astrophysics Data System (ADS)

Petersen, Jan C.; Balslev-Harder, David; Pelevic, Nikola; Brusch, Anders; Persijn, Stefan; Lassen, Mikael

2018-02-01

A photoacoustic (PA) sensor for fast and real-time gas sensing is demonstrated. The PA cell has been designed for flow noise immunity using computational fluid dynamics (CFD) analysis. PA measurements were conducted at different flow rates by exciting molecular C-H stretch vibrational bands of hexane (C6H14) in clean air at 2950cm-1 (3.38 μm) with a custom made mid-infrared interband cascade laser (ICL). The PA sensor will contribute to solve a major problem in a number of industries using compressed air by the detection of oil contaminants in high purity compressed air. We observe a (1σ, standard deviation) sensitivity of 0.4 +/-0.1 ppb (nmol/mol) for hexane in clean air at flow rates up to 2 L/min, corresponding to a normalized noise equivalent absorption (NNEA) coefficient of 2.5×10-9 W cm-1 Hz1/2, thus demonstrating high sensitivity and fast and real-time gas analysis. The PA sensor is not limited to molecules with C-H stretching modes, but can be tailored to measure any trace gas by simply changing the excitation wavelength (i.e. the laser source) making it useful for many different applications where fast and sensitive trace gas measurements are needed.

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.

Low temperature studies of the removal reactions of 1CH2 with particular relevance to the atmosphere of Titan

NASA Astrophysics Data System (ADS)

Douglas, Kevin; Blitz, Mark A.; Feng, Wuhu; Heard, Dwayne E.; Plane, John M. C.; Slater, Eloise; Willacy, Karen; Seakins, Paul W.

2018-03-01

Methylene, CH2, is one of the major photolysis products of methane by Lyman-α radiation and is involved in the photochemistry of the atmospheres of Titan and the giant planets. The kinetics of the reactions of the first excited state of methylene, 1CH2, with He, N2, O2, H2 and CH4 have been measured over the temperature range 43-160 K by pulsed laser photolysis, monitoring 1CH2 removal by laser induced fluorescence. Low temperatures were obtained with either a pulsed Laval expansion (43-134 K) or a, slow flow reaction cell (160 K). The rate coefficients for the reactions with N2, O2, H2 and CH4 all showed a strong negative temperature dependence. In combination with other literature data, the rate coefficients can be parameterised as: kHe(43 < T/K < 800) = (1.90 ± 0.23) × 10-12 × (T/298)1.74±0.16 × exp((88±23)/T) kN2(43 < T / K < 800) = (2.29 ± 1.12) × 10-12 × (T/298)-2.15±1.38 × exp((-74±96)/T) + (3.91 ± 0.78) × 10-11 × exp((-469±114)/T) kO2(43 < T / K < 300) = (6.16 ± 1.09) × 10-11 × (T/298)-0.65±0.14 kH2(43 < T / K < 800) = (1.10 ± 0.04) × 10-10 × (T/298)-0.40±0.06 × exp((11.1±6.9)/T) kCH4(43 < T / K < 475) = (8.20 ± 0.46) × 10-11 × (T/298)-0.93±0.10 × exp((-20.5±12.8)/T) For the reactions of 1CH2 with H2 and CH4, the branching ratio for quenching to ground state, 3CH2, vs chemical reaction was also determined at 160 and 73 K. The values measured (H2: 0.39 ± 0.10 at 160 K, 0.78 ± 0.15 at 73 K; CH4: 0.49 ± 0.09 at 160 K, 0.64 ± 0.19 at 73 K) confirm trends of an increased proportion of reactive loss with increasing temperature determined at higher temperatures. The impacts of the new measurements for Titan's atmosphere have been ascertained using a 1D chemistry and transport model. A significant decrease (∼40%) in the mixing ratio of ethane between 800 and 1550 km is calculated due to the decrease contribution of methyl production from the reaction of 1CH2 with CH4, with smaller increases in the concentrations of ethene and acetylene. Ethene production is enhanced by more methylene being converted to methylidene, CH, and the subsequent reaction of CH with CH4 to generate ethene. Photolysis of ethene is the major route to acetylene formation.

Methane emissions to the troposphere from the Amazon floodplain

NASA Technical Reports Server (NTRS)

Devol, Allen H.; Richey, Jeffrey E.; Clark, Wayne A.; King, Stagg L.; Martinelli, Luiz A.

1988-01-01

The magnitudes of CH4 emissions to the troposphere from the Amazon River floodplain and the mechanism of these emissions were investigated using the data of 94 individual flux measurements made along a 1700-km stretch of the river during July/August 1985. The overall average rate of CH4 emission from wetlands was found to be 390 mg CH4/sq m per day, with the highest emissions (590 mg CH4/sq m per day) attributed to the water surfaces covered by aquatic macrophytes. Ebullition was the dominant mechanism of emission, accounting for 85 percent of the total. Surface-water CH4 concentrations were highly supersaturated, averaging 6.4 micromolar. The annual emission of CH4 from the Amazon Basin to the troposphere, estimated from the area and the known emission rate, is about 10 CH4 Tg/yr, indicating the importance of the area in the global atmospheric CH4 cycle.

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.

Response of soil methane uptake to simulated nitrogen deposition and grazing management across three types of steppe in Inner Mongolia, China.

PubMed

Li, Xianglan; He, Hong; Yuan, Wenping; Li, Linghao; Xu, Wenfang; Liu, Wei; Shi, Huiqiu; Hou, Longyu; Chen, Jiquan; Wang, Zhiping

2018-01-15

The response of soil methane (CH 4 ) uptake to increased nitrogen (N) deposition and grazing management was studied in three types of steppe (i.e., meadow steppe, typical steppe, and desert steppe) in Inner Mongolia, China. The experiment was designed with four simulated N deposition rates such as 0, 50, 100, and 200kgNha -1 , respectively, under grazed and fenced management treatments. Results showed that the investigated steppes were significant sinks for CH 4 , with an uptake flux of 1.12-3.36kgha -1 over the grass growing season and that the magnitude of CH 4 uptake significantly (P<0.05) decreased with increasing N deposition rates. The soil CH 4 uptake rates were highest in the desert steppe, moderate in the typical steppe, and lowest in the meadow steppe. Compared with grazed plots, fencing increased the CH 4 uptake by 4.7-40.2% with a mean value of 20.2% across the three different steppe types. The responses of soil CH 4 uptake to N deposition in the continental steppe varied depending on the N deposition rate, steppe type, and grazing management. A significantly positive correlation between CH 4 uptake and soil temperature was found in this study, whereas no significant relationship between soil moisture and CH 4 uptake occurred. Our results may contribute to the improvement of model parameterization for simulating biosphere-atmosphere CH 4 exchange processes and for evaluating the climate change feedback on CH 4 soil uptake. Copyright © 2017 Elsevier B.V. All rights reserved.

Sensor transition failure in the high flow sampler: Implications for methane emission inventories of natural gas infrastructure.

PubMed

Howard, Touché; Ferrara, Thomas W; Townsend-Small, Amy

2015-07-01

Quantification of leaks from natural gas (NG) infrastructure is a key step in reducing emissions of the greenhouse gas methane (CH4), particularly as NG becomes a larger component of domestic energy supply. The U.S. Environmental Protection Agency (EPA) requires measurement and reporting of emissions of CH4 from NG transmission, storage, and processing facilities, and the high-flow sampler (or high-volume sampler) is one of the tools approved for this by the EPA. The Bacharach Hi-Flow Sampler (BHFS) is the only commercially available high-flow instrument, and it is also used throughout the NG supply chain for directed inspection and maintenance, emission factor development, and greenhouse gas reduction programs. Here we document failure of the BHFS to transition from a catalytic oxidation sensor used to measure low NG (~5% or less) concentrations to a thermal conductivity sensor for higher concentrations (from ~5% to 100%), resulting in underestimation of NG emission rates. Our analysis includes both our own field testing and analysis of data from two other studies (Modrak et al., 2012; City of Fort Worth, 2011). Although this failure is not completely understood, and although we do not know if all BHFS models are similarly affected, sensor transition failure has been observed under one or more of these conditions: (1) Calibration is more than ~2 weeks old; (2) firmware is out of date; or (3) the composition of the NG source is less than ~91% CH4. The extent to which this issue has affected recent emission studies is uncertain, but the analysis presented here suggests that the problem could be widespread. Furthermore, it is critical that this problem be resolved before the onset of regulations on CH4 emissions from the oil and gas industry, as the BHFS is a popular instrument for these measurements. An instrument commonly used to measure leaks in natural gas infrastructure has a critical sensor transition failure issue that results in underestimation of leaks, with implications for greenhouse gas emissions estimates as well as safety.

Kinetic and theoretical studies on the protonation of [Ni(2-SC6H4N){PhP(CH2CH2PPh2)2}]+: nitrogen versus sulfur as the protonation site.

PubMed

Petrou, Athinoula L; Koutselos, Andreas D; Wahab, Hilal S; Clegg, William; Harrington, Ross W; Henderson, Richard A

2011-02-07

The complexes [Ni(4-Spy)(triphos)]BPh(4) and [Ni(2-Spy)(triphos)]BPh(4) {triphos = PhP(CH(2)CH(2)PPh(2))(2), 4-Spy = 4-pyridinethiolate, 2-Spy = 2-pyridinethiolate} have been prepared and characterized both spectroscopically and using X-ray crystallography. In both complexes the triphos is a tridentate ligand. However, [Ni(4-Spy)(triphos)](+) comprises a 4-coordinate, square-planar nickel with the 4-Spy ligand bound to the nickel through the sulfur while [Ni(2-Spy)(triphos)](+) contains a 5-coordinate, trigonal-bipyramidal nickel with a bidentate 2-Spy ligand bound to the nickel through both sulfur and nitrogen. The kinetics of the reactions of [Ni(4-Spy)(triphos)](+) and [Ni(2-Spy)(triphos)](+) with lutH(+) (lut = 2,6-dimethylpyridine) in MeCN have been studied using stopped-flow spectrophotometry, and the two complexes show very different reactivities. The reaction of [Ni(4-Spy)(triphos)](+) with lutH(+) is complete within the deadtime of the stopped-flow apparatus (2 ms) and corresponds to protonation of the nitrogen. However, upon mixing [Ni(2-Spy)(triphos)](+) and lutH(+) a reaction is observed (on the seconds time scale) to produce an equilibrium mixture. The mechanistic interpretation of the rate law has been aided by the application of MSINDO semiempirical and ADF calculations. The kinetics and calculations are consistent with the reaction between [Ni(2-Spy)(triphos)](+) and lutH(+) involving initial protonation of the sulfur followed by dissociation of the nitrogen and subsequent transfer of the proton from sulfur to nitrogen. The factors affecting the position of protonation and the coupling of the coordination state of the 2-pyridinethiolate ligand to the site of protonation are discussed.

Quantification of methane sources in the Athabasca Oil Sands Region of Alberta by aircraft mass balance

NASA Astrophysics Data System (ADS)

Baray, Sabour; Darlington, Andrea; Gordon, Mark; Hayden, Katherine L.; Leithead, Amy; Li, Shao-Meng; Liu, Peter S. K.; Mittermeier, Richard L.; Moussa, Samar G.; O'Brien, Jason; Staebler, Ralph; Wolde, Mengistu; Worthy, Doug; McLaren, Robert

2018-05-01

Aircraft-based measurements of methane (CH4) and other air pollutants in the Athabasca Oil Sands Region (AOSR) were made during a summer intensive field campaign between 13 August and 7 September 2013 in support of the Joint Canada-Alberta Implementation Plan for Oil Sands Monitoring. Chemical signatures were used to identify CH4 sources from tailings ponds (BTEX VOCs), open pit surface mines (NOy and rBC) and elevated plumes from bitumen upgrading facilities (SO2 and NOy). Emission rates of CH4 were determined for the five primary surface mining facilities in the region using two mass-balance methods. Emission rates from source categories within each facility were estimated when plumes from the sources were spatially separable. Tailings ponds accounted for 45 % of total CH4 emissions measured from the major surface mining facilities in the region, while emissions from operations in the open pit mines accounted for ˜ 50 %. The average open pit surface mining emission rates ranged from 1.2 to 2.8 t of CH4 h-1 for different facilities in the AOSR. Amongst the 19 tailings ponds, Mildred Lake Settling Basin, the oldest pond in the region, was found to be responsible for the majority of tailings ponds emissions of CH4 ( > 70 %). The sum of measured emission rates of CH4 from the five major facilities, 19.2 ± 1.1 t CH4 h-1, was similar to a single mass-balance determination of CH4 from all major sources in the AOSR determined from a single flight downwind of the facilities, 23.7 ± 3.7 t CH4 h-1. The measured hourly CH4 emission rate from all facilities in the AOSR is 48 ± 8 % higher than that extracted for 2013 from the Canadian Greenhouse Gas Reporting Program, a legislated facility-reported emissions inventory, converted to hourly units. The measured emissions correspond to an emissions rate of 0.17 ± 0.01 Tg CH4 yr-1 if the emissions are assumed as temporally constant, which is an uncertain assumption. The emission rates reported here are relevant for the summer season. In the future, effort should be devoted to measurements in different seasons to further our understanding of the seasonal parameters impacting fugitive emissions of CH4 and to allow for better estimates of annual emissions and year-to-year variability.

Continuous spin detonation of poorly detonable fuel-air mixtures in annular combustors

NASA Astrophysics Data System (ADS)

Bykovskii, F. A.; Zhdan, S. A.

2017-09-01

This paper reports on the results of experimental investigations of continuous spin detonation of three fuel-air mixtures (syngas-air, CH4/H2-air, and kerosene/H2-air in a flow-type annular cylindrical combustor 503 mm in diameter. The limits of existence of continuous detonation in terms of the specific flow rates of the mixtures (minimum values) are determined. It is found that all gas mixtures, including the least detonable methane-air mixture, with addition of hydrogen can be burned in the continuous spin detonation regime.

Carbon trace gases in lake and beaver pond ice near Thompson, Manitoba, Canada

NASA Astrophysics Data System (ADS)

Kuhlbusch, Thomas A. J.; Zepp, Richard G.

1999-11-01

Concentrations of CO2, CO, and CH4 were measured in beaver pond and lake ice in April 1996 near Thompson, Manitoba to derive information on possible impacts of ice melting on corresponding atmospheric trace gas concentrations. CH4 concentrations in beaver pond and lake ice ranged between 0.3-150 mmol m-3 and 3.1-56.2 μmol m-3, respectively. The corresponding CO concentrations showed no significant differences between the two lakes. They varied between 50 and 250 μmol m-3. These CO concentrations are some of the highest determined in any aquatic system. The differences in CH4 concentrations between lake and pond can be explained by the differences in production and microbial oxidation rates between the two systems. No explanation can be given for the similar CO concentrations. Supersaturation factors for CO were 660±130 and 630±330, and 65-35000 and 0.6-13 for CH4 in the ice of the beaver pond and Troy Lake, respectively. When digging into the beaver pond ice, a continuous flow of bubbles with 0.32±0.06 vol% CH4, 2.2±0.3 vol% CO2, and 482±98 ppb CO coming out of the slash ice for about 20-30 minutes was noticed. Wintertime flux estimates of CH4 and CO showed that they represent at minimum 6.4% and 2.2% of that of the summer. It has to be noted that these wintertime fluxes will mostly be released to the atmosphere during the time of snowmelt, thus a limited time period of weeks.

Effects of cattle slurry acidification on ammonia and methane evolution during storage.

PubMed

Petersen, Søren O; Andersen, Astrid J; Eriksen, Jørgen

2012-01-01

Slurry acidification before storage is known to reduce NH(3) emissions, but recent observations have indicated that CH(4) emissions are also reduced. We investigated the evolution of CH(4) from fresh and aged cattle slurry during 3 mo of storage as influenced by pH adjustment to 5.5 with sulfuric acid. In a third storage experiment, cattle slurry acidified with commercial equipment on two farms was incubated. In the manipulation experiments, effects of acid and sulfate were distinguished by adding hydrochloric acid and potassium sulfate separately or in combination, rather than sulfuric acid. In one experiment sulfur was also added to slurry as the amino acid methionine in separate treatments. In each treatment 20-kg portions of slurry (n = 4) were stored for 95 d. All samples were subsampled nine to 10 times for determination of NH(3) and CH(4) evolution rates using a 2-L flow-through system. In all experiments, the pH of acidified cattle slurry increased gradually to between 6.5 and 7. Acidification of slurry reduced the evolution of CH(4) by 67 to 87%. The greatest reduction was observed with aged cattle slurry, which had a much higher potential for CH(4) production than fresh slurry. Sulfate and methionine amendment to cattle slurry without pH adjustment also significantly inhibited methanogenesis, probably as a result of sulfide production. The study suggests that complex microbial interactions involving sulfur transformations and pH determine the potential for CH(4) emission during storage of cattle slurry, and that slurry acidification may be a cost-effective greenhouse gas mitigation option. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

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

NASA Astrophysics Data System (ADS)

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

2016-04-01

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

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.

Reservoir water level drawdown as a novel, substantial, and manageable control on methane release to the atmosphere

NASA Astrophysics Data System (ADS)

Harrison, J.; Deemer, B. R.; Birchfield, M. K.

2014-12-01

Reservoirs constitute a globally important source of atmospheric methane (CH4). Although it is reasonably well-established that hydrostatic and barometric pressure can influence rates of CH4 release from lake and tidal sediments, the relationship between water-level manipulation and CH4 release from man-made impoundments has not been quantified or characterized. Furthermore, cross-system controls on CH4 production and release to the atmosphere have not been established. We collected CH4 emission (diffusion and ebullition) data for 8 reservoirs in the U.S. Pacific Northwest that are subject to a range of trophic conditions and water level management regimes. Our aim was to: (1) characterize CH4 emissions from these systems, and (2) quantify effects of water level management and eutrophication on CH4 fluxes. Results indicate very high fluxes, in some cases the highest reported reservoir emission rates, and a strong correspondence between lake level reduction and CH4 emissions, including quantitatively important bursts of CH4 bubbling. In one reservoir, drawdown-associated CH4 fluxes accounted for over 25% of annual CH4 emissions in a period of just 16 days (4% of the year). Average CH4 ebullition rates in a reservoir managed for hydropower peaking were nearly three-fold higher than in a paired upstream reservoir managed to maintain a constant water level (528 mg CH4 m-2 d-1 and 187 mg CH4 m-2 d-1 respectively). Highest gas fluxes were observed during the water level drawdown component of the hydropower peaking cycle (14.3 g CH4 m-2 d-1). In addition we observe a strong, positive relationship between eutrophication (as indicated by surface Chl a concentrations) and CH4 production (r2 = 0.88; P<0.001) and between eutrophication and the sensitivity of CH4 emissions to drawdown (r2 = 0.84; P<0.001). This work suggests that manipulation of water levels can significantly affect CH4 emissions from reservoirs to the atmosphere, and that sampling programs that miss drawdown periods may substantially underestimate CH4 fluxes. It also suggests that controlling nutrient loading may reduce greenhouse gas fluxes from surface waters to the atmosphere.

A Computational and Experimental Study of Coflow Laminar Methane/Air Diffusion Flames: Effects of Fuel Dilution, Inlet Velocity, and Gravity

NASA Technical Reports Server (NTRS)

Cao, S.; Ma, B.; Bennett, B. A. V.; Giassi, D.; Stocker, D. P.; Takahashi, F.; Long, M. B.; Smooke, M. D.

2014-01-01

The influences of fuel dilution, inlet velocity, and gravity on the shape and structure of laminar coflow CH4-air diffusion flames were investigated computationally and experimentally. A series of nitrogen-diluted flames measured in the Structure and Liftoff in Combustion Experiment (SLICE) on board the International Space Station was assessed numerically under microgravity (mu g) and normal gravity (1g) conditions with CH4 mole fraction ranging from 0.4 to 1.0 and average inlet velocity ranging from 23 to 90 cm/s. Computationally, the MC-Smooth vorticity-velocity formulation was employed to describe the reactive gaseous mixture, and soot evolution was modeled by sectional aerosol equations. The governing equations and boundary conditions were discretized on a two-dimensional computational domain by finite differences, and the resulting set of fully coupled, strongly nonlinear equations was solved simultaneously at all points using a damped, modified Newton's method. Experimentally, flame shape and soot temperature were determined by flame emission images recorded by a digital color camera. Very good agreement between computation and measurement was obtained, and the conclusions were as follows. (1) Buoyant and nonbuoyant luminous flame lengths are proportional to the mass flow rate of the fuel mixture; computed and measured nonbuoyant flames are noticeably longer than their 1g counterparts; the effect of fuel dilution on flame shape (i.e., flame length and flame radius) is negligible when the flame shape is normalized by the methane flow rate. (2) Buoyancy-induced reduction of the flame radius through radially inward convection near the flame front is demonstrated. (3) Buoyant and nonbuoyant flame structure is mainly controlled by the fuel mass flow rate, and the effects from fuel dilution and inlet velocity are secondary.

Mangroves act as a small methane source: an investigation on 5 pathways of methane emissions from mangroves

NASA Astrophysics Data System (ADS)

Chen, H.; Peng, C.; Guan, W.; Liao, B.; Hu, J.

2017-12-01

The methane (CH4) source strength of mangroves is not well understood, especially for integrating all CH4 pathways. This study measured CH4 fluxes by five pathways (sediments, pneumatophores, water surface, leaves, and stems) from four typical mangrove forests in Changning River of Hainan Island, China, including Kandelia candel , Sonneratia apetala, Laguncularia racemosa and Bruguiera gymnoihiza-Bruguiera sexangula. The CH4 fluxes (mean ± SE) from sediments were 4.82 ± 1.46 mg CH4 m-2 h-1 for those without pneumatophores and 1.36 ± 0.17 mg CH4 m-2 h-1 for those with pneumatophores. Among the three communities with pneumatophores, S. apetala community had significantly greater emission rate than the other two. Pneumatophores in S. apetala were found to significantly decrease CH4 emission from sediments (P < 0.01), while those in B. gymnoihiza-B. sexangula significantly enhanced it (P < 0.05). The CH4 fluxes (mean ± SE) from waters were 3.48 ± 1.11 mg CH4 m-2 h-1, with the highest emission rate in the K. candel community with duck farming. Leaves of mangroves except for K. candel were a weak CH4 sink while stems a weak source. As a whole the 72 ha of mangroves in the Changning river basin emitted about 8.10 Gg CH4 yr-1 with a weighted emission rate of about 1.29 mg CH4 m-2 h-1, therefore only a small methane source to the atmosphere compared to other reported ones. Keywords: Greenhouse Gases; Biogeochemistry; Tropical ecosystems; Methane budget

Rate constants for the reactions of OH with CH3Cl, CH2Cl2, CHCl3, and CH3Br

NASA Technical Reports Server (NTRS)

Hsu, K.-J.; Demore, W. B.

1994-01-01

Rate constants for the reactions of OH with CH3Cl, CH2Cl2, CHCl3, and CH3Br have been measured by a relative rate technique in which the reaction rate of each compound was compared to that of HFC-152a (CH3CHF2) and (for CH2Cl2) HFC-161 (CH3CH2F). Using absolute rate constants for HFC-152a and HFC-161, which we have determined relative to those for CH4, CH3CCl3, and C2H6, temperature dependent rate constants of both compounds were derived. The derived rate constant for CH3Br is in good agreement with recent absolute measurements. However, for the chloromethanes all the rate constants are lower at atmospheric temperatures than previously reported, especially for CH2Cl2 where the present rate constant is about a factor of 1.6 below the JPL 92-20 value. The new rate constant appears to resolve a discrepancy between the observed atmospheric concentrations and those calculated from the previous rate constant and estimated release rates.

Vibrational relaxation in liquid chloroform following ultrafast excitation of the CH stretch fundamental

NASA Astrophysics Data System (ADS)

Sibert, Edwin L.; Rey, Rossend

2002-01-01

Vibrational energy flow in liquid chloroform that follows the ultrafast excitation of the CH stretch fundamental is modeled using semiclassical methods. Relaxation rates are calculated using Landau-Teller theory and a time-dependent method both of which consider a quantum mechanical CHCl3 solute molecule coupled to a classical bath of CHCl3 solvent molecules. Probability flow is examined for several potentials to determine the sensitivity of calculated relaxation rates to the parameters that describe the model potentials. Three stages of relaxation are obtained. Probability is calculated to decay initially to a single acceptor state, a combination state of the solute molecule with two quanta of excitation in the CH bend and one in the CCl stretch, in 13-23 ps depending on the potential model employed. This is followed by rapid and complex intramolecular energy flow into the remaining vibrational degrees of freedom. During this second stage the lowest frequency Cl-C-Cl bend is found to serve as a conduit for energy loss to the solvent. The bottleneck for relaxation back to the ground state is predicted to be the slow 100-200 ps relaxation of the CH bend and CCl stretch fundamentals. Several aspects of the incoherent anti-Stokes scattering that follows strong infrared excitation of the CH fundamental as observed by Graener, Zürl, and Hoffman [J. Phys. Chem. B 101, 1745 (1997)] are elucidated in the present study.

Diffusional limits to the consumption of atmospheric methane by soils

USGS Publications Warehouse

Striegl, Robert G.

1993-01-01

Net transport of atmospheric gases into and out of soil systems is primarily controlled by diffusion along gas partial pressure gradients. Gas fluxes between soil and the atmosphere can therefore be estimated by a generalization of the equation for ordinary gaseous diffusion in porous unsaturated media. Consumption of CH4 by methylotrophic bacteria in the top several centimeters of soil causes the uptake of atmospheric CH4 by aerated soils. The capacity of the methylotrophs to consume CH4 commonly exceeds the potential of CH4 to diffuse from the atmosphere to the consumers. The maximum rate of uptake of atmospheric CH4 by soil is, therefore, limited by diffusion and can be calculated from soil physical properties and the CH4 concentration gradient. The CH4 concentration versus depth profile is theoretically described by the equation for gaseous diffusion with homogeneous chemical reaction in porous unsaturated media. This allows for calculation of the in situ rate of CH4 consumption within specified depth intervals.

Greenhouse gas and ammonia emissions from production of compost bedding on a dairy farm.

PubMed

Fillingham, M A; VanderZaag, A C; Burtt, S; Baldé, H; Ngwabie, N M; Smith, W; Hakami, A; Wagner-Riddle, C; Bittman, S; MacDonald, D

2017-12-01

Recent developments in composting technology enable dairy farms to produce their own bedding from composted manure. This management practice alters the fate of carbon and nitrogen; however, there is little data available documenting how gaseous emissions are impacted. This study measured in-situ emissions of methane (CH 4 ), carbon dioxide (CO 2 ), nitrous oxide (N 2 O), and ammonia (NH 3 ) from an on-farm solid-liquid separation system followed by continuously-turned plug-flow composting over three seasons. Emissions were measured separately from the continuously-turned compost phase, and the compost-storage phase prior to the compost being used for cattle bedding. Active composting had low emissions of N 2 O and CH 4 with most carbon being emitted as CO 2 -C and most N emitted as NH 3 -N. Compost storage had higher CH 4 and N 2 O emissions than the active phase, while NH 3 was emitted at a lower rate, and CO 2 was similar. Overall, combining both the active composting and storage phases, the mean total emissions were 3.9×10 -2 gCH 4 kg -1 raw manure (RM), 11.3gCO 2 kg -1 RM, 2.5×10 -4 g N 2 O kg -1 RM, and 0.13g NH 3 kg -1 RM. Emissions with solid-separation and composting were compared to calculated emissions for a traditional (unseparated) liquid manure storage tank. The total greenhouse gas emissions (CH 4 +N 2 O) from solid separation, composting, compost storage, and separated liquid storage were reduced substantially on a CO 2 -equivalent basis compared to traditional liquid storage. Solid-liquid separation and well-managed composting could mitigate overall greenhouse gas emissions; however, an environmental trade off was that NH 3 was emitted at higher rates from the continuously turned composter than reported values for traditional storage. Crown Copyright © 2017. Published by Elsevier Ltd. All rights reserved.

Low-temperature anaerobic digestion of swine manure in a plug-flow reactor.

PubMed

Massé, Daniel I; Gilbert, Yan; Saady, N M C; Liu, Charle

2013-01-01

A low-temperature (25 degrees C) anaerobic eight-compartment (PF01 to PF08) cascade reactor simulating a plug-flow reactor (PFR) treating pig manure was monitored for a year. The bioreactor was fed at an average loading rate of 2.4 +/- 0.2 g of total chemical oxygen demand (TCOD) per litre of reactor per day for a theoretical hydraulic retention time (HRT) of 67 +/- 7 d. An average of 79% of TCOD was removed from pig manure (converted into biogas and in sediments), whereas specific methane yields ranging from 397 to 482 NL CH4 kg(-1) VS (148.6 to 171.4 NL CH4 kg(-1) TCOD) were obtained. After 150 d, fluctuating performances of the process were observed, associated with solids accumulation in the upstream compartments, preventing the complete anaerobic digestion of swine manure in the compartments PF01 to PF04. Low-temperature anaerobic PFR represents an interesting alternative for the treatment of pig manure and recovery of green energy. Further investigations regarding a modified design, with better accumulating solids management, are needed to optimize the performance of this low-temperature PFR treating pig manure.

A direct numerical simulation study of flame structure and stabilization of an experimental high Ka CH 4/air premixed jet flame

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

Wang, Haiou; Hawkes, Evatt R.; Chen, Jacqueline H.

In the present work, a direct numerical simulation (DNS) of an experimental high Karlovitz number (Ka) CH 4/air piloted premixed flame was analyzed to study the inner structure and the stabilization mechanism of the turbulent flame. A reduced chemical mechanism for premixed CH 4/air combustion with NO x based on GRI-Mech3.0 was used, including 268 elementary reactions and 28 transported species. The evolution of the stretch factor, I0, indicates that the burning rate per unit flame surface area is considerably reduced in the near field and exhibits a minimum at x/D = 8. Downstream, the burning rate gradually increases. Themore » stretch factor is different between different species, suggesting the quenching of some reactions but not others. Comparison between the turbulent flame and strained laminar flames indicates that certain aspects of the mean flame structure can be represented surprisingly well by flamelets if changes in boundary conditions are accounted for and the strain rate of the mean flow is employed; however, the thickening of the flame due to turbulence is not captured. The spatial development of displacement speeds is studied at higher Ka than previous DNS. In contrast to almost all previous studies, the mean displacement speed conditioned on the flame front is negative in the near field, and the dominant contribution to the displacement speed is normal diffusion with the reaction contribution being secondary. Further downstream, reaction overtakes normal diffusion, contributing to a positive displacement speed. The negative displacement speed in the near field implies that the flame front situates itself in the pilot region where the inner structure of the turbulent flame is affected significantly, and the flame stabilizes in balance with the inward flow. Notably, in the upstream region of the turbulent flame, the main reaction contributing to the production of OH, H+O 2⇌O+OH (R35), is weak. Moreover, oxidation reactions, H 2+OH⇌H+H 2O (R79) and CO+OH⇌CO 2+H (R94), are influenced by H 2O and CO 2 from the pilot and are completely quenched. Hence, the entire radical pool of OH, H and O is affected. Furthermore, the fuel consumption layer remains comparably active and generates heat, mainly via the reaction CH 4+OH⇌CH 3+H 2O (R93).« less

A direct numerical simulation study of flame structure and stabilization of an experimental high Ka CH 4/air premixed jet flame

DOE PAGES

Wang, Haiou; Hawkes, Evatt R.; Chen, Jacqueline H.

2017-03-17

In the present work, a direct numerical simulation (DNS) of an experimental high Karlovitz number (Ka) CH 4/air piloted premixed flame was analyzed to study the inner structure and the stabilization mechanism of the turbulent flame. A reduced chemical mechanism for premixed CH 4/air combustion with NO x based on GRI-Mech3.0 was used, including 268 elementary reactions and 28 transported species. The evolution of the stretch factor, I0, indicates that the burning rate per unit flame surface area is considerably reduced in the near field and exhibits a minimum at x/D = 8. Downstream, the burning rate gradually increases. Themore » stretch factor is different between different species, suggesting the quenching of some reactions but not others. Comparison between the turbulent flame and strained laminar flames indicates that certain aspects of the mean flame structure can be represented surprisingly well by flamelets if changes in boundary conditions are accounted for and the strain rate of the mean flow is employed; however, the thickening of the flame due to turbulence is not captured. The spatial development of displacement speeds is studied at higher Ka than previous DNS. In contrast to almost all previous studies, the mean displacement speed conditioned on the flame front is negative in the near field, and the dominant contribution to the displacement speed is normal diffusion with the reaction contribution being secondary. Further downstream, reaction overtakes normal diffusion, contributing to a positive displacement speed. The negative displacement speed in the near field implies that the flame front situates itself in the pilot region where the inner structure of the turbulent flame is affected significantly, and the flame stabilizes in balance with the inward flow. Notably, in the upstream region of the turbulent flame, the main reaction contributing to the production of OH, H+O 2⇌O+OH (R35), is weak. Moreover, oxidation reactions, H 2+OH⇌H+H 2O (R79) and CO+OH⇌CO 2+H (R94), are influenced by H 2O and CO 2 from the pilot and are completely quenched. Hence, the entire radical pool of OH, H and O is affected. Furthermore, the fuel consumption layer remains comparably active and generates heat, mainly via the reaction CH 4+OH⇌CH 3+H 2O (R93).« less

Thermal regulation of methane hydrate dissociation: Implications for gas production models

USGS Publications Warehouse

Circone, S.; Kirby, S.H.; Stern, L.A.

2005-01-01

Thermal self-regulation of methane hydrate dissociation at pressure, temperature conditions along phase boundaries, illustrated by experiment in this report, is a significant effect with potential relevance to gas production from gas hydrate. In surroundings maintained at temperatures above the ice melting point, the temperature in the vicinity of dissociating methane hydrate will decrease because heat flow is insufficient to balance the heat absorbed by the endothermic reaction: CH4??nH2O (s) = CH4 (g) + nH2O (l). Temperature decreases until either all of the hydrate dissociates or a phase boundary is reached. At pressures above the quadruple point, the temperature-limiting phase boundary is that of the dissociation reaction itself. At lower pressures, the minimum temperature is limited by the H2O solid/liquid boundary. This change in the temperature-limiting phase boundary constrains the pressure, temperature conditions of the quadruple point for the CH4-H2O system to 2.55 ?? 0.02 MPa and 272.85 ?? 0.03 K. At pressures below the quadruple point, hydrate dissociation proceeds as the liquid H2O produced by dissociation freezes. In the laboratory experiments, dissociation is not impeded by the formation of ice byproduct per se; instead rates are proportional to the heat flow from the surroundings. This is in contrast to the extremely slow dissociation rates observed when surrounding temperatures are below the H2O solid/liquid boundary, where no liquid water is present. This "anomalous" or "self" preservation behavior, most pronounced near 268 K, cannot be accessed when surrounding temperatures are above the H2O solid/liquid boundary. ?? 2005 American Chemical Society.

Geologic emissions of methane to the atmosphere.

PubMed

Etiope, Giuseppe; Klusman, Ronald W

2002-12-01

The atmospheric methane budget is commonly defined assuming that major sources derive from the biosphere (wetlands, rice paddies, animals, termites) and that fossil, radiocarbon-free CH4 emission is due to and mediated by anthropogenic activity (natural gas production and distribution, and coal mining). However, the amount of radiocarbon-free CH4 in the atmosphere, estimated at approximately 20% of atmospheric CH4, is higher than the estimates from statistical data of CH4 emission from fossil fuel related anthropogenic sources. This work documents that significant amounts of "old" methane, produced within the Earth crust, can be released naturally into the atmosphere through gas permeable faults and fractured rocks. Major geologic emissions of methane are related to hydrocarbon production in sedimentary basins (biogenic and thermogenic methane) and, subordinately, to inorganic reactions (Fischer-Tropsch type) in geothermal systems. Geologic CH4 emissions include diffuse fluxes over wide areas, or microseepage, on the order of 10(0)-10(2) mg m(-2) day(-1), and localised flows and gas vents, on the order of 10(2) t y(-1), both on land and on the seafloor. Mud volcanoes producing flows of up to 10(3) t y(-1) represent the largest visible expression of geologic methane emission. Several studies have indicated that methanotrophic consumption in soil may be insufficient to consume all leaking geologic CH4 and positive fluxes into the atmosphere can take place in dry or seasonally cold environments. Unsaturated soils have generally been considered a major sink for atmospheric methane, and never a continuous, intermittent, or localised source to the atmosphere. Although geologic CH4 sources need to be quantified more accurately, a preliminary global estimate indicates that there are likely more than enough sources to provide the amount of methane required to account for the suspected missing source of fossil CH4.

A five-year study of the impact of nitrogen addition on methane uptake in alpine grassland.

PubMed

Yue, Ping; Li, Kaihui; Gong, Yanming; Hu, Yukun; Mohammat, Anwar; Christie, Peter; Liu, Xuejun

2016-08-30

It remains unclear how nitrogen (N) deposition affects soil methane (CH4) uptake in semiarid and arid zones. An in situ field experiment was conducted from 2010 to 2014 to systematically study the effect of various N application rates (0, 10, 30, and 90 kg N ha(-1) yr(-1)) on CH4 flux in alpine grassland in the Tianshan Mountains. No significant influence of N addition on CH4 uptake was found. Initially the CH4 uptake rate increased with increasing N application rate by up to 11.5% in 2011 and then there was gradual inhibition by 2014. However, the between-year variability in CH4 uptake was very highly significant with average uptake ranging from 52.9 to 106.6 μg C m(-2) h(-1) and the rate depended largely on seasonal variability in precipitation and temperature. CH4 uptake was positively correlated with soil temperature, air temperature and to a lesser extent with precipitation, and was negatively correlated with soil moisture and NO3(-)-N content. The results indicate that between-year variability in CH4 uptake was impacted by precipitation and temperature and was not sensitive to elevated N deposition in alpine grassland.

A five-year study of the impact of nitrogen addition on methane uptake in alpine grassland

PubMed Central

Yue, Ping; Li, Kaihui; Gong, Yanming; Hu, Yukun; Mohammat, Anwar; Christie, Peter; Liu, Xuejun

2016-01-01

It remains unclear how nitrogen (N) deposition affects soil methane (CH4) uptake in semiarid and arid zones. An in situ field experiment was conducted from 2010 to 2014 to systematically study the effect of various N application rates (0, 10, 30, and 90 kg N ha−1 yr−1) on CH4 flux in alpine grassland in the Tianshan Mountains. No significant influence of N addition on CH4 uptake was found. Initially the CH4 uptake rate increased with increasing N application rate by up to 11.5% in 2011 and then there was gradual inhibition by 2014. However, the between-year variability in CH4 uptake was very highly significant with average uptake ranging from 52.9 to 106.6 μg C m−2 h−1 and the rate depended largely on seasonal variability in precipitation and temperature. CH4 uptake was positively correlated with soil temperature, air temperature and to a lesser extent with precipitation, and was negatively correlated with soil moisture and NO3−-N content. The results indicate that between-year variability in CH4 uptake was impacted by precipitation and temperature and was not sensitive to elevated N deposition in alpine grassland. PMID:27571892

Effect of a Hypocretin/Orexin Antagonist on Neurocognitive Performance

DTIC Science & Technology

2013-09-01

Calibration curves were constructed using Chromeleon 6.8.0 software (Dionex, Corp). Amino acids , glutamate and GABA were assayed using HPLC-EC. The...mobile phase consisted of 100 mM Na2HPO4, 22% MEOH, and 3.5% acetonitrile, pH 6.75 and set to a flow rate of 0.4 mL/min. The amino acids were detected...the basal forebrain are affected by ALM and ZOL, neurons that express choline acetyltransferase (ChAT), a marker for ACh, were scored for Fos co

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.

The Coupled Photochemistry of Ammonia and Acetylene: Applications to the Atmospheric Chemistry on Jupiter

NASA Astrophysics Data System (ADS)

Keane, Thomas Christopher

1995-01-01

The existence of hydrogen cyanide (HCN) in the highly reducing atmosphere of Jupiter was a surprising discovery (Tokunaga et al., 1981). Previous studies that tested the theoretical proposal of Kaye and Strobel (1983a) that the HCN observed on Jupiter is the result of NH _3 photolysis in the presence of C _2H_2 established that acetonitrile (CH_3CN) and acetaldazine (CH _3CH=NN=CHCH_3) are important intermediates in HCN formation (Ferris and Ishikawa, 1988). In this study the rates of formation of these compounds, and of other recently detected intermediates, have been determined in static photolysis experiments at 296 K and at temperatures which are closer to those found in the Jovian atmosphere. Experiments were also performed, using a photochemical flow reactor, that allowed for a better approximation of the mixing ratios of reactant gases (8 times 10^{ -4} for NH_3 and 1 times 10^{-5} for C_2H_2) and the process of advection in the Jovian atmosphere. An overall reaction pathway for HCN formation is proposed. Major intermediates and products found in these laboratory simulations that have not yet been observed on Jupiter are acetonitrile (CH_3CN), acetaldazine (CH_3CH=NN=CHCH _3), acetaldehyde hydrazone (CH_3 CH=NNH_2), N-ethylethylideneimine (CH_3CH=NC_2H _5), ethylamine (C_2H _5NH_2) and methylamine (CH _3NH_2). HCN is formed by the photolysis of NH_3/C _2H_2 mixtures (40:5 torr) at 296 K and at low temperature (208 K, 195 K and 180 K) with the highest quantum efficiency for HCN formation observed at 180 K. In static experiments using a high partial pressure of H_2 the quantum yield for HCN formation decreased three-fold relative to the 296 K photolyses when no H_2 was used. An additional ten-fold decrease in the quantum yield for HCN formation occurred when using the flow system. The quantum yields for acetaldazine and acetaldehyde hydrazone formation were found to vary inversely to that for HCN formation. For those static experiments which best simulate Jovian reaction conditions (H_2: NH_3 : C_2H_2 = 600: 7.5: 5 torr, 180 K) the following products and their quantum yields for formation were obtained: C_2H_4 (0.129), CH_3 CH=NN=CHCH_3 (0.079), CH _3CH=NNH_2 (0.049), C_2H_5NH_2 (0.038), CH_3NH_2 (0.003), CH_3CN (0.002), HCN (0.001) and CH_3CH=NC _2H_5 (0.001).

A Multi-scale Approach for CO2 Accounting and Risk Analysis in CO2 Enhanced Oil Recovery Sites

NASA Astrophysics Data System (ADS)

Dai, Z.; Viswanathan, H. S.; Middleton, R. S.; Pan, F.; Ampomah, W.; Yang, C.; Jia, W.; Lee, S. Y.; McPherson, B. J. O. L.; Grigg, R.; White, M. D.

2015-12-01

Using carbon dioxide in enhanced oil recovery (CO2-EOR) is a promising technology for emissions management because CO2-EOR can dramatically reduce carbon sequestration costs in the absence of greenhouse gas emissions policies that include incentives for carbon capture and storage. This study develops a multi-scale approach to perform CO2 accounting and risk analysis for understanding CO2 storage potential within an EOR environment at the Farnsworth Unit of the Anadarko Basin in northern Texas. A set of geostatistical-based Monte Carlo simulations of CO2-oil-water flow and transport in the Marrow formation are conducted for global sensitivity and statistical analysis of the major risk metrics: CO2 injection rate, CO2 first breakthrough time, CO2 production rate, cumulative net CO2 storage, cumulative oil and CH4 production, and water injection and production rates. A global sensitivity analysis indicates that reservoir permeability, porosity, and thickness are the major intrinsic reservoir parameters that control net CO2 injection/storage and oil/CH4 recovery rates. The well spacing (the distance between the injection and production wells) and the sequence of alternating CO2 and water injection are the major operational parameters for designing an effective five-spot CO2-EOR pattern. The response surface analysis shows that net CO2 injection rate increases with the increasing reservoir thickness, permeability, and porosity. The oil/CH4 production rates are positively correlated to reservoir permeability, porosity and thickness, but negatively correlated to the initial water saturation. The mean and confidence intervals are estimated for quantifying the uncertainty ranges of the risk metrics. The results from this study provide useful insights for understanding the CO2 storage potential and the corresponding risks of commercial-scale CO2-EOR fields.

Effects of biochar and wood pellets amendments added to landfill cover soil on microbial methane oxidation: A laboratory column study.

PubMed

Yargicoglu, Erin N; Reddy, Krishna R

2017-05-15

Alternate landfill covers designed to enhance microbial methane (CH 4 ) oxidation and reduce the negative impacts of landfill gas emissions on global climate have recently been proposed and investigated. In this study, the use of biochar as a soil amendment is examined in order to assess the feasibility and effectiveness for enhanced CH 4 removal in landfill covers when incorporated under high compaction conditions and relatively low soil moisture. Four different cover configurations were tested in large soil columns for ∼510 days and potential CH 4 oxidation rates were determined following long-term incubation in small batch assays. Cover designs tested include: a thin biochar layer at 15-18 cm; 2% mixed soil-biochar layer at 20-40 cm; 2% mixed soil-uncharred wood pellets at 20-40 cm; and soil obtained from intermediate cover at an active landfill site. The placement of a thin biochar layer in the cover significantly impacted moisture distribution and infiltration, which in turn affected CH 4 oxidation potential with depth. An increase in CH 4 removal rates was observed among all columns over the 500 day incubation period, with steady-state CH 4 removal efficiencies ranging from ∼60 to 90% in the final stages of incubation (inlet load ∼80 g CH 4  m -2  d -1 ). The thin biochar layer had the lowest average removal efficiency as a result of reduced moisture availability below the biochar layer. The addition of 2% biochar to soil yielded similar CH 4 oxidation rates in terminal assays as the 2% uncharred wood pellet amendment. CH 4 oxidation rates in terminal assays were positively correlated with soil moisture, which was affected by the materials' water holding capacity. The high water holding capacity of biochar led to higher oxidation rates within the thin biochar layer, supporting the initial hypothesis that biochar may confer more favorable physical conditions for methanotrophy. Ultimate performance was apparently affected by soil type and CH 4 exposure history, with the highest oxidation rates observed in the unamended field soil with higher initial methanotrophic activity. Copyright © 2017 Elsevier Ltd. All rights reserved.

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].

Contribution of rice straw carbon to CH4 emission from rice paddies using 13C-enriched rice straw

NASA Astrophysics Data System (ADS)

Watanabe, Akira; Yoshida, Mariko; Kimura, Makoto

1998-04-01

It is generally recognized that the application of rice straw (RS) increases CH4 emission from rice paddies. To estimate the contribution of RS carbon to CH4 emission, a pot experiment was conducted using 13C-enriched RS. The percentage contributions of RS carbon to CH4 emission throughout the rice growth period were 10±1, 32±3, and 43±3% for the treatments with RS applied at the rates of 2, 4, and 6 g kg-1 soil, respectively. The increase in the rate of application of RS increased CH4 emission derived from both RS carbon and other carbon sources. The percentage contribution of RS carbon to CH4 emission was larger in the earlier period (maximum 96%) when the decomposition rate of RS was larger. After RS decomposition had slowed, CH4 emission derived from RS carbon decreased. However, the δ13C values of CH4 emitted from the pots with 13C-enriched RS applied at rates of 4 and 6 g kg-1 soil were significantly higher than those from the pots with natural RS until the harvesting stage. An increased atom-13C% of roots of rice plants growing in the pots with 6 g kg-1 of 13C-enriched RS at around the maximum tiller number stage and a decrease during the following 2 months suggested that rice plants assimilated RS carbon once and then released a portion of it. This supply of RS carbon from roots may be one of the sources of CH4 in the late period of rice growth.

Mechanisms and rates of proton transfer to coordinated carboxydithioates: studies on [Ni(S2CR){PhP(CH2CH2PPh2)2}](+) (R = Me, Et, Bu(n) or Ph).

PubMed

Alwaaly, Ahmed; Clegg, William; Henderson, Richard A; Probert, Michael R; Waddell, Paul G

2015-02-21

The complexes [Ni(S2CR)(triphos)]BPh4 (R = Me, Et, Bu(n) or Ph; triphos = PhP{CH2CH2PPh2}2) have been prepared and characterised. X-ray crystallography (for R = Et, Ph, C6H4Me-4, C6H4OMe-4 and C6H4Cl-4) shows that the geometry of the five-coordinate nickel in the cation is best described as distorted trigonal bipyramidal, containing a bidentate carboxydithioate ligand with the two sulfur atoms spanning axial and equatorial sites, the other axial site being occupied by the central phosphorus of triphos. The reactions of [Ni(S2CR)(triphos)](+) with mixtures of HCl and Cl(-) in MeCN to form equilibrium solutions containing [Ni(SH(S)CR)(triphos)](2+) have been studied using stopped-flow spectrophotometry. The kinetics show that proton transfer is slower than the diffusion-controlled limit and involves at least two coupled equilibria. The first step involves the rapid association between [Ni(S2CR)(triphos)](+) and HCl to form the hydrogen-bonded precursor, {[Ni(S2CR)(triphos)](+)HCl} (K) and this is followed by the intramolecular proton transfer (k) to produce [Ni(SH(S)CR)(triphos)](2+). In the reaction of [Ni(S2CMe)(triphos)](+) the rate law is consistent with the carboxydithioate ligand undergoing chelate ring-opening after protonation. It seems likely that chelate ring-opening occurs for all [Ni(S2CR)(triphos)](+), but only with [Ni(S2CMe)(triphos)](+) is the protonation step sufficiently fast that chelate ring-opening is rate-limiting. With all other systems, proton transfer is rate-limiting. DFT calculations indicate that protonation can occur at either sulfur atom, but only protonation at the equatorial sulfur results in chelate ring-opening. The ways in which protonation of either sulfur atom complicates the analyses and interpretation of the kinetics are discussed.

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.

Temperate forest methane sink diminished by tree emissions.

PubMed

Pitz, Scott; Megonigal, J Patrick

2017-06-01

Global budgets ascribe 4-10% of atmospheric methane (CH 4 ) sinks to upland soils and have assumed until recently that soils are the sole surface for CH 4 exchange in upland forests. Here we report that CH 4 is emitted from the stems of dominant tree species in a temperate upland forest, measured using both the traditional static-chamber method and a new high-frequency, automated system. Tree emissions averaged across 68 observations on 17 trees from May to September were 1.59 ± 0.88 μmol CH 4  m -2  stem h -1 (mean ± 95% confidence interval), while soils adjacent to the trees consumed atmospheric CH 4 at a rate of -4.52 ± 0.64 μmol CH 4  m -2  soil h -1 (P < 0.0001). High-frequency measurements revealed diurnal patterns in the rate of tree-stem CH 4 emissions. A simple scaling exercise suggested that tree emissions offset 1-6% of the growing season soil CH 4 sink and may have briefly changed the forest to a net CH 4 source. © 2017 The Authors. New Phytologist © 2017 New Phytologist Trust.

Effect of summer annuals on ruminal fermentation and methane output in continuous culture

USDA-ARS?s Scientific Manuscript database

Summer annuals (SA) provide forage during the summer “forage slump”, yet research on ruminal fermentation and CH4 output of SA is lacking. A 4-unit, dual-flow continuous culture fermentor system was used to assess nutrient digestibility, VFA production, bacterial protein synthesis, and CH4 output of...

A numerical comparison of cold flow and combustion characteristics for GCH4/GO2 splash platelet injector

NASA Astrophysics Data System (ADS)

Yin, Liang; Liu, Weiqiang

2018-04-01

The differences between cold flow and combustion under the same condition were investigated by the numerical simulations, an eddy dissipation concept (EDC) with 16 species and 41 reactions is considered for the CH4/O2 combustion. Three configurations of the splash platelet injector were selected for these simulations. Results show that cold flow and combustion have evident differences. Compared with cold flow, CH4 mole fraction was more evenly distributed in the combustion chamber head, and the mixing of propellants was lagged by the combustion of multi-elements. However, this conclusion is contrary for the single element. The recirculation zones were observable near the injector faceplate at the combustion condition. Moreover, the cold flow simulation cannot reflect the actual combustion but can provide a reference value for experimental research.

A systematic comparison of two empirical gas-liquid mass transfer determination methodologies to characterize methane biodegradation in stirred tank bioreactors.

PubMed

Muñoz, Raul; Soto, Cenit; Zuñiga, Cristal; Revah, Sergio

2018-07-01

This study aimed at systematically comparing the potential of two empirical methods for the estimation of the volumetric CH 4 mass transfer coefficient (k l a CH4 ), namely gassing-out and oxygen transfer rate (OTR), to describe CH 4 biodegradation in a fermenter operated with a methanotrophic consortium at 400, 600 and 800 rpm. The k l a CH4 estimated from the OTR methodology accurately predicted the CH 4 elimination capacity (EC) under CH 4 mass transfer limiting conditions regardless of the stirring rate (∼9% of average error between empirical and estimated ECs). Thus, empirical CH 4 -ECs of 37.8 ± 5.8, 42.5 ± 5.4 and 62.3 ± 5.2 g CH 4 m -3 h -1 vs predicted CH 4 -ECs of 35.6 ± 2.2, 50.1 ± 2.3 and 59.6 ± 3.4 g CH 4 m -3 h -1 were recorded at 400, 600 and 800 rpm, respectively. The rapid Co 2+ -catalyzed reaction of O 2 with SO 3 -2 in the vicinity of the gas-liquid interphase during OTR determinations, mimicking microbial CH 4 uptake in the biotic experiments, was central to accurately describe the k l a CH4 . Copyright © 2018 Elsevier Ltd. All rights reserved.

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.)

Rate Coefficient for the (4)Heμ + CH4 Reaction at 500 K: Comparison between Theory and Experiment.

PubMed

Arseneau, Donald J; Fleming, Donald G; Li, Yongle; Li, Jun; Suleimanov, Yury V; Guo, Hua

2016-03-03

The rate constant for the H atom abstraction reaction from methane by the muonic helium atom, Heμ + CH4 → HeμH + CH3, is reported at 500 K and compared with theory, providing an important test of both the potential energy surface (PES) and reaction rate theory for the prototypical polyatomic CH5 reaction system. The theory used to characterize this reaction includes both variational transition-state (CVT/μOMT) theory (VTST) and ring polymer molecular dynamics (RPMD) calculations on a recently developed PES, which are compared as well with earlier calculations on different PESs for the H, D, and Mu + CH4 reactions, the latter, in particular, providing for a variation in atomic mass by a factor of 36. Though rigorous quantum calculations have been carried out for the H + CH4 reaction, these have not yet been extended to the isotopologues of this reaction (in contrast to H3), so it is important to provide tests of less rigorous theories in comparison with kinetic isotope effects measured by experiment. In this regard, the agreement between the VTST and RPMD calculations and experiment for the rate constant of the Heμ + CH4 reaction at 500 K is excellent, within 10% in both cases, which overlaps with experimental error.

Emission of greenhouse gases and soil carbon sequestration in a riparian marsh wetland in central Ohio.

PubMed

Nag, Subir K; Liu, Ruiqiang; Lal, Rattan

2017-10-23

Wetlands are a C sink, but they also account for a large natural source of greenhouse gases (GHG), particularly methane (CH 4 ). Soils of wetlands play an important role in alleviating the global climate change regardless of the emission of CH 4 . However, there are uncertainties about the amount of C stored and emitted from wetlands because of the site specific factors. Therefore, the present study was conducted in a temperate riverine flow-through wetland, part of which was covered with emerging macrophyte Typhus latifolia in central Ohio, USA, with the objective to assess emissions of GHGs (CH 4, CO 2 , N 2 O) and measure C and nitrogen (N) stocks in wetland soil in comparison to a reference upland site. The data revealed that CH 4 emission from the open and vegetated wetland ranged from 1.03-0.51 Mg C/ha/y and that of CO 2 varied from 1.26-1.51 Mg C/ha/y. In comparison, CH 4 emission from reference upland site was negligible (0.01 Mg C/ha/y), but CO 2 emission was much higher (3.24 Mg C/ha/y). The stock of C in wetland soil was 85 to 125 Mg C/ha up to 0.3 m depth. The average rate of emission was 2.15 Mg C/ha/y, but the rate of sequestration was calculated as 5.55 Mg C/ha/y. Thus, the wetland was actually a C sink. Emission of N 2 O was slightly higher in vegetated wetland (0.153 mg N 2 O-N/m 2 /h) than the open wetland and the reference site (0.129 mg N 2 O-N/m 2 /h). Effect of temperature on emission of GHGs from the systems was also studied.

Soil-atmospheric exchange of CO2, CH4, and N2O in three subtropical forest ecosystems in southern China

USGS Publications Warehouse

Tang, X.; Liu, S.; Zhou, G.; Zhang, Dongxiao; Zhou, C.

2006-01-01

The magnitude, temporal, and spatial patterns of soil-atmospheric greenhouse gas (hereafter referred to as GHG) exchanges in forests near the Tropic of Cancer are still highly uncertain. To contribute towards an improvement of actual estimates, soil-atmospheric CO2, CH4, and N2O fluxes were measured in three successional subtropical forests at the Dinghushan Nature Reserve (hereafter referred to as DNR) in southern China. Soils in DNR forests behaved as N2O sources and CH4 sinks. Annual mean CO2, N2O, and CH4 fluxes (mean ?? SD) were 7.7 ?? 4.6MgCO2-Cha-1 yr-1, 3.2 ?? 1.2 kg N2ONha-1 yr-1, and 3.4 ?? 0.9 kgCH4-Cha-1 yr-1, respectively. The climate was warm and wet from April through September 2003 (the hot-humid season) and became cool and dry from October 2003 through March 2004 (the cool-dry season). The seasonality of soil CO2 emission coincided with the seasonal climate pattern, with high CO2 emission rates in the hot-humid season and low rates in the cool-dry season. In contrast, seasonal patterns of CH4 and N2O fluxes were not clear, although higher CH4 uptake rates were often observed in the cool-dry season and higher N2O emission rates were often observed in the hot-humid season. GHG fluxes measured at these three sites showed a clear increasing trend with the progressive succession. If this trend is representative at the regional scale, CO2 and N2O emissions and CH4 uptake in southern China may increase in the future in light of the projected change in forest age structure. Removal of surface litter reduced soil CO2 effluxes by 17-44% in the three forests but had no significant effect on CH4 absorption and N2O emission rates. This suggests that microbial CH4 uptake and N2O production was mainly related to the mineral soil rather than in the surface litter layer. ?? 2006 Blackwell Publishing Ltd.

Flow Reactor Studies with Nanosecond Pulsed Discharges at Atmospheric Pressure and Higher

DTIC Science & Technology

2013-10-01

Experiment and model analysis of low temperature C2H4/N2/O2/Ar mixtures suggest intermediate formation of nitromethane . Formation of such nitro and...Large amount of nitromethane (CH3NO2) forms within the plasma region, by CH3+NO2(+M)=CH3NO2(+M). Downstream, CH3NO2 then decomposes. • Current model

Methane production and emissions from four reclaimed and pristine wetlands of Southeastern United States

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

Schipper, L.A.; Reddy, K.R.

Wetlands are significant contributors to global CH[sub 4] emission. We measured CH[sub 4] emissions at two pristine wetlands [Okefenokee swamp and the Everglades (Water Conservation Area 2A)] and two reclaimed wetlands (Sunny Hill Farm and Apopka Marsh) in Southeastern USA, and we attempted to relate emissions to CH[sub 4] production rates of the soil and the soil's biological and chemical properties. Methane emissions through cattail [Typha sp.] and waterilly [Nymphaea ordorata (L.)] ranged from 0.09 to 1.7 g CH[sub 4] m[sup [minus]2] d[sup [minus]1] and exhibited high spatial and temporal variability. Diffusive flux of CH[sub 4] was calculated using dissolvedmore » CH[sub 4] profiles in the soil pore water and accounted for <5% of the plant-mediated emissions. Potential CH[sub 4] production rates were measured as a function of depth using soil samples obtained at 2-cm increments. Methane production rates were the same order of magnitude at all sites (<1-70 ng CH[sub 4]-C g[sup [minus]1] soil C d[sup [minus]1]) and were highest in the surface soils (0-6 cm) at three of the wetland sites, indicating that the predominant source of C available to methanogens was in the surface soils. Methane production rates in the top 24 cm ranged from 0.3 to 1.1 g CH[sub 4] m[sup [minus]2] d[sup [minus]1] and annual C losses due to anaerobic decomposition accounted for between 0.68 and 3.7% of the total C in the surface 24-cm soil depth. 36 refs., 3 figs., 3 tabs.« 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

A new tracer experiment to estimate the methane emissions from a dairy cow shed using sulfur hexafluoride (SF6)

NASA Astrophysics Data System (ADS)

Marik, Thomas; Levin, Ingeborg

1996-09-01

Methane emission from livestock and agricultural wastes contribute globally more than 30% to the anthropogenic atmospheric methane source. Estimates of this number have been derived from respiration chamber experiments. We determined methane emission rates from a tracer experiment in a modern cow shed hosting 43 dairy cows in their accustomed environment. During a 24-hour period the concentrations of CH4, CO2, and SF6, a trace gas which has been released at a constant rate into the stable air, have been measured. The ratio between SF6 release rate and measured SF6 concentration was then used to estimate the ventilation rate of the stable air during the course of the experiment. The respective ratio between CH4 or CO2 and SF6 concentration together with the known SF6 release rate allows us to calculate the CH4 (and CO2) emissions in the stable. From our experiment we derive a total daily mean CH4 emission of 441 LSTP per cow (9 cows nonlactating), which is about 15% higher than previous estimates for German cows with comparable milk production obtained during respiration chamber experiments. The higher emission in our stable experiment is attributed to the contribution of CH4 release from about 50 m3 of liquid manure present in the cow shed in underground channels. Also, considering measurements we made directly on a liquid manure tank, we obtained an estimate of the total CH4 production from manure: The normalized contribution of methane from manure amounts to 12-30% of the direct methane release of a dairy cow during rumination. The total CH4 release per dairy cow, including manure, is 521-530 LSTP CH4 per day.

Biocatalytic methanation of hydrogen and carbon dioxide in an anaerobic three-phase system.

PubMed

Burkhardt, M; Koschack, T; Busch, G

2015-02-01

A new type of anaerobic trickle-bed reactor was used for biocatalytic methanation of hydrogen and carbon dioxide under mesophilic temperatures and ambient pressure in a continuous process. The conversion of gaseous substrates through immobilized hydrogenotrophic methanogenic archaea in a biofilm is a unique feature of this type of reactor. Due to the formation of a three-phase system on the carrier surface and operation as a plug flow reactor without gas recirculation, a complete reaction could be observed. With a methane concentration higher than c(CH4) = 98%, the product gas exhibits a very high quality. A specific methane production of P(CH4) = 1.49 Nm(3)/(m(3)(SV) d) was achieved at a hydraulic loading rate of LR(H2) = 6.0 Nm(3)/(m(3)(SV) d). The relation between trickle flow through the reactor and productivity could be shown. An application for methane enrichment in combination with biogas facilities as a source of carbon dioxide has also been positively proven. Copyright © 2014 Elsevier Ltd. All rights reserved.

Investigating CH4 production in an oxic plant-soil system -a new approach combining isotopic labelling (13C) and inhibitors

NASA Astrophysics Data System (ADS)

Lenhart, Katharina; Keppler, Frank

2017-04-01

Typically, aerated soil are net sinks of atmospheric methane (CH4), being highest in native ecosystems (pristine forests > managed forests > grasslands > crop fields). However, this does not exclude a simultaneous endogenic CH4 production in the plant-soil system, which cannot be detected simply via CH4 flux measurements. Methanogenic archaea producing CH4 under anoxic conditions were thought to be the only biotic source of CH4 in the soil. However, until recently a non-archaeal pathway of CH4 formation is known where CH4 is produced under oxic conditions in plants (Keppler et al. 2006) and fungi (Lenhart et al. 2012). Additionally, abiotic formation of CH4 from soil organic matter was reported (Jugold et al. 2012) and may be ubiquitous in terrestrial ecosystems. The major goal of this project was to determine soil endogenic CH4 sources and to estimate their contribution to the endogenic CH4 production. Especially the effect of plants and fungi on soil CH4 production was investigated. Therefore, a series of experiments was carried out on field fresh soil collected in a grassland and a forest ecosystem under controlled laboratory conditions. By combining selective inhibitors and 13C labelling, CH4 production rates of several CH4 sources were quantified. The major difficulty was to detect the comparatively small flux of CH4 production against the background of the high CH4 consumption rates due to methanotrophic bacteria. Therefore, we supplemented bare soil and soil with vegetation with selective inhibitors and 13C labelled substrates in a closed chamber system. In a first step, CH4 production was determined by the inhibition of CH4 oxidizing bacteria with Difluoromethane (DFM, 2ml l-1). In the following, a 13C labelled substrate (either CO2, Acetate, or Methionine -S-CH3 labelled) was added in combination with a specific inhibitor -either for archaeal methanogenesis (Bromoethanesulfonate), bacteria (Streptomycin), or fungi (Captan, Cycloheximide). Gas samples were taken during the incubation for CH4 and CO2 concentration measurements and isotope ratio mass spectrometry (CH4, CO2). Grassland and forest soils showed differences in CO2 and CH4 production rates. Based on the 13C-CH4 signature we found that all substrates were metabolized to CH4, but to a different degree. Inhibitors reduced CH4 production and conversion of certain substrates to a different degree. Using the example of acetate and cycloheximide, in both soils acetate increased respiration, whereas cycloheximide reduced respiration by 56 and 62 %, respectively. For CH4 production, however, no effect was visible for the grassland soil, but in the forest soil CH4 production increased by 69 %. Cycloheximide inhibited the substrate-induced CH4 production by 63 %, indicating that fungi were responsible for this pathway. Moreover, the finding that fungi use the methyl group of acetate to produce CH4 was also verified with a sterile culture. References Lenhart, K. et al. Evidence for methane production by saprotrophic fungi. Nat Commun 3, 1046, (2012). Keppler, F., et al. Methane emissions from terrestrial plants under aerobic conditions. Nature 439, 187-191 (2006). Jugold, A. et al. Non-microbial methane formation in oxic soils. Biogeosciences 9, 5291-5301, (2012).

Optimization of solid state anaerobic digestion of the OFMSW by digestate recirculation: A new approach

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

Michele, Pognani, E-mail: michele.pognani@unimi.it; Giuliana, D’Imporzano, E-mail: giuliana.dimporzano@unimi.it; Gruppo Ricicla - DiSAA, Università degli Studi di Milano, Biomass and Bioenergy Lab., Parco Tecnologico Padano, Via Einstein, Loc. C.na Codazza, 26900 Lodi

2015-01-15

Highlights: • Solid State Anaerobic Digestion (SSAD) of OFMSW can be optimized by irrigation with digestate. • Digestate spreading allows keeping optimal process parameters and high hydrolysis rate. • The 18.4% of CH{sub 4} was produced in the reactor, leaving the 49.7% in the percolate. • Successive CSTR feed with percolate shows a biogas enriched in methane (more than 80%). • The proposed process allow producing the 68% of OFMSW potential CH{sub 4}, getting high quality organic amendment. - Abstract: Dry anaerobic digestion (AD) of OFMSW was optimized in order to produce biogas avoiding the use of solid inoculum. Doingmore » so the dry AD was performed irrigating the solid waste with liquid digestate (flow rate of 1:1.18–1:0.9 w/w waste/digestate; 21 d of hydraulic retention time – HRT) in order to remove fermentation products inhibiting AD process. Results indicated that a high hydrolysis rate of organic matter (OM) and partial biogas production were obtained directly during the dry AD. Hydrolysate OM was removed from digester by the percolate flow and it was subsequently used to feed a liquid anaerobic digester. During dry AD a total loss of 36.9% of total solids was recorded. Methane balance indicated that 18.4% of potential methane can be produced during dry AD and 49.7% by the percolate. Nevertheless results obtained for liquid AD digestion indicated that only 20.4% and 25.7% of potential producible methane was generated by adopting 15 and 20 days of HRT, probably due to the AD inhibition due to high presence of toxic ammonia forms in the liquid medium.« less

Inverse Modeling of Surface CH4 and δ13C-CH4 Measurements to Understand Recent Trends in Global Methane Emissions

NASA Astrophysics Data System (ADS)

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

2016-12-01

Methane (CH4) is the second most important greenhouse gas with a radiative forcing of 0.97 W/m2 including both direct and indirect effects and a global warming potential of 28 over a 100-year time horizon. Unlike CO2 whose rate of growth in the atmosphere has remained positive and increased in recent decades, the behavior of atmospheric methane is considerably more complex and is much less understood on account of the spatiotemporal variability of its emissions which include biogenic (e.g. wetlands, ruminants, rice agriculture), thermogenic (fossil fuels), and pyrogenic (i.e. biomass burning) sources. After sustained growth during most of the 20th century, the CH4 growth rate declined falling from 15 ppbv/yr during the 1980s to 6 ppbv/yr in the 1990s to near-zero and even negative values in the early 2000s. With some surprise however, the growth rate rebounded in 2007 and has been on average 6 ppbv/yr during the past 10 years. During this same period the 13CH4/12CH4 ratio of atmospheric CH4 also declined suggesting the recent CH4 growth was caused by an increase in 13CH4-depleted biogenic emissions. Here, we provide additional insight into the recent behavior of atmospheric methane by performing a global three-dimensional Bayesian inversion of surface CH4 and 13CH4/12CH4 ratios over the period 1985-2015 using NOAA Global Monitoring Division (GMD) CH4 measurements and the GEOS-Chem chemical-transport model (CTM) at a horizontal grid resolution of 2ox2.5o. The use of the 3-D model allows us to exploit spatial patterns in the global CH4 and 13CH4/12CH4 fields that provide additional constraints on the retrieval of the time-dependent CH4 fluxes. This work follows up on our previous CH4 inversion where we used a 4ox5o horizontal grid for GEOS-Chem to retrieve fluxes from 1985 to 2009. At higher resolution more information is extracted from the observations due to improved model skill and a smaller number of stations aggregated within model grid cells. This increases the weights of the measurements relative to the a priori fluxes in the inversion producing stronger observational constraints on the optimized fluxes. This work assesses the contribution of spatial heterogeneities in the observed CH4 record to the retrieval of global CH4 fluxes and provides a new look into the causes of the recent growth in atmospheric methane.

Vibrational energy transfer in OH X 2Pi(i), v = 2 and 1

NASA Technical Reports Server (NTRS)

Raiche, George A.; Jeffries, Jay B.; Rensberger, Karen J.; Crosley, David R.

1990-01-01

Using an IR-pump/UV-probe method in a flow discharge cell, vibrational energy transfer in OH X 2Pi(i) has been studied. OH is prepared in v = 2 by overtone excitation, and the time evolution of population in v = 2 and 1 monitored by laser-induced fluorescence. Rate constants for vibrational relaxation by the colliders H2O, NH3, CO2, and CH4 were measured. Ratios of rate constants for removal from the two states, k2/k1, range from two to five.

Effects of temperature, ultraviolet radiation and pectin methyl esterase on aerobic methane release from plant material.

PubMed

Bruhn, D; Mikkelsen, T N; Obro, J; Willats, W G T; Ambus, P

2009-11-01

This study examines the effects of different irradiance types on aerobic methane (CH(4)) efflux rates from terrestrial plant material. Furthermore, the role of the enzyme pectin methyl esterase (PME) on CH(4) efflux potential was also examined. Different types of plant tissue and purified pectin were incubated in glass vials with different combinations of irradiation and/or temperature. Purified dry pectin was incubated in solution, and with or without PME. Before and after incubation, the concentration of CH(4) was measured with a gas chromatograph. Rates of CH(4) emission were found to depend exponentially on temperature and linearly on UV-B irradiance. UV-B had a greater stimulating effect than UV-A, while visible light had no effect on emission rates. PME was found to substantially reduce the potential for aerobic CH(4) emissions upon demethylation of pectin.

Sources and flux of natural gases from Mono Lake, California

USGS Publications Warehouse

Oremland, R.S.; Miller, L.G.; Whiticar, Michael J.

1987-01-01

The ability to identify a formation mechanism for natural gas in a particular environment requires consideration of several geochemical factors when there are multiple sources present. Four primary sources of methane have been identified in Mono Lake. Two of these sources were associated with numerous natural gas seeps which occur at various locations in the lake and extend beyond its present boundary; the two other gas sources result from current microbiological processes. In the natural gas seeps, we observed flow rates as high as 160 moles CH4 day-1, and estimate total lakewide annual seep flux to be 2.1 ?? 106 moles CH4. Geochemical parameters (??13CH4,??DCH4,CH4/[C2H6+ C3H8]) and ??14CH4measurements revealed that most of the seeps originate from a paleo-biogenic (??13CH4 = about -70%.). natural gas deposit of Pleistocene age which underlies the current and former lakebed. Gas seeps in the vicinity of hot springs had, in combination with the biogenic gas, a prominent thermogenic gas component resulting from hydrothermal alteration of buried organic matter. Current microbiological processes responsible for sources of natural gas in the lake included pelagic meth- anogenesis and decomposition of terrestrial grasses in the littoral zone. Methanogenesis in the pelagic sediments resulted in methane saturation (2-3 mM at 50 cm; ??13CH4 = about -85%.). Interstitial sulfate decreased from 133 mM at the surface to 35 mM by 110 cm depth, indicating that sulfate-reduction and methanogenesis operated concurrently. Methane diffused out of the sediments resulting in concentrations of about 50 ??M in the anoxic bottom waters. Methane oxidation in the oxic/anoxic boundry lowered the concentration by >98%, but values in surface waters (0.1-1.3??M) were supersaturated with respect to the atmosphere. The ??13CH4 (range = -21.8 to -71.8%.) of this unoxidized residual methane was enriched in 13C relative to methane in the bottom water and sediments. Average outward flux of this methane was 2.77 ?? 107 moles yr-1. A fourth, but minor source of methane (??13CH4 = -55.2%.) was associated with the decomposition of terrestrial grasses taking place in the lake's recently expanded littoral zone. ?? 1987.

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

Effects of nitrogen and phosphorus additions on soil methane uptake in disturbed forests

NASA Astrophysics Data System (ADS)

Zheng, Mianhai; Zhang, Tao; Liu, Lei; Zhang, Wei; Lu, Xiankai; Mo, Jiangming

2016-12-01

Atmospheric nitrogen (N) deposition is generally thought to suppress soil methane (CH4) uptake in natural forests, and phosphorus (P) input may alleviate this negative effect. However, it remains unclear how N and P inputs control soil CH4 uptake in disturbed forests. In this study, soil CH4 uptake rates were measured in two disturbed forests, including a secondary forest (with previous, but not recent, disturbance) and a plantation forest (with recent continuous disturbance), in southern China for 34 months of N and/or P additions: control, N addition (150 kg N ha-1 yr-1), P addition (150 kg P ha-1 yr-1), and NP addition (150 kg N ha-1 yr-1 plus 150 kg P ha-1 yr-1). Mean CH4 uptake rate in control plots was significantly higher in the secondary forest (24.40 ± 0.81 µg CH4-C m-2 h-1) than in the plantation forest (17.07 ± 0.70 µg CH4-C m-2 h-1). CH4 uptake rate had negative relationships with soil water-filled pore space in both forests. In the secondary forest, N, P, and NP additions significantly decreased CH4 uptake by 39.7%, 27.8%, and 37.6%, respectively, but had no significant effects in the plantation forest, indicating that P input does not alleviate the suppression of CH4 uptake by N deposition. Taken together, our findings suggest that reducing anthropogenic disturbance, including harvesting of forest floor, and anthropogenic N and P inputs will increase soil CH4 uptake in disturbed forests, which is important in view of the increased trends in global warming during recent decades.

No limits to peat bog growth? Transport and thermodynamic constraints on anaerobic organic matter decomposition

NASA Astrophysics Data System (ADS)

Blodau, C.; Julia, B.; Siems, M.

2009-05-01

In diffusion dominated systems, for which many thick peat deposits provide a model, slowness of transport and lack of free energy may pose a limit to methanogenic decomposition of organic matter and ultimately to closing the carbon cycle. To test this hypothesis we (I) conducted controlled column experiments with homogenized peat over an 18 month period, (II) investigated transport, in situ respiration pathways, rates and thermodynamic conditions in a nothern peatland, and (III) modelled depth profiles of CO2 and CH4 in the deposits. Vertical transport in the peatland was dominated by diffusion leading to the buildup of DIC and CH4 with depth (5500 µmol L 1 DIC, 500 µmol L 1 CH4). Highest DIC and CH4 production rates occurred close to the water table (decomposition constant kd ~10-3 to 10 4 a-1) and decreased to about kd = 10-7 a-1. The accumulation of metabolic end-products diminished in situ energy yields of acetoclastic methanogenesis to the threshold for microbially mediated processes (-20 to -25 kJ mol-1 CH4). The methanogenic precursor acetate also accumulated (150 µmol L 1). In line with these findings, CH4 was formed by hydrogenotrophic methanogenesis at Gibbs free energies of 35 to 40 kJ mol-1 CH4. This was indicated by an isotopic fractionation αCO2-CH4 of 1.069 to 1.079. Fermentative degradation of acetate, propionate and butyrate attained Gibbs free energies close to 0 kJ mol-1 substrate. In peat columns with homogenenous peat-sand mixtures of 50%, 15% and 5% dry weight, steady state CO2 production also decreased from about 10 to 0 nmol cm-3 d-1 and of CH4 from 1 to 0 nmol cm-3 d-1 with depth. Very similar depth profiles of concentrations and volumetric rates developed near endproduct thresholds of 600µmol CH4 and 10 mmol L-1 CO2, despite the differences in organic matter content. The modeling exercise showed that a consistent development of CH4 concentration profiles over time in the columns could only be accomplished with rates of acetoclastic methanogenesis decreasing to 0 near a critical Gibbs free energy of about -27 KJ mol-1. The results thus suggest that, even in absence of inorganic electron acceptors, respiration rates in peat bogs are likely higher near the redox interface to the atmosphere due to lower respiration endproduct concentrations. Similar effects ensue when rates of transport are elevated or pools of CO2 and CH4 are eliminated. With decomposition being constrained, peat bog growth may occur longer than previously thought.

Controls on gas transfer velocities in a large river

NASA Astrophysics Data System (ADS)

Beaulieu, Jake J.; Shuster, William D.; Rebholz, Jacob A.

2012-06-01

The emission of biogenic gases from large rivers can be an important component of regional greenhouse gas budgets. However, emission rate estimates are often poorly constrained due to uncertainties in the air-water gas exchange rate. We used the floating chamber method to estimate the gas transfer velocity (k) of carbon dioxide (CO2), methane (CH4), and nitrous oxide (N2O) in the Markland Pool of the Ohio River, a large tributary of the Mississippi River (U.S.A). We measured k every two weeks for a year at one site and at 15 additional sites distributed across the length of the pool during two summer surveys. We found that k was positively related to both water currents and wind speeds, with 46% of the gas transfer attributable to water currents at low wind speeds (e.g., 0.5 m s-1) and 11% at higher wind speeds (e.g., >2.0 m s-1). Gas transfer velocity was highly sensitive to wind, possibly because the direction of river flow was often directly opposed to the wind direction. Gas transfer velocity values derived for CH4 were consistently greater than those derived for CO2 when standardized to a Schmidt number of 600 (k600), possibly because the transfer of CH4, a poorly soluble gas, was enhanced by surfacing microbubbles. Additional research to determine the conditions that support microbubble enhanced gas transfer is merited.

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

NASA Astrophysics Data System (ADS)

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

2013-04-01

Permafrost-affected tundra soils are significant sources of the climate-relevant trace gas methane (CH4). The observed accelerated warming of the arctic will cause deeper permafrost thawing, followed by increased carbon mineralization and CH4 formation in water-saturated tundra soils, thus creating a positive feedback to climate change. Aerobic CH4 oxidation is regarded as the key process reducing CH4 emissions from wetlands, but quantification of turnover rates has remained difficult so far. The application of carbon stable isotope fractionation enables the in situ quantification of CH4 oxidation efficiency in arctic wetland soils. The aim of the current study is to quantify CH4 oxidation efficiency in permafrost-affected tundra soils in Russia's Lena River delta based on stable isotope signatures of CH4. Therefore, depth profiles of CH4 concentrations and δ13CH4 signatures were measured and the fractionation factors for the processes of oxidation (αox) and diffusion (αdiff) were determined. Most previous studies employing stable isotope fractionation for the quantification of CH4 oxidation in soils of other habitats (such as landfill cover soils) have assumed a gas transport dominated by advection (αtrans = 1). In tundra soils, however, diffusion is the main gas transport mechanism and diffusive stable isotope fractionation should be considered alongside oxidative fractionation. For the first time, the stable isotope fractionation of CH4 diffusion through water-saturated soils was determined with an αdiff = 1.001 ± 0.000 (n = 3). CH4 stable isotope fractionation during diffusion through air-filled pores of the investigated polygonal tundra soils was αdiff = 1.013 ± 0.003 (n = 18). Furthermore, it was found that αox differs widely between sites and horizons (mean αox = 1.017 ± 0.009) and needs to be determined on a case by case basis. The impact of both fractionation factors on the quantification of CH4 oxidation was analyzed by considering both the potential diffusion rate under saturated and unsaturated conditions and potential oxidation rates. For a submerged, organic-rich soil, the data indicate a CH4 oxidation efficiency of 50% at the anaerobic-aerobic interface in the upper horizon. The improved in situ quantification of CH4 oxidation in wetlands enables a better assessment of current and potential CH4 sources and sinks in permafrost-affected ecosystems and their potential strengths in response to global warming.

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

NASA Astrophysics Data System (ADS)

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

2012-12-01

Permafrost-affected tundra soils are significant sources of the climate-relevant trace gas methane (CH4). The observed accelerated warming of the Arctic will cause a deeper permafrost thawing followed by increased carbon mineralization and CH4 formation in water saturated tundra soils which might cause a positive feedback to climate change. Aerobic CH4 oxidation is regarded as the key process reducing CH4 emissions from wetlands, but quantification of turnover rates has remained difficult so far. The application of carbon stable isotope fractionation enables the in situ quantification of CH4 oxidation efficiency in arctic wetland soils. The aim of the current study is to quantify CH4 oxidation efficiency in permafrost-affected tundra soils in Russia's Lena River Delta based on stable isotope signatures of CH4. Therefore, depth profiles of CH4 concentrations and δ13CH4-signatures were measured and the fractionation factors for the processes of oxidation (αox) and diffusion (αdiff) were determined. Most previous studies employing stable isotope fractionation for the quantification of CH4 oxidation in soils of other habitats (e.g. landfill cover soils) have assumed a gas transport dominated by advection (αtrans = 1). In tundra soils, however, diffusion is the main gas transport mechanism, aside from ebullition. Hence, diffusive stable isotope fractionation has to be considered. For the first time, the stable isotope fractionation of CH4 diffusion through water-saturated soils was determined with an αdiff = 1.001 ± 0.000 (n = 3). CH4 stable isotope fractionation during diffusion through air-filled pores of the investigated polygonal tundra soils was αdiff = 1.013 ± 0.003 (n = 18). Furthermore, it was found that αox differs widely between sites and horizons (mean αox, = 1.017 ± 0.009) and needs to be determined individually. The impact of both fractionation factors on the quantification of CH4 oxidation was analyzed by considering both the potential diffusion rate under saturated and unsaturated conditions and potential oxidation rates. For a submerged organic rich soil, the data indicate a CH4 oxidation efficiency of 50% at the anaerobic-aerobic interface in the upper horizon. The improved in situ quantification of CH4 oxidation in wetlands enables a better assessment of current and potential CH4 sources and sinks in permafrost affected ecosystems and their potential strengths in response to global warming.

The spectroscopic observation of the CH radical in its a4Sigma(-) state

NASA Technical Reports Server (NTRS)

Nelis, Thomas; Brown, John M.; Evenson, Kenneth M.

1988-01-01

The first spectroscopic observation of CH in the a 4Sigma(0-) state are reported. The molecule was generated in a discharge-flow system in the reaction betweeen fluorine atoms and methane or between oxygen atoms and acetylene at a total pressure of about 1 Torr. Several resonances associated with the N = 1 - 0 transitions of 4Sigma(-) CH were observed at three separate laser wavelengths, while those for the N = 2 - 1 transition were observed at two wavelengths. Each observed Zeeman component consists of a well-split doublet arising from proton hyperfine structure. The reasons for assigning the observations to CH in its a 4Sigma(-) state are discussed.

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.

Importance of tunneling in H-abstraction reactions by OH radicals. The case of CH4 + OH studied through isotope-substituted analogs

NASA Astrophysics Data System (ADS)

Lamberts, T.; Fedoseev, G.; Kästner, J.; Ioppolo, S.; Linnartz, H.

2017-03-01

We present a combined experimental and theoretical study focussing on the quantum tunneling of atoms in the reaction between CH4 and OH. The importance of this reaction pathway is derived by investigating isotope substituted analogs. Quantitative reaction rates needed for astrochemical models at low temperature are currently unavailable both in the solid state and in the gas phase. Here, we study tunneling effects upon hydrogen abstraction in CH4 + OH by focusing on two reactions: CH4 + OD → CH3 + HDO and CD4 + OH → CD3 + HDO. The experimental study shows that the solid-state reaction rate RCH4 + OD is higher than RCD4 + OH at 15 K. Experimental results are accompanied by calculations of the corresponding unimolecular and bimolecular reaction rate constants using instanton theory taking into account surface effects. For the work presented here, the unimolecular reactions are particularly interesting as these provide insight into reactions following a Langmuir-Hinshelwood process. The resulting ratio of the rate constants shows that the H abstraction (kCH4 + OD) is approximately ten times faster than D-abstraction (kCD4 + OH) at 65 K. We conclude that tunneling is involved at low temperatures in the abstraction reactions studied here. The unimolecular rate constants can be used by the modeling community as a first approach to describe OH-mediated abstraction reactions in the solid phase. For this reason we provide fits of our calculated rate constants that allow the inclusion of these reactions in models in a straightforward fashion.

Activation of the manganese(I) tricarbonyl core by selective variation of bidentate ligands (L,L'-Bid = N,N' and N,O donor atom sets) in fac-[Mn(CO)3(L,L'-Bid)(CH3OH)](n) complexes.

PubMed

Twala, T N; Schutte-Smith, M; Roodt, A; Visser, H G

2015-02-21

A range of fac-[Mn(CO)3(L,L'-Bid)(H2O)](n) (L,L'-Bid = neutral or monoanionic bidentate ligands with varied L,L' donor atoms, N,N' and N,O, 1,10-phenanthroline, 2,2'-bipyridine, 2-picolinate, 2,4-quinolinate; n = 0, +1) has been synthesized and the methanol substitution has been investigated for the first time. The complexes were characterized by UV/vis, IR and NMR spectroscopy and X-ray crystallographic studies of the compounds fac-[Mn(CO)3(Bipy)(H2O)][CF3SO3] () and fac-[Mn(CO)3(Phen)(H2O)][CF3SO3] () are reported. A two order-of-magnitude of activation for the methanol substitution is induced as manifested by the second order rate constants with (N,N'-Bid) < (N,O-Bid). Forward and reverse rate and stability constants from slow and stopped-flow UV/vis measurements (k1, M(-1) s(-1); k-1, s(-1); K1, M(-1)) for pyridine as entering nucleophile are as follows: fac-[Mn(CO)3(Phen)(CH3OH)](+) (2.39 ± 5) × 10(-3), (1.5 ± 0.3) × 10(-5), 159 ± 32; fac-[Mn(CO)3(2,4-QuinH)(CH3OH)] (4.5 ± 0.2), (4 ± 1) × 10(-2), 113 ± 29. Activation parameters (ΔH, kJ mol(-1); ΔS, J K(-1) mol(-1)) from Eyring plots for entering nucleophiles as indicated are as follows: fac-[Mn(CO)3(Phen)(CH3OH)](+) (bromide ions) 66.7 ± 0.6, -27 ± 2; (pyridine) 80 ± 3, -25 ± 11; fac-[Mn(CO)3(Pico)(CH3OH)] (bromide ions) 68 ± 2, -24 ± 5. A dissociative interchange mechanism is proposed.

Effect of summer throughfall exclusion, summer drought, and winter snow cover on methane fluxes in a temperate forest soil

USGS Publications Warehouse

Borken, W.; Davidson, E.A.; Savage, K.; Sundquist, E.T.; Steudler, P.

2006-01-01

Soil moisture strongly controls the uptake of atmospheric methane by limiting the diffusion of methane into the soil, resulting in a negative correlation between soil moisture and methane uptake rates under most non-drought conditions. However, little is known about the effect of water stress on methane uptake in temperate forests during severe droughts. We simulated extreme summer droughts by exclusion of 168 mm (2001) and 344 mm (2002) throughfall using three translucent roofs in a mixed deciduous forest at the Harvard Forest, Massachusetts, USA. The treatment significantly increased CH4 uptake during the first weeks of throughfall exclusion in 2001 and during most of the 2002 treatment period. Low summertime CH4 uptake rates were found only briefly in both control and exclusion plots during a natural late summer drought, when water contents below 0.15 g cm-3 may have caused water stress of methanotrophs in the A horizon. Because these soils are well drained, the exclusion treatment had little effect on A horizon water content between wetting events, and the effect of water stress was smaller and more brief than was the overall treatment effect on methane diffusion. Methane consumption rates were highest in the A horizon and showed a parabolic relationship between gravimetric water content and CH4 consumption, with maximum rate at 0.23 g H2O g-1 soil. On average, about 74% of atmospheric CH4 was consumed in the top 4-5 cm of the mineral soil. By contrast, little or no CH4 consumption occurred in the O horizon. Snow cover significantly reduced the uptake rate from December to March. Removal of snow enhanced CH4 uptake by about 700-1000%, resulting in uptake rates similar to those measured during the growing season. Soil temperatures had little effect on CH4 uptake as long as the mineral soil was not frozen, indicating strong substrate limitation of methanotrophs throughout the year. Our results suggest that the extension of snow periods may affect the annual rate of CH4 oxidation and that summer droughts may increase the soil CH4 sink of temperate forest soils. ?? 2005 Elsevier Ltd. All rights reserved.

Quantifying sources of methane using light alkanes in the Los Angeles basin, California

NASA Astrophysics Data System (ADS)

Peischl, J.; Ryerson, T. B.; Brioude, J.; Aikin, K. C.; Andrews, A. E.; Atlas, E.; Blake, D.; Daube, B. C.; de Gouw, J. A.; Dlugokencky, E.; Frost, G. J.; Gentner, D. R.; Gilman, J. B.; Goldstein, A. H.; Harley, R. A.; Holloway, J. S.; Kofler, J.; Kuster, W. C.; Lang, P. M.; Novelli, P. C.; Santoni, G. W.; Trainer, M.; Wofsy, S. C.; Parrish, D. D.

2013-05-01

Methane (CH4), carbon dioxide (CO2), carbon monoxide (CO), and C2-C5 alkanes were measured throughout the Los Angeles (L.A.) basin in May and June 2010. We use these data to show that the emission ratios of CH4/CO and CH4/CO2 in the L.A. basin are larger than expected from population-apportioned bottom-up state inventories, consistent with previously published work. We use experimentally determined CH4/CO and CH4/CO2 emission ratios in combination with annual State of California CO and CO2 inventories to derive a yearly emission rate of CH4 to the L.A. basin. We further use the airborne measurements to directly derive CH4 emission rates from dairy operations in Chino, and from the two largest landfills in the L.A. basin, and show these sources are accurately represented in the California Air Resources Board greenhouse gas inventory for CH4. We then use measurements of C2-C5 alkanes to quantify the relative contribution of other CH4 sources in the L.A. basin, with results differing from those of previous studies. The atmospheric data are consistent with the majority of CH4 emissions in the region coming from fugitive losses from natural gas in pipelines and urban distribution systems and/or geologic seeps, as well as landfills and dairies. The local oil and gas industry also provides a significant source of CH4 in the area. The addition of CH4 emissions from natural gas pipelines and urban distribution systems and/or geologic seeps and from the local oil and gas industry is sufficient to account for the differences between the top-down and bottom-up CH4 inventories identified in previously published work.

Rapid Sediment Accumulation Results in High Methane Effluxes from Coastal Sediments

PubMed Central

Lenstra, Wytze; Jong, Dirk; Meysman, Filip J. R.; Sapart, Célia J.; van der Veen, Carina; Röckmann, Thomas; Gonzalez, Santiago; Slomp, Caroline P.

2016-01-01

Globally, the methane (CH4) efflux from the ocean to the atmosphere is small, despite high rates of CH4 production in continental shelf and slope environments. This low efflux results from the biological removal of CH4 through anaerobic oxidation with sulfate in marine sediments. In some settings, however, pore water CH4 is found throughout the sulfate-bearing zone, indicating an apparently inefficient oxidation barrier for CH4. Here we demonstrate that rapid sediment accumulation can explain this limited capacity for CH4 removal in coastal sediments. In a saline coastal reservoir (Lake Grevelingen, The Netherlands), we observed high diffusive CH4 effluxes from the sediment into the overlying water column (0.2–0.8 mol m-2 yr-1) during multiple years. Linear pore water CH4 profiles and the absence of an isotopic enrichment commonly associated with CH4 oxidation in a zone with high rates of sulfate reduction (50–170 nmol cm-3 d-1) both suggest that CH4 is bypassing the zone of sulfate reduction. We propose that the rapid sediment accumulation at this site (~ 13 cm yr-1) reduces the residence time of the CH4 oxidizing microorganisms in the sulfate/methane transition zone (< 5 years), thus making it difficult for these slow growing methanotrophic communities to build-up sufficient biomass to efficiently remove pore water CH4. In addition, our results indicate that the high input of organic matter (~ 91 mol C m-2 yr-1) allows for the co-occurrence of different dissimilatory respiration processes, such as (acetotrophic) methanogenesis and sulfate reduction in the surface sediments by providing abundant substrate. We conclude that anthropogenic eutrophication and rapid sediment accumulation likely increase the release of CH4 from coastal sediments. PMID:27560511

Effects of shifting growth stage and regulating temperature on seasonal variation of CH4 emission from rice

NASA Astrophysics Data System (ADS)

Watanabe, Akira; Yamada, Hiromi; Kimura, Makoto

2001-09-01

Seasonal variations in CH4 emission rates from rice paddies have been reported to have one or more maxima during the middle and late periods of rice growth. The factor affecting an appearance of CH4 emission maxima was examined in three types of pot experiments. In the experiment 1, four rice cultivars with difference in length of the period from transplanting to heading were transplanted on the same days. For the experiment 2, a cultivar was transplanted 4 times with interval of two weeks. In these experiments, the heading differed about a month between the earliest and latest treatments, respectively. However, shifting growth stage of rice plants did not shift the CH4 emission maxima, and the CH4 emission maxima often matched the maxima of daily mean air temperature. The effect of variation in temperature on CH4 emission rate was further investigated in the experiment 3 by placing the rice-planted pots under regulated temperature. Besides the first emission peak of CH4 attributable to rice straw (RS) carbon, three emission peaks corresponding to the peaks of air temperature were detected for the RS-applied pots placed outdoors. These three peaks were not observed or much less conspicuous for the RS-applied pots in a phytotron at 30°C. Temporal decreases in CH4 emission were detected both for the pots placed in the phytotron and outdoors just after the topdressing of (NH4)2SO4, which was considered to be a major cause of irregular disagreement between the variations in CH4 emission rates and in air temperature during the middle period of rice growth.

Methane Emissions from Conventional and Unconventional Natural Gas Production Sites in the Marcellus Shale Basin.

PubMed

Omara, Mark; Sullivan, Melissa R; Li, Xiang; Subramanian, R; Robinson, Allen L; Presto, Albert A

2016-02-16

There is a need for continued assessment of methane (CH4) emissions associated with natural gas (NG) production, especially as recent advancements in horizontal drilling combined with staged hydraulic fracturing technologies have dramatically increased NG production (we refer to these wells as "unconventional" NG wells). In this study, we measured facility-level CH4 emissions rates from the NG production sector in the Marcellus region, and compared CH4 emissions between unconventional NG (UNG) well pad sites and the relatively smaller and older "conventional" NG (CvNG) sites that consist of wells drilled vertically into permeable geologic formations. A top-down tracer-flux CH4 measurement approach utilizing mobile downwind intercepts of CH4, ethane, and tracer (nitrous oxide and acetylene) plumes was performed at 18 CvNG sites (19 individual wells) and 17 UNG sites (88 individual wells). The 17 UNG sites included four sites undergoing completion flowback (FB). The mean facility-level CH4 emission rate among UNG well pad sites in routine production (18.8 kg/h (95% confidence interval (CI) on the mean of 12.0-26.8 kg/h)) was 23 times greater than the mean CH4 emissions from CvNG sites. These differences were attributed, in part, to the large size (based on number of wells and ancillary NG production equipment) and the significantly higher production rate of UNG sites. However, CvNG sites generally had much higher production-normalized CH4 emission rates (median: 11%; range: 0.35-91%) compared to UNG sites (median: 0.13%, range: 0.01-1.2%), likely resulting from a greater prevalence of avoidable process operating conditions (e.g., unresolved equipment maintenance issues). At the regional scale, we estimate that total annual CH4 emissions from 88 500 combined CvNG well pads in Pennsylvania and West Virginia (660 Gg (95% CI: 500 to 800 Gg)) exceeded that from 3390 UNG well pads by 170 Gg, reflecting the large number of CvNG wells and the comparably large fraction of CH4 lost per unit production. The new emissions data suggest that the recently instituted Pennsylvania CH4 emissions inventory substantially underestimates measured facility-level CH4 emissions by >10-40 times for five UNG sites in this study.

First records of a field experiment on fertilizer effects on methane emission from rice fields in Hunan-Province (PR China)

NASA Astrophysics Data System (ADS)

Wassmann, R.; Wang, M. X.; Shangguan, X. J.; Xie, X. L.; Shen, R. X.; Wang, Y. S.; Papen, H.; Rennenberg, H.; Seiler, W.

Fertilizer effects on methane emission from Chinese rice fields were investigated by a praxis-oriented approach applying balanced amendments of N, P and K. The data set obtained covered the emission rates of app. one month in early rice and one month in late rice 1991. An intercomparison between the 4 treatments showed pronounced differences in the magnitudes of methane emission rates. The combined organic/mineral fertilizer application, commonly used as local farming practice, resulted in relatively high seasonal averages of methane emission rates (26.5 mg CH4 m-2 h-1 in early rice and 50.1 mg CH4 m-2 h-1 in late rice). The lowest emission rates were observed in the plot with pure mineral fertilization (6.5 mg CH4 m-2 h-1 in early rice and 14.3 mg CH4 m-2 h-1 in late rice). Pure organic fertilizers by unfermented substances yielded the highest methane emission rates of all field trials (38.6 mg CH4 m-2 h-1 in early rice and 56.2 CH4 m-2 h-1 in late rice). The fertilization with fermented material derived from biogas generators resulted in substantially lower emission rates than the other trials with organic amendments, the seasonal averages corresponded to 15.9 mg CH4 m-2 h-1 (early rice) and 22.5 mg CH4 m-2 h-1 (late rice). Interpretation of the results can be obtained from the different potentials of these fertilizers for methane production. Based on this concept the different methane emission rates observed with organic/mineral, pure mineral and pure unfermented-organic fertilizers could directly be attributed to the different quantities of organic matter incorporated into the soil. The low methane emission from the plot treated with fermented material could be explained by a depletion of potential methane precursors resulting from the preceding fermentation. The results of this investigation provide evidence that the extensive use of specific chemical fertilizers and the application of sludge from the operation of biogas generators could lead to a net reduction of the methane emission from rice fields.

Comment on 'A dramatic decrease in the growth rate of atmospheric methane in the Northern Hemisphere during 1992' by E. J. Dlugokencky et al.

NASA Technical Reports Server (NTRS)

Hogan, Kathleen B.; Harriss, Robert C.

1994-01-01

The carefully measured decrease in the growth rate of atmospheric methane (CH4) in 1992 reported by Dlugokencky et al. (1994) is an impressive accomplishment, and testimony for the importance of maintaining high-quality, long-term monitoring of atmospheric composition. The changing growth rate of atmospheric CH4 has important implications for assessing and understanding the potential magnitude and rates of a future greenhouse gas-induced climate change. Furthermore, the CH4 data from the current Climate Monitoring and Diagnostics Laboratory (CMDL) globally-distributed network of cooperative air sampling sites are clearly the best record of global CH4 trends and distribution currently available. However, we argue briefly here that the speculation by Dlugokencky et al. (1994) on possible mechanisms for the decreased growth rate in 1992 is only one scenario of many that could possibly fit with the constraints imposed by the reported data. Our comments are to (1) illustrate the difficulties of deducing small changes in complex, poorly understood, geographically diverse natural and anthropogenic sources of CH4 from measurements at the remotely-located CMDL sampling sites and (2) emphasize that detailed bottoms-up analyses are necessary to really advance the understanding of changes in source strengths; we are not promoting alternative mechanisms to explain the 1992 decrease in atmospheric CH4.

Influence of aeration on CH4, N2O and NH3 emissions during aerobic composting of a chicken manure and high C/N waste mixture.

PubMed

Shen, Yujun; Ren, Limei; Li, Guoxue; Chen, Tongbin; Guo, Rui

2011-01-01

Co-composting of chicken manure, straw and dry grasses was investigated in a forced aeration system to estimate the effect of aeration rates on NH(3), CH(4) and N(2)O emissions and compost quality. Continuous measurements of gas emissions were carried out and detailed gas emission patterns were obtained using an intermittent-aeration of 30 min on/30 min off at rates of 0.01 (A1), 0.1 (A2) and 0.2 (A3) m(3)min(-1)m(-3). Concentrations of CH(4) and N(2)O at the low aeration rate (A1) were significantly greater than those at the other two rates, but there was no significant difference between the A2 and A3 treatments. CH(4) and N(2)O emissions for this mixture could be controlled when the composting process was aerobic and ammonia emissions were reduced at a lower aeration rate. Comparison of CH(4), N(2)O, NH(3) emissions and compost quality showed that the aeration rate of the A2 treatment was superior to the other two aeration rates. Copyright © 2010 Elsevier Ltd. All rights reserved.

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.

Studies of Elementary Reactions of Chemical Importance in the Atmospheres of Planets

NASA Technical Reports Server (NTRS)

Nesbitt, Fred L.

2001-01-01

The methyl self-reaction was studied at T = 298 K and 202 K and at three different pressures, P = 0.5, 1.0, and 2.1 Torr. The experimental measurements were performed in our discharge flow-mass spectrometer (DF-MS) apparatus. The methyl radicals were generated by the reaction of F with methane. Passing a mixture of molecular fluorine, F2, in helium through a microwave cavity generated the atomic fluorine reagent. The atomic F enters the flow tube through a rear port on the flow tube. The methane reagent enters the flow tube through a movable injector located coaxial in the flow tube. The decay of methyl radical signal was monitored at a mass/charge ratio (m/z) of 15 as a function of the injector distance. To minimize secondary chemistry from the reaction CH3 + F to CH2 + HF the initial [CH4](sub 0)/[F](sub 0) was above 37.0 and typically 100. This ensures a 1:1 relationship between initial [F] and [CH3]. A titration of F with excess Cl2 yields the initial [F](sub 0). Our experimental methodology to accurately measure the mass spectrometer scaling factor, i.e., the relationship between initial signal and [CH3](sub 0) has been improved. Now we measure the CH3 signal decay under exponential decay conditions at low initial [F](sub 0), 3x10(exp 11) molecule/cc, in the presence of Cl2. This minimizes the second-order decay contributed by the CH3 self-reaction and a simple extrapolation of the 1n(signal) vs time plot to t = 0 gives the initial signal. This provides the desired relationship between initial signal at 15 amu and [CH3](sub 0). The resulting calibration is then applied to the observed decay of the CH3 signal at high concentrations of CH3 assuming linearity of this scaling factor.

Economics of Inhaled Oxygen Use as an Acute Therapy for Cluster Headache in the United States of America.

PubMed

O'Brien, Megan; Ford, Janet H; Aurora, Sheena K; Govindan, Sriram; Tepper, Deborah E; Tepper, Stewart J

2017-10-01

Cluster headache (CH) is a primary headache disorder associated with low levels of diagnosis and high unmet medical need. The pain attacks, associated anxiety, and fear in anticipation of the attacks are extremely debilitating to a patient with CH. For acute therapy, treatment guidelines recommend inhalation of high flow oxygen during the period of an attack. However, the use of oxygen for treatment of CH remains largely underutilized. The objectives of the study, which covered each of the US states, were to map the current market landscape of medical grade oxygen for use in CH and to develop a cost simulator based on a patient's needs and geography. Desk research was undertaken to obtain price lists and product catalogs from wholesale and retail suppliers of medical grade oxygen across all US states. Base case scenarios for chronic and episodic forms of CH were assumed. A cost simulator was used to calculate the cost of oxygen use using inputs including the state in USA, tank size and price, exacerbations per year, duration of exacerbation, attacks per day, flow rate and duration of flow. Information was also collected to determine if healthcare insurers covered the costs of home oxygen use for CH. Out of the 42 US states where pricing information of medical grade oxygen was available from suppliers, in 38 states the annual cost of high-flow oxygen for a patient with episodic CH was estimated to be <$1000. In 39 states, the annual cost of high-flow oxygen for a patient with chronic CH was estimated to be <$5000. Most of the home oxygen suppliers were familiar with CH and stocked the special non-rebreather masks and regulators necessary for this condition. It was found that many of the private commercial healthcare insurance providers reimbursed the cost of oxygen use for CH. However, the US Centers for Medicare and Medicaid Services (CMS) maintains there is insufficient evidence for coverage and continues to deny coverage for US Medicare and Medicaid patients. Results from our study showed that the current costs for oxygen use as an acute therapy in CH are not prohibitively expensive for patients and healthcare insurance providers. Apart from CMS, many insurers do reimburse the cost of oxygen use for CH. Our study suggests that further research is needed to determine if a lack of physician awareness about treatments and ways to prescribe are barriers for patients to access the high-flow oxygen treatment. © 2017 American Headache Society.

Unimolecular HCl and HF elimination reactions of 1,2-dichloroethane, 1,2-difluoroethane, and 1,2-chlorofluoroethane: assignment of threshold energies.

PubMed

Duncan, Juliana R; Solaka, Sarah A; Setser, D W; Holmes, Bert E

2010-01-21

The recombination of CH(2)Cl and CH(2)F radicals generates vibrationally excited CH(2)ClCH(2)Cl, CH(2)FCH(2)F, and CH(2)ClCH(2)F molecules with about 90 kcal mol(-1) of energy in a room temperature bath gas. New experimental data for CH(2)ClCH(2)F have been obtained that are combined with previously published studies for C(2)H(4)Cl(2) and C(2)H(4)F(2) to define reliable rate constants of 3.0 x 10(8) (C(2)H(4)F(2)), 2.4 x 10(8) (C(2)H(4)Cl(2)), and 1.9 x 10(8) (CH(2)ClCH(2)F) s(-1) for HCl and HF elimination. The product branching ratio for CH(2)ClCH(2)F is approximately 1. These experimental rate constants are compared to calculated statistical rate constants (RRKM) to assign threshold energies for HF and HCl elimination. The calculated rate constants are based on transition-state models obtained from calculations of electronic structures; the energy levels of the asymmetric, hindered, internal rotation were directly included in the state counting to obtain a more realistic measure for the density of internal states for the molecules. The assigned threshold energies for C(2)H(4)F(2) and C(2)H(4)Cl(2) are both 63 +/- 2 kcal mol(-1). The threshold energies for CH(2)ClCH(2)F are 65 +/- 2 (HCl) and 63 +/- 2 (HF) kcal mol(-1). These threshold energies are 5-7 kcal mol(-1) higher than the corresponding values for C(2)H(5)Cl or C(2)H(5)F, and beta-substitution of F or Cl atoms raises threshold energies for HF or HCl elimination reactions. The treatment presented here for obtaining the densities of states and the entropy of activation from models with asymmetric internal rotations with high barriers can be used to judge the validity of using a symmetric internal-rotor approximation for other cases. Finally, threshold energies for the 1,2-fluorochloroethanes are compared to those of the 1,1-fluorochloroethanes to illustrate substituent effects on the relative energies of the isomeric transition states.

Low Temperature Studies of the Removal Reactions of 1CH2 with Relevance to the Atmosphere of Titan

NASA Astrophysics Data System (ADS)

Douglas, Kevin; Slater, Eloise; Feng, Wuhu; Blitz, Mark; Plane, John; Heard, Dwayne; Seakins, Paul

2017-04-01

The photolysis of methane by UV photons is the primary source of hydrocarbon radicals in the atmosphere of Titan and the giant planets. Although there is still significant uncertainty in the branching ratios of products, the production of the first singlet excited state of methylene, 1CH2, is thought to be a significant channel. Reactions of 1CH2 with methane (R1a) and hydrogen (R2a) are a significant source of methyl radicals, the recombination of which is the primary route to ethane on Titan (R3). The reaction of 1CH2 with acetylene is also a source of propargyl, C3H3, the recombination of which is the primary route to benzene on Titan. However, in addition to these reactions of 1CH2 leading to chemical products, there is also competition between inelastic electronic relaxation to form ground triplet state methylene, 3CH2 (R1b and R2b). Triplet methylene is much less reactive, and cannot undergo the complex insertion elimination reactions of singlet methylene. The main reaction of 3CH2 occurs with other radical species such as H (R4). 1CH2 + CH4 → CH3 + H2 (R1a) 1CH2 + CH4 → 3CH2 + CH4 (R1b) 1CH2 + H2 → CH3 + H (R2a) 1CH2 + H2 → 3CH2 + H2 (R2a) CH3 + CH3 (+M) → C2H6 (R3) 3CH2 + H → CH + H2 (R4) Using pulsed laser photolysis laser-induced fluorescence, we have studied the reaction kinetics for the removal of 1CH2 with N2, H2, CH4, C2H6, C2H4, C2H6, and O2 as a function of temperature. Low temperatures between 43 and 135 K were obtained using a pulsed Laval nozzle apparatus, while data at 160 K was obtained using a low flow reaction cell with cryogenic cooling. In addition to measuring total removal rates, the fraction of 1CH2 removed via electronic relaxation versus chemical reaction to products has also been investigated for H2 and CH4 at 160 and 73 K. Results show that that removal of 1CH2 by electronic relaxation increases with decreasing temperature. These experimental results indicate that the majority of 1CH2 formed in Titan's atmosphere will be rapidly relaxed to its ground state via collisions with both reactive and non-reactive species, and thus is likely to play a less significant role in the formation of larger hydrocarbons than previously thought. However, for a full understanding of the implications of these results, the new measurements have been included in a 1D model of Titan's atmosphere. The model results show a significant reduction in ethane concentrations (10 - 50 %), due to reduction in CH3 production via reactions R1a and R1b. In addition we also observe an increase in ethylene concentrations, the result of increased amounts of 3CH2 reacting with H radicals to form CH (R4), which primarily react with methane to form ethylene. Additional work is also underway to determine branching ratios between reaction and relaxation of 1CH2 with ethane, ethylene, and acetylene. Model results have shown that if a similar trend to reactions with H2 and CH4 is observed, there would be significant reductions in benzene production on Titan.

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

Javahery, G.; Petrie, S.; Wang, J.

Results are reported for the reactions of the fullerene ions C[sub 60[center dot]+], C[sub 70[center dot]+], C[sub 60][sup 2+], C[sub 70][sup 2+], and C[sub 60[center dot]3+] with the nitriles HCN, CH[sub 3]CN, CH[sub 2]CHCN, CH[sub 3]CH[sub 2]CN, CH[sub 2]CHCH[sub 2]CN, CH[sub 3]CH[sub 2]CH[sub 2]CN, (CH[sub 3])[sub 2]CHCN, C[sub 2]N[sub 2], and CH[sub 2](CN)[sub 2]. The reactions were studied using a selected-ion flow tube (SIFT) at 294 [+-] 2 K and a helium buffer gas pressure of 0.35 [+-] 0.01 Torr and exhibited a wide range of chemical behavior. For the monocations C[sub 60][sup [center dot]+] and C[sub 70][sup [center dot]+],more » no detectable reaction occurred with any of the nitriles. For the dications C[sub 60][sup 2+], and C[sub 70][sup 2+], the only primary or secondary product channel evident in all instances was addition: tertiary association was seen to be considerably less efficient than the primary and secondary reactions, and the formation of a quadruple adduct C[sub 60](RCN)[sub 4][sup 2+] was only detected in the reaction with butyronitrile, CH[sub 3]CH[sub 2]CH[sub 2]CN. The observed primary rate coefficients show a very clear dependence upon the molecular complexity of the nitrile: association proceeds more efficiently for nitriles with a higher number of hydrogen atoms. This observation is explained in terms of a model which relates the number of C-H bonds - or, alternatively, the number of internal rotational modes - in the collision complex to the lifetime and probability of stabilization of this complex. 42 refs., 5 figs., 3 tabs.« less

Anaerobic co-digestion of sewage sludge and food waste using temperature-phased anaerobic digestion process.

PubMed

Kim, H W; Han, S K; Shin, H S

2004-01-01

This study was performed to overcome the low efficiency of anaerobic digestion of sewage sludge and food waste by combining temperature-phased digestion, sequencing batch operation, and co-digestion technology. It was demonstrated that the temperature-phased anaerobic sequencing batch reactor (TPASBR) system for the co-digestion of sewage sludge and food waste resulted in enhanced volatile solids (VS) reduction and methane production rate. At the organic loading rate (OLR) of 2.7 g VS/l/d, the TPASBR system showed the higher VS reduction (61.3%), CH4 yield (0.28 l/g VS(added)) and CH4 production rate (0.41 l CH4/l/d) than those (0.29 l CH4/l/d) of the mesophilic two-stage ASBR (MTSASBR). In the specific methanogenic activity (SMA) tests on thermophilic biomass of the TPASBR system, the average SMA of acetate (93 ml CH4/gVSS/d) was much higher than those of propionate (46 ml CH4/g VSS/d) and butyrate (76 ml CH4/g VSS/d). Also, higher specific hydrolytic activity (SHA, 217 mg COD/g VSS/d) of the biomass supported fast hydrolysis under thermophilic conditions. The track study revealed that the most active period of the 24 h cycle was between 6 and 12 h. The enhanced performance of the TPASBR system could be attributed to longer solids retention time, fast hydrolysis, higher CH4 conversion rate, and balanced nutrient condition of co-substrate. It was verified that this combination could be a promising and practical alternative for the simultaneous recycling of two types of organic fraction of municipal solid waste (OFMSW) with high stability.

Kinetics of the Reactions between the Criegee Intermediate CH2OO and Alcohols.

PubMed

Tadayon, Sara V; Foreman, Elizabeth S; Murray, Craig

2018-01-11

Reactions of the simplest Criegee intermediate (CH 2 OO) with a series of alcohols have been studied in a flash photolysis flow reactor. Laser photolysis of diiodomethane at 355 nm in the presence of molecular oxygen was used to produce CH 2 OO, and the absolute number densities were determined as a function of delay time from analysis of broadband transient absorption spectra obtained using a pulsed LED. The kinetics for the reactions of CH 2 OO with methanol, ethanol, and 2-propanol were measured under pseudo-first-order conditions at 295 K, yielding rate constants of (1.4 ± 0.4) × 10 -13 cm 3 s -1 , (2.3 ± 0.6) × 10 -13 cm 3 s -1 , and (1.9 ± 0.5) × 10 -13 cm 3 s -1 , respectively. Complementary ab initio calculations were performed at the CCSD(T)/aug-cc-pVTZ//CCSD/cc-pVDZ level of theory to characterize stationary points on the reaction enthalpy and free energy surfaces and to elucidate the thermochemistry and mechanisms. The reactions proceed over free energy barriers of ∼8 kcal mol -1 to form geminal alkoxymethyl hydroperoxides: methoxymethyl hydroperoxide (MMHP), ethoxymethyl hydroperoxide (EMHP), and isopropoxymethyl hydroperoxide (PMHP). The experimental and theoretical results are compared to reactions of CH 2 OO with other hydroxylic compounds, such as water and carboxylic acids, and trends in reactivity are discussed.

Temperature-Dependent Rate Coefficients for the Reaction of CH2OO with Hydrogen Sulfide.

PubMed

Smith, Mica C; Chao, Wen; Kumar, Manoj; Francisco, Joseph S; Takahashi, Kaito; Lin, Jim Jr-Min

2017-02-09

The reaction of the simplest Criegee intermediate CH 2 OO with hydrogen sulfide was measured with transient UV absorption spectroscopy in a temperature-controlled flow reactor, and bimolecular rate coefficients were obtained from 278 to 318 K and from 100 to 500 Torr. The average rate coefficient at 298 K and 100 Torr was (1.7 ± 0.2) × 10 -13 cm 3 s -1 . The reaction was found to be independent of pressure and exhibited a weak negative temperature dependence. Ab initio quantum chemistry calculations of the temperature-dependent reaction rate coefficient at the QCISD(T)/CBS level are in reasonable agreement with the experiment. The reaction of CH 2 OO with H 2 S is 2-3 orders of magnitude faster than the reaction with H 2 O monomer. Though rates of CH 2 OO scavenging by water vapor under atmospheric conditions are primarily controlled by the reaction with water dimer, the H 2 S loss pathway will be dominated by the reaction with monomer. The agreement between experiment and theory for the CH 2 OO + H 2 S reaction lends credence to theoretical descriptions of other Criegee intermediate reactions that cannot easily be probed experimentally.

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.

The variation of methane flux rates from boreal tree species at the beginning of the growing season

NASA Astrophysics Data System (ADS)

Haikarainen, Iikka; Halmeenmäki, Elisa; Machacova, Katerina; Pihlatie, Mari

2016-04-01

Boreal forests are considered as net sink for atmospheric methane (CH4) because of the CH4 oxidizing bacteria in the aerobic soil layer. However, within the last decades it has become more evident that trees play an important role in the global CH4 budget by offering pathways for anaerobically produced CH4 from deeper soil layers to the atmosphere. Furthermore, trees may also act as independent sources of CH4. To confirm magnitude, variability and the origin of the tree mediated CH4 emissions more research is needed, especially in boreal forests which have been in a minority in such investigation. We measured tree stem and shoot CH4 exchange of three boreal tree species at the beginning of the growing season (13.4.-13.6.2015) at SMEAR II station in Hyytiälä, located in southern Finland (61° 51'N, 24° 17'E, 181 asl). The fluxes were measured from silver birch (Betula pendula), downy birch (B. pubescens) and Norway spruce (Picea abies) on two sites with differing soil type and characteristics (paludified and mineral soil), vegetation and forest structure by using the static chamber technique. Scaffold towers were used for measurements at multiple stem heights and shoots. The aim was to study the vertical profile of CH4 fluxes at stem and shoot level and compare these fluxes among the studied species, and to observe temporal changes in CH4 flux over the beginning of the growing season. We found that all the trees emitted CH4 from their stems and shoots. Overall, the birches showed higher emissions compared to the spruces. The emission rates were considerably larger in the lower parts of the birch stems than upper parts, and these emissions increased during the growing season. The spruces had more variation in the stem CH4 flux, but the emission rates of the upper parts of the stem exceeded the birch emissions at the same height. The shoot fluxes of all the studied trees indicated variable CH4 emissions without a clear pattern regarding the vertical profile and progress of the growing season.

Rate constants and temperature dependences for the reactions of hydroxyl radical with several halogenated methanes, ethanes, and propanes by relative rate measurements

NASA Technical Reports Server (NTRS)

Hsu, K.-J.; DeMore, W. B.

1995-01-01

Rate constants of 15 OH reactions with halogen-substituted alkanes, C1 to C3, were studied using a relative rate technique in the temperature range 283-403 K. Compounds studied were CHF2Cl (22), CHF2Br (22B), CH3F (41), CH2F2 (32), CHF3 (23), CHClFCCl2F (122a), CHCl2CF3 (123), CHClFCF3 (124), CH3CF3 (143a), CH3CH2F (161), CF3CHFCF3 (227ea), CF3CH2CF3 (236fa), CF3CHFCHF2 (236ea), and CHF2CF2CH2F (245ca). Using CH4, CH3CCl3, CF3CF2H, and C2H6 as primary reference standards (JPL 92-20 rate constants), absolute rate constants are derived. Results are in good agreement with previous experimental results for six of the compounds studied, including CHF2Cl, CHF2Br, CH2F2, CH3CF3, CHFClCFCl2, and CF3CHFCF3. For the remainder the relative rate constants are lower than those derived from experiments in which OH loss was used to measure the reaction rate. Comparisons of the derived Arrhenius A factors with previous literature transition-state calculations show order of magnitude agreement in most cases. However, the experimental A factors show a much closer proportionality to the number of H atoms in the molecule than is evident from the transition state calculations. For most of the compounds studied, an A factor of (8 +/- 3)E-13 cm(exp 3)/(molecule s) per C-H bond is observed. A new measurement of the ratio k(CH3CCl3)/k(CH4) is reported that is in good agreement with previous data.

Prescribed Burn at Pine Bluff Arsenal

DTIC Science & Technology

2000-03-01

length (ft) backfire flame length (ft) hf rate of spread (ch/hr) bf rate of spread (ch/hr) Minimum behavior headfire flame length (ft) backfire... flame length (ft) hf rate of spread (ch/hr) bf rate of spread (ch/hr) 8. FUEL AND WEATHER PRESCRIPTION Source of weather: National Weather Service...and left the site. No spots occurred. Backfire flame lengths were 0.2-3 feet through pine needles and grass. Flanking fire flame lengths were 2-4

Pyrolysis of furan in a microreactor

NASA Astrophysics Data System (ADS)

Urness, Kimberly N.; Guan, Qi; Golan, Amir; Daily, John W.; Nimlos, Mark R.; Stanton, John F.; Ahmed, Musahid; Ellison, G. Barney

2013-09-01

A silicon carbide microtubular reactor has been used to measure branching ratios in the thermal decomposition of furan, C4H4O. The pyrolysis experiments are carried out by passing a dilute mixture of furan (approximately 0.01%) entrained in a stream of helium through the heated reactor. The SiC reactor (0.66 mm i.d., 2 mm o.d., 2.5 cm long) operates with continuous flow. Experiments were performed with a reactor inlet pressure of 100-300 Torr and a wall temperature between 1200 and 1600 K; characteristic residence times in the reactor are 60-150 μs. The unimolecular decomposition pathway of furan is confirmed to be: furan (+ M) rightleftharpoons α-carbene or β-carbene. The α-carbene fragments to CH2=C=O + HC≡CH while the β-carbene isomerizes to CH2=C=CHCHO. The formyl allene can isomerize to CO + CH3C≡CH or it can fragment to H + CO + HCCCH2. Tunable synchrotron radiation photoionization mass spectrometry is used to monitor the products and to measure the branching ratio of the two carbenes as well as the ratio of [HCCCH2]/[CH3C≡CH]. The results of these pyrolysis experiments demonstrate a preference for 80%-90% of furan decomposition to occur via the β-carbene. For reactor temperatures of 1200-1400 K, no propargyl radicals are formed. As the temperature rises to 1500-1600 K, at most 10% of the decomposition of CH2=C=CHCHO produces H + CO + HCCCH2 radicals. Thermodynamic conditions in the reactor have been modeled by computational fluid dynamics and the experimental results are compared to the predictions of three furan pyrolysis mechanisms. Uncertainty in the pressure-dependency of the initiation reaction rates is a possible a source of discrepancy between experimental results and theoretical predictions.

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.

Effects of nitrogen fertilisation rate and maturity of grass silage on methane emission by lactating dairy cows.

PubMed

Warner, D; Hatew, B; Podesta, S C; Klop, G; van Gastelen, S; van Laar, H; Dijkstra, J; Bannink, A

2016-01-01

Grass silage is typically fed to dairy cows in temperate regions. However, in vivo information on methane (CH(4)) emission from grass silage of varying quality is limited. We evaluated the effect of two rates of nitrogen (N) fertilisation of grassland (low fertilisation (LF), 65 kg of N/ha; and high fertilisation (HF), 150 kg of N/ha) and of three stages of maturity of grass at cutting: early maturity (EM; 28 days of regrowth), mid maturity (MM; 41 days of regrowth) and late maturity (LM; 62 days of regrowth) on CH(4) production by lactating dairy cows. In a randomised block design, 54 lactating Holstein-Friesian dairy cows (168±11 days in milk; mean±standard error of mean) received grass silage (mainly ryegrass) and compound feed at 80 : 20 on dry matter basis. Cows were adapted to the diet for 12 days and CH(4) production was measured in climate respiration chambers for 5 days. Dry matter intake (DMI; 14.9±0.56 kg/day) decreased with increasing N fertilisation and grass maturity. Production of fat- and protein-corrected milk (FPCM; 24.0±1.57 kg/day) decreased with advancing grass maturity but was not affected by N fertilisation. Apparent total-tract feed digestibility decreased with advancing grass maturity but was unaffected by N fertilisation except for an increase and decrease in N and fat digestibility with increasing N fertilisation, respectively. Total CH(4) production per cow (347±13.6 g/day) decreased with increasing N fertilisation by 4% and grass maturity by 6%. The smaller CH(4) production with advancing grass maturity was offset by a smaller FPCM and lower feed digestibility. As a result, with advancing grass maturity CH(4) emission intensity increased per units of FPCM (15.0±1.00 g CH(4)/kg) by 31% and digestible organic matter intake (33.1±0.78 g CH(4)/kg) by 15%. In addition, emission intensity increased per units of DMI (23.5±0.43 g CH(4)/kg) by 7% and gross energy intake (7.0±0.14% CH(4)) by 9%, implying an increased loss of dietary energy with advancing grass maturity. Rate of N fertilisation had no effect on CH(4) emissions per units of FPCM, DMI and gross energy intake. These results suggest that despite a lower absolute daily CH(4) production with a higher N fertilisation rate, CH(4) emission intensity remains unchanged. A significant reduction of CH(4) emission intensity can be achieved by feeding dairy cows silage of grass harvested at an earlier stage of maturity.

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.

Source limitation of carbon gas emissions in high-elevation mountain streams and lakes

USGS Publications Warehouse

Crawford, John T.; Dornblaser, Mark M.; Stanley, Emily H.; Clow, David W.; Striegl, Robert G.

2015-01-01

Inland waters are an important component of the global carbon cycle through transport, storage, and direct emissions of CO2 and CH4 to the atmosphere. Despite predictions of high physical gas exchange rates due to turbulent flows and ubiquitous supersaturation of CO2—and perhaps also CH4—patterns of gas emissions are essentially undocumented for high mountain ecosystems. Much like other headwater networks around the globe, we found that high-elevation streams in Rocky Mountain National Park, USA, were supersaturated with CO2 during the growing season and were net sources to the atmosphere. CO2concentrations in lakes, on the other hand, tended to be less than atmospheric equilibrium during the open water season. CO2 and CH4 emissions from the aquatic conduit were relatively small compared to many parts of the globe. Irrespective of the physical template for high gas exchange (high k), we found evidence of CO2 source limitation to mountain streams during the growing season, which limits overall CO2emissions. Our results suggest a reduced importance of aquatic ecosystems for carbon cycling in high-elevation landscapes having limited soil development and high CO2 consumption via mineral weathering.

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

NASA Astrophysics Data System (ADS)

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

2012-04-01

Much research effort is focused on identifying global CH4 sources and sinks to estimate their current and potential strength in response to land-use change and global warming. Aerobic CH4 oxidation is regarded as the key process reducing the strength of CH4 emissions in wetlands, but is hitherto difficult to quantify. Recent studies quantify the efficiency of CH4 oxidation based on CH4 stable isotope signatures. The approach utilizes the fact that a significant isotope fractionation occurs when CH4 is oxidized. Moreover, it also considers isotope fractionation by diffusion. For field applications the 'open-system equation' is applied to determine the CH4 oxidation efficiency: fox = (δE - δP)/ (αox - αtrans) where fox is the fraction of CH4 oxidized; δE is δ13C of emitted CH4; δP is δ13C of produced CH4; αox is the isotopic fractionation factor of oxidation; αtrans is the isotopic fractionation factor of transport. We quantified CH4 oxidation in polygonal tundra soils of Russia's Lena River Delta analyzing depth profiles of CH4 concentrations and stable isotope signatures. Therefore, both fractionation factors αox and αtrans were determined for three polygon centers with differing water table positions and a polygon rim. While most previous studies on landfill cover soils have assumed a gas transport dominated by advection (αtrans = 1), other CH4 transport mechanisms as diffusion have to be considered in peatlands and αtrans exceeds a value of 1. At our study we determined αtrans = 1.013 ± 0.003 for CH4 when diffusion is the predominant transport mechanism. Furthermore, results showed that αox differs widely between sites and horizons (αox = 1.013 ± 0.012) and has to be determined for each case. The impact of both fractionation factors on the quantification of CH4 oxidation was estimated by considering both the potential diffusion rate at different water contents and potential oxidation rates. Calculations for a water saturated tundra soil indicated a CH4 oxidation efficiency of 88% in the upper horizon. Using carbon isotope fractionation improves the in situ quantification of CH4 oxidation in wetlands and thus the assessment of current and potential CH4 sources and sinks in these ecosystems.

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.

Toward an annual estimate of methane emissions from Lake Erie

NASA Astrophysics Data System (ADS)

Fernandez, J.; Townsend-Small, A.

2017-12-01

Lake Erie is the shallowest, warmest, and most eutrophic of all of the North American Great Lakes. The central basin of Lake Erie exhibits seasonally hypoxic bottom waters, which contributes to biological methane (CH4) production. Leaks from extensive natural gas wells and pipelines in Canadian waters are a potential source of thermogenic CH4 to the lake. The shallow western basin lacks water column hypoxia, but experiences increasingly frequent algal blooms and hypoxic sediments. Our past research, focused on the central basin, indicated that Lake Erie is a positive source of CH4 during late summer (August - September), emitting 1.3 ± 0.6 × 105 kg CH4-C day. Here, we present a seasonal dataset of CH4 fluxes measured throughout a 16-month period starting in the spring of 2015 and ending late summer in 2016 to estimate an annual lake wide CH4 emission. Our results indicate that the western basin experienced the greatest CH4 emissions, and the highest rates of CH4 flux co-occur with the highest rates of nutrient loading and largest algal blooms near the mouth of the Maumee River. Winter CH4 fluxes were minimal and similar throughout the lake, indicating that natural gas wells are a minimal source of CH4 emissions. Emissions were highest in August and tapered off through the fall and winter, rising again in spring. The estimated annual CH4 emission in Lake Erie was 4.41 × 107 kg CH4-C yr-1. We compared this to other CH4 sources in Michigan and Ohio in the USEPA Greenhouse Gas Reporting Program Database, and found that Lake Erie is second largest emitter of CH4 in Ohio (a landfill in Cincinnati is a larger source), and the largest in Michigan. Recent work has shown that eutrophication in lakes such as Lake Erie may be on the rise due to climate change induced increases in precipitation. If so, these large CH4 emissions may have positive feedback consequences to climate warming. Therefore, more research is needed to indicate whether or not these CH4 emissions are increasing.

TA [2] Continuous, regional methane emissions estimates in northern Pennsylvania gas fields using atmospheric inversions

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

Lauvaux, Thomas

Natural Gas (NG) production activities in the northeastern Marcellus shale have significantly increased in the last decade, possibly releasing large amounts of methane (CH 4) into the atmosphere from the operations at the productions sites and during the processing and transmission steps of the natural gas chain. Based on an intensive aircraft survey, leakage rates from the NG production were quantified in May 2015 and found to be in the order of 0.5% of the total production, higher than reported by the Environmental Protection Agency (EPA) but below the usually observed leakage rates over the shale gases in the US.more » Thanks to the high production rates on average at each well, leakage rates normalized by production appeared to be low in the northeastern Marcellus shale. This result confirms that natural gas production using unconventional techniques in this region is emitting relatively less CH 4 into the atmosphere than other shale reservoirs. The low emissions rate can be explained in part by the high productivity of wells drilled across the northeastern Marcellus region. We demonstrated here that atmospheric monitoring techniques can provide an independent quantification of NG leakage rates using aircraft measurements. The CH 4 analyzers were successfully calibrated at four sites across the region, measuring continuously the atmospheric CH 4 mixing ratios and isotopic 13Ch 4. Our preliminary findings confirm the low leakage rates from tower data collected over September 2015 to November 2016 compared to the aircraft mass-balance estimates in may 2015. However, several episodes revealing large releases of natural gas over several weeks showed that temporal variations in the emissions of CH 4 may increase the actual leakage rate over longer time periods.« less

A novel high-efficiency stable atmospheric microwave plasma device for fluid processing based on ridged waveguide

NASA Astrophysics Data System (ADS)

Xiao, Wei; Huang, Kama; He, Jianbo; Wu, Ying

2017-09-01

The waveguide-based microwave plasma device is widely used to generate atmospheric plasma for some industrial applications. Nevertheless, the traditional tapered waveguide device has limited power efficiency and produces unstable plasma. A novel ridged waveguide with an oblique hole is proposed to produce microwave atmospheric plasma for fluid processing. By using the ridged waveguide, the microwave field can be well focused, which can sustain plasma at relatively low power. Besides, an oblique hole is used to decrease the power reflection and generate a stable plasma torch especially in the case of high flowing rates. Experiments have been performed with the air flowing rates ranging from 500 l h-1 to 1000 l h-1 and the microwave working frequency of 2.45 GHz. The results show that in comparison with the conventional tapered waveguide, this novel device can both sustain plasma at relative low power and increase the power transfer efficiency by 11% from microwave to plasma. Moreover, both devices are used to process the waste gas-CO and CH4. Significantly, the removal efficiency for CO and CH4 can be increased by 19.7% and 32% respectively in the ridged waveguide compared with the tapered waveguide. It demonstrates that the proposed device possesses a great potential in industrial applications because of its high efficiency and stable performance.

Factors influencing CO2 and CH4 emissions from coastal wetlands in the Liaohe Delta, Northeast China

NASA Astrophysics Data System (ADS)

Olsson, L.; Ye, S.; Yu, X.; Wei, M.; Krauss, K. W.; Brix, H.

2015-08-01

Many factors are known to influence greenhouse gas emissions from coastal wetlands, but it is still unclear which factors are most important under field conditions when they are all acting simultaneously. The objective of this study was to assess the effects of water table, salinity, soil temperature and vegetation on CH4 emissions and ecosystem respiration (Reco) from five coastal wetlands in the Liaohe Delta, Northeast China: two Phragmites australis (common reed) wetlands, two Suaeda salsa (sea blite) marshes and a rice (Oryza sativa) paddy. Throughout the growing season, the Suaeda wetlands were net CH4 sinks whereas the Phragmites wetlands and the rice paddy were net CH4 sources emitting 1.2-6.1 g CH4 m-2 yr-1. The Phragmites wetlands emitted the most CH4 per unit area and the most CH4 relative to CO2. The main controlling factors for the CH4 emissions were water table, temperature, soil organic carbon and salinity. The CH4 emission was accelerated at high and constant (or managed) water tables and decreased at water tables below the soil surface. High temperatures enhanced CH4 emissions, and emission rates were consistently low (< 1 mg CH4 m-2 h-1) at soil temperatures < 18 °C. At salinity levels > 18 ppt, the CH4 emission rates were always low (< 1 mg CH4 m-2 h-1) probably because methanogens were out-competed by sulphate-reducing bacteria. Saline Phragmites wetlands can, however, emit significant amounts of CH4 as CH4 produced in deep soil layers are transported through the air-space tissue of the plants to the atmosphere. The CH4 emission from coastal wetlands can be reduced by creating fluctuating water tables, including water tables below the soil surface, as well as by occasional flooding by high-salinity water. The effects of water management schemes on the biological communities in the wetlands must, however, be carefully studied prior to the management in order to avoid undesirable effects on the wetland communities.

Factors influencing CO2 and CH4 emissions from coastal wetlands in the Liaohe Delta, Northeast China

NASA Astrophysics Data System (ADS)

Olsson, L.; Ye, S.; Yu, X.; Wei, M.; Krauss, K. W.; Brix, H.

2015-02-01

Many factors are known to influence greenhouse gas emissions from coastal wetlands, but it is still unclear which factors are most important under field conditions when they are all acting simultaneously. The objective of this study was to assess the effects of water table, salinity, soil temperature and vegetation on CH4 emissions and ecosystem respiration (Reco) from five coastal wetlands in the Liaohe Delta, northeast China: two Phragmites australis (common reed) wetlands, two Suaeda salsa (sea blite) marshes and a rice (Oryza sativa) paddy. Throughout the growing season, the Suaeda wetlands were net CH4 sinks whereas the Phragmites wetlands and the rice paddy were net CH4 sources emitting 1.2-6.1 g CH4 m-2 y-1. The Phragmites wetlands emitted the most CH4 per unit area and the most CH4 relative to CO2. The main controlling factors for the CH4 emissions were water table, temperature and salinity. The CH4 emission was accelerated at high and constant (or managed) water tables and decreased at water tables below the soil surface. High temperatures enhanced CH4 emissions, and emission rates were consistently low (< 1 mg CH4 m-2 h) at soil temperatures <18 °C. At salinity levels > 18 ppt, the CH4 emission rates were always low (< 1 mg CH4 m-2 h-1) probably because methanogens were outcompeted by sulphate reducing bacteria. Saline Phragmites wetlands can, however, emit significant amounts of CH4 as CH4 produced in deep soil layers are transported through the air-space tissue of the plants to the atmosphere. The CH4 emission from coastal wetlands can be reduced by creating fluctuating water tables, including water tables below the soil surface, as well as by occasional flooding by high-salinity water. The effects of water management schemes on the biological communities in the wetlands must, however, be carefully studied prior to the management in order to avoid undesirable effects on the wetland communities.

Methane emissions from the Marcellus Shale in southwestern Pennsylvania and northern West Virginia based on airborne measurements

NASA Astrophysics Data System (ADS)

Ren, Xinrong; Hall, Dolly L.; Vinciguerra, Timothy; Benish, Sarah E.; Stratton, Phillip R.; Ahn, Doyeon; Hansford, Jonathan R.; Cohen, Mark D.; Sahu, Sayantan; He, Hao; Grimes, Courtney; Salawitch, Ross J.; Ehrman, Sheryl H.; Dickerson, Russell R.

2017-04-01

Natural gas production in the U.S. has increased rapidly over the past decade, along with concerns about methane (CH4) leakage (total fugitive emissions), and climate impacts. Quantification of CH4 emissions from oil and natural gas (O&NG) operations is important for establishing scientifically sound, cost-effective policies for mitigating greenhouse gases. We use aircraft measurements and a mass balance approach for three flight experiments in August and September 2015 to estimate CH4 emissions from O&NG operations in the southwestern Marcellus Shale region. We estimate the mean ± 1σ CH4 emission rate as 36.7 ± 1.9 kg CH4 s-1 (or 1.16 ± 0.06 Tg CH4 yr-1) with 59% coming from O&NG operations. We estimate the mean ± 1σ CH4 leak rate from O&NG operations as 3.9 ± 0.4% with a lower limit of 1.5% and an upper limit of 6.3%. This leak rate is broadly consistent with the results from several recent top-down studies but higher than the results from a few other observational studies as well as in the U.S. Environmental Protection Agency CH4 emission inventory. However, a substantial source of CH4 was found to contain little ethane (C2H6), possibly due to coalbed CH4 emitted either directly from coalmines or from wells drilled through coalbed layers. Although recent regulations requiring capture of gas from the completion venting step of the hydraulic fracturing appear to have reduced losses, our study suggests that for a 20 year time scale, energy derived from the combustion of natural gas extracted from this region will require further controls before it can exert a net climate benefit compared to coal.

Methane emissions from the Marcellus Shale in southwestern Pennsylvania and northern West Virginia based on airborne measurements

PubMed Central

Hall, Dolly L.; Vinciguerra, Timothy; Benish, Sarah E.; Stratton, Phillip R.; Ahn, Doyeon; Hansford, Jonathan R.; Cohen, Mark D.; Sahu, Sayantan; He, Hao; Grimes, Courtney; Salawitch, Ross J.; Ehrman, Sheryl H.; Dickerson, Russell R.

2017-01-01

Abstract Natural gas production in the U.S. has increased rapidly over the past decade, along with concerns about methane (CH4) leakage (total fugitive emissions), and climate impacts. Quantification of CH4 emissions from oil and natural gas (O&NG) operations is important for establishing scientifically sound, cost‐effective policies for mitigating greenhouse gases. We use aircraft measurements and a mass balance approach for three flight experiments in August and September 2015 to estimate CH4 emissions from O&NG operations in the southwestern Marcellus Shale region. We estimate the mean ± 1σ CH4 emission rate as 36.7 ± 1.9 kg CH4 s−1 (or 1.16 ± 0.06 Tg CH4 yr−1) with 59% coming from O&NG operations. We estimate the mean ± 1σ CH4 leak rate from O&NG operations as 3.9 ± 0.4% with a lower limit of 1.5% and an upper limit of 6.3%. This leak rate is broadly consistent with the results from several recent top‐down studies but higher than the results from a few other observational studies as well as in the U.S. Environmental Protection Agency CH4 emission inventory. However, a substantial source of CH4 was found to contain little ethane (C2H6), possibly due to coalbed CH4 emitted either directly from coalmines or from wells drilled through coalbed layers. Although recent regulations requiring capture of gas from the completion venting step of the hydraulic fracturing appear to have reduced losses, our study suggests that for a 20 year time scale, energy derived from the combustion of natural gas extracted from this region will require further controls before it can exert a net climate benefit compared to coal. PMID:28603681

Methane emissions from the Marcellus Shale in southwestern Pennsylvania and northern West Virginia based on airborne measurements.

PubMed

Ren, Xinrong; Hall, Dolly L; Vinciguerra, Timothy; Benish, Sarah E; Stratton, Phillip R; Ahn, Doyeon; Hansford, Jonathan R; Cohen, Mark D; Sahu, Sayantan; He, Hao; Grimes, Courtney; Salawitch, Ross J; Ehrman, Sheryl H; Dickerson, Russell R

2017-04-27

Natural gas production in the U.S. has increased rapidly over the past decade, along with concerns about methane (CH 4 ) leakage (total fugitive emissions), and climate impacts. Quantification of CH 4 emissions from oil and natural gas (O&NG) operations is important for establishing scientifically sound, cost-effective policies for mitigating greenhouse gases. We use aircraft measurements and a mass balance approach for three flight experiments in August and September 2015 to estimate CH 4 emissions from O&NG operations in the southwestern Marcellus Shale region. We estimate the mean ± 1 σ CH 4 emission rate as 36.7 ± 1.9 kg CH 4  s -1 (or 1.16 ± 0.06 Tg CH 4  yr -1 ) with 59% coming from O&NG operations. We estimate the mean ± 1 σ CH 4 leak rate from O&NG operations as 3.9 ± 0.4% with a lower limit of 1.5% and an upper limit of 6.3%. This leak rate is broadly consistent with the results from several recent top-down studies but higher than the results from a few other observational studies as well as in the U.S. Environmental Protection Agency CH 4 emission inventory. However, a substantial source of CH 4 was found to contain little ethane (C 2 H 6 ), possibly due to coalbed CH 4 emitted either directly from coalmines or from wells drilled through coalbed layers. Although recent regulations requiring capture of gas from the completion venting step of the hydraulic fracturing appear to have reduced losses, our study suggests that for a 20 year time scale, energy derived from the combustion of natural gas extracted from this region will require further controls before it can exert a net climate benefit compared to coal.

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.

Mortality in children with early detected congenital central hypothyroidism.

PubMed

Zwaveling-Soonawala, Nitash; Naafs, Jolanda C; Verkerk, Paul H; van Trotsenburg, A S Paul

2018-06-07

Approximately 60-80% of patients with congenital central hypothyroidism (CH-C) have multiple pituitary hormone deficiencies (MPHD), making CH-C a potentially life-threatening disease. Data on mortality in CH-C patients, however, are lacking. To study mortality rate in early detected and treated pediatric CH-C patients in the Netherlands and to investigate whether causes of death were related to pituitary hormone deficiencies. Overall mortality rate, infant mortality rate and under-5 mortality rate were calculated in all children with CH-C detected by neonatal screening between 1-1-1995 and 1-1-2013. Medical charts were reviewed to establish causes of death. 139 children with CH-C were identified, of which 138 could be traced (82 MPHD/56 isolated CHC). Total observation time was 1414 years with a median follow up duration of 10.2 years. The overall mortality rate was 10.9% (15/138). Infant mortality rate (IMR) and under-5 mortality rate were 65.2/1000 (9/138) and 101.4/1000 (14/138), respectively, compared to an IMR of 4.7/1000 and under-5 mortality of 5.4/1000 live born children in the Netherlands during the same time period (p<0.0001). Main causes of death were severe congenital malformations in six patients, asphyxia in two patients, and congenital or early neonatal infection in two patients. Pituitary hormone deficiency was noted as cause of death in only one infant. We report an increased mortality rate in early detected CH-C patients which does not seem to be related to endocrine disease. This suggests that mortality due to pituitary insufficiency is low in an early detected and treated CH-C population.

Measurements of an Anomalous Global Methane Increase During 1998

NASA Technical Reports Server (NTRS)

Dlugokencky, E. J.; Walter, B. P.; Masarie, K. A.; Lang, P. M.; Kasischke, E. S.; Hansen, James E. (Technical Monitor)

2001-01-01

Measurements of atmospheric methane from a globally distributed network of air sampling sites indicate that the globally averaged CH4 growth rate increased from an average of 3.9 ppb/yr during 1995-1997 to 12.7 +/- 0.6 ppb in 1998. The global growth rate then decreased to 2.6 +/- 0.6 ppb during 1999, indicating that the large increase in 1998 was an anomaly and not a return to the larger growth rates observed during the late 1970s and early 1980s. The increased growth rate represents an anomalous increase in the imbalance between CH4 sources and sinks equal to approximately 24 Tg CH4 during 1998. Wetlands and boreal biomass burning are sources that may have contributed to the anomaly. During 1998, the globally averaged temperature anomaly was +0.67 C, the largest temperature anomaly in the modern record. A regression model based on temperature and precipitation anomalies was used to calculate emission anomalies of 11.6 Tg CH4 from wetlands north of 30 N and 13 Tg CH4 for tropical wetlands during 1998 compared to average emissions calculated for 1982-1993. In 1999, calculated wetland emission anomalies were negative for high northern latitudes and the tropics, contributing to the low growth rate observed in 1999. Also 1998 was a severe fire year in boreal regions where approximately 1.3x10(exp 5) sq km of forest and peat land burned releasing an estimated 5.7 Tg CH4

Soil Methanotrophy Model (MeMo v1.0): a process-based model to quantify global uptake of atmospheric methane by soil

NASA Astrophysics Data System (ADS)

Murguia-Flores, Fabiola; Arndt, Sandra; Ganesan, Anita L.; Murray-Tortarolo, Guillermo; Hornibrook, Edward R. C.

2018-06-01

Soil bacteria known as methanotrophs are the sole biological sink for atmospheric methane (CH4), a potent greenhouse gas that is responsible for ˜ 20 % of the human-driven increase in radiative forcing since pre-industrial times. Soil methanotrophy is controlled by a plethora of factors, including temperature, soil texture, moisture and nitrogen content, resulting in spatially and temporally heterogeneous rates of soil methanotrophy. As a consequence, the exact magnitude of the global soil sink, as well as its temporal and spatial variability, remains poorly constrained. We developed a process-based model (Methanotrophy Model; MeMo v1.0) to simulate and quantify the uptake of atmospheric CH4 by soils at the global scale. MeMo builds on previous models by Ridgwell et al. (1999) and Curry (2007) by introducing several advances, including (1) a general analytical solution of the one-dimensional diffusion-reaction equation in porous media, (2) a refined representation of nitrogen inhibition on soil methanotrophy, (3) updated factors governing the influence of soil moisture and temperature on CH4 oxidation rates and (4) the ability to evaluate the impact of autochthonous soil CH4 sources on uptake of atmospheric CH4. We show that the improved structural and parametric representation of key drivers of soil methanotrophy in MeMo results in a better fit to observational data. A global simulation of soil methanotrophy for the period 1990-2009 using MeMo yielded an average annual sink of 33.5 ± 0.6 Tg CH4 yr-1. Warm and semi-arid regions (tropical deciduous forest and open shrubland) had the highest CH4 uptake rates of 602 and 518 mg CH4 m-2 yr-1, respectively. In these regions, favourable annual soil moisture content ( ˜ 20 % saturation) and low seasonal temperature variations (variations < ˜ 6 °C) provided optimal conditions for soil methanotrophy and soil-atmosphere gas exchange. In contrast to previous model analyses, but in agreement with recent observational data, MeMo predicted low fluxes in wet tropical regions because of refinements in formulation of the influence of excess soil moisture on methanotrophy. Tundra and mixed forest had the lowest simulated CH4 uptake rates of 176 and 182 mg CH4 m-2 yr-1, respectively, due to their marked seasonality driven by temperature. Global soil uptake of atmospheric CH4 was decreased by 4 % by the effect of nitrogen inputs to the system; however, the direct addition of fertilizers attenuated the flux by 72 % in regions with high agricultural intensity (i.e. China, India and Europe) and by 4-10 % in agriculture areas receiving low rates of N input (e.g. South America). Globally, nitrogen inputs reduced soil uptake of atmospheric CH4 by 1.38 Tg yr-1, which is 2-5 times smaller than reported previously. In addition to improved characterization of the contemporary soil sink for atmospheric CH4, MeMo provides an opportunity to quantify more accurately the relative importance of soil methanotrophy in the global CH4 cycle in the past and its capacity to contribute to reduction of atmospheric CH4 levels under future global change scenarios.

Gas-Phase Chemistry of Trimethyl Phosphite,

DTIC Science & Technology

keywords include: Flowing afterglow; Trimethyl phosphite ; Reaction mechanisms; Phosphorous ; and Nucleophilic displacement....The reactions of trimethyl phosphite were investigated with a series of nucleophiles. Products, branching ratios, and reaction rate constants are...of methoxide to form a new ion-dipole complex (CH3O-(CH3O)2PZ). If an additional acidic hydrogen is available on the nucleophile, the major products

Estimation of Methane Emissions from Slurry Pits below Pig and Cattle Confinements

PubMed Central

Petersen, Søren O.; Olsen, Anne B.; Elsgaard, Lars; Triolo, Jin Mi; Sommer, Sven G.

2016-01-01

Quantifying in-house emissions of methane (CH4) from liquid manure (slurry) is difficult due to high background emissions from enteric processes, yet of great importance for correct estimation of CH4 emissions from manure management and effects of treatment technologies such as anaerobic digestion. In this study CH4 production rates were determined in 20 pig slurry and 11 cattle slurry samples collected beneath slatted floors on six representative farms; rates were determined within 24 h at temperatures close to the temperature in slurry pits at the time of collection. Methane production rates in pig and cattle slurry differed significantly at 0.030 and 0.011 kg CH4 kg-1 VS (volatile solids). Current estimates of CH4 emissions from pig and cattle manure management correspond to 0.032 and 0.015 kg CH4 kg-1, respectively, indicating that slurry pits under animal confinements are a significant source. Fractions of degradable volatile solids (VSd, kg kg-1 VS) were estimated using an aerobic biodegradability assay and total organic C analyses. The VSd in pig and cattle slurry averaged 0.51 and 0.33 kg kg-1 VS, and it was estimated that on average 43 and 28% of VSd in fresh excreta from pigs and cattle, respectively, had been lost at the time of sampling. An empirical model of CH4 emissions from slurry was reparameterised based on experimental results. A sensitivity analysis indicated that predicted CH4 emissions were highly sensitive to uncertainties in the value of lnA of the Arrhenius equation, but much less sensitive to uncertainties in VSd or slurry temperature. A model application indicated that losses of carbon in VS as CO2 may be much greater than losses as CH4. Implications of these results for the correct estimation of CH4 emissions from manure management, and for the mitigation potential of treatments such as anaerobic digestion, are discussed. PMID:27529692

Flow rate and source reservoir identification from airborne chemical sampling of the uncontrolled Elgin platform gas release

NASA Astrophysics Data System (ADS)

Lee, James D.; Mobbs, Stephen D.; Wellpott, Axel; Allen, Grant; Bauguitte, Stephane J.-B.; Burton, Ralph R.; Camilli, Richard; Coe, Hugh; Fisher, Rebecca E.; France, James L.; Gallagher, Martin; Hopkins, James R.; Lanoiselle, Mathias; Lewis, Alastair C.; Lowry, David; Nisbet, Euan G.; Purvis, Ruth M.; O'Shea, Sebastian; Pyle, John A.; Ryerson, Thomas B.

2018-03-01

An uncontrolled gas leak from 25 March to 16 May 2012 led to evacuation of the Total Elgin wellhead and neighbouring drilling and production platforms in the UK North Sea. Initially the atmospheric flow rate of leaking gas and condensate was very poorly known, hampering environmental assessment and well control efforts. Six flights by the UK FAAM chemically instrumented BAe-146 research aircraft were used to quantify the flow rate. The flow rate was calculated by assuming the plume may be modelled by a Gaussian distribution with two different solution methods: Gaussian fitting in the vertical and fitting with a fully mixed layer. When both solution methods were used they compared within 6 % of each other, which was within combined errors. Data from the first flight on 30 March 2012 showed the flow rate to be 1.3 ± 0.2 kg CH4 s-1, decreasing to less than half that by the second flight on 17 April 2012. δ13CCH4 in the gas was found to be -43 ‰, implying that the gas source was unlikely to be from the main high pressure, high temperature Elgin gas field at 5.5 km depth, but more probably from the overlying Hod Formation at 4.2 km depth. This was deemed to be smaller and more manageable than the high pressure Elgin field and hence the response strategy was considerably simpler. The first flight was conducted within 5 days of the blowout and allowed a flow rate estimate within 48 h of sampling, with δ13CCH4 characterization soon thereafter, demonstrating the potential for a rapid-response capability that is widely applicable to future atmospheric emissions of environmental concern. Knowledge of the Elgin flow rate helped inform subsequent decision making. This study shows that leak assessment using appropriately designed airborne plume sampling strategies is well suited for circumstances where direct access is difficult or potentially dangerous. Measurements such as this also permit unbiased regulatory assessment of potential impact, independent of the emitting party, on timescales that can inform industry decision makers and assist rapid-response planning by government.

Gaseous emissions from outdoor concrete yards used by livestock

NASA Astrophysics Data System (ADS)

Misselbrook, T. H.; Webb, J.; Chadwick, D. R.; Ellis, S.; Pain, B. F.

Measurements of ammonia (NH 3), nitrous oxide (N 2O) and methane (CH 4) were made from 11 outdoor concrete yards used by livestock. Measurements of NH 3 emission were made using the equilibrium concentration technique while closed chambers were used to measure N 2O and CH 4 emissions. Outdoor yards used by livestock proved to be an important source of NH 3 emission. Greatest emission rates were measured from dairy cow feeding yards, with a mean of 690 mg NH 3-N m -2 h -1. Smaller emission rates were measured from sheep handling areas, dairy cow collecting yards, beef feeding yards and a pig loading area, with respective mean emission rates of 440, 280, 220 and 140 mg NH 3-N m -2 h -1. Emission rates of N 2O and CH 4 were much smaller and for CH 4, in particular, emission rates were influenced greatly by the presence or absence of dung on the measurement area.

Characterizing CH4 and N2O emissions from an intensive dairy operation in summer and fall in China

NASA Astrophysics Data System (ADS)

Zhu, Gaodi; Ma, Xiaoyuan; Gao, Zhiling; Ma, Wenqi; Li, Jianguo; Cai, Zhenjiang

2014-02-01

Evaluation of the global warming potential of the dairy industry both in China and globally necessitates reliable characterization of CH4 and N2O emissions. However, CH4 and N2O emissions from dairy operations differ with feeds, herd structures and manure management practices, and the lack of N2O and CH4 emission measurements for China, especially for intensive dairy operations, causes substantial uncertainty in accounting for GHGs from dairy operation both in China and globally. In this study, CH4 and N2O emissions during summer to fall period from an intensive feedlot in China were characterized to fill the data gap. The diurnal CH4 emission patterns for milking cows and heifers were driven by the feeding activities and the diurnal N2O patterns by the diurnal changes in temperature. The CH4 emission rates of 397 g head-1 d-1 (23.63 L CH4 kg-1 milk) (in summer) and 279 g head-1 d-1 (in fall) for milking cows and heifers accounted for 5.17% and 7.68% of their daily gross energy intakes, whereas the N2O emission rates of 36.7 g head-1 d-1 (0.85 L N2O kg-1 milk) for milking cows and 24.2 g head-1 d-1 for heifers accounted for 4.25% and 6.86% of the daily feed N intake. The CH4 conversion factor and CH4 emission intensity in the measurement season for intensive dairy operations in China are lower than those for collective operations in China, and the CH4 emission intensity is similar to those in developed countries.

Eight-dimensional quantum reaction rate calculations for the H+CH{sub 4} and H{sub 2}+CH{sub 3} reactions on recent potential energy surfaces

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

Zhou, Yong; Zhang, Dong H., E-mail: zhangdh@dicp.ac.cn

2014-11-21

Eight-dimensional (8D) transition-state wave packet simulations have been performed on two latest potential energy surfaces (PES), the Zhou-Fu-Wang-Collins-Zhang (ZFWCZ) PES [Y. Zhou, B. Fu, C. Wang, M. A. Collins, and D. H. Zhang, J. Chem. Phys. 134, 064323 (2011)] and the Xu-Chen-Zhang (XCZ)-neural networks (NN) PES [X. Xu, J. Chen, and D. H. Zhang, Chin. J. Chem. Phys. 27, 373 (2014)]. Reaction rate constants for both the H+CH{sub 4} reaction and the H{sub 2}+CH{sub 3} reaction are calculated. Simulations of the H+CH{sub 4} reaction based on the XCZ-NN PES show that the ZFWCZ PES predicts rate constants with reasonable highmore » accuracy for low temperatures while leads to slightly lower results for high temperatures, in line with the distribution of interpolation error associated with the ZFWCZ PES. The 8D H+CH{sub 4} rate constants derived on the ZFWCZ PES compare well with full-dimensional 12D results based on the equivalent m-ZFWCZ PES, with a maximum relative difference of no more than 20%. Additionally, very good agreement is shown by comparing the 8D XCZ-NN rate constants with the 12D results obtained on the ZFWCZ-WM PES, after considering the difference in static barrier height between these two PESs. The reaction rate constants calculated for the H{sub 2}+CH{sub 3} reaction are found to be in good consistency with experimental observations.« less

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.

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 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.

Decontamination of 2-Chloroethyl Ethyl Sulfide by Pulsed Corona Plasma

NASA Astrophysics Data System (ADS)

Li, Zhanguo; Hu, Zhen; Cao, Peng; Zhao, Hongjie

2014-11-01

Decontamination of 2-chloroethyl ethyl sulfide (2-CEES, CH3CH2SCH2CH2Cl) by pulsed corona plasma was investigated. The results show that 212.6 mg/m3 of 2-CEES, with the gas flow rate of 2 m3/h, can be decontaminated to 0.09 mg/m3. According to the variation of the inlet and outlet concentration of 2-CEES vapor with retention time, it is found that the reaction of 2-CEES in a pulsed corona plasma system follows the first order reaction, with the reaction rate constant of 0.463 s-1. The decontamination mechanism is discussed based on an analysis of the dissociation energy of chemical bonds and decontamination products. The C-S bond adjacent to the Cl atom will be destroyed firstly to form CH3CH2S· and ·CH2CH2Cl radicals. CH3CH2S· can be decomposed to ·C2H5 and ·S. ·S can be oxidized to SO2, while ·C2H5 can be finally oxidized to CO2 and H2O. The C-Cl bond in the ·CH2CH2Cl radical can be destroyed to form ·CH2CH2. and ·Cl, which can be mineralized to CO2, H2O and HCl. The H atom in the ·CH2CH2Cl radical can also be substituted by ·Cl to form CHCl2-CHCl2.

The methane sink associated to soils of natural and agricultural ecosystems in Italy.

PubMed

Castaldi, Simona; Costantini, Massimo; Cenciarelli, Pietro; Ciccioli, Paolo; Valentini, Riccardo

2007-01-01

In the present work, the CH4 sink associated to Italian soils was calculated by using a process-based model controlled by gas diffusivity and microbial activity, which was run by using a raster-based geographical information system. Georeferenced data included land cover CLC2000, soil properties from the European Soil Database, climatic data from the MARS-STAT database, plus several derived soils properties based on published algorithms applied to the above mentioned databases. Overall CH4 consumption from natural and agricultural sources accounted for a total of 43.3 Gg CH4 yr(-1), with 28.1 Gg CH4 yr(-1) removed in natural ecosystems and 15.1 Gg CH4 yr(-1) in agricultural ecosystems. The highest CH4 uptake rates were obtained for natural areas of Southern Apennines and islands of Sardinia and Sicily, and were mainly associated to areas covered by sclerophyllous vegetation (259.7+/-30.2 mg CH4 m(-2) yr(-1)) and broad-leaved forest (237.5 mg CH4 m(-2) yr(-1)). In terms of total sink strength broad-leaved forests were the dominant ecosystem. The overall contribution of each ecosystem type to the whole CH4 sink depended on the total area covered by the specific ecosystem and on its exact geographic distribution. The latter determines the type of climate present in the area and the dominant soil type, both factors which showed to have a strong influence on CH4 uptake rates. The aggregated CH4 sink, calculated for natural ecosystems present in the Italian region, is significantly higher than previously reported estimates, which were extrapolated from fluxes measured in other temperate ecosystems.

Estimating global natural wetland methane emissions using process modelling: spatio-temporal patterns and contributions to atmospheric methane fluctuations

USGS Publications Warehouse

Zhu, Qiuan; Peng, Changhui; Chen, Huai; Fang, Xiuqin; Liu, Jinxun; Jiang, Hong; Yang, Yanzheng; Yang, Gang

2015-01-01

Aim The fluctuations of atmospheric methane (CH4) that have occurred in recent decades are not fully understood, particularly with regard to the contribution from wetlands. The application of spatially explicit parameters has been suggested as an effective method for reducing uncertainties in bottom-up approaches to wetland CH4 emissions, but has not been included in recent studies. Our goal was to estimate spatio-temporal patterns of global wetland CH4 emissions using a process model and then to identify the contribution of wetland emissions to atmospheric CH4fluctuations. Location Global. Methods A process-based model integrated with full descriptions of methanogenesis (TRIPLEX-GHG) was used to simulate global wetland CH4emissions. Results Global annual wetland CH4 emissions ranged from 209 to 245 Tg CH4 year−1 between 1901 and 2012, with peaks occurring in 1991 and 2012. There is a decreasing trend between 1990 and 2010 with a rate of approximately 0.48 Tg CH4 year−1, which was largely caused by emissions from tropical wetlands showing a decreasing trend of 0.44 Tg CH4 year−1 since the 1970s. Emissions from tropical, temperate and high-latitude wetlands comprised 59, 26 and 15% of global emissions, respectively. Main conclusion Global wetland CH4 emissions, the interannual variability of which was primary controlled by tropical wetlands, partially drive the atmosphericCH4 burden. The stable to decreasing trend in wetland CH4 emissions, a result of a balance of emissions from tropical and extratropical wetlands, was a particular factor in slowing the atmospheric CH4 growth rate during the 1990s. The rapid decrease in tropical wetland CH4emissions that began in 2000 was supposed to offset the increase in anthropogenic emissions and resulted in a relatively stable level of atmospheric CH4 from 2000 to 2006. Increasing wetland CH4 emissions, particularly after 2010, should be an important contributor to the growth in atmospheric CH4 seen since 2007.

Vibrational dynamics of aniline(Ar)1 and aniline(CH4)1 clusters

NASA Astrophysics Data System (ADS)

Nimlos, M. R.; Young, M. A.; Bernstein, E. R.; Kelley, D. F.

1989-11-01

The first excited electronic state (S1) vibrational dynamics of aniline(Ar)1 and aniline(CH4)1 van der Waals (vdW) clusters have been studied using molecular jet and time resolved emission spectroscopic techniques. The rates of intramolecular vibrational energy redistribution (IVR) and vibrational predissociation (VP) as functions of vibrational energy are reported for both clusters. For vibrational energy in excess of the cluster binding energy, both clusters are observed to dissociate. The dispersed emission spectra of these clusters demonstrate that aniline(Ar)1 dissociates to all energetically accessible bare molecule states and that aniline(CH4)1 dissociates selectively to only the bare molecule vibrationless state. The emission kinetics show that in the aniline(Ar)1 case, the initially excited states have nanosecond lifetimes, and intermediate cluster states have very short lifetimes. In contrast, the initially excited aniline(CH4)1 states and other intermediate vibrationally excited cluster states are very short lived (<100 ps), and the intermediate cluster 00 state is observed. These results can be understood semiquantitatively in terms of an overall serial IVR/VP mechanism which consists of the following: (1) the rates of chromophore to vdW mode IVR are given by Fermi's golden rule, and the density of vdW vibrational states is the most important factor in determining the relative [aniline(Ar)1 vs aniline(CH4)1] rates of IVR; (2) IVR among the vdW modes is rapid; and (3) VP rates can be calculated by a restricted vdW mode phase space Rice-Ramsberger-Kassel-Marcus theory. Since the density of vdW states is three orders of magnitude greater for aniline(CH4)1 than aniline(Ar)1 at 700 cm-1, the model predicts that IVR is slow and rate limiting in aniline(Ar)1, whereas VP is slow and rate limiting in aniline(CH4)1. The agreement of these predictions with the experimental results is very good and is discussed in detail.

Experimental measurements of low temperature rate coefficients for neutral-neutral reactions of interest for atmospheric chemistry of Titan, Pluto and Triton: reactions of the CN radical.

PubMed

Morales, Sébastien B; Le Picard, Sébastien D; Canosa, André; Sims, Ian R

2010-01-01

The kinetics of the reactions of cyano radical, CN (X2sigma+) with three hydrocarbons, propane (CH3CH2CH3), propene (CH3CH=CH2) and 1-butyne (CH[triple band]CCH2CH3) have been studied over the temperature range of 23-298 K using a CRESU (Cinétique de Réaction en Ecoulement Supersonique Uniforme or Reaction Kinetics in Uniform Supersonic Flow) apparatus combined with the pulsed laser photolysis-laser induced fluorescence technique. These reactions are of interest for the cold atmospheres of Titan, Pluto and Triton, as they might participate in the formation of nitrogen and carbon bearing molecules, including nitriles, that are thought to play an important role in the formation of hazes and biological molecules. All three reactions are rapid with rate coefficients in excess of 10(-10) cm3 molecule(-1) s(-1) at the lowest temperatures of this study and show behaviour characteristic of barrierless reactions. Temperature dependences, different for each reaction, are compared to those used in the most recent photochemical models of Titan's atmosphere.

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.

HIGH METHANE EMISSIONS FROM A MID-LATITUDE AGRICULTURAL RESERVOIR

EPA Science Inventory

To assess the magnitude of methane (CH4) emissions from reservoirs in agricultural regions, we measured CH4 emission rates from William H. Harsha Lake, located in southwestern Ohio, USA, over a thirteen month period. The reservoir was a strong source of CH4¬ throughout the year,...

A detailed kinetic modeling study of toluene oxidation in a premixed laminar flame

PubMed Central

Tian, Zhenyu; Pitz, William J.; Fournet, René; Glaude, Pierre-Alexander; Battin-Leclerc, Frédérique

2013-01-01

An improved chemical kinetic model for the toluene oxidation based on experimental data obtained in a premixed laminar low-pressure flame with vacuum ultraviolet (VUV) photoionization and molecular beam mass spectrometry (MBMS) techniques has been proposed. The present mechanism consists of 273 species up to chrysene and 1740 reactions. The rate constants of reactions of toluene decomposition, reaction with oxygen, ipso-additions and metatheses with abstraction of phenylic H-atom are updated; new pathways of C4 + C2 species giving benzene and fulvene are added. Based on the experimental observations, combustion intermediates such as fulvenallene, naphtol, methylnaphthalene, acenaphthylene, 2-ethynylnaphthalene, phenanthrene, anthracene, 1-methylphenanthrene, pyrene and chrysene are involved in the present mechanism. The final toluene model leads to an overall satisfactory agreement between the experimentally observed and predicted mole fraction profiles for the major products and most combustion intermediates. The toluene depletion is governed by metathese giving benzyl radicals, ipso-addition forming benzene and metatheses leading to C6H4CH3 radicals. A sensitivity analysis indicates that the unimolecular decomposition via the cleavage of a methyl C-H bond has a strong inhibiting effect, while decomposition via C-C bond breaking, ipso-addition of H-atom to toluene, decomposition of benzyl radicals and reactions related to C6H4CH3 radicals have promoting effect for the consumption of toluene. Moreover, flow rate analysis is performed to illustrate the formation pathways of mono- and polycyclic aromatics. PMID:23762016

Use of Inert Gases to Study the Interaction of Blood Flow and Diffusion during Passive Absorption from the Gastrointestinal Tract of the Rat

PubMed Central

Levitt, Michael D.; Levitt, David G.

1973-01-01

Measurement of the relative absorption rates of inert gases (H2, He, CH4, SF6, and 133Xe) was used to investigate the interaction between diffusion and blood flow during passive absorption from the stomach, small bowel, and colon of the rat. If uptake is blood flow limited, the gases should be absorbed in proportion to their solubilities in blood, but if diffusion limited, uptake should be proportional to the diffusion rate of the gases in mucosal tissues. The observed absorption data were fitted to a series of models of interaction between perfusion and diffusion. A simple model accurately predicted the absorption rates of the gases from all segments of bowel. In this model, gas is absorbed into two distinct blood flows: one which flows in proximity to the lumen and completely equilibrates with the lumen, and a second which is sufficiently rapid and distant from the lumen that its gas uptake is entirely diffusion limited. The fraction of the total absorption attributable to the equilibrating flow can be readily calculated and equalled 93%, 77%, and 33% for the small bowel, colon, and stomach, respectively. Thus the rate of passive absorption of gases from the small bowel is limited almost entirely by the blood flow to the mucosa, and absorption from the stomach is largely limited by the diffusion rate of the gases. The flow which equilibrates with the lumen can be quantitated, and this flow may provide a useful measure of “effective” mucosal blood flow. Images PMID:4719667

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.

Constraining Methane Emissions from Natural Gas Production in Northeastern Pennsylvania Using Aircraft Observations and Mesoscale Modeling

NASA Astrophysics Data System (ADS)

Barkley, Z.; Davis, K.; Lauvaux, T.; Miles, N.; Richardson, S.; Martins, D. K.; Deng, A.; Cao, Y.; Sweeney, C.; Karion, A.; Smith, M. L.; Kort, E. A.; Schwietzke, S.

2015-12-01

Leaks in natural gas infrastructure release methane (CH4), a potent greenhouse gas, into the atmosphere. The estimated fugitive emission rate associated with the production phase varies greatly between studies, hindering our understanding of the natural gas energy efficiency. This study presents a new application of inverse methodology for estimating regional fugitive emission rates from natural gas production. Methane observations across the Marcellus region in northeastern Pennsylvania were obtained during a three week flight campaign in May 2015 performed by a team from the National Oceanic and Atmospheric Administration (NOAA) Global Monitoring Division and the University of Michigan. In addition to these data, CH4 observations were obtained from automobile campaigns during various periods from 2013-2015. An inventory of CH4 emissions was then created for various sources in Pennsylvania, including coalmines, enteric fermentation, industry, waste management, and unconventional and conventional wells. As a first-guess emission rate for natural gas activity, a leakage rate equal to 2% of the natural gas production was emitted at the locations of unconventional wells across PA. These emission rates were coupled to the Weather Research and Forecasting model with the chemistry module (WRF-Chem) and atmospheric CH4 concentration fields at 1km resolution were generated. Projected atmospheric enhancements from WRF-Chem were compared to observations, and the emission rate from unconventional wells was adjusted to minimize errors between observations and simulation. We show that the modeled CH4 plume structures match observed plumes downwind of unconventional wells, providing confidence in the methodology. In all cases, the fugitive emission rate was found to be lower than our first guess. In this initial emission configuration, each well has been assigned the same fugitive emission rate, which can potentially impair our ability to match the observed spatial variability. The current model also does not distinguish between natural gas emissions during the different stages of transportation. We finally discuss the use of additional tracers such as the 13CH4 isotopic ratio and ethane concentrations to separate the various contributors to the regional atmospheric CH4 enhancement.

Infrared Spectroscopy of the Entrance Channel Complex Formed Between the Hydroxyl Radical and Methane in Helium Nanodroplets

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

Raston, Paul L.; Obi, Emmanuel I.; Douberly, Gary E.

Here, the entrance channel complex in the exothermic OH + CH 4 → H 2O + CH 3 reaction has been isolated in helium nanodroplets following the sequential pick-up of the hydroxyl radical and methane. The a-type OH stretching band was probed with infrared depletion spectroscopy, revealing a spectrum qualitatively similar to that previously reported in the gas phase, but with additional substructure that is due to the different internal rotation states of methane (j CH4 = 0, 1, or 2) in the complex. We fit the spectra by assuming the rotational constants of the complex are the same formore » all internal rotation states; however, subband origins are found to decrease with increasing j CH4. Measurements of deuterated complexes have also been made (OD–CH 4, OH–CD 4, and OD–CD 4), the relative linewidths of which provide information about the flow of vibrational energy in the complexes; vibrational lifetime broadening is prominent for OH–CH 4 and OD–CD 4, for which the excited OX stretching state has a nearby CY 4 stretching fundamental (X, Y = H or D).« less

Infrared Spectroscopy of the Entrance Channel Complex Formed Between the Hydroxyl Radical and Methane in Helium Nanodroplets

DOE PAGES

Raston, Paul L.; Obi, Emmanuel I.; Douberly, Gary E.

2017-09-22

Here, the entrance channel complex in the exothermic OH + CH 4 → H 2O + CH 3 reaction has been isolated in helium nanodroplets following the sequential pick-up of the hydroxyl radical and methane. The a-type OH stretching band was probed with infrared depletion spectroscopy, revealing a spectrum qualitatively similar to that previously reported in the gas phase, but with additional substructure that is due to the different internal rotation states of methane (j CH4 = 0, 1, or 2) in the complex. We fit the spectra by assuming the rotational constants of the complex are the same formore » all internal rotation states; however, subband origins are found to decrease with increasing j CH4. Measurements of deuterated complexes have also been made (OD–CH 4, OH–CD 4, and OD–CD 4), the relative linewidths of which provide information about the flow of vibrational energy in the complexes; vibrational lifetime broadening is prominent for OH–CH 4 and OD–CD 4, for which the excited OX stretching state has a nearby CY 4 stretching fundamental (X, Y = H or D).« less

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.

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.

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.;

Characterization of chemical sputtering using the Mark II DiMES porous plug injector in attached and semi-detached divertor plasmas of DIII-D

NASA Astrophysics Data System (ADS)

McLean, A. G.; Davis, J. W.; Stangeby, P. C.; Allen, S. L.; Boedo, J. A.; Bray, B. D.; Brezinsek, S.; Brooks, N. H.; Fenstermacher, M. E.; Groth, M.; Haasz, A. A.; Hollmann, E. M.; Isler, R. C.; Lasnier, C. J.; Mu, Y.; Petrie, T. W.; Rudakov, D. L.; Watkins, J. G.; West, W. P.; Whyte, D. G.; Wong, C. P. C.

2009-06-01

An improved, self-contained gas injection system for the divertor material evaluation system (DiMES) on DIII-D has been employed for in situ study of chemical erosion in the tokamak divertor environment. To minimize perturbation to local plasma, the Mark II porous plug injector (PPI) releases methane through a porous graphite surface at the outer strike point at a rate precisely controlled by a micro-orifice flow restrictor to be approximately equal as that predicted for intrinsic chemical sputtering. Effective photon efficiencies resulting from CH 4 are found to be 58 ± 12 in an attached divertor ( ne ˜ 1.5 × 10 13/cm 3, Te ˜ 25 eV, Tsurf ˜ 450 K), and 94 ± 20 in a semi-detached cold divertor ( ne ˜ 6.0 × 10 13/cm 3, Te ˜ 2-3 eV, Tsurf ˜ 350 K). These values are significantly more than previous measurements in similar plasma conditions, indicating the importance of the injection rate and local re-erosion for the integrity of this analysis. The contribution of chemical versus physical sputtering to the source of C + at the target is assessed through simultaneous measurement of CII line, and CD plus CH-band emissions during release of CH 4 from the PPI, then compared with that seen in intrinsic sputtering.

CH4 concentrations and fluxes in a subtropical metropolitan river network: Watershed urbanization impacts and environmental controls.

PubMed

Wang, Xiaofeng; He, Yixin; Chen, Huai; Yuan, Xingzhong; Peng, Changhui; Yue, Junsheng; Zhang, Qiaoyong; Zhou, Lilei

2018-05-01

Urbanization and greenhouse gas emissions are of great global concern, especially in developing countries such as China. However, little is known about the relationship between the two. In this study, we examined the influences of the urbanization of Chongqing Municipality, which covers an area of 5494km 2 , in China, on the CH 4 emissions of in its metropolitan river network. The results from 84 sampling locations showed an overall mean CH 4 concentration of 0.69±1.37μmol·L -1 and a CH 4 flux from the river network of 1.40±2.53mmolCH 4 m -2 d -1 . The CH 4 concentrations and fluxes presented a clear seasonal pattern, with the highest value in the spring and the lowest in the summer. Such seasonal variations were probably co-regulated by the dilution effect, temperature and supply of fresh organic matter by algal blooms. Another important result was that the CH 4 concentrations and fluxes increased with the degree of urbanization or the proportion of urban land use, being approximately 3-13 times higher in urban and suburban areas than in rural ones. The total nitrogen, dissolved oxygen (O%) and possible sewage discharge, which could affect the in situ CH 4 production and exogenous CH 4 input respectively, were important factors that influenced the spatial patterns of CH 4 in human-dominated river networks, while the nitrogen (N) and phosphorus (P) could be good predictors of the CH 4 emissions in urban watersheds. Hydrologic drivers, including bottom sediment type, flow velocity and river width, were strongly correlated with the CH 4 concentrations and could also affect the spatial variance and predict the CH 4 hotspots in such metropolitan river networks. With increasing urbanization, we should pay more attention to the increasing greenhouse gas emissions associated with urbanization. Copyright © 2017 Elsevier B.V. All rights reserved.

Monitoring the growth of polyoxomolybdate nanoparticles in suspension by flow field-flow fractionation.

PubMed

Chen, Bailin; Jiang, Huijian; Zhu, Yan; Cammers, Arthur; Selegue, John P

2005-03-30

We follow the evolution of polyoxomolybdate nanoparticles in suspensions derived from the keplerate (NH4)42[MoVI72MoV60O372(CH3CO2)30(H2O)72].ca..300H2O.ca..10CH3CO2NH4 ({Mo132}) by flow field-flow fractionation (FlFFF) to monitor the particle-size distribution in situ, atomic force and high-resolution transmission electron microscopy (AFM, SEM, and HRTEM) to confirm particle sizes, inductively coupled plasma-optical emission spectrometry (ICP-OES) to determine the Mo content of the FlFFF-separated fractions, and UV/visible spectroscopy to confirm the identity of the species in suspension. We observe the formation of 3-75-nm polyoxomolybdate particles in suspension and the dynamic growth of {Mo132} crystals.

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.

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.

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.

Factors influencing CO2 and CH4 emissions from coastal wetlands in the Liaohe Delta, northeast China

USGS Publications Warehouse

Olsson, Linda; Ye, Siyuan; Yu, Xueyang; Wei, Mengjie; Krauss, Ken W.; Brix, Hans

2015-01-01

Many factors are known to influence greenhouse gas emissions from coastal wetlands, but it is still unclear which factors are most important under field conditions when they are all acting simultaneously. The objective of this study was to assess the effects of water table, salinity, soil temperature and vegetation on CH4 emissions and ecosystem respiration (Reco) from five coastal wetlands in the Liaohe Delta, northeast China: two Phragmites australis (common reed) wetlands, two Suaeda salsa (sea blite) marshes and a rice (Oryza sativa) paddy. Throughout the growing season, the Suaeda wetlands were net CH4 sinks whereas the Phragmites wetlands and the rice paddy were net CH4sources emitting 1.2–6.1 g CH4 m−2 y−1. The Phragmites wetlands emitted the most CH4 per unit area and the most CH4 relative to CO2. The main controlling factors for the CH4 emissions were water table, temperature and salinity. The CH4 emission was accelerated at high and constant (or managed) water tables and decreased at water tables below the soil surface. High temperatures enhanced CH4 emissions, and emission rates were consistently low (< 1 mg CH4 m−2 h) at soil temperatures <18 °C. At salinity levels > 18 ppt, the CH4 emission rates were always low (< 1 mg CH4 m−2 h−1) probably because methanogens were outcompeted by sulphate reducing bacteria. Saline Phragmites wetlands can, however, emit significant amounts of CH4 as CH4 produced in deep soil layers are transported through the air-space tissue of the plants to the atmosphere. The CH4 emission from coastal wetlands can be reduced by creating fluctuating water tables, including water tables below the soil surface, as well as by occasional flooding by high-salinity water. The effects of water management schemes on the biological communities in the wetlands must, however, be carefully studied prior to the management in order to avoid undesirable effects on the wetland communities.

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.

40 CFR Table A-6 to Subpart A of... - Data Elements That Are Inputs to Emission Equations and for Which the Reporting Deadline Is March...

Code of Federal Regulations, 2013 CFR

2013-07-01

... Equation TT-4). TT 98.466(b)(3) Only fraction of CH4 in landfill gas. TT 98.466(b)(4) Only the methane...) MANDATORY GREENHOUSE GAS REPORTING General Provision Pt. 98, Subpt. A, Table A-6 Table A-6 to Subpart A of.... FF 98.326(h) Only weekly volumetric flow used to calculate CH4 liberated from degasification systems...

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.

Upland beech trees significantly contribute to forest methane exchange

NASA Astrophysics Data System (ADS)

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

2016-04-01

Methane (CH4) can be emitted not only from soil, but also from plants. Fluxes of CH4were predominantly investigated in riparian herbaceous plants, whereas studies on trees, particularly those lacking an aerenchyma, are rare. In soil produced CH4 can be taken up by roots, transported via intercellular spaces and the aerenchyma system, or transpiration stream to aboveground plant tissues and released to the atmosphere via lenticels or stomata. Although CH4 might be also produced by microorganisms living in plant tissues or photochemical processes in plants, these processes are relatively minor. It has been shown that seedlings of European beech (Fagus sylvatica) emit CH4 from its stems despite the lack of an aerenchyma. Our objectives were to determine the CH4 fluxes from mature beech trees and adjacent soil under natural field conditions, and to estimate the role of trees in the CH4exchange within the soil-tree-atmosphere continuum. Measurements were conducted in two mountain beech forests with different geographical and climatic conditions (White Carpathians, Czech Republic; Black Forest, Germany). CH4 fluxes at stems (profile) and root bases level were simultaneously measured together with soil-atmosphere fluxes using static chamber systems followed by chromatographic analysis or continuous laser detection of CH4 concentrations. Our study shows that mature beech trees have the ability to exchange CH4 with the atmosphere. The beech stems emitted CH4 into the atmosphere at the White Carpathians site in the range from 2.00 to 179 μg CH4 m-2 stem area h-1, while CH4 flux rates ranged between -1.34 to 1.73 μg CH4 m-2 h-1 at the Black Forest site. The root bases of beech trees from the White Carpathians released CH4 into the atmosphere (from 0.62 to 49.8 μg CH4 m-2 root area h-1), whereas a prevailing deposition was observed in the Black Forest (from -1.21 to 0.81 μg CH4 m-2 h-1). These fluxes seem to be affected by soil water content and its spatial heterogeneity. Compared to beech trees, forest floor was a sink for CH4 on the both sites. The deposition rates reached -52 and -161 μg CH4 m-2 soil area h-1 at the White Carpathians and Black Forest site, respectively. Concluded, CH4 emissions from upland beech trees significantly contribute to total CH4 flux and have to be counted towards the overall CH4 balance of beech forest. Acknowledgement This 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 DFG project (MA 5826/2-1). We thank Marek Jakubik for technical support and Sinikka Paulus for help by field measurements.

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.

Technical note: A facility for respiration measurements in cattle.

PubMed

Machado, F S; Tomich, T R; Ferreira, A L; Cavalcanti, L F L; Campos, M M; Paiva, C A V; Ribas, M N; Pereira, L G R

2016-06-01

A respiration system consisting of 4 climate-controlled chambers and 1 set of flowmeters and analyzers was constructed and validated. Each chamber had volume of 21.10m(3) (3.68×2.56×2.24m) and was made from steel with double-glazed windows on either side enabling visual contact between animals. The chambers are independently climate-controlled and can maintain temperature and relative humidity in a range from 5 to 45°C and 30 to 80%, respectively. A flow generator and mass flowmeter continuously pull air from each chamber and a slight negative pressure inside the chamber is ensured. Air from all chambers and ambient air share a common gas analysis and data acquisition system for monitoring O2, CO2, and CH4 concentrations over the measurement period, with the cycle time set to 20min. Analyzers are regularly calibrated and the chambers have mean recoveries of 99.0 and 98.0% for CO2 and CH4, respectively. The chambers are equipped with infrared cameras and electronic feed and water bins for intake measurements, as well as sensors for monitoring animal position and heart rate. Data acquisition and analysis software is used to calculate the rate of consumption of O2 and production of CO2 and CH4. The dynamic respiration measurements are integrated with feed intake data and other sensors. The daily gas exchanges are estimated by integration to determine methane emission and heat production. We conducted a trial with 12 lactating 3/4 Holstein × 1/4 Gyr crossbred dairy cows (6 multiparous and 6 primiparous) under 2 feeding regimens (ad libitum or restricted) to validate the system. Two 22-h respiration measurements were obtained from each cow. Restricted-fed cows showed lower values for milk yield, methane emission, and heat production compared with ad libitum-fed animals. We found no difference between groups for CH4 produced per kilogram of dry matter intake. Repeatability for CH4 emission and heat production was high (0.97 and 0.92, respectively). The respiration system described herein is a useful tool for measuring the dynamic and accumulated data of heat production, methane emission, and feed intake. Copyright © 2016 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Amperometric Choline Biosensor Fabricated through Electrostatic Assembly of Bienzyme/Polyelectrolyte Hybrid Layers on Carbon Nanotubes

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

Wang, Jun; Liu, Guodong; Lin, Yuehe

2006-03-01

We report a flow injection amperometric choline biosensors based on the electrostatic assembly of an enzyme of choline oxidase (ChO) and a bi-enzyme of ChO and horseradish peroxidase (HRP) onto multi-wall carbon nanotubes (MWCNT) modified glassy carbon (GC) electrodes. These choline biosensors were fabricated by immobilization of enzymes on the negatively charged MWCNT surface through alternatively assembling a cationic polydiallydiimethylammonium chloride (PDDA) layer and an enzyme layer. Using this layer-by-layer assembling approach, bioactive nanocomposite film of a PDDA/ChO/PDDA/HRP/PDDA/CNT (ChO/HRP/CNT) and a PDDA/ChO/PDDA/ CNT (ChO/ CNT) were fabricated on GC surface, respectively. Owning to the electrocatalytic effect of carbon nanotubes, themore » measurement of faradic responses resulting from enzymatic reactions has been realized at low potential with acceptable sensitivity. It is found the ChO/HRP/CNT biosensor is more sensitive than the ChO/CNT one. Experimental parameters affecting the sensitivity of biosensors, e.g. applied potential, flow rate, etc. were optimized and potential interference was examined. The response time for this choline biosensor is fast (less than a few seconds). The linear range of detection for the choline biosensor is from 5 x 10-5 to 5 x 10-3 M and the detection limit is determined to be about 1.0 x 10-5 M.« less

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.

Contribution of Anthropogenic and Natural Emissions to Global CH4 Balances by Utilizing δ13C-CH4 Observations in CarbonTracker Data Assimilation System (CTDAS)

NASA Astrophysics Data System (ADS)

Kangasaho, V. E.; Tsuruta, A.; Aalto, T.; Backman, L. B.; Houweling, S.; Krol, M. C.; Peters, W.; van der Laan-Luijkx, I. T.; Lienert, S.; Joos, F.; Dlugokencky, E. J.; Michael, S.; White, J. W. C.

2017-12-01

The atmospheric burden of CH4 has more than doubled since preindustrial time. Evaluating the contribution from anthropogenic and natural emissions to the global methane budget is of great importance to better understand the significance of different sources at the global scale, and their contribution to changes in growth rate of atmospheric CH4 before and after 2006. In addition, observations of δ13C-CH4 suggest an increase in natural sources after 2006, which matches the observed increase and variation of CH4 abudance. Methane emission sources can be identified using δ13C-CH4, because different sources produce methane with process-specific isotopic signatures. This study focuses on inversion model based estimates of global anthropogenic and natural methane emission rates to evaluate the existing methane emission estimates with a new δ13C-CH4 inversion system. In situ measurements of atmospheric methane and δ13C-CH4 isotopic signature, provided by the NOAA Global Monitoring Division and the Institute of Arctic and Alpine Research, will be assimilated into the CTDAS-13C-CH4. The system uses the TM5 atmospheric transport model as an observation operator, constrained by ECMWF ERA Interim meteorological fields, and off-line TM5 chemistry fields to account for the atmospheric methane sink. LPX-Bern DYPTOP ecosystem model is used for prior natural methane emissions from wetlands, peatlands and mineral soils, GFED v4 for prior fire emissions and EDGAR v4.2 FT2010 inventory for prior anthropogenic emissions. The EDGAR antropogenic emissions are re-divided into enteric fermentation and manure management, landfills and waste water, rice, coal, oil and gas, and residential emissions, and the trend of total emissions is scaled to match optimized anthropogenic emissions from CTE-CH4. In addition to these categories, emissions from termites and oceans are included. Process specific δ13C-CH4 isotopic signatures are assigned to each emission source to estimate 13CH4 fraction in CH4 emissions. Among the priors, anthropogenic and natural emissions are optimized and others are directly imposed from the prior. A detailed emission estimates of antropogenic and natural CH4 emissions will be constructed in order to provide a more comprehensive understanding of methane emission source divisions.

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.

Thermal decomposition of ethanol. 4. Ab initio chemical kinetics for reactions of H atoms with CH3CH2O and CH3CHOH radicals.

PubMed

Xu, Z F; Xu, Kun; Lin, M C

2011-04-21

The potential energy surfaces of H-atom reactions with CH(3)CH(2)O and CH(3)CHOH, two major radicals in the decomposition and oxidation of ethanol, have been studied at the CCSD(T)/6-311+G(3df,2p) level of theory with geometric optimization carried out at the BH&HLYP/6-311+G(3df,2p) level. The direct hydrogen abstraction channels and the indirect association/decomposition channels from the chemically activated ethanol molecule have been considered for both reactions. The rate constants for both reactions have been calculated at 100-3000 K and 10(-4) Torr to 10(3) atm Ar pressure by microcanonical VTST/RRKM theory with master equation solution for all accessible product channels. The results show that the major product channel of the CH(3)CH(2)O + H reaction is CH(3) + CH(2)OH under atmospheric pressure conditions. Only at high pressure and low temperature, the rate constant for CH(3)CH(2)OH formation by collisonal deactivation becomes dominant. For CH(3)CHOH + H, there are three major product channels; at high temperatures, CH(3)+CH(2)OH production predominates at low pressures (P < 100 Torr), while the formation of CH(3)CH(2)OH by collisional deactivation becomes competitive at high pressures and low temperatures (T < 500 K). At high temperatures, the direct hydrogen abstraction reaction producing CH(2)CHOH + H(2) becomes dominant. Rate constants for all accessible product channels in both systems have been predicted and tabulated for modeling applications. The predicted value for CH(3)CHOH + H at 295 K and 1 Torr pressure agrees closely with available experimental data. For practical modeling applications, the rate constants for the thermal unimolecular decomposition of ethanol giving key accessible products have been predicted; those for the two major product channels taking place by dehydration and C-C breaking agree closely with available literature data.

Transport and thermodynamics constrain belowground carbon turnover in a northern peatland

NASA Astrophysics Data System (ADS)

Beer, Julia; Blodau, Christian

2007-06-01

Rates of anaerobic respiration are of central importance for the long-term burial of carbon (C) in peatlands, which are a relevant sink in the global C cycle. To identify constraints on anaerobic peat decomposition, we determined detailed concentration depth profiles of decomposition end-products, i.e. methane (CH 4) and dissolved inorganic carbon (DIC), along with concentrations of relevant decomposition intermediates at an ombrotrophic Canadian peat bog. The magnitude of in situ net production rates of DIC and CH 4 was estimated by inverse pore-water modeling. Vertical transport in the peat was slow and dominated by diffusion leading to the buildup of DIC and CH 4 with depth (5500 μmol L -1 DIC, 500 μmol L -1 CH 4). Highest DIC and CH 4 production rates occurred close to the water table (decomposition constant kd ˜ 10 -3-10 -4 a -1) or in some distinct zones at depth ( kd ˜ 10 -4 a -1). Deeper into the peat, decomposition proceeded very slowly at about kd = 10 -7 a -1. This pattern could be related to thermodynamic and transport constraints. The accumulation of metabolic end-products diminished in situ energy yields of acetoclastic methanogenesis to the threshold for microbially mediated processes (-20 to -25 kJ mol -1 CH 4). The methanogenic precursor acetate also accumulated (150 μmol L -1). In line with these findings, CH 4 was formed by hydrogenotrophic methanogenesis at Gibbs free energies of -35 to -40 kJ mol -1 CH 4. This was indicated by an isotopic fractionation α-CH of 1.069-1.079. Fermentative degradation of acetate, propionate and butyrate attained Gibbs free energies close to 0 kJ mol -1 substrate. Although methanogenesis was apparently limited by some other factor in some peat layers, transport and thermodynamic constraints likely impeded respiratory processes in the deeper peat. Constraints on the removal of DIC and CH 4 may thus slow decomposition and contribute to the sustained burial of C in northern peatlands.

A comparison of methane emissions following rice paddies conversion to crab-fish farming wetlands in southeast China.

PubMed

Hu, Zhiqiang; Wu, Shuang; Ji, Cheng; Zou, Jianwen; Zhou, Quansuo; Liu, Shuwei

2016-01-01

Rice paddies and aquaculture wetlands are typical agricultural wetlands that constitute one of the important sources of atmospheric methane (CH4). Traditional transplanted rice paddies have been experiencing conversion to pond aquaculture wetlands for pursuing higher economic benefits over the past decades in southeast China. A parallel field experiment was carried out to compare CH4 emissions from a transplanted rice paddy and its converted crab-fish farming wetland in southeast China. Over the rice-growing season, CH4 fluxes averaged 1.86 mg m(-2) h(-1) from rice paddies, and 1.14 and 0.50 mg m(-2) h(-1) for the treatments with or without aquatic vegetation present in the crab-fish farming wetlands, respectively. When averaged across the treatments, seasonal CH4 emissions from crab-fish framing wetlands were 52% lower than those from rice paddies. The CH4 fluxes were negatively related to water dissolved oxygen (DO) concentration but positively related to soil/sediment dissolved organic carbon (DOC) content in crab-fish farming wetlands. Dependence of CH4 fluxes on DO or DOC was intensified by the aquatic vegetation presence. By extrapolating the present CH4 emission rate with the current rice paddy-converted aquaculture cultivation area, the seasonal CH4 emissions from inland aquaculture wetlands during the critical farming stage (20 June to 18 October) were estimated to be 33.6 Gg ha(-1) in southeast China in 2012. Rice paddies conversion to crab-fish farming wetlands might have reduced CH4 emissions by 22-54% in mainland China. Results of this study suggest that the conversion of transplanted rice paddies to crab-fish aquaculture wetlands for higher economic benefits would also lead to a lower ecosystem CH4 release rate.

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

NASA Technical Reports Server (NTRS)

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

1992-01-01

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

High-energy transformations of polyfluoroalkanes. IX pyrolysis of 1,1-difluoroethane

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

Mitin, P.V.; Golovin, A.V.; Grigor`eva, T.Yu.

1994-07-10

Kinetics of the unimolecular thermal dehydrofluorination of 1,1-difluoroethane in a flow reactor is reported. The first-order rate constant is determined; logk[1/c]=(-60,000{plus_minus}2000)/4.569{center_dot}T + 13.33{plus_minus}0.10. 1,1-Difluoroethylene, as a by-product of the pyrolysis of 1,1-difluoroethane, is formed by a radical mechanism, for which a heterogeneous, initiation state is proposed. MNDO calculations show the predominant formation of the CH{sub 3}-CF{sub 2} radical at the initiation stage. For this radical, rate constants of unimolecular 1{r_arrow}2 and 2{r_arrow}1 hydrogen shifts are determined within the framework of the PPKM statistical theory. 17 refs., 4 figs., 2 tabs.

Rapid Chemical Vapor Infiltration of Silicon Carbide Minicomposites at Atmospheric Pressure.

PubMed

Petroski, Kenneth; Poges, Shannon; Monteleone, Chris; Grady, Joseph; Bhatt, Ram; Suib, Steven L

2018-02-07

The chemical vapor infiltration technique is one of the most popular for the fabrication of the matrix portion of a ceramic matrix composite. This work focuses on tailoring an atmospheric pressure deposition of silicon carbide onto carbon fiber tows using the methyltrichlorosilane (CH 3 SiCl 3 ) and H 2 deposition system at atmospheric pressure to create minicomposites faster than low pressure systems. Adjustment of the flow rate of H 2 bubbled through CH 3 SiCl 3 will improve the uniformity of the deposition as well as infiltrate the substrate more completely as the flow rate is decreased. Low pressure depositions conducted at 50 Torr deposit SiC at a rate of approximately 200 nm*h -1 , while the atmospheric pressure system presented has a deposition rate ranging from 750 nm*h -1 to 3.88 μm*h -1 . The minicomposites fabricated in this study had approximate total porosities of 3 and 6% for 10 and 25 SCCM infiltrations, respectively.

Rate constant for the reaction of OH with CH3CCl2F (HCFC-141b) determined by relative rate measurements with CH4 and CH3CCl3

NASA Technical Reports Server (NTRS)

Huder, Karin; Demore, William B.

1993-01-01

Determination of accurate rate constants for OH abstraction is of great importance for the calculation of lifetimes for HCFCs and their impact on the atmosphere. For HCFC-141b there has been some disagreement in the literature for absolute measurements of this rate constant. In the present work rate constant ratios for HCFC-141b were measured at atmospheric pressure in the temperature range of 298-358 K, with CH4 and CH3CCl3 as reference gases. Ozone was photolyzed at 254 nm in the presence of water vapor to produce OH radicals. Relative depletions of 141b and the reference gases were measured by FTIR. Arrhenius expressions for 141b were derived from each reference gas and found to be in good agreement with each other. The combined expression for HCFC-141b which we recommend is 1.4 x 10 exp -12 exp(-1630/T) with k at 298 K being 5.9 x 10 exp -15 cu cm/molec-s. This value is in excellent agreement with the JPL 92-20 recommendation.

Experimental Equipment Validation for Methane (CH4) and Carbon Dioxide (CO2) Hydrates

NASA Astrophysics Data System (ADS)

Saad Khan, Muhammad; Yaqub, Sana; Manner, Naathiya; Ani Karthwathi, Nur; Qasim, Ali; Mellon, Nurhayati Binti; Lal, Bhajan

2018-04-01

Clathrate hydrates are eminent structures regard as a threat to the gas and oil industry in light of their irritating propensity to subsea pipelines. For natural gas transmission and processing, the formation of gas hydrate is one of the main flow assurance delinquent has led researchers toward conducting fresh and meticulous studies on various aspects of gas hydrates. This paper highlighted the thermodynamic analysis on pure CH4 and CO2 gas hydrates on the custom fabricated equipment (Sapphire cell hydrate reactor) for experimental validation. CO2 gas hydrate formed at lower pressure (41 bar) as compared to CH4 gas hydrate (70 bar) while comparison of thermodynamic properties between CH4 and CO2 also presented in this study. This preliminary study could provide pathways for the quest of potent hydrate inhibitors.

Temperate Forest Methane Sink Diminished by Tree Emissions

NASA Astrophysics Data System (ADS)

Megonigal, P.; Pitz, S.

2015-12-01

Global budgets ascribe 4-10% of atmospheric CH4 sinks to upland soils and assume that soils are the sole surface for CH4 exchange between upland forests and the atmosphere. The prevailing dogma that upland forests are sinks of atmospheric CH4 was challenged a decade ago by large discrepancies in bottom-up versus top-down models of CH4 concentrations over upland forests that are still unexplained. Evidence of a novel abiotic mechanism for CH4 production from plant tissue is too small to explain the discrepancy. Alternative hypotheses for this observation have been proposed, but not tested. Here we demonstrate that CH4 is emitted from the stems of dominant tree species in an upland forest. Tree emissions occur throughout the growing season while soils adjacent to the trees are consuming CH4, challenging the concept that forests are uniform sinks of CH4. Scaling by stem surface area showed the forest to be a net CH4 source during a wet sample in June and a reduced CH4 sink by 5% annually. High frequency measurements revealed diurnal cycling in the rate of CH4 emissions, pointing to soils as the CH4 source and transpiration as the most likely pathway for CH4 transport. We propose the forests are smaller CH4 sinks than previously estimated due to stem emissions. Stem emissions may be particularly important in upland tropical forests characterized by high rainfall and transpiration, resolving differences between models and measurements.

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

Remotely sensed MODIS wetland components for assessing the variability of methane emissions in Indian tropical/subtropical wetlands

NASA Astrophysics Data System (ADS)

Bansal, Sangeeta; Katyal, Deeksha; Saluja, Ridhi; Chakraborty, Monojit; Garg, J. K.

2018-02-01

Temperature and area fluctuations in wetlands greatly influence its various physico-chemical characteristics, nutrients dynamic, rates of biomass generation and decomposition, floral and faunal composition which in turn influence methane (CH4) emission rates. In view of this, the present study attempts to up-scale point CH4 flux from the wetlands of Uttar Pradesh (UP) by modifying two-factor empirical process based CH4 emission model for tropical wetlands by incorporating MODIS derived wetland components viz. wetland areal extent and corresponding temperature factors (Ft). This study further focuses on the utility of remotely sensed temperature response of CH4 emission in terms of Ft. Ft is generated using MODIS land surface temperature products and provides an important semi-empirical input for up-scaling CH4 emissions in wetlands. Results reveal that annual mean Ft values for UP wetlands vary from 0.69 (2010-2011) to 0.71(2011-2012). The total estimated area-wise CH4 emissions from the wetlands of UP varies from 66.47 Gg yr-1with wetland areal extent and Ft value of 2564.04 km2 and 0.69 respectively in 2010-2011 to 88.39 Gg yr-1with wetland areal extent and Ft value of 2720.16 km2 and 0.71 respectively in 2011-2012. Temporal analysis of estimated CH4 emissions showed that in monsoon season estimated CH4 emissions are more sensitive to wetland areal extent while in summer season sensitivity of estimated CH4 emissions is chiefly controlled by augmented methanogenic activities at high wetland surface temperatures.

Biochemical methane potential, biodegradability, alkali treatment and influence of chemical composition on methane yield of yard wastes.

PubMed

Gunaseelan, Victor Nallathambi

2016-03-01

In this study, the biochemical CH4 potential, rate, biodegradability, NaOH treatment and the influence of chemical composition on CH4 yield of yard wastes generated from seven trees were examined. All the plant parts were sampled for their chemical composition and subjected to the biochemical CH4 potential assay. The component parts exhibited significant variation in biochemical CH4 potential, which was reflected in their ultimate CH4 yields that ranged from 109 to 382 ml g(-1) volatile solids added and their rate constants that ranged from 0.042 to 0.173 d(-1). The biodegradability of the yard wastes ranged from 0.26 to 0.86. Variation in the biochemical CH4 potential of the yard wastes could be attributed to variation in the chemical composition of the different fractions. In the Thespesia yellow withered leaf, Tamarindus fruit pericarp and Albizia pod husk, NaOH treatment enhanced the ultimate CH4 yields by 17%, 77% and 63%, respectively, and biodegradability by 15%, 77% and 61%, respectively, compared with the untreated samples. The effectiveness of NaOH treatment varied for different yard wastes, depending on the amounts of acid detergent fibre content. Gliricidia petals, Prosopis leaf, inflorescence and immature pod, Tamarindus seeds, Albizia seeds, Cassia seeds and Delonix seeds exhibited CH4 yields higher than 300 ml g(-1) volatile solids added. Multiple linear regression models for predicting the ultimate CH4 yield and biodegradability of yard wastes were designed from the results of this work. © The Author(s) 2016.

A Competitive Kinetics Study of the Reaction of Cl with CS2 in Air at 298 K

NASA Technical Reports Server (NTRS)

Wallington, Timothy J.; Andino, Jean M.; Potts, Alan R.; Wine, Paul H.

1997-01-01

The relative rate technique has been used to investigate the kinetics of the reaction of Cl atoms with carbon disulfide, CS2, at 700 Torr total pressure of air at 298 K. The decay rate of CS2 was measured relative to CH4, CH3Cl and CHF2CL. For experiments using CH4 and CH3Cl references, the decay rate of CS2 was dependent on the ratio of the concentration of the reference to that of CS2. We ascribe this behavior to the generation of OH radicals in the system leading to complicated secondary chemistry. From experiments using CHF2Cl we are able to assign an upper limit of 4 x 10(exp -15) cu cm/(molecule s) for the overall reaction, Cl + CS2 yields products.

Direct observation of unimolecular decay of CH 3 CH 2 CHOO Criegee intermediates to OH radical products

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

Fang, Yi; Liu, Fang; Klippenstein, Stephen J.

2016-07-28

The unimolecular decay of carbonyl oxide intermediates, known as Criegee intermediates, produced in alkene ozonolysis is a significant source of OH radicals in the troposphere. Here, the rate of appearance of OH radical products is examined directly in the time-domain for a prototypical alkyl-substituted Criegee intermediate, CH3CH2CHOO, following vibrational activation under collision-free conditions. Complementary statistical Rice-Ramsperger-Kassel-Marcus calculations of the microcanonical unimolecular decay rate for CH3CH2CHOO are also carried out at energies in the vicinity of the barrier for 1,4 hydrogen atom transfer that leads to OH products. Tunneling through the barrier, derived from high level electronic structure calculations, contributes significantlymore » to the decay rate. Infrared transitions of CH3CH2CHOO are identified in the CH stretch overtone region, which are detected by ultraviolet laser-induced fluorescence of the resultant OH products. The features observed are attributed to CH vibrational excitations and conformational forms utilizing insights from theory. Both experiment and theory yield unimolecular decay rates for CH3CH2CHOO of ca. 10(7) s(-1), which are slower than those obtained for syn-CH3CHOO or (CH3)(2)COO reported previously [Fang et al., J. Chem. Phys. 144, 061102 (2016)] at similar energies. Master equation modeling is also utilized to predict the thermal decay rate of CH3CH2CHOO under atmospheric conditions, giving a rate of 279 s(-1) at 298 K.« less

A first approximation kinetic model to predict methane generation from an oil sands tailings settling basin.

PubMed

Siddique, Tariq; Gupta, Rajender; Fedorak, Phillip M; MacKinnon, Michael D; Foght, Julia M

2008-08-01

A small fraction of the naphtha diluent used for oil sands processing escapes with tailings and supports methane (CH(4)) biogenesis in large anaerobic settling basins such as Mildred Lake Settling Basin (MLSB) in northern Alberta, Canada. Based on the rate of naphtha metabolism in tailings incubated in laboratory microcosms, a kinetic model comprising lag phase, rate of hydrocarbon metabolism and conversion to CH(4) was developed to predict CH(4) biogenesis and flux from MLSB. Zero- and first-order kinetic models, respectively predicted generation of 5.4 and 5.1 mmol CH(4) in naphtha-amended microcosms compared to 5.3 (+/-0.2) mmol CH(4) measured in microcosms during 46 weeks of incubation. These kinetic models also predicted well the CH(4) produced by tailings amended with either naphtha-range n-alkanes or BTEX compounds at concentrations similar to those expected in MLSB. Considering 25% of MLSB's 200 million m(3) tailings volume to be methanogenic, the zero- and first-order kinetic models applied over a wide range of naphtha concentrations (0.01-1.0 wt%) predicted production of 8.9-400 million l CH(4) day(-1) from MLSB, which exceeds the estimated production of 3-43 million l CH(4) day(-1). This discrepancy may result from heterogeneity and density of the tailings, presence of nutrients in the microcosms, and/or overestimation of the readily biodegradable fraction of the naphtha in MLSB tailings.

Reactions of small negative ions with O2(a 1[Delta]g) and O2(X 3[Sigma]g-)

NASA Astrophysics Data System (ADS)

Midey, Anthony; Dotan, Itzhak; Seeley, J. V.; Viggiano, A. A.

2009-02-01

The rate constants and product ion branching ratios were measured for the reactions of various small negative ions with O2(X 3[Sigma]g-) and O2(a 1[Delta]g) in a selected ion flow tube (SIFT). Only NH2- and CH3O- were found to react with O2(X) and both reactions were slow. CH3O- reacted by hydride transfer, both with and without electron detachment. NH2- formed both OH-, as observed previously, and O2-, the latter via endothermic charge transfer. A temperature study revealed a negative temperature dependence for the former channel and Arrhenius behavior for the endothermic channel, resulting in an overall rate constant with a minimum at 500 K. SF6-, SF4-, SO3- and CO3- were found to react with O2(a 1[Delta]g) with rate constants less than 10-11 cm3 s-1. NH2- reacted rapidly with O2(a 1[Delta]g) by charge transfer. The reactions of HO2- and SO2- proceeded moderately with competition between Penning detachment and charge transfer. SO2- produced a SO4- cluster product in 2% of reactions and HO2- produced O3- in 13% of the reactions. CH3O- proceeded essentially at the collision rate by hydride transfer, again both with and without electron detachment. These results show that charge transfer to O2(a 1[Delta]g) occurs readily if the there are no restrictions on the ion beyond the reaction thermodynamics. The SO2- and HO2- reactions with O2(a) are the only known reactions involving Penning detachment besides the reaction with O2- studied previously [R.S. Berry, Phys. Chem. Chem. Phys., 7 (2005) 289-290].

Environmental and vegetation controls on the spatial variability of CH4 emission from wet-sedge and tussock tundra ecosystems in the Arctic.

PubMed

McEwing, Katherine Rose; Fisher, James Paul; Zona, Donatella

Despite multiple studies investigating the environmental controls on CH 4 fluxes from arctic tundra ecosystems, the high spatial variability of CH 4 emissions is not fully understood. This makes the upscaling of CH 4 fluxes from plot to regional scale, particularly challenging. The goal of this study is to refine our knowledge of the spatial variability and controls on CH 4 emission from tundra ecosystems. CH 4 fluxes were measured in four sites across a variety of wet-sedge and tussock tundra ecosystems in Alaska using chambers and a Los Gatos CO 2 and CH 4 gas analyser. All sites were found to be sources of CH 4 , with northern sites (in Barrow) showing similar CH 4 emission rates to the southernmost site (ca. 300 km south, Ivotuk). Gross primary productivity (GPP), water level and soil temperature were the most important environmental controls on CH 4 emission. Greater vascular plant cover was linked with higher CH 4 emission, but this increased emission with increased vascular plant cover was much higher (86 %) in the drier sites, than the wettest sites (30 %), suggesting that transport and/or substrate availability were crucial limiting factors for CH 4 emission in these tundra ecosystems. Overall, this study provides an increased understanding of the fine scale spatial controls on CH 4 flux, in particular the key role that plant cover and GPP play in enhancing CH 4 emissions from tundra soils.

Titan through Time: Evolution of Titan's Atmosphere and its Hydrocarbon Cycle on the Surface

NASA Astrophysics Data System (ADS)

Gilliam, Ashley E.

The Introduction and Appendix i-A outline briefly the history of Titan exploration since its discovery by Christiaan Huygens in 1675 through the recent International Mission of Cassini-Huygens.. Chapter 1: This chapter discusses two possible pathways of loss of the two main gases from Titan's post-accretional atmosphere, methane (CH 4) and ammonia (NH3), by the mechanisms of thermal escape and emission from the interior coupled with thermal escape. Chapter 2: In this chapter, a simple photolysis model is created, where the second most abundant component of the present-day Titan atmosphere, methane (CH4), can either escape the atmosphere or undergo photolytic conversion to ethane (C2H6). Chapter 3: This chapter examines different fluvial features on Titan, identified by the Cassini spacecraft, and evaluates the possibilities of channel formation by two mechanisms: dissolution of ice by a concentrated solution of ammonium sulfate, and by mechanical erosion by flow of liquid ammonia and liquid ethane. Chapter 4: This chapter presents: (1) new explicit mathematical solutions of mixed 1st and 2nd order chemical reactions, represented by ordinary differential first-degree and Riccati equations; (2) the computed present-day concentrations of the three gases in Titan's scale atmosphere, treated as at near-steady state; and (3) an analysis of the reported and computed atmospheric concentrations of CH4, CH 3, and C2H6 on Titan, based on the reaction rate parameters of the species, the rate parameters taken as constants representative of their mean values. Chapter 5: This chapter examines the possible reactions of methane formation in terms of the thermodynamic relationships of the reactions that include pure carbon as graphite, the gases H2, CO2, H2 O, and serpentinization and magnetite formation from olivine fayalite. (Abstract shortened by ProQuest.).

Effects of a temporary HDPE cover on landfill gas emissions: multiyear evaluation with the static chamber approach at an Italian landfill.

PubMed

Capaccioni, Bruno; Caramiello, Cristina; Tatàno, Fabio; Viscione, Alessandro

2011-05-01

According to the European Landfill Directive 1999/31/EC and the related Italian Legislation ("D. Lgs. No. 36/2003"), monitoring and control procedures of landfill gas emissions, migration and external dispersions are clearly requested. These procedures could be particularly interesting in the operational circumstance of implementing a temporary cover, as for instance permitted by the Italian legislation over worked-out landfill sections, awaiting the evaluation of expected waste settlements. A possible quantitative approach for field measurement and consequential evaluation of landfill CO(2), CH(4) emission rates in pairs consists of the static, non-stationary accumulation chamber technique. At the Italian level, a significant and recent situation of periodical landfill gas emission monitoring is represented by the sanitary landfill for non-hazardous waste of the "Fano" town district, where monitoring campaigns with the static chamber have been annually conducted during the last 5 years (2005-2009). For the entire multiyear monitoring period, the resulting CO(2), CH(4) emission rates varied on the whole up to about 13,100g CO(2) m(-2)d(-1) and 3800 g CH(4) m(-2)d(-1), respectively. The elaboration of these landfill gas emission data collected at the "Fano" case-study site during the monitoring campaigns, presented and discussed in the paper, gives rise to a certain scientific evidence of the possible negative effects derivable from the implementation of a temporary HDPE cover over a worked-out landfill section, notably: the lateral migration and concentration of landfill gas emissions through adjacent, active landfill sections when hydraulically connected; and consequently, the increase of landfill gas flux velocities throughout the reduced overall soil cover surface, giving rise to a flowing through of CH(4) emissions without a significant oxidation. Thus, these circumstances are expected to cause a certain increase of the overall GHG emissions from the given landfill site. Copyright © 2010 Elsevier Ltd. All rights reserved.

Reflected shock tube studies of high-temperature rate constants for OH + CH4 --> CH3 + H2O and CH3 + NO2 --> CH3O + NO.

PubMed

Srinivasan, N K; Su, M-C; Sutherland, J W; Michael, J V

2005-03-10

The reflected shock tube technique with multipass absorption spectrometric detection of OH radicals at 308 nm has been used to study the reactions OH + CH(4) --> CH(3) + H(2)O and CH(3) + NO(2) --> CH(3)O + NO. Over the temperature range 840-2025 K, the rate constants for the first reaction can be represented by the Arrhenius expression k = (9.52 +/- 1.62) x 10(-11) exp[(-4134 +/- 222 K)/T] cm(3) molecule(-1) s(-1). Since this reaction is important in both combustion and atmospheric chemistry, there have been many prior investigations with a variety of techniques. The present results extend the temperature range by 500 K and have been combined with the most accurate earlier studies to derive an evaluation over the extended temperature range 195-2025 K. A three-parameter expression describes the rate behavior over this temperature range, k = (1.66 x 10(-18))T(2.182) exp[(-1231 K)/T] cm(3) molecule(-1) s(-1). Previous theoretical studies are discussed, and the present evaluation is compared to earlier theoretical estimates. Since CH(3) radicals are a product of the reaction and could cause secondary perturbations in rate constant determinations, the second reaction was studied by OH radical production from the fast reactions CH(3)O --> CH(2)O + H and H + NO(2) --> OH + NO. The measured rate constant is 2.26 x 10(-11) cm(3) molecule(-1) s(-1) and is not dependent on temperature from 233 to 1700 K within experimental error.

Effects of an experimental water-level drawdown on methane emissions from a eutrophic reservoir

EPA Science Inventory

Reservoirs are a globally significant source of methane (CH4) to the atmosphere. However, emission rate estimates may be biased low due to inadequate monitoring during brief periods of elevated emission rates (i.e. hot-moments). Here we investigate CH4 bubbling (i.e. ebullition...

Combined Ceria Reduction and Methane Reforming in a Solar-Driven Particle-Transport Reactor.

PubMed

Welte, Michael; Warren, Kent; Scheffe, Jonathan R; Steinfeld, Aldo

2017-09-20

We report on the experimental performance of a solar aerosol reactor for carrying out the combined thermochemical reduction of CeO 2 and reforming of CH 4 using concentrated radiation as the source of process heat. The 2 kW th solar reactor prototype utilizes a cavity receiver enclosing a vertical Al 2 O 3 tube which contains a downward gravity-driven particle flow of ceria particles, either co-current or counter-current to a CH 4 flow. Experimentation under a peak radiative flux of 2264 suns yielded methane conversions up to 89% at 1300 °C for residence times under 1 s. The maximum extent of ceria reduction, given by the nonstoichiometry δ (CeO 2-δ ), was 0.25. The solar-to-fuel energy conversion efficiency reached 12%. The syngas produced had a H 2 :CO molar ratio of 2, and its calorific value was solar-upgraded by 24% over that of the CH 4 reformed.

Combined Ceria Reduction and Methane Reforming in a Solar-Driven Particle-Transport Reactor

PubMed Central

2017-01-01

We report on the experimental performance of a solar aerosol reactor for carrying out the combined thermochemical reduction of CeO2 and reforming of CH4 using concentrated radiation as the source of process heat. The 2 kWth solar reactor prototype utilizes a cavity receiver enclosing a vertical Al2O3 tube which contains a downward gravity-driven particle flow of ceria particles, either co-current or counter-current to a CH4 flow. Experimentation under a peak radiative flux of 2264 suns yielded methane conversions up to 89% at 1300 °C for residence times under 1 s. The maximum extent of ceria reduction, given by the nonstoichiometry δ (CeO2−δ), was 0.25. The solar-to-fuel energy conversion efficiency reached 12%. The syngas produced had a H2:CO molar ratio of 2, and its calorific value was solar-upgraded by 24% over that of the CH4 reformed. PMID:28966440

Differentiating biotic from abiotic methane genesis in hydrothermally active planetary surfaces

PubMed Central

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

2012-01-01

Molecular hydrogen (H2) is derived from the hydrothermal alteration of olivine-rich planetary crust. Abiotic and biotic processes consume H2 to produce methane (CH4); however, the extent of either process is unknown. Here, we assess the temporal dependence and limit of abiotic CH4 related to the presence and formation of mineral catalysts during olivine hydrolysis (i.e., serpentinization) at 200 °C and 0.03 gigapascal. Results indicate that the rate of CH4 production increases to a maximum value related to magnetite catalyzation. By identifying the dynamics of CH4 production, we kinetically model how the H2 to CH4 ratio may be used to assess the origin of CH4 in deep subsurface serpentinization systems on Earth and Mars. Based on our model and available field data, low H2/CH4 ratios (less than approximately 40) indicate that life is likely present and active. PMID:22679287

Differentiating biotic from abiotic methane genesis in hydrothermally active planetary surfaces.

PubMed

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

2012-06-19

Molecular hydrogen (H(2)) is derived from the hydrothermal alteration of olivine-rich planetary crust. Abiotic and biotic processes consume H(2) to produce methane (CH(4)); however, the extent of either process is unknown. Here, we assess the temporal dependence and limit of abiotic CH(4) related to the presence and formation of mineral catalysts during olivine hydrolysis (i.e., serpentinization) at 200 °C and 0.03 gigapascal. Results indicate that the rate of CH(4) production increases to a maximum value related to magnetite catalyzation. By identifying the dynamics of CH(4) production, we kinetically model how the H(2) to CH(4) ratio may be used to assess the origin of CH(4) in deep subsurface serpentinization systems on Earth and Mars. Based on our model and available field data, low H(2)/CH(4) ratios (less than approximately 40) indicate that life is likely present and active.

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.

Alterations of choroidal blood flow regulation in young healthy subjects with complement factor H polymorphism.

PubMed

Told, Reinhard; Palkovits, Stefan; Haslacher, Helmuth; Frantal, Sophie; Schmidl, Doreen; Boltz, Agnes; Lasta, Michael; Kaya, Semira; Werkmeister, René M; Garhöfer, Gerhard; Schmetterer, Leopold

2013-01-01

A common polymorphism in the complement factor H gene (rs1061170, Y402H) is associated with a high risk of age-related macular degeneration (AMD). In the present study we hypothesized that healthy young subjects homozygous for the high-risk haplotype (CC) show abnormal choroidal blood flow (ChBF) regulation decades before potentially developing the disease. A total of 100 healthy young subjects were included in the present study, of which 4 subjects were excluded due to problems with genotyping or blood flow measurements. ChBF was measured continuously using laser Doppler flowmetry while the subjects performed isometric exercise (squatting) for 6 minutes. The increase in ChBF was less pronounced than the response in ocular perfusion pressure (OPP), indicating for some degree of choroidal blood flow regulation. Eighteen subjects were homozygous for C, 47 subjects were homozygous for T and 31 subjects were heterozygous (CT). The increase in OPP during isometric exercise was not different between groups. By contrast the increase in ChBF was more pronounced in subjects homozygous for the high risk C allele (p = 0.041). This was also evident from the pressure/flow relationship, where the increase in ChBF in homozygous C carriers started at lower OPPs as compared to the other groups. Our data indicate that the regulation of ChBF is abnormal in rs1061170 CC carriers. So far this polymorphism has been linked to age related macular degeneration (AMD) mainly via inflammatory pathways associated with the complement system dysfunction. Our results indicate that it could also be related to vascular factors that have been implicated in AMD pathogenesis.

Evaluation of methane oxidation activity in waste biocover soil during landfill stabilization.

PubMed

He, Ruo; Wang, Jing; Xia, Fang-Fang; Mao, Li-Juan; Shen, Dong-Sheng

2012-10-01

Biocover soil has been demonstrated to have high CH(4) oxidation capacity and is considered as a good alternative cover material to mitigate CH(4) emission from landfills, yet the response of CH(4) oxidation activity of biocover soils to the variation of CH(4) loading during landfill stabilization is poorly understood. Compared with a landfill cover soil (LCS) collected from Hangzhou Tianziling landfill cell, the development of CH(4) oxidation activity of waste biocover soil (WBS) was investigated using simulated landfill systems in this study. Although a fluctuation of influent CH(4) flux occurred during landfill stabilization, the WBS covers showed a high CH(4) removal efficiency of 94-96% during the entire experiment. In the LCS covers, the CH(4) removal efficiencies varied with the fluctuation of CH(4) influent flux, even negative ones occurred due to the storage of CH(4) in the soil porosities after the high CH(4) influent flux of ~137 gm(-2) d(-1). The lower concentrations of O(2) and CH(4) as well as the higher concentration of CO(2) were observed in the WBS covers than those in the LCS covers. The highest CH(4) oxidation rates of the two types of soil covers both occurred in the bottom layer (20-30 cm). Compared to the LCS, the WBS showed higher CH(4) oxidation activity and methane monooxygenase activity over the course of the experiment. Overall, this study indicated the WBS worked well for the fluctuation of CH(4) influent flux during landfill stabilization. Copyright © 2012 Elsevier Ltd. All rights reserved.

Landscape analysis of methane flux across complex terrain

NASA Astrophysics Data System (ADS)

Kaiser, K. E.; McGlynn, B. L.; Dore, J. E.

2014-12-01

Greenhouse gas (GHG) fluxes into and out of the soil are influenced by environmental conditions resulting in landscape-mediated patterns of spatial heterogeneity. The temporal variability of inputs (e.g. precipitation) and internal redistribution (e.g. groundwater flow) and dynamics (e.g. microbial communities) make predicating these fluxes challenging. Complex terrain can provide a laboratory for improving understanding of the spatial patterns, temporal dynamics, and drivers of trace gas flux rates, requisite to constraining current GHG budgets and future scenarios. Our research builds on previous carbon cycle research at the USFS Tenderfoot Creek Experimental Forest, Little Belt Mountains, Montana that highlighted the relationships between landscape position and seasonal CO2 efflux, induced by the topographic redistribution of water. Spatial patterns and landscape scale mediation of CH4 fluxes in seasonally aerobic soils have not yet been elucidated. We measured soil methane concentrations and fluxes across a full range of landscape positions, leveraging topographic and seasonal gradients, to examine the relationships between environmental variables, hydrologic dynamics, and CH4 production and consumption. We determined that a threshold of ~30% VWC distinguished the direction of flux at individual time points, with the riparian area and uplands having distinct source/sink characteristics respectively. Riparian locations were either strong sources or fluctuated between sink and source behavior, resulting in near neutral seasonal flux. Upland sites however, exhibited significant relationships between sink strength and topographic/energy balance indices. Our results highlight spatial and temporal coherence to landscape scale heterogeneity of CH4 dynamics that can improve estimates of landscape scale CH4 balances and sensitivity to change.

Contribution of photosynthesized carbon to the methane emitted from paddy fields

NASA Astrophysics Data System (ADS)

Minoda, T.; Kimura, M.

1994-09-01

Emission rates of CH4 from paddy soil with and without rice straw applications were measured with pot experiments to estimate the contribution of rice straw to total CH4 emissions during the growing season. The CH4 derived from rice straw was calculated to be 50.4% of the total emission. 13CO2 uptake experiments were carried out three times from Aug. 8 to Sept. 18 to estimate the contribution of photosynthesized carbon to CH4 emission. The contribution percentages of photosynthesized carbon to the total CH4 emitted to the atmosphere were 72-110% around Aug. 8, 29-36% around Aug. 30, and 13-17% around Sept. 18, 1993.

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.

Influence of soil C stocks and interannual climatic variability on the CO2 and CH4 exchange of maize cultivated on mineral and organic soils in NE Germany

NASA Astrophysics Data System (ADS)

Pohl, Madlen; Hagemann, Ulrike; Hoffmann, Mathias; Giebels, Michael; Albiac-Borraz, Elisa; Sommer, Michael; Augustin, Jürgen

2014-05-01

Due to its glacially influenced genesis and land use history, the soils of the Great Plain Region of NE-Germany show large differences in groundwater levels and soil carbon (C) stocks over short distances. Although generally featuring a rather dry climate, trace gas exchange at individual sites may be influenced by i) interannual climatic variability, particularly with respect to precipitation; as well as by ii) variability of soil C stocks. However, it is still unclear how these factors affect fluxes of CO2 and CH4, and if there is any positive or negative feedback on the C source or sink function of different soil types. We present measured and modeled CO2 and CH4 fluxes of minerally fertilized grain maize for three sites located near Paulinenaue, within the so-called Rhin-Havelluch, a shallow and drained paludification mire complex in NE Germany. The sites are characterized by a distinct gradient of 0-1 m soil organic C stocks: i) Arenosol (AR: mineral soil/distant groundwater; 8 000 g C m-2), ii) Gleysol (GL: organic soil/groundwater-dependent; 35 000 g C m-2), and iii) Histosol (HS: organic soil/near groundwater; 45 000 g C m-2). CO2 flux measurements of ecosystem respiration (Reco), net ecosystem exchange (NEE) and gross primary production (GPP; calculated as difference between NEE and Reco) were conducted every four weeks using a flow-through non-steady-state closed chamber system. Measurement gaps of Reco and NEE were filled by using temperature or radiation-based models, respectively. CH4 fluxes were measured bi-weekly using a static closed chamber system with interval sampling, with gap filling via linear interpolation. Cumulated fluxes of CO2-C (Reco, GPP, NEE) and CH4-C were calculated for a period of four consecutive years (2007-2010). The intensity of CO2-C fluxes increased with growing soil organic C stocks (AR < GL < HS). Mean annual values of the years 2008-2010 for Reco ranged between 1 500 g C m-2 and 2 000 g C m-2; annual GPP fluxes ranged from -1 400 g C m-2 to -2 300 g C m-2. NEE balances varied from C source on the mineral AR site (65 g C m-2) to C sink for organic sites (nearly -350 g C m-2). Annual CH4 exchange rates were generally very low < 0.3 g C m-2 and negligible compared to annual CO2 exchange. However, the exceptionally wet summer of 2007 (May to July) resulted in drastically increased CH4 emissions from the groundwater-influenced organic soils, particularly at the HS site where CH4 emissions were nearly 100 times higher emissions than in the following years (28 g C m-2). The excess moisture levels in 2007 also appeared to influence ecosystem CO2 exchange - likely through effects on maize growth - resulting in strongly increased Reco and GPP rates at the mineral AR site and drastically decreased Reco and GPP rates at the flooded HS site. The intensity of gaseous C fluxes seems to strongly depend on interactions between soil C stocks and interannual climatic variability. More detailed conclusions about the nature of these interactions require continuation of these measurements, i.e. long-term investigation.

Carbon-13 Isotopic Abundance and Concentration of Atmospheric Methane for Background Air in the Southern and Northern Hemispheres from 1978 to 1989 (NDP-049)

DOE Data Explorer

Stevens, C. M. [Chemical Technology Division, Argonne National Laboratory, Argonne, Illinois (USA)

2012-01-01

This data package presents atmospheric CH4 concentration and 13C isotopic abundance data derived from air samples collected over the period 1978-1989 at globally distributed clean-air sites. The data set comprises 201 records, 166 from the Northern Hemisphere and 35 from the Southern Hemisphere. The air samples were collected mostly in rural or marine locations remote from large sources of CH4 and are considered representative of tropospheric background conditions. The air samples were processed by isolation of CH4 from air and conversion to CO2 for isotopic analysis by isotope ratio mass spectrometry. These data represent one of the earliest records of 13C isotopic yy!measurements for atmospheric methane and have been used to refine estimates of CH4 emissions, calculate annual growth rates of emissions from changing sources, and provide evidence for changes in the rate of atmospheric removal of CH4. The data records consist of sample collection date; number of samples combined for analysis; sampling location; analysis date; CH4 concentration; 13C isotopic abundance; and flag codes to indicate outliers, repeated analyses, and other information.

The role of Phragmites in the CH4 and CO2 fluxes in a minerotrophic peatland in southwest Germany

NASA Astrophysics Data System (ADS)

van den Berg, Merit; Ingwersen, Joachim; Lamers, Marc; Streck, Thilo

2016-11-01

Peatlands are interesting as a carbon storage option, but are also natural emitters of the greenhouse gas methane (CH4). Phragmites peatlands are particularly interesting due to the global abundance of this wetland plant (Phragmites australis) and the highly efficient internal gas transport mechanism, which is called humidity-induced convection (HIC). The research aims were to (1) clarify how this plant-mediated gas transport influences the CH4 fluxes, (2) which other environmental variables influence the CO2 and CH4 fluxes, and (3) whether Phragmites peatlands are a net source or sink of greenhouse gases. CO2 and CH4 fluxes were measured with the eddy covariance technique within a Phragmites-dominated fen in southwest Germany. One year of flux data (March 2013-February 2014) shows very clear diurnal and seasonal patterns for both CO2 and CH4. The diurnal pattern of CH4 fluxes was only visible when living, green reed was present. In August the diurnal cycle of CH4 was the most distinct, with 11 times higher midday fluxes (15.7 mg CH4 m-2 h-1) than night fluxes (1.41 mg CH4 m-2 h-1). This diurnal cycle has the highest correlation with global radiation, which suggests a high influence of the plants on the CH4 flux. But if the cause were the HIC, it would be expected that relative humidity would correlate stronger with CH4 flux. Therefore, we conclude that in addition to HIC, at least one additional mechanism must be involved in the creation of the convective flow within the Phragmites plants. Overall, the fen was a sink for carbon and greenhouse gases in the measured year, with a total carbon uptake of 221 g C m-2 yr-1 (26 % of the total assimilated carbon). The net uptake of greenhouse gases was 52 g CO2 eq. m-2 yr-1, which is obtained from an uptake of CO2 of 894 g CO2 eq. m-2 yr-1 and a release of CH4 of 842 g CO2 eq. m-2 yr-1.

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.

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.

Infrared absorption of CH3OSO detected with time-resolved Fourier-transform spectroscopy.

PubMed

Chen, Jin-Dah; Lee, Yuan-Pern

2011-03-07

A step-scan Fourier-transform spectrometer coupled with a multipass absorption cell was employed to detect temporally resolved infrared absorption spectra of CH(3)OSO produced upon irradiation of a flowing gaseous mixture of CH(3)OS(O)Cl in N(2) or CO(2) at 248 nm. Two intense transient features with origins near 1152 and 994 cm(-1) are assigned to syn-CH(3)OSO; the former is attributed to overlapping bands at 1154 ± 3 and 1151 ± 3 cm(-1), assigned to the S=O stretching mixed with CH(3) rocking (ν(8)) and the S=O stretching mixed with CH(3) wagging (ν(9)) modes, respectively, and the latter to the C-O stretching (ν(10)) mode at 994 ± 6 cm(-1). Two weak bands at 2991 ± 6 and 2956 ± 3 cm(-1) are assigned as the CH(3) antisymmetric stretching (ν(2)) and symmetric stretching (ν(3)) modes, respectively. Observed vibrational transition wavenumbers agree satisfactorily with those predicted with quantum-chemical calculations at level B3P86∕aug-cc-pVTZ. Based on rotational parameters predicted at that level, the simulated rotational contours of these bands agree satisfactorily with experimental results. The simulation indicates that the S=O stretching mode of anti-CH(3)OSO near 1164 cm(-1) likely makes a small contribution to the observed band near 1152 cm(-1). A simple kinetic model of self-reaction is employed to account for the decay of CH(3)OSO and yields a second-order rate coefficient k=(4 ± 2)×10(-10) cm(3)molecule(-1)s(-1). © 2011 American Institute of Physics.

Evaluating greenhouse gas emissions from hydropower complexes on large rivers in Eastern Washington

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

Arntzen, Evan V.; Miller, Benjamin L.; O'Toole, Amanda C.

2013-03-15

Water bodies, such as freshwater lakes, are known to be net emitters of carbon dioxide (CO2), and methane (CH4). In recent years, significant greenhouse gas (GHG) emissions from tropical, boreal, and mid-latitude reservoirs have been reported. At a time when hydropower is increasing worldwide, better understanding of seasonal and regional variation in GHG emissions is needed in order to develop a predictive understanding of such fluxes within man-made impoundments. We examined power-producing dam complexes within xeric temperate locations in the northwestern United States. Sampling environments on the Snake (Lower Monumental Dam Complex) and Columbia Rivers (Priest Rapids Dam Complex) includedmore » tributary, mainstem, embayment, forebay, and tailrace areas during winter and summer 2012. At each sampling location, GHG measurement pathways included surface gas flux, degassing as water passed through dams during power generation, ebullition within littoral embayments, and direct sampling of hyporheic pore-water. Measurements were also carried out in a free-flowing reach of the Columbia River to estimate unaltered conditions. Surface flux resulted in very low emissions, with reservoirs acting as a sink for CO2 (up to –262 mg m-2 d-1, which is within the range previously reported for similarly located reservoirs). Surface flux of methane remained below 1 mg CH4 m-2d-1, a value well below fluxes reported previously for temperate reservoirs. Water passing through hydroelectric projects acted as a sink for CO2 during winter and a small source during summer, with mean degassing fluxes of –117 and 4.5 t CO2 d-1, respectively. Degassing of CH4 was minimal, with mean fluxes of 3.1 × 10-6 and –5.6 × 10-4 t CH4 d-1 during winter and summer, respectively. Gas flux due to ebullition was greater in coves located within reservoirs than in coves within the free flowing Hanford Reach–and CH4 flux exceeded that of CO2. Methane emissions varied widely across sampling locations, ranging from 10.5 to 1039 mg CH4 m-2 d-1, with mean fluxes of 324 mg CH4 m-2 d-1in Lower Monumental Dam reservoir and 482 mg CH4 m-2d-1 in the Priest Rapids Dam reservoir. The magnitude of methane flux due to ebullition was unexpectedly high, and falls within the range recently reported for other temperate reservoirs around the world, further suggesting that this methane source should be considered in estimates of global greenhouse gas emissions. Methane flux from sediment pore-water within littoral embayments averaged 4.2 mg m-2 d-1 during winter and 8.1 mg m-2 d-1 during summer, with a peak flux of 19.8 mg m-2d-1 (at the same location where CH4 ebullition was also the greatest). Carbon dioxide flux from sediment pore-water averaged approximately 80 mg m-2d-1 with little difference between winter and summer. Similar to emissions from ebullition, flux from sediment pore-water was higher in reservoirs than in the free flowing reach.« less

Estimates of reservoir methane emissions based on a spatially ...

EPA Pesticide Factsheets

Global estimates of methane (CH4) emissions from reservoirs are poorly constrained, partly due to the challenges of accounting for intra-reservoir spatial variability. Reservoir-scale emission rates are often estimated by extrapolating from measurement made at a few locations; however, error and bias associated with this approach can be large and difficult to quantify. Here we use a generalized random tessellation survey (GRTS) design to generate estimates of central tendency and variance at multiple spatial scales in a reservoir. GRTS survey designs are probabilistic and spatially balanced which eliminates bias associated with expert judgment in site selection. GRTS surveys also allow for variance estimates that account for spatial pattern in emission rates. Total CH4 emission rates (i.e. sum of ebullition and diffusive emissions) were 4.8 (±2.1), 33.0 (±10.7), and 8.3 (±2.2) mg CH4 m-2 h-1 in open-waters, tributary associated areas, and the entire reservoir for the period in August 2014 during which 115 sites were sampled across an 7.98 km2 reservoir in Southwestern, Ohio, USA. Tributary areas occupy 12% of the reservoir surface, but were the source of 41% of total CH4 emissions, highlighting the importance of riverine-lacustrine transition zones. Ebullition accounted for >90% of CH4 emission at all spatial scales. Confidence interval estimates that incorporated spatial pattern in CH4 emissions were up to 29% narrower than when spatial independence

Direct observation of unimolecular decay of CH{sub 3}CH{sub 2}CHOO Criegee intermediates to OH radical products

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

Fang, Yi; Liu, Fang; Lester, Marsha I., E-mail: milester@sas.upenn.edu

2016-07-28

The unimolecular decay of carbonyl oxide intermediates, known as Criegee intermediates, produced in alkene ozonolysis is a significant source of OH radicals in the troposphere. Here, the rate of appearance of OH radical products is examined directly in the time-domain for a prototypical alkyl-substituted Criegee intermediate, CH{sub 3}CH{sub 2}CHOO, following vibrational activation under collision-free conditions. Complementary statistical Rice–Ramsperger–Kassel–Marcus calculations of the microcanonical unimolecular decay rate for CH{sub 3}CH{sub 2}CHOO are also carried out at energies in the vicinity of the barrier for 1,4 hydrogen atom transfer that leads to OH products. Tunneling through the barrier, derived from high level electronicmore » structure calculations, contributes significantly to the decay rate. Infrared transitions of CH{sub 3}CH{sub 2}CHOO are identified in the CH stretch overtone region, which are detected by ultraviolet laser-induced fluorescence of the resultant OH products. The features observed are attributed to CH vibrational excitations and conformational forms utilizing insights from theory. Both experiment and theory yield unimolecular decay rates for CH{sub 3}CH{sub 2}CHOO of ca. 10{sup 7} s{sup −1}, which are slower than those obtained for syn-CH{sub 3}CHOO or (CH{sub 3}){sub 2}COO reported previously [Fang et al., J. Chem. Phys. 144, 061102 (2016)] at similar energies. Master equation modeling is also utilized to predict the thermal decay rate of CH{sub 3}CH{sub 2}CHOO under atmospheric conditions, giving a rate of 279 s{sup −1} at 298 K.« less

Bimetallo-radical carbon-hydrogen bond activation of methanol and methane.

PubMed

Cui, Weihong; Zhang, X Peter; Wayland, Bradford B

2003-04-30

Carbon-hydrogen bond cleavage reactions of CH3OH and CH4 by a dirhodium(II) diporphyrin complex with a m-xylyl tether (.Rh(m-xylyl)Rh.(1)) are reported. Kinetic-mechanistic studies show that the substrate reactions are bimolecular and occur through the use of two Rh(II) centers in the molecular unit of 1. Second-order rate constants (T = 296 K) for the reactions of 1 with methanol (k(CH3OH) = 1.45 x 10-2 M-1 s-1) and methane (k(CH4) = 0.105 M-1 s-1) show a clear kinetic preference for the methane activation process. The methanol and methane reactions with 1 have large kinetic isotope effects (k(CH3OH)/k(CD3OD) = 9.7 +/- 0.8, k(CH4)/k(CD4) = 10.8 +/- 1.0, T = 296 K), consistent with a rate-limiting step of C-H bond homolysis through a linear transition state. Activation parameters for reaction of 1 with methanol (DeltaH = 15.6 +/- 1.0 kcal mol-1; DeltaS = -14 +/- 5 cal K-1 mol-1) and methane (DeltaH = 9.8 +/- 0.5 kcal mol-1; DeltaS = -30 +/- 3 cal K-1 mol-1) are reported.

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.

Tests of stratospheric models - The reactions of atomic chlorine with O3 and CH4 at low temperature

NASA Technical Reports Server (NTRS)

Demore, W. B.

1991-01-01

The rate-constant ratio of the photochemical reactions of atomic chlorine with O3 and CH4 was determined using data from laboratory experiments on competitive chlorination of O3/CH4 mixtures at stratospheric temperatures (197-217 K). Two experimental approaches were used: (1) measuring the k1/k2 ratio for the reactions of atomic chlorine with ozone and methane and (2) testing for some of the ClO/CH3O2 chemistry. The chlorine and ozone concentrations were monitored by UV-Vis spectroscopy, and the CH3Cl concentration was measured by FTIR. The results on the k1/k2 ratio are in excellent agreement with the current NASA recommendation (DeMore et al., 1990), being only 12 percent higher. On the other hand, results on the ClO + CH3O2 reaction do not support the rate constant suggested by Simon et al. (1989).

Methane emissions to the atmosphere through aquatic plants

NASA Technical Reports Server (NTRS)

Sebacher, D. I.; Harriss, R. C.; Bartlett, K. B.

1985-01-01

The movement of methane (CH4) from anaerobic sediments through the leaves, stems, and flowers of aquatic plants and into the atmosphere was found to provide a significant pathway for the emission of CH4 from the aquatic substrates of flooded wetlands. Methane concentrations well above the surrounding ambient air levels were found in the mesophyll of 16 varies of aquatic plants and are attributed to transpiration, diffusion, and pressure-induced flow of gaseous CH4 from the roots when they are embedded in CH4-saturated anaerobic sediments. Methane emissions from the emergent parts of aquatic plants were measured using floating chamber techniques and by enclosing the plants in polyethylene bags of known volume. Concentration changes were monitored in the trapped air using syringes and gas chromatographic techniques. Vertical profiles of dissolved CH4 in sediment pore water surrounding the aquatic plants' rhizomes were obtained using an interstitial sampling technique. Methane emissions from the aquatic plants studied varied from 14.8 mg CH4/d to levels too low to be detectable. Rooted and unrooted freshwater aquatic plants were studied as well as saltwater and brackish water plants. Included in the experiment is detailed set of measurements on CH4 emissions from the common cattail (Typha latifolia). This paper illustrates that aquatic plants play an important gas exchange role in the C cycle between wetlands and the atmosphere.

Seasonal variations in methane fluxes in response to summer warming and leaf litter addition in a subarctic heath ecosystem

NASA Astrophysics Data System (ADS)

Pedersen, Emily Pickering; Elberling, Bo; Michelsen, Anders

2017-08-01

Methane (CH4) is a powerful greenhouse gas controlled by both biotic and abiotic processes. Few studies have investigated CH4 fluxes in subarctic heath ecosystems, and climate change-induced shifts in CH4 flux and the overall carbon budget are therefore largely unknown. Hence, there is an urgent need for long-term in situ experiments allowing for the study of ecosystem processes over time scales relevant to environmental change. Here we present in situ CH4 and CO2 flux measurements from a wet heath ecosystem in northern Sweden subjected to 16 years of manipulations, including summer warming with open-top chambers, birch leaf litter addition, and the combination thereof. Throughout the snow-free season, the ecosystem was a net sink of CH4 and CO2 (CH4 -0.27 mg C m-2 d-1; net ecosystem exchange -1827 mg C m-2 d-1), with highest CH4 uptake rates (-0.70 mg C m-2 d-1) during fall. Warming enhanced net CO2 flux, while net CH4 flux was governed by soil moisture. Litter addition and the combination with warming significantly increased CH4 uptake rates, explained by a pronounced soil drying effect of up to 32% relative to ambient conditions. Both warming and litter addition also increased the seasonal average concentration of dissolved organic carbon in the soil. The site was a carbon sink with a net uptake of 60 g C m-2 over the snow-free season. However, warming reduced net carbon uptake by 77%, suggesting that this ecosystem type might shift from snow-free season sink to source with increasing summer temperatures.

Measurements of 14C in ancient ice from Taylor Glacier, Antarctica constrain in situ cosmogenic 14CH4 and 14CO production rates

NASA Astrophysics Data System (ADS)

Petrenko, Vasilii V.; Severinghaus, Jeffrey P.; Schaefer, Hinrich; Smith, Andrew M.; Kuhl, Tanner; Baggenstos, Daniel; Hua, Quan; Brook, Edward J.; Rose, Paul; Kulin, Robb; Bauska, Thomas; Harth, Christina; Buizert, Christo; Orsi, Anais; Emanuele, Guy; Lee, James E.; Brailsford, Gordon; Keeling, Ralph; Weiss, Ray F.

2016-03-01

Carbon-14 (14C) is incorporated into glacial ice by trapping of atmospheric gases as well as direct near-surface in situ cosmogenic production. 14C of trapped methane (14CH4) is a powerful tracer for past CH4 emissions from ;old; carbon sources such as permafrost and marine CH4 clathrates. 14C in trapped carbon dioxide (14CO2) can be used for absolute dating of ice cores. In situ produced cosmogenic 14C in carbon monoxide (14CO) can potentially be used to reconstruct the past cosmic ray flux and past solar activity. Unfortunately, the trapped atmospheric and in situ cosmogenic components of 14C in glacial ice are difficult to disentangle and a thorough understanding of the in situ cosmogenic component is needed in order to extract useful information from ice core 14C. We analyzed very large (≈1000 kg) ice samples in the 2.26-19.53 m depth range from the ablation zone of Taylor Glacier, Antarctica, to study in situ cosmogenic production of 14CH4 and 14CO. All sampled ice is >50 ka in age, allowing for the assumption that most of the measured 14C originates from recent in situ cosmogenic production as ancient ice is brought to the surface via ablation. Our results place the first constraints on cosmogenic 14CH4 production rates and improve on prior estimates of 14CO production rates in ice. We find a constant 14CH4/14CO production ratio (0.0076 ± 0.0003) for samples deeper than 3 m, which allows the use of 14CO for correcting the 14CH4 signals for the in situ cosmogenic component. Our results also provide the first unambiguous confirmation of 14C production by fast muons in a natural setting (ice or rock) and suggest that the 14C production rates in ice commonly used in the literature may be too high.

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

NASA Astrophysics Data System (ADS)

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

2014-12-01

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

Hyperfine excitation of CH in collisions with atomic and molecular hydrogen

NASA Astrophysics Data System (ADS)

Dagdigian, Paul J.

2018-04-01

We investigate here the excitation of methylidene (CH) induced by collisions with atomic and molecular hydrogen (H and H2). The hyperfine-resolved rate coefficients were obtained from close coupling nuclear-spin-free scattering calculations. The calculations are based upon recent, high-accuracy calculations of the CH(X2Π)-H(2S) and CH(X2Π)-H2 potential energy surfaces. Cross-sections and rate coefficients for collisions with atomic H, para-H2, and ortho-H2 were computed for all transitions between the 32 hyperfine levels for CH(X2Π) involving the n ≤ 4 rotational levels for temperatures between 10 and 300 K. These rate coefficients should significantly aid in the interpretation of astronomical observations of CH spectra. As a first application, the excitation of CH is simulated for conditions in typical molecular clouds.

Effect of C/N ratio, aeration rate and moisture content on ammonia and greenhouse gas emission during the composting.

PubMed

Jiang, Tao; Schuchardt, Frank; Li, Guoxue; Guo, Rui; Zhao, Yuanqiu

2011-01-01

Gaseous emission (N2O, CH4 and NH3) from composting can be an important source of anthropogenic greenhouse gas and air pollution. A laboratory scale orthogonal experiment was conducted to estimate the effects of C/N ratio, aeration rate and initial moisture content on gaseous emission during the composting of pig faeces from Chinese Ganqinfen system. The results showed that about 23.9% to 45.6% of total organic carbon (TOC) was lost in the form of CO2 and 0.8% to 7.5% of TOC emitted as CH4. Most of the nitrogen was lost in the form of NH3, which account for 9.6% to 32.4% of initial nitrogen. N2O was also an important way of nitrogen losses and 1.5% to 7.3% of initial total nitrogen was lost as it. Statistic analysis showed that the aeration rate is the most important factor which could affect the NH3 (p = 0.0189), CH4 (p = 0.0113) and N2O (p = 0.0493) emissions significantly. Higher aeration rates reduce the CH4 emission but increase the NH3 and N2O losses. C/N ratio could affect the NH3 (p = 0.0442) and CH4 (p = 0.0246) emissions significantly, but not the N2O. Lower C/N ratio caused higher NH3 and CH4 emissions. The initial moisture content can not influence the gaseous emission significantly. Most treatments were matured after 37 days, except a trial with high moisture content and a low C/N ratio.

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.

Eddy Covariance Measurements of Methane Emissions from a Dairy Farm Waste Lagoon

NASA Astrophysics Data System (ADS)

Sokol, A. B.; Lauvaux, T.; Richardson, S.; Hlywiak, J.; Davis, K. J.; Hristov, A. N.

2016-12-01

Livestock manure management in dairy operations is a known source of methane (CH4), a potent greenhouse gas. Anaerobic waste lagoons are a common manure management technique; thus, their associated CH4 emissions are relevant to national greenhouse gas inventories and local air quality. Our objective was to characterize the variability of summertime CH4 emissions from a lagoon at a dairy facility in central Pennsylvania. Continuous flux measurements were taken over two weeks in July using the eddy covariance method, which uses high-frequency gas concentration and three-dimensional wind speed measurements to calculate turbulent fluxes from a source area. After data filtration based on turbulence characteristics and source area, the average CH4 flux density from the lagoon was estimated to be 99 μmol m-2 s-1. This implies daily lagoon emissions of 881 kg CH4, corresponding to an average emission rate of 340 g CH4 per cow per day. We observed no apparent relationship between emissions and air temperature or relative humidity, though an extended measurement period is needed to better quantify the relationship that is expected to exist between air and/or slurry temperature and CH4 flux. Our measured per-area emission rate is toward the high end of the range of estimates found in the literature. These results contribute to greenhouse gas inventory development and could have important implications for emission mitigation strategies.

Kinetic studies of the reaction of the hydroxymethyl radical with NO and NO sub 2

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

Nesbitt, F.L.; Payne, W.A.; Stief, L.J.

1989-06-29

The absolute rate constant for the reaction CD{sub 2}OH + NO has been measured from 230 to 373 K in a discharge-flow system. The decay of the CD{sub 2}OH radical was monitored in excess NO by collision-free sampling mass spectrometry. At 298 K, k{sub 1} = (2.2 {plus minus} 0.4) {times} 10{sup {minus}12} cm{sup 3}s{sup {minus}1} (2{sigma}) independent of pressure from 0.5 to 1.5 Torr. For the 230-298 K interval, an activation energy of 1.2 kcal/mol is obtained, but k{sub 1} does not appear to change within experimental error on going from 298 to 373 K. The absolute rate constantmore » at 298 K has also been measured for the reaction CH{sub 2}OH + NO{sub 2} by the same technique. The result is k{sub 2} = (8.3 {plus minus} 4.1) {times} 10{sup {minus}12} cm{sup 3} s{sup {minus}1} (2{sigma}). Qualitative detection was made of D{sub 2}CO and H{sub 2}CO as products of these reactions, but no evidence was obtained for the expected accompanying products HNO and HNO{sub 2} nor for the CD{sub 2}OHNO and CH{sub 2}OHNO{sub 2} adducts. It is suggested, partially by analogy with the CH{sub 2}OH + O{sub 2} reaction, that the reaction mechanism in both cases involves initial formation of a vibrationally excited complex that, depending on reaction conditions, can dissociate back to reactants or, after isomerization, dissociate to products. Collisional stabilization of the addition complex may be feasible, but they have no evidence for this under the low-pressure condition of their experiments. The rate constants for reaction of CH{sub 2}OH with O{sub 2}, NO, and NO{sub 2} are briefly compared.« less

The First Year of Solar-Wind Data From the GENESIS Mission

NASA Astrophysics Data System (ADS)

Wiens, R. C.; Barraclough, B. L.; Steinberg, J. T.; Reisenfeld, D. B.; Neugebauer, M.; Burnett, D. S.

2002-12-01

The GENESIS mission was launched in August, 2001, and has been in an L1 halo orbit for over a year. The primary purpose of the mission is to collect solar-wind samples that will be returned to Earth in 2004 for high-precision isotopic and elemental analyses. GENESIS uses conventional ion and electron spectrometers to record solar-wind conditions during collection, and to make real-time determinations of the solar-wind regimes to facilitate collection of separate samples of interstream (IS), coronal hole (CH), and coronal mass ejection (CME) flows. Of particular interest is the use of a bi-directional electron (BDE) index to determine the presence of CMEs. And although GENESIS lacks a magnetometer, the field vector, with sign ambiguity, is determined by the electron direction, and matches other spacecraft magnetometer data well. GENESIS in-situ data and on-board regime determinations are available on the web. The data from Fall, 2001 were characterized by numerous CME regimes (comprising 32% of the time in the 4th quarter, based on the on-board algorithm), with little CH flow (only 2%). A strong CH flow was observed every solar rotation from mid-January through late May. June was quiet, nearly all IS flow. The first and second quarters of 2002 were approximately 28% CME flow, with CH flow dropping from 18% to 6%. The discovery of unexpectedly noticeable BDE signals during CH flows at 1 AU (Steinberg et al., 2002) caused us early on to modify our regime selection algorithm to accommodate these. The on-board algorithm intentionally errs on the side of overestimating CME flows in order to keep the CH sample more pure. Comparisons have been made of various compositional parameters determined by Genesis (Barraclough et al., this meeting) and by ACE SWICS (Reisenfeld et al., this meeting) for times corresponding to the Genesis collection periods for each of the three regimes. The Genesis L1 halo orbit is ~0.8 x 0.25 million km radius, somewhat larger than the ~0.3 x 0.2 and ~0.7 x 0.2 million km orbits of ACE and SOHO, respectively, presenting excellent opportunities for multi-spacecraft observations at L1.

Temperature dependence of the Cl atom reaction with deuterated methanes.

PubMed

Sauer, Frank; Portmann, Robert W; Ravishankara, A R; Burkholder, James B

2015-05-14

Kinetic isotope effect (KIE) and reaction rate coefficients, k1-k4, for the gas-phase reaction of Cl atoms with (12)CH3D (k1), (12)CH2D2 (k2), (12)CHD3 (k3), and (12)CD4 (k4) over the temperature range 223-343 K in 630 Torr of synthetic air are reported. Rate coefficients were measured using a relative rate technique with (12)CH4 as the primary reference compound. Fourier transform infrared spectroscopy was used to monitor the methane isotopologue loss. The obtained KIE values were (12)CH3D: KIE1(T) = (1.227 ± 0.004) exp((43 ± 5)/T); (12)CH2D2: KIE2(T) = (1.14 ± 0.20) exp((191 ± 60)/T); (12)CHD3: KIE3(T) = (1.73 ± 0.34) exp((229 ± 60)/T); and (12)CD4: KIE4(T) = (1.01 ± 0.3) exp((724 ± 19)/T), where KIEx(T) = kCl+(12)CH4(T)/kx(T). The quoted uncertainties are at the 2σ (95% confidence) level and represent the precision of our data. The following Arrhenius expressions and 295 K rate coefficient values (in units of cm(3) molecule(-1) s(-1)) were derived from the above KIE using a rate coefficient of 7.3 × 10(-12) exp(-1280/T) cm(3) molecule(-1) s(-1) for the reaction of Cl with (12)CH4: k1(T) = (5.95 ± 0.70) × 10(-12) exp(-(1323 ± 50)/T), k1(295 K) = (6.7 ± 0.8) × 10(-14); k2(T) = (6.4 ± 1.3) × 10(-12) exp(-(1471 ± 60)/T), k2(295 K) = (4.4 ± 0.9) × 10(-14); k3(T) = (4.2 ± 1.0) × 10(-12) exp(-(1509 ± 60)/T), k3(295 K) = (2.53 ± 0.6) × 10(-14); and k4(T) = (7.13 ± 2.3) × 10(-12) exp(-(2000 ± 120)/T), k4(295 K) = (0.81 ± 0.26) × 10(-14). The reported uncertainties in the pre-exponential factors are 2σ and include estimated systematic errors in our measurements and the uncertainty in the reference reaction rate coefficient. The results from this study are compared with previously reported room-temperature rate coefficients for each of the deuterated methanes as well as the available temperature dependent data for the Cl atom reactions with CH3D and CD4. A two-dimensional atmospheric chemistry model was used to examine the implications of the present results to the atmospheric lifetime and vertical variation in the loss of the deuterated methane isotopologues. The relative contributions of the reactions of OH, Cl, and O((1)D) to the loss of the isotopologues in the stratosphere were also examined. The results of the calculations are described and discussed.

Reaction mechanisms in the organometallic vapor phase epitaxial growth of GaAs

NASA Technical Reports Server (NTRS)

Larsen, C. A.; Buchan, N. I.; Stringfellow, G. B.

1988-01-01

The decomposition mechanisms of AsH3, trimethylgallium (TMGa), and mixtures of the two have been studied in an atmospheric-pressure flow system with the use of D2 to label the reaction products which are analyzed in a time-of-flight mass spectrometer. AsH3 decomposes entirely heterogeneously to give H2. TMGa decomposes by a series of gas-phase steps, involving methyl radicals and D atoms to produce CH3D, CH4, C2H6, and HD. TMGa decomposition is accelerated by the presence of AsH3. When the two are mixed, as in the organometallic vapor phase epitaxial growth of GaAs, both compounds decompose in concert to produce only CH4. A likely model is that of a Lewis acid-base adduct that forms and subsequently eliminates CH4.

Reaction mechanisms in the organometallic vapor phase epitaxial growth of GaAs

NASA Astrophysics Data System (ADS)

Larsen, C. A.; Buchan, N. I.; Stringfellow, G. B.

1988-02-01

The decomposition mechanisms of AsH3, trimethylgallium (TMGa), and mixtures of the two have been studied in an atmospheric-pressure flow system with the use of D2 to label the reaction products which are analyzed in a time-of-flight mass spectrometer. AsH3 decomposes entirely heterogeneously to give H2. TMGa decomposes by a series of gas-phase steps, involving methyl radicals and D atoms to produce CH3D, CH4, C2H6, and HD. TMGa decomposition is accelerated by the presence of AsH3. When the two are mixed, as in the organometallic vapor phase epitaxial growth of GaAs, both compounds decompose in concert to produce only CH4. A likely model is that of a Lewis acid-base adduct that forms and subsequently eliminates CH4.

Identifying the limitations of conventional biofiltration of diffuse methane emissions at long-term operation.

PubMed

Gómez-Cuervo, S; Hernández, J; Omil, F

2016-08-01

There is growing international concern about the increasing levels of greenhouse gases in the atmosphere, particularly CO2 and methane. The emissions of methane derived from human activities are associated with large flows and very low concentrations, such as those emitted from landfills and wastewater treatment plants, among others. The present work was focused on the biological methane degradation at diffuse concentrations (0.2% vv(-1)) in a conventional biofilter using a mixture of compost, perlite and bark chips as carrier. An extensive characterization of the process was carried out at long-term operation (250 days) in a fully monitored pilot plant, achieving stable conditions during the entire period. Operational parameters such as waterings, nitrogen addition and inlet loads and contact time influences were evaluated. Obtained results indicate that empty bed residence times within 4-8 min are crucial to maximize elimination rates. Waterings and the type of nitrogen supplied in the nutrient solution (ammonia or nitrate) have a strong impact on the biofilter performance. The better results compatible with a stable operation were achieved using nitrate, with elimination capacities up to 7.6 ± 1.1 g CH4 m(-3 )h(-1). The operation at low inlet concentrations (IC) implied that removal rates obtained were quite limited (ranging 3-8 g CH4 m(-3 )h(-1)); however, these results could be significantly increased (up to 20.6 g CH4 m(-3) h(-1)) at higher IC, which indicates that the mass transfer from the gas to the liquid layer surrounding the biofilm is a key limitation of the process.

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.

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.

Tripropellant Engine Study

NASA Technical Reports Server (NTRS)

Wheeler, D. B.

1977-01-01

The feasibility of modifying the space shuttle main engine (SSME) for dual mode operation was investigated. Various high power cycle engine configurations derived from the SSME were configurations that will allow sequential burning of LOX/hydrocarbon and LOX/hydrogen were studied in order to identify concepts that make maximum use of SSME hardware and best satisfy the dual mode booster engine system application. Engine cycles were formulated for LOX/RP-1, LOX/CH4, and LOX/C3H8 propellants. Flow rates and operating cycles were established and the adaptability of the major components of the SSME was evaluated.

Chemical Evolution of Groundwater Near a Sinkhole Lake, Northern Florida: 2. Chemical Patterns, Mass Transfer Modeling, and Rates of Mass Transfer Reactions

NASA Astrophysics Data System (ADS)

Katz, Brian G.; Plummer, L. Niel; Busenberg, Eurybiades; Revesz, Kinga M.; Jones, Blair F.; Lee, Terrie M.

1995-06-01

Chemical patterns along evolutionary groundwater flow paths in silicate and carbonate aquifers were interpreted using solute tracers, carbon and sulfur isotopes, and mass balance reaction modeling for a complex hydrologic system involving groundwater inflow to and outflow from a sinkhole lake in northern Florida. Rates of dominant reactions along defined flow paths were estimated from modeled mass transfer and ages obtained from CFC-modeled recharge dates. Groundwater upgradient from Lake Barco remains oxic as it moves downward, reacting with silicate minerals in a system open to carbon dioxide (CO2), producing only small increases in dissolved species. Beneath and downgradient of Lake Barco the oxic groundwater mixes with lake water leakage in a highly reducing, silicate-carbonate mineral environment. A mixing model, developed for anoxic groundwater downgradient from the lake, accounted for the observed chemical and isotopic composition by combining different proportions of lake water leakage and infiltrating meteoric water. The evolution of major ion chemistry and the 13C isotopic composition of dissolved carbon species in groundwater downgradient from the lake can be explained by the aerobic oxidation of organic matter in the lake, anaerobic microbial oxidation of organic carbon, and incongruent dissolution of smectite minerals to kaolinite. The dominant process for the generation of methane was by the CO2 reduction pathway based on the isotopic composition of hydrogen (δ2H(CH4) = -186 to -234‰) and carbon (δ13C(CH4) = -65.7 to -72.3‰). Rates of microbial metabolism of organic matter, estimated from the mass transfer reaction models, ranged from 0.0047 to 0.039 mmol L-1 yr-1 for groundwater downgradient from the lake.

Gas phase kinetics of the OH + CH3CH2OH reaction at temperatures of the interstellar medium (T = 21-107 K).

PubMed

Ocaña, A J; Blázquez, S; Ballesteros, B; Canosa, A; Antiñolo, M; Albaladejo, J; Jiménez, E

2018-02-21

Ethanol, CH 3 CH 2 OH, has been unveiled in the interstellar medium (ISM) by radioastronomy and it is thought to be released into the gas phase after the warm-up phase of the grain surface, where it is formed. Once in the gas phase, it can be destroyed by different reactions with atomic and radical species, such as hydroxyl (OH) radicals. The knowledge of the rate coefficients of all these processes at temperatures of the ISM is essential in the accurate interpretation of the observed abundances. In this work, we have determined the rate coefficient for the reaction of OH with CH 3 CH 2 OH (k(T)) between 21 and 107 K by employing the pulsed and continuous CRESU (Cinétique de Réaction en Ecoulement Supersonique Uniforme, which means Reaction Kinetics in a Uniform Supersonic Flow) technique. The pulsed laser photolysis technique was used for generating OH radicals, whose time evolution was monitored by laser induced fluorescence. An increase of approximately 4 times was observed for k(21 K) with respect to k(107 K). With respect to k(300 K), the OH-reactivity at 21 K is enhanced by two orders of magnitude. The obtained T-expression in the investigated temperature range is k(T) = (2.1 ± 0.5) × 10 -11 (T/300 K) -(0.71±0.10) cm 3 molecule -1 s -1 . In addition, the pressure dependence of k(T) has been investigated at several temperatures between 21 K and 90 K. No pressure dependence of k(T) was observed in the investigated ranges. This may imply that this reaction is purely bimolecular or that the high-pressure limit is reached at the lowest total pressure experimentally accessible in our system. From our results, k(T) at usual IS temperatures (∼10-100 K) is confirmed to be very fast. Typical rate coefficients can be considered to range within about 4 × 10 -11 cm 3 molecule -1 s -1 at 100 K and around 1 × 10 -10 cm 3 molecule -1 s -1 at 20 K. The extrapolation of k at the lowest temperatures of the dense molecular clouds of ISM is also discussed in this paper.

Gas phase kinetics of the OH + CH3CH2OH reaction at temperatures of the interstellar medium (T = 21-10^7 K)

NASA Astrophysics Data System (ADS)

Ocaña, A. J.; Blázquez, S.; Ballesteros, B.; Canosa, A.; Antiñolo, M.; Albaladejoab, J.; Jiménez, E.

2018-02-01

Ethanol, CH3CH2OH, has been unveiled in the interstellar medium (ISM) by radioastronomy and it is thought to be released into the gas phase after the warm-up phase of the grain surface, where it is formed. Once in the gas phase, it can be destroyed by different reactions with atomic and radical species, such as hydroxyl (OH) radicals. The knowledge of the rate coefficients of all these processes at temperatures of the ISM is essential in the accurate interpretation of the observed abundances. In this work, we have determined the rate coefficient for the reaction of OH with CH3CH2OH (k(T)) between 21 and 10^7 K by employing the pulsed and continuous CRESU (Cinétique de Réaction en Ecoulement Supersonique Uniforme, which means Reaction Kinetics in a Uniform Supersonic Flow) technique. The pulsed laser photolysis technique was used for generating OH radicals, whose time evolution was monitored by laser induced fluorescence. An increase of approximately 4 times was observed for k(21 K) with respect to k(10^7 K). With respect to k(300 K), the OH-reactivity at 21 K is enhanced by two orders of magnitude. The obtained T-expression in the investigated temperature range is k(T) = (2.1 ± 0.5) × 10^-11 (T/300 K)-(0.71±0.10) cm^3 molecule^-1 s^-1. In addition, the pressure dependence of k(T) has been investigated at several temperatures between 21 K and 90 K. No pressure dependence of k(T) was observed in the investigated ranges. This may imply that this reaction is purely bimolecular or that the high-pressure limit is reached at the lowest total pressure experimentally accessible in our system. From our results, k(T) at usual IS temperatures (˜10-100 K) is confirmed to be very fast. Typical rate coefficients can be considered to range within about 4 × 10^-11 cm^3 molecule^-1 s^-1 at 100 K and around 1 × 10^-10 cm^3 molecule^-1 s^-1 at 20 K. The extrapolation of k at the lowest temperatures of the dense molecular clouds of ISM is also discussed in this paper.

Rate Coefficient Measurements of the Reaction CH3+O2+CH3O+O

NASA Technical Reports Server (NTRS)

Hwang, S. M.; Ryu, Si-Ok; DeWitt, K. J.; Rabinowitz, M. J.

1999-01-01

Rate coefficients for the reaction CH3 + O2 = CH3O + O were measured behind reflected shock waves in a series of lean CH4-O2-Ar mixtures using hydroxyl and methyl radical diagnostics. The rate coefficients are well represented by an Arrhenius expression given as k = (1.60(sup +0.67, -0.47)) X 10(exp 13) exp(- 15813 +/- 587 K/T)cc/mol s. This expression, which is valid in the temperature range 1575-1822 K, supports the downward trend in the rate coefficients that has been reported in recent determinations. All measurements to date, including the present study, have been to some extent affected by secondary reactions. The complications due to secondary reactions, choice of thermochemical data, and shock-boundary layer interactions that affect the determination of the rate coefficients are examined.

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

A start-up of psychrophilic anaerobic sequence batch reactor digesting a 35 % total solids feed of dairy manure and wheat straw.

PubMed

Saady, Noori M Cata; Massé, Daniel I

2015-12-01

Zero liquid discharge is currently an objective in livestock manure management to minimize water pollution. This paper reports the start-up phase of a novel psychrophilic (20 °C) dry anaerobic digestion of dairy manure with bedding fed at 35 % total solids and an organic loading rate of 3.0 g total chemical oxygen demand kg(-1) inoculum day(-1) in anaerobic sequence batch reactors. The specific methane (CH4) yield ranged from 165.4 ± 9.8 to 213.9 ± 13.6 NL CH4 kg(-1) volatile solids (VS) with an overall average of 188 ± 17 NL CH4 kg(-1) VS during 11 successive start-up cycles (231 days) and a maximum CH4 production rate of 10.2 ± 0.6 NL CH4 kg(-1) VS day(-1). The inoculum-to-substrate (VS-based) ratio ranged from 4.06 to 4.47. Although methanogenesis proceeded fairly well the hydrolysis seemed to be the rate limiting step. It is possible start up psychrophilic dry anaerobic digestion of cow feces and wheat straw at feed TS of 35 % within 7-10 successive cycles (147-210 days).

Reduced net atmospheric CH4 consumption is a sustained response to elevated CO2 in a temperate forest

USDA-ARS?s Scientific Manuscript database

We compared nearly continuously from 1998 until 2006 rates of soil atmosphere CH4 exchange at permanently established sampling sites in a temperate loblolly pine (Pinus taeda) forest exposed to ambient (control plots; approx. 380 uL L-1) or elevated (ambient + 200 uL L-1) CO2. Net atmospheric CH4 co...

Novel Organophosphate Ligand O-(2-Fluoroethyl)-O-(p-Nitrophenyl)Methylphosphonate: Synthesis, Hydrolytic Stability and Analysis of the Inhibition and Reactivation of Cholinesterases.

PubMed

Chao, Chih-Kai; Ahmed, S Kaleem; Gerdes, John M; Thompson, Charles M

2016-11-21

The organophosphate O-(2-fluoroethyl)-O-(p-nitrophenyl) methyphosphonate 1 is the first-in-class, fluorine-18 radiolabeled organophosphate inhibitor ([ 18 F]1) of acetylcholinesterase (AChE). In rats, [ 18 F]1 localizes in AChE rich regions of the brain and other tissues where it likely exists as the (CH 3 )( 18 FCH 2 CH 2 O)P(O)-AChE adduct (ChE-1). Characterization of this adduct would define the inhibition mechanism and subsequent postinhibitory pathways and reactivation rates. To validate this adduct, the stability (hydrolysis) of 1 and ChE-1 reactivation rates were determined. Base hydrolysis of 1 yields p-nitrophenol and (CH 3 ) (FCH 2 CH 2 O)P(O)OH with pseudo first order rate constants (k obsd ) at pH 7.4 (PBS) of 3.25 × 10 -4 min -1 (t 1/2 = 35.5 h) at 25 °C and 8.70 × 10 -4 min -1 (t 1/2 = 13.3 h) at 37 °C. Compound 1 was a potent inhibitor of human acetylcholinesterase (HuAChE; k i = 7.5 × 10 5 M -1 min -1 ), electric eel acetylcholinesterase (EEAChE) (k i = 3.0 × 10 6 M -1 min -1 ), and human serum butyrylcholinesterase (HuBChE; 1.95 × 10 5 M -1 min -1 ). Spontaneous and oxime-mediated reactivation rates for the (CH 3 ) (FCH 2 CH 2 O)P(O)-serine ChE adducts using 2-PAM (10 μM) were (a) HuAChE 8.8 × 10 -5 min -1 (t 1/2 = 131.2 h) and 2.41 × 10 -2 min -1 (t 1/2 = 0.48 h), (b) EEAChE 9.32 × 10 -3 min -1 (t 1/2 = 1.24 h) and 3.33 × 10 -2 min -1 (t 1/2 = 0.35 h), and (c) HuBChE 1.16 × 10 -4 min -1 (t 1/2 = 99.6 h) and 4.19 × 10 -2 min -1 (t 1/2 = 0.27 h). All ChE-1 adducts undergo rapid and near complete restoration of enzyme activity following addition of 2-PAM (30 min), and no aging was observed for either reactivation process. The fast reactivation rates and absence of aging of ChE-1 adducts are explained on the basis of the electron-withdrawing fluorine group that favors the nucleophilic reactivation processes but disfavors cation-based dealkylation aging mechanisms. Therefore, the likely fate of radiolabeled compound 1 in vivo is the formation of (CH 3 )(FCH 2 CH 2 O)P(O)-serine adducts and monoacid (CH 3 )(FCH 2 CH 2 O)P(O)OH from hydrolysis and reactivation.

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.

Methane emissions from a human-dominated lowland coastal river network (Shanghai, China)

NASA Astrophysics Data System (ADS)

Wang, D.; Yu, Z.

2017-12-01

Evasion of methane (CH4) in streams and rivers play a critical role in global carbon (C) cycle, offsetting the C uptake by terrestrial ecosystems. However, little is known about CH4 emissions from lowland coastal rivers profoundly modified by anthropogenic perturbations. Here, we report results from a long-term, large-scale study of CH4 partial pressures (pCH4) and evasion rates in the Shanghai river network. The spatiotemporal variability of pCH4 was examined along a land-use gradient and the annual CH4 evasion were estimated to assess its role in regional C budget. During the study period, the median pCH4 from 87 surveyed rivers was 241 μatm. CH4 was oversaturated throughout the river network, CH4 hotpots were concentrated in the small urban rivers and highly discharge-dependent. The annual median fCH4 for each site ranged from 3.1 mg C•m-2•d-1 to 296.6 mg C•m-2•d-1. The annual CH4 evasion were 105 Gg CO2-eq•yr-1 and 96 Gg CO2-eq•yr-1 for the entire river network and the mainland rivers, respectively. Given the rapid urbanization in global coastal areas, more research is needed to quantify the role of lowland coastal rivers as a major landscape C source in global C budget.

Methane emissions partially offset “blue carbon” burial in mangroves

PubMed Central

Maher, Damien T.

2018-01-01

Organic matter burial in mangrove forests results in the removal and long-term storage of atmospheric CO2, so-called “blue carbon.” However, some of this organic matter is metabolized and returned to the atmosphere as CH4. Because CH4 has a higher global warming potential than the CO2 fixed in the organic matter, it can offset the CO2 removed via carbon burial. We provide the first estimate of the global magnitude of this offset. Our results show that high CH4 evasion rates have the potential to partially offset blue carbon burial rates in mangrove sediments on average by 20% (sensitivity analysis offset range, 18 to 22%) using the 20-year global warming potential. Hence, mangrove sediment and water CH4 emissions should be accounted for in future blue carbon assessments.

Regeneration of meniscus tissue using adipose mesenchymal stem cells-chondrocytes co-culture on a hybrid scaffold: In vivo study.

PubMed

Moradi, Lida; Vasei, Mohammad; Dehghan, Mohammad M; Majidi, Mohammad; Farzad Mohajeri, Saeed; Bonakdar, Shahin

2017-05-01

The meniscus has poor intrinsic regenerative capacity and its damage inevitably leads to articular cartilage degeneration. We focused on evaluating the effects of Polyvinyl alcohol/Chitosan (PVA/Ch) scaffold seeded by adipose-derived mesenchymal stem cell (ASC) and articular chondrocytes (AC) in meniscus regeneration. The PVA/Ch scaffolds with different molar contents of Ch (Ch1, Ch2, Ch4 and Ch8) were cross-linked by pre-polyurethane chains. By increasing amount of Ch tensile modulus was increased from 83.51 MPa for Ch1 to 110 MPa for Ch8 while toughness showed decrease from 0.33 mJ/mm 3 in Ch1 to 0.11 mJ/mm 3 in Ch8 constructs. Moreover, swelling ratio and degradation rate increased with an increase in Ch amount. Scanning electron microscopy imaging was performed for pore size measurement and cell attachment. At day 21, Ch4 construct seeded by AC showed the highest expression with 24.3 and 22.64 folds increase in collagen II and aggrecan (p ≤ 0.05), respectively. Since, the mechanical properties, water uptake and degradation rate of Ch4 and Ch8 compositions had no statistically significant differences, Ch4 was selected for in vivo study. New Zealand rabbits were underwent unilateral total medial meniscectomy and AC/scaffold, ASC/scaffold, AC-ASC (co-culture)/scaffold and cell-free scaffold were engrafted. At 7 months post-implantation, macroscopic, histologic, and immunofluorescent studies for regenerated meniscus revealed better results in AC/scaffold group followed by AC-ASC/scaffold and ASC/scaffold groups. In the cell-free scaffold group, there was no obvious meniscus regeneration. Articular cartilages were best preserved in AC/scaffold group. The best histological score was observed in AC/scaffold group. Our results support that Ch4 scaffold seeded by AC alone can successfully regenerate meniscus in tearing injury and ASC has no significant contribution in the healing process. Copyright © 2017 Elsevier Ltd. All rights reserved.

Effect of land use on methane flux from soil.

PubMed

Chan, A S; Parkin, T B

2001-01-01

The precise effects of natural and disturbed terrestrial systems on the atmospheric CH4 pool are uncertain. This study was conducted to quantify and compare CH4 fluxes from a variety of ecosystems in central Iowa. We investigated agricultural systems under different management practices, a hardwood forest site, native and restored prairies, and a municipal landfill. Flux measurements were obtained using a closed-chamber method, and measurements were compiled by sampling over the 1993 and 1994 growing seasons. In 1993, most of the agricultural sites were net CH4 producers with cumulative CH4 fluxes ranging from -0.02 to 3.19 g m(-2) over the 258-d sampling season, while the natural ecosystems were net CH4 consumers, with cumulative seasonal fluxes ranging from -0.27 to -0.07 g m-2 258 d(-1). In 1994, only the landfill and the agricultural site treated with broadcast liquid swine manure (LSM) were net CH4 producers, while the remainder of the natural and agricultural ecosystems were net CH4 consumers, with mean seasonal flux rates ranging from -0.43 to -0.008 g m(-2) 271 d(-1). We hypothesize that the differences in CH4 fluxes between the two years are due to differences in rainfall. To illustrate the integration between land use and CH4 flux, we computed an area-weighted soil CH4 flux for the state of Iowa. Our calculations yielded a net average soil CH4 flux of 139,000 Mg CH4 for 1993 and 1994.

Biogas production from Pongamia biomass wastes and a model to estimate biodegradability from their composition.

PubMed

Gunaseelan, Victor Nallathambi

2014-02-01

In this study, I investigated the chemical characteristics, biochemical methane potential, conversion kinetics and biodegradability of untreated and NaOH-treated Pongamia plant parts, and pod husk and press cake from the biodiesel industry to evaluate their suitability as an alternative feedstock for biogas production. The untreated Pongamia seeds exhibited the maximum CH4 yield of 473 ml g (-1) volatile solid (VS) added. Yellow, withered leaves gave a yield as low as 122 ml CH4 g (-1) VS added. There were significant variations in the CH4 production rate constants, which ranged from 0.02 to 0.15 d (-1), and biodegradability, which ranged from 0.25 to 0.98. NaOH treatment of leaf and pod husk, which were highly rich in fibers, increased the yields by 15-22% and CH4 production rate constants by 20-75%. Utilization of Pongamia wastes in biogas digesters not only influences the economics of biodiesel production but also yields CH4 fuel and protects the environment. The experimental data from this study were used to develop a multiple regression model, which could estimate biodegradability based on biochemical characteristics. The model predicted the biodegradability of previously published biomass wastes (r(2) = 0.88) from their biochemical composition. The theoretical CH4 yields estimated as 350 ml g(-1) chemical oxygen demand destroyed are much higher than the experimental yields as 100% biodegradability is assumed for each substrate. Upon correcting the theoretical CH4 yields with biodegradability data obtained from chemical analyses of substrates, their ultimate CH4 yields could be predicted rapidly.

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

New High-Frequency Measurements of CH4, N2O and SF6 from a High-Altitude Station in the Eastern Himalayas of India and Derived Emissions Estimates

NASA Astrophysics Data System (ADS)

Ganesan, A. L.; Chatterjee, A.; Salameh, P.; Harth, C. M.; Rigby, M.; Manning, A. J.; Hall, B. D.; Ghosh, S. K.; Muhle, J.; Meredith, L. K.; Mandal, T. K.; Weiss, R. F.; Prinn, R. G.

2012-12-01

We present new in situ measurements from a station in Darjeeling, India (27.03°N, 88.26°E, 2200 m above sea level). These measurements comprise the first high-frequency dataset of methane (CH4), nitrous oxide (N2O) and sulfur hexafluoride (SF6) collected in India. Measurements are made with a gas chromatographic system, using a flame ionization detector (GC-FID) for CH4 and an electron capture detector (GC-ECD) for N2O and SF6. Measurements have been linked to calibration scales used in the Advanced Global Atmospheric Gases Experiment (AGAGE, Tohoku University for CH4 and Scripps institution of Oceanography 1998 and 2005, for N2O and SF6, respectively). Preliminary results show a significant diurnal cycle for CH4, consistent with upslope flows bringing local emissions from the town and valley to the site during the day and downslope flows bringing cleaner air at night. This nighttime decrease in mixing ratio could be attributed to a variety of factors, including reduced local emissions or sampling of cleaner, free tropospheric air from aloft. Underlying this local signal is a much larger regional influence, which is driven by the large-scale meteorology that governs which upwind regions contribute to the measured mole fractions at the site. We also investigate local influences on N2O and SF6, which are much smaller than CH4 or negligible, because of their comparatively weaker nearby sources. We present emissions estimates for India using the high-resolution UK Met Office Lagrangian particle dispersion model, the Numerical Atmospheric dispersion Modeling Environment (NAME). Air histories generated using NAME reveal that the site regularly intercepts air from important rice-growing and biomass burning regions of Northern India. This unique dataset allows further constraints to be placed on "top-down" estimates of emissions from these CH4 sources. Further constraints will also be possible for regional agricultural sources of N2O and South-Asian SF6, both of which are under-sampled and poorly understood at present.

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

Future methane emissions from animals

NASA Astrophysics Data System (ADS)

Anastasi, C.; Simpson, V. J.

1993-04-01

The future global emission of CH4 from enteric fermentation in animals has been estimated for cattle, sheep, and buffalo, which together contribute approximately 91% of the total CH4 emitted from domesticated animals at present. A simple model has been used to relate livestock levels to the national human populations for each country involved in breeding the three species included in this analysis. United Nations population predictions to 2025 were then included in the model to estimate future CH4 emissions. A variational analysis was carried out to investigate the effect of future changes in both the land available for grazing and the nutritional content of feedstocks. Results suggest that the total emission of CH4 from enteric fermentation in domestic animals will increase from 84 Tg CH4 per year (Tg = 1012 g) in 1990 to 119 (±12) Tg CH4 yr-1 by 2025. These values correspond to an average rate of increase over the next 35 years of 1.0 Tg CH4 yr-1.

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

PubMed

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

2017-02-01

Streams are typically supersaturated in carbon dioxide (CO 2 ) and methane (CH 4 ), and are recognized as important components of regional carbon (C) emissions in northern landscapes. Whereas there is consensus that in most of the systems the CO 2 emitted by streams represents C fixed in the terrestrial ecosystem, the pathways delivering this C to streams are still not well understood. We assessed the contribution of direct soil CO 2 injection versus the oxidation of soil-derived dissolved organic C (DOC) and CH 4 in supporting CO 2 supersaturation in boreal streams in Québec. We measured the concentrations of CO 2 , CH 4 and DOC in 43 streams and adjacent soil waters during summer base-flow period. A mass balance approach revealed that all three pathways are significant, and that the mineralization of soil-derived DOC and CH 4 accounted for most of the estimated stream CO 2 emissions (average 75% and 10%, respectively), and that these estimated contributions did not change significantly between the studied low order (≤3) streams. Whereas some of these transformations take place in the channel proper, our results suggest that they mainly occur in the hyporheic zones of the streams. Our results further show that stream CH 4 emissions can be fully explained by soil CH 4 inputs. This study confirms that these boreal streams, and in particular their hyporheic zones, are extremely active processors of soil derived DOC and CH 4 , not just vents for soil produced CO 2 . Copyright © 2016 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.

Cometabolic biodegradation of trichloroethylene in microcosms

USGS Publications Warehouse

Kane, Allen C.; Wilson, Timothy P.; Fischer, Jeffrey M.

1997-01-01

Laboratory microcosms were used to determine the concentrations of oxygen (O2) and methane (CH4) that optimize trichloroethylene (TCE) biodegradation in sediment and ground-water samples from a TCE-contaminated aquifer at Picatinny Arsenal, Morris County, New Jersey. The mechanism for degradation is the cometabolic activity of methanotrophic bacteria. The laboratory data will be used to support a field study designed to demonstrate the effectiveness of combining air sparging with cometabolic degradation of TCE for the purpose of aquifer remediation. Microcosms were constructed in autoclaved 250-mL (milliliter) amber glass bottles with valves for repeated headspace sampling. Equal volumes (25 mL) of sediment and ground water, collected from a depth of 40 feet, were added. TCE was added to attain initial aqueous concentrations equal to the field level of 1,400 mu g/L (micrograms per liter). Nine microcosms were constructed with initial headspace O2 concentrations of 5%, 10%, or 14% and CH4 concentrations of 0.5%, 3%, or 5%, with nitrogen making up the balance. Sterile controls, controls without CH4, and controls without sediment were also constructed. A 4-mL gas sample was removed periodically and TCE, O2 , CH4 , and carbon dioxide (CO2) concentrations were measured by using gas chromatography. As biodegradation proceeded, the decrease in O2, CH4 , and TCE concentrations and the production of CO2 were monitored. An initial acclimation period of at least 100 days was observed in those microcosms in which significant microbial activity occurred, as determined from decreases in O2 and CH4 concentrations and an increase in CO2 content. Degradation of TCE occurred with O2 concentrations of 2.7 to 8.7% and CH4 concentrations of 0.5 to 3.5%. Microcosms that initially contained 10% O2 and 3% CH4 showed the greatest microbial activity and the greatest amount of TCE degradation. The greatest rates of TCE degradation occurred when O2 and CH4 headspace concentrations reached levels of 7.7 to 8.7% and 1.7 to 2.7%, respectively, which correspond to aqueous concentrations of 2.9 to 3.5 mg/L and 0.4 to 0.6 mg/L, respectively. Over these ranges, TCE degradation rates ranged from 15 to 20 mu g of TCE per kilogram of sediment per day. Analysis of the control microcosms indicated that these TCE degradation rates are much greater than those attributable to experimental variation. The results indicate that the microbial community of the sediment is capable of TCE degradation and that significant rates of degradation can be achieved with obtainable O2 and CH4 concentrations.

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.

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.

Transport, anoxia and energy control on anaerobic respiration and methanogenesis in anoxic peat soils

NASA Astrophysics Data System (ADS)

Bonaiuti, Simona; Blodau, Christian; Knorr, Klaus-Holger

2017-04-01

In deep and permanently water saturated peat deposits, extremely low diffusive transport and concomitant build-up of metabolic end-products, i.e of dissolved inorganic carbon (DIC) and methane (CH4), have been found to slow-down anaerobic respiration and methanogenesis. Such accumulation of DIC and CH4 lowers the Gibbs free energy yield of terminal respiration and methanogenesis, which can inhibit the course of anaerobic metabolic processes. In particular, this affects terminal steps of the breakdown of organic carbon (C), such as methanogenesis, acetogenesis and fermentation processes, which occur near thermodynamic minimum energy thresholds. This effect is thus of critical importance for the long-term C sequestration, as the slow-down of decomposition ultimately regulates the long-term fate of C in deep peat deposits. The exact controls of this observed slow-down of organic matter mineralization are not yet fully understood. Moreover, altered patterns of water or gas transport due to predicted changes in climate may affect these controls in peat soils. Therefore, the aim of this study was to investigate how burial of peat leads to an inactivation of anaerobic decomposition and to investigate the effects of advective water transport and persistently anoxic conditions on anaerobic decomposition, temporal evolution of thermodynamic energy yields to methanogenesis and methanogenic pathways. To this end, we conducted a column experiment with homogenized, ombrotrophic peat over a period of 300 days at 20˚ C. We tested i) a control treatment under diffusive transport only, ii) an advective flow treatment with a flow of 10 mm d-1, and iv) an anoxic treatment to evaluate changes in decomposition in absence of oxygen in the unsaturated zone of the cores. A slow-down of anaerobic respiration and methanogenesis generally set in at larger depths after 150 days at CH4 concentrations of 0.6-0.9 mmol L-1 and DIC concentrations of 6-12 mmol L-1. This effect occurred at higher concentration levels and faster than previously observed. Advective water transport effectively extended the zone of methanogenesis down to 40 cm depth until inhibiting conditions were reached, although net turnover at greater depths was not affected. Strictly anoxic conditions in the unsaturated zone, where diffusive transport is high, had little effect on accelerating anaerobic decomposition. The slow-down of net production rates of CO2 and CH4 agreed well with the decline over time of Gibbs free energies available to methanogenesis, supporting a thermodynamic constraint on decomposition in deeper peat deposits. Keywords: Peatlands; Anaerobic decomposition; Methanogenesis; Production rates; Advection; Anoxia; Thermodynamic calculations.

N2O and CH4 emissions from N-fertilized rice paddy soil can be mitigated by wood vinegar application at an appropriate rate

NASA Astrophysics Data System (ADS)

Sun, Haijun; Feng, Yanfang; Ji, Yang; Shi, Weiming; Yang, Linzhang; Xing, Baoshan

2018-07-01

To understand the impacts of wood vinegar (WV), a by-product of biochar production, on N2O and CH4 emissions and their total global warming potential (GWPt) from N-fertilized rice paddy soil, a soil column experiment was conducted using three treatments: 240 kg urea-N ha-1 accompanied with 0, 5, and 10 t WV ha-1, respectively. Results showed that N2O and CH4 emission flux patterns were dominated by water regime of rice growth cycle, which was independent with WV application. The total N2O, CH4 emission loads and GWPt over rice season of three N received treatments were 6.41-8.85 kg ha-1, 127.7-405.0 kg ha-1, and 5.24-12.03 t CO2-e ha-1, respectively. Rice seasonal N2O and CH4 emissions were synchronously mitigated by 22.4% and 36.4%, respectively, when WV was applied at 5 t ha-1. Consequently, 5 t ha-1 WV treatment reduced 31.5% of GWPt compared with the urea treatment. In addition, 10 t ha-1 WV treatment exerted a more positive effect on suppressing N2O with 27.6% reduction. However, it increased GWPt by 57.2% because its CH4 emission load was increased by 101.8%. In conclusion, WV amendment applied at an appropriate rate (5 t ha-1) or combination with other CH4 control technologies were suggested to reduce both N2O and CH4 emissions and thereby the GWPt in N-fertilized rice paddy soil.

Greenhouse gas balance of blanket peat bog restoration from forestry in the Flow Country, Scotland

NASA Astrophysics Data System (ADS)

Hermans, Renée; Subke, Jens-Arne; Cowie, Neil; Arn Teh, Yit; Andersen, Roxane

2017-04-01

The Flow country in the far north of Scotland has the largest expanse of blanket peat bog in Europe. With peat depths of up to several metres, this area represents a significant carbon store. Large parts of the Flows were drained for afforestation with non-native conifers during the 1980s, which resulted in considerable damage to the peat, leading to significant carbon loss. To restore the peatland, the Royal Society for the Protection of Birds (RSPB) started in the late 1990s to fell trees and block drains. Over 2200 ha of forestry are felled. The main objective of this study is to measure the impact of forest removal on the budget of three main greenhouse gases, CO2, CH4 and N2O. Local variations in fluxes were measured using dark closed chambers. In order to capture abiotic conditions likely to determine microbial activity and therefor CO2, CH4 and N2O production, I record water table depth as well as soil moisture and soil temperature (both measured at 5 and 20 cm deep). These measurements are done in near pristine bog (control plot), in forest (control plot), in recently felled areas and in areas that were felled up to 19 years ago, creating a chronosequence to follow the effects of restoration. Results indicate only small differences in annual CO2 flux to the atmosphere between sites, with only the 19-year old restored site showing higher fluxes than forest control plots. However some seasonal differences in CO2 flux between land cover are evident. CH4 fluxes from forest are significantly lower than from bog and the site restored 17 years ago, and N2O fluxes are very low in all sites with no significant differences between sites. Sites where forests were removed recently (< 1 year previously) show a high degree of variability in CH4 fluxes, indicating potential flux spikes from disturbance. There is a positive correlation between soil temperature and CO2 and CH4 flux. Soil moisture varies a lot between bog, restored sites and forest, however there does not seem to be a direct correlation between soil moisture at the surface and CO2 and CH4 fluxes. Peatlands store big amounts of carbon, therefore there is a high level of importance to quantify the impact of various restoration techniques used.

Acoustic Monitoring of Ebullitive Flux from a Mire Ecosystem in Subarctic Sweden

NASA Astrophysics Data System (ADS)

Burke, S. A.; Varner, R. K.; Palace, M. W.; Wik, M.; Crill, P. M.; McCalley, C. K.; Amante, J.

2012-12-01

Methane (CH4) is a potent green house gas with wetlands being the largest natural source to the atmosphere. Studies in the Stordalen Mire, a dynamic peatland complex 11km east of the Abisko Scientific Research Station (ANS) in northern Sweden, that focused on CH4 transport to the atmosphere from peatlands have shown increased emissions over the past decades. Ebullitive flux (bubbling) is a potentially significant pathway of CH4 from mire/lake ecosystems. Ebullitive fluxes were successfully monitored acoustically in peat and lakes in 2011. This work expands those measurements with installation of sensors in ponds and permafrost thaw margins in 2012. Eighteen acoustic sensors were installed in peat (6), pond (6), and lake (6) sites at Stordalen Mire. Recorders collected acoustic data continuously from each sensor and gas samples were collected from the traps at least once per week beginning 7 July. The CH4 concentration in the gas was measured using gas chromatography and selected samples were also analyzed for 13C-CH4 using a Quantum Cascade Laser (QCL). The acoustic data were evaluated using a MATLAB program for determine the timing and volume of each ebullition event. The CH4 ebullitive flux from the peat was greater in July 2011 than during the same period in 2012. In comparison, the ponds and thaw margins released CH4 at a faster rate in 2012 than was observed in the peat and lake sensors in 2011. Inter-annual differences in ebullitive rates suggest that weather scale differences between years may control CH4 ebullitive flux. 13C-CH4 measured in the pore waters of pond sediment suggests that not all ponds are dominated by the same production processes. However, 13C-CH4 measured in bubbles and sediments are not different, implying little or no oxidation of CH4 during transport to the water surface. Our data suggests that changes in atmospheric pressure and water table height correlated with the ebullitive release in all three sub-ecosystems.

A novel pathway of direct methane production and emission by eukaryotes including plants, animals and fungi: An overview

NASA Astrophysics Data System (ADS)

Liu, Jiangong; Chen, Huai; Zhu, Qiuan; Shen, Yan; Wang, Xue; Wang, Meng; Peng, Changhui

2015-08-01

Methane (CH4) is a powerful greenhouse gas with a global warming potential 28 times that of carbon dioxide (CO2). CH4 is responsible for approximately 20% of the Earth's warming since pre-industrial times. Knowledge of the sources of CH4 is crucial due to the recent substantial interannual variability of growth rates and uncertainties regarding individual sources. The prevailing paradigm is that methanogenesis carried out by methanogenic archaea occurs primarily under strictly anaerobic conditions. However, in the past decade, studies have confirmed direct CH4 release from three important kingdoms of eukaryotes-Plantae, Animalia and Fungi-even in the presence of oxygen. This novel CH4 production pathway has been aptly termed ;aerobic CH4 production; to distinguish it from the well-known anaerobic CH4 production pathway, which involves catalytic activity by methanogenic archaeal enzymes. In this review, we collated recent experimental evidence from the published literature and documented this novel pathway of direct CH4 production and emission by eukaryotes. The mechanisms involved in this pathway may be related to protective strategies of eukaryotes in response to changing environmental stresses, with CH4 a by-product or end-product during or at the end of the process(es) that originates from organic methyl-type compounds. Based on the existing, albeit uncertain estimates, plants seem to contribute less to the global CH4 budget (3-24%) compared to previous estimates (10-37%). We still lack estimates of CH4 emissions by animals and fungi. Overall, there is an urgent need to identify the precursors for this novel CH4 source and improve our understanding of the mechanisms of direct CH4 production and the impacts of environmental stresses. An estimate of this new CH4 source, which was not considered as a CH4 source by the Intergovernmental Panel on Climate Change (IPCC) (2013), could be useful for better quantitation of the global CH4 budget.

Investigations on the "Extreme" Microbial Methane Cycle within the Sediments of an Acidic Impoundment of the Inactive Sulfur Bank Mercury Mine: Herman Pit, Clear Lake, California.

NASA Astrophysics Data System (ADS)

Oremland, R. S.; Baesman, S. M.; Miller, L. G.; Wei, J. H. C.; Welander, P. V.

2014-12-01

The inactive Sulfur Bank Mercury Mine is located in a volcanic region having geothermal flow and gas inputs into the Herman Pit impoundment. The acidic (pH 2 - 4) waters of the Herman Pit are permeated by hundreds of continuous flow gas seeps that contain CO2, H2S and CH4. We sampled one seep and found it to be composed of 95 % CO2 and 5 % CH4, in agreement with earlier measurements. Only a trace of ethane (10 - 20 ppm) was found and propane was below detection, resulting in a high CH4/C2H6 + C3H8 ratio of > 5,000, while the δ13CH4 and the δ13CO2 were respectively - 24 and - 11 per mil. Collectively, these results suggested a complex origin for the methane, being made up of a thermogenic component resulting from pyrolysis of buried organics, along with an active methanogenic portion. The relatively 12C-enriched value for the CO2 suggested a reworking of the ebullitive methane by methanotrophic bacteria. We found that dissolved methane in the collected water from 2-4 m depth was high (~ 400 µM), which would support methanotrophy in the lake's aerobic biomes. We therefore tested the ability of bottom sediments to consume methane by conducting aerobic incubations of slurried bottom sediments. Methane was removed from the headspace of live slurries, and subsequent additions of methane to the headspace over the course of 2-3 months resulted in faster removal rates suggesting a buildup of the population of methanotrophs. This activity could be transferred to an artificial medium originally devised for the cultivation of acidophilic iron oxidizing bacteria (Silverman and Lundgren, 1959; J. Bacteriol. 77: 642 - 647), suggesting the possibility of future cultivation of acidophilic methanotrophs. A successful extraction of some hopanoid compounds from the sediments was achieved, although the results were too preliminary at the time of this writing to identify any hopanoids specifically linked to methanotrophic bacteria. Further efforts to amplify functional genes for methane oxidizing bacteria (e.g., pMMO) from extracted sediment DNA are underway.

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.

Contribution of tropical wetland and biomass burning emissions to the methane growth rate: new insights from lower tropospheric partial column retrievals

NASA Astrophysics Data System (ADS)

Yin, Y.; Worden, J. R.; Bloom, A. A.; Frankenberg, C.

2017-12-01

Atmospheric CH4 concentration stabilized in the early 2000s and began to increase again since 2007. Recent literature has explored various explanations for possible causes of the growth rate change in CH4 with considerable contradictions among each other, suggesting this problem being ill-conditioned with currently available observations. Satellite observations of CH4 in the near infrared (NIR) with full column sensitivity began with SCIAMACHY (2003-2012) and extend to the present with GOSAT (2009-). Observations in the thermal infrared (TIR) such as from TES (2004-2011) and CrIS (2012-) provide data in the free troposphere. Combining the information pieces from TIR and NIR, we could resolve the lower tropospheric partial column of CH4 that is more sensitive to the surface methane fluxes. Here, using a newly developed lower tropospheric partial column retrieval and supplemented by MOPITT CO retrievals, we discuss the interannual variations of tropical CH4 emissions from wetland and biomass burning respectively, and further, we explore the relationship between those fluxes and climate variability.

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.

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.

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.

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

Ethane ocean on Titan

NASA Technical Reports Server (NTRS)

Lunine, J. I.; Stevenson, D. J.; Yung, Y.L.

1983-01-01

Voyager I radio occultation data is employed to develop a qualitative model of an ethane ocean on Titan. It is suggested that the ocean contains 25 percent CH4 and that the ocean is in dynamic equilibrium with an N2 atmosphere. Previous models of a CH4 ocean are discounted due to photolysis rates of CH4 gas. Tidal damping of Titan's orbital eccentricity is taken as evidence for an ocean layer approximately 1 km deep, with the ocean floor being covered with a solid C2H2 layer 100 to 200 m thick. The photolytic process disrupting the CH4, if the estimates of the oceanic content of CH4 are correct, could continue for at least one billion years. Verification of the model is dependent on detecting CH4 clouds in the lower atmosphere, finding C2H6 saturation in the lower troposphere, or obtaining evidence of a global ocean.

Rate Coefficient Measurements of the Reaction CH3 + O2 = CH3O + O

NASA Technical Reports Server (NTRS)

Hwang, S. M.; Ryu, Si-Ok; DeWitt, K. J.; Rabinowitz, M. J.

1999-01-01

Rate coefficients for the reaction CH3 + O2 = CH3O + O were measured behind reflected shock waves in a series of lean CH4-O2-Ar mixtures using hydroxyl and methyl radical diagnostics. The rate coefficients are well represented by an Arrhenius expression given as k = (1.60(sup +0.67, sub -0.47 ) x 10(exp 13) e(-15813 +/- 587 K/T)/cubic cm.mol.s. This expression, which is valid in the temperature range 1575-1822 K, supports the downward trend in the rate coefficients that has been reported in recent determinations. All measurements to date, including the present study, have been to some extent affected by secondary reactions. The complications due to secondary reactions, choice of thermochemical data, and shock-boundary layer interactions that affect the determination of the rate coefficients are examined.

Experimental study of heterogeneous organic chemistry induced by far ultraviolet light: Implications for growth of organic aerosols by CH3 addition in the atmospheres of Titan and early Earth

NASA Astrophysics Data System (ADS)

Hong, Peng; Sekine, Yasuhito; Sasamori, Tsutoni; Sugita, Seiji

2018-06-01

Formation of organic aerosols driven by photochemical reactions has been observed and suggested in CH4-containing atmospheres, including Titan and early Earth. However, the detailed production and growth mechanisms of organic aerosols driven by solar far ultraviolet (FUV) light remain poorly constrained. We conducted laboratory experiments simulating photochemical reactions in a CH4sbnd CO2 atmosphere driven by the FUV radiations dominated by the Lyman-α line. In the experiments, we analyzed time variations in thickness and infrared spectra of solid organic film formed on an optical window in a reaction cell. Gas species formed by FUV irradiation were also analyzed and compared with photochemical model calculations. Our experimental results show that the growth rate of the organic film decreases as the CH4/CO2 ratio of reactant gas mixture decreases, and that the decrease becomes very steep for CH4/CO2 < 1. Comparison with photochemical model calculations suggests that polymerizations of gas-phase hydrocarbons, such as polyynes and aromatics, cannot account for the growth rate of the organic film but that the addition reaction of CH3 radicals onto the organic film with the reaction probability around 10-2 can explain the growth rate. At CH4/CO2 < 1, etching by O atom formed by CO2 photolysis would reduce or inhibit the growth of the organic film. Our results suggest that organic aerosols would grow through CH3 addition onto the surface during the precipitation of aerosol particles in the middle atmosphere of Titan and early Earth. On Titan, effective CH3 addition would reduce C2H6 production in the atmosphere. On early Earth, growth of aerosol particles would be less efficient than those on Titan, possibly resulting in small-sized monomers and influencing UV shielding.

A Critical Assessment of Microbiological Biogas to Biomethane Upgrading Systems.

PubMed

Rittmann, Simon K-M R

2015-01-01

Microbiological biogas upgrading could become a promising technology for production of methane (CH(4)). This is, storage of irregular generated electricity results in a need to store electricity generated at peak times for use at non-peak times, which could be achieved in an intermediate step by electrolysis of water to molecular hydrogen (H(2)). Microbiological biogas upgrading can be performed by contacting carbon dioxide (CO(2)), H(2) and hydrogenotrophic methanogenic Archaea either in situ in an anaerobic digester, or ex situ in a separate bioreactor. In situ microbiological biogas upgrading is indicated to require thorough bioprocess development, because only low volumetric CH(4) production rates and low CH(4) fermentation offgas content have been achieved. Higher volumetric production rates are shown for the ex situ microbiological biogas upgrading compared to in situ microbiological biogas upgrading. However, the ex situ microbiological biogas upgrading currently suffers from H(2) gas liquid mass transfer limitation, which results in low volumetric CH(4) productivity compared to pure H(2)/CO(2) conversion to CH(4). If waste gas utilization from biological and industrial sources can be shown without reduction in volumetric CH(4) productivity, as well as if the aim of a single stage conversion to a CH(4) fermentation offgas content exceeding 95 vol% can be demonstrated, ex situ microbiological biogas upgrading with pure or enrichment cultures of methanogens could become a promising future technology for almost CO(2)-neutral biomethane production.

Tracer-Based Determination of Vortex Descent in the 1999-2000 Arctic Winter

NASA Technical Reports Server (NTRS)

Greenblatt, Jeffery B.; Jost, Hans-Juerg; Loewenstein, Max; Podolske, James R.; Hurst, Dale F.; Elkins, James W.; Schauffler, Sue M.; Atlas, Elliot L.; Herman, Robert L.; Webster, Christopher R.

2001-01-01

A detailed analysis of available in situ and remotely sensed N2O and CH4 data measured in the 1999-2000 winter Arctic vortex has been performed in order to quantify the temporal evolution of vortex descent. Differences in potential temperature (theta) among balloon and aircraft vertical profiles (an average of 19-23 K on a given N2O or CH4 isopleth) indicated significant vortex inhomogeneity in late fall as compared with late winter profiles. A composite fall vortex profile was constructed for November 26, 1999, whose error bars encompassed the observed variability. High-latitude, extravortex profiles measured in different years and seasons revealed substantial variability in N2O and CH4 on theta surfaces, but all were clearly distinguishable from the first vortex profiles measured in late fall 1999. From these extravortex-vortex differences, we inferred descent prior to November 26: 397+/-15 K (1sigma) at 30 ppbv N2O and 640 ppbv CH4, and 28+/-13 K above 200 ppbv N2O and 1280 ppbv CH4. Changes in theta were determined on five N2O and CH4 isopleths from November 26 through March 12, and descent rates were calculated on each N2O isopleth for several time intervals. The maximum descent rates were seen between November 26 and January 27: 0.82+/-0.20 K/day averaged over 50-250 ppbv N2O. By late winter (February 26-March 12), the average rate had decreased to 0.10+/-0.25 K/day. Descent rates also decreased with increasing N2O; the winter average (November 26-March 5) descent rate varied from 0.75+/-0.10 K/day at 50 ppbv to 0.40+/-0.11 K/day at 250 ppbv. Comparison of these results with observations and models of descent in prior years showed very good overall agreement. Two models of the 1999-2000 vortex descent, SLIMCAT and REPROBUS, despite theta offsets with respect to observed profiles of up to 20 K on most tracer isopleths, produced descent rates that agreed very favorably with the inferred rates from observation.

The Effect of a Reduction in Microbial Diversity on Greenhouse Gas Production in Alaskan Tundra Soils.

NASA Astrophysics Data System (ADS)

Wagner, R.; Oechel, W. C.; Lipson, D.

2017-12-01

Atmospheric methane accounts for 20% of the warming potential of all greenhouse gases, has increased by 150% since pre-industrial times, and has the potential to double again over the next century. Microbially mediated CH4 emissions from natural wetlands represent the highest uncertainty in relative contributions to atmospheric CH4 levels of all CH4 sources, with Arctic wetlands currently experiencing twice the rate of warming as the rest of the planet. Notwithstanding the central role that the soil microbial community plays, and the high uncertainty in CH4 emissions from this ecosystem, surprisingly little research has been done to directly connect the microbial community structure to methane production rates. This is especially disconcerting given that most current CH4 emission models completely neglect microbial characteristics, despite the fact that the soil microbial community is predicted to be heavily impacted by a changing climate. Here, the effect of an artificial reduction in soil microbial α-diversity was investigated with regard to methane production and respiration rates. The microbial community was serially diluted followed by re-inoculation of sterilized Arctic soils in a mesocosm experiment. Methane production and respiration rates were measured, metagenomic sequencing was performed to determine microbial community diversity measures, and the effect of the oxidation state of iron was investigated. Preliminary results indicate that microbial communities with reduced α-diversity have lowered respiration rates in these soils. Analyses are ongoing and are expected to provide critical observations linking the role of soil microbial community diversity and greenhouse gas production in Arctic tundra ecosystems.

Seasonal variation in methane emission from stored slurry and solid manures

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

Husted, S.

1994-05-01

Methane (CH{sub 4}) is an important greenhouse gas and recent inventories have suggested that livestock manure makes a significant contribution to global CH{sub 4} emissions. The emission of CH{sub 4} from stored pig slurry, cattle slurry, pig solid manure, and cattle solid manure was followed during a 1-yr period. Methane emission was determined by dynamic chambers. Emission rates followed a ln-normal distribution for all four manures, Indicating large spatial and seasonal variation& Monthly geometric means for pig slurry, cattle slurry, pig solid manure, and cattle solid manure varied from 0.4 to 35.8, 0.0 to 34.5, 0.4 to 142.1, and 0.1more » to 42.7 g CH{sub 4} m{sup -3} d{sup -1}, respectively. For slurries CH{sub 4} emission rates increased significantly with storage temperatures, the Q{sub 10} value ranging from 14 to 5.7 depending on slurry type. The presence of a natural surface crust reduced CH{sub 4} emission from slurry by a factor of 11 to 12. Surface crust effects declined with increasing slurry temperature. Solid manures stored in dungheaps showed significant heat production. Pig solid manure temperatures were maintained at 30 to 60{degrees}C throughout most of the year, while cattle solid manure temperatures were close to ambient levels until late spring, when heat production was initiated. Methanogenesis in solid manure also increased with increasing temperatures. For pig solid manure, CH{sub 4} emission rates peaked at 35 to 45{degrees}C. No distinct temperature optimum could be detected for cattle solid manure, however, temperatures rarely exceeded 45{degrees}C. The Q{sub 10} values for dungheaps ranged from 2.7 to 10.3 depending on-manure type and Q{sub 10} temperature interval. Annual CH{sub 4} emissions from pig slurry, cattle slurry, pig solid manure, and cattle solid manure were estimated at 8.9, 15.5, 27.3, and 5.3 kg animal{sup -1} yr{sup -1}, respectively. 27 refs., 6 figs., 2 tabs.« less

Spatial heterogeneity of within-stream methane concentrations

NASA Astrophysics Data System (ADS)

Crawford, John T.; Loken, Luke C.; West, William E.; Crary, Benjamin; Spawn, Seth A.; Gubbins, Nicholas; Jones, Stuart E.; Striegl, Robert G.; Stanley, Emily H.

2017-05-01

Streams, rivers, and other freshwater features may be significant sources of CH4 to the atmosphere. However, high spatial and temporal variabilities hinder our ability to understand the underlying processes of CH4 production and delivery to streams and also challenge the use of scaling approaches across large areas. We studied a stream having high geomorphic variability to assess the underlying scale of CH4 spatial variability and to examine whether the physical structure of a stream can explain the variation in surface CH4. A combination of high-resolution CH4 mapping, a survey of groundwater CH4 concentrations, quantitative analysis of methanogen DNA, and sediment CH4 production potentials illustrates the spatial and geomorphic controls on CH4 emissions to the atmosphere. We observed significant spatial clustering with high CH4 concentrations in organic-rich stream reaches and lake transitions. These sites were also enriched in the methane-producing mcrA gene and had highest CH4 production rates in the laboratory. In contrast, mineral-rich reaches had significantly lower concentrations and had lesser abundances of mcrA. Strong relationships between CH4 and the physical structure of this aquatic system, along with high spatial variability, suggest that future investigations will benefit from viewing streams as landscapes, as opposed to ecosystems simply embedded in larger terrestrial mosaics. In light of such high spatial variability, we recommend that future workers evaluate stream networks first by using similar spatial tools in order to build effective sampling programs.

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.

Response of surface CH4 and CO2 fluxes to whole ecosystem warming and elevated CO2 in a boreal black spruce peatland, northern Minnesota

NASA Astrophysics Data System (ADS)

Hsieh, I. F.; Gill, A. L.; Finzi, A.

2017-12-01

Potential increase in peatland C losses by environmental change has been presented by impacting the balance of CO2 and CH4 sequestration and release. While temperature warming may accelerate the temperature-sensitive processes and release CO2 and CH4 from peat C stores, factors associated with warming and that associated with elevated CO2 concentration may alter the intrinsic characteristics of CO2 and CH4 emission from peatland. By leveraging Spruce and Peatland Responses Under Changing Environments (SPRUCE) experiment, we measured peat surface CO2 and CH4 fluxes and their i13C signatures across a gradient of warming temperatures in a boreal black spruce peat bog in 2015 and 2016 growing seasons. Elevated CO2 (eCO2) treatment was added to the warming experiment in June, 2016. Our results show both CH4 and CO2 flux increased with warming temperature in the two-year measurement period. Total emission for both gases were higher in 2016 with whole ecosystem warming than that in 2015 with deep peat heat warming. The 2016 increase in CO2 emission was significantly larger in the hummock microtopographic position compared to hollows. The opposite was true for CH4 fluxes, where the increase was strongest in the hollows. In fact, CH4 flux from hummocks declined in 2016 compared to 2015, suggesting lower overall rates of CH4 production and/or greater rates of methanotrophy. The increase (less depleted) in i13C -CH4 signatures suggest acetoclastic methanogensis increased its contribution to total CH4 production across the growing season and in response to experimental warming, while hydrogenotrophic methanogenesis dominated total CH4 production. On the contrary, results of i13C-CO2 show no significant change in the contribution of different sources to total CO2 emission through time or across warming temperature. On the other hand, i13C-CO2 signatures under CO2 fumigation in 2016 was significantly depleted since the eCO2 initiation, indicating a rapid increase in plant productivity and the subsequent belowground transfer of photosynthate. Our results emphasize the susceptibleness of northern peat bog to changes in the environment by illustrating measureable influences of whole ecosystem warming and elevated CO2 on greenhouse gases emission.

Methane emissions and contaminant degradation rates at sites affected by accidental releases of denatured fuel-grade ethanol

NASA Astrophysics Data System (ADS)

Sihota, Natasha J.; Mayer, K. Ulrich; Toso, Mark A.; Atwater, Joel F.

2013-08-01

The recent increase in the use of denatured fuel-grade ethanol (DFE) has enhanced the probability of its environmental release. Due to the highly labile nature of ethanol (EtOH), it is expected to rapidly biodegrade, increasing the potential for inducing methanogenic conditions in the subsurface. As environmental releases of DFE can be expected to occur at the ground surface or in the vadose zone (e.g., due to surficial spills from rail lines or tanker trucks and leaking underground storage tanks), the potential for methane (CH4) generation at DFE spill sites requires evaluation. An assessment is needed because high CH4 generation rates may lead to CH4 fluxes towards the ground surface, which is of particular concern if spills are located close to human habitation—related to concerns of soil vapor intrusion (SVI). This work demonstrates, for the first time, the measurement of surficial gas release rates at large volume DFE spill sites. Two study sites, near Cambria and Balaton, in MN are investigated. Total carbon emissions at the ground surface (summing carbon dioxide (CO2) and CH4 emissions) are used to quantify depth-integrated DFE degradation rates. Results from both sites demonstrate that substantial CO2 and CH4 emissions do occur—even years after a spill. However, large total carbon fluxes, and CH4 emissions in particular, were restricted to a localized area within the DFE source zone. At the Balaton site, estimates of total DFE carbon losses in the source zone ranged between 5 and 174 μmol m- 2 s- 1, and CH4 effluxes ranged between non-detect and 9 μmol m- 2 s- 1. At the Cambria site estimates of total DFE carbon losses in the source zone ranged between 8 and 500 μmol m- 2 s- 1, and CH4 effluxes ranged between non-detect and 393 μmol m- 2 s- 1. Substantial CH4 accumulation, coupled with oxygen (O2) depletion, measured in samples collected from custom-designed gas collection chambers at the Cambria site suggests that the development of explosion or asphyxiation hazards is possible in confined spaces above a rapidly degrading DFE release. However, the results also indicate that the development of such hazards is locally constrained, will require a high degree of soil moisture, close proximity to the source zone, a good connection between the soil and the confined space, and poorly aerated conditions.

Methane emissions and contaminant degradation rates at sites affected by accidental releases of denatured fuel-grade ethanol.

PubMed

Sihota, Natasha J; Mayer, K Ulrich; Toso, Mark A; Atwater, Joel F

2013-08-01

The recent increase in the use of denatured fuel-grade ethanol (DFE) has enhanced the probability of its environmental release. Due to the highly labile nature of ethanol (EtOH), it is expected to rapidly biodegrade, increasing the potential for inducing methanogenic conditions in the subsurface. As environmental releases of DFE can be expected to occur at the ground surface or in the vadose zone (e.g., due to surficial spills from rail lines or tanker trucks and leaking underground storage tanks), the potential for methane (CH4) generation at DFE spill sites requires evaluation. An assessment is needed because high CH4 generation rates may lead to CH4 fluxes towards the ground surface, which is of particular concern if spills are located close to human habitation-related to concerns of soil vapor intrusion (SVI). This work demonstrates, for the first time, the measurement of surficial gas release rates at large volume DFE spill sites. Two study sites, near Cambria and Balaton, in MN are investigated. Total carbon emissions at the ground surface (summing carbon dioxide (CO2) and CH4 emissions) are used to quantify depth-integrated DFE degradation rates. Results from both sites demonstrate that substantial CO2 and CH4 emissions do occur-even years after a spill. However, large total carbon fluxes, and CH4 emissions in particular, were restricted to a localized area within the DFE source zone. At the Balaton site, estimates of total DFE carbon losses in the source zone ranged between 5 and 174 μmol m(-2) s(-1), and CH4 effluxes ranged between non-detect and 9 μmol m(-2) s(-1). At the Cambria site estimates of total DFE carbon losses in the source zone ranged between 8 and 500 μmol m(-2) s(-1), and CH4 effluxes ranged between non-detect and 393 μmol m(-2) s(-1). Substantial CH4 accumulation, coupled with oxygen (O2) depletion, measured in samples collected from custom-designed gas collection chambers at the Cambria site suggests that the development of explosion or asphyxiation hazards is possible in confined spaces above a rapidly degrading DFE release. However, the results also indicate that the development of such hazards is locally constrained, will require a high degree of soil moisture, close proximity to the source zone, a good connection between the soil and the confined space, and poorly aerated conditions. Copyright © 2013 Elsevier B.V. All rights reserved.

Modeling methane and nitrous oxide emissions from direct-seeded rice systems

NASA Astrophysics Data System (ADS)

Simmonds, Maegen B.; Li, Changsheng; Lee, Juhwan; Six, Johan; van Kessel, Chris; Linquist, Bruce A.

2015-10-01

Process-based modeling of CH4 and N2O emissions from rice fields is a practical tool for conducting greenhouse gas inventories and estimating mitigation potentials of alternative practices at the scale of management and policy making. However, the accuracy of these models in simulating CH4 and N2O emissions in direct-seeded rice systems under various management practices remains a question. We empirically evaluated the denitrification-decomposition model for estimating CH4 and N2O fluxes in California rice systems. Five and nine site-year combinations were used for calibration and validation, respectively. The model was parameterized for two cultivars, M206 and Koshihikari, and able to simulate 30% and 78% of the variation in measured yields, respectively. Overall, modeled and observed seasonal CH4 emissions were similar (R2 = 0.85), but there was poor correspondence in fallow period CH4 emissions and in seasonal and fallow period N2O emissions. Furthermore, management effects on seasonal CH4 emissions were highly variable and not well represented by the model (0.2-465% absolute relative deviation). Specifically, simulated CH4 emissions were oversensitive to fertilizer N rate but lacked sensitivity to the type of seeding system (dry seeding versus water seeding) and prior fallow period straw management. Additionally, N2O emissions were oversensitive to fertilizer N rate and field drainage. Sensitivity analysis showed that CH4 emissions were highly sensitive to changes in the root to total plant biomass ratio, suggesting that it is a significant source of model uncertainty. These findings have implications for model-directed field research that could improve model representation of paddy soils for application at larger spatial scales.

Greenhouse gas measurements from a UK network of tall towers: technical description and first results

NASA Astrophysics Data System (ADS)

Stanley, Kieran M.; Grant, Aoife; O'Doherty, Simon; Young, Dickon; Manning, Alistair J.; Stavert, Ann R.; Spain, T. Gerard; Salameh, Peter K.; Harth, Christina M.; Simmonds, Peter G.; Sturges, William T.; Oram, David E.; Derwent, Richard G.

2018-03-01

A network of three tall tower measurement stations was set up in 2012 across the United Kingdom to expand measurements made at the long-term background northern hemispheric site, Mace Head, Ireland. Reliable and precise in situ greenhouse gas (GHG) analysis systems were developed and deployed at three sites in the UK with automated instrumentation measuring a suite of GHGs. The UK Deriving Emissions linked to Climate Change (UK DECC) network uses tall (165-230 m) open-lattice telecommunications towers, which provide a convenient platform for boundary layer trace gas sampling. In this paper we describe the automated measurement system and first results from the UK DECC network for CO2, CH4, N2O, SF6, CO and H2. CO2 and CH4 are measured at all of the UK DECC sites by cavity ring-down spectroscopy (CRDS) with multiple inlet heights at two of the three tall tower sites to assess for boundary layer stratification. The short-term precisions (1σ on 1 min means) of CRDS measurements at background mole fractions for January 2012 to September 2015 is < 0.05 µmol mol-1 for CO2 and < 0.3 nmol mol-1 for CH4. Repeatability of standard injections (1σ) is < 0.03 µmol mol-1 for CO2 and < 0.3 nmol mol-1 for CH4 for the same time period. N2O and SF6 are measured at three of the sites, and CO and H2 measurements are made at two of the sites, from a single inlet height using gas chromatography (GC) with an electron capture detector (ECD), flame ionisation detector (FID) or reduction gas analyser (RGA). Repeatability of individual injections (1σ) on GC and RGA instruments between January 2012 and September 2015 for CH4, N2O, SF6, CO and H2 measurements were < 2.8 nmol mol-1, < 0.4 nmol mol-1, < 0.07 pmol mol-1, < 2 nmol mol-1 and < 3 nmol mol-1, respectively. Instrumentation in the network is fully automated and includes sensors for measuring a variety of instrumental parameters such as flow, pressures, and sampling temperatures. Automated alerts are generated and emailed to site operators when instrumental parameters are not within defined set ranges. Automated instrument shutdowns occur for critical errors such as carrier gas flow rate deviations. Results from the network give good spatial and temporal coverage of atmospheric mixing ratios within the UK since early 2012. Results also show that all measured GHGs are increasing in mole fraction over the selected reporting period and, except for SF6, exhibit a seasonal trend. CO2 and CH4 also show strong diurnal cycles, with night-time maxima and daytime minima in mole fractions.

Determination of GHG and ammonia emissions from stored dairy cattle slurry by using a floating dynamic chamber.

PubMed

Minato, Keiko; Kouda, Yasuyuki; Yamakawa, Masaaki; Hara, Satoshi; Tamura, Tadashi; Osada, Takashi

2013-02-01

We developed a system for measuring emissions from stored slurry by using a floating dynamic chamber. CH(4) , CO(2) , N(2) O and NH(3) emitted from the storage tank of a dairy cattle farm in eastern Hokkaido were measured during summer 2008 (7/16-8/6), fall 2008 (10/2-10/26), spring 2009 (6/2-6/21) and winter 2009 (3/11). Average daily gas emission rates in summer, fall and spring were, respectively, 54.8, 54.2 and 34.3 g/m(2) for CH(4) ; 602, 274 and 254 g/m(2) for CO(2) ; 55.4, 68.2 and trace mg/m(2) for N(2) O; and 0.55, 0.73 and 0.46 g/m(2) for NH(3) . CH(4) , CO(2) and NH(3) emission rates during the brief measurement period in winter were reduced to 1/4, 1/23 and 1/2, respectively, of summer emission rate levels. All gas emissions showed diurnal fluctuation and were greatest during the daytime, when the ambient temperature rose. CH(4) , NH(3) and CO(2) emissions increased significantly during the daytime, and the daily emission (in grams) of each gas was positively correlated with maximum daily temperature. According to the combined spring, summer and fall measurements, the CH(4) , N(2) O and NH(3) annual emission factors were 1.42% (g CH(4) /g volatile solids), 0.02% (g N(2) O-N/g total N) and 0.43% (g NH(3) -N/g total N), respectively. © 2012 The Authors. Animal Science Journal © 2012 Japanese Society of Animal Science.

Contrast between the mechanisms for dissociative electron attachment to CH3SCN and CH3NCS.

PubMed

Miller, Thomas M; Viggiano, Albert A; Shuman, Nicholas S

2018-05-14

The kinetics of thermal electron attachment to methyl thiocyanate (CH 3 SCN), methyl isothiocyanate (CH 3 NCS), and ethyl thiocyanate (C 2 H 5 SCN) were measured using flowing afterglow-Langmuir probe apparatuses at temperatures between 300 and 1000 K. CH 3 SCN and C 2 H 5 SCN undergo inefficient dissociative attachment to yield primarily SCN - at 300 K (k = 2 × 10 -10 cm 3 s -1 ), with increasing efficiency as temperature increases. The increase is well described by activation energies of 0.17 eV (CH 3 SCN) and 0.14 eV (C 2 H 5 SCN). CN - product is formed at <1% branching at 300 K, increasing to ∼30% branching at 1000 K. Attachment to CH 3 NCS yields exclusively SCN - ionic product but at a rate at 300 K that is below our detection threshold (k < 10 -12 cm 3 s -1 ). The rate coefficient increases rapidly with increasing temperature (k = 6 × 10 -11 cm 3 s -1 at 600 K), in a manner well described by an activation energy of 0.51 eV. Calculations at the B3LYP/def2-TZVPPD level suggest that attachment to CH 3 SCN proceeds through a dissociative state of CH 3 SCN - , while attachment to CH 3 NCS initially forms a weakly bound transient anion CH 3 NCS -* that isomerizes over an energetic barrier to yield SCN - . Kinetic modeling of the two systems is performed in an attempt to identify a kinetic signature differentiating the two mechanisms. The kinetic modeling reproduces the CH 3 NCS data only if dissociation through the transient anion is considered.

Contrast between the mechanisms for dissociative electron attachment to CH3SCN and CH3NCS

NASA Astrophysics Data System (ADS)

Miller, Thomas M.; Viggiano, Albert A.; Shuman, Nicholas S.

2018-05-01

The kinetics of thermal electron attachment to methyl thiocyanate (CH3SCN), methyl isothiocyanate (CH3NCS), and ethyl thiocyanate (C2H5SCN) were measured using flowing afterglow-Langmuir probe apparatuses at temperatures between 300 and 1000 K. CH3SCN and C2H5SCN undergo inefficient dissociative attachment to yield primarily SCN- at 300 K (k = 2 × 10-10 cm3 s-1), with increasing efficiency as temperature increases. The increase is well described by activation energies of 0.17 eV (CH3SCN) and 0.14 eV (C2H5SCN). CN- product is formed at <1% branching at 300 K, increasing to ˜30% branching at 1000 K. Attachment to CH3NCS yields exclusively SCN- ionic product but at a rate at 300 K that is below our detection threshold (k < 10-12 cm3 s-1). The rate coefficient increases rapidly with increasing temperature (k = 6 × 10-11 cm3 s-1 at 600 K), in a manner well described by an activation energy of 0.51 eV. Calculations at the B3LYP/def2-TZVPPD level suggest that attachment to CH3SCN proceeds through a dissociative state of CH3SCN-, while attachment to CH3NCS initially forms a weakly bound transient anion CH3NCS-* that isomerizes over an energetic barrier to yield SCN-. Kinetic modeling of the two systems is performed in an attempt to identify a kinetic signature differentiating the two mechanisms. The kinetic modeling reproduces the CH3NCS data only if dissociation through the transient anion is considered.

Greenhouse gas exchange in West African savanna ecosystems - how important are emissions from termite mounds?

NASA Astrophysics Data System (ADS)

Brümmer, C.; Brüggemann, N.

2012-04-01

Savannas cover large areas of the Earth's surface and play an important role in global carbon and nitrogen cycling. In this study, we present the soil-atmosphere exchange of N2O, CH4, and CO2 during two field campaigns throughout the growing seasons 2005 and 2006 at a natural savanna site that was not subject to human disturbances except for annual burning, and four agricultural sites planted with sorghum (n=2), cotton and peanut in Burkina Faso. The annual N2O emission of the nature reserve site amounted to 0.52 kg N2O-N ha-1 yr-1 in 2005 and to 0.67 kg N2O-N ha-1 yr-1 in 2006, whereas the calculated average annual N2O release of the crop sites was only 0.19 and 0.20 kg N2O-N ha-1 yr-1 in 2005 and 2006, respectively. As a result of a temporal up-scaling approach, a lower bound of annual N2O release could be given for two fertilized sorghum plots, that is, 0.83 kg N2O-N ha-1 yr-1 for a highly fertilized plot and 0.44 kg N2O-N ha-1 yr-1 for a moderately fertilized plot. During the rainy season both CH4 uptake in the range of up to 20 μg CH4-C m-2 h-1 as well as CH4 emission up to 300 μg CH4-C m-2 h-1 were observed at the nature reserve site, which was on average a CH4 source of 87.4 and 30.8 μg CH4-C m-2 h-1 in 2005 and 2006, respectively. All crop sites were on average weak CH4 sinks without significant seasonal variation. Uptake rates ranged between 2.5 and 8.7 μg CH4-C m-2 h-1. Occasionally very low net CH4 emission was observed after heavy rainfall events. Mean annual CH4 rates could be estimated to 2.48 kg CH4-C ha-1 yr-1 and -0.68 kg CH4-C ha-1 yr-1 for the nature reserve site and the crop sites, respectively. Trace gas emissions from termite (Cubitermes fungifaber) mounds that were almost exclusively found at the nature reserve were one order of magnitude higher for N2O and CO2, and two orders of magnitude higher for CH4 than soil emissions of the respective trace gas. Termite N2O, CH4 and CO2 release at the nature reserve contributed only 3.2%, 8.1% and 0.4% to total soil N2O, CH4 and CO2 emissions, respectively.

Infrared spectroscopy of solid normal hydrogen doped with CH3F and O2 at 4.2 K: CH3F:O2 complex and CH3F migration

NASA Astrophysics Data System (ADS)

Abouaf-Marguin, L.; Vasserot, A.-M.

2011-04-01

Double doping of solid normal hydrogen with CH3F and O2 at about 4.2 K gives evidence of (ortho-H2)n:CH3F clusters and of O2:CH3F complex formation. FTIR analysis of the time evolution of the spectra in the region of the v3 C-F stretching mode indicates that these clusters behave very differently from (ortho-H2)n:H2O clusters. The main point is the observed migration of CH3F molecules in solid para-H2 at 4.2 K which differs from that of H2O under identical experimental conditions. This is confirmed by an increase over time of the integrated intensity of the CH3F:O2 complex with a rate constant K = 2.7(2) . 10-4 s-1.

Partitioning microbial respiration between jet fuel and native organic matter in an organic-rich long time-contaminated aquifer.

PubMed

Bugna, G C; Chanton, J P; Stauffer, T B; MacIntyre, W G; Libelo, E L

2005-07-01

The relative importance of jet fuel biodegradation relative to the respiration of natural organic matter in a contaminated organic-rich aquifer underlying a fire training area at Tyndall Air Force Base, Florida, USA was determined with isotopic measurements. Thirteen wells were sampled and analyzed for BTX (benzene, toluene, xylene), dissolved inorganic carbon (DIC) and CH4 concentrations, and delta13C and 14C of DIC. Results range from non-detectable to 3790 ppb, 1.4-24 mM, 0.2-776 microM, +5.8 per thousand to -22 per thousand, and from 52 to 99 pmc, respectively. Residual fuel was confined to two center wells underlying the fire training area. DIC and CH4 concentrations were elevated down-gradient of the contamination, but also at sites that were not in the apparent flow path of the contaminated groundwater. DIC exhibited greatest delta13C enrichment at highest DIC and CH4 concentrations indicating that CH4 production was an important respiration mode. Radiocarbon-depleted DIC was observed at sites with high hydrocarbon concentrations and down-gradient of the site. The results indicate that while natural attenuation was not rapidly reducing the quantity of free product overlying the aquifer at the site of contamination, it was at least constraining its flow away from the spill site. Apparently under the conditions of this study, BTX was degraded as rapidly as it was dissolved.

Sources of atmospheric methane in the south Florida environment

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

Harriss, R.C.; Sebacher, D.I.; Bartlett, K.B.

1988-09-01

Direct measurement of methane (CH{sub 4}) flux from wetland ecosystems of south Florida demonstrates that freshwater wet prairies and inundated saw-grass marsh are the dominant sources of atmospheric CH{sub 4} in the region. Fluctuations in soil moisture are an important environmental factor controlling both seasonal and interannual fluctuations in CH{sub 4} emissions from undisturbed wetlands. Land use estimates for 1,900 and 1,973 were used to calculate regional CH{sub 4} flux. Human settlement in south Florida has modified wetland sources of CH{sub 4}, reducing the natural prairies and marsh sources by 37%. During the same period, impoundments and disturbed wetlands weremore » created which produce CH{sub 4} at rates approximately 50% higher than the natural wetlands they replaced. Preliminary estimates of urban and ruminant sources of CH{sub 4} based on extrapolation from literature data indicate these sources may now contribute approximately 23% of the total regional source. It was estimated that the integrated effects of urban and agricultural development in south Florida between 1,900 and 1,973 resulted in a 26% enhancement in CH{sub 4} flux to the troposphere. 35 refs., 3 figs., 6 tabs.« less

Effects of experimental warming and mowing on greenhouse gas fluxes in an alpine meadow on the Tibetan Plateau

NASA Astrophysics Data System (ADS)

Wang, Jinsong; Quan, Quan; Sun, Jian; Niu, Shuli

2017-04-01

Rapid climate change and intensified human activities on the Tibetan Plateau may alter the magnitude and direction of greenhouse gas (GHG) emissions, affecting the climate change impact on these fragile ecosystems. We conducted a controlled experiment to investigate the effects of warming and mowing (simulation of grazing) on soil CO2, CH4 and N2O fluxes in an alpine meadow in eastern Tibetan Plateau between August 2015 and July 2016. Three levels of temperature (C, ambient temperature; W1, < 2 °C warming at 5 cm soil depth by infrared heaters; and W2, > 2 °C warming) were combined with two levels of mowing treatment (UM, un-mowing; and M, mowing). GHG fluxes were measured once an hour using static chamber. Both CO2 emission and CH4 uptake rates showed a seasonal fluctuation, with the maximum value occurred in late summer and the minimum in winter. However, N2O flux did not show a strong seasonal pattern. High level of warming (W2) regardless of mowing significantly increased CO2 emission and CH4 uptake by 15.4 % and 38.2 % averaged over the year, compared with no-warming (C). Moderate warming (W1) did not have significant effects on either CO2 or CH4 fluxes. N2O flux was reduced by 54.1% by W2 and 15.7% by W1 warming. Mowing alone increased CH4 uptake and N2O emission by 18.0 % and 12.7%, respectively, but had no significant effect on CO2 flux. The interactions between warming and mowing were detected in CO2 and CH4 fluxes. Among all treatments, W2UM in general had the highest rates of CO2 emission and CH4 uptake but the lowest rate of N2O flux, while CUM and CM showed the opposite. In addition, warming induced increase in CH4 uptake and decline in N2O release had very limited ability to offset the enhanced CO2 emission, resulting in a net positive feedback of the three GHGs to climate warming. Furthermore, daily CO2 flux increased exponentially with soil temperature at 5 cm. CH4 flux correlated negatively with soil temperature but positively with soil moisture.

Quantifying methane emissions from coal and natural gas sources along the northwestern Appalachian

NASA Astrophysics Data System (ADS)

Barkley, Z.; Lauvaux, T.; Davis, K. J.; Fried, A.

2017-12-01

According to the EPA's 2012 gridded inventory (Maasakkers et al., 2016), more than 10% of all CH4 emissions in the U.S. are located along the western edge of the Appalachian with the majority of these emissions coming from natural gas infrastructure and coal mines. However, top-down studies of unconventional wells in southwestern Pennsylvania have found emission rates to be much higher than EPA estimates (Caulton et al., 2014, Ren et al., 2017). Furthermore, although 9 of the 10 largest sources of CH4 in the EPA Greenhouse Gas Reporting Program are coal mines located in this region, no top down studies have been performed to assess the accuracy of these enormous point sources. This study uses aircraft data from the ACT-America flight campaign in conjunction with techniques previously used to solve for CH4 emissions from the northeastern Marcellus (Barkley et al., 2017) to quantify the total CH4 flux from the western Pennsylvania/West Virginia region and constrain emissions from natural gas and coal with an upper limit for each source. We use the WRF-Chem mesoscale model at 3 km resolution to simulate CH4 enhancements from a customized emissions inventory and compare the modelled enhancements to observations from 7 flights that were downwind of coal and gas sources. Coal and natural gas emissions are adjusted in the model to minimize a cost function that accounts for the difference between the modelled and observed CH4 values, and a range of likely combinations for natural gas and coal emission rates are obtained for each flight. We then overlap this range of likely emission rates across all flights to further limit the range of possible emission rates. Influence functions created using a lagrangian particle dispersion model for segments of each flight provide information on what area emissions are being optimized for. Preliminary results find that CH4 emissions from gas and coal along the northwestern Appalachian are lower than EPA estimates by 20-50%. In particular, upper limits on CH4 emissions from unconventional natural gas are less than 1% of total production, significantly lower than previous top-down estimates in the region. Future work will use ethane data to better distinguish between coal and natural gas emissions, and expand these analyses to other study regions explored in the ACT-America aircraft campaign.

Methane emission to the atmosphere from landfills in the Canary Islands

NASA Astrophysics Data System (ADS)

Hernández, Pedro A.; Asensio-Ramos, María; Rodríguez, Fátima; Alonso, Mar; García-Merino, Marta; Amonte, Cecilia; Melián, Gladys V.; Barrancos, José; Rodríguez-Delgado, Miguel A.; Hernández-Abad, Marta; Pérez, Erica; Alonso, Monica; Tassi, Franco; Raco, Brunella; Pérez, Nemesio M.

2017-04-01

Methane (CH4) is one of the most powerful greenhouse gases, and is increasing in the atmosphere by 0.6% each year (Intergovernmental Panel on Climate Change, IPCC, 2013). This gas is produced in landfills in large quantities following the anaerobic degradation of organic matter. The IPCC has estimated that more than 10% of the total anthropogenic emissions of CH4 are originated in landfills. Even after years of being no operative (closed), a significant amount of landfill gas could be released to the atmosphere through its surface as diffuse or fugitive degassing. Many landfills currently report their CH4 emissions to the atmosphere using model-based methods, which are based on the rate of production of CH4, the oxidation rate of CH4 and the amount of CH4 recovered (Bingemer and Crutzen, 1987). This approach often involves large uncertainties due to inaccuracies of input data and many assumptions in the estimation. In fact, the estimated CH4 emissions from landfills in the Canary Islands published by the Spanish National Emission and Pollutant Sources Registration (PRTR-Spain) seem to be overestimated due to the use of protocols and analytical methodologies based on mathematical models. For this reason, direct measurements to estimate CH4 emissions in landfills are essential to reduce this uncertainty. In order to estimate the CH4 emissions to the atmosphere from landfills in the Canary Islands 23 surveys have been performed since 1999. Each survey implies hundreds of CO2and CH4 efflux measurements covering the landfill surface area. Surface landfill CO2 efflux measurements were carried out at each sampling site by means of a portable non-dispersive infrared spectrophotometer (NDIR) model LICOR Li800 following the accumulation chamber method. Samples of landfill gases were taken in the gas accumulated in the chamber and CO2 and CH4 were analyzed using a double channel VARIAN 4900 micro-GC. The CH4 efflux measurent was computed combining CO2 efflux and CH4/CO2 ratio. To quantify the the diffuse or fugitive CO2 and CH4 emission, gas efflux contour maps were constructed using sequential Gaussian simulation (sGs) as interpolation method. Considering that (a) there are 5 controlled landfills in the Canary Islands, (b) the average area of the 23 studied cells is 0.17 km2 and (c) the mean value of the CH4 emission estimated for the studied cells range between 6.9 and 8.1 kt km-2 y-1, the estimated CH4 emission to the atmosphere from landfills in the Canary Islands showed a range of 7.0 - 7.8 kt y-1. On the contrary and for the same period of time, the PRTR-Spain estimates CH4 emission in the order of 10.3 - 14.9 kt y-1, nearly two times our estimated value. This result demonstrates the need to perform direct measurements to estimate the surface fugitive emission of CH4 from landfills. Bingemer, H. G., and P. J. Crutzen (1987). The production of methane from solid wastes, J. Geophys. Res. 92, 2182-2187

Vertical gradients in carbon flow and methane production in a sulfate-rich oil sands tailings pond.

PubMed

Stasik, Sebastian; Wendt-Potthoff, Katrin

2016-12-01

Oil sands tailings ponds are primary storage basins for tailings produced during oil sands processing in Alberta (Canada). Due to microbial metabolism, methane production contributes to greenhouse gas emissions, but positively affects tailings densification, which is relevant for operational water re-use. Depending on the age and depth of tailings, the activity of sulfate-reducing bacteria (SRB) may control methanogenesis due to the competition for substrates. To assess the depth-related impact of sulfate reduction on CH 4 emissions, original tailings of two vicinal pond profiles were incubated in anoxic microcosms with/without molybdate as selective inhibitor of microbial sulfate reduction. Integrating methane production rates, considerable volumes of CH 4 emissions (∼5.37 million L d -1 ) may be effectively prevented by the activity of SRB in sulfidic tailings between 3.5 and 7.5 m. To infer metabolic potentials controlling methanogenic pathways, a set of relevant organic acids (acetate, formate, propionate, butyrate, lactate) was added to part of the microcosms. Generally, organic acid transformation shifted with depth, with highest rates (305-446 μmol L -1  d -1 ) measured in fresh tailings at 5.5-7.5 m. In all depths, a transient accumulation of acetate revealed its importance as key intermediate during organic matter decomposition. SRB dominated the transformation of acetate, butyrate and propionate, but were not essential for lactate and formate turnover. Acetate as methanogenic substrate was important only at 13.5 m. At 1-7.5 m, methanogenesis significantly increased in presence of organic acids, most likely due to the syntrophic oxidation of acetate to CO 2 by SRB and subsequent conversion to CH 4 . Copyright © 2016 Elsevier Ltd. All rights reserved.

The Effects of Exercise on Pharmacokinetics and Pharmacodynamics of Physostigmine in Rats

DTIC Science & Technology

1989-02-15

Phy ( cholinesterase activity ) are likely to be altered by exercise due to altered blood flow rates to liver and pH of muscle. During exercise...concurrent acute exercise on the ChE activity in RBC aad tissues and in blood biochemical parameters in rats. Phy has been reported to reduce the...Springfield, Illinois. Also, we have studied the effect of exercise training, Phy and training + Phy on ChE activity in RBC and tissues and on blood biochemi

Quantifying sources of methane and light alkanes in the Los Angeles Basin, California

NASA Astrophysics Data System (ADS)

Peischl, Jeff; Ryerson, Thomas; Atlas, Elliot; Blake, Donald; Brioude, Jerome; Daube, Bruce; de Gouw, Joost; Frost, Gregory; Gentner, Drew; Gilman, Jessica; Goldstein, Allen; Harley, Robert; Holloway, John; Kuster, William; Santoni, Gregory; Trainer, Michael; Wofsy, Steven; Parrish, David

2013-04-01

We use ambient measurements to apportion the relative contributions of different source sectors to the methane (CH4) emissions budget of a U.S. megacity. This approach uses ambient measurements of methane and C2-C5 alkanes (ethane through pentanes) and includes source composition information to distinguish between methane emitted from landfills and feedlots, wastewater treatment plants, tailpipe emissions, leaks of dry natural gas in pipelines and/or local seeps, and leaks of locally produced (unprocessed) natural gas. Source composition information can be taken from existing tabulations or developed by direct sampling of emissions using a mobile platform. By including C2-C5 alkane information, a linear combination of these source signatures can be found to match the observed atmospheric enhancement ratios to determine relative emissions strengths. We apply this technique to apportion CH4 emissions in Los Angeles, CA (L.A.) using data from the CalNex field project in 2010. Our analysis of L.A. atmospheric data shows the two largest CH4 sources in the city are emissions of gas from pipelines and/or from geologic seeps (47%), and emissions from landfills (40%). Local oil and gas production is a relatively minor source of CH4, contributing 8% of total CH4 emissions in L.A. Absolute CH4 emissions rates are derived by multiplying the observed CH4/CO enhancement ratio by State of California inventory values for carbon monoxide (CO) emissions in Los Angeles. Apportioning this total suggests that emissions from the combined natural and anthropogenic gas sources account for the differences between top-down and bottom-up CH4 estimates previously published for Los Angeles. Further, total CH4 emission attributed in our analysis to local gas extraction represents 17% of local production. While a derived leak rate of 17% of local production may seem unrealistically high, it is qualitatively consistent with the 12% reported in a recent state inventory survey of the L.A. oil and gas industry.

Canceling buoyancy of gaseous fuel flames in a gravitational environment using an ion-driven wind.

PubMed

Papac, M J; Dunn-Rankin, D

2006-09-01

Electric fields applied to combustion plasmas can be used to manipulate the thermofluid flow field to reduce buoyant forces and, hence, convection in locations near and within the flame. The resulting flow field is similar to that which is obtained in microgravity. Previous work has shown that buoyancy is modified in a non-premixed methane-air capillary flame when it burns in a capillary-to-plane configuration and an electric field is applied, and that regions of neutral or microbuoyancy exist, as indicated by the examined temperature and oxidizer profiles. The aim of this article is to examine in more detail this microbuoyancy condition and the coupling between the ion wind and resulting thermofluid flow field. To this end, the voltage-current characteristics (VCC) of CH4, C2H2, C2H4, C2H6, and C3H8 are measured and compared. Soot generated in the C2H(X) and propane flames lead to a hysteresis in the VCC curve whereby increased sooting leads to lower ion currents at constant flow rates and applied potentials. Buoyancy regimes for these flames in this configuration are determined. Methane can achieve the highest flow rate without sooting at the microbuoyant condition, and does not exhibit hysteresis in the VCC for the flow rates examined here. Furthermore, in this geometry, the microbuoyant condition for methane is found to coincide with ion current saturation when the capillary-to-plane distance is varied. These results allow for several simplifications to be made when modeling the flame at these conditions: the imposition of a spherical flame boundary with known ion current, and negligible recombination in the domain.

Current rates and mechanisms of subsea permafrost degradation in the East Siberian Arctic Shelf

NASA Astrophysics Data System (ADS)

Shakhova, Natalia; Semiletov, Igor; Gustafsson, Orjan; Sergienko, Valentin; Lobkovsky, Leopold; Dudarev, Oleg; Tumskoy, Vladimir; Grigoriev, Michael; Mazurov, Alexey; Salyuk, Anatoly; Ananiev, Roman; Koshurnikov, Andrey; Kosmach, Denis; Charkin, Alexander; Dmitrevsky, Nicolay; Karnaukh, Victor; Gunar, Alexey; Meluzov, Alexander; Chernykh, Denis

2017-06-01

The rates of subsea permafrost degradation and occurrence of gas-migration pathways are key factors controlling the East Siberian Arctic Shelf (ESAS) methane (CH4) emissions, yet these factors still require assessment. It is thought that after inundation, permafrost-degradation rates would decrease over time and submerged thaw-lake taliks would freeze; therefore, no CH4 release would occur for millennia. Here we present results of the first comprehensive scientific re-drilling to show that subsea permafrost in the near-shore zone of the ESAS has a downward movement of the ice-bonded permafrost table of ~14 cm year-1 over the past 31-32 years. Our data reveal polygonal thermokarst patterns on the seafloor and gas-migration associated with submerged taliks, ice scouring and pockmarks. Knowing the rate and mechanisms of subsea permafrost degradation is a prerequisite to meaningful predictions of near-future CH4 release in the Arctic.

In situ measurements of the photochemical formation rates and optical properties of organic aerosols in CH4/CO2 mixtures.

NASA Astrophysics Data System (ADS)

Adamkovics, M.; Boering, K. A.

2003-12-01

The presence of photochemically-generated hazes has a significant impact on radiative transfer in planetary atmospheres. While the rates of particle formation have been inferred from photochemical or microphysical models constrained to match observations, these rates have not been determined experimentally. Thus, the fundamental kinetics of particle formation are not known and remain highly parameterized in planetary atmospheric models. We have developed instrumentation for measuring the formation rates and optical properties of organic aerosols produced by irradiating mixtures of precursor gases via in situ optical (633nm) scattering and online quadrupole mass spectrometry (1-200 amu). Results for the generation of particulate hydrocarbons from the irradiation of pure, gas-phase CH4 as well as CH4/CO2 mixtures with vacuum ultraviolet (120-160nm) light, along with simultaneous measurements of the evolution of higher gas-phase hydrocarbons will be presented.

Nutrient loading enhances methane flux in an ombrotrophic bog

NASA Astrophysics Data System (ADS)

Bubier, Jill L.; Juutinen, Sari; Moore, Tim; Arnkil, Sini; Humphreys, Elyn; Marincak, Brenden; Roy, Cameron; Larmola, Tuula

2017-04-01

Peatlands are significant sources of atmospheric methane (CH4) and emission rates may be affected by atmospheric nutrient inputs and associated changes in vegetation. In a long-term (10-15 yr) fertilization experiment at a nutrient-poor, Sphagnum moss- and dwarf shrub-dominated bog in eastern Canada, we tested the effect of ammonium nitrate (NH4NO3,0 to 6.4 g N m-2 yr-1) and potassium phosphate (KH2PO4,5 g P m-2 yr-1) on fluxes of CH4. Fluxes were measured using a closed chamber technique over the growing seasons of 2005 and 2015. The effect of long-term field treatments on aerobic consumption and anaerobic production potentials of CH4 was tested by laboratory incubations of peat samples, as well as an amendment with KH2PO4on anaerobic production potentials at the water table. Over the 10-15 yr, three levels of N plus PK addition and N-only addition of 6.4g N m-2yr-1 decreased the abundance of Sphagnum and Polytrichum mosses, increased the growth and coverage of dwarf shrubs, and caused a decline in surface elevation and thus a higher water table. Overall, CH4 flux was small, ˜ 12 mg m-2 d-1 in the control plots, primarily because of the low water table (30 to 50 cm beneath the peat surface), but flux varied as a function of water table position and treatment. KH2PO4 addition was associated with the highest fluxes: in the 5th treatment year, the PK treatment had the largest CH4 flux (˜25 mg m-2 d-1), whereas in the 15th year the 6.4NPK treatment had the largest flux (˜50 mg m-2 d-1). Rates of potential production and consumption of CH4in laboratory incubations of peat samples were associated with position relative to the water table. Anaerobic potential CH4production was largest in the PK treatment and overall was marginally increased by PK amendment; there were no clear effects of NH4NO3 on CH4 production. The major increase in CH4 flux appearing in the long term seemed to be result of the change in water table position owing to peat subsidence and loss of moss, plus potential stimulation of CH4 production by PK.

Rapid Growth of Nanostructured Diamond Film on Silicon and Ti–6Al–4V Alloy Substrates

PubMed Central

Samudrala, Gopi K.; Vohra, Yogesh K.; Walock, Michael J.; Miles, Robin

2014-01-01

Nanostructured diamond (NSD) films were grown on silicon and Ti–6Al–4V alloy substrates by microwave plasma chemical vapor deposition (MPCVD). NSD Growth rates of 5 μm/h on silicon, and 4 μm/h on Ti–6Al–4V were achieved. In a chemistry of H2/CH4/N2, varying ratios of CH4/H2 and N2/CH4 were employed in this research and their effect on the resulting diamond films were studied by X-ray photoelectron spectroscopy, Raman spectroscopy, scanning electron microscopy, and atomic force microscopy. As a result of modifying the stock cooling stage of CVD system, we were able to utilize plasma with high power densities in our NSD growth experiments, enabling us to achieve high growth rates. Substrate temperature and N2/CH4 ratio have been found to be key factors in determining the diamond film quality. NSD films grown as part of this study were shown to contain 85% to 90% sp3 bonded carbon. PMID:28788461

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.

Interannual variation in methane emissions from tropical wetlands triggered by repeated El Niño Southern Oscillation

USGS Publications Warehouse

Zhu, Qiuan; Peng, Changhui; Ciais, Philippe; Jiang, Hong; Liu, Jinxun; Bousquet, Philippe; Li, Shiqin; Chang, Jie; Fang, Xiuqin; Zhou, Xiaolu; Chen, Huai; Liu, Shirong; Lin, Guanghui; Gong, Peng; Wang, Meng; Wang, Han; Xiang, Wenhua; Chen, Jing

2017-01-01

Methane (CH4) emissions from tropical wetlands contribute 60%–80% of global natural wetland CH4 emissions. Decreased wetland CH4 emissions can act as a negative feedback mechanism for future climate warming and vice versa. The impact of the El Niño–Southern Oscillation (ENSO) on CH4 emissions from wetlands remains poorly quantified at both regional and global scales, and El Niño events are expected to become more severe based on climate models’ projections. We use a process-based model of global wetland CH4 emissions to investigate the impacts of the ENSO on CH4 emissions in tropical wetlands for the period from 1950 to 2012. The results show that CH4 emissions from tropical wetlands respond strongly to repeated ENSO events, with negative anomalies occurring during El Niño periods and with positive anomalies occurring during La Niña periods. An approximately 8-month time lag was detected between tropical wetland CH4 emissions and ENSO events, which was caused by the combined time lag effects of ENSO events on precipitation and temperature over tropical wetlands. The ENSO can explain 49% of interannual variations for tropical wetland CH4 emissions. Furthermore, relative to neutral years, changes in temperature have much stronger effects on tropical wetland CH4 emissions than the changes in precipitation during ENSO periods. The occurrence of several El Niño events contributed to a lower decadal mean growth rate in atmospheric CH4 concentrations throughout the 1980s and 1990s and to stable atmospheric CH4 concentrations from 1999 to 2006, resulting in negative feedback to global warming.

Interannual variation in methane emissions from tropical wetlands triggered by repeated El Niño Southern Oscillation.

PubMed

Zhu, Qiuan; Peng, Changhui; Ciais, Philippe; Jiang, Hong; Liu, Jinxun; Bousquet, Philippe; Li, Shiqin; Chang, Jie; Fang, Xiuqin; Zhou, Xiaolu; Chen, Huai; Liu, Shirong; Lin, Guanghui; Gong, Peng; Wang, Meng; Wang, Han; Xiang, Wenhua; Chen, Jing

2017-11-01

Methane (CH 4 ) emissions from tropical wetlands contribute 60%-80% of global natural wetland CH 4 emissions. Decreased wetland CH 4 emissions can act as a negative feedback mechanism for future climate warming and vice versa. The impact of the El Niño-Southern Oscillation (ENSO) on CH 4 emissions from wetlands remains poorly quantified at both regional and global scales, and El Niño events are expected to become more severe based on climate models' projections. We use a process-based model of global wetland CH 4 emissions to investigate the impacts of the ENSO on CH 4 emissions in tropical wetlands for the period from 1950 to 2012. The results show that CH 4 emissions from tropical wetlands respond strongly to repeated ENSO events, with negative anomalies occurring during El Niño periods and with positive anomalies occurring during La Niña periods. An approximately 8-month time lag was detected between tropical wetland CH 4 emissions and ENSO events, which was caused by the combined time lag effects of ENSO events on precipitation and temperature over tropical wetlands. The ENSO can explain 49% of interannual variations for tropical wetland CH 4 emissions. Furthermore, relative to neutral years, changes in temperature have much stronger effects on tropical wetland CH 4 emissions than the changes in precipitation during ENSO periods. The occurrence of several El Niño events contributed to a lower decadal mean growth rate in atmospheric CH 4 concentrations throughout the 1980s and 1990s and to stable atmospheric CH 4 concentrations from 1999 to 2006, resulting in negative feedback to global warming. © 2017 John Wiley & Sons Ltd.

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.

Thermokarst lake methanogenesis along a complete talik profile

USGS Publications Warehouse

Heslop, J.K.; Walter Anthony, K.M.; Sepulveda-Jauregui, A.; Martinez-Cruz, K.; Bondurant, A.; Grosse, G.; Jones, Miriam C.

2015-01-01

Thermokarst (thaw) lakes emit methane (CH4) to the atmosphere formed from thawed permafrost organic matter (OM), but the relative magnitude of CH4 production in surface lake sediments vs. deeper thawed permafrost horizons is not well understood. We assessed anaerobic CH4 production potentials from various depths along a 590 cm long lake sediment core that captured the entire sediment package of the talik (thaw bulb) beneath the center of an interior Alaska thermokarst lake, Vault Lake, and the top 40 cm of thawing permafrost beneath the talik. We also studied the adjacent Vault Creek permafrost tunnel that extends through ice-rich yedoma permafrost soils surrounding the lake and into underlying gravel. Our results showed CH4 production potentials were highest in the organic-rich surface lake sediments, which were 151 cm thick (mean ± SD: 5.95 ± 1.67 μg C–CH4 g dw−1 d−1; 125.9 ± 36.2 μg C–CH4 g C−1org d−1). High CH4 production potentials were also observed in recently thawed permafrost (1.18 ± 0.61 μg C–CH4g dw−1 d−1; 59.60± 51.5 μg C–CH4 g C−1org d−1) at the bottom of the talik, but the narrow thicknesses (43 cm) of this horizon limited its overall contribution to total sediment column CH4 production in the core. Lower rates of CH4 production were observed in sediment horizons representing permafrost that has been thawing in the talik for a longer period of time. No CH4 production was observed in samples obtained from the permafrost tunnel, a non-lake environment. Our findings imply that CH4production is highly variable in thermokarst lake systems and that both modern OM supplied to surface sediments and ancient OM supplied to both surface and deep lake sediments by in situ thaw and shore erosion of yedoma permafrost are important to lake CH4 production.

Synthesis and structural characterization of group 4 metal carboxylates for nanowire production.

PubMed

Boyle, Timothy J; Yonemoto, Daniel T; Doan, Thu Q; Alam, Todd M

2014-12-01

The synthesis and characterization of a series of group 4 carboxylate derivatives ([M(ORc)4] where M = Ti, Zr, Hf) was undertaken for potential utility as precursors to ceramic nanowires. The attempted syntheses of the [M(ORc)4] precursors were undertaken from the reaction of [M(OBu(t))4] with a select set of carboxylic acids (H-ORc where ORc = OPc (O2CCH(CH3)2), OBc (O2CC(CH3)3), ONc (O2CCH2C(CH3)3)). The products were identified by single-crystal X-ray diffraction studies as [Ti(η(2)-OBc)3(OBu(t))] (1), [Zr2(μ3-O)(μ-OPc)4(μ,η(2)-OPc)(η(2)-OPc)]2 (2), [H]2[Zr(η(2)-OBc)2(OBc)2(OBc)2] (3), [Zr(μ-ONc)2(η(2)-ONc)2]2 (4), or [Hf(μ-ORc)2(η(2)-ORc)2]2 [ORc = OPc (5), OBc (6, shown), ONc (7)]. The majority of compounds (4-7) were isolated as dinuclear species with a dodecahedral-like (CN-8) bonding mode around the metals due to chelation and bridging of the ORc ligand. The two monomers (1 and 3) were found to adopt a capped trigonal prismatic and CN-8 geometry, respectively, due to chelating ORc and terminal ORc or OBu(t) ligands. The metals of the oxo-species 2 were isolated in octahedral and CN-8 arrangements. These compounds were then processed by electrospinning methods (applied voltage 10 kV, flow rate 30-60 μL/min, electric field 0.5 kV/cm), and wire-like morphologies were isolated using compounds 4, 6 (shown), and 7.

Spatial heterogeneity of within-stream methane concentrations

USGS Publications Warehouse

Crawford, John T.; Loken, Luke C.; West, William E.; Crary, Benjamin; Spawn, Seth A.; Gubbins, Nicholas; Jones, Stuart E.; Striegl, Robert G.; Stanley, Emily H.

2017-01-01

Streams, rivers, and other freshwater features may be significant sources of CH4 to the atmosphere. However, high spatial and temporal variabilities hinder our ability to understand the underlying processes of CH4 production and delivery to streams and also challenge the use of scaling approaches across large areas. We studied a stream having high geomorphic variability to assess the underlying scale of CH4 spatial variability and to examine whether the physical structure of a stream can explain the variation in surface CH4. A combination of high-resolution CH4 mapping, a survey of groundwater CH4 concentrations, quantitative analysis of methanogen DNA, and sediment CH4 production potentials illustrates the spatial and geomorphic controls on CH4 emissions to the atmosphere. We observed significant spatial clustering with high CH4 concentrations in organic-rich stream reaches and lake transitions. These sites were also enriched in the methane-producing mcrA gene and had highest CH4 production rates in the laboratory. In contrast, mineral-rich reaches had significantly lower concentrations and had lesser abundances of mcrA. Strong relationships between CH4and the physical structure of this aquatic system, along with high spatial variability, suggest that future investigations will benefit from viewing streams as landscapes, as opposed to ecosystems simply embedded in larger terrestrial mosaics. In light of such high spatial variability, we recommend that future workers evaluate stream networks first by using similar spatial tools in order to build effective sampling programs.

Continuous hydrogen and methane production from Agave tequilana bagasse hydrolysate by sequential process to maximize energy recovery efficiency.

PubMed

Montiel Corona, Virginia; Razo-Flores, Elías

2018-02-01

Continuous H 2 and CH 4 production in a two-stage process to increase energy recovery from agave bagasse enzymatic-hydrolysate was studied. In the first stage, the effect of organic loading rate (OLR) and stirring speed on volumetric hydrogen production rate (VHPR) was evaluated in a continuous stirred tank reactor (CSTR); by controlling the homoacetogenesis with the agitation speed and maintaining an OLR of 44 g COD/L-d, it was possible to reach a VHPR of 6 L H 2 /L-d, equivalent to 1.34 kJ/g bagasse. In the second stage, the effluent from CSTR was used as substrate to feed a UASB reactor for CH 4 production. Volumetric methane production rate (VMPR) of 6.4 L CH 4 /L-d was achieved with a high OLR (20 g COD/L-d) and short hydraulic retention time (HRT, 14 h), producing 225 mL CH 4 /g-bagasse equivalent to 7.88 kJ/g bagasse. The two-stage continuous process significantly increased energy conversion efficiency (56%) compared to one-stage hydrogen production (8.2%). Copyright © 2017 Elsevier Ltd. All rights reserved.

Effect of water on methane adsorption on the kaolinite (0 0 1) surface based on molecular simulations

NASA Astrophysics Data System (ADS)

Zhang, Bin; Kang, Jianting; Kang, Tianhe

2018-05-01

CH4 adsorption isotherms of kaolinite with moisture contents ranging from 0 to 5 wt% water, the effects of water on maximum adsorption capacity, kaolinite swelling, and radial distribution function were modelled by the implementing combined Monte Carlo (MC) and molecular dynamics (MD) simulations at 293.15 K (20 °C) and a pressure range of 1-20 MPa. The simulation results showed that the absolute adsorption of CH4 on both dry and moist kaolinite followed a Langmuir isotherm within the simulated pressure range, and both the adsorption capacity and the rate of CH4 adsorption decreased with the water content increases. The adsorption isosteric heats of CH4 on kaolinite decreased linearly with increasing water content, indicating that at higher water contents, the interaction energy between the CH4 and kaolinite was weaker. The interaction between kaolinite and water dominates and was the main contributing factor to kaolinite clay swelling. Water molecules were preferentially adsorbed onto oxygen and hydrogen atoms in kaolinite, while methane showed a tendency to be adsorbed only onto oxygen. The simulation results of our study provide the quantitative analysis of effect of water on CH4 adsorption capacity, adsorption rate, and interaction energy from a microscopic perspective. We hope that our study will contribute to the development of strategies for the further exploration of coal bed methane and shale gas.

Development of an algorithm to meaningfully interpret patterns in street-level methane concentrations

NASA Astrophysics Data System (ADS)

von Fischer, Joseph; Salo, Jessica; Griebenow, Claire; Bischak, Linde; Cooley, Daniel; Ham, Jay; Schumacher, Russ

2013-04-01

Methane (CH4) is an important greenhouse gas that has 70x greater heat forcing per molecule than CO2 over its ~10 year atmospheric residence time. Given this short residence time, there has been a surge of interest in mitigating anthropogenic CH4 sources because they will have a more immediate effect on warming rates. Recent observations of CH4 concentrations around the city of Boston reveal that natural gas distribution systems can have a very large number of leaks. However, there are a number of conceptual and practical challenges associated with interpretation of CH4 data gathered by car at the street level. In this presentation, we detail our efforts to develop an "algorithm" or set of standard practices for interpreting these patterns based on our own findings. At the most basic, we have evaluated approaches for vehicle driving patterns and management of the raw data. We also identify techniques for evaluating data quality and discerning when elevated CH4 may be due to other vehicles (e.g., CNG-powered city buses). We then compare methods for identifying "peaks" in CH4 concentration, and we discuss several approaches for relating concentration, space and wind data to emission rates. Finally, we provide some considerations for how the data from individual peaks might be aggregated to larger spatial scales.

Low temperature rate coefficients for the reactions of 1CH2 with reactive and non-reactive species, and the implications for Titan's atmosphere

NASA Astrophysics Data System (ADS)

Douglas, Kevin; Slater, Eloise; Blitz, Mark; Plane, John; Heard, Dwayne; Seakins, Paul

2016-04-01

The Cassini-Huygens mission to Titan revealed unexpectedly large amounts of benzene in the troposphere, and confirmed the absence of a global ethane ocean as predicted by photochemical models of methane conversion over the lifetime of the solar system. An important chemical intermediate in both the production and loss of benzene and ethane is the first electronically excited state of methylene, 1CH2. For example, at room temperature an important reaction of 1CH2 is with acetylene (R1a), leading to the formation of propargyl (C3H3)[1]. The subsequent recombination of propargyl radicals is the major suggested route to benzene in Titan's atmosphere (R2)[2]. In addition to reaction of 1CH2 leading to products, there is also competition between inelastic electronic relaxation to form the ground triplet state 3CH2 (R1b). This ground state 3CH2 has a markedly different reactivity to the singlet, reacting primarily with methyl radicals (CH3) to form ethene (R3). As methyl radical recombination is the primary route to ethane (R4)[3], reactions of 1CH2 will also heavily influence the ethane budget on Titan. 1CH2 + C2H2 → C3H3 + H (R1a) 1CH2 + C2H2 → 3CH2 + C2H2 (R1b) C3H3 + C3H3 → C6H6 (R2) 3CH2 + CH3 → C2H4 + H (R3) CH3 + CH3 (+ M) → C2H6 (R4) Thus this competition between chemical reaction and electronic relaxation in the reactions of 1CH2 with H2, CH4, C2H4, and C2H6 will play an important role in determining the benzene and ethane budgets on Titan. Despite this there are no measurements of any rate constants for 1CH2 at temperatures relevant to Titan's atmosphere (60 - 170 K). Using a pulsed Laval nozzle apparatus coupled with pulsed laser photolysis laser-induced fluorescence, the low temperature reaction kinetics for the removal of 1CH2 with nitrogen, hydrogen, methane, ethane, ethene, acetylene, and oxygen, have been studied. The results revealed an increase in the removal rate of 1CH2 at temperatures below 200 K, with a sharp increase of around a factor of 5 observed at 45±5 K. In addition to measuring total removal rates of 1CH2, the fraction of 1CH2 removed via electronic relaxation verses chemical reaction to products has also been investigated. Results for the reactive species ethane, ethene, and acetylene at 45±5 K, and for hydrogen and methane at 73±9 K indicate that following reactions with 1CH2, removal of 1CH2 is predominantly due to electronic relaxation (> 95 %) and not chemical reaction to products. This is in agreement with previous studies that show that with decreasing temperature, the fraction of reactive removal of 1CH2 to chemical products decreases while the fraction of removal by electronic relaxation increases[4][5]. These results indicate that 1CH2 formed in Titan's atmosphere will be rapidly relaxed to it's ground state via collisions with both reactive and non-reactive species, and thus will play a less significant role in the formation of larger hydrocarbons than previously thought. However for a full understanding of the implications of these results, the new measurements are to be included in a 1D model of Titan's atmosphere to determine the impact of the laboratory measurements on observation/model agreement. [1] K. Gannon et. al., J. Phys. Chem. A, (2010), 114, 9413 [2] E.H. Wilson, S.K. Atreya, J. Geophys. Res., (2004), 109, 6002 [3] M. Fulchignoni, Nature, (2005), 438, 785 [4] K. Gannon, Faraday Discuss., (2010), 147, 173 [5] K. Gannon, J. Phys. Chem. A, (2008), 112, 9575

Temperature Dependent Rate Coefficients for the Gas-Phase Reaction of the OH Radical with Linear (L2, L3) and Cyclic (D3, D4) Permethylsiloxanes.

PubMed

Bernard, François; Papanastasiou, Dimitrios K; Papadimitriou, Vassileios C; Burkholder, James B

2018-05-03

Permethylsiloxanes are emitted into the atmosphere during production and use as personal care products, lubricants, and cleaning agents. The predominate atmospheric loss process for permethylsiloxanes is expected to be via gas-phase reaction with the OH radical. In this study, rate coefficients, k(T), for the OH radical gas-phase reaction with the two simplest linear and cyclic permethylsiloxanes were measured using a pulsed laser photolysis-laser induced fluorescence technique over the temperature range of 240-370 K and a relative rate method at 294 K: hexamethyldisiloxane ((CH 3 ) 3 SiOSi(CH 3 ) 3 , L 2 ), k 1 ; octamethyltrisiloxane ([(CH 3 ) 3 SiO] 2 Si(CH 3 ) 2 , L 3 ), k 2 ; hexamethylcyclotrisiloxane ([-Si(CH 3 ) 2 O-] 3 , D 3 ), k 3 ; and octamethylcyclotetrasiloxane ([-Si(CH 3 ) 2 O-] 4 , D 4 ), k 4 . The obtained k(294 K) values and temperature-dependence expressions for the 240-370 K temperature range are (cm 3 molecule -1 s -1 , 2σ absolute uncertainties): k 1 (294 K) = (1.28 ± 0.08) × 10 -12 , k 1 ( T) = (1.87 ± 0.18) × 10 -11 exp(-(791 ± 27)/ T); k 2 (294 K) = (1.72 ± 0.10) × 10 -12 , k 2 ( T) = 1.96 × 10 -13 (T/298) 4.34 exp(657/ T); k 3 (294 K) = (0.82 ± 0.05) × 10 -12 , k 3 ( T) = (1.29 ± 0.19) × 10 -11 exp(-(805 ± 43)/ T); and k 4 (294 K) = (1.12 ± 0.10) × 10 -12 , k 4 ( T) = (1.80 ± 0.26) × 10 -11 exp(-(816 ± 43)/ T). The cyclic molecules were found to be less reactive than the analogous linear molecule with the same number of -CH 3 groups, while the linear and cyclic permethylsiloxane reactivity both increase with the increasing number of CH 3 - groups. The present results are compared with previous rate coefficient determinations where available. The permethylsiloxanes included in this study are atmospherically short-lived compounds with estimated atmospheric lifetimes of 11, 8, 17, and 13 days, respectively.

A theoretical study of three gas-phase reactions involving the production or loss of methane cations.

PubMed

Baptista, Leonardo; da Silveira, Enio F

2014-10-21

Hydrocarbon ions are important species in flames, spectroscopy and the interstellar medium. Their importance is reflected in the extensive body of literature on the structure and reactivity of carbocations. However, the geometry, electronic structure and reactivity of carbocations are difficult to assess. This study aims to contribute to the current knowledge of this subject by presenting a quantum mechanics description of methane cation dissociation using multiconfigurational methods. The geometric and electronic parameters of the minimum structure were determined for three main reaction paths: the dissociation CH4(+)→ CH2(+) + H2 and the dissociation-recombination processes CH4(+)↔ CH3(+) + H. The electronic and energetic effects of these reactions were analyzed, and it was found that each reaction path has a strong dependence on the methodology used as well as a strong multiconfigurational character during dissociation. The first doublet excited states are inner-shell excited states and may correspond to the ions that are expected to be formed after electron detachment. The rate coefficient for each reaction path was determined using variational transition state theory and RRKM/master equation calculations. The major dissociation paths, with their rate coefficients at the high-pressure limit, are CH4(+)(X(~)(2)B1) → CH3(+)(A(2)A1') + H((2)S) (k∞(T) = 1.42 × 10(+14) s(-1) exp(-37.12/RT)) and CH4(+)(X(~)(2)B1) → CH2(+)(A(2)A1) + H2((2)Σg(+)) (k∞(T) = 9.18 × 10(+14) s(-1) exp(-55.77/RT)). Our findings help to explain the abundance of ions formed from CH4 in the interstellar medium and to build models of chemical evolution.

Electron acceptor-based regulation of microbial greenhouse gas production from thawing permafrost

NASA Astrophysics Data System (ADS)

Bak, Ebbe; Jones, Eleanor; Yde, Jacob; Hodson, Andy; Mallon, Gunnar; Fisnter, Kai

2017-04-01

Permafrost contains about 35% of the global soil organic carbon (0-3 m depth). As a consequence of global warming, the active layer thickness is steadily increasing and its organic carbon is becoming available for degradation, causing a concomitant release of CO2 and CH4. The climate forcing feedbacks of permafrost thaw are determined by the rate of organic carbon degradation and to which degree it is released as CO2 or CH4. Methane is produced under anoxic conditions, but the factors that regulate its production are poorly constrained. In this study, we investigate how CH4 production is influenced by the presence of competing anaerobic processes with focus on the role of iron and sulfate reduction. We have collected permafrost cores to 2.2 meters depth from three different lowland sites in Adventdalen on Svalbard. From these cores, we have prepared anoxic batch incubation for each 25 cm depth interval and followed the production of CO2 and CH4 as well as the iron and sulfate reduction. This approach allows us to monitor the rate of the CO2 and CH4 production as well as to investigate the correlation between CH4 production and competing anaerobic respiration processes in the active layer as well in the permafrost. These investigations are accompanied by characterization of the carbon, iron and sulfate content in the soil and will be followed by characterization of the microbial community structure. The aim of this study is to get a better understanding of how the availability of sulfate and iron and the microbial community structure regulate the production of CO2 and CH4 in thawing permafrost, and to elucidate how the rate of the organic carbon degradation changes with depth in permafrost-affected soils. This study improves our understanding of climate feedback mechanisms operating during permafrost thaw.

Enhanced simulations of CH4 and CO2 production in permafrost-affected soils address soil moisture controls on anaerobic decomposition

NASA Astrophysics Data System (ADS)

Graham, D. E.; Zheng, J.; Moon, J. W.; Painter, S. L.; Thornton, P. E.; Gu, B.; Wullschleger, S. D.

2017-12-01

Rapid warming of Arctic ecosystems exposes soil organic carbon (SOC) to accelerated microbial decomposition, leading to increased emissions of carbon dioxide (CO2) and methane (CH4) that have a positive feedback on global warming. The magnitude, timing, and form of carbon release will depend not only on changes in temperature, but also on biogeochemical and hydrological properties of soils. In this synthesis study, we assessed the decomposability of thawed organic carbon from active layer soils and permafrost from the Barrow Environmental Observatory across different microtopographic positions under anoxic conditions. The main objectives of this study were to (i) examine environmental conditions and soil properties that control anaerobic carbon decomposition and carbon release (as both CO2 and CH4); (ii) develop a common set of parameters to simulate anaerobic CO2 and CH4 production; and (iii) evaluate uncertainties generated from representations of pH and temperature effects in the current model framework. A newly developed anaerobic carbon decomposition framework simulated incubation experiment results across a range of soil water contents. Anaerobic CO2 and CH4 production have different temperature and pH sensitivities, which are not well represented in current biogeochemical models. Distinct dynamics of CH4 production at -2° C suggest methanogen biomass and growth rate limit activity in these near-frozen soils, compared to warmer temperatures. Anaerobic CO2 production is well constrained by the model using data-informed labile carbon pool and fermentation rate initialization to accurately simulate its temperature sensitivity. On the other hand, CH4 production is controlled by water content, methanogenesis biomass, and the presence of alternative electron acceptors, producing a high temperature sensitivity with large uncertainties for methanogenesis. This set of environmental constraints to methanogenesis is likely to undergo drastic changes due to permafrost thawing, and extrapolation of methanogenesis rates into a future warmer climate remains challenging.

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

PubMed

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

2015-04-01

Accurately quantifying methane (CH4) and nitrous oxide (N2O) emissions from beef operations in China is necessary to evaluate the contribution of beef cattle to greenhouse gas budgets at the national and global level. Methane and N2O emissions from two intensive beef feedlots in the North China Plain, one with a restricted feeding strategy and high manure collection frequency and the other with an ad libitum feeding strategy and low manure collection frequency, were quantified in the fall and spring seasons using an inverse dispersion technique. The diel pattern of CH4 from the beef feedlot with an ad libitum feed strategy (single peak during a day) differed from that under a restricted feeding condition (multiple peaks during a day), but little difference in the diel pattern of N2O emissions between two feeding strategies was observed. The two-season average CH4 emission rates of the two intensive feedlots were 230 and 198gCH4animal(-1)d(-1) and accounted for 6.7% and 6.8% of the gross energy intake, respectively, indicating little impact of the feeding strategy and manure collection frequency on the CH4 conversion factor at the feedlot level. However, the average N2O emission rates (21.2g N2Oanimal(-1)d(-1)) and conversion factor (8.5%) of the feedlot with low manure collection frequency were approximately 131% and 174% greater, respectively, than the feedlot under high frequency conditions, which had a N2O emission rate and conversion factor of 9.2g N2Oanimal(-1)d(-1) and 3.1%, respectively, indicating that increasing manure collection frequency played an important role in reducing N2O emissions from beef feedlots. In addition, comparison indicated that China's beef and dairy cattle in feedlots appeared to have similar CH4 conversion factors. Copyright © 2015 Elsevier Inc. All rights reserved.

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.

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

Ruser, R.; Schilling, R.; Steindl, H.

This study was conducted to determine the effect of soil compaction and N fertilization on the fluxes of N{sub 2}O and CH{sub 4} in a soil planted with potato (Solanum tuberosum L.). Fluxes of N{sub 2}O and CH{sub 4} were measured weekly for 1 yr on two differently fertilized fields. For the potato cropping period (May-September) these fluxes were quantified separately for the ridges covering two-thirds of the total field area, and for the uncompacted and the tractor-traffic-compacted interrow soils, each of which made up one-sixth of the field area. The annual N{sub 2}O-N emissions for the low and themore » high rates of N fertilization were 8 and 16 kg ha{sup {minus}1}, respectively. The major part (68%) of the total N{sub 2}O release from the fields during the cropping period was emitted from the compacted tractor tramlines; emissions from the ridges made up only 23%. The annual CH{sub 4}-C uptake was 140 and 118 g ha{sup {minus}1} for the low and high levels of fertilization, respectively. The ridge soil and the uncompacted interrow had mean CH{sub 4}-C oxidation rates of 3.8 and 0.8 {micro}g m{sup {minus}2} h{sup {minus}1}, respectively; however, the tractor-compacted soil released CH{sub 4} at 2.1 {micro}g CH{sub 4}-C m{sup {minus}2} h{sup {minus}1}. The results indicate that soil compaction was probably the main reason for increased N{sub 2}O emission and reduced CH{sub 4} uptake of potato-cropped fields.« less

Greenhouse gas emissions from oilfield-produced water in Shengli Oilfield, Eastern China.

PubMed

Yang, Shuang; Yang, Wei; Chen, Guojun; Fang, Xuan; Lv, Chengfu; Zhong, Jiaai; Xue, Lianhua

2016-08-01

Greenhouse gas (GHG) emissions from oil and gas systems are an important component of the GHG emission inventory. To assess the carbon emissions from oilfield-produced water under atmospheric conditions correctly, in situ detection and simulation experiments were developed to study the natural release of GHG into the atmosphere in the Shengli Oilfield, the second largest oilfield in China. The results showed that methane (CH4) and carbon dioxide (CO2) were the primary gases released naturally from the oilfield-produced water. The atmospheric temperature and release time played important roles in determining the CH4 and CO2 emissions under atmospheric conditions. Higher temperatures enhanced the carbon emissions. The emissions of both CH4 and CO2 from oilfield-produced water were highest at 27°C and lowest at 3°C. The bulk of CH4 and CO2 was released from the oilfield-produced water during the first release period, 0-2hr, for each temperature, with a maximum average emission rate of 0.415gCH4/(m(3)·hr) and 3.934gCO2/(m(3)·hr), respectively. Then the carbon emissions at other time periods gradually decreased with the extension of time. The higher solubility of CO2 in water than CH4 results in a higher emission rate of CH4 than CO2 over the same release duration. The simulation proved that oilfield-produced water is one of the potential emission sources that should be given great attention in oil and gas systems. Copyright © 2016. Published by Elsevier B.V.

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.

Radiation chemistry in the Jovian stratosphere - Laboratory simulations

NASA Technical Reports Server (NTRS)

Mcdonald, Gene D.; Thompson, W. R.; Sagan, Carl

1992-01-01

The results of the present low-pressure/continuous-flow laboratory simulations of H2/He/CH4/NH3 atmospheres' plasma-induced chemistry indicate radiation yields of both hydrocarbon and N2-containing organic compounds which increase with decreasing pressure. On the basis of these findings, upper limits of 1 million-1 billion molecules/sq cm/sec are established for production rates of major auroral-chemistry species in the Jovian stratosphere. It is noted that auroral processes may account for 10-100 percent of the total abundances of most of the observed polar-region organic species.

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.

Annual methane budgets of sheep grazing systems were regulated by grazing intensities in the temperate continental steppe: A two-year case study

NASA Astrophysics Data System (ADS)

Ma, Lei; Zhong, Mengying; Zhu, Yuhao; Yang, Helong; Johnson, Douglas A.; Rong, Yuping

2018-02-01

Methane (CH4) emission from animal husbandry accounts for a large percentage of anthropogenic contributions to CH4 emissions. Fully understanding of grazing management effects on the CH4 budget is essential for mitigating CH4 emissions in the temperate grazing steppe systems. Annual CH4 budgets for the sheep grazed steppes at various grazing intensities, un-grazing (UG, 0 sheep ha-1year-1), defer grazing (DG, 1.0 sheep ha-1 year-1), moderate grazing (MG, 1.43 sheep ha-1year-1), and heavy grazing (HG, 2.43 sheep ha-1year-1) were assessed across 2012-2014 in the agro-pastoral region of northern China. Annual soil CH4 uptake averaged across 2012-2014 were 1.1 ± 0.1, 2.4 ± 0.2, 2.2 ± 0.2, and 1.3 ± 0.1 kg CH4-C ha-1 for UG, DG (only 2013-2014), MG and HG sites. Non-growing season CH4 uptake comprised 50.0 ± 4.3% of annual CH4 uptake in 2012-2013 and 37.7 ± 2.0% in 2013-2014. DG and MG significantly promoted annual soil CH4 uptake (P < 0.05), while there was no difference between HG and UG (P > 0.05). Bell-shaped relationship was presented between stocking rates and soil CH4 uptake (r2 = 0.59, P < 0.05). Annual soil CH4 uptake significant linearly and positively correlated with root biomass (r2 = 0.30, P < 0.05). Annual CH4 budgets for the grazed grasslands were -1.1 ± 0.1, 5.7 ± 0.6, 11.5 ± 1.5 and 15.5 ± 1.3 kg CH4-C ha-1 year-1 in UG, DG (only 2013-2014), MG and HG across 2012-2014. Soil CH4 uptake could offset 29.7 ± 5.6, 15.9 ± 4.3 and 6.8 ± 1.0% of total annual CH4 emissions from sheep, sheepfold and faeces in DG, MG, and HG. All grazed steppes are sources for atmospheric CH4 and the magnitude is regulated by grazing intensities. Sheep CH4 emissions for 1-g liveweight gain were 0.21, 0.32 and 0.37 g CH4-C in DG, MG and HG, respectively. DG is the recommended grazing management in this region to achieve greater herbage mass, higher sheep performance and lower CH4 emissions simultaneously.

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.

Historic CH4 Records from Antarctic and Greenland Ice Cores, Antarctic Firn Data, and Archived Air Samples from Cape Grim, Tasmania

DOE Data Explorer

Etheridge, D. M. [Division of Atmospheric Research, CSIRO, Aspendale, Victoria, Australia; Steele, L. P. [Division of Atmospheric Research, CSIRO, Aspendale, Victoria, Australia; Francey, R. J. [Division of Atmospheric Research, CSIRO, Aspendale, Victoria, Australia; Langenfelds, R. L. [Division of Atmospheric Research, CSIRO, Aspendale, Victoria, Australia

2002-01-01

The Antarctic CH4 records presented here are derived from three ice cores obtained at Law Dome, East Antarctica (66°44'S, 112°50'E, 1390 meters above mean sea level). Law Dome has many qualities of an ideal ice core site for the reconstruction of past concentrations of atmospheric gases; these qualities include: negligible melting of the ice sheet surface, low concentrations of impurities, regular stratigraphic layering undisturbed by wind stress at the surface or differential ice flow at depth, and a high snow accumulation rate. Further details on the site, drilling, and cores are provided by Etheridge et al. (1998), Etheridge et al. (1996), Etheridge and Wookey (1989), and Morgan et al. (1997). The two Greenland ice cores are from the Summit region (72°34' N, 37°37' W, 3200 meters above mean sea level). Lower snow accumulation rate there results in lower air-age resolution, and measurements presented here cover only the pre-industrial period (until 1885). More details about these measurements are presented in Etheridge et al. (1998). Additionally, this site contains firn data from Core DE08-2, and archived air samples from Cape Grim, Tasmania, for comparison.

Gas Leak Detection by Dilution of Atmospheric Oxygen

PubMed Central

Lambrecht, Armin; Maier, Eric; Strahl, Thomas; Herbst, Johannes

2017-01-01

Gas leak detection is an important issue in infrastructure monitoring and industrial production. In this context, infrared (IR) absorption spectroscopy is a major measurement method. It can be applied in an extractive or remote detection scheme. Tunable laser spectroscopy (TLS) instruments are able to detect CH4 leaks with column densities below 10 ppm·m from a distance of 30 m in less than a second. However, leak detection of non-IR absorbing gases such as N2 is not possible in this manner. Due to the fact that any leaking gas displaces or dilutes the surrounding background gas, an indirect detection is still possible. It is shown by sensitive TLS measurements of the ambient background concentration of O2 that N2 leaks can be localized with extractive and standoff methods for distances below 1 m. Minimum leak rates of 0.1 mbar·L/s were determined. Flow simulations confirm that the leakage gas typically effuses in a narrow jet. The sensitivity is mainly determined by ambient flow conditions. Compared to TLS detection of CH4 at 1651 nm, the indirect method using O2 at 761 nm is experimentally found to be less sensitive by a factor of 100. However, the well-established TLS of O2 may become a universal tool for rapid leakage screening of vessels that contain unknown or inexpensive gases, such as N2. PMID:29206133

Methane emissions from Alaska Arctic tundra - An assessment of local spatial variability

NASA Technical Reports Server (NTRS)

Morrissey, L. A.; Livingston, G. P.

1992-01-01

The findings of an extensive midsummer survey of CH4 emissions measurements representing the Alaska Arctic tundra are presented. Variability in rates of emissions was similar in magnitude on local and regional scales, ranging from 0 to 286.5 mg/sq m/d overall and often varying across two orders of magnitude within 0.5 m distances. Primary control on rates of emission was determined by the substrate and position of the water table relative to the surface. Emission rates in the Arctic Foothills ranged from 0.2 mg/sq m/d for tussock tundra to 55.53 mg/sq m/d over wet meadows. Plant-mediated release of CH4 to the atmosphere was directly proportional to green leaf area and represented 92-98 percent of the total emission rates over vegetated sites. The results suggest the current published emission rates may have overestimated the contribution of boreal ecosystems to the global CH4 budget by several fold.

Are Makemake and Eris Sputnik Planets?

NASA Astrophysics Data System (ADS)

Grundy, William M.; Umurhan, Orkan M.

2017-10-01

Makemake and Eris have high albedos (Sicardy et al. 2011; Ortiz et al. 2012) and show strong spectral absorption by CH4 ice (Licandro et al. 2006; Brown et al. 2007; Dumas et al. 2007). Energetic space radiation breaks C-H bonds in CH4 producing fragments that recombine into dark, red macromolecular materials (tholins, e.g., Johnson et al. 1987; Thompson et al. 1987; Strazzulla et al. 1991). This fact, coupled with Pluto's strong CH4 ice absorption bands and high albedo led Stern (1988) to pose the question "why is Pluto bright?". New Horizons has confirmed that Pluto refreshes its surface via seasonal volatile transport (e.g., Stern et al. 2015). However, one part of Pluto refreshes itself in a different way, too. This is the informally named Sputnik Planitia, a vast plain of volatile ice partly filling a probable impact basin. The ice is thick enough to act as a barrier to internal radiogenic heat flow, which drives convective overturning on 105 to 106 year timescales (e.g., McKinnon et al. 2016; Trowbridge et al 2016). Vigorous convection in Sputnik mixes radiolytic products from the surface down into the bulk of the ice, diluting it, and thus maintaining the high albedo of the surface.We propose that the surfaces of Eris and Makemake are similarly refreshed by convection in deep volatile ice deposits, perhaps covering the majority of their surfaces, unlike Pluto's Sputnik, which only covers a small fraction. The local fluxes of energetic radiation dictate production rates for tholin. Assuming steady-state production over the age of the solar system and mixing into the volatile ice, the colors and albedos of the bodies can be used to estimate the thickness of the volatile ice into which the tholin has been diluted through convective mixing. Likewise, for plausible radiogenic internal heat production, lower limits can be set on the thickness of the ice, to support convective mixing. We don't know the rheological properties of mixed N2+CH4 ice, let alone what happens when plausible additional contaminants, such as CO, Ar, C2H2, C2H4, C2H6, etc. are added, but bounding cases for N2-dominated and CH4-dominated ice compositions can be calculated.

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.

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.

Patterns of in-soil methane production and atmospheric emission among different land covers of a Lake Erie estuarine wetland

NASA Astrophysics Data System (ADS)

Rey Sanchez, C.; Morin, T. H.; Stefanik, K. C.; Angle, J.; Wrighton, K. C.; Bohrer, G.

2017-12-01

Wetland soils store a great amount of carbon, but also accumulate and emit methane (CH4), a powerful greenhouse gas. To better understand the vertical and horizontal spatial variability of CH4 emissions, we monitored production and fluxes of CH4 in Old Woman Creek, an estuarine wetland of Lake Erie, Ohio, during the growing seasons of 2015 and 2016. Our combined observation methods targeted three different scales: 1) the eddy covariance technique provided continuous high frequency observations integrated over a large spatial footprint; 2) monthly chamber measurements provided sparse point measurements of fluxes in four distinct land-cover types in the wetland: open water, emergent vegetation (Typha spp.), floating vegetation (Nelumbo spp.) and mud flats; and 3) in-situ porewater dialysis samplers, "peepers", provided vertical CH4 concentration data in the soil at the same locations and temporal time steps as the chambers. In addition, we studied gene transcripts to quantify methanogenesis activity along the vertical soil profile. Using integrated chamber and EC measurements, we found an average surface emission rate from Typha, the most abundant vegetated land cover, of 219.4 g CH4-C m-2 y-1, which was much higher than rates reported in similar emergent vegetation types in other wetlands. There was large spatial variation of flux rates, with mud flats having the highest rates of CH4 emission, followed by Nelumbo and Typha patches, and with open water having the lowest emissions. Within the soil column, we applied a numerical model to convert soil methane concentrations to emissions rates. We found that, contrary to current ideas of methane production, most methane was being produced in the well-oxygenated surface soils, probably in anoxic microsites within the oxic layer. Our metatranscriptomic data supported these findings, clearly showing nine times greater methanogenic activity in oxic surface soils relative to deeper anoxic soils. Combined, our results provide important insights for the representation of processes of methane production and consumption in models, which can largely affect the estimates of methane emission from wetlands.

High resolution FTIR spectroscopic study of the ν4 band of CH 3CHF 2 enclosed in a flow of cold N 2 gas

NASA Astrophysics Data System (ADS)

Appadoo, Dominique R. T.; Robertson, Evan G.; McNaughton, Don

2003-01-01

An enclosive flow cooling (EFC) cell has been constructed, and coupled to a Brüker IFS 120HR high resolution Fourier transform spectrometer to record rotationally cold absorption spectra of gases of atmospheric interest at high spectral resolution. The new system has been characterized using N 2O, revealing that rotational temperatures as cold as 110 K are readily attainable using liquid nitrogen as a cryogen. Infrared spectra of the ν4 band of 1,1-difluoroethane (R152a), CH 3CHF 2, cooled in the EFC cell have been measured at a resolution of 0.0019 cm-1. Eight hundred and twenty rovibrational transitions of the weak ν4 band with 2⩽ J'⩽46 and Kc'⩽16 were assigned and fitted to Watson's A-reduced Hamiltonian. The ν4 CH 3 symmetric deformation ( a/c-type) was found to be coupled to the ν13 asymmetric deformation ( b-type) via an a-axis Coriolis interaction. In the ensuing analysis, values of spectroscopic constants were obtained for both the ν4 and dark ν13 states. Supporting ab initio calculations up to the MP2/TZV+(3 df,3 p) level are presented.

Laboratory Study of the OH + Permethylsiloxane (L2, L3, D3, and D4) Reaction Rate Coefficients Between 240 and 370 K

NASA Astrophysics Data System (ADS)

Burkholder, J. B.; Bernard, F.; Papadimitriou, V. C.

2016-12-01

The atmospheric chemistry of organosiloxanes has recently been implicated in the formation of new particles as well as regional and indoor air quality. Methylsiloxanes with Si<6 are relatively volatile compounds with either linear or cyclic molecular structures. Methylsiloxanes are found in consumer goods such as cosmetics, textiles, health care and household products and in industrial applications as solvents and lubricants. They are released into the atmosphere during manufacturing, use, and disposal and have been observed in the atmosphere in ppb levels in certain locations. However, the fundamental chemical properties of this class of compounds, particularly their reactivity with the OH radical, are presently not fully characterized. In this work, the temperature dependence of the rate coefficients for the OH radical reaction with the simplest linear (L2 and L3) and cyclic (D3 and D4) siloxanes were measured: OH + (CH3)3SiOSi(CH3)3 = Products L2OH + [(CH3)3SiO]2Si(CH3)2 = Products L3OH + [-Si(CH3)2O-]3 = Products D3OH + [-Si(CH3)2O-]4 = Products D4OH rate coefficients were measured under pseudo-first conditions in OH over the temperature range 240-370 K using a pulsed laser photolysis-laser induced fluorescence (PLP-LIF) technique and at 296 K using a relative rate method. The present results are compared with available literature data where possible and discrepancies are discussed. The results from this work will be discussed in terms of the atmospheric lifetimes of these methylsiloxanes and the reactivity trends for this class of compound.

Sunflower Oil and Nannochloropsis oculata Microalgae as Sources of Unsaturated Fatty Acids for Mitigation of Methane Production and Enhancing Diets' Nutritive Value.

PubMed

Gomaa, Ali S; Kholif, Ahmed E; Kholif, Abdelkader M; Salama, Reda; El-Alamy, Hamza A; Olafadehan, Olurotimi A

2018-02-28

The objective of this assay was to investigate the effect of adding sunflower oil, Nannochloropsis oculata microalgae and their mixture at 0, 1, 2, 3, 4, and 5% to three total mixed rations (TMRs) with different concentrate:forage ratios (40C:60F, 50C:50F, and 60C:40F) on in vitro gas production (GP), methane (CH 4 ) production, and nutrient degradability. Asymptotic GP, GP rate, CH 4 concentration/g acid detergent fiber (ADF), dry matter (DM) degradability (DMD), short chain fatty acids (SCFAs), and ruminal bacteria population increased, but neutral detergent fiber (NDF) degradability (NDFD), ADF degradability (ADFD), and protozoa count decreased with increasing concentrate level in the TMR. Methane production/g DM and NDF was higher for 50C:50F TMR. Sunflower oil reduced asymptotic GP, lag time, CH 4 production/g ADF, ammonia-N (NH 3 -N), and SCFA. Compared to the control treatments, additives decreased GP rate, while sunflower oil/N. oculata mixture increased DMD and NDFD. All additives at 5% increased GP rate and lag time and decreased CH 4 production/g DM, ADF, and NDF, ruminal NH 3 -N, and protozoa count. All additives at 2% increased DMD, NDFD and ADFD, SCFA, and bacteria population. Supplementation of TMR, containing different concentrate:forage ratios, with sunflower oil, N. oculata, and sunflower oil/N. oculata mixture at different doses modified in vitro GP, CH 4 production, and nutrient degradability.

Beyond the Methanogenic Black-Box: Greenhouse Gas Fluxes (CO2, CH4, N2O) as Evidence for Wetlands as Dynamic Redox Systems

NASA Astrophysics Data System (ADS)

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

2015-12-01

Seminal wetland research in the 1990s demonstrated that annual methane (CH4) fluxes scaled positively with ecosystem production across distinctive wetlands globally. This relationship implies a model of flooded wetland ecosystems as 'methanogenic black-boxes'; poised at a low redox state, and tending to release a fixed fraction of incoming annual productivity as CH4. In contrast, recent studies have reported high ratios of carbon dioxide (CO2) to CH4 emissions, and are adding to a body of evidence suggesting wetlands can vary more widely in their redox state. To explore this apparent incongruence we used principles of redox thermodynamics and laboratory experiments to develop predictions of wetland greenhouse gas (GHG) fluxes under different redox regimes. We then used a field study to test the hypothesis that ecosystem seasonality in gross primary productivity (GPP) and temperature would drive changes in GHG emissions, mediated by a dynamic - as opposed to static - redox regime. We estimated wetland GHG emissions from an emergent marsh in the Sacramento Delta, CA from March 2014-2015. We measured CO2, CH4 and N2O emissions via diffusion and ebullition with manual sampling, and whole-ecosystem fluxes of CO2 and CH4 using eddy-covariance. Ebullition and diffusive CH4 fluxes were strongly seasonal, with minimum rates (0.86 and 0.35 mg C-CH­­4 m-2 yr-1, respectively) during winter, and maximum rates (1.3 and 1.8 g C-CH­­4 m-2 yr-1, respectively) during the summer growing season. In contrast, winter diffusive CO2 fluxes (494 g C-CO2 m-2 yr-1) and fall bubble CO2 concentrations (1.49%) were highest, despite being seasons of lower GPP, temperature, and CH4 flux. Further, diffusive and ebullition fluxes of N2O showed zero net flux only during spring and summer months, whereas the wetland was a significant source of N2O during winter (81.2 ± 24.4 mg N-N2O m-2 yr-1). These seasonal flux dynamics contradict a 'methanogenic black box' model of wetland redox, which predicts carbon limitation of, and concurrent maxima in, heterotrophic CO2 and CH4 emissions, and no significant N2O emissions. Rather these results suggest that wetlands can function as dynamic redox environments where GHG emission rate and composition varies predictably in time with seasonal changes in GPP and temperature.

Design and experimental verification of a photoacoustic flow sensor using computational fluid dynamics.

PubMed

Lassen, Mikael; Balslev-Harder, David; Brusch, Anders; Pelevic, Nikola; Persijn, Stefan; Petersen, Jan C

2018-02-01

A photoacoustic (PA) sensor for fast and real-time gas sensing is demonstrated. The PA sensor is a stand-alone system controlled by a field-programmable gate array. The PA cell has been designed for flow noise immunity using computational fluid dynamics (CFD) analysis. The aim of the CFD analysis was to investigate and minimize the influence of the gas distribution and flow noise on the PA signal. PA measurements were conducted at different flow rates by exciting molecular C-H stretch vibrational bands of hexane (C 6 H 14 ) and decane (C 10 H 22 ) molecules in clean air at 2950  cm -1 (3.38 μm) with a custom-made mid-infrared interband cascade laser. We observe a (1σ, standard deviation) sensitivity of 0.4±0.1  ppb (nmol/mol) for hexane in clean air at flow rates up to 1.7 L/min, corresponding to a normalized noise equivalent absorption coefficient of 2.5×10 -9   W cm -1   Hz -1/2 , demonstrating high sensitivity and fast real-time gas analysis. An Allan deviation analysis for decane shows that the detection limit at optimum integration time is 0.25 ppbV (nmol/mol).

Highly effective synthesis of a cobalt(ii) metal-organic coordination polymer by using continuous flow chemistry.

PubMed

Gong, Chunhua; Zhang, Junyong; Zeng, Xianghua; Xie, Jingli

2016-12-20

The coordination polymer [Co 2 L 4 (H 2 O) 2 ]·CH 3 CN·H 2 O (HL = (E)-2-[2-(4-chlorophenyl)vinyl]-8-hydroxyquinoline) has been achieved with 95% yield by using an Asia flow synthesis system (chip reactor). Compared with the conventional batch-type methods such as diffusion, reflux and solvothermal reactions, higher yielding reactions carried out in a flow reactor have demonstrated that this technique is a powerful strategy to obtain coordination compounds.

Integrated biogas upgrading and hydrogen utilization in an anaerobic reactor containing enriched hydrogenotrophic methanogenic culture.

PubMed

Luo, Gang; Angelidaki, Irini

2012-11-01

Biogas produced by anaerobic digestion, is mainly used in a gas motor for heat and electricity production. However, after removal of CO(2) , biogas can be upgraded to natural gas quality, giving more utilization possibilities, such as utilization as autogas, or distant utilization by using the existing natural gas grid. The current study presents a new biological method for biogas upgrading in a separate biogas reactor, containing enriched hydrogenotrophic methanogens and fed with biogas and hydrogen. Both mesophilic- and thermophilic anaerobic cultures were enriched to convert CO(2) to CH(4) by addition of H(2) . Enrichment at thermophilic temperature (55°C) resulted in CO(2) and H(2) bioconversion rate of 320 mL CH(4) /(gVSS h), which was more than 60% higher than that under mesophilic temperature (37°C). Different dominant species were found at mesophilic- and thermophilic-enriched cultures, as revealed by PCR-DGGE. Nonetheless, they all belonged to the order Methanobacteriales, which can mediate hydrogenotrophic methanogenesis. Biogas upgrading was then tested in a thermophilic anaerobic reactor under various operation conditions. By continuous addition of hydrogen in the biogas reactor, high degree of biogas upgrading was achieved. The produced biogas had a CH(4) content, around 95% at steady-state, at gas (mixture of biogas and hydrogen) injection rate of 6 L/(L day). The increase of gas injection rate to 12 L/(L day) resulted in the decrease of CH(4) content to around 90%. Further study showed that by decreasing the gas-liquid mass transfer by increasing the stirring speed of the mixture the CH(4) content was increased to around 95%. Finally, the CH(4) content around 90% was achieved in this study with the gas injection rate as high as 24 L/(L day). Copyright © 2012 Wiley Periodicals, Inc.

Enhanced methane emissions from tropical wetlands during the 2011 La Niña

PubMed Central

Pandey, Sudhanshu; Houweling, Sander; Krol, Maarten; Aben, Ilse; Monteil, Guillaume; Nechita-Banda, Narcisa; Dlugokencky, Edward J.; Detmers, Rob; Hasekamp, Otto; Xu, Xiyan; Riley, William J.; Poulter, Benjamin; Zhang, Zhen; McDonald, Kyle C.; White, James W. C.; Bousquet, Philippe; Röckmann, Thomas

2017-01-01

Year-to-year variations in the atmospheric methane (CH4) growth rate show significant correlation with climatic drivers. The second half of 2010 and the first half of 2011 experienced the strongest La Niña since the early 1980s, when global surface networks started monitoring atmospheric CH4 mole fractions. We use these surface measurements, retrievals of column-averaged CH4 mole fractions from GOSAT, new wetland inundation estimates, and atmospheric δ13C-CH4 measurements to estimate the impact of this strong La Niña on the global atmospheric CH4 budget. By performing atmospheric inversions, we find evidence of an increase in tropical CH4 emissions of ∼6–9 TgCH4 yr−1 during this event. Stable isotope data suggest that biogenic sources are the cause of this emission increase. We find a simultaneous expansion of wetland area, driven by the excess precipitation over the Tropical continents during the La Niña. Two process-based wetland models predict increases in wetland area consistent with observationally-constrained values, but substantially smaller per-area CH4 emissions, highlighting the need for improvements in such models. Overall, tropical wetland emissions during the strong La Niña were at least by 5% larger than the long-term mean. PMID:28393869

Evaluation of thermodynamically favourable operating conditions for production of hydrogen in three different reforming technologies

NASA Astrophysics Data System (ADS)

Seo, Y.-S.; Shirley, A.; Kolaczkowski, S. T.

With the aid of thermodynamic analysis using AspenPlus™, the characteristics of three different types of reforming process are investigated. These include: steam-methane reforming (SMR), partial oxidation (POX) and autothermal reforming (ATR). Thereby, favourable operating conditions are identified for each process. The optimum steam-to-carbon (S:C) ratio of the SMR reactor is found to be 1.9. The optimum air ratio of the POX reactor is 0.3 at a preheat temperature of 312 °C. The optimum air ratio and S:C ratio of the ATR reactor are 0.29 and 0.35, respectively at a preheat temperature of 400 °C. Simulated material and energy balances show that the CH 4 flow rates required to generate 1 mol s -1 of hydrogen are 0.364 mol s -1 for POX, 0.367 mol s -1 for ATR and 0.385 mol s -1 for the SMR. These results demonstrate that the POX reforming system has the lowest energy cost to produce the same amount of hydrogen from CH 4.

Artificial leaf device for solar fuel production.

PubMed

Amao, Yutaka; Shuto, Naho; Furuno, Kana; Obata, Asami; Fuchino, Yoshiko; Uemura, Keiko; Kajino, Tsutomu; Sekito, Takeshi; Iwai, Satoshi; Miyamoto, Yasushi; Matsuda, Masatoshi

2012-01-01

Solar fuels, such as hydrogen gas produced from water and methanol produced from carbon dioxide reduction by artificial photosynthesis, have received considerable attention. In natural leaves the photosynthetic proteins are well-organized in the thylakoid membrane. To develop an artificial leaf device for solar low-carbon fuel production from CO2, a chlorophyll derivative chlorin-e6 (Chl-e6; photosensitizer), 1-carboxylundecanoyl-1'-methyl-4,4'-bipyrizinium bromide, iodide (CH3V(CH2)9COOH; the electron carrier) and formate dehydrogenase (FDH) (the catalyst) immobilised onto a silica-gel-based thin layer chromatography plate (the Chl-V-FDH device) was investigated. From luminescence spectroscopy measurements, the photoexcited triplet state of Chl-e6 was quenched by the CH3V(CH2)9COOH moiety on the device, indicating the photoinduced electron transfer from the photoexcited triplet state of Chl-e6 to the CH3V(CH2)9COOH moiety. When the CO2-saturated sample solution containing NADPH (the electron donor) was flowed onto the Chl-V-FDH device under visible light irradiation, the formic acid concentration increased with increasing irradiation time.

Measurement and prediction of enteric methane emission

NASA Astrophysics Data System (ADS)

Sejian, Veerasamy; Lal, Rattan; Lakritz, Jeffrey; Ezeji, Thaddeus

2011-01-01

The greenhouse gas (GHG) emissions from the agricultural sector account for about 25.5% of total global anthropogenic emission. While CO2 receives the most attention as a factor relative to global warming, CH4, N2O and chlorofluorocarbons (CFCs) also cause significant radiative forcing. With the relative global warming potential of 25 compared with CO2, CH4 is one of the most important GHGs. This article reviews the prediction models, estimation methodology and strategies for reducing enteric CH4 emissions. Emission of CH4 in ruminants differs among developed and developing countries, depending on factors like animal species, breed, pH of rumen fluid, ratio of acetate:propionate, methanogen population, composition of diet and amount of concentrate fed. Among the ruminant animals, cattle contribute the most towards the greenhouse effect through methane emission followed by sheep, goats and buffalos, respectively. The estimated CH4 emission rate per cattle, buffaloe, sheep and goat in developed countries are 150.7, 137, 21.9 and 13.7 (g/animal/day) respectively. However, the estimated rates in developing countries are significantly lower at 95.9 and 13.7 (g/animal/day) per cattle and sheep, respectively. There exists a strong interest in developing new and improving the existing CH4 prediction models to identify mitigation strategies for reducing the overall CH4 emissions. A synthesis of the available literature suggests that the mechanistic models are superior to empirical models in accurately predicting the CH4 emission from dairy farms. The latest development in prediction model is the integrated farm system model which is a process-based whole-farm simulation technique. Several techniques are used to quantify enteric CH4 emissions starting from whole animal chambers to sulfur hexafluoride (SF6) tracer techniques. The latest technology developed to estimate CH4 more accurately is the micrometeorological mass difference technique. Because the conditions under which animals are managed vary greatly by country, CH4 emissions reduction strategies must be tailored to country-specific circumstances. Strategies that are cost effective, improve productivity, and have limited potential negative effects on livestock production hold a greater chance of being adopted by producers. It is also important to evaluate CH4 mitigation strategies in terms of the total GHG budget and to consider the economics of various strategies. Although reductions in GHG emissions from livestock industries are seen as high priorities, strategies for reducing emissions should not reduce the economic viability of enterprises.

Soil methane and CO2 fluxes in rainforest and rubber plantations

NASA Astrophysics Data System (ADS)

Lang, Rong; Blagodatsky, Sergey; Goldberg, Stefanie; Xu, Jianchu

2017-04-01

Expansion of rubber plantations in South-East Asia has been a land use transformation trend leading to losses of natural forest cover in the region. Besides impact on ecosystem carbon stocks, this conversion influences the dynamics of greenhouse gas fluxes from soil driven by microbial activity, which has been insufficiently studied. Aimed to understand how land use change affects the soil CO2 and CH4 fluxes, we measured surface gas fluxes, gas concentration gradient, and 13C signature in CH4 and soil organic matter in profiles in a transect in Xishuangbanna, including a rainforest site and three rubber plantation sites with age gradient. Gas fluxes were measured by static chamber method and open chamber respiration system. Soil gases were sampled from installed gas samplers at 5, 10, 30, and 75cm depth at representative time in dry and rainy season. The soil CO2 flux was comparable in rainforest and old rubber plantations, while young rubber plantation had the lowest rate. Total carbon content in the surface soil well explained the difference of soil CO2 flux between sites. All sites were CH4 sinks in dry season and uptake decreased in the order of rainforest, old rubber plantations and young rubber plantation. From dry season to rainy season, CH4 consumption decreased with increasing CH4 concentration in the soil profile at all depths. The enrichment of methane by 13CH4 shifted towards to lowerδ13C, being the evidence of enhanced CH4 production process while net surface methane flux reflected the consumption in wet condition. Increment of CH4 concentration in the profile from dry to rainy season was higher in old rubber plantation compared to rainforest, while the shifting of δ13CH4 was larger in rainforest than rubber sites. Turnover rates of soil CO2 and CH4 suggested that the 0-5 cm surface soil was the most active layer for gaseous carbon exchange. δ13C in soil organic matter and soil moisture increased from rainforest, young rubber plantation to old rubber plantations. Conversion the forest into rubber plantation decreased soil respiration in young plantation and it recovered during rubber development. However, the CH4consumption by tropical upland forest soil decreased in converted rubber plantations of all ages, with more decrement in old plantation. Change forest into rubber plantations weakened the soil function as CH4 sink.

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.

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.

Biogasification of papaya processing wastes

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

Yang, P.Y.; Weitzenhoff, M.H.; Moy, J.H.

1984-01-01

Biogasification of papaya processing wastes for pollution control and energy utilization is feasible. The biogasification process with sludge recycling permits smaller reactor volume without any deterioration of CH4 production rate and CH4 content. Appropriate design and operational criteria for biogasification processing of papaya wastes were developed.

Large CH4 production fueled by autochthonous OC in an anoxic sediment

NASA Astrophysics Data System (ADS)

Grasset, Charlotte; Mendonça, Raquel; Villamor Saucedo, Gabriella; Sobek, Sebastian

2017-04-01

River damming and human-induced eutrophication both affect river and lake functioning, increase organic carbon (OC) sedimentation rates and generate anoxic conditions in bottom waters. Under these conditions, OC in sediments is decomposed into CO2 and CH4, a high potential greenhouse gas. It has been shown that the decomposition of land-derived (allochthonous) OC is inhibited at anoxic conditions, compared to OC internally produced (autochthonous). However, the overall extent and end products (CO2 or CH4) of anoxic decomposition remain poorly known for different types of OC, making it difficult to judge the effect of river damming and eutrophication on greenhouse gas emissions from inland waters. We incubated different types of allochthonous OC (terrestrial plants) and autochthonous OC (phytoplankton and aquatic vascular plants) in an anoxic sediment during 130 days. We aimed to test 1) if this addition of relatively fresh OC resulted in an increase of CH4 production and 2) if autochthonous OC would produce more CH4 than allochthonous OC. We assessed the contribution to CH4 production of the different OC sources (i.e. sediment or added OC) with stable isotope measurements. We found that the addition of relatively fresh OC greatly increased CH4 production. Autochthonous OC generally produced more CH4 than allochthonous OC, but the overall extent of CH4 production was highly variable between the different autochthonous OC types. The d13C-CH4 measurements indicated that CH4 originated exclusively from the added OC. We conclude that the production of CH4 is likely to to be high in eutrophic as well as in artificial lakes, especially when these systems have anoxic bottom waters and high internal primary productivity and thus a high supply of autochthonous OC to the sediment. The current expansion of reservoir construction in concert with almost globally prevalent anthropogenic eutrophication are therefore likely to increase CH4 production in inland waters.

Deep peat warming increases surface methane and carbon dioxide emissions in a black spruce-dominated ombrotrophic bog.

PubMed

Gill, Allison L; Giasson, Marc-André; Yu, Rieka; Finzi, Adrien C

2017-12-01

Boreal peatlands contain approximately 500 Pg carbon (C) in the soil, emit globally significant quantities of methane (CH 4 ), and are highly sensitive to climate change. Warming associated with global climate change is likely to increase the rate of the temperature-sensitive processes that decompose stored organic carbon and release carbon dioxide (CO 2 ) and CH 4 . Variation in the temperature sensitivity of CO 2 and CH 4 production and increased peat aerobicity due to enhanced growing-season evapotranspiration may alter the nature of peatland trace gas emission. As CH 4 is a powerful greenhouse gas with 34 times the warming potential of CO 2 , it is critical to understand how factors associated with global change will influence surface CO 2 and CH 4 fluxes. Here, we leverage the Spruce and Peatland Responses Under Changing Environments (SPRUCE) climate change manipulation experiment to understand the impact of a 0-9°C gradient in deep belowground warming ("Deep Peat Heat", DPH) on peat surface CO 2 and CH 4 fluxes. We find that DPH treatments increased both CO 2 and CH 4 emission. Methane production was more sensitive to warming than CO 2 production, decreasing the C-CO 2 :C-CH 4 of the respired carbon. Methane production is dominated by hydrogenotrophic methanogenesis but deep peat warming increased the δ 13 C of CH 4 suggesting an increasing contribution of acetoclastic methanogenesis to total CH 4 production with warming. Although the total quantity of C emitted from the SPRUCE Bog as CH 4 is <2%, CH 4 represents >50% of seasonal C emissions in the highest-warming treatments when adjusted for CO 2 equivalents on a 100-year timescale. These results suggest that warming in boreal regions may increase CH 4 emissions from peatlands and result in a positive feedback to ongoing warming. © 2017 John Wiley & Sons Ltd.

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.

Digital radiography reject analysis: data collection methodology, results, and recommendations from an in-depth investigation at two hospitals.

PubMed

Foos, David H; Sehnert, W James; Reiner, Bruce; Siegel, Eliot L; Segal, Arthur; Waldman, David L

2009-03-01

Reject analysis was performed on 288,000 computed radiography (CR) image records collected from a university hospital (UH) and a large community hospital (CH). Each record contains image information, such as body part and view position, exposure level, technologist identifier, and--if the image was rejected--the reason for rejection. Extensive database filtering was required to ensure the integrity of the reject-rate calculations. The reject rate for CR across all departments and across all exam types was 4.4% at UH and 4.9% at CH. The most frequently occurring exam types with reject rates of 8% or greater were found to be common to both institutions (skull/facial bones, shoulder, hip, spines, in-department chest, pelvis). Positioning errors and anatomy cutoff were the most frequently occurring reasons for rejection, accounting for 45% of rejects at CH and 56% at UH. Improper exposure was the next most frequently occurring reject reason (14% of rejects at CH and 13% at UH), followed by patient motion (11% of rejects at CH and 7% at UH). Chest exams were the most frequently performed exam at both institutions (26% at UH and 45% at CH) with half captured in-department and half captured using portable x-ray equipment. A ninefold greater reject rate was found for in-department (9%) versus portable chest exams (1%). Problems identified with the integrity of the data used for reject analysis can be mitigated in the future by objectifying quality assurance (QA) procedures and by standardizing the nomenclature and definitions for QA deficiencies.

Tracer-based Determination of Vortex Descent in the 1999/2000 Arctic Winter

NASA Technical Reports Server (NTRS)

Greenblatt, Jeffrey B.; Jost, Hans-Juerg; Loewenstein, Max; Podolske, James R.; Hurst, Dale F.; Elkins, James W.; Schauffler, Sue M.; Atlas, Elliot L.; Herman, Robert L.; Webster, Chrisotopher R.

2002-01-01

A detailed analysis of available in situ and remotely sensed N2O and CH4 data measured in the 1999/2000 winter Arctic vortex has been performed in order to quantify the temporal evolution of vortex descent. Differences in potential temperature (theta) among balloon and aircraft vertical profiles (an average of 19-23 K on a given N2O or CH4 isopleth) indicated significant vortex inhomogeneity in late fall as compared with late winter profiles. A composite fall vortex profile was constructed for 26 November 1999, whose error bars encompassed the observed variability. High-latitude extravortex profiles measured in different years and seasons revealed substantial variability in N2O and CH4 on theta surfaces, but all were clearly distinguishable from the first vortex profiles measured in late fall 1999. From these extravortex-vortex differences we inferred descent prior to 26 November: as much as 397 plus or minus 15 K (lsigma) at 30 ppbv N2O and 640 ppbv CH4, and falling to 28 plus or minus 13 K above 200 ppbv N2O and 1280 ppbv CH4. Changes in theta were determined on five N2O and CH4 isopleths from 26 November through 12 March, and descent rates were calculated on each N2O isopleth for several time intervals. The maximum descent rates were seen between 26 November and 27 January: 0.82 plus or minus 0.20 K/day averaged over 50- 250 ppbv N2O. By late winter (26 February to 12 March), the average rate had decreased to 0.10 plus or minus 0.25 K/day. Descent rates also decreased with increasing N2O; the winter average (26 November to 5 March) descent rate varied from 0.75 plus or minus 0.10 K/day at 50 ppbv to 0.40 plus or minus 0.11 K/day at 250 ppbv. Comparison of these results with observations and models of descent in prior years showed very good overall agreement. Two models of the 1999/2000 vortex descent, SLIMCAT and REPROBUS, despite theta offsets with respect to observed profiles of up to 20 K on most tracer isopleths, produced descent rates that agreed very favorably with the inferred rates from observation.

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.

CO2 injection into submarine, CH4-hydrate bearing sediments: Parameter studies towards the development of a hydrate conversion technology

NASA Astrophysics Data System (ADS)

Deusner, Christian; Bigalke, Nikolaus; Kossel, Elke; Haeckel, Matthias

2013-04-01

In the recent past, international research efforts towards exploitation of submarine and permafrost hydrate reservoirs have increased substantially. Until now, findings indicate that a combination of different technical means such as depressurization, thermal stimulation and chemical activation is the most promising approach for producing gas from natural hydrates. Moreover, emission neutral exploitation of CH4-hydrates could potentially be achieved in a combined process with CO2 injection and storage as CO2-hydrate. In the German gas hydrate initiative SUGAR, a combination of experimental and numerical studies is used to elucidate the process mechanisms and technical parameters on different scales. Experiments were carried out in the novel high-pressure flow-through system NESSI (Natural Environment Simulator for sub-Seafloor Interactions). Recent findings suggest that the injection of heated, supercritical CO2 is beneficial for both CH4 production and CO2 retention. Among the parameters tested so far are the CO2 injection regime (alternating vs. continuous injection) and the reservoir pressure / temperature conditions. Currently, the influence of CO2 injection temperature is investigated. It was shown that CH4 production is optimal at intermediate reservoir temperatures (8 ° C) compared to lower (2 ° C) and higher temperatures (10 ° C). The reservoir pressure, however, was of minor importance for the production efficiency. At 8 ° C, where CH4- and CO2-hydrates are thermodynamically stable, CO2-hydrate formation appears to be slow. Eventual clogging of fluid conduits due to CO2-rich hydrate formation force open new conduits, thereby tapping different regions inside the CH4-hydrate sample volume for CH4gas. In contrast, at 2 ° C immediate formation of CO2-hydrate results in rapid and irreversible obstruction of the entire pore space. At 10 ° C pure CO2-hydrates can no longer be formed. Consequently the injected CO2 flows through quickly and interaction with the reservoir is minimized. Our results clearly indicate that the formation of mixed CH4-CO2-hydrates is an important aspect in the conversion process. The experimental studies have shown that the injection of heated CO2 into the hydrate reservoir induces a variety of spatial and temporal processes which result in substantial bulk heterogeneity. Current numerical simulators are not able to predict these process dynamics and it is important to improve available transport-reaction models (e.g. to include the effect of bulk sediment permeability on the conversion dynamics). Our results confirm that experimental studies are important to better understand the mechanisms of hydrate dissociation and conversion at CO2-injection conditions as a basis towards the development of a suitable hydrate conversion technology. The application of non-invasive analytical methods such as Magnetic Resonance Imaging (MRI) and Raman microscopy are important tools, which were applied to resolve process dynamics on the pore scale. Additionally, the NESSI system is being modified to allow high-pressure flow-through experiments under triaxial loading to better simulate hydrate-sediment mechanics. This aspect is important for overall process development and evaluation of process safety issues.

Growth of boron doped hydrogenated nanocrystalline cubic silicon carbide (3C-SiC) films by Hot Wire-CVD

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

Pawbake, Amit; Tata Institute of Fundamental Research, Colaba, Mumbai 400 005; Mayabadi, Azam

Highlights: • Boron doped nc-3C-SiC films prepared by HW-CVD using SiH{sub 4}/CH{sub 4}/B{sub 2}H{sub 6}. • 3C-Si-C films have preferred orientation in (1 1 1) direction. • Introduction of boron into SiC matrix retard the crystallanity in the film structure. • Film large number of SiC nanocrystallites embedded in the a-Si matrix. • Band gap values, E{sub Tauc} and E{sub 04} (E{sub 04} > E{sub Tauc}) decreases with increase in B{sub 2}H{sub 6} flow rate. - Abstract: Boron doped nanocrystalline cubic silicon carbide (3C-SiC) films have been prepared by HW-CVD using silane (SiH{sub 4})/methane (CH{sub 4})/diborane (B{sub 2}H{sub 6}) gasmore » mixture. The influence of boron doping on structural, optical, morphological and electrical properties have been investigated. The formation of 3C-SiC films have been confirmed by low angle XRD, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), Fourier transform infra-red (FTIR) spectroscopy and high resolution-transmission electron microscopy (HR-TEM) analysis whereas effective boron doping in nc-3C-SiC have been confirmed by conductivity, charge carrier activation energy, and Hall measurements. Raman spectroscopy and HR-TEM analysis revealed that introduction of boron into the SiC matrix retards the crystallanity in the film structure. The field emission scanning electron microscopy (FE-SEM) and non contact atomic force microscopy (NC-AFM) results signify that 3C-SiC film contain well resolved, large number of silicon carbide (SiC) nanocrystallites embedded in the a-Si matrix having rms surface roughness ∼1.64 nm. Hydrogen content in doped films are found smaller than that of un-doped films. Optical band gap values, E{sub Tauc} and E{sub 04} decreases with increase in B{sub 2}H{sub 6} flow rate.« less

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

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.

Methanogenesis, Mesospheric Clouds, and Global Habitability

NASA Technical Reports Server (NTRS)

Pueschel, Rudolf F.; Condon, Estelle P. (Technical Monitor)

2000-01-01

Hyperthermophilic methanogens can exist in a deep hot biosphere up to 110 C, or 10 km deep. Methane (CH4) itself is thermodynamically stable to depths of 300 km. Geologic (microbial plus abiogenic thermal) methane is transported upward, attested to by its association with helium, to form petroleum pools. Near or at the surface, geologic CH4 mixes with other natural and with anthropogenic CH4 yielding annual emissions into the atmosphere of 500 Tg, of which 200 Tg are natural and 300 Tg are man-made. The atmospheric lifetime of CH4, a greenhouse gas 20 times more effective than CO2 in raising global temperatures, is approximately 10 years. It is removed from the atmosphere mainly by reactions with hydroxyl radical (OH) to form CO2, but also by dry soil and by conversion to H2O in the stratosphere and middle atmosphere. A sudden rise in atmospheric temperatures by 9-12 C some 55 million years ago has been explained by the release in a few thousand years of three trillion tons of CH4 out of 15 trillion tons that had formed beneath the sea floor. What prevented this CH4-induced greenhouse effect from running away? An analog to the CH4-burp of 55 million years ago is the CH4-doubling over the past century which resulted in a increase in upper level H2O from 4.3 ppmv to 6 ppmv. This 30% increase in H2O vapor yielded a tenfold increase in brightness of polar mesospheric clouds because of a strong dependence of the ice particle nucleation rate on the water saturation ratios. Models show that at a given temperature the optical depth of mesospheric clouds scales as [H2O]beta with beta varying between 4 and 8. Radiative transfer tools applied to mesospheric particles suggest that an optical depth of approximately one, or 1000 times the current mesospheric cloud optical depth, would result in tropospheric cooling of about 10 K. Assuming beta=6, a thousandfold increase in optical thickness would require a three-fold increase of H2O, or a 20-fold increase of CH4. At the current rate of anthropogenic emissions this is expected to occur within the next 1000 years. This timescale is also commensurate with what has been assumed for the CH4- burp 55 million years ago.

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.

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

Isotopic constraints on methane's global sources and ENSO-dependence

NASA Astrophysics Data System (ADS)

Schaefer, Hinrich; Mikaloff Fletcher, Sara; Veidt, Cora; Lassey, Keith; Brailsford, Gordon; Bromley, Tony; Dlugokencky, Ed; Englund Michel, Sylvia; Miller, John; Levin, Ingeborg; Lowe, Dave; Martin, Ross; Vaughn, Bruce; White, James; Nichol, Sylvia

2017-04-01

Atmospheric levels of the potent greenhouse gas methane (CH4) have been rising since the industrial revolution, except for a plateau during the early 2000s. Stable carbon isotopes in methane (delta-13CH4) provide constraints on the budget changes associated with the plateau's onset and its end. We present a reconstruction of annual global delta-13CH4 averages based on a global network of stations, whose trends are indicative of global methane source and sink activity. A box model analysis shows that from the mid-1990s methane emissions with the characteristic thermogenic delta-13CH4 signature reduced, implying persistently lower emissions from fossil fuel productions as the cause of the plateau. However, variations in hydroxyl, the main CH4 sink, provide an equably plausible explanation for the plateau onset that may also account for strong variability in emission-vs-removal rates during the plateau period. In contrast, the renewed CH4 rise since 2006 can only be explained by increasing emissions with a biogenic isotope signature, i.e. agriculture or wetlands. We present correlation studies that test whether ENSO activity controls atmospheric delta-13CH4, and by extension methane levels, through tropical wetland emissions.

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.

Antibacterial Efficacy of Several Surgical Hand Preparation Products Used by Veterinary Students.

PubMed

Chou, Po-Yen; Doyle, Aimie J; Arai, Shiori; Burke, Pierre J; Bailey, Trina R

2016-05-01

To compare the antibacterial efficacy of different surgical hand antisepsis protocols used by veterinary students. Prospective, randomized, controlled study. Third year veterinary students (n=45). The participants were randomly assigned to 4 of the following 12 hand preparation product/time combinations: nonabrasive hand scrub method with 4% chlorhexidine gluconate (CH); hand rub with a mixture of 30% 1-propanol and 45% 2-propanol solution (MPS), 70% 2-propanol solution (IPS), or 61% ethanol solution with 1% chlorhexidine gluconate (ES/CH), with a contact time of 1.5, 3, or 5 minutes. Antibacterial efficacy was assessed after surgical hand preparation and at the end of surgery. Log reductions of total bacterial colony forming unit (CFU)/mL and positive aerobic culture rates were compared using multivariable analysis of variance and multivariable logistic regression, respectively. After surgical hand preparation, CH and ES/CH provided significantly higher log CFU reduction and lower positive culture rate for Gram-positive and spore-forming bacteria compared to MPS and IPS. Increase in contact time did not provide significant improvement in bacterial reduction. At the end of surgery, ES/CH provided significantly higher log CFU reduction compared to IPS and lower positive culture rate for Gram-positive bacteria compared to CH, MPS, and IPS. Increase in contact time significantly improved log CFU reduction in ES/CH and MPS groups. In our population of veterinary students ES/CH hand rubs or CH scrubs were more effective in reducing bacterial CFU during surgical hand preparation than MPS or IPS. © Copyright 2016 by The American College of Veterinary Surgeons.

Carbon and nitrogen dynamics and greenhouse gas emissions in constructed wetlands treating wastewater: a review

NASA Astrophysics Data System (ADS)

Jahangir, M. M. R.; Richards, K. G.; Healy, M. G.; Gill, L.; Müller, C.; Johnston, P.; Fenton, O.

2016-01-01

The removal efficiency of carbon (C) and nitrogen (N) in constructed wetlands (CWs) is very inconsistent and frequently does not reveal whether the removal processes are due to physical attenuation or whether the different species have been transformed to other reactive forms. Previous research on nutrient removal in CWs did not consider the dynamics of pollution swapping (the increase of one pollutant as a result of a measure introduced to reduce a different pollutant) driven by transformational processes within and around the system. This paper aims to address this knowledge gap by reviewing the biogeochemical dynamics and fate of C and N in CWs and their potential impact on the environment, and by presenting novel ways in which these knowledge gaps may be eliminated. Nutrient removal in CWs varies with the type of CW, vegetation, climate, season, geographical region, and management practices. Horizontal flow CWs tend to have good nitrate (NO3-) removal, as they provide good conditions for denitrification, but cannot remove ammonium (NH4+) due to limited ability to nitrify NH4+. Vertical flow CWs have good NH4+ removal, but their denitrification ability is low. Surface flow CWs decrease nitrous oxide (N2O) emissions but increase methane (CH4) emissions; subsurface flow CWs increase N2O and carbon dioxide (CO2) emissions, but decrease CH4 emissions. Mixed species of vegetation perform better than monocultures in increasing C and N removal and decreasing greenhouse gas (GHG) emissions, but empirical evidence is still scarce. Lower hydraulic loadings with higher hydraulic retention times enhance nutrient removal, but more empirical evidence is required to determine an optimum design. A conceptual model highlighting the current state of knowledge is presented and experimental work that should be undertaken to address knowledge gaps across CWs, vegetation and wastewater types, hydraulic loading rates and regimes, and retention times, is suggested. We recommend that further research on process-based C and N removal and on the balancing of end products into reactive and benign forms is critical to the assessment of the environmental performance of CWs.

Hydrogen and Methane Generation in Serpentinizing Systems: An Experimental Perspective

NASA Astrophysics Data System (ADS)

McCollom, T. M.; Klein, F.

2018-05-01

Experimental studies indicate rates of serpentinization as well as H2 and CH4 production are very sluggish at low temperatures. Temperatures >200–300 C or prolonged reaction times may be required to produce significant H2 and CH4 within icy worlds.

Effects of three methane mitigation agents on parameters of kinetics of total and hydrogen gas production, ruminal fermentation and hydrogen balance using in vitro technique.

PubMed

Wang, Min; Wang, Rong; Yang, Shan; Deng, Jin Ping; Tang, Shao Xun; Tan, Zhi Liang

2016-02-01

Methane (CH4 ) can be mitigated through directly inhibiting methanogen activity and starving methanogens by hydrogen (H2 ) sink. Three types of mechanism (i.e. bromoethanesulphonate (BES), nitrate and emodin) and doses of CH4 mitigation agents were employed to investigate their pathways of CH4 inhibition. Results indicated that both BES and emodin inhibited CH4 production and altered H2 balance, which could be accompanied by decreased dry matter disappearance (DMD), fractional rate of gH2 formation, volatile fatty acid (VFA) production, ability to produce and use reducing equivalences and molecular H2 , and increased final asymptotic gH2 production, time to the peak of gH2 , discrete lag time of gH2 production and fermentation efficiency. However, emodin decreased gas volume produced by rapidly fermentable components of substrate and the rate of fermentation at early stage of incubation, while BES supplementation inhibited gas volume produced by both rapidly and slowly fermentable components of substrate and the rate of fermentation at middle or late stage of incubation. The nitrate supplementation inhibited CH4 production without affecting VFA profile, because of its dual role as H2 sink and being toxic to methanogens. Nitrate supplementation had more complicated pattern of fermentation, VFA production and profile and H2 balance in comparison to BES and emodin supplementation. © 2015 Japanese Society of Animal Science.

Sourcing methane and carbon dioxide emissions from a small city: Influence of natural gas leakage and combustion.

PubMed

Chamberlain, Samuel D; Ingraffea, Anthony R; Sparks, Jed P

2016-11-01

Natural gas leakage and combustion are major sources of methane (CH 4 ) and carbon dioxide (CO 2 ), respectively; however, our understanding of emissions from cities is limited. We mapped distribution pipeline leakage using a mobile CH 4 detection system, and continuously monitored atmospheric CO 2 and CH 4 concentrations and carbon isotopes (δ 13 C-CO 2 and δ 13 C-CH 4 ) for one-year above Ithaca, New York. Pipeline leakage rates were low (<0.39 leaks mile -1 ), likely due to the small extent of cast iron and bare steel within the distribution pipeline system (2.6%). Our atmospheric monitoring demonstrated that the isotopic composition of locally emitted CO 2 approached the δ 13 C range of natural gas combustion in winter, correlating to natural gas power generation patterns at Cornell's Combined Heat and Power Plant located 600 m southeast of the monitoring site. Atmospheric CH 4 plumes were primarily of natural gas origin, were observed intermittently throughout the year, and were most frequent in winter and spring. No correlations between the timing of atmospheric natural gas CH 4 plumes and Cornell Plant gas use patterns could be drawn. However, elevated CH 4 and CO 2 concentrations were observed coincident with high winds from the southeast, and the plant is the only major emission source in that wind sector. Our results demonstrate pipeline leakage rates are low in cities with a low extent of leak prone pipe, and natural gas power facilities may be an important source of urban and suburban emissions. Copyright © 2016 Elsevier Ltd. All rights reserved.

Anaerobic digestion of paunch in a CSTR for renewable energy production and nutrient mineralization

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

Nkemka, Valentine Nkongndem; Marchbank, Douglas H.; Hao, Xiying, E-mail: xiying.hao@agr.gc.ca

Highlights: • Anaerobic digestion and nutrient mineralization of paunch in a CSTR. • Low CH{sub 4} yield and high CH{sub 4} productivity was obtained at an OLR of 2.8 g VS L{sup −1} day{sup −1.} • Post-digestion of the digestate resulted in a CH{sub 4} yield of 0.067 L g{sup −1} VS. • Post-digestion is recommended for further digestate stabilization. - Abstract: A laboratory study investigated the anaerobic digestion of paunch in a continuous stirred tank reactor (CSTR) for the recovery of biogas and mineralization of nutrients. At an organic loading rate (OLR) of 2.8 g VS L{sup −1} day{supmore » −1} with a 30-day hydraulic retention time (HRT), a CH{sub 4} yield of 0.213 L g{sup −1} VS and CH{sub 4} production rate of 0.600 L L{sup −1} day{sup −1} were obtained. Post-anaerobic digestion of the effluent from the CSTR for 30 days at 40 °C recovered 0.067 L g{sup −1} VS as CH{sub 4}, which was 21% of the batch CH{sub 4} potential. Post-digestion of the effluent from the digestate obtained at this OLR is needed to meet the stable effluent criteria. Furthermore, low levels of soluble ions such as K{sup +}, Ca{sup 2+} and Mg{sup 2+} were found in the liquid fraction of the digestate and the remainder could have been retained in the solid digestate fraction. This study demonstrates the potential of biogas production from paunch in providing renewable energy. In addition, recovery of plant nutrients in the digestate is important for a sustainable agricultural system.« less

Response of the oceanic methane hydrate inventory to future climate change (AR5 RCP 4.5 - 8.5)

NASA Astrophysics Data System (ADS)

Hunter, S. J.; Goldobin, D.; Haywood, A. M.; Ridgwell, A. J.; Rees, J.

2012-12-01

We present results from a study designed to look at the change in global methane hydrate volume in response to AR5 Representative Concentration Pathways (Fifth Assessment Report RCP). We use bottom water conditions derived from 12 climate models within the CMIP5 multi-model ensemble along with a series of linear sea-level models to define boundary conditions. We model the change in global hydrate stability zone volume and hydrate inventory from the pre-industrial era and forward model through the RCP scenarios (to 2100 and 2300) to 5 kyr into the future. We find that thermal effects (i.e. warming induced hydrate dissociation) are dominant even when accompanied by extreme rates of sea level rise (i.e. 15 and 20 mm yr-1). Over the coming century dissociation is focussed within the top 100 m of Arctic and Subarctic sediments, beneath < ˜500 m water depth. Assuming a simple model of hydrate fill fraction (with a nominal 1% average hydrate-fill fraction) estimated globally integrated hydrate dissociation rates at ˜2100 are 120, 140 and 180 Tg CH4 yr-1 for RCP 4.5, 6.0 and 8.5 and at year ˜2300 are 150 and 600 Tg CH4 yr-1 under ECP 4.5 and 8.5 respectively. Under the unmitigated business-as-usual scenario (RCP 8.5) globally-integrated CH4 fluxes from hydrate dissociation could exceed estimates of natural sea-floor levels by 2100. Subsequent oxidation of resulting CH4 within the water column would significantly reduce atmospheric release rates to between ˜0.7 and ˜1.4 Tg CH4 yr-1 at ˜2100.

Comparative Study of Alternative Fuel Icing Inhibitor Additive Properties & Chemical Analysis of Metal Speciation in Aviation Fuels

DTIC Science & Technology

2010-08-01

paraffins, olefins, cyclo-parafins ( naphthenes ), aromatics and a host of trace species. Petroleum distillates such as jet fuels are also a complex...LC method consisted of: Mobile Phase: 95% CH3OH + 0.1% (vol) Acetic Acid 5% De-Ionized H2O Injection Volume: 5 µL Needle Wash in Flush...Port for 20 seconds using mobile phase CH3OH + 0.1% (vol) Acetic- Acid Run Time: 10 minute Post Time: 1 minute Binary Pump SL Flow Rate: 0.3 ml/min

Top-down Estimate of Methane Emissions from Natural Gas Production in Northeastern Pennsylvania Using Aircraft and Tower Observations

NASA Astrophysics Data System (ADS)

Barkley, Z.; Lauvaux, T.; Davis, K. J.; Deng, A.; Miles, N. L.; Richardson, S.; Martins, D. K.; Cao, Y.; Sweeney, C.; McKain, K.; Schwietzke, S.; Smith, M. L.; Kort, E. A.

2016-12-01

Leaks in natural gas infrastructure release CH4, a potent greenhouse gas, into the atmosphere. The estimated emission rate associated with the production and transportation of natural gas is uncertain, hindering our understanding of the energy's greenhouse footprint. This study presents two applications of inverse methodology for estimating regional emission rates from natural gas production and gathering facilities in northeastern Pennsylvania. First, we used the WRF-Chem mesoscale model at 3km resolution to simulate CH4 enhancements and compared them to observations obtained from a three-week flight campaign in May 2015 over the Marcellus shale region. Methane emission rates were adjusted to minimize the errors between aircraft observations and the model-simulated concentrations for each flight. Second, we present the first tower-based high resolution atmospheric inversion of CH4 emission rates from unconventional natural gas production activities. A year of continuous CH4 and calibrated δ13C isotope measurements were collected at four tower locations in northeastern Pennsylvania. The adjoint model used here combines a backward-in-time Lagrangian Particle Dispersion Model coupled with the WRF-Chem model at the same resolution. The prior for both optimization systems was compiled for major sources of CH4 within the Mid-Atlantic states, accounting for emissions from natural gas sources as well as emissions related to farming, waste management, coal, and other sources. Optimized natural gas emission rates are found to be 0.36% of total gas production, with a 2σ confidence interval between 0.27-0.45% of production. We present the results from the tower inversion over one year at 3km resolution providing additional information on spatial and temporal variability of emission rates from production and gathering facilities within the natural gas industry in comparison to flux estimates from the aircraft campaign.

Rate of warming affects temperature sensitivity of anaerobic peat decomposition and greenhouse gas production.

PubMed

Sihi, Debjani; Inglett, Patrick W; Gerber, Stefan; Inglett, Kanika S

2018-01-01

Temperature sensitivity of anaerobic carbon mineralization in wetlands remains poorly represented in most climate models and is especially unconstrained for warmer subtropical and tropical systems which account for a large proportion of global methane emissions. Several studies of experimental warming have documented thermal acclimation of soil respiration involving adjustments in microbial physiology or carbon use efficiency (CUE), with an initial decline in CUE with warming followed by a partial recovery in CUE at a later stage. The variable CUE implies that the rate of warming may impact microbial acclimation and the rate of carbon-dioxide (CO 2 ) and methane (CH 4 ) production. Here, we assessed the effects of warming rate on the decomposition of subtropical peats, by applying either a large single-step (10°C within a day) or a slow ramping (0.1°C/day for 100 days) temperature increase. The extent of thermal acclimation was tested by monitoring CO 2 and CH 4 production, CUE, and microbial biomass. Total gaseous C loss, CUE, and MBC were greater in the slow (ramp) warming treatment. However, greater values of CH 4 -C:CO 2 -C ratios lead to a greater global warming potential in the fast (step) warming treatment. The effect of gradual warming on decomposition was more pronounced in recalcitrant and nutrient-limited soils. Stable carbon isotopes of CH 4 and CO 2 further indicated the possibility of different carbon processing pathways under the contrasting warming rates. Different responses in fast vs. slow warming treatment combined with different endpoints may indicate alternate pathways with long-term consequences. Incorporations of experimental results into organic matter decomposition models suggest that parameter uncertainties in CUE and CH 4 -C:CO 2 -C ratios have a larger impact on long-term soil organic carbon and global warming potential than uncertainty in model structure, and shows that particular rates of warming are central to understand the response of wetland soils to global climate change. © 2017 John Wiley & Sons Ltd.

In situ methane and nitrous oxide fluxes in soil from a transect in Hennequin Point, King George Island, Antarctic.

PubMed

Vieira, Frederico Costa Beber; Pereira, Antônio Batista; Bayer, Cimélio; Schünemann, Adriano Luis; Victoria, Filipe de Carvalho; de Albuquerque, Margéli Pereira; de Oliveira, Cássio Strassburger

2013-01-01

The study aimed at to determine the magnitude of the methane (CH(4)) and nitrous oxide (N(2)O) flux rates in soils at Hennequin Point, King George Island, Antarctic, under different slope positions, vegetal covers and presence of skuas, as well as to evaluate the main soil and climate factors that are involved with the flux of such gases. In situ gas sampling (closed chamber method) was performed in four sites along a transect involving a skua nesting field in a moraine with 5% and 100% of surface covered by vegetal, and two poor-drained soils in the toeslope (a bare alluvium soil and a poor-drained moss field with 100% soil cover). Flux rates ranged from -0.86±0.45 to 2.75±1.52 μg N(2)O-N m(-2) h(-1) and -12.26±3.05 to 1.42±1.31 μg CH(4)-C m(-2) h(-1). The soil totally covered by vegetal in the skua field had the largest CH(4) influx rates. However, this benefic effect was counterbalanced by the greatest N(2)O efflux rates from this soil, resulting in the largest contribution to the global warming potential among the soils evaluated. Flux rates were closely related to soil temperature, but no significant relation was observed with mineral N contents and water-filled pore space. In turn, accumulated CH(4) and N(2)O emissions were closely related to the total N and total organic C stocks in the soil. Net CH(4) influx predominated even in the poor-drained soils, suggesting that the coarse soil texture avoided critical anaerobic conditions. No significant changes in flux rates were observed for sampling time along the day. Copyright © 2012 Elsevier Ltd. All rights reserved.

Current rates and mechanisms of subsea permafrost degradation in the East Siberian Arctic Shelf

PubMed Central

Shakhova, Natalia; Semiletov, Igor; Gustafsson, Orjan; Sergienko, Valentin; Lobkovsky, Leopold; Dudarev, Oleg; Tumskoy, Vladimir; Grigoriev, Michael; Mazurov, Alexey; Salyuk, Anatoly; Ananiev, Roman; Koshurnikov, Andrey; Kosmach, Denis; Charkin, Alexander; Dmitrevsky, Nicolay; Karnaukh, Victor; Gunar, Alexey; Meluzov, Alexander; Chernykh, Denis

2017-01-01

The rates of subsea permafrost degradation and occurrence of gas-migration pathways are key factors controlling the East Siberian Arctic Shelf (ESAS) methane (CH4) emissions, yet these factors still require assessment. It is thought that after inundation, permafrost-degradation rates would decrease over time and submerged thaw-lake taliks would freeze; therefore, no CH4 release would occur for millennia. Here we present results of the first comprehensive scientific re-drilling to show that subsea permafrost in the near-shore zone of the ESAS has a downward movement of the ice-bonded permafrost table of ∼14 cm year−1 over the past 31–32 years. Our data reveal polygonal thermokarst patterns on the seafloor and gas-migration associated with submerged taliks, ice scouring and pockmarks. Knowing the rate and mechanisms of subsea permafrost degradation is a prerequisite to meaningful predictions of near-future CH4 release in the Arctic. PMID:28639616

Methane emission from ruminants and solid waste: A critical analysis of baseline and mitigation projections for climate and policy studies

NASA Astrophysics Data System (ADS)

Matthews, E.

2012-12-01

Current and projected estimates of methane (CH4) emission from anthropogenic sources are numerous but largely unexamined or compared. Presented here is a critical appraisal of CH4 projections used in climate-chemistry and policy studies. We compare emissions for major CH4 sources from several groups, including our own new data and RCP projections developed for climate-chemistry models for the next IPCC Assessment Report (AR5). We focus on current and projected baseline and mitigation emissions from ruminant animals and solid waste that are both predicted to rise dramatically in coming decades, driven primarily by developing countries. For waste, drivers include increasing urban populations, higher per capita waste generation due to economic growth and increasing landfilling rates. Analysis of a new global data base detailing waste composition, collection and disposal indicates that IPCC-based methodologies and default data overestimate CH4 emission for the current period which cascades into substantial overestimates in future projections. CH4 emission from solid waste is estimated to be ~10-15 Tg CH4/yr currently rather than the ~35 Tg/yr often reported in the literature. Moreover, emissions from developing countries are unlikely to rise rapidly in coming decades because new management approaches, such as sanitary landfills, that would increase emissions are maladapted to infrastructures in these countries and therefore unlikely to be implemented. The low current emission associated with solid waste (~10 Tg), together with future modest growth, implies that mitigation of waste-related CH4 emission is a poor candidate for slowing global warming. In the case of ruminant animals (~90 Tg CH4/yr currently), the dominant assumption driving future trajectories of CH4 emission is a substantial increase in meat and dairy consumption in developing countries to be satisfied by growing animal populations. Unlike solid waste, current ruminant emissions among studies exhibit a narrow range that does not necessarily signal low uncertainty but rather a reliance on similar animal statistics and emission factors. The UN Food and Agriculture Organization (FAO) projects 2000-2030 growth rates of livestock for most developing countries at 2% to >3% annually. However, the assumption of rapidly rising meat consumption is not supported by current trends nor by resource availability. For example, increased meat consumption in China and other developing countries is poultry and pork that do not affect CH4 emissions, suggesting that the rapid growth projected for all animals, boosting growth in CH4 emission, will not occur. From a resource standpoint, large increases in cattle, sheep and goat populations, especially for African countries (~60% by 2030), are not supportable on arid grazing lands that require very low stocking rates and semi-nomadic management. Increases projected for African animal populations would require either that about 2/3 more animals are grazed on increasingly drier lands or that all non-forested areas become grazing lands. Similar to solid waste, future methane emission from ruminant animals is likely to grow modestly although animals are not a likely candidate for CH4 mitigation due to their dispersed distribution throughout widely varying agricultural systems under very local management.

Methanotrophy within the water column of a large meromictic tropical lake (Lake Kivu, East Africa)

NASA Astrophysics Data System (ADS)

Morana, C.; Borges, A. V.; Roland, F. A. E.; Darchambeau, F.; Descy, J.-P.; Bouillon, S.

2015-04-01

The permanently stratified Lake Kivu is one of the largest freshwater reservoirs of dissolved methane (CH4) on Earth. Yet CH4 emissions from its surface to the atmosphere have been estimated to be 2 orders of magnitude lower than the CH4 upward flux to the mixed layer, suggesting that microbial CH4 oxidation is an important process within the water column. A combination of natural abundance stable carbon isotope analysis (δ13C) of several carbon pools and 13CH4-labelling experiments was carried out during the rainy and dry season to quantify (i) the contribution of CH4-derived carbon to the biomass, (ii) methanotrophic bacterial production (MBP), and (iii) methanotrophic bacterial growth efficiency (MBGE), defined as the ratio between MBP and gross CH4 oxidation. We also investigated the distribution and the δ13C of specific phospholipid fatty acids (PLFAs), used as biomarkers for aerobic methanotrophs. Maximal MBP rates were measured in the oxycline, suggesting that CH4 oxidation was mainly driven by oxic processes. Moreover, our data revealed that methanotrophic organisms in the water column oxidized most of the upward flux of CH4, and that a significant amount of CH4-derived carbon was incorporated into the microbial biomass in the oxycline. The MBGE was variable (2-50%) and negatively related to CH4 : O2 molar ratios. Thus, a comparatively smaller fraction of CH4-derived carbon was incorporated into the cellular biomass in deeper waters, at the bottom of the oxycline where oxygen was scarce. The aerobic methanotrophic community was clearly dominated by type I methanotrophs and no evidence was found for an active involvement of type II methanotrophs in CH4 oxidation in Lake Kivu, based on fatty acids analyses. Vertically integrated over the water column, the MBP was equivalent to 16-60% of the average phytoplankton particulate primary production. This relatively high magnitude of MBP, and the substantial contribution of CH4-derived carbon to the overall biomass in the oxycline, suggest that methanotrophic bacteria could potentially sustain a significant fraction of the pelagic food web in the deep, meromictic Lake Kivu.

Thermokarst lake methanogenesis along a complete talik profile

DOE PAGES

Heslop, J. K.; Walter Anthony, K. M.; Sepulveda-Jauregui, A.; ...

2015-07-24

Here, thermokarst (thaw) lakes emit methane (CH 4) to the atmosphere formed from thawed permafrost organic matter (OM), but the relative magnitude of CH 4 production in surface lake sediments vs. deeper thawed permafrost horizons is not well understood. We assessed anaerobic CH 4 production potentials from various depths along a 590 cm long lake sediment core that captured the entire sediment package of the talik (thaw bulb) beneath the center of an interior Alaska thermokarst lake, Vault Lake, and the top 40 cm of thawing permafrost beneath the talik. We also studied the adjacent Vault Creek permafrost tunnel thatmore » extends through ice-rich yedoma permafrost soils surrounding the lake and into underlying gravel. Our results showed CH 4 production potentials were highest in the organic-rich surface lake sediments, which were 151 cm thick (mean ± SD: 5.95 ± 1.67 μg C–CH 4 g dw –1 d –1; 125.9 ± 36.2 μg C–CH 4 g C −1 org d –1). High CH 4 production potentials were also observed in recently thawed permafrost (1.18 ± 0.61 μg C–CH 4g dw –1 d –1; 59.60± 51.5 μg C–CH 4 g C −1 org d –1) at the bottom of the talik, but the narrow thicknesses (43 cm) of this horizon limited its overall contribution to total sediment column CH 4 production in the core. Lower rates of CH 4 production were observed in sediment horizons representing permafrost that has been thawing in the talik for a longer period of time. No CH 4 production was observed in samples obtained from the permafrost tunnel, a non-lake environment. Our findings imply that CH 4 production is highly variable in thermokarst lake systems and that both modern OM supplied to surface sediments and ancient OM supplied to both surface and deep lake sediments by in situ thaw and shore erosion of yedoma permafrost are important to lake CH 4 production.« less

Thermokarst lake methanogenesis along a complete talik profile

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

Heslop, J. K.; Walter Anthony, K. M.; Sepulveda-Jauregui, A.

Here, thermokarst (thaw) lakes emit methane (CH 4) to the atmosphere formed from thawed permafrost organic matter (OM), but the relative magnitude of CH 4 production in surface lake sediments vs. deeper thawed permafrost horizons is not well understood. We assessed anaerobic CH 4 production potentials from various depths along a 590 cm long lake sediment core that captured the entire sediment package of the talik (thaw bulb) beneath the center of an interior Alaska thermokarst lake, Vault Lake, and the top 40 cm of thawing permafrost beneath the talik. We also studied the adjacent Vault Creek permafrost tunnel thatmore » extends through ice-rich yedoma permafrost soils surrounding the lake and into underlying gravel. Our results showed CH 4 production potentials were highest in the organic-rich surface lake sediments, which were 151 cm thick (mean ± SD: 5.95 ± 1.67 μg C–CH 4 g dw –1 d –1; 125.9 ± 36.2 μg C–CH 4 g C −1 org d –1). High CH 4 production potentials were also observed in recently thawed permafrost (1.18 ± 0.61 μg C–CH 4g dw –1 d –1; 59.60± 51.5 μg C–CH 4 g C −1 org d –1) at the bottom of the talik, but the narrow thicknesses (43 cm) of this horizon limited its overall contribution to total sediment column CH 4 production in the core. Lower rates of CH 4 production were observed in sediment horizons representing permafrost that has been thawing in the talik for a longer period of time. No CH 4 production was observed in samples obtained from the permafrost tunnel, a non-lake environment. Our findings imply that CH 4 production is highly variable in thermokarst lake systems and that both modern OM supplied to surface sediments and ancient OM supplied to both surface and deep lake sediments by in situ thaw and shore erosion of yedoma permafrost are important to lake CH 4 production.« less

Non-microbial methane emissions from soils

NASA Astrophysics Data System (ADS)

Wang, Bin; Hou, Longyu; Liu, Wei; Wang, Zhiping

2013-12-01

Traditionally, methane (CH4) is anaerobically formed by methanogenic archaea. However, non-microbial CH4 can also be produced from geologic processes, biomass burning, animals, plants, and recently identified soils. Recognition of non-microbial CH4 emissions from soils remains inadequate. To better understand this phenomenon, a series of laboratory incubations were conducted to examine effects of temperature, water, and hydrogen peroxide (H2O2) on CH4 emissions under both aerobic and anaerobic conditions using autoclaved (30 min, 121 °C) soils and aggregates (>2000 μm, A1; 2000-250 μm, A2; 250-53 μm, M1; and <53 μm, M2). Results show that applying autoclaving to pre-treat soils is effective to inhibit methanogenic activity, ensuring the CH4 emitted being non-microbial. Responses of non-microbial CH4 emissions to temperature, water, and H2O2 were almost identical between aerobic and anaerobic conditions. Increasing temperature, water of proper amount, and H2O2 could significantly enhance CH4 emissions. However, the emission rates were inhibited and enhanced by anaerobic conditions without and with the existence of H2O2, respectively. As regards the aggregates, aggregate-based emission presented an order of M1 > A2 > A1 > M2 and C-based emission an order of M2 > M1 > A1 > A2, demonstrating that both organic carbon quantity and property are responsible for CH4 emissions from soils at the scale of aggregate. Whole soil-based order of A2 > A1 > M1 > M2 suggests that non-microbial CH4 release from forest soils is majorly contributed by macro-aggregates (i.e., >250 μm). The underlying mechanism is that organic matter through thermal treatment, photolysis, or reactions with free radicals produce CH4, which, in essence, is identical with mechanisms of other non-microbial sources, indicating that non-microbial CH4 production may be a widespread phenomenon in nature. This work further elucidates the importance of non-microbial CH4 formation which should be distinguished from the well-known microbial CH4 formation in order to define both roles in the atmospheric CH4 global budget.

Intermediate-scale community-level flux of CO 2 and CH 4 in a Minnesota peatland: Putting the SPRUCE project in a global context

DOE PAGES

Hanson, Paul J.; Gill, Allison; Xu, Xiaofeng; ...

2016-08-20

Peatland measurements of CO 2 and CH 4 flux were obtained at scales appropriate to the in situ biological community below the tree layer to demonstrate representativeness of the spruce and peatland responses under climatic and environmental change (SPRUCE) experiment. Surface flux measurements were made using dual open-path analyzers over an area of 1.13 m 2 in daylight and dark conditions along with associated peat temperatures, water table height, hummock moisture, atmospheric pressure and incident radiation data. Observations from August 2011 through December 2014 demonstrated seasonal trends correlated with temperature as the dominant apparent driving variable. The S1-Bog for themore » SPRUCE study was found to be representative of temperate peatlands in terms of CO 2 and CH 4 flux. Maximum net CO 2 flux in midsummer showed similar rates of C uptake and loss: daytime surface uptake was -5 to -6 µmol m -2 s -1 and dark period loss rates were 4–5 µmol m -2 s -1 (positive values are carbon lost to the atmosphere). Maximum midsummer CH4-C flux ranged from 0.4 to 0.5 µmol m -2 s -1 and was a factor of 10 lower than dark CO 2–C efflux rates. Midwinter conditions produced near-zero flux for both CO 2 and CH 4 with frozen surfaces. Integrating temperature-dependent models across annual periods showed dark CO 2–C and CH 4–C flux to be 894 ± 34 and 16 ± 2 gC m -2 y -1, respectively. Net ecosystem exchange of carbon from the shrub-forb-Sphagnum-microbial community (excluding tree contributions) ranged from -3.1 gCO2–C m -2 y -1 in 2013, to C losses from 21 to 65 gCO 2–C m -2 y -1 for the other years.« less

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.

CH{sub 4} and N{sub 2}O emissions from China’s beef feedlots with ad libitum and restricted feeding in fall and spring seasons

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

Lin, Zhi; Liao, Wenhua; Yang, Yuanyuan

Accurately quantifying methane (CH{sub 4}) and nitrous oxide (N{sub 2}O) emissions from beef operations in China is necessary to evaluate the contribution of beef cattle to greenhouse gas budgets at the national and global level. Methane and N{sub 2}O emissions from two intensive beef feedlots in the North China Plain, one with a restricted feeding strategy and high manure collection frequency and the other with an ad libitum feeding strategy and low manure collection frequency, were quantified in the fall and spring seasons using an inverse dispersion technique. The diel pattern of CH{sub 4} from the beef feedlot with anmore » ad libitum feed strategy (single peak during a day) differed from that under a restricted feeding condition (multiple peaks during a day), but little difference in the diel pattern of N{sub 2}O emissions between two feeding strategies was observed. The two-season average CH{sub 4} emission rates of the two intensive feedlots were 230 and 198 g CH{sub 4} animal{sup −1} d{sup −1} and accounted for 6.7% and 6.8% of the gross energy intake, respectively, indicating little impact of the feeding strategy and manure collection frequency on the CH{sub 4} conversion factor at the feedlot level. However, the average N{sub 2}O emission rates (21.2 g N{sub 2}O animal{sup −1} d{sup −1}) and conversion factor (8.5%) of the feedlot with low manure collection frequency were approximately 131% and 174% greater, respectively, than the feedlot under high frequency conditions, which had a N{sub 2}O emission rate and conversion factor of 9.2 g N{sub 2}O animal{sup −1} d{sup −1} and 3.1%, respectively, indicating that increasing manure collection frequency played an important role in reducing N{sub 2}O emissions from beef feedlots. In addition, comparison indicated that China’s beef and dairy cattle in feedlots appeared to have similar CH{sub 4} conversion factors. - Highlights: • CH{sub 4} and N{sub 2}O emissions from China’s beef feedlots were provided in the first time. • Feeding strategies determined the diurnal pattern of feedlot CH{sub 4} emission. • Frequency of manure collection played an important role in N{sub 2}O from feedlots.« less

Between-cow variation in digestion and rumen fermentation variables associated with methane production.

PubMed

Cabezas-Garcia, E H; Krizsan, S J; Shingfield, K J; Huhtanen, P

2017-06-01

A meta-analysis based on an individual-cow data set was conducted to investigate the effects of between-cow variation and related animal variables on predicted CH 4 emissions from dairy cows. Data were taken from 40 change-over studies consisting of a total of 637 cow/period observations. Animal production and rumen fermentation characteristics were measured for 154 diets in 40 studies; diet digestibility was measured for 135 diets in 34 studies, and ruminal digestion kinetics was measured for 56 diets in 15 studies. The experimental diets were based on grass silage, with cereal grains or by-products as energy supplements, and soybean or canola meal as protein supplements. Average forage:concentrate ratio across all diets on a dry matter basis was 59:41. Methane production was predicted from apparently fermented substrate using stoichiometric principles. Data were analyzed by mixed-model regression using diet and period within experiment as random effects, thereby allowing the effect of experiment, diet, and period to be excluded. Dry matter intake and milk yield were more repeatable experimental measures than rumen fermentation, nutrient outflow, diet digestibility, or estimated CH 4 yield. Between-cow coefficient of variation (CV) was 0.010 for stoichiometric CH 4 per mol of volatile fatty acids and 0.067 for predicted CH 4 yield (CH 4 /dry matter intake). Organic matter digestibility (OMD) also displayed little between-cow variation (CV = 0.013), indicating that between-cow variation in diet digestibility and rumen fermentation pattern do not markedly contribute to between cow-variation in CH 4 yield. Digesta passage rate was much more variable (CV = 0.08) between cows than OMD or rumen fermentation pattern. Increased digesta passage rate is associated with improved energetic efficiency of microbial N synthesis, which partitions fermented substrate from volatile fatty acids and gases to microbial cells that are more reduced than fermented carbohydrates. Positive relationships were observed between CH 4 per mol of volatile fatty acids versus OMD and rumen ammonia N concentration versus OMD; and negative relationships between the efficiency of microbial N synthesis versus OMD and digesta passage rate versus OMD, suggesting that the effects of these variables on CH 4 yield were additive. It can be concluded that variations in OMD and efficiency in microbial N synthesis resulting from variations in digesta passage contribute more to between-animal variation in CH 4 emissions than rumen fermentation pattern. Copyright © 2017 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

Tidal variability of CO2 and CH4 emissions from the water column within a Rhizophora mangrove forest (New Caledonia).

PubMed

Jacotot, Adrien; Marchand, Cyril; Allenbach, Michel

2018-08-01

We performed a preliminary study to quantify CO 2 and CH 4 emissions from the water column within a Rhizophora spp. mangrove forest. Mean CO 2 and CH 4 emissions during the studied period were 3.35±3.62mmolCm -2 h -1 and 18.30±27.72μmolCm -2 h -1 , respectively. CO 2 and CH 4 emissions were highly variable and mainly driven by tides (flow/ebb, water column thickness, neap/spring). Indeed, an inverse relationship between the magnitude of the emissions and the thickness of the water column above the mangrove soil was observed. δ 13 CO 2 values ranged from -26.88‰ to -8.6‰, suggesting a mixing between CO 2 -enriched pore waters and lagoon incoming waters. In addition, CO 2 and CH 4 emissions were significantly higher during ebb tides, mainly due to the progressive enrichment of the water column by diffusive fluxes as its residence time over the forest floor increased. Eventually, we observed higher CO 2 and CH 4 emissions during spring tides than during neap tides, combined to depleted δ 13 CO 2 values, suggesting a higher contribution of soil-produced gases to the emissions. These higher emissions may result from higher renewable of the electron acceptor and enhanced exchange surface between the soil and the water column. This study shows that CO 2 and CH 4 emissions from the water column were not negligible and must be considered in future carbon budgets in mangroves. Copyright © 2018 Elsevier B.V. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2015-09-01

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

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

NASA Astrophysics Data System (ADS)

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

2016-03-01

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

Biotransformation and biodegradation of selected nitroaromatics under anaerobic conditions

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

Razo-Flores, E.; Lettinga, G.; Field, J.A.

The fate of four nitroaromatic compounds (5-nitrosalicylate, 5NSA; 4-nitrobenzoate, 4NBc; 2,4-dinitrotoluene, 2,4DNT; nitrobenzene, NB) was studied in 160 mL laboratory-scale upward-flow anaerobic sludge bed reactors supplied with a mixture of volatile fatty acids and/or glucose as electron donors. All the nitroaromatics were transformed stoichiometrically to their corresponding aromatic amines. After prolonged reactor operation, 5NSA and 4NBc were completely mineralized to CH[sub 4] and CO[sub 2], whereas 2,4DNT was partially transformed to a nonidentified and nondegradable metabolite. Batch nitro-reduction experiments indicated that the position of the nitro group in relation to the other substituents in the aromatic ring plays a keymore » role in the rate of the nitro-group reduction. The results obtained indicate that certain nitroaromatic compounds can be completely mineralized and serve as a carbon and energy source for anaerobic bacteria.« less

DEVELOPMENT OF AN EMPIRICAL MODEL OF METHANE EMISSIONS FROM LANDFILLS

EPA Science Inventory

The report gives results of a field study of 21 U.S. landfills with gas recovery systems, to gather information that can be used to develop an empirical model of methane (CH4) emissions. Site-specific information includes average CH4 recovery rate, landfill size, tons of refuse (...

High methane emissions from a midlatitude reservoir draining an agricultural watershed

EPA Science Inventory

To assess the magnitude of methane (CH4) emissions from reservoirs in mid-latitude agricultural regions, we measured CH4 and carbon dioxide (CO2) emission rates from William H. Harsha Lake, an agricultural impacted reservoir located in southwestern Ohio, USA, over a thirteen mont...

Methane emission through ebullition from an estuarine mudflat: 2. Field observations and modeling of occurrence probability

NASA Astrophysics Data System (ADS)

Chen, Xi; Schäfer, Karina V. R.; Slater, Lee

2017-08-01

Ebullition can transport methane (CH4) at a much faster rate than other pathways, albeit over limited time and area, in wetland soils and sediments. However, field observations present large uncertainties in ebullition occurrences and statistic models are needed to describe the function relationship between probability of ebullition occurrence and water level changes. A flow-through chamber was designed and installed in a mudflat of an estuarine temperate marsh. Episodic increases in CH4 concentration signaling ebullition events were observed during ebbing tides (15 events over 456 ebbing tides) and occasionally during flooding tides (4 events over 455 flooding tides). Ebullition occurrence functions were defined using logistic regression as the relative initial and end water levels, as well as tidal amplitudes were found to be the key functional variables related to ebullition events. Ebullition of methane was restricted by a surface frozen layer during winter; melting of this layer during spring thaw caused increases in CH4 concentration, with ebullition fluxes similar to those associated with large fluctuations in water level around spring tides. Our findings suggest that initial and end relative water levels, in addition to tidal amplitude, partly regulate ebullition events in tidal wetlands, modulated by the lunar cycle, storage of gas bubbles at different depths and seasonal changes in the surface frozen layer. Maximum tidal strength over a few days, rather than hourly water level, may be more closely associated with the possibility of ebullition occurrence as it represents a trade-off time scale in between hourly and lunar periods.

Subsurface injection of combustion power plant effluent as a solid-phase carbon dioxide storage strategy

NASA Astrophysics Data System (ADS)

Darnell, K. N.; Flemings, P. B.; DiCarlo, D.

2017-06-01

Long-term geological storage of CO2 may be essential for greenhouse gas mitigation, so a number of storage strategies have been developed that utilize a variety of physical processes. Recent work shows that injection of combustion power plant effluent, a mixture of CO2 and N2, into CH4 hydrate-bearing reservoirs blends CO2 storage with simultaneous CH4 production where the CO2 is stored in hydrate, an immobile, solid compound. This strategy creates economic value from the CH4 production, reduces the preinjection complexity since costly CO2 distillation is circumvented, and limits leakage since hydrate is immobile. Here we explore the phase behavior of these types of injections and describe the individual roles of H2O, CO2, CH4, and N2 as these components partition into aqueous, vapor, hydrate, and liquid CO2 phases. Our results show that CO2 storage in subpermafrost or submarine hydrate-forming reservoirs requires coinjection of N2 to maintain two-phase flow and limit plugging.

Preparation and optimization of self-assembled chondroitin sulfate-nisin nanogel based on quality by design concept.

PubMed

Mohtashamian, Shahab; Boddohi, Soheil; Hosseinkhani, Saman

2018-02-01

Self-assembled nanogel was prepared by electrostatic complexation of two oppositely charged biological macromolecules, which were cationic nisin and anionic chondroitin sulfate (ChS). The critical factors affected the physical properties of ChS-nisin nanogel was screened and optimized by Plackett-Burman design (PB) and central composite design (CCD). The independent factors selected were: concentration ratio of nisin to ChS, injection rate of nisin solution, buffer solvent type, magnetic stirring rate, pH of initial buffer solution, centrifuge-cooling temperature, and centrifuge rotation speed. Among these factors, concentration ratio changed the entrapment efficiency and loading capacity significantly. In addition, the hydrodynamic diameter and loading capacity were significantly influenced by injection rate and pH of initial buffer solution. The optimized nanogel structure was obtained by concentration ratio of 6.4mg/mL nisin to 1mg/mL ChS, pH of buffer solution at 4.6, and nisin solution injection rate of 0.2mL/min. The observed values of dependent responses were close to predicted values confirmed by model from response surface methodology. The results obviously showed that quality by design concept (QbD) could be effectively applied to optimize the developed ChS-nisin nanogel. Copyright © 2017 Elsevier B.V. All rights reserved.

Metal-Organic Frameworks as Highly Active Electrocatalysts for High-Energy Density, Aqueous Zinc-Polyiodide Redox Flow Batteries.

PubMed

Li, Bin; Liu, Jian; Nie, Zimin; Wang, Wei; Reed, David; Liu, Jun; McGrail, Pete; Sprenkle, Vincent

2016-07-13

The new aqueous zinc-polyiodide redox flow battery (RFB) system with highly soluble active materials as well as ambipolar and bifunctional designs demonstrated significantly enhanced energy density, which shows great potential to reduce RFB cost. However, the poor kinetic reversibility and electrochemical activity of the redox reaction of I3(-)/I(-) couples on graphite felts (GFs) electrode can result in low energy efficiency. Two nanoporous metal-organic frameworks (MOFs), MIL-125-NH2 and UiO-66-CH3, that have high surface areas when introduced to GF surfaces accelerated the I3(-)/I(-) redox reaction. The flow cell with MOF-modified GFs serving as a positive electrode showed higher energy efficiency than the pristine GFs; increases of about 6.4% and 2.7% occurred at the current density of 30 mA/cm(2) for MIL-125-NH2 and UiO-66-CH3, respectively. Moreover, UiO-66-CH3 is more promising due to its excellent chemical stability in the weakly acidic electrolyte. This letter highlights a way for MOFs to be used in the field of RFBs.

Evaluation of thermal infrared hyperspectral imagery for the detection of onshore methane plumes: Significance for hydrocarbon exploration and monitoring

NASA Astrophysics Data System (ADS)

Scafutto, Rebecca DeĺPapa Moreira; de Souza Filho, Carlos Roberto; Riley, Dean N.; de Oliveira, Wilson Jose

2018-02-01

Methane (CH4) is the main constituent of natural gas. Fugitive CH4 emissions partially stem from geological reservoirs (seepages) and leaks in pipelines and petroleum production plants. Airborne hyperspectral sensors with enough spectral and spatial resolution and high signal-to-noise ratio can potentially detect these emissions. Here, a field experiment performed with controlled release CH4 sources was conducted in the Rocky Mountain Oilfield Testing Center (RMOTC), Casper, WY (USA). These sources were configured to deliver diverse emission types (surface and subsurface) and rates (20-1450 scf/hr), simulating natural (seepages) and anthropogenic (pipeline) CH4 leaks. The Aerospace Corporation's SEBASS (Spatially-Enhanced Broadband Array Spectrograph System) sensor acquired hyperspectral thermal infrared data over the experimental site with 128 bands spanning the 7.6 μm-13.5 μm range. The data was acquired with a spatial resolution of 0.5 m at 1500 ft and 0.84 m at 2500 ft above ground level. Radiance images were pre-processed with an adaptation of the In-Scene Atmospheric Compensation algorithm and converted to emissivity through the Emissivity Normalization algorithm. The data was processed with a Matched Filter. Results allowed the separation between endmembers related to the spectral signature of CH4 from the background. Pixels containing CH4 signatures (absorption bands at 7.69 μm and 7.88 μm) were highlighted and the gas plumes mapped with high definition in the imagery. The dispersion of the mapped plumes is consistent with the wind direction measured independently during the experiment. Variations in the dimension of mapped gas plumes were proportional to the emission rate of each CH4 source. Spectral analysis of the signatures within the plumes shows that CH4 spectral absorption features are sharper and deeper in pixels located near the emitting source, revealing regions with higher gas density and assisting in locating CH4 sources in the field accurately. These results indicate that thermal infrared hyperspectral imaging can support the oil industry profusely, by revealing new petroleum plays through direct detection of gaseous hydrocarbon seepages, serving as tools to monitor leaks along pipelines and oil processing plants, while simultaneously refining estimates of CH4 emissions.

Effects of permafrost thaw on carbon emissions under aerobic and anaerobic environments in the Great Hing'an Mountains, China.

PubMed

Song, Changchun; Wang, Xianwei; Miao, Yuqing; Wang, Jiaoyue; Mao, Rong; Song, Yanyu

2014-07-15

The carbon (C) pool of permafrost peatland is very important for the global C cycle. Little is known about how permafrost thaw could influence C emissions in the Great Hing'an Mountains of China. Through aerobic and anaerobic incubation experiments, we studied the effects of permafrost thaw on CH4 and CO2 emissions. The rates of CH4 and CO2 emissions were measured at -10, 0 and 10°C. Although there were still C emissions below 0°C, rates of CH4 and CO2 emissions significantly increased with permafrost thaw under aerobic and anaerobic conditions. The C release under aerobic conditions was greater than under anaerobic conditions, suggesting that permafrost thaw and resulting soil environment change should be important influences on C emissions. However, CH4 stored in permafrost soils could affect accurate estimation of CH4 emissions from microbial degradation. Calculated Q10 values in the permafrost soils were significantly higher than values in active-layer soils under aerobic conditions. Our results highlight that permafrost soils have greater potential decomposability than soils of the active layer, and such carbon decomposition would be more responsive to the aerobic environment. © 2013 Elsevier B.V. All rights reserved.

Effect of Feed Gas Flow Rate on CO2 Absorption through Super Hydrophobic Hollow Fiber membrane Contactor

NASA Astrophysics Data System (ADS)

Kartohardjono, Sutrasno; Alexander, Kevin; Larasati, Annisa; Sihombing, Ivander Christian

2018-03-01

Carbon dioxide is pollutant in natural gas that could reduce the heating value of the natural gas and cause problem in transportation due to corrosive to the pipeline. This study aims to evaluate the effects of feed gas flow rate on CO2 absorption through super hydrophobic hollow fiber contactor. Polyethyleneglycol-300 (PEG-300) solution was used as absorbent in this study, whilst the feed gas used in the experiment was a mixture of 30% CO2 and 70% CH4. There are three super hydrophobic hollow fiber contactors sized 6 cm and 25 cm in diameter and length used in this study, which consists of 1000, 3000 and 5000 fibers, respectively. The super hydrophobic fiber membrane used is polypropylene-based with outer and inner diameter of about 525 and 235 μm, respectively. In the experiments, the feed gas was sent through the shell side of the membrane contactor, whilst the absorbent solution was pumped through the lumen fibers. The experimental results showed that the mass transfer coefficient, flux, absorption efficiency for CO2-N2 system and CO2 loading increased with the feed gas flow rate, but the absorption efficiency for CO2-N2 system decreased. The mass transfer coefficient and the flux, at the same feed gas flow rate, decreased with the number of fibers in the membrane contactor, but the CO2 absorption efficiency and the CO2 loading increased.

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

Simulating CH4 and N2O emissions from direct-seeded rice systems using the DeNitrification DeComposition (DNDC) model

NASA Astrophysics Data System (ADS)

Simmonds, M.; Li, C.; Lee, J.; Six, J.; Van Kessel, C.; Linquist, B.

2015-12-01

Process-based modeling of CH4 and N2O emissions from rice fields is a practical tool for conducting greenhouse gas inventories and estimating mitigation potentials of alternative practices at the scales of management and policy-making. However, few studies have evaluated site-level model performance in side-by-side field trials of various management practices during both the growing season and fallow periods. We empirically evaluated the DeNitrification-DeComposition (DNDC) model for estimating CH4 and N2O fluxes in California rice systems under varying management (N fertilizer application rate, type of seeding system, fallow period straw and water management), soil environments, and weather conditions. Five and nine site-year combinations were used for calibration and validation, respectively. The model was parameterized for two cultivars, M206 and Koshihikari, and able to simulate 30% and 78% of the measured variation in yields, respectively. A major strength of DNDC was in estimating general site-level seasonal CH4 emissions (R2 = 0.85). However, a major limitation was in simulating finer resolution of differences in CH4 emissions (or lack thereof) among side-by-side management treatments (range of 0.2-465% relative absolute deviation). Additionally, DNDC did not satisfactorily simulate fallow period CH4 emissions, or seasonal and fallow period N2O emissions across all sites with the exception of a few cases. Specifically, simulated CH4 emissions were oversensitive to fertilizer N rates, but lacked sensitivity to the type of seeding system and prior fallow period straw management. Additionally, N2O emissions were oversensitive to fertilizer N rates and field drainage. Sensitivity analysis showed that CH4 emissions were highly sensitive to changes in the root to total plant biomass ratio. Overall, uncertainty in model predictions was attributed to uncertainty in both the input parameters due to in-field spatiotemporal variability of soil properties, and in the model structure (e.g., genotype by environment interactions, clay effects, and simulation routines for field drainage, and diffusion and ebullition of gasses). These findings have implications for model-directed field research that could improve model uncertainty for application at larger spatial scales.

Atmospheric chemistry of cyc-CF2CF2CF2CH=CH-: Kinetics, products, and mechanism of gas-phase reaction with OH radicals, and atmospheric implications

NASA Astrophysics Data System (ADS)

Guo, Qin; Zhang, Ni; Uchimaru, Tadafumi; Chen, Liang; Quan, Hengdao; Mizukado, Junji

2018-04-01

The rate constants for the gas-phase reactions of cyc-CF2CF2CF2CH=CH- with OH radicals were determined by a relative rate method between 253 and 328 K. The rate constant k1 at 298 K was measured to be (1.08 ± 0.04) × 10-13 cm3 molecule-1 s-1, and the Arrhenius expression was k1 = (3.72 ± 0.14) × 10-13 exp [(-370 ± 12)/T]. The atmospheric lifetime of cyc-CF2CF2CF2CH=CH- was calculated to be 107 d. The products and mechanism for the reaction of cyc-CF2CF2CF2CH=CH- with OH radicals were also investigated. CO, CO2, and COF2 were identified as the main carbon-containing products following the OH-initiated reaction. Moreover, the radiative efficiency (RE) was determined to be 0.143 W m-2 ppb-1, and the global warming potentials (GWPs) for 20, 100, and 500 yr were 54, 15, and 4, respectively. The photochemical ozone creation potential of the title compound was estimated to be 1.3.

Experimental and theoretical study of the gas phase reaction of ethynyl radical with methane (HCC+CH 4)

NASA Astrophysics Data System (ADS)

Ceursters, Benny; Thi Nguyen, Hue Minh; Peeters, Jozef; Tho Nguyen, Minh

2000-10-01

Absolute rate coefficients of the reaction of ethynyl radical with methane were measured for the first time at higher temperatures by a pulsed laser photolysis/chemiluminescence (PLP/CL) technique. Ethynyl radicals (HCC) radicals were generated pulsewise upon excimer laser photodissociation of acetylene at 193 nm and pseudo-first-order exponential decays of thermalized HCC were monitored in real-time by the CH( A2Δ → X2Π ) chemiluminescence produced by their reaction with O 2. The rate coefficients k(HCC+CH 4), over 295⩽T ( K)<800 , exhibit strong non-Arrhenius behaviour, being k(T)=1.39×10 -18T 2.34±0.40exp[(380±180) K/T] cm3 molecule-1 s-1. Calculations at the CCSD(T)/aug-cc-pvTZ level reveal that the direct H-abstraction yielding HCCH+CH 3 has the lowest energy barrier of about 10 kJ mol -1.

Development of temporary subtropical wetlands induces higher gas production

PubMed Central

Canterle, Eliete B.; da Motta Marques, David; Rodrigues, Lúcia R.

2013-01-01

Temporary wetlands are short-term alternative ecosystems formed by flooding for irrigation of areas used for rice farming. The goal of this study is to describe the development cycle of rice fields as temporary wetlands in southern Brazil, evaluating how this process affect the gas production (CH4 and CO2) in soil with difference % carbon and organic matter content. Two areas adjacent to Lake Mangueira in southern Brazil were used during a rice-farming cycle. One area had soil containing 1.1% carbon and 2.4% organic matter, and the second area had soil with 2.4% carbon and 4.4% organic matter. The mean rates of gas production were 0.04 ± 0.02 mg CH4 m−2 d−1 and 1.18 ± 0.30 mg CO2 m−2 d−1 in the soil area with the lower carbon content, and 0.02 ± 0.03 mg CH4 m−2 d−1 and 1.38 ± 0.41 mg CO2 m−2 d−1 in the soil area with higher carbon content. Our results showed that mean rates of CO2 production were higher than those of CH4 in both areas. No statistically significant difference was observed for production of CH4 considering different periods and sites. For carbon dioxide (CO2), however, a Two-Way ANOVA showed statistically significant difference (p = 0.05) considering sampling time, but no difference between areas. The results obtained suggest that the carbon and organic matter contents in the soil of irrigated rice cultivation areas may have been used in different ways by soil microorganisms, leading to variations in CH4 and CO2 production. PMID:23508352

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.

Methane exchange at the peatland forest floor - automatic chamber system exposes the dynamics of small fluxes

NASA Astrophysics Data System (ADS)

Korkiakoski, Mika; Tuovinen, Juha-Pekka; Aurela, Mika; Koskinen, Markku; Minkkinen, Kari; Ojanen, Paavo; Penttilä, Timo; Rainne, Juuso; Laurila, Tuomas; Lohila, Annalea

2017-04-01

We measured methane (CH4) exchange rates with automatic chambers at the forest floor of a nutrient-rich drained peatland in 2011-2013. The fen, located in southern Finland, was drained for forestry in 1969 and the tree stand is now a mixture of Scots pine, Norway spruce, and pubescent birch. Our measurement system consisted of six transparent chambers and stainless steel frames, positioned on a number of different field and moss layer compositions. Gas concentrations were measured with an online cavity ring-down spectroscopy gas analyzer. Fluxes were calculated with both linear and exponential regression. The use of linear regression resulted in systematically smaller CH4 fluxes by 10-45 % as compared to exponential regression. However, the use of exponential regression with small fluxes ( < 2.5 µg CH4 m-2 h-1) typically resulted in anomalously large absolute fluxes and high hour-to-hour deviations. Therefore, we recommend that fluxes are initially calculated with linear regression to determine the threshold for low fluxes and that higher fluxes are then recalculated using exponential regression. The exponential flux was clearly affected by the length of the fitting period when this period was < 190 s, but stabilized with longer periods. Thus, we also recommend the use of a fitting period of several minutes to stabilize the results and decrease the flux detection limit. There were clear seasonal dynamics in the CH4 flux: the forest floor acted as a CH4 sink particularly from early summer until the end of the year, while in late winter the flux was very small and fluctuated around zero. However, the magnitude of fluxes was relatively small throughout the year, ranging mainly from -130 to +100 µg CH4 m-2 h-1. CH4 emission peaks were observed occasionally, mostly in summer during heavy rainfall events. Diurnal variation, showing a lower CH4 uptake rate during the daytime, was observed in all of the chambers, mainly in the summer and late spring, particularly in dry conditions. It was attributed more to changes in wind speed than air or soil temperature, which suggest that physical rather than biological phenomena are responsible for the observed variation. The annual net CH4 exchange varied from -104 ± 30 to -505 ± 39 mg CH4 m-2 yr-1 among the six chambers, with an average of -219 mg CH4 m-2 yr-1 over the 2-year measurement period.

Atmospheric chemistry of CF3CF═CH2 and (Z)-CF3CF═CHF: Cl and NO3 rate coefficients, Cl reaction product yields, and thermochemical calculations.

PubMed

Papadimitriou, Vassileios C; Lazarou, Yannis G; Talukdar, Ranajit K; Burkholder, James B

2011-01-20

Rate coefficients, k, for the gas-phase reactions of Cl atoms and NO(3) radicals with 2,3,3,3-tetrafluoropropene, CF(3)CF═CH(2) (HFO-1234yf), and 1,2,3,3,3-pentafluoropropene, (Z)-CF(3)CF═CHF (HFO-1225ye), are reported. Cl-atom rate coefficients were measured in the fall-off region as a function of temperature (220-380 K) and pressure (50-630 Torr; N(2), O(2), and synthetic air) using a relative rate method. The measured rate coefficients are well represented by the fall-off parameters k(0)(T) = 6.5 × 10(-28) (T/300)(-6.9) cm(6) molecule(-2) s(-1) and k(∞)(T) = 7.7 × 10(-11) (T/300)(-0.65) cm(3) molecule(-1) s(-1) for CF(3)CF═CH(2) and k(0)(T) = 3 × 10(-27) (T/300)(-6.5) cm(6) molecule(-2) s(-1) and k(∞)(T) = 4.15 × 10(-11) (T/300)(-0.5) cm(3) molecule(-1) s(-1) for (Z)-CF(3)C═CHF with F(c) = 0.6. Reaction product yields were measured in the presence of O(2) to be (98 ± 7)% for CF(3)C(O)F and (61 ± 4)% for HC(O)Cl in the CF(3)CF═CH(2) reaction and (108 ± 8)% for CF(3)C(O)F and (112 ± 8)% for HC(O)F in the (Z)-CF(3)CF═CHF reaction, where the quoted uncertainties are 2σ (95% confidence level) and include estimated systematic errors. NO(3) reaction rate coefficients were determined using absolute and relative rate methods. Absolute measurements yielded upper limits for both reactions between 233 and 353 K, while the relative rate measurements yielded k(3)(295 K) = (2.6 ± 0.25) × 10(-17) cm(3) molecule(-1) s(-1) and k(4)(295 K) = (4.2 ± 0.5) × 10(-18) cm(3) molecule(-1) s(-1) for CF(3)CF═CH(2) and (Z)-CF(3)CF═CHF, respectively. The Cl-atom reaction with CF(3)CF═CH(2) and (Z)-CF(3)CF═CHF leads to decreases in their atmospheric lifetimes and global warming potentials and formation of a chlorine-containing product, HC(O)Cl, for CF(3)CF═CH(2). The NO(3) reaction has been shown to have a negligible impact on the atmospheric lifetimes of CF(3)CF═CH(2) and (Z)-CF(3)CF═CHF. The energetics for the reaction of Cl, NO(3), and OH with CF(3)CF═CH(2) and (Z)-CF(3)CF═CHF in the presence of O(2) were investigated using density functional theory (DFT).

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.